Inferences from Microfractures and Geochemistry in Dynamic Shale-CO2 Packed Bed Experiments

NASA Astrophysics Data System (ADS)

Radonjic, M.; Olabode, A.

2016-12-01

Subsurface storage of large volumes of carbondioxide (CO2) is expected to have long term rock-fluid interactions impact on reservoir and seal rocks properties. Caprocks, particularly sedimentary types, are the ultimate hydraulic barrier in carbon sequestration. The mineralogical components of sedimentary rocks are geochemically active under enormous earth stresses, which generate high pressure and temperature conditions. It has been postulated that in-situ mineralization can lead to flow impedance in natural fractures in the presence of favorable geochemical and thermodynamic conditions. This experimental modelling research investigated the impact of in-situ geochemical precipitation on conductivity of fractures. Geochemical analyses were performed on four different samples of shale rocks, effluent fluids and recovered precipitates both before and after CO2-brine flooding of crushed shale rocks at moderately high temperature and pressure conditions. The results showed that most significant diagenetic changes in shale rocks after flooding with CO2-brine, reflected in the effluent fluid with predominantly calcium based minerals dissolving and precipitating under experimental conditions. Major and trace elements in the effluent (using ICP-OES analysis) indicated that multiple geochemical reactions are occurring with almost all of the constituent minerals participating. The geochemical composition of precipitates recovered after the experiments showed diagenetic carbonates and opal as the main constituents. The bulk rock showed little changes in composition except for sharper and more refined peaks on XRD analysis, suggesting that a significant portion of the amorphous content of the rocks have been removed via dissolution by the slightly acid CO2-brine fluid that was injected. Micro-indentation results captured slight reduction in the hardness of the shale rocks and this reduction appeared dependent on diagenetic quartz content. It can be inferred that convective reactive transport of dissolved minerals are involved in nanoscale precipitation-dissolution processes in shale. This reactive transport of dissolved minerals can occlude micro-fracture flow paths, thereby improving shale caprock seal integrity with respect to leakage risk under CO2 sequestration conditions.

The effect of iron content and dissolved O2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1996-01-01

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

PubMed

Yang, Changbing; Hovorka, Susan D; Delgado-Alonso, Jesus; Mickler, Patrick J; Treviño, Ramón H; Phillips, Straun

2014-12-02

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

Element uptake and physiological responses of Lactuca sativa upon co-exposures to tourmaline and dissolved humic acids.

PubMed

Jia, Weili; Wang, Cuiping; Ma, Chuanxin; Wang, Jicheng; Sun, Hongwen

2018-06-01

Element migration and physiological response in Lactuca sativa upon co-exposure to tourmaline (T) and dissolved humic acids (DHAs) were investigated. Different fractions of DHA 1 and DHA 4 and three different doses of T were introduced into Hoagland's solution. The results indicated that T enhanced the contents of elements such as N and C, Si and Al in the roots and shoots. The correlation between TF values of Si and Al (R 2  = 0.7387) was higher than that of Si and Mn (R 2  = 0.4961) without the presence of DHAs. However, both DHA 1 and DHA 4 increased the correlation between Si and Mn, but decreased the one between Si and Al. CAT activities in T treatments were positively correlated to the contents of N and Al in the shoots, whose R 2 was 0.9994 and 0.9897, respectively. In the co-exposure of DHAs and tourmaline, DHA 4 exhibited more impacts on element uptake, CAT activities, as well as ABA contents in comparison with the presence of DHA 1 , regardless of the T exposure doses. These results suggested that DHAs have effects on mineral element behaviors and physiological response in Lactuca sativa upon exposure to tourmaline for the first time, which had great use in guiding soil remediation.

Effects of Air Contact on Growth, Inorganic Carbon Sources, and Nitrogen Uptake by an Amphibious Freshwater Macrophyte.

PubMed Central

Madsen, T. V.; Breinholt, M.

1995-01-01

Callitriche cophocarpa Sendtner is a heterophyllous amphibious macrophyte that produces apical rosettes of floating leaves. The importance of air contact for inorganic carbon and N uptake and for growth was investigated. Plants were grown with the floating rosette in contact with air of various humidities (10, 50, and >90% relative humidity) and with the submerged parts in N-free water at 350 [mu]M free CO2 and the roots in sediment with low or high NH3-N content. Humidity greatly affected the transpiration rate, whereas growth rate and N content were unaffected and were comparable to values measured for fully submerged shoots. Air contact had, however, a significant impact on growth when the free CO2 concentration in the water was low. Thus, the growth rate of shoots with air contact was about 3 times faster than the rate of fully submerged shoots when grown at air-equilibrium concentration of dissolved free CO2 in the water (16 [mu]M). This difference decreased with increased dissolved free CO2 concentration in the water, and the two shoot types grew at the same rate when the submerged shoots received >350 [mu]M free CO2. The quantitative importance of the floating rosette for total carbon uptake declined also with decreased ratio of floating rosette to total shoot weight. It is concluded that floating rosettes can enhance the inorganic carbon uptake of Callitriche. In contrast, air contact is of minor importance for nutrient transport. PMID:12228350

Soil nitrate accumulation dominates the nonlinear responses of soil CO2 and CH4 fluxes to multi-level nitrogen addition in a temperate needle-broadleaved mixed forest

NASA Astrophysics Data System (ADS)

Fang, Huajun

2017-04-01

The responses of soil-atmosphere carbon (C) exchange fluxes to increased atmospheric nitrogen (N) deposition are controversial, leading to great uncertainty in the evaluation on the C sink capacity of global forest ecosystems elicited by anthropogenic N inputs. To date, we hardly knew how much was the critical level of N input for the alteration of the soil C fluxes, and what factors controlled the changes in soil CO2 and CH4 fluxes under N enrichment. Nine levels of urea addition experiment (0, 10, 20, 40, 60, 80, 100, 120, 140 kg N ha-1 yr-1) was conducted in the needle-broadleaved mixed forest in Changbai Mountain, Northeast China. Soil CO2 and CH4 fluxes were monitored weekly using the static chamber and gas chromatograph technique. Environmental variables (soil temperature and moisture in the 0-10 cm depth) and dissolved N (NH4+-N, NO3-N, total dissolved N (TDN), and dissolved organic N (DON)) in the organic layer and the 0-10 cm mineral soil layer were simultaneously measured. High rates of N addition (≥ 60 kg N ha-1 yr-1) significantly increased soil NO3-N contents in the organic layer and the mineral layer by 120%-180% and 56.4%-84.6%, respectively. However, N application did not lead to a significant accumulation of soil NH4+-N contents in the two soil layers except for a few treatments. N addition at a low rate of 10 kg N ha-1 yr-1 significantly promoted soil CO2 emission and CH4 uptake, whereas high rate of N addition (140 kg N ha-1 yr-1) significantly inhibited them. Significant negative relationships were observed between changes in soil CO2 emission and CH4 uptake and changes in soil NO3-N and moisture contents under N enrichment. These results suggest that soil nitrification and NO3-N accumulation could be important regulators of soil CO2 emission and CH4 uptake in the temperate needle-broadleaved mixed forest. The nonlinear responses to exogenous N inputs and the critical levels for the alteration of soil C fluxes should be considered in the ecological process models.

Using CDOM optical properties for estimating DOC concentrations and pCO 2 in the Lower Amazon River

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

Valerio, Aline de Matos; Kampel, Milton; Vantrepotte, Vincent

Colored dissolved organic matter (CDOM) is largely responsible for the optical properties of freshwaters and coastal areas and can be used as a proxy to assess the non-optical carbon content as the dissolved organic carbon (DOC) and the partial pressure of carbon dioxide (pCO 2). Nevertheless, riverine studies that explores the former relationship are more challenging due to the spectral mixture caused by the high content of inorganic materials in the suspended sediment. Here we evaluate the spatial-temporal variability of CDOM, DOC and pCO 2, as well as the potential of CDOM absorption coefficient (aCDOM(412)) for estimating DOC concentration andmore » pCO 2 along the lower Amazon River. Our results revealed differences in the dissolved organic matter (DOM) quality between clear water (CW) tributaries and the Amazon River mainstem. A linear relationship between DOC and CDOM was observed when tributaries and mainstem are evaluated separately (Amazon waters: N=42, R2=0.74; CW: N= 13, R2 = 0.57). However, this linear relationship was not observed during periods of higher rainfall and river discharge, requiring a model specific to these time periods to be developed (N = 25, R2 = 0.58). A strong linear positive relation was found between aCDOM(412) and pCO 2( N=69, R2=0.65) along the lower river. pCO 2 was less affected by the optical difference between tributaries and mainstem water or by the presence of higher hygrometric conditions when compared to CDOM to DOC relationships. Including the river water temperature in the model improves our ability to estimate pCO 2 (N=69; R2 = 0.80). Our results also illustrate the complexity of DOM temporal dynamics in the lower Amazon River where the occurrence of extreme high and low discharge due to factors such as El Niño, can significantly alter the expected seasonal oscillation, as was the case during this study period. The ability to remotely assess both DOC and pCO 2 from CDOM optical properties highlight the importance of using remote sensing data for monitoring carbon dynamics in large running water systems worldwide.« less

On the losses of dissolved CO(2) during champagne serving.

PubMed

Liger-Belair, Gérard; Bourget, Marielle; Villaume, Sandra; Jeandet, Philippe; Pron, Hervé; Polidori, Guillaume

2010-08-11

Pouring champagne into a glass is far from being consequenceless with regard to its dissolved CO(2) concentration. Measurements of losses of dissolved CO(2) during champagne serving were done from a bottled Champagne wine initially holding 11.4 +/- 0.1 g L(-1) of dissolved CO(2). Measurements were done at three champagne temperatures (i.e., 4, 12, and 18 degrees C) and for two different ways of serving (i.e., a champagne-like and a beer-like way of serving). The beer-like way of serving champagne was found to impact its concentration of dissolved CO(2) significantly less. Moreover, the higher the champagne temperature is, the higher its loss of dissolved CO(2) during the pouring process, which finally constitutes the first analytical proof that low temperatures prolong the drink's chill and helps it to retain its effervescence during the pouring process. The diffusion coefficient of CO(2) molecules in champagne and champagne viscosity (both strongly temperature-dependent) are suspected to be the two main parameters responsible for such differences. Besides, a recently developed dynamic-tracking technique using IR thermography was also used in order to visualize the cloud of gaseous CO(2) which flows down from champagne during the pouring process, thus visually confirming the strong influence of champagne temperature on its loss of dissolved CO(2).

Dissolved organic carbon content and characteristics in relation to carbon dioxide partial pressure across Poyang Lake wetlands and adjacent aquatic systems in the Changjiang basin.

PubMed

Wang, Huaxin; Jiao, Ruyuan; Wang, Fang; Zhang, Lu; Yan, Weijin

2016-12-01

Dissolved organic carbon (DOC) plays diverse roles in carbon biogeochemical cycles. Here, we explored the link between DOC and pCO 2 using high-performance size-exclusion chromatography (HPSEC) with UV 254 detection and excitation emission matrix (EEM) fluorescence spectroscopy to determine the molecular weight distribution (MW) and the spectral characteristics of DOC, respectively. The relationship between DOC and pCO 2 was investigated in the Poyang Lake wetlands and their adjacent aquatic systems. The results indicated significant spatial variation in the DOC concentrations, MW distributions, and pCO 2 . The DOC concentration was higher in the wetlands than in the rivers and lakes. pCO 2 was high in wetlands in which the dominant vegetation was Phragmites australis, whereas it was low in wetlands in which Carex tristachya was the dominant species. DOC was divided into five fractions according to MW, as follows: super-low MW (SLMW, <1 kDa); low MW (LMW, 1-2.5 kDa); intermediate MW (IMW, 2.5-3.5 kDa); high MW (HMW, 3.5-6 kDa); and super-high MW (SMW, > 40 kDa). Rivers contained high proportions of HMW and extremely low amounts of SLMW, whereas wetlands had relatively high proportions of SLMW. The proportion of SMW (SMW p ) was particularly high in wetlands. We found that pCO 2 significantly positively correlated with the proportion of IMW, and significantly negatively correlated with SMW p . These data improve our understanding of the MW of bioavailable DOC and its conversion to CO 2 . The present results demonstrate that both the content and characteristics of DOC significantly affect pCO 2 . pCO 2 and DOC must be studied further to help understanding the role of the wetland on the regional CO 2 budget. Copyright © 2016 Elsevier Ltd. All rights reserved.

Changes in soil characteristics and C dynamics after mangrove clearing (Vietnam).

