Atmospheric dispersion of natural carbon dioxide emissions on Vulcano Island, Italy

NASA Astrophysics Data System (ADS)

Granieri, D.; Carapezza, M. L.; Barberi, F.; Ranaldi, M.; Ricci, T.; Tarchini, L.

2014-07-01

La Fossa quiescent volcano and its surrounding area on the Island of Vulcano (Italy) are characterized by intensive, persistent degassing through both fumaroles and diffuse soil emissions. Periodic degassing crises occur, with marked increase in temperature and steam and gas output (mostly CO2) from crater fumaroles and in CO2 soil diffuse emission from the crater area as well as from the volcano flanks and base. The gas hazard of the most inhabited part of the island, Vulcano Porto, was investigated by simulating the CO2 dispersion in the atmosphere under different wind conditions. The DISGAS (DISpersion of GAS) code, an Eulerian model based on advection-diffusion equations, was used together with the mass-consistent Diagnostic Wind Model. Numerical simulations were validated by measurements of air CO2 concentration inside the village and along the crater's rim by means of a Soil CO2 Automatic Station and a Tunable Diode Laser device. The results show that in the village of Vulcano Porto, the CO2 air concentration is mostly due to local soil degassing, while the contribution from the crater gas emission is negligible at the breathing height for humans and always remains well below the lowest indoor CO2 concentration threshold recommended by the health authorities (1000 ppm). Outdoor excess CO2 maxima up to 200 ppm above local background CO2 air concentration are estimated in the center of the village and up to 100 ppm in other zones. However, in some ground excavations or in basements the health code threshold can be exceeded. In the crater area, because of the combined effect of fumaroles and diffuse soil emissions, CO2 air concentrations can reach 5000-7000 ppm in low-wind conditions and pose a health hazard for visitors.

Secular Variations of Soil CO2 Efflux at Santa Ana-Izalco-Coatepeque Volcanic Complex, El Salvador, Central America

NASA Astrophysics Data System (ADS)

Olmos, R.; Barahona, F.; Cartagena, R.; Soriano, T.; Salazar, J.; Hernandez, P.; Perez, N.; Lopez, D.

2002-12-01

The Santa Ana-Izalco-Coatepeque volcanic complex (2,365 m elevation), located 40 Km west of San Salvador, consists of the Coatepeque collapse caldera (a 6.5 x 10.5 Km elliptical depression), the Santa Ana and Izalco stratovolcanoes, as well as numerous cinder cones and explosion craters. The summit of the Santa Ana volcano contains an acid lake where hot springs, gas bubbling and intense fumarolic emissions occur. A volcanic plume, usually driven by the NE trades, may be seen rising up to 500 m from the summit crater of the Santa Ana volcano. The goal of this study is to provide a multidisciplinary approach for the volcanic surveillance by means of performing geochemical continuous monitoring of diffuse CO2 emission rate in addition to seismic monitoring. Temporal variations of soil CO2 efflux measured at Cerro Pacho dome, Coatepeque caldera, by means of the accumulation chamber method and using a CO2 efflux continuous monitoring station developed by WEST Systems (Italy). From May 2001 till May 2002, CO2 efflux ranged from 4.3 to 327 gm-2d-1, with a median value of 98 and a quartile range of 26 gm-2d-1. Two distinct diffuse CO2 degassing periods have been observed: (1) an increasing trend from May to July 2001, and (2) a stationary period from November 2001 to May 2002. The increasing-trend period may be due to the anomalous plume degassing at the Santa Ana volcano during 2001 and soon after the January and February 2001 earthquakes. Temporal variations of CO2 efllux during the second period seem to be coupled with those of barometric pressure and wind speed at different time scales, though most of the variance is contained at diurnal and semi-diurnal frequencies. These observations can help to explain the existence of a persistent behavior (Hurst exponent, H=0.934 +/- 0.0039) within the diffuse CO2 degassing phenomena. However, further observations are in progress to understand the long-term memory of diffuse CO2 degassing at the Santa Ana volcanic complex.

Diffuse gas emissions at the Ukinrek Maars, Alaska: Implications for magmatic degassing and volcanic monitoring

USGS Publications Warehouse

Evans, William C.; Bergfeld, D.; McGimsey, R.G.; Hunt, A.G.

2009-01-01

Diffuse CO2 efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO2 efflux, in many places exceeding 1000 g m-2 d-1, was found in conspicuous zones of plant damage or kill that cover 30,000-50,000 m2 in area. Total diffuse CO2 emission was estimated at 21-44 t d-1. Gas vents 3-km away at The Gas Rocks produce 0.5 t d-1 of CO2 that probably derives from the Ukinrek Maars basalt based on similar ??13C values (???-6???), 3He/4He ratios (5.9-7.2 RA), and CO2/3He ratios (1-2 ?? 109) in the two areas. A lower 3He/4He ratio (2.7 RA) and much higher CO2/3He ratio (9 ?? 1010) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO2 emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas-water-rock interactions play a major role in the location, magnitude and chemistry of the emissions.

A model of diffuse degassing at three subduction-related volcanoes

NASA Astrophysics Data System (ADS)

Williams-Jones, Glyn; Stix, John; Heiligmann, Martin; Charland, Anne; Sherwood Lollar, Barbara; Arner, N.; Garzón, Gustavo V.; Barquero, Jorge; Fernandez, Erik

Radon, CO2 and δ13C in soil gas were measured at three active subduction-related stratovolcanoes (Arenal and Poás, Costa Rica; Galeras, Colombia). In general, Rn, CO2 and δ13C values are higher on the lower flanks of the volcanoes, except near fumaroles in the active craters. The upper flanks of these volcanoes have low Rn concentrations and light δ13C values. These observations suggest that diffuse degassing of magmatic gas on the upper flanks of these volcanoes is negligible and that more magmatic degassing occurs on the lower flanks where major faults and greater fracturing in the older lavas can channel magmatic gases to the surface. These results are in contrast to findings for Mount Etna where a broad halo of magmatic CO2 has been postulated to exist over much of the edifice. Differences in radon levels among the three volcanoes studied here may result from differences in age, the degree of fracturing and faulting, regional structures or the level of hydrothermal activity. Volcanoes, such as those studied here, act as plugs in the continental crust, focusing magmatic degassing towards crater fumaroles, faults and the fractured lower flanks.

Diffuse CO2 degassing monitoring of Cerro Negro volcano, Nicaragua

NASA Astrophysics Data System (ADS)

Hernández, Pedro A.; Alonso, Mar; Ibarra, Martha; Rodríguez, Wesly; Melián, Gladys V.; Saballos, Armando; Barrancos, José; Pérez, Nemesio M.; Álvarez, Julio; Martínez, William

2017-04-01

We report the results of fourteen soil CO2 efflux surveys by the closed accumulation chamber method at Cerro Negro volcano, Nicaragua. The surveys were undertaken from 1999 to 2016 to constrain the diffuse CO2 emission from this volcano and to evaluate the spatial and temporal variations of CO2 degassing rate in relation to the eruptive cycle. Cerro Negro is an active basaltic volcano belonging to the active Central American Volcanic Arc which includes a 1,100 Km long chain of 41 active volcanoes from Guatemala to Panama. Cerro Negro first erupted in 1850 and has experienced 21 eruptive eruptions with inter eruptive average periods between 7 and 9 years. Since the last eruption occurred on 5 August 1999, with erupted lava flows and ash clouds together with gas emissions, a collaborative research program between INETER and ITER/INVOLCAN has been established for monitoring diffuse CO2 emissions from this volcano. The first survey carried out at Cerro Negro was in December 1999, just 3 months after the 1999 eruption, with a total diffuse CO2 emission output estimated on 1,869 ± 197 td-1. The second survey carried out in March 2003, three years after the eruption, yielded a value of 432 ± 54 td-1. Both values that can be considered within the post-eruptive phase. The last survey performed at Cerro Negro was in November 2016, with an estimated diffuse CO2 emission of 63 ± 14 tṡd-1and soil CO2 efflux values ranging from non-detectable (˜0.5 g m-2 d-1) up to 7264 g m-2 d-1. The long-term record of diffuse CO2 emissions at Cerro Negro shows small temporal variations in CO2 emissions with a peak in 2004 (256 ± 26 td-1) followed by a peak in seismicity. Except this value, the rest of estimated values can be considered within the inter-eruptive phase, period during which a decreasing trend on the total diffuse CO2 output has been observed, with estimates between 10 and 83 tṡd-1. Regarding to the spatial distribution of diffuse CO2 values, most of relatively high CO2 efflux values were measured along the 1995 and 1999 craters together with higher soil H2S efflux and soil temperatures, and always close to the fumarolic areas, suggesting a structural control of the degassing process. The observed relationship between the long-term record of diffuse CO2 emissions and volcanic-seismic activity indicates that monitoring CO2 emission is an important geochemical tool for the volcanic surveillance at Cerro Negro.

Diffuse degassing survey at the Higashi Izu monogenetic volcano field, Japan

NASA Astrophysics Data System (ADS)

Notsu, Kenji; Pérez, Nemesio M.; Fujii, Naoyuki; Hernández, Pedro A.; Mori, Toshiya; Padrón, Eleazar; Melián, Gladys

2016-04-01

The Higashi-Izu monogenetic volcanic group, which consists of more than 60 volcanoes, overlies the polygenetic volcanoes in the eastern part of the Izu peninsula, Japan, which are distributed over the area of 350 km2. Some of the monogenetic volcanoes are located on northwest-southeast alignments, suggesting that they developed along fissures. Recent volcanic activity occurred offshore, e.g., at the Izu-Oshima volcano, which erupted in 1986 and a submarine eruption of the small new Teishi knoll off eastern Izu Peninsula in 1989 (Hasebe et al., 2001). This study was carried out to investigate the possible relationship of diffuse CO2 emission and the recent seismic activity recorded NE of Higashi Izu monogenetic volcanic field, to quantify the rate at which CO2 is diffusely degassed from the studied area including Omuroyama volcano and to identify the structures controlling the degassing process. Measurements were carried out over a three day period from 8-10 July 2013. Diffuse CO2 emission surveys were always carried out following the accumulation chamber method and spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. Soil gas samples were collected at 30-40 cm depth by withdrawal into 60 cc hypodermic syringes to characterize the chemical and isotopic composition of the soil gas. At Omurayama volcano, soil CO2 efflux values ranged from non-detectable to 97.5 g m-2 d-1, while at the seismic swarm zone ranged from 1.5 to 233.2 g m-2 d-1 and at the fault zone ranged from 5.7 to 101.2 g m-2 d-1. Probability-plot technique of all CO2 efflux data showed two different populations, background with a mean of 8.7 g m-2 d-1 and peak with a mean of 92.7 g m-2 d-1. In order to strength the deep seated contribution to the soil gases at the studied are, carbon isotopic analysis were performed in the CO2 gas. Soil gases (He, CO2 and N2) showed a clear mixing trend between air composition and a rich CO2 end member, suggesting the influence of a deep magmatic reservoir on the soil degassing at the studied area. To estimate the total diffuse CO2 output released from Omurayama, the average of 100 simulations was considered, giving an average of 22 ± 2 t d-1 of diffuse CO2 released by Miharayama. Regarding to the geochemical transects along the Amagi Road and perpendicular to the fault, CO2 efflux values >9xBackground were observed close to the location of the fault. These results show possible linear positive anomalies may be caused by the presence of the active fault which has a higher porosity than surrounding soils, allowing an increased flux of CO2 to reach the surface from depth. References: Hasebe et al., 2001. Bull. Volcanol., 63, 377.

Fumarole/plume and diffuse CO2 emission from Sierra Negra volcano, Galapagos archipelago

NASA Astrophysics Data System (ADS)

Padron, E.; Hernandez Perez, P. A.; Perez, N.; Theofilos, T.; Melian, G.; Barrancos, J.; Virgil, G.; Sumino, H.; Notsu, K.

2009-12-01

The active shield-volcano Sierra Negra is part of the Galapagos hotspot. Sierra Negra is the largest shield volcano of Isabela Island, hosting a 10 km diameter caldera. Ten historic eruptions have occurred and some involved a frequently visited east caldera rim fissure zone called Volcan Chico. The last volcanic event occurred in October 2005 and lasted for about a week, covering approximately twenty percent of the eastern caldera floor. Sierra Negra volcano has experienced some significant changes in the chemical composition of its volcanic gas discharges after the 2005 eruption. This volcanic event produced an important SO2 degassing that depleted the magmatic content of this gas. Not significant changes in the MORB and plume-type helium contribution were observed after the 2005 eruption, with a 65.5 % of MORB and 35.5 % of plume contribution. In 2006 a visible and diffuse gas emission study was performed at the summit of Sierra Negra volcano, Galapagos, to evaluate degassing rate from this volcanic system. Diffuse degassing at Sierra Negra was mainly confined in three different DDS: Volcan Chico, the southern inner margin of the caldera, and Mina Azufral. These areas showed also visible degassing, which indicates highly fractured areas where volcano-hydrothermal fluids migrate towards surface. A total fumarole/plume SO2 emission of 11 ± 2 td-1 was calculated by mini-DOAS ground-based measurements at Mina Azufral fumarolic area. Molar ratios of major volcanic gas components were also measured in-situ at Mina Azufral with a portable multisensor. The results showed H2S/SO2, CO2/SO2 and H2O/SO2 molar ratios of 0.41, 52.2 and 867.9, respectively. Multiplying the observed SO2 emission rate times the observed (gas)i/SO2 mass ratio we have estimated other volatiles emission rates. The results showed that H2O, CO2 and H2S emission rates from Sierra Negra are 562, 394, and 2.4 t d-1, respectively. The estimated total output of diffuse CO2 emission from the summit of Sierra Negra was 989 ± 85 t d-1. Estimated diffuse/plume CO2 emission ratio was 2.5.

Monitoring diffuse degassing in monogenetic volcanic field during seismic-volcanic unrest: the case of Tenerife North-West Rift Zone (NWRZ), Canary Islands, Spain

NASA Astrophysics Data System (ADS)

García, E.; Botelho, A. H.; Regnier, G. S. G.; Rodríguez, F.; Alonso Cótchico, M.; Melián, G.; Asensio-Ramos, M.; Padrón, E.; Hernández, P. A.; Pérez, N. M.

2017-12-01

Tenerife North-West Rift-Zone (NWRZ) is the most active volcano of the oceanic active volcanic island of Tenerife and the scenario of three historical eruptions (Boca Cangrejo S. XVI, Arenas Negras 1706 and Chinyero 1909). Since no visible degassing (fumaroles, etc.) at Tenerife NWRZ occurs, a geochemical monitoring program at Tenerife NWRZ was established mainly consisting on performing soil CO2 efflux surveys (50 surveys since 2000) to evaluate the temporal and spatial variations of soil CO2 efflux measurements and the diffuse CO2 emission rate. To do so, about 340 sampling sites were selected for each survey to obtain a homogeneous distribution after taking into consideration the local geology, structure, and accessibility. Measurements of soil CO2 efflux were performed in situ by means of a portable non-dispersive infrared sensor following the accumulation chamber method. The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 46.6 g m-2 d-1. Statistical-graphical analysis of the 2017 data show two different geochemical populations; background (B) and peak (P) represented by 93.3% and 1.9% of the total data, respectively. The geometric means of the B and P populations are 2.4 and 19.1 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed at the N-W side of the volcanic rift. To estimate the diffuse CO2 emission in metric tons per day released from Tenerife NWRZ (75 km2) for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by the Tenerife NWRZ volcano was 297 ± 13 t d-1. This 2017 diffuse CO2 emission rate value is relatively higher than the estimated background value (144 t d-1) and falls within the estimated background range (72 - 321 t d-1) observed for Tenerife NWRZ volcano during the 2000-2017 period. The observed temporal variation in the diffuse CO2 degassing output during this period does not seem to be driven by external factors and it shows a clear temporal correlation with the onsets of seismic activity (Hernández et al., 2017, Bull. Volcanol.). Monitoring the diffuse CO2 emission contributes to detect early warning signals of volcanic unrest at the Tenerife North-West Rift-Zone volcano.

Diffuse CO2 degassing studies to reveal hidden geothermal resources in oceanic volcanic islands: The Canarian archipelago case study

NASA Astrophysics Data System (ADS)

Rodríguez, F.; Perez, N. M.; García-Merino, M.; Padron, E.; Melián, G.; Asensio-Ramos, M.; Hernandez Perez, P. A.; Padilla, G.; Barrancos, J.; Cótchico, M. A.

2016-12-01

The Canary Islands, owing to their recent volcanism, are the only Spanish territory with potential high enthalpy geothermal resources. The final goal of geothermal exploration in a specific area is to locate and define the size, shape, structure of hidden geothermal resources, and determine their characteristics (fluid type, temperature, chemical composition an ability to produce energy). At those areas where there is not any evidence of endogenous fluids manifestations at surface, that traditionally evidence the presence of an active geothermal system) the geochemical methods for geothermal exploration must include soil gas surveys. This is the case of five mining licenses for geothermal exploration in the Canay Islands, four in Tenerife and one in Gran Canaria Island. We report herein the results of diffuse CO2 emission studies in the five mining licenses during 2011-2014. The primary objective of the study was to sort the possible geothermal potential of these five mining licenses, thus reducing the uncertainty inherent to the selection of the areas with highest geothermal potential for future exploration works. The criterion used to sort the different areas was the contribution of volcano-hydrothermal CO2 in the degassing at each study area. Several hundreds of measurements of diffuse CO2 emission, soil CO2 concentration and isotopic composition were performed at each study area. Based in three different endmembers (biogenic, atmospheric and deep-seated CO2) with different CO2 concentrations (100, 0.04 and 100% respectively) and isotopic compositions (-20, -8 and -3 per mil vs. VPDB respectively) a mass balance to distinguish the different contribution of each endmember in the soil CO2 at each sampling site was made. The percentage of the volcano-hydrothermal contribution in the current diffuse CO2 degassing was in the range 2-19%.The Abeque mining license, that comprises part of the north-west volcanic rift of Tenerife, seemed to show the highest geothermal potential, with an average of 19% of CO2 being released from deep sources, followed by Atidama (south east of Gran Canaria) and Garehagua (southern volcanic rift of Tenerife), with 17% and 12% respectively.

Carbon dioxide degassing and thermal energy release at Vesuvio (Italy)

NASA Astrophysics Data System (ADS)

Frondini, F.; Chiodini, G.; Caliro, S.; Cardellini, C.; Granieri, D.

2003-04-01

At Vesuvio, basing on the data of the CO2 flux surveys carried out in April and May 2000, are discharged about 130 t d-1 of CO2 through soil diffuse degassing. In the crater area the distribution of the soil temperatures show a general correspondence between the CO2 flux anomalies and the high temperatures, suggesting that the heating of the soil is mainly due to the condensation of the rising volcanic-hydrothermal fluids. Considering that the original H2O/CO2 ratio of hydrothermal fluids is recorded by fumarolic effluents, the steam associated to the CO2 output has been computed and amount to is 475 t d-1. The energy produced by the steam condensation and cooling of the liquid phase is 1.26 1012 J d-1 (14.6 MW). The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodical CO2 flux surveys, can constitute a powerful tool to monitor the activity of the volcano.

Spatial and temporal variations of diffuse CO_{2} degassing at the Tenerife North-South Rift Zone (NSRZ) volcano (Canary Islands) during the period 2002-2016

NASA Astrophysics Data System (ADS)

Rodríguez, Fátima; McCollum, John J. K.; Orland, Elijah D. M.; Barrancos, José; Padilla, Germán D.; Calvo, David; Amonte, Cecilia; Pérez, Nemesio M.

2017-04-01

Subaerial volcanic activity on Tenerife (2034 km2), the largest island of the Canary archipelago, started 14 My ago and 4 volcanic eruptions have occurred in historical times during the last 300 years. The main volcano-structural and geomorphological features of Tenerife are (i) the central volcanic complex, nowadays formed by Las Cañadas caldera, a volcanic depression measuring 16×9 km that resulted from multiple vertical collapses and partially filled by post-caldera volcanic products and (ii) the triple junction-shaped rift system, formed by numerous aligned monogenetic cones. Up to 297 mafic monogenetic cones have been recognized on Tenerife, and they represent the most common eruptive activity occurring on the island during the last 1 My (Dóniz et al., 2008). The North-South Rift Zone (NSRZ) of Tenerife comprises at least 139 cones. The main structural characteristic of the NSRZ of the island is an apparent absence of a distinct ridge, and a fan shaped distribution of monogenetic cones. Since there are currently no visible gas emissions at the NSRZ, diffuse degassing surveys have become an important geochemical tool for the surveillance of this volcanic system. Five diffuse CO2 degassing surveys have been carried out at NSRZ of Tenerife since 2002, the last one in the summer period of 2016, to evaluate the spatio-temporal variations of CO2 degassing as a volcanic surveillance tool for the NSRZ of Tenerife. At each survey, around 600 sampling sites were selected to cover homogenously the study area (325 km2) using the accumulation chamber method. The diffuse CO2 output ranged from 78 to 707 t/d in the study period, with the highest emission rate measured in 2015. The backgroung emission rate was estimated in 300 t/d. The last results the soil CO2 efflux values ranged from non-detectable up to 24.7 g m-2 d-1. The spatial distribution map, constructed following the sequential Gaussian simulation (sGs) procedure, showed the highest CO2 values as multiple isolated anomalies and did not show a clear relation with the main volcano-structural features of the area. The CO2 output released to the atmosphere in a diffuse way has been estimated at 524 t d-1, which represents a value lower than the previous one (707 t d-1 at summer of 2015) but higher than the background emission rate. These changes in the temporal series confirm the need of periodic diffuse emission surveys in the area as a powerful volcanic surveillance tool in volcanic systems where visible gas emanations are absent. References: Dóniz et al., 2008. J. Volcanol. Geotherm. Res. 173, 185.

Izu-Oshima volcano, Japan: ten years of geochemical monitoring by means of CO2 soil diffuse degassing

NASA Astrophysics Data System (ADS)

Hernandez Perez, P. A.; Mori, T.; Notsu, K.; Morita, M.; Padron, E.; Onizawa, S.; Melián, G.; Sumino, H.; Asensio-Ramos, M.; Nogami, K.; Yamane, K.; Perez, N. M.

2016-12-01

Izu-Oshima is an active volcanic island located around 100 km SSW of Tokyo. The centre of the island is occupied by a caldera complex with a diameter of 3 km. A large post-caldera cone known as Mt. Mihara is located at the south-western quadrant of the caldera. Izu-Oshima has erupted 74 times, consisting mainly in fissure eruptions, both inside and outside of the caldera. The last eruption of Izu-Oshima occurred in 1986. Since 2007, eight soil gas surveys have been carried out to investigate the spatial and temporal evolution of diffuse CO2 emission from this volcanic system and to identify those structures controlling the degassing process. Diffuse CO2 emission surveys were always carried out following the accumulation chamber method. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. The location of the CO2 anomalies has always shown a close relationship with the structural characteristics of Miharayama, with most of the gas discharged from the rim of the summit crater. Temporal evolution of diffuse CO2 emission rate from Mt. Miharayama has shown a good temporal correlation with the main two peaks of seismic activity occur when highest CO diffuse emissions were computed, March 2007, August 2010 and July 2011, may be associated with fluid pressure fluctuations in the volcanic system due stress changes at depth. In order to strength the contribution of deep seated gases, we performed carbon isotopic analysis of soil gas samples at selected sites during 2010, 2013, 2015 and 2016 surveys. At isotopic compositions lighter than - 6‰, the soil CO2 effluxes were always low, while at heavier isotopic compositions an increasing number of points are characterized by relatively high soil CO efflux. Soil CO2 efflux peak values (xB) showed also a good correlation with the observed seismicity, with the largest value computed on June 2013. This parameter is a geochemical expression of the magnitude of the anomalous degassing, and the observed change in the trend may indicate an increase of the seismic-volcanic activity in the next future. Therefore, performing regularly soil CO2 efflux surveys seems to be an effective geochemical surveillance tool Izu-Oshima volcano in order to detect a change in the tendency of the CO2 emission rate in case of future episodes of volcanic unrest.

Diffuse degassing at Longonot volcano, Kenya: Implications for CO2 flux in continental rifts

NASA Astrophysics Data System (ADS)

Robertson, Elspeth; Biggs, Juliet; Edmonds, Marie; Clor, Laura; Fischer, Tobias P.; Vye-Brown, Charlotte; Kianji, Gladys; Koros, Wesley; Kandie, Risper

2016-11-01

Magma movement, fault structures and hydrothermal systems influence volatile emissions at rift volcanoes. Longonot is a Quaternary caldera volcano located in the southern Kenyan Rift, where regional extension controls recent shallow magma ascent. Here we report the results of a soil carbon dioxide (CO2) survey in the vicinity of Longonot volcano, as well as fumarolic gas compositions and carbon isotope data. The total non-biogenic CO2 degassing is estimated at < 300 kg d- 1, and is largely controlled by crater faults and fractures close to the summit. Thus, recent volcanic structures, rather than regional tectonics, control fluid pathways and degassing. Fumarolic gases are characterised by a narrow range in carbon isotope ratios (δ13C), from - 4.7‰ to - 6.4‰ (vs. PDB) suggesting a magmatic origin with minor contributions from biogenic CO2. Comparison with other degassing measurements in the East African Rift shows that records of historical eruptions or unrest do not correspond directly to the magnitude of CO2 flux from volcanic centres, which may instead reflect the current size and characteristics of the subsurface magma reservoir. Interestingly, the integrated CO2 flux from faulted rift basins is reported to be an order of magnitude higher than that from any of the volcanic centres for which CO2 surveys have so far been reported.

Syn-eruptive CO2 Degassing of Submarine Lavas Flows: Constraints on Eruption Dynamics

NASA Astrophysics Data System (ADS)

Soule, S. A.; Boulahanis, B.; Fundis, A.; Clague, D. A.; Chadwick, B.

2013-12-01

At fast- and intermediate-spreading rate mid-ocean ridges, quenched lava samples are commonly supersaturated in CO2 with concentrations similar to the pressure/depth of shallow crustal melt lenses. This supersaturation is attributed to rapid ascent and decompression rates that exceed the kinetic rates of bubble nucleation and growth. During emplacement, CO2 supersaturated lavas experience nearly isothermal and isobaric conditions over a period of hours. A recent study has demonstrated systematic decreases in CO2 with increasing transport distance (i.e. time) along a single flow pathway within the 2005-06 eruption at the East Pacific Rise (~2500 m.b.s.l.). Based on analysis of vesicle population characteristics and complementary noble gas measurements, it is proposed that diffusion of CO2 into bubbles can be used as a basis to model the gas loss from the melt and thus place constraints on the dynamics of the eruption. We suggest that submarine lava flows represent a natural experiment in degassing that isolates conditions of low to moderate supersaturation and highlights timescales of diffusion and vesiculation processes that are relevant to shallow crustal and conduit processes in subaerial basaltic volcanic systems. Here we report a new suite of volatile concentration analyses and vesicle size distributions from the 2011 eruption of Axial Volcano along the Juan de Fuca Ridge (~1500 m.b.s.l.). The lava flows from this eruption are mapped by differencing of repeat high-resolution bathymetric surveys, so that the geologic context of the samples is known. In addition, in-situ instrument records record the onset of the eruption and place constraints on timing that can be used to verify estimates of eruption dynamics derived from degassing. This sample suite provides a comprehensive view of the variability in volatile concentrations within a submarine eruption and new constraints for evaluating models of degassing and vesiculation. Initial results show systematic variability in CO2 supersaturation along eruptive fissures as well as with increasing distance along flows pathways providing constraints on threshold decompression rates required to nucleate and grow bubbles in a basaltic melt, timescales of degassing in natural systems, and the properties of consequent vesicle populations.

Experimental studies and physically substantiated model of carbon dioxide emission from the exposed cultural layer of Velikii Novgorod

NASA Astrophysics Data System (ADS)

Smagin, A. V.; Dolgikh, A. V.; Karelin, D. V.

2016-04-01

The results of quantitative assessment and modeling of carbon dioxide emission from urban pedolithosediments (cultural layer) in the central part of Velikii Novgorod are discussed. At the first stages after the exposure of the cultural layer to the surface in archaeological excavations, very high CO2 emission values reaching 10-15 g C/(m2 h) have been determined. These values exceed the normal equilibrium emission from the soil surface by two orders of magnitude. However, they should not be interpreted as indications of the high biological activity of the buried urban sediments. A model based on physical processes shows that the measured emission values can be reliably explained by degassing of the soil water and desorption of gases from the urban sediments. This model suggests the diffusion mechanism of the transfer of carbon dioxide from the cultural layer into the atmosphere; in addition, it includes the equations to describe nonequilibrium interphase interactions (sorption-desorption and dissolution-degassing of CO2) with the first-order kinetics. With the use of statistically reliable data on physical parameters—the effective diffusion coefficient as dependent on the aeration porosity, the effective solubility, the Henry constant for the CO2 sorption, and the kinetic constants of the CO2 desorption and degassing of the soil solution—this model reproduces the experimental data on the dynamics of CO2 emission from the surface of the exposed cultural layer obtained by the static chamber method.

Mapping the Spatial Distribution of CO2 release from Kīlauea Volcano, Hawaii, USA

NASA Astrophysics Data System (ADS)

Elias, T.; Werner, C. A.; Kern, C.; Sutton, A. J.; Hauri, E. H.; Kelly, P. J.

2014-12-01

Kīlauea Volcano is a large emitter of volcanic CO2 with emission rates ranging from 7500-30,000 t/d. However, Kīlauea presents a challenging situation for CO2 emission rate measurement in that the main source of SO2 is the active vent in Halema'uma'u Crater, whereas CO2 emits mainly from a large (> 1km2) diffuse region east of the vent. Previous researchers recognized this issue and advocated for the use of a plume-integrated concentration ratio paired with the SO2 emission to determine CO2 emission rates; however, this worked best prior to the opening of the summit vent in 2008, or when SO2emission was still diffuse as opposed to focused degassing from the vent. We used two techniques to study the spatial distribution and temporal variability of CO2 release from the summit caldera in July, 2014. Eddy covariance measurements made at 14 locations in the area of diffuse emission resulted in elevated fluxes that generally ranged from 500 to > 5000 g/m2d, or typical of other volcanic and hydrothermal areas worldwide. MultiGas measurements of the CO2 and SO2 concentration in air at 1-m above the ground identified approximately seven areas of elevated area of CO2 degassing in the caldera. The CO2 concentrations in air were spatially well correlated to approximately 100 m and displayed anisotropy that was consistent with the measured wind direction. Areas of highest CO2 concentration correlated with the areas of highest flux using the eddy covariance method and were found near the middle of the caldera approximately 1 km NE of the active vent. This area overlies the inferred location of the shallow summit reservoir, and is characterized by linear fractures with adhered sublimate deposits at the surface. A few of the fractures are visibly fuming, but much of the degassing in the area is not apparent. Future work includes monitoring the fluxes in this area over time, and attempting to quantify emission rates from the areas of measured flux.

Decadal-scale variability of diffuse CO2 emissions and seismicity revealed from long-term monitoring (1995–2013) at Mammoth Mountain, California, USA

USGS Publications Warehouse

Werner, Cynthia A.; Bergfeld, Deborah; Farrar, Chris; Doukas, Michael P.; Kelly, Peter; Kern, Christoph

2014-01-01

Mammoth Mountain, California, is a dacitic volcano that has experienced several periods of unrest since 1989. The onset of diffuse soil CO2 emissions at numerous locations on the flanks of the volcano began in 1989–1990 following an 11-month period of heightened seismicity. CO2 emission rates were measured yearly from 1995 to 2013 at Horseshoe Lake (HSL), the largest tree kill area on Mammoth Mountain, and measured intermittently at four smaller degassing areas around Mammoth from 2006 to 2013. The long-term record at HSL shows decadal-scale variations in CO2 emissions with two peaks in 2000–2001 and 2011–2012, both of which follow peaks in seismicity by 2–3 years. Between 2000 and 2004 emissions gradually declined during a seismically quiet period, and from 2004 to 2009 were steady at ~ 100 metric tonnes per day (t d− 1). CO2emissions at the four smaller tree-kill areas also increased by factors of 2–3 between 2006 and 2011–2012, demonstrating a mountain-wide increase in degassing. Delays between the peaks in seismicity and degassing have been observed at other volcanic and hydrothermal areas worldwide, and are thought to result from an injection of deep CO2-rich fluid into shallow subsurface reservoirs causing a pressurization event with a delayed transport to the surface. Such processes are consistent with previous studies at Mammoth, and here we highlight (1) the mountain-wide response, (2) the characteristic delay of 2–3 years, and (3) the roughly decadal reoccurrence interval for such behavior. Our best estimate of total CO2 degassing from Mammoth Mountain was 416 t d− 1 in 2011 during the peak of emissions, over half of which was emitted from HSL. The cumulative release of CO2 between 1995 and 2013 from diffuse emissions is estimated to be ~ 2–3 Mt, and extrapolation back to 1989 gives ~ 4.8 Mt. This amount of CO2 release is similar to that produced by the mid-sized (VEI 3) 2009 eruption of Redoubt Volcano in Alaska (~ 2.3 Mt over 11 months), and significantly lower than long-term emissions from hydrothermal areas such as Solfatara in Campi Flegrei, Italy (16 Mt over 28 years).

Monitoring diffuse degassing in monogentic volcanic field during a quiescent period: the case of Cumbre Vieja (La Palma,Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Burns, F.; Cole, M.; Vaccaro, W.; Alonso Cótchico, M.; Melián, G.; Asensio-Ramos, M.; Padron, E.; Hernandez Perez, P. A.; Perez, N. M.

2017-12-01

Volcanic activity at La Palma (Canary Islands) in the last 123 ka has taken place exclusively at the southern part of the island, where Cumbre Vieja volcano, which is characterized by a main north-south rift zone 20 km long and up to 1950 m in elevation and covering an area of 220 km2 with vents located also at the northwest and northeast. Cumbre Vieja is the most active basaltic volcano in the Canaries with 7 historical eruptions being San Juan (1949) and Teneguía (1971) the most recent ones. Since no visible degassing (fumaroles, etc.) at Cumbre Vieja occurs, our geochemical program for the volcanic surveillance of Cumbre Vieja is mainly focused on diffuse degassing monitoring. Diffuse CO2 emission surveys are yearly performed in summer to minimize the influence of meteorological variations. About 570 sampling sites were selected for each survey to obtain a homogeneous distribution after taking into consideration the local geology, structure, and accessibility. Measurements of soil CO2 efflux were performed in situ by means of a portable non-dispersive infrared sensor following the accumulation chamber method. The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 47.7 g m-2 d-1. Statistical-graphical analysis of the data show two different geocheleemical populations; background (B) and peak (P) represented by 98.2% and 1.8% of the total data, respectively. The geometric means of the B and P populations are 2.9 and 36.5 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed both flanks of the main N-S volcanic rift. To estimate the diffuse CO2 emission in metric tons per day released from Cumbre Vieja (220 km2) for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by Cumbre Vieja was at 801 ± 27 t d-1, value relatively higher than the background average of CO2 emission estimated on 374 t d-1 and within the background range of 132 t d-1 (-1σ) and 1.254 t d-1 (+1σ) observed at Cumbre Vieja volcano during the period 2001-2013 (Padrón et al., 2015. Bull. Volcanol. 77:28). Monitoring the diffuse CO2 emission contributes to detect early warning signals of volcanic unrest at Cumbre Vieja volcano.

Diffuse Emission of Carbon Dioxide From Irazú Volcano, Costa Rica, Central America

NASA Astrophysics Data System (ADS)

Galindo, I.; Melian, G.; Ramirez, C.; Salazar, J.; Hernandez, P.; Perez, N.; Fernandez, M.; Notsu, K.

2001-12-01

Irazú (3,432 m) is a stratovolcano situated 50 Km east of San José, the capital of Costa Rica. Major geomorphological features at Irazú are five craters (Main Crater, Diego de La Haya, Playa Hermosa, La Laguna and El Piroclástico), and at least 10 satellitic cones which are located on its southern flank. Its eruptive history is known from 1723. Since then, have ocurred at least 23 eruptions. All known Holocene eruptions have been explosive. The focus of eruptions at the summit crater complex has migrated to the west towards the historically active crater from 1963 to 1965. Diffuse degassing studies are becoming an additional geochemical tool for volcanic surveillance. The purpose of this study is to evaluate the spatial distribution of diffuse CO2 emission as well as CO2 efflux from Irazú volcano. A soil CO2 flux survey of 201 sampling sites was carried out at the summit of Irazú volcano in March 2001. Sampling site distribution covered an area of 3.5 Km2. Soil CO2 efflux measurements were performed by means of a portable NDIR sensor LICOR-800. Soil CO2 efflux values ranged from non-detectable values to 316.1 gm-2d-1 Statistical-graphical analysis of the data showed three overlapping geochemical populations. The background mean is 3 gm-2d-1 and represents 91.3 % of the total data. Peak group showed a mean of 18 gm-2d-1 and represented 1.2 % of the data. Anomalous CO2 flux values are mainly detected in the South sector of the main crater, where landslides have previously occurred. Diffuse CO2 degassing rate of the study area yields 44.2 td-1.

Fumarole/plume and diffuse CO2 emission from Sierra Negra caldera, Galapagos archipelago

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Hernández, Pedro A.; Pérez, Nemesio M.; Toulkeridis, Theofilos; Melián, Gladys; Barrancos, José; Virgili, Giorgio; Sumino, Hirochika; Notsu, Kenji

2012-08-01

Measurements of visible and diffuse gas emission were conducted in 2006 at the summit of Sierra Negra volcano, Galapagos, with the aim to better characterize degassing after the 2005 eruption. A total SO2 emission of 11 ± 2 t day-1 was derived from miniature differential optical absorption spectrometer (mini-DOAS) ground-based measurements of the plume emanating from the Mini Azufral fumarolic area, the most important site of visible degassing at Sierra Negra volcano. Using a portable multigas system, the H2S/SO2, CO2/SO2, and H2O/SO2 molar ratios in the Mina Azufral plume emissions were found to be 0.41, 52.2, and 867.9, respectively. The corresponding H2O, CO2, and H2S emission rates were 562, 394, and 3 t day-1, respectively. The total output of diffuse CO2 emissions from the summit of Sierra Negra volcano was 990 ± 85 t day-1, with 605 t day-1 being released by a deep source. The diffuse-to-plume CO2 emission ratio was about 1.5. Mina Azufral fumaroles released gasses containing 73.6 mol% of H2O; the main noncondensable components amounted to 97.4 mol% CO2, 1.5 mol% SO2, 0.6 mol% H2S, and 0.35 mol% N2. The higher H2S/SO2 ratio values found in 2006 as compared to those reported before the 2005 eruption reveal a significant hydrothermal contribution to the fumarolic emissions. 3He/4He ratios measured at Mina Azufral fumarolic discharges showed values of 17.88 ± 0.25 R A , indicating a mid-ocean ridge basalts (MORB) and a Galapagos plume contribution of 53 and 47 %, respectively.

Carbon monoxide degassing from seismic fault zones in the Basin and Range province, west of Beijing, China

NASA Astrophysics Data System (ADS)

Sun, Yutao; Zhou, Xiaocheng; Zheng, Guodong; Li, Jing; Shi, Hongyu; Guo, Zhengfu; Du, Jianguo

2017-11-01

Degassing of carbon monoxide (CO), which plays a significant role in the contribution of deep carbon to the atmosphere, commonly occurs within active fault zones. CO degassing from soil to the atmosphere in the Basin and Range province, west of Beijing (BRPB), China, was investigated by in-situ field measurements in the active fault zones. The measured concentrations of CO in soil gas in the BRPB ranged from 0.29 × 10-6 to 1.1 × 10-6 with a mean value of 0.6 × 10-6, which is approximately twice as large as that in the atmosphere. Net fluxes of CO degassing ranged from -48.6 mg m-2 d-1 to 12.03 mg m-2 d-1. The diffusion of CO from soil to the atmosphere in the BRPB was estimated to be at least 7.6 × 103 ton/a, which is comparable to the corresponding result of about 1.2 × 104 ton/a for CO2. CO concentrations were spatially heterogeneous with clearly higher concentrations along the NE-SW trending in the BRPB. These elevated values of CO concentrations were also coincident with the region with low-velocity and high conductivity in deep mantle, and high Poisson's ratio in the crust, thereby suggesting that CO degassing from the soil might be linked to upwelling of the asthenospheric mantle. Other sources of CO in the soil gas are suggested to be dominated by chemical reactions between deep fluids and carbonate minerals (e.g., dolomite, limestone, and siderite) in country rocks. Biogenic processes may also contribute to the CO in soil gas. The spatial distribution patterns of CO concentrations are coincident with the stress field, suggesting that the concentrations of CO could be a potential indicator for crustal stress field and, hence is potential useful for earthquake monitoring in the BRPB.

Fault Networks in the Northwestern Albuquerque Basin and Their Potential Role in Controlling Mantle CO2 Degassing and Fluid Migration from the Valles Caldera

NASA Astrophysics Data System (ADS)

Smith, J. R.; Crossey, L. J.; Karlstrom, K. E.; Fischer, T. P.; Lee, H.; McGibbon, C. J.

2015-12-01

The Rio Grande rift (RGR) has Quaternary and active volcanism and faulting that provide a field laboratory for examining links between mantle degassing and faults as fluid conduits. Diffuse and spring CO2 flux measurements were taken at 6 sites in the northwestern Albuquerque Basin (NWAB) and Valles caldera geothermal system. All sites progress to the southwest from the 1.25 Ma Valles caldera, down the rift-related Jemez fault network, to intersect with the Nacimiento fault system. Mantle CO2 and He degassing are well documented at 5 of 6 sites, with decreasing 3He/4He ratios away from the caldera. The instrument used to measure CO2 flux was an EGM-4 CO2 gas analyzer (PP systems) with an accumulation chamber. Carbonic springs at Penasco Springs (PS) and San Ysidro (SY), and the carbonate-cemented Sand Hill Fault (SHF) were targeted, all near the western border of the RGR. The SHF has no spring activity, had the smallest maximum flux of all the sites (8 g/m2d), but carbonate along the fault zone (<2 m wide) attest to past CO2 flux. The other two sites are equal distance (30-40 km) between the SHF site and Valles caldera sites. These sites have active carbonic springs that precipitate travertine mounds. Our work suggests these sites reflect intersections of the Nacimiento fault with NE trending faults that connect to the Jemez fault network. The maximum diffuse flux recorded at SY (297 g/m2d) and PS (25 g/m2d) are high, especially along the fault and near springs. At SY and PS the instruments capacity was exceeded (2,400 g/m2d) at 6 of 9 springs. Interpretations indicate a direct CO2 flux through a fault-related artesian aquifer system that is connected to magmatic gases from the caldera. Maximum diffuse flux measurements of Alamo Canyon (20,906 g/m2d), Sulphur Springs (2,400 g/m2d) and Soda Dam (1,882 g/m2d) at Valles caldera geothermal sites are comparable to Yellowstone geothermal systems. We use geospatial analysis and local geologic mapping to examine relationships of CO2 flux to structure. Travertine mounds can create impermeable barriers that modify near-surface degassing patterns, making it difficult to decipher where CO2 and fluids preferentially migrate up the damage zones in the hanging-wall or footwall. Future work will utilize grids to more accurately assess the localized affect fault zones have on CO2 flux rates.

A missing element of the deep carbon cycle: CO2 degassing estimates from rift length analysis during Pangea fragmentation

NASA Astrophysics Data System (ADS)

Brune, S.; Williams, S.; Müller, D.

2016-12-01

The deep carbon cycle connects CO2 within the atmosphere and oceans to the vast CO2 reservoir in Earth's mantle: subducted lithosphere carries CO2 into the mantle, while extensional plate boundaries and arc volcanoes release it back to Earth's surface. The length of plate boundaries thereby exerts first-order control on global CO2 fluxes on geological time scales. Here we provide a worldwide census of extensional plate boundary length from the Triassic to present day, in one million year time intervals, using a novel analysis technique (Brune et al. 2016, Nature, doi:10.1038/nature18319). The most extensive rift phase during the fragmentation of Pangea occurred in the Cretaceous with extension along the South Atlantic (9700 km) and North Atlantic rifts (9100 km), within East Gondwana (8500 km), and the failed African rift systems (4900 km). The combined extent of these and several smaller rifts amounts to more than 30.000 km of simultaneously active continental rifting. It is well-accepted that volcanoes at plate boundaries release large amounts of CO2 from the Earth's interior. Recent work, however, revealed the importance of deep-cutting faults and diffuse degassing on CO2 emissions in the East African rift (Lee et al. 2016, Nature Geoscience, doi: 10.1038/ngeo2622). Upscaling these measured CO2 fluxes to all concurrently active global rift zones, we compute first-order estimates of total rift-related CO2 degassing rates for the last 240 Myr. Our results show that rift-related CO2 release rates may have reached 600 Mt/yr in the Early Cretaceous, while Cenozoic rates rarely exceeded 200 Mt/yr. By comparison, present-day estimates of CO2 release at mid-ocean ridges range between 53 and 97 Mt/yr. We suggest that rift-related degassing during supercontinental breakup played a major role in maintaining high atmospheric CO2 concentrations through Mesozoic times, which exceeded Quaternary values by 400%.

Hazardous indoor CO2 concentrations in volcanic environments.

PubMed

Viveiros, Fátima; Gaspar, João L; Ferreira, Teresa; Silva, Catarina

2016-07-01

Carbon dioxide is one of the main soil gases released silently and permanently in diffuse degassing areas, both in volcanic and non-volcanic zones. In the volcanic islands of the Azores (Portugal) several villages are located over diffuse degassing areas. Lethal indoor CO2 concentrations (higher than 10 vol %) were measured in a shelter located at Furnas village, inside the caldera of the quiescent Furnas Volcano (S. Miguel Island). Hazardous CO2 concentrations were detected not only underground, but also at the ground floor level. Multivariate regression analysis was applied to the CO2 and environmental time series recorded between April 2008 and March 2010 at Furnas village. The results show that about 30% of the indoor CO2 variation is explained by environmental variables, namely barometric pressure, soil water content and wind speed. The highest indoor CO2 concentrations were recorded during bad weather conditions, characterized by low barometric pressure together with rainfall periods and high wind speed. In addition to the spike-like changes observed on the CO2 time series, long-term oscillations were also identified and appeared to represent seasonal variations. In fact, indoor CO2 concentrations were higher during winter period when compared to the dry summer months. Considering the permanent emission of CO2 in various volcanic regions of the world, CO2 hazard maps are crucial and need to be accounted by the land-use planners and authorities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anomalous increase of diffuse CO_{2} emission from Brava (Cape Verde): evidence of volcanic unrest or increase gas release from a stationary magma body?

NASA Astrophysics Data System (ADS)

García-Merino, Marta; García-Hernández, Rubén; Montrond, Eurico; Dionis, Samara; Fernandes, Paulo; Silva, Sonia V.; Alfama, Vera; Cabral, Jeremías; Pereira, Jose M.; Padrón, Eleazar; Pérez, Nemesio M.

2017-04-01

Brava (67 km2) is the southwestern most and the smallest inhabited island of the Cape Verde archipelago. It is located 18 km west of Fogo Island and rises 976 m from the sea level. Brava has not any documented historical eruptions, but its Holocene volcanism and relatively high seismic activity clearly indicate that it is an active volcanic island. Since there have been no historic eruptions in Brava, volcanic hazard awareness among the population and the authorities is very low; therefore, its volcano monitoring program is scarce. With the aim of helping to provide a multidisciplinary monitoring program for the volcanic surveillance of the island, diffuse CO2 emission surveys have been carried out since 2010; approximately every 2 years. Soil CO2 efflux measurements are periodically performed at ˜ 275 observation sites all over the island and after taking into consideration their accessibility and the island volcano-structural characteristics. At each sampling site, soil CO2 efflux measurement was performed by means of a portable NDIR sensor according to the accumulation chamber method. To quantify the total diffuse CO2 emission from Brava volcanic system, soil CO2 efflux maps were constructed using sequential Gaussian simulations (sGs). An increase trend of diffuse CO2 emission rate from 42 to 681 t d-1at Brava was observed; just one year prior the 2014-2015 Fogo eruption and almost three years before the anomalous seismic activity recorded on August 2016 with more than 1000 seismic events registered by the INMG on August 1st, 2016 (Bruno Faria, personal communication). Due to this anomalous seismic activity, a diffuse CO2 emission survey at Brava was performed from August 2 to 10, 2016, and the estimated degassing rate yield a value about 72 t d-1; typical background values. An additional survey was carried out from October 22 to November 6, 2016. For this last survey, the estimated diffuse CO2 emission from Brava showed the highest observed value with a degassing rate about 1.700 t d-1. These observed changes on diffuse CO2 emission are geochemical evidences which seem to support a volcanic unrest for the recent anomalous seismic activity registered at Brava.

Multi-scale observations of the variability of magmatic CO2 emissions, Mammoth Mountain, CA, USA

NASA Astrophysics Data System (ADS)

Lewicki, J. L.; Hilley, G. E.

2014-09-01

One of the primary indicators of volcanic unrest at Mammoth Mountain is diffuse emission of magmatic CO2, which can effectively track this unrest if its variability in space and time and relationship to near-surface meteorological and hydrologic phenomena versus those occurring at depth beneath the mountain are understood. In June-October 2013, we conducted accumulation chamber soil CO2 flux surveys and made half-hourly CO2 flux measurements with automated eddy covariance and accumulation chamber (auto-chamber) instrumentation at the largest area of diffuse CO2 degassing on Mammoth Mountain (Horseshoe Lake tree kill; HLTK). Estimated CO2 emission rates for HLTK based on 20 June, 30 July, and 24-25 October soil CO2 flux surveys were 165, 172, and 231 t d- 1, respectively. The average (June-October) CO2 emission rate estimated for this area was 123 t d- 1 based on an inversion of 4527 eddy covariance CO2 flux measurements and corresponding modeled source weight functions. Average daily eddy covariance and auto-chamber CO2 fluxes consistently declined over the four-month observation time. Wavelet analysis of auto-chamber CO2 flux and environmental parameter time series was used to evaluate the periodicity of, and local correlation between these variables in time-frequency space. Overall, CO2 emissions at HLTK were highly dynamic, displaying short-term (hourly to weekly) temporal variability related to meteorological and hydrologic changes, as well as long-term (monthly to multi-year) variations related to migration of CO2-rich magmatic fluids beneath the volcano. Accumulation chamber soil CO2 flux surveys were also conducted in the four additional areas of diffuse CO2 degassing on Mammoth Mountain in July-August 2013. Summing CO2 emission rates for all five areas yielded a total for the mountain of 311 t d- 1, which may suggest that emissions returned to 1998-2009 levels, following an increase from 2009 to 2011.

Multi-scale observations of the variability of magmatic CO2 emissions, Mammoth Mountain, CA, USA

USGS Publications Warehouse

Lewicki, Jennifer L.; Hilley, George E.

2014-01-01

One of the primary indicators of volcanic unrest at Mammoth Mountain is diffuse emission of magmatic CO2, which can effectively track this unrest if its variability in space and time and relationship to near-surface meteorological and hydrologic phenomena versus those occurring at depth beneath the mountain are understood. In June–October 2013, we conducted accumulation chamber soil CO2 flux surveys and made half-hourly CO2 flux measurements with automated eddy covariance and accumulation chamber (auto-chamber) instrumentation at the largest area of diffuse CO2 degassing on Mammoth Mountain (Horseshoe Lake tree kill; HLTK). Estimated CO2 emission rates for HLTK based on 20 June, 30 July, and 24–25 October soil CO2 flux surveys were 165, 172, and 231 t d− 1, respectively. The average (June–October) CO2 emission rate estimated for this area was 123 t d− 1 based on an inversion of 4527 eddy covariance CO2 flux measurements and corresponding modeled source weight functions. Average daily eddy covariance and auto-chamber CO2 fluxes consistently declined over the four-month observation time. Wavelet analysis of auto-chamber CO2 flux and environmental parameter time series was used to evaluate the periodicity of, and local correlation between these variables in time–frequency space. Overall, CO2 emissions at HLTK were highly dynamic, displaying short-term (hourly to weekly) temporal variability related to meteorological and hydrologic changes, as well as long-term (monthly to multi-year) variations related to migration of CO2-rich magmatic fluids beneath the volcano. Accumulation chamber soil CO2 flux surveys were also conducted in the four additional areas of diffuse CO2 degassing on Mammoth Mountain in July–August 2013. Summing CO2 emission rates for all five areas yielded a total for the mountain of 311 t d− 1, which may suggest that emissions returned to 1998–2009 levels, following an increase from 2009 to 2011.

The influence of magma degassing on entrapment pressures recorded in olivine-hosted melt inclusions

NASA Astrophysics Data System (ADS)

Gaetani, G. A.

2013-12-01

The concentrations of H2O and CO2 in olivine-hosted melt inclusions provide estimates for the pressures at which they were entrapped, and represent an important source of information on the depths at which basaltic magmas crystallize [1]. Results from recent dehydration experiments demonstrate that diffusive loss of H2O from melt inclusions, driven by degassing of the external magma, leads to significant decreases to pressure within the inclusion [2, 3]. This, in turn, lowers the solubility of CO2 in the included melt causing a vapor to exsolve and form a bubble. This process has the potential to significantly modify estimates of entrapment pressures derived from volatile concentrations in olivine hosted melt inclusions. I have developed a quantitative model that describes this process, allowing the influence of degassing on entrapment pressures to be rigorously evaluated. Diffusive loss of H2O from the inclusions was determined using the model of [3]. An equation of state (EOS) for the silicate melt was taken from the results of [4] and [5], while the EOS for H2O-CO2 vapor was taken from [6]. The solubilities of H2O and CO2 in the silicate melt were derived from VolatileCalc [7]. Modeling results demonstrate that degassing of H2O-rich magma produces significant pressure drops, so that entrapment pressures never exceed crustal values and always represent a minimum. Conversely, degassing of H2O-poor magma does not significantly perturb the H2O content of olivine-hosted melt inclusions. Therefore, these inclusions preserve reliable records of the pressures at which they were entrapped. These results are consistent with a global compilation of olivine-hosted melt inclusion entrapment pressures presented by [3]. References: [1] Wanless, VD, and Shaw, AM, Nature Geosci, 5, 651-655 (2012); [2] Gaetani, GA, et al., Geology, 40, 915-918 (2012); [3] Bucholz, CE, et al., Earth Planet Sci Lett, 374, 145-155 (2013); [4] Lange, R. A., and Carmichael, ISE, Geochim Cosmochim Acta, 51, 2931-2946, (1987); [5] Kress, VC, and Carmichael, ISE, Contrib Mineral Petrol, 108, 82-92 (1991); [6] Duan, Z, and Zhang, Z, Geochim Cosmochim Acta, 70, 2311-2324 (2006); [7] Newman, S, and Lowenstern, JB, Comput Geosci, 28, 597-604 (2002).

Diffuse volcanic emissions of carbon dioxide from Vulcano Island, Italy.

PubMed

Baubron, J C; Allard, P; Toutain, J P

1990-03-01

RECENT investigations on Mount Etna (Sicily)(1-3) have revealed that volcanoes may release abundant carbon dioxide not only from their active craters, but also from their flanks, as diffuse soil emanations. Here we present analyses of soil gases and air in water wells on Vulcano Island which provide further evidence of such lateral degassing. Nearly pure carbon dioxide, enriched in helium and radon, escapes from the slopes of the Fossa active cone, adding a total output of 30 tonnes per day to the fumarolic crater discharge ( 180 tonnes CO(2) per day). This emanation has similar He/CO(2) and (13)C/(12)C ratios to those of the crater fumaroles (300%ndash;500 degrees C) and therefore a similar volcanic origin. Gases rich in carbon dioxide also escape at sea level along the isthmus between the Fossa and Vulcanello volcanic cones, but their depletion in both He and (13)C suggests a distinct source. Diffuse volcanic gas emanations, once their genetic link with central fumarole degassing has been demonstrated, can be used for continuous volcano monitoring, at safe distances from active craters. Such monitoring has been initiated at Vulcano, where soil and well emanations of nearly pure CO(2) themselves represent a threat to the local population.

Diffuse degassing He/CO2 ratio before and during the 2011-12 El Hierro submarine eruption, Canary Islands

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Hernández, Pedro A.; Melián, Gladys V.; Barrancos, José; Padilla, Germán; Pérez, Nemesio M.; Dionis, Samara; Rodríguez, Fátima; Asensio-Ramos, María; Calvo, David

2015-04-01

El Hierro Island (278 km2) is the youngest and the SW-most of the Canary Islands. On July 16, 2011, a seismic-volcanic crisis started with the occurrence of more than 11,900 seismic events and significant deformation along the island, culminating with the eruption onset in October 12. Since at El Hierro Islands there are not any surface geothermal manifestation (fumaroles, etc), we have focused our studies on soil degassing surveys. Between July 2011 to March 2012, seventeen diffuse CO2 and He emissions soil gas surveys were undertaken at El Hierro volcanic system (600 observation sites) with the aim to investigate the relationship between their temporal variations and the volcanic activity (Padrón et al., 2013; Melián et al., 2014). Based on the diffuse He/CO2 emission ratio, a sharp increase before the eruption onset was observed, reaching the maximum value on September 26 (6.8×10-5), sixteen days before the occurrence of the eruption. This increase coincided with an increase in seismic energy release during the volcanic unrest and occurred together with an increase on the 3He/4He isotopic ratio in groundwaters from a well in El Hierro Island (Padrón et al., 2013; from 2-3 RA to 7.2 RA where RA = 3He/4He ratio in air), one month prior to the eruption onset. Early degassing of new gas-rich magma batch at depth could explain the observed increase on the He/CO2 ratio, causing a preferential partitioning of CO2 in the gas phase with respect to the He, due to the lower solubility of CO2 than that of He in basaltic magmas. During the eruptive period (October 2011-March 2012) the prevalence of a magmatic CO2-dominated component is evident, as indicated by the generally lower He/CO2 ratios and high 3He/4He values (Padrón et al., 2013). The onset of the submarine eruption might have produced a sudden release of volcanic gases, and consequently, a decrease in the volcanic gas pressure of the magma bodies moving beneath the island, reflected by a drastic decrease in the diffuse helium emissions measured after the eruption onset. Therefore, this study shows that higher diffuse He/CO2 emission ratios preceded the 2011-2012 El Hierro submarine eruption, clearly show the critical role that both gas species can play in the prediction of major volcanic events and demonstrates the importance of performing soil He and CO2 surveys as a useful geochemical monitoring tool in active volcanic regions. Padrón et al. (2013) Geology 41(5), 539-542; Melián et al. (2014) JGR, 119: 6976-6991, doi:10.1002/2014JB011013

Carbon degassing from the lithosphere

NASA Astrophysics Data System (ADS)

Mörner, Nils-Axel; Etiope, Giuseppe

2002-06-01

So far, the role of present-day Earth degassing in global C budget and climate effects has been focused to volcanic emissions. The non-volcanic escape of CO 2-CH 4 from the upper mantle, from carbonate bearing rocks in the crust, from hydrocarbon accumulations and from surface deposits and processes is here discussed in detail. An inventory of recent available data is presented. For the first time, a so large quantity of data is considered altogether showing clearly that the geological flux of carbon was previously significantly underestimated. Several lines of evidence show that non-volcanic C fluxes in «colder» environments are much greater than generally assumed. Local and regional data suggest that metamorphic decarbonation, hydrocarbon leakage and mud volcanoes could be significant CO 2-CH 4 sources at global scale. Moreover, extensive surface gas-geochemical observations, including soil-atmosphere flux investigations, open the possibility that ecosystems controlled by biogenic activity (soil, permafrost, seawater) can host important components of endogenous C gas (geogas), even in the absence of surface gas manifestations. This would imply the existence of a geological diffuse, background emission over large areas of our planet. New theories concerning the occurrence of pervasive geogas and lithospheric processes of C-gas production («lithospheric loss in rigidity») can be taken as novel reference and rationale for re-evaluating geological sources of CO 2 and CH 4, and an important endeavour and work prospect for the years to come. Our survey shows that it is still very hard to arrive at a meaningful estimate of the lithospheric non-volcanic degassing into the atmosphere. Orders of 10 2-10 3 Mt CO 2/year can be provisionally considered. Assuming as lower limit for a global subaerial volcanic degassing 300 Mt/year, the lithosphere may emit directly into the atmosphere at least 600 Mt CO 2/year (about 10% of the C source due to deforestation and land-use exchange), an estimate we still consider conservative. It is likely that temporal variations of lithosphere degassing, at Quaternary and secular scale, may influence the atmospheric C budget. The present-day lithosphere degassing would seem higher than the value considered to balance at Ma time-scale the CO 2 uptake due to silicate weathering.

Anomalous Diffuse CO2 Emission Changes at San Vicente Volcano Related to Earthquakes in El Salvador, Central America

NASA Astrophysics Data System (ADS)

Salazar, J.; Hernandez, P.; Perez, N.; Barahona, F.; Olmos, R.; Cartagena, R.; Soriano, T.; Notsu, K.; Lopez, D.

2001-12-01

San Vicente or Chichontepeque (2,180 m a.s.l.) is a composite andesitic volcano located 50 Km east of San Salvador. Its paired edifice rises from the so-called Central Graben, an extensional structure parallel to the Pacific coast, and has been inactive for the last 3000 yrs. Fumaroles (98.2°C ) and hot spring waters are present along radial faults at two localities on the northern slope of the volcano (Aguas Agrias and El Infiernillo). CO2 is the most abundant component in the dry gas (>90%) and its mean isotopic composition (δ 13C(CO2)=-2.11 ‰ and 3He/4He of 6.9 Ra) suggests a magmatic origin for the CO2. These manifestations are supposed to be linked to a 1,200 m depth 250°C reservoir with a CO2 partial pressure of 14 bar extended beneath the volcano (Aiuppa et al., 1997). In February 13, 2001, a 6.6 magnitude earthquake with epicenter about 20 Km W of San Vicente damaged and destroyed many towns and villages in the north area of the volcano causing some deceases. In addition, two seismic swarms were recorded beneath the northeastern flank of the volcano in April and May 2001. Searching for any link between the actual seismic activity and changes in the diffuse CO2 degassing at San Vicente, an NDIR instrument for continuos monitoring of the diffuse CO2 degassing was set up at Aguas Agrias in March 2001. Soil CO2 efflux and several meteorological and soil physical variables were measured in an hourly basis. Very significative pre-seismic and post-seismic relationships have been found in the observed diffuse CO2 efflux temporal variations related to the May 2001 seismic swarms. A sustained 50% increase on the average diffuse CO2 efflux was observed 8 days before the May 8, 5.1 magnitude earthquake. This pre-seismic behaviour may be considered a precursor of the May 2001 seismic swarm at San Vicente volcano. However, about a three-fold increase in the diffuse CO2 efflux was also observed after the intense seismicity recorded on May 8-9. These preliminary results suggest that changes in the fluid pore-pressure within faults/fractures associated to the volcanic roots may be triggering, enhancing and responding (aperture and closure of fractures) to the local seismicity in the area of San Vicente volcano.

Double, Double Toil and Trouble: The Melt Inclusion Bubble

NASA Astrophysics Data System (ADS)

Rasmussen, D. J.; Plank, T. A.

2017-12-01

Melt inclusions provide a powerful means for probing the depth of magmatic processes and volatile budgets of magmas. Both objectives require that the inclusions accurately record the volatile content of the entrapped melt. However, post-entrapment cooling and diffusive loss of water lead to a decrease in internal pressure, resulting in volatile exsolution (importantly CO2) and vapor bubble growth in inclusions. Several methods have been developed recently that attempt to reconstruct the entrapped CO2 contents, but the methods yield inconsistent results. Here we report on new homogenization experiments and attempt to reconcile inconsistencies in CO2 reconstruction methods. Experiments were conducted on olivine-hosted melt inclusions from Seguam volcano using a piston cylinder apparatus at 500 MPa, 1150-1170 °C, hydrous conditions, and a run duration of 1-2 hours. FTIR analyses of the homogenized inclusions show some diffusive water gain (≤1 wt% excess) relative to unheated inclusions (most 4 wt%). Inclusions from this same sample were previously reconstructed using Raman addition (RA; Moore et al., 2015), and we have constituted the CO2 with two different computational approaches: the ideal gas law (IGL; Shaw et al., 2010) and a bubble growth model (BG; Riker, 2005). CO2 and S contents of heated inclusions are correlated, defining a S-CO2 degassing path. Relative to this empirical degassing path, IGL results are offset to higher CO2 (100s-1000s of ppm) or lower S (100s of ppm), while RA and BG results overlap and are offset to lower CO2 (≤100s of ppm) or higher S (≤100s of ppm). Because S contents of heated and unheated inclusions have similar ranges, we attribute the discrepancy to CO2. High values of CO2 from the IGL correction may be because CO2 diffusion cannot keep pace with bubble growth during rapid cooling upon eruption. Mass balance calculations indicate that a minute amount of carbonate, which could escape detection by Raman, would affect CO2 content, providing an explanation for low values of CO2 determined by RA. The discrepancy in the BG results might relate to diffusive loss of H+ and uncertainties (e.g., temperature) involved with the calculation. Thus, homogenization via heating has advantages over other techniques in constituting the CO2 of inclusions, and may lead to a more accurate computational method.

Unraveling the dynamics of magmatic CO2 degassing at Mammoth Mountain, California

NASA Astrophysics Data System (ADS)

Peiffer, Loïc; Wanner, Christoph; Lewicki, Jennifer L.

2018-02-01

The accumulation of magmatic CO2 beneath low-permeability barriers may lead to the formation of CO2-rich gas reservoirs within volcanic systems. Such accumulation is often evidenced by high surface CO2 emissions that fluctuate over time. The temporal variability in surface degassing is believed in part to reflect a complex interplay between deep magmatic degassing and the permeability of degassing pathways. A better understanding of the dynamics of CO2 degassing is required to improve monitoring and hazards mitigation in these systems. Owing to the availability of long-term records of CO2 emissions rates and seismicity, Mammoth Mountain in California constitutes an ideal site towards such predictive understanding. Mammoth Mountain is characterized by intense soil CO2 degassing (up to ∼1000 t d-1) and tree kill areas that resulted from leakage of CO2 from a CO2-rich gas reservoir located in the upper ∼4 km. The release of CO2-rich fluids from deeper basaltic intrusions towards the reservoir induces seismicity and potentially reactivates faults connecting the reservoir to the surface. While this conceptual model is well-accepted, there is still a debate whether temporally variable surface CO2 fluxes directly reflect degassing of intrusions or variations in fault permeability. Here, we report the first large-scale numerical model of fluid and heat transport for Mammoth Mountain. We discuss processes (i) leading to the initial formation of the CO2-rich gas reservoir prior to the occurrence of high surface CO2 degassing rates and (ii) controlling current CO2 degassing at the surface. Although the modeling settings are site-specific, the key mechanisms discussed in this study are likely at play at other volcanic systems hosting CO2-rich gas reservoirs. In particular, our model results illustrate the role of convection in stripping a CO2-rich gas phase from a rising hydrothermal fluid and leading to an accumulation of a large mass of CO2 (∼107-108 t) in a shallow gas reservoir. Moreover, we show that both, short-lived (months to years) and long-lived (hundreds of years) events of magmatic fluid injection can lead to critical pressures within the reservoir and potentially trigger fault reactivation. Our sensitivity analysis suggests that observed temporal fluctuations in surface degassing are only indirectly controlled by variations in magmatic degassing and are mainly the result of temporally variable fault permeability. Finally, we suggest that long-term CO2 emission monitoring, seismic tomography and coupled thermal-hydraulic-mechanical modeling are important for CO2-related hazard mitigation.

Diffuse Carbon Dioxide Degassing Monitoring at Santa Ana-Izalco-Coatepeque Volcanic System, El Salvador, Central America

NASA Astrophysics Data System (ADS)

Olmos, R.; Barahona, F.; Cartagena, R.; Soriano, T.; Salazar, J.; Hernandez, P.; Perez, N.; Notsu, K.; Lopez, D.

2001-12-01

Santa Ana volcanic complex (0.22 Ma), located 40 Km west of San Salvador, comprises Santa Ana, Izalco, and Cerro Verde stratovolcanoes, the Coatepeque collapse caldera, as well as several cinder cones and explosion craters. Most recent activity has occurred at Izalco (1966) and Santa Ana which shows a permanent acidic crater lake with an intense fumarolic activity. In addition, Santa Ana exhibits a SO2-rich rising plume though no local seismicity has been reported. Weak fumarolic activity is also present at two locations within the Santa Ana volcanic complex: the summit crater of Izalco and Cerro Pacho at Coatepeque caldera. Other important structural features of this volcanic complex are two fault/fissure systems running NNW-SSE that can be identified by the alignment of the stratovolcanoes and numerous cinder cones and explosion craters. In January 2001, a 7.6 magnitude earthquake occurred about 150 Km SE of Santa Ana volcano. A soil gas and CO2 efflux survey was performed to evaluate the impact of this seismic event upon the diffuse degassing rates in Santa Ana volcanic complex in March 2001. A total of 450 soil gas and diffuse CO2 efflux measurements were carried out covering an area of 209.5 Km2. CO2 efflux ranged from non-detectable values to 293 gm-2d-1, with a median of 8.9 gm-2d-1 and an upper quartile of 5.2 gm-2d-1. The CO2 efflux spatial distribution reveals the existence of areas with CO2 efflux higher than 60 gm-2d-1 associated to the fault/fissure systems of NNW-SSE orientation. One of these areas, Cerro Pacho, was selected for the continuous monitoring of diffuse CO2 efflux in late May 2001. Secular variations of diffuse CO2 efflux ranged from 27.4 to 329 gm-2d-1 with a median of 130 gm-2d-1 and a quartile range of 59.3 gm-2d-1. An increasing trend of 43 gm-2d-1 was observed between May and August 2001 overlapped to high-frequency minor fluctuations related to meteorological variables' changes. However, a larger observation time-span is needed to understand the influence of the rainy-season and meteorological parameters in the observed CO2 efflux time series.

Are closed landfills free of CH_{4} emissions? A case study of Arico's landfill, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Barrancos, José; Cook, Jenny; Phillips, Victoria; Asensio-Ramos, María; Melián, Gladys; Hernández, Pedro A.; Pérez, Nemesio M.

2016-04-01

Landfills are authentic chemical and biological reactors that introduce in the environment a wide amount of gas pollutants (CO2, CH4, volatile organic compounds, etc.) and leachates. Even after years of being closed, a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as non-controlled emission. The study of the spatial-temporal distribution of diffuse emissions provides information of how a landfill degassing takes place. The main objective of this study was to estimate the diffuse uncontrolled emission of CH4 into the atmosphere from the closed Arico's landfill (0.3 km2) in Tenerife Island, Spain. To do so, a non-controlled biogenic gas emission survey of nearly 450 sampling sites was carried out during August 2015. Surface gas sampling and surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases, CO2 and CH4, were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux was computed combining CO2 efflux and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. The total diffuse CH4 emission was estimated in 2.2 t d-1, with CH4 efflux values ranging from 0-922 mg m-2 d-1. This type of studies provides knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

Unraveling the dynamics of magmatic CO2 degassing at Mammoth Mountain, California

USGS Publications Warehouse

Pfeiffer, Loic; Wanner, Christoph; Lewicki, Jennifer L.

2018-01-01

The accumulation of magmatic CO2 beneath low-permeability barriers may lead to the formation of CO2-rich gas reservoirs within volcanic systems. Such accumulation is often evidenced by high surface CO2 emissions that fluctuate over time. The temporal variability in surface degassing is believed in part to reflect a complex interplay between deep magmatic degassing and the permeability of degassing pathways. A better understanding of the dynamics of CO2 degassing is required to improve monitoring and hazards mitigation in these systems. Owing to the availability of long-term records of CO2 emissions rates and seismicity, Mammoth Mountain in California constitutes an ideal site towards such predictive understanding. Mammoth Mountain is characterized by intense soil CO2 degassing (up to ∼1000 t d−1) and tree kill areas that resulted from leakage of CO2 from a CO2-rich gas reservoir located in the upper ∼4 km. The release of CO2-rich fluids from deeper basaltic intrusions towards the reservoir induces seismicity and potentially reactivates faults connecting the reservoir to the surface. While this conceptual model is well-accepted, there is still a debate whether temporally variable surface CO2 fluxes directly reflect degassing of intrusions or variations in fault permeability. Here, we report the first large-scale numerical model of fluid and heat transport for Mammoth Mountain. We discuss processes (i) leading to the initial formation of the CO2-rich gas reservoir prior to the occurrence of high surface CO2 degassing rates and (ii) controlling current CO2 degassing at the surface. Although the modeling settings are site-specific, the key mechanisms discussed in this study are likely at play at other volcanic systems hosting CO2-rich gas reservoirs. In particular, our model results illustrate the role of convection in stripping a CO2-rich gas phase from a rising hydrothermal fluid and leading to an accumulation of a large mass of CO2 (∼107–108 t) in a shallow gas reservoir. Moreover, we show that both, short-lived (months to years) and long-lived (hundreds of years) events of magmatic fluid injection can lead to critical pressures within the reservoir and potentially trigger fault reactivation. Our sensitivity analysis suggests that observed temporal fluctuations in surface degassing are only indirectly controlled by variations in magmatic degassing and are mainly the result of temporally variable fault permeability. Finally, we suggest that long-term CO2 emission monitoring, seismic tomography and coupled thermal–hydraulic–mechanical modeling are important for CO2-related hazard mitigation.

Volatiles and energy released by Puracé volcano

NASA Astrophysics Data System (ADS)

Maldonado, Luisa Fernanda Meza; Inguaggiato, Salvatore; Jaramillo, Marco Tulio; Valencia, Gustavo Garzón; Mazot, Agnes

2017-12-01

Total CO2 output of Puracé volcano (Colombia) was estimated on the basis of fluids discharged by fumaroles, soil gases, and dissolved carbon species in the aquifer. The soil CO2 emission was computed from a field survey of 512 points of CO2 soil flux measurements at the main degassing areas of Puracé volcano. The CO2 flux from Puracé's plume was estimated using an indirect method, that used the SO2 plume flux and CO2/SO2 ratio of the main high temperature fumarole. The total output of CO2 was estimated at ≅ 1500 t/day. The main contribution of CO2 comes from the plume (summit degassing) and from soil degassing that emit 673 and 812 t/day, respectively. The contributions of summit and soil degassing areas are comparable, indicating an intermediate degassing style partitioned between closed and open conduit systems. The estimated water vapor discharge (as derived from the chemical composition of the fumaroles, the H2O/CO2 ratio, and the SO2 plume flux) allowed calculation of the total thermal energy (fumarolic, soil degassing, and aquifer) released from the Puracé volcanic system. This was 360 MW.

Soil CO2 efflux measurement network by means of closed static chambers to monitor volcanic activity at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Amonte, Cecilia; García-Merino, Marta; Asensio-Ramos, María; Melián, Gladys; García-Hernández, Rubén; Pérez, Aaron; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Tenerife (2304 km2) is the largest of the Canary Islands and has developed a central volcanic complex (Cañadas edifice), that started to grow about 3.5 My ago. Coeval with the construction of the Cañadas edifice, shield basaltic volcanism continued until the present along three rift zones oriented NW-SE, NE-SW and NS (hereinafter referred as NW, NE and NS respectively). Main volcanic historical activity has occurred along de NW and NE rift-zones, although summit cone of Teide volcano, in central volcanic complex, is the only area of the island where surface geothermal manifestations are visible. Uprising of deep-seated gases occurs along the aforementioned volcanic structures causing diffuse emissions at the surface environment of the rift-zones. In the last 20 years, there has been considerable interest in the study of diffuse degassing as a powerful tool in volcano monitoring programs. Diffuse degassing studies are even more important volcanic surveillance tool at those volcanic areas where visible manifestations of volcanic gases are absent. Historically, soil gas and diffuse degassing surveys in volcanic environments have focused mainly on CO2 because it is, after water vapor, the most abundant gas dissolved in magma. One of the most popular methods used to determine CO2 fluxes in soil sciences is based on the absorption of CO2 through an alkaline medium, in its solid or liquid form, followed by gravimetric, conductivity, or titration analyses. In the summer of 2016, a network of 31 closed static chambers was installed, covering the three main structural zones of Tenerife (NE, NW and NS) as well as Cañadas Caldera with volcanic surveillance porpoises. 50 cc of 0.1N KOH solution is placed inside the chamber to absorb the CO2 released from the soil. The solution is replaced weekly and the trapped CO2 is then analyzed at the laboratory by titration. The are expressed as weekly integrated CO2 efflux values. The CO2 efflux values ranged from 3.2 to 12.9 gṡm-2ṡd-1, with average values of 7.0 gṡm-2ṡd-1 for the NE rift-zone and 6.4 gṡm-2ṡd-1 for NW and NS rift-zones. The most significant CO2 efflux values were observed in the NE rift-zone, with maximum values of 12.5 gṡm-2ṡd-1. To investigate the origin of the soil CO2 at the three volcanic rifts, soil gas samples were weekly taken on the head space of the closed chambers to study the chemical composition and the isotopic composition of the CO2. Collected gas samples can be considered as CO2-enriched air, showing concentrations of CO2 in the range 370-22,448 ppmV, with average values of 2,859 ppmV, 1,396 ppmV and 1,216 ppmV for the NE, NW and NS rift-zones, respectively. The CO2isotopic composition, expressed as dxzC-CO2, indicates that most of the sampling sites exhibited CO2 composed by different mixing degrees between atmospheric and biogenic CO2 with slight inputs of deep-seated CO2, with mean values of -17.5‰ -13.6‰ and -16.4‰ for the NE, NW and NS rift-zones, respectively. The methodology presented here represents an inexpensive method that might help to detect early warning signals of future unrest episodes in Tenerife.

Carbon dioxide diffuse emission from the soil: ten years of observations at Vesuvio and Campi Flegrei (Pozzuoli), and linkages with volcanic activity

NASA Astrophysics Data System (ADS)

Granieri, D.; Avino, R.; Chiodini, G.

2010-01-01

Carbon dioxide flux from the soil is regularly monitored in selected areas of Vesuvio and Solfatara (Campi Flegrei, Pozzuoli) with the twofold aim of i) monitoring spatial and temporal variations of the degassing process and ii) investigating if the surface phenomena could provide information about the processes occurring at depth. At present, the surveyed areas include 15 fixed points around the rim of Vesuvio and 71 fixed points in the floor of Solfatara crater. Soil CO2 flux has been measured since 1998, at least once a month, in both areas. In addition, two automatic permanent stations, located at Vesuvio and Solfatara, measure the CO2 flux and some environmental parameters that can potentially influence the CO2 diffuse degassing. Series acquired by continuous stations are characterized by an annual periodicity that is related to the typical periodicities of some meteorological parameters. Conversely, series of CO2 flux data arising from periodic measurements over the arrays of Vesuvio and Solfatara are less dependent on external factors such as meteorological parameters, local soil properties (porosity, hydraulic conductivity) and topographic effects (high or low ground). Therefore we argue that the long-term trend of this signal contains the “best” possible representation of the endogenous signal related to the upflow of deep hydrothermal fluids.

Spatial and temporal variations of diffuse CO2 degassing at El Hierro volcanic system: Relation to the 2011-2012 submarine eruption

NASA Astrophysics Data System (ADS)

Melián, Gladys; Hernández, Pedro A.; Padrón, Eleazar; Pérez, Nemesio M.; Barrancos, José; Padilla, Germán.; Dionis, Samara; Rodríguez, Fátima; Calvo, David; Nolasco, Dacil

2014-09-01

We report herein the results of extensive diffuse CO2 emission surveys performed on El Hierro Island in the period 1998-2012. More than 17,000 measurements of the diffuse CO2 efflux were carried out, most of them during the volcanic unrest period that started in July 2011. Two significant precursory signals based on geochemical and geodetical studies suggest that a magma intrusion processes might have started before 2011 in El Hierro Island. During the preeruptive and eruptive periods, the time series of the diffuse CO2 emission released by the whole island experienced two significant increases. The first started almost 2 weeks before the onset of the submarine eruption, reflecting a clear geochemical anomaly in CO2 emission, most likely due to increasing release of deep-seated magmatic gases to the surface. The second one, between 24 October and 27 November 2011, started before the most energetic seismic events of the volcanic-seismic unrest. The data presented here demonstrate that combined continuous monitoring studies and discrete surveys of diffuse CO2 emission provide important information to optimize the early warning system in volcano monitoring programs and to monitor the evolution of an ongoing volcanic eruption, even though it is a submarine eruption.

Is Earth coming out of the recent ice house age in the long-term? - constraints from probable mantle CO2-degassing reconstructions

NASA Astrophysics Data System (ADS)

Hartmann, Jens; Li, Gaojun; West, A. Joshua

2017-04-01

Enhanced partial melting of mantle material probably started when the subduction motor started around 3.2 Ga ago as evidenced by the formation history of the continental crust. Carbon is degassing due partial melting as it is an incompatible element. Therefore, mantle carbon degassing rates would change with time proportionally to the reservoir mantle concentration evolution and the ocean crust production rate, causing a distinct CO2-degassing rate change with time. The evolution of the mantle degassing rate has some implications for the reconstruction of the carbon cycle and therefore climate and Earth surface processes rates, as CO2-degassing rates are used to constrain or to balance the atmosphere-ocean-crust carbon cycle system. It will be shown that compilations of CO2-degassing from relevant geological sources are probably exceeding the established CO2-sink terrestrial weathering, which is often used to constrain long-term mantle degassing rates to close the carbon cycle on geological time scales. In addition, the scenarios for the degassing dynamics from the mantle sources suggest that the mantle is depleting its carbon content since 3 Ga. This has further implications for the long-term CO2-sink weathering. Results will be compared with geochemical proxies for weathering and weathering intensity dynamics, and will be set in context with snow ball Earth events and long-term emplacement dynamics of mafic areas as Large Igneous Provinces. Decreasing mantle degassing rates since about 2 Ga suggest a constraint for the evolution of the carbon cycle and recycling potential of the amount of subducted carbon. If the given scenarios hold further investigation, the contribution of mantle degassing to climate forcing (directly and via recycling) will decrease further.

Evolution of CO2 in lakes Monoun and Nyos, Cameroon, before and during controlled degassing

USGS Publications Warehouse

Kusakabe, M.; Ohba, T.; Issa,; Yoshida, Y.; Satake, H.; Ohizumi, T.; Evans, William C.; Tanyileke, G.; Kling, G.W.

2008-01-01

Evolution of CO2 in Lakes Monoun and Nyos (Cameroon) before and during controlled degassing is described using results of regular monitoring obtained during the last 21 years. The CO2(aq) profiles soon after the limnic eruptions were estimated for Lakes Monoun and Nyos using the CTD data obtained in October and November 1986, respectively. Based on the CO2(aq) profiles through time, the CO2 Content and its change over time were calculated for both lakes. The CO2 accumulation rate calculated from the pre-degassing data, was constant after the limnic eruption at Lake Nyos (1986-2001), whereas the rate appeared initially high (1986-1996) but later slowed down (1996-2003) at Lake Monoun. The CO2 concentration at 58 m depth in Lake Monoun in January 2003 was very close to saturation due to the CO2 accumulation. This situation is suggestive of a mechanism for the limnic eruption, because it may take place spontaneously without receiving an external trigger. The CO2 content of the lakes decreased significantly after controlled degassing started in March 2001 at Lake Nyos and in February 2003 at Lake Monoun. The current content is lower than the content estimated soon after the limnic eruption at both lakes. At Monoun the degassing rate increased greatly after February 2006 due to an increase of the number of degassing pipes and deepening of the pipe intake depth. The current CO2 content is ???40% of the maximum content attained just before the degassing started. At current degassing rates the lower chemocline will subside to the degassing pipe intake depth of 93 m in about one year. After this depth is reached, the gas removal rate will progressively decline because water of lower CO2(aq) concentration will be tapped by the pipes. To keep the CO2 content of Lake Monoun as small as possible, it is recommended to set up a new, simple device that sends deep water to the surface since natural recharge of CO2 will continue. Controlled degassing at Lake Nyos since 2001 has also reduced the CO2 content. It is currently slightly below the level estimated after the limnic eruption in 1986. However, the current CO2 content still amounts to 80% of the maximum level of 14.8 giga moles observed in January 2001. The depth of the lower chemocline may reach the pipe intake depth of 203 m within a few years. After this situation is reached the degassing rate with the current system will progressively decline, and it would take decades to remove the majority of dissolved gases even if the degassing system keeps working continuously. Additional degassing pipes must be installed to speed up gas removal from Lake Nyos in order to make the area safer for local populations. Copyright ?? 2008 by The Geochemical Society of Japan.

Geochemical monitoring of Taal volcano (Philippines) by means of diffuse CO2 degassing studies

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Hernández, Pedro A.; Arcilla, Carlo; Pérez, Nemesio M.; Lagmay, Alfredo M.; Rodríguez, Fátima; Quina, Gerald; Alonso, Mar; Padilla, Germán D.; Aurelio, Mario A.

2017-04-01

Observing changes in the discharge rate of CO2 is an important part of volcanic monitoring programs, because it is released by progressive depressurization of magma during ascent and reach the surface well before their parental magma. Taal Volcano in Southwest Luzon, Philippines, lies between a volcanic arc front facing the subduction zone along the Manila Trench and a volcanic field formed from extension beyond the arc front. Taal Volcano Island is formed by a main tuff cone surrounded by several smaller tuff cones, tuff rings and scoria cones. This island is located in the center of the 30 km wide Taal Caldera, now filled by Taal Lake. To monitor the volcanic activity of Taal volcano is a priority task in the Philippines, because several million people live within a 20-km radius of Taal's caldera rim. During the last period of volcanic unrest from 2010 to 2011, the main crater lake of Taal volcano released the highest diffuse CO2 emission rates through the water surface reported to date by volcanic lakes worldwide. The maximum CO2 emission rate measured in the study period occurred two months before the strongest seismic activity recorded during the unrest period (Arpa et al., 2013, Bull Volcanol 75:747). After the unrest period, diffuse CO2 emission has remained in the range 532-860 t/d in the period 2013-2016. In January 2016, an automatic geochemical station to monitor in a continuous mode the diffuse CO2 degassing in a selected location of Taal, was installed in January 2016 to improve the early warning system at the volcano. The station is located at Daang Kastila, at the northern portion of the main crater rim. It measures hourly the diffuse CO2 efflux, atmospheric CO2 concentration, soil water content and temperature, wind speed and direction, air temperature and humidity, rainfall, and barometric pressure. The 2016 time series show CO2 efflux values in the range 20-690 g m-2 d-1.Soil temperature, heavily influenced by rainfall, ranged between 74 and 96oC. Although short-temp fluctuations in the diffuse CO2 emission time series at Daang Kastila were partially driven by meteorological parameters, the main CO2 efflux changes were not driven by fluctuations of meteorological variables such as wind speed or barometric pressure and seem clearly to be associated with fluid pressure fluctuations in the volcanic system. These results showed the potential of applying continuous and discrete monitoring of soil CO2 efflux to improve and optimize the detection of early warning signals of future volcanic unrest at Taal volcano.

Variable mixing and degassing of mantle CO2 within continental subsurface water bodies evidenced by compared gas geochemistry and fluid-phase equilibrium modeling

NASA Astrophysics Data System (ADS)

Virgile, R.

2016-12-01

The continental degassing of mantle volatiles is known from a variety of areas characterized by Asthenosphere updoming, such as the US Basin and Range and the European Cenozoic Rift System. Mantle degassing is there usually associated to magmatic provinces where non-volcanic upwellings of cold to hot waters are frequently associated with high CO2 gas loads. The resulting aquifers, springs and mofets express variable gas compositions which are often attributed to the mixing of crustal and mantle CO2, and less often to the variable degassing states of the waters. Indeed, the compositions of water and gas in CO2, δ13C and the noble gases may justify both models. However, the implications of each model for the bulk degassing mass quantification of mantle volatiles are drastically different, and would therefore need to be confirmed or rejected on a case by case basis. We introduce here a new model for predicting fluid phase equilibrium for systems comprising CO2-CH4-H2-H2S-N2-O2-He-Ne-Ar-Kr-Xe-H2O-NaCl at shallow subsurface conditions (1-250 bars, 0-150°C). The model was applied in P-T conditions comparable to non-volcanic CO2 degassing systems, where initial fluids were defined as variable mixtures of air equilibrated water (AEW) and mantle volatiles (CO2, He, CO2/3He = 5 x109). Literature data from European non-volcanic mantle degassing systems were compiled and compared to different modeling scenarios. The distribution of the CO2/3He (from 108 to 1012) and N2/3He (from 106 to 1011) ratios in natural samples are consistent with the open system degassing of initial fluids at depths above 2000m, with variable recharges of AEW. Initial single phase fluids are composed of up to 300 mol.m-3 CO2, 7 x10-3 mol.m-3 He and N2 with typical AEW contents (0.5 mol.m-3). Most degassed systems correspond to 98% degassed initial fluids, which incorporated up to 10% of fresh AEW subsequently to degassing. Our results suggest that fluid phase fractionation effects alone are sufficient to generate the range of compositions observed in the studied natural water-gas systems, without the need to invoke a crustal CO2 end-member.

New evidence of CO2 soil degassing anomalies on Piton de la Fournaise volcano and the link with volcano tectonic structures

NASA Astrophysics Data System (ADS)

Liuzzo, M.; Di Muro, A.; Giudice, G.; Michon, L.; Ferrazzini, V.; Gurrieri, S.

2015-12-01

Piton de la Fournaise (PdF) is recognized as one of the world's most active volcanoes in terms of eruptive frequency and the substantial quantity of lava produced. Yet with the sole exception of rather modest intracrateric fumarole activity, this seems to be in contrast with an apparent absence of any type of natural fluid emission during periods of quiescence. Measurement campaigns were undertaken during a long-lasting quiescent period (2012-2014) and just after a short-lived summit eruption (June 2014) in order to identify potential degassing areas in relation to the main structural features of the volcano (e.g., rift zones) with the aim of developing a broader understanding of the geometry of the plumbing and degassing system. In order to assess the possible existence of anomalous soil CO2 flux, 513 measurements were taken along transects roughly orthogonal to the known tectonic lineaments crossing PdF edifice. In addition, 53 samples of gas for C isotope analysis were taken at measurement points that showed a relatively high CO2 concentration in the soil. CO2 flux values range from 10 to 1300 g m-2 d-1 while δ13C are between -26.6 and -8‰. The results of our investigation clearly indicate that there is a strong spatial correlation between the anomalous high values of diffusive soil emissions and the main rift zones cutting the PdF massif and, moreover, that generally high soil CO2 fluxes show a δ13C signature clearly related to a magmatic origin.

Monitoring diffuse degassing in monogentic volcanic field during magmatic reactivation: the case of El Hierro (Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Morales-Ocaña, C.; Feldman, R. C.; Pointer, Z. R.; Rodríguez, F.; Asensio-Ramos, M.; Melián, G.; Padrón, E.; Hernández, P. A.; Pérez, N. M.

2017-12-01

El Hierro (278 km2), the younger, smallest and westernmost island of the Canarian archipelago, is a 5-km-high edifice constructed by rapid constructive and destructive processes in 1.12 Ma, with a truncated trihedron shape and three convergent ridges of volcanic cones. It experienced a submarine eruption from 12 October, 2011 and 5 March 2012, off its southern coast that was the first one to be monitored from the beginning in the Canary Islands. As no visible emanations occur at the surface environment of El Hierro, diffuse degassing studies have become a useful geochemical tool to monitor the volcanic activity in this volcanic island. Diffuse CO2 emission has been monitored at El Hierro Island since 1998 in a yearly basis, with much higher frequency in the period 2011-2012. At each survey, about 600 sampling sites were selected to obtain a homogeneous distribution. Measurements of soil CO2 efflux were performed in situ following the accumulation chamber method. During pre-eruptive and eruptive periods, the diffuse CO2 emission released by the whole island experienced significant increases before the onset of the submarine eruption and the most energetic seismic events of the volcanic-seismic unrest (Melián et al., 2014. J. Geophys. Res. Solid Earth, 119, 6976-6991). The soil CO2 efflux values of the 2017 survey ranged from non-detectable to 53.1 g m-2 d-1. Statistical-graphical analysis of the data show two different geochemical populations; background (B) and peak (P) represented by 77.6% and 22.4% of the total data, respectively, with geometric means of 1.8 and 9.2 g m-2 d-1, respectively. Most of the area showed B values while the P values were mainly observed at the interception center of the three convergent ridges and the north of the island. To estimate the diffuse CO2 emission for the 2017 survey, we ran about 100 sGs simulations. The estimated 2017 diffuse CO2 output released to atmosphere by El Hierro was at 1,150 ± 42 t d-1, value higher than the background average of CO2 emission estimated on 422 t d-1 and slightly higher than the background range of 181 t d-1 (-1σ) and 930 t d-1 (+1σ) estimated at El Hierro volcano during the quiescence period 1998-2010 (Melián et al., 2014, JGR). Monitoring the diffuse CO2 emission has proven to be a very effective tool to detect early warning signals of volcanic unrest at El Hierro.

Gas hazard assessment in the touristic area of Levante Beach (Vulcano island, Italy)

NASA Astrophysics Data System (ADS)

Carapezza, Maria Luisa; Di Piazza, Andrea; Gattuso, Alessandro; Ranaldi, Massimo; Sortino, Francesco; Tarchini, Luca

2016-04-01

Since the last eruption occurred at "La Fossa" in 1888-1890, Vulcano remained in a quiescence state characterized by an intense fumarolic activity. The main degassing manifestations are concentrated in La Fossa crater area (high temperature fumaroles) and in the area of Vulcano Porto, between Levante Beach and Faraglioni (medium-low temperature fumaroles). In addition the entire volcanic edifice of La Fossa, its base and the area of Vulcano Porto are characterized by en extensive soil CO2 diffuse degassing. In the last century episodic "crises" have occurred with increase of temperature, gas output and compositional changes of the crater fumaroles indicating an increase of the magmatic component in the discharged fluids. These episodic crises occurred in 1916-1924, in 1988-1993, in 1996 and in 2004-2006. During the period 1988-1990, the accumulation of CO2 in morphological depressions or excavation provoked the death for asphyxiation of two children in the area of Vulcano Porto and of some small animals at the base of the crater area. In April 2015, a child lost his senses while playing at Levante Beach; he was rescued by an air ambulance to the hospital of Lipari. According to the national chronicle (La Repubblica, 22 June 2015), doctors attributed the malaise to a high CO2 air concentration. Soon after this event the Major of Lipari installed at Levante Beach some panels informing tourists on gas hazard. In summer 2015 we performed a geochemical survey of the Levante Beach sector (onshore and offshore) and of the mud pool, estimating the diffuse and viscous gas flux and the air gas concentration in order to evaluate the degassing level. The total gas flux in the Levante Beach area, from 0.3 km2, has been estimated in 1 t/day of CO2 and 16,1 kg/day of H2S; values comparable with those of the 2009 and 2011 campaigns. In addition, a soil CO2 flux survey of the target area at La Fossa crater was performed, ascertaining that the degassing rate was within the range of the inter-crisis period (CO2 = 200 t/day). In the mud pool area, continuous measurements of CO2 and H2S air concentration were also carried out for a period of a week. The CO2 concentration was almost always higher than in the normal unpolluted air. Concentration of H2S displayed high values (maximum of 43 ppm), with the TWA (10 ppm) and STEL (15 ppm) H2S thresholds frequently exceeded. Offshore, gas concentration in atmosphere over the submarine vents of the Levante Beach, displayed extremely high concentrations of H2S (values up to 1000 ppm) and CO2 (8.6 vol.%). these values may cause serious adverse health consequences on the exposed people even in periods when the volcanic activity is not considered high or anomalous.

The development of a new database of gas emissions: MAGA, a collaborative web environment for collecting data

NASA Astrophysics Data System (ADS)

Cardellini, C.; Chiodini, G.; Frigeri, A.; Bagnato, E.; Aiuppa, A.; McCormick, B.

2013-12-01

The data on volcanic and non-volcanic gas emissions available online are, as today, incomplete and most importantly, fragmentary. Hence, there is need for common frameworks to aggregate available data, in order to characterize and quantify the phenomena at various spatial and temporal scales. Building on the Googas experience we are now extending its capability, particularly on the user side, by developing a new web environment for collecting and publishing data. We have started to create a new and detailed web database (MAGA: MApping GAs emissions) for the deep carbon degassing in the Mediterranean area. This project is part of the Deep Earth Carbon Degassing (DECADE) research initiative, lunched in 2012 by the Deep Carbon Observatory (DCO) to improve the global budget of endogenous carbon from volcanoes. MAGA database is planned to complement and integrate the work in progress within DECADE in developing CARD (Carbon Degassing) database. MAGA database will allow researchers to insert data interactively and dynamically into a spatially referred relational database management system, as well as to extract data. MAGA kicked-off with the database set up and a complete literature survey on publications on volcanic gas fluxes, by including data on active craters degassing, diffuse soil degassing and fumaroles both from dormant closed-conduit volcanoes (e.g., Vulcano, Phlegrean Fields, Santorini, Nysiros, Teide, etc.) and open-vent volcanoes (e.g., Etna, Stromboli, etc.) in the Mediterranean area and Azores. For each geo-located gas emission site, the database holds images and description of the site and of the emission type (e.g., diffuse emission, plume, fumarole, etc.), gas chemical-isotopic composition (when available), gas temperature and gases fluxes magnitude. Gas sampling, analysis and flux measurement methods are also reported together with references and contacts to researchers expert of the site. Data can be accessed on the network from a web interface or as a data-driven web service, where software clients can request data directly from the database. This way Geographical Information Systems (GIS) and Virtual Globes (e.g., Google Earth) can easily access the database, and data can be exchanged with other database. In details the database now includes: i) more than 1000 flux data about volcanic plume degassing from Etna (4 summit craters and bulk degassing) and Stromboli volcanoes, with time averaged CO2 fluxes of ~ 18000 and 766 t/d, respectively; ii) data from ~ 30 sites of diffuse soil degassing from Napoletan volcanoes, Azores, Canary, Etna, Stromboli, and Vulcano Island, with a wide range of CO2 fluxes (from les than 1 to 1500 t/d) and iii) several data on fumarolic emissions (~ 7 sites) with CO2 fluxes up to 1340 t/day (i.e., Stromboli). When available, time series of compositional data have been archived in the database (e.g., for Campi Flegrei fumaroles). We believe MAGA data-base is an important starting point to develop a large scale, expandable data-base aimed to excite, inspire, and encourage participation among researchers. In addition, the possibility to archive location and qualitative information for gas emission/sites not yet investigated, could stimulate the scientific community for future researches and will provide an indication on the current uncertainty on deep carbon fluxes global estimates.

Carbon isotope constraints on degassing of carbon dioxide from Kilauea Volcano

USGS Publications Warehouse

Gerlach, T.M.; Taylor, B.E.

1990-01-01

We examine models for batch-equilibrium and fractional-equilibrium degassing of CO2 from magma at Kilauea Volcano. The models are based on 1. (1) the concept of two-stage degassing of CO2 from magma supplied to the summit chamber, 2. (2) C isotope data for CO2 in eruptive and noneruptive (quiescent) gases from Kilauea and 3. (3) data for the isotopic fractionation of C between CO2 and C dissolved in tholeiitic basalt melt. The results of our study indicate that 1. (1) both eruptive and noneruptive degassing of CO2 most closely approach a batch equilibrium process, 2. (2) the ??13C of parental magma supplied to the summit chamber is in the range -4.1 to-3.4??? and 3. (3) the ??13C of melt after summit chamber degassing is in the range -7 to -8???, depending upon the depth of equilibration. We also present ??13C data for CO2 in eruptive gases from the current East Rift Zone eruption. These are the first C isotope data for CO2 in high-temperature (>900??C) eruptive gases from Kilauea; they have a mean ??13C value of -7.82 ?? 0.24??? and are similar to those predicted for the melt after summit chamber degassing. The minor role played by fractional degassing of ascending magma at Kilauea means that exsolved CO2 tends to remain entrained in and coherent with its host melt during ascent from both mantle source regions and crustal magma reservoirs. This has important implications for magma dynamics at Kilauea. ?? 1990.

Magma ascent and lava flow emplacement rates during the 2011 Axial Seamount eruption based on CO2 degassing

NASA Astrophysics Data System (ADS)

Jones, M. R.; Soule, S. A.; Gonnermann, H. M.; Le Roux, V.; Clague, D. A.

2018-07-01

Quantitative metrics for eruption rates at mid-ocean ridges (MORs) would improve our understanding of the structure and formation of the uppermost oceanic crust and would provide a means to link volcanic processes with the conditions of the underlying magmatic system. However, these metrics remain elusive because no MOR eruptions have been directly observed. The possibility of disequilibrium degassing in mid-ocean ridge basalts (MORB), due to high eruptive depressurization rates, makes the analysis of volatile concentrations in MORB glass a promising method for evaluating eruption rates. In this study, we estimate magma ascent and lava flow emplacement rates during the 2011 eruption of Axial Seamount based on numerical modeling of diffusion-controlled bubble growth and new measurements of dissolved volatiles, vesicularity, and vesicle size distributions in erupted basalts. This dataset provides a unique view of the variability in magma ascent (∼0.02-1.2 m/s) and lava flow rates (∼0.1-0.7 m/s) during a submarine MOR eruption based on 50 samples collected from a >10 km long fissure system and three individual lava flow lobes. Samples from the 2011 eruption display an unprecedented range in dissolved CO2 concentrations, nearly spanning the full range observed on the global MOR system. The variable vesicularity and dissolved CO2 concentrations in these samples can be explained by differences in the extent of degassing, dictated by flow lengths and velocities during both vertical ascent and horizontal flow along the seafloor. Our results document, for the first time, the variability in magma ascent rates during a submarine eruption (∼0.02-1.2 m/s), which spans the global range previously proposed based on CO2 degassing. The slowest ascent rates are associated with hummocky flows while faster ascent rates produce channelized sheet flows. This study corroborates degassing-based models for eruption rates using comparisons with independent methods and documents the relationship between eruption dynamics, magma ascent rates, and the morphology of eruptive products. Globally, this approach allows interrogation of the processes that govern mid-ocean ridge eruptions and influence the formation of the oceanic crust.

Short-term variations of diffuse CO2 emission from the summit crater of Teide volcano, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Melián, Gladys V.; Ocampo, Stephany; Nisbet, Andrew; McKnight, Samara; Monzón, Tania; Asensio-Ramos, María; Alonso, Mar; Rodríguez, Fátima; García-Merino, Marta; Amonte, Cecilia; Pérez, Nemesio M.

2017-04-01

Teide volcano in Tenerife, Canary Islands, is characterized by the presence of a weak fumarolic system, steamy ground, and high rates of diffuse CO2 degassing all around this area. The temperature of the fumaroles (83˚ C) corresponds to the boiling point of water at discharge conditions. Previous diffuse CO2 surveys have shown to be an important tool to detect early warnings of possible impending volcanic unrests at Tenerife Island (Melián et al., 2012; Pérez et al., 2013). During June, July and August 2016, twelve soil gas surveys were performed at the summit crater of Teide volcano in order to evaluate short-term variations of diffuse CO2 degassing pattern. Soil CO2 efflux and soil temperature were always measured at the same 38 observation sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Soil CO2 diffuse effluxes were estimated according to the accumulation chamber method and using a non-dispersive infrared (NDIR) LICOR-820 CO2analyzer. Soil CO2 efflux values presented a range from non-detectable (˜0.5 gṡm-2ṡd-1) to 10.8 kgṡm-2ṡd-1, with an average value of 2.7 kgṡm-2ṡd-1, while soil temperature ranged from 13.1 to 83.6˚ C with a mean value of 55.6˚ C. Sequential Gaussian simulations (sGs) were used for mapping and estimate the volcanic diffuse CO2 emission at each survey. The highest values of diffuse CO2 efflux were measured along the east (>8 kgṡm-2ṡd-1) and west (>5 kgṡm-2ṡd-1) sectors of the crater. Areas with highest diffuse CO2 effluxes were also characterized by a relatively high soil temperature (>60˚ C) and by an intense hydrothermal alteration. Weekly diffuse CO2 emission variations from the summit crater during the study period showed a range between 13.5 and 24.7 tṡd-1 with an average value of 18.9 tṡd-1. During these 3 months, the seismic activity rate was about 10 seismic events per month registered by the Instituto Geográfico Nacional (IGN; http://www.ign.es). We compared these observed weekly variations with monthly variations of a longer period with similar seismic rate such as 2014 (about 8 seismic events per month, and values ranged from 15.6 to 22.4 tṡd-1, and an average value of 19.0 tṡd-1. These values are in the same order than the observed during our study. However, for a longer period of observation, from 1999 to 2010, diffuse CO2 emission rates varied from 2.2 to 36.3 tṡd-1, with a mean value of 15.7 tṡd-1 (Melián et al., 2012). The long-term variations observed in the diffuse CO2 emission rates during this period of 10 years were significantly higher than short-term variations observed in the period of study. It is also important to note that the volcanic-seismic crisis of 2004 occurred with an increase on the CO2 emission from Teide summit crater (Melián et al., 2012). This study shows that during periods of seismic tranquility, diffuse CO2 emission rates will not suffer significant variations, whether performed on a weekly or monthly basis. References: Melián et al., 2012. Bull. Volcanol. DOI 10.1007/s00445-012-0613-1 Pérez et al., 2013. J. Geol. Soc. DOI 10.1144/jgs2012-125 .