PubMed

Grellier, Séraphine; Janeau, Jean-Louis; Dang Hoai, Nhon; Nguyen Thi Kim, Cuc; Le Thi Phuong, Quynh; Pham Thi Thu, Thao; Tran-Thi, Nhu-Trang; Marchand, Cyril

2017-09-01

Of the blue carbon sinks, mangroves have one of the highest organic matter (OM) storage capacities in their soil due to low mineralization processes resulting from waterlogging. However, mangroves are disappearing worldwide because of demographic increases. In addition to the loss of CO 2 fixation, mangrove clearing can strongly affect soil characteristics and C storage. The objectives of the present study were to quantify the evolution of soil quality, carbon stocks and carbon fluxes after mangrove clearing. Sediment cores to assess physico-chemical properties were collected and in situ CO 2 fluxes were measured at the soil-air interface in a mangrove of Northern Vietnam. We compared a Kandelia candel mangrove forest with a nearby zone that had been cleared two years before the study. Significant decrease of clay content and an increase in bulk density for the upper 35cm in the cleared zone were observed. Soil organic carbon (OC) content in the upper 35cm decreased by >65% two years after clearing. The quantity and the quality of the carbon changed, with lower carbon to nitrogen ratios, indicating a more decomposed OM, a higher content of dissolved organic carbon, and a higher content of inorganic carbon (three times higher). This highlights the efficiency of mineralization processes following clearing. Due to the rapid decrease in the soil carbon content, CO 2 fluxes at sediment interface were >50% lower in the cleared zone. Taking into account carbonate precipitation after OC mineralization, the mangrove soil lost ~10MgOCha -1 yr -1 mostly as CO 2 to the atmosphere and possibly as dissolved forms towards adjacent ecosystems. The impacts on the carbon cycle of mangrove clearing as shown by the switch from a C sink to a C source highlight the importance of maintaining these ecosystems, particularly in a context of climate change. Copyright © 2017 Elsevier B.V. All rights reserved.

More on the losses of dissolved CO(2) during champagne serving: toward a multiparameter modeling.

PubMed

Liger-Belair, Gérard; Parmentier, Maryline; Cilindre, Clara

2012-11-28

Pouring champagne into a glass is far from being inconsequential with regard to the dissolved CO(2) concentration found in champagne. Three distinct bottle types, namely, a magnum bottle, a standard bottle, and a half bottle, were examined with regard to their loss of dissolved CO(2) during the service of successively poured flutes. Whatever the bottle size, a decreasing trend is clearly observed with regard to the concentration of dissolved CO(2) found within a flute (from the first to the last one of a whole service). Moreover, when it comes to champagne serving, the bottle size definitely does matter. The higher the bottle volume, the better its buffering capacity with regard to dissolved CO(2) found within champagne during the pouring process. Actually, for a given flute number in a pouring data series, the concentration of dissolved CO(2) found within the flute was found to decrease as the bottle size decreases. The impact of champagne temperature (at 4, 12, and 20 °C) on the losses of dissolved CO(2) found in successively poured flutes for a given standard 75 cL bottle was also examined. Cold temperatures were found to limit the decreasing trend of dissolved CO(2) found within the successively poured flutes (from the first to the last one of a whole service). Our experimental results were discussed on the basis of a multiparameter model that accounts for the major physical parameters that influence the loss of dissolved CO(2) during the service of a whole bottle type.

Gas buildup in Lake Nyos, Cameroon: The recharge process and its consequences

USGS Publications Warehouse

Evans, William C.; Kling, G.W.; Tuttle, M.L.; Tanyileke, G.; White, L.D.

1993-01-01

The gases dissolved in Lake Nyos, Cameroon, were quantified recently (December 1989 and September 1990) by two independent techniques: in-situ measurements using a newly designed probe and laboratory analyses of samples collected in pre-evacuated stainless steel cylinders. The highest concentrations of CO2 and CH4 were 0.30 mol/kg and 1.7 mmol/kg, respectively, measured in cylinders collected 1 m above lake bottom. Probe measurements of in-situ gas pressure at three different stations showed that horizontal variations in total dissolved gas were negligible. Total dissolved-gas pressure near the lake bottom is 1.06 MPa (10.5 atm), 50% as high as the hydrostatic pressure of 2.1 MPa (21 atm). Comparing the CO2 profile constructed from the 1990 data to one obtained in May 1987 shows that CO2 concentrations have increased at depths to below 150 m. Based on these profiles, the average rate of CO2 input to bottom waters was 2.6 ?? 108 mol/a. Increased deep-water temperatures require an average heat flow of 0.32 MW into the hypolimnion over the same time period. The transport rates of CO2, heat, and major ions into the hypolimnion suggest that a low-temperature reservoir of free CO2 exists a short distance below lake bottom and that convective cycling of lake water through the sediments is involved in transporting the CO2 into the lake from the underlying diatreme. Increased CH4 concentrations at all depths below the oxycline and a high 14C content (41% modern) in the CH4 4 m above lake bottom show that much of the CH4 is biologically produced within the lake. The CH4 production rate may vary with time, but if the CO2 recharge rate remains constant, CO2 saturation of the entire hypolimnion below 50 m depth would require ???140 a, given present-day concentrations. ?? 1993.

Dissolved gas geochemical signatures of the ground waters related to the 2011 El Hierro magmatic reactivation

NASA Astrophysics Data System (ADS)

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

2012-04-01

El Hierro Island is the south westernmost and the youngest island of the Canary archipelago (<1.2 My). Since 16 July, an anomalous seismicity at El Hierro Island was recorded by IGN seismic network. After the occurrence of more than 10,000 seismic events, volcanic tremor was recorded since 05:15 on October 10, by all of the seismic stations on the island, with highest amplitudes recorded in the southernmost station. During the afternoon of 12 October a large light-green coloured area was observed in the sea to the south of La Restinga village (at the southernmost part of El Hierro island), suggesting the existence of a submarine eruption. Since October 12, frequent episodes of, turbulent gas emission and foaming, and the appearance of steamy lava fragments has been observed on the sea surface. Instituto Volcanologico de Canarias (INVOLCAN) started a hydrogeochemical program on August 2011 in order to evaluate the temporal evolution of dissolved gases on four different observation points (vertical and horizontal wells) of El Hierro. Three wells are located on the north of the island (where the seismic activity occurred at the beginning of the volcano-seismic unrest) and one horizontal well (gallery) in the south. At each observation point the concentration of dissolved helium, CO2, N2, O2 and Ar and the isotopic composition of He, C-CO2 and Ar have been measured three times per week. Significant increases on the dissolved gases content, mainly on CO2 and He/CO2 ratio, have been measured at all the observation points prior to the increasing of released seismic energy. Isotopic composition of dissolved helium, measured as 3He/4He ratio, showed an significant increase (from 1-3 RA up to 7.2 RA, being RA the isotopic 3He/4He ratio on air) at all the observation points 20 days before the occurrence of the submarine eruption and these relatively high 3He/4He values have been maintained along the volcanic unrest period. The isotopic composition of CO2 has showed also significant changes in relation to the release of seismic energy. The results observed on this dissolved gases study have been tremendously beneficial on the volcanic surveillance tools to study and forecast the evolution of the seismic-volcanic crisis.

Effects of biochar and maize straw on the short-term carbon and nitrogen dynamics in a cultivated silty loam in China.

PubMed

Zhu, Li-Xia; Xiao, Qian; Shen, Yu-Fang; Li, Shi-Qing

2017-01-01

Application of maize straw and biochar can potentially improve soil fertility and sequester carbon (C) in the soil, but little information is available about the effects of maize straw and biochar on the mineralization of soil C and nitrogen (N). We conducted a laboratory incubation experiment with five treatments of a cultivated silty loam, biochar produced from maize straw and/or maize straw: soil only (control), soil + 1 % maize straw (S), soil + 4 % biochar (B1), soil + 4 % biochar + 1 % maize straw (B1S), and soil + 8 % biochar + 1 % maize straw (B2S). CO 2 emissions, soil organic C, dissolved organic C, easily oxidized C, total N, mineral N, net N mineralization, and microbial biomass C and N of three replicates were measured periodically during the 60-day incubation using destructive sampling method. C mineralization was highest in treatment S, followed by B2S, B1S, the control, and B1. Total net CO 2 emissions suggested that negative or positive priming effect may occur between the biochar and straw according to the biochar addition rate, and biochar mineralization was minimal. By day 35, maize straw, irrespective of the rate of biochar addition, significantly increased microbial biomass C and N but decreased dissolved organic N. Biochar alone, however, had no significant effect on either microbial biomass C or N but decreased dissolved organic N. Mixing the soil with biochar and/or straw significantly increased soil organic C, easily oxidized C and total N contents, and decreased dissolved organic N content. Dissolved organic C contents showed mixed results. Notably, N was immobilized in soil mixed with straw and/or biochar, but the effect was stronger for soil mixed with straw, which may cause N deficiency for plant growth. The application of biochar and maize straw can thus affect soil C and N cycles, and the appropriate proportion of biochar and maize straw need further studies to increase C sequestration.

Comparative performance of CO2 measuring methods: marine aquaculture recirculation system application

USGS Publications Warehouse

Pfeiffer, T.J.; Summerfelt, S.T.; Watten, B.J.

2011-01-01

Many methods are available for the measurement of dissolved carbon dioxide in an aqueous environment. Standard titration is the typical field method for measuring dissolved CO2 in aquaculture systems. However, titrimetric determination of dissolved CO2 in marine water aquaculture systems is unsuitable because of the high dissolved solids, silicates, and other dissolved minerals that interfere with the determination. Other methods used to measure dissolved carbon dioxide in an aquaculture water included use of a wetted CO2 probe analyzer, standard nomographic methods, and calculation by direct measurements of the water's pH, temperature, and alkalinity. The determination of dissolved CO2 in saltwater based on partial pressure measurements and non-dispersive infra-red (NDIR) techniques with a CO2 gas analyzer are widely employed for oceanic surveys of surface ocean CO2 flux and are similar to the techniques employed with the head space unit (HSU) in this study. Dissolved carbon dioxide (DC) determination with the HSU using a infra-red gas analyzer (IRGA) was compared with titrimetric, nomographic, calculated, and probe measurements of CO2 in freshwater and in saltwater with a salinity ranging from 5.0 to 30 ppt, and a CO2 range from 8 to 50 mg/L. Differences in CO2 measurements between duplicate HSUs (0.1–0.2 mg/L) were not statistically significant different. The coefficient of variation for the HSU readings averaged 1.85% which was better than the CO2 probe (4.09%) and that for the titrimetric method (5.84%). In all low, medium and high salinity level trials HSU precision was good, averaging 3.39%. Differences existed between comparison testing of the CO2 probe and HSU measurements with the CO2 probe readings, on average, providing DC estimates that were higher than HSU estimates. Differences between HSU and titration based estimates of DC increased with salinity and reached a maximum at 32.2 ppt. These differences were statistically significant (P < 0.05) at all salinity levels greater than 0.3 ppt. Results indicated reliable replicated results from the head space unit with varying salinity and dissolved carbon dioxide concentrations.

Photosynthetic fractionation of 13C and concentrations of dissolved CO2 in the central equatorial Pacific during the last 255,000 years

NASA Technical Reports Server (NTRS)

Jasper, J. P.; Hayes, J. M.; Mix, A. C.; Prahl, F. G.

1994-01-01

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C [is equivalent to epsilon(p)] in a central equatorial Pacific sediment core that spans the last approximately 255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic composition of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon(p), derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 [is equivalent to c(e)] based on a new, site-specific calibration of the relationship between epsilon(p) and c(e). The calibration was based on reassessment of existing epsilon(p) versus c(e) data, which support a physiologically based model in which epsilon(p) is inversely related to c(e). Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index U(K/37). Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon(p) and 1/c(e). These are discussed in detail and it is concluded that the observed record of epsilon(p) most probably reflects significant variations in delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from approximately 110 microatmospheres during glacial intervals (ocean > atmosphere) to approximately 60 microatmospheres during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p<0.01) inverse correlations of delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Modeling Closed Equilibrium Systems of H2O-Dissolved CO2-Solid CaCO3.

PubMed

Tenno, Toomas; Uiga, Kalev; Mashirin, Alexsey; Zekker, Ivar; Rikmann, Ergo

2017-04-27

In many places in the world, including North Estonia, the bedrock is limestone, which consists mainly of CaCO 3 . Equilibrium processes in water involving dissolved CO 2 and solid CaCO 3 play a vital role in many biological and technological systems. The solubility of CaCO 3 in water is relatively low. Depending on the concentration of dissolved CO 2 , the solubility of CaCO 3 changes, which determines several important ground- and wastewater parameters, for example, Ca 2+ concentration and pH. The distribution of ions and molecules in the closed system solid H 2 O-dissolved CO 2 -solid CaCO 3 is described in terms of a structural scheme. Mathematical models were developed for the calculation of pH and concentrations of ions and molecules (Ca 2+ , CO 3 2- , HCO 3 - , H 2 CO 3 , CO 2 , H + , and OH - ) in the closed equilibrium system at different initial concentrations of CO 2 in the water phase using an iteration method. The developed models were then experimentally validated.