Precursory diffuse carbon dioxide degassing signature related to a 5.1 magnitude earthquake in El Salvador, Central America

NASA Astrophysics Data System (ADS)

Salazar, J. M. L.; Pérez, N. M.; Hernández, P. A.; Soriano, T.; Barahona, F.; Olmos, R.; Cartagena, R.; López, D. L.; Lima, R. N.; Melián, G.; Galindo, I.; Padrón, E.; Sumino, H.; Notsu, K.

2002-12-01

Anomalous changes in the diffuse emission of carbon dioxide have been observed before some of the aftershocks of the 13 February 2001 El Salvador earthquake (magnitude 6.6). A significant increase in soil CO 2 efflux was detected 8 days before a 5.1 magnitude earthquake on 8 May 2001 25 km away from the observation site. In addition, pre- and co-seismic CO 2 efflux variations have also been observed related to the onset of a seismic swarm beneath San Vicente volcano on May 2001. Strain changes and/or fluid pressure fluctuations prior to earthquakes in the crust are hypothesized to be responsible for the observed variations in gas efflux at the surface environment of San Vicente volcano.

Diffuse CO2 degassing monitoring for the volcanic surveillance of Tenerife North-East Rift Zone (NERZ) volcano, Canary Islands

NASA Astrophysics Data System (ADS)

Rodríguez, F.; Thomas, G. E.; Wong, T.; García, E.; Melián, G.; Padron, E.; Asensio-Ramos, M.; Hernández, P. A.; Perez, N. M.

2017-12-01

The North East Rift zone of Tenerife Island (NERZ, 210 km2) is one of the three major volcanic rift-zones of the island. The most recent eruptive activity along the NERZ took place in the 1704-1705 period with eruptions of Siete Fuentes, Fasnia and Arafo volcanoes. Since fumarolic activity is nowadays absent at the NERZ, soil CO2 degassing monitoring represent a potential geochemical tool for its volcanic surveillance. The aim of this study is to report the results of the last CO2 efflux survey performed in June 2017, with 658 sampling sites. In-situ measurements of CO2 efflux from the surface environment of the NERZ were performed by means of a portable non-dispersive infrared spectrophotometer (NDIR) following the accumulation chamber method. To quantify the total CO2 emission, soil CO2 efflux spatial distribution maps were constructed using Sequential Gaussian Simulation (SGS) as interpolation method. The diffuse CO2 emission values ranged between 0 - 41.1 g m-2 d-1. The probability plot technique applied to the data allowed to distinguish two different geochemical populations; background (B) and peak (P) represented by 81.8% and 18.2% of the total data, respectively, with geometric means of 3.9 and 15.0 g m-2 d-1, respectively. The average map constructed with 100 equiprobable simulations showed an emission rate of 1,361±35 t d-1. This value relatively higher than the background average of CO2 emission estimated on 415 t d-1 and slightly higher than the background range of 148 t d-1 (-1σ) and 1,189 t d-1 (+1σ) observed at the NERZ. This study reinforces the importance of performing soil CO2 efflux surveys as an effective surveillance volcanic tool in the NERZ.

Precursory signals of the 2014-15 Fogo eruption (Cape Verde) detected by surface CO2 emission and heat flow observations

NASA Astrophysics Data System (ADS)

Pérez, Nemesio M.; Dionis, Samara; Fernandes, Paulo; Barrancos, José; Rodríguez, Fátima; Bandomo, Zuleyka; Hernández, Pedro A.; Melián, Gladys V.; Silva, Sónia; Padilla, Germán; Padrón, Eleazar; Cabral, Jeremias; Calvo, David; Asensio-Ramos, María; Pereira, José Manuel; Gonçalves, António A.; Barros, Inocencio; Semedo, Helio

2015-04-01

On November 23, 2014 a new eruption occurred at Fogo volcano (Cape Verde) after 19 years of the last eruptive event in 1995. In the case of the 1995 Fogo eruption, a volcano monitoring program for the volcanic surveillance of Fogo did not exist. On the contrary, a simple and multidisciplinary volcano monitoring program was initiated since 2007 to detect early warning signals of a new volcanic unrest such as the 2014-15 Fogo eruption. Diffuse CO2 emission surveys at the summit crater of Pico do Fogo volcano were periodically carried out from May 2007 to October 2014 to provide this multidisciplinary approach and to monitor potential volcanic activity changes. During this 7 year period, CO2 efflux ranged from non detectable (< 1.5 g m-2 d-1) up to relatively high (61.9 kg m-2 d-1) values. The observed average δ13C- CO2 values related to these diffuse CO2 emission surveys ranged from -22.1 to 1.6 ‰, and surface heat flux measurements, following the method of Dawson (1964), showed also a wide range of values from 0.1 to 460 W m-2. Areas with the highest observed CO2 efflux values were also characterized by a relatively high soil temperature and an intense surface hydrothermal alteration, which supports that degassing process is primary controlled by an advective mechanism generated by geothermal gradients (convection). Two periods of anomalous diffuse CO2 emission were observed between February 2009 to February 2010 and March to August 2014, respectively. Rest of surveys showed the lowest variability on diffuse CO2 emission, ranging from 23 to 186 t d-1 (average = 86 t d-1). The first anomalous period was characterized by a sharp increase on diffuse CO2 emission, suggesting the first magma intrusion beneath Pico do Fogo volcano. This observation is also supported by a significant change on the δ13C- CO2 signature from May 2009 (-10.2 ‰) to February 2010 (-6.1‰) of the diffuse CO2 degassing, indicating an enrichment on the magmatic CO2 component. On February 2010, the diffuse CO2 emission rate was 219 ± 36 t d-1 (Dionis et al., 2015). The second anomalous period started on March 2014, eight months before the 2014-15 Fogo eruption onset, and reached a relatively high value of 337 ± 119 t d-1 on August 30, 2014. It was likely caused by rising of magmatic gases from a second magma intrusion which ended on an eruption. Heat flow temporal evolution during the observation period also shows a quasi-continuous increase before the eruption onset, with the maximum observed heat flow (16.4 ± 3.4 MW) on March 2014. These geochemical and geophysical evidences are clearly precursory signals of the 2014-15 Fogo eruption. Dawson, G.B. (1964), N Z J Geol Geophys 7:155-171; Dionis S. et al. (2015), Bull. Volcanol., in press

Bubble formation, vesicularity and fractionation of noble gases during MORB degassing

NASA Astrophysics Data System (ADS)

Sator, N.; Guillot, B. B.; Aubry, G.

2012-12-01

The fractionation of noble gases in oceanic basalts gives information on the source region and on the transport of volatiles up to the seafloor. For instance, the large distribution (~1-1,000) of the 4He/40Ar* ratio in mid-ocean ridge basalts (MORB), is interpreted as the signature of different degassing scenarios taking place at depth. Thus, a low value of this ratio is explained by a closed system degassing whereas a high value is assigned either to an open system degassing (where vesicles are lost in a magma chamber or at depth during magma ascent) or to a kinetic disequilibrium induced by a rapid magma ascent just prior eruption. Unfortunately, CO2 has a very low solubility in basaltic melts at pressure corresponding to the seafloor and an overwhelming majority of erupted lavas have lost their pristine volatile contents. However notable exceptions are the popping rocks characterized by a large vesicularity, a high CO2 content and a 4He/40Ar* ratio compatible with the expected U/K ratio of the upper mantle. Those samples likely have experienced a CO2 exsolution at about 35 km depth in the oceanic mantle. So, the very existence of these exceptional MORB samples suggests that CO2-rich melts could be present at a greater depth. Thus, explosive eruptions near ocean spreading centers are well documented (Hekinian et al., 2000) and are associated with volcaniclastic deposits containing highly vesicular basalts, a feature which suggests that this volcanism is driven by CO2-rich magmas (Helo et al., 2011). But how much CO2-rich are these magmas, that is the question. The objective of this study is to use molecular dynamics simulation (MD) to evaluate the vesicularity and the fractionation of noble gases in a degassing MORB melt. A previous simulation study (Guillot and Sator, 2011) has shown that the solubility of CO2 in basaltic melts increases steadily with the pressure and deviates significantly from the Henry's law at high pressures. From the CO2 solubility curve and the equations of state of the two coexisting phases, deduced from the MD simulation, we have evaluated the evolution of the vesicularity of a MORB melt at depth as function of its initial CO2 contents. An excellent agreement is obtained between our results and data on MORB samples collected at oceanic ridges. A conclusion is that CO2-rich magmas may exist at 100 km depth or more in the oceanic mantle. Moreover, we have evaluated the partitioning and the fractionation of noble gases between the CO2-saturated melt and supercritical CO2 vesicles as function of the pressure. We show that the large distribution of the 4He/40Ar* ratio reported in the literature can be explained if the magma experiences a suite of vesiculation and vesicle loss during ascent. Finally, by applying a pressure drop to a volatile bearing melt (CO2+noble gas), the MD simulation reveals the main steps of bubble formation and noble gas transfer at the nanometric scale. A key result is that the transfer of noble gases is found to be concomitant with CO2 bubble nucleation, a finding which suggests that the difference in diffusivity between He and Ar in the degassing melt has practically no effect on the 4He/40Ar* ratio measured in the vesicles. Guillot B., Sator N. (2011), GCA 75, 1829-1857 Hekinian et al. (2000), J. Volcanol. Geotherm. Res. 98, 49-77 Helo et al. (2011), Nature Geoscience 4, 260-263

Geophysical image of the hydrothermal system of Merapi volcano

NASA Astrophysics Data System (ADS)

Byrdina, S.; Friedel, S.; Vandemeulebrouck, J.; Budi-Santoso, A.; Suhari; Suryanto, W.; Rizal, M. H.; Winata, E.; Kusdaryanto

2017-01-01

We present an image of the hydrothermal system of Merapi volcano based on results from electrical resistivity tomography (ERT), self-potential, and CO2 flux mappings. The ERT models identify two distinct low-resistivity bodies interpreted as two parts of a probably interconnected hydrothermal system: at the base of the south flank and in the summit area. In the summit area, a sharp resistivity contrast at ancient crater rim Pasar-Bubar separates a conductive hydrothermal system (20-50 Ω m) from the resistive andesite lava flows and pyroclastic deposits (2000-50,000 Ω m). The existence of preferential fluid circulation along this ancient crater rim is also evidenced by self-potential data. The significative diffuse CO2 degassing (with a median value of 400 g m-2 d-1) is observed in a narrow vicinity of the active crater rim and close to the ancient rim of Pasar-Bubar. The total CO2 degassing across the accessible summital area with a surface of 1.4 ṡ 105 m2 is around 20 t d-1. Before the 2010 eruption, Toutain et al. (2009) estimated a higher value of the total diffuse degassing from the summit area (about 200-230 t d-1). This drop in the diffuse degassing from the summit area can be related to the decrease in the magmatic activity, to the change of the summit morphology, to the approximations used by Toutain et al. (2009), or, more likely, to a combination of these factors. On the south flank of Merapi, the resistivity model shows spectacular stratification. While surficial recent andesite lava flows are characterized by resistivity exceeding 100,000 Ω m, resistivity as low as 10 Ω m has been encountered at a depth of 200 m at the base of the south flank and was interpreted as a presence of the hydrothermal system. No evidence of the hydrothermal system is found on the basis of the north flank at the same depth. This asymmetry might be caused by the asymmetry of the heat supply source of Merapi whose activity is moving south or/and to the asymmetry in topography caused by the presence of Merbabu volcano in the north. On the basis of our results we suggest that stratified pyroclastic deposits on the south flank of Merapi screen and separate the flow of hydrothermal fluids with the gaseous part rising through the crater rims, while the liquid part is flowing downwards to the base of the edifice.

Increased degassing from the Southern Central American Volcanic Arc in response to crustal stress change following the 2012 Nicoya earthquake?

NASA Astrophysics Data System (ADS)

de Moor, M. J.; Kern, C.; Fischer, T. P.; Avard, G.; Aiuppa, A.; Protti, M.; Muller, C.; Alvarez, J.; Saballos, J. A.; Galle, B.

2016-12-01

The aim of this work is to provide an updated assessment of SO2 and CO2 fluxes from the Southern Central America Volcanic Arc (SCAVA) for the period 2015-2016. We present over 300 new ground-based remote sensing sulfur dioxide flux measurements (DOAS traverses) conducted at 10 volcanoes in Costa Rica and Nicaragua, representing the most comprehensive assessment of volcanic gas flux at SCAVA to date. The data were filtered to exclude measurements directly associated with eruptive activity. The SO2 flux from this 500km section of arc is thus conservatively estimated at 4622 ± 1586 tons/day (unfiltered average of the data yields 6114 ± 1956 tons/day SO2). Our best estimate is about double that of any previous estimations (data from 1972-2013). We attribute this increase in part to our more complete assessment of the arc, as previous studies considered fluxes from only 5 to 7 of the SCAVA volcanoes. Additionally,a greater number of SCAVA volcanoes have had eruptions in 2015-2016 than in any two-year period since 1980. A possible explanation for increased degassing and volcanic activity is a change in crustal stress regime following the 2012 Nicoya earthquake (Mw = 7.8). GPS data show that the SCAVA has experienced a dramatic change from compression to extension, potentially opening conduits for volatiles and magmas to rise from the mantle and lower crustal regions. The dominant contributors to volcanic degassing at SCAVA are Masaya and Turrialba volcanoes, which show average passive degassing SO2 fluxes of 1984 ± 890 T/d and 1672 ± 925 T/d respectively during 2015-2016. High-quality MultiGAS time series datasets for both of these volcanoes provide robust measurements of CO2/SO2 values associated with SO2 flux measurement at these volcanoes. Based on these data we estimate the CO2 flux from Masaya at 5487 ± 1800 T/d and from Turrialba at 4873 ± 2053 T/d. Combining our arc SO2 flux data with gas composition data for the other volcanoes as well as estimations of available diffuse CO2 degassing we estimate the total CO2 flux from the arc at 13544 ± 6037 T/d (1.12 x 1011 mol/yr). Our estimation of volcanic CO2 outgassing is approximately equal to estimates of C input into the SCAVA subduction zone.

Carbon dioxide degassing at the groundwater-stream-atmosphere interface: isotopic equilibration and hydrological mass balance in a sandy watershed

NASA Astrophysics Data System (ADS)

Deirmendjian, Loris; Abril, Gwenaël

2018-03-01

Streams and rivers emit significant amounts of CO2 and constitute a preferential pathway of carbon transport from terrestrial ecosystems to the atmosphere. However, the estimation of CO2 degassing based on the water-air CO2 gradient, gas transfer velocity and stream surface area is subject to large uncertainties. Furthermore, the stable isotope signature of dissolved inorganic carbon (δ13C-DIC) in streams is strongly impacted by gas exchange, which makes it a useful tracer of CO2 degassing under specific conditions. For this study, we characterized the annual transfers of dissolved inorganic carbon (DIC) along the groundwater-stream-river continuum based on DIC concentrations, stable isotope composition and measurements of stream discharges. We selected a homogeneous, forested and sandy lowland watershed as a study site, where the hydrology occurs almost exclusively through drainage of shallow groundwater (no surface runoff). We observed the first general spatial pattern of decreases in pCO2 and DIC and an increase in δ13C-DIC from groundwater to stream orders 1 and 2, which was due to the experimentally verified faster degassing of groundwater 12C-DIC compared to 13C-DIC. This downstream enrichment in 13C-DIC could be modelled by simply considering the isotopic equilibration of groundwater-derived DIC with the atmosphere during CO2 degassing. A second spatial pattern occurred between stream orders 2 and 4, consisting of an increase in the proportion of carbonate alkalinity to the DIC accompanied by the enrichment of 13C in the stream DIC, which was due to the occurrence of carbonate rock weathering downstream. We could separate the contribution of these two processes (gas exchange and carbonate weathering) in the stable isotope budget of the river network. Thereafter, we built a hydrological mass balance based on drainages and the relative contribution of groundwater in streams of increasing order. After combining with the dissolved CO2 concentrations, we quantified CO2 degassing for each stream order for the whole watershed. Approximately 75% of the total CO2 degassing from the watershed occurred in first- and second-order streams. Furthermore, from stream order 2-4, our CO2 degassing fluxes compared well with those based on stream hydraulic geometry, water pCO2, gas transfer velocity, and stream surface area. In first-order streams, however, our approach showed CO2 fluxes that were twice as large, suggesting that a fraction of degassing occurred as hotspots in the vicinity of groundwater resurgence and was missed by conventional stream sampling.

CO2, SO2, and H2S Degassing Related to the 2009 Redoubt Eruption, Alaska

NASA Astrophysics Data System (ADS)

Werner, C. A.; Kelly, P. J.; Evans, W.; Doukas, M. P.; McGimsey, R. G.; Neal, C. A.

2012-12-01

The 2009 eruption of Redoubt Volcano, Alaska was particularly well monitored for volcanic gas emissions with 35 airborne measurements of CO2, SO2, and H2S that span from October 2008 to August 2010. Increases in CO2 degassing were detected up to 5 months prior to the eruption and varied between 3630 and 9020 tonnes per day (t/d) in the 6 weeks prior to the eruption. Increased pre-eruptive CO2 degassing was accompanied by comparatively low S emission, resulting in molar C/S ratios that ranged between 30-60. However, the C/S ratio dropped to 2.4 coincident with the first phreatic explosion on March 15, 2009, and remained steady during the explosive (March 22 - April 4, 2009), effusive dome-building (April 5 - July 1, 2009), and waning phases (August 2009 onward) of the eruption. Observations of ice-melt rates, melt water discharge, and water chemistry in the months leading up to the eruption suggested that surface waters represented drainage from surficial, perched reservoirs of condensed magmatic steam and glacial meltwater. While the surface waters were capable of scrubbing many thousands of t/d of SO2, sampling of these fluids revealed that only a few hundred tonnes of SO2 was reacting to a dissolved component each day. This is also much less than the ~ 2100 t/d SO2 expected from degassing of magma in the upper crust (3-6.5 km), where petrologic analysis shows the final magma equilibration occurred. Thus, the high pre-eruptive C/S ratios observed could reflect bulk degassing of upper-crustal magma followed by nearly complete loss of SO2 in a magmatic-hydrothermal system. Alternatively, high C/S ratios could be attributed to degassing of low silica andesitic magma that intruded into the mid-crust in the 5 months prior to eruption; modeling suggests that mixing of this magma with pre-existing high silica andesite magma or mush would have caused a reduction of the C/S ratio to a value consistent with that measured during the eruption. Monitoring emissions regularly throughout the eruptive phases showed that the magmatic system degassed primarily as a closed system with approximately 59 and 66 % of the total CO2 and SO2, respectively, emitted during the explosive and dome growth periods. Maximum emission rates measured with airborne techniques were 33,110 t/d CO2, 16,650 t/d SO2, and 1230 t/d H2S. Pre-eruptive open system degassing accounted for only 14% of the total CO2 and 4% of total SO2, whereas post-eruptive passive degassing was responsible for 27 and 30 % of the total CO2 and SO2 with measurements extending over one year following the cessation of dome extrusion. SO2 made up on average 92% of the total sulfur degassing throughout the eruption. Primary volatile contents calculated from degassing and erupted magma volumes range from 0.9-2.1 wt. % CO2 and 0.27 - 0.56 wt. % S. Similar trends between volumes of estimated degassed magma and observed erupted magma during the eruptive period point to primary volatile contents of 1.25 wt. % CO2 and 0.35 wt. % S. Assuming these values, up to 30% additional unerupted magma degassed in the year following final dome emplacement.

A global census of continental rift activity since 250 Ma reveals a missing element of the deep carbon cycle

NASA Astrophysics Data System (ADS)

Brune, Sascha; Williams, Simon; Müller, Dietmar

2017-04-01

The deep carbon cycle connects CO2 concentrations within the atmosphere to the vast carbon reservoir in Earth's mantle: subducted lithosphere carries carbon into the mantle, while extensional plate boundaries and arc volcanoes release it back to Earth's surface. The length of plate boundaries thereby exerts first-order control on global CO2 fluxes on geological time scales. Here we provide a global census of rift length from the Triassic to present day, combining a new plate reconstruction analysis technique with data from the geological rift record. We find that the most extensive rift phase during the fragmentation of Pangea occurred in the Jurassic/Early Cretaceous with extension along the South Atlantic (9700 km) and North Atlantic rifts (9100 km), within East Gondwana (8500 km), the failed African rift systems (4900 km), and between Australia and Antarctica (3700 km). The combined extent of these and other rift systems amounts to more than 50.000 km of simultaneously active continental rifts. During the Late Cretaceous, in the aftermath of this massive rift episode, the global rift length dropped by 60% to 20.000 km. We further show that a second pronounced rift episode starts in the Eocene with global rift lengths of up to 30.000 km. It is well-accepted that volcanoes at plate boundaries release large amounts of CO2 from the Earth's interior. Recent work, however, highlights the importance of deep-cutting faults and diffuse degassing on CO2 emissions in the East African Rift, which appear to be comparable to CO2 release rates at mid-ocean ridges worldwide. Upscaling measured CO2 fluxes from East Africa to all concurrently active global rift zones with due caution, we compute the first-order history of cumulative rift-related CO2 degassing rates for the last 250 Myr. We demonstrate that rift-related CO2 release in the Early Cretaceous may have reached 400% of present-day rates. In first-order agreement with paleo-atmospheric CO2 concentrations from proxy indicators, our degassing rates correlate with the two distinct periods of elevated atmospheric CO2 in the Mesozoic and Cenozoic. Compiling the length of other plate boundaries through time (mid-ocean ridges, subduction zones, continental arcs), we do not find such a correlation with the paleo-CO2 record, which leads us to suggest that rift-related degassing constitutes an important element of the deep carbon cycle.

Effect of degassing temperature on specific surface area and pore volume measurements of biochar

NASA Astrophysics Data System (ADS)

Sigmund, Gabriel; Hüffer, Thorsten; Kah, Melanie; Hofmann, Thilo

2017-04-01

Specific surface area, pore volume, and pore size distribution are key biochar properties that have been related to water and nutrient cycling, microbial activity as well as sorption potential for organic compounds. Specific surface area and pore volume are commonly determined by measurement of physisorption of N2 and/or CO2. The measurement requires prior degassing of the samples, which may change the structure of the materials. Information on degassing temperature is rarely reported in literature, and recommendations differ considerably between existing guidelines for biochar characterization. Therefore, the influence of degassing temperature on N2 and CO2physisorption measurements was investigated by systematically degassing a range of materials, including four biochars, Al2O3 and carbon nanotubes at different temperatures (105 ˚ C, 150 ˚ C, 200 ˚ C, 250 ˚ C and 300 ˚ C for ≥ 14 h each). Measured specific surface area and pore volume increased with increasing degassing temperature for all biochars. Additional surface area and pore volume may have become available as components in biochars volatilized during the degassing phase. The results of our study showed that (i) degassing conditions change material properties, and influence physisorption measurements for biochar (ii) comparison between parameters derived from different degassing protocols may not be appropriate, and (iii) degassing protocols should be harmonized in the biochar community [1]. [1] Sigmund, et al. (2016), "Biochar total surface area and total pore volume determined by N2 and CO2 physisorption are strongly influenced by degassing temperature", STOTEN, doi: http://dx.doi.org/10.1016/j.scitotenv.2016.12.023.

CO2 Degassing Estimates from Rift Length Analysis since Pangea Fragmentation: A Key Component of the Deep Carbon Cycle?

NASA Astrophysics Data System (ADS)

Brune, S.; Williams, S.; Müller, D.

2017-12-01

The deep carbon cycle links the carbon content of crust and mantle to Earth's surface: extensional plate boundaries and arc volcanoes release CO2 to the ocean and atmosphere while subducted lithosphere carries carbon back into the mantle. The length of extensional and convergent plate boundaries therefore exerts first-order control on solid Earth CO2 degassing rates. Here we provide a global census of plate boundary length for the last 200 million years. Focusing on rift systems, we find that the most extensive rift phase during the fragmentation of Pangea occurred in the Jurassic/Early Cretaceous with more than 50.000 km of simultaneously active continental rifts. During the Late Cretaceous, in the aftermath of this pervasive rift episode, the global rift length dropped by 60% to 20,000 km. We further find that a second pronounced rift episode with global rift lengths of up to 30,000 km started in Eocene times. A close geological link between CO2 degassing and faulting has been documented in currently active rift systems worldwide. Regional-scale CO2 flux densities at rift segments in Africa, Europe, and New Zealand feature an annual average value of 200 t of CO2 per km2. Assuming that the release of CO2 scales with rift length, we show that rift-related CO2 degassing rates during the two major Mesozoic and Cenozoic rift episodes reached more than 300% of present-day values. Most importantly, the timing of enhanced CO2 degassing from continental rifts correlates with two well-known periods of elevated atmospheric CO2 in the Mesozoic and Cenozoic as evidenced by multiple independent proxy indicators. Compiling the length of other plate boundaries (mid-ocean ridges, subduction zones, continental arcs) through time, we do not reproduce such a correlation. Finally, we conduct numerical carbon cycle models that account for key feedback-mechanisms of the long-term carbon cycle. We find that only those models that feature a strong rift degassing component reproduce the timing and amplitude of the paleo-CO2 record. We therefore suggest that rift-related degassing constitutes a key component of the deep carbon cycle.

Degassing of CO2, SO2, and H2S associated with the 2009 eruption of Redoubt Volcano, Alaska

USGS Publications Warehouse

Werner, Cynthia A.; Kelly, Peter; Doukas, Michael P.; Lopez, Taryn; Pfeffer, Melissa; McGimsey, Robert G.; Neal, Christina

2013-01-01

The 2009 eruption of Redoubt Volcano, Alaska was particularly well monitored for volcanic gas emissions. We report 35 airborne measurements of CO2, SO2, and H2S emission rates that span from October 2008 to August 2010. The magmatic system degassed primarily as a closed system although minor amounts of open system degassing were observed in the 6 months prior to eruption on March 15, 2009 and over 1 year following cessation of dome extrusion. Only 14% of the total CO2 was emitted prior to eruption even though high emissions rates (between 3630 and 9020 t/d) were observed in the final 6 weeks preceding the eruption. A minor amount of the total SO2 was observed prior to eruption (4%), which was consistent with the low emission rates at that time (up to 180 t/d). The amount of the gas emitted during the explosive and dome growth period (March 15–July 1, 2009) was 59 and 66% of the total CO2and SO2, respectively. Maximum emission rates were 33,110 t/d CO2, 16,650 t/d SO2, and 1230 t/d H2S. Post-eruptive passive degassing was responsible for 27 and 30% of the total CO2 and SO2, respectively. SO2 made up on average 92% of the total sulfur degassing throughout the eruption. Magmas were vapor saturated with a C- and S-rich volatile phase, and regardless of composition, the magmas appear to be buffered by a volatile composition with a molar CO2/SO2 ratio of ~ 2.4. Primary volatile contents calculated from degassing and erupted magma volumes range from 0.9 to 2.1 wt.% CO2 and 0.27–0.56 wt.% S; whole-rock normalized values are slightly lower (0.8–1.7 wt.% CO2 and 0.22–0.47 wt.% S) and are similar to what was calculated for the 1989–90 eruption of Redoubt. Such contents argue that primary arc magmas are rich in CO2 and S. Similar trends between volumes of estimated degassed magma and observed erupted magma during the eruptive period point to primary volatile contents of 1.25 wt.% CO2 and 0.35 wt.% S. Assuming these values, up to 30% additional unerupted magma degassed in the year following final dome emplacement.

Degassing of CO2, SO2, and H2S associated with the 2009 eruption of Redoubt Volcano, Alaska

NASA Astrophysics Data System (ADS)

Werner, Cynthia; Kelly, Peter J.; Doukas, Michael; Lopez, Taryn; Pfeffer, Melissa; McGimsey, Robert; Neal, Christina

2013-06-01

The 2009 eruption of Redoubt Volcano, Alaska was particularly well monitored for volcanic gas emissions. We report 35 airborne measurements of CO2, SO2, and H2S emission rates that span from October 2008 to August 2010. The magmatic system degassed primarily as a closed system although minor amounts of open system degassing were observed in the 6 months prior to eruption on March 15, 2009 and over 1 year following cessation of dome extrusion. Only 14% of the total CO2 was emitted prior to eruption even though high emissions rates (between 3630 and 9020 t/d) were observed in the final 6 weeks preceding the eruption. A minor amount of the total SO2 was observed prior to eruption (4%), which was consistent with the low emission rates at that time (up to 180 t/d). The amount of the gas emitted during the explosive and dome growth period (March 15-July 1, 2009) was 59 and 66% of the total CO2 and SO2, respectively. Maximum emission rates were 33,110 t/d CO2, 16,650 t/d SO2, and 1230 t/d H2S. Post-eruptive passive degassing was responsible for 27 and 30% of the total CO2 and SO2, respectively. SO2 made up on average 92% of the total sulfur degassing throughout the eruption. Magmas were vapor saturated with a C- and S-rich volatile phase, and regardless of composition, the magmas appear to be buffered by a volatile composition with a molar CO2/SO2 ratio of ~ 2.4. Primary volatile contents calculated from degassing and erupted magma volumes range from 0.9 to 2.1 wt.% CO2 and 0.27-0.56 wt.% S; whole-rock normalized values are slightly lower (0.8-1.7 wt.% CO2 and 0.22-0.47 wt.% S) and are similar to what was calculated for the 1989-90 eruption of Redoubt. Such contents argue that primary arc magmas are rich in CO2 and S. Similar trends between volumes of estimated degassed magma and observed erupted magma during the eruptive period point to primary volatile contents of 1.25 wt.% CO2 and 0.35 wt.% S. Assuming these values, up to 30% additional unerupted magma degassed in the year following final dome emplacement.

Spatial variability in degassing at Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Ilanko, Tehnuka; Oppenheimer, Clive; Kyle, Philip; Burgisser, Alain

2015-04-01

Erebus volcano on Ross Island, Antarctica, hosts an active phonolitic lava lake, along with a number of persistently degassing vents in its summit crater. Flank degassing also occurs through ice caves and towers. The longevity of the lake, and its stable convection, have been the subject of numerous studies, including Fourier transform infrared (FTIR) spectroscopy of the lava lake. Two distinct gas compositions were previously identified in the main lava lake plume (Oppenheimer et al., 2009; 2011): a persistent 'conduit' gas with a more oxidised signature, ascribed to degassing through a permeable magma conduit; and a H2O- and SO2- enriched 'lake' composition that increases and decreases cyclically due to shallow degassing of incoming magma batches. During the past decade of annual field seasons on Erebus, gas compositions have been measured through FTIR spectroscopy at multiple sites around Erebus volcano, including flank degassing through an ice cave (Warren Cave). We present measurements from four such vents, and compare their compositions to those emitted from the main lava lake. Summit degassing involves variable proportions of H2O, CO2, CO, SO2, HF, HCl, OCS. Cyclicity is evident in some summit vents, but with signatures indicative of shallower magmatic degassing than that of the lava lake. By contrast, flank degassing at Warren Cave is dominated by H2O, CO2, and CH4. The spatial variability in gas compositions within the summit crater suggests an alternative origin for 'conduit' and 'lake' degassing to previous models that assume permeability in the main conduit. Rather, the two compositions observed in main lake degassing may be a result of decoupled 'conduit' gas and pulses of magma rising through discrete fractures before combining in the lake floor or the main plume. Smaller vents around the crater thus emit isolated 'lake' or 'conduit' compositions while their combined signature is observed in the lava lake. We suggest that this separation between gas sources is enabled by a complex shallow fracture network, collapses of which also promote frequent changes to crater morphology. Flank degassing results from decoupling and ascent of CO2-rich gas through deeper fractures, and re-equilibration to lower temperatures and pressures.

Geochemical evidence for a magmatic CO2 degassing event at Mammoth Mountain, California, September-December 1997

USGS Publications Warehouse

McGee, K.A.; Gerlach, T.M.; Kessler, R.; Doukas, M.P.

2000-01-01

Recent time series soil CO2 concentration data from monitoring stations in the vicinity of Mammoth Mountain, California, reveal strong evidence for a magmatic degassing event during the fall of 1997 lasting more than 2 months. Two sensors at Horseshoe Lake first recorded the episode on September 23, 1997, followed 10 days later by a sensor on the north flank of Mammoth Mountain. Direct degassing from shallow intruding magma seems an implausible cause of the degassing event, since the gas released at Horseshoe Lake continued to be cold and barren of other magmatic gases, except for He. We suggest that an increase in compressional strain on the area south of Mammoth Mountain driven by movement of major fault blocks in Long Valley caldera may have triggered an episode of increased degassing by squeezing additional accumulated CO2 from a shallow gas reservoir to the surface along faults and other structures where it could be detected by the CO2 monitoring network. Recharge of the gas reservoir by CO2 emanating from the deep intrusions that probably triggered deep long-period earthquakes may also have contributed to the degassing event. The nature of CO2 discharge at the soil-air interface is influenced by the porous character of High Sierra soils and by meteorological processes. Solar insolation is the primary source of energy for the Earth atmosphere and plays a significant role in most diurnal processes at the Earth surface. Data from this study suggest that external forcing due largely to local orographic winds influences the fine structure of the recorded CO2 signals.

Enhance performance of micro direct methanol fuel cell by in situ CO2 removal using novel anode flow field with superhydrophobic degassing channels

NASA Astrophysics Data System (ADS)

Liang, Junsheng; Luo, Ying; Zheng, Sheng; Wang, Dazhi

2017-05-01

Capillary blocking caused by CO2 bubbles in anode flow field (AFF) is one of the bottlenecks for performance improvement of a micro direct methanol fuel cell (μDMFC). In this work, we present a novel AFF structure with nested layout of hydrophilic fuel channels and superhydrophobic degassing channels which can remove most of CO2 from AFF before it is released to the fuel channels. The new AFFs are fabricated on Ti substrates by using micro photochemical etching combined with anodization and fluorination treatments. Performance of the μDMFCs with and without superhydrophobic degassing channels in their AFF is comparatively studied. Results show that the superhydrophobic degassing channels can significantly speed up the exhaust of CO2 from the AFF. CO2 clogging is not observed in the new AFFs even when their comparison AFFs have been seriously blocked by CO2 slugs under the same operating conditions. 55% and 60% of total CO2 produced in μDMFCs with N-serpentine and N-spiral AFF can be respectively removed by the superhydrophobic degassing channels. The power densities of the μDMFCs equipped with new serpentine and spiral AFFs are respectively improved by 30% and 90% compared with those using conventional AFFs. This means that the new AFFs developed in this work can effectively prevent CO2-induced capillary blocking in the fuel channels, and finally significantly improve the performance of the μDMFCs.

Asymmetrical hydrothermal system below Merapi volcano imaged by geophysical data.

NASA Astrophysics Data System (ADS)

Byrdina, Svetlana; Friedel, Sven; Budi-Santoso, Agus; Suryanto, Wiwit; Suhari, Aldjarishy; Vandemeulebrouck, Jean; Rizal, Mohhamed H.; Grandis, Hendra

2017-04-01

A high-resolution image of the hydrothermal system of Merapi volcano is obtained using electrical resistivity tomography (ERT), self-potential, and CO2 flux mappings. The ERT inversions identify two distinct low-resistivity bodies, at the base of the south flank and in the summit area, that represent likely two parts of an interconnected hydrothermal system. In the summit area, the extension of the hydrothermal system is clearly limited by the main geological structures which are actual and ancient craters. A sharp resistivity contrast at ancient crater rim Pasar-Bubar separates a conductive hydrothermal system (20 - 50 Ωm) from the resistive andesite lava flows and pyroclastic deposits (2000 - 50 000 Ωm). High diffuse CO2 degassing (with a median value of 400g m -2 d -1) is observed in a narrow vicinity of the active crater rim and close to the Pasar-Bubar. The existence of preferential fluid circulation along this ancient crater rim is also evidenced by self-potential data. The total CO2 degassing across the accessible summit area with a surface of 1.4 · 10 5 m 2 is around 20 td -1. Before the 2010 eruption, Toutain et al. (2009) estimated a higher value of the total diffuse degassing from the summit area (about 200 - 230 td -1). This drop in the diffuse degassing can be related to the decrease in the magmatic activity, to the change of the summit morphology or to a combination of these factors. On the south flank of Merapi, the resistivity model shows spectacular stratification. While surficial recent andesite lava flows are characterized by resistivity exceeding 100 000 Ωm, resistivity as low as 10 Ωm has been encountered at a depth of 200 m at the base of the south flank and was interpreted as a presence of the hydrothermal system. We suggest that a sandwich-like structure of stratified pyroclastic deposits on the flanks of Merapi screen and separate the flow of hydrothermal fluids with the degassing occurring mostly through the fractured crater rims, while the liquid water flows down to the base of the volcanic dome. Our ERT results suggest the existence of a peripheral hydrothermal system below the south and west flanks in agreement with previous electromagnetic studies. In contrast, no evidence of hydrothermal system is found below the north flank, where the resistivity values are too high to be assigned to a hydrothermal system, at least to the ERT investigation depth. A probable cause of this asymmetry could be a non-axial location of the magmatic heat source. Such non-axial location of the magmatic source relative to the edifice is suggested by the shift of the volcanic activity to the south as proposed in the geological model by Camus et al, (2000). In addition, the hypocenters of seismic events located by Budi-Santoso et al, (2013) seem to be distributed to the SW from the active crater suggesting that the magma conduits and likely, the magmatic source, are shifted to the SW with respect to the actual crater.

Sink- or Source-driven Phanerozoic carbon cycle?

NASA Astrophysics Data System (ADS)

Godderis, Y.; Donnadieu, Y.; Maffre, P.; Carretier, S.

2017-12-01

The Phanerozoic evolution of the atmospheric CO2 level is controlled by the fluxes entering or leaving the exospheric system. Those fluxes (including continental weathering, magmatic degassing, organic carbon burial, oxidation of sedimentary organic carbon) are intertwined, and their relative importance in driving the global carbon cycle evolution may have fluctuated through time. Deciphering the causes of the Phanerozoic climate evolution thus requires a holistic and quantitative approach. Here we focus on the role played by the paleogeographic configuration on the efficiency of the CO2 sink by continental silicate weathering, and on the impact of the magmatic degassing of CO2. We use the spatially resolved numerical model GEOCLIM (geoclimmodel.worpress.com) to compute the response of the silicate weathering and atmospheric CO2 to continental drift for 22 time slices of the Phanerozoic. Regarding the CO2 released by the magmatic activity, we reconstruct several Phanerozoic histories of this flux, based on published indexes. We calculate the CO2 evolution for each degassing scenario, and accounting for the paleogeographic setting. We show that the paleogeographic setting is a main driver of the climate from 540 Ma to about the beginning of the Jurassic. Regarding the role of the magmatic degassing, the various reconstructions do not converge towards a single signal, and thus introduce large uncertainties in the calculated CO2 level over time. Nevertheless, the continental dispersion, which prevails since the Jurassic, promotes the CO2 consumption by weathering and forces atmospheric CO2 to stay low. Warm climates of the "middle" Cretaceous and early Cenozoic require enhanced CO2 degassing by magmatic activity. In summary, the Phanerozoic climate evolution can be hardly assigned to a single process, but is the result of complex and intertwined processes.

Spatially Variable CO2 Degassing in the Main Ethiopian Rift: Implications for Magma Storage, Volatile Transport, and Rift-Related Emissions

NASA Astrophysics Data System (ADS)

Hunt, Jonathan A.; Zafu, Amdemichael; Mather, Tamsin A.; Pyle, David M.; Barry, Peter H.

2017-10-01

Deep carbon emissions from historically inactive volcanoes, hydrothermal, and tectonic structures are among the greatest unknowns in the long-term (˜Myr) carbon cycle. Recent estimates of diffuse CO2 flux from the Eastern Rift of the East African Rift System (EARS) suggest this could equal emissions from the entire mid-ocean ridge system. We report new CO2 surveys from the Main Ethiopian Rift (MER, northernmost EARS), and reassess the rift-related CO2 flux. Since degassing in the MER is concentrated in discrete areas of volcanic and off-edifice activity, characterization of such areas is important for extrapolation to a rift-scale budget. Locations of hot springs and fumaroles along the rift show numerous geothermal areas away from volcanic edifices. With these new data, we estimate total CO2 emissions from the central and northern MER as 0.52-4.36 Mt yr-1. Our extrapolated flux from the Eastern Rift is 3.9-32.7 Mt yr-1 CO2, overlapping with lower end of the range presented in recent estimates. By scaling, we suggest that 6-18 Mt yr-1 CO2 flux can be accounted for by magmatic extension, which implies an important role for volatile-enriched lithosphere, crustal assimilation, and/or additional magmatic intrusion to account for the upper range of flux estimates. Our results also have implications for the nature of volcanism in the MER. Many geothermal areas are found >10 km from the nearest volcanic center, suggesting ongoing hazards associated with regional volcanism.

Spatial and temporal variations of diffuse CO_{2} degassing at the N-S volcanic rift-zone of Tenerife (Canary Islands, Spain) during 2002-2015 period

NASA Astrophysics Data System (ADS)

Alonso, Mar; Ingman, Dylan; Alexander, Scott; Barrancos, José; Rodríguez, Fátima; Melián, Gladys; Pérez, Nemesio M.

2016-04-01

Tenerife is the largest of the Canary Islands and, together with Gran Canaria Island, is the only one with a central volcanic complex that started to grow at about 3.5 Ma. Nowadays the central complex is formed by Las Cañadas caldera, a volcanic depression measuring 16×9 km that resulted from multiple vertical collapses and was partially filled by post-caldera volcanic products. Up to 297 mafic monogenetic cones have been recognized on Tenerife, and they represent the most common eruptive activity occurring on the island during the last 1 Ma (Dóniz et al., 2008). Most of the monogenetic cones are aligned following a triple junction-shaped rift system, as result of inflation produced by the concentration of emission vents and dykes in bands at 120o to one another as a result of minimum stress fracturing of the crust by a mantle upwelling. The main structural characteristic of the southern volcanic rift (N-S) of the island is an apparent absence of a distinct ridge, and a fan shaped distribution of monogenetic cones. Four main volcanic successions in the southern volcanic rift zone of Tenerife, temporally separated by longer periods (˜70 - 250 ka) without volcanic activity, have been identified (Kröchert and Buchner, 2008). Since there are currently no visible gas emissions at the N-S rift, diffuse degassing surveys have become an important geochemical tool for the surveillance of this volcanic system. We report here the last results of diffuse CO2 efflux survey at the N-S rift of Tenerife, performed using the accumulation chamber method in the summer period of 2015. The objectives of the surveys were: (i) to constrain the total CO2 output from the studied area and (ii) to evaluate occasional CO2 efflux surveys as a volcanic surveillance tool for the N-S rift of Tenerife. Soil CO2 efflux values ranged from non-detectable up to 31.7 g m-2 d-1. A spatial distribution map, constructed following the sequential Gaussian simulation (sGs) procedure, did not show an apparent relation between higher diffuse CO2 emission values and the main N-S axis of the rift. The total CO2 output released to the atmosphere in a diffuse way has been estimated at 707 t d-1, which represents a value three times higher than the average of the three studies conducted previously. This observed increase suggests the occurrence of an episodic enhanced magmatic (endogenous) contribution. This also confirms the need of periodic diffuse emission surveys in the area as a powerful volcanic surveillance tool, mainly in volcanic systems where visible gas emanations are absent. References: Dóniz et al., 2008. J. Volcanol. Geotherm. Res. 173, 185. Kröchert and Buchner, 2008. Geol. Mag. 146, 161.

Natural sources of greenhouse gases: carbon dioxide emissions from volcanoes

USGS Publications Warehouse

Gerlach, Terrence

1990-01-01

Volcanic degassing of carbon dioxide plays an important role in keeping the atmosphere-ocean portion of the carbon geochemical cycle in balance. The atmosphere-ocean carbon deficit requires replenishment of 6??1012 mol CO2/yr, and places an upper limit on the output of carbon dioxide from volcanoes. The CO2 output of the global mid-oceanic ridge system is ca. 0.7??1012 mol/yr, thus supplying only a fraction of the amount needed to balance the carbon deficit. The carbon dioxide flux from subaerial volcanoes is poorly known, but it appears to be at least as large as the mid-oceanic ridge flux. Much (perhaps most) of the CO2 emitted from volcanoes is degassed noneruptively. This mode of degassing may lead to impacts on the environment and biosphere that are fundamentally different in character from those envisioned in published scenarios, which are based on the assumption that CO2 degassing occurs predominantly by eruptive processes. Although the flux of carbon dioxide from volcanoes is poorly constrained at present, it is clearly two orders of magnitude lower than the anthropogenic output of CO2.

Dynamics of carbon dioxide emission at Mammoth Mountain, California

USGS Publications Warehouse

Rogie, J.D.; Kerrick, Derrill M.; Sorey, M.L.; Chiodini, G.; Galloway, D.L.

2001-01-01

Mammoth Mountain, a dormant volcano in the eastern Sierra Nevada, California, has been passively degassing large quantities of cold magmatic CO2 since 1990 following a 6-month-long earthquake swarm associated with a shallow magmatic intrussion in 1989. A search for any link between gas discharge and volcanic hazard at this popular recreation area led us to initiate a detailed study of the degassing process in 1997. Our continuous monitoring results elucidate some of the physical controls that influence dynamics in flank CO2 degassing at this volcano. High coherence between variations in CO2 efflux and variations in atmospheric pressure and wind speed imply that meteorological parameters account for much, if not all of the variability in CO2 efflux rates. Our results help explain differences among previously published estimates of CO2 efflux at Mammoth Mountain and indicate that the long-term (annual) CO2 degassing rate has in fact remained constant since ~ 1997. Discounting the possibility of large meteorologically driven temporal variations in gas efflux at other volcanoes may result in spurious interpretations of transients do not reflect actual geologic processes. ?? 2001 Elsevier Science B.V. All rights reserved.

Geochemical variation of groundwater in the Abruzzi region: earthquakes related signals?

NASA Astrophysics Data System (ADS)

Cardellini, C.; Chiodini, G.; Caliro, S.; Frondini, F.; Avino, R.; Minopoli, C.; Morgantini, N.

2009-12-01

The presence of a deep and inorganic source of CO2 has been recently recognized in Italy on the basis of the deeply derived carbon dissolved in the groundwater. In particular, the regional map of CO2 Earth degassing shows that two large degassing structures affect the Tyrrhenian side of the Italian peninsula. The northern degassing structure (TRDS, Tuscan Roman degassing structure) includes Tuscany, Latium and part of Umbria regions (~30000 km2) and releases > 6.1 Mt/y of deeply derived CO2. The southern degassing structure (CDS, Campanian degassing structure) affects the Campania region (~10000 km2) and releases > 3.1 Mt/y of deeply derived CO2. The total CO2 released by TRDS and CDS (> 9.2 Mt/y) is globally significant, being ~10% of the estimated present-day total CO2 discharge from sub aerial volcanoes of the Earth. The comparison between the map of CO2 Earth degassing and of the location of the Italian earthquakes highlights that the anomalous CO2 flux suddenly disappears in the Apennine in correspondence of a narrow band where most of the seismicity concentrates. A previous conceptual model proposed that in this area, at the eastern borders of TRDS and CDS plumes, the CO2 from the mantle wedge intrudes the crust and accumulate in structural traps generating over-pressurized reservoirs. These CO2 over-pressurized levels can play a major role in triggering the Apennine earthquakes, by reducing fault strength and potentially controlling the nucleation, arrest, and recurrence of both micro and major (M>5) earthquakes. The 2009 Abruzzo earthquakes, like previous seismic crises in the Northern Apennine, occurred at the border of the TRDS, suggesting also in this case a possible role played by deeply derived fluids in the earthquake generation. In order to investigate this process, detailed hydro-geochemical campaigns started immediately after the main shock of the 6th of April 2009. The surveys include the main springs of the area which were previously studied in detail, during a campaign performed ten years ago, constituting a pre-crisis reference case. The new data includes the determination of the main dissolved ions, the dissolved gases (CO2, CH4, N2, Ar, He) and the stable isotopes of the water (H, O), CO2 (13C) and He (3He/4He). All the springs collected in 2009 show a systematic increase in the content of the deeply derived CO2 dissolved in the aquifers, respect to the 1997. The origin of this regional variation is still under investigation. A monthly sampling of the main spring has been programmed in order to differentiate the variation derived by seasonal processes from eventual signals linked to seismic processes. The first results will be presented and discussed.

NanoSIMS results from olivine-hosted melt embayments: Magma ascent rate during explosive basaltic eruptions

NASA Astrophysics Data System (ADS)

Lloyd, Alexander S.; Ruprecht, Philipp; Hauri, Erik H.; Rose, William; Gonnermann, Helge M.; Plank, Terry

2014-08-01

The explosivity of volcanic eruptions is governed in part by the rate at which magma ascends and degasses. Because the time scales of eruptive processes can be exceptionally fast relative to standard geochronometers, magma ascent rate remains difficult to quantify. Here we use as a chronometer concentration gradients of volatile species along open melt embayments within olivine crystals. Continuous degassing of the external melt during magma ascent results in diffusion of volatile species from embayment interiors to the bubble located at their outlets. The novel aspect of this study is the measurement of concentration gradients in five volatile elements (CO2, H2O, S, Cl, F) at fine-scale (5-10 μm) using the NanoSIMS. The wide range in diffusivity and solubility of these different volatiles provides multiple constraints on ascent timescales over a range of depths. We focus on four 100-200 μm, olivine-hosted embayments erupted on October 17, 1974 during the sub-Plinian eruption of Volcán de Fuego. H2O, CO2, and S all decrease toward the embayment outlet bubble, while F and Cl increase or remain roughly constant. Compared to an extensive melt inclusion suite from the same day of the eruption, the embayments have lost both H2O and CO2 throughout the entire length of the embayment. We fit the profiles with a 1-D numerical diffusion model that allows varying diffusivities and external melt concentrations as a function of pressure. Assuming a constant decompression rate from the magma storage region at approximately 220 MPa to the surface, H2O, CO2 and S profiles for all embayments can be fit with a relatively narrow range in decompression rates of 0.3-0.5 MPa/s, equivalent to 11-17 m/s ascent velocity and an 8 to 12 minute duration of magma ascent from ~ 10 km depth. A two stage decompression model takes advantage of the different depth ranges over which CO2 and H2O degas, and produces good fits given an initial stage of slow decompression (0.05-0.3 MPa/s) at high pressure (> 145 MPa), with similar decompression rates to the single-stage model for the shallower stage. The magma ascent rates reported here are among the first for explosive basaltic eruptions and demonstrate the potential of the embayment method for quantifying magmatic timescales associated with eruptions of different vigor.

[Partial pressure of CO2 and CO2 degassing fluxes of Huayuankou and Xiaolangdi Station affected by Xiaolangdi Reservoir].

PubMed

Zhang, Yong-ling; Yang, Xiao-lin; Zhang, Dong

2015-01-01

According to periodic sampling analysis per month in Xiaolangdi station and Huayuankou station from November 2011 to October 2012, combined with continuous sampling analysis of Xiaolangdi Reservoir during runoff and sediment control period in 2012, partial pressure of CO2 (pCO2) in surface water were calculated based on Henry's Law, pCO2 features and air-water CO2 degassing fluxes of Huayuankou station and Xiaolangdi station affected by Xiaolangdi Reservoir were studied. The results were listed as follows, when Xiaolangdi Reservoir operated normally, pCO2 in surface water of Xiaolangdi station and Huayuankou station varied from 82 to 195 Pa and from 99 to 228 Pa, moreover, pCO2 in surface water from July to September were distinctly higher than those in other months; meanwhile, pCO, in surface water from Huayuankou station were higher than that from Xiaolangdi station. During runoff and sediment control period of Xiaolangdi Reservoir, two hydrological stations commonly indicated that pCO2 in surface water during water draining were obviously lower than those during sediment releasing. Whether in the period of normal operation or runoff and sediment control, pCO2 in surface water had positive relations to DIC content in two hydrological stations. Since the EpCO,/AOU value was higher than the theoretical value of 0. 62, the biological aerobic respiration effect had distinct contribution to pCO2. Throughout the whole year, air-water CO2 degassing fluxes from Xiaolangdi station and Huayuankou station were 0.486 p.mol (m2 s) -l and 0.588 pmol (m2 x s)(-1) respectively; When Xiaolangdi Reservoir operated normally, air-water CO, degassing fluxes in Huayuankou station were higher than that in Xiaolangdi station; during runoff and sediment control from Xiaolangdi Reservoir, two hydrological stations had one observation result in common, namely, air-water CO2 degassing fluxes in the period of water draining were obviously lower than that in the period of sediment releasing.

[Effect of different heat treatment on the bonding strength of porcelain and Co-Cr alloy].

PubMed

Liao, Juan-kun; Ye, Jian-tao; Zhu, Feng; Zhang, Cui-cui; Wen, Xiao-shan; Zhang, Yi-ping; Li, Bo-hua

2011-12-01

To investigate and compare the effect of different heat treatment on the metal- ceramic bonding strength and the interfacial microstructure of the Co-Cr alloy. Thirty specimens were made according to ISO 9693,and then divided into 3 groups (n=10) through the measurements .Group A(degassed 60s):degassed and then maintained 60s in 980 degrees centigrade Group B(degassed 60s and preoxidation 60s): degassed and maintained 60s in 980 degrees centigrade, then were maintained continuously for 60s in 980 degrees centigrade after re-gassed,Group C(degassed 120s): degassed and maintained 120s in 980 degrees centigrade. The bonding strengths of the three groups were evaluated through three point bending test. Six specimens divided into 3 group were made in the same method to observe the metal-ceramic interface through scanning electronic microscope(SEM) and energy dispersive spectrum(EDS).The bonding strength data were analyzed using ANOVA and Bonferroni's test by SPSS13.0 software package. The mean value of bonding strength was (39.03±2.70)MPa for group A, (34.43±2.36)MPa for group B, (31.65±1.49)MPa for group C, respectively. There were significant difference between every two groups (P<0.05). SEM demonstrated that the width of interfacial transition layer was 12.3-16.4μm in group A, 15.2-21.8μm in group B and 26.3-32.2μm in group C. Higher metal-ceramic bonding strength for Co-Cr alloy will be formed under the situation of degassed,and maintained 60s in 980 degrees centigrade ; while extending degassed time, prolonging the heat maintained time and preoxidation after degassing will reduce metal-ceramic bonding strength.

Volatiles in glasses from the HSDP2 drill core

NASA Astrophysics Data System (ADS)

Seaman, Caroline; Sherman, Sarah Bean; Garcia, Michael O.; Baker, Michael B.; Balta, Brian; Stolper, Edward

2004-09-01

H2O, CO2, S, Cl, and F concentrations are reported for 556 glasses from the submarine section of the 1999 phase of HSDP drilling in Hilo, Hawaii, providing a high-resolution record of magmatic volatiles over ˜200 kyr of a Hawaiian volcano's lifetime. Glasses range from undegassed to having lost significant volatiles at near-atmospheric pressure. Nearly all hyaloclastite glasses are degassed, compatible with formation from subaerial lavas that fragmented on entering the ocean and were transported by gravity flows down the volcano flank. Most pillows are undegassed, indicating submarine eruption. The shallowest pillows and most massive lavas are degassed, suggesting formation by subaerial flows that penetrated the shoreline and flowed some distance under water. Some pillow rim glasses have H2O and S contents indicating degassing but elevated CO2 contents that correlate with depth in the core; these tend to be more fractionated and could have formed by mixing of degassed, fractionated magmas with undegassed magmas during magma chamber overturn or by resorption of rising CO2-rich bubbles by degassed magmas. Intrusive glasses are undegassed and have CO2 contents similar to adjacent pillows, indicating intrusion shallow in the volcanic edifice. Cl correlates weakly with H2O and S, suggesting loss during low-pressure degassing, although most samples appear contaminated by seawater-derived components. F behaves as an involatile incompatible element. Fractionation trends were modeled using MELTS. Degassed glasses require fractionation at p? ≈ 5-10 bars. Undegassed low-SiO2 glasses require fractionation at p? ≈ 50 bars. Undegassed and partially degassed high-SiO2 glasses can be modeled by coupled crystallization and degassing. Eruption depths of undegassed pillows can be calculated from their volatile contents assuming vapor saturation. The amount of subsidence can be determined from the difference between this depth and the sample's depth in the core. Assuming subsidence at 2.5 mm/y, the amount of subsidence suggests ages of ˜500 ka for samples from the lower 750 m of the core, consistent with radiometric ages. H2O contents of undegassed low-SiO2 HSDP2 glasses are systematically higher than those of high-SiO2 glasses, and their H2O/K2O and H2O/Ce ratios are higher than typical tholeiitic pillow rim glasses from Hawaiian volcanoes.

An experimental study of the fluid-melt partitioning of volatiles (H2O, CO2, S) during the degassing of ascending basalt

NASA Astrophysics Data System (ADS)

Le Gall, Nolwenn; Pichavant, Michel; Di Carlo, Ida; Scaillet, Bruno

2017-04-01

We performed decompression experiments to constrain the fluid-melt partitioning of volatiles (H2O, CO2, S) in ascending basalt magmas associated with violent eruptions. Experiments were conducted in an internally heated pressure vessel under oxidizing conditions (fO2: NNO+1.1) so that all sulphur occurs as sulfate (S6+) in the melt. Volatile-bearing (2.72 ± 0.02 wt% H2O, 1291 ± 85 ppm CO2, 1535 ± 369 ppm S) melts, prepared from Stromboli pumice, were synthesized at 1200°C and 200 MPa, decompressed between 150 and 25 MPa at constant rates of 39 and 78 kPa/s (or 1.5 and 3 m/s), and rapidly quenched. Run products were characterized both chemically (by IR spectroscopy and electron microprobe analysis) and texturally (by scanning electron microscopy), and then compared with Stromboli pumice products (glass inclusions, volcanic gases). In H2O-CO2-S-bearing basaltic melts, bubbles start to nucleate heterogeneously on Fe sulfides for supersaturation pressures ΔPHeN ≤ 1 MPa and to nucleate homogeneously for ΔPHoN < 50 MPa (ΔPHeN and ΔPHoN are the difference between the saturation pressure and the pressure at which heterogeneous and homogeneous bubble nucleation are observed, respectively). Bubble growth, coalescence and outgassing occur in addition to continuous bubble nucleation, which is sustained by the preservation of CO2 supersaturated melts during decompression. In addition to model the degassing behaviour of sulphur (and also of CO2 and H2O), our experiments aim to assist in the interpretation of geochemical observables. On the one hand, the volatile degassing trend recorded by Stromboli natural glasses (unsealed glass embayments) was closely experimentally simulated, with a coupled decrease of H2O and S whereas CO2 concentrations remain elevated. On the other hand, the experimental H2O/CO2 and CO2/SO2 fluid molar ratios, calculated by mass balance, both reproduced or closely approached the lower ranges of gas ratios measured at Stromboli for quiescent magma degassing and explosive activity. Compared to models that attribute a deep origin to CO2-rich fluxes and high CO2/SO2 gas ratios, our experimental observations support a model of low pressure (Pf << 25 MPa) explosive degassing of CO2-rich melts generated as a result of disequilibrium degassing to generate Strombolian paroxysms.

Monitoring quiescent volcanoes by diffuse He degassing: case study Teide volcano

NASA Astrophysics Data System (ADS)

Pérez, Nemesio M.; Melián, Gladys; Asensio-Ramos, María; Padrón, Eleazar; Hernández, Pedro A.; Barrancos, José; Padilla, Germán; Rodríguez, Fátima; Calvo, David; Alonso, Mar

2016-04-01

Tenerife (2,034 km2), the largest of the Canary Islands, is the only island that has developed a central volcanic complex (Teide-Pico Viejo stratovolcanoes), characterized by the eruption of differentiated magmas. This central volcanic complex has been built in the intersection of the three major volcanic rift-zones of Tenerife, where most of the historical volcanic activity has taken place. The existence of a volcanic-hydrothermal system beneath Teide volcano is suggested by the occurrence of a weak fumarolic system, steamy ground and high rates of diffuse CO2 degassing all around the summit cone of Teide (Pérez et al., 2013). Diffuse emission studies of non-reactive and/or highly mobile gases such as helium have recently provided promising results to detect changes in the magmatic gas component at surface related to volcanic unrest episodes (Padrón et al., 2013). The geochemical properties of He minimize the interaction of this noble gas on its movement toward the earth's surface, and its isotopic composition is not affected by subsequent chemical reactions. It is highly mobile, chemically inert, physically stable, non-biogenic, sparingly soluble in water under ambient conditions, almost non-adsorbable, and highly diffusive with a diffusion coefficient ˜10 times that of CO2. As part of the geochemical monitoring program for the volcanic surveillance of Teide volcano, yearly surveys of diffuse He emission through the surface of the summit cone of Teide volcano have been performed since 2006. Soil He emission rate was measured yearly at ˜130 sampling sites selected in the surface environment of the summit cone of Teide volcano (Tenerife, Canary Islands), covering an area of ˜0.5 km2, assuming that He emission is governed by convection and diffusion. The distribution of the sampling sites was carefully chosen to homogeneously cover the target area, allowing the computation of the total He emission by sequential Gaussian simulation (sGs). Nine surveys have been carried out since 2006, showing an average emission rate of 8.0 kg/d. This value showed an anomalous increase up to 29 kg/d in the summer of 2010. The number of seismic events registered in and around Tenerife Island by the National Geographic Institute (IGN) reached also the highest value (1,176) in 2010. This excellent agreement between both times series suggest that the anomalous seismicity registered in 2010 was likely due to strain/stress changes caused by input of magmatic fluids beneath the central volcanic system of the island. These results suggest that monitoring of He degassing rates in oceanic volcanic islands is an excellent early warning geochemical precursory signal for volcanic unrest. References Padrón et al., 2013. Geology, DOI: 10.1130/G34027.1. Pérez et al., 2013. J. Geol. Soc., DOI: 10.1144/jgs2012-125.

Monitoring fugitive CH4 and CO2 emissions from a closed landfill at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Asensio-Ramos, María; Tompkins, Mitchell R. K.; Turtle, Lara A. K.; García-Merino, Marta; Amonte, Cecilia; Rodrígez, Fátima; Padrón, Eleazar; Melián, Gladys V.; Padilla, Germán; Barrancos, José; Pérez, Nemesio M.

2017-04-01

Solid waste must be managed systematically to ensure environmental best practices. One of the ways to manage this huge problem is to systematic dispose waste materials in locations such as landfills. However, landfills could face possible threats to the environment such as groundwater pollution and the release of landfill gases (CH4, volatile organic compounds, etc.) to the atmosphere. These structures should be carefully filled, monitored and maintained while they are active and for up to 30 years after they are closed. Even after years of being closed, a systematically amount of landfill gas could be released to the atmosphere through its surface in a diffuse and fugitive form. During the period 1999-2016, we have studied the spatial-temporal distribution of the surface fugitive emission of CO2 and CH4 into the atmosphere in a cell in the Arico's municipal landfill (0.3 km2) at Tenerife, Canary Islands, Spain. This cell was operative until 2004, when it was filled and closed. Monitoring these diffuse landfill emissions provides information of how the closed landfill is degassing. To do so, we have performed 9 gas emission surveys during the period 1999-2016. Surface landfill CO2 efflux measurements were carried out at around 450 sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases taken in the chamber were analyzed using a double channel VARIAN 4900 micro-GC. CH4 efflux measurements were computed combining CO2 efflux measurements and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. In general, a decrease in the CO2 emission is observed since the cell was closed (2004) to the present. The total CO2 and CH4 diffuse emissions estimated in the 2016 survey were 4.54 ± 0.14 t d-1 and 268.65 ± 17.99 t d-1, respectively. These types of studies provide knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

Plate tectonic controls on atmospheric CO2 levels since the Triassic.

PubMed

Van Der Meer, Douwe G; Zeebe, Richard E; van Hinsbergen, Douwe J J; Sluijs, Appy; Spakman, Wim; Torsvik, Trond H

2014-03-25

Climate trends on timescales of 10s to 100s of millions of years are controlled by changes in solar luminosity, continent distribution, and atmosphere composition. Plate tectonics affect geography, but also atmosphere composition through volcanic degassing of CO2 at subduction zones and midocean ridges. So far, such degassing estimates were based on reconstructions of ocean floor production for the last 150 My and indirectly, through sea level inversion before 150 My. Here we quantitatively estimate CO2 degassing by reconstructing lithosphere subduction evolution, using recent advances in combining global plate reconstructions and present-day structure of the mantle. First, we estimate that since the Triassic (250-200 My) until the present, the total paleosubduction-zone length reached up to ∼200% of the present-day value. Comparing our subduction-zone lengths with previously reconstructed ocean-crust production rates over the past 140 My suggests average global subduction rates have been constant, ∼6 cm/y: Higher ocean-crust production is associated with longer total subduction length. We compute a strontium isotope record based on subduction-zone length, which agrees well with geological records supporting the validity of our approach: The total subduction-zone length is proportional to the summed arc and ridge volcanic CO2 production and thereby to global volcanic degassing at plate boundaries. We therefore use our degassing curve as input for the GEOCARBSULF model to estimate atmospheric CO2 levels since the Triassic. Our calculated CO2 levels for the mid Mesozoic differ from previous modeling results and are more consistent with available proxy data.

Plate tectonic controls on atmospheric CO2 levels since the Triassic

PubMed Central

Van Der Meer, Douwe G.; Zeebe, Richard E.; van Hinsbergen, Douwe J. J.; Sluijs, Appy; Spakman, Wim; Torsvik, Trond H.

2014-01-01

Climate trends on timescales of 10s to 100s of millions of years are controlled by changes in solar luminosity, continent distribution, and atmosphere composition. Plate tectonics affect geography, but also atmosphere composition through volcanic degassing of CO2 at subduction zones and midocean ridges. So far, such degassing estimates were based on reconstructions of ocean floor production for the last 150 My and indirectly, through sea level inversion before 150 My. Here we quantitatively estimate CO2 degassing by reconstructing lithosphere subduction evolution, using recent advances in combining global plate reconstructions and present-day structure of the mantle. First, we estimate that since the Triassic (250–200 My) until the present, the total paleosubduction-zone length reached up to ∼200% of the present-day value. Comparing our subduction-zone lengths with previously reconstructed ocean-crust production rates over the past 140 My suggests average global subduction rates have been constant, ∼6 cm/y: Higher ocean-crust production is associated with longer total subduction length. We compute a strontium isotope record based on subduction-zone length, which agrees well with geological records supporting the validity of our approach: The total subduction-zone length is proportional to the summed arc and ridge volcanic CO2 production and thereby to global volcanic degassing at plate boundaries. We therefore use our degassing curve as input for the GEOCARBSULF model to estimate atmospheric CO2 levels since the Triassic. Our calculated CO2 levels for the mid Mesozoic differ from previous modeling results and are more consistent with available proxy data. PMID:24616495

Quiescent hydrogen sulfide and carbon dioxide degassing from Mount Baker, Washington

USGS Publications Warehouse

McGee, K.A.; Doukas, M.P.; Gerlach, T.M.

2001-01-01

Volcanic H2S emission rate data are scant despite their importance in understanding magma degassing. We present results from direct airborne plume measurements of H2S and CO2 on a 21-orbit survey at eleven different altitudes around Mount Baker volcano in September 2000 utilizing instrumentation mounted in a light aircraft. Measured emission rates of H2S and CO2 were 5.5 td-1 and 187 td-1 respectively. Maximum concentrations of H2S and CO2 encountered within the 4-km-wide plume were 75 ppb and 2 ppm respectively. Utilizing the H2S signal as a marker for the plume allows the corresponding CO2 signal to be more easily and accurately distinguished from ambient CO2 background. This technique is sensitive enough for monitoring weakly degassing volcanoes in a pre-eruptive condition when scrubbing by hydrothermal fluid or aquifers might mask the presence of more acid magmatic gases such as SO2.

The persistent and pernicious myth of the early CO2-N2 atmospheres of terrestrial planets

NASA Astrophysics Data System (ADS)

Shaw, G. H.

2009-12-01

The accepted model for early atmospheres of terrestrial planets has settled on a CO2-N2 composition. Unfortunately, while it is largely based on a brilliant geological analysis by Rubey, there is no compelling evidence whatsoever for such a composition as the first “permanent” atmosphere for Earth or any other planet. In fact, geological discoveries of the past 50+ years reveal several problems with a CO2-N2 atmosphere, some of which Rubey recognized in his own analysis. He clearly addressed the problem of timing of degassing, concluding that early massive degassing of CO2 would produce readily observed and profound effects, which are not evident. Modeling and constraints on the timing of planetary accretion and core formation indicate massive early degassing. If early degassing emitted CO2-N2, the effects are concealed. Plate tectonic recycling is not a solution, as conditions would have persisted beyond the time of the earliest rocks, which do not show the effects. Attempts to return degassed CO2 to the mantle are not only ad hoc, but inconsistent with early thermal structure of the Earth. Second, production of prebiotic organic compounds from a CO2-N2 atmosphere has been a nagging problem. At best this has been addressed by invoking hydrogen production from the mantle to provide reducing capacity. While hydrogen may be emitted in volcanic eruptions, it is exceedingly difficult to imagine this process generating enough organics to yield high concentrations in a global ocean. The recent fashion of invoking organic synthesis at deep-sea vents suffers from the same problem: how to achieve sufficient concentrations of organics in a global ocean by abiotic synthesis when hydrothermal activity stirs the solution and carries the prebiotic products off to great dilution? Suggesting life began at deep-sea vents, and continues to carry on chemosynthesis there, begs the question. Unless you get high enough concentrations of prebiotics by abiotic processes, you simply don’t get life. Third, solutions invoking high atmospheric CO2 as the answer to the faint young sun problem encounter exactly the same problems associated with prompt degassing of CO2. Fourth, the carbon isotope record, in which early carbonaceous deposits show signs of photosynthetic fractionation of carbon are problematical if most of the primary surface and near-surface carbon was CO2. Finally, the delay in oxidation of Earth’s surface following oxygenic photosynthesis is problematical if early photosynthesizers had a vast CO2 source from early degassing. Given an abundant food supply, what prevented early cyanobacteria from rapidly oxidizing the surface? Although discovery of CO2-rich atmospheres on Venus and Mars seem to support CO2 as the primary surface carbon reservoir, these atmospheres are the result of atmospheric evolution, particularly loss of H to space. ALL of these problems disappear with early degassing of reduced gases such as CH4 and NH3. Considerations of meteoritic compositions, accretionary processes, and early atmosphere/hydrosphere chemical processing all support reduced gases as dominant in the early atmospheres of the terrestrial planets. The time has come to revert to any earlier idea of strongly reducing conditions on early terrestrial planet surfaces, followed by long-term evolutionary trends toward oxidation.

One year of geochemical monitoring of groundwater in the Abruzzi region after the 2009 earthquakes.

NASA Astrophysics Data System (ADS)

Chiodini, Giovanni; Caliro, Stefano; Cardellini, Carlo; Avino, Rosario; Monopoli, Carmine; Inguaggiato, Salvatore; Frondini, Francesco

2010-05-01

The presence of a deep and inorganic source of CO2 has been recently recognized in Italy on the basis of the deeply derived carbon dissolved in the groundwater. In particular, the regional map of CO2 Earth degassing shows that two large degassing structures (Tuscan Roman degassing structure, TRDS, and Campanian degassing structure, CDS) affect the Tyrrhenian side of the Italian peninsula. The comparison between the map of CO2 Earth degassing and of the location of the Italian earthquakes highlights that the anomalous CO2 flux suddenly disappears in the Apennine in correspondence of a narrow band where most of the seismicity concentrates. A previous conceptual model proposed that in this area, at the eastern borders of TRDS and CDS, the CO2 from the mantle wedge intrudes the crust and accumulate in structural traps generating over-pressurized reservoirs. These CO2 over-pressurized levels can play a major role in triggering the Apennine earthquakes. The 2009 Abruzzo earthquakes, like previous seismic crises in the Northern Apennine, occurred at the border of the TRDS, suggesting also in this case a possible role played by deeply derived fluids in the earthquake generation. Detailed hydro-geochemical campaigns, with a monthly frequency, started immediately after the main shock of the 6th of April 2009. The new campaigns include the main springs of the area which were previously studied in detail, during a campaign performed ten years ago, constituting a pre-crisis reference case. Almost one year of geochemical data of the main dissolved ions, of dissolved gases (CO2, CH4, N2, Ar, He) and of the stable isotopes of the water (H, O), CO2 (13C) and He (3He/4He), highlight both that the epicentral area of L'Aquila earthquakes is affected by an important process of CO2 Earth degassing and that that the gases dissolved in the groundwater reflects the input in to the aquifers of a deep gas phase, CO2- rich, with an high He content and with low 3He/4He ratios, similar to the gases emitted by natural manifestations located in the northern Apennines which are fed by deep pressurized reservoirs. Furthermore a systematic increase in the content of the deeply derived CO2 dissolved in the aquifers occurred respect to the July 1997 samples. This increase, followed by a gentle decline of the anomaly, can be compatible with the occurrence of an episode of deep CO2 degassing concurrently with the earthquakes. The origin of this regional variation is under investigation and, at the present moment, an unambiguous interpretation of the data is not possible because the lack of a systematic monitoring of the springs before the seismic events and because eventual seasonal effects on observed variation in CO2 flux are still under investigation.

Mind the gap: non-biological processes contributing to soil CO2 efflux.

PubMed

Rey, Ana

2015-05-01

Widespread recognition of the importance of soil CO2 efflux as a major source of CO2 to the atmosphere has led to active research. A large soil respiration database and recent reviews have compiled data, methods, and current challenges. This study highlights some deficiencies for a proper understanding of soil CO2 efflux focusing on processes of soil CO2 production and transport that have not received enough attention in the current soil respiration literature. It has mostly been assumed that soil CO2 efflux is the result of biological processes (i.e. soil respiration), but recent studies demonstrate that pedochemical and geological processes, such as geothermal and volcanic CO2 degassing, are potentially important in some areas. Besides the microbial decomposition of litter, solar radiation is responsible for photodegradation or photochemical degradation of litter. Diffusion is considered to be the main mechanism of CO2 transport in the soil, but changes in atmospheric pressure and thermal convection may also be important mechanisms driving soil CO2 efflux greater than diffusion under certain conditions. Lateral fluxes of carbon as dissolved organic and inorganic carbon occur and may cause an underestimation of soil CO2 efflux. Traditionally soil CO2 efflux has been measured with accumulation chambers assuming that the main transport mechanism is diffusion. New techniques are available such as improved automated chambers, CO2 concentration profiles and isotopic techniques that may help to elucidate the sources of carbon from soils. We need to develop specific and standardized methods for different CO2 sources to quantify this flux on a global scale. Biogeochemical models should include biological and non-biological CO2 production processes before we can predict the response of soil CO2 efflux to climate change. Improving our understanding of the processes involved in soil CO2 efflux should be a research priority given the importance of this flux in the global carbon budget. © 2014 John Wiley & Sons Ltd.

NanoSIMS results from olivine-hosted melt embayments: Modeling ascent rate in explosive basaltic eruptions

NASA Astrophysics Data System (ADS)

Lloyd, A. S.; Plank, T.; Ruprecht, P.; Hauri, E. H.; Gonnermann, H. M.; Rose, W. I.

2012-12-01

A critical parameter governing the explosivity of volcanic eruptions is the rate at which magma ascends and degases, because this affects bubble nucleation, coalescence, and ultimately fragmentation. Although several methods have been used to determine magma ascent rates, it remains a poorly constrained parameter for most eruptions. One promising method employs diffusion modeling of H2O and CO2 concentration gradients in melt embayments/open melt inclusions [1,2]. Here we utilize the fine spatial resolution of the nanoSIMS to obtain concentration gradients for five volatile species, improving upon previous efforts that were more limited in spatial resolution (FTIR, [1]) and in number of volatile analytes (H2O only by BSE, [2]). Focusing on explosive basaltic eruptions, for which very little is known about ascent rates, we chose ash and lapilli samples from the Oct 1974 sub-plinian eruption of Volcán de Fuego. Glassy, olivine-hosted embayments with evidence of outlet bubbles were analyzed by nanoSIMS at a minimum distance between spots of 15 μm. Major element zonation in the embayments was investigated by EMP, and high resolution BSE images were captured to complement the nanoSIMS spot measurements for H2O (as in [2]). We report analyses for 5 embayments that vary in length from 100 to 350 μm. Low-solubility volatiles (CO2, H2O, S) decrease towards the embayment outlet, consistent with diffusive reequilibration with the more-degassed surrounding melt. High-solubility volatiles (Cl, F) increase towards the outlet, apparently behaving as magmaphile elements. Major elements exhibit constant concentrations along the embayment, except for a 20-50 μm wide zone near the embayment outlet, perhaps representing a boundary layer at the outlet bubble, where concentrations vary consistent with olivine and clinopyroxene microlite growth. BSE grayscale values are thus affected by both H2O diffusion and major element zonation at the embayment outlet, and cannot be used to estimate H2O concentration gradients [2]. Forward modeling of CO2 and H2O profiles takes into account temperature- and composition-dependent diffusivities and a closed-system degassing path for the exterior magma (as observed in melt inclusions from the same sample). Assuming a constant decompression rate from 200 MPa and an initial composition of 600 ppm CO2 and 4.3 wt% H2O at 1030°C, models yield preliminary results with very rapid ascent times (100 s, or 2 MPa/s). A two-stage model, however, allows slower decompression during CO2 exsolution (0.1 MPa/s) and faster ascent when H2O begins to exsolve (1.5 MPa/s), for total ascent times on the order of 10 to 20 minutes. This example highlights the additional constraints that come from measuring multiple diffusing species. [1] Liu et al, JGR, 2007 [2] Humphreys et al, EPSL, 2008.

Development of a prototype for dissolved CO2 rapid measurement and preliminary tests

NASA Astrophysics Data System (ADS)

Li, Meng; Guo, Jinjia; Zhang, Zhihao; Luo, Zhao; Qin, Chuan; Zheng, Ronger

2017-10-01

The measurements of dissolved CO2 in seawater is of great significance for the study of global carbon cycle. At present, the commercial sensors used for dissolved CO2 measurements are mostly equipped with permeable membranes for the purpose of gas-liquid separation, with the advantages of easy operation, low cost, etc.. However, most of these devices measure CO2 after reaching gas equilibrium, so it takes a few minutes to respond, which limited its applications in rapid measurements. In this paper, a set of prototype was developed for the rapid measurements of dissolved CO2. The system was built basing the direct absorption TDLAS. To detect the CO2 absorption line located at 4991.26 cm-1 , a fiber-coupled DFB laser operating at 2004 nm was selected as the light source. A Herriott type multi-pass cavity with an effective optical path length of 10 m and an inner volume of 90 mL was used for absorption measurements. A detection limit of 26 μatm can be obtained with this compact cavity. To realize the rapid measurements of dissolved CO2, a degasser with high degassing rate was necessary. A hollow fiber membrane with a large permeable area used in this paper can achieve degassing rate up to 2.88 kPa/min. Benefitted from the high degassing rate of the degasser and high sensitivity of the compact TDLAS system, a rapid measurement of dissolved CO2 in water can be achieved within 1s time, and the response time of the prototype when the dissolved CO2 concentration changed abruptly in actual measurement was 15 s. To evaluate the performance of the prototype, comparison measurements were carried out with a commercial mass spectrometer. The dissolved CO2 in both seawater and tap-water was measured, and the experimental results showed good consistent trends with R2 of 0.973 and 0.931. The experimental results proved the feasibility of dissolved CO2 rapid measurement. In the near future, more system evaluation experiments will be carried out and the system will be further optimized focusing on the underwater in-situ detection system.

Microbiological and Geochemical Survey of CO2-Dominated Mofette and Mineral Waters of the Cheb Basin, Czech Republic.

PubMed

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO 2 at the surface that occurs in the form of CO 2 -rich mineral springs and wet and dry mofettes. So far, the influence of CO 2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO 2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas ) and iron (e.g., Gallionella, Sideroxydans ) cycling shaped the core community. Additionally, CO 2 -influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe 2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments.

Microbiological and Geochemical Survey of CO2-Dominated Mofette and Mineral Waters of the Cheb Basin, Czech Republic

PubMed Central

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO2 at the surface that occurs in the form of CO2-rich mineral springs and wet and dry mofettes. So far, the influence of CO2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas) and iron (e.g., Gallionella, Sideroxydans) cycling shaped the core community. Additionally, CO2-influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments. PMID:29321765

Potential links between continental rifting, CO2 degassing and climate change through time

NASA Astrophysics Data System (ADS)

Brune, Sascha; Williams, Simon E.; Müller, R. Dietmar

2017-12-01

The concentration of CO2 in the atmosphere is a key influence on Earth's climate. Today, significant quantities of CO2 are emitted at continental rifts, suggesting that the spatial and temporal extent of rift systems may have influenced deep carbon fluxes and thus climate change throughout geological time. Here we test this hypothesis by conducting a worldwide census of continental rift lengths over the last 200 million years. We estimate tectonic CO2 release rates through time and show that along the extensive Mesozoic and Cenozoic rift systems, rift-related CO2 degassing rates reached more than 300% of present-day values. Using a numerical carbon cycle model, we find that two prominent periods of enhanced rifting 160 to 100 million years ago and after 55 million years ago coincided with greenhouse climate episodes, during which atmospheric CO2 concentrations were more than three times higher than today. We therefore propose that continental fragmentation and long-term climate change could plausibly be linked via massive CO2 degassing in rift systems.

Multi-component gas emission measurements of the active lava lake of Nyiragongo, DR Congo

NASA Astrophysics Data System (ADS)

Bobrowski, N.; Giuffrida, G. B.; Yalire, M.; Lübcke, P.; Arellano, S.; Balagizi, C.; Calabrese, S.; Galle, B.; Tedesco, D.

2017-10-01

Between 2007 and 2011 four measurement campaigns (June 2007, July 2010, June 2011, and December 2011) were carried out at the crater rim of Nyiragongo volcano, DR Congo. Nyiragongo is one of the most active volcanoes in Africa. The ground-based remote sensing technique Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), which uses scattered sunlight, the in-situ Multi-Component Gas Analyzer System (Multi-GAS) and alkaline impregnated filter were simultaneously applied during all field trips. The bromine monoxide to sulfur dioxide (BrO/SO2) and carbon dioxide to sulfur dioxide (CO2/SO2) molar ratios were determined, among other ratios. During the different field trips variations of the level of the lava lake up to several tens of meters were observed during intervals of the order of minutes up to days and also between the years. The measured gas ratios presented covariations with the lava lake level changes. BrO/SO2 ratios and CO2/SO2 ratios showed similar behavior. Annual CO2/SO2 and BrO/SO2 average values are generally positively correlated. In June 2011 increased BrO/SO2 as well as increased CO2/SO2 ratios have been observed before a sudden decrease of the lava lake. Overall the Cl/S ratio, determined by filter-pack sampling, shows an increasing trend with time, which is accompanied by a decreasing sulfur dioxide flux, the later measured nearly continuously by automated MAX-DOAS instruments since 2004. Mean gas emission fluxes of CO2, Cl and 'minimum-BrO' fluxes are calculated using their ratio to SO2. The first two show an increase with time, in contrast to the SO2 fluxes. A simple conceptual model is proposed which can explain in particular the June 2011 data, but as well our entire data set. The proposed model takes up the idea of convective magma cells inside the conduit and the possible temporary interruption of part of the cycling. We propose than two alternatives to explain the observed gas emission variation: 1. It is assumed that the diffuse and fumarolic degassing could have significant influence on measured gas composition. The measured gas composition might rather represent a gas mixture of plume, diffuse and fumarolic degassing than only representing the volcanic plume. 2. It is proposed that the interruption of the convection has taken place in the upper part of the conduit and deep degassing of CO2 and bromine initially continues while mixing already with gas emissions from an ageing source, which is characterized by an already diminishing sulfur content. These complex process but as well as the gas mixing of different sources, could explain general features of our dataset, but can unfortunately neither be confirmed nor disproven by the data available today.

Measuring H2O and CO2 Emissions in the Mud Volcano region of Yellowstone using Open Path FTIR

NASA Astrophysics Data System (ADS)

Moyer, D. K.; Sealing, C. R.; Carn, S. A.; Vanderkluysen, L.

2017-12-01

Magma degassing is an important factor in many aspects of monitoring active volcanic zones and mitigating associated hazards. The monitoring of these emissions in concentration, flux, and species ratios is important for detecting signs of unrest as well as understanding the natural cycle and budget of volatile species. However, standard gas measurement methods suffer from either low temporal resolution (e.g., direct sampling of fumaroles) or are limited to measuring a small range of species (e.g., MiniDOAS, MultiGAS). In order to establish a carbon budget of active gas sources at a volcano with a dynamic hydrothermal system, we carried out a survey of mud pots and fumaroles at Yellowstone National Park using Open-Path Fourier Transform Infrared Spectroscopy, or OP-FTIR, which allows for a temporal resolution as low as one measurement every 10 seconds. We placed an active infrared (IR) source behind the target gas plume and identified gas species from the presence of their absorption feature in measured spectra in the 2.5 to 25 µm range. From these, we derived pathlength concentrations for a wide range of gases, including: water vapor, carbon dioxide, and methane. During our September 2016 campaign in the Mud Volcano thermal area, we measured CO2 concentrations of 400 ppm in emissions from the Churning Cauldron acid-sulfate mud pot, with an H2O/CO2 ratio of 8; at Sulphur Cauldron and One Hundred Springs Plain, CO2 concentrations reached 200 ppm above background atmospheric values. We derived a CO2 flux of 8.15 T/d, 0.43 T/d and .00025 T/d, respectively, at these three acid-sulfate sources, within range of gas channeling-based estimates from the late 1990s. Previous accumulation chamber studies estimate the CO2 soil diffuse degassing in the Mud Volcano thermal region at 283.15 T/d, indicating that mud pots are minor contributors of CO2 emissions in this area, representing 3% of diffuse emissions. Due to the high acquisition rate and the abundance of water droplets in the plume, spectra were too noisy to reliably detect methane at these locations. Future work will focus on the measurement of trace gases at these same locations by increasing the acquisition time.

Non-Volcanic release of CO2 in Italy: quantification, conceptual models and gas hazard

NASA Astrophysics Data System (ADS)

Chiodini, G.; Cardellini, C.; Caliro, S.; Avino, R.

2011-12-01

Central and South Italy are characterized by the presence of many reservoirs naturally recharged by CO2 of deep provenance. In the western sector, the reservoirs feed hundreds of gas emissions at the surface. Many studies in the last years were devoted to (i) elaborating a map of CO2 Earth degassing of the region; (ii) to asses the gas hazard; (iii) to develop methods suitable for the measurement of the gas fluxes from different types of emissions; (iv) to elaborate the conceptual model of Earth degassing and its relation with the seismic activity of the region and (v) to develop physical numerical models of CO2 air dispersion. The main results obtained are: 1) A general, regional map of CO2 Earth degassing in Central Italy has been elaborated. The total flux of CO2 in the area has been estimated in ~ 10 Mt/a which are released to the atmosphere trough numerous dangerous gas emissions or by degassing spring waters (~ 10 % of the CO2 globally estimated to be released by the Earth trough volcanic activity). 2) An on line, open access, georeferenced database of the main CO2 emissions (~ 250) was settled up (http://googas.ov.ingv.it). CO2 flux > 100 t/d characterise 14% of the degassing sites while CO2 fluxes from 100 t/d to 10 t/d have been estimated for about 35% of the gas emissions. 3) The sites of the gas emissions are not suitable for life: the gas causes many accidents to animals and people. In order to mitigate the gas hazard a specific model of CO2 air dispersion has been developed and applied to the main degassing sites. A relevant application regarded Mefite d'Ansanto, southern Apennines, which is the largest natural emission of low temperature CO2 rich gases, from non-volcanic environment, ever measured in the Earth (˜2000 t/d). Under low wind conditions, the gas flows along a narrow natural channel producing a persistent gas river which has killed over a period of time many people and animals. The application of the physical numerical model allowed us to define the zones which potentially can be affected by dangerous CO2 concentration at breathing height for humans. 4) Many evidences indicate that at depth, in the seismic zone of the Apennines, the gas can be stored in over-pressurized reservoirs. Such gas reservoirs have been taught to have played a major role in triggering the seismicity of the last two main crises occurred in the area (Colfiorito 1997 and L'Aquila 2009).

Conditions for oceans on Earth-like planets orbiting within the habitable zone: importance of volcanic CO{sub 2} degassing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@astrobio.k.u-tokyo.ac.jp

2014-08-01

Earth-like planets in the habitable zone (HZ) have been considered to have warm climates and liquid water on their surfaces if the carbonate-silicate geochemical cycle is working as on Earth. However, it is known that even the present Earth may be globally ice-covered when the rate of CO{sub 2} degassing via volcanism becomes low. Here we discuss the climates of Earth-like planets in which the carbonate-silicate geochemical cycle is working, with focusing particularly on insolation and the CO{sub 2} degassing rate. The climate of Earth-like planets within the HZ can be classified into three climate modes (hot, warm, and snowballmore » climate modes). We found that the conditions for the existence of liquid water should be largely restricted even when the planet is orbiting within the HZ and the carbonate-silicate geochemical cycle is working. We show that these conditions should depend strongly on the rate of CO{sub 2} degassing via volcanism. It is, therefore, suggested that thermal evolution of the planetary interiors will be a controlling factor for Earth-like planets to have liquid water on their surface.« less

Volcanic gas composition changes during the gradual decrease of the gigantic degassing activity of Miyakejima volcano, Japan, 2000-2015

NASA Astrophysics Data System (ADS)

Shinohara, Hiroshi; Geshi, Nobuo; Matsushima, Nobuo; Saito, Genji; Kazahaya, Ryunosuke

2017-02-01

The composition of volcanic gases discharged from Miyakejima volcano has been monitored during the intensive degassing activity that began after the eruption in 2000. During the 15 years from 2000 to 2015, Miyakejima volcano discharged 25.5 Mt of SO2, which required degassing of 3 km3 of basaltic magma. The SO2 emission rate peaked at 50 kt/day at the end of 2000 and quickly decreased to 5 kt/day by 2003. During the early degassing period, the volcanic gas composition was constant with the CO2/SO2 = 0.8 (mol ratio), H2O/SO2 = 35, HCl/SO2 = 0.08, and SO2/H2S = 15. The SO2 emission rate decreased gradually to 0.5 kt/day by 2012, and the gas composition also changed gradually to CO2/SO2 = 1.5, H2O/SO2 = 150, HCl/SO2 = 0.15, and SO2/H2S = 6. The compositional changes are not likely caused by changes in degassing pressure or volatile heterogeneity of a magma chamber but are likely attributed to an increase of hydrothermal scrubbing caused by large decrease of the volcanic gas emission rate, suggesting a supply of gases with constant composition during the 15 years. The intensive degassing was modeled based on degassing of a convecting magma conduit. The gradual SO2 emission rate that decrease without changes in volcanic gas composition is attributed to a reduction of diameter of the convecting magma conduit.

Observed anomalous changes on diffuse CO2 emission at the summit crater of Teide volcano (Tenerife, Canary Islands, Spain): a geochemical evidence of volcanic unrest?

NASA Astrophysics Data System (ADS)

Perez, N. M.; Melián, G.; Asensio-Ramos, M.; Padrón, E.; Alonso Cótchico, M.; Hernández, P. A.; Rodríguez, F.; D'Auria, L.; García-Merino, M.; Padilla, G. D.; Burns, F.; Amonte, C.; García, E.; García-Hernández, R.; Barrancos, J.; Morales-Ocaña, C.; Calvo, D.; Vela, V.; Pérez, A.

2017-12-01

Tenerife (2034 km2) is the largest of the Canary Islands and hosts a central volcanic complex, Las Cañadas, which is characterized by the eruption of differentiated magmas. Laying inside Las Cañadas a twin stratovolcanoes system Pico Viejo and Teide, has been developed. Although Teide volcano shows weak fumarolic system, volcanic gas emissions observed in the summit area are mainly controlled by high rates of diffuse CO2 degassing. Soil CO2 efflux surveys have been performed at the summit crater of Teide volcano since 1999 according to the accumulation chamber method to monitor changes of volcanic activity. Soil CO2 efflux and soil temperature have been measured in sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Historical seismic activity in Tenerife has been mainly characterized by low- to moderate-magnitude events (M <2.5), and most of epicenters clustered in an offshore area SE of Tenerife. Very few earthquakes have occurred in other areas, including Teide volcano. Since November 2016 more than 100 small magnitude earthquakes, with typical features of the microseismicity of hydrothermal systems, at depths usually ranging between 5 and 15 km located beneath Teide volcano have been recorded. On January 6th 2017 a M=2.5 earthquake was recorded in the area, being one of the strongest events recorded since 2004. Between October 11 and December 13, 2016, a continuous increase on the diffuse CO2 emission was registered preceding the occurrence of the 2.5 seismic event, from 21.3±2.0 to 101.7±20.7 t d-1. In Febraury 2017, the diffuse CO2 emission rate showed a maximum value (176±35 t/d) and has remained at relatively high values in the range 67-176 t/d. The observed increase on the diffuse CO2 emission, likely due to the increase of fluid pressure in the hydrothermal-magmatic system of Tenerife, might be a geochemical evidence of a future volcanic unrest at Tenerife Island.

Degassing history of water, sulfur, and carbon in submarine lavas from Kilauea Volcano, Hawaii

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dixon, J.E.; Stolper, E.M.; Clague, D.A.

1991-05-01

Major, minor, and dissolved volatile element concentrations were measured in tholeiitic glasses from the submarine portion (Puna Ridge) of the east rift zone of Kilauea Volcano, Hawaii. Dissolved H{sub 2}O and S concentrations display a wide range relative to nonvolatile incompatible elements at all depths. This range cannot be readily explained by fractional crystallization, degassing of H{sub 2}O and S during eruption on the seafloor, or source region heterogeneities. Dissolved CO{sub 2} concentrations, in contrast, show a positive correlation with eruption depth and typically agree within error with the solubility at that depth. The authors propose that most magmas alongmore » the Puna Ridge result from (1) mixing of a relatively volatile-rich, undegassed component with magmas that experienced low pressure (perhaps subaerial) degassing during which substantial H{sub 2}O, S, and CO{sub 2} were lost, followed by (2) fractional crystallization of olivine, clinopyroxene, and plagioclase from this mixture to generate a residual liquid; and (3) further degassing, principally of CO{sub 2} for samples erupted deeper than 1,000 m, during eruption on the seafloor. They predict that average Kilauean primary magmas with 16% MgO contain {approximately}0.47 wt % H{sub 2}0, {approximately}900 ppm S, and have {delta}D values of {approximately}{minus}30 to {minus}40%. The model predicts that submarine lavas from wholly submarine volcanoes (i.e., Loihi), for which there is no opportunity to generate the degassed end member by low pressure degassing, will be enriched in volatiles relative to those from volcanoes whose summits have breached the sea surface (i.e., Kilauea and Mauna Loa).« less

Delayed, disequilibrium degassing in rhyolite magma: Decompression experiments and implications for explosive volcanism

USGS Publications Warehouse

Mangan, M.; Sisson, T.

2000-01-01

Recent numerical models and analog shock tube experiments show that disequilibrium degassing during magma ascent may lead to violent vesiculation very near the surface. In this study a series of decompression experiments using crystal-free, rhyolite melt were conducted to examine the development of large supersaturations due to delayed, homogenous (spontaneous) bubble nucleation. Melts were saturated at 900??C and 200 MPa with either 5.2 wt% dissolved H2O, or with 4.2 wt% H2O and 640 ppm CO2, and isothermally decompressed at linear rates of either 0.003, 0.025, or 8.5 MPa/s to final pressures between 25 and 175 MPa. Additional isobaric saturation experiments (900??C, 200-25 MPa) using pure H2O or mixed H2O-CO2 fluids establish reference equilibrium solubility curves/values. Homogenous nucleation is triggered in both H2O-only and H2O-CO2 experiments once the supersaturation pressure (??Pss) reaches ?? 120-150 MPa and the melt contains ?? two times its equilibrium water contents. Bubble number density and nucleation rate depend on the supersaturation pressure, with values on the order of 102/cm3 and < 1/cm3/s for ??Pss~120 MPa; 106/cm3 and 103-105/cm3/s for ??Pss??~130-150 MPa; and 107/cm3 and 106/cm3/s for ??Pss??160-175 MPa. Nucleation rates are consistent with classical nucleation theory, and infer an activation energy for nucleation of 1.5 x 10-18 J/nucleus, a critical bubble radius of 2 x 10-9 m, and an effective surface tension for rhyolite at 5.2 wt% H2O and 900??C of 0.10-0.11 N/m. The long nucleation delay limits the time available for subsequent diffusion such that disequilibrium dissolved H2O and CO2 contents persist to the end of our runs. The disequilibrium degassing paths inferred from our experiments contrast markedly with the equilibrium or quasi-equilibrium paths found in other studies where bubble nucleation occurs heterogenously on crystals or other discontinuities in the melt at low ??Pss. Homogenous and heterogenous nucleation rates are comparable, however, as are bubble number densities, so that at a given decompression rate it appears that nucleation mechanism, rather than nucleation rate, determines degassing efficiency by fixing the pressure (depth) at which vesiculation commences and hence the time available for equilibration prior to eruption. Although real systems are probably never truly crystal-free, our results show that rhyolitic magmas containing up to 104 crystals/cm3, and perhaps as high as 106 crystals/cm3, are controlled by homogenous, rather than heterogenous, nucleation during ascent. ?? 2000 Elsevier Science B.V. All rights reserved.

Kilauea volcano: the degassing of a hot spot

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerlach, T.M.

1986-03-01

Hot spots such as Kilauea volcano can degas by a one-stage eruptive process or a two-stage process involving eruptive and noneruptive degassing. One stage degassing occurs during sustained summit eruptions and causes a direct environmental impact. Although generally less efficient than the one-stage degassing process, two stage degassing can cause 1 to 2 orders of magnitude greater impact in just a few hours during flank eruptions. Hot spot volcanos with resupplied crustal magma chambers may be capable of maintaining an equivalent impact from CO/sub 2/ and S outgassing during both eruptive and noneruptive periods. On average, a hot spot volcanomore » such as Kilauea is a minor polluter compared to man.« less

A multidisciplinary study in the geodynamic active western Eger rift (Central Europe): The Quaternary volcanic complex Mytina and the recent CO2-degassing zone Hartousov

NASA Astrophysics Data System (ADS)

Flechsig, C.; Heinicke, J.; Kaempf, H. W.; Nickschick, T.; Mrlina, J.

2013-12-01

The Eger rift (Central Europe) belongs to the European Cenozoic rift system and represents an approximately 50 km wide and 300 km long ENE-WSW striking continental rift that formed during the Upper Cretaceous-Tertiary transition. This rift zone is one of the most active seismic regions in Central Europe. Especially, the western part of the Eger rift area is dominated by ongoing hidden magmatic processes in the intra-continental lithospheric mantle. Besides of known quaternary volcanoes, these processes take place in absence of any presently active volcanism at the surface. However, they are expressed by a series of phenomena distributed over a relatively large area, like occurrence of repeated earthquake swarms, surface exhalation of mantle-derived and CO2-enriched fluids at mofettes and mineral springs, and enhanced heat flow. At present this is the only known intra-continental region where such deep-seated, active lithospheric processes currently occur. The aim of the project is to investigate the tectonic/geologic near surface structure and the degassing processes of the mofette field of Hartousov, where soil gas measurements (concentration and flux rate) in an area of appr. 3x2 km traced a permeable NS extended segment of a fault zone and revealed highly permeable Diffuse Degassing Structures (DDS). The second target is volcanic environment of the Quaternary volcanic complex Mytina maar and the cinder cone Zelezna hurka/Eisenbühl. The investigations are intended to clarify: a) the spatio-temporal reconstruction of the maar complex, and the palaeo volcanic scenario (geological model, tectonic settings, distribution of pyroclastica, b) the geological structure and the tectonic control of the recent degassing zone, and c) the comperative interpretation of both regions in the consideration of potential future volcanic risk assessment in sub-regions of the western Eger Rift. To investigate both regions the following methods are used: geoelectrics, geomagnetics, shallow seismics, gravity and CO2-soil gas measurements, petrographic/petrophysical and remote sensing data. The results will be serve as for better understanding of geologic, volcanic and tectonic settings of the two regions as well as for the preparation of the ICDP drilling project 'Drilling the Eger rift' with a multidisciplinary approach consisting of geophysical, geochemical and other disciplines to understand the role of crustal fluid activity for swarm earthquake generation.

MAGA, a new database of gas natural emissions: a collaborative web environment for collecting data.

NASA Astrophysics Data System (ADS)

Cardellini, Carlo; Chiodini, Giovanni; Frigeri, Alessandro; Bagnato, Emanuela; Frondini, Francesco; Aiuppa, Alessandro

2014-05-01

The data on volcanic and non-volcanic gas emissions available online are, as today, are incomplete and most importantly, fragmentary. Hence, there is need for common frameworks to aggregate available data, in order to characterize and quantify the phenomena at various scales. A new and detailed web database (MAGA: MApping GAs emissions) has been developed, and recently improved, to collect data on carbon degassing form volcanic and non-volcanic environments. MAGA database allows researchers to insert data interactively and dynamically into a spatially referred relational database management system, as well as to extract data. MAGA kicked-off with the database set up and with the ingestion in to the database of the data from: i) a literature survey on publications on volcanic gas fluxes including data on active craters degassing, diffuse soil degassing and fumaroles both from dormant closed-conduit volcanoes (e.g., Vulcano, Phlegrean Fields, Santorini, Nysiros, Teide, etc.) and open-vent volcanoes (e.g., Etna, Stromboli, etc.) in the Mediterranean area and Azores, and ii) the revision and update of Googas database on non-volcanic emission of the Italian territory (Chiodini et al., 2008), in the framework of the Deep Earth Carbon Degassing (DECADE) research initiative of the Deep Carbon Observatory (DCO). For each geo-located gas emission site, the database holds images and description of the site and of the emission type (e.g., diffuse emission, plume, fumarole, etc.), gas chemical-isotopic composition (when available), gas temperature and gases fluxes magnitude. Gas sampling, analysis and flux measurement methods are also reported together with references and contacts to researchers expert of each site. In this phase data can be accessed on the network from a web interface, and data-driven web service, where software clients can request data directly from the database, are planned to be implemented shortly. This way Geographical Information Systems (GIS) and Virtual Globes (e.g., Google Earth) could easily access the database, and data could be exchanged with other database. At the moment the database includes: i) more than 1000 flux data about volcanic plume degassing from Etna and Stromboli volcanoes, ii) data from ~ 30 sites of diffuse soil degassing from Napoletan volcanoes, Azores, Canary, Etna, Stromboli, and Vulcano Island, several data on fumarolic emissions (~ 7 sites) with CO2 fluxes; iii) data from ~ 270 non volcanic gas emission site in Italy. We believe MAGA data-base is an important starting point to develop a large scale, expandable data-base aimed to excite, inspire, and encourage participation among researchers. In addition, the possibility to archive location and qualitative information for gas emission/sites not yet investigated, could stimulate the scientific community for future researches and will provide an indication on the current uncertainty on deep carbon fluxes global estimates

Melt inclusion constraints on volatile systematics and degassing history of the 2014-2015 Holuhraun eruption, Iceland

NASA Astrophysics Data System (ADS)

Bali, E.; Hartley, M. E.; Halldórsson, S. A.; Gudfinnsson, G. H.; Jakobsson, S.

2018-02-01

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H2O, CO2, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014-2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500-1700 ppm CO2, 0.13-0.16 wt% H2O, 60-80 ppm Cl, 130-240 ppm F and 500-800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures ≥ 0.4 GPa ( 12 km depth) promoting deep degassing of CO2. Prior to the onset of degassing, the melt CO2 content may have reached 3000-4000 ppm, with the total magmatic CO2 budget estimated at 23-55 Mt. SO2 release commenced at 0.12 GPa ( 3.6 km depth), eventually leading to entrapment of SO2 vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H2O, 5.9-7.7 Mt CO2, and 11.3 Mt of SO2 over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H2O, where field measurements may be heavily biased by the incorporation of meteoric water.

Volatile emissions from the crater and flank of Oldoinyo Lengai volcano, Tanzania

USGS Publications Warehouse

Koepenick, K.W.; Brantley, S.L.; Thompson, J.M.; Rowe, G.L.; Nyblade, A.A.; Moshy, C.