Significance of CO2 donor on the production of succinic acid by Actinobacillus succinogenes ATCC 55618

PubMed Central

2011-01-01

Background Succinic acid is a building-block chemical which could be used as the precursor of many industrial products. The dissolved CO2 concentration in the fermentation broth could strongly regulate the metabolic flux of carbon and the activity of phosphoenolpyruvate (PEP) carboxykinase, which are the important committed steps for the biosynthesis of succinic acid by Actinobacillus succinogenes. Previous reports showed that succinic acid production could be promoted by regulating the supply of CO2 donor in the fermentation broth. Therefore, the effects of dissolved CO2 concentration and MgCO3 on the fermentation process should be investigated. In this article, we studied the impacts of gaseous CO2 partial pressure, dissolved CO2 concentration, and the addition amount of MgCO3 on succinic acid production by Actinobacillus succinogenes ATCC 55618. We also demonstrated that gaseous CO2 could be removed when MgCO3 was fully supplied. Results An effective CO2 quantitative mathematical model was developed to calculate the dissolved CO2 concentration in the fermentation broth. The highest succinic acid production of 61.92 g/L was obtained at 159.22 mM dissolved CO2 concentration, which was supplied by 40 g/L MgCO3 at the CO2 partial pressure of 101.33 kPa. When MgCO3 was used as the only CO2 donor, a maximal succinic acid production of 56.1 g/L was obtained, which was just decreased by 7.03% compared with that obtained under the supply of gaseous CO2 and MgCO3. Conclusions Besides the high dissolved CO2 concentration, the excessive addition of MgCO3 was beneficial to promote the succinic acid synthesis. This was the first report investigating the replaceable of gaseous CO2 in the fermentation of succinic acid. The results obtained in this study may be useful for reducing the cost of succinic acid fermentation process. PMID:22040346

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.

Aquatic export of young dissolved and gaseous carbon from a pristine boreal fen: Implications for peat carbon stock stability.

PubMed

Campeau, Audrey; Bishop, Kevin H; Billett, Michael F; Garnett, Mark H; Laudon, Hjalmar; Leach, Jason A; Nilsson, Mats B; Öquist, Mats G; Wallin, Marcus B

2017-12-01

The stability of northern peatland's carbon (C) store under changing climate is of major concern for the global C cycle. The aquatic export of C from boreal peatlands is recognized as both a critical pathway for the remobilization of peat C stocks as well as a major component of the net ecosystem C balance (NECB). Here, we present a full year characterization of radiocarbon content ( 14 C) of dissolved organic carbon (DOC), carbon dioxide (CO 2 ), and methane (CH 4 ) exported from a boreal peatland catchment coupled with 14 C characterization of the catchment's peat profile of the same C species. The age of aquatic C in runoff varied little throughout the year and appeared to be sustained by recently fixed C from the atmosphere (<60 years), despite stream DOC, CO 2 , and CH 4 primarily being sourced from deep peat horizons (2-4 m) near the mire's outlet. In fact, the 14 C content of DOC, CO 2 , and CH 4 across the entire peat profile was considerably enriched with postbomb C compared with the solid peat material. Overall, our results demonstrate little to no mobilization of ancient C stocks from this boreal peatland and a relatively large resilience of the source of aquatic C export to forecasted hydroclimatic changes. © 2017 The Authors Global Change Biology Published by John Wiley & Sons Ltd.

Evaluation of calcium-bearing material for treatment of CO2 leakage-induced pollution

NASA Astrophysics Data System (ADS)

Park, J.; Park, M.; Jeong, H. Y.

2017-12-01

Several Ca2+-bearing materials were evaluated for their capability to treat CO2 leakage-induced pollution for the application of permeable reactive barriers (PRBs). In this regard, a series of batch experiments were carried out with Portland cement, quick lime (CaO), and gypsum (CaSO4). Each of these materials was added to 50 mL of CO2-saturated solutions ( 7.5-8.5 mM) in serum vials sealed with Teflon-coated grey butyl stopper. Subsequently, the resultant batches were agitated at room temperature for 24 h. At predetermined intervals, each vial was sacrificed to monitor changes in pH, EC, and dissolved CO2 concentration. Despite the pH-neutralizing capacity, 0.15 g of Portland cement did not lower any dissolved CO2. When amended with 0.05 g of Ca(OH)2 or Mg(OH)2, the cement at this loading could sequester dissolved CO2, with the former being more effective. Even without such amendments, the cement at or greater than 0.2 g was shown to completely sequester dissolved CO2. In case of quick lime, its loading as low as 0.05 g instantaneously removed all dissolved CO2, which was also noted for Portland cement at 0.5 g. For gypsum, its loading at 0.12 g was not effective for immobilizing dissolved CO2. By both X-ray diffraction (XRD) and thermogravimetry (TG) analyses, the CO2 sequestration by Ca2+-bearing materials was found to be mainly due to the formation of calcite (CaCO3). Funding source: The "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

Olivine-hosted Melt Inclusions: Insights into Highly Explosive Basaltic Volcanism from Alkali-rich Magma at Sunset Crater, AZ

NASA Astrophysics Data System (ADS)

Allison, C. M.; Roggensack, K.; Clarke, A. B.

2017-12-01

Sunset Crater volcano, an alkali basalt scoria cone in northern Arizona, erupted ca. 1085 AD, producing a large tephra blanket through sub-Plinian activity during its most explosive period. Primary melt inclusions (MIs) in free olivine crystals from the tephra were analyzed to study magma characteristics and storage conditions. We compare MIs from the early-erupted Strombolian deposit to those of sub-Plinian units to identify magma properties related to eruptive style. All MIs are faceted and closely similar in composition exhibiting minor post entrapment crystallization (3-15%). MIs are relatively dry (0.5-1.5 wt% H2O) but CO2-rich (1,200-3000 ppm). Most MIs contain >1 wt% H2O and >2,000 ppm CO2. MI vapor bubbles are ubiquitous in Sunset Crater samples ranging in size from 1 to 10 vol% of the MI in typical samples or 3 vol% on average. However, based on MI shrinkage caused by the decrease of olivine and melt densities with lower temperatures, only bubbles smaller than 3 vol% can result from post-entrapment cooling alone. We conclude that larger MI bubbles likely include volume contributions from pre-entrapment vapor. Raman spectroscopy, calibrated with synthetic CO2 inclusions, shows that the bubbles contain CO2 vapor and carbonate crystals have been observed on the bubble walls. Total MI CO2 contents, representing dissolved CO2 plus vapor bubble (if less than 3 vol% in size), range up to 4500 ppm. If no size constraint is applied to the vapor bubbles, the maximum total CO2 content (dissolved + vapor) reaches 6,500 ppm. These volatile abundances exceed the current experimental data on volatile solubility in alkali basalts. Fluid-saturated H2O-CO2 solubility experiments at 1200 °C between 400 and 600 MPa were conducted on the bulk Sunset Crater composition to account for the enhanced CO2 solubility of alkali-rich magma and accurately constrain solubility. This experimental data and the resulting calibrated thermodynamic model, indicates that MIs record depths up to 17 km, assuming fluid saturation. We do not observe any significant differences between MIs from Strombolian and sub-Plinian phases, suggesting that while a high CO2 content may drive rapid magma ascent and be partly responsible for highly explosive eruptions, shallower processes may play an important role in the final eruptive character.

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.

High-pressure sorption of nitrogen, carbon dioxide, and their mixtures on Argonne Premium Coals

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

Andreas Busch; Yves Gensterblum; Bernhard M. Krooss

2007-06-15

Gas sorption isotherms have been measured for carbon dioxide and nitrogen and their binary mixture (N{sub 2}/CO{sub 2} {approximately} 80/20) on three different moisture-equilibrated coals from the Argonne Premium Coal Sample Program by the U.S. Department of Energy, varying in rank from 0.25 to 1.68% vitrinite reflectance (VR{sub r}). The measurements were conducted at 55 C and at pressures up to 27 MPa for the pure gases and up to 10 MPa for the gas mixture. The effects of the large differences in equilibrium moisture contents (0.8 to 32.2%) on sorption capacity were estimated on the basis of the aqueousmore » solubility of CO{sub 2} and N{sub 2} at experimental conditions. Especially for the Beulah-Zap coal with an equilibrium moisture content of {approximately} 32%, the amount of dissolved CO{sub 2} contributes significantly to the overall storage capacity, whereas the amounts of N{sub 2} dissolved in the moisture water are low and can be neglected. Sorption measurements with nitrogen/carbon dioxide mixtures showed very low capacities for N{sub 2}. For Illinois coal, these excess sorption values were even slightly negative, probably due to small volumetric effects (changes in condensed phase volume). The evolution of the composition of the free gas phase in contact with the coal sample has been monitored continuously during each pressure step of the sorption tests. This composition changed strongly over time. Apparently, CO{sub 2} reaches sorption sites very quickly initially and is subsequently partly replaced by N{sub 2} molecules until concentration equilibration is reached. 18 refs., 10 figs., 2 tabs.« less

A new device for continuous monitoring the CO2 dissolved in water

NASA Astrophysics Data System (ADS)

de Gregorio, S.; Camarda, M.; Cappuzzo, S.; Giudice, G.; Gurrieri, S.; Longo, M.

2009-04-01

The measurements of dissolved CO2 in water are common elements of industrial processes and scientific research. In order to perform gas dissolved measurements is required to separate the dissolved gaseous phase from water. We developed a new device able to separate the gases phase directly in situ and well suitable for continuous measuring the CO2 dissolved in water. The device is made by a probe of a polytetrafluorethylene (PTFE) tube connected to an I.R. spectrophotometer (I.R.) and a pump. The PTFE is a polymeric semi-permeable membrane and allows the permeation of gas in the system. Hence, this part of the device is dipped in water in order to equilibrate the probe headspace with the dissolved gases. The partial pressure of the gas i in the headspace at equilibrium (Pi) follows the Henry's law: Pi=Hi•Ci, where Hi is the Henry's constant and Ci is the dissolved concentration of gas i. After the equilibrium is achieved, the partial pressure of CO2 inside the tube is equal to the partial pressure of dissolved CO2. The concentration of CO2 is measured by the I.R. connected to the tube. The gas is moved from the tube headspace to the I.R. by using the pump. In order to test the device and assess the best operating condition, several experimental were performed in laboratory. All the test were executed in a special apparatus where was feasible to create controlled atmospheres. Afterward the device has been placed in a draining tunnel sited in the Mt. Etna Volcano edifice (Italy). The monitored groundwater intercepts the Pernicana Fault, along which degassing phenomena are often observed. The values recorded by the station result in agreement with monthly directly measurements of dissolved CO2 partial pressure.

Effect of high carbon dioxide atmosphere packaging and soluble gas stabilization pre-treatment on the shelf-life and quality of chicken drumsticks.

PubMed

Al-Nehlawi, A; Saldo, J; Vega, L F; Guri, S

2013-05-01

The effects of an aerobic modified atmosphere packaging (MAP) (70% CO2, 15% O2 and 15% N2) with and without a CO2 3-h soluble gas stabilization (SGS) pre-treatment of chicken drumsticks were determined for various package and product quality characteristics. The CO2 dissolved into drumsticks was determined. The equilibrium between CO2 dissolved in drumsticks and CO2 in head space was reached within 48h after packaging, showing highest values of CO2 in SGS pre-treated samples. This greater availability of CO2 resulted in lower counts of TAB and Pseudomonas in SGS than in MAP drumsticks. Package collapse was significantly reduced in SGS samples. The average of CO2 dissolved in the MAP treatment was 567mg CO2kg(-1) of chicken and, 361mg CO2kg(-1) of chicken during the MAP treatment, in SGS pre-treated samples. This difference could be the quantity of CO2 dissolved during SGS pre-treatment. These results highlight the advantages of using SGS versus traditional MAP for chicken products preservation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Quantification of dissolved organic carbon at very low levels in natural ice samples by a UV-induced oxidation method.

PubMed

Preunkert, S; Legrand, M; Stricker, P; Bulat, S; Alekhina, I; Petit, J R; Hoffmann, H; May, B; Jourdain, B

2011-01-15

The study of chemical impurities trapped in solid precipitation and accumulated in polar ice sheets and high-elevation, midlatitude cold glaciers over the last several hundreds of years provides a unique way to reconstruct our changing atmosphere from the preindustrial era to the present day. Numerous ice core studies of inorganic species have already evaluated the effects of growing anthropogenic emissions of SO(2) or NO(x) on the chemical composition of the atmosphere in various regions of the world. While it was recently shown that organic species dominate the atmospheric aerosol mass, the contribution of anthropogenic emissions to their budget remains poorly understood. The study of organics in ice is at the infancy stage, and it still is difficult to draw a consistent picture of the organic content of polar ice from sparse available data. A UV oxidation method and IR quantification of CO(2) was optimized to obtain measurements of dissolved organic carbon content as low as a few ppbC. Stringent working conditions were defined to prevent contamination during the cleaning of ice. Measurements in various ice cores corresponding to preindustrial times revealed dissolved organic carbon content of less than 10 ppbC in Antarctica and up to 75 ppbC in alpine ice.

Popping Rocks Revealed: Investigations from 14°N on the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Wanless, V. D.; Jones, M.; Kurz, M. D.; Soule, S. A.; Fornari, D. J.; Bendana, S.; Mittelstaedt, E. L.