1996-01-01

As a comparison to airborne infrared (IR) flux measurements, ground-based sampling of fumarole and soil gases was used to characterize the quiescent degassing of CO2 from Oldoinyo Lengai volcano. Aerial and ground-based measurements are in good agreement: ???75% of the aerially measured CO2 flux at Lengai (0.05-0.06 ?? 1012 mol yr-1 or 6000-7200 tonnes CO2 d-1) can be attributed to seven large crater vents. In contrast to Etna and Vulcano Island, where 15-50% of the total CO2 flux emanates diffusely through the volcanic flanks, diffuse emissions were measured only within 500 m of the crater rim at Lengai, contributing < 2% of the total flux. The lack of extensive flank emissions may reflect the dimensions of the magma chamber and/or the lack of a shallow fluid flow system. Thermodynamic restoration of fumarole analyses shows that gases are the most CO2-rich and H2O-poor reported for any volcano, containing 64-74% CO2, 24-34% H2O, 0.88-1.0% H2, 0.1-0.4% CO and < 0.1% H2S, HCl, HF, and CH4. Volatile emissions of S, Cl, and F at Oldoiyno Lengai are estimated as 4.5, 1.5, and 1.0 ?? 107 mol yr-1, respectively. Accuracy of the airborne technique was also assessed by measuring the C emission rate from a coal-burning power plant. CO2 fluxes were measured within ??10% near the plant; however, poor resolution at increased distances caused an underestimation of the flux by a factor of 2. The relatively large CO2 fluxes measured for alkaline volcanoes such as Oldoinyo Lengai or Etna may indicate that midplate volcanoes represent a large, yet relatively unknown, natural source of CO2.

Soil degassing at the Los Humeros geothermal field (Mexico)

NASA Astrophysics Data System (ADS)

Peiffer, Loïc; Carrasco-Núñez, Gerardo; Mazot, Agnès; Villanueva-Estrada, Ruth Esther; Inguaggiato, Claudio; Bernard Romero, Rubén; Rocha Miller, Roberto; Hernández Rojas, Javier

2018-05-01

The Los Humeros geothermal field is the third most important producer of geothermal electricity (70 MW) in Mexico. Geothermal fluids are hosted in fractured andesitic lavas and mostly consist of high enthalpy steam with limited water content (vapor fraction > 0.9). Despite the high reservoir temperature ( 300-400 °C), thermal manifestations at the surface are scarce and locally appear as steaming grounds, weak steam vents and advanced argillic alteration. Geothermal fluid upflow from the reservoir towards the surface is limited by welded ignimbrite deposits that act as a low-permeability barrier. In this study, we present the first measurements of CO2, CH4 and H2S degassing rates from the soil performed at Los Humeros. Flux measurements were complemented with δ13C composition of degassing CO2 and soil temperatures to discuss gas origin and thermal anomalies. We measured high soil degassing rates (up to 7530 g m-2 d-1 CO2, 33 g m-2 d-1 CH4 and 22 g m-2 d-1 H2S) in three localized areas (Humeros North - HN, Humeros South - HS and Xalapazco - XA) as well as high soil temperatures reaching the boiling temperature at the local altitude (90.6 °C). The particular location of these three areas suggests that the steam-dominated reservoir degases to the surface through permeable faults crossing the ignimbritic deposits. The remaining surveyed areas are characterized by weak CO2 fluxes (≤44 g m-2 d-1), non-detectable CH4 and H2S fluxes, and lower soil temperatures (5-21 °C). The compositions in δ13CCO2 from HN-HS-XA areas (δ13CCO2 = -7.94 to -2.73‰) reflect a magmatic source with some possible contribution from the sedimentary basement, as well as fractionation induced by boiling and CO2 dissolution in shallow water bodies. We also discuss the processes causing the spread in CO2/CH4 flux ratios. Finally, we estimate the heat output from the three high degassing areas to a value of 16.4 MWt.

Diffusion of Water through Olivine and Clinopyroxene: Implications for Melt Inclusion Fidelity

NASA Astrophysics Data System (ADS)

Plank, T. A.; Lloyd, A. S.; Ferriss, E.

2016-12-01

The maximum H2O concentrations measured in olivine-hosted melt inclusions (MIs) from arc tephra fall within a narrow range of 3-5 wt%. A major question is whether this reflects parental water concentrations or diffusive exchange through the host crystal during storage and ascent. Laboratory experiments have shown that water can diffuse through 500 micron olivine in minutes to days at 1100°C. We have tested these predictions with a natural experiment using volatile (H2O, CO2, S) diffusion along melt embayments to constrain ascent rates during the 1974 eruption of Volcan Fuego to 5-8 minutes from 7 km depth [1]. Thus, olivine-hosted MIs may move from their storage region to the surface during some eruptions rapidly enough to retain almost all of their original water. Only the smallest MIs (< 30 microns) will lose any water during such fast ascent, even for the fastest diffusion mechanism through olivine. We have also assessed the potential for clinopyroxene (cpx) to retain water (as H+) during magma ascent. In the same 1974 Fuego deposits, cpx crystals show H-loss on their rims and even from their interiors. Such diffusive loss in 5-8 minutes requires rapid diffusion of H in cpx, comparable to olivine and melt, and consistent with our recent laboratory experiments dehydrating Fe-bearing cpx [2]. Although H-diffusion is dependent on the site occupancy, all sites may lose H rapidly in cpx with Mg# < 92.5. While cpx and olivine may lose H during ascent and degassing, olivine-hosted MIs stand a better chance of retaining water due to the very low partitioning of water in olivine (D 0.001). The most favorable conditions for faithful retention of parental water concentrations involve a) rapid ascent (< hr.) from H2O-undersaturated reservoirs (prior to major water degassing), b) minerals with low partition coefficients for water, c) large crystals (>500 microns) and large melt inclusions (>50 microns), and 4) rapid post-eruptive cooling (< 1min, clast sizes < 1 cm). The rapid diffusion of H through olivine and cpx presents a challenge to MI fidelity, but not necessarily if the above conditions are met. [1] Lloyd et al., 2014, JVGR. [2] Ferriss et al., 2016, AmMin.

Geochemical monitoring of the Tenerife North-East Rift Zone (NERZ) volcano (Canary Islands) by means of diffuse CO_{2} degassing surveys

NASA Astrophysics Data System (ADS)

Barrancos, José; O'Neill, Ryan; Gould, Catherine E.; Padilla, Germán; Rodríguez, Fátima; Amonte, Cecilia; Padrón, Eleazar; Pérez, Nemesio M.

2017-04-01

Tenerife is the largest of the Canary Islands (2100 km2) and the North East Rift (NERZ) volcano is one of the three active volcanic rift-zones of the island (210 km2). The last eruptive activity at NERZ volcano occurred in 1704 and 1705, with three volcanic eruptions: Siete Fuentes, Fasnia and Arafo. In order to provide a multidisciplinary approach to monitor potential volcanic activity changes at the NERZ volcano, diffuse CO2 emission surveys have been undertaken in a yearly basis since 2001. This study shows the results of the last soil CO2 efflux survey undertaken in summer 2016, with 600 soil gas sampling sites homogenously distributed. Soil CO2 efflux measurements were performed at the surface environment by means of a portable non-dispersive infrared spectrophotometer (NDIR) LICOR Li800 following the accumulation chamber method. Soil CO2 efflux values ranged from non-detectable (˜0.5 g m-2 d-1) up to 70 g m-2 d-1, with an average value of 8.8 g m-2 d-1. In order to distinguish the existence of different geochemical populations on the soil CO2 efflux data, a Sinclair graphical analysis was done. The average value of background population was 2.9 g m-2 d-1 and that of peak population was 67.8 g m-2 d-1, value that has been increasing since the year 2014. To quantify the total CO2 emission rate from the NERZ volcano a sequential Gaussian simulation (sGs) was used as interpolation method to construct soil CO2 emission contour maps. The diffuse CO2 emission rate for the studied area was estimated in 1,675 ± 47 t d-1. If we compare the 2016 results with those ones obtained in previous surveys since 2001, two main pulses on diffuse CO2 emission are identified, the first one in 2007 and the second one between during 2014 and 2016. This long-term variation on the diffuse CO2 emission doesn't seem to be masked by the external-meteorological variations. However, the first peak precedes the anomalous seismicity recorded in and around Tenerife Island between 2009 and 2011, suggesting changes in strain-stress at depth as a possible cause of the observed changes in the diffuse CO2 emission rate. On the other hand, the second peak seems to be related to later changes in the seismicity, such as the seismic activity that occurred in Tenerife at the end of 2016. Again, this study demonstrates the importance of studies of soil CO2 efflux at the NERZ volcano of Tenerife island as an effective volcanic monitoring tool.

Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations.

PubMed

Visser, Ate; Schaap, Joris D; Broers, Hans Peter; Bierkens, Marc F P

2009-01-26

The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2=69%), as well as the 3H (R2=79%) and 3He (R2=76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (+/-2 sigma) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.

Cyclic degassing of Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Ilanko, Tehnuka; Oppenheimer, Clive; Burgisser, Alain; Kyle, Philip

2015-06-01

Field observations have previously identified rapid cyclic changes in the behaviour of the lava lake of Erebus volcano. In order to understand more fully the nature and origins of these cycles, we present here a wavelet-based frequency analysis of time series measurements of gas emissions from the lava lake, obtained by open-path Fourier transform infrared spectroscopy. This reveals (i) a cyclic change in total gas column amount, a likely proxy for gas flux, with a period of about 10 min, and (ii) a similarly phased cyclic change in proportions of volcanic gases, which can be explained in terms of chemical equilibria and pressure-dependent solubilities. Notably, the wavelet analysis shows a persistent periodicity in the CO2/CO ratio and strong periodicity in H2O and SO2 degassing. The `peaks' of the cycles, defined by maxima in H2O and SO2 column amounts, coincide with high CO2/CO ratios and proportionally smaller increases in column amounts of CO2, CO, and OCS. We interpret the cycles to arise from recharge of the lake by intermittent pulses of magma from shallow depths, which degas H2O at low pressure, combined with a background gas flux that is decoupled from this very shallow magma degassing.

Absorption of the Martian regolith: Specific surface area and missing CO(sub 2)

NASA Technical Reports Server (NTRS)

Zent, A. P.; Fanale, F. P.; Postawko, S. E.

1987-01-01

For most estimates of available regolith and initial degassed CO(sub 2) inventories, it appears that any initial inventory must have been lost to space or incorporated into carbonates. Most estimates of the total available degassed CO(sub 2) inventory are only marginally sufficient to allow for a major early greenhouse effect. It is suggested that the requirements for greenhouse warming to produce old dessicated terrain would be greatly lessened if groundwater brines rather than rainfall were involved and if a higher internal gradient were involved to raise the water (brine) table, leading to more frequent sapping.

Neon diffusion kinetics and implications for cosmogenic neon paleothermometry in feldspars

NASA Astrophysics Data System (ADS)

Tremblay, Marissa M.; Shuster, David L.; Balco, Greg; Cassata, William S.

2017-05-01

Observations of cosmogenic neon concentrations in feldspars can potentially be used to constrain the surface exposure duration or surface temperature history of geologic samples. The applicability of cosmogenic neon to either application depends on the temperature-dependent diffusivity of neon isotopes. In this work, we investigate the kinetics of neon diffusion in feldspars of different compositions and geologic origins through stepwise degassing experiments on single, proton-irradiated crystals. To understand the potential causes of complex diffusion behavior that is sometimes manifest as nonlinearity in Arrhenius plots, we compare our results to argon stepwise degassing experiments previously conducted on the same feldspars. Many of the feldspars we studied exhibit linear Arrhenius behavior for neon whereas argon degassing from the same feldspars did not. This suggests that nonlinear behavior in argon experiments is an artifact of structural changes during laboratory heating. However, other feldspars that we examined exhibit nonlinear Arrhenius behavior for neon diffusion at temperatures far below any known structural changes, which suggests that some preexisting material property is responsible for the complex behavior. In general, neon diffusion kinetics vary widely across the different feldspars studied, with estimated activation energies (Ea) ranging from 83.3 to 110.7 kJ/mol and apparent pre-exponential factors (D0) spanning three orders of magnitude from 2.4 × 10-3 to 8.9 × 10-1 cm2 s-1. As a consequence of this variability, the ability to reconstruct temperatures or exposure durations from cosmogenic neon abundances will depend on both the specific feldspar and the surface temperature conditions at the geologic site of interest.

Mantle Volatiles and Global Carbon Flux and Budget

NASA Astrophysics Data System (ADS)

Zhang, Y.

2014-12-01

The global volcanic carbon flux to the surface of Earth is a fundamental parameter in understanding the global carbon cycle that includes deep carbon as well as the degassing history of the mantle. The flux has been estimated before (e.g., Marty and Tolstikhin, 1998). Recent progress has significantly revised some of the parameters used in the estimation, e.g., the oceanic 3He flux has been re-evaluated (Bianchi et al., 2010) to be only about half of the earlier widely-used estimate, and numerous subaerial volcanic degassing data are now available. In this report, a new attempt is made to assess the global carbon flux and budget. Rather than dividing the carbon flux by categories of MORB, Plumes and Arcs, we estimate the global carbon flux by considering oceanic and subaerial volcanism. The oceanic 3He flux is 527±102 mol/yr (Bianchi et al., 2010). Most of the flux is from spreading ridges with only minor contributions from submarine oceanic hotspots or arc volcanism. Hence, the mean CO2/3He ratio in MORB is applied to estimate oceanic flux of CO2. The subaerial CO2 flux is based on evaluation of different arc segments and is messier to compute. Literature estimates use estimated SO2 flux in the last tens of years combined with estimated CO2/SO2 degassing ratios (Hilton et al., 2002; Fischer, 2008). Assuming that the last tens of years are representative of recent geological times in terms of volcanic degassing, the estimated global CO2 flux still depends critically on a couple of arcs that are main contributors of the subaerial volcanic CO2 flux, and those seem to have been rather loosely constrained before. Using recently available data (although there are still holes), we derive a new global subaerial volcanic CO2 flux. By combining with oceanic volcanic CO2 flux, we obtain at a new global flux. The significance of the new estimate to the global volatile budget will be discussed.

Surface Degassing Rates of Carbon Dioxide, Helium and Hydrogen at Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Salazar, P.; Morales, A.; Lima, R.; Castro, L.; Galindo, I.; Salazar, J.; Hernandez, P.; Perez, N.

2001-12-01

Tenerife is the largest island of the Canarian archipelago (2,034 Km2), and its most recent eruption took place along the NW rift-zone in 1909, Chinyero volcano. Water supply is mainly obtained from its ground water reservoir which is reached by thousands of well and galleries. Some galleries showed an enriched-CO2 inner atmosphere because of a continuous magmatic degassing process, which is also affecting the ground water chemistry. Gas emission studies through galleries could provide a 3-D picture of the degassing model for Tenerife. An in situ method was applied for measuring CO2, He and H2 fluxes from a horizontal drilling "gallery" by means of a tracer gas method. Methane (99.995%) was applied as a tracer and injected into the gallery "Fuente del Valle" at known flow, 38 mL/min. Well mixed gas and tracer were regularly analyzed, every 5 minutes, by means of a VARIAN 2002P microGC from April 27 to May 2, 2000. CO2 and CH4 measurements were performed by means of a 10 m Poraplot Q column at 40° C, a TCD, and He as gas carrier. He, Ne and H2 measurements were analyzed by means of a 20 m high resolution Molecular Sieve 5Å column at 60° C, a TCD, and Ar as gas carrier. (CH4)gas/(CH4)air ratio was >1000 during this experiment. CO2 concentrations seem to be affected by short-term meteorological fluctuations and showed a range from 23 to 30%. An strong correlation is observed between CO2 content and He/Ne ratios, which ranged from 0.320 to 0.390. CO2 flux ranged from 1.5 to 5.5 Kg/d showing an average of 2.9 +/- 0.7 Kg/d. Secular variations of CO2 flux showed regularly peak levels almost every 12 hours. Assuming that a number of 100 galleries at Tenerife might release this level of CO2, the island subsurface degassing rate of CO2 could account for 300 Kg/d. Observed He flux ranged 2.8 to 9.0 mg/d showing an average of 5.0 +/- 1.2 mg/d. In the case of H2, flux levels ranged from 2.5 to 7.0 mg/d showing an average of 4.5 +/- 0.9 mg/d. Subsurface degassing rate monitoring could be a potential geochemical tool for seismic-volcanic surveillance at Tenerife.

Eighteen years of geochemical monitoring at the oceanic active volcanic island of El Hierro (Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Asensio-Ramos, María; Alonso, Mar; Sharp, Emerson; Woods, Hannah; Barrancos, José; Pérez, Nemesio M.

2016-04-01

We report herein the latest results of a diffuse CO2 efflux survey at El Hierro volcanic system carried out during the summer period of 2015 to constrain the total CO2 output from the studied area a during post-eruptive period. El Hierro Island (278 km2) is the youngest and the SW-most of the Canary Islands. On July 16, 2011, a seismic-volcanic crisis started with the occurrence of more than 11,900 seismic events and significant deformation along the island. On October 10, 2011, the dominant character of seismicity changed dramatically from discrete earthquakes to continuous tremor, a clear indication that magma was rapidly approaching the surface immediately before the onset of the eruption, October 12. Eruption was declared over on 5 March, 2012. In order to monitor the volcanic activity of El Hierro Island, from 1998 to 2015 diffuse CO2 emission studies have been performed at El Hierro volcanic system in a yearly basis (˜600 observation sites) according to the accumulation chamber method. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. To quantify the total CO2 emission from the studied area, 100 simulations for each survey have been performed. During the eruption period, soil CO2 efflux values range from non-detectable (˜0.5 g m-2 d-1) up to 457 g m-2 d-1, reaching in November 27, 2011, the maximum CO2 output estimated value of all time series, 2,398 t d-1, just before the episodes of maximum degassing observed as vigorous bubbling at the sea surface and an increment in the amplitude of the tremor signal. During the 2015 survey, soil CO2 efflux values ranged from non-detectable up to 41 g m-2 d-1. The spatial distribution of diffuse CO2 emission values seemed to be controlled by the main volcano structural features of the island. The total diffuse CO2 output released to atmosphere was estimated at 575 ± 24 t d-1, value slightly higher that the background CO2 emission estimated at 422 t d-1 (Melián et al., 2014). The above data demonstrate that discrete surveys of diffuse CO2 emission provide important information to optimize the early warning system in volcano monitoring programs and to monitor the evolution of an ongoing volcanic eruption, even though it is a submarine eruption. References: Melián et al., 2014. J. Geophys. Res. DOI: 10.1002/2014JB011013.

Modeling CO2 degassing and pH in a stream-aquifer system

USGS Publications Warehouse

Choi, J.; Hulseapple, S.M.; Conklin, M.H.; Harvey, J.W.

1998-01-01

Pinal Creek, Arizona receives an inflow of ground water with high dissolved inorganic carbon (57-75 mg/l) and low pH (5.8-6.3). There is an observed increase of in-stream pH from approximately 6.0-7.8 over the 3 km downstream of the point of groundwater inflow. We hypothesized that CO2 gas-exchange was the most important factor causing the pH increase in this stream-aquifer system. An existing transport model, for coupled ground water-surface water systems (OTIS), was modified to include carbonate equilibria and CO2 degassing, used to simulate alkalinity, total dissolved inorganic carbon (C(T)), and pH in Pinal Creek. Because of the non-linear relation between pH and C(T), the modified transport model used the numerical iteration method to solve the non-linearity. The transport model parameters were determined by the injection of two tracers, bromide and propane. The resulting simulations of alkalinity, C(T) and pH reproduced, without fitting, the overall trends in downstream concentrations. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that C(T) and pH in stream water were controlled by the mixing of ground water with stream water and CO2 degassing. The relative importance of these two processes varied spatially depending on the hydrologic conditions, such as stream flow velocity and whether a reach gained or lost stream water caused by the interaction with the ground water. The coupled transport model with CO2 degassing and generalized sensitivity analysis presented in this study can be applied to evaluate carbon transport and pH in other coupled stream-ground water systems.An existing transport model for coupled groundwater-surface water systems was modified to include carbonate equilibria and CO2 degassing. The modified model was used to simulate alkalinity, total dissolved inorganic carbon (CT) and pH in Pinal Creek. The model used the numerical iteration method to solve the nonlinear relation between pH and CT. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that CT and pH in the stream water were controlled by the mixing of groundwater with stream water and CO2 degassing.

The effect of regional groundwater on carbon dioxide and methane emissions from a lowland rainforest stream in Costa Rica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oviedo-Vargas, Diana; Genereux, David P.; Dierick, Diego

In the tropical rainforest at La Selva Biological Station in Costa Rica, regional bedrock groundwater high in dissolved carbon discharges into some streams and wetlands, with the potential for multiple cascading effects on ecosystem carbon pools and fluxes. We investigated carbon dioxide (CO 2) and methane (CH 4) degassing from two streams at La Selva: the Arboleda, where ~1/3 of the streamflow is from regional groundwater, and the Taconazo, fed exclusively by local groundwater recharged within the catchment. The regional groundwater inflow to the Arboleda had no measurable effect on stream gas exchange velocity, dissolved CH 4 concentration, or CHmore » 4 emissions but significantly increased stream CO 2 concentration and degassing. CO 2 evasion from the reach of the Arboleda receiving regional groundwater (lower Arboleda) averaged 5.5 mol C m -2 d -1, ~7.5x higher than the average (0.7 mol C m -2 d -1) from the stream reaches with no regional groundwater inflow (the Taconazo and upper Arboleda). Carbon emissions from both streams were dominated by CO 2; CH 4 accounted for only 0.06-1.70% of the total (average of both streams: 5 x10 -3 mol C m -2 d -1). Annual stream degassing fluxes normalized by watershed area were 48 and 299 g C m -2 for the Taconazo and Arboleda, respectively. CO 2 degassing from the Arboleda is a significant carbon flux, similar in magnitude to the average net ecosystem exchange estimated by eddy covariance. As a result, examining the effects of catchment connections to underlying hydrogeological systems can help avoid overestimation of ecosystem respiration and advance our understanding of carbon source/sink status and overall terrestrial ecosystem carbon budgets.« less

The effect of regional groundwater on carbon dioxide and methane emissions from a lowland rainforest stream in Costa Rica

DOE PAGES

Oviedo-Vargas, Diana; Genereux, David P.; Dierick, Diego; ...

2015-12-22

In the tropical rainforest at La Selva Biological Station in Costa Rica, regional bedrock groundwater high in dissolved carbon discharges into some streams and wetlands, with the potential for multiple cascading effects on ecosystem carbon pools and fluxes. We investigated carbon dioxide (CO 2) and methane (CH 4) degassing from two streams at La Selva: the Arboleda, where ~1/3 of the streamflow is from regional groundwater, and the Taconazo, fed exclusively by local groundwater recharged within the catchment. The regional groundwater inflow to the Arboleda had no measurable effect on stream gas exchange velocity, dissolved CH 4 concentration, or CHmore » 4 emissions but significantly increased stream CO 2 concentration and degassing. CO 2 evasion from the reach of the Arboleda receiving regional groundwater (lower Arboleda) averaged 5.5 mol C m -2 d -1, ~7.5x higher than the average (0.7 mol C m -2 d -1) from the stream reaches with no regional groundwater inflow (the Taconazo and upper Arboleda). Carbon emissions from both streams were dominated by CO 2; CH 4 accounted for only 0.06-1.70% of the total (average of both streams: 5 x10 -3 mol C m -2 d -1). Annual stream degassing fluxes normalized by watershed area were 48 and 299 g C m -2 for the Taconazo and Arboleda, respectively. CO 2 degassing from the Arboleda is a significant carbon flux, similar in magnitude to the average net ecosystem exchange estimated by eddy covariance. As a result, examining the effects of catchment connections to underlying hydrogeological systems can help avoid overestimation of ecosystem respiration and advance our understanding of carbon source/sink status and overall terrestrial ecosystem carbon budgets.« less

Sources of Magmatic Volatiles Discharging from Subduction Zone Volcanoes

NASA Astrophysics Data System (ADS)

Fischer, T.

2001-05-01

Subduction zones are locations of extensive element transfer from the Earth's mantle to the atmosphere and hydrosphere. This element transfer is significant because it can, in some fashion, instigate melt production in the mantle wedge. Aqueous fluids are thought to be the major agent of element transfer during the subduction zone process. Volatile discharges from passively degassing subduction zone volcanoes should in principle, provide some information on the ultimate source of magmatic volatiles in terms of the mantle, the crust and the subducting slab. The overall flux of volatiles from degassing volcanoes should be balanced by the amount of volatiles released from the mantle wedge, the slab and the crust. Kudryavy Volcano, Kurile Islands, has been passively degassing at 900C fumarole temperatures for at least 40 years. Extensive gas sampling at this basaltic andesite cone and application of CO2/3He, N2/3He systematics in combination with C and N- isotopes indicates that 80% of the CO2 and approximately 60% of the N 2 are contributed from a sedimentary source. The mantle wedge contribution for both volatiles is, with 12% and 17% less significant. Direct volatile flux measurements from the volcano using the COSPEC technique in combination with direct gas sampling allows for the calculation of the 3He flux from the volcano. Since 3He is mainly released from the astenospheric mantle, the amount of mantle supplying the 3He flux can be determined if initial He concentrations of the mantle melts are known. The non-mantle flux of CO2 and N2 can be calculated in similar fashion. The amount of non-mantle CO2 and N2 discharging from Kudryavy is balanced by the amount of CO2 and N2 subducted below Kudryavy assuming a zone of melting constrained by the average spacing of the volcanoes along the Kurile arc. The volatile budget for Kudryavy is balanced because the volatile flux from the volcano is relatively small (75 t/day (416 Mmol/a) SO2, 360 Mmol/a of non-mantle CO2 and 5.4 Mmol/a of non-mantle N2). Other subduction zone volcanoes are currently degassing a much more substantial amount of volatiles. Popocatepetl, Mexico, has degassed approximately 14 Mt of SO2 to the atmosphere over the past 6 years (Witter et al. 2000). Satsuma-Iwojima, Japan, has degassed for longer than 800 years and is currently releasing 500-1000 tones/day (Kazahaya et al. 2000). At these volcanoes CO2 and N2 discharges from the magma should also be balanced by the supply from slab and crustal sources. The rate of subduction off Mexico and Japan, however, is similar to the rate at the Kuriles. Therefore, large amounts of slab derived volatiles must be, in some fashion, stored in the "subduction factory" to supply the large amounts degassing passively from these volcanoes. Kazahaya et al. (2000) Seventh Field Workshop on Volcanic Gases, IAVCEI. Witter et al (2000) Seventh Field Workshop on Volcanic Gases, IAVCEI.

Precursory diffuse CO2 emission signature of the 2011 El Hierro submarine eruption, Canary Islands

NASA Astrophysics Data System (ADS)

Pérez, N. M.; Padilla, G. D.; Padrón, E.; Hernández, P. A.; Melián, G. V.; Barrancos, J.; Dionis, S.; Rodríguez, F.; Nolasco, D.; Calvo, D.; Hernández, I.; Peraza, M. D.

2012-04-01

El Hierro is the youngest and southernmost island of the Canarian archipelago and represents the summit of a volcanic shield elevating from the surrounding seafloor at depth of 4000 m to up to 1501 m above sea level. The island is believed to be near the present hotspot location in the Canaries with the oldest subaerial rocks dated at 1.12 Ma. The subaerial parts of the El Hierro rift zones (NE, NW and S Ridges) are characterized by tightly aligned dyke complexes with clusters of cinder cones as their surface expressions. Since 16 July, an anomalous seismicity at El Hierro Island was recorded by IGN seismic network. Volcanic tremor started at 05:15 on 10 October, followed on the afternoon of 12 October by a green discolouration of seawater, strong bubbling and degassing, and abundant bombs on a decimetre scale found floating on the ocean surface offshore, southwest of La Restinga village, indicating the occurrence of a submarine volcanic eruption at approximately 2 km far the coast line of La Restinga. Further episodes have occurred during November, December 2011 and January 2012, with turbulent water, foam rings, and volcanic material again reaching the sea surface. In order to improve the volcanic surveillance program of El Hierro Island and to provide a multidisciplinary approach, a continuous geochemical station to measure CO2 efflux was installed on September 2003 in Llanos de Guillen, the interception center of the three volcanic-rift zones of the island, with the aim of detecting changes in the diffuse emission of CO2 related to the seismic or volcanic activity. The station measures on an hourly basis the CO2 and H2S efflux, the CO2 and H2S air concentrations, the soil water content and temperature and the atmospheric parameters: wind speed and direction, air temperature and humidity and barometric pressure. The meteorological parameters together with the air CO2 concentration are measured 1 m above the ground and the soil water content and soil temperature are measured 40-cm deep, and recorded contemporaneously with CO2 efflux. Although time series of CO2 efflux showed background (4-5 g m-2 d-1) values before the July 16, when the seismic unrest started, and still August 30, some significant increases up to 10 g m-2 d-1 was measured prior the occurrence of peaks on the seismic energy release. Since the end of August, coinciding with a migration of the hypocenters of the seismic activity toward the south part of the island, the CO2 efflux time series started a relatively constant increase during 1 month, reaching a maximum of 19 g m-2 d-1 one week before the occurrence of the submarine volcanic eruption. Since October 5 till present, including the whole eruptive period, the CO2 efflux time series have shown a general decrease trend but with some significant emission peaks prior the occurrence of important seismic energy release episodes. This station has revealed as an important observation point to evaluate the volcanic activity of El Hierro Island since diffuse degassing of carbon dioxide seems to be associated with fluid pressure fluctuations in the volcanic system. These results demonstrated the potential of applying continuous monitoring of soil CO2 efflux to improve and optimize the detection of early warning signals of future volcanic unrest episodes at El Hierro.

Obsidian Pyroclasts: Where Do They Come From and What Can They Tell Us?

NASA Astrophysics Data System (ADS)

Watkins, J. M.; Gardner, J. E.; Befus, K.

2016-12-01

Models for how volcanic gases behave during volcanic eruptions are constructed from measurements of volatiles (δD, H2O and CO2) in melt that has been quenched to glass. Volatile measurements on obsidian pyroclasts from Mono Craters, California, have been central to the development of open- versus closed-system and equilibrium versus non-equilibrium degassing models, and these models have been applied to the interpretation of volatile data from volcanic centers worldwide. Even for the well-studied Mono Craters system, however, there are several different degassing models that are compatible with existing data, and the origin of the vesicle-poor obsidian pyroclasts (upon which the degassing models have been built) remains ambiguous. To better establish the link between the volatiles in the pyroclasts and volcanic eruption processes, we combine textural analysis with area maps of CO2 and H2O. We show that obsidian pyroclasts are heterogeneous with respect to dissolved CO2 and H2O, and that many clasts have multiple textural and chemical domains that are sutured together. The observations suggest that clasts are assembled from non-equilibrated juvenile melt and ash during repeated melt fracturing and healing, ash sintering, and shearing along conduit margins. Melt fracturing promotes gas extraction from magma, whereas healing promotes gas resorption and glass densification. Some of the clasts have bands or patches of elevated CO2 associated with cuspate vesicles, which are evidence for CO2-rich vapor fluxing through the magmatic system. Collectively, the data support a model of open-system, non-equilibrium degassing with intermittent regassing caused by increases in pressure and exposure to different vapor compositions.

Using CO2 and He Concentrations in Hydrothermal Fluids to Constrain Along-Axis Magma Chamber Dimensions at 9°N, EPR

NASA Astrophysics Data System (ADS)

Lilley, M. D.; Lupton, J. E.; Olson, E. J.

2002-12-01

Magmatic degassing is a common occurrence in subaerial volcanoes and has been reported in shallow submarine volcanoes. It has been speculated that mid-ocean ridge magma chambers may exhibit degassing behavior but to date there has been no direct documentation of its occurrence. Based on very high CO2 and He concentrations, we believe that we now have evidence for a degassing magma chamber at 9°N, East Pacific Rise. M Vent, in the immediate vicinity of the 1991 eruption, exhibited high and relatively stable CO2 concentrations in excess of 150 mmol/kg for at least eight years post-eruption. Such high values are many times the value that can be extracted from basalt by hydrothermal fluid and have previously been seen only at Axial and Loihi Seamounts. Two vents about one km south (Bio 9 and P Vents) had CO2 concentrations around 50 mmol/kg in 1991 which increased to maxima near 200 mmol/kg in 1993. We believe this represents a southward movement of the magma body in this area. He concentrations were also elevated at all the vents but showed different temporal trends from CO2 and reached maximum values in 1994. 3He/heat ratios are significantly different between M and Bio 9 and P Vents implying that separate magma bodies with differing degrees of degassing underlie the two areas. We have seen similarly high concentrations of CO2 and He at 31.8°S on the East Pacific Rise (Lupton et al., 1999) and suggest that magmatic degassing into the hydrothermal convection cell is occurring there as well. This work indicates that the concentrations of magmatic gases in hydrothermal fluids may provide fine scale data bearing on the locations and along-axis dimensions of magma chambers. Reference: Lupton, J., D. Butterfield, M. Lilley, J. Ishibashi, D. Hey and L. Evans, Gas chemistry of hydrothermal fluids along the East Pacific Rise, 5°S to 32°S, EOS, 80, F1099, 1999.

Gas emissions from failed and actual eruptions from Cook Inlet Volcanoes, Alaska, 1989-2006

USGS Publications Warehouse

Werner, C.A.; Doukas, M.P.; Kelly, P.J.

2011-01-01

Cook Inlet volcanoes that experienced an eruption between 1989 and 2006 had mean gas emission rates that were roughly an order of magnitude higher than at volcanoes where unrest stalled. For the six events studied, mean emission rates for eruptions were ~13,000 t/d CO2 and 5200 t/d SO2, but only ~1200 t/d CO2 and 500 t/d SO2 for non-eruptive events (‘failed eruptions’). Statistical analysis suggests degassing thresholds for eruption on the order of 1500 and 1000 t/d for CO2 and SO2, respectively. Emission rates greater than 4000 and 2000 t/d for CO2 and SO2, respectively, almost exclusively resulted during eruptive events (the only exception being two measurements at Fourpeaked). While this analysis could suggest that unerupted magmas have lower pre-eruptive volatile contents, we favor the explanations that either the amount of magma feeding actual eruptions is larger than that driving failed eruptions, or that magmas from failed eruptions experience less decompression such that the majority of H2O remains dissolved and thus insufficient permeability is produced to release the trapped volatile phase (or both). In the majority of unrest and eruption sequences, increases in CO2 emission relative to SO2 emission were observed early in the sequence. With time, all events converged to a common molar value of C/S between 0.5 and 2. These geochemical trends argue for roughly similar decompression histories until shallow levels are reached beneath the edifice (i.e., from 20–35 to ~4–6 km) and perhaps roughly similar initial volatile contents in all cases. Early elevated CO2 levels that we find at these high-latitude, andesitic arc volcanoes have also been observed at mid-latitude, relatively snow-free, basaltic volcanoes such as Stromboli and Etna. Typically such patterns are attributed to injection and decompression of deep (CO2-rich) magma into a shallower chamber and open system degassing prior to eruption. Here we argue that the C/S trends probably represent tapping of vapor-saturated regions with high C/S, and then gradual degassing of remaining dissolved volatiles as the magma progresses toward the surface. At these volcanoes, however, C/S is often accentuated due to early preferential scrubbing of sulfur gases. The range of equilibrium degassing is consistent with the bulk degassing of a magma with initial CO2 and S of 0.6 and 0.2 wt.%, respectively, similar to what has been suggested for primitive Redoubt magmas.

Environmental impact of CO2, Rn, Hg degassing from the rupture zones produced by Wenchuan M s 8.0 earthquake in western Sichuan, China.

PubMed

Zhou, Xiaocheng; Chen, Zhi; Cui, Yueju

2016-10-01

The concentrations and flux of CO2, (222)Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M s 8.0 earthquake in order to assess the environmental impact of degassing of CO2, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO2, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO2, Rn and Hg concentration in soil gas showed that (1) the concentration of CO2 in the epicenter of Wenchuan M s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO2, Rn and Hg degassing rate indicated that (1) the CO2 in soil gas was characterized by a mean [Formula: see text] of -20.4 ‰ and by a mean CO2 flux of 88.1 g m(-2) day(-1), which were in the range of the typical values for biologic CO2 degassing. The maximum of soil CO2 flux reached values of 399 g m(-2) day(-1) in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m(-2) s(-1); (3) the soil Hg flux was lower, ranging from -2.5 to 18.7 n g m(-2) h(-1) and increased from south to north. The mean flux over the all profiles was 4.2 n g m(-2) h(-1). The total output of CO2 and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km(2) were approximately 0.57 Mt year(-1) and 688.19 g year(-1). It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO2 and Rn, were needed in some houses.

Neon diffusion kinetics and implications for cosmogenic neon paleothermometry in feldspars

DOE PAGES

Tremblay, Marissa M.; Shuster, David L.; Balco, Greg; ...

2017-02-20

Observations of cosmogenic neon concentrations in feldspars can potentially be used to constrain the surface exposure duration or surface temperature history of geologic samples. The applicability of cosmogenic neon to either application depends on the temperature-dependent diffusivity of neon isotopes. Here in this work, we investigate the kinetics of neon diffusion in feldspars of different compositions and geologic origins through stepwise degassing experiments on single, proton-irradiated crystals. To understand the potential causes of complex diffusion behavior that is sometimes manifest as nonlinearity in Arrhenius plots, we compare our results to argon stepwise degassing experiments previously conducted on the same feldspars.more » Many of the feldspars we studied exhibit linear Arrhenius behavior for neon whereas argon degassing from the same feldspars did not. This suggests that nonlinear behavior in argon experiments is an artifact of structural changes during laboratory heating. However, other feldspars that we examined exhibit nonlinear Arrhenius behavior for neon diffusion at temperatures far below any known structural changes, which suggests that some preexisting material property is responsible for the complex behavior. In general, neon diffusion kinetics vary widely across the different feldspars studied, with estimated activation energies (E a) ranging from 83.3 to 110.7 kJ/mol and apparent pre-exponential factors (D 0) spanning three orders of magnitude from 2.4 ×10 -3 to 8.9 × 10 -1 cm 2 s -1. Finally, as a consequence of this variability, the ability to reconstruct temperatures or exposure durations from cosmogenic neon abundances will depend on both the specific feldspar and the surface temperature conditions at the geologic site of interest.« less

Application of the LI-COR CO2 analyzer to volcanic plumes: a case study, volcán Popocatépetl, Mexico, June 7 and 10, 1995

USGS Publications Warehouse

Gerlach, T.M.; Delgado, H.; McGee, K.A.; Doukas, M.P.; Venegas, J.J.; Cardenas, L.

1997-01-01

Volcanic CO2 emission rate data are sparse despite their potential importance for constraining the role of magma degassing in the biogeochemical cycle of carbon and for assessing volcanic hazards. We used a LI-COR CO2 analyzer to determine volcanic CO2 emission rates by airborne measurements in volcanic plumes at Popocatépetl volcano on June 7 and 10, 1995. LI-COR sample paths of ∼72 m, compared with ∼1 km for the analyzer customarily used, together with fast Fourier transforms to remove instrument noise from raw data greatly improve resolution of volcanic CO2 anomalies. Parametric models fit to background CO2 provide a statistical tool for distinguishing volcanic from ambient CO2. Global Positioning System referenced flight traverses provide vastly improved data on the shape, coherence, and spatial distribution of volcanic CO2 in plume cross sections and contrast markedly with previous results based on traverse stacking. The continuous escape of CO2 and SO2 from Popocatépetl was fundamentally noneruptive and represented quiescent magma degassing from the top of a magma chamber ∼5 km deep. The average CO2 emission rate for January-June 1995 is estimated to be at least 6400 t d−1, one of the highest determined for a quiescently degassing volcano, although correction for downwind dispersion effects on volcanic CO2 indicates a higher rate of ∼9000 t d−1. Analysis of random errors indicates emission rates have 95% confidence intervals of ∼±20%, with uncertainty contributed mostly by wind speed variance, although the variance of plume cross-sectional areas during traversing is poorly constrained and possibly significant.

Precursory diffuse CO2 and H2S emission signatures of the 2011-2012 El Hierro submarine eruption, Canary Islands

NASA Astrophysics Data System (ADS)

Pérez, Nemesio M.; Padilla, Germán D.; Padrón, Eleazar; Hernández, Pedro A.; Melián, Gladys V.; Barrancos, José; Dionis, Samara; Nolasco, Dácil; Rodríguez, Fátima; Calvo, David; Hernández, Íñigo

2012-08-01

On October 12, 2011, a submarine eruption began 2 km off the coast of La Restinga, south of El Hierro Island. CO2 and H2S soil efflux were continuously measured during the period of volcanic unrest by using the accumulation chamber method at two different geochemical stations, HIE01 and HIE07. Recorded CO2 and H2S effluxes showed precursory signals that preceded the submarine eruption. Beginning in late August, the CO2 efflux time series started increasing at a relatively constant rate over one month, reaching a maximum of 19 gm-2d-1 one week before the onset of the submarine volcanic eruption. The H2S efflux time series at HIE07 showed a pulse in H2S emission just one day before the initiation of the submarine eruption, reaching peak values of 42 mg m-2 d-1, 10 times the average H2S efflux recorded during the observation period. Since CO2 and H2S effluxes are strongly influenced by external factors, we applied a multiple regression analysis to remove their contribution. A statistical analysis showed that the long-term trend of the filtered data is well correlated with the seismic energy. We find that these geochemical stations are important monitoring sites for evaluating the volcanic activity of El Hierro and that they demonstrate the potential of applying continuous monitoring of soil CO2 and H2S efflux to improve and optimize the detection of early warning signals of future volcanic unrest episodes at El Hierro. Continuous diffuse degassing studies would likely prove useful for monitoring other volcanoes during unrest episodes.

Mantle to surface degassing of alkalic magmas at Erebus volcano, Antarctica

USGS Publications Warehouse

Oppenheimer, C.; Moretti, R.; Kyle, P.R.; Eschenbacher, A.; Lowenstern, J. B.; Hervig, R.L.; Dunbar, N.W.

2011-01-01

Continental intraplate volcanoes, such as Erebus volcano, Antarctica, are associated with extensional tectonics, mantle upwelling and high heat flow. Typically, erupted magmas are alkaline and rich in volatiles (especially CO2), inherited from low degrees of partial melting of mantle sources. We examine the degassing of the magmatic system at Erebus volcano using melt inclusion data and high temporal resolution open-path Fourier transform infrared (FTIR) spectroscopic measurements of gas emissions from the active lava lake. Remarkably different gas signatures are associated with passive and explosive gas emissions, representative of volatile contents and redox conditions that reveal contrasting shallow and deep degassing sources. We show that this unexpected degassing signature provides a unique probe for magma differentiation and transfer of CO2-rich oxidised fluids from the mantle to the surface, and evaluate how these processes operate in time and space. Extensive crystallisation driven by CO2 fluxing is responsible for isobaric fractionation of parental basanite magmas close to their source depth. Magma deeper than 4kbar equilibrates under vapour-buffered conditions. At shallower depths, CO2-rich fluids accumulate and are then released either via convection-driven, open-system gas loss or as closed-system slugs that ascend and result in Strombolian eruptions in the lava lake. The open-system gases have a reduced state (below the QFM buffer) whereas the closed-system gases preserve their deep oxidised signatures (close to the NNO buffer). ?? 2011 Elsevier B.V.

Petrology and volatile content of magmas erupted from Tolbachik Volcano, Kamchatka, 2012-13

NASA Astrophysics Data System (ADS)

Plechov, Pavel; Blundy, Jon; Nekrylov, Nikolay; Melekhova, Elena; Shcherbakov, Vasily; Tikhonova, Margarita S.

2015-12-01

We report petrography, and bulk rock, mineral and glass analyses of eruptive products of the 2012-13 eruption of Tolbachik volcano, Central Kamchatka Depression, Russia. Magmas are shoshonitic in composition, with phenocrysts of olivine and plagioclase; clinopyroxene phenocrysts are scarce. Samples collected as bombs from the active vent, from liquid lava at the active lava front, and as naturally solidified ;toothpaste; lava allow us to quantify changes in porosity and crystallinity that took place during 5.25 km of lava flow and during solidification. Olivine-hosted melt inclusions from rapidly-cooled, mm-size tephra have near-constant H2O contents (1.19 ± 0.1 wt%) over a wide range of CO2 contents (< 900 ppm), consistent with degassing. The groundmass glasses from tephras lie at the shallow end of this degassing trend with 0.3 wt% H2O and 50 ppm CO2. The presence of small saturation, rather than shrinkage, bubbles testifies to volatile saturation at the time of entrapment. Calculated saturation pressures are 0.3 to 1.7 kbar, in agreement with the depths of earthquake swarms during November 2012 (0.6 to 7.5 km below the volcano). Melt inclusions from slowly-cooled and hot-collected lavas have H2O contents that are lower by an order of magnitude than tephras, despite comparable CO2 contents. We ascribe this to diffusive H2O loss through olivine host crystals during cooling. The absence of shrinkage bubbles in the inclusions accounts for the lack of reduction in dissolved CO2 (and S and Cl). Melt inclusions from tephras experienced < 3 wt% post-entrapment crystallisation. Melt inclusion entrapment temperatures are around 1080 °C. Compared to magmas erupted elsewhere in the Kluchevskoy Group, the 2012-13 Tolbachik magmas appear to derive from an unusually H2O-poor and K2O-rich basaltic parent.

A homemade sand-volcano in a gassy alluvial plain (Medolla, Italy): when shallow drilling triggers violent degassing

NASA Astrophysics Data System (ADS)

Capaccioni, Bruno; Coltorti, Massimo; Todesco, Micol; Cremoni, Stefano; Di Giuseppe, Dario; Faccini, Barbara; Tessari, Umberto

2017-04-01

Sand volcanoes are remarkable geological features which form when shallow, water-saturated sand deposits are set in motion and reach the surface. This commonly occurs during earthquakes, as a result of liquefaction of waterlogged bodies, but some of these sand emissions are unrelated to seismic events. We present the case of a sand eruption triggered by a Cone Penetration Test (CPT) near Medolla (Italy), on the 10th of October 2014. A large amount of natural gas (CO2 and CH4)was erupted together with a mixture of water and sand, creating a sand volcano. The event was recorded and its evolution and final result were analyzed from several points of view. Our multidisciplinary approach involved morphological and sedimentological studies on the sand-volcano, chemical and isotopic analysis of discharged gases, repeated measurements of gas flux on the drill hole and of diffuse degassing in the surrounding area and numerical modelling of the aquifer feeding the discharge. Our results suggest that a geyser discharging a mixture of gas and water, capable of building a sand volcano, requires the presence of a shallow pressurized reservoir (1.2 MPa) where water coexists with a small amount of exsolved gas (a volume fraction of 0.05). The violent degassing occurred in Medolla confirms the role that a free gas phase may have in favoring the mobilization of liquid water and loose deposits, even in the absence of a seismic event.

Deep magmatic degassing versus scrubbing: Elevated CO2 emissions and C/S in the lead-up to the 2009 eruption of Redoubt Volcano, Alaska

USGS Publications Warehouse

Werner, Cynthia A.; Evans, William C.; Kelly, Peter; McGimsey, Robert G.; Pfeffer, Melissa; Doukas, Michael P.; Neal, Christina

2012-01-01

We report CO2, SO2, and H2S emission rates and C/S ratios during the five months leading up to the 2009 eruption of Redoubt Volcano, Alaska. CO2emission rates up to 9018 t/d and C/S ratios ≥30 measured in the months prior to the eruption were critical for fully informed forecasting efforts. Observations of ice-melt rates, meltwater discharge, and water chemistry suggest that surface waters represented drainage from surficial, perched reservoirs of condensed magmatic steam and glacial meltwater. These fluids scrubbed only a few hundred tonnes/day of SO2, not the >2100 t/d SO2expected from degassing of magma in the mid- to upper crust (3–6.5 km), where petrologic analysis shows the final magmatic equilibration occurred. All data are consistent with upflow of a CO2-rich magmatic gas for at least 5 months prior to eruption, and minimal scrubbing of SO2by near-surface groundwater. The high C/S ratios observed could reflect bulk degassing of mid-crustal magma followed by nearly complete loss of SO2in a deep magmatic-hydrothermal system. Alternatively, high C/S ratios could be attributed to decompressional degassing of low silica andesitic magma that intruded into the mid-crust in the 5 months prior to eruption, thereby mobilizing the pre-existing high silica andesite magma or mush in this region. The latter scenario is supported by several lines of evidence, including deep long-period earthquakes (−28 to −32 km) prior to and during the eruption, and far-field deformation following the onset of eruptive activity.

Interactions between tectonics, silicate weathering, and climate explored with carbon cycle modeling

NASA Astrophysics Data System (ADS)

Penman, D. E.; Caves Rugenstein, J. K.; Ibarra, D. E.; Winnick, M.

2017-12-01

Earth's long-term carbon cycle is thought to benefit from a stabilizing negative feedback in the form of CO2 consumption by the chemical weathering of silicate minerals: during periods of elevated atmospheric pCO2, chemical weathering rates increase, thus consuming more atmospheric CO2 and cooling global climate, whereas during periods of low pCO2, weathering rates decrease, allowing buildup of CO2 in the atmosphere and warming. At equilibrium, CO2 consumption by silicate weathering balances volcanic CO2 degassing at a specific atmospheric pCO2 dictated by the relationship between total silicate weathering rate and pCO2: Earth's "weathering curve." We use numerical carbon cycle modeling to demonstrate that the shape and slope of the weathering curve is crucial to understanding proposed tectonic controls on pCO2 and climate. First, the shape of the weathering curve dictates the equilibrium response of the carbon cycle to changes in the rate of background volcanic/solid Earth CO2 degassing, which has been suggested to vary significantly with plate tectonic reorganizations over geologic timescales. Second, we demonstrate that if tectonic events can significantly change the weathering curve, this can act as an effective driver of pCO2 and climate on tectonic timescales by changing the atmospheric pCO2 at which silicate weathering balances a constant volcanic/solid Earth degassing rate. Finally, we review the complex interplay of environmental factors that affect modern weathering rates in the field and highlight how the resulting uncertainty surrounding the shape of Earth's weathering curve significantly hampers our ability to quantitatively predict the response of pCO2 and climate to tectonic forcing, and thus represents a substantial knowledge gap in Earth science. We conclude with strategies for closing this knowledge gap by using precise paleoclimatic reconstructions of intervals with known tectonic forcings.

Smart Nanofibers Self-Assembled from Dumbbell-Shaped Rod Amphiphiles

DTIC Science & Technology

2011-09-01

using JEOL-JEM 2100. MALDI-TOF-MS was performed on a Bruker Microflex LRF20 using α-cyano-4-hydroxy cinnamic acid (CHCA) as matrix. Preparative high...and 4,4’-biphenyl diboronic acid (28.8 mg, 0.12 mmol) were dissolved in degassed THF (25 ml). Degassed 2 M aqueous Na2CO3 (25 ml) was added to the

A degassing instrument for analysing CO2 dissolved in natural water

NASA Astrophysics Data System (ADS)

Durham, Brian; Pfrang, Christian

2017-04-01

Arising from our EGU 2017 presentation (http://meetingorganizer.copernicus.org/EGU2016/posters/20564, X2 352), interest has been expressed in its application to the analysis of the hydrocarbonate ion [HCO3-] in atmospheric water. Arising from the historic difficulty in analysing the aqueous [HCO3-] ion ('it is in all our reagents', pers. comm. UK laboratory) the classic determination has been to measure a suite of other anions and cations including [H+] via pH, and to treat the balance of negative charge as a measure of [HCO3-]. From this balance, dissolved CO2 can be inferred via the dissociation constant as published for pure water. CO2 + H2O ⇓♢[HCO3-] + [H+] K1 = 4.2 x 10-7 Our EGU 2016 presentation sought to determine how the ionic environment in 263 UK rain samples can influence the above equilibrium, which is work in progress. In the mean time we have received the following expression of interest from an atmospheric science advisory group. …….. is very interested in the role of H-carbonate in the ion balance of precipitation. They have had some discussions recently about the best approach to infer H-carbonate currently discussing the possibility of sending you samples from other locations for analysis. We have duly offered to use our degassing instrument to corroborate current analyses in a batch of 'blind' samples, and to provide a design for a basic degasser that water quality laboratories could evaluate in house. This paper therefore presents a circuit for degassing CO2 from water samples irrespective of whether in atmospheric equilibrium or supersaturated, including a prototype 4-way distribution and collection valve which it is hoped will make the analysis intuitive and therefore open to automation.

Volcanic soil gas 4He/CO2 ratio: a useful geochemical tool for eruption forecasting

NASA Astrophysics Data System (ADS)

Asensio-Ramos, M.; Perez, N. M.; Padron, E.; Melián, G.; Hernandez Perez, P. A.; Padilla, G.; Barrancos, J.; Rodríguez, F.; Sumino, H.; Calvo, D.

2016-12-01

Magmatic gases that percolate through volcano's porous flanks in a non-visible (diffuse) way disturb the chemical composition of soil gases at the surface environment of the volcano, generating enrichments of CO2, He and other gases. Two of the gases which have attracted attention in soil degassing studies are He and CO2 because both species have similar low solubility in silicate melts. However, once they are exsolved from the melts, their movement through the crust towards the surface is very different: CO2, which is a reactive gas, is affected by the occurrence of interfering processes, while interaction of He during its ascent is minimum. Their geochemical differences yield higher relative He/CO2 ratios in the fumarole gases than is actually present in the magma, but it decreases when the magma reservoir reaches enough pressure to generate incipient fracture systems approaching the eruption. In this work, we present quasi daily estimations of diffusive He through the whole surface of El Hierro, the youngest island of the Canarian archipelago, considering He emission data reported in the literature (Padrón et al., 2013. Geology, 41, 539-542), using the same procedure as for diffuse CO2 emission time series (Melián et al., 2014. J. Geophys. Res., 119, 6976-6991). After the occurrence of more than 11,000 seismic events, a shallow submarine eruption about 2 km off the south coast in the southernmost part of El Hierro, started in October 12, 2011 and lasted for 5 month. The herein presented methodology enables the calculation of the diffuse He/CO2 emission ratio of the entire island during the volcanic unrest. Two different emission peaks for both He and CO2, with approximately the same delay between them ( 23 days), were observed. The combination of both time series resulted in a drastic increase in the He/CO2 emission ratio of the island (up to 1.1×10-3) two weeks before the eruption onset. Additionally, a second significant He/CO2 emission peak (up to 5.5×10-4) was observed between 3 and 4 November, some days before the highest lava emission period. The detailed time series of He/CO2 emission ratio during El Hierro 2011-2012 submarine eruption presented here demonstrate the importance of its continuous monitoring in active volcanic regions, mainly in areas without visible manifestations of volcanic fluid discharges.

Carbon dioxide diffuse emission and thermal energy release from hydrothermal systems at Copahue-Caviahue Volcanic Complex (Argentina)

NASA Astrophysics Data System (ADS)

Chiodini, Giovanni; Cardellini, Carlo; Lamberti, María Clara; Agusto, Mariano; Caselli, Alberto; Liccioli, Caterina; Tamburello, Giancarlo; Tassi, Franco; Vaselli, Orlando; Caliro, Stefano

2015-10-01

The north-western sector of Caviahue caldera (Argentina), close to the active volcanic system of Copahue, is characterized by the presence of several hydrothermal sites that host numerous fumarolic emissions, anomalous soil diffuse degassing of CO2 and hot soils. In March 2014, measurements of soil CO2 fluxes in 5 of these sites (namely, Las Máquinas, Las Maquinitas I, Las Maquinitas II, Anfiteatro, and Termas de Copahue) allowed an estimation that 165 t of deeply derived CO2 is daily released. The gas source is likely related to a relatively shallow geothermal reservoir containing a single vapor phase as also suggested by both the geochemical data from the 3 deep wells drilled in the 1980s and gas geoindicators applied to the fumarolic discharges. Gas equilibria within the H-C-O gas system indicate the presence of a large, probably unique, single phase vapor zone at 200-210 °C feeding the hydrothermal manifestations of Las Máquinas, Las Maquinitas I and II and Termas de Copahue. A natural thermal release of 107 MW was computed by using CO2 as a tracer of the original vapor phase. The magmatic signature of the incondensable fumarolic gases, the wide expanse of the hydrothermal areas and the remarkable high amount of gas and heat released by fluid expulsion seem to be compatible with an active magmatic intrusion beneath this portion of the Caviahue caldera.

Puhimau thermal area: a window into the upper east rift zone of Kilauea Volcano, Hawaii?

USGS Publications Warehouse

McGee, K.A.; Sutton, A.J.; Elias, T.; Doukas, M.P.; Gerlach, T.M.

2006-01-01

We report the results of two soil CO2 efflux surveys by the closed chamber circulation method at the Puhimau thermal area in the upper East Rift Zone (ERZ) of Kilauea volcano, Hawaii. The surveys were undertaken in 1996 and 1998 to constrain how much CO2 might be reaching the ERZ after degassing beneath the summit caldera and whether the Puhimau thermal area might be a significant contributor to the overall CO2 budget of Kilauea. The area was revisited in 2001 to determine the effects of surface disturbance on efflux values by the collar emplacement technique utilized in the earlier surveys. Utilizing a cutoff value of 50 g m−2 d−1 for the surrounding forest background efflux, the CO2 emission rates for the anomaly at Puhimau thermal area were 27 t d−1 in 1996 and 17 t d−1 in 1998. Water vapor was removed before analysis in all cases in order to obtain CO2 values on a dry air basis and mitigate the effect of water vapor dilution on the measurements. It is clear that Puhimau thermal area is not a significant contributor to Kilauea's CO2 output and that most of Kilauea's CO2 (8500 t d−1) is degassed at the summit, leaving only magma with its remaining stored volatiles, such as SO2, for injection down the ERZ. Because of the low CO2 emission rate and the presence of a shallow water table in the upper ERZ that effectively scrubs SO2 and other acid gases, Puhimau thermal area currently does not appear to be generally well suited for observing temporal changes in degassing at Kilauea.

A practical CO2 flux remote sensing technique

NASA Astrophysics Data System (ADS)

Queisser, Manuel; Burton, Mike

2017-04-01

An accurate quantification of CO2 flux from both natural and anthropogenic sources is of great interest in various areas of the Earth, environmental and atmospheric sciences. As emitted excess CO2 quickly dilutes into the 400 ppm ambient CO2 concentration and degassing often occurs diffusively, measuring CO2 fluxes is challenging. Therefore, fluxes are usually derived from grids of in-situ measurements, which are labour intensive measurements. Other than a safe measurement distance, remote sensing offers quick, spatially integrated and thus a more thorough measurement of gas fluxes. Active remote sensing combines these merits with operation independent of sunlight or clear sky conditions. Due to their weight and size, active remote sensing platforms for CO2, such as LIDAR, cannot easily be applied in the field or transported overseas. Moreover, their complexity requires a rather lengthy setup procedure to be undertaken by skilled personal. To meet the need for a rugged, practical CO2 remote sensing technique to scan volcanic plumes, we have developed the CO2 LIDAR. It measures 1-D column densities of CO2 with sufficient sensitivity to reveal the contribution of magmatic CO2. The CO2 LIDAR has been mounted inside a small aircraft and used to measure atmospheric column CO2 concentrations between the aircraft and the ground. It was further employed on the ground, measuring CO2 emissions from mud volcanism. During the measurement campaign the CO2 LIDAR demonstrated reliability, portability, quick set-up time (10 to 15 min) and platform independence. This new technique opens the possibility of rapid, comprehensive surveys of point source, open-vent CO2 emissions, as well as emissions from more diffuse sources such as lakes and fumarole fields. Currently, within the proof-of-concept ERC project CarbSens, a further reduction in size, weight and operational complexity is underway with the goal to commercialize the platform. Areas of potential applications include fugitive CO2 detection at carbon capture and storage sites, volcano monitoring and bottom-up quantification of CO2 fluxes, such as from urban areas or natural sources.

Increasing CO2 flux at Pisciarelli, Campi Flegrei, Italy

NASA Astrophysics Data System (ADS)

Queißer, Manuel; Granieri, Domenico; Burton, Mike; Arzilli, Fabio; Avino, Rosario; Carandente, Antonio

2017-09-01

The Campi Flegrei caldera is located in the metropolitan area of Naples (Italy) and has been undergoing different stages of unrest since 1950, evidenced by episodes of significant ground uplift followed by minor subsidence, increasing and fluctuating emission strengths of water vapor and CO2 from fumaroles, and periodic seismic crises. We deployed a scanning laser remote-sensing spectrometer (LARSS) that measured path-integrated CO2 concentrations in the Pisciarelli area in May 2017. The resulting mean CO2 flux is 578 ± 246 t d-1. Our data suggest a significant increase in CO2 flux at this site since 2015. Together with recent geophysical observations, this suggests a greater contribution of the magmatic source to the degassing and/or an increase in permeability at shallow levels. Thanks to the integrated path soundings, LARSS may help to give representative measurements from large regions containing different CO2 sources, including fumaroles, low-temperature vents, and degassing soils, helping to constrain the contribution of deep gases and their migration mechanisms towards the surface.

Anomalous changes of diffuse CO_{2} emission and seismic activity at Teide volcano, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

García-Hernández, Rubén; Melián, Gladys; D'Auria, Luca; Asensio-Ramos, María; Alonso, Mar; Padilla, Germán D.; Rodríguez, Fátima; Padrón, Eleazar; Barrancos, José; García-Merino, Marta; Amonte, Cecilia; Pérez, Aarón; Calvo, David; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Tenerife (2034 km2) is the largest of the Canary Islands and hosts four main active volcanic edifices: three volcanic rifts and a central volcanic complex, Las Cañadas, which is characterized by the eruption of differentiated magmas. Laying inside Las Cañadas a twin stratovolcanoes system, Pico Viejo and Teide, has been developed. Although there are no visible gas emanations along the volcanic rifts of Tenerife, the existence of a volcanic-hydrothermal system beneath Teide volcano is suggested by the occurrence of a weak fumarolic system, steamy ground and high rates of diffuse CO2 degassing all around the summit cone of Teide. Soil CO2 efflux surveys have been performed at the summit crater of Teide volcano since 1999, to determine the diffuse CO2 emission from the summit crater and to evaluate the temporal variations of CO2 efflux and their relationships with seismic-volcanic activity. Soil CO2 efflux and soil temperature have been always measured at the same 38 observation sites homogeneously distributed within an area of about 6,972 m2 inside the summit crater. Soil CO2 diffuse effluxes were estimated according to the accumulation chamber method by means of a non-dispersive infrared (NDIR) LICOR-820 CO2 analyzer. Historical seismic activity in Tenerife has been characterized by low- to moderate-magnitude events (M <2.5), and most of the earthquake's epicenters have been clustered in an offshore area SE of Tenerife. However, very few earthquakes have occurred in other areas, including Teide volcano. At 12:18 of January 6, 2017, the Canary Seismic Network belonged to the Instituto Volcanológico de Canarias (INVOLCAN) registered an earthquake of M 2.5 located in the vertical of Teide volcano with a depth of 6.6 km. It was the strongest earthquake located inside Cañadas caldera since 2004. Between October 11 and December 13, 2016, a continuous increase on the diffuse CO2 emission was registered, from 21.3 ± 2.0 to 101.7 ± 20.7 t d-1, suggesting the occurrence of future increase in the seismic-volcanic activity. In fact, this precursory signal preceded the occurrence of the 2.5 seismic event and no significant horizontal and vertical displacements were registered by the Canary GPS network belonged to INVOLCAN. This seismic event was probably due to the increase of fluid pressure in the hydrothermal-magmatic system of Tenerife. With the aim of investigate the relationship of the observed temporal variation on diffuse CO2 emission and the seismic event occurred beneath Teide volcano in January 6, 2016, the anomalous peak of diffuse CO2 emission was tested following the Material Failure Forecast Method (FFM). To do so, a Geochemical Window Precursory Signal (GWPS) was selected between October 11 and December 13, 2016. Plotting the inverse of diffuse CO2 emission rate versus time, the interception of the linear fit of the data with the time axis indicates the theoretical moment when seismicity is most likely to occur. Surprisingly, interception of the linear fit occurred for a time window between January 6 and 9, 2017, showing an excellent correlation with the occurrence of the M 2.5 earthquake registered at Teide in January 6, 2017.

Melt fracturing and healing: A mechanism for degassing and origin of silicic obsidian

USGS Publications Warehouse

Cabrera, A.; Weinberg, R.F.; Wright, H.M.N.; Zlotnik, S.; Cas, Ray A.F.

2011-01-01

We present water content transects across a healed fault in pyroclastic obsidian from Lami pumice cone, Lipari, Italy, using synchrotron Fourier transform infrared spectroscopy. Results indicate that rhyolite melt degassed through the fault surface. Transects define a trough of low water content coincident with the fault trace, surrounded on either side by high-water-content plateaus. Plateaus indicate that obsidian on either side of the fault equilibrated at different pressure-temperature (P-T) conditions before being juxtaposed. The curves into the troughs indicate disequilibrium and water loss through diffusion. If we assume constant T, melt equilibrated at pressures differing by 0.74 MPa before juxtaposition, and the fault acted as a low-P permeable path for H2O that diffused from the glass within time scales of 10 and 30 min. Assuming constant P instead, melt on either side could have equilibrated at temperatures differing by as much as 100 ??C, before being brought together. Water content on the fault trace is particularly sensitive to post-healing diffusion. Its preserved value indicates either higher temperature or lower pressure than the surroundings, indicative of shear heating and dynamic decompression. Our results reveal that water contents of obsidian on either side of the faults equilibrated under different P-T conditions and were out of equilibrium with each other when they were juxtaposed due to faulting immediately before the system was quenched. Degassing due to faulting could be linked to cyclical seismic activity and general degassing during silicic volcanic activity, and could be an efficient mechanism of producing low-water-content obsidian. ?? 2011 Geological Society of America.

Carbon isotope and abundance systematics of Icelandic geothermal gases, fluids and subglacial basalts with implications for mantle plume-related CO2 fluxes

NASA Astrophysics Data System (ADS)

Barry, P. H.; Hilton, D. R.; Füri, E.; Halldórsson, S. A.; Grönvold, K.

2014-06-01

We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He-Ne (geothermal) and He-Ne-Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (δ13C), from -18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in δ13C values, from -27.2‰ to -3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low δ13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ∼531 ± 64 ppm CO2 with δ13C values of -2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower δ13C fractionation factor will result in lower source estimates and larger uncertainties associated with the initial δ13C estimate. Degassing can adequately explain low CO2 contents in basalts; however, degassing alone is unlikely to generate the entire spectrum of observed δ13C variations, and we suggest that melt-crust interaction, involving a low δ13C component, may also contribute to observed signatures. Using representative samples, the CO2 flux from Iceland is estimated using three independent methods: (1) combining measured CO2/3He values (in gases and basalts) with 3He flux estimates (Hilton et al., 1990), (2) merging basaltic emplacement rates of Iceland with pre-eruptive magma source estimates of ∼531 ± 64 ppm CO2, and (3) combining fluid CO2 contents with estimated regional fluid discharge rates. These methods yield CO2 flux estimates from of 0.2-23 × 1010 mol a-1, which represent ∼0.1-10% of the estimated global ridge flux (2.2 × 1012 mol a-1; Marty and Tolstikhin, 1998).

Chemical diffusion during isobaric degassing of magma

NASA Astrophysics Data System (ADS)

von Aulock, Felix W.; Kennedy, Ben M.; Lavallée, Yan; Henton-de Angelis, Sarah; Oze, Christopher; Morgan, Daniel J.; Clesham, Steve

2014-05-01

During ascent of magma, volatiles exsolve and bubbles form. Volatiles can either escape through a permeable network of bubbles in an open system or be trapped in non-connected pores during closed system degassing. Geochemical studies have shown that in most cases both- open system and closed system degassing take place at the same time. During cooling of the melt, diffusion slows down and eventually diffusional gradients get frozen in, preserving a history of degassing and rehydration during bubble growth, bubble collapse and crystal growth. We present data from experiments in which natural obsidian was degassed at atmospheric pressures at 950ºC over timescales of 3-24h. During bubble growth, a skin formed, at the outer edge of the sample, effectively prohibiting any degassing of its interior. Diffusion gradients were measured across the glass surrounding vesicles, and across this impermeable skin. Water contents were analyzed with synchrotron sourced Fourier transform infrared spectroscopy and several major, minor and trace elements were mapped using synchrotron sourced X-ray fluorescence spectroscopy. The samples show a dimpled surface, as well as signs of oxidation and growth of submicroscopic crystals. Water contents around bubbles decrease in simple heating experiments (from ~0.13 wt. % down to ~0.1 wt. %), whereas slight rehydration of the vesicle wall can be observed when a second, cooler step at 850ºC follows the initial 950ºC. Water gradients towards the outside of the sample decrease linearly to a minimum of ~0.045 wt. %, far below the solubility of water in melts at these temperatures. We mapped the distribution of K, Ca, Fe, Ti, Mn, Rb, Sr, Y and Zr. Especially the trace elements show a decrease towards the outside of the sample, whereas K, Fe, Ca and Ti generally do not show significant partitioning between melt and gas/crystal phase. Several effects could attribute to the distribution of these elements, such as the crystal growth and exchange with atmospheric oxygen, and detailed models of the diffusion of these elements will have to verify the mechanisms of elemental partitioning during degassing Our experiments show that even on a small scale, open system and closed system degassing inherently coexist. This manifests itself in different elemental distribution in the quenched glass. Water distribution gradients can be explained with diffusion during exsolution and rehydration during cooling, however, the surface of the sample is undersaturated in water. Some trace elements follow the same pattern, even though they might not be considered as volatile. Therefore we suggest that chemical gradients may be partially induced by the growth of sub-microscopic crystals and by exchange with the atmosphere. Crystal rich, volatile poor outer skins, as produced in the experiments of this study, have locally drastically increased viscosities and can therefore withstand higher pressures during foaming of the interior of the sample. This self sealing of magma could be an important process on different scales of magma degassing, from bread crust bombs to rising magma in conduits.

Push from the Pacific

NASA Astrophysics Data System (ADS)

Jaccard, Samuel L.; Galbraith, Eric D.

2018-05-01

Enhanced upwelling and CO2 degassing from the subpolar North Pacific during a warm event 14,000 years ago may have helped keep atmospheric CO2 levels high enough to propel the Earth out of the last ice age.

Degassing procedure for ultrahigh vacuum

NASA Technical Reports Server (NTRS)

Moore, B. C.

1979-01-01

Calculations based on diffusion coefficients and degassing rates for stainless-steel vacuum chambers indicate that baking at lower temperatures for longer periods give lower ultimate pressures than rapid baking at high temperatures. Process could reduce pressures in chambers for particle accelerators, fusion reactors, material research, and other applications.

Regional Groundwater Discharge Drives High Carbon Dioxide Emissions from a Lowland Tropical Rainforest Stream

NASA Astrophysics Data System (ADS)

Oviedo-Vargas, D.; Dierick, D.; Genereux, D. P.; Oberbauer, S. F.; Osburn, C. L.

2015-12-01

Field measurements of carbon (C) fluxes are fundamental for understanding global C cycling, and the C source/sink status of ecosystems. In the tropical rainforest at La Selva Biological Station in Costa Rica, old regional bedrock groundwater (gw) high in dissolved inorganic C discharges into some streams and wetlands with possible impacts on ecosystem C pools and fluxes. We investigated carbon dioxide (CO2) and methane (CH4) degassing from two streams at La Selva: the Arboleda, where ~1/3 of the streamflow is from regional gw, and the Taconazo, fed exclusively by much younger local gw recharged within the catchment. In two reaches (upper and lower) of the Arboleda and Taconazo streams, emissions were determined from tracer injections. In the lower Arboleda (the only reach receiving regional gw) CO2 fluxes (fCO2) averaged 5.5 mol C per m2 of stream surface per day, ~7.5x higher than the average (0.7 mol C m-2 d-1) from the stream reaches with no regional gw inflow (the Taconazo and upper Arboleda). The regional gw inflow had no measurable effect on CH4 emissions. To further understand the dynamics of enhanced CO2 degassing from the lower Arboleda, we examined spatiotemporal patterns in fCO2 using floating chambers. Both static and drifting chambers revealed high spatial heterogeneity in fCO2 at the scale of 5 to 30 m reaches. Temporal trends were highly localized; in two of three subreaches surveyed repeatedly, fCO2 increased with stream discharge and did not differ between wet and dry seasons, but the third subreach showed the opposite behavior. Results from static and drifting chambers deviated 31% and -36%, respectively, from tracer injection results. CO2 degassing from the Arboleda is a large C flux; when averaged over the watershed area it is similar in magnitude to the net ecosystem exchange measured by eddy covariance. Elevated CO2 emissions from the Arboleda stream are consistent with measurements of higher CO2 concentration in the air above the Arboleda stream, and low 14C in plants growing near the Arboleda weir, a zone of high stream gas exchange where geological CO2 low in 14C is degassed from the stream and taken up by riparian plants. The outcomes of this research contribute to the understanding of how catchment connections to underlying hydrogeological systems can affect terrestrial ecosystem C budgets.

Magma surge from the mantle: the Father's Day Eruption, Kīlauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Salem, L. C.; Edmonds, M.; Maclennan, J.; Houghton, B. F.; Poland, M. P.

2015-12-01

The geometry of the shallow plumbing system of Kīlauea Volcano, Hawai'i, is constrained by both geophysical and petrologic studies, yet the loci of lower crustal magma storage and timescales of magma ascent are almost entirely unknown. The petrography and texture of erupted magmas are largely overprinted by processes in the shallow reservoir and conduit. Direct petrological evidence for lower crustal storage and transport is enigmatic but exists in the form of fine-scale crystal zoning in the cores of olivine phenocrysts, in the geochemical heterogeneity of melt inclusions and in fluid inclusion density. The 2007 Father's Day intrusion and eruption occurred at the culmination of a surge in magma supply to the summit reservoir and during a period of heightened CO2 outgassing flux. The erupted lavas provide an opportunity to analyze atypically primitive melts, with > 8.5 wt% MgO in the whole rock, which have undergone relatively little shallow crustal processing. We characterise melt inclusions and their host olivine crystals through a detailed study of olivine morphology, diffusion modelling, and melt and fluid inclusion geochemistry. We show that the melt inclusions preserve primitive geochemical heterogeneity, which we use to reconstruct fractionation, mixing and degassing processes through the crust. We infer timescales and pressures of magma ascent, storage, and CO2 degassing through the crustal plumbing system. These observations are interpreted in the context of the exceptionally detailed set of volcano monitoring data at Kīlauea Volcano.

Diffuse CO_{2} and ^{222}Rn degassing monitoring of Ontake volcano, Japan

NASA Astrophysics Data System (ADS)

Alonso, Mar; Sagiya, Takeshi; Meneses-Gutiérrez, Ángela; Padrón, Eleazar; Hernández, Pedro A.; Pérez, Nemesio M.; Melián, Gladys; Padilla, Germán D.

2017-04-01

Mt. Ontake (3067 m.a.s.l.) is a stratovolcano located in central Honsu and around 100 Km northeast of Nagoya, Japan, with the last eruption occurring on September 27, 2014, killing 57 people, and creating a 7-10 km high ash plume (Kagoshima et. al., 2016). There were no significant earthquakes that might have warned authorities in the lead up to the phreatic eruption, caused by ground water flashing to steam in a hydrothermal explosion. At the time of the eruption there was no operational geochemical surveillance program. In order to contribute to the strengthening of this program, the Disaster Mitigation Research Center of Nagoya University and the Volcanological Institute of Canary Islands started a collaborative program. To do so, an automatic geochemical station was installed at Ontake volcano and a survey of diffuse CO2efflux and other volatiles was carried out at the surface environment of selected areas of the volcano. The station was installed 10.9 km east away from the eruptive vent, where some earthquakes occurred, and consists of a soil radon (Rn) monitor (SARAD RTM-2010-2) able to measure 222Rn and 220Rn activities. Monitoring of radon is an important geochemical tool to forecast earthquakes and volcanic eruptions due to its geochemical properties. Rn ascends from the lower to the upper part of earth's crust mainly through cracks or faults and its transport needs the existence of a naturally occurring flux of a carrier gas. Regarding to the soil gas survey, it was carried out in August 2016 with 183 measurement points performed in an area of 136 km2. Measurements of soil CO2 efflux were carried out following the accumulation chamber method by means of a portable soil CO2 efflux instrument. To estimate the total CO2 output, sequential Gaussian simulation (sGs) was used allowing the interpolation of the measured variable at not-sampled sites and assess the uncertainly of the total diffuse emission of carbon dioxide estimated for the entire studied area. The total emission rate of diffuse CO2 efflux was expressed as the mean value of 100 equiprobable sGs realizations, and its uncertainly was considered as one standard deviation of the 100 emission rates obtained after the sGs procedure. Soil CO2 efflux values ranged from 0.266 gm-2d-1 up to 66.238 gm-2d-1 with an average value of 23.350 gm-2d-1. The estimated average value for the total diffuse CO2 released for the Mt. Ontake volcanic complex during this study was 3,149 ± 98 td-1, with the main contributions arising from the NE zone of the complex. It is expected for future surveys to increase the density of sampling points and to sample the areas near the crater in order to obtain a better approximation of the diffuse CO2 efflux emission as well as obtain a long-term evolution to understand the dynamics of diffuse CO2 emission and its relationship with the volcanic activity of Mt. Ontake.

Quantification of carbon dioxide emissions of Ciomadul, the youngest volcano of the Carpathian-Pannonian Region (Eastern-Central Europe, Romania)

NASA Astrophysics Data System (ADS)

Kis, Boglárka-Mercédesz; Ionescu, Artur; Cardellini, Carlo; Harangi, Szabolcs; Baciu, Călin; Caracausi, Antonio; Viveiros, Fátima

2017-07-01

We provide the first high-resolution CO2 flux data for the Neogene to Quaternary volcanic regions of the entire Carpathian-Pannonian Region, Eastern-Central Europe, and estimate the CO2 emission of the seemingly inactive Ciomadul volcanic complex, the youngest volcano of this area. Our estimate includes data from focused and diffuse CO2 emissions from soil. The CO2 fluxes of focused emissions range between 277 and 8172 g d- 1, corresponding to a CO2 output into the atmosphere between 0.1 and 2.98 t per year. The investigated areas for diffuse soil gas emissions were characterized by wide range of CO2 flux values, at Apor Baths, ranging from 1.7 × 101 to 8.2 × 104 g m- 2 d- 1, while at Lăzărești ranging between 1.43 and 3.8 × 104 g m- 2 d- 1. The highest CO2 focused gas fluxes at Ciomadul were found at the periphery of the youngest volcanic complex, which could be explained either by tectonic control across the brittle older volcanic edifices or by degassing from a deeper crustal zone resulting in CO2 flux at the periphery of the supposed melt-bearing magma body beneath Ciomadul. The estimate of the total CO2 output in the area is 8.70 × 103 t y- 1, and it is consistent with other long (> 10 kyr) dormant volcanoes with similar age worldwide, such as in Italy and USA. Taking into account the isotopic composition of the gases that indicate deep origin of the CO2 emissions, this yields further support that Ciomadul may be considered indeed a dormant, or PAMS volcano (volcano with potentially active magma storage) rather than an inactive one. Furthermore, hazard of CO2 outpourings has to be taken into account and it has to be communicated to the visitors. Finally, we suggest that CO2 output of dormant volcanic systems has to be also accounted in the estimation of the global volcanic CO2 budget.

Geochemical exploration of a promissory Enhanced Geothermal System (EGS): the Acoculco caldera, Mexico.

NASA Astrophysics Data System (ADS)

Peiffer, Loic; Romero, Ruben Bernard; Pérez-Zarate, Daniel; Guevara, Mirna; Santoyo Gutiérrez, Edgar

2014-05-01

The Acoculco caldera (Puebla, Mexico) has been identified by the Mexican Federal Electricity Company (in Spanish 'Comisión Federal de Electricidad', CFE) as a potential Enhanced Geothermal System (EGS) candidate. Two exploration wells were drilled and promising temperatures of ~300° C have been measured at a depth of 2000 m with a geothermal gradient of 11oC/100m, which is three times higher than the baseline gradient measured within the Trans-Mexican Volcanic Belt. As usually observed in Hot Dry Rock systems, thermal manifestations in surface are scarce and consist in low-temperature bubbling springs and soil degassing. The goals of this study were to identify the origin of these fluids, to estimate the soil degassing rate and to explore new areas for a future detailed exploration and drilling activities. Water and gas samples were collected for chemical and isotopic analysis (δ18O, δD, 3He/4He, 13C, 15N) and a multi-gas (CO2, CH4, H2S) soil survey was carried out using the accumulation chamber method. Springs' compositions indicate a meteoric origin and the dissolution of CO2 and H2S-rich gases, while gas compositions reveal a MORB-type origin mixed with some arc-type contribution. Gas geothermometry results are similar to temperatures measured during well drilling (260° C-300° C). Amongst all measured CO2 fluxes, only 5% (mean: 5543 g m-2 day-1) show typical geothermal values, while the remaining fluxes are low and correspond to biogenic degassing (mean: 18 g m-2 day-1). The low degassing rate of the geothermal system is a consequence of the intense hydrothermal alteration observed in the upper 800 m of the system which acts as an impermeable caprock. Highest measured CO2 fluxes (above > 600 g m-2 day-1) have corresponding CH4/CO2 flux ratios similar to mass ratios of sampled gases, which suggest an advective fluid transport. To represent field conditions, a numerical model was also applied to simulate the migration of CO2 towards the surface through a shallow aquifer under fully saturated conditions. By changing some of the aquifer properties (i.e., depth, permeability and porosity), it was found how geothermal CO2 fluxes can show values similar to a biogenic background flux. Future field work at Acoculco will include δ13C analysis together with soil flux measurements for a better discrimination of the degassing origin, and a thinner flux measurement grid will be defined for a better detection of any possible gas flux anomaly.

Atmospheric contribution of gas emissions from Augustine volcano, Alaska during the 2006 eruption

USGS Publications Warehouse

McGee, K.A.; Doukas, M.P.; McGimsey, R.G.; Neal, C.A.; Wessels, R.L.

2008-01-01

Airborne surveillance of gas emissions from Augustine for SO2, CO2 and H2S showed no evidence of anomalous degassing from 1990 through May 2005. By December 20, 2005, Augustine was degassing 660 td-1 of SO2, and ten times that by January 4, 2006. The highest SO2 emission rate measured during the 2006 eruption was 8650 td-1 (March 1); for CO2, 13000 td-1 (March 9), and H2S, 8 td-1 (January 19). Thirty-four SO2 measurements were made from December 2005 through 2006, with 9 each for CO2 and H2S. Augustine released 1 ?? 106 tonnes of CO2 to the atmosphere during 2006, a level similar to the output of a medium-sized natural gas-fired power plant, and thus was not a significant contributor of greenhouse gas to the atmosphere compared to anthropogenic sources. Augustine released about 5 ?? 105 tonnes of SO2 during 2006, similar to that released in 1976 and 1986.

Three-year decline of magmatic CO2 emissions from soils of a Mammoth Mountain tree kill: Horseshoe Lake, CA, 1995-1997

USGS Publications Warehouse

Gerlach, T.M.; Doukas, M.P.; McGee, K.A.; Kessler, R.

1998-01-01

We used the closed chamber method to measure soil CO2 efflux over a three-year period at the Horseshoe Lake tree kill (HLTK) - the largest tree kill on Mammoth Mountain in central eastern California. Efflux contour maps show a significant decline in the areas and rates of CO2 emission from 1995 to 1997. The emission rate fell from 350 t d-1 (metric tons per day) in 1995 to 130 t d-1 in 1997. The trend suggests a return to background soil CO2 efflux levels by early to mid 1999 and may reflect exhaustion of CO2 in a deep reservoir of accumulated gas and/or mechanical closure or sealing of fault conduits transmitting gas to the surface. However, emissions rose to 220 t d-1 on 23 September 1997 at the onset of a degassing event that lasted until 5 December 1997. Recent reservoir recharge and/or extension-enhanced gas flow may have caused the degassing event.

Sea level fall during glaciation stabilized atmospheric CO2 by enhanced volcanic degassing

PubMed Central

Hasenclever, Jörg; Knorr, Gregor; Rüpke, Lars H.; Köhler, Peter; Morgan, Jason; Garofalo, Kristin; Barker, Stephen; Lohmann, Gerrit; Hall, Ian R.

2017-01-01

Paleo-climate records and geodynamic modelling indicate the existence of complex interactions between glacial sea level changes, volcanic degassing and atmospheric CO2, which may have modulated the climate system’s descent into the last ice age. Between ∼85 and 70 kyr ago, during an interval of decreasing axial tilt, the orbital component in global temperature records gradually declined, while atmospheric CO2, instead of continuing its long-term correlation with Antarctic temperature, remained relatively stable. Here, based on novel global geodynamic models and the joint interpretation of paleo-proxy data as well as biogeochemical simulations, we show that a sea level fall in this interval caused enhanced pressure-release melting in the uppermost mantle, which may have induced a surge in magma and CO2 fluxes from mid-ocean ridges and oceanic hotspot volcanoes. Our results reveal a hitherto unrecognized negative feedback between glaciation and atmospheric CO2 predominantly controlled by marine volcanism on multi-millennial timescales of ∼5,000–15,000 years. PMID:28681844

Recent observations of carbon and sulfur gas emissions from Tavurvur, Bagana and Ulawun (Papua New Guinea) with a combination of ground- and air-borne direct and remote sensing techniques

NASA Astrophysics Data System (ADS)

Arellano, Santiago; Galle, Bo; Mulina, Kila; Wallius, Julia; McCormick, Brendan; Salem, Lois; D'aleo, Roberto; Itikarai, Ima; Tirpitz, Lukas; Bobrowski, Nicole; Aiuppa, Alessandro

2017-04-01

Satellite observations reveal that volcanoes from Papua New Guinea contributed with ca. 15{%} of the global emission of volcanic sulfur dioxide (SO2) during the period 2005-2014. Relatively little is known about their carbon dioxide (CO2) outputs and more recent levels and dynamics of degassing activity. During September 2016 we conducted measurements of the CO2/SO2 ratio and the SO2 flux from Tavurvur, Bagana and Ulawun volcanoes using a combination of remote sensing and direct sampling techniques. Tavurvur exhibits low-level passive degassing from a modestly active vent and few other intra-crater fumaroles, which made access possible for direct measurements of the CO2/SO2 ratio with a compact Multi-GAS instrument. A wide-field of view pointing DOAS monitor was deployed for longer term monitoring of the SO2 flux from a distance of about 2 km. Bagana degasses continuously with occasional emissions of ash, and its SO2 flux, plume velocity and height was constrained by simultaneous scanning and dual-beam DOAS measurements. Molar ratios in the plume of Bagana were measured by the compact Multi-GAS aboard a multi-rotor UAV, up to a height of 1.6 km above ground. Ulawun showed continuous passive degassing and measurements with the UAV, up to an altitude of ca. 1.8 km, and mobile-DOAS traverses from a car were used to constrain its gas emission. Here we present an overview of the challenging conditions, measurement strategies and results of this campaign that forms part of the ongoing international effort DECADE aiming to better quantify the global gas emission of carbon- and sulfur containing species from volcanoes.

Pinatubo Lake Chemistry and Degassing 1991-2010

NASA Astrophysics Data System (ADS)

Schwandner, F. M.; Newhall, C. G.; Christenson, B. W.; Apfelbeck, C. A.; Arpa, M. C. B.; Vaquilar, R.; Bariso, E.

2016-12-01

We review the history of degassing, bathymetry and water chemistry of the crater lake of Mt. Pinatubo (Philippines) using data obtained during 1991-2001, and 2010. In late 1992, the initial small lake had a significant acid-sulfate component from a volcanic degassing through a hydrothermal system and the lake, and anhydrite dissolution. Subsequently, this component was "drowned" by rainfall (2-4 m/y), meteoric groundwater draining from the crater walls into the lake, and a few neutral chloride crater wall springs. Conductivity-Temperature-Depth (CTD) measurements in August 2000 found a strong inverted thermal gradient below 20m depth, reaching over 70°C at 50-60 m depth. By January 2001 the lake had homogenized and was much cooler (27°C at all depths), and it was again well-mixed and still cool when re-surveyed in June 2001 and November 2010. By 2010, the lake was well mixed, at neutral pH, with no significant vertical or horizontal structure. Bubbling of a predominantly carbon dioxide (CO2) gas phase persists throughout the lake's history, some from 1991-92 magma and some from degassing of the long-standing (pre-1991) hydrothermal system fed from a deeper magmatic or mantle source. Crater wall fumaroles emit boiling-point hydrothermal gases dominated by water, air, and CO2.

Carbon dioxide and hydrogen sulfide degassing and cryptic thermal input to Brimstone Basin, Yellowstone National Park, Wyoming

USGS Publications Warehouse

Bergfeld, D.; Evans, William C.; Lowenstern, J. B.; Hurwitz, S.

2012-01-01

Brimstone Basin, a remote area of intense hydrothermal alteration a few km east of the Yellowstone Caldera, is rarely studied and has long been considered to be a cold remnant of an ancient hydrothermal system. A field campaign in 2008 confirmed that gas emissions from the few small vents were cold and that soil temperatures in the altered area were at background levels. Geochemical and isotopic evidence from gas samples (3He/4He ~ 3RA, δ13C-CO2 ~ − 3‰) however, indicate continuing magmatic gas input to the system. Accumulation chamber measurements revealed a surprisingly large diffuse flux of CO2 (~ 277 t d-1) and H2S (0.6 t d-1). The flux of CO2 reduces the 18O content of the overlying cold groundwater and related stream waters relative to normal meteoric waters. Simple isotopic modeling reveals that the CO2 likely originates from geothermal water at a temperature of 93 ± 19 °C. These results and the presence of thermogenic hydrocarbons (C1:C2 ~ 100 and δ13C-CH4 = − 46.4 to − 42.8‰) in gases require some heat source at depth and refute the assumption that this is a “fossil” hydrothermal system.

Comparison of Spring and Cave Drip Water in Westcave Preserve, Central Texas May Reveal Epikarst CO2 Degassing

NASA Astrophysics Data System (ADS)

Carlson, P.; Banner, J. L.; Casteel, R. C.; Breecker, D.

2013-12-01

The cave at Westcave Preserve, in central Texas, is a unique location to study karst processes due to its low, nearly atmospheric cave-air CO2 levels and seasonally variable temperature. The source of water that drips into the cave, however, has not been constrained, limiting interpretation of climate proxies in the cave. It is possible that a nearby spring and the cave drip-waters share a common source. Alternatively, the drip-waters could represent precipitation that has infiltrated the host rock. These hypotheses should be tested using Sr isotope ratios and/or other tracers. If they do share a common source, analysis of dissolved inorganic carbon (DIC) concentration , δ13CDIC, and cation concentrations of the two waters could provide insight into epikarst processes such as CO2 degassing and prior calcite precipitation (PCP) that are otherwise difficult to constrain. Westcave Preserve includes outcrops of the Hensell Sand, the Cow Creek Limestone, and the Hammett Shale, with a small cave at the contact between the Cow Creek and Hammett formations. The overlying Hensell Sand contains water that emerges at the surface as a spring near the cave. Water also drips directly into the cave, forming speleothems. Previous research has established that although δ18O values of rainfall in the area vary seasonally, between -10.5 and 1.1‰ with a weighted mean of -6.5‰ (VSMOW), the drip-water varies only between -4.7 and -4.3‰ with a weighted mean of -4.5‰ (Feng et al., in review). This suggests a large well-mixed reservoir above the cave. The soils above the cave have high CO2 of up to 17,500 ppmv, but because the cave is shallow with multiple large openings, cave CO2 levels are near-atmospheric (Casteel and Banner, in review). This creates a steep CO2 gradient between the soil and the cave air. The spring water DIC is nearly in carbon-isotope equilibrium with the soil CO2, suggesting that soil respiration, here controlled by C3 plants, is the primary source of CO2 for this reservoir. The drip water δ13CDIC is higher than the spring water (-10.3‰ versus -13.0‰). Although the spring water has higher DIC concentration than the drip water, with mean values of 128 mg/L C versus 113 mg/L C, respectively, preliminary data suggest that for some drips, the drip water DIC concentrations and δ13CDIC may vary with spring DIC values. We propose that if the spring and the drip water prove to be derived from the same source, the differences in DIC and δ13CDIC between spring and drip water are due to epikarst CO2 degassing as the water percolates down the CO2 gradient toward the cave ceiling. If the spring represents the source of the drip water, the calculated δ13 value of degassed CO2 is -33.3‰, assuming no PCP. PCP may occur, leading to a δ13C of degassed CO2 lower than calculated, but would result in a decrease or no change in δ13CDIC and therefore does not explain the observed difference between spring water and drip water.

Open-path FTIR spectroscopy of magma degassing processes during eight lava fountains on Mount Etna

NASA Astrophysics Data System (ADS)

La Spina, Alessandro; Burton, Mike; Allard, Patrick; Alparone, Salvatore; Murè, Filippo

2016-04-01

In June-July 2001 a series of 16 discrete lava fountain paroxysms occurred at the Southeast summit crater (SEC) of Mount Etna, preceding a 28-day long violent flank eruption. Each paroxysm was preceded by lava effusion, growing seismic tremor and a crescendo of Strombolian explosive activity culminating into powerful lava fountaining up to 500m in height. During 8 of these 16 events we could measure the chemical composition of the magmatic gas phase (H2O, CO2, SO2, HCl, HF and CO), using open-path Fourier transform infrared (OP-FTIR) spectrometry at ˜1-2km distance from SEC and absorption spectra of the radiation emitted by hot lava fragments. We show that each fountaining episode was characterized by increasingly CO2-rich gas release, with CO2/SO2and CO2/HCl ratios peaking in coincidence with maxima in seismic tremor and fountain height, whilst the SO2/HCl ratio showed a weak inverse relationship with respect to eruption intensity. Moreover, peak values in both CO2/SO2ratio and seismic tremor amplitude for each paroxysm were found to increase linearly in proportion with the repose interval (2-6 days) between lava fountains. These observations, together with a model of volatile degassing at Etna, support the following driving process. Prior to and during the June-July 2001 lava fountain sequence, the shallow (˜2km) magma reservoir feeding SEC received an increasing influx of deeply derived carbon dioxide, likely promoted by the deep ascent of volatile-rich primitive basalt that produced the subsequent flank eruption. This CO2-rich gas supply led to gas accumulation and overpressure in SEC reservoir, generating a bubble foam layer whose periodical collapse powered the successive fountaining events. The anti-correlation between SO2/HCl and eruption intensity is best explained by enhanced syn-eruptive degassing of chlorine from finer particles produced during more intense magma fragmentation.

Volcanic volatile budgets and fluxes inferred from melt inclusions from post-shield volcanoes in Hawaii and the Canary Islands

NASA Astrophysics Data System (ADS)

Moore, L.; Gazel, E.; Bodnar, R. J.; Carracedo, J. C.

2017-12-01

Pre-eruptive volatile contents of volcanic melts recorded by melt inclusions are useful for estimating rates of deep earth ingassing and outgassing on geologic timescales. Ocean island volcanoes may erupt melts derived from recycled material and thus have implications regarding the degree to which volatile-bearing phases like magnesite can survive subduction and be recycled by intraplate magmatism. However, melt inclusions affected by degassing will not reflect the original volatile content of the primary melt. Post-shield ocean island volcanoes are thought to erupt volatile-rich melts that ascend quickly, crystallizing in deep reservoirs and are more likely to reflect the composition of the primary melt. In this study, we compare melt inclusions from post-shield volcanoes, Haleakala (East Maui, Hawaii) and Tenerife (Canary Islands), to estimate the volatile budgets of two presumably plume-related ocean-island settings. Melt inclusions from Haleakala contain up to 1.5 wt% CO2, up to 1.3 wt% H2O, and about 2000 ppm of S. The CO2 concentration is similar to estimates for primary CO2 concentrations for Hawaii, suggesting that the melt inclusions in this study trapped a melt that underwent minimal degassing. Assuming a melt production rate of 2 km3/ka for postshield Hawaiian volcanism, the average fluxes of CO2 and S are about 80 t/year and 10 t/year respectively. Melt inclusions from Tenerife contain up to 1 wt% CO2, up to 2 wt% H2O, and about 4000 ppm of S. Assuming a melt production rate of 0.8 km3/ka for the northeast rift zone of Tenerife, the average fluxes of CO2 and S are about 20 t/year and 8 t/year respectively. The concentration of CO2 is lower than estimates of the primary melt CO2 content based on CO2/Nb from El Hierro. This may indicate that the inclusions trapped a melt that had degassed significantly, or that some of the CO2 in the inclusions has been sequestered in carbonate daughter crystals, which were observed in abundance.

CO2 Degassing at Kilauea Volcano: Implications for Primary Magma, Summit Reservoir Dynamics, and Magma Supply Monitoring

NASA Astrophysics Data System (ADS)

Gerlach, T. M.; McGee, K. A.; Elias, T.; Sutton, A. J.; Doukas, M. P.

2001-12-01

We report a new CO2 emission rate of 8,500 tons/day (t/d) for the summit of Kilauea Volcano, a result several times larger than previous estimates. It is based on 12 experiments on three occasions over four years constraining the SO2 emission rate and the average CO2/SO2 of emissions along the 5.4-km summit COSPEC traverse (by COSPEC, NDIR CO2 analyzer, and CP-FTIR). The core of the summit plume is at ground level along the traverse and gives average CO2/SO2 values that are representative of the overall summit emission, even though CO2 and SO2 variations are commonly uncorrelated. CO2 and SO2 concentrations exceed background by 200-1,000 ppm and 1-7 ppm respectively. Nighttime measurements exclude Park auto exhaust as a source of CO2. The summit CO2 emission rate is nearly constant (95% confidence interval = 300 t/d), despite variable summit SO2 emission rates (62-240 t/d) and CO2/SO2 (54-183). Including other known CO2 emissions on the volcano (mainly from the Pu`u `O`o eruption) gives a total emission rate of about 8,800 t/d. Thus summit CO2 emissions comprise 97% of the total known CO2 output, consistent with the hypothesis that all primary magma supplied to Kilauea arrives under the summit caldera and is thoroughly degassed of excess CO2. A persistent large CO2 anomaly of 200-1,000 ppm indicates the entry to the summit reservoir is beneath a km2-area east of Halemaumau. The bulk CO2 content of primary magma is about 0.70 wt%, inferred from the CO2 emission rate and Kilauea's magma supply rate (0.18 km3/y [Cayol et al., Science, 288, 2343, 2000]). Most of the CO2 is present as exsolved vapor (3.6-11.7 vol%) at summit reservoir depths (2-7 km), making the primary magma strongly buoyant. Magma chamber replenishment models show that robust turbulent mixing of primary and reservoir magma prevents frequent eruption of buoyant primary magma in the summit region. The escape of 90-95% of the CO2 from the summit reservoir provides a potential proxy for monitoring the magma supply rate. Streaming CO2-rich vapor causes fractional degassing of H2O and SO2 from reservoir magma, but scrubbing minimizes summit SO2 emissions.

Redox change during magma ascent; Observation from three volcanoes and implication for gas monitoring

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Oppenheimer, Clive; Schipper, Ian C.; Hartley, Magaret; Scaillet, Bruno; Gaillard, Fabrice; Peters, Nial; Kyle, Phil

2015-04-01

The oxidation state of volcanic gases dictates their speciation and hence their reactivity in the atmosphere. It has become increasingly recognized that the oxidation state of a magma can be strongly affected by degassing. The oxidation state of gases will equally be impacted and the composition of gases emitted by volcanoes will therefore be function of the magma degassing history. This presentation will show results from three volcanoes where the oxidation state of the magma has been tracked during degassing. At Erebus and Laki we used Fe X-ray absorption near-edge structure spectroscopy (XANES) on extensive suites of melt inclusions and glasses, while at Surtsey we used S-Kα peak shifts measurements by electron microprobe (EPMA) on melt inclusions, embayment and glasses. At all three locations we found that a strong reduction of both Fe and S is associated with magma ascent. At Erebus this reduction is greatest, corresponding to a fall in magmatic fO2 of more than two log units. We propose that sulfur degassing can explain the observed evolution of the redox state with ascent and show that forward modeling using initial melt composition can successfully predict the composition of the gas phase measured at the surface. We suggest that the redox state of volcanic gases (expressed in term of redox couples: H2O/H2, SO2/H2S and CO2/CO) can be used to monitor the depth of gas-melt segregation at active volcanoes.

Degassing vs. eruptive styles at Mt. Etna volcano (Sicily, Italy): Volatile stocking, gas fluxing, and the shift from low-energy to highly-explosive basaltic eruptions

NASA Astrophysics Data System (ADS)

Moretti, Roberto; Métrich, Nicole; Di Renzo, Valeria; Aiuppa, Alessandro; Allard, Patrick; Arienzo, Ilenia

2017-04-01

Basaltic magmas can transport and release large amounts of volatiles into the atmosphere, especially in subduction zones, where slab-derived fluids enrich the mantle wedge. Depending on magma volatile content, basaltic volcanoes thus display a wide spectrum of eruptive styles, from common Strombolian-type activity to Plinian events. Mt. Etna in Sicily, is a typical basaltic volcano where the volatile control on such a variable activity can be investigated. Based on a melt inclusion study in products from Strombolian or lava-fountain activity to Plinian eruptions, here we show that for the same initial volatile content, different eruptive styles reflect variable degassing paths throughout the composite Etnean plumbing system. The combined influence of i) crystallization, ii) deep degassing and iii) CO2 gas fluxing can explain the evolution of H2O, CO2, S and Cl in products from such a spectrum of activity. Deep crystallization produces the CO2-rich gas fluxing the upward magma portions, which will become buoyant and easily mobilized in small gas-rich batches stored within the plumbing system. When reaching gas dominated conditions (i.e., a gas/melt mass ratio of 0.3 and CO2,gas/H2Ogas molar ratio 5 ), these will erupt effusively or mildly explosively, whilst in case of the 122 BC Plinian eruption, open-system degassing conditions took place within the plumbing system, such that continuous CO2-fluxing determined gas accumulation on top of the magmatic system. The emission of such a cap in the early eruptive phase triggered the arrival of deep H2O-rich whose fast decompression and bubble nucleation lead to the highly explosive character, enhanced by abundant microlite crystallization and consequent increase of magma effective viscosity. This could explain why open system basaltic systems like Etna may experience highly explosive or even Plinian episodes during eruptions that start with effusive to mildly explosive phases. The proposed mechanism also determines a depression of chlorine contents in CO2-fluxed (and less explosive) magmas with respect to those feeding Plinian events like 122 BC one. The opposite is seen for sulfur: low to mild-explosive fluxed magmas are S-enriched, whereas the 122 BC Plinian products are relatively S-poor, likely because of early sulfide separation accompanying magma crystallization. The proposed mechanism involving CO2 separation and fluxing may suggest a subordinate role for variable mixing of different sources having different degrees of K-enrichment. However, such a mechanism requires further experimental studies about the effects on S and Cl dissolution and does not exclude self-mixing between degassed and undegassed batches within the Etna plumbing system. Finally, our findings may represent a new interpretative tool for the geochemical and petrological monitoring of plume gas discharges and melt inclusions, and allow tracking the switch from mild-explosive to highly explosive or even Plinian events at Etna.

Constraints on magma processes, subsurface conditions, and total volatile flux at Bezymianny Volcano in 2007–2010 from direct and remote volcanic gas measurements

USGS Publications Warehouse

Lopez, Taryn; Ushakov, Sergey; Izbekov, Pavel; Tassi, Franco; Cahill, Cathy; Neill, Owen; Werner, Cynthia A.