2017-12-01

The popping rock, recovered in dredge 2πD43 in 1985, is commonly considered to be one of the most representative samples of undegassed upper mantle, based on high volatile and noble gas abundances. While this basalt is used to reconstruct mantle volatile contents and CO2 fluxes from mid-ocean ridges (MOR), the origin of the popping rock has remained ambiguous due to a lack of geologic context. Here, we present results from the first combined geochemical, geophysical, and geologic investigation of popping rocks from 14N on the Mid-Atlantic Ridge. By combining lava compositions with high-resolution bathymetric maps, we show that the popping rocks are confined to a single geographic area, at the transition between magmatic and tectonic segments. Fifteen popping rocks were collected in situ using the Alvin submersible in 2016. X-ray microtomography indicates that these lavas have variable vesicle abundances; including the highest vesicularities (>19%) recorded for any MOR basalt. Dissolved CO2 contents (163-175 ppm) are similar to proximal non-popping rocks and are in equilibrium at their eruption depths (>3600 m); however, total CO2 contents (based on vesicularity, dissolved CO2, and vesicle gas contents) are higher than non-popping rocks, ranging from 2800-14150 ppm. The popping rocks have average 3He/4He ratios of 8.17 ± 0.1 Ra and 4He concentrations of 1.84e-5 to 7.67e-5 cc/g STP. Compared to non-popping lavas, the popping rocks have a narrow range of major and trace element concentrations, suggesting little to no crystallization occurred during ascent or eruption. REE patterns and trace element ratios are indistinguishable in the popping rocks (La/Sm = 2.89 ± 0.05), indicating similar mantle sources and extents of melting. Based on lava compositions and spatial distribution, we suggest that the popping rocks at 14N were produced under similar magmatic conditions and erupted over short timescales, perhaps during a series of closely timed eruptions.

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.

Experimental study on effects of geologic heterogeneity in enhancing dissolution trapping of supercritical CO2

NASA Astrophysics Data System (ADS)

Agartan, Elif; Trevisan, Luca; Cihan, Abdullah; Birkholzer, Jens; Zhou, Quanlin; Illangasekare, Tissa H.

2015-03-01

Dissolution trapping is one of the primary mechanisms that enhance the storage security of supercritical carbon dioxide (scCO2) in saline geologic formations. When scCO2 dissolves in formation brine produces an aqueous solution that is denser than formation brine, which leads to convective mixing driven by gravitational instabilities. Convective mixing can enhance the dissolution of CO2 and thus it can contribute to stable trapping of dissolved CO2. However, in the presence of geologic heterogeneities, diffusive mixing may also contribute to dissolution trapping. The effects of heterogeneity on mixing and its contribution to stable trapping are not well understood. The goal of this experimental study is to investigate the effects of geologic heterogeneity on mixing and stable trapping of dissolved CO2. Homogeneous and heterogeneous media experiments were conducted in a two-dimensional test tank with various packing configurations using surrogates for scCO2 (water) and brine (propylene glycol) under ambient pressure and temperature conditions. The results show that the density-driven flow in heterogeneous formations may not always cause significant convective mixing especially in layered systems containing low-permeability zones. In homogeneous formations, density-driven fingering enhances both storage in the deeper parts of the formation and contact between the host rock and dissolved CO2 for the potential mineralization. On the other hand, for layered systems, dissolved CO2 becomes immobilized in low-permeability zones with low-diffusion rates, which reduces the risk of leakage through any fault or fracture. Both cases contribute to the permanence of the dissolved plume in the formation.

Phytoplankton responses to atmospheric metal deposition in the coastal and open-ocean Sargasso Sea

PubMed Central

Mackey, Katherine R. M.; Buck, Kristen N.; Casey, John R.; Cid, Abigail; Lomas, Michael W.; Sohrin, Yoshiki; Paytan, Adina

2012-01-01

This study investigated the impact of atmospheric metal deposition on natural phytoplankton communities at open-ocean and coastal sites in the Sargasso Sea during the spring bloom. Locally collected aerosols with different metal contents were added to natural phytoplankton assemblages from each site, and changes in nitrate, dissolved metal concentration, and phytoplankton abundance and carbon content were monitored. Addition of aerosol doubled the concentrations of cadmium (Cd), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), and nickel (Ni) in the incubation water. Over the 3-day experiments, greater drawdown of dissolved metals occurred in the open ocean water, whereas little metal drawdown occurred in the coastal water. Two populations of picoeukaryotic algae and Synechococcus grew in response to aerosol additions in both experiments. Particulate organic carbon increased and was most sensitive to changes in picoeukaryote abundance. Phytoplankton community composition differed depending on the chemistry of the aerosol added. Enrichment with aerosol that had higher metal content led to a 10-fold increase in Synechococcus abundance in the oceanic experiment but not in the coastal experiment. Enrichment of aerosol-derived Co, Mn, and Ni were particularly enhanced in the oceanic experiment, suggesting the Synechococcus population may have been fertilized by these aerosol metals. Cu-binding ligand concentrations were in excess of dissolved Cu in both experiments, and increased with aerosol additions. Bioavailable free hydrated Cu2+ concentrations were below toxicity thresholds throughout both experiments. These experiments show (1) atmospheric deposition contributes biologically important metals to seawater, (2) these metals are consumed over time scales commensurate with cell growth, and (3) growth responses can differ between distinct Synechococcus or eukaryotic algal populations despite their relatively close geographic proximity and taxonomic similarity. PMID:23181057

Elevated CO2 facilitates C and N accumulation in a rice paddy ecosystem.

PubMed

Guo, Jia; Zhang, Mingqian; Wang, Xiaowen; Zhang, Weijian

2015-03-01

Elevated CO2 can stimulate wetland carbon (C) and nitrogen (N) exports through gaseous and dissolved pathways, however, the consequent influences on the C and N pools are still not fully known. Therefore, we set up a free-air CO2 enrichment experiment in a paddy field in Eastern China. After five year fumigation, we studied C and N in the plant-water-soil system. The results showed: (1) elevated CO2 stimulated rice aboveground biomass and N accumulations by 19.1% and 12.5%, respectively. (2) Elevated CO2 significantly increased paddy soil TOC and TN contents by 12.5% and 15.5%, respectively in the 0-15 cm layer, and 22.7% and 26.0% in the 15-30 cm soil layer. (3) Averaged across the rice growing period, elevated CO2 greatly increased TOC and TN contents in the surface water by 7.6% and 11.4%, respectively. (4) The TOC/TN ratio and natural δ15N value in the surface soil showed a decreasing trend under elevated CO2. The above results indicate that elevated CO2 can benefit C and N accumulation in paddy fields. Given the similarity between the paddies and natural wetlands, our results also suggest a great potential for long-term C and N accumulation in natural wetlands under future climate patterns. Copyright © 2015. Published by Elsevier B.V.

Variation in the carbon cycle of the Sevastopol Bay (Black Sea)

NASA Astrophysics Data System (ADS)

Orekhova, N. A.; Konovalov, S. K.

2018-01-01

Continuous increase in CO2 inventory in the ocean results in dramatic changes in marine biogeochemistry, e.g. acidification. That is why temporal and spatial variabilities in atmospheric pCO2 and dissolved inorganic carbon, including CO2, pH and alkalinity in water, as well as organic and inorganic carbon in bottom sediments have to be studied together making possible to resolve the key features of the carbon cycle transformation. A 30% increase of pCO2 in the Sevastopol Bay for 2008 - 2016 evidences changes in the DIC components ratios and a significant decrease in the ability to absorb atmospheric CO2 by surface waters. High organic carbon content in the bottom sediments and predominance of organic carbon production in the biological pump at inner parts of the bay reveal ongoing transformation of the carbon cycle. This has negative consequences for recreation, social and economic potentials of the Sevastopol region.

Biomass hydrolysis inhibition at high hydrogen partial pressure in solid-state anaerobic digestion.

PubMed

Cazier, E A; Trably, E; Steyer, J P; Escudie, R

2015-08-01

In solid-state anaerobic digestion, so-called ss-AD, biogas production is inhibited at high total solids contents. Such inhibition is likely caused by a slow diffusion of dissolved reaction intermediates that locally accumulate. In this study, we investigated the effect of H2 and CO2 partial pressure on ss-AD. Partial pressure of H2 and/or CO2 was artificially fixed, from 0 to 1 557mbars for H2 and from 0 to 427mbars for CO2. High partial pressure of H2 showed a significant effect on methanogenesis, while CO2 had no impact. At high [Formula: see text] , the overall substrate degradation decreased with no accumulation of metabolites from acidogenic bacteria, indicating that the hydrolytic activity was specifically impacted. Interestingly, such inhibition did not occur when CO2 was added with H2. This result suggests that CO2 gas transfer is probably a key factor in ss-AD from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Raman Spectroscopic Measurements of Co2 Dissolved in Seawater for Laser Remote Sensing in Water

NASA Astrophysics Data System (ADS)

Somekawa, Toshihiro; Fujita, Masayuki

2016-06-01

We examined the applicability of Raman lidar technique as a laser remote sensing tool in water. The Raman technique has already been used successfully for measurements of CO2 gas dissolved in water and bubbles. Here, the effect of seawater on CO2 Raman spectra has been evaluated. A frequency doubled Q-switched Nd:YAG laser (532 nm) was irradiated to CO2 gas dissolved in a standard seawater. In seawater, the Raman signals at 984 and 1060-1180 cm-1 from SO42- were detected, which shows no spectral interference caused by Raman signals derived from CO2.

Dissolved carbon dioxide and oxygen concentrations in purge of vacuum-packaged pork chops and the relationship to shelf life and models for estimating microbial populations.

PubMed

Adams, K R; Niebuhr, S E; Dickson, J S

2015-12-01

The objectives of this study were to determine the dissolved CO2 and O2 concentrations in the purge of vacuum-packaged pork chops over a 60 day storage period, and to elucidate the relationship of dissolved CO2 and O2 to the microbial populations and shelf life. As the populations of spoilage bacteria increased, the dissolved CO2 increased and the dissolved O2 decreased in the purge. Lactic acid bacteria dominated the spoilage microflora, followed by Enterobacteriaceae and Brochothrix thermosphacta. The surface pH decreased to 5.4 due to carbonic acid and lactic acid production before rising to 5.7 due to ammonia production. A mathematical model was developed which estimated microbial populations based on dissolved CO2 concentrations. Scanning electron microscope images were also taken of the packaging film to observe the biofilm development. The SEM images revealed a two-layer biofilm on the packaging film that was the result of the tri-phase growth environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modeling the Losses of Dissolved CO(2) from Laser-Etched Champagne Glasses.

PubMed

Liger-Belair, Gérard

2016-04-21

Under standard champagne tasting conditions, the complex interplay between the level of dissolved CO2 found in champagne, its temperature, the glass shape, and the bubbling rate definitely impacts champagne tasting by modifying the neuro-physicochemical mechanisms responsible for aroma release and flavor perception. On the basis of theoretical principles combining heterogeneous bubble nucleation, ascending bubble dynamics, and mass transfer equations, a global model is proposed, depending on various parameters of both the wine and the glass itself, which quantitatively provides the progressive losses of dissolved CO2 from laser-etched champagne glasses. The question of champagne temperature was closely examined, and its role on the modeled losses of dissolved CO2 was corroborated by a set of experimental data.

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.

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

NASA Technical Reports Server (NTRS)

Pawley, Alison R.; Holloway, John R.; Mcmillan, Paul F.

1992-01-01

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Reconstructing mantle volatile contents through the veil of degassing

NASA Astrophysics Data System (ADS)

Tucker, J.; Mukhopadhyay, S.; Gonnermann, H. M.

2014-12-01

The abundance of volatile elements in the mantle reveals critical information about the Earth's origin and evolution such as the chemical constituents that built the Earth and material exchange between the mantle and exosphere. However, due to magmatic degassing, volatile element abundances measured in basalts usually do not represent those in undegassed magmas and hence in the mantle source of the basalts. While estimates of average mantle concentrations of some volatile species can be obtained, such as from the 3He flux into the oceans, volatile element variability within the mantle remains poorly constrained. Here, we use CO2-He-Ne-Ar-Xe measurements in basalts and a new degassing model to reconstruct the initial volatile contents of 8 MORBs from the Mid-Atlantic Ridge and Southwest Indian Ridge that span a wide geochemical range from depleted to enriched MORBs. We first show that equilibrium degassing (e.g. Rayleigh degassing), cannot simultaneously fit the measured CO2-He-Ne-Ar-Xe compositions in MORBs and argue that kinetic fractionation between bubbles and melt lowers the dissolved ratios of light to heavy noble gas species in the melt from that expected at equilibrium. We present a degassing model (after Gonnermann and Mukhopadhyay, 2007) that explicitly accounts for diffusive fractionation between melt and bubbles. The model computes the degassed composition based on an initial volatile composition and a diffusive timescale. To reconstruct the undegassed volatile content of a sample, we find the initial composition and degassing timescale which minimize the misfit between predicted and measured degassed compositions. Initial 3He contents calculated for the 8 MORB samples vary by a factor of ~7. We observe a correlation between initial 3He and CO2 contents, indicating relatively constant CO2/3He ratios despite the geochemical diversity and variable gas content in the basalts. Importantly, the gas-rich popping rock from the North Atlantic, as well as the average mantle ratio computed from the ridge 3He flux and independently estimated CO2 content fall along the same correlation. This observation suggests that undegassed CO2 and noble gas concentrations can be reconstructed in individual samples through measurement of noble gases and CO2 in erupted basalts.

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.

Predicting possible effects of H2S impurity on CO2 transportation and geological storage.