2013-01-01

Direct and remote measurements of volcanic gas composition, SO2 flux, and eruptive SO2 mass from Bezymianny Volcano were acquired between July 2007 and July 2010. Chemical composition of fumarolic gases, plume SO2 flux from ground and air-based ultraviolet remote sensing (FLYSPEC), and eruptive SO2 mass from Ozone Monitoring Instrument (OMI) satellite observations were used along with eruption timing to elucidate magma processes and subsurface conditions, and to constrain total volatile flux. Bezymianny Volcano had five explosive magmatic eruptions between May 2007 and June 2010. The most complete volcanic gas datasets were acquired for the October 2007, December 2009, and May 2010 eruptions. Gas measurements collected prior to the October 2007 eruption have a relatively high ratio of H2O/CO2 (81.2), a moderate ratio of CO2/S (5.47), and a low ratio of S/HCl (0.338), along with moderate SO2 and CO2 fluxes of 280 and 980 t/d, respectively, and high H2O and HCl fluxes of ~ 45,000 and ~ 440 t/d, respectively. These results suggest degassing of shallow magma (consistent with observations of lava extrusion) along with potential minor degassing of a deeper magma source. Gas measurements collected prior to the December 2009 eruption are characterized by relatively low H2O/CO2 (4.13), moderate CO2/S (6.84), and high S/HCl (18.7) ratios, along with moderate SO2 and CO2 fluxes of ~ 220 and ~ 1000 t/d, respectively, and low H2O and HCl fluxes of ~ 1700 and ~ 7 t/d, respectively. These trends are consistent with degassing of a deeper magma source. Fumarole samples collected ~ 1.5 months following the May 2010 eruption are characterized by high H2O/CO2 (63.0), low CO2/S (0.986), and moderate S/HCl (6.09) ratios. These data are consistent with degassing of a shallow, volatile-rich magma source, likely related to the May eruption. Passive and eruptive SO2 measurements are used to calculate a total annual SO2 mass of 109 kt emitted in 2007, with passive emissions comprising ~ 87–95% of the total. Total annual volatile masses for the study period are estimated to range from 1.1 × 106 to 18 × 106 t/year. Annual CO2 masses are ~ 8 to 40 times larger than can be explained by degassing of dissolved CO2 within eruptive magma, suggesting that the eruptive magma contained a significant quantity of exsolved volatiles sourced either from the eruptive melt or unerupted magma at depth. Variable total volatile fluxes ranging from ~ 3000 t/d in 2009 to ~ 49,000 t/d in 2007 are attributed to variations in the depth of gas exsolution and separation from the melt under open-system degassing conditions. We propose that exsolved volatiles are quickly transported to the surface from ascending magma via permeable flow through a bubble and/or fracture network within the conduit and thus retain their equilibrium composition at the time of segregation from melt. The composition of surface CO2 and H2O emissions from 2007 to 2009 are compared with modeled exsolved fluid compositions for a magma body ascending from entrapment depths to estimate depth of fluid exsolution and separation from the melt. We find that at the time of sample collection magma had already begun ascent from the mid-crustal storage region and was located at maximum depths of ~ 3.7 km in August 2007, approximately 2 months prior to the next magmatic eruption, and ~ 4.6 km in July of 2009 approximately five months prior to the next magmatic eruption. These findings suggest that the exsolved gas composition at Bezymianny Volcano may be used to detect magma ascent prior to eruption.

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high-frequency gas monitoring.

PubMed

de Moor, J Maarten; Aiuppa, A; Avard, G; Wehrmann, H; Dunbar, N; Muller, C; Tamburello, G; Giudice, G; Liuzzo, M; Moretti, R; Conde, V; Galle, B

2016-08-01

Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high-frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO 2 -rich gas (CO 2 /S total  > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur-rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8-10 km deep, whereas the shallow magmatic gas source is at ~3-5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H 2 S/SO 2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO 2 and H 2 S/SO 2  > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H 2 S/SO 2  < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high-temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity.

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high‐frequency gas monitoring

PubMed Central

Aiuppa, A.; Avard, G.; Wehrmann, H.; Dunbar, N.; Muller, C.; Tamburello, G.; Giudice, G.; Liuzzo, M.; Moretti, R.; Conde, V.; Galle, B.

2016-01-01

Abstract Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high‐frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2‐rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur‐rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8–10 km deep, whereas the shallow magmatic gas source is at ~3–5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high‐temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity. PMID:27774371

Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high-frequency gas monitoring

NASA Astrophysics Data System (ADS)

de Moor, J. Maarten; Aiuppa, A.; Avard, G.; Wehrmann, H.; Dunbar, N.; Muller, C.; Tamburello, G.; Giudice, G.; Liuzzo, M.; Moretti, R.; Conde, V.; Galle, B.

2016-08-01

Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high-frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2-rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur-rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is 8-10 km deep, whereas the shallow magmatic gas source is at 3-5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high-temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity.

Testing Binary Mixing Models for Lavas Erupted Along the Reykjanes Ridge: Insights From C-He Relationships

NASA Astrophysics Data System (ADS)

de Leeuw, G. A.; Hilton, D. R.; Shaw, A. M.; Murton, B. J.; Taylor, R. N.

2002-12-01

We report new CO2 abundance and isotope data for 36 basalt glasses erupted along the Reykjanes Ridge between latitudes 57.5 and 63°N. Lavas can be divided into (a) water-rich samples (~0.4 wt.%), erupted at depths < 775m north of 61.5°N, and (b) samples with water ~ 0.2 wt.%, erupted at depths of 620 - 2060 m and located between 57.5 and 61.5°N. Based upon He-Pb isotope systematics (Hilton et al., EPSL, 2000), deeper samples (category b) lie along binary mixing trajectories between plume-like (3He/4He ~ 30RA; 206Pb/204Pb ~ 18.7) and MORB-like endmembers (3He/4He ~ 8RA; 206Pb/204Pb ~ 18.0). Shallow samples (category a) do not fall on mixing trajectories: consistent with volatile loss followed by addition of a crustal contaminant, resulting in lower 3He/4He ratios. The aim of this study is to test whether binary mixing trends are observed using C-He relationships. All samples were analyzed using incremental heating techniques which allows for resolution of vesicle-sited CO2 from CO2 dissolved within the glass matrix. Results show that samples north of 61.5 °N (category a) have low CO2 contents in both the vesicle (2-37 ppm) and dissolved (15-61 ppm) phases. The isotopic composition of the CO2 varies between -8 and -34‰ (vesicle) and -6 and -10‰ (glass). The combined effect of low CO2 concentrations and low δ13C values are consistent with extensive gas loss +/- contamination of volatile-poor magmas with an isotopically-light C component. In contrast, samples in category b have significantly higher CO2 abundances (vesicles: 7-318 ppm; glass: 9-200 ppm) and higher and less variable δ13C values (vesicles: -5 to -26‰ ; glass: -4 to -11‰ ). This suggests that category b samples have not been subjected to the same degree of degassing and/or contamination as samples in category a. By combining the vesicle-sited CO2 abundances with He-contents determined by crushing (Hilton, op. cit), CO2/3He ratios for the vesicle phase can be derived. We observe high ratios (3x109 to 2x1010) in the more degassed category a samples. Category b CO2/3He ratios show a trend from low CO2/3He values (3x108) and MORB-like 206Pb/204Pb to high CO2/3He values (up to 2x1010) and more radiogenic 206Pb/204Pb. There are two possible explanations for the observed trends: 1) degassing followed by contamination with a high CO2/3He crustal component. This process controls C-He relationships in low concentration (highly degassed) samples close to Iceland. 2) mixing between a MORB-like source (CO2/3He ~ 2x109) and an enriched source with a higher initial CO2/3He value. This process controls samples in category b.

No effect of H2O degassing on the oxidation state of magmatic liquids

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2016-08-01

The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

Abundance and isotope systematics of carbon in subglacial basalts, geothermal gases and fluids from Iceland's rift zones

NASA Astrophysics Data System (ADS)

Barry, P. H.; Hilton, D. R.; Fueri, E.; Halldorsson, S. A.; Fischer, T. P.; Gronvold, K.

2010-12-01

P. H. BARRY1*, D. R. HILTON1, E. FÜRI1, S.A. HALLDÓRSON1, T.P. FISCHER2, K. GRONVOLD3 1 Scripps Institution of Oceanography, UCSD, La Jolla, California 92093, USA (*Correspondence: pbarry@ucsd.edu). 2University of New Mexico, Albuquerque, NM 87131, USA. 3University of Iceland, Askja, Sturlugata 7, IS-101, Reykjavik, Iceland Carbon dioxide (CO2) is the dominant non-aqueous volatile species found in oceanic basalts and geothermal fluids and serves as the carrier gas for trace volatiles such as He and other noble gases. The aim of this study is to identify the superimposed effects of degassing and crustal contamination on the CO2 systematics of the Icelandic hotspot in order to reveal and characterize the carbon abundance and isotopic features of the underlying mantle source. Our approach involves coupling CO2 with He, utilizing the sensitivity of 3He/4He ratios to reveal mantle and crustal inputs. We report new C-isotope (δ13C) and abundance characteristics for a suite of 47 subglacial basalts and 50 geothermal gases and fluids from Iceland. CO2 contents in hyaloclastite glasses are extremely low (10-100 ppm) and likely residual following extensive degassing whereas geothermal fluids are dominated by CO2 (>90 %). C-isotopes range from -27.2 to -3.6 ‰ (vs. PDB) for basalts and from -18.8 to 2.86 ‰ (vs. PDB) for geothermal samples (mean = -4.2 ± 3.6 ‰). CO2/3He ratios range from 108 to 1012 for basalts and from 105 to 1012 for geothermal samples: In both cases, our results extend He-CO2 relationships over a much broader range than reported previously [1]. Taken together, these data suggest that several processes including mixing, degassing, and/or syn- or post-eruptive crustal contamination may act to modify CO2 source characteristics. Equilibrium degassing models are compatible with ~75 % of the basalt data, and preliminary results indicate that initial Icelandic source characteristics are ~500 ppm CO2 and δ13C ~ -5 ‰ (vs. PDB). These values are high compared to N-MORB mantle source estimates (72-134 ppm) based upon CO2/Nb ratios [2, 3]; however, they are in good agreement with those from submarine glasses on adjacent segments from the Reykjanes and Kolbeinsey ridges [4,5]. Significantly, the model-derived δ13C estimate is close to the mean Icelandic geothermal value, implying that fluids closely resemble source values, i.e. they likely represent the exsolved component. Integrating the estimated source CO2 content with magma production values of 0.079 km3/yr [6] yields a CO2 flux of ~1.2 x 1011 mol CO2 yr-1for Iceland, representing ~ 5.4 % of the total carbon ridge flux of 2.2 x 1012 mol CO2 yr-1 [7]. Thus, the average CO2 flux estimate for Iceland is ~2.2 x 108 mol CO2 yr-1km-1 strike of ridge axis, which compares to an overall ridge flux (including Iceland) of ~2.9 x 107 mol CO2 yr-1km-1. This difference highlights both heterogeneity in source volatile contents and magma production rates as important controls for determining mantle CO2 fluxes. [1] Poreda et al., 1992 [2] Saal et al., 2002. [3] Shaw et al., 2010. [4] de Leeuw, 2007 [5] Macpherson et al., 2005. [6] Thordarson et al., 2007 [7] Marty et al., 1998.

Quantification of the CO2 emitted from volcanic lakes in Pico Island (Azores)

NASA Astrophysics Data System (ADS)

Andrade, César; Cruz, José; Viveiros, Fátima; Branco, Rafael

2017-04-01

This study shows the results of the diffuse CO2 degassing surveys performed in lakes from Pico volcanic Island (Azores archipelago, Portugal). Detailed flux measurements using the accumulation chamber method were made at six lakes (Capitão, Caiado, Paul, Rosada, Peixinho and Negra) during two field campaigns, respectively, in winter (February 2016) and late summer (September 2016). Pico is the second largest island of the Azores archipelago with an area of 444.8 km2; the oldest volcanic unit is dated from about 300,000 years ago. The edification of Pico was mainly due to Hawaiian and Strombolian type volcanic activity, resulting in pahoehoe and aa lava flows of basaltic nature, as well as scoria and spatter cones. Three main volcanic complexes are identified in the island, namely (1) the so-called Montanha Volcanic Complex, corresponding to a central volcano located in the western side of the island that reaches a maximum altitude of 2351 m, (2) the São Roque-Piedade Volcanic Complex, and (3) the Topo-Lajes Volcanic Complex, this last one corresponding to the remnants of a shield volcano located in the south coast. The studied lakes are spread along the São Roque-Piedade Volcanic Complex at altitudes between 785 m and 898 m. Three are associated with depressions of undifferentiated origin (Caiado, Peixinho, Negra), two with depressions of tectonic origin (Capitão, Paul), while Rosada lake is located inside a scoria cone crater. The lakes surface areas vary between 1.25x10-2 and 5.38x10-2 km2, and the water column maximum depth is 7.9 m (3.5-7.9 m). The water storage ranges between 3.6x104 to 9.1x104 m3, and the estimated residence time does not exceed 1.8x10-1 years. A total of 1579 CO2 flux measurements were made during both surveys (868 in summer and 711 in the winter campaign), namely 518 in Caiado lake (293; 225), 358 in Paul (195; 163), 279 in Capitão (150, 129), 200 in Rosada (106, 94), 171 in Peixinho (71, 100) and 53 measurements in Negra lake. Negra Lake was only sampled in the summer season. The CO2 flux values range between 0.68 g m-2 d-1 (Paul lake) and 20.47 g m-2 d-1 (Negra). The total CO2 emission varies between 0.03 t d-1 (Negra and Peixinho lakes) and 0.30 t d-1 (Caiado lake) for the summer surveys, and between 0.04 t d-1 (Rosada lake) and 0.26 t d-1 (Caiado lake) for the winter data. The higher CO2 emission is observed for Rosada lake (8.89 t km-2 d-1) during summer and the lower corresponds to the Negra lake (1.67 t km-2 d-1) during summer. Considering the set of the studied volcanic lakes, the CO2 emission sums up to 64 t d-1 (winter campaign) and 72 t d-1 (summer). These emissions are probably mainly associated to a biogenic source, but the characterization of the CO2 emission in these volcanic lakes during periods of quiescence is relevant for any seismo-volcanic monitoring programme. Key words: volcanic lakes, CO2 flux, diffuse degassing, Pico Island, Azores

Review of calcium carbonate polymorph precipitation in spring systems

NASA Astrophysics Data System (ADS)

Jones, Brian

2017-05-01

Many spring deposits throughout the world are characterized by spectacular deposits of calcium carbonate that are formed of various combinations of aragonite and calcite, and in very rare cases vaterite. The factors that control the precipitation of the aragonite and calcite have been the subject of considerable debate that has been based on natural precipitates and information gained from numerous laboratory experiments. Synthesis of this information indicates that there is probably no single universal factor that controls calcite and aragonite precipitation in all springs. Instead, the reason for aragonite as opposed to calcite precipitation should be ascertained by considering the following ordered series of possibilities for each system. First, aragonite, commonly with calcite as a co-precipitate, will form from spring water that has a high CO2 content and rapid CO2 degassing, irrespective of the Mg:Ca ratio and scale of precipitation. Second, aragonite can be precipitated from waters that have low levels of CO2 degassing provided that the Mg:Ca ratio is high enough to inhibit calcite precipitation. Third, the presence of biofilms may lead to the simultaneous precipitation of aragonite and calcite (irrespective of CO2 degassing or Mg:Ca ratio) either within the different microdomains that develop in the biofilm or because of diurnal changes in various geochemical parameters associated with the biofilm. Although the precipitation of calcite and aragonite has commonly been linked directly to water temperature, there is no clear evidence for this proposition. It is possible, however, that temperature may be influencing another parameter that plays a more direct role in the precipitation of these CaCO3 polymorphs. Despite the advances that have been made, the factors that ultimately control calcite and aragonite are still open to debate because this long-standing problem has still not been fully resolved.

Determination of free CO2 in emergent groundwaters using a commercial beverage carbonation meter

NASA Astrophysics Data System (ADS)

Vesper, Dorothy J.; Edenborn, Harry M.

2012-05-01

SummaryDissolved CO2 in groundwater is frequently supersaturated relative to its equilibrium with atmospheric partial pressure and will degas when it is conveyed to the surface. Estimates of dissolved CO2 concentrations can vary widely between different hydrochemical facies because they have different sources of error (e.g., rapid degassing, low alkalinity, non-carbonate alkalinity). We sampled 60 natural spring and mine waters using a beverage industry carbonation meter, which measures dissolved CO2 based on temperature and pressure changes as the sample volume is expanded. Using a modified field protocol, the meter was found to be highly accurate in the range 0.2-35 mM CO2. The meter provided rapid, accurate and precise measurements of dissolved CO2 in natural waters for a range of hydrochemical facies. Dissolved CO2 concentrations measured in the field with the carbonation meter were similar to CO2 determined using the pH-alkalinity approach, but provided immediate results and avoided errors from alkalinity and pH determination. The portability and ease of use of the carbonation meter in the field made it well-suited to sampling in difficult terrain. The carbonation meter has proven useful in the study of aquatic systems where CO2 degassing drives geochemical changes that result in surficial mineral precipitation and deposition, such as tufa, travertine and mine drainage deposits.

Fracture healing in a magma: An experimental approach and implications for volcanic seismicity and degassing

NASA Astrophysics Data System (ADS)

Yoshimura, Shumpei; Nakamura, Michihiko

2010-09-01

The healing of magmatic fractures is considered essential to repetitive seismicity and the closure of degassing paths during emplacement of lavas. To estimate the healing time of magmatic fractures, we performed healing experiments on rhyolitic melts at 850°-1000°C and 1.6-3.2 MPa for 0.5-94 h. Two cylindrical obsidian cores were juxtaposed on surfaces prepared by cutting the cores both with and without polishing. These were annealed in an open-system cell. The contact interface became coherent and finally disappeared. The water content across the contact initially decreased toward the interface via diffusive dehydration, but later homogenized. This change was interpreted to reflect atomic-scale closure of the interface, probably by chemical bonding. We defined this closure interval as microscopic healing time and determined this by fitting the measured profiles with a diffusion model. The microscopic healing time was strongly dependent on temperature and roughness of the interface and was, for the nonpolished interfaces, 67-74, 4.0-4.9, and 0.36-0.38 h at 850°, 900°, and 950°C, respectively, whereas for the polished examples it was 1-3 and 0.5-0.6 h at 850° and 900°C, respectively. This microscopic healing time is consistent with the period of actual seismicity and is prolonged sufficiently to permit the formation of millimeter-thick bubble-free obsidian layers along fractures in vesicular lavas through bubble resorption due to diffusive degassing.

Gas emission from diffuse degassing structures (DDS) of the Cameroon volcanic line (CVL): Implications for the prevention of CO2-related hazards

NASA Astrophysics Data System (ADS)

Issa; Ohba, T.; Chako Tchamabé, B.; Padrón, E.; Hernández, P.; Eneke Takem, E. G.; Barrancos, J.; Sighomnoun, D.; Ooki, S.; Nkamdjou, Sigha; Kusakabe, M.; Yoshida, Y.; Dionis, S.

2014-08-01

In the mid-1980s, lakes Nyos and Monoun violently released massive gas, mainly magmatic CO2 killing about 1800 people. Subsequent geochemical surveys and social studies indicate that lakes Nyos and Monoun event is cyclic in nature and may occur anywhere in the about 37 other volcanic lakes located in the corridor of the Cameroon volcanic line (CVL). This potential threat motivated us to check if, alike Nyos and Monoun, the internal dynamic of the other lakes is also controlled by inputs of deep-seated-derived CO2 and attempt to measure and provide comprehensive insights on the passive gas emission along the CVL. This knowledge shall contribute to the prevention of volcanic lake-related hazards in Cameroon and the refinement of the Global Carbon Cycle. We used in situ fixation and dry gas phase sampling methods to determine CO2 origin and the concentration, and the accumulation chamber technique to measure diffuse CO2 emission from nine lakes and on soil at Nyos Valley and Mount Manenguba Caldera. The results suggest that, although in minor concentrations (compared to Nyos and Monoun), ranging from 0.56 mmol kg- 1 to 8.75 mmol kg- 1, the bottom waters of some lakes also contain measurable magmatic CO2 with δ13C varies from - 4.42‰ to - 9.16‰ vs. PDB. That finding implies that, under certain circumstances, e.g. increase to volcanic and/or tectonic activities along the CVL, the concerned lakes could develop a Nyos-type behavioural scheme. The diffuse gas emission results indicate that the nine surveyed lakes release approximately 3.69 ± 0.37 kt km- 2 yr- 1 of CO2 to the atmosphere; extrapolation to the approximately 39 volcanic lakes located on the CVL yields an approximate CO2 output of 27.37 ± 0.5 kt km- 2 yr- 1, representing 0.023% of the global CO2 output from volcanic lakes. In addition to the precedent value, the gas removal operation in lakes Nyos and Monoun released approximately 2.52 ± 0.46 × 108 mol km- 2 yr- 1 CO2 to the atmosphere from January 2001 to March 2013, more than double the per-area CO2 released by the Yellowstone volcanic system. The CO2 emission from soil was estimated to be 4.57 ± 1.30 kt km- 2 yr- 1; the soil gas geochemistry of the Mount Manenguba Caldera also indicates a dominant magma-derived CO2 (mean δ13C = - 8.6‰ vs. VPDB).

Endogenous gas hazard at Pizzillo (Stromboli Island, Italy)

NASA Astrophysics Data System (ADS)

Tarchini, L.; Carapezza, M. L.; Ranaldi, M.; Ricci, T.

2009-04-01

In open-conduit volcanoes like Stromboli or Etna, the major degassing is associated to the plume emission from the craters. However the presence of faults and fractures acts as preferential pathway for gas escaping to the surface, thus there is also a relevant CO2 diffuse degassing from the soil from most of the edifice. In the inhabited areas on these volcanoes, natural gases can accumulate in houses generating potential hazards. Pizzillo is one of the anomalous degassing zone located near the sea shore, in the inhabited area of Stromboli. It is well known to local people for the presence of a mofette lethal to small animals and of a shallow thermal aquifer (T= 35-42 °C). It has a high dissolved CO2 content and is mostly fed by sea water and heated by gas rising from depth. High CO2 concentration has been found in the soil (17 % and 40 %, at 50 and 100 cm depth). Chemical and isotopic data of soil gas indicate a deep magmatic provenance. Interesting anomalies of CO2 and other dissolved gases, including C and He isotopes, have been recorded in this thermal shallow aquifer before the 2002 eruption onset and the 5 April 2003 paroxysm, suggesting an increasing input of gas released from an uprising magma body. The presence in this coastal zone of NE-SW trending fractures is confirmed also by the results of a shallow electromagnetic survey carried out in 2004 using a multifrequency (625 to 19,925 Hz) GEM 300 with investigation depth of 30 to 50 m depending on ground resistivity. Most of the CO2 emission of Pizzillo occurs along a N64E° trending fracture extending uphill toward Rina Grande, and along which a series of flank collapses occurred. The CO2 soil flux map, carried out over 3200 m2, delineates two anomalies oriented NE-SW on both sides of an house, that is severely exposed to gas hazard. This house, where people mostly live during summer, is located just in the middle of the most CO2 soil emissive zone. It has a window very near to the rock cut from where most CO2 is emitted. As such a location is severely exposed to gas hazard, indoor CO2 air concentration was repeatedly measured within a ground room where the gas, denser than air, could accumulate up to reach dangerous levels. An automatic Dräger X-am 7000 devise, which records CO2 concentration every minute, was used; it was placed at 10 cm from the ground. The first measures, carried out from 29 July to 2 August 2006, gave very dangerous concentration values up to 8 vol.% that were always recorded in periods of no or very low wind. A longer survey was carried out from 7 March to 15 May 2007, during and after the last Stromboli eruption, with some interruptions due to power cuts. Results confirm the high gas hazard of this house, as immediately lethal CO2 air concentration (10 %) is often reached or exceeded. In order to ascertain from where the gas was coming, a second Dräger was placed on the windowsill at 2 m from the ground. Results clearly show that CO2 was mostly entering the room from this window, as very high concentrations were found with peaks shortly preceding those recorded near the ground. This prevented to recommend room aeration, which is the most elementary precautionary measure in these cases. We suggested the owner to wall up that window and impermeabilise the floor. During five days of measurements, carried out in January 2008 after the completion of these works, [CO2] was mostly at its normal air value.

Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

NASA Astrophysics Data System (ADS)

Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

2018-04-01

The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

Fluid geochemistry and soil gas fluxes (CO2-CH4-H2S) at a promissory Hot Dry Rock Geothermal System: The Acoculco caldera, Mexico

NASA Astrophysics Data System (ADS)

Peiffer, L.; Bernard-Romero, R.; Mazot, A.; Taran, Y. A.; Guevara, M.; Santoyo, E.

2014-09-01

The Acoculco caldera has been recognized by the Mexican Federal Electricity Company (CFE) as a Hot Dry Rock Geothermal System (HDR) and could be a potential candidate for developing an Enhanced Geothermal System (EGS). Apart from hydrothermally altered rocks, geothermal manifestations within the Acoculco caldera are scarce. Close to ambient temperature bubbling springs and soil degassing are reported inside the caldera while a few springs discharge warm water on the periphery of the caldera. In this study, we infer the origin of fluids and we characterize for the first time the soil degassing dynamic. Chemical and isotopic (δ18O-δD) analyses of spring waters indicate a meteoric origin and the dissolution of CO2 and H2S gases, while gas chemical and isotopic compositions (N2/He, 3He/4He, 13C, 15N) reveal a magmatic contribution with both MORB- and arc-type signatures which could be explained by an extension regime created by local and regional fault systems. Gas geothermometry results are in agreement with temperature measured during well drilling (260 °C-300 °C). Absence of well-developed water reservoir at depth impedes re-equilibration of gases upon surface. A multi-gas flux survey including CO2, CH4 and H2S measurements was performed within the caldera. Using the graphical statistical analysis (GSA) approach, CO2 flux measurements were classified in two populations. Population A, representing 95% of measured fluxes is characterized by low values (mean: 18 g m- 2 day- 1) while the remaining 5% fluxes belonging to Population B are much higher (mean: 5543 g m- 2 day- 1). This low degassing rate probably reflects the low permeability of the system, a consequence of the intense hydrothermal alteration observed in the upper 800 m of volcanic rocks. An attempt to interpret the origin and transport mechanism of these fluxes is proposed by means of flux ratios as well as by numerical modeling. Measurements with CO2/CH4 and CO2/H2S flux ratios similar to mass ratios of sampled gases were considered as reflecting advective transport. A numerical model of CO2 migration in the subsoil system under fully water and gas saturated conditions was performed using the TOUGH2 code in order to reproduce semi-quantitatively field measurements. The main results show that high flux values produced by advective geothermal degassing can be very localized and that low and heterogeneous permeability conditions can induce low advective CO2 flux values. Therefore, in this case the populations discriminated by the GSA method should not be interpreted in terms of origin and/or transport mechanism but rather in terms of permeability conditions.

CO 2-rich komatiitic melt inclusions in Cr-spinels within beach sand from Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Shimizu, Kenji; Shimizu, Nobumichi; Komiya, Tsuyoshi; Suzuki, Katsuhiko; Maruyama, Shigenori; Tatsumi, Yoshiyuki

2009-10-01

The volatile content of komatiite is a key to constrain the thermal and chemical evolution of the deep Earth. We report the volatile contents with major and trace element compositions of ~ 80 melt inclusions in chromian spinels (Cr-spinels) from beach sands on Gorgona Island, Colombia. Gorgona Island is a ~ 90 Ma volcanic island, where picrites and the youngest komatiites known on the Earth are present. Melt inclusions are classified into three types on the basis of their host Cr-spinel compositions: low Ti (P type), high Ti with high Cr # (K1 type) and high Ti with low Cr # (K2 type). Chemical variations of melt inclusions in the Cr-spinels cover all of the island's lava types. P-type inclusions mainly occur in the picrites, K1-type in high-TiO 2 komatiites (some enriched basalts: E-basalts) and K2-type in low-TiO 2 komatiites. The H 2O and CO 2 contents of melt inclusions within Cr-spinels from the beach sand are highly variable (H 2O: 0.03-0.9 wt.%; CO 2: 40-4000 ppm). Evaluation of volatile content is not entirely successful because of compositional alterations of the original melt by degassing, seawater/brine assimilation and post-entrapment modification of certain elements and volatiles. However, the occurrence of many melt inclusions with low H 2O/K 2O ratios indicates that H 2O/K 2O of Gorgona komatiite is not much different from that of modern mid-oceanic ridge basalt (MORB) or oceanic island basalt. Trend of CO 2/Nb and Zr/Y ratios, accounted for by two-component mixing between the least degassed primary komatiite and low-CO 2/Nb evolved basalt, allow us to estimate a primary CO 2/Nb ratio of 4000 ± 2200 or a CO 2 content of 0.16 ± 0.09 wt.%. The determined CO 2/Nb ratio is unusually high, compared to that of MORB (530). Although the presence of CO 2 in the Gorgona komatiite does not affect the magma generation temperature, CO 2 degassing may have contributed to the eruption of high-density magmas. High CO 2/Nb and the relatively anhydrous nature of Gorgona komatiite provide possible resolution to one aspect of the hydrous komatiite debate.

Anthropogenic and natural methane emissions from a shale gas exploration area of Quebec, Canada.

PubMed

Pinti, Daniele L; Gelinas, Yves; Moritz, Anja M; Larocque, Marie; Sano, Yuji

2016-10-01

The increasing number of studies on the determination of natural methane in groundwater of shale gas prospection areas offers a unique opportunity for refining the quantification of natural methane emissions. Here methane emissions, computed from four potential sources, are reported for an area of ca. 16,500km(2) of the St. Lawrence Lowlands, Quebec (Canada), where Utica shales are targeted by the petroleum industry. Methane emissions can be caused by 1) groundwater degassing as a result of groundwater abstraction for domestic and municipal uses; 2) groundwater discharge along rivers; 3) migration to the surface by (macro- and micro-) diffuse seepage; 4) degassing of hydraulic fracturing fluids during first phases of drilling. Methane emissions related to groundwater discharge to rivers (2.47×10(-4) to 9.35×10(-3)Tgyr(-1)) surpass those of diffuse seepage (4.13×10(-6) to 7.14×10(-5)Tgyr(-1)) and groundwater abstraction (6.35×10(-6) to 2.49×10(-4)Tgyr(-1)). The methane emission from the degassing of flowback waters during drilling of the Utica shale over a 10- to 20-year horizon is estimated from 2.55×10(-3) to 1.62×10(-2)Tgyr(-1). These emissions are from one third to sixty-six times the methane emissions from groundwater discharge to rivers. This study shows that different methane emission sources need to be considered in environmental assessments of methane exploitation projects to better understand their impacts. Copyright © 2016 Elsevier B.V. All rights reserved.

Continuous in situ measurements of volcanic gases with a diode-laser-based spectrometer: CO2 and H2O concentration and soil degassing at Vulcano (Aeolian islands: Italy).

PubMed

De Rosa, Maurizio; Gagliardi, Gianluca; Rocco, Alessandra; Somma, Renato; De Natale, Paolo; De Natale, Giuseppe

2007-04-20

We report on a continuous-measurement campaign carried out in Vulcano (Aeolian islands, Sicily), devoted to the simultaneous monitoring of CO2 and H2O concentrations. The measurements were performed with an absorption spectrometer based on a semiconductor laser source emitting around a 2-microm wavelength. The emitted radiation was selectively absorbed by two molecular ro-vibrational transitions specific of the investigated species. Data for CO2 and H2O concentrations, and CO2 soil diffusive flux using an accumulation chamber configuration, were collected at several interesting sampling points on the island (Porto Levante beach- PLB, Fossa Grande Crater - FOG- and Valley of Palizzi, PAL). CO2/H2O values, measured on the ground, are very similar (around 0.019 (+/- 0.006)) and comparable to the previous discrete detected values of 0.213 (Fumarole F5-La Fossa crater rim) and 0.012 (Fumarole VFS - Baia Levante beach) obtaid during the 1977-1993 heating phase of the crater fumaroles. In this work much more homogeneous values are found in different points of the three sites investigated. The field work, although carried out in a limited time window (25th-28th August 2004), pointed out the new apparatus is suitable for continuous gas monitoring of the two species and their ratios, which are important geochemical indicators of volcanic activity, for which other reliable continuous monitoring systems are not yet available.

Vapor segregation and loss in basaltic melts

USGS Publications Warehouse

Edmonds, M.; Gerlach, T.M.

2007-01-01

Measurements of volcanic gases at Pu'u'O??'o??, Kilauea Volcano, Hawai'i, reveal distinct degassing regimes with respect to vapor segregation and loss during effusive activity in 2004-2005. Three styles of vapor loss are distinguished by the chemical character of the emitted volcanic gases, measured by open path Fourier transform infrared spectroscopy: 1 persistent continuous gas emission, 2 gas piston events, and 3 lava spattering. Persistent continuous gas emission is associated with magma ascent and degassing beneath the crater vents, then eruption of the degassed magma from flank vents. Gas piston events are the result of static gas accumulation at depths of 400-900 m beneath Pu'u'O??'o??. A CO2-rich gas slug travels up the conduit at a few meters per second, displacing magma as it expands. Lava spattering occurs due to dynamic bubble coalescence in a column of relatively stagnant magma. The Large gas bubbles are H2O rich and are generated by open-system degassing at depths of <150 m. Static gas accumulation and dynamic bubble coalescence are both manifestations of vapor segregation in basaltic melts, but their implications differ. Accumulation and segregation of CO2-rich vapor at depth does not deplete the melt of H2O (required to drive lava fountains near to the surface) and therefore gas piston events can occur interspersed with lava fountaining activity. Lava spattering, however, efficiently strips H2O-rich vapor from magma beneath the crater vents; the magma must then erupt effusively from vents on the flank of the cone. ?? 2007 The Geological Society of America.

Vapor segregation and loss in basaltic melts

NASA Astrophysics Data System (ADS)

Edmonds, Marie; Gerlach, Terrence M.

2007-08-01

Measurements of volcanic gases at Pu'u‘Ō’ō, Kilauea Volcano, Hawai'i, reveal distinct degassing regimes with respect to vapor segregation and loss during effusive activity in 2004-2005. Three styles of vapor loss are distinguished by the chemical character of the emitted volcanic gases, measured by open path Fourier transform infrared spectroscopy: (1) persistent continuous gas emission, (2) gas piston events, and (3) lava spattering. Persistent continuous gas emission is associated with magma ascent and degassing beneath the crater vents, then eruption of the degassed magma from flank vents. Gas piston events are the result of static gas accumulation at depths of 400-900 m beneath Pu'u‘Ō’ō. A CO2-rich gas slug travels up the conduit at a few meters per second, displacing magma as it expands. Lava spattering occurs due to dynamic bubble coalescence in a column of relatively stagnant magma. The large gas bubbles are H2O rich and are generated by open-system degassing at depths of <150 m. Static gas accumulation and dynamic bubble coalescence are both manifestations of vapor segregation in basaltic melts, but their implications differ. Accumulation and segregation of CO2-rich vapor at depth does not deplete the melt of H2O (required to drive lava fountains near to the surface) and therefore gas piston events can occur interspersed with lava fountaining activity. Lava spattering, however, efficiently strips H2O-rich vapor from magma beneath the crater vents; the magma must then erupt effusively from vents on the flank of the cone.

Using fumarolic inert gas composition to investigate magma dynamics at Campi Flegrei (Italy)

NASA Astrophysics Data System (ADS)

Chiodini, G.; Caliro, S.; Paonita, A.; Cardellini, C.

2013-12-01

Since 2000 the Campi Flegrei caldera sited in Neapolitan area (Italy), has showed signs of reactivation, marked by ground uplift, seismic activity, compositional variations of fumarolic effluents from La Solfatara, an increase of the fumarolic activity as well as of soil CO2 fluxes. Comparing long time series of geochemical signals with ground deformation and seismicity, we show that these changes are at least partially caused by repeated injections of magmatic fluid into the hydrothermal system. The frequency of these degassing episodes has increased in the last years, causing pulsed uplift episodes and swarms of low magnitude earthquakes. We focus here in the inert gas species (CO2-He-Ar-N2) of Solfatara fumaroles which displayed in the time spectacular and persistent variation trends affecting all the monitored vents. The observed variations, which include a continuous decrease of both N2/He and N2/CO2 ratios since 1985, paralleled by an increase of He/CO2, can not be explained neither with changes in processes of boiling-condensation in the local hydrothermal system nor with changes in the mixing proportions between a magmatic vapour and hydrothermal fluids. Consequently we investigated the possibility that the trends of inert gas species are governed by changes in the conditions controlling magma degassing at depth. We applied a magma degassing model, with the most recent updates for inert gas solubilities, after to have included petrologic constraints from the ranges of melt composition and reservoir pressure at Campi Flegrei. The model simulations for mafic melts (trachybasalt and shoshonite) show a surprising agreement with the measured data. Both decompressive degassing of an ascending magma and mixing between magmatic fluids exsolved at various levels along the ascent path can explain the long-time geochemical changes. Our work highlights that, in caldera systems where the presence of hydrothermal aquifers commonly masks the magmatic signature of reactive volatiles, inert gases are the preferred species to achieve information on the dynamics and structure of the magma plumbing systems.

Prodigious emission rates and magma degassing budget of major, trace and radioactive volatile species from Ambrym basaltic volcano, Vanuatu island Arc

NASA Astrophysics Data System (ADS)

Allard, P.; Aiuppa, A.; Bani, P.; Métrich, N.; Bertagnini, A.; Gauthier, P.-J.; Shinohara, H.; Sawyer, G.; Parello, F.; Bagnato, E.; Pelletier, B.; Garaebiti, E.

2016-08-01

Ambrym volcano, in the Vanuatu arc, is one of the most active volcanoes of the Southwest Pacific region, where persistent lava lake and/or Strombolian activity sustains voluminous gas plume emissions. Here we report on the first comprehensive budget for the discharge of major, minor, trace and radioactive volatile species from Ambrym volcano, as well as the first data for volatiles dissolved in its basaltic magma (olivine-hosted melt inclusions). In situ MultiGAS analysis of H2O, CO2, SO2 and H2S in crater rim emissions, coupled with filter-pack determination of SO2, halogens, stable and radioactive metals demonstrates a common magmatic source for volcanic gases emitted by its two main active craters, Benbow and Marum. These share a high water content ( 93 mol%), similar S/Cl, Cl/F, Br/Cl molar ratios, similar (210Po/210Pb) and (210Bi/210Pb) activity ratios, as well as comparable proportions in most trace metals. Their difference in CO2/SO2 ratio (1.0 and 5.6-3.0, respectively) is attributed to deeper gas-melt separation at Marum (Strombolian explosions) than Benbow (lava lake degassing) during our measurements in 2007. Airborne UV sensing of the SO2 plume flux (90 kg s- 1 or 7800 tons d- 1) demonstrates a prevalent degassing contribution ( 65%) of Benbow crater in that period and allows us to quantify the total volatile fluxes during medium-level eruptive activity of the volcano. Results reveal that Ambrym ranks among the most powerful volcanic gas emitters on Earth, producing between 5% and 9% of current estimates for global subaerial volcanic emissions of H2O, CO2, HCl, Cu, Cr, Cd, Au, Cs and Tl, between 10% and 17% of SO2, HF, HBr, Hg, 210Po and 210Pb, and over 30% of Ag, Se and Sn. Global flux estimates thus need to integrate its contribution and be revised accordingly. Prodigious gas emission from Ambrym does not result from an anomalous volatile enrichment nor a differential excess degassing of its feeding basalt: this latter contains relatively modest dissolved amounts of H2O (≤ 1.3 wt%), CO2 ( 0.10 wt%), S (0.075 wt%) and Cl (0.05 wt%), and its degassing under prevalent closed-system conditions well reproduces the composition of emitted volcanic gases. Instead, we show that the gas discharge is sustained by a very high basalt supply rate of 25 m3 s- 1, from a large ( 0.5 km3) magma reservoir probably emplaced at 3.8 km depth below the summit caldera according to both the H2O-CO2 content of bubble-free melt inclusions and preliminary seismic data. Radioactive disequilibria in the volcanic gases constrain that this reservoir may be entirely renewed in about 240 days. The comparatively low magma extrusion rate requires extensive convective overturn of the basaltic magma column and recycling of the unerupted (denser) degassed magma in the plumbing system, in agreement with textural features of erupted products. Finally, our results suggest that the Indian MORB-type mantle source of Ambrym basalts is modestly enriched in slab-derived water and other volatiles, in agreement with the prevalent volcanoclastic nature of subducted sediments and their lower subduction rate under the central Vanuatu arc due to its collision with the D'Entrecasteaux Ridge.

Degassing of reduced carbon from planetary basalts.

PubMed

Wetzel, Diane T; Rutherford, Malcolm J; Jacobsen, Steven D; Hauri, Erik H; Saal, Alberto E

2013-05-14

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

CO 2 release variations during the last 2000 years at the Colli Albani volcano (Roma, Italy) from speleothems studies

NASA Astrophysics Data System (ADS)

Tuccimei, P.; Giordano, G.; Tedeschi, M.

2006-03-01

The Colli Albani is the quiescent volcano that dominates the southwestern skyline of Roma (Italy). The last eruption occurred during the Holocene, from the eccentric Albano maar, along its western slope. The volcano is presently affected by cyclic seismic swarms, ground uplift and diffuse CO 2 degassing. The degassing has caused several deadly incidents during the last years and constitutes a major civil protection concern, as the volcano slopes are densely inhabited. Nevertheless, the volcano does not have a permanent monitoring network, and the background level and anomalous CO 2 levels, the relationship between the gas release and the seismic and ground deformation activity at the Colli Albani are still to be defined. The aim of this work is to define the historical record of CO 2 release. Evidences of deep CO 2 periodic release during the last 2000 years in the area of Colli Albani volcano (Roma, Italy) are offered from speleothems studies. A Roman-age stone mine, now used for mushroom cultivation, is decorated with actively growing speleothems, characterised by depositional hiatuses. Different levels of four stalactites, separated by depositional unconformities, and several samples from a single depositional cycle belonging to a stalagmite have been dated by U/Th method and analysed for their O and C isotopic composition. Eight cycles of deposition have been identified from 90-110 A.D. to 1350-1370 A.D., some of which are recognised across different speleothems. The age gap dividing different growth layers is in the order of one to few hundred years giving a temporal span for periodic interruption of speleothems deposition. O and C isotopic analyses performed on the samples collected from a single cycle (the oldest) have shown that the composition of the mother solutions was initially mainly meteoric and that a progressive increase in the input of a deep component rich in CO 2 (up to a proportion of 20-30%) occurred just before the interruption of the speleothem deposition. This could be due to a progressive increase of the acidity of the water solutions that caused the undersaturation of fluids. If we extrapolate this mechanism to the other cycles of deposition, being characterised by analogue isotopic compositions, we can hypothesise periods of deposition interrupted by episodes of CO 2 release which in the Colli Albani volcano are often recorded in coincidence with earthquakes. Therefore we have correlated the hiatuses with some of the largest historical earthquakes interesting to the city of Rome.

The Hartousov Mofette Field in the Cheb Basin, Western Eger Rift (Czech Republic/Europe): a Comperative Geoelectric, Sedimentologic and Soil Gas Study of a Magmatic Diffuse Degassing Structure

NASA Astrophysics Data System (ADS)

Flechsig, C.; Schuetze, C.; Bussert, R.

2008-12-01

The mofette field of Hartoušov is located in the Cheb Basin, a shallow Neogene intracontinental basin in Central Europe. The north-eastern part of the Cheb Basin is one of the most seismically active regions of Central Europe. Seismic activity in the Cheb Basin has mainly a swarm-like character. The numerous cold CO2 emanations (>99 Vol.% CO2) at the surface of the basin are supposed to be generally connected to the seismic activity and to stem from the upper mantle. The Hartoušov mofette field has been investigated by combining geophysical measurements (geoelectrical resistivity tomography, self potential) with sedimentological studies (grain size, Corg, mineralogy) and soil gas (CO2 flux and CO2 concentration) data. Key question of the research was to evaluate the structural and sedimentological control at a CO2 degassing location. The investigations reveal a positive correlation between areas of high soil gas (CO2) concentration and flux with geophysical anomalies (negative self potential, positive structures of low electrical resistivity) as well as with specific sediment properties (content of pyrite and organic material, occurrence of dispersed pebbles, uplifted clay layer). These features are thought to be directly or indirectly related to the magmatic caused CO2 flow. Soil gas (CO2) measurements indicate areas of high CO2 content to be marked by anomalous vegetation patterns. These anomalies spread out with a linear trend, suggesting a fault control on gas ascent. Places of highest gas flow form small hummocks, with minor depressions on top. Negative geoelectrical self potentials at such locations were interpreted considering as having been caused by a downward movement of the meteoric water balancing the upward CO2 flux. The top of a pre-Quaternary clay-rich unit with a high content of smectite is highest in the location nearest to the mofette showing the most intense CO2 emanation. Most probably the clays form a domal feature below this mofette, as confirmed by the 3-D geoelectric measurements by low electrical resistivities. The driving force behind the updoming of the clays might be the pressure of uprising CO2. Additionally, the more intense swelling of smectite due to higher rates of fluid flow at these locations might also contribute to this phenomenon. Isolated quartz pebbles dispersed in fine-grained sediments could have been transported upward by gas jets bonded to vents during periods or events of intense gas emanation. The model for the sedimentation at the active mofettes has to consider its bonding to deep-seated faults, the presence of sediment deformation structures due to gas pressure, upward transport of sediment particles by gas jets and reducing conditions caused by the magmatic CO2 flux.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, S.N.; Schaefer, S.J.; Calvache V., M.L.

Global emission of carbon dioxide by subaerial volcanoes is calculated, using CO{sub 2}/SO{sub 2} from volcanic gas analyses and SO{sub 2} flux, to be 34 {plus minus} 24 {times} 10{sup 12} g CO{sub 2}/yr from passive degassing and 31 {plus minus} 22 {times} 10{sup 12} g CO{sub 2}/yr from eruptions. Volcanic CO{sub 2} presently represents only 0.22% of anthropogenic emissions but may have contributed to significant greenhouse' effects at times in Earth history. Models of climate response to CO{sub 2} increases may be tested against geological data.

Stable Isotope Measurements of Martian Atmospheric CO2 at the Phoenix Landing Site

NASA Astrophysics Data System (ADS)

Niles, Paul B.; Boynton, William V.; Hoffman, John H.; Ming, Douglas W.; Hamara, Dave

2010-09-01

Carbon dioxide is a primary component of the martian atmosphere and reacts readily with water and silicate rocks. Thus, the stable isotopic composition of CO2 can reveal much about the history of volatiles on the planet. The Mars Phoenix spacecraft measurements of carbon isotopes [referenced to the Vienna Pee Dee belemnite (VPDB)] [δ13CVPDB = -2.5 ± 4.3 per mil (‰)] and oxygen isotopes [referenced to the Vienna standard mean ocean water (VSMOW)] (δ18OVSMOW = 31.0 ± 5.7‰), reported here, indicate that CO2 is heavily influenced by modern volcanic degassing and equilibration with liquid water. When combined with data from the martian meteorites, a general model can be constructed that constrains the history of water, volcanism, atmospheric evolution, and weathering on Mars. This suggests that low-temperature water-rock interaction has been dominant throughout martian history, carbonate formation is active and ongoing, and recent volcanic degassing has played a substantial role in the composition of the modern atmosphere.

Interaction of ultra-depleted MORBs with plagioclase: implications for CO2/Ba ratios

NASA Astrophysics Data System (ADS)

Shimizu, K.; Hauri, E.; Saal, A. E.; Perfit, M. R.; Hekinian, R.

2017-12-01

Carbon in Earth's upper mantle can significantly reduce its solidus temperature, which in turn can affect other physical properties through generation of partial melt. Carbon content in the depleted upper mantle can be estimated using ultra-depleted mid-ocean ridge basalt (UD-MORB) glasses and melt inclusions that are undersaturated in CO2. CO2 has been shown to behave as a highly incompatible element during mantle melting both through natural samples and experiments. Given its highly incompatible behavior, CO2/Ba and CO2/Nb ratios in CO2 undersaturated UD-MORBs have been used to estimate the CO2/Ba and CO2/Nb ratios and carbon content in Earth's upper mantle. A potential issue with part of this approach is the effect of melt-plagioclase chemical interaction on the CO2/Ba ratios in UD-MORBs. Plagioclase is ubiquitous in the oceanic crust and is enriched in Ba relative to other phases. Chemical interactions (assimilation and/or diffusion) between MORB melts and plagioclase bearing rocks have been shown to affect the Ba (and Sr and Eu) concentrations in MORBs, implying that such processes may also affect their CO2/Ba ratio. Hence, understanding the effect of chemical interaction between plagioclase and UD-MORBs is important for having better constraints on CO2/Ba ratio and carbon content in Earth's upper mantle. In this study, we report on the compositions of olivine-hosted melt inclusions and glasses from the Siqueiros and Garrett transform faults. A subset of melt inclusions in lavas from both transform faults show potential signatures of chemical interaction with plagioclase such as low CO2/Ba, Nb/Ba, and Nd/Sr. CO2 degassing cannot explain the low CO2/Ba ratio in the samples as they are undersaturated in CO2. To better understand the effect of chemical interaction with plagioclase on the composition of UD-MORBs, we model end-member scenarios, which are (1) assimilation of plagioclase and (2) diffusion of elements from plagioclase into the UD-MORBs. In general, the trends produced by these end-member scenarios bracket those observed in the samples (trends between CO2/Ba, Nb/Ba, and Nd/Sr as well as between Al2O3, FeO, and MgO). Hence, chemical interaction with plagioclase may affect the CO2/Ba ratio in UD-MORBs, and care should be taken to evaluate this effect using Nd/Sr and Nb/Ba ratios.

The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

2016-09-01

Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

Abundant carbon in the mantle beneath Hawai`i

NASA Astrophysics Data System (ADS)

Anderson, Kyle R.; Poland, Michael P.

2017-09-01

Estimates of carbon concentrations in Earth’s mantle vary over more than an order of magnitude, hindering our ability to understand mantle structure and mineralogy, partial melting, and the carbon cycle. CO2 concentrations in mantle-derived magmas supplying hotspot ocean island volcanoes yield our most direct constraints on mantle carbon, but are extensively modified by degassing during ascent. Here we show that undegassed magmatic and mantle carbon concentrations may be estimated in a Bayesian framework using diverse geologic information at an ocean island volcano. Our CO2 concentration estimates do not rely upon complex degassing models, geochemical tracer elements, assumed magma supply rates, or rare undegassed rock samples. Rather, we couple volcanic CO2 emission rates with probabilistic magma supply rates, which are obtained indirectly from magma storage and eruption rates. We estimate that the CO2 content of mantle-derived magma supplying Hawai`i’s active volcanoes is 0.97-0.19+0.25 wt%--roughly 40% higher than previously believed--and is supplied from a mantle source region with a carbon concentration of 263-62+81 ppm. Our results suggest that mantle plumes and ocean island basalts are carbon-rich. Our data also shed light on helium isotope abundances, CO2/Nb ratios, and may imply higher CO2 emission rates from ocean island volcanoes.

Thermal desorption of CO and H2 from degassed 304 and 347 stainless steel

NASA Technical Reports Server (NTRS)

Rezaie-Serej, S.; Outlaw, R. A.

1994-01-01

Thermal desorption spectroscopy (TDS), along with Auger electron spectroscopy, was used to study the desorption of H2 and CO from baked 304 and 347 stainless-steel samples exposed only to residual gases. Both 347 and 304 samples gave identical TDS spectra. The spectra for CO contained a sharp leading peak centered in the temperature range 410-440C and an exponentially increasing part for temperatures higher than 500C, with a small peak around 600C appearing as a shoulder. The leading peak followed a second-order desorption behavior with an activation energy of 28+/-2 kcal/mol, suggesting that the rate-limiting step for this peak is most likely a surface reaction that produces the CO molecules in the surface layer. The amount of desorbed CO corresponding to this peak was approximately 0.5X10(exp 14) molecules/cm(exp 2) . The exponentially rising part of the CO spectrum appeared to originate from a bulk diffusion process. The TDS spectrum for H2 consisted of a main peak centered also in the temperature range 410-440C, with two small peaks appearing as shoulders at approximately 500 and 650C. The main peak in this case also displayed a second-order behavior with an activation energy of 14+/-2 kcal/mol. The amount of desorbed H2, approximately 1.9X 10(exp 15) molecules/cm(exp 2) , appeared to be independent of the concentration of hydrogen in the bulk, indicating that the majority of the desorbed H2 originated from the surface layer.

Comparing eruptions of varying intensity at Kilauea via melt inclusion analysis

NASA Astrophysics Data System (ADS)

Ferguson, D. J.; Plank, T. A.; Hauri, E. H.; Houghton, B. F.; Gonnermann, H. M.; Swanson, D. A.; Blaser, A. P.

2013-12-01

Over the past 500 years explosive summit eruptions from Kilauea volcano, Hawaii, have exhibited a range of eruption magnitudes, from large basaltic sub-plinian events to Hawaiian lava fountains of various intensity. Knowledge of the factors controlling such dramatic changes in explosivity and mass discharge rate is vital for understanding the dynamics of explosive basaltic magma systems, but these remain poorly constrained. At Kilauea this information also has important implications for hazard assessment, as future eruptions may be far larger than those observed historically. To investigate the processes associated with eruptions of varying magnitudes we have analyzed the composition and dissolved volatile contents (H2O-CO2-S-Cl-F) of olivine-hosted melt inclusions, sampled from tephra deposits associated with three eruptions of different sizes: a moderate lava-fountain (1959 Episode of Kilauea Iki); an exceptionally high lava-fountain (1500 CE Keanakāko'i reticulite) and a basaltic sub-plinian eruption (1650 CE Keanakāko'i layer 6 scoria). Over this time period (~500 years) we find no major shifts in the major element composition of primary melts feeding the Kilauea magmatic system, and melt inclusions from all eruptions record similar maximum water (~0.7 wt% H2O) and CO2 (~300 ppm) contents, regardless of eruption magnitude. Co-variations between other volatile species, such as CO2 and S, do not support a role for excess volatiles (i.e. CO2) in the larger eruptions via ';gas-fluxing'. Our data therefore suggests that major shifts in eruptive magnitude are unlikely to be linked to either changes in the primary volatile content of the melts or excess gas supplied by open-system degassing of deeper melts. Rather we find evidence for significant variations in the shallow degassing behavior of magmas associated with the larger Keanakāko'i eruptions (sub-plinian and strong lava-fountaining events) compared to that from less vigorous moderate Kilauea Iki lava-fountaining events. On plots of CO2 versus H2O, Kilauea Iki MI's record volatile contents consistent with equilibrium degassing of magma rising from a depth of ~3 km. In contrast, the volatile contents of melts from the more explosive eruptions appear to be strongly affected by degassing processes at shallow depths (< 300 m), indicating variations in the ascent and storage of melts over this time-period. These changes in storage conditions may be linked to variations in the depth of the summit caldera, which was significantly greater during the older more explosive eruptive phases.

Halogen degassing during ascent and eruption of water-poor basaltic magma

USGS Publications Warehouse

Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

2009-01-01

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

First volcanic CO2 budget estimate for three actively degassing volcanoes in the Central American Volcanic Arc

NASA Astrophysics Data System (ADS)

Robidoux, Philippe; Aiuppa, Alessandro; Conde, Vladimir; Galle, Bo; Giudice, Gaetano; Avard, Geoffroy; Muñoz, Angélica

2014-05-01

CO2 is a key chemical tracer for exploring volcanic degassing mechanisms of basaltic magmatic systems (1). The rate of CO2 release from sub-aerial volcanism is monitored via studies on volcanic plumes and fumaroles, but information is still sparse and incomplete for many regions of the globe, including the majority of the volcanoes in the Central American Volcanic Arc (2). Here, we use a combination of remote sensing techniques and in-situ measurements of volcanic gas plumes to provide a first estimate of the CO2 output from three degassing volcanoes in Central America: Turrialba, in Costa Rica, and Telica and San Cristobal, in Nicaragua. During a field campaign in March-April 2013, we obtained (for the three volcanoes) a simultaneous record of SO2 fluxes (from the NOVAC network (3)) and CO2 vs. SO2 concentrations in the near-vent plumes (obtained via a temporary installed fully-automated Multi-GAS instrument (4)). The Multi-GAS time-series allowed to calculate the plume CO2/SO2 ratios for different intervals of time, showing relatively stable gas compositions. Distinct CO2 - SO2 - H2O proportions were observed at the three volcanoes, but still within the range of volcanic arc gas (5). The CO2/SO2 ratios were then multiplied by the SO2 flux in order to derive the CO2 output. At Turrialba, CO2/SO2 ratios fluctuated, between March 12 and 19, between 1.1 and 5.7, and the CO2flux was evaluated at ~1000-1350 t/d (6). At Telica, between March 23 and April 8, a somewhat higher CO2/SO2 ratio was observed (3.3 ± 1.0), although the CO2 flux was evaluated at only ~100-500 t/d (6). At San Cristobal, where observations were taken between April 11 and 15, the CO2/SO2 ratio ranged between 1.8 and 7.4, with a mean CO2 flux of 753 t/d. These measurements contribute refining the current estimates of the total CO2 output from the Central American Volcanic Arc (7). Symonds, R.B. et al., (2001). J. Volcanol. Geotherm. Res., 108, 303-341 Burton, M. R. et al. (2013). Reviews in Mineralogy & Geochemistry, 75, 323-354 Galle et al., (2010). J. Geophys. Res., 115, D05304 Aiuppa, A. et al. (2009). J. Volcanol. Geotherm. Res.,182, 221-230 Shinohara, H. (2008). Rev. Geophys., 46, RG4005 Conde, V. et al. (2013). International Journal of Earth Sciences, (submitted) Mather et al (2006). J. Volcanol. Geotherm. Res., 149, 297-311

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. L. Lewicki; G. E. Hilley; L. Dobeck

A set of CO2 flux, geochemical, and hydrologic measurement techniques was used to characterize the source of and quantify gaseous and dissolved CO2 discharges from the area of Soda Springs, southeastern Idaho. An eddy covariance system was deployed for approximately one month near a bubbling spring and measured net CO2 fluxes from - 74 to 1147 g m- 2 d- 1. An inversion of measured eddy covariance CO2 fluxes and corresponding modeled source weight functions mapped the surface CO2 flux distribution within and quantified CO2 emission rate (24.9 t d- 1) from a 0.05 km2 area surrounding the spring. Soilmore » CO2 fluxes (< 1 to 52,178 g m- 2 d- 1) were measured within a 0.05 km2 area of diffuse degassing using the accumulation chamber method. The estimated CO2 emission rate from this area was 49 t d- 1. A carbon mass balance approach was used to estimate dissolved CO2 discharges from contributing sources at nine springs and the Soda Springs geyser. Total dissolved inorganic carbon (as CO2) discharge for all sampled groundwater features was 57.1 t d- 1. Of this quantity, approximately 3% was derived from biogenic carbon dissolved in infiltrating groundwater, 35% was derived from carbonate mineral dissolution within the aquifer(s), and 62% was derived from deep source(s). Isotopic compositions of helium (1.74–2.37 Ra) and deeply derived carbon (d13C approximately 3‰) suggested contribution of volatiles from mantle and carbonate sources. Assuming that the deeply derived CO2 discharge estimated for sampled groundwater features (approximately 35 t d- 1) is representative of springs throughout the study area, the total rate of deeply derived CO2 input into the groundwater system within this area could be ~ 350 t d- 1, similar to CO2 emission rates from a number of quiescent volcanoes.« less

Ecosystem CO2 and CH4 exchange in a mixed tundra and a fen within a hydrologically diverse Arctic landscape: 1. Modeling versus measurements

NASA Astrophysics Data System (ADS)

Grant, R. F.; Humphreys, E. R.; Lafleur, P. M.

2015-07-01

CO2 and CH4 exchange are strongly affected by hydrology in landscapes underlain by permafrost. Hypotheses for these effects in the model ecosys were tested by comparing modeled CO2 and CH4 exchange with CO2 fluxes measured by eddy covariance from 2006 to 2009, and with CH4 fluxes measured with surface chambers in 2008, along a topographic gradient at Daring Lake, NWT. In an upland tundra, rises in net CO2 uptake in warmer years were constrained by declines in CO2 influxes when vapor pressure deficits (D) exceeded 1.5 kPa and by rises in CO2 effluxes with greater active layer depth. Consequently, net CO2 uptake rose little with warming. In a lowland fen, CO2 influxes declined less with D and CO2 effluxes rose less with warming, so that rises in net CO2 uptake were greater than those in the tundra. Greater declines in CO2 influxes with warming in the tundra were modeled from greater soil-plant-atmosphere water potential gradients that developed under higher D in drained upland soil, and smaller rises in CO2 effluxes with warming in the fen were modeled from O2 constraints to heterotrophic and belowground autotrophic respiration from a shallow water table in poorly drained lowland soil. CH4 exchange modeled during July and August indicated very small influxes in the tundra and larger effluxes characterized by afternoon emission events caused by degassing of warming soil in the fen. Emissions of CH4 modeled from degassing during soil freezing in October-November contributed about one third of the annual total.

An estimate of gas emissions and magmatic gas content from Kilauea volcano

USGS Publications Warehouse

Greenland, L.P.; Rose, William I.; Stokes, J.B.

1985-01-01

Emission rates of CO2 have been measured at Kilauea volcano, Hawaii, in the east-rift eruptive plume and CO2 and SO2 have been measured in the plume from the noneruptive fumaroles in the summit caldera. These data yield an estimate of the loading of Kilauean eruptive gases to the atmosphere and suggest that such estimates may be inferred directly from measured lava volumes. These data, combined with other chemical and geologic data, suggest that magma arrives at the shallow summit reservoir containing (wt.%) 0.32% H2O, 0.32% CO2 and 0.09% S. Magma is rapidly degassed of most of its CO2 in the shallow reservoir before transport to the eruption site. Because this summit degassing yields a magma saturated and in equilibrium with volatile species and because transport of the magma to the eruption site occurs in a zone no shallower than the summit reservoir, we suggest that eruptive gases from Kilauea characteristically should be one of two types: a 'primary' gas from fresh magma derived directly from the mantle and a carbon-depleted gas from magma stored in the summit reservoir. ?? 1995.

Magma fracturing and degassing associated with obsidian formation: The explosive–effusive transition

USGS Publications Warehouse

Cabrera, Agustin; Weinberg, Roberto; Wright, Heather M.

2015-01-01

This paper explores the role of melt fracturing in degassing rhyolitic volcanic systems. The Monte Pilato-Rocche Rosse eruptions in Italy evolved from explosive to effusive in style, and H2O content in quenched glasses changed over time from relatively H2O-rich (~ 0.90 wt.%) to H2O-poor dense obsidian (~ 0.10–0.20 wt.%). In addition, healed fractures have been recorded in all different eruptive materials, from the glass of early-erupted tube pumice and rinds of breadcrusted obsidian pyroclasts, to the glass of late-erupted dense obsidian pyroclasts, and throughout the final effusive Rocche Rosse lava flow. These rocks show multiple fault sets, some with crenulated fault planes indicating resumption of viscous flow after faulting, complex obsidian breccias with evidence for post-brecciation folding and stretching, and centimetre- to metre-thick tuffisite preserved in pyroclasts and lava, representing collapsed foam due to fracturing of vesicle walls. These microstructural observations indicate that multiple fracturing and healing events occurred during both explosive and effusive eruptions. H2O content in glass decreases by as much as 0.14 wt.% towards healed fractures/faults and decreases in stretched obsidian breccias towards regions of intense brecciation. A drop in pressure and/or increase in temperature along fractures caused diffusive H2O migration through melt towards fracture surfaces. Repetitive and pervasive fracturing and healing thereby create conditions for diffusive H2O loss into fractures and subsequent escape through permeable paths. This type of progressive magma degassing provides a potential mechanism to explain the formation of dense obsidian and the evolution from explosive to effusive eruption style.

Evolution of C-O-H-N volatile species in the magma ocean during core formation.

NASA Astrophysics Data System (ADS)

Dalou, C.; Le Losq, C.; Hirschmann, M. M.; Jacobsen, S. D.; Fueri, E.

2017-12-01

The composition of the Hadean atmosphere affected how life began on Earth. Magma ocean degassing of C, O, H, and N was a key influence on the composition of the Hadean atmosphere. To identify the nature of degassed C-O-H-N species, we determined their speciation in reduced basaltic glasses (in equilibrium with Fe-C-N metal alloy, synthetized at 1400 and 1600 ºC and 1.2-3 GPa) via Raman spectroscopy. We addressed the effect of oxygen fugacity (fO2) on C-O-H-N speciation between IW-2.3 and IW-0.4, representing the evolution of the shallow upper mantle fO2 during the Hadean. We observe H2, NH2, NH3, CH3, CH4, CO, N2, and OH species in all glasses. With increasing ƒO2, our results support the formation of OH groups at the expense of N-H and C-H bonds in the melt, implying the equilibria at IW-2: (1) 2OH- (melt) + ½ N2 (melt) ↔ NH2 (melt) + 2 O2- (melt) , (2) 2OH- (melt) + ½ N2 (melt) + ½ H2 (melt) ↔ NH3 (melt) + 2 O2- (melt) . With increasing fO2, eqs. (1) and (2) shift to the left. From IW-2 to IW, we also observe an increase in the intensity of the NH2 peak relative to NH3. Carbon is present as CH3, CH4, and CO in all our glasses. While CO is likely the main carbon specie under reduced conditions (e.g., Armstrong et al. 2015), CH species should remain stable from moderately (IW-0.4) to very reduced (IW-3; Ardia et al. 2014; Kadik et al. 2015, 2017) conditions in hydrous silicate glasses following the equilibria: (3) 3OH- (melt) + C (graphite) ↔ CH3 (melt) + 3O2- (melt) , (4) 4OH- (melt) + C (graphite) ↔ CH4 (melt) + 4O2- (melt) . With increasing fO2, eqs. (3) and (4) shift to the left. As metal segregation and core formation drove the ƒO2 of the magma ocean from IW-4 to IW during the Hadean (Rubie et al. 2011), the nature of species degassed by the magma ocean should have evolved during that time. The C-O-H-N species we observe dissolved in our reduced glasses may not directly correspond to those degassed (Schaeffer and Fegley, 2007), but a better understanding of species abundances and gas phase equilibria should constrain the contribution of magma ocean degassing to the Hadean atmosphere. As reactions involving CO, N2, and OH are sufficient to form amino acids, and NH2, NH3, CH3, and CH4 are amino acid components, the availability of such reduced molecules for outgassing from the magma ocean suggest a central role in the formation of the first organic molecules.

A Model of Volcanic Outgassing for Earth's Early Atmosphere

NASA Astrophysics Data System (ADS)

Dhaliwal, J. K.; Kasting, J. F.; Zhang, Z.

2017-12-01

We build on historical paradigms of volcanic degassing [1] to account for non-linear relations among C-O-H-S volatiles, their speciation, solubility and concentrations in magmatic melts, and the resulting contribution to atmospheric volatile inventories. We focus on the build-up of greenhouse-relevant carbon species (CO2 and CH4) and molecular oxygen to better understand the environments of early life and the Great Oxygenation Event [2,3,4]. The mantle is an important reservoir of C-O-H-S volatiles [5], and melt concentrations depend on temperature, pressure and oxygen fugacity. We present a preliminary chemical model that simulates volatile concentrations released into the Earth's atmosphere at 1 bar, or pressures corresponding to the early Earth prior to 2.4 Ga. We maintain redox balance in the system using H+ [2, 6] because the melt oxidation state evolves with volatile melt concentrations [7] and affects the composition of degassed compounds. For example, low fO2 in the melt degasses CO, CH4, H2S and H2 while high fO2 yields CO2, SO2 and H2O [1,8,9]. Our calculations incorporate empirical relations from experimental petrology studies [e.g., 10, 11] to account for inter-dependencies among volatile element solubility trends. This model has implications for exploring planetary atmospheric evolution and potential greenhouse effects on Venus and Mars [12]­, and possibly exoplanets. A future direction of this work would be to link this chemical degassing model with different tectonic regimes [13] to account for degassing and ingassing, such as during subduction. References: [1] Holland, H. D. (1984) The chemical evolution of the atmosphere and oceans [2] Kasting, J. F. (2013) Chem. Geo. 362, 13-25 [3] Kasting, J.F. (1993) Sci. 259, 920-926 [4] Duncan, M.S. & Dasgupta, R. (2017) Nat. Geoscience 10, 387-392. [5] Hier-Majumder, S. & Hirschmann, M.M. (2017) G3, doi: 10.1002/2017GC006937 [6] Gaillard, F. et al. (2003) GCA 67, 2427- 2441 [7] Moussalam, Y. et al. (2014) EPSL 393, 200-209 [8] Holloway, J. R. & Blank, J. G. (1994) Rev. in Min. 30, 187-187 [9] Hirschmann, M. M. (2012) EPSL 341, 48-57 [10] Iacono-Marziano, G. et al. (2012) GCA 97, 1-23 [11] O'Neill, H. St. C. & Mavrogenes, J.A. (2002) J. of Pet. 6, 1049-1087 [12] Gaillard, F. & Scaillet, B. (2014) EPSL 403, 307-316. [13] Rozel, A.B. et al. (2017) Nature 545, 332-335.

Constraining pre-eruptive volatile contents and degassing histories in submarine lavas

NASA Astrophysics Data System (ADS)

Jones, M.; Soule, S. A.; Liao, Y.; Le Roux, V.; Brodsky, H.; Kurz, M. D.

2017-12-01

Vesicle textures in submarine lavas have been used to calculate total (pre-eruption) volatile concentrations in mid-ocean ridge basalts (MORB), which provide constraints on upper mantle volatile contents and CO2 fluxes along the global MOR. In this study, we evaluate vesicle size distributions and volatile contents in a suite of 20 MORB samples, which span the range of typical vesicularities and bubble number densities observed in global MORB. We demonstrate that 2D imaging coupled with traditional stereological methods closely reproduces vesicle size distributions and vesicularities measured using 3D x-ray micro-computed tomography (μ-CT). We further demonstrate that x-ray μ-CT provides additional information about bubble deformation and clustering that are linked to bubble nucleation and lava emplacement dynamics. The validation of vesicularity measurements allows us to evaluate the methods for calculating total CO2 concentrations in MORB using dissolved volatile content (SIMS), vesicularity, vesicle gas density, and equations of state. We model bubble and melt contraction during lava quenching and show that the melt viscosity prevents bubbles from reaching equilibrium at the glass transition temperature. Thus, we suggest that higher temperatures should be used to calculate exsolved volatile concentrations based on observed vesicularities. Our revised method reconciles discrepancies between exsolved volatile contents measured by gas manometry and calculated from vesicularity. In addition, our revised method suggests that some previous studies may have overestimated MORB volatile concentrations by up to a factor of two, with the greatest differences in samples with the highest vesicularities (e.g., `popping rock' 2πD43). These new results have important implications for CO2/Nb of `undegassed' MORB and global ridge CO2 fluxes. Lastly, our revised method yields constant total CO2 concentrations in sample suites from individual MOR eruptions that experienced syn-eruptive degassing. These results imply closed-system degassing during magma ascent and emplacement following equilibration at the depth of melt storage in the crust.

Carbon dioxide emissions from the flat bottom and shallow Nam Theun 2 Reservoir: drawdown area as a neglected pathway to the atmosphere

NASA Astrophysics Data System (ADS)

Deshmukh, Chandrashekhar; Guérin, Frédéric; Vongkhamsao, Axay; Pighini, Sylvie; Oudone, Phetdala; Sopraseuth, Saysoulinthone; Godon, Arnaud; Rode, Wanidaporn; Guédant, Pierre; Oliva, Priscia; Audry, Stéphane; Zouiten, Cyril; Galy-Lacaux, Corinne; Robain, Henri; Ribolzi, Olivier; Kansal, Arun; Chanudet, Vincent; Descloux, Stéphane; Serça, Dominique

2018-03-01

Freshwater reservoirs are a significant source of CO2 to the atmosphere. CO2 is known to be emitted at the reservoir surface by diffusion at the air-water interface and downstream of dams or powerhouses by degassing and along the river course. In this study, we quantified total CO2 emissions from the Nam Theun 2 Reservoir (Lao PDR) in the Mekong River watershed. The study started in May 2009, less than a year after flooding and just a few months after the maximum level was first reached and lasted until the end of 2013. We tested the hypothesis that soils from the drawdown area would be a significant contributor to the total CO2 emissions.Total inorganic carbon, dissolved and particulate organic carbon and CO2 concentrations were measured in 4 pristine rivers of the Nam Theun watershed, at 9 stations in the reservoir (vertical profiles) and at 16 stations downstream of the monomictic reservoir on a weekly to monthly basis. CO2 bubbling was estimated during five field campaigns between 2009 and 2011 and on a weekly monitoring, covering water depths ranging from 0.4 to 16 m and various types of flooded ecosystems in 2012 and 2013. Three field campaigns in 2010, 2011 and 2013 were dedicated to the soils description in 21 plots and the quantification of soil CO2 emissions from the drawdown area. On this basis, we calculated total CO2 emissions from the reservoir and carbon inputs from the tributaries. We confirm the importance of the flooded stock of organic matter as a source of carbon (C) fuelling emissions. We show that the drawdown area contributes, depending on the year, from 40 to 75 % of total annual gross emissions in this flat and shallow reservoir. Since the CO2 emissions from the drawdown zone are almost constant throughout the years, the large interannual variations result from the significant decrease in diffusive fluxes and downstream emissions between 2010 and 2013. This overlooked pathway in terms of gross emissions would require an in-depth evaluation for the soil organic matter and vegetation dynamics to evaluate the actual contribution of this area in terms of net modification of gas exchange in the footprint of the reservoir, and how it could evolve in the future.

Geochemical and geophysical monitoring activities in Campo de Calatrava Volcanic Field (Spain)

NASA Astrophysics Data System (ADS)

Luengo-Oroz, Natividad; Villasante-Marcos, Víctor; López-Díaz, Rubén; Calvo, Marta; Albert, Helena; Domínguez Cerdeña, Itahiza

2017-04-01

The Campo de Calatrava Volcanic Field (CCVF) or Spanish Central Volcanic Zone is located in central continental Spain (Ciudad Real province) and covers about 5000 km2. It includes around 240 eruptive centers, mainly monogenetic basaltic cones but also explosive maar structures. According to K-Ar geochronology, its main activity phase occurred during Pliocene and Pleistocene epochs (between 5 and 1.7 Ma) and involved alkaline to ultraalkaline magmas, although an older ultrapotassic phase is dated around 8.7-6.4 Ma. However, some recent works have proposed Holocene ages for some of the volcanic products, opening the possibility of considering the CCVF "active" according to international standards. Responding to this situation, the Instituto Geográfico Nacional (IGN) has initiated geochemical and geophysical monitoring activities in the CCVF. Here, we describe these ongoing efforts and we report results about groundwater geochemistry at several natural highly-gaseous springs in the area (hervideros), as well as soil temperature, CO2 diffuse flux from the soil and electrical self-potential data mapped on a small degassing structure called La Sima. In order to analyze microseismicity or any seismic anomaly in the CCVF, a seismic station has also been installed close to this degassing structure. Physicochemical parameters (temperature, pH, Eh and electric conductivity) were measured in situ in four springs and samples were taken in order to analyze major ions and trace elements. Total composition of dissolved gases and helium isotopic ratios were also determined. To complete soil temperature, self-potential and gas prospections performed in La Sima, soil gases were sampled at the bottom of the structure at a depth of 20 cm. Analysis of the total gas composition found 957400 ppm of CO2. Low values of O2 and N2 were also detected (5600 and 24800 ppm respectively).

Is there an Alternative for the Huge Impact-Generated Atmosphere?

NASA Astrophysics Data System (ADS)

Gerasimov, M. V.; Dikov, Y. P.; Yakovlev, O. I.; Wlotzka, F.

1998-01-01

The Earth's primordial atmosphere is considered to be the result of impact degassing during planetary accretion. Experiments on the decomposition of a serpentine and calcite during a shock wave loading showed that a rather efficient decomposition could be achieved beginning with the impact velocities that corresponded to escape velocities of a relatively small (about Moon-sized) planetary embryo. During further accumulation of planetary mass, the decomposition of serpentine and carbonates with the release of H2O and CO2 (gases considered to be the main product of impact degassing) into the primordial atmosphere was considered to be complete. The sink rate of H2O and CO2 from the primordial atmosphere was evaluated mainly as atmospheric impact erosion, thermal and EW-driven escape from the atmosphere, hydration and carboniza60n of surface minerals, dissolution of gases in magma ocean, loss of water for oxidation of Fe, etc. The growth of the atmosphere was considered to be a result of source and sink processes during each impact event. The rehydration of 100% of degassed material during an impact is considered to be an end effect when no hydrous atmosphere is formed. But even a small efficiency of impact degassing (the ratio of volatiles that remain in the atmosphere after an impact to the amount delivered by a planetesimal) was calculated to produce an abundant H2O-CO2 atmosphere. During a set of impact simulation experiments we have investigated the chemistry of volatiles and their interaction behavior with condensing silicates at conditions similar to impact vaporization. First, the experiments showed that the gas mixture was not limited only by H20 and CO2 during high-temperature vaporization of silicates, a wide variety of gases were formed, including oxides [SO2, CO2, CO (CO/CO2 approximately 1), H20] and reduced gas components (H2, H2S, CS2, COS, and hydrocarbons). Second, experiments on high-temperature vaporization of mafic and ultramafic rocks and minerals in water and/or CO2 containing atmospheres showed that condensing silicates provide intense trapping of water and/or CO2 during the hot stage of vapor cloud expansion. The amount of water trapped by formation of different hydroxides could be about 10 wt% of silicate mass. The trapping of atmospheric CO2 is proceeded by the formation of carbonates, carbides, hydrocarbons, and elemental C phases. Preliminary results indicate that Ni is also trapped by formation of -NO3, -H2N, and -CN phases. The maximum concentrations of trapped CO2 and N were measured up to 4 wt% and 0.1 wt% respectively. Trapping is efficient even at low partial gas pressures. Impact-induced trapping of atmospheric gases was not accounted for by theoretical models, but it seems to be an efficient process controlling the atmospheric mass. The ratio of volatiles added to the atmosphere after an impact to the amount delivered by a planetesimal can only be positive but sufficiently negative as well. During the impact of a planetesimal analogous to an ordinary chondrite on the growing Earth with a dense atmosphere, the removal of gases from the atmosphere seems to be more probable as a result of release and trapping processes. The capacity of the sink buffer exceeds the whole planetary volatile inventory. The trapping efficiency of gases inside the vapor plume suggests a model for the formation of a primordial atmosphere of moderate density.

A new sulfur and carbon degassing inventory for the Southern Central American Volcanic Arc: The importance of accurate time-series datasets and possible tectonic processes responsible for temporal variations in arc-scale volatile emissions

USGS Publications Warehouse

de Moor, Maarten; Kern, Christoph; Avard, Geoffroy; Muller, Cyril; Aiuppa, Sandro; Saballos, Armando; Ibarra, Martha; LaFemina, Peter; Protti, Mario; Fischer, Tobias

2017-01-01

This work presents a new database of SO2 and CO2 fluxes from the Southern Central American Volcanic Arc (SCAVA) for the period 2015–2016. We report ∼300 SO2 flux measurements from 10 volcanoes and gas ratios from 11 volcanoes in Costa Rica and Nicaragua representing the most extensive available assessment of this ∼500 km arc segment. The SO2 flux from SCAVA is estimated at 6,240 ± 1,150 T/d, about a factor of three higher than previous estimations (1972–2013). We attribute this increase in part to our more complete assessment of the arc. Another consideration in interpreting the difference is the context of increased volcanic activity, as there were more eruptions in 2015–2016 than in any period since ∼1980. A potential explanation for increased degassing and volcanic activity is a change in crustal stress regime (from compression to extension, opening volcanic conduits) following two large (Mw > 7) earthquakes in the region in 2012. The CO2 flux from the arc is estimated at 22,500 ± 4,900 T/d, which is equal to or greater than estimates of C input into the SCAVA subduction zone. Time‐series data sets for arc degassing need to be improved in temporal and spatial coverage to robustly constrain volatile budgets and tectonic controls. Arc volatile budgets are strongly influenced by short‐lived degassing events and arc systems likely display significant short‐term variations in volatile output, calling for expansion of nascent geochemical monitoring networks to achieve spatial and temporal coverage similar to traditional geophysical networks.

A New Sulfur and Carbon Degassing Inventory for the Southern Central American Volcanic Arc: The Importance of Accurate Time-Series Data Sets and Possible Tectonic Processes Responsible for Temporal Variations in Arc-Scale Volatile Emissions

NASA Astrophysics Data System (ADS)

de Moor, J. M.; Kern, C.; Avard, G.; Muller, C.; Aiuppa, A.; Saballos, A.; Ibarra, M.; LaFemina, P.; Protti, M.; Fischer, T. P.

2017-12-01

This work presents a new database of SO2 and CO2 fluxes from the Southern Central American Volcanic Arc (SCAVA) for the period 2015-2016. We report ˜300 SO2 flux measurements from 10 volcanoes and gas ratios from 11 volcanoes in Costa Rica and Nicaragua representing the most extensive available assessment of this ˜500 km arc segment. The SO2 flux from SCAVA is estimated at 6,240 ± 1,150 T/d, about a factor of three higher than previous estimations (1972-2013). We attribute this increase in part to our more complete assessment of the arc. Another consideration in interpreting the difference is the context of increased volcanic activity, as there were more eruptions in 2015-2016 than in any period since ˜1980. A potential explanation for increased degassing and volcanic activity is a change in crustal stress regime (from compression to extension, opening volcanic conduits) following two large (Mw > 7) earthquakes in the region in 2012. The CO2 flux from the arc is estimated at 22,500 ± 4,900 T/d, which is equal to or greater than estimates of C input into the SCAVA subduction zone. Time-series data sets for arc degassing need to be improved in temporal and spatial coverage to robustly constrain volatile budgets and tectonic controls. Arc volatile budgets are strongly influenced by short-lived degassing events and arc systems likely display significant short-term variations in volatile output, calling for expansion of nascent geochemical monitoring networks to achieve spatial and temporal coverage similar to traditional geophysical networks.

Continuous in situ measurements of volcanic gases with a diode-laser-based spectrometer: CO2 and H2O concentration and soil degassing at Vulcano (Aeolian islands: Italy)

PubMed Central

De Rosa, Maurizio; Gagliardi, Gianluca; Rocco, Alessandra; Somma, Renato; De Natale, Paolo; De Natale, Giuseppe

2007-01-01

We report on a continuous-measurement campaign carried out in Vulcano (Aeolian islands, Sicily), devoted to the simultaneous monitoring of CO2 and H2O concentrations. The measurements were performed with an absorption spectrometer based on a semiconductor laser source emitting around a 2-μm wavelength. The emitted radiation was selectively absorbed by two molecular ro-vibrational transitions specific of the investigated species. Data for CO2 and H2O concentrations, and CO2 soil diffusive flux using an accumulation chamber configuration, were collected at several interesting sampling points on the island (Porto Levante beach- PLB, Fossa Grande Crater – FOG- and Valley of Palizzi, PAL). CO2/H2O values, measured on the ground, are very similar (around 0.019 (± 0.006)) and comparable to the previous discrete detected values of 0.213 (Fumarole F5-La Fossa crater rim) and 0.012 (Fumarole VFS – Baia Levante beach) obtaid during the 1977–1993 heating phase of the crater fumaroles. In this work much more homogeneous values are found in different points of the three sites investigated. The field work, although carried out in a limited time window (25th–28th August 2004), pointed out the new apparatus is suitable for continuous gas monitoring of the two species and their ratios, which are important geochemical indicators of volcanic activity, for which other reliable continuous monitoring systems are not yet available. PMID:17448243

Degassing Lakes Nyos and Monoun: Defusing certain disaster

USGS Publications Warehouse

Kling, G.W.; Evans, William C.; Tanyileke, G.; Kusakabe, M.; Ohba, T.; Yoshida, Y.; Hell, J.V.

2005-01-01

Since the catastrophic releases of CO2 in the 1980s, Lakes Nyos and Monoun in Cameroon experienced CO2 recharge at alarming rates of up to 80 mol/m2 per yr. Total gas pressures reached 8.3 and 15.6 bar in Monoun (2003) and Nyos (2001), respectively, resulting in gas saturation levels up to 97%. These natural hazards are distinguished by the potential for mitigation to prevent future disasters. Controlled degassing was initiated at Nyos (2001) and Monoun (2003) amid speculation it could inadvertently destabilize the lakes and trigger another gas burst. Our measurements indicate that water column structure has not been compromised by the degassing and local stability is increasing in the zones of degassing. Furthermore, gas content has been reduced in the lakes ???12-14%. However, as gas is removed, the pressure at pipe inlets is reduced, and the removal rate will decrease over time. Based on 12 years of limnological measurements we developed a model of future removal rates and gas inventory, which predicts that in Monoun the current pipe will remove ???30% of the gas remaining before the natural gas recharge balances the removal rate. In Nyos the single pipe will remove ???25% of the gas remaining by 2015; this slow removal extends the present risk to local populations. More pipes and continued vigilance are required to reduce the risk of repeat disasters. Our model indicates that 75-99% of the gas remaining would be removed by 2010 with two pipes in Monoun and five pipes in Nyos, substantially reducing the risks. ?? 2005 by The National Academy of Sciences of the USA.

Degassing of reduced carbon from planetary basalts

PubMed Central

Wetzel, Diane T.; Rutherford, Malcolm J.; Jacobsen, Steven D.; Hauri, Erik H.; Saal, Alberto E.

2013-01-01

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential. PMID:23569260

H2S in Shallow Groundwater: Hydrogeochemical Processes, Degassing Experiments and Health Impacts

NASA Astrophysics Data System (ADS)

Broers, H. P.; Weert, J. D.; Bouma, R.

2016-12-01

Hydrogen sulfide is known to be a hazardous gas even at rather low concentrations and may pose a serious health risk. Occurrences of H2S in groundwater and degassing into the atmosphere are known for volcanic or tectonic active regions, coal mining or gypsum dissolution regions. We studied the occurrence and origin of H2S in shallow groundwater and its degassing into air after pumping in a setting of shallow unconsolidated deposits in the south of the Netherlands, where the sulfate source is antropogenic. We measured H2S concentrations in water using a field photo spectrometer and the degassing into air with a Jerome 631. We analyzed for macro-ions and determined the apparent 3H/3He age to assess the origin of the sulfide in the groundwater. H2S was formed in-situ within organic-rich and carbonate free sediments and peat layers of a fluvio-glacial sediment series in groundwater that infiltrated approximately 15 years ago. Sulfate is omnipresent in Dutch shallow groundwater due to historical atmospheric inputs of SOx, sulfur inputs from intensive livestock farming and subsurface production of sulfate from pyrite oxidation following nitrate leaching from agricultural fields (Zhang et al. 2009 GCA, 2012 AppGeochem). The co-existence of H2S and sulfate in our groundwater appears to be determined by the low pH of the water (4.8-5.5) which limits the precipitation of mackinawite or amorphous FeS. Mapping the combination of observations wells with pH < 5.5, sulfate > 75 mg/L and Fe > 10 mg/l delineated large areas where H2S appeared to be present in concentration between 0.1 and 1.0 mg/L S2- in water. Degassing of groundwater with 0.7 mg S2-/L into a contained volume of air yielded concentrations > 50 ppmv within 15 minutes. Using the degassing rates observed in the experiments and assuming equilibrium degassing, we calibrated a simple model which describes the inflow of water, the degassing and the export of gas in relation to wind velocity. We used the model to evaluate scenario's of human exposure for typical private and commercial uses. The private uses are at largest risk for exposure to harmful concentrations of H2S in air, due to closer exposure distances towards the degassing water, especially under conditions of low wind speeds. Indeed, a health incident was reported at a site where groundwater was pumped into a children's water play.

Abundant carbon in the mantle beneath Hawai`i

USGS Publications Warehouse

Anderson, Kyle R.; Poland, Michael

2017-01-01

Estimates of carbon concentrations in Earth’s mantle vary over more than an order of magnitude, hindering our ability to understand mantle structure and mineralogy, partial melting, and the carbon cycle. CO2 concentrations in mantle-derived magmas supplying hotspot ocean island volcanoes yield our most direct constraints on mantle carbon, but are extensively modified by degassing during ascent. Here we show that undegassed magmatic and mantle carbon concentrations may be estimated in a Bayesian framework using diverse geologic information at an ocean island volcano. Our CO2 concentration estimates do not rely upon complex degassing models, geochemical tracer elements, assumed magma supply rates, or rare undegassed rock samples. Rather, we couple volcanic CO2 emission rates with probabilistic magma supply rates, which are obtained indirectly from magma storage and eruption rates. We estimate that the CO2content of mantle-derived magma supplying Hawai‘i’s active volcanoes is 0.97−0.19+0.25 wt%—roughly 40% higher than previously believed—and is supplied from a mantle source region with a carbon concentration of 263−62+81 ppm. Our results suggest that mantle plumes and ocean island basalts are carbon-rich. Our data also shed light on helium isotope abundances, CO2/Nb ratios, and may imply higher CO2 emission rates from ocean island volcanoes.

Problems and advances in the use of magmatic degassing during subglacial eruptions to reconstruct palaeo-ice thicknesses

NASA Astrophysics Data System (ADS)

Tuffen, Hugh; Owen, Jacqueline; Denton, Joanna S.

2010-05-01

The degassing of magmatic volatiles during eruptions beneath ice sheets and glaciers, as recorded by the dissolved volatile content quenched in volcanic rocks, could provide powerful new constraints on former ice thicknesses in volcanic areas. As volcanic rocks are readily dateable using radiometric methods, subglacial volcanoes may therefore provide crucial information on Quaternary palaeo-environmental fluctuations. The use of a degassing-based reconstruction technique would be particularly valuable when studying deposits that were erupted entirely subglacially and therefore lack other diagnostic indicators of ice thickness such as subglacial-subaerial transitions. In order for magma degassing to potentially record palaeo-ice thicknesses a number of factors need to be considered[1,2], which include whether non-equilibrium degassing may have occurred, whether samples have undergone post-eruption hydration, are strongly compositionally heterogeneous, or have moved post-quenching, whether the quenching pressure reflected loading by rock, ice or meltwater, and whether pressure may have deviated significantly from glaciostatic due to meltwater drainage. Degassing during individual eruptions may be considerably more complex than anticipated[2], making interpretation of results challenging. Examples from both rhyolitic and basaltic eruptions in Iceland and elsewhere will be used to illustrate these important factors. The analytical techniques used to measure volatile concentrations need to improve on the common practise of using infra-red spectroscopy alone to determine H2O contents in one part of a sample. Multiple analyses are required to quantify the degree of heterogeneity within samples and techniques such as manometry, ion microprobe or electron microprobe are required to analyse other species (CO2, S, F, Cl). CO2 is particularly important as only trace amounts, beneath the detection limits of commonly-used analytical techniques (30 ppm), strongly affect the solubility-pressure relationships of water in silicate melts[1]. Measurement of the initial volatile contents of magmas, as recorded in melt inclusions, is also needed to provide full insight into the degassing path from the chamber to the surface. More evidence for non-glaciostatic pressures and abrupt changes in pressure during subglacial eruptions needs to be gathered from detailed measurements of volatile concentrations and combined with geological evidence for changes in subglacial meltwater drainage. Studies of deposits with good secondary constraints on ice thickness (from direct observations of recent eruptions or other geological evidence for ancient eruptions) are also required in order to assess the reliability of using volatile degassing to reconstruct palaeo-ice thicknesses. We are beginning to gain limited understanding of the behaviour of magmatic volatiles during subglacial eruptions, and to realise their potential for palaeo-environmental reconstructions. However, there remain many substantial and fundamental gaps in our knowledge that must be addressed in future research. [1] Tuffen, H., Owen, J., Denton, J. S. (2010) Magma degassing during subglacial eruptions and its use to reconstruct palaeo-ice thicknesses. Earth Science Reviews, in press. [2] Owen, J., Tuffen, H., McGarvie, D. W., Pinkerton, H., Wilson, L. The use of magmatic water to reconstruct palaeo-ice thicknesses during subglacial rhyolitic eruptions. Poster presentation, this session.

Experimental magma degassing: The revenge of the deformed bubbles

NASA Astrophysics Data System (ADS)

Marxer, H.; Bellucci, P.; Ulmer, S.; Nowak, M.

2013-12-01

We performed decompression experiments with a hydrated phonolitic melt at a T of 1323 K in an internally heated pressure vessel to investigate the effect of decompression method and rate on melt degassing. Samples were decompressed from 200 to 75 MPa with step-wise and continuous decompression (SD/CD) at nominal decompression rates (DRs) of 0.0028-1.7 MPa/s. At target P the samples were quenched rapidly under isobaric conditions with 150 K/s. The vesiculated glass products were compared in terms of bubble number density (BND), bubble size distribution (BSD) and residual H2O content. Almost all capsules were deformed after decompression: the initially crimped headspaces were expanded and the walls were inflexed in the capsule center. We postulate that the deformation is primarily due to the change in molar volume V(m) of exsolved H2O during rapid quench. Bubble growth in the melt contributes to the deformation by capsule expansion, but the main problem is the shrinkage and collapse of bubbles during cooling. In first approximation, the texture of the vesiculated melt is not frozen until the glass transition T (~773 K for this composition, [1]) is reached. From 1323 K to T(g) the melt will display viscous behavior. For a final P of 75 MPa, V(m) of the exsolved H2O at T(g) is only ~25% of V(m) at 1323 K [2]. The fluid P in the bubbles is therefore continuously decreasing during quench. In combination with constant external P, the bubbles can either contract isometrically, get deformed (flattened) or even become dented by sucking melt inwards, which can be observed in some glass products. The shrinkage of bigger bubbles in the capsules is sometimes affecting the whole vesicle texture in a sample. FPA-FTIR measurements did not reveal H2O diffusion profiles towards bubbles [3]. H2O concentration gradients around bubbles are expected to be disturbed or annihilated due to melt transport. All derived BSDs of our samples were corrected to resemble the bubble sizes prior to rapid quench. For a volumetric loss of 75% at a final P of 75 MPa, the initial diameter of a bubble in the melt has to be ~1.5x the diameter of a bubble in the glass. At DRs of >0.17 MPa/s the decompression method has only minor influence on melt degassing. SD and CD result in BNDs of 10^4-10^5 mm^-3. Fast P drop leads to immediate super-saturation with H2O in the melt. At high DRs, the diffusional transport of H2O is very limited and therefore bubble nucleation is the predominant degassing process. CD rates of ≤0.17 MPa/s provide sufficient time for H2O diffusion into existing bubbles. BNDs of CD samples with low DRs are several orders of magnitude lower than for SD experiments. In contrast to SD, bubble growth is the favored degassing mechanism. CD samples quenched at different target P at 0.024 MPa/s trace an equilibrium degassing path in terms of residual H2O content in the glass. SD techniques, as used in many studies before, are therefore not suitable to simulate melt degassing at continuous magma ascent. [1] Giordano, D; Russell, JK; Dingwell, DB; 2008. EPSL, 271: 123-134. [2] Duan, ZH; Zhang, ZG; 2006. GCA, 70: 2311-2324. [3] Marxer, H; Nowak, M; 2013. EJM, in press.

Soil gas geochemistry in relation to eruptive fissures on Timanfaya volcano, Lanzarote Island (Canary Islands, Spain)

NASA Astrophysics Data System (ADS)

Padrón, Eleazar; Padilla, Germán; Hernández, Pedro A.; Pérez, Nemesio M.; Calvo, David; Nolasco, Dácil; Barrancos, José; Melián, Gladys V.; Dionis, Samara; Rodríguez, Fátima

2013-01-01

We report herein the first results of an extensive soil gas survey performed on Timanfaya volcano on May 2011. Soil gas composition at Timanfaya volcano indicates a main atmospheric source, slightly enriched in CO2 and He. Soil CO2 concentration showed a very slight deep contribution of the Timanfaya volcanic system, with no clear relation to the main eruptive fissures of the studied area. The existence of soil helium enrichments in Timanfaya indicates a shallow degassing of crustal helium and other possible deeper sources probably form cooling magma bodies at depth. The main soil helium enrichments were observed in good agreement with the main eruptive fissures of the 1730-36 eruption, with the highest values located at those areas with a higher density of recent eruptive centers, indicating an important structural control for the leakage of helium at Timanfaya volcano. Atmospheric air slightly polluted by deep-seated helium emissions, CO2 degassed from a cooling magma body, and biogenic CO2, might be the most plausible explanation for the existence of soil gas. Helium is a deep-seated gas, exhibiting important emission rates along the main eruptive fissure of the 1730-36 eruption of Timanfaya volcano.

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

Titanite-bearing calc-silicate rocks constrain timing, duration and magnitude of metamorphic CO2 degassing in the Himalayan belt

NASA Astrophysics Data System (ADS)

Rapa, Giulia; Groppo, Chiara; Rolfo, Franco; Petrelli, Maurizio; Mosca, Pietro; Perugini, Diego

2017-11-01

The pressure, temperature, and timing (P-T-t) conditions at which CO2 was produced during the Himalayan prograde metamorphism have been constrained, focusing on the most abundant calc-silicate rock type in the Himalaya. A detailed petrological modeling of a clinopyroxene + scapolite + K-feldspar + plagioclase + quartz ± calcite calc-silicate rock allowed the identification and full characterization - for the first time - of different metamorphic reactions leading to the simultaneous growth of titanite and CO2 production. The results of thermometric determinations (Zr-in-Ttn thermometry) and U-Pb geochronological analyses suggest that, in the studied lithology, most titanite grains grew during two nearly consecutive episodes of titanite formation: a near-peak event at 730-740 °C, 10 kbar, 30-26 Ma, and a peak event at 740-765 °C, 10.5 kbar, 25-20 Ma. Both episodes of titanite growth are correlated with specific CO2-producing reactions and constrain the timing, duration and P-T conditions of the main CO2-producing events, as well as the amounts of CO2 produced (1.4-1.8 wt% of CO2). A first-order extrapolation of such CO2 amounts to the orogen scale provides metamorphic CO2 fluxes ranging between 1.4 and 19.4 Mt/yr; these values are of the same order of magnitude as the present-day CO2 fluxes degassed from spring waters located along the Main Central Thrust. We suggest that these metamorphic CO2 fluxes should be considered in any future attempts of estimating the global budget of non-volcanic carbon fluxes from the lithosphere.

A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

NASA Technical Reports Server (NTRS)

Niles, P. B.; Socki, R. A.; Hredzak, P. L.

2007-01-01

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

Development of a laser remote sensing instrument to measure sub-aerial volcanic CO2 fluxes

NASA Astrophysics Data System (ADS)

Queisser, Manuel; Burton, Mike

2016-04-01

A thorough quantification of volcanic CO2 fluxes would lead to an enhanced understanding of the role of volcanoes in the geological carbon cycle. This would enable a more subtle understanding of human impact on that cycle. Furthermore, variations in volcanic CO2 emissions are a key to understanding volcanic processes such as eruption phenomenology. However, measuring fluxes of volcanic CO2 is challenging as volcanic CO2 concentrations are modest compared with the ambient CO2 concentration (~400 ppm) . Volcanic CO2 quickly dilutes with the background air. For Mt. Etna (Italy), for instance, 1000 m downwind from the crater, dispersion modelling yields a signal of ~4 ppm only. It is for this reason that many magmatic CO2 concentration measurements focus on in situ techniques, such as direct sampling Giggenbach bottles, chemical sensors, IR absorption spectrometers or mass spectrometers. However, emission rates are highly variable in time and space. Point measurements fail to account for this variability. Inferring 1-D or 2-D gas concentration profiles, necessary to estimate gas fluxes, from point measurements may thus lead to erroneous flux estimations. Moreover, in situ probing is time consuming and, since many volcanoes emit toxic gases and are dangerous as mountains, may raise safety concerns. In addition, degassing is often diffuse and spatially extended, which makes a measurement approach with spatial coverage desirable. There are techniques that allow to indirectly retrieve CO2 fluxes from correlated SO2 concentrations and fluxes. However, they still rely on point measurements of CO2 and are prone to errors of SO2 fluxes due to light dilution and depend on blue sky conditions. Here, we present a new remote sensing instrument, developed with the ERC project CO2Volc, which measures 1-D column amounts of CO2 in the atmosphere with sufficient sensitivity to reveal the contribution of magmatic CO2. Based on differential absorption LIDAR (DIAL) the instrument measures the absorption, and therefore path amount, of CO2 in the atmosphere. The kit has been optimized to be rugged, man-portable and to use little power (~ 70W). By flying the instrument over a volcanic plume we will be able to swiftly determine CO2 fluxes. This opens the possibility of rapid, comprehensive surveys of both point source, open-vent CO2 emissions, as well as emissions from more diffuse sources such as lakes and fumarole fields. We present initial test results from the new instrument. We believe that the CO2 LIDAR could make a major contribution to volcano monitoring. Potential follow-on applications include environmental monitoring, such as fugitive CO2 detection in storage sites or urban monitoring of car and ship emissions.

Experimental study of lunar and SNC (Mars) magmas

NASA Technical Reports Server (NTRS)

Rutherford, Malcolm J.

1994-01-01

The overall objectives of this research were to evaluate the role of C-O-S-Cl degassing processes in explaining vesiculation, oxidation state and fire-fountaining of lunar magmas by analysis of individual lunar glass spherules, and by experimental determination of equilibrium abundances and diffusion rates of C, S and Cl melt species in lunar glass compositions; and to determine possible primitive SNC magma compositions and the mineralogy of the mantle from which they were derived, and to evaluate P, T, XH2O etc. conditions at which they crystallize to form the SNC meteorites. After funding for one year, a project on the A15 volcanic green glass has been completed to the point of writing a first manuscript. Carbon-oxygen species C-O and CO2 are below detection limits (20 ppm) in these glasses, but there is up to 500 ppm S with concentrations both increasing and decreasing toward the spherule margins. Calculations and modeling indicate that C species could have been present in the volcanic gases, however. In a second project, experiments with low PH2O have resulted in refined estimates of the early intercumulus melt composition in the Chassigny meteorite which is generally accepted as a sample from Mars.

Transport of dissolved carbon and CO2 degassing from a river system in a mixed silicate and carbonate catchment

NASA Astrophysics Data System (ADS)

Khadka, Mitra B.; Martin, Jonathan B.; Jin, Jin

2014-05-01

Assessing the origin, transformation and transport of terrestrially derived carbon in river systems is critical to regional and global carbon cycles, particularly in carbonate terrains, which represent the largest carbon reservoir on the earth’s surface. For this reason, we evaluated sources, cycling, and fluxes of dissolved organic and inorganic carbon (DOC and DIC) and riverine CO2 degassing to the atmosphere in the Santa Fe River in north-central Florida, a sub-tropical river that flows across two distinct hydrogeological settings of a region dominated by carbonate karst. One setting occurs in the upper river catchment, where the carbonate Floridan aquifer is confined by the siliciclastic Hawthorn Group, while the other setting occurs in the lower catchment where the river flows across the unconfined Floridan aquifer. The upper catchment is characterized by DOC-rich and DIC-poor water and the DIC has more variable and lower δ13C values compared to the lower catchment. The river in the upper catchment degasses more CO2 to the atmosphere (1156 g C m-2 yr-1) than in the lower catchment (402 g C m-2 yr-1) because soil respired carbon and organic matter decomposition increase dissolved CO2 concentration, much of which is consumed during carbonate dissolution reactions in the lower catchment. The CO2 flux from the water surface to the atmosphere during a flood event is three times greater than during base flow, suggesting that excess precipitation flushes soil organic carbon to the river through interflow and enhances the loss of terrestrial carbon via river water to the atmosphere. Our values of CO2 fluxes to the atmosphere lie within the range of fluxes from the world’s rivers, but fluxes from the carbonate dominated region are at the low end, while fluxes from the siliciclastic region are at the high end. These results indicate that catchment lithologies, particularly whether carbonate or siliciclastic, as well as flow, are critical to carbon budgets in rivers and thus are linked to the global carbon cycle.

2D and 3D high resolution seismic imaging of shallow Solfatara crater in Campi Flegrei (Italy): new insights on deep hydrothermal fluid circulation processes

NASA Astrophysics Data System (ADS)

De Landro, Grazia; Gammaldi, Sergio; Serlenga, Vincenzo; Amoroso, Ortensia; Russo, Guido; Festa, Gaetano; D'Auria, Luca; Bruno, Pier Paolo; Gresse, Marceau; Vandemeulebrouck, Jean; Zollo, Aldo

2017-04-01

Seismic tomography can be used to image the spatial variation of rock properties within complex geological media such as volcanoes. Solfatara is a volcano located within the Campi Flegrei still active caldera, characterized by periodic episodes of extended, low-rate ground subsidence and uplift called bradyseism accompanied by intense seismic and geochemical activities. In particular, Solfatara is characterized by an impressive magnitude diffuse degassing, which underlines the relevance of fluid and heat transport at the crater and prompted further research to improve the understanding of the hydrothermal system feeding the surface phenomenon. In this line, an active seismic experiment, Repeated Induced Earthquake and Noise (RICEN) (EU Project MEDSUV), was carried out between September 2013 and November 2014 to provide time-varying high-resolution images of the structure of Solfatara. In this study we used the datasets provided by two different acquisition geometries: a) A 2D array cover an area of 90 x 115 m ^ 2 sampled by a regular grid of 240 vertical sensors deployed at the crater surface; b) two 1D orthogonal seismic arrays deployed along NE-SW and NW-SE directions crossing the 400 m crater surface. The arrays are sampled with a regular line of 240 receiver and 116 shots. We present 2D and 3D tomographic high-resolution P-wave velocity images obtained using two different tomographic methods adopting a multiscale strategy. The 3D image of the shallow (30-35 m) central part of Solfatara crater is performed through the iterative, linearized, tomographic inversion of the P-wave first arrival times. 2D P-wave velocity sections (60-70 m) are obtained using a non-linear travel-time tomography method based on the evaluation of a posteriori probability density with a Bayesian approach. The 3D retrieved images integrated with resistivity section and temperature and CO2 flux measurements , define the following characteristics: 1. A depth dependent P-wave velocity layer down to 14 m, with Vp<700m/s typical of poorly-consolidated tephra and affected by CO2 degassing; 2. An intermediate layer, deepening towards the mineralized liquid-saturated area (Fangaia), interpreted as permeable deposits saturated with condensed water; 3. A deep, confined high velocity anomaly associated with a CO2 reservoir. With the 2D profiles we can image up to around 70 m depth: the first 30 m are characterized by features and velocities comparable to those of the 3D profiles, deeper, between 40-60 m depth, were found two low velocity anomalies, that probably indicate a preferential via for fluid degassing. These features are expression of an area located between the Fangaia, which is water saturated and replenished from deep aquifers, and the main fumaroles that are the superficial relief of deep rising CO2 flux. So, the changes in the outgassing rate greatly affects the shallow hydrothermal system, which can be used as a near-surface "mirror" of fluid migration processes occurring at greater depths.