PubMed

Ji, Xiaoyan; Zhu, Chen

2013-01-02

For CO(2) geological storage, permitting impurities, such as H(2)S, in CO(2) streams can lead to a great potential for capital and energy savings for CO(2) capture and separation, but it also increases costs and risk management for transportation and storage. To evaluate the cost-benefits, using a recently developed model (Ji, X.; Zhu, C. Geochim. Cosmochim. Acta 2012, 91, 40-59), this study predicts phase equilibria and thermodynamic properties of the system H(2)S-CO(2)-H(2)O-NaCl under transportation and storage conditions and discusses potential effects of H(2)S on transportation and storage. The prediction shows that inclusion of H(2)S in CO(2) streams may lead to two-phase flow. For H(2)S-CO(2) mixtures, at a given temperature, the bubble and dew pressures decrease with increasing H(2)S content, while the mass density increases at low pressures and decreases at high pressures. For the CO(2)-H(2)S-H(2)O system, the total gas solubility increases while the mass density of the aqueous solution with dissolved gas decreases. For the CO(2)-H(2)S-H(2)O-NaCl system, at a given temperature, pressure and NaCl concentration, the solubility of the gas mixture in aqueous phase increases with increasing H(2)S content and then decreases, while the mass density of aqueous solution decreases and may be lower than the mass density of the solution without gas dissolution.

The Effects of Elevated pCO2, Hypoxia and Temperature on ...

EPA Pesticide Factsheets

Estuarine fish are acclimated to living in an environment with rapid and frequent changes in temperature, salinity, pH, and dissolved oxygen (DO) levels; the physiology of these organisms is well suited to cope with extreme thermal, hypercapnic, and hypoxic stress. While the adverse effects of low dissolved oxygen levels on estuarine fish has been well-documented, the interaction between low DO and elevated pCO2 is not well understood. There is some evidence that low DO and elevated pCO2 interact antagonistically, however little information exists on how projected changes of pCO2 levels in near-shore waters may affect estuarine species, and how these changes may specifically interact with dissolved oxygen and temperature. We explored the survivability of 7-day post fertilization sheepshead minnow, Cyprinodon variegatus, using short term exposure to the combined effects of elevated pCO2 (~1300 µatm; IPCC RCP 8.5) and low dissolved oxygen levels (~2 mg/L). Additionally, we determined if the susceptibility of these fish to elevated pCO2 and low DO was influenced by increases in temperature from 27.5°C to 35°C. Results from this study and future studies will be used to identify estuarine species and lifestages sensitive to the combined effects of elevated pCO2 and low dissolved oxygen. This project was created in order to better understand the interactive effects of projected pCO2 levels and hypoxia in estuarine organisms. This work is currently focused on the se

UNDERSTANDING AND MANAGING RISKS POSED BY BRINES CONTAINING DISSOLVED CARBON DIOXIDE

EPA Science Inventory

Geologic disposal of supercritical carbon dioxide in saline aquifers and depleted oil and gas fields will cause large volumes of brine to become saturated with dissolved CO₂ at concentrations of 50 g/l or more.  As CO₂ dissolves in brine, the brine de...

Greenhouse Gas Dynamics in Streams and Riparian Floodplains located within Forested Landscapes of the US Northeast: Impact of Key Floodplain Geomorphic Features on Greenhouse Gas Production in a Forested Watershed in Northern New York State, USA.

NASA Astrophysics Data System (ADS)

Serchan, S. P.; Vidon, P.

2015-12-01

This study measured dissolved greenhouse gas (GHG) concentrations in interstitial water and stream across various "hotspots" in headwater catchments of Archer Creek watershed, New York, USA. Results indicated that stream water was hyper saturated with methane (CH4), and moderately saturated with carbon dioxide (CO2), and nitrous oxide (N2O). The values of dissolved CO2 (88.3 μmol/L), dissolved CH4 (1.2 μmol/L), and dissolved N2O (0.02 μmol/L) found in the stream were 5.8, 432, and 2.3 times in excess of atmospheric equilibrium, respectively. Results of dissolved GHG measured in interstitial water across various sites: riparian dry (RZ-Dry), riparian wet (RZ-Wet), riparian mucky (RZ-Mucky), pool with fine textured bed sediments (IS-fine-sedpool), pool with coarse textured bed sediments (IS-coarse-sed-pool), and riffles (Riffle) indicated high variations in the degree of saturation of all three GHG. RZ-Mucky, RZ-Wet, and IS-fine-sedpool sites were hotspots of CH4 and CO2 relative to other sites. RZ-Dry sites were hotspots of N2O. Multiple linear regression models indicated that dissolved oxygen (D.O.) and dissolved organic carbon (DOC) influenced dissolved CO2 and CH4 at most of the sites. Relationships between dissolved N2O and predictor variables were highly variable across all sites. Patterns of dissolved N2O in relatively oxic RZ-Dry sites (D.O. 5.3 mg/L) were positively correlated with nitrate (NO3) indicating nitrification as a dominant process in N2O production. In contrast, patterns of dissolved N2O were positively correlated with ammonium (NH4+) at RZ-Wet and RZ-Mucky sites where concentrations of D.O. were significantly lower compared to other sites.

Towards explaining excess CO2 production in wetlands - the roles of solid and dissolved organic matter as electron acceptors and of substrate quality

NASA Astrophysics Data System (ADS)

Knorr, Klaus-Holger; Gao, Chuanyu; Agethen, Svenja; Sander, Michael

2017-04-01

To understand carbon storage in water logged, anaerobic peatlands, factors controlling mineralization have been studied for decades. Temperature, substrate quality, water table position and the availability of electron acceptors for oxidation of organic carbon have been identified as major factors. However, many studies reported an excess carbon dioxide (CO2) production over methane (CH4) that cannot be explained by available electron acceptors, and peat soils did not reach strictly methanogenic conditions (i.e., a stoichiometric formation ratio of 1:1 of CO2 to CH4). It has been hypothesized that peat organic matter (OM) provides a previously unrecognized electron acceptor for microbial respiration, elevating CO2 to CH4 ratios. Microbial reduction of dissolved OM has been shown in the mid 90's, but only recently mediated electrochemical techniques opened the possibility to access stocks and changes in electron accepting capacities (EAC) of OM in dissolved and solid form. While it was shown that the EAC of OM follows redox cycles of microbial reduction and O2 reoxidation, changes in the EAC of OM were so far not related quantitatively to CO2 production. We therefore tested if CO2 production in anoxic peat incubations is balanced by the consumption of electron acceptors if EAC of OM is included. We set up anoxic incubations with peat and monitored production of CO2 and CH4, and changes in EAC of OM in the dissolved and solid phase over time. Interestingly, in all incubations, the EAC of dissolved OM was poorly related to CO2 and CH4 production. Instead, dissolved OM was rapidly reduced at the onset of the incubations and thereafter remained in reduced form. In contrast, the decrease in the EAC of particulate (i.e. non-dissolved) OM was closely linked to the observed production of non-methanogenic CO2. Thereby, the total EAC of the solid OM pool by far exceeded the EAC of the dissolved OM pool. Over the course of eight week incubations, measured decreases in the EAC of total NOM could explain 22-38 % of excess CO2 production in a weakly decomposed peat, 30-67 % of excess CO2 production in a well decomposed peat, and >100 % of excess CO2 production in a peat that had been exposed to oxygen for > 1 year. In this latter peat, EAC by OM explained 45-57 % of CO2 production, while reduction of sulfate available in this material readily explained the remaining fraction. Despite having considerable uncertainty arising from methodological challenges, the collected data demonstrated that accounting for the EACs of solid and dissolved OM may fully explain excess CO2 production. As we conservatively assumed a carbon oxidation state of zero for our budget calculations, a higher oxidation state of C in NOM as suggested by elemental analysis would result in electron equivalent budgets between EAC decreases and CO2 formation even closer to 100 %. A higher oxidation state of mineralized carbon seemed especially likely for weakly decomposed peat, as this material had higher concentrations of oxygen and showed the largest percentage of formed CO2 that could not be explained based on OM reduction.

Sol-gel Synthesis, Photo- and Electrocatalytic Properties of Mesoporous TiO2 Modified with Transition Metal Ions

NASA Astrophysics Data System (ADS)

Smirnova, N.; Petrik, I.; Vorobets, V.; Kolbasov, G.; Eremenko, A.

2017-03-01

Mesoporous nanosized titania films modified with Co2+, Ni2+, Mn3+, and Cu2+ ions have been produced by templated sol-gel method and characterized by optical spectroscopy, X-ray diffraction (XRD), and Brunauer, Emmett, and Teller (BET) surface area measurement. Band gap energy and the position of flat band potentials were estimated by photoelectrochemical measurements. The films doped with transition metals possessed higher photocurrent quantum yield, as well as photo- and electrochemical activity compared to undoped samples. Mn+/TiO2 (M-Co, Ni, Mn, Cu) electrodes with low dopant content demonstrate high efficiency in electrocatalytic reduction of dissolved oxygen. Polarization curves of TiO2, TiO2/Ni2+, TiO2/Co2+/3+, and TiO2/Mn3+ electrodes contain only one current wave (oxygen reduction current). It means that reaction proceeds without the formation of an intermediate product H2O2.

Dynamics of gas-driven eruptions: Experimental simulations using CO2-H2O-polymer system

NASA Astrophysics Data System (ADS)

Zhang, Youxue; Sturtevant, B.; Stolper, E. M.

1997-02-01

We report exploratory experiments simulating gas-driven eruptions using the CO2-H2O system at room temperature as an analog of natural eruptive systems. The experimental apparatus consists of a test cell and a large tank. Initially, up to 1.0 wt% of CO2 is dissolved in liquid water under a pressure of up to 735 kPa in the test cell. The experiment is initiated by suddenly reducing the pressure of the test cell to a typical tank pressure of 10 kPa. The following are the main results: (1) The style of the process depends on the decompression ratio. There is a threshold decompression ratio above which rapid eruption occurs. (2) During rapid eruption, there is always fragmentation at the liquid-vapor interface. Fragmentation may also occur in the flow interior. (3) Initially, the top of the erupting column ascends at a constant acceleration (instead of constant velocity). (4) Average bubble radius grows as t2/3. (5) When viscosity is 20 times that of pure water or greater, a static foam may be stable after expansion to 97% vesicularity. The experiments provide several insights into natural gas-driven eruptions, including (1) the interplay between bubble growth and ascent of the erupting column must be considered for realistic modeling of bubble growth during gas-driven eruptions, (2) buoyant rise of the bubbly magma is not necessary during an explosive volcanic eruption, and (3) CO2-driven limnic eruptions can be explosive. The violence increases with the initial CO2 content dissolved in water.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that the presence of H2O enhances CO2 solubility at low to moderate H2O abundance. One implication of these results is that volatile-saturated magmas will behave differently depending on H2O abundance. Magmas with low H2O abundance could undergo isobaric degassing through addition of a CO2-rich fluid.

Methane and Carbon Dioxide Production Rates in Lake Sediments from Sub-Arctic Sweden

NASA Astrophysics Data System (ADS)

DeStasio, J.; Halloran, M.; Erickson, L. M.; Varner, R. K.; Johnson, J. E.; Setera, J.; Prado, M. F.; Wik, M.; Crill, P. M.

2013-12-01

Ecosystems at high latitudes are undergoing rapid change due to amplified arctic warming. Lakes in these regions are sources of both methane (CH4) and carbon dioxide (CO2) to the atmosphere and will likely be impacted by elevated temperatures. Because of the potential increase in the release of organic carbon due to thawing permafrost, it is believed that methanogenesis rates within neighboring fresh water sediments will display a positive feedback response, by increasing CH4 emission to the atmosphere. We studied CH4 production potential of sediments using cores from three lakes in the Stordalen Mire complex in sub-Arctic, Sweden: Inre Harrsjön, Mellan Harrsjön, and Villasjön. Sediment cores were incubated to determine CO2 and CH4 production rates and were analyzed for CH4 concentrations, dissolved inorganic carbon (DIC) concentrations, total organic carbon (TOC) concentrations, as well as carbon, nitrogen and sulfur content. Our results from the Villasjön cores indicate that CH4 production rates were highest at the same sediment depths as peak dissolved CH4 concentrations, with maximum values between depths of approximately 10cm and 30cm. Additionally, the highest observed CH4 production rates were in sediments from areas within Villasjön known to have the highest rates of CH4 ebullition. CO2 production rates were generally highest within surface sediments ranging from about 4cm to 11cm in depth, with production rates displaying a steady decrease below 11cm. Additionally, observed CO2 production rates correlated with total organic carbon (TOC) concentrations with respect to sediment depth, but displayed no relationship with dissolved inorganic carbon (DIC). Further analysis will be conducted to determine how CH4 and CO2 production characteristics vary between sediment core samples, as well as isotopic analysis of select samples taken from each lake.

Behavioral Response of Hermit Crabs (Clibanarius digueti) to Dissolved Carbon Dioxide

NASA Astrophysics Data System (ADS)

Maier, H. J.