MaGa, a web-based collaborative database for gas emissions: a tool to improve the knowledge on Earth degassing

NASA Astrophysics Data System (ADS)

Frigeri, A.; Cardellini, C.; Chiodini, G.; Frondini, F.; Bagnato, E.; Aiuppa, A.; Fischer, T. P.; Lehnert, K. A.

2014-12-01

The study of the main pathways of carbon flux from the deep Earth requires the analysis of a large quantity and variety of data on volcanic and non-volcanic gas emissions. Hence, there is need for common frameworks to aggregate available data and insert new observations. Since 2010 we have been developing the Mapping Gas emissions (MaGa) web-based database to collect data on carbon degassing form volcanic and non-volcanic environments. MaGa uses an Object-relational model, translating the experience of field surveyors into the database schema. The current web interface of MaGa allows users to browse the data in tabular format or by browsing an interactive web-map. Enabled users can insert information as measurement methods, instrument details as well as the actual values collected in the field. Measurements found in the literature can be inserted as well as direct field observations made by human-operated instruments. Currently the database includes fluxes and gas compositions from active craters degassing, diffuse soil degassing and fumaroles both from dormant volcanoes and open-vent volcanoes from literature survey and data about non-volcanic emission of the Italian territory. Currently, MaGa holds more than 1000 volcanic plume degassing fluxes, data from 30 sites of diffuse soil degassing from italian volcanoes, and about 60 measurements from fumarolic and non volcanic emission sites. For each gas emission site, the MaGa holds data, pictures, descriptions on gas sampling, analysis and measurement methods, together with bibliographic references and contacts to researchers having experience on each site. From 2012, MaGa developments started to be focused towards the framework of the Deep Earth Carbon Degassing research initiative of the Deep Carbon Observatory. Whithin the DECADE initiative, there are others data systems, as EarthChem and the Smithsonian Institution's Global Volcanism Program. An interoperable interaction between the DECADE data systems is being planned. MaGa is showing good potentials to improve the knowledge on Earth degassing firstly by making data more accessible and encouraging participation among researchers, and secondly by allowing to observe and explore, for the first time, a gas emission dataset with spatial and temporal extents never analyzed before.

No effect of H2O degassing on the oxidation state of hydrous rhyolite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations in six obsidian samples from the Mexican and Cascade arcs

NASA Astrophysics Data System (ADS)

Waters, L.; Lange, R. A.

2011-12-01

The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not including dissolved water), oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 4.2 to 7.5 wt%. Both the oxidation state and water concentration are known prior to eruption, at the time of phenocryst growth. After eruption, the rhyolites lost nearly all of their volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of rhyolite magmas, which requires that dissolved water has no resolvable affect on the activity ratio of the iron oxide components in melt.

Degassing dynamics of basaltic lava lake at a top-ranking volatile emitter: Ambrym volcano, Vanuatu arc

NASA Astrophysics Data System (ADS)

Allard, Patrick; Burton, Mike; Sawyer, Georgina; Bani, Philipson

2016-08-01

Persistent lava lakes are rare on Earth and provide volcanologists with a remarkable opportunity to directly investigate magma dynamics and degassing at the open air. Ambrym volcano, in Vanuatu, is one of the very few basaltic arc volcanoes displaying such an activity and voluminous gas emission, but whose study has long remained hampered by challenging accessibility. Here we report the first high temporal resolution (every 5 s) measurements of vigorous lava lake degassing inside its 300 m deep Benbow crater using OP-FTIR spectroscopy. Our results reveal a highly dynamic degassing pattern involving (i) recurrent (100-200 s) short-period oscillations of the volcanic gas composition and temperature, correlating with pulsated gas emission and sourced in the upper part of the lava lake, (ii) a continuous long period (∼8 min) modulation probably due to the influx of fresh magma at the bottom of the lake, and (iii) discrete CO2 spike events occurring in coincidence with the sequential bursting of meter-sized bubbles, which indicates the separate ascent of large gas bubbles or slugs in a feeder conduit with estimated diameter of 6 ± 1 m. This complex degassing pattern, measured with unprecedented detail and involving both coupled and decoupled magma-gas ascent over short time scales, markedly differs from that of quieter lava lakes at Erebus and Kilauea. It can be accounted for by a modest size of Benbow lava lake and its very high basalt supply rate (∼20 m3 s-1), favouring its rapid overturn and renewal. We verify a typical basaltic arc signature for Ambrym volcanic gas and, based on contemporaneous SO2 flux measurements, we evaluate huge emission rates of 160 Gg d-1 of H2O, ∼10 Gg d-1 of CO2 and ∼8 Gg d-1 of total acid gas (SO2, HCl and HF) during medium activity of the volcano in 2008. Such rates make Ambrym one of the three most powerful volcanic gas emitters at global scale, whose atmospheric impact at local and regional scale may be considerable.

Continental Arcs as Both Carbon Source and Sink in Regulating Long Term Climate

NASA Astrophysics Data System (ADS)

Jiang, H.; Lee, C. T.

2017-12-01

The long-term variability of atmospheric pCO2 is determined by the balance between the rate of geologic inputs of CO­­2 (e.g., magmatic/metamorphic degassing, carbonate weathering) and the rate of carbonate precipitation driven by silicate weathering. The Late Cretaceous-Early Cenozoic was characterized by elevated atmospheric pCO2 and greenhouse climate, likely due to increased magmatic flux from mid-ocean ridges and, in particular, continental arcs. However, it has been suggested that continental arc magmatism is accompanied by rapid uplift and erosion due to magmatic/tectonic thickening of the crust, thus continental arcs likely enhance the chemical weathering flux, in turn increasing the carbon sink. To assess the contribution of continental arcs to global carbon inputs and sinks, we conducted a case study in the Cretaceous Peninsular Ranges batholith (PRB) and associated forearc basin in southern California, USA, representing one segment of the Cretaceous Cordillera arc-forearc system. Arc magmatism occurred between 170-85 Ma, peaking at 100 Ma, but erosion of the arc continues into the early Eocene, with forearc sediments representing this protracted arc unroofing. During magmatism, we estimate the CO2 degassing flux from the PRB was at least 5-25*105 mol·km-2·yr-1. By calculating the depletion of Ca and Mg in the forearc sediments relative to their arc protoliths, we estimate the silicate weathering/carbonate precipitation flux to be 106 mol·km-2·yr-1 during Late Cretaceous magmatism, decreasing to 105 mol·km-2·yr-1 by the Early Eocene. We show that during active continental arc magmatism, the CO2 degassing flux is comparable to CO2 consumption driven by silicate weathering in the arc. However, after magmatism ends, a regional imbalance arises in which the arc no longer contributes to CO2 inputs but continued silicate weathering of the arc drives carbonate precipitation such that the arc indirectly becomes CO2 sink. We propose that the development of continental arcs increases weatherability through mountain building processes, and therefore may affect the strength of the global negative feedback between silicate weathering and climate. Future studies are needed to quantify the variability in weathering feedback strength associated with global continental arc development.

Degassing of H2O in a phonolitic melt: A closer look at decompression experiments

NASA Astrophysics Data System (ADS)

Marxer, Holger; Bellucci, Philipp; Nowak, Marcus

2015-05-01

Melt degassing during magma ascent is controlled by the decompression rate and can be simulated in decompression experiments. H2O-bearing phonolitic melts were decompressed at a super-liquidus T of 1323 K in an internally heated argon pressure vessel, applying continuous decompression (CD) as well as to date commonly used step-wise decompression (SD) techniques to investigate the effect of decompression method on melt degassing. The hydrous melts were decompressed from 200 MPa at nominal decompression rates of 0.0028-1.7 MPa·s- 1. At final pressure (Pfinal), the samples were quenched rapidly at isobaric conditions with ~ 150 K·s- 1. The bubbles in the quenched samples are often deformed and dented. Flow textures in the glass indicate melt transport at high viscosity. We suggest that this observation is due to bubble shrinkage during quench. This general problem was mostly overlooked in the interpretation of experimentally degassed samples to date. Bubble shrinkage due to decreasing molar volume (Vm) of the exsolved H2O in the bubbles occurs during isobaric rapid quench until the melt is too viscous too relax. The decrease of Vm(H2O) during cooling at Pfinal of the experiments results in a decrease of the bubble volume by a shrinking factor Bs: At nominal decompression rates > 0.17 MPa·s- 1 and a Pfinal of 75 MPa, the decompression method has only minor influence on melt degassing. SD and CD result in high bubble number densities of 104-105 mm- 3. Fast P drop leads to immediate supersaturation with H2O in the melt. At such high nominal decompression rates, the diffusional transport of H2O is limited and therefore bubble nucleation is the predominant degassing process. The residual H2O contents in the melts decompressed to 75 MPa increase with nominal decompression rate. After homogeneous nucleation is triggered, CD rates ≤ 0.024 MPa·s- 1 facilitate continuous reduction of the supersaturation by H2O diffusion into previously nucleated bubbles. Bubble number densities of CD samples with low nominal decompression rates are several orders of magnitude lower than for SD experiments and the bubble diameters are larger. The reproducibility of MSD experiments with low nominal decompression rates is worse than for CD runs. Commonly used SD techniques are therefore not suitable to simulate melt degassing during continuous magma ascent with low ascent rates.

Riverine CO2 supersaturation and outgassing in a subtropical monsoonal mountainous area (Three Gorges Reservoir Region) of China

NASA Astrophysics Data System (ADS)

Li, Siyue; Ni, Maofei; Mao, Rong; Bush, Richard T.

2018-03-01

Rivers are an important source of CO2 to the atmosphere, however, mountainous rivers and streams with high emission rates are not well studied particularly in China. We report the first detailed investigation on monsoonal mountainous rivers in the Three Gorges Reservoir (TGR) region, with a focus on the riverine CO2 partial pressure (pCO2), CO2 degassing and their potential controls. The pCO2 levels ranged from 50 to 6019 μatm with averages of 1573 (SD. ±1060) in dry Autumn and 1276 (SD. ±1166) μatm in wet Summer seasons. 94% of samples were supersaturated with CO2 with respect to the atmospheric equilibrium (410 μatm). Monsoonal precipitation controlled pCO2 seasonality, with both the maximal and minimal levels occurring in the wet season, and showing the overall effects of dilution. Riverine pCO2 could be predicted better in the dry season using pH, DO% and DTP, whereas pH and DOC were better predictors in the wet season. We conclude that in-situ respiration of allochthonous organic carbon, rather than photosynthesis, resulted in negative relationships between pCO2 and DO and pH, and thus CO2 supersaturation. Photosynthetic primary production was effectively limited by rapid flow velocity and short residence time. The estimated water-to-air CO2 emission rate in the TGR rivers was 350 ± 319 in the Autumn and lower, yet more variable at 326 ± 439 mmol/m2/d in Summer. Our calculated CO2 areal fluxes were in the upper-level magnitude of published data, demonstrating the importance of mountainous rivers and streams as a global greenhouse gas source, and urgency for more detailed studies on CO2 degassing, to address a global data gap for these environments.

Popping rocks from the Mid-Atlantic Ridge: Insights into mantle volatile concentrations and degassing dynamics

NASA Astrophysics Data System (ADS)

Jones, M.; Soule, S. A.; Kurz, M. D.; Wanless, V. D.; Le Roux, V.; Klein, F.; Mittelstaedt, E. L.; Curtice, J.

2016-12-01

During a 1985 cruise, the Mid-Atlantic Ridge (MAR) near 14°N yielded an unusually vesicular mid-ocean ridge (MOR) basalt that popped upon recovery from the seafloor due to the release of trapped volatiles. This `popping rock' has been inferred to be representative of primitive, undegassed magmas from the upper mantle due to its high volatile concentrations. Thus, the sample has been used to constrain CO2 flux from the MOR system, upper mantle volatile concentrations, and magma degassing dynamics. However, the lack of geologic context for the original popping rock raises questions about whether it truly reflects the volatile content of its mantle source. Here, we present results from a 2016 cruise to the MAR aimed at characterizing the geologic context of popping rocks and understanding their origins. The newly recovered samples display differences in volatile concentrations and vesicularities between popping and non-popping rocks. These differences may be related to geologic setting and eruption dynamics with potential implications for mantle volatile concentrations. Volatile concentrations in the outer quenched margin of new samples were measured by ion microprobe to elucidate degassing systematics, brine/magma interactions, and popping rock formation. The large variability in dissolved H2O (0.05-0.77 wt%) can be attributed to spatially variable brine contamination. Dissolved CO2 concentrations (153-356 ppm) are likely controlled by initial volatile concentrations and variable degrees of degassing. The subset of popping samples display low dissolved CO2 concentrations (161-178 ppm) and moderate dissolved H2O concentrations (.44-.50 wt%) and are at equilibrium with their eruption depth based on solubility calculations. X-ray microtomography reveals vesicularity in newly collected popping rocks exceeding 19%, making these samples the most highly vesicular recovered from the MAR. The total gas contents in the basaltic glasses are inferred from dissolved volatile concentrations and vesicularity. These calculations are aided by analysis of gas contents in vesicles by confocal Raman spectroscopy and vacuum crushing experiments. The preliminary results and seafloor observations allow an evaluation of the origins of popping rocks and their implications for mantle volatile concentrations.

Degassing of basaltic magma: decompression experiments and implications for interpreting the textures of volcanic rocks

NASA Astrophysics Data System (ADS)

Le Gall, Nolwenn; Pichavant, Michel; Cai, Biao; Lee, Peter; Burton, Mike

2017-04-01

Decompression experiments were performed to simulate the ascent of basaltic magma, with the idea of approaching the textural features of volcanic rocks to provide insights into degassing processes. The experiments were conducted in an internally heated pressure vessel between NNO-1.4 and +0.9. H2O-only (4.9 wt%) and H2O-CO2-bearing (0.71-2.45 wt% H2O, 818-1094 ppm CO2) melts, prepared from Stromboli pumice, were synthesized at 1200°C and 200 MPa, continuously decompressed between 200 and 25 MPa at a rate of either 39 or 78 kPa/s (or 1.5 and 3 m/s, respectively), and rapidly quenched. Run products were characterized both texturally (by X-ray computed tomography and scanning electron microscopy) and chemically (by IR spectroscopy and electron microprobe analysis), and then compared with products from basaltic Plinian eruptions and Stromboli paroxysms (bubble textures, glass inclusions). The obtained results demonstrate that textures are controlled by the kinetics of nucleation, growth, coalescence and outgassing of the bubbles, as well as by fragmentation, which largely depend on the presence of CO2 in the melt and the achievement in chemical equilibrium. Textures of the H2O-only melts result from two nucleation events, the first at high pressure (200 < P < 150 MPa) and the second at low pressure (50 < P < 25 MPa), preceding fragmentation. Both events, restricted to narrow P intervals, are driven by melt H2O supersaturation. In contrast, textures of the H2O-CO2-bearing basaltic melts result from continuous bubble nucleation, which is driven by the generation of melts supersaturated in CO2. This persistent non-equilibrium degassing causes the bubbles to evolve through power law distributions, as small bubbles continue to form and grow. This is what is observed in Plinian products. From our results, the evolution to mixed power law-exponential distributions, as found in Stromboli products, is indicative of the prevalence of bubble coalescence and an evolution toward chemical equilibrium. In line with this, a strong correlation was found between experimental and natural bubble textures (bubble number densities, shapes, sizes and distributions), having implications for interpreting bubbles in volcanic rocks and quantifying magma ascent rates. Next step will be to perform in situ decompression experiments to simulate both degassing and crystallization of basaltic magma during ascent in the shallow volcanic conduit (P < 50 MPa), using synchrotron X-ray imaging. The obtained 4D (3D + time) data will help us refine our understanding of magma ascent processes. This experimental programme requires first technology adaptation and development, which is in progress.

Water in Volcanic Glass: From Volcanic Degassing to Secondary Hydration

NASA Astrophysics Data System (ADS)

Seligman, A. N.; Bindeman, I. N.; Palandri, J. L.; Watkins, J. M.; Ross, A. M.

2015-12-01

Volcanic glass contains both primary magmatic and secondary meteoric dissolved water, which can have distinguishable hydrogen isotopic ratios. We analyzed compositionally and globally diverse volcanic glass from recent to 640 ka for their δD (‰, VSMOW) and H2Ot (wt.%) on the TC/EA MAT 253 continuous flow system. We find that rhyolite glass is hydrated faster than basaltic glass, and in the majority of glasses an increase in age and total water content leads to a decrease in δD (‰), which is opposite the trend for magmatic degassing, while a few equatorial glasses have little change in δD (‰). To better understand these results, we imaged 6 tephra clasts ranging in age and chemical composition using BSE (by FEI SEM) down to a resolution of ~1 mm. Mafic tephra have lower vesicle number densities (N/mm2 = 25-77) than silicic tephra (736) and thicker average bubble walls (0.07 mm) than silicic tephra (0.02 mm). Lengths of water diffusion were modeled by finite difference using H2Ot concentration-dependent diffusion coefficients for diffusion of water into basalt and rhyolite glass using Zhang et al. (2007) and Ni and Zhang (2008) diffusion parameterizations extrapolated to surface temperatures. Due to the 106 times slower diffusion, water only diffused ~10-5 mm into basaltic glass and ~10 mm into rhyolitic glass after 1000 years. These hydration rates match our H2Ot wt.% values for basaltic tephra, and would cause a rhyolite glass, with an average bubble wall thickness of 0.02 mm as described above, to already be fully hydrated with ~3.0-3.5 wt.% H2Ot after ~1000 years, which is similar to what we observe. Results here are our initial steps in understanding water diffusion rates at ambient temperature in basalt and rhyolite tephra, and the isotopic changes that occur during hydration, which have implications for research in physical volcanology (quantities of residual magmatic water) and paleoenvironments (low temperature hydration rates and isotopic changes of glass).

H2O-CO2-S-Cl partitioning and mixing in rhyolitic melts and fluid - Implications on closed-system degassing in rhyolite

NASA Astrophysics Data System (ADS)

Ding, S.; Webster, J. D.

2017-12-01

Magmatic degassing involving multiple volatile components (C, O, H, S, Cl, etc.) is one of the key factors influencing the timing and nature of volcanic eruptions, and the chemistry of volcanic gases released to the surface. In particular, exsolution of these volatiles from silicic magma during ascent could trigger explosive volcanic eruptions, which can exert strong impacts on surface temperature, ecology and human health. However, quantitative evaluation of this process in silicic magma remains ambiguous due to the lack of experiments in such chemically complex systems. Rhyolite-fluid(s) equilibria experiments were conducted in an IHPVat 100-300 MPa and 800 ° C to determine the solubilities, fluid-melt partitioning, and mixing properties of H2O, CO2, S, and Cl in the oxygen fugacity (fO2) range of FMQ to FMQ+3. The integrated bulk fluids contain up to 94 mol% H2O, 32 mol% CO2, 1 mol% S and 1mol% Cl. Rhyolite melt dissolved 20- 770 ppm CO2 and 4-7 wt.% H2O, varying with pressure, fluid composition, and fO2. Concentrations of H2O and CO2 in melt from C-O-H-S-Cl- bearing experiments at 100 and 200 MPa, and from C-O-H only experiments are generally consistent with the predictions of existing CO2-H2O solubility models based on the C-O-H only system [1-4], while the solubilities of H2O and CO2 in melt with addition of S±Cl at 300 MPa are less than those of the C-O-H- only system. This reduction in H2O and CO2 solubilities exceeds the effects of simple dilution of the coexisting fluid owing to addition of other volatiles, and rather, reflects complex mixing relations. Rhyolite melt also dissolved 20-150 ppm S and 850-2000 ppm Cl, varying with pressure. At 300 MPa, S concentrations in the melt change with fO2. The partitioning of CO2 and S between fluid and melt varies as a function of fluid composition and fO2. Solubilities and complex mixing relationships of CO2, H2O, S and Cl revealed in our experiments can be applied to massive rhyolitic eruptions like those of the Bishop tuff, Toba tuff and Pinatubo to better understand the degassing process, to estimate fluid compositions, and thus, to evaluate the potential environmental impacts of these super eruptions. [1] Ghiorso amd Gualda, 2015, CMP; [2] Liu et al., 2005, J. Volcanol. Geotherm. Res.; [3] Newman and Lowenstern, 2002, Comput. Geosci.; [3] Tamic et al., 2001, Chem. Geol..

Evidence of water degassing during emplacement and crystallization of 2.7 Ga komatiites from the Agnew-Wiluna greenstone belt, Western Australia

NASA Astrophysics Data System (ADS)

Fiorentini, M. L.; Beresford, S. W.; Stone, W. E.; Deloule, E.

2012-07-01

Komatiites are ancient volcanic rocks, mostly over 2.7 billion years old, which formed through >30% partial melting of the mantle. This study addresses the crucial relationship between volcanology and physical manifestation of primary magmatic water content in komatiites of the Agnew-Wiluna greenstone belt, Western Australia, and documents the degassing processes that occurred during the emplacement and crystallization of these magmas. The Agnew-Wiluna greenstone belt of Western Australia contains three co-genetic komatiite units that (1) display laterally variable volcanological features, including thick cumulates and spinifex-textured units, and (2) were emplaced as both lava flows and intrusions at various locations. Komatiite sills up to 500 m thick contain widespread occurrence of hydromagmatic amphibole in orthocumulate- and mesocumulate-textured rocks, which contain ca. 40-50 wt% MgO and <3 wt% TiO2. Conversely, komatiite flows do not contain any volatile-bearing mineral phases: ~150-m-thick flows only contain vesicles, amygdales and segregation structures, whereas <5-10-m-thick flows lack any textural and petrographic evidence of primary volatile contents. The main results of this study demonstrate that komatiites from the Agnew-Wiluna greenstone belt, irrespective of their initial water content, have degassed upon emplacement, flow and crystallization. More importantly, data show that komatiite flows most likely degassed more water than komatiite intrusions. Komatiite degassing may have indirectly influenced numerous physical and chemical parameters of the water from the primordial oceans and hence indirectly contributed to the creation of a complex zonation at the interface between water and seafloor.

Time-Resolved Gravimetric Method To Assess Degassing of Roasted Coffee.

PubMed

Smrke, Samo; Wellinger, Marco; Suzuki, Tomonori; Balsiger, Franz; Opitz, Sebastian E W; Yeretzian, Chahan

2018-05-30

During the roasting of coffee, thermally driven chemical reactions lead to the formation of gases, of which a large fraction is carbon dioxide (CO 2 ). Part of these gases is released during roasting while part is retained inside the porous structure of the roasted beans and is steadily released during storage or more abruptly during grinding and extraction. The release of CO 2 during the various phases from roasting to consumption is linked to many important properties and characteristics of coffee. It is an indicator for freshness, plays an important role in shelf life and in packaging, impacts the extraction process, is involved in crema formation, and may affect the sensory profile in the cup. Indeed, and in view of the multiple roles it plays, CO 2 is a much underappreciated and little examined molecule in coffee. Here, we introduce an accurate, quantitative, and time-resolved method to measure the release kinetics of gases from whole beans and ground coffee using a gravimetric approach. Samples were placed in a container with a fitted capillary to allow gases to escape. The time-resolved release of gases was measured via the weight loss of the container filled with coffee. Long-term stability was achieved using a customized design of a semimicro balance, including periodic and automatic zero value measurements and calibration procedures. The novel gravimetric methodology was applied to a range of coffee samples: (i) whole Arabica beans and (ii) ground Arabica and Robusta, roasted to different roast degrees and at different speeds (roast air temperatures). Modeling the degassing rates allowed structural and mechanistic interpretation of the degassing process.

First data on the volatile fluxes from passively degassing volcanoes of the Kuril Island arc

NASA Astrophysics Data System (ADS)

Melnikov, Dmitry; Malik, Nataliya; Chaplygin, Ilya; Zelenski, Mikhail

2017-04-01

We report the first data on the volatile fluxes from passively degassing volcanoes of Kuril Island arc in the North-Western Pacific measured in 2015-2016. Four volcanoes: Ebeko on the northern Paramushir Island, Kuntomintar and Pallace on the Central Shiashkotan and Ketoy islands, and Kudryavy on the southern Iturup island are representative for the whole Kuril arc as having the largest and strongest fumarolic fields among 40 of the active volcanoes of the arc. The fluxes were measured using scanning DOAS, remote miniDOAS, plume MultiGas and direct sampling techniques using the SO2 flux from the DOAS data and ratios measured by MultiGas (SO2/CO2, SO2/H2S, SO2/H2O) and direct sampling (SO2/HCl). For Kudryavy volcano the ratios were applied that have been measured by Taran et al. (1995) and Fischer et al. (1998) using direct sampling. Until now, for Kuril arc only the SO2 flux from Kudryavy was measured by the COSPEC technique in 1995 by Fischer et al. (1998) with an average SO2 flux of 75 t/d. Our data give for Kudryavy in October 2016 a value of 340 t/d. The total measured SO2 flux in 2015-2016 from the passively degassing volcanoes of the Kuril arc is near 1000 t/d. This value is an excellent agreement with the estimation made in Taran (2009) using a comparative plume height technique based on visual observations. Averaged fluxes (in ton/day) of mayor (Range of vent temperatures °C, SO2, CO2, H2O, HCl, total flux) components of volcanic emissions from Kurilian volcanoes in 2016: Ebeko - 97-490 °C, 100 (SO2), 81 (CO2), 1120 (H2O), 17 (HCl), 1319; Kuntomintar - 130-260 °C, 54 (SO2), 157 (CO2), 1064 (H2O), 8 (HCl), 1283; Pallas - 140-720 °C, 450 (SO2), 78 (CO2), 3800 (H2O), 120 (HCl), 4448; Kudryavy - 130-920 °C, 340 (SO2), 131 (CO2), 4445 (H2O), 85 (HCl), 5001. Total (± 20%): 930 (SO2), 450 (CO2), 10400 (H2O), 230 (HCl), 12050 (total flux). This work was supported by grant from the Russian Science Foundation # 15-17-20011. References: Taran et al. (1995) GCA, 59, 1741-1761; Fischer et al. (1998) EPSL, 160, 81-96; Taran (2009) GCA, 73, 1067-1091

Volatile contents of mafic-to-intermediate magmas at San Cristóbal volcano in Nicaragua

NASA Astrophysics Data System (ADS)

Robidoux, P.; Aiuppa, A.; Rotolo, S. G.; Rizzo, A. L.; Hauri, E. H.; Frezzotti, M. L.

2017-02-01

San Cristóbal volcano in northwest Nicaragua is one of the most active basaltic-andesitic stratovolcanoes of the Central American Volcanic Arc (CAVA). Here we provide novel constraints on the volcano's magmatic plumbing system, by presenting the first direct measurements of major volatile contents in mafic-to-intermediate glass inclusions from Holocene and historic-present volcanic activity. Olivine-hosted (forsterite [Fo] < 80; Fo< 80) glass inclusions from Holocene tephra layers contain moderate amounts of H2O (0.1-3.3 wt%) and S and Cl up to 2500 μg/g, and define the mafic (basaltic) endmember component. Historic-present scoriae and tephra layers exhibit more-evolved olivines (Fo69-72) that contain distinctly lower volatile contents (0.1-2.2 wt% H2O, 760-1675 μg/g S, and 1021-1970 μg/g Cl), and represent a more-evolved basaltic-andesitic magma. All glass inclusions are relatively poor in CO2, with contents reaching 527 μg/g (as measured by nanoscale secondary ion mass spectrometry), suggesting pre- to postentrapment CO2 loss to a magmatic vapor. We use results of Raman spectroscopy obtained in a population of small (< 50 μm) inclusions with CO2-bearing shrinkage bubbles (3-12 μm) to correct for postentrapment CO2 loss to bubbles, and to estimate the original minimum CO2 content in San Cristóbal parental melts at 1889 μg/g, which is consistent with the less-CO2-degassed melt inclusions (MI) (> 1500 μg/g) found in Nicaragua at Cerro Negro, Nejapa, and Granada. Models of H2O and CO2 solubilities constrain the degassing pathway of magmas up to 425 MPa ( 16 km depth), which includes a deep CO2 degassing step (only partially preserved in the MI record), followed by coupled degassing of H2O and S plus crystal fractionation at magma volatile saturation pressures from ∼ 195 to < 10 MPa. The variation in volatile contents from San Cristóbal MI is interpreted to reflect (1) Holocene eruptive cycles characterized by the rapid emplacement of basaltic magma batches, saturated in volatiles, at depths of 3.8-7.4 km, and (2) the ascent of more-differentiated and cogenetic volatile-poor basaltic andesites during historic-present eruptions, having longer residence times in the shallowest (< 3.4 km) and hence coolest regions of the magmatic plumbing system. We also report the first measurements of the compositions of noble-gas isotopes (He, Ne, and Ar) in fluid inclusions in olivine and pyroxene crystals. While the measured 40Ar/36Ar ratios (300-304) and 4He/20Ne ratios (9-373) indicate some degree of air contamination, the 3He/4He ratios (7.01-7.20 Ra) support a common mantle source for Holocene basalts and historic-present basaltic andesites. The magmatic source is interpreted as generated by a primitive MORB-like mantle, that is influenced to variable extents by distinct slab fluid components for basalts (Ba/La 76 and U/Th 0.8) and basaltic andesites (Ba/La 86 and U/Th 1.0) in addition to effects of magma differentiation. These values for the geochemical markers are particularly high, and their correlation with strong plume CO2/S ratios from San Cristóbal is highly consistent with volatile recycling at the CAVA subduction zone, where sediment involvement in mantle fluids influences the typical relatively C-rich signature of volcanic gases in Nicaragua.

Evidence for a sulfur-undersaturated lunar interior from the solubility of sulfur in lunar melts and sulfide-silicate partitioning of siderophile elements

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Seegers, A. X.; Eising, J.; Tomassen, B. G. J.; Webers, F. P. F.; Berndt, J.; Klemme, S.; Matveev, S.; van Westrenen, W.

2018-06-01

Sulfur concentrations at sulfide saturation (SCSS) were determined for a range of low- to high-Ti lunar melt compositions (synthetic equivalents of Apollo 14 black and yellow glass, Apollo 15 green glass, Apollo 17 orange glass and a late-stage lunar magma ocean melt, containing between 0.2 and 25 wt.% TiO2) as a function of pressure (1-2.5 GPa) and temperature (1683-1883 K). For the same experiments, sulfide-silicate partition coefficients were derived for elements V, Cr, Mn, Co, Cu, Zn, Ga, Ge, As, Se, Mo, Sn, Sb, Te, W and Pb. The SCSS is a strong function of silicate melt composition, most notably FeO content. An increase in temperature increases the SCSS and an increase in pressure decreases the SCSS, both in agreement with previous work on terrestrial, lunar and martian compositions. Previously reported SCSS values for high-FeO melts were combined with the experimental data reported here to obtain a new predictive equation to calculate the SCSS for high-FeO lunar melt compositions. Calculated SCSS values, combined with previously estimated S contents of lunar low-Ti basalts and primitive pyroclastic glasses, suggest their source regions were not sulfide saturated. Even when correcting for the currently inferred maximum extent of S degassing during or after eruption, sample S abundances are still > 700 ppm lower than the calculated SCSS values for these compositions. To achieve sulfide saturation in the source regions of low-Ti basalts and lunar pyroclastic glasses, the extent of degassing of S in lunar magma would have to be orders of magnitude higher than currently thought, inconsistent with S isotopic and core-to-rim S diffusion profile data. The only lunar samples that could have experienced sulfide saturation are some of the more evolved A17 high-Ti basalts, if sulfides are Ni- and/or Cu rich. Sulfide saturation in the source regions of lunar melts is also inconsistent with the sulfide-silicate partitioning systematics of Ni, Co and Cu. Segregation of significant quantities of (non)-stoichiometric sulfides during fractional crystallization would result in far larger depletions of Ni, Co and Cu than observed, whereas trends in their abundances are more likely explained by olivine fractionation. The sulfide exhaustion of the lunar magma source regions agrees with previously proposed low S abundances in the lunar core and mantle, and by extension with relatively minor degassing of S during the Moon-forming event. Our results support the hypothesis that refractory chalcophile and highly siderophile element systematics of low-Ti basalts and pyroclastic glasses reflect the geochemical characteristics of their source regions, instead of indicating the presence of residual sulfides in the lunar interior.

Undegassed Carbon Content from a Highly Depleted Segment of the Mid-Atlantic Ridge (1-5°S): Evidence from Melt Inclusions

NASA Astrophysics Data System (ADS)

Le Voyer, M.; Kelley, K. A.; Cottrell, E.; Hauri, E. H.

2014-12-01

As carbon solubility is low in basalts, MORB contain little dissolved CO2 (189±61 ppm, 1σ, n=600 [1]). A global negative correlation between CO2/Nb (proxy for amount of CO2 lost by degassing) and Ba/La (proxy for source enrichment) indicates that depleted MORB are less affected by degassing than enriched MORB: CO2/Nb ratios range from 0-100 for samples with Ba/La>4, while CO2/Nb range from 50 to 400 for samples with Ba/La<4 [1]. To assess the CO2 content of undegassed MORB, we analyzed the volatile content of 70 olivine-hosted, glassy melt inclusions (MIs) from four basalts dredged along MAR 1-5°S, a ridge segment that produces highly depleted MORB in terms of trace element enrichment and radiogenic isotopes [2, 3]. MIs contain CO2 contents (180-1420 ppm) that are higher than their respective matrix glasses (130-220 ppm, typical for vapor-saturated melts erupted at 3-5 km b.s.l.). One of the four dredges (EN061 5D-3Ag) contains MIs that do not exhibit shrinkage bubbles. For this sample only, we find a positive correlation between the CO2 content (240-770 ppm) and the Cl content (6-20 ppm) of the MIs that is not found in the matrix glasses (see Fig.). We infer that the correlation between CO2 and Cl, both highly incompatible in silicate minerals during fractional crystallization, is strong evidence for vapor-undersaturation, as any CO2 degassing would have erased the correlation. Together with MIs from the Siqueiros Fracture Zone [4] and from northern Iceland [5], the MIs from EN061 5D-3Ag may represent another occurrence of carbon-undersaturated MORB. Our results will be used to model the primary carbon content of MORB and of the depleted upper mantle. Note that the average Cl content of the matrix glasses (20±1 ppm) is higher than those of the MIs (12±3 ppm, see Fig.). This indicates either that the matrix glasses assimilated a small amount of seawater Cl, or that the MIs are all more depleted than the matrix glass. We will acquire major and trace element data in order to further investigate the origin of the low Cl and high CO2 contents in these MIs. Ref. [1] Le Voyer et al. 2014 Goldschmidt abstr. [2] Schilling et al. 1994 JGR 99 [3] Kelley et al. 2013 G3 [4] Saal et al. 2002 Nature 419 [5] Hauri and Saal 2009 EOS Fall suppl. AGU abstr.

Caldera unrest driven by CO2-induced drying of the deep hydrothermal system.

PubMed

Moretti, R; Troise, C; Sarno, F; De Natale, G

2018-05-29

Interpreting volcanic unrest is a highly challenging and non-unique problem at calderas, since large hydrothermal systems may either hide or amplify the dynamics of buried magma(s). Here we use the exceptional ground displacement and geochemical datasets from the actively degassing Campi Flegrei caldera (Southern Italy) to show that ambiguities disappear when the thermal evolution of the deep hydrothermal system is accurately tracked. By using temperatures from the CO 2 -CH 4 exchange of 13 C and thermodynamic analysis of gas ascending in the crust, we demonstrate that after the last 1982-84 crisis the deep hydrothermal system evolved through supercritical conditions under the continuous isenthalpic inflow of hot CO 2 -rich gases released from the deep (~8 km) magma reservoir of regional size. This resulted in the drying of the base of the hot hydrothermal system, no more buffered along the liquid-vapour equilibrium, and excludes any shallow arrival of new magma, whose abundant steam degassing due to decompression would have restored liquid-vapour equilibrium. The consequent CO 2 -infiltration and progressive heating of the surrounding deforming rock volume cause the build-up of pore pressure in aquifers, and generate the striking temporal symmetry that characterizes the ongoing uplift and the post-1984 subsidence, both originated by the same but reversed deformation mechanism.

Geological implications of a permeability-depth curve for the continental crust

USGS Publications Warehouse

Ingebritsen, S.E.; Manning, C.E.

1999-01-01

The decrease in permeability (k) of the continental crust with depth (z), as constrained by geothermal data and calculated fluid flux during metamorphism, is given by log k = -14 - 3.2 log z, where A is in meters squared and z is in kilometers. At moderate to great crustal depths (>???5 km), this curve is defined mainly by data from prograde metamorphic systems, and is thus applicable to orogenic belts where the crust is being thickened and/or heated; lower permeabilities may occur in stable cratonic regions. This k-z relation implies that typical metamorphic fluid flux values of ???10-11 m/s are consistent with fluid pressures significantly above hydrostatic values. The k-z curve also predicts that metamorphic CO2 flux from large orogens may be sufficient to cause significant climatic effects, if retrograde carbonation reactions are minimal, and suggests a significant capacity for diffuse degassing of Earth (1015-1016 g/yr) in tectonically active regions.

Constraining magma ascent and degassing paths with olivine- and clinopyroxene-hosted melt inclusions: Evidence for multiple depths of crystallization and boundary-layer entrapment

NASA Astrophysics Data System (ADS)

Lloyd, A. S.; Newcombe, M. E.; Plank, T. A.

2016-12-01

Although olivine-hosted melt inclusions (MIs) remain the gold standard for recovering volatile concentrations of primitive magmas, later-fractionating minerals may be more appropriate for assessing magma storage conditions immediately prior to eruption. We present volatile analyses of MIs entrapped in early (Mg# 81-83) olivine and later (Mg# 70-80) clinopyroxene (Cpx) from the 1977 eruption of Seguam volcano, to assess the ascent history prior to this violent strombolian eruption. The olivine-hosted MIs contain average volatile concentrations (n=16) of 3.79 wt% H2O, 167 ppm CO2, 592 ppm Cl, and 133 ppm F, consistent with an entrapment pressure of 200 to 300 MPa ( 10-13 km depth) if the CO2 contained in the bubble is taken into account (Moore et al., 2015). Cpx phenocrysts contain two distinct MI assemblages; the inner assemblage consists of randomly distributed, rounded MIs which never contain a vapor bubble. Average volatile concentrations of the inner assemblage MIs (n=11) are 0.96 wt% H2O, 98 ppm CO2, 798 ppm Cl, and 280 ppm F, consistent with an entrapment at much shallower depth, 2 km. The outer assemblage contains inclusions too small for routine volatile analysis. Inner assemblage Cpx-hosted MIs preserve average enrichments of 1.3x and 2x for Cl and F respectively, and are similarly enriched in incompatible minor and trace elements (up to a factor of 5x). Two potential scenarios can explain these observations. The enrichments may represent the entrapment of an unrelated highly-fractionated, shallow magma (which is unsupported by the whole rock record at Seguam). A second possibility is enrichment through boundary layer entrapment during a period of rapid crystal growth during ascent through the upper crust. Boundary layer entrapment during MI formation is further supported by a negative correlation between the degree of enrichment and the diffusivity of individual elements, which is consistent with growth rates 10-8 m/s. Although the olivine-hosted MIs record a volatile-rich storage region, the later-fractionating Cpx indicate a phase of rapid crystallization, likely driven by water loss from the melt at shallow depths. This work highlights the information added by analyzing multiple phases in order to reconstruct the degassing path of magma prior to eruption.

Eruption Depths, Magma Storage and Magma Degassing at Sumisu Caldera, Izu-Bonin Arc: Evidence from Glasses and Melt Inclusions

NASA Astrophysics Data System (ADS)

Johnson, E. R.

2015-12-01

Island arc volcanoes can become submarine during cataclysmal caldera collapse. The passage of a volcanic vent from atmospheric to under water environment involves complex modifications of the eruption style and subsequent transport of the pyroclasts. Here, we use FTIR measurements of the volatile contents of glass and melt inclusions in the juvenile pumice clasts in the Sumisu basin and its surroundings (Izu-Bonin arc) to investigate changes in eruption depths, magma storage and degassing over time. This study is based on legacy cores from ODP 126, where numerous unconsolidated (<65 ka), extremely thick (few m to >250 m), massive to normally graded pumice lapilli-tuffs were recovered over four cores (788C, 790A, 790B and 791A). Glass and clast geochemistry indicate the submarine Sumisu caldera as the source of several of these pumice lapilli-tuffs. Glass chips and melt inclusions from these samples were analyzed using FTIR for H2O and CO2 contents. Glass chips record variable H2O contents; most chips contain 0.6-1.6 wt% H2O, corresponding to eruption depths of 320-2100 mbsl. Variations in glass H2O and pressure estimates suggest that edifice collapse occurred prior-to or during eruption of the oldest of these samples, and that the edifice may have subsequently grown over time. Sanidine-hosted melt inclusions from two units record variably degassed but H2O-rich melts (1.1-5.6 wt% H2O). The lowest H2O contents overlap with glass chips, consistent with degassing and crystallization of melts until eruption, and the highest H2O contents suggest that large amounts of degassing accompanied likely explosive eruptions. Most inclusions, from both units, contain 2-4 wt% H2O, which further indicates that the magmas crystallized at pressures of ~50-100 MPa, or depths ~400-2800 m below the seafloor. Further glass and melt inclusion analyses, including major element compositions, will elucidate changes in magma storage, degassing and evolution over time.

Unraveling the effect of primary versus secondary processes on the volatile content of MORB glasses: an example from the equatorial Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Le Voyer, M.; Hauri, E. H.; Kelley, K. A.; Cottrell, E.

2012-12-01

We report the volatile contents of 20 basaltic glasses from the 1987 cruise of the R/V Robert Conrad to the equatorial Mid-Atlantic Ridge (RC2806, 7°S-5°N). Schilling (pers. comm.) reported that these samples exploded, or "popped," on the deck of the ship, similar to what was reported for the 2πD43 popping rock [1]. We therefore anticipated that they may not have degassed significantly. The goal of this study is to discuss the origin of their volatiles (primary vs. secondary) and the amount of degassing. In terms of major, trace and isotopic compositions [2, 3, 4], the samples are very similar to the other basalts from this location, following the same along-ridge spatial variations, with a strong influence from the Sierra Leone plume at 1.7°N. Unlike 2πD43 (vesicularity of 17-18 vol% [1]), our samples have low vesicularities (< a few vol%, indicating fluid-saturation), more typical of MORBs. They contain 0.32-1.00 wt% H2O, 120-210 ppm CO2, 80-520 ppm F, 770-1200 ppm S and 60-320 ppm Cl dissolved in the glass (determined by SIMS). H2O, F, Cl and S are negatively correlated with MgO, indicating the influence of crystallization. To free ourselves from this effect, we compare each volatile element with a non-volatile trace element with similar incompatibility. First, using the Cl, K and Ti systematics, we determined that at least 4 out of the 20 samples have suffered from seawater-like contamination (assimilation of either pure seawater or an igneous component previously altered by seawater). Second, for the 16 uncontaminated samples, good correlations (R2≥0.9) between Cl and K, F and P, and H2O and Ce, indicate that Cl, F and H2O did not degass significantly. When plotted against the distance along the ridge axis, we find that the F/P (and Cl/K, to a smaller extent) increase with proximity to the Sierra Leone hotspot, and correlate with radiogenic isotopes. Thus these volatile enrichments reflect source variation. When plotted against Nb and Dy, respectively, CO2 and S do not show any clear tendencies. The trend (R2=0.7) between the CO2 contents and their calculated H2O-CO2 saturation pressures (Psat, 315-526 bar [5]) indicates that some of the CO2 variation is due to equilibrium degassing of a CO2-rich fluid phase (77-98 mol% CO2). By comparing the Psat with the collection pressure (3440-4530 mbsl, i.e. 337-444 bar), we found that half of the samples are affected by variable degrees of supersaturation (up to 82 bars in the deepest sample with the smallest vesicularity). This non-equilibrium state could be caused by a delay in bubble formation due to rapid ascent rates [6]. Finally, unlike CO2, S is poorly correlated with Psat, but displays a very good correlation with FeO*, indicating S saturation and partitioning of S into a sulfide phase rather than into a fluid phase. [1] Javoy and Pineau, 1991, EPSL 105, 598-611. [2] Schilling et al., 1994, JGR 99,12005-12028. [3] Schilling et al., 1995, JGR 100,10057-10076. [4] Hannigan et al., 2001, Chem. Geol. 175, 397-428. [5]: Dixon and Stolper, 1995, JPet 36, 1633-1646. [6] Dixon et al., 1988, EPSL 90, 87-104.

Intense magmatic degassing through the lake of Copahue volcano, 2013-2014

NASA Astrophysics Data System (ADS)

Tamburello, G.; Agusto, M.; Caselli, A.; Tassi, F.; Vaselli, O.; Calabrese, S.; Rouwet, D.; Capaccioni, B.; Di Napoli, R.; Cardellini, C.; Chiodini, G.; Bitetto, M.; Brusca, L.; Bellomo, S.; Aiuppa, A.

2015-09-01

Here we report on the first assessment of volatile fluxes from the hyperacid crater lake hosted within the summit crater of Copahue, a very active volcano on the Argentina-Chile border. Our observations were performed using a variety of in situ and remote sensing techniques during field campaigns in March 2013, when the crater hosted an active fumarole field, and in March 2014, when an acidic volcanic lake covered the fumarole field. In the latter campaign, we found that 566 to 1373 t d-1 of SO2 were being emitted from the lake in a plume that appeared largely invisible. This, combined with our derived bulk plume composition, was converted into flux of other volcanic species (H2O ~ 10989 t d-1, CO2 ~ 638 t d-1, HCl ~ 66 t d-1, H2 ~ 3.3 t d-1, and HBr ~ 0.05 t d-1). These levels of degassing, comparable to those seen at many open-vent degassing arc volcanoes, were surprisingly high for a volcano hosting a crater lake. Copahue's unusual degassing regime was also confirmed by the chemical composition of the plume that, although issuing from a hot (65°C) lake, preserves a close-to-magmatic signature. EQ3/6 models of gas-water-rock interaction in the lake were able to match observed compositions and demonstrated that magmatic gases emitted to the atmosphere were virtually unaffected by scrubbing of soluble (S and Cl) species. Finally, the derived large H2O flux (10,988 t d-1) suggested a mechanism in which magmatic gas stripping drove enhanced lake water evaporation, a process likely common to many degassing volcanic lakes worldwide.

C-13/C-12 of atmospheric CO2 in the Amazon basin - Forest and river sources

NASA Technical Reports Server (NTRS)

Quay, Paul; King, Stagg; Wilbur, Dave; Richey, Jeffrey; Wofsy, Steven

1989-01-01

Results are presented of measurements of the CO2 concentrations and C-13/C-12 ratios in CO2 in air samples collected from within the Amazonian rain forest and over the Amazon river between 1982 and 1987. Results indicate the presence of a diurnal cycle in the CO2 concentration and the C-13/C-12 ratio. It was found that the CO2 input to air in the forest was derived from the soil respiration, and the CO2 input to air over the Amazon river was derived from the degassing of CO2 from the river. It was also found that plants growing at heights lower than 7 m assimilate soil-derived CO2 with a low C-13/C-12 ratio.

Geochemical and textural constraints on degassing processes in sub-Plinian eruptions: case-study of the Greenish Pumice eruption of Mount Somma-Vesuvius

NASA Astrophysics Data System (ADS)

Zdanowicz, G.; Boudon, G.; Balcone-Boissard, H.; Cioni, R.; Mundula, F.; Orsi, G.; Civetta, L.; Agrinier, P.

2018-04-01

Plinian eruptions are characterized by high intensity and an overall steady character, and result in a stable convective column. The main processes controlling the dynamics of such steady and stable plume systems have been extensively investigated. Conversely, sub-Plinian eruptions are unsteady, as recorded by the large variability of the products and deposits. Our knowledge of the processes creating this unsteadiness on various timescales remains limited, and still requires more observations as well as theoretical and experimental investigation. Here, we focus on the sub-Plinian eruption of the Greenish Pumice (GP, 19,265 ± 105 BP), Mt. Somma-Vesuvius (Italy). On the basis of coupled geochemical and textural analyses of samples from the well-established stratigraphy of the GP deposits, we investigate volatiles (H2O, CO2, F, Cl) to better constrain the unsteady sub-Plinian eruptive style. This allows us to carry out a detailed study of the degassing processes in relation to the eruption dynamics. We find that degassing by open-system processes generally dominates throughout the entire eruption, but alternates with episodes of closed-system degassing. The fluctuating degassing regimes, responsible for the variable magma ascent rate within the conduit, are also responsible for the eruptive column instability. Volatile behavior is well correlated with textural heterogeneities of the eruptive products. Both reflect higher conduit heterogeneity than for Plinian eruptions, where we find a higher horizontal gradient in magma ascent velocity due to a smaller conduit diameter.

Eruption and Degassing Processes in a Supervolcanic System: The Volatile Record Preserved in Melt Inclusions from the 3.49Ma Tara Ignimbrite in the Central Andes

NASA Astrophysics Data System (ADS)

Grocke, S.; de Silva, S. L.; Schmitt, A. K.; Wallace, P. J.

2010-12-01

Analysis of H2O and CO2 in quartz and sanidine-hosted melt inclusions from one of the youngest supervolcanic eruptions in the Altiplano Puna Volcanic Complex (APVC) in the Central Andes provides information on crystallization depths and eruption and degassing processes. At least 740 km3 of high-K, metaluminous, rhyodacite to rhyolite magma erupted from the Guacha Caldera in southwest Bolivia, producing three phases of the 3.49 Ma Tara Ignimbrite: a Plinian fall-deposit, an extensive ignimbrite, and several post-caldera domes. Infrared spectroscopic analyses of quartz-hosted melt inclusions from Tara Plinian pumice have H2O contents of ~4.5 wt % and variable CO2 contents (110-300 ppm), corresponding to vapor saturation pressures up to 180 MPa. In contrast, sanidine-hosted melt inclusions from the Plinian-fall deposit contain bubbles, lower water contents (1.4-2.2 wt %) and lower CO2 (87-143 ppm). These vesiculated melt inclusions and low volatile contents suggest that the sanidine crystals leaked on their ascent to the surface and therefore do not record accurate pre-eruptive melt volatile contents. In contrast, quartz-hosted melt inclusions from post-caldera dome samples contain lower H2O contents of 2.5-3.5 wt % (average 2.9 wt %) and no detectable CO2, corresponding to vapor saturation pressures of 50-90 MPa. These data indicate that the preeruptive plinian stage Tara magma was vapor saturated at the time of melt inclusion entrapment and stored between 5-6 km, while those from the post-caldera domes were trapped at 2-3 km. Differences in CO2 between Plinian and dome melt inclusions require that the post-caldera dome quartzes represent a different generation of crystals that grew as the magma slowly rose and progressively degassed at 2-3 km. During this shallow crystallization, the magma evolved further and eventually fed the post-caldera domes, one of which is a high-Si rhyolite. Consistent with this interpretation, melt inclusions from post-caldera dome samples contain lower OH/H2Om that indicate slower cooling rates compared to Plinian samples. The volatile record from pre and post-caldera deposits therefore reflects an eruptive history that was strongly influenced by volatile evolution within the Tara magma.

CO2 outburst events in relation to seismicity: Constraints from microscale geochronology, geochemistry of late Quaternary vein carbonates, SW Turkey

NASA Astrophysics Data System (ADS)

Ünal-İmer, Ezgi; Uysal, I. Tonguç; Zhao, Jian-Xin; Işık, Veysel; Shulmeister, James; İmer, Ali; Feng, Yue-Xing

2016-08-01

Vein and breccia carbonates precipitated in a highly fractured/faulted carbonate bedrock in SW Turkey were investigated through high-resolution U-series geochronology, microstructural and geochemical studies including C-O-Sr isotope and rare-earth element and yttrium (REY) analyses. Petrographical observations and geochronological data are interpreted as evidence that the calcite veins formed through a crack-seal mechanism, mostly accompanied/initiated by intensive hydraulic fracturing of the host limestone in response to high-pressure fluids, which is manifested by multi-stage breccia deposits. Microscale U-series dates (272.6-20.5 kyr) and geochemical compositions of the vein/breccia samples provide information on the timing and mechanism of the vein formation and identify the source of CO2-bearing fluids responsible for the carbonate precipitation. δ18OVPDB and δ13CVPDB values of the calcite veins range between -5.9 and -1.7‰, and -10.6 and -4.6‰, respectively. The isotopic compositions of the veins show highly fluctuating values as calcite grew successively perpendicular to vein walls, which, in combination with microstructural and geochronological constraints, are interpreted to reflect episodic CO2 degassing events associated with seismic and aseismic deformation. Oxygen and Sr isotope compositions (δ18OVPDB: -5.9 to -1.7‰; 87Sr/86Sr: 0.7082 to 0.7085) together with REY concentrations indicate deep infiltration of meteoric waters with various degrees of interactions mostly with the host limestone and siliciclastic parts of the basement rocks. Oxygen and carbon isotope compositions suggest CO2 degassing through intensive limestone dissolution. While majority of the veins display similar Post-Archaean Australian Shale (PAAS)-normalised REY variations, some of the veins show positive EuPAAS anomalies, which could be indicative of contributions from a deeply derived, heated, and reduced fluid component, giving rise to multiple fluid sources for the calcite veins. Vein calcite formed in fault-induced fractures offers insights into structural features, genetic characterisation of the parental fluids, and late Quaternary degassing of subsurface CO2 accumulations.

Reconciling Gases With Glasses: Magma Degassing, Overturn and Mixing at Kilauea Volcano, Hawai`i

NASA Astrophysics Data System (ADS)

Edmonds, M.; Gerlach, T. M.

2006-12-01

Our understanding of the volatile budget at Kilauea Volcano is based on measurements of the abundance of volatile elements in volcanic glasses and gases. Observations of volcanic gases gave rise to a fundamental model describing volatile fractionation between the summit and rift zone during the current eruption [Gerlach and Graeber, 1985]. Other workers' analysis of glasses from the Puna Ridge, Kilauea Iki and Pu`u `O`o indicate that magma degassing, drain-back, mixing and assimilation are important processes at Kilauea Volcano. Volcanic gases have not illustrated these kinds of processes clearly in the past, owing to infrequent and poorly resolved data. New, detailed studies of volcanic gas emissions have refined our understanding of volatile degassing and magma budgets at Kilauea Volcano. Open Path Fourier Transform Infra-Red spectroscopy measurements carried out during 2004-2005 allow retrieval of the relative abundances of the major volatile species H2O, CO2 and SO2, which together make up >99 vol% of the magmatic vapor phase. The proportions of these gases vary over time and space and can be used to infer magma transport, ascent, degassing, overturn and mixing and gas segregation processes within the plumbing system of Kilauea Volcano. Gases from Pu`u `O`o in 2004-2005 display a range in composition. A trend relates molar C/S to the total H2O content of the gases over time and space; total H2O ranges from 60-98 mol %, while molar C/S ranges from <0.01 to >50. The range in volcanic gas composition over time and space is caused by magma degassing, overturn and mixing of partially degassed magma with fresh primary magma beneath Pu`u `O`o. Measurements of the mean rate of magma degassing (from SO2 emissions) and mean lava effusion rate (from geophysical measurements of lava tube flux) suggest that a larger volume (DRE) of magma is degassing than is being erupted, on average. This analysis suggests that magma storage in the Rift Zone might be important during eruptions as well as between them; this has important implications for volcano monitoring. Application of this new, remote and accurate technique to measure volcanic gases allows data concerning the volatile budget, both from glasses and from gases, to be reconciled and used in tandem to provide more detailed and complete models for magma migration, storage and transport at Kilauea Volcano.

Investigating the deepest part of a volcano plumbing system: Evidence for an active magma path below the western flank of Piton de la Fournaise (La Réunion Island)

NASA Astrophysics Data System (ADS)

Boudoire, G.; Liuzzo, M.; Di Muro, A.; Ferrazzini, V.; Michon, L.; Grassa, F.; Derrien, A.; Villeneuve, N.; Bourdeu, A.; Brunet, C.; Giudice, G.; Gurrieri, S.

2017-07-01

Peripheral diffuse degassing of CO2 from the soil occurs across the western flank of Piton de la Fournaise volcano (La Réunion Island, Indian Ocean) along a narrow zone. In this area, carbon isotopic analysis on soil gas samples highlights significant mixing between magmatic and organic end-members. The zones with the strongest magmatic signature (highest δ13C) overlap spatial distribution of hypocenters recorded shortly before and during volcano reactivation and allow discriminating a N135° degassing lineament, with a minimum length of 11 km and 140 ± 20 m-width. Such orientation is in accordance with that of an old dyke network along the rift zone and with N120-130° and N140-155° lineaments related to the inheritance of oceanic lithosphere structures. Our findings show that this N135° lineament represents a preferential magmatic pathway for deep magma transfer below the volcano flank. Moreover, spatial distributions of recent eccentric cones indicate a well-founded possibility that future eruptions may by-pass the shallow plumbing system of the central area of the volcano, taking a lateral pathway along this structure. Our results also confirm that Piton de la Fournaise activity is linked to a laterally shifted plumbing system and represent a major improvement in identifying the main high-risk area on the densely populated western flank of the volcano.

Isotopic Insights Into the Degassing and Secondary Hydration Rates of Volcanic Glass From the 1980 Eruptions of Mount St. Helens

NASA Astrophysics Data System (ADS)

Seligman, A. N.; Bindeman, I. N.; Van Eaton, A. R.; Hoblitt, R. P.

2016-12-01

Following eruption, volcanic glass undergoes hydration in its depositional environment, which overprints the history of magmatic degassing recorded in the glass. However, the rates of secondary hydration of volcanic glass used for paleoclimate studies are poorly constrained. Here, we present our results of a natural experiment using products of the 1980 eruptions of Mount St. Helens. We measured the δD of extracted water and the δ18O of the bulk glass of samples collected during the dry summer months of 1980 and compared them with material resampled in August of 2015. Results demonstrate that only samples collected from the subsurface near gas escape pipes show elevated water concentrationss (near 2.0 wt.%) and low δD (-110 to -130 ‰) and δ18O (6.0 to 6.6 ‰) values, and that the initial process of secondary hydration is not always a simple addition of low δD waters at ambient temperature. On average, the 2015 surface samples have slightly higher water contents (0.1-0.2 wt.%) and similar δ18O (6.8 - 6.9 ‰) to those collected in 1980. Given the moderate vesicularity of the samples and the slow rate of surface temperature diffusion, we attribute these observations to hydration during cooling, with only little exchange after. We also compare our results to rapidly quenched air fall pumice from the May 18th eruption, which shows moderate δD values (-74 ‰) and water concentrations (0.3 wt.%) that are closer to those for the 1980 samples. Surprisingly, the 2015 surface samples show higher δD values (+15 ‰), which we attribute to any of four possibilities: (1) evaporation or (2) degassing of underlying deposits; (3) exchange of hydrogen with local vegetation; and/or (4) microlite crystallization that aided diffusion of water. Reconstructed δD-H2O trends for the Mount St. Helens samples collected in 1980 support previous studies proposing that exsolved volatiles were trapped within a rapidly rising magma that degassed at shallow depths. The dacitic Mount St. Helens (with rhyolitic groundmass) trend overlaps with crystal-poor rhyolitic eruptions studied previously, suggesting similar behavior of volatiles upon exsolution.

Reducing the Geothermal Exploration Risk by Carbon Dioxide Soil Flux Investigations

NASA Astrophysics Data System (ADS)

Carapezza, Maria Luisa; Barberi, Franco; Ranaldi, Massimo; Ricci, Tullio; Tarchini, Luca; De Simone, Gabriele; Gattuso, Alessandro; Silvestri, Mario

2013-04-01

In the exploration of medium to high enthalpy geothermal resources it happens rather frequently that deep wells find high temperatures but are not productive because they don't cross any permeable fractured reservoir. Because of the high cost of deep drillings, this aspect represents one of the main economic risks of geothermal exploration. A detailed survey of diffuse CO2 soil flux may allow to identify from the surface the permeable portions of a deep-seated actively degassing geothermal reservoir, drastically reducing this risk. In order to test the effectiveness of CO2 soil flux as a geothermal exploration tool we selected two volcanic areas north of Rome, Latera caldera and Marta zone near lake Bolsena, both hosting a geothermal reservoir with T>200 °C and where productive and non-productive wells had been drilled in the past. We proved that in both zones productive wells are located on high CO2 soil flux zones, whereas the not-productive wells are sited on low flux areas. In addition the surveys allowed to identify some as yet unexplored portions of the geothermal reservoirs where future wells should be conveniently located. Use of the same technique in the medium enthalpy geothermal system of Torre Alfina, Central Italy (T=140°C) showed that the presence of a thick impervious rock cover may be very effective in preventing gas leakages from the reservoir to the surface. Promising results have been obtained also by CO2 soil flux surveys in some geothermal areas of Honduras (Platanares, Azacualpa) and Costa Rica (Las Pailas). Obviously, CO2 flux cannot provide any estimate of temperature at depth, which has to be assessed with other geochemical or geophysical exploration techniques.

The composition of volcanic gas issuing from Pu`u `O`o, Kilauea Volcano, Hawaii, 2004-5

NASA Astrophysics Data System (ADS)

Edmonds, M.; Gerlach, T. M.; Herd, R. A.; Sutton, A. J.; Elias, T.

2005-12-01

The eruption of lava is accompanied by prodigious quantities of volcanic gases at Kilauea Volcano. Although sophisticated gas monitoring methods have been implemented at Pu`u `O`o, it is logistically difficult to gather data regularly on the full suite of volcanic gases emitted from crater and flank vents. Since March 2004, Open Path Fourier Transform Infrared Spectroscopy has been carried out, using incandescent vents as a source of infra red (IR) radiation. Strong IR sources, high gas concentrations and short optical pathlengths allow the regular determination of 7 volcanic gas species from vents which are usually too dangerous to approach for direct gas sampling. The data show that a) the gas composition exhibits a significant amount of variation over time and b) different crater vents, just 40-100 metres apart, emit different gas compositions and the gas composition is generally highly variable spatially around the cone and upper flow-field degassing sources (vents, skylights, hornitos). The main degassing site within Pu`u `O`o, the East Pond vent, has emitted gas of a very similar composition to that measured in 1983-5, throughout most of 2004-5: typically 75-85 mol% H2O, 10-13% SO2, 0.1-3.0% CO2, 0.3-0.6% HCl, 0.1-0.5% HF, 0.1-0.8% H2S and 0.015-0.025% CO. The most highly variable species over time and space are CO2, HF, H2S and CO. Data collected during February 2005 show cyclic variations in gas composition during lava spattering activity, which occurred every 10-20 minutes at the East Pond vent inside the crater of Pu`u `O`o. The volcanic gas was rich in CO2, HCl, H2S and CO during and immediately after the spatter episode, which involved the spray of lava from the vent 10-30 metres into the air. During the next 10-15 minutes, after spattering, the volcanic gas gradually became more water-rich, it lost its CO2 and H2S components and the HCl/HF ratio decreased. We interpret these changes to be due to the upward migration of discrete bubbles from tens of metres depth beneath the volcanic vent, which burst at the surface and cause expulsion of lava and gas. Between larger, deep-derived bubbles bursting at the surface, degassing, of mainly water, takes place from the topmost part of the magma column.

Study on the Removal of Gases in RH Refining Progress through Experiments Using Vacuum Induction Furnace

NASA Astrophysics Data System (ADS)

Niu, Deliang; Liu, Qingcai; Wang, Zhu; Ren, Shan; Lan, Yuanpei; Xu, Minren

Removal of gas is the major function of RH degasser. To optimize the RH refining craft in Chongqing Iron and Steel Co. Ltd, the degassing effect of RH degasser at different degrees of vacuum was investigated using a vacuum induction furnace. In addition, the effect of processing time on the gas content dissolved in molten steel was also studied. The results showed that degree of vacuum was one of the important factors that determined the degassing efficiency in RH refining process. High vacuum degree is helpful in the removal of gas, especially in the removal of [H] dissolved in molten steel. The processing time could be reduced from 25-30 min to 15 minutes and gas content could also meet the demand of RH refining.

Diffuse degassing through magmatic arc crust (Invited)

NASA Astrophysics Data System (ADS)

Manning, C. E.; Ingebritsen, S.

2013-12-01

The crust of magmatic arcs plays an important role in the volatile cycle at convergent margins. The fluxes of subduction- and arc-related volatiles such as H2O, C, Cl, S are poorly known. It is commonly believed that gases emitted from volcanoes account nearly quantitatively for the volatiles that cross the Moho beneath the volcanic front. This volcanic degassing may occur during eruption, emission from summit fumaroles and hot springs, or more 'diffuse' delivery to volcano flanks. However, several observations suggest that volatiles also transit arc crust by even more diffuse pathways, which could account for significant volatile loss on long time and length scales. Active metamorphism of arc crust produces crustal-scale permeability that is sufficient to transport a large volume of subducted volatiles (Ingebritsen and Manning, 2002, PNAS, 99, 9113). Arc magmas may reach volatile saturation deeper than the maximum depths recorded by melt inclusions (e.g., Blundy et al., 2010, EPSL, 290, 289), and exhumed sections of magmatic arc crust typically record voluminous plutons reflecting magma crystallization and volatile loss at depths well below the volcanic edifice. At shallower depths, topographically driven meteoric groundwater systems can absorb magmatic volatiles and transport them laterally by tens of km (e.g., James et al., 1999, Geology, 27, 823; Evans et al., 2002, JVGR, 114, 291). Hydrothermal ore deposits formed at subvolcanic depths sequester vast amounts of volatiles, especially sulfur, that are only returned to the surface on the time scale of exhumation and/or erosion. Water-rich metamorphic fluids throughout the crust can readily carry exsolved volcanic gases because the solubilities of volatile bearing minerals such as calcite, anhydrite, and fluorite are quite high at elevated pressure and temperature (e.g., Newton and Manning, 2002, Am Min, 87, 1401; 2005, J Pet, 46, 701; Tropper and Manning, 2007, Chem Geol, 242, 299). Taken together, these considerations dictate that volatile entrainment in the metamorphic/meteoric fluid-flow system represents a highly diffuse pathway for degassing through arc crust which must be taken into account in models of volatile cycling at convergent margins.

Preliminary assessment of the state of CO2 soil degassing on the flanks of Gede volcano (West Java, Indonesia)

NASA Astrophysics Data System (ADS)

Kunrat, S. L.; Schwandner, F. M.

2013-12-01

Gede Volcano (West Java) is part of an andesitic stratovolcano complex consisting of Pangrango in the north-west and Gede in the south-east. The last recorded eruptive activity was a phreatic subvolcanian ash eruption in 1957. Current activity is characterized by episodic swarms at 2-4 km depth, and low-temperature (~160°C) crater degassing in two distinct summit crater fumarolic areas. Hot springs occur in the saddle between the Gede and Pangrango edifice, as well as on the NE flank base. The most recent eruptive events produced pyroclastic material, their flow deposits concentrate toward the NE. A collaborative effort between the Center for Volcanology and Geological Hazard Mitigation (CVGHM), Geological Agency and the Earth Observatory of Singapore (EOS) is since 2010 aimed at upgrading the geophysical and geochemical monitoring network at Gede Volcano. To support the monitoring instrumentation upgrades under way, surveys of soil CO2 degassing have been performed on the flanks of Gede, in circular and radial traverses.The goal was to establish a spatial distribution of flank CO2 fluxes, and to allow smart siting for continuous gas monitoring stations. Crater fluxes were not surveyed, as its low-temperature hydrothermal system is likely prone to large hydraulic changes in this tropical environment, resulting in variable permeability effects that might mask signals from deeper reservoir or conduit degassing. The high precipitation intensity in the mountains of tropical Java pose challenges to this method, since soil gas permeability is largely controlled by soil moisture content. Simultaneous soil moisture measurements were undertaken. The soil CO2 surveys were carried out using a LI-8100A campaign flux chamber instrument (LICOR Biosciences, Lincoln, Nebraska). This instrument has a very precise and highly stable sensor and an atmospheric pressure equilibrator, making it highly sensitive to low fluxes. It is the far superior choice for higher precision low-flux flank surveys in tropical environments. The mean flank fluxes measured were 19.8 g/m2/day in 2011, 11.7 g/m2/day in 2012 and 7.6 g/m2/day in early 2013. The mean flank flux for all the surveys is 17.9 g/m2/day. Statistical analysis of the data set reveals at least three distinct flux populations. Results from 2011, 2012 and 2013 indicate that flank fluxes were as high as 112.5g/m2/day, suggesting recent intrusive activity. The spatial distribution of fluxes indicates a strong focus on the NE sector. This finding appears concurrent with an area previously documented as continuously subsiding and filled with recent pyroclastic deposits (Philiboisan et al.2011, G3 Vol.12(11), Fig.15). The surveys also permit selection and validation of sites for continuous CO2 monitoring stations, representing medium and low flank flux populations.

Diffusion-driven D/H fractionation in silicates during hydration, dehydration and degassing

NASA Astrophysics Data System (ADS)

Roskosz, Mathieu; Laporte, Didier; Deloule, Etienne; Ingrin, Jannick; Remusat, Laurent; Depecker, Christophe; Leroux, Hugues

2017-04-01

Understanding how degassing occurs during accretion and differentiation is crucial to explain the water budget of planetary bodies. In this context, the hydrogen isotopic signature of water in mantle minerals and melts is particularly useful to trace reservoirs and their interactions. Nonetheless, little is known on the influence of mantle processes on the D/H signatures of silicates. In this study, we performed controlled hydration/dehydration experiments. We explore the possibility that diffusion-driven fractionation could affect the D/H signature of partially hydrated amorphous or molten silicates and nominally anhydrous minerals (NAMs). High purity synthetic fused silica samples were annealed at between 200 and 1000°C at 20 mbar water partial pressure for 1 to 30 days. Dehydration of initially hydrated silica was also performed at 1000°C for a few hours. A set of rhyolitic samples previously synthesized in order to study bubble nucleation during magma decompression was also analyzed. Finally a natural grossular monocrystal (Zillertaler Alps, Austria), partially dehydrated in air at 800°C for 10 hours was studied. Water content and speciation were measured both by Fourier-Transform Infra-Red and Raman spectroscopies. Isotopic analyses were performed with the IMS 1270 and 1280 ion microprobes. The silica samples, the rhyolitic glasses and the grossular monocrystal exhibit typical water concentration profiles. In all cases, water speciation does not change significantly along concentration profiles. Concerning D/H signatures, no isotopic variation is detectable across amorphous silica and rhyolitic glasses. The situation is however very different in the grossular monocrystal. A strong isotopic gradient appears correlated to the water concentration profile. Our data are interpreted in terms of diffusion mechanisms in both amorphous (and molten) silicates and NAMs. Hydration, dehydration and magma degassing are probably not able to promote large diffusion-driven fractionation of hydrogen in amorphous silicates. Conversely, the diffusion of water through the structure of NAMs affects the overall isotopic composition of dissolved water.

Effects of pH2O, pH2 and fO2 on the Diffusion of H-Bearing Species in Lunar Basalt and an Iron-Free Basaltic Analog at 1 atm

NASA Astrophysics Data System (ADS)

Newcombe, M. E.; Beckett, J. R.; Baker, M. B.; Newman, S.; Guan, Y.; Eiler, J. M.; Stolper, E. M.

2016-12-01

We have conducted water diffusion experiments in synthetic Apollo 15 "yellow glass" (LG) and an iron-free basaltic analog melt (AD) at 1 atm and 1350 °C over a range of fO2 conditions from IW-2.2 to IW+6.7 and over a range of pH2/pH2O from nominally zero to 10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to 430 ppm. Many studies of water diffusion at higher water concentrations indicate that the apparent diffusivity of total water (D*water; see [1]) in silicate melts is highly concentration dependent at water contents >0.1 wt% (e.g., [1]). However, water concentration gradients in each of our AD and LG experiments are well described by models in which D*water is assumed to be constant. Best-fit values of D*water obtained for our AD and LG experiments are consistent with a modified speciation model [2] in which both molecular water and hydroxyl are allowed to diffuse, and in which hydroxyl is the dominant diffusing species at the low total water concentrations of our experiments. Water concentration gradients generated during hydration and dehydration experiments conducted simultaneously propagate approximately equal distances into the melt and have the same concentration of water dissolved in the melt at the melt-vapor interface, suggesting that hydration and dehydration are symmetric under the conditions of our experiments. Best-fit values of D*water for our LG experiments vary within a factor of 2 over a range of pH2/pH2O from 0.007 to 9.7 (a range of ƒO2 from IW-2.2 to IW+4.9) and a water concentration range from 80 ppm to 280 ppm. The relative insensitivity of D*water to variations in pH2 suggests that loss of H during the degassing of the lunar melts described by [3] was not primarily by loss of dissolved H2. The value of D*water chosen by [3] for modeling diffusive degassing of lunar volcanic glasses is within a factor of three of our measured value in LG melt at 1350 °C. [1] Zhang et al. (1991) GCA 55, 441-456; [2] Ni et al. (2013) GCA 103, 36-48; [3] Saal et al. (2008) Nature 454, 192-195.

Secular trends in plume composition of Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Ilanko, Tehnuka; Oppenheimer, Clive; Kyle, Philip; Burgisser, Alain

2015-04-01

Long-lived active lava lakes, such as that in the summit crater of Erebus volcano, Antarctica, provide a rare insight into sustained magma convection and degassing over long timescales. Erebus lava lake has been persistently active since 1972, and potentially for several decades or more previously (Ross, 1847). Since the 1970s, regular scientific expeditions, lasting a few weeks in the austral summers, have made observations of the lake activity. Annual Fourier transform infrared (FTIR) spectroscopic gas measurements began in 2004 (Oppenheimer and Kyle, 2008; Oppenheimer et al., 2009), yielding an extensive, if discontinuous, time series of infrared absorption spectra. These data, once processed, provide insights into temporal evolution of the gas geochemistry in terms of seven molecular species: H2O, CO2, CO, SO2, HCl, HF, and OCS. FTIR spectroscopic data are now available over ten field seasons, totalling roughly 1.8 million spectra and increasing each year. This period spans changes to crater morphology, fluctuations in lava lake surface area (Jones et al., 2014), and two episodes of increased explosive activity (2005-06 and 2013). The dataset captures both long-term degassing trends and short-lived features, such as cyclicity in gas emissions during passive degassing (Ilanko et al., 2015) and compositions released by explosive bubble-burst eruptions. We consider the longer-term changes to gas ratios occurring within (i.e. over days to weeks) and between annual field seasons, their potential causes, and their relationship to observations of eruptive behaviour and crater morphology.

Carbon isotope exchange between CO2 and CH4 in hydrothermal fluids from the Tuscan-Roman and Campanian degassing systems (central-southern Italy)

NASA Astrophysics Data System (ADS)

Tassi, F.; Fiebig, J.; Nocentini, M.; Vaselli, O.

2010-12-01

The carbon isotope composition in CO2 and CH4 are commonly used as exploration tools and diagnostic indicators to investigate the origin of endogenous gases. At temperature <200 °C both proportions and isotope ratios of these two gases are considered to be largely controlled by processes (i.e. bacterial activity, thermal hydrolysis, and cracking of organic matter) that are mainly dictated by kinetics. Recent investigations on abiogenic generation of CH4 suggest that at temperatures as low as 100 °C, CH4 production from CO2 has halftimes in the order of 1 year. The present work is based on the d13C-CO2 and d13C-CH4 values of more than 83 gas discharges from the Tuscan-Roman and Campanian degassing systems (central-southern Italy). The main aims are to i) investigate the processes regulating the chemical and isotopic compositions of CO2 and CH4 and ii) verify the use of the CO2-CH4 carbon isotopic equilibrium for evaluating the temperature of deep hydrothermal reservoirs. Our results show that the d13C-CH4 values, with few exceptions related to local production of biogenic CH4 at shallow depth, are > -40 ‰ V-PDB. The most intriguing feature of the measured d13C-CH4 values is that they progressively decrease from the peri-Tyrrhenian area, where productive geothermal systems and active volcanoes are located, to East, i.e. approaching the CH4-rich reservoirs that mark the Adriatic side of the Italian peninsula. The d13C-CO2 values are substantially spanning from a thermometamorphic to a mantle degassing CO2 and do not show any preferential spatial distribution. Secondary carbon isotope fractionation caused by interaction with relatively shallow aquifers may contribute to the scatter of d13C-CO2 values, considering the high solubility of CO2 in liquid water. However, the CO2-CH4 isotopic compositions of fluids from the high temperature geothermal systems characterizing the Tyrrhenian coast of central-southern Italy, i.e. Larderello, Mt. Amiata, Manziana and Phlegrean Fields, provide apparent equilibrium temperatures in the range of those directly measured in production wells and/or estimated on the basis of the CH4-CO2 chemical geothermometer. These results are consistent with the fact that the carbon isotopic equilibrium in the CO2-CH4 system has to be preceded by that of the chemical exchange because the latter has a kinetic rate 400 times faster than the isotopic partitioning. The observed agreement between measured and/or inferred aquifer temperatures with apparent carbon isotopic equilibration supports recent findings that CO2 and CH4 can attain carbon isotopic equilibrium in high-enthalpy hydrothermal systems. The d13C-CH4 values of gas discharges located eastward, toward the Appennine sedimentary chain, are likely produced by mixing of high temperature fluids from the geothermal areas and a relatively cold deep aquifer characterized by biogenic CH4: The higher distance from the geothermal-volcanic systems, the higher fraction of low temperature fluids.

Magmatic gas emissions at Holocene volcanic features near Mono Lake, California, and their relation to regional magmatism

USGS Publications Warehouse

Bergfeld, D.; Evans, William C.; Howle, James F.; Hunt, Andrew G.

2015-01-01

Silicic lavas have erupted repeatedly in the Mono Basin over the past few thousand years, forming the massive domes and coulees of the Mono Craters chain and the smaller island vents in Mono Lake. We report here on the first systematic study of magmatic CO2 emissions from these features, conducted during 2007–2010. Most notably, a known locus of weak steam venting on the summit of North Coulee is actually enclosed in a large area (~ 0.25 km2) of diffuse gas discharge that emits 10–14 t/d of CO2, mostly at ambient temperature. Subsurface gases sampled here are heavily air-contaminated, but after standard corrections are applied, show average δ13C-CO2 of − 4.72‰, 3He/4He of 5.89RA, and CO2/3He of 0.77 × 1010, very similar to the values in fumarolic gas from Mammoth Mountain and the Long Valley Caldera immediately to the south of the basin. If these values also characterize the magmatic gas source at Mono Lake, where CO2 is captured by the alkaline lake water, a magmatic CO2 upflow beneath the lake of ~ 4 t/d can be inferred. Groundwater discharge from the Mono Craters area transports ~ 13 t/d of 14C-dead CO2 as free gas and dissolved carbonate species, and adding in this component brings the estimated total magmatic CO2 output to 29 t/d for the two silicic systems in the Mono Basin. If these emissions reflect intrusion and degassing of underlying basalt with 0.5 wt.% CO2, a modest intrusion rate of 0.00075 km3/yr is indicated. Much higher intrusion rates are required to account for CO2 emissions from Mammoth Mountain and the West Moat of the Long Valley Caldera.

Detecting and Correcting Melt Inclusion Modification

NASA Astrophysics Data System (ADS)

Cottrell, E.; Kelley, K. A.

2008-12-01

Post entrapment diffusive modification of melt inclusions may mute or erase primary signatures. Corrections for post-entrapment crystallization (PEC) and Fe-loss are routinely applied and, because recent experimental studies suggest rapid diffusion of trace components into and out of olivine-hosted inclusions, the ability to discriminate between primary and secondary signatures is now even more critical. Two tools may assist in this endeavor. XANES measurements of Fe3+/ΣFe ratios in undegassed ol-hosted basaltic melt inclusions from global arcs are 16-36% (n=16), significantly higher than the 7-10% commonly assumed, and higher than in MORB or BABB lavas (Kelley and Cottrell, this mtg). The Fe3+/ΣFe ratios indicate melt-host equilibrium, with significantly less PEC or Fe-loss than would have been otherwise assumed. We conclude that Fe2+ diffusion has been minimal; therefore the residence time of these primitive inclusions in an evolved magma must have been short. Fe3+/ΣFe correlates positively with water concentration, but not with CO2 and S concentrations or Mg#. The oxidized nature of arc lavas and melt inclusions may therefore indicate an oxidized source rather than late-stage degassing or fractionation. Trace element concentrations evolve with time if an inclusion is out of equilibrium with its host. The numerical model of Cottrell et al., 2002, makes specific predictions about how suites of melt inclusions evolve, creating a tool to detect post-entrapment modification. Recent laboratory measurements of REE diffusion in olivine greatly diverge (at 1300°C, 1015 vs 1019m2/s). If REE diffusivity is extremely fast, melt inclusion HREE diversity shouldn't survive more than a few years in a magma chamber; but if slow, HREE variance could be preserved for >104 yrs. Model analysis of published suites of ol-hosted inclusions indicates that either REE diffusion is quite slow, or the residence time of melt inclusions at high temperature is very short. Loss of variance in suites of pl-hosted inclusions is consistent with long (>103 yrs) residence times. Suites of ol- and pl-hosted inclusions from the same magmatic system can therefore bracket residence times if diffusivities are known, or put reasonable bounds on diffusion rates.

Carbon dioxide in magmas and implications for hydrothermal systems

USGS Publications Warehouse

Lowenstern, J. B.

2001-01-01

This review focuses on the solubility, origin, abundance, and degassing of carbon dioxide (CO2) in magma-hydrothermal systems, with applications for those workers interested in intrusion-related deposits of gold and other metals. The solubility of CO2 increases with pressure and magma alkalinity. Its solubility is low relative to that of H2O, so that fluids exsolved deep in the crust tend to have high CO2/H2O compared with fluids evolved closer to the surface. Similarly, CO2/H2O will typically decrease during progressive decompression- or crystallization-induced degassing. The temperature dependence of solubility is a function of the speciation of CO2, which dissolves in molecular form in rhyolites (retrograde temperature solubility), but exists as dissolved carbonate groups in basalts (prograde). Magnesite and dolomite are stable under a relatively wide range of mantle conditions, but melt just above the solidus, thereby contributing CO2 to mantle magmas. Graphite, diamond, and a free CO2-bearing fluid may be the primary carbon-bearing phases in other mantle source regions. Growing evidence suggests that most CO2 is contributed to arc magmas via recycling of subducted oceanic crust and its overlying sediment blanket. Additional carbon can be added to magmas during magma-wallrock interactions in the crust. Studies of fluid and melt inclusions from intrusive and extrusive igneous rocks yield ample evidence that many magmas are vapor saturated as deep as the mid crust (10-15 km) and that CO2 is an appreciable part of the exsolved vapor. Such is the case in both basaltic and some silicic magmas. Under most conditions, the presence of a CO2-bearing vapor does not hinder, and in fact may promote, the ascent and eruption of the host magma. Carbonic fluids are poorly miscible with aqueous fluids, particularly at high temperature and low pressure, so that the presence of CO2 can induce immiscibility both within the magmatic volatile phase and in hydrothermal systems. Because some metals, including gold, can be more volatile in vapor phases than coexisting liquids, the presence of CO2 may indirectly aid the process of metallogenesis by inducing phase separation.

Diffusive Soil Degassing of Radon and Carbon Dioxide at Ilopango Caldera, El Salvador, Central America

NASA Astrophysics Data System (ADS)

Ransom, L.; Lopez, D. L.; Hernandez, P.

2001-12-01

Ilopango Caldera lies 10 Km east of San Salvador, El Salvador and holds Ilopango Lake, the largest body of fresh water in El Salvador. There is currently no observed fumarolic activity within the caldera system. However, the last eruption occurred in 1880. In November - December, 1999, radon gas concentrations (pCi/l) were measured using a Pylon AB5 radon monitor, and flux of CO2 (g/m2/day) was determined using the accumulation chamber method at 106 sampling stations around the lake, along and across the caldera walls. Gas samples were also collected to determine the isotopic composition of C in CO2. CO2 fluxes did not show high values characteristic of other volcanic systems, values ranged from 0.7 to 9.2 g/m2/day with an average value of 3.9. These values are similar to the low values of the background population observed in nearby San Salvador volcano. Highest values are observed to the east and west of the lake. Isotopic values for C in soil gases do not show an important magmatic component. Radon concentrations present three distinct populations with the highest values occurring to the southwest. Thoron concentrations are higher close to the caldera walls than inside the caldera due to the possible higher rock fracturing in that region. Measurements taken in March 2001, after the January 13 and February 13, 2001 earthquakes did not show significant variations in CO2 fluxes. However, radon concentrations varied due to the high seismicity that lasted several months after these earthquakes. These results suggest that the magmatic system of Ilopango Caldera is not emitting high fluxes of CO2 to the atmosphere throughout the caldera soils. Subaquatic emissions of CO2 have not been evaluated. However, subaquatic hydrothermal discharges have not been identified at this calderic lake.

Helium and Carbon Isotope and Relative Abundance Relationships in Lau Basin Basalts: Resolving Mantle Source Composition from Degassing and Contamination Effects

NASA Astrophysics Data System (ADS)

Vukajlovich, D. J.; Hilton, D. R.; Castillo, P. R.; Hawkins, J. W.

2005-12-01

The Lau Basin has multiple mantle source components including contributions from the Indian and Pacific MORB sources, Tonga-Kermadec Arc and Samoan plume. In order to characterize the volatile systematics of these various sources and to map their spatial distribution, we have sampled basaltic glasses from over 50 dredge sites covering all known spreading centers in the basin as well as many off-axis seamounts. Here, we report He abundance and isotope results obtained by crushing, in addition to CO2 released through stepped heating, from sites at the Mangatolu Triple Junction (MTJ), Rochambeau Bank (RB), Peggy Ridge, and the Northern, Eastern and Central Lau Spreading Centers. High 3He/4He ratios from RB (up to 23 RA, where RA = air 3He/4He) confirm the presence of a plume component in the northwestern Lau Basin (Poreda, EPSL, 1985). Central and Eastern Lau Spreading Center basalts have 3He/4He ratios between 8.3 and 9.4 RA, consistent with a depleted, MORB-like mantle source with little influence from slab or crustal helium. In contrast, the large range in helium isotope ratios of MTJ samples (0.85 to 7.9 RA) and the correlation between low He abundances (~2 - 3 × 10-9 cm3/g) and low helium isotope ratios suggests the volatiles in this region have been severely affected by degassing and additions of radiogenic (crustal) He. CO2 abundances and carbon isotopes for samples from RB vary from 70 to 119 ppm ([CO2]total) with δ13Cvesicle falling between -12.3 to -14.8 ‰ and δ13Cdissolved lying between -9.3 to -10.7 ‰. In the MTJ, low helium concentration samples have δ13C as low as -27.4 ‰ and [CO2]total as low as 7.6ppm; interestingly, this region also has samples with the highest measured values (up to -6.3 ‰ and 132ppm total C). Combining the carbon and helium data, CO2/3He ratios in the MTJ range from arc-like values (~1010) to sediment or crustal values (~1013) showing the superimposition of degassing and/or contamination effects on a predominant slab-like signature. High 3He/4He samples from RB have CO2 /3He ratios similar to the upper mantle value (2 × 109), as at other back-arc localities exhibiting a high 3He/4He (plume) component (e.g. the Manus Basin; Shaw et al., GCA, 2004). Continuing analytical work will complete our He-C survey of the Lau Basin, identifying samples suitable for further effort involving Ne, Ar, H2O plus other tracers of interest. Presently, we are modeling degassing/contamination effects to identify the nature and distribution of mantle source components throughout the Lau Basin. The volatile characteristics of the high 3He/4He samples are of particular interest as they provide insight into the different recycling and storage histories of volatiles between distinct mantle reservoirs.

Constraining the presence and abundance of an excess gas phase prior to the June 1991 eruption of Mt Pinatubo (Philippines) using S-isotopes

NASA Astrophysics Data System (ADS)

Bouvet de Maisonneuve, C.; Fiege, A.; Fabbro, G.; Kubo, A. I.

2016-12-01

Large explosive eruptions typically release orders of magnitude more S to the atmosphere than expected based on degassing of the erupted magma. To explain this, an excess, accumulated vapor phase is often proposed. Resolving the presence, composition, and source of such an exsolved volatile phase is essential, as it will drive eruptions towards increased explosivity. Integration of melt inclusion (MI) volatile contents (H, C, S, Cl, F) with S isotope data on melt inclusions, and sulfur-bearing minerals (anhydrite) can provide information on pre- and syn-eruptive degassing. The June 1991 eruption of Mt Pinatubo is an ideal candidate for such a study as it injected a >17 Mt of SO2 into the stratosphere, corresponding to a S excess release of a factor close to 100. The erupted magma was oxidized (QFM+3) and should therefore yield a clear isotopic trend. Volatile contents in glassy but vesicular quartz-hosted MIs were measured by SIMS and yield <3 wt% H2O and <100 ppm S but up to 1500 ppm CO2, in agreement with previous measurements. The MIs with few but large vapor bubbles (avoided during analysis) have lower H2O and CO2 contents and smaller standard deviations. The MIs with many small bubbles have higher volatile contents and standard deviations because the gas phase was not avoided during analysis. We observed scattered S contents and highly variable S isotope compositions for all MIs, which could be due to the presence of submicron S phases. Thus, we homogenized a batch of MIs under P-T-fO2 conditions that best correspond to pre-eruptive conditions. The δ34S for quartz-hosted MIs ranges from -1 to +14 ‰ and δ34S vs. S-H-C content trends are used to infer open or closed system degassing processes. In the near future, anhydrites and melt inclusions in other mineral hosts (amphibole and plagioclase) will be investigated in order to reconstruct the degassing history of the 1991 Pinatubo magma and to trace the S source.

A window into the future of the Earth, hidden in the jungles of Costa Rica's volcanoes

NASA Astrophysics Data System (ADS)

Fisher, J. B.; Schwandner, F. M.; Asner, G. P.; Schimel, D.; Norby, R. J.; Keller, M.; Pavlick, R.; Braverman, A. J.; Pieri, D. C.; Diaz, J. A.; Gutierrez, M.; Duarte, E. A.; Lewicki, J. L.; Manning, C. E.; Deering, C. D.; Seibt, U.; Miller, G. R.; Drewry, D.; Chambers, J.

2017-12-01

The CO2 fertilization response of the terrestrial biosphere contributes among the largest sensitivities and uncertainties across projections of the Earth's future. The source of that uncertainty can be pinpointed to the largest fluxes in the biosphere: the tropics. Free Air CO2 Enrichment (FACE) experiments have contributed immensely to our understanding of short-term CO2 fertilization, but, outside of a small pilot study in development, have been absent in the tropics. This is largely due to numerous hurdles of not only conducting such experiments in challenging environments, but also due to the need to expand their extent considerably to encompass the enormous diversity of species-level responses, in addition to the need for multi-decadal scale responses. As such, we have remained at a critical impasse in our ability to advance understanding of the response of the tropical biosphere to increasing CO2. Recent discoveries have found a cluster of volcanoes degassing CO2 into tropical ecosystems in Costa Rica at concentrations similar to future Earth atmosphere levels. The degassing has been occurring persistently from 10s to 100s of years over 10s to 100s of square kilometers, at different levels depending on the volcano. Fortuitously, this provides a natural "experiment" across a range of conditions needed to assess a widespread and long-lived tropical ecosystem response to elevated CO2: tree species will have had time to shift in composition, traits, structure, and function. Nonetheless, due both to the challenges with assessing these changes on the ground, and heterogeneity causing problems with coarse-scale satellite remote sensing observations, this "window" into the future of the Earth has remained veiled. Here, we describe an airborne-based plan designed to uncover this gem hidden in the jungles of Costa Rica's volcanoes.

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field, Taupo Volcanic Zone, New Zealand

USGS Publications Warehouse

Rissmann, C.; Christenson, B.; Werner, C.; Leybourne, M.; Cole, J.; Gravley, D.

2012-01-01

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20a of production (116MW e). Soil CO2 degassing was quantified with 2663 CO2 flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (Wm -2) using published soil temperature heat flow functions. Both CO2 flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO 2 gas samples were also analysed for stable C isotopes. Following 20a of production, current CO2 emissions equated to 111??6.7T/d. Observed heat flow was 70??6.4MW, compared with a pre-production value of 122MW. This 52MW reduction in surface heat flow is due to production-induced drying up of all alkali-Cl outflows (61.5MW) and steam-heated pools (8.6MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali-Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18MW (from 25MW to 43.3??5MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20a of production, with an observed heat flow of 26.7??3MW and a CO 2 emission rate of 39??3T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali-Cl outflows once contributed significantly to the natural surface heat flow (~50%) they contributed little (<1%) to pre-production CO 2 emissions due to the loss of >99% of the original CO 2 content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO 2 release to the atmosphere from the high temperature reservoir at Ohaaki. The CO 2 flux and heat flow surveys indicate that despite 20a of production the variability in location, spatial extent and magnitude of CO 2 flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60gm -2d -1) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO 2 diffuses through porous media of the soil zone. For high-flux sites (>300gm -2d -1), the ?? 13CO 2 signature (-7.4??0.3??? OHW and -6.5??0.6??? OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO 2 source for each respective upflow. Flux thresholds of <30gm -2d -1 for purely diffusive gas transport, between 30 and 300gm -2d -1 for combined diffusive-advective transport, and ???300gm -2d -1 for purely advective gas transport at Ohaaki were assigned. ?? 13CO 2 values and cumulative probability plots of CO 2 flux data both identified a threshold of ~15gm -2d -1 by which background (atmospheric and soil respired) CO 2 may be differentiated from hydrothermal CO 2. ?? 2011 Elsevier Ltd.

Using titanite petrochronology to monitor CO2-degassing episodes from the Himalayas

NASA Astrophysics Data System (ADS)

Rapa, Giulia; Groppo, Chiara; Rolfo, Franco; Petrelli, Maurizio; Mosca, Pietro

2017-04-01

Metamorphic degassing from active collisional orogens supplies a significant fraction of CO2 to the atmosphere, playing a fundamental role in the long-term (> 1 Ma) global carbon cycle (Gaillardet & Galy, 2008). The petro-chronologic study of the CO2-source rocks (e.g. calc-silicate rocks) in collisional settings is therefore fundamental to understand the nature, timing, duration and magnitude of the orogenic carbon cycle. So far, the incomplete knowledge of these systems hindered a reliable quantitative modelling of metamorphic CO2 fluxes. A detailed petrological modelling of a clinopyroxene + scapolite + K-feldspar + plagioclase + biotite + zoisite ± calcite calc-silicate rock from central Nepal Himalaya allowed us to identify and fully characterize - for the first time - different metamorphic reactions that led to the simultaneous growth of titanite and production of CO2. These reactions involve biotite (rather than rutile) as the Ti-bearing reactant counterpart of titanite. The results of petrological modelling combined with Zr-in-Ttn thermometry and U-Pb geochronology suggest that in the studied sample, most titanite grains grew during two nearly continuous episodes of titanite formation: a near-peak event at 730-740°C, 10 kbar, 25.5±1.5 Ma, and a peak event at 740-765°C, 10.5 kbar, 22±3 Ma. Both episodes of titanite growth are correlated to specific CO2-producing reactions, thus allowing to constrain the timing, duration and P-T conditions of the main CO2-producing events, as well as the amounts of CO2 produced. Assuming that fluids released at a depth of ca. 30 km are able to reach the Earth's surface 10 Ma after their production, it is therefore possible to speculate on the role exerted by the Himalayan orogenesis on the climate in the past. Gaillardet J. & Galy A. (2008): Himalaya-carbon sink or source? Science, 320, 1727-1728.

Geochemical constraints on volatile sources and subsurface conditions at Mount Martin, Mount Mageik, and Trident Volcanoes, Katmai Volcanic Cluster, Alaska

NASA Astrophysics Data System (ADS)

Lopez, T.; Tassi, F.; Aiuppa, A.; Galle, B.; Rizzo, A. L.; Fiebig, J.; Capecchiacci, F.; Giudice, G.; Caliro, S.; Tamburello, G.

2017-11-01

We use the chemical and isotopic composition of volcanic gases and steam condensate, in situ measurements of plume composition and remote measurements of SO2 flux to constrain volatile sources and characterize subvolcanic conditions at three persistently degassing and seismically active volcanoes within the Katmai Volcanic Cluster (KVC), Alaska: Mount Martin, Mount Mageik and Trident. In situ plume measurements of gas composition were collected at all three volcanoes using MultiGAS instruments to calculate gas ratios (e.g. CO2/H2S, SO2/H2S and H2O/H2S), and remote measurements of SO2 column density were collected from Mount Martin and Mount Mageik by ultraviolet spectrometer systems to calculate SO2 fluxes. Fumaroles were directly sampled for chemical and isotopic composition from Mount Mageik and Trident. Mid Ocean Ridge Basalt (MORB)-like 3He/4He ratios ( 7.2-7.6 Rc/RA) within Mount Mageik and Trident's fumarole emissions and a moderate SO2 flux ( 75 t/d) from Mount Martin, combined with gas compositions dominated by H2O, CO2 and H2S from all three volcanoes, indicate magma degassing and active hydrothermal systems in the subsurface of these volcanoes. Mount Martin's gas emissions have the lowest CO2/H2S ratio ( 2-4) and highest SO2 flux compared to the other KVC volcanoes, indicative of shallow magma degassing. Geothermometry techniques applied to Mount Mageik and Trident's fumarolic gas compositions suggest that their hydrothermal reservoirs are located at depths of 0.2 and 4 km below the surface, respectively. Observations of an unusually reducing gas composition at Trident and organic material in the near-surface soils suggest that thermal decomposition of sediments may be influencing gas composition. When the measured gas compositions from Mount Mageik and Trident are compared with previous samples collected in the late 1990's, relatively stable magmatic-hydrothermal conditions are inferred for Mount Mageik, while gradual degassing of residual magma and contamination by shallow crustal fluids is inferred for Trident. The isotopic composition of volcanic gases emitted from Mount Mageik and Trident reflect mixing of subducted slab, mantle and crustal volatile sources, with organic sediment and carbonate being the predominant sources. Considering the close proximity of the target volcanoes in comparison with the depth to the subducted slab we speculate that Aleutian Arc volatiles are fed by a relatively homogeneous subducted fluid and that much of the apparent variability in volatile provenance can be explained by shallow crustal volatile sources and/or processes.

Fundamental Studies of Clay and Clay-rich Mineral Reactions with H2O-CO2 Fluids: Application to Geological Carbon Dioxide Sequestration

NASA Astrophysics Data System (ADS)

Chizmeshya, A. V.

2016-12-01

Geological sequestration is currently being actively developed as a near-term, large-scale carbon sequestration technology in which supercritical carbon dioxide (scCO2) is injected below-ground into saline aquifers, depleted and existing oil and gas reservoir. Implementation strongly depends on the specific geological profile of each candidate injection site. Caprock formations that contain swellable clay minerals are of particular concern, since interaction with injected CO2 may produce complex local structural effects related to shrinkage, desiccation, and plastic response leading to CO2 escape. The current knowledge-base on rock-brine-CO2 interactions often relies on semi-empirical geochemical modeling and autoclave experiments, which necessitate quenching (de-gassing) to ambient conditions for characterization. To avoid these effects we used a moissanite-based microreaction system (Diefenbacher, J et al Rev. Mod. Inst., 76 15103 (2005)) which enables in situ synchrotron characterization of interactions under constant CO2 activity. Synchrotron studies were performed at the GSECARS sector of the Argonne National Lab APS to systematically determine the response of representative Ca- and Na-montmorillonites (STx-1, SWy-1) clays to dry/wet scCO2 (H2O-rich) fluids at T and P encountered in typical aquifers. Our main findings for hydrated STx-1 are that desiccation occurs spontaneously on the scale of minutes-hours over a wide range of conditions in dry scCO2 via release of H2O with volume changes as large as 19% in relation to the initial volume. Desiccation was not observed in wet scCO2, or in corresponding saline solutions containing 1-3 M NaCl, but quenching to ambient conditions from low-pressures leads to re-hydration in STx-1 suggesting a pressure-dependent diffusion barrier for H2O from the clay into bulk scCO2. Similar desiccation transitions with smaller volume changes of 5-9% were also observed in SWy-1 at P 140 atm and T 40 C. At high pressures ( 200 atm) minor lamellar expansion was sometimes found in STx-1 suggesting the possible intercalation of CO2. Our diffraction studies reveal an intriguing relationship between the critical dehydration temperatures and pressures, with bounds defined by critical properties of CO2.

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Degassing-induced crystallization in silicate melt inclusion: evaluating the role of post-entrapment changes in melt inclusion from the SW volcanic flows of Deccan Large Igneous Province (Deccan LIP) lava.

NASA Astrophysics Data System (ADS)

Rani Choudhary, Babita

2017-04-01

Melt inclusions represent sampling of magma during their growth in magma chambers and during ascent to the surface. Several studies of melt inclusions in Large Igneous Provinces (LIPs) in different parts of the world have been documented in the literature (Sobolev et al. 2011; Kamenetsky et al. 2012). Melt inclusions study from Deccan LIP can provide new insights into the physio-chemical conditions and evolution of this important LIP. The Deccan LIP was fissure eruption mainly emplaced over a very short duration at 66 Ma (Schoene et al. 2015). To better characterize and explain the diversity in geochemical composition, petrogenesis and volatile degassing, melt inclusions studies have been carried out in clinopyroxene and plagioclase feldspar from a suite of samples in the Western Ghats section. Samples were obtained from the upper three formations (the Wai subgroup). The inclusions are primary and range in shape and size varies from a few microns, up to 100 microns. The inclusions are crystalline, and contain daughter phases. Some are glassy, with or without a shrinkage bubble. The melt inclusions show substantial variations in major element composition. Inclusions are significantly enriched in TiO2 (3.68 to 0.08 wt%) and FeO (18.3 to 2.63 wt%). SiO2 ranges from 43.4-66.8 wt% and classification diagrams of total alkali (Na2O+K2O) Vs. silica melt inclusions show that most inclusions are of sub-alkaline to mildly alkaline composition. Al2O3 ranges from 9.7- 22.4wt % and MgO 18.3-1.6. EPMA measurements demonstrated the presence of daughter crystals, such as magnetite and titanomagnetite, and high FeO, TiO2 and CaO within melt inclusions among the silicate daughter crystal clusters. Volatiles are determined have wide range in composition in both plagioclase- and pyroxene-hosted melt inclusions by using FTIR technique, values up to 2wt% H2Ototal and 1808 ppm CO2. Moreover the variability in composition and volatiles the melt from the samples in a single flow suggests that trapped melts were significantly affected by degassing and the post-entrapment changes. After each hiatus of the magmatic pulse the differentiated residual magma was enriched in Fe-Mg-Ti. Post-entrapment crystal aggregates contribute to the alteration of the melt phase within the inclusions (Choudhary and Jadhav 2010) i.e. fractionating tholeiitic lavas follow a trend that reflected by iron saturation until Fe-Ti oxides start to precipitate. Compositional concentrations are affected by diffusion from the plagioclase host into the inclusion, e.g. precipitation of host, resulting the high Al2O3 .Therefore melt inclusions showed evolved fractionated melt with the presence of aggregated crystals indicating that formation of these Fe-Ti oxides have occurred in an aqueous condition. As well, the formation of daughter mineral assemblages (titanomagnetite, and magnetite crystallization inside the inclusions) promotes the diffusion of hydrogen out of the inclusions.

Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

PubMed

Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2015-03-01

A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A decade of global volcanic SO2 emissions measured from space

NASA Astrophysics Data System (ADS)

Carn, S. A.; Fioletov, V. E.; McLinden, C. A.; Li, C.; Krotkov, N. A.

2017-03-01

The global flux of sulfur dioxide (SO2) emitted by passive volcanic degassing is a key parameter that constrains the fluxes of other volcanic gases (including carbon dioxide, CO2) and toxic trace metals (e.g., mercury). It is also a required input for atmospheric chemistry and climate models, since it impacts the tropospheric burden of sulfate aerosol, a major climate-forcing species. Despite its significance, an inventory of passive volcanic degassing is very difficult to produce, due largely to the patchy spatial and temporal coverage of ground-based SO2 measurements. We report here the first volcanic SO2 emissions inventory derived from global, coincident satellite measurements, made by the Ozone Monitoring Instrument (OMI) on NASA’s Aura satellite in 2005-2015. The OMI measurements permit estimation of SO2 emissions from over 90 volcanoes, including new constraints on fluxes from Indonesia, Papua New Guinea, the Aleutian Islands, the Kuril Islands and Kamchatka. On average over the past decade, the volcanic SO2 sources consistently detected from space have discharged a total of ~63 kt/day SO2 during passive degassing, or ~23 ± 2 Tg/yr. We find that ~30% of the sources show significant decadal trends in SO2 emissions, with positive trends observed at multiple volcanoes in some regions including Vanuatu, southern Japan, Peru and Chile.

A decade of global volcanic SO2 emissions measured from space

PubMed Central

Carn, S. A.; Fioletov, V. E.; McLinden, C. A.; Li, C.; Krotkov, N. A.

2017-01-01

The global flux of sulfur dioxide (SO2) emitted by passive volcanic degassing is a key parameter that constrains the fluxes of other volcanic gases (including carbon dioxide, CO2) and toxic trace metals (e.g., mercury). It is also a required input for atmospheric chemistry and climate models, since it impacts the tropospheric burden of sulfate aerosol, a major climate-forcing species. Despite its significance, an inventory of passive volcanic degassing is very difficult to produce, due largely to the patchy spatial and temporal coverage of ground-based SO2 measurements. We report here the first volcanic SO2 emissions inventory derived from global, coincident satellite measurements, made by the Ozone Monitoring Instrument (OMI) on NASA’s Aura satellite in 2005–2015. The OMI measurements permit estimation of SO2 emissions from over 90 volcanoes, including new constraints on fluxes from Indonesia, Papua New Guinea, the Aleutian Islands, the Kuril Islands and Kamchatka. On average over the past decade, the volcanic SO2 sources consistently detected from space have discharged a total of ~63 kt/day SO2 during passive degassing, or ~23 ± 2 Tg/yr. We find that ~30% of the sources show significant decadal trends in SO2 emissions, with positive trends observed at multiple volcanoes in some regions including Vanuatu, southern Japan, Peru and Chile. PMID:28275238

A Decade of Global Volcanic SO2 Emissions Measured from Space

NASA Technical Reports Server (NTRS)

Carn, S. A.; Fioletov, V. E.; McLinden, C. A.; Li, C.; Krotkov, N. A.

2017-01-01

The global flux of sulfur dioxide (SO2) emitted by passive volcanic degassing is a key parameter that constrains the fluxes of other volcanic gases (including carbon dioxide, CO2) and toxic trace metals (e.g., mercury). It is also a required input for atmospheric chemistry and climate models, since it impacts the tropospheric burden of sulfate aerosol, a major climate-forcing species. Despite its significance, an inventory of passive volcanic degassing is very difficult to produce, due largely to the patchy spatial and temporal coverage of ground-based SO2 measurements. We report here the first volcanic SO2 emissions inventory derived from global, coincident satellite measurements, made by the Ozone Monitoring Instrument (OMI) on NASA's Aura satellite in 2005-2015. The OMI measurements permit estimation of SO2 emissions from over 90 volcanoes, including new constraints on fluxes from Indonesia, Papua New Guinea, the Aleutian Islands, the Kuril Islands and Kamchatka. On average over the past decade, the volcanic SO2 sources consistently detected from space have discharged a total of approximately 63 kt/day SO2 during passive degassing, or approximately 23 +/- 2 Tg/yr. We find that approximately 30% of the sources show significant decadal trends in SO2 emissions, with positive trends observed at multiple volcanoes in some regions including Vanuatu, southern Japan, Peru and Chile.

A decade of global volcanic SO2 emissions measured from space.

PubMed

Carn, S A; Fioletov, V E; McLinden, C A; Li, C; Krotkov, N A

2017-03-09

The global flux of sulfur dioxide (SO 2 ) emitted by passive volcanic degassing is a key parameter that constrains the fluxes of other volcanic gases (including carbon dioxide, CO 2 ) and toxic trace metals (e.g., mercury). It is also a required input for atmospheric chemistry and climate models, since it impacts the tropospheric burden of sulfate aerosol, a major climate-forcing species. Despite its significance, an inventory of passive volcanic degassing is very difficult to produce, due largely to the patchy spatial and temporal coverage of ground-based SO 2 measurements. We report here the first volcanic SO 2 emissions inventory derived from global, coincident satellite measurements, made by the Ozone Monitoring Instrument (OMI) on NASA's Aura satellite in 2005-2015. The OMI measurements permit estimation of SO 2 emissions from over 90 volcanoes, including new constraints on fluxes from Indonesia, Papua New Guinea, the Aleutian Islands, the Kuril Islands and Kamchatka. On average over the past decade, the volcanic SO 2 sources consistently detected from space have discharged a total of ~63 kt/day SO 2 during passive degassing, or ~23 ± 2 Tg/yr. We find that ~30% of the sources show significant decadal trends in SO 2 emissions, with positive trends observed at multiple volcanoes in some regions including Vanuatu, southern Japan, Peru and Chile.

Thermal History and Volatile Partitioning between Proto-Atmosphere and Interior of Mars Accreted in a Solar Nebula

NASA Astrophysics Data System (ADS)

Saito, Hiroaki; Kuramoto, Kiyoshi

2015-11-01

Recent precise Hf-W chronometry of Martian meteorites reveals that Mars had likely reached the half of its present mass within 3 Myr from the birth of the solar system (Dauphas and Pourmand, 2011). Hence, the accretion is considered to almost proceed within the solar nebula associated with the capture of nebula gas components. At the same time, the impact degassing may inevitably occur because impact velocity increases high enough for such degassing when a proto-planet gets larger than around lunar size. Thus, we can expect the formation of a hybrid-type proto-atmosphere that consists of nebula gas and degassed one.This study analyzes the thermal structure of this proto-atmosphere sustained by accretional heating by building a 1D radiative-convective equilibrium model. Raw materials of Mars are supposed to be volatile-rich on the basis of the geochemical systematics of Mars meteorites (Dreibus and Wanke, 1988). The composition of degassed component comprised of H2, H2O, CH4, and CO is determined by chemical equilibrium with silicate and metal under the physical condition of locally heated region generated by each impact (Kuramoto, 1997). Degassed component lies beneath the nebula gas atmosphere at altitudes below the compositional boundary height that would change depending on the amount of degassed component. The accretion time is taken to be from 1 to 6 Myr.Our model predicts that the surface temperature exceeds the liquidus temperature of rock when a proto Mars grows larger than 0.7 times of its present mass for the longest accretion time case. In this case, the magma ocean mass just after the end of accretion is 0.2 times of its present mass if heat transfer and heat sources such as short-lived radionuclides are neglected in the interior. The corresponding amount of water dissolved into the magma ocean would be around 1.8 times the present Earth ocean mass. These results suggest that the earliest Mars would be hot enough to form deep magma oceans, which promotes the core-mantle differentiation, and wet sufficient to make a deep-water ocean.

Rates of volcanic CO2 degassing from airborne determinations of SO2 Emission rates and plume CO2SO2: test study at Pu′u ′O′o Cone, Kilauea Volcano, Hawaii

USGS Publications Warehouse

Gerlach, Terrence M.; McGee, Kenneth A.; Sutton, A. Jefferson; Elias, Tamar

1998-01-01

We present an airborne method that eliminates or minimizes several disadvantages of the customary plume cross-section sampling method for determining volcanic CO2 emission rates. A LI-COR CO2analyzer system (LICOR), a Fourier transform infrared spectrometer system (FTIR), and a correlation spectrometer (COSPEC) were used to constrain the plume CO2/SO2 and the SO2 emission rate. The method yielded a CO2 emission rate of 300 td−1 (metric tons per day) for Pu′u ′O′o cone, Kilauea volcano, on 19 September 1995. The CO2/SO2 of 0.20 determined from airborne LICOR and FTIR plume measurements agreed with the CO2/SO2 of 204 ground-based samples collected from vents over a 14-year period since the Pu′u ′O′o eruption began in January 1983.

Carbon dioxide and helium emissions from a reservoir of magmatic gas beneath Mammoth Mountain, California

USGS Publications Warehouse

Sorey, M.L.; Evans, William C.; Kennedy, B.M.; Farrar, C.D.; Hainsworth, L.J.; Hausback, B.

1998-01-01

Carbon dioxide and helium with isotopic compositions indicative of a magmatic source (??13C = -4.5 to -5???, 3He/4He = 4.5 to 6.7 RA) are discharging at anomalous rates from Mammoth Mountain, on the southwestern rim of the Long Valley caldera in eastern California. The gas is released mainly as diffuse emissions from normal-temperature soils, but some gas issues from steam vents or leaves the mountain dissolved in cold groundwater. The rate of gas discharge increased significantly in 1989 following a 6-month period of persistent earthquake swarms and associated strain and ground deformation that has been attributed to dike emplacement beneath the mountain. An increase in the magmatic component of helium discharging in a steam vent on the north side of Mammoth Mountain, which also began in 1989, has persisted until the present time. Anomalous CO2 discharge from soils first occurred during the winter of 1990 and was followed by observations of several areas of tree kill and/or heavier than normal needlecast the following summer. Subsequent measurements have confirmed that the tree kills are associated with CO2 concentrations of 30-90% in soil gas and gas flow rates of up to 31,000 g m-2 d-1 at the soil surface. Each of the tree-kill areas and one area of CO2 discharge above tree line occurs in close proximity to one or more normal faults, which may provide conduits for gas flow from depth. We estimate that the total diffuse CO2 flux from the mountain is approximately 520 t/d, and that 30-50 t/d of CO2 are dissolved in cold groundwater flowing off the flanks of the mountain. Isotopic and chemical analyses of soil and fumarolic gas demonstrate a remarkable homogeneity in composition, suggesting that the CO2 and associated helium and excess nitrogen may be derived from a common gas reservoir whose source is associated with some combination of magmatic degassing and thermal metamorphism of metasedimentary rocks. Furthermore, N2/Ar ratios and nitrogen isotopic values indicate that the Mammoth Mountain gases are derived from sources separate from those that supply gas to the hydrothermal system within the Long Valley caldera. Various data suggest that the Mammoth Mountain gas reservoir is a large, low-temperature cap over an isolated hydrothermal system, that it predates the 1989 intrusion, and that it could remain a source of gas discharge for some time.

Degassing system from the magma reservoir of Miyakejima volcano revealed by GPS observations

NASA Astrophysics Data System (ADS)

Oikawa, J.; Nakao, S.; Matsushima, T.

2013-12-01

Miyake-jima is a volcanic island located approximately 180 km south of Tokyo. The island is an active basaltic volcano that was dormant for a 17-year period between an eruption in 1983 and June 26, 2000, when it again became active. The volcanic activity that occurred in 2000 is divided into the following four stages: the magma intrusion stage, summit subsidence stage, summit eruptive stage, and degassing stage (Nakada et al., 2001). Earthquake swarm activity began on June 26, 2000, accompanied by large-scale crustal deformation. This led to a summit eruption on July 8, 2000. Based on the pattern of hypocenter migration and the nature of crustal deformation, it was estimated that magma migrated from beneath the summit of Miyake-jima to the northwest during the magma intrusion stage. The rapid collapse of the summit took place between July 8 and the beginning of August 2000 (summit subsidence stage). Large-scale eruptions took place on August 10, 18, and 29, 2000 (explosion stage). The eruptions largely ceased after August 29, followed by the release of large amounts of gas from the summit crater (degassing stage). In this study, we examined the location of the magma reservoir during the degassing stage based on crustal deformation observed by GPS. By comparing the amounts of degassing and volume change of the magma reservoir, as determined from crustal deformation, we determined the mechanism of degassing and the nature of the magma reservoir-vent system. According to observations by the Japan Meteorological Agency, a large amount of volcanic gas began to be released from Miyake-jima in September 2000 (Kazahaya et al., 2003). Approximately 42,000 tons/day of SO2 was released during the period between September 2000 and January 2001. Analysis of GPS data during the period [Figure 1] indicates a source of crustal deformation on the south side of the summit crater wall at a depth of 5.2 km. The rate of volume change was -3.8 x 106 m3/month [Figure 2]. As the volume is equivalent to the volume occupied by the volatile components such as SO2, H2O, CO2 dissolved in the magma, it is proposed that contraction of the magma reservoir reflects degassing of its volatile components. The observations indicate that the magma reservoir is connected to the summit crater by a magma-filled vent. Convection within the vent carries volatile-rich magma upward to the crater, where volcanic gas is released by degassing. The depleted magma is then carried into the magma reservoir, which contracts due to the loss of volume originally occupied by the volcanic gas. Figure 1 shows displacements per month. Vectors show the horizontal movements. Contours and shading indicate vertical displacement. Figure 2 shows theoretical displacement assuming the Mogi model.

Fumarole emissions at Mount St. Helens volcano, June 1980 to October 1981: Degassing of a magma-hydrothermal system

USGS Publications Warehouse

Gerlach, T.M.; Casadevall, T.J.

1986-01-01

This study is an investigation of the chemical changes in the Mount St. Helens fumarole gases up to October 1981, the sources of the fumarole gases, and the stability of gas species in the shallow magma system. These problems are investigated by calculations of element compositions, thermodynamic equilibria, and magmatic volatile-hydrothermal steam mixing models. The fumarole gases are treated as mixtures of magmatic volatiles and hydrothermal steam formed by magma degassing and boiling of local waters in a dryout zone near conduit and dome magma. The magmatic volatile fraction is significant in fumaroles with temperatures in excess of the magma cracking-temperature (??? 700??C) - i.e., the temperature below which cracking is induced by thermal stresses during cooling and solidification. Linear composition changes of the fumarole gases over time appear to be the result of a steady decline in the magmatic volatile mixing fraction, which may be due to the tapping of progressively volatile-depleted magma. The maximum proportion of hydrothermal steam in the fumaroles rose from about 25-35% in September 1980 to around 50-70% by October 1981. Fractional degassing of magmatic CO2 and sulfur also contributed to the chemical changes in the fumarole gases. The steady chemical changes indicate that replenishment of the magma system with undegassed magma was not significant between September 1980 and September 1981. Extrapolations of chemical trends suggest that fumarole gases emitted at the time of formation of the first dome in mid-June 1980 were more enriched in a magmatic volatile fraction and contained a minimum of 9% CO2. Calculations show H2S is the predominant sulfur species in Mount St. Helens magma below depths of 200 m. Rapid release of gases from magma below this depth is a plausible mechanism for producing the high H2S/SO2 observed in Mount St. Helens plumes during explosive eruptions. This study suggests that dacite-andesite volcanos may emit gases richer in CO2 during the earlier episodes of an eruptive cycle and burden the atmosphere with much more H2S than SO2 during explosive eruptions. ?? 1986.

Heat flow vs. atmospheric greenhouse on early Mars

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Postawko, S. E.

1991-01-01

Researchers derived a quantitative relationship between the effectiveness of an atmospheric greenhouse and internal heat flow in producing the morphological differences between earlier and later Martian terrains. The derivation is based on relationships previously derived by other researchers. The reasoning may be stated as follows: the CO2 mean residence time in the Martian atmosphere is almost certainly much shorter than the total time span over which early climate differences are thought to have been sustained. Therefore, recycling of previously degassed CO2 quickly becomes more important than the ongoing supply of juvenile CO2. If so, then the atmospheric CO2 pressure, and thereby the surface temperature, may be approximated mathematically as a function of the total degassed CO2 in the atmosphere plus buried material and the ratio of the atmospheric and regolith mean residence times. The latter ratio can also be expressed as a function of heat flow. Hence, it follows that the surface temperature may be expressed as a function of heat flow and the total amount of available CO2. However, the depth to the water table can simultaneously be expressed as a function of heat flow and the surface temperature (the boundary condition). Therefore, for any given values of total available CO2 and regolith conductivity, there exist coupled independent equations which relate heat flow, surface temperature, and the depth to the water table. This means we can now derive simultaneous values of surface temperature and the depth of the water table for any value of the heat flow. The derived relationship is used to evaluate the relative importance of the atmospheric greenhouse effect and the internal regolith thermal gradient in producing morphological changes for any value of the heat flow, and to assess the absolute importance of each of the values of the heat flow which are thought to be reasonable on independent geophysical grounds.

Vapor saturation and accumulation in magmas of the 1989-1990 eruption of Redoubt Volcano, Alaska

USGS Publications Warehouse

Gerlach, Terrance M.; Westrich, Henry R.; Casadevall, Thomas J.; Finnegan, David L.

1994-01-01

The 1989–1990 eruption of Redoubt Volcano, Alaska, provided an opportunity to compare petrologic estimates of SO2 and Cl emissions with estimates of SO2 emissions based on remote sensing data and estimates of Cl emissions based on plume sampling. In this study, we measure the sulfur and chlorine contents of melt inclusions and matrix glasses in the eruption products to determine petrologic estimates of SO2 and Cl emissions. We compare the results with emission estimates based on COSPEC and TOMS data for SO2 and data for Cl/SO2 in plume samples. For the explosive vent clearing period (December 14–22, 1989), the petrologic estimate for SO2 emission is 21,000 tons, or ~12% of a TOMS estimate of 175,000 tons. For the dome growth period (December 22, 1989 to mid-June 1990), the petrologic estimate for SO2 emission is 18,000 tons, or ~3% of COSPEC-based estimates of 572,000–680,000 tons. The petrologic estimates give a total SO2 emission of only 39,000 tons compared to an integrated TOMS/COSPEC emission estimate of ~1,000,000 tons for the whole eruption, including quiescent degassing after mid-June 1990. Petrologic estimates also appear to underestimate Cl emissions, but apparent HCl scavenging in the plume complicates Cl emission comparisons. Several potential sources of ‘excess sulfur’ often invoked to explain petrologic SO2 deficits are concluded to be unlikely for the 1989–1990 Redoubt eruption — e.g., breakdown of sulfides, breakdown of anhydrite, release of SO2 from a hydrothermal system, degassing of commingled infusions of basalt in the magma chamber, and syn-eruptive degassing of sulfur from melt present in non-erupted magma. Leakage and/or diffusion of sulfur from melt inclusions do not provide convincing explanations for the petrologic SO2 deficits either. The main cause of low petrologic estimates for SO2 is that melt inclusions do not represent the total sulfur content of the Redoubt magmas, which were vapor-saturated magmas carrying most of their sulfur in an accumulated vapor phase. Almost all the sulfur of the SO2 emissions was present prior to emission as accumulated magmatic vapor at 6–10 km depth in the magma that supplied the eruption; whole-rock normalized concentrations of gaseous excess S in these magmas remained at ~0.2 wt.% throughout the eruption, equivalent to ~0.7 vol.% at depth. Data for CO2 emissions during the eruption indicate that CO2 at whole-rock concentrations of ~0.6 wt.% in the erupted magma was a key factor in creating the vapor saturation and accumulation condition making a vapor phase source of excess sulfur possible at depth. When explosive volcanism involves magma with accumulated vapor, melt inclusions do not provide a sufficient basis for predicting SO2 emissions. Thus, petrologic estimates made for SO2 emissions during explosive eruptions of the past may be too low and may significantly underestimate impacts on climate and the chemistry of the atmosphere.

Assessing Magmatic Processes and Hazards at two Basaltic Monogenetic Centers: Volcan Jorullo, Mexico, and Blue Lake Maar, Oregon

NASA Astrophysics Data System (ADS)

Johnson, E. R.; Cashman, K.; Wallace, P.; Delgado Granados, H.

2007-05-01

Although monogenetic basaltic volcanoes exhibit a wide variety of eruption styles, the origin of this diversity is poorly understood and often ignored when assessing volcanic hazards. To better understand magmatic processes and hazards associated with these eruptions, we have studied two monogenetic centers with differing behavior: Volcan Jorullo, a cinder cone in Mexico, and Blue Lake, a maar in the Oregon High Cascades. Although compositionally similar (medium-K basalt to basaltic andesite), their eruptive styles and products are quite different. Jorullo had violent strombolian eruptions that deposited alternating beds of ash and tephra, as well as lava flows. In contrast, Blue Lake exhibited initial phreatomagmatism that formed a 100m deep crater and produced surge deposits. This activity was followed by magmatic eruptions that produced deposits of tephra and bombs, but no lava flows. The diversity in eruptive style at these two centers reflects different magma ascent and crystallization processes, deduced using olivine-hosted melt inclusions. Jorullo melt inclusions trap variably degassed melts (0.5-5 wt% H2O; 0-1000 ppm CO2), with associated crystallization pressures that decrease from early (<4 kbars) to late (<100 bars) in the eruption. These data support the formation of a shallow storage region beneath the volcano that facilitated both crystallization and magma degassing, which is consistent with effusion of degassed lavas from the base of the cone throughout the eruption. In contrast, Blue Lake inclusions trap melts with a restricted range of volatiles (2.6-4 wt% H2O; 677-870 ppm CO2) corresponding to crystallization pressures of 2.2-3.2 kbars. This suggests that the magma feeding Blue Lake stalled in the upper crust and crystallized before ascending rapidly to the surface, without further crystallization of olivine or shallow storage. This is consistent with both the observed unstratified tephra deposits (indicating single rather than pulsatory eruptions) and the absence of lava flows. Our data suggest that in spite of similar compositions and volatile contents, these two volcanoes produced distinctive eruption styles. Although external water clearly played an important role in the eruption at Blue Lake, both volcanoes had explosive, magmatic volatile-driven eruptions. These eruptions clearly show that monogenetic centers are capable of a wide variety of eruptive styles and hazards, which may depend in large part on processes of magma ascent, degassing, and crystallization.

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands.

PubMed

Nolasco, Dácil; Lima, R Noemí; Hernández, Pedro A; Pérez, Nemesio M

2008-01-01

[corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm. The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.

Mantle to surface degassing of carbon- and sulphur-rich alkaline magma at El Hierro, Canary Islands

NASA Astrophysics Data System (ADS)

Longpré, Marc-Antoine; Stix, John; Klügel, Andreas; Shimizu, Nobumichi

2017-02-01

Basaltic volcanoes transfer volatiles from the mantle to the surface of the Earth. The quantification of deep volatile fluxes relies heavily on estimates of the volatile content of primitive magmas, the best archive of which is provided by melt inclusions. Available data from volcanoes producing mafic alkaline lavas in a range of tectonic settings suggest high volatile fluxes, but information remains sparse, particularly for intraplate ocean islands. Here we present measurements of volatile and trace element concentrations, as well as sulphur speciation, in olivine-hosted melt inclusions and matrix glasses from quenched basanite lava balloon samples from the 2011-2012 submarine eruption at El Hierro, Canary Islands. The results reveal remarkably high concentrations of dissolved volatiles and incompatible trace elements in this magma, with ∼80 ppm Nb and up to 3420 ppm CO2, 3.0 wt.% H2O and 5080 ppm S. Reconstructed primitive CO2 contents, considering CO2/Nb systematics and possible CO2 sequestration in shrinkage bubbles, reach weight percent levels, indicating that carbon is a major constituent of Canary Island magmas at depth and that exsolution of a CO2-rich fluid begins in the mantle at pressures in excess of 1 GPa. Correlations between sulphur concentration, sulphur speciation and water content suggest strong reduction of an initially oxidised mantle magma, likely controlled by coupled H2O and S degassing. This late-stage redox change may have triggered sulphide saturation, recorded by globular sulphide inclusions in clinopyroxene and ulvöspinel. The El Hierro basanite thus had a particularly high volatile-carrying capacity and released a minimum of 1.3-2.1 Tg CO2 and 1.8-2.9 Tg S to the environment, causing substantial stress on the local submarine ecosystem. These results highlight the important contribution of alkaline ocean island volcanoes, such as the Canary Islands, to volatile fluxes from the mantle.

Carbon Dioxide Emissions From Kill Zones Around the Resurgent Dome, Long Valley Caldera, CA

NASA Astrophysics Data System (ADS)

Bergfeld, D.; Evans, W. C.; Farrar, C. D.; Howle, J. F.

2004-12-01

An episode of seismic unrest beneath the resurgent dome at Long Valley caldera (LVC) in eastern California began in 1980 and is associated with approximately 80 cm of cumulative uplift on parts of the dome since that time. Studies of hydrologic and geochemical parameters can be useful in determining the source of uplift; and of particular relevance here, studies of diffuse soil degassing and temperature have been used to examine relations between gas emissions, uplift, and energy release. We present results from an eighteen-month investigation of soil temperature, soil-gas chemistry and CO2 efflux from fourteen discrete areas of vegetation kill that have appeared inside the caldera over the past two decades. Compared with the tree-kill around Mammoth Mountain on the southwest rim of the caldera, dead zones we studied around the resurgent dome are small. Individually the areas cover between 800 and 36,000 m2. All of the areas have some sites with elevated CO2 flux and elevated soil temperature. \\delta 13C values of CO2 from sites in eight of the studied areas are between -5.7 and -3.9\\permil, and are within the range of magmatic CO2. Results from the flux measurements indicate that on average total CO2 emissions from four of the areas sum about 10 tonnes per day. The other vegetation kill areas currently have only a few sites that exhibit anomalous soil temperatures and CO2 flux, and CO2 emissions from these areas are typically less than 0.3 of a tonne per day. The chemical composition of gas emissions from thermal ground in kill zones located 1.5 to 2 km northwest of the Casa Diablo geothermal power plant demonstrate a connection between some of the dead areas and perturbations related to geothermal fluid production. These results and estimates of thermal output from two of the high flux grids are used to evaluate the premise that the gaseous and thermal anomalies are related to magmatic intrusion beneath the resurgent dome.

Sources of volatiles in basalts from the Galapagos Archipelago: deep and shallow evidence

NASA Astrophysics Data System (ADS)

Peterson, M. E.; Saal, A. E.; Hauri, E. H.; Werner, R.; Hauff, S. F.; Kurz, M. D.; Geist, D.; Harpp, K. S.

2010-12-01

The study of volatiles (H2O, CO2, F, S, and Cl) is important because volatiles assert a strong influence on mantle melting and magma crystallization, as well as on the viscosity and rheology of the mantle. Despite this importance, there have been a minimal number of volatile studies done on magmas from the four main mantle sources that define the end member compositions of the Galapagos lavas. For this reason, we here present new volatile concentrations of 89 submarine glass chips from dredges collected across the archipelago during the SONNE SO158, PLUM02, AHA-NEMO, and DRIFT04 cruises. All samples, with the exception of six, were collected at depths greater than 1000m. Major elements (E-probe), and volatile and trace elements (SIMS), are analyzed on the same glass chip, using 4 chips per sample, to better represent natural and analytical variation. Trace element contents reveal three main compositional groups: an enriched group typical of OIB, a group with intermediate compositions, and a group with a depleted trace element composition similar to MORB. The absolute ranges of volatile contents for all three compositional groups are .098-1.15wt% for H2O, 10.7-193.7 ppm for CO2, 61.4-806.5 ppm for F, 715.8-1599.2 ppm for S and 3.8-493.3 for Cl. The effect of degassing, sulfide saturation and assimilation of hydrothermally altered material must be understood before using the volatile content of submarine glasses to establish the primary volatile concentration of basalts and their mantle sources. CO2 has a low solubility in basaltic melts causing it to extensively degas. Based on the CO2/Nb ratio, we estimate the extent of degassing for the Galapagos lavas to range from approximately undegassed to 90% degassed. We demonstrate that 98% of the samples are sulfur undersaturated. Therefore, sulfur will behave as a moderately incompatible element during magmatic processes. Finally, we evaluate the effect of assimilation of hydrothermally altered material on the volatile content of the lavas. This process is evident when volatile/refractory element ratios are compared to the trace elements indicative of interaction between melt and the oceanic lithosphere such as a positive Sr anomaly (Sr*) in a primitive mantle normalized diagram. This is indicative of the interaction of basaltic melts with plagioclase cumulates. For the Galapagos depleted submarine glasses, we find a positive correlation between Sr* and all volatile/refractory element ratios suggesting significant volatile input from melt-lithosphere interaction. These samples, due to their low trace element concentrations, readily show the alteration signature, thus making the establishment of their primitive volatile content difficult. As a result, we will present the primary volatile concentrations for the trace element intermediate and enriched groups after careful consideration for degassing, sulfide saturation, and assimilation of hydrothermally altered material.

Degassing behavior of Mt. Etna volcano (Italy) before and during the 2008-2009 eruption, inferred from crater plume and soil gas measurements

NASA Astrophysics Data System (ADS)

Salerno, Giuseppe; La Spina, Alessandro; Giammanco, Salvatore; Burton, Michael; Caltabiano, Tommaso; Murè, Filippo; Randazzo, Daniele; Lopez, Manuela; Bruno, Nicola; Longo, Vincenza

2010-05-01

The evolution of magmatic degassing that preceded and accompanied the 2008-2009 Mt. Etna eruption was monitored by using a combination of: i) near-daily SO2 flux measurements; ii) calculated HCl and HF fluxes, obtained combining the daily SO2 flux values with discrete FTIR measurements of SO2/HCl and SO2/HF molar ratios; iii) periodic soil CO2 flux measurements. Thanks to the differential release of magmatic gas species from an ascending magma body we were able to track the magma transfer process in the volcano plumbing system from depth (< 5 km) to the surface. Our data suggest that the intermittent paroxysmal activity that mainly affected the South-East Crater (SEC) during 2007, displayed the efficient but complex nature of Mt. Etna's plumbing system, with gas-rich magma ascending and degassing via the central conduit system prior to eruption at the peripheral SEC. Conversely, the 15 month long 2008-09 eruption event was characterized by quasi steady state magma supply. The calculated volume of magma required to produce the observed SO2 flux during the 2008-2009 eruption closely matches the volume of erupted magma. This "eruptive" steady-state would indicate an almost perfect process of magma migration and eruption at the surface, without substantial storage within the volcano plumbing system.

CO 2-fluxing collapses metal mobility in magmatic vapour

DOE PAGES

van Hinsberg, V. J.; Berlo, K.; Migdisov, A. A.; ...

2016-05-18

Magmatic systems host many types of ore deposits, including world-class deposits of copper and gold. Magmas are commonly an important source of metals and ore-forming fluids in these systems. In many magmatic-hydrothermal systems, low-density aqueous fluids, or vapours, are significant metal carriers. Such vapours are water-dominated shallowly, but fluxing of CO 2-rich vapour exsolved from deeper magma is now recognised as ubiquitous during open-system magma degassing. Furthermore, we show that such CO 2-fluxing leads to a sharp drop in element solubility, up to a factor of 10,000 for Cu, and thereby provides a highly efficient, but as yet unrecognised mechanismmore » for metal deposition.« less

Hydrogen isotope investigation of amphibole and glass in dacite magmas erupted in 1980-1986 and 2005 at Mount St. Helens, Washington

USGS Publications Warehouse

Underwood, S.J.; Feeley, T.C.; Clynne, M.A.

2013-01-01

In active, shallow, sub-volcanic magma conduits the extent of the dehydrogenation–oxidation reaction in amphibole phenocrysts is controlled by energetic processes that cause crystal lattice damage or conditions that increase hydrogen diffusivity in magmatic phases. Amphibole phenocrysts separated from dacitic volcanic rocks erupted from 1980 to 1986 and in 2005 at Mount St. Helens (MSH) were analyzed for δD, water content and Fe3+/Fe2+, and fragments of glassy groundmass were analyzed for δD and water content. Changes in amphibole δD values through time are evaluated within the context of carefully observed volcanic eruption behavior and published petrological and geochemical investigations. Driving forces for amphibole dehydrogenation include increase in magma oxygen fugacity, decrease in amphibole hydrogen fugacity, or both. The phenocryst amphibole (δD value c. –57‰ and 2 wt % H2O) in the white fallout pumice of the May 18, 1980 plinian eruptive phase is probably little modified during rapid magma ascent up an ∼7 km conduit. Younger volcanic rocks incorporate some shallowly degassed dacitic magma from earlier pulses, based on amphibole phenocryst populations that exhibit varying degrees of dehydrogenation. Pyroclastic rocks from explosive eruptions in June–October 1980 have elevated abundances of mottled amphibole phenocrysts (peaking in some pyroclastic rocks erupted on July 22, 1980), and extensive amphibole dehydrogenation is linked to crystal damage from vesiculation and pyroclastic fountain collapse that increased effective hydrogen diffusion in amphibole. Multiple amphibole δD populations in many 1980 pyroclastic rocks combined with their groundmass characteristics (e.g. mixed pumice textures) support models of shallow mixing prior to, or during, eruption as new, volatile-rich magma pulses blended with more oxidized, degassed magma. Amphibole dehydrogenation is quenched at the top surface of MSH dacite lava lobes, but the diversity in the δDamph populations in original fresh lava flow surfaces may occur from blending magma domains with different ascent histories in the sub-volcanic environment immediately before eruption. Multi-stage open-system magma degassing operated in each parcel of magma rising toward the surface, whereas the magma below ∼7 km was a relatively closed system, at least to the October 1986 eruption based on the large population of minimally dehydrogenated, rim-free amphibole in the lavas. Magma degassing and possibly H isotope exchange with low-δD fluids around the roof zone may have accompanied the ∼1·5 km upward migration of the 1980 magma body. The low-δDamph (c. –188 to –122‰) oxy-amphibole phenocrysts in lava spines extruded in May 2005 reflect dehydrogenation as ascending viscous magma degassed and crystallized, and fractures that admitted oxygen into the hot solidified lava spine interior facilitated additional iron oxidation.

Gas geochemistry and preliminary CO2 output estimation from the island of Kos (Greece)

NASA Astrophysics Data System (ADS)

D'Alessandro, Walter; Daskalopoulou, Kyriaki; Calabrese, Sergio; Longo, Manfredi; Kyriakopoulos, Konstantinos; Gagliano, Antonina Lisa

2017-04-01

Several gas samples have been collected from natural gas manifestations at the island of Kos. Most of them are found underwater along the southern coast of the island. On land two anomalous degassing areas have been recognized. These are characterised by lack of vegetation and after long dry periods by the presence of sulfate salts efflorescences. Almost all the gases are CO2-dominated (CO2 ranging from 88 to 99%) with minor amounts of N2 (up to 7%) and CH4 (up to 2.6%). Only the on-land manifestations have also significant contents of H2 (up to 0.2%) and H2S (up to 0.3%). Only one underwater manifestation is N2-dominated (61-99%) with CH4 (0.6-11%) and low CO2 (0.1-26%). The isotopic composition of He shows values ranging from 0.84 to 6.72 R/RA indicating a sometimes strong mantle contribution with the highest values measured in two of the most strongly degassing areas (Paradise Beach and Volcania). C-isotopic composition of CO2 is in the range from -3.6 to 0.6 ‰ vs V-PDB with most of the values around -1‰ indicating a mixed mantle - limestones origin. Isotopic composition of CH4, ranging from -21.5 to 2.8‰ for C and from -143 to 36‰ for H, points to a geothermal origin with sometimes evident secondary oxidation processes. CO2-flux measurements showed values up to about 10,000 g/m2/day in the areas of Volcania and Kokkino Nero and up to about 50,000 g/m2/day at Paradise beach. Preliminary CO2 output estimations gave values of 8.8 and 4 tons/day for the first two areas respectively and of 2.7 tons/day for the latter. The total output of the island (15.5 tons/day) should be considered a minimum estimation because of the incomplete coverage of the area and is comparable to the other active volcanic/geothermal systems of Greece (Nisyros, Nea Kameni and Methana).

Adventive hydrothermal circulation on Stromboli volcano (Aeolian Islands, Italy) revealed by geophysical and geochemical approaches: Implications for general fluid flow models on volcanoes

NASA Astrophysics Data System (ADS)

Finizola, A.; Ricci, T.; Deiana, R.; Cabusson, S. Barde; Rossi, M.; Praticelli, N.; Giocoli, A.; Romano, G.; Delcher, E.; Suski, B.; Revil, A.; Menny, P.; Di Gangi, F.; Letort, J.; Peltier, A.; Villasante-Marcos, V.; Douillet, G.; Avard, G.; Lelli, M.

2010-09-01

On March 15th 2007 a paroxysmal explosion occurred at the Stromboli volcano. This event generated a large amount of products, mostly lithic blocks, some of which impacted the ground as far as down to 200 m a.s.l., about 1.5 km far away from the active vents. Two days after the explosion, a new vapour emission was discovered on the north-eastern flank of the volcanic edifice, at 560 m a.s.l., just above the area called "Nel Cannestrà". This new vapour emission was due to a block impact. In order to investigate the block impact area to understand the appearance of the vapour emission, we conducted on May 2008 a multidisciplinary study involving Electrical Resistivity Tomography (ERT), Ground Penetrating Radar (GPR), Self-Potential (SP), CO 2 soil diffuse degassing and soil temperature surveys. This complementary data set revealed the presence of an anomalous conductive body, probably related to a shallow hydrothermal level, at about 10-15 m depth, more or less parallel to the topography. It is the first time that such a hydrothermal fluid flow, with a temperature close to the water boiling point (76 °C) has been evidenced at Stromboli at this low elevation on the flank of the edifice. The ERT results suggest a possible link between (1) the main central hydrothermal system of Stromboli, located just above the plumbing system feeding the active vents, with a maximum of subsurface soil temperature close to 90 °C and limited by the NeoStromboli summit crater boundary and (2) the investigated area of Nel Cannestrà, at ~ 500 m a.s.l., a buried eruptive fissure active 9 ka ago. In parallel, SP and CO 2 soil diffuse degassing measurements suggest in this sector at slightly lower elevation from the block impact crater a magmatic and hydrothermal fluid rising system along the N41° regional fault. A complementary ERT profile, on May 2009, carried out from the NeoStromboli crater boundary down to the block impact crater displayed a flank fluid flow apparently connected to a deeper system. The concept of shallow hydrothermal level have been compared to similar ERT results recently obtained on Mount Etna and La Fossa cone of Vulcano. This information needs to be taken into account in general fluid flow models on volcanoes. In particular, peripheral thermal waters (as those bordering the north-eastern coast of Stromboli) could be contaminated by hydrothermal and magmatic fluids coming from regional faults but also from the summit.

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Preservation of raw milk with CO2. Sensory evaluation of heat-processed milks.

PubMed

Amigo, L; Olano, A; Calvo, M M

1995-04-01

The effect of CO2 on the growth of psychrotrophic milk spoilage organisms was studied, both in raw fresh milk and in pure cultures of three species of Pseudomonas growing in sterilised milk. Changes of sensory properties of CO2-treated samples after heat treatment were also analysed. Inhibition of psychrotrophic growth at 7 degrees C in milk treated with CO2 to a pH 6.2 or 6.0 was impaired by a gradual reduction of the CO2 content during storage. Growth inhibition was considerably improved by pH adjustment at 24-h intervals. Sensory analysis showed significant differences between non-acidified and acidified samples after heat treatment at 75 degrees C for 20 s or 110 degrees C for 5 min. No sensory differences were found between non-acidified and acidified milks degassed before heat treatment.

Diffuse CO2 fluxes from Santiago and Congro volcanic lakes (São Miguel, Azores archipelago)

NASA Astrophysics Data System (ADS)

Andrade, César; Cruz, José; Viveiros, Fátima; Branco, Rafael

2017-04-01

Diffuse CO2 degassing occurring in Santiago and Congro lakes, both located in depressions associated to maars from São Miguel Island (Azores, Portugal), was studied through detailed flux measurements. Four sampling campaigns were developed between 2013 and 2016 in each water body, split by the cold and wet seasons. São Miguel has an area of 744.6 km2, being the largest island of the archipelago. The geology of the island is dominated by three quiescent central volcanoes (Sete Cidades, Fogo and Furnas), linked by volcanic fissural zones (Picos and Congro Fissural Volcanic systems). The oldest volcanic systems of the island are located in its eastern part (Povoação-Nordeste). Santiago lake, with a surface area of 0.26 km2 and a depth of 30.5 m, is located inside a maar crater in the Sete Cidades volcano at an altitude of 355 m. The watershed of the lake has an area of 0.97 km2 and a surface flow estimated as 1.54x10 m3/a. A total of 1612 CO2 flux measurements using the accumulation chamber method were made at Santiago lake, 253 in the first campaign (November 2013), and 462, 475 and 422 in the three other campaigns, respectively, in April 2014, September 2016 and December 2016. The total CO2 flux estimated for this lake varies between 0.4 t d-1 and 0.59 t d-1, for the surveys performed, respectively, in November 2013 and September 2016; higher CO2 outputs of 1.57 and 5.87 t d-1 were calculated for the surveys carried out in April 2014 and December 2016. These higher CO2 emissions were associated with a period without water column stratification. Similarly to Santiago lake, Congro lake is located inside a maar, in the Congro Fissural Volcanic system, and has a surface area of 0.04 km2 with 18.5 m depth and a storage of about 2.4x105 m3/a. The lake, located at an altitude of 420 m, is fed by a watershed with an area of 0.33 km2 and a runoff estimated as about 8x104 m3/a. In Congro lake a total of 713 CO2 flux measurements were performed during four surveys from November 2013 to February 2016. The CO2 flux output was estimated as ranging between 0.06 t d-1 and 0.31 t d-1; the lower CO2 emission occurred in July 2015 and should reflect the stratification of the water column that prevents the CO2 flux release at the lake surface. Considering both volcanic lakes, the mean CO2 emissions, standardized per area, in the cold season were ˜14.9 t km-2 d-1 and ˜7.1 t km-2 d-1, respectively, for Santiago and Congro lakes. During summer period, CO2 emissions were lower in both lakes (˜1.9 t km-2 d-1 and ˜4.1 t km-2 d-1 for Santiago and Congro, correspondingly), what is explained by the lake stratification. Due to the organic processes that occur in the lakes, the CO2 emission is mostly associated to a biogenic origin, but a volcanic influence cannot be excluded and further research using carbon isotopic data is crucial to discriminate the CO2 sources. Key words: volcanic lakes, CO2 flux, maars, São Miguel Island

Morphological control of La0.7Sr0.3Co0.2Fe0.8O3-δ and La0.7Sr0.3MnO3-δ catalytic membrane using PEG-H2O additive

NASA Astrophysics Data System (ADS)

Iqbal, R. M.; Nurherdiana, S. D.; Hartanto, D.; Othman, M. H. D.; Fansuri, H.

2018-04-01

Methane is the primary combustible component in non condensable part of natural gas. It is a promising source for syngas (CO and H2) production by partial oxidation method. The conversion of methane to syngas by partial oxidation method needs a controlled amount of oxygen. Membrane which has asymmetric structure and selectively permeates oxygen can be used to supply just enough oxygen to the reaction. One pathway to the fabricate asymmetric membrane is phase inversion method with an addition of PEG to increase pore size. La0.7Sr0.3Co0.2Fe0.8O3-δ (LSCF 7328) and Laa0.7Sr0.3MnO3-δ (LSM 73) powder were synthesized by solid-state method and they were characterized by XRD. The green membrane was prepared by phase inversion method. A dope solution was made by mixing LSCF 7328 or LSM 73 powder with PEG and stirred them in NMP for 24 h. PESf was then added into the dope solution and the stirring was continued to another 24 h. The resulted dope solution was degassed by immersing the solution inside and conical flask in an ultrasonic bath to remove air bubbles. The degassed mixture was then casted by spreading it on a glass surface (with a thickness of 2 mm) followed by immersion in a water bath for 24 h to coagulate the degassed mixture. Membrane morphology was characterized by Scanning Electron Microscopy (SEM) while the decomposition temperature of the polymer binder was analyzed by Thermogravimetric Analyzer (TGA). The XRD results show that phase of LSCF 7328 and LSM 73 are similar to LaCoO3 and LaMnO3, respectively. It indicated that the perovskite synthesis was successful. SEM micrograph of membrane cross sections show that the green membrane have finger like pores and a dense layer. Pores also appear on top and bottom surface of the membrane. Based on TGA results, the highest weight lost of green membrane at 550-600°C which represents the decomposition of PESf binder.

Basalt-Limestone and Andesite-Limestone Interaction in the Arc Crust - Implications for Volcanic Degassing of CO2

NASA Astrophysics Data System (ADS)

Carter, L. B.; Dasgupta, R.

2014-12-01

Volcanically emitted CO2 is generally mantle-derived, but high degassing rates at some arcs (e.g. Merapi [1] and Colli Albani Volcanic District [2]) are thought to be affected by magma-carbonate interaction in the upper plate. However, the effects of depth, temperature, and composition on this process are poorly known. We experimentally simulated magma (50%)-limestone (50%) wallrock interactions at 0.5-1.0 GPa, 1100-1200 °C using pure calcite and a hydrous (~3-5 wt.% H2O) melt (basalt, andesite, or dacite). At 1.0 GPa, 1200 °C starting melts are superliquidus, whereas in the presence of calcite, Ca-rich cpx ± Ca-scapolite are produced. With increasing T, basalt-calcite interaction causes the melt, on a volatile-free basis, to become silica-poor and Ca-rich with alumina decreasing as cpx becomes more CaTs-rich. The same trend is seen with all starting melt compositions as P decreases at a constant T (1200 °C), producing melts similar to ultracalcic (CaO/Al2O3>>1) melt inclusions found in arc settings. Shifting from basalt to andesite has little effect on SiO2 and CaO of the reacted melt (e.g. 37 wt.% SiO2, 42 wt.% CaO at 0.5 GPa, 1200 °C), whereas Al2O3 of andesite-derived reacted melt is lower, likely a result of lower alumina in the starting andesite. Wall-rock calcite consumption is observed to increase with increasing T, decreasing P, and increasing melt XSiO2. At 0.5 GPa between 1100 and 1200 °C, our basalt experiments yield carbonate assimilation from 22 to 48 wt.%. This decreases to 20 wt.% at 1.0 GPa, 1200 °C, whereas an andesitic composition assimilates 59 to 52 wt.% from 0.5 to 1.0 GPa at 1200 °C. The higher assimilation in andesite-added runs at high-T is because of lower silicate liquidus as evidenced by lower modal proportion or absence of cpx ± scapolite. Using a magma flux rate estimated for Mt. Vesuvius [3], we obtain a CO2 outflux for a single such volcano experiencing arc magma-calcite reaction [4] of at least 2-4% of the present-day global arc flux of CO2 [5]. Therefore, greater lengths of continental arcs with carbonate strata in some geologic time periods might have caused excess degassing of CO2. [1] Troll et al. (2012) GRL 11, 1-6; [2] Freda et al. (2008) Lithos 101, 397-415; [3] Scandone et al. (2008) JVGR 170, 167-180; [4] Iacono Marziano et al. (2009) Geol 37, 319-322; [5] Sano & Williams (1996) GRL 23, 2749-2752.

Resistivity structure of the Furnas hydrothermal system (Azores archipelago, Portugal) from AMT and ERT imaging.

NASA Astrophysics Data System (ADS)

Byrdina, Svetlana; Vandemeulebrouck, Jean; Rath, Volker; Silva, Catarina; Hogg, Colin; Kiyan, Duygu; Viveiros, Fatima; Eleuterio, Joana; Gresse, Marceau

2016-04-01

The Furnas volcanic complex is located in the eastern part of the São Miguel Island and comprises a 5 km × 8 km summit depression filled by two nested calderas with several craters and a lake. Present-day volcanic activity of Furnas volcano is mostly located in the northern part of the caldera, within the Furnas village and north to Furnas Lake, where hydrothermal manifestations are mainly fumarolic fields, steam vents, thermal springs, and intense soil diffuse degassing. Considering the Furnas volcano as a whole, the total integrated CO2 efflux is extremely high, with a total amount of CO2 close to 1000 ton per day (Viveiros et al., 2009). We present the first results of an electrical resistivity tomography (ERT), combined with audio-magneto-telluric (AMT) measurements aligned along two profiles inside the caldera. The purpose of this survey is to delimit the extent, the geometry, and the depth of the hydrothermal system and to correlate the deep resistivity structure with high resolution cartography of diffuse CO2 flux (Viveiros et al, 2015). The ERT and AMT methods are complementary in terms of resolution and penetration depth: ERT can image the structural details of shallow hydrothermal system (down to 100 m in our study) while AMT can image at lower resolution deeper structures at the roots of a volcano (down to 4 km in our study). Our first independent 2D inversions of the ERT-AMT data show a good agreement between the surficial and deeper features. Below the main fumarole area we observe a low resistivity body (less than 1 Ohmm) which corresponds well to the high CO2 flux at the surface and is associated with an extended conductive body at larger depth. These results strongly suggest the presence of hydrothermal waters at depth or/and the presence of altered clay-rich material. On a larger scale however, the geometry of the conducting zones differs slightly from what was expected from earlier surface studies, and may not be directly related to fault zones mapped at the surface. These slight, but measurable discrepancies might have different origins but they stress the necessity of 3D modelling and the importance of the joint inversion of the data which we consider as a next step in our work.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Molecular modeling of diffusion coefficient and ionic conductivity of CO2 in aqueous ionic solutions.

PubMed

Garcia-Ratés, Miquel; de Hemptinne, Jean-Charles; Bonet Avalos, Josep; Nieto-Draghi, Carlos

2012-03-08

Mass diffusion coefficients of CO(2)/brine mixtures under thermodynamic conditions of deep saline aquifers have been investigated by molecular simulation. The objective of this work is to provide estimates of the diffusion coefficient of CO(2) in salty water to compensate the lack of experimental data on this property. We analyzed the influence of temperature, CO(2) concentration,and salinity on the diffusion coefficient, the rotational diffusion, as well as the electrical conductivity. We observe an increase of the mass diffusion coefficient with the temperature, but no clear dependence is identified with the salinity or with the CO(2) mole fraction, if the system is overall dilute. In this case, we notice an important dispersion on the values of the diffusion coefficient which impairs any conclusive statement about the effect of the gas concentration on the mobility of CO(2) molecules. Rotational relaxation times for water and CO(2) increase by decreasing temperature or increasing the salt concentration. We propose a correlation for the self-diffusion coefficient of CO(2) in terms of the rotational relaxation time which can ultimately be used to estimate the mutual diffusion coefficient of CO(2) in brine. The electrical conductivity of the CO(2)-brine mixtures was also calculated under different thermodynamic conditions. Electrical conductivity tends to increase with the temperature and salt concentration. However, we do not observe any influence of this property with the CO(2) concentration at the studied regimes. Our results give a first evaluation of the variation of the CO(2)-brine mass diffusion coefficient, rotational relaxation times, and electrical conductivity under the thermodynamic conditions typically encountered in deep saline aquifers.

Quantitative models for magma degassing and ground deformation (bradyseism) at Campi Flegrei, Italy: Implications for future eruptions

USGS Publications Warehouse

Bodnar, R.J.; Cannatelli, C.; de Vivo, B.; Lima, A.; Belkin, H.E.; Milia, A.

2007-01-01

Campi Flegrei (Phlegrean Fields) is an active volcanic center near Naples, Italy. Numerous eruptions have occurred here during the Quaternary, and repeated episodes of slow vertical ground movement (bradyseism) have been documented since Roman times. Here, we present a quantitative model that relates deformation episodes to magma degassing and fracturing at the brittle-ductile transition in a magmatic-hydrothermal enviromnent. The model is consistent with field and laboratory observations and predicts that uplift between 1982 and 1984 was associated with crystallization of ???0.83 km3 of H2O-saturated magma at 6 km depth. During crystallization, ???6.2 ?? 1010 kg of H2O and 7.5 ?? 108 kg of CO2, exsolved from the magma and generated ???7 ?? 1015 J of mechanical (P??V) energy to drive the observed uplift. For comparison, ???1017 J of thermal energy was released during the 18 May 1980 lateral blast at Mount St. Helens. ?? 2007 The Geological Society of America.

Paleotemperatures at the lunar surfaces from open system behavior of cosmogenic 38Ar and radiogenic 40Ar

DOE PAGES

Shuster, David L.; Cassata, William S.

2015-02-10

The simultaneous diffusion of both cosmogenic 38Ar and radiogenic 40Ar from solid phases is controlled by the thermal conditions of rocks while residing near planetary surfaces. Combined observations of 38Ar/ 37Ar and 40Ar/ 39Ar ratios during stepwise degassing analyses of neutron-irradiated Apollo samples can distinguish between diffusive loss of Ar due to solar heating of the rocks and that associated with elevated temperatures during or following impact events; the data provide quantitative constraints on the durations and temperatures of each process. From sequentially degassed 38Ar/ 37Ar ratios can be calculated a spectrum of apparent 38Ar exposure ages versus the cumulativemore » release fraction of 37Ar, which is particularly sensitive to conditions at the lunar surface typically over ~106–108 year timescales. Due to variable proportions of K- and Ca-bearing glass, plagioclase and pyroxene, with variability in the grain sizes of these phases, each sample will have distinct sensitivity to, and therefore different resolving power on, past near-surface thermal conditions. Furthermore, we present the underlying assumptions, and the analytical and numerical methods used to quantify the Ar diffusion kinetics in multi-phase whole-rock analyses that provide these constraints.« less

Solubility of C-O-H volatiles in graphite-saturated martian basalts and application to martian atmospheric evolution

NASA Astrophysics Data System (ADS)

Stanley, B. D.; Hirschmann, M. M.; Withers, A. C.

2012-12-01

The modern martian atmosphere is thin, leading to surface conditions too cold to support liquid water. Yet, there is evidence of liquid surface water early in martian history that is commonly thought to require a thick CO2 atmosphere. Our previous work follows the analysis developed by Holloway and co-workers (Holloway et al. 1992; Holloway 1998), which predicts a linear relationship between CO2 and oxygen fugacity (fO2) in graphite-saturated silicate melts. At low oxygen fugacity, the solubility of CO2 in silicate melts is therefore very low. Such low calculated solubilities under reducing conditions lead to small fluxes of CO2 associated with martian magmatism, and therefore production of a thick volcanogenic CO2 atmosphere could require a prohibitively large volume of mantle-derived magma. The key assumption in these previous calculations is that the carbonate ion is the chief soluble C-O-H species. The results of the calculations would not be affected appreciably if molecular CO2, rather than carbonate ion, were an important species, but could be entirely different if there were other appreciable C-species such as CO, carbonyl (C=O) complexes, carbide (Si-C), or CH4. Clearly, graphite-saturated experiments are required to explore how much volcanogenic C may be degassed by reduced martian lavas. A series of piston-cylinder experiments were performed on synthetic martian starting materials over a range of oxygen fugacities (IW+2.3 to IW-0.9), and at pressures of 1-3 GPa and temperatures of 1340-1600 °C in Pt-graphite double capsules. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and range from 0.0026-0.50 wt%. CO2 solubilities change by one order of magnitude with an order of magnitude change in oxygen fugacity, as predicted by previous work. Secondary ion mass spectrometry (SIMS) determinations of C contents in glasses range from 0.0131-0.2626 wt%. C contents determined by SIMS are consistently higher than CO2 contents determined by FTIR. This difference, termed excess C, is attributed to the presence of other reduced C-species, such as carbonyls and amides (which have C=O and N-H bonds), detected using FTIR in reduced graphite-saturated martian basalts. An atmosphere produced by degassing of magmas similar to this study would be richer in C-O-H species than previously modeled using only CO2 and could create a much warmer climate that stabilizes liquid water on the ancient martian surface.

Using dissolved gas analysis to investigate the performance of an organic carbon permeable reactive barrier for the treatment of mine drainage

USGS Publications Warehouse

Williams, R.L.; Mayer, K.U.; Amos, R.T.; Blowes, D.W.; Ptacek, C.J.; Bain, J.G.

2007-01-01

The strongly reducing nature of permeable reactive barrier (PRB) treatment materials can lead to gas production, potentially resulting in the formation of gas bubbles and ebullition. Degassing in organic C based PRB systems due to the production of gases (primarily CO2 and CH4) is investigated using the depletion of naturally occurring non-reactive gases Ar and N2, to identify, confirm, and quantify chemical and physical processes. Sampling and analysis of dissolved gases were performed at the Nickel Rim Mine Organic Carbon PRB, which was designed for the treatment of groundwater contaminated by low quality mine drainage characterized by slightly acidic pH, and elevated Fe(II) and SO4 concentrations. A simple 4-gas degassing model was used to analyze the dissolved gas data, and the results indicate that SO4 reduction is by far the dominant process of organic C consumption within the barrier. The data provided additional information to delineate rates of microbially mediated SO4 reduction and confirm the presence of slow and fast flow zones within the barrier. Degassing was incorporated into multicomponent reactive transport simulations for the barrier and the simulations were successful in reproducing observed dissolved gas trends.

Do volcanic gases represent equilibrium volatile concentrations? Some insights from a model of diffusive fractionation during rapid bubble growth

NASA Astrophysics Data System (ADS)

Baker, D. R.

2012-12-01

Measurements of volcanic gas compositions are often presumed to be directly related to equilibrium compositions of fluids exsolved at depth in magmatic systems that rapidly escape into the atmosphere. In particular, changes in the ratios of volatile species concentrations in volcanic gases have been interpreted to reflect influx of new magma batches or changes in the degassing depth. However, other mechanisms can also yield changes in volcanic gas compositions. One such mechanism is diffusive fractionation during rapid bubble growth. Such fractionation can occur because radial growth rates of bubbles in magmas are estimated to be in the range of 10-6 to 10-3 m s-1 and diffusion coefficients of minor volatiles (e.g., Cl, F, S, CO2) are orders of magnitude slower, 10-12 to 10-9 m2 s-1. Thus a bubble that rapidly grows and subsequently loses its volatiles to the surface may contribute a fluid sample whose concentration is affected by the interplay between the kinetics of bubble growth and volatile diffusion in the melt. A finite difference code was developed to calculate the effects of rapid bubble growth on the concentration of minor elements in the bubble for a spherical growth geometry. The bubble is modeled with a fixed growth rate and a constant equilibrium fluid-melt partition coefficient, KD. Bubbles were modeled to grow to a radius of 50 μm, the size at which the dominant bubble growth mechanism appears to change from diffusion to coalescence. The critical variables that control the departure from equilibrium behavior are the K D and the ratio of the growth velocity, V, to the diffusivity, D. Modeling bubble growth in a magma chamber at 100 MPa demonstrates that when KD is in the range of 10 to 1000 at low V/D values (e.g., 103 m-1) the composition of the fluid is at, or near, equilibrium with the melt. However, as V/D increases the bubble composition deviates increasingly from equilibrium. For V/D ratios of 105 and equilibrium KD's of either 50 or 100 (similar to estimates for S), a bubble with a 50 μm radius will contain a fluid whose concentration was apparently determined by a KD of less than 10. These models also demonstrate that the combination of rapid bubble growth with slow diffusion can deplete the melt in the volatile species only within the immediate neighborhood, on the order of 100 μm. If bubbles are spaced further apart the melts may retain significant concentrations of dissolved volatiles, which could lead to secondary and tertiary nucleation events. These models for diffusive fractionation during rapid bubble growth suggest that changes in the ratios of minor elements in volcanic gases may be influenced by bubble growth rate changes. Volatiles with lower diffusivities and volatiles with very high or very low partition coefficients will be more influenced by this process. Diffusive fractionation may be responsible for the drop in the CO2/SO2 ratios sometimes observed prior to large eruptions of Stromboli volcano.

Annual cycle of magmatic CO2 in a tree-kill soil at Mammoth Mountain, California: implications for soil acidification

USGS Publications Warehouse

McGee, K.A.; Gerlach, T.M.

1998-01-01

Time-series sensor data reveal significant short-term and seasonal variations of magmatic CO2 in soil over a 12 month period in 1995-1996 at the largest tree-kill site on Mammoth Mountain, central-eastern California. Short-term variations leading to ground-level soil CO2 concentrations hazardous and lethal to humans were triggered by shallow faulting in the absence of increased seismicity or intrusion, consistent with tapping a reservoir of accumulated CO2, rather than direct magma degassing. Hydrologic processes closely modulated seasonal variations in CO2 concentrations, which rose to 65%-100% in soil gas under winter snowpack and plunged more than 25% in just days as the CO2 dissolved in spring snowmelt. The high efflux of CO2 through the tree-kill soils acts as an open-system CO2 buffer causing infiltration of waters with pH values commonly of < 4.2, acid loading of up to 7 keqH+.ha-1.yr-1, mobilization of toxic Al3+, and long-term decline of soil fertility.

Towards a consistent mantle carbon flux estimate: Insights from volatile systematics (H 2O/Ce, δD, CO 2/Nb) in the North Atlantic mantle (14° N and 34° N)

NASA Astrophysics Data System (ADS)

Cartigny, Pierre; Pineau, Françoise; Aubaud, Cyril; Javoy, Marc

2008-01-01

In order to better characterise mantle CO 2/Nb-variability, we obtained and compiled major and trace elements, content and isotope composition of both CO 2 and water on two series of mid-ocean ridge basalt (MORB) samples dredged at ˜ 14° N ( n = 6) and 34° N ( n = 11) on the mid-Atlantic ridge. All samples are carbon-saturated. One, the so-called popping rock 2ΠD43 kept its vesicles, the initial (pre-degassing) C-contents of the 16 other samples being reconstructed from their assumed degassing history. For water, the samples show large variations, from 1300 to 6900 ppm and from 1900 to 7900 ppm with associated δD-values ranging from - 55 to - 79‰ and from - 55 to - 88‰ for samples at 14° N and 34° N respectively. For carbon, the inferred initial predegassing contents vary greatly, from 660 to 14,700 ppmCO 2 and from 1400 to 57,600 ppmCO 2 for samples at 14° N and 34° N respectively. Measured Nb-contents range from 4.5 to 29.6 ppm show both good agreement with previously published data and positive correlations with reconstructed initial CO 2-contents. The mean CO 2/Nb range from ˜ 570 to ˜ 730 at 14° N and 34° N respectively. CO 2 and Nb data for the two undegassed samples available so far (i.e. the popping rock of the present study and the basaltic glasses from the Siqueiros transform fault from the study of Saal et al., 2002) show significant variations in CO 2/Nb over a factor of 2 and thus questions the constant CO 2/Nb previously emphasised for these two samples, this view being supported by CO 2/Nb-ratios of samples whose initial C-contents were reconstructed. For incompatible elements such as Ce, K and including water, a comparison of the geochemical characteristics of transform fault basaltic magmatism with other MORB systems shows magma transform fault magmatism to be unrepresentative of mantle compositions. Assuming a more appropriate average MORB CO 2/Nb-ratio of ˜ 530 and a mean MORB Nb-content of 3.31-1.8+3.99, we computed a mantle carbon flux of 2.3-1.3+2.7 × 10 12 mol/yr, a value actually consistent with that derived from C/ 3He systematics.

The comparative limnology of Lakes Nyos and Monoun, Cameroon

USGS Publications Warehouse

Kling, George; Evans, William C; Tanyileke, Gregory

2015-01-01

Lakes Nyos and Monoun are known for the dangerous accumulation of CO2 dissolved in stagnant bottom water, but the shallow waters that conceal this hazard are dilute and undergo seasonal changes similar to other deep crater lakes in the tropics. Here we discuss these changes with reference to climatic and water-column data collected at both lakes during the years following the gas release disasters in the mid-1980s. The small annual range in mean daily air temperatures leads to an equally small annual range of surface water temperatures (ΔT ~6–7 °C), reducing deep convective mixing of the water column. Weak mixing aids the establishment of meromixis, a requisite condition for the gradual buildup of CO2 in bottom waters and perhaps the unusual condition that most explains the rarity of such lakes. Within the mixolimnion, a seasonal thermocline forms each spring and shallow diel thermoclines may be sufficiently strong to isolate surface water and allow primary production to reduce PCO2 below 300 μatm, inducing a net influx of CO2 from the atmosphere. Surface water O2 and pH typically reach maxima at this time, with occasional O2 oversaturation. Mixing to the chemocline occurs in both lakes during the winter dry season, primarily due to low humidity and cool night time air temperature. An additional period of variable mixing, occasionally reaching the chemocline in Lake Monoun, occurs during the summer monsoon season in response to increased frequency of major storms. The mixolimnion encompassed the upper ~40–50 m of Lake Nyos and upper ~15–20 m of Lake Monoun prior to the installation of degassing pipes in 2001 and 2003, respectively. Degassing caused chemoclines to deepen rapidly. Piping of anoxic, high-TDS bottom water to the lake surface has had a complex effect on the mixolimnion. Algal growth stimulated by increased nutrients (N and P) initially stimulated photosynthesis and raised surface water O2 in Lake Nyos, but O2 removal through oxidation of iron was also enhanced and appeared to dominate at Lake Monoun. Depth-integrated O2 contents decreased in both lakes as did water transparency. No dangerous instabilities in water-column structure were detected over the course of degassing. While Nyos-type lakes are extremely rare, other crater lakes can pose dangers from gas releases and monitoring is warranted.

Study of the influence of the supersaturation coefficient on scaling rate using the pre-calcified surface of a quartz crystal microbalance.

PubMed

Cheap-Charpentier, Hélène; Horner, Olivier; Lédion, Jean; Perrot, Hubert

2018-05-29

Scale deposition is a common issue in industrial plants, which creates technical problems, i.e. reduction of heat transfer, decrease of flow rate due to an obstruction of pipes. Therefore, the development of some appropriate methods based on well suitable in situ sensors to evaluate and predict the scaling propensity of water is a major concern in current research. This would be a good strategy for the optimization of anti-scaling treatments. In this study, scaling tests were carried out using a sensitive sensor, which has been developed using a quartz crystal microbalance with a pre-calcified electrode surface (SQCM). This technique allowed studying the influence of the supersaturation on the scaling rate. The set-up was tested with different water samples which were brought to a given supersaturation coefficient by degassing the dissolved CO 2 . The prediction of the scaling propensity of water was then possible through the relationship between the scaling rate on a pre-calcified surface and the supersaturation coefficient. In addition, the kinetics of CaCO 3 deposit on the pre-calcified SQCM surface was found to be slower for natural water than for synthetic water (same calcium concentration). Furthermore, the activation energy for scale deposit, in synthetic water, was found to be 22 kJ.mol -1 , which may be related to the diffusion of ions and/or CaCO 3 nuclei in solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Static feed water electrolysis module

NASA Technical Reports Server (NTRS)

Powell, J. D.; Schubert, F. H.; Jensen, F. C.

1974-01-01

An advanced static feed water electrolysis module (SFWEM) and associated instrumentation for generating breathable O2 was developed. The system also generates a H2 byproduct for use in an air revitalization system for O2 recovery from metabolic CO2. Special attention was given to: (1) eliminating water feed compartment degassing, (2) eliminating need for zero gravity condenser/separators, (3) increasing current density capability, and (4) providing a self contained module so that operation is independent of laboratory instrumentation and complicated startup/shutdown procedures.

Year-round CH4 and CO2 flux dynamics in two contrasting freshwater ecosystems of the subarctic

NASA Astrophysics Data System (ADS)

Jammet, Mathilde; Dengel, Sigrid; Kettner, Ernesto; Parmentier, Frans-Jan W.; Wik, Martin; Crill, Patrick; Friborg, Thomas

2017-11-01

Lakes and wetlands, common ecosystems of the high northern latitudes, exchange large amounts of the climate-forcing gases methane (CH4) and carbon dioxide (CO2) with the atmosphere. The magnitudes of these fluxes and the processes driving them are still uncertain, particularly for subarctic and Arctic lakes where direct measurements of CH4 and CO2 emissions are often of low temporal resolution and are rarely sustained throughout the entire year. Using the eddy covariance method, we measured surface-atmosphere exchange of CH4 and CO2 during 2.5 years in a thawed fen and a shallow lake of a subarctic peatland complex. Gas exchange at the fen exhibited the expected seasonality of a subarctic wetland with maximum CH4 emissions and CO2 uptake in summer, as well as low but continuous emissions of CH4 and CO2 throughout the snow-covered winter. The seasonality of lake fluxes differed, with maximum CO2 and CH4 flux rates recorded at spring thaw. During the ice-free seasons, we could identify surface CH4 emissions as mostly ebullition events with a seasonal trend in the magnitude of the release, while a net CO2 flux indicated photosynthetic activity. We found correlations between surface CH4 emissions and surface sediment temperature, as well as between diel CO2 uptake and diel solar input. During spring, the breakdown of thermal stratification following ice thaw triggered the degassing of both CH4 and CO2. This spring burst was observed in 2 consecutive years for both gases, with a large inter-annual variability in the magnitude of the CH4 degassing. On the annual scale, spring emissions converted the lake from a small CO2 sink to a CO2 source: 80 % of total annual carbon emissions from the lake were emitted as CO2. The annual total carbon exchange per unit area was highest at the fen, which was an annual sink of carbon with respect to the atmosphere. Continuous respiration during the winter partly counteracted the fen summer sink by accounting for, as both CH4 and CO2, 33 % of annual carbon exchange. Our study shows (1) the importance of overturn periods (spring or fall) for the annual CH4 and CO2 emissions of northern lakes, (2) the significance of lakes as atmospheric carbon sources in subarctic landscapes while fens can be a strong carbon sink, and (3) the potential for ecosystem-scale eddy covariance measurements to improve the understanding of short-term processes driving lake-atmosphere exchange of CH4 and CO2.

Melt Heterogeneity and Degassing at MT Etna from Melt Inclusions

NASA Astrophysics Data System (ADS)

Salem, L. C.; Edmonds, M.; Maclennan, J.; Corsaro, R. A.

2014-12-01

The melts feeding Mt Etna, Italy, are rich in volatiles and drive long-lasting powerful eruptions of basaltic magma in both effusive and explosive styles of activity. The volatile systematics of the volcanic system are well understood through melt inclusion and volcanic gas studies. Etna's melts are generated from a complex mantle setting, with subduction-related chemical modifications as well as OIB-type features, and then the melts must travel through thick carbonate-rich crust. The continual influx of mantle-derived volatile-rich magma controls the major compositional and eruptive features of Mount Etna and magma mixing has been recognized as an important process driving large eruptions [Kamenetsky, 2007]. Our study focusses on the 1669 eruption, the largest in historical times. Olivine-hosted melt inclusions were analyzed for volatile, trace and major elements using electron microprobe and ion probe (SIMS). We use volatile systematics and geochemical data to deconvolve mantle-derived heterogeneity from melt mixing and crystal fractionation. Our data are well described by a mixing trend between two distinct melts: a CO2-rich (CO2~1000ppm), incompatible trace element depleted melt (La/Yb~16), and a CO2-poor, enriched melt. The mixing also generates a strong correlation between Sr and CO2 in the melt inclusions dataset, reflecting the presence of a strong Sr anomaly in one of the end-member melts. We investigate the origin of this Sr anomaly by considering plagioclase dissolution and crustal assimilation. We also investigate degassing processes in the crust and plumbing system of the volcano. We compare our results with similar studies of OIB and arc-related basalts elsewhere and assess the implications for linking eruption size and style with the nature of the mantle-derived melts. Kamenetsky et al. (2007) Geology 35, 255-258.

Gas discharges in fumarolic ice caves of Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Fischer, T. P.; Curtis, A. G.; Kyle, P. R.; Sano, Y.

2013-12-01

Fumarolic ice caves and towers on Erebus are the surface expression of flank degassing on the world's southernmost active volcano. The caves are formed by warm gases and steam escaping from small vents on the lava flow floors that melts the overlying ice and snow. Extremophiles in the caves may be analogues for extraterrestrial environments. Over the past four Austral summers, mapping, gas and thermal monitoring conducted under the Erebus Caves Project has provided insights into the ice cave formation processes and the relationships between cave structures, magmatic processes, and weather. Gas samples were collected during the 2012 - 2013 field season in 4 ice caves (Warren, Harry's Dream, Sauna, Haggis Hole) as well as the thermal ground at Tramway Ridge. The vents at all of these sites are characterized by diffuse degassing through loose lava or cracks in the lava flow floor. Vent temperatures ranged from 5 to 17°C in most caves and at Tramway Ridge. In Sauna cave the temperature was 40°C. Gases were sampled by inserting a perforated 1 m long, 5 mm diameter stainless steel tube, into the vents or hot ground. Giggenbach bottles, copper tubes and lead glass bottles were connected in series. The gases were pumped at a slow rate (about 20 ml per minute) using a battery pump for 12-24 hours to flush the system. After flushing samples were collected for later analyses. All samples are dominated by atmospheric components, however, carbon dioxide (0.1 to 1.9%), methane (0.005 to 0.01%), hydrogen (0.002 to 0.07%), and helium (0.0009 to 0.002 %) are above air background. Nitrogen (average 74%) and oxygen (23.5%) are slightly below and above air values, respectively. Helium isotopes show minor input of mantle derived helium-3 with 3He4He ratios ranging from 1.03 to 1.18 RA (where RA is the ratio of air). This represents the first detection of hydrogen and helium in the caves. Methane could be produced by anaerobic respiration of subsurface microbes or hydrothermal reactions. We are confident that the atmospheric component is not the result of sampling procedure but intrinsic to the ice cave system. In addition to carbon dioxide, magmatic gases emitted from Erebus lava lake contain significant amounts of SO2, HCl, HF, CO and H2 [1,2]. The acid magmatic gases (SO2, HCl, HF) and a significant amount of the CO2 are likely absorbed by the subsurface ice/water system. The atmospheric components (Ar, nitrogen, oxygen) likely enter the system at shallow levels. The relative abundances of these components reflect degassing fractionation of these volatiles from liquid water at low temperatures, suggesting the presence of liquid water in the subsurface. [1] Oppenheimer, C., Kyle, P.R., 2008. Probing the magma plumbing of Erebus volcano, Antarctica, by open-path FTIR spectroscopy of gas emissions. J. Vol. Geoth. Res. 177, 743-754. [2] Moussallam, Y., Oppenheimer, C., et al., 2012. Hydrogen emission from Erebus volcano, Antarctica. Bull. Volcan 74, 2109-2120.

A Calcium-in-Olivine Geohygrometer and its Application to Subduction Zone Magmatism

NASA Astrophysics Data System (ADS)

Gavrilenko, M.; Herzberg, C. T.; Vidito, C. A.; Carr, M. J.; Tenner, T.; Ozerov, A.

2016-12-01

Calcium contents of subduction zone olivines are lower than those for olivines from modern MORB, Archean komatiites, and Hawaii (Fig. 1). A role for magmatic H2O is likely for subduction zone olivines, and we have explored the suggestion by [1] that H2O has affected the partitioning of CaO between olivine and silicate melt. We provide a provisional calibration of DCaOOl/L as a function of magmatic MgO and H2O, based on nominally anhydrous experiments (Fig. 2) and minimally degassed H2O contents of olivine-hosted melt inclusions (Fig. 3). The low diffusivity of Ca in olivine [2], when compared to that of H+ [3, 4, 5, 6], might help to retain the memory of magmatic water that is otherwise lost by diffusion and degassing. Application of our geohygrometer (Fig. 4) typically yields 3 to 4 wt. % magmatic H2O at the Kamchatka and Central American arcs for olivines having 1000 ppm Ca, which agrees with H2O maxima from melt inclusion studies [7]; Cerro Negro and Shiveluch volcanoes are exceptions, with about 6% H2O. Our geohygrometer is by no means a replacement for more accurate methods of H2O analysis, but it has the advantage of applicability in cases where olivine-hosted melt inclusions do not exist (or in case when melt inclusions are partly or completely degassed). Additionally, application of the geohygrometer to core-rim olivine Ca analyses has the potential to reveal changes in magmatic H2O, as revealed by Klyuchevskoy and Shiveluch volcanoes. High precision EMPA analyses with 10-20 µm spatial resolution on some olivine grains from Klyuchevskoy and Shiveluch show a decrease in Ca content from core centers to the rim contacts. Our geohygrometer indicates the olivine grains may record changing magmatic H2O. Furthermore, high Mg numbers and Ni contents indicate these are mantle olivines, and the inferred H2O may be recording entry from the slab to the mantle wedge, a prediction that will be tested by SIMS analyses. References: [1] Feig et al. (2006) CMP, 152(5):611-638. [2] Coogan et al. (2005) Geochimica et Cosmochimica Acta, 69(14):3683-3694. [3] Hauri (2002) Chem. Geology, 183(1-4):115-141. [4] Portnyagin et al. (2008) EPSL, 272(3-4):541-552. [5] Gaetani et al. (2012) Geology, 40(10):915-918. [6] Bucholz et al. (2013) EPSL, 374:145-155. [7] Plank et al. (2013) EPSL, 364:168-179.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Using Heavy Noble Gases to Help Determine Mantle vs Lithospheric Contributions and CO2 Residence Times in Southwestern US Hot Springs

NASA Astrophysics Data System (ADS)

Whyte, C. J.; Karlstrom, K. E.; Crossey, L. J.; Darrah, T.

2017-12-01

Climate change has placed a particular importance on the understanding of carbon cycling, especially on continental scales, resulting in the necessity to quantify the rates and timing on which CO2 is released into the atmosphere by volcanic and tectonic processes. Recent studies have identified mantle-derived 3He and excess CO2 in springs and groundwaters across the conterminous US, suggesting that there may be great unknowns in the rates and scales of magmatic CO2 release in the global carbon budget. Further, it remains uncertain if these fluids are merely passive remnants of past magmatic events or instead result from ongoing mantle degassing. Understanding these processes and timescales by studying CO2 fluxes alone can be challenging because CO2 is highly reactive in the subsurface. CO2 is both formed and degraded by microbial processes, rapidly dissolves into waters, and can be readily released from carbonate-rich lithologies by water-rock interactions. By comparison, chemically-inert tracers such as noble gases provide one potential technique for identifying and constraining fluid sources and migration histories in the subsurface. Primordial isotopes (e.g., 3He and 129Xe) provide unambiguous indications of mantle-derived fluids, and heavier noble gases (e.g., Ne, Ar, Kr, Xe) provide a suite of potential tracers that can help de-convolve the extent of mixing between crust and mantle and discern between lithospheric and asthenospheric mantle fluids. Additionally, the low production rate of the radiogenic xenon isotopes (e.g., 134Xe, 136Xe) may help determine the relative residence time of mantle CO2 degassing in continental settings, providing important constraints on CO2 storage in the mantle and lithosphere in quiescent tectonic settings. To test these hypotheses, we analyzed a suite of noble gas isotopic compositions in hot springs in the Colorado Plateau and Rocky Mountains, US. Many samples display resolvable excesses in 3He and 129Xe relative to air-saturated water with variable excesses in 40Ar* and radiogenic xenon isotopes. Excess 3He and 129Xe are consistent with mantle contributions, while variable abundances of radiogenic gases reflect the relative mixtures of air-saturated water, mantle, lithosphere, and the crust providing insight on their history during crustal emplacement.

Geochemical surveys in the Lusi mud eruption

NASA Astrophysics Data System (ADS)

Sciarra, Alessandra; Mazzini, Adriano; Etiope, Giuseppe; Inguaggiato, Salvatore; Hussein, Alwi; Hadi J., Soffian

2016-04-01

The Lusi mud eruption started in May 2006 following to a 6.3 M earthquake striking the Java Island. In the framework of the Lusi Lab project (ERC grant n° 308126) we carried out geochemical surveys in the Sidoarjo district (Eastern Java Island, Indonesia) to investigate the gas bearing properties of the Watukosek fault system that crosses the Lusi mud eruption area. Soil gas (222Rn, CO2, CH4) concentration and flux measurements were performed 1) along two detailed profiles (~ 1km long), trending almost W-E direction, and 2) inside the Lusi embankment (about 7 km2) built to contain the erupted mud. Higher gas concentrations and fluxes were detected at the intersection with the Watukosek fault and the antithetic fault system. These zones characterized by the association of higher soil gas values constitute preferential migration pathways for fluids towards surface. The fractures release mainly CO2 (with peaks up to 400 g/m2day) and display higher temperatures (up to 41°C). The main shear zones are populated by numerous seeps that expel mostly CH4. Flux measurements in the seeping pools reveal that φCO2 is an order of magnitude higher than that measured in the fractures, and two orders of magnitude higher for φCH4. An additional geochemical profile was completed perpendicularly to the Watukosek fault escarpement (W-E direction) at the foots of the Penanngungang volcano. Results reveal CO2 and CH4 flux values significantly lower than those measured in the embankment, however an increase of radon and flux measurements is observed approaching the foots of the escarpment. These measurements are complemented with a database of ~350 CH4 and CO2 flux measurements and some soil gas concentrations (He, H2, CO2, CH4 and C2H6) and their isotopic analyses (δ13C-CH4, δD-CH4 and δ13C-CO2). Results show that the whole area is characterized by diffused gas release through seeps, fractures, microfractures and soil degassing. The collected results shed light on the origin of the seeping gases. Statistical analyses over the 7 km2 area allowed us to estimate the full amount of gas currently released. Flux estimates from the crater zone suggest an order of magnitude higher than those measured from the surrounding region.

Kinetics of CO2 diffusion in human carbonic anhydrase: a study using molecular dynamics simulations and the Markov-state model.

PubMed

Chen, Gong; Kong, Xian; Lu, Diannan; Wu, Jianzhong; Liu, Zheng

2017-05-10

Molecular dynamics (MD) simulations, in combination with the Markov-state model (MSM), were applied to probe CO 2 diffusion from an aqueous solution into the active site of human carbonic anhydrase II (hCA-II), an enzyme useful for enhanced CO 2 capture and utilization. The diffusion process in the hydrophobic pocket of hCA-II was illustrated in terms of a two-dimensional free-energy landscape. We found that CO 2 diffusion in hCA-II is a rate-limiting step in the CO 2 diffusion-binding-reaction process. The equilibrium distribution of CO 2 shows its preferential accumulation within a hydrophobic domain in the protein core region. An analysis of the committors and reactive fluxes indicates that the main pathway for CO 2 diffusion into the active site of hCA-II is through a binding pocket where residue Gln 136 contributes to the maximal flux. The simulation results offer a new perspective on the CO 2 hydration kinetics and useful insights toward the development of novel biochemical processes for more efficient CO 2 sequestration and utilization.

Carbon dioxide emissions from Deccan volcanism and a K/T boundary greenhouse effect

NASA Technical Reports Server (NTRS)

Caldeira, Ken; Rampino, Michael R.

1990-01-01

A greenhouse warming caused by increased emissions of carbon dioxide from the Deccan Traps volcanism has been suggested as the cause of the terminal Cretaceous extinctions on land and in the sea. Total eruptive and noneruptive CO2 output by the Deccan eruptions (from 6 to 20 x 10 to the 16th moles) over a period of several hundred thousand years is estimated based on best estimates of the CO2 weight fraction of the original basalts and basaltic melts, the fraction of CO2 degassed, and the volume of the Deccan Traps eruptions. Results of a model designed to estimate the effects of increased CO2 on climate and ocean chemistry suggest that increases in atmospheric pCO2 due to Deccan Traps CO2 emissions would have been less than 75 ppm, leading to a predicted global warming of less than 1 C over several hundred thousand years. It is concluded that the direct climate effects of CO2 emissions from the Deccan eruptions would have been too weak to be an important factor in the end-Cretaceous mass extinctions.

Carbon dioxide emissions from Deccan volcanism and a K/T boundary greenhouse effect.

PubMed

Caldeira, K; Rampino, M R

1990-08-01

A greenhouse warming caused by increased emissions of carbon dioxide from the Deccan Traps volcanism has been suggested as the cause of the terminal Cretaceous extinctions on land and in the sea. We estimate total eruptive and noneruptive CO2 output by the Deccan eruptions (from 6 to 20 x 10(16) moles) over a period of several hundred thousand years based on best estimates of the CO2 weight fraction of the original basalts and basaltic melts, the fraction of CO2 degassed, and the volume of the Deccan Traps eruptions. Results of a model designed to estimate the effects of increased CO2 on climate and ocean chemistry suggest that increases in atmospheric pCO2 due to Deccan Traps CO2 emissions would have been less than 75 ppm, leading to a predicted global warming of less than 1 degree C over several hundred thousand years. We conclude that the direct climate effects of CO2 emissions from the Deccan eruptions would have been too weak to be an important factor in the end-Cretaceous mass extinctions.

Long period seismicity and very long period infrasound driven by shallow magmatic degassing at Mount Pagan, Mariana Islands

USGS Publications Warehouse

Lyons, John; Haney, Matt; Werner, Cynthia A.; Kelly, Peter; Patrick, Matthew R.; Kern, Christoph; Trusdell, Frank A.

2016-01-01

Long period (LP) seismicity and very long period infrasound (iVLP) were recorded during continuous degassing from Mount Pagan, Mariana Islands, in July 2013 to January 2014. The frequency content of the LP and iVLP events and delay times between the two arrivals were remarkably stable and indicate nearly co-located sources. Using phase-weighted stacking over similar events to dampen noise, we find that the LP source centroid is located 60 m below and 180 m west of the summit vent. The moment tensor reveals a volumetric source modeled as resonance of a subhorizontal sill intersecting a dike. We model the seismoacoustic wavefields with a coupled earth-air 3-D finite difference code. The ratios of pressure to velocity measured at the infrasound arrays are an order of magnitude larger than the synthetic ratios, so the iVLP is not the result of LP energy transmitting into the atmosphere at its epicenter. Based on crater shape and dimensions determined by structure from motion, we model the iVLP as acoustic resonance of an exponential horn. The source of the continuous plume from gas analysis is shallow magmatic degassing, which repeatedly pressurized the dike-sill portion of the conduit over the 7 months of observation. Periodic gas release caused the geologically controlled sill to partially collapse and resonate, while venting of gas at the surface triggered resonance in the crater. LP degassing only accounts for ~12% of total degassing, indicating that most degassing is relatively aseismic and that multiple active pathways exist beneath the vent.

The K-PG boundary: how geological events lead to collapse of marine primary producers

NASA Astrophysics Data System (ADS)

Hir guillaume, Le; frederic, Fluteau; yves, Goddéris

2017-04-01

The cause(s) of Cretaceous/Paleogene (K-Pg) mass extinction event is a matter of debate since three decades. A first scenario connects the K-Pg crisis with the Chicxulub impact while the second scenario evokes the emplacement of the Deccan traps in India as the cause for the K-Pg biodiversity collapse. Pierazzo et al. (1998) estimated that the extraterrestrial bolide lead to an instantaneously CO2 degassing ranging from 880 Gt to 2,960 Gt into the atmosphere, together with a massive release of SO2 ranging from 150 to 460 Gt.. Self et al. (2006, 2008) and Chenet et al. (2009) suggested that the emplacement of the Deccan traps released 15,000 Gt to 35,000 Gt of CO2 and 6,800 Gt to 17,000 Gt of SO2 over a 250 kyr-long period (Schoene et al., 2015). To decipher and quantify the long term environmental consequences of both events, we tested different scenarios: a pulse-like magmatic degassing, a bolide impact, and a combination of both. To understand the environmental changes and quantify biodiversity responses, we improve GEOCLIM, a coupled climate-carbon numerical model, by implementing a biodiversity model in which marine species are described by specific death/born rates, sensitivity to abiotic factors (temperature, pH, dissolved O2, calcite saturation state) and feeding relationships, each of these characteristics is assigned randomly. Preliminary simulations accounting for the eruption of the Deccan traps show that successive cooling events (S-aerosols effect) combined with a progressive acidification of surface water (caused by CO2 and SO2 injections) cause a major collapse of the marine biomass. Additional simulations in which Chicxulub impact, different community structures of primary producers will be discussed.

Spatio-temporal variation in δ13CDIC of a tropical eutrophic estuary (Cochin estuary, India) and adjacent Arabian Sea

NASA Astrophysics Data System (ADS)

Bhavya, P. S.; Kumar, Sanjeev; Gupta, G. V. M.; Sudharma, K. V.; Sudheesh, V.

2018-02-01

Carbon isotopic composition of dissolved inorganic carbon (δ13CDIC) in the Cochin estuary, a tropical eutrophic estuary along the southwest coast of India, and the adjacent coastal Arabian Sea was measured to understand spatio-temporal variability in sources and processes controlling inorganic carbon (C) dynamics in this estuarine-coastal system. δ13CDIC in the Cochin estuary showed wide variation during three different seasons (premonsoon: - 12.2 to - 3.26‰; monsoon: - 13.6 to - 5.69‰; and postmonsoon: - 6.34 to + 0.79‰). Detailed mixing curve approximation modeling along with relationships of δ13CDIC with dissolved oxygen and nutrients suggest dominant role of freshwater mixing and degassing of CO2 on DIC dynamics during wet seasons (premonsoon and monsoon). Excess CO2 brought in by rivers and in situ production due to respiration in the Cochin estuary result into one of the highest pCO2 observed in estuarine systems, leading to its degassing. During postmonsoon, a relatively dry period with high salinity, calcite precipitation was a major process with calcite saturation index > 1 at few locations. Relatively lower average surface values of δ13CDIC in the coastal Arabian Sea (premonsoon: + 0.95‰; monsoon: + 0.88‰; and postmonsoon: + 0.66‰) compared to the predicted open ocean value along with mixing curve modeling suggest dominance of respiration/organic matter (OM) degradation over primary productivity. Estuarine influence on coastal DIC dynamics was observed in nearshore region ( 10 km), whereas evidence of upwelling was found at farther locations.

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study.

PubMed

Hafeez, Sarah; Fan, X; Hussain, Arshad; Martín, C F

2015-09-01

CO2 is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO2) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R(2), the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion. Copyright © 2015. Published by Elsevier B.V.

Fault-controlled CO2 leakage from natural reservoirs in the Colorado Plateau, East-Central Utah

NASA Astrophysics Data System (ADS)

Jung, Na-Hyun; Han, Weon Shik; Watson, Z. T.; Graham, Jack P.; Kim, Kue-Young

2014-10-01

The study investigated a natural analogue for soil CO2 fluxes where CO2 has naturally leaked on the Colorado Plateau, East-Central Utah in order to identify various factors that control CO2 leakage and to understand regional-scale CO2 leakage processes in fault systems. The total 332 and 140 measurements of soil CO2 flux were made at 287 and 129 sites in the Little Grand Wash (LGW) and Salt Wash (SW) fault zones, respectively. Measurement sites for CO2 flux involved not only conspicuous CO2 degassing features (e.g., CO2-driven springs/geysers) but also linear features (e.g., joints/fractures and areas of diffusive leakage around a fault damage zone). CO2 flux anomalies were mostly observed along the fault traces. Specifically, CO2 flux anomalies were focused in the northern footwall of the both LGW and SW faults, supporting the existence of north-plunging anticlinal CO2 trap against south-dipping faults as well as higher probability of the north major fault traces as conduits. Anomalous CO2 fluxes also appeared in active travertines adjacent to CO2-driven cold springs and geysers (e.g., 36,259 g m-2 d-1 at Crystal Geyser), ancient travertines (e.g., 5,917 g m-2 d-1), joint zones in sandstone (e.g., 120 g m-2 d-1), and brine discharge zones (e.g., 5,515 g m-2 d-1). These observations indicate that CO2 has escaped through those pathways and that CO2 leakage from these fault zones does not correspond to point source leakage. The magnitude of CO2 flux is progressively reduced from north (i.e. the LGW fault zone, ∼36,259 g m-2 d-1) to south (i.e. the SW fault zone, ∼1,428 g m-2 d-1) despite new inputs of CO2 and CO2-saturated brine to the northerly SW fault from depth. This discrepancy in CO2 flux is most likely resulting from the differences in fault zone architecture and associated permeability structure. CO2-rich fluids from the LGW fault zone may become depleted with respect to CO2 during lateral transport, resulting in an additional decrease in CO2 fluxes within the SW fault zone. In other words, CO2 and CO2-charged brine originating from the LGW fault zone could migrate southward over 10-20 km through a series of high-permeable aquifers (e.g., Entrada, Navajo, Kayenta, Wingate, and White Rim Sandstones). These CO2-rich fluids could finally reach the southernmost Tumbleweed and Chaffin Ranch Geysers across the SW fault zone. The potential lateral transport of both CO2 and CO2-laden brine can be further supported by similar CO2/3He and 3He/4He ratios of gas and a systematic chemical evolution of water emitted from the regional springs and geysers, which suggest the same crustal origins of CO2 and CO2-rich brine for the region.

Volatiles in melt inclusions from Icelandic magmas

NASA Astrophysics Data System (ADS)

Nichols, A. R.; Wysoczanski, R. J.; Carroll, M. R.

2006-12-01

Melt inclusions hosted in olivine crystals from the glassy rims of subglacially erupted pillow basalts on Iceland have been analysed for volatiles, major elements and trace elements. Volatile measurements were undertaken using Fourier-Transform InfraRed spectroscopy utilising a novel technique which enables unexposed and much smaller inclusions than were previously possible to be analysed. Major elements were measured using electron microprobe and trace elements by laser ablation-inductively coupled plasma-mass spectrometry. Comparison between initial results from the inclusions and the compositions of the bulk glasses show that the inclusions are less evolved and contain more H2O at the same MgO content. In addition many of the inclusions have higher H2O/K2O than their bulk glasses and some even contain CO2 (up to 629 ppm), which is below detection limits in the bulk glasses. This indicates that these inclusions are less affected by degassing. Two inclusions have extreme H2O/K2O (> 10), possibly suggesting that they have assimilated hydrous crustal material. The volatile and major element compositions of the bulk glasses have been used to suggest that the Iceland mantle plume is wet. However, trace element measurements show that enriched Iceland magmas have lower H2O/Ce than the adjacent Reykjanes Ridge. This could reflect syn-eruptive degassing or mixing between undegassed and recycled degassed magmas. Alternatively Iceland magmas could be derived from the EM (enriched mantle) component, which is believed to represent recycled oceanic crust. It is suggested that this material is efficiently dehydrated during the subduction process, so even though it has an enriched character, H2O is relatively depleted. As a result, EM melts have higher absolute H2O contents than mid- ocean ridge basalts (MORB), but lower H2O/Ce (or other H2O-incompatible element ratios), which has led to EM plumes being termed `dampspots'. The inclusion data will be presented in this context. Their compositions will show how the melt has evolved, enabling the relative roles of degassing, crystallisation and assimilation in the volatile systematics to be examined.

CO2 driven weathering vs plume driven weathering as inferred from the groundwater of a persistently degassing basaltic volcano: Mt. Etna

NASA Astrophysics Data System (ADS)

Liotta, Marcello; D'Alessandro, Walter

2016-04-01

At Mt. Etna the presence of a persistent volcanic plume provides large amounts of volcanogenic elements to the bulk deposition along its flanks. The volcanic plume consists of solid particles, acidic droplets and gaseous species. After H2O and CO2, S, Cl and F represent the most abundant volatile elements emitted as gaseous species from the craters. During rain events acidic gases interact rapidly with droplets lowering the pH of rain. This process favors the dissolution and dissociation of the most acidic gases. Under these conditions, the chemical weathering of volcanic rocks and ashes is promoted by the acid rain during its infiltration. Subsequently during groundwater circulation, chemical weathering of volcanic rocks is also driven by the huge amount of deep magmatic carbon dioxide (CO2) coming up through the volcanic edifice and dissolving in the water. These two different weathering steps occur under very different conditions. The former occurs in a highly acidic environment (pH < 4) and the reaction rates depend strongly on the pH, while the latter usually occurs under slightly acidic conditions since the pH has been already neutralized by the interaction with volcanics rocks. The high content of chlorine is mainly derived from interactions between the plume and rainwater, while the total alkalinity can be completely ascribed to the dissociation of carbonic acid (H2CO3) after the hydration of CO2. The relative contributions of plume-derived elements/weathering and CO2-driven weathering has been computed for each element. In addition, the comparison between the chemical compositions of the bulk deposition and of groundwater provides a new understanding about the mobility of volatile elements. Other processes such as ion exchange, iddingsite formation, and carbonate precipitation can also play roles, but only to minor extents. The proposed approach has revealed that the persistent plume strongly affects the chemical composition of groundwater at Mt. Etna and probably also at other volcanoes characterized by huge open-conduit degassing activity.

Long-term geochemical surveillance of fumaroles at Showa-Shinzan dome, Usu volcano, Japan

USGS Publications Warehouse

Symonds, R.B.; Mizutani, Y.; Briggs, P.H.

1996-01-01

This study investigates 31 years of fumarole gas and condensate (trace elements) data from Showa-Shinzan, a dacitic dome-cryptodome complex that formed during the 1943-1945 eruption of Usu volcano. Forty-two gas samples were collected from the highest-temperature fumarole, named A-1, from 1954 (800??C) to 1985 (336??C), and from lower-temperature vents. Condensates were collected contemporaneously with the gas samples, and we reanalyzed ten of these samples, mostly from the A-1 vent, for 32 cations and three anions. Modeling using the thermochemical equilibrium program, SOLVGAS, shows that the gas samples are mild disequilibrium mixtures because they: (a) contain unequilibrated sedimentary CH4 and NH3; (b) have unequilibrated meteoric water; or (c) lost CO, either by air oxidation or by absorption by the sodium hydroxide sampling solution. SOLVGAS also enabled us to restore the samples by removing these disequilibrium effects, and to estimate their equilibrium oxygen fugacities and amounts of S2 and CH4. The restored compositions contain > 98% H2O with minor to trace amounts of CO2, H2, HCl, SO2, HF, H2S, CO, S2 and CH4. We used the restored gas and condensate data to test the hypotheses that these time-series compositional data from the dome's fumaroles provide: (1) sufficient major-gas data to analyze long-term degassing trends of the dome's magma-hydrothermal system without the influence of sampling or contamination effects; (2) independent oxygen fugacity-versus-temperature estimates of the Showa-Shinzan dacite; (3) the order of release of trace elements, especially metals, from magma; and (4) useful information for assessing volcanic hazards. The 1954-1985 restored A-1 gas compositions confirm the first hypothesis because they are sufficient to reveal three long-term degassing trends: (1) they became increasingly H2O-rich with time due to the progressive influx of meteoric water into the dome; (2) their C/S and S/Cl ratios decreased dramatically while their Cl/F ratios stayed roughly constant, indicating the progressive outgassing of less soluble components (F ??? Cl > S > C) from the magma reservoir; and (3) their H2O/H2, CO2/CO and H2S/SO2 ratios increased significantly in concert with equilibrium changes expected for the ??? 500??C temperature drop. When plotted against reciprocal temperature, the restored-gas log oxygen fugacities follow a tight linear trend from 800??C to NNO + 2.5 at ??? 400??C. This trend largely disproves the second hypothesis because the oxygen fugacities for the < 800??C restored gases can only be explained by mixing of hot magmatic gases with ??? 350??C steam from superheated meteoric water. But above 800??C this trend intersects the opposing linear trend for other Usu eruptive products, implying a log oxygen fugacity of -11.45 at 902??C for the Showa-Shinzan magma. The time-series trace-element data also disprove the third hypothesis because rock- and incrustation-particle contaminants in the condensates account for most of the trace-element variation. Nonetheless, highly volatile elements like B and As are relatively unaffected by this particle contamination, and they show similar time-series trends as Cl and F. Finally, except for infrequent sampling around the 1977 Usu eruption, the results generally confirm the fourth hypothesis, since the time-series trends for the major gases and selected trace elements indicate that, with time, the system cooled, degassed and was infiltrated by meteoric water, all of which are positive signs that volcanic activity declined over the 31-year history. This study also suggests that second boiling of shallow magma within and possibly beneath the cryptodome sustained magmatic degassing for at least 20 years after emplacement.

Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

PubMed

Zhang, Saijin; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Grandbois, Russell; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Wellman, Dawn; Santschi, Peter H

2013-09-03

The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.

Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2016-11-01

Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

Carbon isotope systematics of Turrialba volcano, Costa Rica, using a portable cavity ring-down spectrometer

NASA Astrophysics Data System (ADS)

Malowany, K. S.; Stix, J.; de Moor, J. M.; Chu, K.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2017-07-01

Over the past two decades, activity at Turrialba volcano, Costa Rica, has shifted from hydrothermal to increasingly magmatic in character, with enhanced degassing and eruption potential. We have conducted a survey of the δ13C signatures of gases at Turrialba using a portable field-based CRDS with comparison to standard IRMS techniques. Our δ13C results of the volcanic plume, high-temperature vents, and soil gases reveal isotopic heterogeneity in the CO2 gas composition at Turrialba prior to its recent phase of eruptive activity. The isotopic value of the regional fault system, Falla Ariete (-3.4 ± 0.1‰), is in distinct contrast with the Central crater gases (-3.9 ± 0.1‰) and the 2012 high-temperature vent (-4.4 ± 0.2‰), an indication that spatial variability in δ13C may be linked to hydrothermal transport of volcanic gases, heterogeneities in the source composition, or magmatic degassing. Isotopic values of CO2 samples collected in the plume vary from δ13C of -5.2 to -10.0‰, indicative of mixing between atmospheric CO2 (-9.2 ± 0.1‰), and a volcanic source. We compare the Keeling method to a traditional mixing model (hyperbolic mixing curve) to estimate the volcanic source composition at Turrialba from the plume measurements. The predicted source compositions from the Keeling and hyperbolic methods (-3.0 ± 0.5‰ and -3.9 ± 0.4‰, respectively) illustrate two potential interpretations of the volcanic source at Turrialba. As of the 29 October 2014, Turrialba has entered a new eruptive period, and continued monitoring of the summit gases for δ13C should be conducted to better understand the dominant processes controlling δ13C fractionation at Turrialba.

Proton transport by phosphate diffusion--a mechanism of facilitated CO2 transfer

PubMed Central

1976-01-01

We have measured CO2 fluxes across phosphate solutions at different carbonic anhydrase concentrations, bicarbonate concentration gradients, phosphate concentrations, and mobilities. Temperature was 22-25 degrees C, the pH of the phosphate solutions was 7.0-7.3. We found that under physiological conditions of pH and pCO2 a facilitated diffusion of CO2 occurs in addition to free diffusion when (a) sufficient carbonic anhydrase is present, and (b) a concentration gradient of HCO3- is established along with a pCO2 gradient, and (c) the phosphate buffer has a mobility comparable to that of bicarbonate. When the phosphate was immobilized by attaching 0.25-mm-long cellulose particles, no facilitation of CO2 diffusion was detectable. A mechanism of facilitated CO2 diffusion in phosphate solutions analogous to that in albumin solutions was proposed on the basis of these findings: bicarbonate diffusion together with a facilitated proton transport by phosphate diffusion. A mathematical model of this mechanism was formulated. The CO2 fluxed predicted by the model agree quantitatively with the experimentally determined fluxes. It is concluded that a highly effective proton transport mechanism acts in solutions of mobile phosphate buffers. By this mechanism; CO2 transfer may be increased up to fivefold and proton transfer may be increased to 10,000-fold. PMID:6619

Tiny crystals give away the where and when of magma ascent

NASA Astrophysics Data System (ADS)

Ruth, D. C. S.; Costa Rodriguez, F.; Bouvet de Maisonneuve, C.; Franco, L.; Cortes, J. A.; Calder, E.

2016-12-01

Open vent volcanoes exhibit passive degassing and can transition to explosive behavior, with limited or no warning. Melt inclusion chemistry and volatile contents have been used to infer the inner dynamics of magma storage, recharge, degassing, and eruption triggering mechanisms. However, the interpretation of melt inclusion chemistry is ambiguous because it cannot constrain the residence times of the host crystals, which could have various sources and growth histories. To resolve this issue we combine diffusion chronometry and melt inclusion entrapment pressures from olivine crystals sourced from the 2008 eruption of Llaima volcano (Chile). Olivine crystals (core Fo70-84, rim Fo77-84) are dominantly reverse zoned, although normal zoned and complex zoned crystals are observed. These data reflect mixing between the mafic injecting magma and the crystal-rich resident magma. Fe/Mg diffusion timescales range between 16 and 1375 days. The diffusion data show a non-uniform distribution with no discernible peaks, indicating that magma injection is likely progressive, rather than punctuated. Entrapment pressures range between 8 and 151 MPa, overlapping with an inferred crystal-rich region. Longer timescales correspond to higher pressures, strongly suggesting a link between magma residence time and ascent from depth. To our knowledge, this relationship has not been previously demonstrated. We infer that mafic magma intruded at depths of 5 km below the edifice and mingled with a pre-existing crystal-mush 3 yr before the eruption. Magma migration and mingling continued and stalled at 2.5 km depth about a year prior to the eruption. Precursory activity such as volcano-tectonic and long period seismicity, and a series of minor explosions overlap with the diffusion times 6 months before the eruption. Similar diffusion timescales have been reported for eruptions at other open vent volcanoes. Our study provides the first temporal and spatial constraints on magma storage and ascent before an eruption. Furthermore at Llaima, and potentially open vent systems, the progressive nature of magma injection suggests that additional processes (e.g. variable ascent rates, changing viscosity, etc.) are needed to trigger an eruption.

Rates of Earth degassing

NASA Technical Reports Server (NTRS)

Onions, R. K.