2016-02-01

CO2 induced ocean acidification is currently changing the population dynamics of marine organisms. This can involve increased stress in populations, and alteration in individual physiology, which can eventually be expressed through an organism's behavior. If sustained, CO2 induced ocean acidification has the potential to cause major impacts on marine food chains, including on services they provide. The purpose of this study was to understand whether and how ocean acidification affects the behavior of hermit crab Clibanarius digueti, a crustacean inhabiting the littoral zone. We hypothesized that an increase in dissolved carbonic acid would modify grazing and individual movement, because an increase in acidification alters the normal chemical composition of the water and potentially the physiology of C. digueti. A model tidal pool experiment consisting of two tanks (control and treatment) inhabited with seven living C. digueti was set up in the Ocean Biome of Biosphere-2. Each tank was also provided with uninhabited shells: two Turbo fluctuosa and four Cerithium sp. Gaseous CO2 was dissolved into the treatment tank and measured as dissolved CO2 by using a NaOH titration method. Additionally, water conditions were characterized for light and temperature. Two trials were run in this experiment with tanks and treatments interchanged in each trial. We found a marked treatment effect on C. digueti behavior. The population experiencing increased CO2 performed daily shell changes after first day of exposure for each of the 4-day trials, as compared to individuals unexposed to dissolved CO2, that experienced no shell changes. From this study we conclude that the behavior of C. Digueti can be a good indicator of changes in dissolved CO2. This would allow us to better interpret patterns in marine animal behavior in response to climate change.

Numerical studies of CO2 and brine leakage into a shallow aquifer through an open wellbore

NASA Astrophysics Data System (ADS)

Wang, Jingrui; Hu, Litang; Pan, Lehua; Zhang, Keni

2018-03-01

Industrial-scale geological storage of CO2 in saline aquifers may cause CO2 and brine leakage from abandoned wells into shallow fresh aquifers. This leakage problem involves the flow dynamics in both the wellbore and the storage reservoir. T2Well/ECO2N, a coupled wellbore-reservoir flow simulator, was used to analyze CO2 and brine leakage under different conditions with a hypothetical simulation model in water-CO2-brine systems. Parametric studies on CO2 and brine leakage, including the salinity, excess pore pressure (EPP) and initially dissolved CO2 mass fraction, are conducted to understand the mechanism of CO2 migration. The results show that brine leakage rates increase proportionally with EPP and inversely with the salinity when EPP varies from 0.5 to 1.5 MPa; however, there is no CO2 leakage into the shallow freshwater aquifer if EPP is less than 0.5 MPa. The dissolved CO2 mass fraction shows an important influence on the CO2 plume, as part of the dissolved CO2 becomes a free phase. Scenario simulation shows that the gas lifting effect will significantly increase the brine leakage rate into the shallow freshwater aquifer under the scenario of 3.89% dissolved CO2 mass fraction. The equivalent porous media (EPM) approach used to model the wellbore flow has been evaluated and results show that the EPM approach could either under- or over-estimate brine leakage rates under most scenarios. The discrepancies become more significant if a free CO2 phase evolves. Therefore, a model that can correctly describe the complex flow dynamics in the wellbore is necessary for investigating the leakage problems.

Hydrocarbonates in atmospheric precipitation of Moscow: Monitoring data and analysis

NASA Astrophysics Data System (ADS)

Eremina, I. D.; Aloyan, A. E.; Arutyunyan, V. O.; Larin, I. K.; Chubarova, N. E.; Yermakov, A. N.

2017-05-01

Based on atmospheric precipitation monitoring data for Moscow, we have revealed a number of episodes when the content of hydrocarbonates repeatedly surpasses the equilibrium level. These facts are associated with the complex structure of precipitation, which is caused by differences in the chemical composition of condensation nuclei. As a result, the underlying surface involves two groups of drops with acidities of different nature. The acidity of the first ("metal") group is determined by the carbonate equilibrium with atmospheric CO2 and dissolved carbonates of alkaline and alkaline earth metals. The acidity of the second ("ammonium") group is characterized by the balance between ammonia absorbed from the air and atmospheric acids. Because of this, the precipitation acidity measured during the monitoring is regulated not only in the air but also in the condensate collector. The mixing of the metal and ammonium groups of precipitation is accompanied by only a partial conversion of hydrocarbonates into dissolved CO2. Its termination is hindered when CO2 actually ceases to enter the atmosphere due to mass-exchange deceleration. As a result, the content of hydrocarbonates in the collector exceeds the equilibrium level. Some estimates indicate that the acidity of the ammonia component of precipitation can be much higher than the acidity according to monitoring data. This should be taken into account in estimating the health and environmental impacts. The true level of acid rain hazard can be estimated only by measuring the acidity of individual drops, whereas the results obtained with modern tools of monitoring can underestimate this hazard.

Supersaturation of dissolved H(2) and CO (2) during fermentative hydrogen production with N(2) sparging.

PubMed

Kraemer, Jeremy T; Bagley, David M

2006-09-01

Dissolved H(2) and CO(2) were measured by an improved manual headspace-gas chromatographic method during fermentative H(2) production with N(2) sparging. Sparging increased the yield from 1.3 to 1.8 mol H(2)/mol glucose converted, although H(2) and CO(2) were still supersaturated regardless of sparging. The common assumption that sparging increases the H(2) yield because of lower dissolved H(2) concentrations may be incorrect, because H(2) was not lowered into the range necessary to affect the relevant enzymes. More likely, N(2) sparging decreased the rate of H(2) consumption via lower substrate concentrations.

Effect of multi-element addition of Alnico alloying elements on structure and magnetic properties of SmCo5-based ribbons

NASA Astrophysics Data System (ADS)

Bian, Lu-peng; Li, Ying; Han, Xu-hao; Cheng, Jin-yun; Qin, Xiao-ning; Zhao, Yan-qiu; Sun, Ji-bing

2018-02-01

New SmCo5 + x wt% Alnico composite ribbons melt-spun at 40 m/s are designed by multi-element addition of Alnico alloy into SmCo5 matrix, and their structure and magnetic properties are investigated. The results show that the main phase in x ≤ 2.5 ribbons is Sm(Co,M)5, whereas the main phase changes into Sm(Co,M)7 at x = 4.0-8.5, and simultaneously that the content of Al-rich and amorphous phases increases with increasing x. The hard magnetic properties of the ribbons are found to improve with an increase in Alnico content, and particularly the average magnetic properties reach maximum, i.e., Hc = 19.6 ± 1.2 kOe, Mr = 47.7 ± 3.4 emu/g and M2T = 59.1 ± 5.6 emu/g, at x = 4.0. The main reasons for such improvement are that the finer grains divided by three grain boundaries exist in main phase, the dispersed Al-Ni and Al-Co-rich phases distribute in grains and grain boundaries, and the Fe-rich Alnico alloying elements dissolve into Sm(Co,M)7 matrix phase. However, when x > 4.0, the gradually increasing Al-Co and amorphous phases lead to the reduction of hard magnetic properties.

The Sulu Sea as Carbon Dioxide Sink

NASA Astrophysics Data System (ADS)

Ferrera, C. M.; Jacinto, G. S.; Chen, C. T. A.

2016-12-01

The Sulu Sea, one of the marginal seas in the West Pacific and the largest internal sea in the Philippines, is characterized by its unique deep water ventilation pattern and high sediment organic carbon and CaCO3 content. Studies on the dissolved CO2 system in the Sulu Sea have remarkably shown that anthropogenic CO2 has already penetrated to the bottom of this 5km-deep basin, albeit limited to a dataset from a single station in December 1996. To further understand the role of this tropical marginal sea as CO2 sink and to assess its behavior as a CO2 sink during the 11-year period, water samples for dissolved CO2 parameters from two deep stations of high productivity and low productivity were collected in December 2007/January 2008 and were compared with the 1996 data. Results suggest that the surface waters in the low productivity region might have been acidifying at a rate of -0.0012 pH unit yr-1. Atmospheric CO2 increased at +1.9 ppmv yr-1 and seawater fCO2 at +3.30 μatm yr-1. Through deep water ventilation, anthropogenic CO2 has penetrated the water column thereby making the deeper waters a sink of anthropogenic CO2. But then the presence and dissolution of CaCO3 deposits at the sea floor and along the Sulu Sea slopes as a result of the reaction with this anthropogenic CO2 probably neutralizes the acidification at depths as shown by the increase in total alkalinity (+0.57 μmol kg-1 yr-1), and facilitates further uptake of CO2 from the atmosphere. Therefore, productivity at Sulu Sea surface waters results to sequestration of CO2 from the atmosphere to the sediment sink through organic carbon and CaCO3 deposits. While high temperature and low productivity surface waters make the Sulu Sea a source of CO2 to the atmosphere, ventilation patterns make the deep waters of the Sulu Sea an efficient sink for anthropogenic CO2. Given the larger area occupied by the CO2 sink deep waters compared to the CO2 source surface waters including an upwelling area, the Sulu Sea could possibly be a "net" CO2 sink, an important contribution to the otherwise underestimated inventory of CO2 from marginal seas.

Measured Fluid Flow in an Active H2O-CO2 Geothermal Well as an Analog to Fluid Flow in Fractures on Mars: Preliminary Report

NASA Technical Reports Server (NTRS)

Kieffer, Susan W.; Brown, K. L.; Simmons, Stuart F.; Watson, Arnold

2004-01-01

Water in the Earth's crust generally contains dissolved gases such as CO2. Models for both 'Blue Mars' (H2O-driven processes) and 'White Mars' (CO2-driven processes) predict liquid H2O with dissolved CO2 at depth. The fate of dissolved CO2 as this mixture rises toward the surface has not been quantitatively explored. Our approach is a variation on NASA's 'Follow the Water' as we 'Follow the Fluid' from depth to the surface in hydrothermal areas on Earth and extrapolate our results to Mars. This is a preliminary report on a field study of fluid flow in a producing geothermal well. For proprietary reasons, the name and location of this well cannot be revealed, so we have named it 'Earth1' for this study.

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.

Exogenous addition of H2 for an in situ biogas upgrading through biological reduction of carbon dioxide into methane.

PubMed

Mulat, Daniel Girma; Mosbæk, Freya; Ward, Alastair James; Polag, Daniela; Greule, Markus; Keppler, Frank; Nielsen, Jeppe Lund; Feilberg, Anders

2017-10-01

Biological reduction of CO 2 into CH 4 by exogenous addition of H 2 is a promising technology for upgrading biogas into higher CH 4 content. The aim of this work was to study the feasibility of exogenous H 2 addition for an in situ biogas upgrading through biological conversion of the biogas CO 2 into CH 4. Moreover, this study employed systematic study with isotope analysis for providing comprehensive evidence on the underlying pathways of CH 4 production and upstream processes. Batch reactors were inoculated with digestate originating from a full-scale biogas plant and fed once with maize leaf substrate. Periodic addition of H 2 into the headspace resulted in a completely consumption of CO 2 and a concomitant increase in CH 4 content up to 89%. The microbial community and isotope analysis shows an enrichment of hydrogenotrophic Methanobacterium and the key role of hydrogenotrophic methanogenesis for biogas upgrading to higher CH 4 content. Excess H 2 was also supplied to evaluate its effect on overall process performance. The results show that excess H 2 addition resulted in accumulation of H 2 , depletion of CO 2 and inhibition of the degradation of acetate and other volatile fatty acids (VFA). A systematic isotope analysis revealed that excess H 2 supply led to an increase in dissolved H 2 to the level that thermodynamically inhibit the degradation of VFA and stimulate homo-acetogens for production of acetate from CO 2 and H 2 . The inhibition was a temporary effect and acetate degradation resumed when the excess H 2 was removed as well as in the presence of stoichiometric amount of H 2 and CO 2 . This inhibition mechanism underlines the importance of carefully regulating the H 2 addition rate and gas retention time to the CO 2 production rate, H 2 -uptake rate and growth of hydrogenotrophic methanogens in order to achieve higher CH 4 content without the accumulation of acetate and other VFA. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of ameliorating soil acidity with dolomite on the priming of soil C content and CO2 emission.

PubMed

Shaaban, Muhammad; Wu, Lei; Peng, Qi-An; van Zwieten, Lukas; Chhajro, Muhammad Afzal; Wu, Yupeng; Lin, Shan; Ahmed, Muhammad Mahmood; Khalid, Muhammad Salman; Abid, Muhammad; Hu, Ronggui

2017-04-01

Lime or dolomite is commonly implemented to ameliorate soil acidity. However, the impact of dolomite on CO 2 emissions from acidic soils is largely unknown. A 53-day laboratory study was carried out to investigate CO 2 emissions by applying dolomite to an acidic Acrisol (rice-rapeseed rotation [RR soil]) and a Ferralsol (rice-fallow/flooded rotation [RF soil]). Dolomite was dosed at 0, 0.5, and 1.5 g 100 g -1 soil, herein referred to as CK, L, and H, respectively. The soil pH (H2O) increased from 5.25 to 7.03 and 7.62 in L and H treatments of the RR soil and from 5.52 to 7.27 and 7.77 in L and H treatments of the RF soil, respectively. Dolomite application significantly (p ≤ 0.001) increased CO 2 emissions in both RR and RF soils, with higher emissions in H as compared to L dose of dolomite. The cumulative CO 2 emissions with H dose of dolomite were greater 136% in the RR soil and 149% in the RF soil as compared to CK, respectively. Dissolved organic carbon (DOC) and microbial biomass carbon (MBC) increased and reached at 193 and 431 mg kg -1 in the RR soil and 244 and 481 mg kg -1 in the RF soil by H treatments. The NH 4 - -N and NO 3 - -N were also increased by dolomite application. The increase in C and N contents stimulated microbial activities and therefore higher respiration in dolomite-treated soil as compared to untreated. The results suggest that CO 2 release in dolomite-treated soils was due to the priming of soil C content rather than chemical reactions.