1994-01-01

The degassing of the Earth during accretion is constrained by Pu-U-I-Xe systematics. Degassing was much more efficient during the first 100-200 Ma than subsequently, and it was more complete for Xe than for the lighter gases. More than 90 percent of the degassed Xe escaped from the atmosphere during this period. The combination of fractional degassing of melts and rare gas escape from the atmosphere is able to explain the deficit of terrestrial Xe as a simple consequence of this early degassing history. By the time Xe was quantitatively retained in the atmosphere, the abundances of Kr and the lighter gases in the Earth's interior were similar to or higher than the present-day atmospheric abundances. Subsequent transfer of these lighter rare gases into the atmosphere requires a high rate of post-accretion degassing and melt production. Considerations of Pu-U-Xe systematics suggest that relatively rapid post-accretion degassing was continued to ca. 4.1-4.2 Ga. The present-day degassing history of the Earth is investigated through consideration of rare gas isotope abundances. Although the Earth is a highly degassed body, depleted in rare gases by many orders of magnitude relative to their solar abundances, it is at the present-day losing primordial rare gases which were trapped at the time of accretion.

Effects of Degassing on the Microstructure, Chemistry, and Estimated Mechanical Properties of a Cryomilled Al-Mg Alloy

NASA Astrophysics Data System (ADS)

Hofmeister, Clara; Zhou, Le; Kellogg, Frank; Giri, Anit; Cho, Kyu; Sohn, Yongho

2018-04-01

Nanostructured aluminum alloys produced through cryomilling have generated interest due to their potential to create consolidated parts with high strength and low density. Degassing prior to consolidation minimizes adsorbed and absorbed volatiles, but is accompanied by microstructural changes such as grain growth, dislocation annihilation, and formation of dispersoids. These changes can influence the mechanical behavior of consolidated components. Cryomilled AA5083 was degassed at temperatures from 473 K to 773 K (200 °C to 500 °C) with a vacuum at or below 2.7 × 10-3 Pa. Grain size in the as-cryomilled powder (ranging from 21 to 34 nm) increased with higher degassing temperature and reached a maximum size of up to 70 to 80 nm. The dislocation density of 1.11 × 1015 m-2 in as-cryomilled powder decreased to 1.56 × 1014 m-2 for powder degassed at 773 K (500 °C). The Al6(MnFeCr) dispersoid formed when powders were degassed at or above 573 K (300 °C). Oxygen and nitrogen concentrations were unaffected by degassing; however, hydrogen concentration decreased with increasing degassing temperature to a minimum of 45 ± 3.16 ppm. Evolutions in composition and microstructure in cryomilled AA5083 were correlated to the strengthening mechanisms of grain size reduction (i.e., Hall-Petch), dislocation forest, and Orowan. However, strengthening by grain size reduction was the dominant strengthening mechanism.

Elevated gas flux and trace metal degassing from the 2014-2015 fissure eruption at the Bárðarbunga volcanic system, Iceland

NASA Astrophysics Data System (ADS)

Gauthier, Pierre-Jean; Sigmarsson, Olgeir; Gouhier, Mathieu; Haddadi, Baptiste; Moune, Séverine

2016-03-01

The 2014 Bárðarbunga rifting event in Iceland resulted in a 6-month long eruption at Holuhraun. This eruption was characterized by high lava discharge rate and significant gas emission. The SO2 flux for the first 3 months was measured with satellite sensors and the petrologic method. High-resolution time series of the satellite data give 1200 kg/s that concurs with 1050 kg/s obtained from melt inclusion minus degassed lava sulfur contents scaled to the mass of magma produced. A high-purity gas sample, with elevated S/Cl due to limited chlorine degassing, reveals a similar degassing pattern of trace metals as observed at Kīlauea (Hawai'i) and Erta Ale (Ethiopia). This suggests a common degassing mechanism at mantle plume-related volcanoes. The trace metal fluxes, calculated from trace element to sulfur ratios in the gas sample and scaled to the sulfur dioxide flux, are 1-2 orders of magnitude stronger at Holuhraun than Kīlauea and Erta Ale. In contrast, volcanoes at convergent margins (Etna and Stromboli, Italy) have 1-2 orders of magnitude higher trace element fluxes, most likely caused by abundant chlorine degassing. This emphasizes the importance of metal degassing as chlorine species. Short-lived disequilibria between radon daughters, 210Pb-210Bi-210Po measured in the gas, suggest degassing of a continuously replenished magma batch beneath the eruption site. Earlier and deep degassing phase of carbon dioxide and polonium is inferred from low (210Po/210Pb) in the gas, consistent with magma transfer rate of 0.75 m/s.

Weathering on a stagnant lid planet: Prospects for habitability?

NASA Astrophysics Data System (ADS)

Foley, B. J.

2016-12-01

Plate tectonics plays a major role in the operation of the long term carbon cycle on Earth, which in turn buffers Earth's climate by regulating atmospheric CO2 levels. As a result, plate tectonics has long been considered to be essential for maintaining habitable conditions over geologic timescales. In particular, plate tectonics returns carbon to the mantle through subduction, allowing for long-lived CO2 degassing to the atmosphere, and plate tectonics sustains a large supply of fresh, weatherable rock at the surface through continual uplift, orogeny, and seafloor spreading. Without a large supply of fresh rock weathering can become supply-limited, where no climate regulating weathering feedback occurs. However, another mechanism for supplying fresh rock to the surface is through volcanism. Volcanism occurs on rocky planets, at least for some portion of their history, regardless of their mode of surface tectonics. In this presentation I assess whether a stagnant lid planet can avoid supply-limited weathering, and thus buffer its climate through the weathering feedback, when the supply of fresh rock is provided solely by volcanism. A simple analysis shows that the amount of CO2 in the mantle is critical for determining whether volcanic degassing overwhelms the supply of rock produced by eruptions, leading to supply-limited weathering and a hot climate, or not. Models of the coupled evolution of climate, mantle temperature, and volcanic rate are then used to determine how long a habitable climate could be maintained on a stagnant lid planet, and how different initial conditions influence this timescale. The results have important implications for the prospects for habitability of stagnant lid planets.

Exchange of adsorbed H2O and CO2 between the regolith and atmosphere of Mars caused by changes in surface insolation

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Cannon, W. A.

1974-01-01

Estimates have been made of the capacity of the Martian regolith to exchange adsorbed H2O and CO2 with the atmosphere-plus-cap system (APCS). These estimates are based upon measured isotherms for H2O and CO2 adsorption on pulverized basalt at low temperatures and on theoretical considerations. A unit column (1 sq cm) of regolith with a deep subsurface temperature of -77 C, considered average for the disk, will contain about 0.4 g of adsorbed CO2 and about 1 g of adsorbed H2O per meter of depth. Under favorable circumstances the top 3 cm can exchange much more H2O with the lower atmosphere each day than is necessary to produce the diurnal brightening. The process appears to be seasonally reversible. The total regolith may contain, in the adsorbed phase alone, as much as 1% of the H2O and 5% of the CO2 surface inventories expected for a hypothetical Mars that has experienced degassing as intensive as that of earth.

Effects of Water Amount on the Surface Environment of Terrestrial Planets: High Pressure Ice and Carbon Cycle

NASA Astrophysics Data System (ADS)

Nakayama, Akifumi; Abe, Yutaka

2015-12-01

Terrestrial planets with several wt% of H2O in extrasolar planetary systems are theoretically predicted in the habitable zone [Raymond et al., 2004]. Such planets are expected to be covered by an ocean entirely (called as “ocean planets”). Amount of atmospheric CO2 (PCO2) is important for surface environment because CO2 is a strong greenhouse gas. PCO2 is determined by a race between degassing and sink through weathering on carbon cycle. On an ocean planet, seafloor weathering is important because continental weathering can’t work [Abbot et al., 2012]. In addition, ocean planets with large water amount may have high-pressure (HP) ice on the seafloor [Leger et al., 2004]. Since the ocean floor is covered by ice in such case, it has been thought that any weathering processes will not work and PCO2 will be extremely high. When plate tectonics works, heat flow from oceanic crust decreases with distance from the mid ocean ridge. Therefore, HP ice near the mid ocean ridge will be kept solid-liquid coexistent state at the melting point because of high heat flow. Seafloor weathering works in this region. The seafloor weathering under this condition efficiently works because weathering temperature is kept melting point regardless of surface temperature. Thus, our aim is to clarify the relationship between water amount and surface environment focusing seafloor environment. We develop a carbon cycle model considering the seafloor weathering. Our major assumptions are following; 1) Earth-sized ocean planets with various water amount, 2) Degassing rate is depended on the total amount of carbon and total carbon inventory is proportional to the surface water amount. We investigated thermal state of HP ice and determined effective weathering region where HP ice is coexistent with water, then we investigated the PCO2 in equilibrium state where degassing and regassing are balanced. As a result, forming of HP ice may cause snowball state due to high weathering rate. When solar incident flux and heat flow from mantle are the present Earth’s value and a ratio of CO2 / H2O inventory is carbonaceous chondrite composition, a planet with large ocean which is larger than 90 Earth’s ocean mass lapses into snowball state. It was previously believed that forming of HP ice supports warm climate; rather, forming of HP ice could cause snowball state.

Diffusion sampler testing at Naval Air Station North Island, San Diego County, California, November 1999 to January 2000

USGS Publications Warehouse

Vroblesky, Don A.; Peters, Brian C.

2000-01-01

Volatile organic compound concentrations in water from diffusion samplers were compared to concentrations in water obtained by low-flow purging at 15 observation wells at the Naval Air Station North Island, San Diego, California. Multiple diffusion samplers were installed in the wells. In general, comparisons using bladder pumps and diffusion samplers showed similar volatile organic carbon concentrations. In some wells, sharp concentration gradients were observed, such as an increase in cis-1,2-dichloroethene concentration from 100 to 2,600 micrograms per liter over a vertical distance of only 3.4 feet. In areas where such sharp gradients were observed, concentrations in water obtained by low-flow sampling at times reflected an average concentration over the area of influence; however, concentrations obtained by using the diffusion sampler seemed to represent the immediate vicinity of the sampler. When peristaltic pumps were used to collect ground-water samples by low-flow purging, the volatile organic compound concentrations commonly were lower than concentrations obtained by using diffusion samplers. This difference may be due to loss of volatiles by degassing under negative pressures in the sampling lines induced while using the peristaltic pump, mixing in the well screen, or possible short-circuiting of water from an adjacent depth. Diffusion samplers placed in buckets of freephase jet fuel (JP-5) and Stoddard solvent from observation wells did not show evidence of structural integrity loss during the 2 months of equilibration, and volatile organic compounds detected in the free-phase fuel also were detected in the water from the diffusion samplers.

Water, CO2, Cl, and F in melt inclusions in phenocrysts from three Holocene explosive eruptions, Crater Lake, Oregon

USGS Publications Warehouse

Bacon, C.R.; Newman, S.; Stolper, E.

1992-01-01

Rare melt inclusions ~100 ??m in diameter trapped near the boundaries of corroded patchy zones in plagioclase phenocrysts from Plinian pumice of three Holocene eruptions were analyzed by IR spectroscopy for molecular H2O, OH groups, and CO2 and by electron microprobe for Cl and F. The three rhyodacitic eruptions, each of which began with a Plinian phase, occurred over ~200 yr. The Llao Rock and Cleetwood eruptions ended with degassed lava flows and the subsequent climatic eruption with voluminous ignimbrite. Location of melt inclusions near boundaries of patchy zones, which are mantled by oscillatory-zoned overgrowths, suggests that their H2O concentrations represent magmatic values significantly before eruption. -from Authors

Basaltic scoria fallout deposits from Ambrym volcano (Vanuatu archipelago): Textural and geochemical evidence of plinian eruptive styles

NASA Astrophysics Data System (ADS)

Balcone-Boissard, H.; Boudon, G.; Poulain, P.

2017-12-01

Plinian eruptions are among the most threatening volcanic hazard responsible of gas and solid particles release into atmosphere leading to potential damages at various spatial and time scales. Such explosive activity generally involves differentiated magmas, silica-rich enough to behave as viscous media and volatile-rich enough to generate significant overpressure in ascending magma. In some rare cases, Plinian eruptions can occur with more basic magmas as basalts. Few eruptions are now recognized on Earth, on Etna (122 BC), Masaya (Fontana) or Tarawera (1886). On Ambrym volcano (Vanuatu), the caldera formation was the result of several large eruptions including some Plinian events dated around 2000 yr. BP. By applying joint textural and geochemical investigations of a representative stratigraphic section of one of these eruptions we present new arguments to discuss the origin of such explosivity for basic magma. To achieve this goal we establish a degassing budget (H2O, CO2, SO2, F, Cl) through the petrological investigation by comparing melt inclusion and residual glass. We compare these results to those of quantitative textural description of pumice clasts through SEM images treated using Image J software, thus linking textural and geochemical arguments. We thus highlight that a low volatile content is not responsible of the overpressure leading to explosivity. Textural characteristics evidence vesicle organisation and low microlite content close that described for Plinian eruption involving differentiated melt. Degassing processes occur following a closed-system degassing evolution well correlated with textural parameters. By comparison to deposits of other basaltic Plinian eruptions, we show that for 122 BC eruption of Mt Etna, textural signature is diverse although we also evidence closed-system degassing processes. This study also permits to confirm that Ambrym is a valuable contributor to halogen release into the atmosphere at a time of reflexion on volcanic halogen contribution to atmosphere budget.

Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

NASA Astrophysics Data System (ADS)

Deng, Yuying; Li, Yingzhou; Li, Long

2018-04-01

Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

Major diffusion leaks of clamp-on leaf cuvettes still unaccounted: how erroneous are the estimates of Farquhar et al. model parameters?

PubMed

Rodeghiero, Mirco; Niinemets, Ulo; Cescatti, Alessandro

2007-08-01

Estimates of leaf gas-exchange characteristics using standard clamp-on leaf chambers are prone to errors because of diffusion leaks. While some consideration has been given to CO(2) diffusion leaks, potential water vapour diffusion leaks through chamber gaskets have been neglected. We estimated diffusion leaks of two clamp-on Li-Cor LI-6400 (Li-Cor, Inc., Lincoln, NE, USA) leaf chambers with polymer foam gaskets and enclosing either 2 or 6 cm(2) leaf area, and conducted a sensitivity analysis of the diffusion leak effects on Farquhar et al. photosynthesis model parameters - the maximum carboxylase activity of ribulose 1 x 5-bisphosphate carboxylase/oxygenase (Rubisco) (V(cmax)), capacity for photosynthetic electron transport (J(max)) and non-photorespiratory respiration rate in light (R(d)). In addition, net assimilation rate (A(n)) versus intercellular CO(2) (C(i)) responses were measured in leaves of Mediterranean evergreen species Quercus ilex L. enclosing the whole leaf chamber in a polyvinyl fluoride bag flushed with the exhaust air of leaf chamber, thereby effectively reducing the CO(2) and water vapour gradients between ambient air and leaf chamber. For the empty chambers, average diffusion leak for CO(2), K(CO2), (molar flow rate corresponding to unit CO(2) mole fraction difference) was ca. 0.40 micromol s(-1). K(CO2) increased ca. 50% if a dead leaf was clamped between the leaf chamber. Average diffusion leak for H(2)O was ca. 5- to 10-fold larger than the diffusion leak for CO(2). Sensitivity analyses demonstrated that the consequence of a CO(2) diffusion leak was apparent enhancement of A(n) at high CO(2) mole fraction and reduction at lower CO(2) mole fraction, and overall compression of C(i) range. As the result of these modifications, Farquhar et al. model parameters were overestimated. The degree of overestimation increased in the order of V(cmax) < J(max) < R(d), and was larger for smaller chambers and for leaves with lower photosynthetic capacity, leading to overestimation of all three parameters by 70-290% for 2 cm(2), and by 10-60% for 6 cm(2) chamber. Significant diffusion corrections (5-36%) were even required for leaves with high photosynthetic capacity measured in largest chamber. Water vapour diffusion leaks further enhanced the overestimation of model parameters. For small chambers and low photosynthetic capacities, apparent C(i) was simulated to decrease with increasing A(n) because of simultaneous CO(2) and H(2)O diffusion leaks. Measurements in low photosynthetic capacity Quercus ilex leaves enclosed in 2 cm(2) leaf chamber exhibited negative apparent C(i) values at highest A(n). For the same leaves measured with the entire leaf chamber enclosed in the polyvinyl fluoride bag, C(i) and A(n) increased monotonically. While the measurements without the bag could be corrected for diffusion leaks, the required correction in A(n) and transpiration rates was 100-500%, and there was large uncertainty in Farquhar et al. model parameters derived from 'corrected'A(n)/C(i) response curves because of uncertainties in true diffusion leaks. These data demonstrate that both CO(2) and water vapour diffusion leaks need consideration in measurements with clamp-on leaf cuvettes. As plants in natural environments are often characterized by low photosynthetic capacities, cuvette designs need to be improved for reliable measurements in such species.

One year of real-time radon monitoring at Stromboli volcano and the effect of environmental parameters on 222Rn concentrations

NASA Astrophysics Data System (ADS)

Cigolini, C.; Laiolo, M.; Coppola, D.; Piscopo, D.; Bertolino, S.

2009-12-01

Real-time radon monitoring at Stromboli volcano has been operative within the last two years. In this contribution we will discuss the recent one-year-long time series analyses in the light of environmental parameters. Two sites for real-time monitoring have been identified by means of a network of periodic radon surveys in order to locate the areas of more efficient response to seismic transients and/or volcanic degassing. Two real-time stations are positioned at Stromboli: one at the summit and located along a fracture zone where the gas flux is concentrated, and the second one at a lower altitude in a sector of diffuse degassing. The signals of the two time-series are essentially concordant but radon concentrations are considerably higher at the summit station. Raw data show that there is a negative correlation between radon emissions and seasonal temperature variations, whereas the correlation with atmospheric pressure is negative for the site of diffuse degassing and sligthly positive for the station lacated along the summit fracture zone. These data and the previously collected ones show that SW winds may substantially decrease radon concentrations at the summit station. Multivarite regression statistics on the radon signals in the light of the above enviromental parameters and tidal forces, may contribute to better idenfify the correlation between radon emissions and variations in volcanic activity. Fig. 1. Radon monitoring stations at Stromboli and the two major summit faults. Stars identify sites for real-time monitoring: LSC and PZZ. The diamond is the location of the automated Labronzo Station. Full dots are stations for periodic measurements using alpha track-etches detectors and E-PERM® electrets. Inset with the location of Stromboli and the major structures of the Aeolian arc.

TiO2 as diffusion barrier at Co/Alq3 interface studied by x-ray standing wave technique

NASA Astrophysics Data System (ADS)

Phatak Londhe, Vaishali; Gupta, A.; Ponpandian, N.; Kumar, D.; Reddy, V. R.

2018-06-01

Nano-scale diffusion at the interfaces in organic spin valve thin films plays a vital role in controlling the performance of magneto-electronic devices. In the present work, it is shown that a thin layer of titanium dioxide at the interface of Co/Alq3 can act as a good diffusion barrier. The buried interfaces of Co/Alq3/Co organic spin valve thin film has been studied using x-ray standing waves technique. A planar waveguide is formed with Alq3 layer forming the cavity and Co layers as the walls of the waveguide. Precise information about diffusion of Co into Alq3 is obtained through excitation of the waveguide modes. It is found that the top Co layer diffuses deep into the Alq3 resulting in incorporation of 3.1% Co in the Alq3 layer. Insertion of a 1.7 nm thick barrier layer of TiO2 at Co/Alq3 interface results in a drastic reduction in the diffusion of Co into Alq3 to a value of only 0.4%. This suggests a better performance of organic spin valve with diffusion barrier of TiO2.

New Evidence for the Low-Pressure Origin of Lava-Hyaloclastite Sequences in South Iceland

NASA Astrophysics Data System (ADS)

Banik, T.; Hoskuldsson, A.; Miller, C. F.; Furbish, D. J.; Wallace, P. J.

2011-12-01

In the Sida-Fljotshverfi District of south Iceland, Pleistocene basaltic lava forms flame-like apophyses, dikes, and disaggregation structures (cf. Bergh and Sigvaldason, 1991; Smellie, 2008) that invade overlying hyaloclastite. These features are exposed in valley walls composed of at least 14 (Bergh and Sigvaldason, 1991) paired basalt-hyaloclastite +/- diamictite depositional units. These units are dominated by hyaloclastite deposits that reach over 100 m in thickness, with underlying lava up to 50 m thick. Apophyses as well as underlying lavas show "kubbaberg" or cube jointing, indicating rapid cooling due to formation in a wet environment and suggesting that hyaloclastite and lava were emplaced virtually concurrently, while hyaloclastite was wet and weak. Dissolved volatile concentrations in glass give an indication of ambient pressure on quenching and cessation of degassing. Sulfur contents in basaltic glasses from chilled margins of lava and from hyaloclastite glasses obtained by electron microprobe (lava glasses range from 0-525 ppm with the majority of samples less than 300 ppm; hyaloclastite glasses have 0-900 ppm S) suggest degassing at shallow depths (< a few hundred m) or at the surface. This is further supported by FTIR analyses for CO2 and H2O contents in both glass types that yield low total water contents (0-0.570 %, although the vast majority of samples fall below 0.2 %, for the lava glasses; hyaloclastite glasses are 0-0.147%) and no measureable CO2, indicating quenching pressures for over half of both the lava and the hyaloclastite samples were near atmospheric P. These data support an eruption that occurred under significantly lower-pressure conditions than previously proposed (Smellie, 2008). The presence of a large volume of hyaloclastite as well as extensive lava suggests the possibility of eruptions with both subglacial and subaerial phases. In one possible scenario, a subglacial eruption under a shallow glacier may have produced hyaloclastite that was incorporated into a meltwater lake-draining jökulhlaup. Ensuing subaerial lava from the ongoing eruption flowed onto still-plastic hyaloclastite and sank to its base. Thermal modeling suggests that influx of heat from the underlying lava resulted in increased fluid pressure in the hyaloclastite matrix. Fracturing of the chilled rind that had formed atop the lava permitted injection of lava into the overlying hyaloclastite. Diffusion of pressure away from the injection site dragged the matrix apart, facilitating propagation of lava upward to form the apophyses.

Nitrous Oxide Production in Co- Versus Counter-Diffusion Nitrifying Biofilms

NASA Astrophysics Data System (ADS)

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2016-06-01

For the application of biofilm processes, a better understanding of nitrous oxide (N2O) formation within the biofilm is essential for design and operation of biofilm reactors with minimized N2O emissions. In this work, a previously established N2O model incorporating both ammonia oxidizing bacteria (AOB) denitrification and hydroxylamine (NH2OH) oxidation pathways is applied in two structurally different biofilm systems to assess the effects of co- and counter-diffusion on N2O production. It is demonstrated that the diffusion of NH2OH and oxygen within both types of biofilms would form an anoxic layer with the presence of NH2OH and nitrite ( ), which would result in a high N2O production via AOB denitrification pathway. As a result, AOB denitrification pathway is dominant over NH2OH oxidation pathway within the co- and counter-diffusion biofilms. In comparison, the co-diffusion biofilm may generate substantially higher N2O than the counter-diffusion biofilm due to the higher accumulation of NH2OH in co-diffusion biofilm, especially under the condition of high-strength ammonium influent (500 mg N/L), thick biofilm depth (300 μm) and moderate oxygen loading (~1-~4 m3/d). The effect of co- and counter-diffusion on N2O production from the AOB biofilm is minimal when treating low-strength nitrogenous wastewater.

Nitrous Oxide Production in Co- Versus Counter-Diffusion Nitrifying Biofilms

PubMed Central

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2016-01-01

For the application of biofilm processes, a better understanding of nitrous oxide (N2O) formation within the biofilm is essential for design and operation of biofilm reactors with minimized N2O emissions. In this work, a previously established N2O model incorporating both ammonia oxidizing bacteria (AOB) denitrification and hydroxylamine (NH2OH) oxidation pathways is applied in two structurally different biofilm systems to assess the effects of co- and counter-diffusion on N2O production. It is demonstrated that the diffusion of NH2OH and oxygen within both types of biofilms would form an anoxic layer with the presence of NH2OH and nitrite ( ), which would result in a high N2O production via AOB denitrification pathway. As a result, AOB denitrification pathway is dominant over NH2OH oxidation pathway within the co- and counter-diffusion biofilms. In comparison, the co-diffusion biofilm may generate substantially higher N2O than the counter-diffusion biofilm due to the higher accumulation of NH2OH in co-diffusion biofilm, especially under the condition of high-strength ammonium influent (500 mg N/L), thick biofilm depth (300 μm) and moderate oxygen loading (~1–~4 m3/d). The effect of co- and counter-diffusion on N2O production from the AOB biofilm is minimal when treating low-strength nitrogenous wastewater. PMID:27353382

Estimation of the geothermal potential of the Caldara di Manziana site in the Mts Sabatini Volcanic District (Central Italy) by integrating geochemical data and 3D-GIS modelling.

NASA Astrophysics Data System (ADS)

Ranaldi, Massimo; Lelli, Matteo; Tarchini, Luca; Carapezza, Maria Luisa; Patera, Antonio

2016-04-01

High-enthalpy geothermal fields of Central Italy are hosted in deeply fractured carbonate reservoirs occurring in thermally anomalous and seismically active zones. However, the Mts. Sabatini volcanic district, located north of Rome, has an interesting deep temperatures (T), but it is characterized by low to very low seismicity and permeability in the reservoir rocks (mostly because of hydrothermal self-sealing processes). Low PCO2 facilitates the complete sealing of the reservoir fractures, preventing hot fluids rising and, determining a low CO2 flux at the surface. Conversely, high CO2 flux generally reflects a high pressure of CO2, suggesting that an active geothermal reservoir is present at depth. In Mts. Sabatini district, the Caldara of Manziana (CM) is the only zone characterized by a very high CO2 flux (188 tons/day) from a surface of 0.15 km2) considering both the diffuse and viscous CO2 emission. This suggests the likely presence of an actively degassing geothermal reservoir at depth. Emitted gas is dominated by CO2 (>97 vol.%). Triangular irregular networks (TINs) have been used to represent the morphology of the bottom of the surficial volcanic deposits, the thickness of the impervious formation and the top of the geothermal reservoir. The TINs, integrated by T-gradient and deep well data, allowed to estimate the depth and the temperature of the top of the geothermal reservoir, respectively to ~-1000 m from the surface and to ~130°C. These estimations are fairly in agreement with those obtained by gas chemistry (818

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Measurement of CO2 diffusivity for carbon sequestration: a microfluidic approach for reservoir-specific analysis.

PubMed

Sell, Andrew; Fadaei, Hossein; Kim, Myeongsub; Sinton, David

2013-01-02

Predicting carbon dioxide (CO(2)) security and capacity in sequestration requires knowledge of CO(2) diffusion into reservoir fluids. In this paper we demonstrate a microfluidic based approach to measuring the mutual diffusion coefficient of carbon dioxide in water and brine. The approach enables formation of fresh CO(2)-liquid interfaces; the resulting diffusion is quantified by imaging fluorescence quenching of a pH-dependent dye, and subsequent analyses. This method was applied to study the effects of site-specific variables--CO(2) pressure and salinity levels--on the diffusion coefficient. In contrast to established, macro-scale pressure-volume-temperature cell methods that require large sample volumes and testing periods of hours/days, this approach requires only microliters of sample, provides results within minutes, and isolates diffusive mass transport from convective effects. The measured diffusion coefficient of CO(2) in water was constant (1.86 [± 0.26] × 10(-9) m(2)/s) over the range of pressures (5-50 bar) tested at 26 °C, in agreement with existing models. The effects of salinity were measured with solutions of 0-5 M NaCl, where the diffusion coefficient varied up to 3 times. These experimental data support existing theory and demonstrate the applicability of this method for reservoir-specific testing.

Molecular simulations of a CO2/CO mixture in MIL-127

NASA Astrophysics Data System (ADS)

Chokbunpiam, Tatiya; Fritzsche, Siegfried; Parasuk, Vudhichai; Caro, Jürgen; Assabumrungrat, Suttichai

2018-03-01

Adsorption and diffusion of an equimolar feed mixture of CO2 and CO in MIL-127 at three different temperatures and pressures up to 12 bar were investigated by molecular simulations. The adsorption was simulated using Gibbs-Ensemble Monte Carlo (GEMC). The structure of the adsorbed phase and the diffusion in the MIL were investigated using Molecular Dynamics (MD) simulations. The adsorption selectivity of MIL-127 for CO2 over CO at 233 K was about 15. When combining adsorption and diffusion selectivities, a membrane selectivity of about 12 is predicted. For higher temperatures, both adsorption and diffusion selectivity are found to be smaller.

Non-volcanic CO2 Earth degassing: Case of Mefite d'Ansanto (southern Apennines), Italy

NASA Astrophysics Data System (ADS)

Chiodini, G.; Granieri, D.; Avino, R.; Caliro, S.; Costa, A.; Minopoli, C.; Vilardo, G.

2010-06-01

Mefite d'Ansanto, southern Apennines, Italy is the largest natural emission of low temperature CO2 rich gases, from non-volcanic environment, ever measured in the Earth. The emission is fed by a buried reservoir, made up of permeable limestones and covered by clayey sediments. We estimated a total gas flux of ˜2000 tons per day. Under low wind conditions, the gas flows along a narrow natural channel producing a persistent gas river which has killed over a period of time people and animals. The application of a physical numerical model allowed us to define the zones which potentially can be affected by dangerous CO2 concentration at breathing height for humans. The geometry of the Mefite gas reservoir is similar to those designed for sequestering CO2 in geological storage projects where huge amounts of CO2 should be injected in order to reduce atmospheric CO2 concentration. The approach which we have used at Mefite to define hazardous zones for the human health can be applied also in case of large CO2 leakages from storage sites, a phenomena which, even if improbable, can not be ruled out.

Explosive origin of silicic lava: Textural and δD-H2O evidence for pyroclastic degassing during rhyolite effusion

NASA Astrophysics Data System (ADS)

Castro, Jonathan M.; Bindeman, Ilya N.; Tuffen, Hugh; Ian Schipper, C.

2014-11-01

A long-standing challenge in volcanology is to explain why explosive eruptions of silicic magma give way to lava. A widely cited idea is that the explosive-to-effusive transition manifests a two-stage degassing history whereby lava is the product of non-explosive, open-system gas release following initial explosive, closed-system degassing. Direct observations of rhyolite eruptions indicate that effusive rhyolites are in fact highly explosive, as they erupt simultaneously with violent volcanic blasts and pyroclastic fountains for months from a common vent. This explosive and effusive overlap suggests that pyroclastic processes play a key role in rendering silicic magma sufficiently degassed to generate lava. Here we use precise H-isotope and magmatic H2O measurements and textural evidence to demonstrate that effusion results from explosion(s)-lavas are the direct product of brittle deformation that fosters batched degassing into transient pyroclastic channels (tuffisites) that repetitively and explosively vent from effusing lava. Our measurements show, specifically that D/H ratios and H2O contents of a broad suite of explosive and effusive samples from Chaitén volcano (hydrous bombs, Plinian pyroclasts, tuffisite veins, and lava) define a single and continuous degassing trend that links wet explosive pyroclasts (∼ 1.6 wt.% H2O, δD = - 76.4 ‰) to dry obsidian lavas (∼ 0.13 wt.% H2O, δD = - 145.7 ‰). This geochemical pattern is best fit with batched degassing model that comprises small repeated closed-system degassing steps followed by pulses of vapour extraction. This degassing mechanism is made possible by the action of tuffisite veins, which, by tapping already vesicular or brecciated magma, allow batches of exsolved gas to rapidly and explosively escape from relatively isolated closed-system domains and large tracts of conduit magma by giving them long-range connectivity. Even though tuffisite veins render magma degassed and capable of effusing, they are nonetheless the avenues of violent gas and particle transport and thus have the potential to drive explosions when they become blocked or welded shut. Thus the effusion of silicic lava, traditionally thought to be relatively benign process, presents a particularly hazardous form of explosive volcanism.

Evaluating greenhouse gas emissions from hydropower complexes on large rivers in Eastern Washington

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arntzen, Evan V.; Miller, Benjamin L.; O'Toole, Amanda C.

2013-03-15

Water bodies, such as freshwater lakes, are known to be net emitters of carbon dioxide (CO2), and methane (CH4). In recent years, significant greenhouse gas (GHG) emissions from tropical, boreal, and mid-latitude reservoirs have been reported. At a time when hydropower is increasing worldwide, better understanding of seasonal and regional variation in GHG emissions is needed in order to develop a predictive understanding of such fluxes within man-made impoundments. We examined power-producing dam complexes within xeric temperate locations in the northwestern United States. Sampling environments on the Snake (Lower Monumental Dam Complex) and Columbia Rivers (Priest Rapids Dam Complex) includedmore » tributary, mainstem, embayment, forebay, and tailrace areas during winter and summer 2012. At each sampling location, GHG measurement pathways included surface gas flux, degassing as water passed through dams during power generation, ebullition within littoral embayments, and direct sampling of hyporheic pore-water. Measurements were also carried out in a free-flowing reach of the Columbia River to estimate unaltered conditions. Surface flux resulted in very low emissions, with reservoirs acting as a sink for CO2 (up to –262 mg m-2 d-1, which is within the range previously reported for similarly located reservoirs). Surface flux of methane remained below 1 mg CH4 m-2d-1, a value well below fluxes reported previously for temperate reservoirs. Water passing through hydroelectric projects acted as a sink for CO2 during winter and a small source during summer, with mean degassing fluxes of –117 and 4.5 t CO2 d-1, respectively. Degassing of CH4 was minimal, with mean fluxes of 3.1 × 10-6 and –5.6 × 10-4 t CH4 d-1 during winter and summer, respectively. Gas flux due to ebullition was greater in coves located within reservoirs than in coves within the free flowing Hanford Reach–and CH4 flux exceeded that of CO2. Methane emissions varied widely across sampling locations, ranging from 10.5 to 1039 mg CH4 m-2 d-1, with mean fluxes of 324 mg CH4 m-2 d-1in Lower Monumental Dam reservoir and 482 mg CH4 m-2d-1 in the Priest Rapids Dam reservoir. The magnitude of methane flux due to ebullition was unexpectedly high, and falls within the range recently reported for other temperate reservoirs around the world, further suggesting that this methane source should be considered in estimates of global greenhouse gas emissions. Methane flux from sediment pore-water within littoral embayments averaged 4.2 mg m-2 d-1 during winter and 8.1 mg m-2 d-1 during summer, with a peak flux of 19.8 mg m-2d-1 (at the same location where CH4 ebullition was also the greatest). Carbon dioxide flux from sediment pore-water averaged approximately 80 mg m-2d-1 with little difference between winter and summer. Similar to emissions from ebullition, flux from sediment pore-water was higher in reservoirs than in the free flowing reach.« less

Mantle Degassing and Atmosphere Evolution

NASA Astrophysics Data System (ADS)

Zhang, Y.

2011-12-01

Noble gas isotopes have provided much of our understanding of Earth's early history [1-3]. Various degassing models have been developed, including degassing of the whole mantle, degassing of all gases at similar relative rate [1], solubility-controlled degassing [2], and steady-state degassing models [4]. This report will evaluate various degassing models using recent data. For example, helium outgassing flux has been lowered by more than a factor of two based on sophisticated ocean general circulation models [5], which also impacts on the estimated degassing flux of carbon. Years of measurements and progress have allowed isotopic ratios of various mantle reservoirs being pieced together [6]. For example, 129Xe/130Xe in OIB mantle is found to be lower than that in MORB mantle [7]. Missing Xe has been found to be a non-issue [8]. Nucleogenic 21Ne production rate relative radiogenic 4He has been revised [9-10], which leads to an interesting neon paradox that nucleogenic 21Ne production in the whole silicate Earth is barely enough to supply nucleogenic 21Ne in air. 40Ar/36Ar ratio in BSE seems to be much lower than any OIB samples, another interesting paradox. Although non-nucleogenic mantle neon is solar, nonradiogenic mantle argon is atmospheric [11]. For Kr and Xe, the jury is still out. When mantle degassing models are evaluated using volatile data of the MORB and OIB, solubility-controlled degassing is able to reconcile more data than other degassing models. On the other hand, the vailable data seem to indicate that atmosphere evolution is more than mantle degassing; there may be significant contribution to the atmosphere from impact degassing and other sources. Furthermore, we are now suffering from too many data so that understanding the whole picture is elusive. [1] Allegre et al. (1986/87) EPSL 81, 127-150. [2] Zhang & Zindler (1989) J. Geophys. Res. 94, 13719-13737. [3] Zhang (1998) Geochim. Cosmochim. Acta 62, 3185-3189. [4] Pocelli & Wasserburg (1995) Geochim. Cosmochim. Acta 59, 4921-4937. [5] Bianchi et al. (2010) EPSL 297, 379-386. [6] Jackson et al. (2009) EPSL 287, 519-528. [7] Graham (2002) Rev. Mineral. Geochem. 47, 247-317. [8] Zhang (2002) Earth-Sci. Rev. 59, 235-263. [9] Yatsevich and Honda (1997).

Development of new measuring technique using sound velocity for CO2 concentration in Cameroonian volcanic lakes

NASA Astrophysics Data System (ADS)

Sanemasa, M.; Saiki, K.; Kaneko, K.; Ohba, T.; Kusakabe, M.; Tanyileke, G.; Hell, J.

2012-12-01

1. Introduction Limnic eruptions at Lakes Monoun and Nyos in Cameroon, which are sudden degassing of magmatic CO2 dissolved in the lake water, occurred in 1984 and 1986, respectively. The disasters killed about 1800 people around the lakes. Because of ongoing CO2 accumulation in the bottom water of the lakes, tragedy of limnic eruptions will possibly occur again. To prevent from further disasters, artificial degassing of CO2 from the lake waters has been undergoing. Additionally, CO2 monitoring of the lake waters is needed. Nevertheless, CO2 measurement is done only once or twice a year because current methods of CO2 measurement, which require chemical analysis of water samples, are not suitable for frequent measurement. In engineering field, on the other hand, a method to measure salt concentration using sound velocity has been proposed (Kleis and Sanchez, 1990). This method allows us to evaluate solute concentration fast. We applied the method to dissolved CO2 and examined the correlation between sound velocity and CO2 concentration in laboratory experiment. Furthermore, using the obtained correlation, we tried to estimate the CO2 concentration of waters in the Cameroonian lakes. 2. Laboratory experiment We examined the correlation between sound velocity and CO2 concentration. A profiler (Minos X, made by AML oceanography) and pure water were packed in cylindrical stainless vessel and high-pressure CO2 gas was injected to produce carbonated water. The profiler recorded temperature, pressure and sound velocity. Change of sound velocity was defined as difference of sound velocity between carbonated water and pure water under the same temperature and pressure conditions. CO2 concentration was calculated by Henry's law. The result indicated that the change of sound velocity [m s-1] is proportional to CO2 concentration [mmol kg-1], and the coefficient is 0.021 [m kg s-1 mmol-1]. 3. Field application Depth profiles of sound velocity, pressure, and temperature of Lakes Nyos and Monoun were measured in March 2012, and CO2 concentration was calculated using the results of laboratory experiment. The CO2 concentration profiles by Sound Velocity Method were compared to estimated profile of 2012 by chemical analysis with correction using results of Kusakabe et al., 2008. The CO2 concentration profile estimated by Sound Velocity Method looks overestimated. This may be the effect of bicarbonate salt little existed in laboratory experiment. The change of sound velocity was evaluated as a linear function of CO2 and bicarbonate ion concentration by multiple regression analysis. Coefficient for the change of sound velocity of CO2 concentration in Lake Nyos agrees with the laboratory experiment within the precision of 10%. On the other hand, in Lake Monoun, the difference of coefficient is larger than 50%. In Lake Monoun, CO2 concentration may be estimated incorrectly because CO2/bicarbonate ratio seems to have changed. From these results, we concluded that Sound Velocity Method is useful to measure CO2 concentration quantitatively as far as the CO2/bicarbonate ratio does not change. The method is also applicable as an early diagnosis when the CO2 profile changes by a sudden CO2 injection to the lakes.

Cratonic roots and lower crustal seismicity: Investigating the role of deep intrusion in the Western rift, Africa

NASA Astrophysics Data System (ADS)

Drooff, C.; Ebinger, C. J.; Lavayssiere, A.; Keir, D.; Oliva, S. J.; Tepp, G.; Gallacher, R. J.

2017-12-01

Improved seismic imaging beneath the African continent reveals lateral variations in lithospheric thickness, and crustal structure, complementing a growing crust and mantle xenolith data base. Border fault systems in the active cratonic rifts of East Africa are characterized by lower crustal seismicity, both in magmatic sectors and weakly magmatic sectors, providing constraints on crustal rheology and, in some areas, magmatic fluid migration. We report new seismicity data from magmatic and weakly magmatic sectors of the East African rift zone, and place the work in the context of independent geophysical and geochemical studies to models for strain localization during early rifting stages. Specifically, multidisciplinary studies in the Magadi Natron rift sectors reveal volumetrically large magmatic CO2 degassing along border faults with seismicity along projections of surface dips to the lower crust. The magmatic CO2 degassing and high Vp/Vs ratios and reflectivity of the lower crust implies that the border fault serves a conduit between the lower crustal underplating and the atmospheric. Crustal xenoliths in the Eastern rift sector indicate a granulitic lower crust, which is relatively weak in the presence of fluids, arguing against a strong lower crust. Within magmatic sectors, seismic, structural, and geochemistry results indicate that frequent lower crustal earthquakes are promoted by elevated pore pressures from volatile degassing along border faults, and hydraulic fracture around the margins of magma bodies. Within some weakly magmatic sectors, lower crustal earthquakes also occur along projections of border faults to the lower crust (>30 km), and they are prevalent in areas with high Vp/Vs in the lower crust. Within the southern Tanganyika rift, focal mechanisms are predominantly normal with steep nodal planes. Our comparative studies suggest that pervasive metasomatism above a mantle plume, and melt extraction in thin zones between cratonic roots, lead to high pore pressures that promote brittle failure in the lower crust, even in areas with no surface expression of magmatism.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Chemistry and fluxes of magmatic gases powering the explosive trachyandesitic phase of Eyjafjallajokull 2010 eruption: constraints on degassing magma volumes and processes

NASA Astrophysics Data System (ADS)

Allard, P.; Burton, M. R.; Oskarsson, N.; Michel, A.; Polacci, M.

2010-12-01

The 2010 Eyjafjallajökull eruption developed in two distinct phases, with initial lateral effusion of alkali basalt since March 20, followed by highly explosive extrusion of a quite homogenous and crystal-poor trachyandesitic magma [1] through the central volcano ice cap between April 14 and May 24. As usual, magmatic volatiles played a key role in the eruption dynamics. Here we report on the chemical composition and the mass output of magmatic gases powering intense explosive activity during the second eruptive phase in early May. On May 8 we could measure the composition of magmatic gases directly issuing from the eruptive vents, by using OP-FTIR spectroscopy from the crater rim (~900 m distance) and molten lava blocks as IR radiation source. FTIR spectra reveal a variable mixture between two gas components equally rich in H2O (91.3 mol%) and CO2 (8%) but differing in their SO2/HCl ratio (up to 3.5 for the main one and 0.5 for the Cl-richer second one). Analysis of S-Cl-F in ash leachates and in ash and lava bomb samples (pyrohydrolysis) show that this second component was generated by greater chlorine loss during extensive magma fragmentation into fine ash. S/Cl and Cl/F ratios from both these analyses and solar occultation FTIR plume sensing indicate a modest fluorine content in emitted gas and its preferential adsorption onto solid particles during plume transport. DOAS traverses under the volcanic plume (4-6 km height), though hampered by dense ash load, gave most reliable SO2 fluxes of 4500-6600 tons d-1 on May 9, consistent with OMI satellite data [2]. These imply the daily co-emission of 7.2x105 tons of H2O, 1.5x105 tons of CO2, 2000 tons of HCl and ≤200 tons of HF. Eyjafjallajökull thus produced more hydrous and relatively CO2-poorer gas, in much greater quantities, during that stage than during its first basaltic phase [3]. Linear variations of dissolved S with TiO2/FeO ratio in nearby Katla alkali magmas [4] suggest possible pre-eruptive S contents of 0.17-0.19 and 0.14-0.16 wt% in Eyjafjallajökull alkali basalt and trachyandesite, respectively. With 0.03 wt% of residual S measured in erupted lavas, we compute the degassing of ~106 m3 d-1 of trachyandesite in early May, compared to only ~3.5x105 m3 d-1 of basalt in early April. The alkali basalt was petrologically equilibrated at ≤2 kbar and 1150°C [1] but, given the CO2/S ratio of basaltic gases from the first phase [3], might have initially contained ≥1 wt% of carbon dioxide at greater depth. Early CO2 exsolution from this uprising basalt and its interaction with more evolved magma in a shallower reservoir beneath Eyjafjallajökull could have generated enough overpressure for triggering the eruption. [1] N. Oskarsson, 2010, http://www.earthice.hi.is/; [2] P. Labazuy et al., OPGC-LMV, Clermont-Ferrand, France, April 2010, http://wwwobs.univ-bpclermont.fr/; [3] Burton et al., Gas composition and flux report, March 2010, http://www.earthice.hi.is/; [4] Thordarson et al., In: Volcanic Degassing, Geol. Soc. London, special public. 213, 2006.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, B.; Renault, R.W.

Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The wallsmore » of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.« less

Generation and evolution of hydrothermal fluids at Yellowstone: Insights from the Heart Lake Geyser Basin

NASA Astrophysics Data System (ADS)

Lowenstern, J. B.; Bergfeld, D.; Evans, W. C.; Hurwitz, S.

2012-01-01

We sampled fumaroles and hot springs from the Heart Lake Geyser Basin (HLGB), measured water and gas discharge, and estimated heat and mass flux from this geothermal area in 2009. The combined data set reveals that diverse fluids share an origin by mixing of deep solute-rich parent water with dilute heated meteoric water, accompanied by subsequent boiling. A variety of chemical and isotopic geothermometers are consistent with a parent water that equilibrates with rocks at 205°C ± 10°C and then undergoes 21% ± 2% adiabatic boiling. Measured diffuse CO2 flux and fumarole compositions are consistent with an initial dissolved CO2 concentration of 21 ± 7 mmol upon arrival at the caldera boundary and prior to southeast flow, boiling, and discharge along the Witch Creek drainage. The calculated advective flow from the basin is 78 ± 16 L s-1of parent thermal water, corresponding to 68 ± 14 MW, or ˜1% of the estimated thermal flux from Yellowstone. Helium and carbon isotopes reveal minor addition of locally derived crustal, biogenic, and meteoric gases as this fluid boils and degasses, reducing the He isotope ratio (Rc/Ra) from 2.91 to 1.09. The HLGB is one of the few thermal areas at Yellowstone that approaches a closed system, where a series of progressively boiled waters can be sampled along with related steam and noncondensable gas. At other Yellowstone locations, steam and gas are found without associated neutral Cl waters (e.g., Hot Spring Basin) or Cl-rich waters emerge without significant associated steam and gas (Upper Geyser Basin).

Generation and evolution of hydrothermal fluids at Yellowstone: Insights from the Heart Lake Geyser Basin

USGS Publications Warehouse

Lowenstern, J. B.; Bergfeld, D.; Evans, William C.; Hurwitz, S.

2012-01-01

We sampled fumaroles and hot springs from the Heart Lake Geyser Basin (HLGB), measured water and gas discharge, and estimated heat and mass flux from this geothermal area in 2009. The combined data set reveals that diverse fluids share an origin by mixing of deep solute-rich parent water with dilute heated meteoric water, accompanied by subsequent boiling. A variety of chemical and isotopic geothermometers are consistent with a parent water that equilibrates with rocks at 205°C ± 10°C and then undergoes 21% ± 2% adiabatic boiling. Measured diffuse CO2 flux and fumarole compositions are consistent with an initial dissolved CO2 concentration of 21 ± 7 mmol upon arrival at the caldera boundary and prior to southeast flow, boiling, and discharge along the Witch Creek drainage. The calculated advective flow from the basin is 78 ± 16 L s−1 of parent thermal water, corresponding to 68 ± 14 MW, or –1% of the estimated thermal flux from Yellowstone. Helium and carbon isotopes reveal minor addition of locally derived crustal, biogenic, and meteoric gases as this fluid boils and degasses, reducing the He isotope ratio (Rc/Ra) from 2.91 to 1.09. The HLGB is one of the few thermal areas at Yellowstone that approaches a closed system, where a series of progressively boiled waters can be sampled along with related steam and noncondensable gas. At other Yellowstone locations, steam and gas are found without associated neutral Cl waters (e.g., Hot Spring Basin) or Cl-rich waters emerge without significant associated steam and gas (Upper Geyser Basin).

Red blood cell thickness is evolutionarily constrained by slow, hemoglobin-restricted diffusion in cytoplasm.

PubMed

Richardson, Sarah L; Swietach, Pawel

2016-10-25

During capillary transit, red blood cells (RBCs) must exchange large quantities of CO 2 and O 2 in typically less than one second, but the degree to which this is rate-limited by diffusion through cytoplasm is not known. Gas diffusivity is intuitively assumed to be fast and this would imply that the intracellular path-length, defined by RBC shape, is not a factor that could meaningfully compromise physiology. Here, we evaluated CO 2 diffusivity (D CO2 ) in RBCs and related our results to cell shape. D CO2 inside RBCs was determined by fluorescence imaging of [H + ] dynamics in cells under superfusion. This method is based on the principle that H + diffusion is facilitated by CO 2 /HCO 3 - buffer and thus provides a read-out of D CO2 . By imaging the spread of H + ions from a photochemically-activated source (6-nitroveratraldehyde), D CO2 in human RBCs was calculated to be only 5% of the rate in water. Measurements on RBCs containing different hemoglobin concentrations demonstrated a halving of D CO2 with every 75 g/L increase in mean corpuscular hemoglobin concentration (MCHC). Thus, to compensate for highly-restricted cytoplasmic diffusion, RBC thickness must be reduced as appropriate for its MCHC. This can explain the inverse relationship between MCHC and RBC thickness determined from >250 animal species.

Carbon fluxes in an acid rain impacted boreal headwater catchment

NASA Astrophysics Data System (ADS)

Marx, Anne; Hintze, Simone; Jankovec, Jakub; Sanda, Martin; Dusek, Jaromir; Vogel, Tomas; van Geldern, Robert; Barth, Johannes A. C.

2016-04-01

Terrestrial carbon export via inland aquatic systems is a key process in the budget of the global carbon cycle. This includes loss of carbon to the atmosphere via gas evasion from rivers or reservoirs as well as carbon fixation in freshwater sediments. Headwater streams are the first endmembers of the transition of carbon between soils, groundwater and surface waters and the atmosphere. In order to quantify these processes the experimental catchment Uhlirska (1.78 km2) located in the northern Czech Republic was studied. Dissolved inorganic, dissolved organic and particulate organic carbon (DIC, DOC, POC) concentrations and isotopes were analyzed in ground-, soil -and stream waters between 2014 and 2015. In addition, carbon dioxide degassing was quantified via a stable isotope modelling approach. Results show a discharge-weighted total carbon export of 31.99 g C m-2 yr-1 of which CO2 degassing accounts 79 %. Carbon isotope ratios (δ13C) of DIC, DOC, and POC (in ‰ VPDB) ranged from -26.6 to -12.4 ‰ from -29.4 to -22.7 ‰ and from -30.6 to -26.6 ‰ respectively. The mean values for DIC are -21.8 ±3.8 ‰ -23.6 ±0.9 ‰ and -19.5 ±3.0 ‰ for soil, shallow ground and surface water compartments. For DOC, these compartments have mean values of -27.1 ±0.3 ‰ -27.0 ±0.8 ‰ and -27.4 ±0.7 ‰Ṁean POC value of shallow groundwaters and surface waters are -28.8 ±0.8 ‰ and -29.3 ±0.5 ‰ respectively. These isotope ranges indicate little turnover of organic material and predominant silicate weathering. The degassing of CO2 caused an enrichment of the δ13C-DIC values of up to 6.8 ‰ between a catchment gauge and the catchment outlet over a distance of 866 m. In addition, the Uhlirska catchment has only negligible natural sources of sulphate, yet SO42- accounts for 21 % of major stream water ions. This is most likely a remainder from acid rain impacts in the area.

The influence of different diffusion pattern to the sub- and super-critical fluid flow in brown coal

NASA Astrophysics Data System (ADS)

Peng, Peihuo

2018-03-01

Sub- and super-critical CO2 flowing in nanoscale pores are recently becoming of great interest due to that it is closely related to many engineering applications, such as geological burial and sequestration of carbon dioxide, Enhanced Coal Bed Methane recovery ( ECBM), super-critical CO2 fracturing and so on. Gas flow in nanopores cannot be described simply by the Darcy equation. Different diffusion pattern such as Fick diffusion, Knudsen diffusion, transitional diffusion and slip flow at the solid matrix separate the seepage behaviour from Darcy-type flow. According to the principle of different diffusion pattern, the flow of sub- and super-critical CO2 in brown coal was simulated by numerical method, and the results were compared with the experimental results to explore the contribution of different diffusion pattern and swelling effect in sub- and super-critical CO2 flow in nanoscale pores.

A two-dimensional microscale model of gas exchange during photosynthesis in maize (Zea mays L.) leaves.

PubMed

Retta, Moges; Ho, Quang Tri; Yin, Xinyou; Verboven, Pieter; Berghuijs, Herman N C; Struik, Paul C; Nicolaï, Bart M

2016-05-01

CO2 exchange in leaves of maize (Zea mays L.) was examined using a microscale model of combined gas diffusion and C4 photosynthesis kinetics at the leaf tissue level. Based on a generalized scheme of photosynthesis in NADP-malic enzyme type C4 plants, the model accounted for CO2 diffusion in a leaf tissue, CO2 hydration and assimilation in mesophyll cells, CO2 release from decarboxylation of C4 acids, CO2 fixation in bundle sheath cells and CO2 retro-diffusion from bundle sheath cells. The transport equations were solved over a realistic 2-D geometry of the Kranz anatomy obtained from light microscopy images. The predicted responses of photosynthesis rate to changes in ambient CO2 and irradiance compared well with those obtained from gas exchange measurements. A sensitivity analysis showed that the CO2 permeability of the mesophyll-bundle sheath and airspace-mesophyll interfaces strongly affected the rate of photosynthesis and bundle sheath conductance. Carbonic anhydrase influenced the rate of photosynthesis, especially at low intercellular CO2 levels. In addition, the suberin layer at the exposed surface of the bundle sheath cells was found beneficial in reducing the retro-diffusion. The model may serve as a tool to investigate CO2 diffusion further in relation to the Kranz anatomy in C4 plants. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Aquaporins and membrane diffusion of CO2 in living organisms.

PubMed

Kaldenhoff, Ralf; Kai, Lei; Uehlein, Norbert

2014-05-01

Determination of CO2 diffusion rates in living cells revealed inconsistencies with existing models about the mechanisms of membrane gas transport. Mainly, these discrepancies exist in the determined CO2 diffusion rates of bio-membranes, which were orders of magnitudes below those for pure lipid bilayers or theoretical considerations as well as in the observation that membrane insertion of specific aquaporins was rescuing high CO2 transport rates. This effect was confirmed by functional aquaporin protein analysis in heterologous expression systems as well as in bacteria, plants and partly in mammals. This review summarizes the arguments in favor of and against aquaporin facilitated membrane diffusion of CO2 and reports about its importance for the physiology of living organisms. Most likely, the aquaporin tetramer forming an additional fifth pore is required for CO2 diffusion facilitation. Aquaporin tetramer formation, membrane integration and disintegration could provide a mechanism for regulation of cellular CO2 exchange. The physiological importance of aquaporin mediated CO2 membrane diffusion could be shown for plants and cyanobacteria and partly for mammals. Taking the mentioned results into account, consequences for our current picture of cell membrane transport emerge. It appears that in some or many instances, membranes might not be as permeable as it was suggested by current bio-membrane models, opening an additional way of controlling the cellular influx or efflux of volatile substances like CO2. This article is part of a Special Issue entitled Aquaporins. © 2013.

The effect of physical back-diffusion of 13CO2 tracer on the coupling between photosynthesis and soil CO2 efflux in grassland.

PubMed

Burri, Susanne; Sturm, Patrick; Baur, Thomas; Barthel, Matti; Knohl, Alexander; Buchmann, Nina

2014-01-01

Pulse labelling experiments provide a common tool to study short-term processes in the plant-soil system and investigate below-ground carbon allocation as well as the coupling of soil CO(2) efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO(2) efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO(2) efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical (13)CO(2) tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO(2) efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO(2) efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO(2) efflux rates could be related to daytime rates of gross primary productivity (R(2)=0.84). Moreover, pronounced diurnal patterns in the δ(13)C of soil CO(2) efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ(13)C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO(2) efflux in grassland at the diurnal time scale.

Heterogeneity in mantle carbon content from CO2-undersaturated basalts

PubMed Central

Le Voyer, M.; Kelley, K.A.; Cottrell, E.; Hauri, E.H.

2017-01-01

The amount of carbon present in Earth's mantle affects the dynamics of melting, volcanic eruption style and the evolution of Earth's atmosphere via planetary outgassing. Mantle carbon concentrations are difficult to quantify because most magmas are strongly degassed upon eruption. Here we report undegassed carbon concentrations from a new set of olivine-hosted melt inclusions from the Mid-Atlantic Ridge. We use the correlations of CO2 with trace elements to define an average carbon abundance for the upper mantle. Our results indicate that the upper mantle carbon content is highly heterogeneous, varying by almost two orders of magnitude globally, with the potential to produce large geographic variations in melt fraction below the volatile-free solidus. Such heterogeneity will manifest as variations in the depths at which melt becomes interconnected and detectable, the CO2 fluxes at mid-ocean ridges, the depth of the lithosphere-asthenosphere boundary, and mantle conductivity. PMID:28082738

Volcano-tectonic structures and CO2-degassing patterns in the Laacher See basin, Germany

NASA Astrophysics Data System (ADS)

Goepel, Andreas; Lonschinski, Martin; Viereck, Lothar; Büchel, Georg; Kukowski, Nina

2015-07-01

The Laacher See Volcano is the youngest (12,900 year BP) eruption center of the Quarternary East-Eifel Volcanic Field in Germany and has formed Laacher See, the largest volcanic lake in the Eifel area. New bathymetric data of Laacher See were acquired by an echo sounder system and merged with topographic light detection and ranging (LiDAR) data of the Laacher See Volcano area to form an integrated digital elevation model. This model provides detailed morphological information about the volcano basin and results of sediment transport therein. Morphological analysis of Laacher See Volcano indicates a steep inner crater wall (slope up to 30°) which opens to the south. The Laacher See basin is divided into a deep northern and a shallower southern part. The broader lower slopes inclined with up to 25° change to the almost flat central part (maximum water depth of 51 m) with a narrow transition zone. Erosion processes of the crater wall result in deposition of volcaniclastics as large deltas in the lake basin. A large subaqueous slide was identified at the northeastern part of the lake. CO2-degassing vents (wet mofettes) of Laacher See were identified by a single-beam echo sounder system through gas bubbles in the water column. These are more frequent in the northern part of the lake, where wet mofettes spread in a nearly circular-shaped pattern, tracing the crater rim of the northern eruption center of the Laacher See Volcano. Additionally, preferential paths for gas efflux distributed concentrically inside the crater rim are possibly related to volcano-tectonic faults. In the southern part of Laacher See, CO2 vents occur in a high spatial density only within the center of the arc-shaped structure Barschbuckel possibly tracing the conduit of a tuff ring.

Evidence for degassing of fresh magma during the 2004-2008 eruption of Mount St. Helens: Subtle signals from the hydrothermal system

USGS Publications Warehouse

Bergfeld, Deborah; Evans, William C.; Spicer, Kurt R.; Hunt, Andrew G.; Kelly, Peter

2017-01-01

Results from chemical and isotopic analyses of water and gas collected between 2002 and 2016 from sites on and around Mount St. Helens are used to assess magmatic degassing related to the 2004-2008 eruption. During 2005 the chemistry of hot springs in The Breach of Mount St. Helens showed no obvious response to the eruption, and over the next few years, changes were subtle, giving only slight indications of perturbations in the system. By 2010 however, water chemistry, temperatures, and isotope compositions (δD and δ18O) clearly indicated some inputs of volatiles and heat associated with the eruption, but the changes were such that they could be attributed to a pre-existing, gas depleted magma. An increase of ~ 1.5‰ in the δ13C values of dissolved carbon in the springs was noted in 2006 and continued through 2009, a change that was mirrored by a similar shift in δ13C-CO2 in bubble gas emissions. These changes require input of a new source of carbon to the hydrothermal system and provide clear evidence of CO2 from an undegassed body of magma. Rising trends in 3He/4He ratios in gas also accompanied the increases in δ13C. Since 2011 maximum RC/RA values are ≥ 6.4 and are distinctly higher than 5 samples collected between 1986 and 2002, and provide additional evidence for some involvement of new magma as early as 2006, and possibly earlier, given the unknown time needed for CO2 and He to traverse the system and arrive at the springs.

CO2 diffusion in champagne wines: a molecular dynamics study.

PubMed

Perret, Alexandre; Bonhommeau, David A; Liger-Belair, Gérard; Cours, Thibaud; Alijah, Alexander

2014-02-20

Although diffusion is considered as the main physical process responsible for the nucleation and growth of carbon dioxide bubbles in sparkling beverages, the role of each type of molecule in the diffusion process remains unclear. In the present study, we have used the TIP5P and SPC/E water models to perform force field molecular dynamics simulations of CO2 molecules in water and in a water/ethanol mixture respecting Champagne wine proportions. CO2 diffusion coefficients were computed by applying the generalized Fick's law for the determination of multicomponent diffusion coefficients, a law that simplifies to the standard Fick's law in the case of champagnes. The CO2 diffusion coefficients obtained in pure water and water/ethanol mixtures composed of TIP5P water molecules were always found to exceed the coefficients obtained in mixtures composed of SPC/E water molecules, a trend that was attributed to a larger propensity of SPC/E water molecules to form hydrogen bonds. Despite the fact that the SPC/E model is more accurate than the TIP5P model to compute water self-diffusion and CO2 diffusion in pure water, the diffusion coefficients of CO2 molecules in the water/ethanol mixture are in much better agreement with the experimental values of 1.4 - 1.5 × 10(-9) m(2)/s obtained for Champagne wines when the TIP5P model is employed. This difference was deemed to rely on the larger propensity of SPC/E water molecules to maintain the hydrogen-bonded network between water molecules and form new hydrogen bonds with ethanol, although statistical issues cannot be completely excluded. The remarkable agreement between the theoretical CO2 diffusion coefficients obtained within the TIP5P water/ethanol mixture and the experimental data specific to Champagne wines makes us infer that the diffusion coefficient in these emblematic hydroalcoholic sparkling beverages is expected to remain roughly constant whathever their proportions in sugars, glycerol, or peptides.

Effective diffusion coefficients of gas mixture in heavy oil under constant-pressure conditions

NASA Astrophysics Data System (ADS)

Li, Huazhou Andy; Sun, Huijuan; Yang, Daoyong

2017-05-01

We develop a method to determine the effective diffusion coefficient for each individual component of a gas mixture in a non-volatile liquid (e.g., heavy oil) at high pressures with compositional analysis. Theoretically, a multi-component one-way diffusion model is coupled with the volume-translated Peng-Robinson equation of state to quantify the mass transfer between gas and liquid (e.g., heavy oil). Experimentally, the diffusion tests have been conducted with a PVT setup for one pure CO2-heavy oil system and one C3H8-CO2-heavy oil system under constant temperature and pressure, respectively. Both the gas-phase volume and liquid-phase swelling effect are simultaneously recorded during the measurement. As for the C3H8-CO2-heavy oil system, the gas chromatography method is employed to measure compositions of the gas phase at the beginning and end of the diffusion measurement, respectively. The effective diffusion coefficients are then determined by minimizing the discrepancy between the measured and calculated gas-phase composition at the end of diffusion measurement. The newly developed technique can quantify the contributions of each component of mixture to the bulk mass transfer from gas into liquid. The effective diffusion coefficient of C3H8 in the C3H8-CO2 mixture at 3945 ± 20 kPa and 293.85 K, i.e., 18.19 × 10^{ - 10} {{m}}^{ 2} / {{s}}, is found to be much higher than CO2 at 3950 ± 18 kPa and 293.85 K, i.e., 8.68 × 10^{ - 10} {{m}}^{ 2} / {{s}}. In comparison with pure CO2, the presence of C3H8 in the C3H8-CO2 mixture contributes to a faster diffusion of CO2 from the gas phase into heavy oil and consequently a larger swelling factor of heavy oil.

Isotopic study of the origin of sulfur and carbon in Solfatara fumaroles, Campi Flegrei caldera

NASA Astrophysics Data System (ADS)

Allard, P.; Maiorani, A.; Tedesco, D.; Cortecci, G.; Turi, B.

1991-08-01

Isotopic study of the origin of sulfur and carbon in the hottest (Solfatara) fumaroles of Campi Flegrei caldera, Southern Italy, was carried out on gas samples collected between 1983 and 1988, i.e. during and after the 1982-1984 seismo-volcanic crisis. The results for sulfur (H 2S), the first ever reported on these gases, indicate a mean ∂ 34S of -0.3±0.3‰ (range: -0.7 to +0.1‰ ) versus Canyon Diablo Troilite standard, consistent with an igneous derivation of this element, from either active magma degassing or/and leaching of reduced sulfur-bearing minerals in the volcanic layers. The lack of peculiar ∂ 34S variation during and after the crisis suggests that the chemical variation of H 2S and S/C ratio in the fumaroles (increase and then decrease by a factor 3) were not due to a changing origin of sulfur. The mean ∂ 13C of carbon (CO 2) over the period of survey, -1.6±0.2‰ (range: -1.9 to -1.3‰) versus PDB standard, is similar to the values obtained before the crisis (since 1970). Such an isotopic constancy requires a large and stable source of carbon feeding the fumaroles. The measured ∂ 13C values are much higher than those typical of primary mantle-magmatic carbon ( -6±2‰) and plot within the ∂13C range for marine carbonates ( 0±2‰). Such high values may reflect either (a) 13C-fractionation during degassing of CO 2 from the underlying (⩽5 km depth) magma chamber or (b) the contribution of heavy CO 2 of sedimentary origin, derived from either thermometamorphism of Mesozoic limestone series embedding the magma chamber or, possibly, past contamination of the local mantle by subducted sediments. Various arguments, among which volcanological evidence of an isolated and cooling magma reservoir (which would have been extensively degassed and, so, depleted in 13C along with time), the low 3He/ 4He ratios and the broad 13C-enrichment of volcanic fluids in the region, and geochemical evidence of crust-magma fluid interactions, suggest that a considerable fraction (⩾60%) of CO 2 in Solfatara fumaroles derives from carbonate sediments in the basement. The contribution of magma-derived CO 2 may be higher within the central part of the caldera (including Solfatara crater) than toward its western margin, where fumarolic and geothermal well gases exhibit lower 3He/ 4He ratios and still higher ∂13C values. Such a geochemical pattern is consistent with the central distribution of ground deformation and seismicity during the 1982-1984 crisis and with the idea of a residual magma body, confined beneath the central part of the structure. Alternatively, higher ∂13C and lower 3He/ 4He ratios toward the western margin may result from dilution of Solfatara-type gas during progressively deeper water boiling. Finally, accepting that Solfatara CO 2 derives from simple crustal mixing between magmatic and sedimentary carbon, its constant isotopic composition (together with the constant He isotope ratio) would restrict the possibility of magma intrusion and/or higher magmatic gas input as mechanisms responsible for the 1982-1984 events. However, this conclusion would no more hold true if the magma itself, or even its mantle source, were previously contaminated by crustal carbon.

Assessing the health risks of natural CO2 seeps in Italy

PubMed Central

Roberts, Jennifer J.; Wood, Rachel A.; Haszeldine, R. Stuart

2011-01-01

Industrialized societies which continue to use fossil fuel energy sources are considering adoption of Carbon Capture and Storage (CCS) technology to meet carbon emission reduction targets. Deep geological storage of CO2 onshore faces opposition regarding potential health effects of CO2 leakage from storage sites. There is no experience of commercial scale CCS with which to verify predicted risks of engineered storage failure. Studying risk from natural CO2 seeps can guide assessment of potential health risks from leaking onshore CO2 stores. Italy and Sicily are regions of intense natural CO2 degassing from surface seeps. These seeps exhibit a variety of expressions, characteristics (e.g., temperature/flux), and location environments. Here we quantify historical fatalities from CO2 poisoning using a database of 286 natural CO2 seeps in Italy and Sicily. We find that risk of human death is strongly influenced by seep surface expression, local conditions (e.g., topography and wind speed), CO2 flux, and human behavior. Risk of accidental human death from these CO2 seeps is calculated to be 10-8 year-1 to the exposed population. This value is significantly lower than that of many socially accepted risks. Seepage from future storage sites is modeled to be less that Italian natural flux rates. With appropriate hazard management, health risks from unplanned seepage at onshore storage sites can be adequately minimized. PMID:21911398

Swarm intelligence application for optimization of CO2 diffusivity in polystyrene-b-polybutadiene-b-polystyrene (SEBS) foaming

NASA Astrophysics Data System (ADS)

Sharudin, Rahida Wati; Ajib, Norshawalina Muhamad; Yusoff, Marina; Ahmad, Mohd Aizad

2017-12-01

Thermoplastic elastomer SEBS foams were prepared by using carbon dioxide (CO2) as a blowing agent and the process is classified as physical foaming method. During the foaming process, the diffusivity of CO2 need to be controlled since it is one of the parameter that will affect the final cellular structure of the foam. Conventionally, the rate of CO2 diffusion was measured experimentally by using a highly sensitive device called magnetic suspension balance (MSB). Besides, this expensive MSB machine is not easily available and measurement of CO2 diffusivity is quite complicated as well as time consuming process. Thus, to overcome these limitations, a computational method was introduced. Particle Swarm Optimization (PSO) is a part of Swarm Intelligence system which acts as a beneficial optimization tool where it can solve most of nonlinear complications. PSO model was developed for predicting the optimum foaming temperature and CO2 diffusion rate in SEBS foam. Results obtained by PSO model are compared with experimental results for CO2 diffusivity at various foaming temperature. It is shown that predicted optimum foaming temperature at 154.6 °C was not represented the best temperature for foaming as the cellular structure of SEBS foamed at corresponding temperature consisted pores with unstable dimension and the structure was not visibly perceived due to foam shrinkage. The predictions were not agreed well with experimental result when single parameter of CO2 diffusivity is considered in PSO model because it is not the only factor that affected the controllability of foam shrinkage. The modification on the PSO model by considering CO2 solubility and rigidity of SEBS as additional parameters needs to be done for obtaining the optimum temperature for SEBS foaming. Hence stable SEBS foam could be prepared.

New ground-based lidar enables volcanic CO2 flux measurements.

PubMed

Aiuppa, Alessandro; Fiorani, Luca; Santoro, Simone; Parracino, Stefano; Nuvoli, Marcello; Chiodini, Giovanni; Minopoli, Carmine; Tamburello, Giancarlo

2015-09-01

There have been substantial advances in the ability to monitor the activity of hazardous volcanoes in recent decades. However, obtaining early warning of eruptions remains challenging, because the patterns and consequences of volcanic unrests are both complex and nonlinear. Measuring volcanic gases has long been a key aspect of volcano monitoring since these mobile fluids should reach the surface long before the magma. There has been considerable progress in methods for remote and in-situ gas sensing, but measuring the flux of volcanic CO2-the most reliable gas precursor to an eruption-has remained a challenge. Here we report on the first direct quantitative measurements of the volcanic CO2 flux using a newly designed differential absorption lidar (DIAL), which were performed at the restless Campi Flegrei volcano. We show that DIAL makes it possible to remotely obtain volcanic CO2 flux time series with a high temporal resolution (tens of minutes) and accuracy (<30%). The ability of this lidar to remotely sense volcanic CO2 represents a major step forward in volcano monitoring, and will contribute improved volcanic CO2 flux inventories. Our results also demonstrate the unusually strong degassing behavior of Campi Flegrei fumaroles in the current ongoing state of unrest.

CO2 and H2O Contents of Melt Inclusions from the 1891 Basaltic Balloon Eruption of Foerstner Submarine Volcano, Italy

NASA Astrophysics Data System (ADS)

Balcanoff, J. R.; Carey, S.; Kelley, K. A.; Boesenberg, J. S.

2016-12-01

Eruptions that produce basaltic balloon products are an uncommon eruption style only observed in five cases during historical times. Basaltic balloon products form in gas rich shallow submarine eruptions, which produce large hollow clasts with sufficient buoyancy to float on seawater. Foerstner submarine volcano, off the coast of Pantelleria (Italy), erupted with this style in 1891 and is the only eruption where the vent site (250 m water depth) has been studied and sampled in detail with remotely operated vehicles (ROVs). Here, we report Fournier Transform Infrared Spectroscopy (FTIR) and electron microprobe (EMP) analyses of major elements and dissolved volatiles in melt inclusions from olivine and plagioclase phenocrysts picked from highly vesicular clasts recovered from the seafloor. The trachybasaltic melt is enriched in alkalis with notably high phosphorus (1.82-2.38 wt%), and melt inclusions show elevated H2O concentrations of 0.17 to 1.2 wt.% and highly elevated CO2 concentrations of 928 to 1864 ppm. Coexisting matrix glass is completely degassed with respect to carbon dioxide but has variable water contents up to 0.19 %. The maximum carbon dioxide value implies saturation at 1.5 kb, or 4.5 km below the volcano. Trends in the CO2 and H2O data are most compatible with calculated open system degassing behavior. This is consistent with a proposed balloon formation mechanism involving a hybrid strombolian eruption style with the potential accumulation of gas-rich pockets below the vent as gas bubbles moved upwards independent of the low viscosity basaltic melt. Discharge of the gas-rich pockets led to the discharge of meter-sized slugs of magma with large internal vesicles (several tens of centimeters). A subset of these clasts had bulk densities that were lower than seawater, allowing them to rise to the sea surface where they either exploded or became water saturated and sank back to the seafloor.

Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond.

PubMed

Li, Li; Yang, Deshuai; Fisher, Trevor R; Qiao, Qi; Yang, Zhen; Hu, Na; Chen, Xiangshu; Huang, Liangliang

2017-10-24

The loading-dependent diffusion behavior of CH 4 , CO 2 , SO 2 , and their binary mixtures in ZIF-10 has been investigated in detail by using classical molecular dynamics simulations. Our simulation results demonstrate that the self-diffusion coefficient D i of CH 4 molecules decreases sharply and monotonically with the loading while those of both CO 2 and SO 2 molecules initially display a slight increase at low uptakes and follow a slow decrease at high uptakes. Accordingly, the interaction energies between CH 4 molecules and ZIF-10 remain nearly constant regardless of the loading due to the absence of hydrogen bonds (HBs), while the interaction energies between CO 2 (or SO 2 ) and ZIF-10 decease rapidly with the loading, especially at small amounts of gas molecules. Such different loading-dependent diffusion and interaction mechanisms can be attributed to the relevant HB behavior between gas molecules and ZIF-10. At low loadings, both the number and strength of HBs between CO 2 (or SO 2 ) molecules and ZIF-10 decrease obviously as the loading increases, which is responsible for the slight increase of their diffusion coefficients. However, at high loadings, their HB strength increases with the loading. Similar loading-dependent phenomena of diffusion, interaction, and HB behavior can be observed for CH 4, CO 2 , and SO 2 binary mixtures in ZIF-10, only associated with some HB competition between CO 2 and SO 2 molecules in the case of the CO 2 /SO 2 mixture.

Carbon dioxide partial pressure and 13C content of north temperate and boreal lakes at spring ice melt

USGS Publications Warehouse

Striegl, Robert G.; Kortelainen, Pirkko; Chanton, J.P.; Wickland, K.P.; Bugna, G.C.; Rantakari, M.

2001-01-01

Carbon dioxide (CO2) accumulates under lake ice in winter and degasses to the atmosphere after ice melt. This large springtime CO2 pulse is not typically considered in surface-atmosphere flux estimates, because most field studies have not sampled through ice during late winter. Measured CO2 partial pressure (pCO2) of lake surface water ranged from 8.6 to 4,290 Pa (85-4,230 ??atm) in 234 north temperate and boreal lakes prior to ice melt during 1998 and 1999. Only four lakes had surface pCO2 less than or equal to atmospheric pCO2, whereas 75% had pCO2 >5 times atmospheric. The ??13CDIC (DIC = ??CO2) of 142 of the lakes ranged from -26.28??? to +0.95.???. Lakes with the greatest pCO2 also had the lightest ??13CDIC, which indicates respiration as their primary CO2 source. Finnish lakes that received large amounts of dissolved organic carbon from surrounding peatlands had the greatest pCO2. Lakes set in noncarbonate till and bedrock in Minnesota and Wisconsin had the smallest pCO2 and the heaviest ??13CDIC, which indicates atmospheric and/or mineral sources of C for those lakes. Potential emissions for the period after ice melt were 2.36 ?? 1.44 mol CO2 m-2 for lakes with average pCO2 values and were as large as 13.7 ?? 8.4 mol CO2 m-2 for lakes with high pCO2 values.

Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

NASA Astrophysics Data System (ADS)

Hartley, Margaret E.; Shorttle, Oliver; Maclennan, John; Moussallam, Yves; Edmonds, Marie

2017-12-01

The redox state of volcanic products determines their leverage on the oxidation of Earth's oceans and atmosphere, providing a long-term feedback on oxygen accumulation at the planet's surface. An archive of redox conditions in volcanic plumbing systems from a magma's mantle source, through crustal storage, to eruption, is carried in pockets of melt trapped within crystals. While melt inclusions have long been exploited for their capacity to retain information on a magma's history, their permeability to fast-diffusing elements such as hydrogen is now well documented and their retention of initial oxygen fugacities (fO2) could be similarly diffusion-limited. To test this, we have measured Fe3+/ΣFe by micro-XANES spectroscopy in a suite of 65 olivine-hosted melt inclusions and 9 matrix glasses from the AD 1783 Laki eruption, Iceland. This eruption experienced pre-eruptive mixing of chemically diverse magmas, syn-eruptive degassing at the vent, and post-eruptive degassing during lava flow up to 60 km over land, providing an ideal test of whether changes in the fO2 of a magma may be communicated through to its cargo of crystal-hosted melt inclusions. Melt inclusions from rapidly quenched tephra samples have Fe3+/ΣFe of 0.206 ± 0.008 (ΔQFM of +0.7 ± 0.1), with no correlation between their fO2 and degree of trace element enrichment or differentiation. These inclusions preserve the redox conditions of the mixed pre-eruptive Laki magma. When corrected for fractional crystallisation to 10 wt.% MgO, these inclusions record a parental magma [Fe3+/ΣFe](10) of 0.18 (ΔQFM of +0.4), significantly more oxidised than the Fe3+/ΣFe of 0.10 that is often assumed for Icelandic basalt magmas. Melt inclusions from quenched lava selvages are more reduced than those from the tephra, having Fe3+/ΣFe between 0.133 and 0.177 (ΔQFM from -0.4 to +0.4). These inclusions have approached equilibrium with their carrier lava, which has been reduced by sulfur degassing. The progressive re-equilibration of fO2 between inclusions and carrier melts occurs on timescales of hours to days, causing a drop in the sulfur content at sulfide saturation (SCSS) and driving the exsolution of immiscible sulfide globules in the inclusions. Our data demonstrate the roles of magma mixing, progressive re-equilibration, and degassing in redox evolution within magmatic systems, and the open-system nature of melt inclusions to fO2 during these processes. Redox heterogeneity present at the time of inclusion trapping may be overprinted by rapid re-equilibration of melt inclusion fO2 with the external environment, both in the magma chamber and during slow cooling in lava at the surface. This can decouple the melt inclusion archives of fO2, major and trace element chemistry, and mask associations between fO2, magmatic differentiation and mantle source heterogeneity unless the assembly of diverse magmas is rapidly followed by eruption. Our tools for understanding the redox conditions of magmas are thus limited; however, careful reconstruction of pre- and post-eruptive magmatic history has enabled us to confirm the relatively oxidised nature of ocean island-type mantle compared to that of mid-ocean ridge mantle.

Evaluation of Electroplated Co-P Film as Diffusion Barrier Between In-48Sn Solder and SiC-Dispersed Bi2Te3 Thermoelectric Material

NASA Astrophysics Data System (ADS)

Li, Siyang; Yang, Donghua; Tan, Qing; Li, Liangliang

2015-06-01

The diffusion barrier property of Co-P film as a buffer layer between SiC-dispersed Bi2Te3 bulk material and In-48Sn solder was investigated. A Co-P film with thickness of ~6 µm was electroplated on SiC-dispersed Bi2Te3 substrate, joined with In-48Sn solder by a reflow process, and annealed at 100°C for up to 625 h. The formation and growth kinetics of intermetallic compounds (IMCs) at the interface between the In-48Sn and substrate were studied using transmission electron microscopy and scanning electron microscopy with energy-dispersive x-ray spectroscopy. The results showed that crystalline Co(In,Sn)3 formed as an irregular layer adjacent to the solder side at the solder/Co-P interface due to diffusion of Co towards the solder, and a small amount of amorphous Co45P13In12Sn30 appeared at the Co-P side because of diffusion of In and Sn into Co-P. The growth of Co(In,Sn)3 and Co45P13In12Sn30 during solid-state aging was slow, being controlled by interfacial reaction and diffusion, respectively. For comparison, In-48Sn/Bi2Te3-SiC joints were prepared and the IMCs in the joints analyzed. Without a diffusion barrier, In penetrated rapidly into the substrate, which led to the formation of amorphous In x Bi y phase in crystalline In4Te3 matrix. These IMCs grew quickly with prolongation of the annealing time, and their growth was governed by volume diffusion of elements. The experimental data demonstrate that electroplated Co-P film is an effective diffusion barrier for use in Bi2Te3-based thermoelectric modules.

Ultrafast syn-eruptive degassing and ascent trigger high-energy basic eruptions.

PubMed

Giuffrida, Marisa; Viccaro, Marco; Ottolini, Luisa

2018-01-09

Lithium gradients in plagioclase are capable of recording extremely short-lived processes associated with gas loss from magmas prior to extrusion at the surface. We present SIMS profiles of the 7 Li/ 30 Si ion ratio in plagioclase crystals from products of the paroxysmal sequence that occurred in the period 2011-2013 at Mt. Etna (Italy) in an attempt to constrain the final ascent and degassing processes leading to these powerful eruptions involving basic magma. The observed Li concentrations reflect cycles of Li addition to the melt through gas flushing, and a syn-eruptive stage of magma degassing driven by decompression that finally produce significant Li depletion from the melt. Modeling the decreases in Li concentration in plagioclase by diffusion allowed determination of magma ascent timescales that are on the order of minutes or less. Knowledge of the storage depth beneath the volcano has led to the quantification of a mean magma ascent velocity of ~43 m/s for paroxysmal eruptions at Etna. The importance of these results relies on the application of methods, recently used exclusively for closed-system volcanoes producing violent eruptions, to open-conduit systems that have generally quiet eruptive periods of activity sometimes interrupted by sudden re-awakening and the production of anomalously energetic eruptions.

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth’s oxygenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brounce, Maryjo; Stolper, Edward; Eiler, John

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The leastmore » degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.« less

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth's oxygenation.

PubMed

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-22

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity ( f O 2 ). Volcanic degassing is a source of these elements to Earth's surface; therefore, variations in mantle f O 2 may influence the f O 2 at Earth's surface. However, degassing can impact magmatic f O 2 before or during eruption, potentially obscuring relationships between the f O 2 of the solid Earth and of emitted gases and their impact on surface f O 2 We show that low-pressure degassing resulted in reduction of the f O 2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher f O 2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower f O 2 than modern magmas. Estimates of f O 2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth’s oxygenation

PubMed Central

Stolper, Edward; Eiler, John

2017-01-01

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere. PMID:28784788

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth's oxygenation

NASA Astrophysics Data System (ADS)

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-01

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

USGS Publications Warehouse

Newman, S.; Lowenstern, J. B.

2002-01-01

We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

NASA Astrophysics Data System (ADS)

Newman, Sally; Lowenstern, Jacob B.

2002-06-01

We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

Experimental evidence for carbonate precipitation and CO 2 degassing during sea ice formation

NASA Astrophysics Data System (ADS)

Papadimitriou, S.; Kennedy, H.; Kattner, G.; Dieckmann, G. S.; Thomas, D. N.

2004-04-01

Chemical and stable carbon isotopic modifications during the freezing of artificial seawater were measured in four 4 m 3 tank incubations. Three of the four incubations were inoculated with a nonaxenic Antarctic diatom culture. The 18 days of freezing resulted in 25 to 27 cm thick ice sheets overlying the residual seawater. The ice phase was characterized by a decrease in temperature from -1.9 to -2.2°C in the under-ice seawater down to -6.7°C in the upper 4 cm of the ice sheet, with a concurrent increase in the salinity of the under-ice seawater and brine inclusions of the ice sheet as a result of physical concentration of major dissolved salts by expulsion from the solid ice matrix. Measurements of pH, total dissolved inorganic carbon (C T) and its stable isotopic composition (δ 13C T) all exhibited changes, which suggest minimal effect by biological activity during the experiment. A systematic drop in pH and salinity-normalized C T by up to 0.37 pH SWS units and 376 μmol C kg -1 respectively at the lowest temperature and highest salinity part of the ice sheet were coupled with an equally systematic 13C enrichment of the C T. Calculations based on the direct pH and C T measurements indicated a steady increase in the in situ concentration of dissolved carbon dioxide (CO 2(aq)) with time and increasing salinity within the ice sheet, partly due to changes in the dissociation constants of carbonic acid in the low temperature-high salinity range within sea ice. The combined effects of temperature and salinity on the solubility of CO 2 over the range of conditions encountered during this study was a slight net decrease in the equilibrium CO 2(aq) concentration as a result of the salting-out overriding the increase in solubility with decreasing temperature. Hence, the increase in the in situ CO 2(aq) concentration lead to saturation or supersaturation of the brine inclusions in the ice sheet with respect to atmospheric pCO 2 (≈3.5 × 10 -4 atm). When all physico-chemical processes are considered, we expect CO 2 degassing and carbonate mineral precipitation from the brine inclusions of the ice sheet, which were saturated or highly supersaturated with respect to both the anhydrous (calcite, aragonite, vaterite) and hydrated (ikaite) carbonate minerals.

The role of residual (undegassed) and environmental waters in pyroclastic volcanic glass in nature and experiments (Invited)

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Seligman, A. N.; Nolan, G. S.; Lundstrom, C.; Martin, E.; Lowenstern, J. B.; Palandri, J. L.

2013-12-01

The advent and calibration of the Thermal Combustion Element Analyzer (TCEA) continuous flow system coupled with the large-radius mass spectrometer, at the University of Oregon, permits precise (×0.02 wt.% H2O, ×1-3‰ D/H) measurements in 1-10 mg of volcanic glass (0.1 wt.% H2O requires ~10 mg glass). This is a 10-100 time reduction in sample size over previous methods, which permits the targeting of small amounts of the freshest concentrate. In combination with the FTIR, we use the TCEA to research problems involving the mechanisms and timescales of volcanic ash hydration on both natural and laboratory timescales using isotopically-labeled water, D/H-H2O pathways of volcanic degassing, water content and D/H in recently erupted volcanic ash, and the mechanisms of tephra-hydration by isotopically-distinct rain and glacial meltwaters. The talk will review new results: 1) Water content determined by FTIR (OH and H2O) and TCEA give excellent correspondence for basaltic and rhyolitic glasses, including FTIR measurements for irregular ash particles mixed in equal proportion with KBr and molded into pellets. 2) Nominally-anhydrous (<0.1-0.2 wt.% water) volcanic ash actually contains appreciable 'undegassed', variably low-δD water (up to ~0.6 wt.%). 3) Long term exposure experiments involving ash placed in isotopically-labeled water does not lead to water uptake or δ18O exchange at 20, 40, or 70 °C over two years of laboratory exposure, but does involve up to 15% deuterium exchange relative to the full exchange equilibria. This provides a word of caution in using δD values of ash as a paleoenvironmental tool. 4) Degassing of environmentally-hydrated ash (4 wt.% water) leads to neglegeable δD exchange, signifying nearly zero-fractionation upon loss of predominantly H2Omol water. 5) Glacial vs. intergacial water can be recognized in hydrated glasses. 6) Subaqueous perlites from Yellowstone have an onion-skin distribution of water with water-poor cores, as determined by the scanning FTIR technique. 7) Thermal diffusion experiments achieve up to a 144‰ range in δD across a 300-600°C temperature change; this has implications for explaining natural variations in δD in high temperature environments due to high diffusivity of hydrogen. 8) We report results of δ18O in extracted water in glass and discuss isotopic offsets due to incomplete oxygen extraction from OH groups. 9) We apply these methods to submarine glasses, and degassing tephra products of the same eruption.

Gas composition of the January 1983 eruption of Kilauea Volcano, Hawaii

USGS Publications Warehouse

Greenland, L.P.

1984-01-01

Gas collections were made from a ???900??C vent both by conventional evacuated-bottle/wet-chemical techniques and by manual pumping of flowthrough bottles. The complete analyses suggest an equilibrium assemblage quenched at 1,010??C, about midway between fountain and vent temperatures. I suggest that the very low C S ratio is due to degassing of CO2 during storage of the magma in a shallow reservoir before eruption. The two sampling techniques yielded analytical data in mutual agreement. ?? 1984.

The History of Exosphere Carbon Storage and Consequences for Mantle-Exosphere Volatile Fluxes

NASA Astrophysics Data System (ADS)

Hirschmann, M. M.

2009-05-01

The storage of volatiles in the mantle and their fluxes between the mantle and the near surface environment (exosphere) are constrained in part from the history of volatile storage in the exosphere. Evidence for the early formation of the oceans indicates extensive initial degassing of the mantle, but raises the question as to the fate of the carbon that must have been degassed with the H2O. Long-term storage of carbon in the exosphere is thought to require large continental areas, as carbon in the oceanic domain is rapidly returned to the mantle. Consequently, early degassing of the mantle may have been followed by rapid massive return of carbon to the mantle via subduction, leading to very high H/C ratios in the early exosphere. Alternatively, the C may have been lost to space by impact ablation of a Venus-like CO2-rich atmosphere. Less plausibly, the C could have remained in the exosphere stored in the oceanic domain but somehow escaping recyling to the mantle. Assuming that exosphere carbon storage was in fact limited by continental area, gradual regrowth of the carbon exosphere budget would then parallel that of growth of the continents. Interestingly, this suggests that the relatively high H/C ratio of the modern exosphere compared to the mantle (Hirschmann and Dasgupta, 2009), is a remnant of very early Earth processes which have not been erased by subsequent volatile fluxes. A key problem with this scenario, however, is that the gradual regrowth of the exosphere carbon budget cannot have occurred with parallel growth of the exosphere H2O budget. Otherwise, there would have been substantial growth of the oceans coinciding with continental growth, which violates constraints from continental freeboard. This requires either that outgassing of carbon exceeded that of H2O, or that H2O subduction has been more efficient than CO2 subduction. The former is unlikely unless typical degrees of melting are very small. On the other hand, petrologic constraints generally suggest that carbon subduction is more efficient than H2O subduction. One possible explanation is that hotter Archean subduction zones effectively stripped carbon from subducting slabs, thereby facilitating growth of the exosphere carbon budget.

Highly CO2-supersaturated melts in the Pannonian lithospheric mantle - A transient carbon reservoir?

NASA Astrophysics Data System (ADS)

Créon, Laura; Rouchon, Virgile; Youssef, Souhail; Rosenberg, Elisabeth; Delpech, Guillaume; Szabó, Csaba; Remusat, Laurent; Mostefaoui, Smail; Asimow, Paul D.; Antoshechkina, Paula M.; Ghiorso, Mark S.; Boller, Elodie; Guyot, François

2017-08-01

Subduction of carbonated crust is widely believed to generate a flux of carbon into the base of the continental lithospheric mantle, which in turn is the likely source of widespread volcanic and non-volcanic CO2 degassing in active tectonic intracontinental settings such as rifts, continental margin arcs and back-arc domains. However, the magnitude of the carbon flux through the lithosphere and the budget of stored carbon held within the lithospheric reservoir are both poorly known. We provide new constraints on the CO2 budget of the lithospheric mantle below the Pannonian Basin (Central Europe) through the study of a suite of xenoliths from the Bakony-Balaton Highland Volcanic Field. Trails of secondary fluid inclusions, silicate melt inclusions, networks of melt veins, and melt pockets with large and abundant vesicles provide numerous lines of evidence that mantle metasomatism affected the lithosphere beneath this region. We obtain a quantitative estimate of the CO2 budget of the mantle below the Pannonian Basin using a combination of innovative analytical and modeling approaches: (1) synchrotron X-ray microtomography, (2) NanoSIMS, Raman spectroscopy and microthermometry, and (3) thermodynamic models (Rhyolite-MELTS). The three-dimensional volumes reconstructed from synchrotron X-ray microtomography allow us to quantify the proportions of all petrographic phases in the samples and to visualize their textural relationships. The concentration of CO2 in glass veins and pockets ranges from 0.27 to 0.96 wt.%, higher than in typical arc magmas (0-0.25 wt.% CO2), whereas the H2O concentration ranges from 0.54 to 4.25 wt.%, on the low end for estimated primitive arc magmas (1.9-6.3 wt.% H2O). Trapping pressures for vesicles were determined by comparing CO2 concentrations in glass to CO2 saturation as a function of pressure in silicate melts, suggesting pressures between 0.69 to 1.78 GPa. These values are generally higher than trapping pressures for fluid inclusions determined by Raman spectroscopy and microthermometry (0.1-1.1 GPa). The CO2/silicate melt mass ratios in the metasomatic agent that percolated through the lithospheric mantle below the Pannonian Basin are estimated to be between 9.0 and 25.4 wt.%, values consistent with metasomatism either by (1) silicate melts already supersaturated in CO2 before reaching lithospheric depths or (2) carbonatite melts that interacted with mantle peridotite to generate carbonated silicic melts. Taking the geodynamical context of the Pannonian Basin and our calculations of the CO2/silicate melt mass ratios in the metasomatic agent into account, we suggest that slab-derived melts initially containing up to 25 wt.% of CO2 migrated into the lithospheric mantle and exsolved CO2-rich fluid that became trapped in secondary fluid inclusions upon fracturing of the peridotite mineral matrix. We propose a first-order estimate of 2000 ppm as the minimal bulk CO2 concentration in the lithospheric mantle below the Pannonian Basin. This transient carbon reservoir is believed to be degassed through the Pannonian Basin due to volcanism and tectonic events, mostly focused along the lithospheric-scale regional Mid-Hungarian shear Zone.

Degassing of metals and metalloids from erupting seamount and mid-ocean ridge volcanoes: Observations and predictions

NASA Astrophysics Data System (ADS)

Rubin, Ken

1997-09-01

Recently, it has been reported that the element polonium degasses from mid-ocean ridge and seamount volcanoes during eruptions. Published and new observations on other volatile metal and metalloid elements can also be interpreted as indicating significant degassing of magmatic vapors during submarine eruptions. This process potentially plays an important role in the net transfer of chemical elements from erupting volcanoes to seawater in addition to that arising from sea floor hydrothermal systems. In this paper, a framework is constructed for predicting and assessing semiquantitatively the potential magnitude and chemical fingerprints in the water column of metal and metalloid degassing using (1) predictions from a summary of element volatilities during mafic subaerial volcanism worldwide and (2) limited data from submarine volcanic effusives. The latter include analyses of polonium and trace metals in near-volcano water masses sampled following a submarine eruption at Loihi seamount, Hawaii (1000 m bsl) in 1996. The element volatility predictions and observations show good agreement, considering the limited dataset. Some of the highest volatility main group and transition element enrichments in seawater over Loihi are predicted by the degassing mass transfer model I present. When expanded to cover all submarine volcanic activity, it is predicted that exit fluxes of these elements are up to 10 2-10 3 greater by degassing than by normal MOR hydrothermalism. In contrast, MOR exit fluxes of low volatility alkali and alkaline earth elements are likely 10 2-10 6 greater from hydrothermal inputs. Degassing inputs to the ocean are probably highly episodic, occurring almost entirely during eruptions; these are times of enhanced and abnormal hydrothermalism as well. Although major hydrothermal and degassing events may not be chemically recognizable in real water masses as wholly distinct entities, it is nevertheless possible to predict to what extent each process flavors the effluents of the other. Degassing at mid-ocean ridges may explain a variety of observations previously ascribed to complexities occurring during hydrothermal venting and/or fluid ascent in the buoyant hydrothermal plumes above ridges.

Selectivity and self-diffusion of CO2 and H2 in a mixture on a graphite surface

PubMed Central

Trinh, Thuat T.; Vlugt, Thijs J. H.; Hägg, May-Britt; Bedeaux, Dick; Kjelstrup, Signe

2013-01-01

We performed classical molecular dynamics (MD) simulations to understand the mechanism of adsorption from a gas mixture of CO2 and H2 (mole fraction of CO2 = 0.30) and diffusion along a graphite surface, with the aim to help enrich industrial off-gases in CO2, separating out H2. The temperature of the system in the simulation covered typical industrial conditions for off-gas treatment (250–550 K). The interaction energy of single molecules CO2 or H2 on graphite surface was calculated with classical force fields (FFs) and with Density Functional Theory (DFT). The results were in good agreement. The binding energy of CO2 on graphite surface is three times larger than that of H2. At lower temperatures, the selectivity of CO2 over H2 is five times larger than at higher temperatures. The position of the dividing surface was used to explain how the adsorption varies with pore size. In the temperature range studied, the self-diffusion coefficient of CO2 is always smaller than of H2. The temperature variation of the selectivities and the self-diffusion coefficient imply that the carbon molecular sieve membrane can be used for gas enrichment of CO2. PMID:24790965

Continental degassing of 4He by surficial discharge of deep groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aggarwal, Pradeep K.; Matsumoto, Takuya; Sturchio, Neil C.

2014-12-01

Radiogenic He-4 is produced by the decay of uranium and thorium in the Earths mantle and crust. From here, it is degassed to the atmosphere(1-5) and eventually escapes to space(1,5,6). Assuming that all of the He-4 produced is degassed, about 70% of the total He-4 degassed from Earth comes from the continental crust(2,-5,7). However, the outgoing flux of crustal He-4 has not been directly measured at the Earths surface(2) and the migration pathways are poorly understood(2-4,7,8). Here we present measurements of helium isotopes and the long-lived cosmogenic radio-isotope Kr-81 in the deep, continental-scale Guarani aquifer in Brazil and show thatmore » crustal He-4 reaches the atmosphere primarily by the surficial discharge of deep groundwater. We estimate that He-4 in Guarani groundwater discharge accounts for about 20% of the assumed global flux from continental crust, and that other large aquifers may account for about 33%. Old groundwater ages suggest that He-4 in the Guarani aquifer accumulates over half- to one-million-year timescales. We conclude that He-4 degassing from the continents is regulated by groundwater discharge, rather than episodic tectonic events, and suggest that the assumed steady state between crustal production and degassing of He-4, and its resulting atmospheric residence time, should be re-examined« less

Surprisingly rich in H2O Soils of Mars: a Consequence of mild Degassing

NASA Astrophysics Data System (ADS)

Kochemasov, G. G.

2003-04-01

SURPRISINGLY RICH IN H2O SOILS OF MARS: A CONSEQUENCE OF MILD DEGASSING G.Kochemasov, IGEM RAS, 35 Staromonetny, Moscow 119017, kochem@igem.ru The wave planetology [1, 2] connects principal structural characteristics of celestial bodies with their orbital properties (ellipticities &orbital frequencies). In this respect terrestrial planets Venus, Earth, Mars are suitable for comparisons not only of solid bodies structures but also of their gaseous envelopes. Their atmospheric structures closely follow structures of their solid spheres [2]: tectonic granulations in all spheres depend on the planets' orbital frequencies: 1/0.62 y - 1/1 y - ? y. Granula sizes are pR/6, pR/4, pR/2, thus Venus is fine-grained, Earth medium-grained, Mars coarse-grained. Longer orbital periods -coarser tectonic granulas -slower wave oscillations. Finer tectonic structures -more frequent oscillations -more complete degassing. Three planets confirm this conclusion. Venus is covered with a thick dense atmosphere, Mars possesses very weak transparent one, Earth is in the middle. Venus is more thoroughly shaken out and released of its volatiles than Earth &Mars. This is proved also by a large amount if nitrogen in its CO2-atmosphere and by a very low ratio in it of radiogenic to primordial Ar (Venus 1, Earth 300, Mars 3000 [3]). Compare "sweeping" volatiles out of the planets. In a sphere of radius R there are 55.7 grains of radius pR/12 (Venus), 16.5 grains of radius pR/8 (Earth), 2.06 grains of radius pR/4 (Mars). Venus is 3.38 times finer-grained than Earth and 27.04 times than Mars. Venusian wavelength 6000 km (pR/3) gives frequency 0.07 khz, terrestrial wavelength 10000 km (pR/2) gives 0.03 khz, martian 10660 km (pR/1) 0.025 khz. Venusian oscillations 2.33 times more frequent than terrestrial ones and 2.8 times more frequent than martian ones. If planets outgassing is proportional to the square (outgassing goes through surface) of the production of granulation and oscillation frequency, then Venus is 62 times more outgassed than Earth [(3.38 x 2.33)2=62.1] and 5732 times more outgassed than Mars [(27.04 x 2.8)2=5732.3]. Taking into account the smaller martian mass (1/10 of E. &M.) one would expect this outgassing difference to be 5732 x 10=57320 times. Actually venusian atmosphere is 90 times more massive than terrestrial one and ~ 18000 times than martian one. A rather high discrepancy between V &M (actually 18000, calculated 57320) is probably due to high amounts of frozen CO2 &H2O (Odyssey data) in near-surface layers constantly supplying volatiles into atmosphere, but basic reason is probably in the higher ellipticity of the martian orbit promoting volatile sweeping. So, Mars is slighter degassed than Earth &Venus. Ref.: [1] Kochemasov G.G. (1999) Geophys. Res. Abstr., v.1, #3,700; [2] Ibid.(2002) 36th Vernadsky-Brown microsymp. "Topics in Comparative Planetology", Moscow, Abstr., CD-ROM; [3]Pollack J.B., Black D.C. (1979) Science, v. 205, # 4401, 56-59.

Diffusion coefficients significant in modeling the absorption rate of carbon dioxide into aqueous blends of N-methyldiethanolamine and diethanolamine and of hydrogen sulfide into aqueous N-methyldiethanolamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, M.E.; Marshall, T.L.; Rowley, R.L.

1998-07-01

Absorption rates of gaseous CO{sub 2} into aqueous blends of N-methyldiethanolamine (MDEA) and diethanolamine (DEA) and of gaseous H{sub 2}S into aqueous MDEA were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. A numerical model for absorption, diffusion, and reaction of CO{sub 2} and H{sub 2}S in blends of MDEA, DEA, and water was developed. The model was used to regress diffusion coefficients of bicarbonate, carbamate, and MDEAH{sub 2}CO{sub 3} for the case of CO{sub 2} absorption and of bisulfide ion for the case of H{sub 2}S absorption from measured absorption rates. CO{sub 2} absorptionmore » rates and diffusion coefficients of bicarbonate, carbamate, and MDEAH{sub 2}CO{sub 3} were obtained at 298.2 K and 318.2 K in aqueous solutions containing 50 mass % total amine at DEA:MDEA mole ratios of 1:20, 1:4, 1L3, and 2:3. H{sub 2}S absorption rates and diffusion coefficients of bisulfide ion were obtained at 298.2 K and 318.2 K in aqueous solutions containing 20, 35, and 50 mass % MDEA.« less

The flight of Arcadia: spatial CO2/SO2 variations in a cross section above the Nord East crater of Etna volcano

NASA Astrophysics Data System (ADS)

Giuffrida, Giovanni; Calabrese, Sergio; Bobrowski, Nicole; Finkenzeller, Henning; Pecoraino, Giovannella; Scaglione, Sarah

2015-04-01

The CO2/SO2 ratio in volcanic plumes of open conduit volcanoes can provide useful information about the magma depth inside a conduit and the possible occurrence of an eruptive event. Moreover, the same CO2 measurement when combined with a SO2 flux measurement, commonly carried out at many volcanoes nowadays, is used to contribute to an improved estimate of global volcanic CO2 budget. Today worldwide at 13 volcanoes automated in-situ instruments (known as Multi-GAS stations) are applied to continuously determine CO2/SO2 ratios and to use this signal as additional parameter for volcanic monitoring. Usually these instruments carry out measurements of half an hour 4 - 6 times/day and thus provide continuous CO2/SO2 values and their variability. The stations are located at crater rims in a position that according to the prevailing winds is invested by the plume. Obviously, although the stations are carefully positioned, it is inevitable that other sources than the plume itself, e.g. soil degassing and surrounding fumaroles, contribute and will be measured as well, covering the 'real' values. Between July and September 2014 experiments were carried out on the North East crater (NEC) of Mount Etna, installing a self-made cable car that crossed the crater from one side to the other. The basket, called "Arcadia", was equipped with an automated standard Multi-GAS station and a GPS, which acquired at high frequency (0.5 Hz) the following parameters : CO2, SO2, H2S, Rh, T, P and geo-coordinates. The choice of NEC of the volcano Etna was based on its accessibility, the relative small diameter (about 230 m) and the presence of a relatively constant and rather concentrated plume. Actually, NEC belongs also to the monitoring network EtnaPlume (managed by the INGV of Palermo). The aim of these experiments was to observe variations of each parameter, in particular the fluctuation of the CO2/SO2 ratio within the plume, moving from the edge to the center of the crater. The gained results give a first possibility to understand if common measurements carried out at the edge of a crater are subject to over- or underestimation and about the order of derivations caused by other sources than the plume. A preliminary analysis results in a lower CO2/SO2 ratio in the central part of the crater versus the more peripheral one. The deviation between the average CO2/SO2 ratio and the center of the plume ranges from a minimum of 58% up to a maximum of 74%. An increased CO2/SO2 emission could be caused by the influence of soil and/or fumarolic degassing at the crater rim. This interpretation leads us to the conclusion that measurements by fixed installed stations might overestimate the CO2/SO2 ratio compared to values originating from the "pure" plume. Further on, it means that variations of up to 74 % (in our experiment) don't necessarily correlate with volcanic activity changes.

Impact of mesophyll diffusion on estimated global land CO 2 fertilization

DOE PAGES

Sun, Ying; Gu, Lianhong; Dickinson, Robert E.; ...

2014-10-13

In C 3 plants, CO 2 concentrations drop considerably along mesophyll diffusion pathways from substomatal cavities to chloroplasts where CO 2 assimilation occurs. Global carbon cycle models have not explicitly represented this internal drawdown and so overestimate CO 2 available for carboxylation and underestimate photosynthetic responsiveness to atmospheric CO 2. An explicit consideration of mesophyll diffusion increases the modeled cumulative CO 2 fertilization effect (CFE) for global gross primary production (GPP) from 915 PgC to 1057 PgC for the period of 1901 to 2010. This increase represents a 16% correction, large enough to explain the persistent overestimation of growth ratesmore » of historical atmospheric CO 2 by Earth System Models. Without this correction, the CFE for global GPP is underestimated by 0.05 PgC yr -1ppm -1. This finding implies that the contemporary terrestrial biosphere is more CO 2-limited than previously thought.« less

Experimental Evidence for Fast Lithium Diffusion and Isotope Fractionation in Water-bearing Rhyolitic Melts at Magmatic Conditions

NASA Astrophysics Data System (ADS)

Cichy, S. B.; Till, C. B.; Roggensack, K.; Hervig, R. L.; Clarke, A. B.

2015-12-01

The aim of this work is to extend the existing database of experimentally-determined lithium diffusion coefficients to more natural cases of water-bearing melts at the pressure-temperature range of the upper crust. In particular, we are investigating Li intra-melt and melt-vapor diffusion and Li isotope fractionation, which have the potential to record short-lived magmatic processes (seconds to hours) in the shallow crust, especially during decompression-induced magma degassing. Hydrated intra-melt Li diffusion-couple experiments on Los Posos rhyolite glass [1] were performed in a piston cylinder at 300 MPa and 1050 °C. The polished interfaces between the diffusion couples were marked by addition of Pt powder for post-run detection. Secondary ion mass spectrometry analyses indicate that lithium diffuses extremely fast in the presence of water. Re-equilibration of a hydrated ~2.5 mm long diffusion-couple experiment was observed during the heating period from room temperature to the final temperature of 1050 °C at a rate of ~32 °C/min. Fractionation of ~40‰ δ7Li was also detected in this zero-time experiment. The 0.5h and 3h runs show progressively higher degrees of re-equilibration, while the isotope fractionation becomes imperceptible. Li contamination was observed in some experiments when flakes filed off Pt tubing were used to mark the diffusion couple boundary, while the use of high purity Pt powder produced better results and allowed easier detection of the diffusion-couple boundary. The preliminary lithium isotope fractionation results (δ7Li vs. distance) support findings from [2] that 6Li diffuses substantially faster than 7Li. Further experimental sets are in progress, including lower run temperatures (e.g. 900 °C), faster heating procedure (~100 °C/min), shorter run durations and the extension to mafic systems. [1] Stanton (1990) Ph.D. thesis, Arizona State Univ., [2] Richter et al. (2003) GCA 67, 3905-3923.

Lunar volatiles: a clue for understanding the evolution of the Moon and a resource to its exploration

NASA Astrophysics Data System (ADS)

Gerasimov, Mikhail

Introduction: The discovery of noticeable hydrogen concentration (believed to be in the form of water) in the polar regions was among the most exciting recent events in the exploration of the Moon. Concentration of water in polar regolith was estimated at a level of 4-6 wt.% [1,2]. Such high concentration of water in polar regolith on volatiles depleted Moon is probably a result of migration of water molecules from its hot equatorial latitudes to cold traps of the northern and southern polar regions. These depositions of volatiles on one hand contain important information on the evolution of the Moon and on the other hand their utilization can be a bases for the future human exploration. The question about diversity and source of the volatiles is still open. Sources of lunar volatiles: Three main possible sources of the Lunar polar volatiles are: Degassing of the interior. Endogenous source of volatiles is provided by degassing of heated interior of planetary bodies. In this case chemical composition of released gases reflects thermodynamic equilibrium of gases over typical magmas at temperatures around 1000°C. The composition of such gas mixtures is characterized by domination of H2O, CO2, and SO2 over other H, C, and S containing components. CO/CO2 ratio here is typically far below 0.1 level. Hydrocarbons are mainly aromatic hydrocarbons, alkanes, and cycloalkanes. Sulfur containing gases are mainly SO2, H2S, and Sx. Isotopic ratios of volatile elements should be the same as for the bulk Moon. Interaction of solar wind protons with surface rocks. Energetic solar wind protons with the absence of an atmospheric shield can react with oxygen of surface rocks and produce water molecules as end product. Such a mechanism provides a source of mainly water on the Moon with solar hydrogen isotopes and Moon rocks oxygen isotopes. Degassing of impacting meteorites and comets. Volatiles of impacting meteorites and comets are released into transient atmosphere. It was shown experimentally [3] that the forming gases are qualitatively similar for various rocky materials including meteorites of different classes. Such gas mixtures have the following characteristics: the CO/CO2 ratio is ³1, hydrocarbons are presented mainly by alkenes and PAHs, sulfur containing gases are presented by SO2, CS2, H2S, and COS in decreasing sequence, production of HCN, and noticeable release of water. Isotopic composition of volatile elements reflects the projectile to target proportion of their source. Gas-analytic package (GAP) of the Lunar-Resource mission: It is very important to investigate all the inventory of polar volatiles as well as isotopic composition of volatile elements to understand the real source of lunar volatiles and to evaluate their validity as a resource for the Moon exploration. The GAP is aimed on comprehensive investigation of the inventory of volatiles in the regolith of polar regions. It consists of three instruments: 1) Thermal Analyzer; 2) Gas Chromatograph with Tunable Diode Laser Absorption Spectrometer for isotopic measurements of H, O, and C in evolved gases; and 3) Neutral Gas Mass-Spectrometer. References: [1] Mitrofanov, I. G. et al. 2010. Science 330: 483-486. [2] Colaprete, A. et al. 2010. Science 330: 463-468. [3] Gerasimov, M.V. 2002. Geological Society of America Special Paper 356: 705-716. Acknowledgements: This work was supported by P-22 Program of the RAS.

CO2 dynamics in the Amargosa Desert: Fluxes and isotopic speciation in a deep unsaturated zone

USGS Publications Warehouse

Walvoord, Michelle Ann; Striegl, Robert G.; Prudic, David E.; Stonestrom, David A.

2005-01-01

Natural unsaturated-zone gas profiles at the U.S. Geological Survey's Amargosa Desert Research Site, near Beatty, Nevada, reveal the presence of two physically and isotopically distinct CO2 sources, one shallow and one deep. The shallow source derives from seasonally variable autotrophic and heterotrophic respiration in the root zone. Scanning electron micrograph results indicate that at least part of the deep CO2 source is associated with calcite precipitation at the 110-m-deep water table. We use a geochemical gas-diffusion model to explore processes of CO2 production and behavior in the unsaturated zone. The individual isotopic species 12CO2, 13CO2, and 14CO2 are treated as separate chemical components that diffuse and react independently. Steady state model solutions, constrained by the measured δ13C (in CO2), and δ14C (in CO2) profiles, indicate that the shallow CO2 source from root and microbial respiration composes ∼97% of the annual average total CO2 production at this arid site. Despite the small contribution from deep CO2 production amounting to ∼0.1 mol m−2 yr−1, upward diffusion from depth strongly influences the distribution of CO2 and carbon isotopes in the deep unsaturated zone. In addition to diffusion from deep CO2 production, 14C exchange with a sorbed CO2 phase is indicated by the modeled δ14C profiles, confirming previous work. The new model of carbon-isotopic profiles provides a quantitative approach for evaluating fluxes of carbon under natural conditions in deep unsaturated zones.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

PubMed

Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

2008-07-24

The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

Understanding the stability of surface nanobubbles.

PubMed

Wang, Shuo; Liu, Minghuan; Dong, Yaming

2013-05-08

Surface nanobubbles emerging at solid-liquid interfaces show extreme stability. In this paper, the stability of surface nanobubbles in degassed water is discussed and investigated by AFM. The result demonstrates that surface nanobubbles are kinetically stable and the liquid/gas interface is gas impermeable. The force modulation experiment further proves that there is a layer coating on nanobubbles. These critical properties suggest that surface nanobubbles may be stabilized by a layer which has a great diffusive resistance.

Markov-state model for CO2 binding with carbonic anhydrase under confinement

NASA Astrophysics Data System (ADS)

Chen, Gong; Xu, Weina; Lu, Diannan; Wu, Jianzhong; Liu, Zheng

2018-01-01

Enzyme immobilization with a nanostructure material can enhance its stability and facilitate reusability. However, the apparent activity is often compromised due to additional diffusion barriers and complex interactions with the substrates and solvent molecules. The present study elucidates the effects of the surface hydrophobicity of nano-confinement on CO2 diffusion to the active site of human carbonic anhydrase II (CA), an enzyme that is able to catalyze CO2 hydration at extremely high turnover rates. Using the Markov-state model in combination with coarse-grained molecular dynamics simulations, we demonstrate that a hydrophobic cage increases CO2 local density but hinders its diffusion towards the active site of CA under confinement. By contrast, a hydrophilic cage hinders CO2 adsorption but promotes its binding with CA. An optimal surface hydrophobicity can be identified to maximize both the CO2 occupation probability and the diffusion rate. The simulation results offer insight into understanding enzyme performance under nano-confinement and help us to advance broader applications of CA for CO2 absorption and recovery.

Constraining the Sulfur Dioxide Degassing Flux from Turrialba Volcano, Costa Rica Using Unmanned Aerial System Measurements

NASA Technical Reports Server (NTRS)

Xi, Xin; Johnson, Matthew S.; Jeong, Seongeun; Fladeland, Matthew; Pieri, David; Diaz, Jorge Andres; Bland, Geoffrey L.

2016-01-01

Observed sulfur dioxide (SO2)mixing ratios onboard unmanned aerial systems (UAS) duringMarch 11-13, 2013 are used to constrain the three-day averaged SO2 degassing flux fromTurrialba volcanowithin a Bayesian inverse modeling framework. A mesoscale model coupled with Lagrangian stochastic particle backward trajectories is used to quantify the source-receptor relationships at very high spatial resolutions (i.e., b1 km). The model shows better performance in reproducing the near-surface meteorological properties and observed SO2 variations when using a first-order closure non-local planetary boundary layer (PBL) scheme. The optimized SO2 degassing fluxes vary from 0.59 +/- 0.37 to 0.83 +/- 0.33 kt d-1 depending on the PBL scheme used. These fluxes are in good agreement with ground-based gas flux measurements, and correspond to corrective scale factors of 8-12 to the posteruptive SO2 degassing rate in the AeroCom emission inventory. The maximum a posteriori solution for the SO2 flux is highly sensitive to the specification of prior and observational errors, and relatively insensitive to the SO2 loss term and temporal averaging of observations. Our results indicate relatively low degassing activity but sustained sulfur emissions from Turrialba volcano to the troposphere during March 2013. This study demonstrates the utility of low-cost small UAS platforms for volcanic gas composition and flux analysis.

Methane emission to the atmosphere from landfills in the Canary Islands

NASA Astrophysics Data System (ADS)

Hernández, Pedro A.; Asensio-Ramos, María; Rodríguez, Fátima; Alonso, Mar; García-Merino, Marta; Amonte, Cecilia; Melián, Gladys V.; Barrancos, José; Rodríguez-Delgado, Miguel A.; Hernández-Abad, Marta; Pérez, Erica; Alonso, Monica; Tassi, Franco; Raco, Brunella; Pérez, Nemesio M.

2017-04-01

Methane (CH4) is one of the most powerful greenhouse gases, and is increasing in the atmosphere by 0.6% each year (Intergovernmental Panel on Climate Change, IPCC, 2013). This gas is produced in landfills in large quantities following the anaerobic degradation of organic matter. The IPCC has estimated that more than 10% of the total anthropogenic emissions of CH4 are originated in landfills. Even after years of being no operative (closed), a significant amount of landfill gas could be released to the atmosphere through its surface as diffuse or fugitive degassing. Many landfills currently report their CH4 emissions to the atmosphere using model-based methods, which are based on the rate of production of CH4, the oxidation rate of CH4 and the amount of CH4 recovered (Bingemer and Crutzen, 1987). This approach often involves large uncertainties due to inaccuracies of input data and many assumptions in the estimation. In fact, the estimated CH4 emissions from landfills in the Canary Islands published by the Spanish National Emission and Pollutant Sources Registration (PRTR-Spain) seem to be overestimated due to the use of protocols and analytical methodologies based on mathematical models. For this reason, direct measurements to estimate CH4 emissions in landfills are essential to reduce this uncertainty. In order to estimate the CH4 emissions to the atmosphere from landfills in the Canary Islands 23 surveys have been performed since 1999. Each survey implies hundreds of CO2and CH4 efflux measurements covering the landfill surface area. Surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Samples of landfill gases were taken in the gas accumulated in the chamber and CO2 and CH4 were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux measurent was computed combining CO2 efflux and CH4/CO2 ratio. To quantify the the diffuse or fugitive CO2 and CH4 emission, gas efflux contour maps were constructed using sequential Gaussian simulation (sGs) as interpolation method. Considering that (a) there are 5 controlled landfills in the Canary Islands, (b) the average area of the 23 studied cells is 0.17 km2 and (c) the mean value of the CH4 emission estimated for the studied cells range between 6.9 and 8.1 kt km-2 y-1, the estimated CH4 emission to the atmosphere from landfills in the Canary Islands showed a range of 7.0 - 7.8 kt y-1. On the contrary and for the same period of time, the PRTR-Spain estimates CH4 emission in the order of 10.3 - 14.9 kt y-1, nearly two times our estimated value. This result demonstrates the need to perform direct measurements to estimate the surface fugitive emission of CH4 from landfills. Bingemer, H. G., and P. J. Crutzen (1987). The production of methane from solid wastes, J. Geophys. Res. 92, 2182-2187

Resistance to CO2 diffusion in cuticular membranes of amphibious plants and the implication for CO2 acquisition.

PubMed

Frost-Christensen, Henning; Floto, Franz

2007-01-01

Cuticular membranes (CMs) were isolated from leaves of amphibious and submerged plants and their CO2 resistances were determined as a contribution to establish quantitatively the series of resistances met by CO2 diffusing from bulk water to the chloroplasts of submerged leaves. The isolation was performed enzymatically; permeabilities were determined and converted to resistances. The range of permeance values was 3 to 43 x 10(-6) m s(-1) corresponding to resistance values of 23 to 295 x 10(3) s m(-1), i.e. of the same order of magnitude as boundary layer resistances. The sum of boundary layer, CM, leaf cell and carboxylation resistances could be contained within the total diffusion resistance as determined from the photosynthetic CO2 affinity of the leaf. From the same species, the aerial leaf CM resistance was always higher than the aquatic leaf CM resistance. In a terrestrial plant, the CM resistance to CO2 diffusion was found lower in leaves developed submerged.

Volatile Emissions from Hot Spring Basin, Yellowstone National Park, USA

NASA Astrophysics Data System (ADS)

Werner, C.; Hurwitz, S.; Bergfeld, D.; Evans, W. C.; Lowenstern, J. B.; Jaworowski, C.; Heasler, H.

2007-12-01

The flux and composition of magmatic volatiles were characterized for Hot Spring Basin (HSB), Yellowstone National Park, in August 2006. Diffuse fluxes of CO2 (228 sites) from thermal soil were elevated, with a population distribution similar to that of other acid-sulfate areas in Yellowstone. Thus the estimated diffuse emission rate at HSB is proportionately larger than other areas due to its large area, and could be as high as 1000 td-1 CO2. The diffuse flux of H2S was only above detection limits at 20 of the 31 sites measured. The estimated diffuse H2S emission rate was ~ 4 td-1. Good correlation exists between the log of CO2 flux and shallow soil temperatures, indicating linked steam and gas upflow in the subsurface. The correlation between CO2 and H2S fluxes is weak, and the CO2 / H2S diffuse flux ratio was higher than in fumarolic ratios of CO2 to H2S. This suggests that various reactions, e.g., native sulfur deposition, act to remove H2S from the original gas stream in the diffuse low- temperature environment. Dissolved sulfate flux through Shallow Creek, which drains part of HSB, was ~ 4 td-1. Comparing dissolved sulfate flux to estimates of primary emission of H2S based on fumarolic gas geochemistry gives first order estimates of the sulfur consumed in surficial or subsurface mineral deposition. Total C and S outputs from HSB are comparable to other active volcanic systems.

Measurement of diffusion coefficients important in modeling the absorption rate of carbon dioxide into aqueous N-methyldiethanolamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rowley, R.L.; Adams, M.E.; Marshall, T.L.

1997-03-01

Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The modelmore » was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.« less

Redox Interactions between Iron and Carbon in Planetary Mantles: Implications for Degassing and Melting Processes

NASA Technical Reports Server (NTRS)

Martin, A.; Righter, K.

2009-01-01

Carbon stability in planetary mantles has been studied by numerous authors because it is thought to be the source of C-bearing atmospheres and of C-rich lavas observed at the planetary surface. In the Earth, carbonaceous peridotites and eclogites compositions have been experimentally studied at mantle conditions [1] [2] [3]. [4] showed that the fO2 variations observed in martian meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Based on thermodynamic calculations [4] and [5] inferred that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond), and equilibrium with melts would be a source of CO2 for the martian atmosphere. Considering the high content of iron in the Martian mantle (approx.18.0 wt% FeO; [6]), compared to Earth s mantle (8.0 wt% FeO; [7]) Fe/C redox interactions should be studied in more detail.

Garan performs TCS Water Loop Degassing in Columbus

NASA Image and Video Library

2011-04-08

ISS027-E-011325 (8 April 2011) --- NASA astronaut Ron Garan, Expedition 27 flight engineer, works on degassing the water loop of the running Water Pump Assembly 2 / Thermal Control System (WPA2/TCS) in the Columbus laboratory of the International Space Station.

Garan performs TCS Water Loop Degassing in Columbus

NASA Image and Video Library

2011-04-08

ISS027-E-011324 (8 April 2011) --- NASA astronaut Ron Garan, Expedition 27 flight engineer, works on degassing the water loop of the running Water Pump Assembly 2 / Thermal Control System (WPA2/TCS) in the Columbus laboratory of the International Space Station.

Science development on volcanology flawed by the Spanish IGN

NASA Astrophysics Data System (ADS)

Pérez, Nemesio M.; Schmincke, Hans-Ulrich

2016-04-01

Scientists performing research activities in the field of volcanology, related more specifically to volcano monitoring in the Canary Islands, recently discovered that not all seismic events that occurred in the country had been listed in the Spanish National Seismic Catalogue and its related data base. The National Geographic Institute (IGN) is the legal Spanish institution in-charge of the National Seismic Catalogue, together with volcanic surveillance in Spain. It was therefore a huge surprise to discover that the number of seismic events registered in and around Tenerife Island in 2010, and according to the national catalogue, was only approximately 60, while the real number of seismic events recorded by the IGN in the region was 1,176. The existence of two different accounts of seismic activity registered by the IGN in and around Tenerife Island, keeping one for the public eye, while hiding the other one from even the scientific community, is not only illegal but also unscientific, hindering the progress of science. In addition, most importantly it is detrimental for timely forecasting of sudden/instantaneous dynamic events, such as major earthquakes and/or volcanic eruptions which might spell disaster for the population, the economy of the island, and severely impact tourism. This unethical behaviour by IGN's volcanological staff has already caused damage to open scientific discussions; a key parameter for scientific development. A scientific contribution was recently published using data from 15 years of research on diffuse CO2 emission monitoring from the summit cone of Teide volcano (Pérez et al., 2013). The seismic data that was used to discuss the observed temporal variations of the degassing pattern from Teide volcano came from the National Seismic Catalogue. In contrast it is obvious that the observed variations on diffuse CO2 emission from Teide volcano from 1997 to 2011 provided a better scientific explanation when using the real seismic data that had been concealed for several years by IGN's volcanological staff. References Pérez et al., 2013. J. Geol. Soc., DOI: 10.1144/jgs2012-125.

Explaining CO2 fluctuations observed in snowpacks

NASA Astrophysics Data System (ADS)

Graham, Laura; Risk, David

2018-02-01

Winter soil carbon dioxide (CO2) respiration is a significant and understudied component of the global carbon (C) cycle. Winter soil CO2 fluxes can be surprisingly variable, owing to physical factors such as snowpack properties and wind. This study aimed to quantify the effects of advective transport of CO2 in soil-snow systems on the subdiurnal to diurnal (hours to days) timescale, use an enhanced diffusion model to replicate the effects of CO2 concentration depletions from persistent winds, and use a model-measure pairing to effectively explore what is happening in the field. We took continuous measurements of CO2 concentration gradients and meteorological data at a site in the Cape Breton Highlands of Nova Scotia, Canada, to determine the relationship between wind speeds and CO2 levels in snowpacks. We adapted a soil CO2 diffusion model for the soil-snow system and simulated stepwise changes in transport rate over a broad range of plausible synthetic cases. The goal was to mimic the changes we observed in CO2 snowpack concentration to help elucidate the mechanisms (diffusion, advection) responsible for observed variations. On subdiurnal to diurnal timescales with varying winds and constant snow levels, a strong negative relationship between wind speed and CO2 concentration within the snowpack was often identified. Modelling clearly demonstrated that diffusion alone was unable to replicate the high-frequency CO2 fluctuations, but simulations using above-atmospheric snowpack diffusivities (simulating advective transport within the snowpack) reproduced snow CO2 changes of the observed magnitude and speed. This confirmed that wind-induced ventilation contributed to episodic pulsed emissions from the snow surface and to suppressed snowpack concentrations. This study improves our understanding of winter CO2 dynamics to aid in continued quantification of the annual global C cycle and demonstrates a preference for continuous wintertime CO2 flux measurement systems.

Third prize: the impact of fluid environment manipulation on shockwave lithotripsy artificial calculi fragmentation rates.

PubMed

Méndez-Probst, Carlos E; Fernadez, Alfonso; Erdeljan, Petar; Vanjecek, Maaike; Cadieux, Peter A; Razvi, Hassan

2011-03-01

Studies have suggested that shockwave lithotripsy (SWL) stone fragmentation rates can be affected by characteristics of the fluid media surrounding the stone, although evidence to implicate the impact of urine specific gravity (SG) is limited and inconclusive. Our aim is to further explore the impact fluid media and SGs have on stone fragmentation using a variable focus lithotripter. Artificial stones were presoaked for 24 hours in urine and then shocked in various fluid media including artificial urine (SG 1.010 control, 1.020, and 1.07), human pooled urine (HPU), degassed HPU, Pentastarch, 100% and 30% contrast, degassed 30% contrast, 100% ethanol, deionized water (dH(2)O), degassed dH(2)O, 5% glucose, Ringer lactate, 0.9% saline, glycerol, whole blood, and lubricating gel. After soaking, SWL using the Modulith SLX-F2 electromagnetic lithotripter was performed. Fragments were dried and sieved using a 4-mm diameter opening grid. Fragments >4 mm were weighed and fragmentation coefficients (FCs) calculated (pre-SWL weight - post-SWL weight)/(pre-SWL weight) × 100. Fifteen stones were shocked for each fluid group. Fluid type, viscosity, and degassing all significantly impacted stone fragmentation. While the solutions' SG, per se, did not appear to affect stone fragmentation, the use of degassed 30% contrast significantly improved stone destruction over the SG 1.010 artificial urine control (95.3% vs 71.4, P < 0.01). Furthermore, degassing improved comminution rates by increasing the number of completely fragmented stones (FC = 100%). Using degassed 30% contrast, 12/15 stones were completely fragmented, compared with only 2/15 in the control group (P = 0.007). Among the whole blood, glycerol, and lubricating gel groups, only 1/15, 0/15, and 1/15 stones reached 100% FC respectively in the narrow focus, possibly because of the detrimental impact of increased viscosity. Different fluid media can significantly affect FC in vitro. Among the various fluids tested, degassed 30% contrast significantly increased the FC and total number of completely fragmented stones.

First System-Wide Estimates of Air-Sea Exchange of Carbon Dioxide in the Chesapeake Bay

NASA Astrophysics Data System (ADS)

Herrmann, M.; Najjar, R.; Menendez, A.

2016-02-01

Estuaries are estimated to play a major role in the global carbon cycle by degassing between 0.25 and 0.4 Pg C y-1, comparable to the uptake of atmospheric CO2 by continental shelf waters and as much as one quarter of the uptake of atmospheric CO2 by the open ocean. However, the global estimates of estuarine CO2 gas exchange are highly uncertain mostly due to limited data availability and extreme heterogeneity of coastal systems. Notably, the air-water CO2 flux for the largest U.S. estuary, the Chesapeake Bay, is yet unknown. Here we provide first system-level CO2 gas exchange estimates for the Chesapeake Bay, using data from the Chesapeake Bay Water Quality Monitoring Program (CBWQMP) and other data sources. We focus on the main stem of the Chesapeake Bay; hence, tributaries, such as the tidal portions of the Potomac and James Rivers, are not included in this first estimation of the flux. The preliminary results show the Bay to be a net source of CO2 to the atmosphere, outgassing on average 0.2 Tg C yr-1 over the study period, between 1985 and 2013. The spatial and temporal variability of the gas exchange will be discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@eps.s.u-tokyo.ac.jp

The climatic evolution of the Earth depends strongly on the evolution of the insolation from the Sun and the amount of the greenhouse gasses, especially CO{sub 2} in the atmosphere. Here, we investigate the evolution of the climate of hypothetical Earths around stars whose masses are different from the solar mass with a luminosity evolution model of the stars, a mantle degassing model coupled with a parameterized convection model of the planetary interiors, and an energy balance climate model of the planetary surface. In the habitable zone (HZ), the climate of the planets is initially warm or hot, depending onmore » the orbital semimajor axes. We found that, in the inner HZ, the climate of the planets becomes hotter with time owing to the increase in the luminosity of the central stars, while, in the outer HZ, it becomes colder and eventually globally ice-covered owing to the decrease in the CO{sub 2} degassing rate of the planets. The orbital condition for maintaining the warm climate similar to the present Earth becomes very limited, and more interestingly, the planet orbiting in the outer HZ becomes globally ice-covered after a certain critical age (∼3 Gyr for the hypothetical Earth with standard parameters), irrespective of the mass of the central star. This is because the critical age depends on the evolution of the planets and planetary factors, rather than on the stellar mass. The habitability of the Earth-like planet is shown to be limited with age even though it is orbiting within the HZ.« less

Travertines associated with the Alhama-Jaraba thermal waters (NE, Spain): Genesis and geochemistry

NASA Astrophysics Data System (ADS)

Asta, Maria P.; Auqué, Luis F.; Sanz, Francisco J.; Gimeno, Maria J.; Acero, Patricia; Blasco, Mónica; García-Alix, Antonio; Gómez, Javier; Delgado-Huertas, Antonio; Mandado, Juan

2017-01-01

Freshwater carbonates are interesting archives in palaeoenvironmental reconstructions. However, more studies of those systems are needed to fully understand past environments. In this work the actively-forming travertines of the Alhama-Jaraba thermal system were studied for the first time in order to evaluate the relationship between the geochemical and mineralogical composition and the environmental conditions during their formation. With that aim, a combination of petrographical, mineralogical, geochemical and stable isotope analyses were carried out. These carbonates provide a natural laboratory for the study of the effect of different variables (natural and anthropogenic) on carbonate precipitation. The results showed that there is a close relationship between the mineralogy of the solid precipitates and the formation temperature, and only the samples formed from overheated waters (40-60 °C) show significant concentrations of aragonite. Aragonite-bearing samples show higher concentrations in Sr, Ba and U while calcitic solids are enriched in Mg. These differences could be attributed to mineralogy, temperature or different precipitation rates. The geochemical evaluation of the chemistry of both the solids and their parental waters suggests that differences in the rate of CO2-degassing and, in some cases, evaporation are the primary environmental controls on isotopic compositions. In addition, the results show that, if strong evaporation and CO2-degassing are involved, calcite precipitation occurs under conditions of isotopic disequilibrium with its parental water. The results of our study are useful to interpret old depositional environments and palaeotemperatures.

A new site for 85Kr measurements on groundwater samples

NASA Astrophysics Data System (ADS)

Lange, T.; Hebert, D.

2001-06-01

As a part of a new 85Kr laboratory, which is currently being established at the Institute of Applied Physics in Freiberg, Germany, a modified CO 2 extractor for krypton sampling is used. The operation principle is simple and contamination-safe with a reasonable effort. Continuously pumped under pressure, the water passes a Venturi-type nozzle and degasses due to relaxing. The extracted gas mixture then enters a recirculation system flowing through a CO 2 trap (NaOH), molecular sieves and a cooled charcoal trap, where krypton and other components are adsorbed. Remaining gases reenter the system at the Venturi-type nozzle. To keep the circulation alive an additional helium support is needed. In a simple field experiment, extraction efficiencies up to 0.8 for 222Rn have been measured.

Modeling crustal deformation and rupture processes related to upwelling of deep CO2-rich fluids during the 1965-1967 Matsushiro Earthquake Swarm in Japan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cappa, F.; Rutqvist, J.; Yamamoto, K.

2009-05-15

In Matsushiro, central Japan, a series of more than 700,000 earthquakes occurred over a 2-year period (1965-1967) associated with a strike-slip faulting sequence. This swarm of earthquakes resulted in ground surface deformations, cracking of the topsoil, and enhanced spring-outflows with changes in chemical compositions as well as carbon dioxide (CO{sub 2}) degassing. Previous investigations of the Matsushiro earthquake swarm have suggested that migration of underground water and/or magma may have had a strong influence on the swarm activity. In this study, employing coupled multiphase flow and geomechanical modelling, we show that observed crustal deformations and seismicity can have been drivenmore » by upwelling of deep CO{sub 2}-rich fluids around the intersection of two fault zones - the regional East Nagano earthquake fault and the conjugate Matsushiro fault. We show that the observed spatial evolution of seismicity along the two faults and magnitudes surface uplift, are convincingly explained by a few MPa of pressurization from the upwelling fluid within the critically stressed crust - a crust under a strike-slip stress regime near the frictional strength limit. Our analysis indicates that the most important cause for triggering of seismicity during the Matsushiro swarm was the fluid pressurization with the associated reduction in effective stress and strength in fault segments that were initially near critically stressed for shear failure. Moreover, our analysis indicates that a two order of magnitude permeability enhancement in ruptured fault segments may be necessary to match the observed time evolution of surface uplift. We conclude that our hydromechanical modelling study of the Matsushiro earthquake swarm shows a clear connection between earthquake rupture, deformation, stress, and permeability changes, as well as large-scale fluid flow related to degassing of CO{sub 2} in the shallow seismogenic crust. Thus, our study provides further evidence of the important role of deep fluid sources in earthquake fault dynamics and surface deformations.« less

Remaining gaps for "safe" CO2 storage: the INGV CO2GAPS vision of "learning by doing" monitoring geogas leakage, reservoirs contamination/mixing and induced/triggered seismicity

NASA Astrophysics Data System (ADS)

Quattrocchi, F.; Vinciguerra, S.; Chiarabba, C.; Boschi, E.; Anselmi, M.; Burrato, P.; Buttinelli, M.; Cantucci, B.; Cinti, D.; Galli, G.; Improta, L.; Nazzari, M.; Pischiutta, M.; Pizzino, L.; Procesi, M.; Rovelli, A.; Sciarra, A.; Voltattorni, N.

2012-12-01

The CO2GAPS project proposed by INGV is intended to build up an European Proposal for a new kind of research strategy in the field of the geogas storage. Aim of the project would be to fill such key GAPS concerning the main risks associated to CO2 storage and their implications on the entire Carbon Capture and Storage (CCS) process, which are: i) the geogas leakage both in soils and shallow aquifers, up to indoor seepage; ii) the reservoirs contamination/mixing by hydrocarbons and heavy metals; iii) induced or triggered seismicity and microseismicity, especially for seismogenic blind faults. In order to consider such risks and make the CCS public acceptance easier, a new kind of research approach should be performed by: i) a better multi-disciplinary and "site specific" risk assessment; ii) the development of more reliable multi-disciplinary monitoring protocols. In this view robust pre-injection base-lines (seismicity and degassing) as well as identification and discrimination criteria for potential anomalies are mandatory. CO2 injection dynamic modelling presently not consider reservoirs geomechanical properties during reactive mass-transport large scale simulations. Complex simulations of the contemporaneous physic-chemical processes involving CO2-rich plumes which move, react and help to crack the reservoir rocks are not totally performed. These activities should not be accomplished only by the oil-gas/electric companies, since the experienced know-how should be shared among the CCS industrial operators and research institutions, with the governments support and overview, also flanked by a transparent and "peer reviewed" scientific popularization process. In this context, a preliminary and reliable 3D modelling of the entire "storage complex" as defined by the European Directive 31/2009 is strictly necessary, taking into account the above mentioned geological, geochemical and geophysical risks. New scientific results could also highlighting such opportunities recently shown by strategic researches on the synergies between the use of underground space (e.g. CH4, CO2 storage and deep geothermics) for energetic supplying purposes. The CO2GAPS approach would merge together geomechanical and geochemical data with seismic velocity and anisotropy properties of the crust, induced seismicity data, gravimetry, EM techniques, and "early alarm" procedures for leakage/cracks detection in shallow geo-spheres (e.g. abandoned wells, naturally seismic and degassing zones). Moreover, a full merging of those data is necessary for a reliable 3D-Earth modelling and the subsequent reactive transport simulations. CO2GAPS vision would apply and verify these issues working on several European selected sites, taking also into account complex systems such as "inland" active faulted blocks close to potential off-shore CO2 storage sites, ECBM faulted prone-areas, "inland" injection test site and CO2 natural faulted analogues. The purpose of these activities focus on the study of long-term fate of stored CO2, leakage mechanisms through the cap-rock and/or abandoned wells, cement wells reactivity, as well as the effects of impurities in the CO2 streams, their removal costs, the use of tracers and the role of biota.

Diffusivity of Carbon Dioxide in Aqueous Solutions under Geologic Carbon Sequestration Conditions.

PubMed

Perera, Pradeep N; Deng, Hang; Schuck, P James; Gilbert, Benjamin

2018-04-26

Accurate assessment of the long-term security of geologic carbon sequestration requires knowledge of the mobility of carbon dioxide in brines under pressure and temperature conditions that prevail in subsurface aquifers. Here, we report Raman spectroscopic measurements of the rate of CO 2 diffusion in water and brines as a function of pressure, salinity, and concentration of CO 2 . In pure water at 50 ± 2 °C and 90 ± 2 bar, we find the diffusion coefficient, D, to be (3.08 ± 0.03) × 10 -9 m 2 /s, a value that is consistent with a recent microfluidic study but lower than earlier PVT measurements. Under reservoir conditions, salinity affects the mobility of CO 2 significantly and D decreased by 45% for a 4 M solution of NaCl. We find significant differences of diffusivity of CO 2 in brines (0-4 M NaCl), in both the absolute values and the trend compared to the Stokes-Einstein prediction under our experimental conditions. We observe that D decreases significantly at the high CO 2 concentrations expected in subsurface aquifers (∼15% reduction at 0.55 mol/kg of CO 2 ) and provides an empirical correction to the commonly reported D values that assume a tracer concentration dependence on diffusivity.

Energetics of CO2 and H2O adsorption on zinc oxide.

PubMed

Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

2014-08-05

Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

Atomistic simulations of CO2 and N2 within cage-type silica zeolites.

PubMed

Madison, Lindsey; Heitzer, Henry; Russell, Colin; Kohen, Daniela

2011-03-01

The behavior of CO(2) and N(2), both as single components and as binary mixtures, in two cage-type silica zeolites was studied using atomistic simulations. The zeolites considered, ITQ-3 and paradigm cage-type zeolite ZK4 (the all-silica analog of LTA), were chosen so that the principles illustrated can be generalized to other adsorbent/adsorbate systems with similar topology and types of interactions. N(2) was chosen both because of the potential uses of N(2)/CO(2) separations and because it differs from CO(2) most significantly in the magnitude of its Coulombic interactions with zeolites. Despite similarities between N(2) and CO(2) diffusion in other materials, we show here that the diffusion of CO(2) within cage-type zeolites is dominated by an energy barrier to diffusion located at the entrance to the narrow channels connecting larger cages. This barrier originates in Coulombic interactions between zeolites and CO(2)'s quadrupole and results in well-defined orientations for the diffusing molecules. Furthermore, CO(2)'s favorable electrostatic interactions with the zeolite framework result in preferential binding in the windows between cages. N(2)'s behavior, in contrast, is more consistent with that of molecules previously studied. Our analysis suggests that CO(2)'s behavior might be common for adsorbates with quadrupoles that interact strongly with a material that has narrow windows between cages.

Thermal analysis of a diffusion bonded Er3+,Yb3+:glass/Co2+: MgAl2O4 microchip lasers

NASA Astrophysics Data System (ADS)

Belghachem, Nabil; Mlynczak, Jaroslaw; Kopczynski, krzysztof; Mierczyk, Zygmunt; Gawron, Michal

2016-10-01

The analysis of thermal effects in a diffusion bonded Er3+,Yb3+:glass/Co2+:MgAl2O4 microchip laser is presented. The analysis is performed for both wavelengths at 940 nm and at 975 nm as well as for two different sides of pumping, glass side and saturable absorber side. The heat sink effect of Co2+:MgAl2O4, as well as the impact of the thermal expansion and induced stress on the diffusion bonding are emphasised. The best configurations for reducing the temperature peaks, the Von Mises stresses on the diffusion bonding, and the thermal lensing are determined.

Horizon Partitioning of Soil CO2 Sources and their Isotopic Composition (13C) in a Pinus Sylvestris Stand

NASA Astrophysics Data System (ADS)

Goffin, S.; Parent, F.; Plain, C.; Maier, M.; Schack-Kirchner, H.; Aubinet, M.; Longdoz, B.

2012-12-01

The overall aim of this study is to contribute to a better understanding of mechanisms behind soil CO2 efflux using carbon stable isotopes. The approach combines a soil multilayer analysis and the isotopic tool in an in situ study. The specific goal of this work is to quantify the origin and the determinism of 13CO2 and 12CO2 production processes in the different soil layers using the gradient-efflux approach. To meet this, the work includes an experimental setup and a modeling approach. The experimental set up (see also communication of Parent et al., session B008) comprised a combination of different systems, which were installed in a Scot Pine temperate forest at the Hartheim site (Southwestern Germany). Measurements include (i) half hourly vertical profiles of soil CO2 concentration (using soil CO2 probes), soil water content and temperature; (ii) half hourly soil surface CO2 effluxes (automatic chambers); (iii) half hourly isotopic composition of surface CO2 efflux and soil CO2 concentration profile and (iv) estimation of soil diffusivity through laboratory measurements conducted on soil samples taken at several depths. Using the data collected in the experimental part, we developed and used a diffusive transport model to simulate CO2 (13CO2 and 12CO2) flows inside and out of the soil based on Fick's first law. Given the horizontal homogeneity of soil physical parameters in Hartheim, we treated the soil as a structure consisting of distinctive layers of 5 cm thick and expressed the Fick's first law in a discrete formalism. The diffusion coefficient used in each layer was derived from (i) horizon specific relationships, obtained from laboratory measurements, between soil relative diffusivity and its water content and (ii) the soil water content values measured in situ. The concentration profile was obtained from in situ measurements. So, the main model inputs are the profiles of (i) CO2 (13CO2 and 12CO2) concentration, (ii) soil diffusion coefficient and (iii) soil water content. Once the diffusive fluxes deduced at each layer interface, the CO2 (13CO2 and 12CO2) production profile was calculated using the (discretized) mass balance equation in each layer. The results of the Hartheim measurement campaign will be presented. The CO2 source vertical profile and its link with the root and the Carbon organic content distribution will be showed. The dynamic of CO2 sources and their isotopic signature will be linked to climatic variables such soil temperature and soil water content. For example, we will show that the dynamics of CO2 sources was mainly related to temperature while changing of isotopic signature was more correlated to soil moisture.

Diffusion mechanism in the sodium-ion battery material sodium cobaltate.

PubMed

Willis, T J; Porter, D G; Voneshen, D J; Uthayakumar, S; Demmel, F; Gutmann, M J; Roger, M; Refson, K; Goff, J P

2018-02-16

High performance batteries based on the movement of Li ions in Li x CoO 2 have made possible a revolution in mobile electronic technology, from laptops to mobile phones. However, the scarcity of Li and the demand for energy storage for renewables has led to intense interest in Na-ion batteries, including structurally-related Na x CoO 2 . Here we have determined the diffusion mechanism for Na 0.8 CoO 2 using diffuse x-ray scattering, quasi-elastic neutron scattering and ab-initio molecular dynamics simulations, and we find that the sodium ordering provides diffusion pathways and governs the diffusion rate. Above T ~ 290 K the so-called partially disordered stripe superstructure provides channels for quasi-1D diffusion, and melting of the sodium ordering leads to 2D superionic diffusion above T ~ 370 K. We obtain quantitative agreement between our microscopic study of the hopping mechanism and bulk self-diffusion measurements. Our approach can be applied widely to other Na- or Li-ion battery materials.

Fault-Related CO 2 Degassing, Geothermics, and Fluid Flow in Southern California Basins--Physiochemical Evidence and Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garven, Grant

2015-08-11

Our studies have had an important impact on societal issues. Experimental and field observations show that CO 2 degassing, such as might occur from stored CO 2 reservoir gas, can result in significant stable isotopic disequilibrium. In the offshore South Ellwood field of the Santa Barbara channel, we show how oil production has reduced natural seep rates in the area, thereby reducing greenhouse gases. Permeability is calculated to be ~20-30 millidarcys for km-scale fault-focused fluid flow, using changes in natural gas seepage rates from well production, and poroelastic changes in formation pore-water pressure. In the Los Angeles (LA) basin, ourmore » characterization of formation water chemistry, including stable isotopic studies, allows the distinction between deep and shallow formations waters. Our multiphase computational-based modeling of petroleum migration demonstrates the important role of major faults on geological-scale fluid migration in the LA basin, and show how petroleum was dammed up against the Newport-Inglewood fault zone in a “geologically fast” interval of time (less than 0.5 million years). Furthermore, these fluid studies also will allow evaluation of potential cross-formational mixing of formation fluids. Lastly, our new study of helium isotopes in the LA basin shows a significant leakage of mantle helium along the Newport Inglewood fault zone (NIFZ), at flow rates up to 2 cm/yr. Crustal-scale fault permeability (~60 microdarcys) and advective versus conductive heat transport rates have been estimated using the observed helium isotopic data. The NIFZ is an important deep-seated fault that may crosscut a proposed basin decollement fault in this heavily populated area, and appears to allow seepage of helium from the mantle sources about 30 km beneath Los Angeles. The helium study has been widely cited in recent weeks by the news media, both in radio and on numerous web sites.« less

Watershed-scale drivers of air-water CO2 exchanges in two lagoonal, North Carolina (USA) estuaries

NASA Astrophysics Data System (ADS)

Van Dam, B.; Crosswell, J.; Anderson, I. C.; Paerl, H. W.

2017-12-01

Riverine loading of nutrients and organic matter act in concert to modulate CO2 fluxes in estuaries, yet quantitative relationships between these factors remain poorly defined. This study explored watershed-scale mechanisms responsible for the relatively low CO2 fluxes observed in two microtidal, lagoonal estuaries. Air-water CO2 fluxes were quantified with 74 high-resolution spatial surveys in the neighboring New River Estuary (NewRE) and Neuse River Estuary (NeuseRE), North Carolina, which experience a common climatology, but differ in marine versus riverine influence. Annually, both estuaries were relatively small sources of CO2 to the atmosphere, 12.5 and 16.3 mmol C m2 d-1 in the NeuseRE and NewRE, respectively. Variations in riverine alkalinity and inorganic carbon loading caused zones of minimum buffering capacity to occur at different locations in each estuary, enhancing the sensitivity of estuarine inorganic C chemistry to acidification. Large-scale pCO2 variations were driven by changes in freshwater age (akin to residence time), which modulate nutrient and organic carbon supply and phytoplankton flushing. Greatest pCO2 under-saturation was observed at intermediate freshwater ages, between 2-3 weeks. Biological controls on CO2 fluxes were obscured by variable inputs of river-borne CO2, which drove CO2 degassing in the river-dominated NeuseRE. Internally produced CO2 exceeded river-borne CO2 in the marine-dominated NewRE, suggesting that net ecosystem heterotrophy, rather than riverine inputs, drove CO2 fluxes in this system. Although annual CO2 fluxes were similar between systems, watershed-specific hydrologic factors led to disparate controls on internal carbonate chemistry, which can influence overall ecosystem health and response to future perturbation.

Watershed-Scale Drivers of Air-Water CO2 Exchanges in Two Lagoonal North Carolina (USA) Estuaries

NASA Astrophysics Data System (ADS)

Van Dam, Bryce R.; Crosswell, Joseph R.; Anderson, Iris C.; Paerl, Hans W.

2018-01-01

Riverine loading of nutrients and organic matter act in concert to modulate CO2 fluxes in estuaries, yet quantitative relationships between these factors remain poorly defined. This study explored watershed-scale mechanisms responsible for the relatively low CO2 fluxes observed in two microtidal, lagoonal estuaries. Air-water CO2 fluxes were quantified with 74 high-resolution spatial surveys in the neighboring New River Estuary (NewRE) and Neuse River Estuary (NeuseRE), North Carolina, which experience a common climatology but differ in marine versus riverine influence. Annually, both estuaries were relatively small sources of CO2 to the atmosphere, 12.5 and 16.3 mmol C m-2 d-1 in the NeuseRE and NewRE, respectively. Large-scale pCO2 variations were driven by changes in freshwater age, which modulates nutrient and organic carbon supply and phytoplankton flushing. Greatest pCO2 undersaturation was observed at intermediate freshwater ages, between 2 and 3 weeks. Biological controls on CO2 fluxes were obscured by variable inputs of river-borne CO2, which drove CO2 degassing in the river-dominated NeuseRE. Internally produced CO2 exceeded river-borne CO2 in the marine-dominated NewRE, suggesting that net ecosystem heterotrophy, rather than riverine inputs, drove CO2 fluxes in this system. Variations in riverine alkalinity and inorganic carbon loading caused zones of minimum buffering capacity to occur at different locations in each estuary, enhancing the sensitivity of estuarine inorganic C chemistry to acidification. Although annual CO2 fluxes were similar between systems, watershed-specific hydrologic factors led to disparate controls on internal carbonate chemistry, which can influence ecosystem biogeochemical cycling, trophic state, and response to future perturbations.

Evaluation of advanced bladder technology

NASA Technical Reports Server (NTRS)

Christensen, M. V.; Pasternak, R. A.

1972-01-01

Research conducted during this period is reported. Studies presented include: (1) diffusion and permeation of CO2, O2, N2, and NO2 through polytetra fluoroethylene; (2) diffusion, permeation and solubility of simple gases (CO2, O2, N2, CH4, C2H6, C3H8, and C2H4) through a copolymer of hexafluoro propylene and tetrafluoro ethylene (FEP); (3) viscous flow and diffusion of gases throug small apertures; (4) diffusion and permeation of O2, N2, CO2, CH4, C2H6, and C3H8 through nitroso rubber; and (5) results of gas transport studies with carborane siloxane, nitroso rubber, silicone membrane, krytox coating on teflon, and FEP coated glass cloth. Publications generated under this program are listed.

Is the wall of a cellulose fiber saturated with liquid whether or not permeable with CO2 dissolved molecules? Application to bubble nucleation in champagne wines.

PubMed

Liger-Belair, Gérard; Topgaard, Daniel; Voisin, Cédric; Jeandet, Philippe

2004-05-11

In this paper, the transversal diffusion coefficient D perpendicular of CO2 dissolved molecules through the wall of a hydrated cellulose fiber was approached, from the liquid bulk diffusion coefficient of CO2 dissolved molecules modified by an obstruction factor. The porous network between the cellulose microfibrils of the fiber wall was assumed being saturated with liquid. We retrieved information from previous NMR experiments on the self-diffusion of water in cellulose fibers to reach an order of magnitude for the transversal diffusion coefficient of CO2 molecules through the fiber wall. A value of about D perpendicular approximately 0.2D0 was proposed, D0 being the diffusion coefficient of CO2 molecules in the liquid bulk. Because most of bubble nucleation sites in a glass poured with carbonated beverage are cellulose fibers cast off from paper or cloth which floated from the surrounding air, or remaining from the wiping process, this result directly applies to the kinetics of carbon dioxide bubble formation from champagne and sparkling wines. If the cellulose fiber wall was impermeable with regard to CO2 dissolved molecules, it was suggested that the kinetics of bubbling would be about three times less than it is.

Micropore Formation of [Zn2(Oxac) (Taz)2]·(H2O)2.5 via CO2 Adsorption.

PubMed

Zubir, Moondra; Hamasaki, Atom; Iiyama, Taku; Ohta, Akira; Ohki, Hiroshi; Ozeki, Sumio

2017-01-24

As-synthesized [Zn 2 (Oxac) (Taz) 2 ]·(H 2 O) 2.5 , referred to as ZOTW 2.5 , was prepared from aqueous methanol solutions of Zn 5 (CO 3 ) 2 (OH) 6 and two kinds of ligands of 1,2,4-triazole (Taz) and oxalic acid (Oxac) at 453 K for 12 h. The crystal structure was determined by the Rietveld method. As-synthesized ZOTW 2.5 was pretreated at 383 K and 1 mPa for t pt h, ZOTW x (t pt h). ZOTW x (≥3h) showed a type I adsorption isotherm for N 2 at 77 K having a saturation amount (V s ) of 180 mg/g, but that pretreated shortly showed only 1/10 in V s . CO 2 was adsorbed at 303 K in sigmoid on nonporous ZOTW x (≤2h) and in Langmuir-type on ZOTW x (≥3h) to reach the adsorption amount of 120 mg/g at 700 Torr. N 2 adsorption on ZOTW x (≤2h)deCO 2 , degassed after CO 2 adsorption on ZOTW x (≤2h), was promoted 5-fold from 180 mg/g on ZOTW x (t pt h) and ZOTW x (≥3h)deCO 2 up to ca. 1000 mg/g. The interaction of CO 2 and H 2 O molecules in micropores may lead to a new route for micropore formation.

Anaerobic treatment of municipal wastewater using the UASB-technology.

PubMed

Urban, I; Weichgrebe, D; Rosenwinkel, K-H

2007-01-01

The anaerobic treatment of municipal wastewater enables new applications for the reuse of wastewater. The effluent could be used for irrigation as the included nutrients are not affected by the treatment. Much more interesting now are renewable energies and the retrenchment of CO(2) emission. With the anaerobic treatment of municipal wastewater, not only can the CO(2) emission be reduced but "clean" energy supply can be gained by biogas. Most important for the sustainability of this process is the gathering of methane from the liquid effluent of the reactor, because the negative climate-relevant effect from the degassing methane is much higher than the positive effect from saving CO(2) emission. In this study, UASB reactors were used with a flocculent sludge blanket for the biodegradation of the carbon fraction in the wastewater with different temperatures and concentrations. It could be shown that the positive effect is much higher for municipal wastewater with high concentrations in hot climates.

Total sulfur dioxide emissions and pre-eruption vapor-saturated magma at Mount St. Helens, 1980-88

NASA Astrophysics Data System (ADS)

Gerlach, T. M.; McGee, K. A.

1994-12-01

SO2 from explosive volcanism can cause significant climatic and atmospheric impacts, but the source of the sulfur is controversial. Total ozone mapping spectrometer (TOMS), correlation spectrometer (COSPEC), and ash leachate data for Mount St. Helens from the time of the climactic eruption on 18 May 1980 to the final stages of non-explosive degassing in 1988 give a total SO2 emission of 2 Mt. COSPEC data show a sharp drop in emission rate that was apparently controlled by a decreasing rate of magma supply. A total SO2 emission of only 0.08 Mt is estimated from melt inclusion data and the conventional assumption that the main sulfur source was pre-eruption melt; commonly invoked sources of 'excess sulfur' (anhydrite decomposition, basaltic magma, and degassing of non-erupted magma) are unlikely in this case. Thus melt inclusions may significantly underestimate SO2 emissions and impacts of explosive volcanism on climate and the atmosphere. Measured CO2 emissions, together with the H2O content of melt inclusions and experimental solubility data, indicate the Mount St. Helens dacite was vapor-saturated at depth prior to ascent and suggest that a vapor phase was the main source of sulfur for the 2-Mt of SO2. A vapor source is consistent with experimental studies on the Mount St. Helens dacite and removes the need for a much debated shallow magma body.

Physical Parameters of Vulcanian Eruptions at Pichincha Volcano, Ecuador: Bomb Morphologies and Textures

NASA Astrophysics Data System (ADS)

Wright, H. M.; Cashman, K.; Rosi, M.; Cioni, R.

2003-12-01

Vulcanian eruptions are common at many volcanoes around the world. These eruptions occur in energetic pulses and eject relatively small amounts of material. Each blast event (vulcanian eruption) has been inferred to represent a "throat-clearing" process that ejects a conduit plug. As such, we can examine the ejected material to reconstruct the conduit stratigraphy. The recent sequence of vulcanian eruptions at Guagua Pichincha volcano provides an opportunity to learn more about the dynamics of and pressurization conditions preceding vulcanian eruptions. From late 1999 - mid 2000, Pichincha experienced a series of vulcanian eruptions that ejected ballistic bombs, which now cover the surface of the crater. Bomb types range from dense to highly vesicular, with many exhibiting the breadcrusting that is ubiquitous in vulcanian deposits. Clast morphology varies with clast density, with slightly vesicular bombs having thick, glassy crusts and widely spaced cracks, whereas more vesicular bombs have thinner crusts and more closely spaced, regular crack patterns. The wide range of clast types appears to represent the stratigraphy of the conduit prior to each eruptive event, with denser blocks formed from more degassed magma near the top of the pre-eruptive conduit plug and more vesicular blocks representing deeper, less degassed levels in the conduit. This study uses the ballistic bombs, including the abundant breadcrust bombs, to learn more about conduit processes during a typical vulcanian eruption. In particular, we use the rapidly quenched crusts of breadcrust bombs, which preserve pre-eruptive conduit material, to determine gradients in volatile and crystal content in the conduit. The volatile content (both H2O and CO2) of the pre-eruptive melt was determined from FTIR spectroscopic analysis of bomb rind matrix glass. These values reach up to 1.2 wt% water and 10 ppm CO2, equivalent to 15 MPa maximum recorded presusure, or approximately 600 meters maximum depth. Coincident with the volatile gradient, microlite populations in bombs with dense, glassy crusts have uniform tabular shapes, whereas microlites in bombs with vesicular rinds have more variable crystal shapes. Insight into these degassing and crystallization conditions may help us understand pressurization mechanisms for the eruptions. The differences between the ballistic bombs will provide a picture of the conduit prior to eruption.

Redox-stratification controlled biofilm (ReSCoBi) for completely autotrophic nitrogen removal: the effect of co- versus counter-diffusion on reactor performance.

PubMed

Terada, Akihiko; Lackner, Susanne; Tsuneda, Satoshi; Smets, Barth F

2007-05-01

A multi-population biofilm model for completely autotrophic nitrogen removal was developed and implemented in the simulation program AQUASIM to corroborate the concept of a redox-stratification controlled biofilm (ReSCoBi). The model considers both counter- and co-diffusion biofilm geometries. In the counter-diffusion biofilm, oxygen is supplied through a gas-permeable membrane that supports the biofilm while ammonia (NH(4)(+)) is supplied from the bulk liquid. On the contrary, in the co-diffusion biofilm, both oxygen and NH(4)(+) are supplied from the bulk liquid. Results of the model revealed a clear stratification of microbial activities in both of the biofilms, the resulting chemical profiles, and the obvious effect of the relative surface loadings of oxygen and NH(4)(+) (J(O(2))/J(NH(4)(+))) on the reactor performances. Steady-state biofilm thickness had a significant but different effect on T-N removal for co- and counter-diffusion biofilms: the removal efficiency in the counter-diffusion biofilm geometry was superior to that in the co-diffusion counterpart, within the range of 450-1,400 microm; however, the efficiency deteriorated with a further increase in biofilm thickness, probably because of diffusion limitation of NH(4)(+). Under conditions of oxygen excess (J(O(2))/J(NH(4)(+)) > 3.98), almost all NH(4)(+) was consumed by aerobic ammonia oxidation in the co-diffusion biofilm, leading to poor performance, while in the counter-diffusion biofilm, T-N removal efficiency was maintained because of the physical location of anaerobic ammonium oxidizers near the bulk liquid. These results clearly reveal that counter-diffusion biofilms have a wider application range for autotrophic T-N removal than co-diffusion biofilms. (c) 2006 Wiley Periodicals, Inc.

Composite δ13C and petrographic 195-355 ka record from Frasassi cave (central Italy) stalagmites: investigating drivers of speleothem calcite carbon isotope signals.

NASA Astrophysics Data System (ADS)

Vanghi, V.; Borsato, A.; Frisia, S.; Drysdale, R.; Hellstrom, J. C.; Bajo, P.; Montanari, A.

2016-12-01

Carbon isotope ratio of speleothem calcite is known to be a proxy for climate-dependent soil CO2 production. One of the paradigms is that, ideally, C stable isotope incorporation occurred in equilibrium. Yet, the process of degassing in the cave commonly results in δ13C values more positive than theoretically expected for speleothems formed in temperate-humid settings. Fabrics then provide the benchmark to unravel local, regional and global significance of speleothem δ13C. The δ13C time-series from two precisely U-Th dated Frasassi stalagmites covering the interval from 195 ka to 355 ka (Marine Isotope Stages 7 - 10) were interpreted on the basis of the sequence of fabrics. Columnar fabrics indicated deposition under constant kinetic fractionation, whereby δ13C shifts through time reflected a combination of atmospheric CO2 concentration changes and soil efficiency variability, controlled by regional mean annual temperature. Given that the δ13C values are constantly more-positive-than-expected because of the effect of degassing, shifts to more positive δ13C values above a baseline of -7 permil during glacials are here interpreted as driven by low soil efficiency and higher contribution of atmospheric CO2 (Breecker et al. 2012, Borsato et al. 2015). The comparison of high resolution δ13C curves with atmospheric pCO2 and benthic δ18O records further suggests that hemispheric temperature changes driven by insolation modulated the δ13C shifts above or below the baseline. Thus, a -3‰ shift from glacial to interglacial at terminations IV and III is here ascribed to changes in atmospheric pCO2 (Schubert and Jahren 2012). More open fabrics mark warmer conditions and increased soil productivity and are associated with more negative δ13C. In conclusion, only by coupling petrography and geochemical properties the global and local drivers of δ13C anomalies in stalagmites from this deep cave could be distinguished. Borsato et al. (2015), Earth Surface Processes and Landforms 40 (9), 1158-1170. Breecker et al. (2012), Geochimica et Cosmochimica Acta 96 (1), 230-246. Schubert and Jahren (2012), Geochimica et Cosmochimica Acta 96, 29-43.

Structural control on the CO2 release west of Mt. Epomeo resurgent block (Ischia, Italy)

NASA Astrophysics Data System (ADS)

de Vita, S.; Marotta, E.; Ventura, G.; Chiodini, G.

2003-04-01

Volcanism at Ischia started more than 150 ka B.P. and continued until the last eruption occurred in 1302 A.D. Ischia is dominated by the caldera forming eruption of Mt. Epomeo Green Tuff (55 ka), which was followed by block resurgence inside the caldera from 33 ka B.P. Resurgence influenced the volcanic activity determining the conditions for magma ascent mainly along the eastern edge of the resurgent block. The resurgent area has a poligonal shape resulting from reactivation of regional faults and by activation of faults related to volcanotectonism. The western sector is bordered by inward dipping, high angle strike-slip/reverse faults testifying a compressional stress regime in this area. These features are cut by late outward dipping normal faults due to gravitational stress. The activity of the volcanic system is testified by seismicity and thermal manifestations. Fumarolic activity concentrates along the faults that borders westward the Mt. Epomeo resurgent block, where the Green Tuff overlies fractured lavas. The structural data show that, outside the most active degassing zone, fractures show a NNW-SSE strike and dip toward Mt. Epomeo. These fractures delimit the northern sector of Mt. Epomeo and show strike and dip consistent with the inward dipping reverse faults. Inside the degassing area fractures show a NW-SE strike and dip outward Mt. Epomeo. These gravity-related faults cut the lavas where the hydrothermal circulation is active. The dip direction of the NW-SE striking fractures within the degassing zone is not consistent with that of the strike-slip/reverse faults (i.e. towards NE) but agrees well with that of the gravity-induced faults (dip direction towards SW). Inside the degassing zone, NW-SE striking faults with lengths not exceeding the hydrothermalized extension occur. This arrangement indicate that the syn-resurgence faults act as permeability barriers, whereas the youngest faults act as the main fluid pathway.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

Origin and z-distribution of Galactic diffuse [C II] emission

NASA Astrophysics Data System (ADS)

Velusamy, T.; Langer, W. D.

2014-12-01

Context. The [C ii] emission is an important probe of star formation in the Galaxy and in external galaxies. The GOT C+ survey and its follow up observations of spectrally resolved 1.9 THz [C ii] emission using Herschel HIFI provides the data needed to quantify the Galactic interstellar [C ii] gas components as tracers of star formation. Aims: We determine the source of the diffuse [C ii] emission by studying its spatial (radial and vertical) distributions by separating and evaluating the fractions of [C ii] and CO emissions in the Galactic ISM gas components. Methods: We used the HIFI [C ii] Galactic survey (GOT C+), along with ancillary H i, 12CO, 13CO, and C18O data toward 354 lines of sight, and several HIFI [C ii] and [C i] position-velocity maps. We quantified the emission in each spectral line profile by evaluating the intensities in 3 km s-1 wide velocity bins, "spaxels". Using the detection of [C ii] with CO or [C i], we separated the dense and diffuse gas components. We derived 2D Galactic disk maps using the spaxel velocities for kinematic distances. We separated the warm and cold H2 gases by comparing CO emissions with and without associated [C ii]. Results: We find evidence of widespread diffuse [C ii] emission with a z-scale distribution larger than that for the total [C ii] or CO. The diffuse [C ii] emission consists of (i) diffuse molecular (CO-faint) H2 clouds and (ii) diffuse H i clouds and/or WIM. In the inner Galaxy we find a lack of [C ii] detections in a majority (~62%) of H i spaxels and show that the diffuse component primarily comes from the WIM (~21%) and that the H i gas is not a major contributor to the diffuse component (~6%). The warm-H2 radial profile shows an excess in the range 4 to 7 kpc, consistent with enhanced star formation there. Conclusions: We derive, for the first time, the 2D [C ii] spatial distribution in the plane and the z-distributions of the individual [C ii] gas component. From the GOT C+ detections we estimate the fractional [C ii] emission tracing (i) H2 gas in dense and diffuse molecular clouds as ~48% and ~14%, respectively, (ii) in the H i gas ~18%, and (iii) in the WIM ~21%. Including non-detections from H i increases the [C ii] in H i to ~27%. The z-scale distributions FWHM from smallest to largest are [C ii] sources with CO, ~130 pc, (CO-faint) diffuse H2 gas, ~200 pc, and the diffuse H i and WIM, ~330 pc. When combined with [C ii], CO observations probe the warm-H2 gas, tracing star formation. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Real-time radon monitoring at Stromboli volcano: influence of environmental parameters on 222Rn degassing

NASA Astrophysics Data System (ADS)

Cigolini, C.; Ripepe, M.; Poggi, P.; Laiolo, M.

2008-12-01

Two real-time stations for radon monitoring are currently operative at Stromboli volcano. The 222Rn electronic dosimeters are interfaced with an electronic board connected to a radiomodem for wireless data transfer (through a directional antenna) to a receiving station at the volcano observatory (COA). Radon activity data and enviromental parameters (soil temperature and atmospheric pressure) are sampled every 15 minutes and are instantaneously elaborated and transferred via web so that they can be checked in remote. Collected time series show that there is an overall inverse correlation between radon emissions and seasonal temperature variations. Signal processing analysis show that radon emissions in sectors of diffuse degassing are modulated by tidal forces as well. In addition, radon activities recorded at the summit station, located along the summit fracture zone where the gas flux is concentrated, are positively correlated with changes in atmospheric pressure and confirm the occurrence of the 'atmospheric stack effect'. It is not excluded that this process may play an active role in modulating Stromboli explosivity.

Ar-40/Ar-39 age of the Shergotty achondrite and implications for its post-shock thermal history

NASA Technical Reports Server (NTRS)

Bogard, D. D.; Nyquist, L. E.; Husain, L.

1979-01-01

Ar-40/Ar-39 measurements are used to determine the age of the Shergotty achondrite and the chronology of the shock event responsible for the complete conversion of its plagioclase to maskelynite is discussed. Apparent ages are found to vary between 240 and 640 million years for the whole rock sample, with a plateau age of 254 million years for a maskelynite separate. The Rb-Sr age of 165 million years determined by Nyquist at al (1978) suggests that the maskelynite as well as the whole rock was incompletely degassed. Argon diffusion characteristics indicate a post-shock cooling time greater than 1000 years and a burial depth greater than 300 m for a thermal model of a cooling ejecta blanket of variable thickness. It is concluded that the shock event which degassed the argon and reset the Rb-Sr systematics occurred between 165 and 250 million years ago when the parent body experienced a collision in the asteroid belt.

Influence of Liquid Structure on Fickian Diffusion in Binary Mixtures of n-Hexane and Carbon Dioxide Probed by Dynamic Light Scattering, Raman Spectroscopy, and Molecular Dynamics Simulations.

PubMed

Klein, Tobias; Wu, Wenchang; Rausch, Michael Heinrich; Giraudet, Cédric; Koller, Thomas M; Fröba, Andreas Paul

2018-06-11

This study contributes to a fundamental understanding how the liquid structure in a model system consisting of weakly associative n-hexane ( n-C 6 H 14 ) and carbon dioxide (CO 2 ) influences the Fickian diffusion process. For this, the benefits of light scattering experiments and molecular dynamics (MD) simulations at macroscopic thermodynamic equilibrium were combined synergistically. Our reference Fickian diffusivities measured by dynamic light scattering (DLS) revealed an unusual trend with increasing CO 2 mole fractions up to a CO 2 concentration of about 70 mol%, which agrees with our simulation results. The molecular impacts on the Fickian diffusion were analyzed by MD simulations, where kinetic contributions related to the Maxwell-Stefan (MS) diffusivity and structural contributions quantified by the thermodynamic factor were studied separately. Both the MS diffusivity and the thermodynamic factor indicate the deceleration of Fickian diffusion compared to an ideal mixture behavior. Computed radial distribution functions as well as a significant blue-shift of the CH-stretching modes of n-C 6 H 14 identified by Raman spectroscopy show that the slowing-down of the diffusion is caused by a structural organization in the binary mixtures over a broad concentration range in the form of self-associated n-C 6 H 14 and CO 2 domains. These networks start to form close to the infinite dilution limits and seem to have their largest extent at a solute-solvent transition point at about 70 mol% of CO 2 . The current results not only improve the general understanding of mass diffusion in liquids, but also serve to develop sound prediction models for Fick diffusivities.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

It's the little things that matter most: The role of volatiles in volcanoes and their magmatic roots

NASA Astrophysics Data System (ADS)

Keller, T.; Suckale, J.

2017-12-01

Many volcanic eruptions are driven by volatiles - mostly H2O and CO2 - that degas from magmas rising up beneath the volcano. Gas expands during ascent, thus frequently creating lavas with upward of 50% vesicularity. That is a particularly compelling observation considering that volatiles are only present at concentrations of order 100 ppm in the mantle source. Yet, even at these small concentrations, volatiles significantly lower the peridotite solidus. That leads to the production of reactive volatile-rich melts at depth, which has important consequences for melt transport in the asthenosphere. Thus, volatiles have a pivotal role both at the beginning and the end of the magmatic storyline. A growing amount of observational evidence provides various perspectives on these systems. Volcanic products are characterised increasingly well by geochemical and petrological data. And, volcano monitoring now often provides continuous records of degassing flux and composition. What is missing to better interpret these data are coupled fluid mechanic and thermodynamic models that link melt production and reactive transport in the mantle and crust with degassing-driven volcanic activity at the surface. Such models need to describe the deformation and segregation of multiple material phases (liquids, solids, gases) and track the reactive transport of diverse chemical components (major elements, trace elements, volatiles). I will present progress towards a generalization of existing two-phase model for melt transport in the mantle, extending them to three-phase flows appropriate for magma circulation and degassing in volcanoes. What sets the two environments apart is the presence of a compressible vapor in volcanoes. Also, volcanic degassing may occur by convecting suspensions as well as porous segregation. The model framework we are developing for these processes is based on mixture theory. Uncovering the underlying physics that connects these diverse expressions of magma transport will provide an opportunity to gain deeper insights into magmatic and volcanic phenomena as related rather than separate processes. In time we may thus come to more fully understand how it is that the little things that are mantle volatiles do matter most in volcanoes and their magmatic roots.

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

Switchable Ionic Liquids: An Environmentally Friendly Medium to Synthesise Nanoparticulate Green Rust

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lao, David; Kukkadapu, Ravi; Kovarik, Libor

Under anoxic conditions, a novel nanoparticulate green rust with carbonate (nano GR) was synthesized by addition of methanol to degassed switchable ionic liquid (SWIL) solution comprised of 1-hexanol, diazabicycloundec-7-ene (DBU), CO2 and Fe(C2H3O2)2 (Fe(OAc)2). Variable temperature Mössbauer spectroscopy studies indicated the product to be predominantly GR while TEM-SAED method confirmed it be nanoparticulate in nature. Experiments with and without methanol in the SWIL medium suggest that methanol may be responsible for Fe(II) oxidation to Fe(III) necessary for GR formation. Studies with Ar instead of CO2 trigger gas indicated that CO2 is essential for GR formation. Conditions to generate CO32- anionmore » was most likely provided by basic environment of the medium. The nano GR suspension was very reactive and instantaneously oxidized completely to a reddish-brown precipitate upon exposure to ambient atmosphere. The nature of the oxidized sample is not certain. The oxidized product, however, appears to be a mix of ferric green rust- [GR(CO32-]*; major] and ferrihydrite-like minerals. To our knowledge, this is first report of use of environmentally-friendly SWIL reagents to synthesize very reactive nano GR materials.« less

Magma degassing: novel experiments with multiple volatile species on H2O, CO2, S and Cl and development of a new thermodynamic model

NASA Astrophysics Data System (ADS)

Lesne, P.; Witham, F.; Kohn, S.; Blundy, J.; Botcharnikov, R. E.; Behrens, H.

2010-12-01

Geochemical measurements, from chemistry of melt inclusion to gas fluxes and compositions, give important clues to help understand magma and gas transport from a magma chamber towards the surface. These data are of the utmost importance to constrain models of the mass transport processes occurring in volcanic systems. Experimental work is central to testing such models. The behaviour of water and carbon dioxide fluids in basaltic melts have been well studied in previous works (i.e. Dixon et al., 1995; Newman & Lowenstern, 2002; Papale et al., 2006). The various models agree that the gases exsolved at high pressures are rich in CO_{2}, and at lower pressures, when most of the CO_{2} has already moved to the fluid phase, H_{2}O strongly partitions into the fluid and the melt become dehydrated (e.g. Newman & Lowenstern, 2002; Papale et al, 2006). S and Cl are much less abundant in the atmosphere than H_{2}O and CO_{2} and therefore give much higher signal ratio to noise ratios than volcanogenic H_{2}O and CO_{2}. H_{2}O, CO_{2}, S and Cl being the major volatiles measured at vent in melt inclusions in volcanic systems, a detailed model of S and Cl behaviour in basaltic melts is highly valuable in order to better understand volcanic gas emissions, and to test models of degassing processes. We have developed a model for mixed C-O-H-S-Cl fluids in equilibrium with basalt. The model is based on the premise that the volumetrically dominant volatile components, H_{2}O and CO_{2}, will determine the behaviour of S and Cl. Equilibrium experiments between a C-O-H-S-Cl fluid and basaltic melts from Stromboli and Masaya have been performed, at 1150°C, under oxidized conditions and at pressure from 25 to 400MPa. Analyses of volatiles dissolved in the melt and determined fluid composition allow us to determine equilibrium constants and partition coefficients of S and Cl between a CO_{2}-H_{2}O-rich fluid phase and basaltic melt. Equilibrium constants were parameterized using a S-rich basaltic composition (Stromboli), and have been tested against independent S-poor basaltic composition melts for Stromboli, and two volatile compositions from Masaya volcano. Our model reproduces all these experimental data with good agreement. The geochemical model will be published as a user-friendly software package, SolEx, to allow easy prediction of melt and fluid phase chemistries. We hope that this will facilitate comparisons between fluid-mechanical models of volcanic behaviour and measurements of melt inclusion chemistry and emitted gas compositions and fluxes. Dixon et al., 1995, J. Pet., 36, 1607-1631; Newman & Lowenstern, 2002, Computers & Geosciences, 28, 597-604; Papale et al., 2006, Chem. Geol., 229, 78-95.

Inversely Estimating the Vertical Profile of the Soil CO2 Production Rate in a Deciduous Broadleaf Forest Using a Particle Filtering Method

PubMed Central

Sakurai, Gen; Yonemura, Seiichiro; Kishimoto-Mo, Ayaka W.; Murayama, Shohei; Ohtsuka, Toshiyuki; Yokozawa, Masayuki

2015-01-01

Carbon dioxide (CO2) efflux from the soil surface, which is a major source of CO2 from terrestrial ecosystems, represents the total CO2 production at all soil depths. Although many studies have estimated the vertical profile of the CO2 production rate, one of the difficulties in estimating the vertical profile is measuring diffusion coefficients of CO2 at all soil depths in a nondestructive manner. In this study, we estimated the temporal variation in the vertical profile of the CO2 production rate using a data assimilation method, the particle filtering method, in which the diffusion coefficients of CO2 were simultaneously estimated. The CO2 concentrations at several soil depths and CO2 efflux from the soil surface (only during the snow-free period) were measured at two points in a broadleaf forest in Japan, and the data were assimilated into a simple model including a diffusion equation. We found that there were large variations in the pattern of the vertical profile of the CO2 production rate between experiment sites: the peak CO2 production rate was at soil depths around 10 cm during the snow-free period at one site, but the peak was at the soil surface at the other site. Using this method to estimate the CO2 production rate during snow-cover periods allowed us to estimate CO2 efflux during that period as well. We estimated that the CO2 efflux during the snow-cover period (about half the year) accounted for around 13% of the annual CO2 efflux at this site. Although the method proposed in this study does not ensure the validity of the estimated diffusion coefficients and CO2 production rates, the method enables us to more closely approach the “actual” values by decreasing the variance of the posterior distribution of the values. PMID:25793387

The mechanistic basis of internal conductance: a theoretical analysis of mesophyll cell photosynthesis and CO2 diffusion.

PubMed

Tholen, Danny; Zhu, Xin-Guang

2011-05-01

Photosynthesis is limited by the conductance of carbon dioxide (CO(2)) from intercellular spaces to the sites of carboxylation. Although the concept of internal conductance (g(i)) has been known for over 50 years, shortcomings in the theoretical description of this process may have resulted in a limited understanding of the underlying mechanisms. To tackle this issue, we developed a three-dimensional reaction-diffusion model of photosynthesis in a typical C(3) mesophyll cell that includes all major components of the CO(2) diffusion pathway and associated reactions. Using this novel systems model, we systematically and quantitatively examined the mechanisms underlying g(i). Our results identify the resistances of the cell wall and chloroplast envelope as the most significant limitations to photosynthesis. In addition, the concentration of carbonic anhydrase in the stroma may also be limiting for the photosynthetic rate. Our analysis demonstrated that higher levels of photorespiration increase the apparent resistance to CO(2) diffusion, an effect that has thus far been ignored when determining g(i). Finally, we show that outward bicarbonate leakage through the chloroplast envelope could contribute to the observed decrease in g(i) under elevated CO(2). Our analysis suggests that physiological and anatomical features associated with g(i) have been evolutionarily fine-tuned to benefit CO(2) diffusion and photosynthesis. The model presented here provides a novel theoretical framework to further analyze the mechanisms underlying diffusion processes in the mesophyll.

The Mechanistic Basis of Internal Conductance: A Theoretical Analysis of Mesophyll Cell Photosynthesis and CO2 Diffusion1[W][OA

PubMed Central

Tholen, Danny; Zhu, Xin-Guang

2011-01-01

Photosynthesis is limited by the conductance of carbon dioxide (CO2) from intercellular spaces to the sites of carboxylation. Although the concept of internal conductance (gi) has been known for over 50 years, shortcomings in the theoretical description of this process may have resulted in a limited understanding of the underlying mechanisms. To tackle this issue, we developed a three-dimensional reaction-diffusion model of photosynthesis in a typical C3 mesophyll cell that includes all major components of the CO2 diffusion pathway and associated reactions. Using this novel systems model, we systematically and quantitatively examined the mechanisms underlying gi. Our results identify the resistances of the cell wall and chloroplast envelope as the most significant limitations to photosynthesis. In addition, the concentration of carbonic anhydrase in the stroma may also be limiting for the photosynthetic rate. Our analysis demonstrated that higher levels of photorespiration increase the apparent resistance to CO2 diffusion, an effect that has thus far been ignored when determining gi. Finally, we show that outward bicarbonate leakage through the chloroplast envelope could contribute to the observed decrease in gi under elevated CO2. Our analysis suggests that physiological and anatomical features associated with gi have been evolutionarily fine-tuned to benefit CO2 diffusion and photosynthesis. The model presented here provides a novel theoretical framework to further analyze the mechanisms underlying diffusion processes in the mesophyll. PMID:21441385

The ratios of carbon and non-radiogenic helium and argon isotopes in the mantle and crustal rocks

NASA Technical Reports Server (NTRS)

Lokhov, K.; Levsky, L.

1994-01-01

The studies of the relations of carbon and primary isotopes of noble gases were carried out on the natural gases and on the mantle rocks from the mantle M-type sources, which represent the degassed mantle reservoir (MORB's). These works has the aim of estimation of the values of the C/3He ratios in the deep mantle fluids to determine the flux of the mantle CO2 on the basis of known flux of primary mantle 3He. It was found, that in the natural gases the values of the C/3He ratios fall into the range from 1 times E plus 6 to 1 times E plus 15, and in the fluids of MORB's are constant near 2 times E plus 9. We have studied the mantle rocks from the relatively undergassed mantle P minus type sources: continental; Baikal Rift (Siberia), Mongolia, Catalonia (Spain), Pannonia Depression (central Europe) and ocean; Spietzbergen isl., Hawaii isl., Canarian isl. It ws found, that in mantle xenolites and the host alkaline basalts from the continental rifts and ocean islands, the values of the C/3He ratios fall into the range from E plus 11 to E plus 15 (and this result needed to be explained; the higher carbon to helium ratios is relatively undergassed mantle reservoir compared with the degassed one, requires whether hilly compatibility of helium compared with carbon, whether additional flux of 3He to the degassed mantle reservoir). From the other hand it was found that in the mantle rocks from the sources of P minus and M minus types, continental carbonatites, the values of the C/36Ar ratios are constant in the range from E plus 9 to E plus 10, the close values have the MORB's also.

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

Eruption and degassing dynamics of the major August 2015 Piton de la Fournaise eruption

NASA Astrophysics Data System (ADS)

Di Muro, Andrea; Arellano, Santiago; Aiuppa, Alessandro; Bachelery, Patrick; Boudoire, Guillaume; Coppola, Diego; Ferrazzini, Valerie; Galle, Bo; Giudice, Gaetano; Gurioli, Lucia; Harris, Andy; Liuzzo, Marco; Metrich, Nicole; Moune, Severine; Peltier, Aline; Villeneuve, Nicolas; Vlastelic, Ivan

2016-04-01

Piton de la Fournaise (PdF) shield volcano is one of the most active basaltic volcanoes in the World with one eruption every nine months, on average. This frequent volcanic activity is broadly bimodal, with frequent small volume, short lived eruptions (< 30 Mm3, most being < 10 Mm3) and less frequent relatively large (50-210 Mm3) and long lasting (months) eruptions. After the major caldera forming event of 2007, the volcano produced several short lived small volume summit to proximal eruptions of relatively evolved cotectic magmas and relatively long repose periods (up to 3.5 years between 2010 and 2014). The August 2015 eruption was the first large (45±15 Mm3) and long lasting (2 months) eruption since 2007 and the only event to be fully monitored by the new gas geochemical network of Piton de la Fournaise volcanological observatory (DOAS, MultiGaS, diffuse CO2 soil emissions). Regular lava and tephra sampling was also performed for geochemical and petrological analysis. The eruption was preceded by a significant increase in CO2 soil emissions at distal soil stations (ca. 15 km from the summit), with CO2 enrichment also being recorded at summit low temperature fumaroles. Eruptive products were spectacularly zoned, with plagioclase and pyroxene being abundant in the early erupted products and olivine being the main phase in the late-erupted lavas. Total gas emissions at the eruptive vent underwent a decrease during the first half of the eruption and then an increase, mirroring the time evolution of magma discharge rate (from 5-10 m3/s in September to 15-30 m3/s in late-October) and the progressive change in magma composition. In spite of significant evolution in magma and gas output, CO2/SO2 ratios in high temperature gases remained quite low (< 0.3) and with little temporal change. Geochemical data indicated that this relatively long-lived eruption corresponded to the progressive drainage of most of the shallow part of PdF plumbing system, triggered by a new pulse of deep magma. While erupted magma and high temperature gases were mostly provided by the shallow part of the system, distal sites and summit low temperature fumaroles recorded a deeper triggering mechanism.

Subsurface Growth of CoSi2 by Deposition of Co on Si-Capped CoSi2 Seed Regions

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; George, T.; Pike, W. T.

1991-01-01

At a growth temperature of 800 C, Co deposited on Si(111) diffuses through a Si cap and exhibits oriented growth on buried CoSi2 grains, a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2 provided the thickness of the Si cap is less than a critical value between 100 and 200 nm for a deposition rate of 0.01 nm/s. Steady-state endotaxy is modeled under the assumption that the process is controlled by Co diffusion.

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

NASA Astrophysics Data System (ADS)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels in these 14 rhyolitic magmas, no effect is detected. Therefore, it can be robustly concluded that degassing of substantial amounts of the H2O component (≤ 6.5 wt%), by itself, does not induce oxidation in erupted magmas, particularly those more iron-rich than rhyolites (e.g., arc basalts).

Evolution of the Martian atmosphere

NASA Technical Reports Server (NTRS)

Pepin, R. O.

1993-01-01

Evolution of Mars' noble gases through two stages of hydrodynamic escape early in planetary history has been proposed previously by the author. In the first evolutionary stage of this earlier model, beginning at a solar age of approximately 50 m.y., fractionating escape of a H2-rich primordial atmosphere containing CO2, N2, and the noble gases in roughly the proportions found in primitive carbonaceous (CI) chondrites is driven by intense extreme-ultraviolet (EUV) leads to a long (approximately 80 m.y.) period of quiescence, followed by an abrupt degassing of remnant H2, CO2, and N2 from the mantle and of solar-composition noble gases lighter than Xe from the planet's volatile-rich accretional core. Degassed H refuels hydrodynamic loss in a waning but still potent solar EUV flux. Atmospheric Xe, Kr, and Ar remaining at the end of this second escape stage, approximately 4.2 G.y. ago, have evolved to their present-day abundances and compositions. Residual Ne continues to be modified by accretion of solar wind gases throughout the later history of the planet. This model does not address a number of processes that now appear germane to Martian atmospheric history. One, gas loss and fractionation by sputtering, has recently been shown to be relevant. Another, atmospheric erosion, appears increasingly important. In the absence then of a plausible mechanism, the model did not consider the possibility of isotopic evolution of noble gases heavier than Ne after the termination of hydrodynamic escape. Subsequent non-thermal loss of N was assumed, in an unspecified way, to account for the elevation of N from the model value of approximately 250 percent at the end of the second escape stage to approximately 620 percent today. Only qualitative attention was paid to the eroding effects of impact on abundances of all atmophilic species prior to the end of heavy bombardment approximately 3.8 G.y. ago. No attempt was made to include precipitation and recycling of carbonates in tracking the pressure and isotopic history of CO2.

Application of gas diffusion biocathode in microbial electrosynthesis from carbon dioxide.

PubMed

Bajracharya, Suman; Vanbroekhoven, Karolien; Buisman, Cees J N; Pant, Deepak; Strik, David P B T B

2016-11-01

Microbial catalysis of carbon dioxide (CO 2 ) reduction to multi-carbon compounds at the cathode is a highly attractive application of microbial electrosynthesis (MES). The microbes reduce CO 2 by either taking the electrons or reducing the equivalents produced at the cathode. While using gaseous CO 2 as the carbon source, the biological reduction process depends on the dissolution and mass transfer of CO 2 in the electrolyte. In order to deal with this issue, a gas diffusion electrode (GDE) was investigated by feeding CO 2 through the GDE into the MES reactor for its reduction at the biocathode. A combination of the catalyst layer (porous activated carbon and Teflon binder) and the hydrophobic gas diffusion layer (GDL) creates a three-phase interface at the electrode. So, CO 2 and reducing equivalents will be available to the biocatalyst on the cathode surface. An enriched inoculum consisting of acetogenic bacteria, prepared from an anaerobic sludge, was used as a biocatalyst. The cathode potential was maintained at -1.1 V vs Ag/AgCl to facilitate direct and/or hydrogen-mediated CO 2 reduction. Bioelectrochemical CO 2 reduction mainly produced acetate but also extended the products to ethanol and butyrate. Average acetate production rates of 32 and 61 mg/L/day, respectively, with 20 and 80 % CO 2 gas mixture feed were achieved with 10 cm 2 of GDE. The maximum acetate production rate remained 238 mg/L/day for 20 % CO 2 gas mixture. In conclusion, a gas diffusion biocathode supported bioelectrochemical CO 2 reduction with enhanced mass transfer rate at continuous supply of gaseous CO 2 . Graphical abstract ᅟ.

Diffuse He degassing from Cumbre Vieja volcano, La Palma, Canary Islands

NASA Astrophysics Data System (ADS)

Asensio-Ramos, María; De Jongh, Marli E.; Lamfers, Kristen R.; Alonso, Mar; Amonte, Cecilia; Padrón, Eleazar; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Helium is considered as an ideal geochemical tracer due to its geochemical properties: chemical inertness, physical stability and practical insolubility in water under normal conditions. These characteristics, together with its high mobility on the crust, make the presence of helium anomalies on the surface environment of a volcanic system to be related to deep fluid migration controlled by volcano-tectonic features, also providing valuable information about the location and characteristics of the gas source and the fracturing of the crust. The recent results reported by Padrón et al. (2013) clearly show importance of helium emission studies for the prediction of major volcanic events and the importance of continuous monitoring of this gas in active volcanic regions. La Palma Island (708.32 km2) is located at the northwestern end of the Canarian Archipelago. Subaerial volcanic activity on this island started ˜2.0 My ago and has taken place exclusively at the southern part in the last 123 ka. Cumbre Vieja volcano, the most active basaltic volcano of the Canary Islands, was built in this zone, including a main north-south rift area 20 km long and up to 1,950 m in elevation, with vents located also at the northwest and northeast. Padrón et al., (2012) showed that helium is mainly emitted along both N-S and N-W rift of Cumbre Vieja, being, therefore, zones of enhanced permeability for deep gas migration and preferential routes for degassing. This work represents a continuation of the results obtained by Padrón et al. (2012) until the year 2016. Each study covered the 220 km2 of Cumbre Vieja with an average of 570 homogenously distributed sampling points. At each sampling site, soil gas samples were collected at 40 cm depth by withdrawing the gas aliquots into 60 cc hypodermic syringes. He content in the soil gases was analyzed by means of quadrupole mass spectrometry (QMS). Atmospheric gas was used periodically to calibrate the instrument. To estimate the helium emission rate at each sampling point, a pure diffusive model was applied following the Fick's law. Thus, assuming a pure diffusive mechanism, the helium emission was estimated between 18 and 38 kg d-1 in the studied period (2002-2016). Helium efflux contour maps were constructed using sequential Gaussian simulation (sGs) as interpolation method. In most of the surveys, helium enrichments in the soil layer with respect to the air concentration measured on Cumbre Vieja indicate a strong structural control in the degassing processes of the volcano and the excess helium seems to be emitted mainly along both N-S and N-W rifts of the volcano. This work reinforce the importance of performing helium emission studies as an important volcano monitoring technique that might help to detect early warning signals of volcanic unrest in oceanic volcanic islands. References: Padrón et al., (2012). Chem. Geol. 312-313, 138-147. Padrón et al. (2013). Geology 41(5), 539-542.

Late Coupled Evolution of Venus' Atmosphere and the Effects of Meteoritic Impacts

NASA Astrophysics Data System (ADS)

Gillmann, C.; Tackley, P. J.; Golabek, G.

2013-12-01

We investigate what mechanisms and events could have led to the divergent evolution of Venus and Earth. We propose develop our investigation of the post-magma-ocean history of the atmosphere and surface conditions on Venus through a coupled model of mantle/atmosphere evolution by including meteoritic impacts in our previous work. Our main focuses are mechanisms that deplete or replenish the atmosphere: volcanic degassing, atmospheric escape and impacts. Atmospheric escape modeling involves two different aspects. During the first few hundreds of million years, hydrodynamic escape is dominant. A significant portion of the early atmosphere can be thus removed. For later evolution, on the other hand, non-thermal escape becomes the main process as observed by the ASPERA instrument and modeled in various recent numerical studies. The atmosphere is replenished by volcanic degassing, using an adapted version of the StagYY mantle dynamics model (Armann and Tackley, 2012) and including episodic lithospheric overturn. The evolving surface temperature is calculated from CO2 and water in the atmosphere with a gray radiative-convective atmosphere model. This surface temperature in turn acts as a boundary condition for the mantle dynamics model and has an influence on the convection, volcanism and subsequent degassing. We take into account the effects of meteorites in our simulations by adapting each relevant part of the model. They can bring volatiles as well as erode the atmosphere. Mantle dynamics are modified since the impact itself can also bring large amounts of energy to the mantle. A 2D distribution of the thermal anomaly due to the impact is used and can lead to melting. Volatile evolution due to impacts (especially the large ones) is heavily debated so we test a broad range of impactor parameters (size, velocity, timing) and test different assumptions related to impact erosion going from large eroding power (Ahrens 1993) to recent parameterization (Shuvalov, 2009, 2010). We obtain a Venus-like behavior for the solid planet and atmospheric evolution leading to present-day conditions. Without any impact, CO2 pressure seems unlikely to vary much over the history of the planet, only slightly increasing due to degassing. A late build-up of the atmosphere with several resurfacing events seems unlikely. On the other hand, water pressure is strongly sensitive to volcanic activity and varies rapidly leading to variations in surface temperatures of up to 200K, which have been identified to have an effect on volcanic activity. We observe a clear correlation between low temperature and mobile lid regime. Impacts can strongly change this picture. While small (less than kilometer scale) meteorites have a negligible effect, medium ones are able to bring volatiles to the planet and generate melt both at the impact and later on, due to volcanic events they triggered due to the changes they make to mantle dynamics. A significant amount of volatiles (compared to present-day atmosphere) can be released on a short timescale, which can increase the surface temperature by tens of Kelvin. Larger impactors (~100 km) have even stronger effects as they can blow upwards of 10% of the atmosphere away, depending on the parameters. Removing more than 80% of the atmosphere on the impact is clearly feasible. In these cases, later degassing is also massive, which mitigates the volatile sink.

The Himalayas of Nepal, a natural laboratory for the search and measurement of CO2 discharge

NASA Astrophysics Data System (ADS)

Girault, Frédéric; Koirala, Bharat P.; Bhattarai, Mukunda; Rajaure, Sudhir; Richon, Patrick; Perrier, Frédéric

2010-05-01

Large CO2 flux has been found in the Trisuli Valley, North of Kathmandu, Central Nepal, in 2005. This leakage zone is located in the vicinity of the Syabru-Bensi hot springs, and is characterized by an average flux of CO2 of 6500±1100 g m-2 day-1 over an area of 15 m × 15 m (Perrier et al., Earth and Planetary Science Letters, 2009). The site is also located close to the Main Central Thrust Zone (MCT Zone), one of the large Himalayan thrust, connected at depth to the Main Himalayan Thrust, the main thrust currently accommodating the India-Tibet collision (Bollinger et al., Journal of Geophysical Research, 2004). Isotopic carbon ratios (δ13C) indicate that this CO2 may come from metamorphic reactions at about 15 km of depth (Becker et al., Earth and Planetary Science Letters, 2008; Evans et al., Geochemistry Geophysics Geosystems, 2008). Actually, this zone was originally found because of the large δ13C found in the water of the hot springs suggesting degassing (Evans et al., Geochemistry Geophysics Geosystems, 2008). In 2007, another zone of CO2 discharge was discovered 250 m away from the main Syabru-Bensi hot springs. This new zone, located next to the road and easy to access all over the year, was intensely studied, from the end of 2007 to the beginning of 2009. In this zone, an average value of CO2 flux of 1700±300 g m-2 d-1 was obtained over an area of about 40 m × 10 m. Using CO2 flux data from repeated measurements, similar flux values were observed during the dry winter season and the wet summer period (monsoon) (Girault et al., Journal of Environmental Radioactivity, 2009). Thus, in addition to fundamental issues related to global CO2 balance in orogenic belts and tectonically active zones, these small scale (100-meter) CO2 discharge sites emerge as a potentially useful laboratory for detailed methodological studies of diffusive and advective gas transport. Recently, the search for further gas discharge zones has been carried out using various clues: the presence of a hot spring with high δ13C, of H2S smell, of hot spots in thermal images, of a geological contact, of self-potential anomalies (Byrdina et al., Journal of Geophysical Research, 2009) or of large radon-222 flux. Preliminary results about the failures or successes of the various methods will be given in the Trisuli and Langtang valleys (Central Nepal), in the Kali Gandaki valley (Western Nepal) and in the Thuli Bheri valley (Lower Dolpo, Far Western Nepal). These various sites also offer an opportunity to test the optimal estimation of total CO2 flux, using the least amount of experimental measurements. Preliminary results complemented by simulations will also be given on the total CO2 flux. In parallel, monitoring methods are being studied in the Syabru-Bensi pilot site. First, CO2 flux has been studied as a function of time using repeated measurements. Furthermore, the high radon content of the geological CO2 allows cost-effective monitoring using BARASOL probes. More than two years of data are already available and give hints on the use of radon to follow CO2 discharge as a function of time. These first results show how experimental studies carried out in natural discharge zones provide a rich laboratory to test the methodological approaches useful for CO2 leakage and monitoring.

New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

NASA Astrophysics Data System (ADS)

Sade, Ziv; Halevy, Itay

2017-10-01

CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

Shock-induced devolatization of calcium sulfate and implications for K-T extinctions

NASA Technical Reports Server (NTRS)

Chen, Guangqing; Tyburczy, James A.; Ahrens, Thomas J.

1993-01-01

Calcium sulfate devolatization during the impact at Chicxulub, Mexico and dispersal in the stratosphere of the resultant sulfuric acid aerosol have been suggested as a possible mechanism for the Cretaceous-Tertiary extinctions. In this paper, we investigated two shock-induced devolatization reactions of calcium sulfate up to 42 GPa in the laboratory: CaSO4 + SiO2 yields CaSiO3 + SO3(degassed) and CaSO4 yields CaO + SO2(degassed) + 1/2 O2(degassed). We found both to proceed to a much less extent than calculated by equilibrium thermodynamic calculations. Reaction products are found to be 10(exp -2) times those calculated for equilibrium. Consequently our estimate of the amount of sulfur oxides degassed into the atmosphere from shock devolatization of CaS04 in the Chicxulub lithographic section (6x10(exp 15)-2x10(exp 16)g in sulfur mass) is lower by a factor of 70 to 400 than previous estimates; the related environmental stress arising from the resultant global cooling of approximately 4 K and fallout of acid rain does not appear to suffice to explain the widespread K-T extinctions.

A record of more than 500,000 years of large-volume travertine formation in the southwestern United States and links between paleohydrology, paleoclimate, and landscape evolution

NASA Astrophysics Data System (ADS)

Priewisch, A.; Crossey, L. J.; Embid, E.; Karlstrom, K. E.; Polyak, V.; Asmerom, Y.; Ricketts, J. W.

2011-12-01

CO2 springs and associated travertine deposits offer a unique tool to better understand Cenozoic paleohydrology and paleoclimate in the context of geomorphic and neotectonic evolution of the southwestern United States. Travertine accumulations represent places of persistent and significant mantle CO2 degassing in high discharge spring systems that are found along faults and above magmatic systems. They complement speleothem records from the same regions in that they can provide better links to the surface geomorphic and neotectonic systems. New Mexico and Arizona host several exceptionally well-preserved, large-volume travertine deposits that extend from 10 - 60 km2, with thicknesses ranging from 15 to more than 60 m. Precise U-series and stable isotope analyses are underway for large travertine platforms at Mesa del Oro, NM (~27 km2), Riley North and South Mesa, NM (~60 km2), Mesa Aparejo/Belen Quarries, NM (~13 km2), and Springerville, AZ (~30 km2). New ages for the travertine deposits at Mesa del Oro are 56 ka, 253 ka, 361 ka, and more than 500 ka. The travertine deposits at Riley North and South Mesa are older than 500 ka and 207/287 ka, respectively. At Mesa Aparejo, travertine ages are 312 ka and more than 500 ka. U/Th dates from Springerville, AZ show that major travertine accumulations occurred over several time intervals: 36-100 ka, 200-280 ka and 300-350 ka. Stable isotope analyses overlap substantially, exhibiting high δ13C values, +2.0% to +8.3%, and δ18O values that range from -13.5% to -4%. High δ13C values are interpreted to be caused by rapid CO2 degassing while the range of δ18O values is interpreted to represent changing water temperatures and mixing trends of groundwater. U-series data show that travertine deposition at all of these localities overlapped temporally and that major aggradation and high volume deposition was not steady, but occurred episodically at 36-100, 200-280, and 300-380 ka. Times of high accumulation rates are interpreted as times of high groundwater flow and hence as a proxy for regional paleohydrology/paleoclimate controls while the locations of the travertine occurrences (along faults of the Jemez lineament and Rio Grande rift) reflect more local CO2-discharge (tectonic) controls. These travertine occurrences are important indicators of the extent of past natural CO2 leakage that can inform carbon sequestration models both in areas of modern CO2 gas fields (Springerville) and at sites of potential paleo-gas fields. The travertine platforms now occupy positions high in the landscape (inverted topography) and also provide data on the scales and timing of regional landscape denudation.

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

USGS Publications Warehouse

Mandeville, C.W.; Webster, J.D.; Tappen, C.; Taylor, B.E.; Timbal, A.; Sasaki, A.; Hauri, E.; Bacon, C.R.

2009-01-01

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43??N, long. 122??W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing. Sulfur isotope analyses of climactic rhyodacitic whole rocks yield ??34S values of 2.8-14.8??? with corresponding matrix glass values of 2.4-13.2???. ??34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in ??34S from -0.4??? to 5.8??? and from -0.1??? to 3.5???, respectively. Initial ??34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0???. Hydrogen isotope (??D) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values ??f -103 to -53??? and 0.23-1.74 wt%, respectively. Values of ??D and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted ??D, and mantle ??18O values, have elevated ??34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth's atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14??? (to ??34S values of 14??? or more here) and hydrogen isotopic compositions by 90??? (to ??D values of -127??? in this case). ?? 2009 Elsevier Ltd.

Carbon dioxide emission rate of Kīlauea Volcano: Implications for primary magma and the summit reservoir

USGS Publications Warehouse

Gerlach, T.M.; McGee, K.A.; Elias, T.; Sutton, A.J.; Doukas, M.P.

2002-01-01

 We report a CO2 emission rate of 8500 metric tons per day (t d−1) for the summit of Kīlauea Volcano, several times larger than previous estimates. It is based on three sets of measurements over 4 years of synchronous SO2 emission rates and volcanic CO2/SO2concentration ratios for the summit correlation spectrometer (COSPEC) traverse. Volcanic CO2/SO2 for the traverse is representative of the global ratio for summit emissions. The summit CO2 emission rate is nearly constant, despite large temporal variations in summit CO2/SO2 and SO2 emission rates. Summit CO2 emissions comprise most of Kīlauea's total CO2 output (∼9000 t d−1). The bulk CO2 content of primary magma determined from CO2emission and magma supply rate data is ∼0.70 wt %. Most of the CO2 is present as exsolved vapor at summit reservoir depths, making the primary magma strongly buoyant. Turbulent mixing with resident reservoir magma, however, prevents frequent eruptions of buoyant primary magma in the summit region. CO2 emissions confirm that the magma supply enters the edifice through the summit reservoir. A persistent several hundred parts per million CO2 anomaly arises from the entry of magma into the summit reservoir beneath a square kilometer area east of Halemaumau pit crater. Since most of the CO2 in primary magma is degassed in the summit, the summit CO2 emission rate is an effective proxy for the magma supply rate. Both scrubbing of SO2 and solubility controls on CO2and S in basaltic melt cause high CO2/SO2 in summit emissions and spatially uncorrelated distributions of CO2 and SO2 in the summit plume.

Evidence of degassing-induced oxidation of relatively oxidized K-rich magmas caused by degassing of dissolved SO­42- (S6+) component in the melt to SO2 (S4+) in the gas phase

NASA Astrophysics Data System (ADS)

Pu, X.; Lange, R. A.; Moore, G. M.

2016-12-01

Near Volcán Colima in the Mexican volcanic arc, nine cones erupted minette, leucite basanite and basanite. These K-rich lavas have high post-eruptive Fe3+/FeT ratios (≤0.63) and sulfur contents (≤ 1004 ppm) (Carmichael et al., 2006). Olivine-hosted melt inclusions record ≤ 6.2wt% H2O and ≤ 6700ppm sulfur (Vigouroux et al., 2008). Here, we test whether the post-eruptive Fe3+/FeT ratios, measured by titration on fresh lavas, reflect magmatic values or a change in oxidation state during degassing. To constrain pre-eruptive fO2 (ilmenite is absent), the most Mg-rich olivine analyzed in each sample, together with a Fe-Mg KD (olivine-melt) of 0.355 (from hydrous experiments of Righter and Carmichael (1996) on a minette and the Jayasuriya et al. (2004) model to relate melt Fe2+/Fe3+ ratio to melt temperature and fO2), were used to obtain the Fe3+/FeT ratio at the onset of olivine crystallization. The resulting Fe3+/FeT ratios (0.31-0.41) and ΔNNO values (1.2-2.4) for the nine K-rich magmas are systematically lower than the post-eruptive values, which suggests that degassing induced oxidation may have occurred. In addition, the pre-eruptive Fe3+/FeT ratios and ΔNNO values are higher than those (0.19-0.31 and -0.2 to +1.2, respectively) documented for calc-alkaline basalts from Michoacán-Guanajuato Volcanic Field (MGVF) using a similar method (Pu et al., 2016). Because a similar increase between pre- and post-eruptive Fe3+/FeT ratios is not found in the MGVF samples, we infer that the increase between the pre- and post-eruptive Fe3+/FeT ratios in the K-rich samples is caused by the relatively high solubility of sulfate (S6+ in CaSO4 component) in the relatively oxidized (ΔNNO ≤ 2.4) potassic melts, which then degassed as S4+ (SO2). We deduce that oxidation caused by degassing of sulfur can only occur in melts that were already relatively oxidized, because the degassing-induced oxidation process requires an initial high concentration of sulfate in the melt phase.