The symbiotic relationship between dominant canopy trees and soil microbes affects the nitrogen source utilization of co-existing understory trees

NASA Astrophysics Data System (ADS)

Iwaoka, C.; Hyodo, F.; Taniguchi, T.; Shi, W.; Du, S.; Yamanaka, N.; Tateno, R.

2017-12-01

The symbiotic relationship between dominant canopy trees and soil microbes such as mycorrhiza or nitrogen (N) fixer are important determinants of soil N dynamics of a forest. However, it is not known how and to what extent the symbiotic relationship of dominant canopy trees with soil microbes affect the N source of co-existing trees in forest. We measured the δ15N of surface soils (0-10 cm), leaves, and roots of the dominant canopy trees and common understory trees in an arbuscular mycorrhizal N-fixing black locust (Robinia pseudoacacia) plantation and an ectomycorrhizal oak (Quercus liaotungensis) natural forest in a China dryland. We also analyzed the soil dissolved N content in soil extracts and absorbed by ion exchange resin, and soil ammonia-oxidizer abundance using real-time PCR. The δ15N of soil and leaves were higher in the black locust forest than in the oak forest, although the δ15N of fine roots was similar in the two forests, in co-existing understory trees as well as dominant canopy trees. Accordingly, the δ15N of leaves was similar to or higher than that of fine roots in the black locust forest, whereas it was consistently lower than that of fine roots in the oak forest. In the black locust forest, the soil dissolved organic N and ammonium N contents were less abundant but the nitrate N contents in soils and absorbed by the ion exchange resin and ammonia-oxidizer abundance were greater, due to N fixation or less uptake of organic N from arbuscular mycorrhiza. In contrast, the soil dissolved organic N and ammonium N contents were more abundant in the oak forest, whereas the N content featured very low nitrate, due to ectomycorrhizal ability to access organic N. These results suggest that the main N source is nitrate N in the black locust forest, but dissolved organic N or ammonium N in the oak forest. N fixation or high N loss due to high N availability would cause high δ15N in soil and leaves in black locust forest. On the other hand, low soil N availability in the oak forest may make 15N fractionation more active in roots via mycorrhizal association, resulting in higher δ15N in fine roots than in leaves. In conclusion, the symbiotic relationship between dominant canopy trees and soil microbes affected the N source of not only the dominant trees but also co-existing understory trees via the control of soil N dynamics.

C-O volatiles in Apollo 15 and Apollo 17 picritic glasses

NASA Technical Reports Server (NTRS)

Rutherford, Malcolm J.; Fogel, Robert A.

1993-01-01

A15 and A17 primitive picritic glasses have been examined by FTIR for the presence of dissolved C-O species to determine the role of C-O gasses on driving lunar fire-fountains. A15 green and yellow glasses were extensively studied and found to be free of dissolved C species down to FTIR detection limits (10-100 ppm; species and sample specific). Preliminary data on A17 orange glasses are similarly devoid of FTIR detectable C-O species. Re-analyses of the C-O driving mechanism theory for mare volcanism demonstrates the need to determine the fO2 of the lunar interior; the factor that most critically determined the role of C gasses in the fire-fountaining events. Oxygen fugacities equivalent to IW-0.5 and above imply dissolved CO3(=) in the primitive glasses at levels above FTIR detection. The f02's below IW-0.5 imply concentrations of CO3(=) below FTIR detection. Recent data suggesting lunar mantle fO2's of IW-2 or less, strongly mitigate against finding FTIR measurable dissolved CO3(=) consistent with the findings of this study.

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.

Release of Dissolved CO2 from Water in Laboratory Porous Media Following Rapid Depressurization

NASA Astrophysics Data System (ADS)

Crews, J. B.; Cooper, C. A.

2011-12-01

A bench-top laboratory study is undertaken to investigate the effects of seismic shocks on brine aquifers into which carbon dioxide has been injected for permanent storage. Long-term storage in deep saline aquifers has been proposed and studied as one of the most viable near-term options for sequestering fossil fuel-derived carbon dioxide from the atmosphere to curb anthropogenic climate change. Upon injection into the subsurface, it is expected that CO2, as either a gas or supercritical fluid, will mix convectively with the formation water. The possibility exists, however, that dissolved CO2 will come out of solution as a result of an earthquake. The effect is similar to that of slamming an unsealed container of carbonated beverage on a table; previously dissolved CO2 precipitates, forms bubbles, and rises due to buoyancy. In this study, we measure the change in gas-phase CO2 concentration as a function of the magnitude of the shock and the initial concentration of CO2. In addition, we investigate and seek to characterize the nucleation and transport of CO2 bubbles in a porous medium after a seismic shock. Experiments are conducted using a Hele-Shaw cell and a CCD camera to quantify the fraction of dissolved CO2 that comes out of solution as a result of a sharp mechanical impulse. The data are used to identify and constrain the conditions under which CO2 comes out of solution and, further, to understand the end-behavior of the precipitated gas-phase CO2 as it moves through or is immobilized in a porous medium.

Organic matter exudation by Emiliania huxleyi under simulated future ocean conditions

NASA Astrophysics Data System (ADS)

Borchard, C.; Engel, A.

2012-01-01

Emiliania huxleyi (strain B 92/11) was exposed to different growth, CO2 and temperature conditions in phosphorous controlled chemostats, to investigate effects on organic carbon exudation, and partitioning between the pools of particulate organic carbon (POC) and dissolved organic carbon (DOC). 14C incubation measurements for primary production (PP) and for extracellular release (ER) were performed. Chemical analysis included amount and composition of high molecular weight dissolved combined carbohydrates (>1 kDa, HMW-dCCHO), particulate combined carbohydrates (pCCHO) and the carbon content of transparent exopolymer particles (TEP-C). Applied CO2 and temperature conditions were 300, 550 and 900 μatm pCO2 at 14 °C, and additionally 900 μatm pCO2 at 18 °C simulating a greenhouse ocean scenario. A reduction in growth rate from μ =0.3 d-1 to μ =0.1 d-1 induced the most profound effect on the performance of E. huxleyi, relative to the effect of elevated CO2 and temperature. At μ =0.3 d-1, PP was significantly higher at elevated CO2 and temperature. DO14C production correlated to PO14C production in all cultures, resulting in similar percentages of extracellular release (DO14C/PP × 100; PER) of averaged 3.74 ± 0.94%. At μ =0.1 d-1, PO14C decreased significantly, while exudation of DO14C increased, thus leading to a stronger partitioning from the particulate to the dissolved pool. Maximum PER of 16.3 ± 2.3% were observed at μ =0.1 d-1 at greenhouse conditions. Concentrations of HMW-dCCHO and pCCHO were generally higher at μ =0.1 d-1 compared to μ =0.3 d-1. At μ =0.3 d-1, pCCHO concentration increased significantly along with elevated CO2 and temperature. Despite of high PER, the percentage of HMW-dCCHO was smallest at greenhouse conditions. However, highest TEP-formation was observed under greenhouse conditions, together with a pronounced increase in pCCHO concentration, suggesting a stronger partitioning of PP from DOC to POC by coagulation of exudates. Our results imply that greenhouse condition will enhance exudation processes in E. huxleyi and may affect organic carbon partitioning in the ocean due to an enhanced transfer of HMW-dCCHO to TEP by aggregation processes.

Bursts of CO2 released during freezing offer a new perspective on avoidance of winter embolism in trees.

PubMed

Lintunen, A; Lindfors, L; Kolari, P; Juurola, E; Nikinmaa, E; Hölttä, T

2014-12-01

Woody plants can suffer from winter embolism as gas bubbles are formed in the water-conducting conduits when freezing occurs: gases are not soluble in ice, and the bubbles may expand and fill the conduits with air during thawing. A major assumption usually made in studies of winter embolism formation is that all of the gas dissolved in the xylem sap is trapped within the conduits and forms bubbles during freezing. The current study tested whether this assumption is actually valid, or whether efflux of gases from the stem during freezing reduces the occurrence of embolism. CO2 efflux measurements were conducted during freezing experiments for saplings of three Scots pine (Pinus sylvestris) and three Norway spruce (Picea abies) trees under laboratory conditions, and the magnitudes of the freezing-related bursts of CO2 released from the stems were analysed using a previously published mechanistic model of CO2 production, storage, diffusion and efflux from a tree stem. The freezing-related bursts of CO2 released from a mature Scots pine tree growing in field conditions were also measured and analysed. Substantial freezing-related bursts of CO2 released from the stem were found to occur during both the laboratory experiments and under field conditions. In the laboratory, the fraction of CO2 released from the stem ranged between 27 and 96 % of the total CO2 content within the stem. All gases dissolved in the xylem sap are not trapped within the ice in the stem during freezing, as has previously been assumed, thus adding a new dimension to the understanding of winter embolism formation. The conduit water volume not only determines the volume of bubbles formed during freezing, but also the efficiency of gas efflux out of the conduit during the freezing process. © The Author 2014. Published by Oxford University Press on behalf of the Annals of Botany Company.

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.

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.

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

Dissolved CO2 Increases Breakthrough Porosity in Natural Porous Materials.

PubMed

Yang, Y; Bruns, S; Stipp, S L S; Sørensen, H O

2017-07-18

When reactive fluids flow through a dissolving porous medium, conductive channels form, leading to fluid breakthrough. This phenomenon is caused by the reactive infiltration instability and is important in geologic carbon storage where the dissolution of CO 2 in flowing water increases fluid acidity. Using numerical simulations with high resolution digital models of North Sea chalk, we show that the breakthrough porosity is an important indicator of dissolution pattern. Dissolution patterns reflect the balance between the demand and supply of cumulative surface. The demand is determined by the reactive fluid composition while the supply relies on the flow field and the rock's microstructure. We tested three model scenarios and found that aqueous CO 2 dissolves porous media homogeneously, leading to large breakthrough porosity. In contrast, solutions without CO 2 develop elongated convective channels known as wormholes, with low breakthrough porosity. These different patterns are explained by the different apparent solubility of calcite in free drift systems. Our results indicate that CO 2 increases the reactive subvolume of porous media and reduces the amount of solid residual before reactive fluid can be fully channelized. Consequently, dissolved CO 2 may enhance contaminant mobilization near injection wellbores, undermine the mechanical sustainability of formation rocks and increase the likelihood of buoyance driven leakage through carbonate rich caprocks.

Increasing shallow groundwater CO2 and limestone weathering, Konza Prairie, USA

USGS Publications Warehouse

Macpherson, G.L.; Roberts, J.A.; Blair, J.M.; Townsend, M.A.; Fowle, D.A.; Beisner, K.R.

2008-01-01

In a mid-continental North American grassland, solute concentrations in shallow, limestone-hosted groundwater and adjacent surface water cycle annually and have increased steadily over the 15-year study period, 1991-2005, inclusive. Modeled groundwater CO2, verified by measurements of recent samples, increased from 10-2.05 atm to 10-1.94 atm, about a 20% increase, from 1991 to 2005. The measured groundwater alkalinity and alkaline-earth element concentrations also increased over that time period. We propose that carbonate minerals dissolve in response to lowered pH that occurs during an annual carbonate-mineral saturation cycle. The cycle starts with low saturation during late summer and autumn when dissolved CO2 is high. As dissolved CO2 decreases in the spring and early summer, carbonates become oversaturated, but oversaturation does not exceed the threshold for precipitation. We propose that groundwater is a CO2 sink through weathering of limestone: soil-generated CO2 is transformed to alkalinity through dissolution of calcite or dolomite. The annual cycle and long-term increase in shallow groundwater CO2 is similar to, but greater than, atmospheric CO2. ?? 2008 Elsevier Ltd. All rights reserved.

Edaphic factors controlling summer (rainy season) greenhouse gas emissions (CO2 and CH4) from semiarid mangrove soils (NE-Brazil).

PubMed

Nóbrega, Gabriel N; Ferreira, Tiago O; Siqueira Neto, M; Queiroz, Hermano M; Artur, Adriana G; Mendonça, Eduardo De S; Silva, Ebenezer De O; Otero, Xosé L

2016-01-15

The soil attributes controlling the CO2, and CH4 emissions were assessed in semiarid mangrove soils (NE-Brazil) under different anthropogenic activities. Soil samples were collected from different mangroves under different anthropogenic impacts, e.g., shrimp farming (Jaguaribe River); urban wastes (Cocó River) and a control site (Timonha River). The sites were characterized according to the sand content; physicochemical parameters (Eh and pH); total organic C; soil C stock (SCS) and equivalent SCS (SCSEQV); total P and N; dissolved organic C (DOC); and the degree of pyritization (DOP). The CO2 and CH4 fluxes from the soils were assessed using static closed chambers. Higher DOC and SCS and the lowest DOP promote greater CO2 emission. The CH4 flux was only observed at Jaguaribe which presented higher DOP, compared to that found in mangroves from humid tropical climates. Semiarid mangrove soils cannot be characterized as important greenhouse gas sources, compared to humid tropical mangroves.

Heavy metals content in acid mine drainage at abandoned and active mining area

NASA Astrophysics Data System (ADS)

Hatar, Hazirah; Rahim, Sahibin Abd; Razi, Wan Mohd; Sahrani, Fathul Karim

2013-11-01

This study was conducted at former Barite Mine, Tasik Chini and former iron mine Sungai Lembing in Pahang, and also active gold mine at Lubuk Mandi, Terengganu. This study was conducted to determine heavy metals content in acid mine drainage (AMD) at the study areas. Fourteen water sampling stations within the study area were chosen for this purpose. In situ water characteristic determinations were carried out for pH, electrical conductivity (EC), redox potential (ORP) and total dissolved solid (TDS) using multi parameter YSI 556. Water samples were collected and analysed in the laboratory for sulfate, total acidity and heavy metals which follow the standard methods of APHA (1999) and HACH (2003). Heavy metals in the water samples were determined directly using Inductive Coupled Plasma Mass Spectrometry (ICP-MS). Data obtained showed a highly acidic mean of pH values with pH ranged from 2.6 ± 0.3 to 3.2 ± 0.2. Mean of electrical conductivity ranged from 0.57 ± 0.25 to 1.01 ± 0.70 mS/cm. Redox potential mean ranged from 487.40 ± 13.68 to 579.9 ± 80.46 mV. Mean of total dissolved solids (TDS) in AMD ranged from 306.50 ± 125.16 to 608.14 ± 411.64 mg/L. Mean of sulfate concentration in AMD ranged from 32.33 ± 1.41 to 207.08 ± 85.06 mg/L, whereas the mean of total acidity ranged from 69.17 ± 5.89 to 205.12 ± 170.83 mgCaCO3/L. Heavy metals content in AMD is dominated by Fe, Cu, Mn and Zn with mean concentrations range from 2.16 ± 1.61 to 36.31 ± 41.02 mg/L, 0.17 ± 0.13 to 11.06 ± 2.85 mg/L, 1.12 ± 0.65 to 7.17 ± 6.05 mg/L and 0.62 ± 0.21 to 6.56 ± 4.11 mg/L, respectively. Mean concentrations of Ni, Co, As, Cd and Pb were less than 0.21, 0.51, 0.24, 0.05 and 0.45 mg/L, respectively. Significant correlation occurred between Fe and Mn, Cu, Zn, Co and Cd. Water pH correlated negatively with all the heavy metals, whereas total acidity, sulfate, total dissolved solid, and redox potential correlated positively. The concentration of heavy metals in the AMD appeared to be influenced by acidity and the formation of Fe, Mn oxide and hydroxide.

[Modeling the Influencing Factors of Karstification and Karst Carbon Cycle in Laboratory].

PubMed

Zhao, Rui-yi; Lü, Xian-fu; Duan, Yi-fan

2015-08-01

To analyze the influencing factors of karstification and karst carbon cycle, a simulation experiment was carried out and 6 soil columns were designed. The results showed that the content of H2O4, hydrodynamic condition and thickness of the soil had important influence on karstification and karst carbon cycle. For the soil columns which were covered by the same thickness of soil, the concentrations of Ca2+ + Mg2+ and SO4(2-) followed the order of B20-2 > B20-1 > B20-3, B50-2 > B50-1 > B50-3. This meant that input of H2SO4 enhanced the karstification and increasing infiltration water had significant dilution effect on the chemical properties. For the soil columns with different thickness of soil but with the same slag pile and hydrodynamic conditions, the concentrations of Ca2+ + Mg2+ and SO4(2-) followed the order of B50-1 > B20-1, B50-2 > B20-2, B50-3 > B20-3. It was demonstrated that more carbonate rock was dissolved under the thick soil columns. In addition, the net consumption of CO2 mainly depended on the content of H2SO4 in this experiment due to slight contribution of H2CO3 to carbonate rock dissolution. More content of H2SO4 brought about less net consumption of C02, but B50-2 was an exception. Organic matter and other nutrients might be input into deep soil with the slag pile, and they promoted the production of soil C)2. Therefore, more CO2 was consumed due to the increased contribution of H2CO to karstification.

Field Tests of Real-time In-situ Dissolved CO2 Monitoring for CO2 Leakage Detection in Groundwater

NASA Astrophysics Data System (ADS)

Yang, C.; Zou, Y.; Delgado, J.; Guzman, N.; Pinedo, J.

2016-12-01

Groundwater monitoring for detecting CO2 leakage relies on groundwater sampling from water wells drilled into aquifers. Usually groundwater samples are required be collected periodically in field and analyzed in the laboratory. Obviously groundwater sampling is labor and cost-intensive for long-term monitoring of large areas. Potential damage and contamination of water samples during the sampling process can degrade accuracy, and intermittent monitoring may miss changes in the geochemical parameters of groundwater, and therefore signs of CO2 leakage. Real-time in-situ monitoring of geochemical parameters with chemical sensors may play an important role for CO2 leakage detection in groundwater at a geological carbon sequestration site. This study presents field demonstration of a real-time in situ monitoring system capable of covering large areas for detection of low levels of dissolved CO2 in groundwater and reliably differentiating natural variations of dissolved CO2 concentration from small changes resulting from leakage. The sand-alone system includes fully distributed fiber optic sensors for carbon dioxide detection with a unique sensor technology developed by Intelligent Optical Systems. The systems were deployed to the two research sites: the Brackenridge Field Laboratory where the aquifer is shallow at depths of 10-20 ft below surface and the Devine site where the aquifer is much deeper at depths of 140 to 150 ft. Groundwater samples were periodically collected from the water wells which were installed with the chemical sensors and further compared to the measurements of the chemical sensors. Our study shows that geochemical monitoring of dissolved CO2 with fiber optic sensors could provide reliable CO2 leakage signal detection in groundwater as long as CO2 leakage signals are stronger than background noises at the monitoring locations.

Inorganic carbon loading as a primary driver of dissolved carbon dioxide concentrations in the lakes and reservoirs of the contiguous United States

USGS Publications Warehouse

McDonald, Cory P.; Stets, Edward; Striegl, Robert G.; Butman, David

2013-01-01

Accurate quantification of CO2 flux across the air-water interface and identification of the mechanisms driving CO2 concentrations in lakes and reservoirs is critical to integrating aquatic systems into large-scale carbon budgets, and to predicting the response of these systems to changes in climate or terrestrial carbon cycling. Large-scale estimates of the role of lakes and reservoirs in the carbon cycle, however, typically must rely on aggregation of spatially and temporally inconsistent data from disparate sources. We performed a spatially comprehensive analysis of CO2 concentration and air-water fluxes in lakes and reservoirs of the contiguous United States using large, consistent data sets, and modeled the relative contribution of inorganic and organic carbon loading to vertical CO2 fluxes. Approximately 70% of lakes and reservoirs are supersaturated with respect to the atmosphere during the summer (June–September). Although there is considerable interregional and intraregional variability, lakes and reservoirs represent a net source of CO2 to the atmosphere of approximately 40 Gg C d–1 during the summer. While in-lake CO2 concentrations correlate with indicators of in-lake net ecosystem productivity, virtually no relationship exists between dissolved organic carbon and pCO2,aq. Modeling suggests that hydrologic dissolved inorganic carbon supports pCO2,aq in most supersaturated systems (to the extent that 12% of supersaturated systems simultaneously exhibit positive net ecosystem productivity), and also supports primary production in most CO2-undersaturated systems. Dissolved inorganic carbon loading appears to be an important determinant of CO2concentrations and fluxes across the air-water interface in the majority of lakes and reservoirs in the contiguous United States.

The Role of CO2 on Silica Undersaturated Melt Structure: Implication for Melt Physical Properties

NASA Astrophysics Data System (ADS)

Scaillet, B.; Morizet, Y.; Paris, M.; Gaillard, F.

2012-12-01

Silica undersaturated melts such as nephelinite and melilitite are very peculiar magmatic materials. Their occurrence on the Earth surface is often associated with carbonatites melts. These low-silica melts can dissolve a large quantity of CO2 issued from mantle fluid metasomatism. However, the melt structure, the way CO2 dissolves into these melts and the effect of different alkalis element are poorly constrained. We present preliminary experimental results on the melt structure of synthetic nephelinite (NBO/T = 1.25) and Ca-melilitite (NBO/T = 2.50) synthesized in the NKCMAS system and equilibrated at high-pressure (200-300 MPa), high-temperature (1250°C) with an excess C-O-H fluid phase. The nephelinite glasses were synthesized with varying K2O / K2O+Na2O (0-10 mol.% K2O) ratio so as to investigate the differential effect of those two cations. All experiments were conducted under oxidizing conditions (ΔNNO+5) resulting in binary fluid phase composition with CO2 and H2O species. The silicate melt structure, CO2 solubility and speciation were investigated using Micro-Raman and Solid State NMR spectroscopies for 13C, 1H, 29Si, 27Al and 23Na nuclei. The replacement of Na by K does not change the nephelinite melt structure for volatile-free sample suggesting that the basicity of these glasses is not dramatically affected by the presence of mixed alkali. Within 5 mol.% K2O, the CO2 solubility (measured in relative to Raman signature of the melt structure) is only slightly affected with an increasing CO2 solubility with increasing K2O content. As a function of pressure, we observe an increase in CO2 solubility consistent with previous studies. The 13C NMR investigation of the CO2 speciation show three different carbonates environments for CO2 in nephelinite melts attributed to non-network carbonates: 1) 170 ppm shift assigned to NBO-carb. Na or K; 2) 169 ppm assigned to NBO-carb. Ca; and 3) 165 ppm assigned to isolated Na+..CO32- carbonates. As K2O is increased into the nephelinite melt, the isolated Na+..CO32- disappears. In Ca-rich melilitite, only the component at 169 ppm is present. Preliminary results on the melt structure changes suggest that for both melts the CO2 dissolution induces a significant increase in the polymerization of the melt with increasing CO2 content. For Ca-melilitite, the polymerization increases by about 10% with a change in the measured NBO/T from 2.26 to 2.05 in volatile-free and CO2-bearing glasses, respectively. For nephelinite, the polymerization is more important (>20%) with a change in the measured NBO/T from 1.77 to 1.36 in volatile-free and CO2-bearing glasses, respectively. Those changes are unexplained considering that the identified carbonates units are non-network carbonates. However, if confirmed this result has a major impact on melt viscosity as the melt polymerization is often associated with increasing melt viscosity.

The impact of dissolved organic carbon and bacterial respiration on pCO2 in experimental sea ice

NASA Astrophysics Data System (ADS)

Zhou, J.; Kotovitch, M.; Kaartokallio, H.; Moreau, S.; Tison, J.-L.; Kattner, G.; Dieckmann, G.; Thomas, D. N.; Delille, B.

2016-02-01

Previous observations have shown that the partial pressure of carbon dioxide (pCO2) in sea ice brines is generally higher in Arctic sea ice compared to those from the Antarctic sea ice, especially in winter and early spring. We hypothesized that these differences result from the higher dissolved organic carbon (DOC) content in Arctic seawater: Higher concentrations of DOC in seawater would be reflected in a greater DOC incorporation into sea ice, enhancing bacterial respiration, which in turn would increase the pCO2 in the ice. To verify this hypothesis, we performed an experiment using two series of mesocosms: one was filled with seawater (SW) and the other one with seawater with an addition of filtered humic-rich river water (SWR). The addition of river water increased the DOC concentration of the water from a median of 142 μmol Lwater-1 in SW to 249 μmol Lwater-1 in SWR. Sea ice was grown in these mesocosms under the same physical conditions over 19 days. Microalgae and protists were absent, and only bacterial activity has been detected. We measured the DOC concentration, bacterial respiration, total alkalinity and pCO2 in sea ice and the underlying seawater, and we calculated the changes in dissolved inorganic carbon (DIC) in both media. We found that bacterial respiration in ice was higher in SWR: median bacterial respiration was 25 nmol C Lice-1 h-1 compared to 10 nmol C Lice-1 h-1 in SW. pCO2 in ice was also higher in SWR with a median of 430 ppm compared to 356 ppm in SW. However, the differences in pCO2 were larger within the ice interiors than at the surfaces or the bottom layers of the ice, where exchanges at the air-ice and ice-water interfaces might have reduced the differences. In addition, we used a model to simulate the differences of pCO2 and DIC based on bacterial respiration. The model simulations support the experimental findings and further suggest that bacterial growth efficiency in the ice might approach 0.15 and 0.2. It is thus credible that the higher pCO2 in Arctic sea ice brines compared with those from the Antarctic sea ice were due to an elevated bacterial respiration, sustained by higher riverine DOC loads. These conclusions should hold for locations and time frames when bacterial activity is relatively dominant compared to algal activity, considering our experimental conditions.

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.

Long-Duration Carbon Dioxide Anesthesia of Fish Using Ultra Fine (Nano-Scale) Bubbles.

PubMed

Kugino, Kenji; Tamaru, Shizuka; Hisatomi, Yuko; Sakaguchi, Tadashi

2016-01-01

We investigated whether adding ultrafine (nano-scale) oxygen-carrying bubbles to water concurrently with dissolved carbon-dioxide (CO2) could result in safe, long-duration anesthesia for fish. To confirm the lethal effects of CO2 alone, fishes were anesthetized with dissolved CO2 in 20°C seawater. Within 30 minutes, all fishes, regardless of species, died suddenly due to CO2-induced narcosis, even when the water was saturated with oxygen. Death was attributed to respiration failure caused by hypoxemia. When ultrafine oxygen-carrying bubbles were supplied along with dissolved CO2, five chicken grunts were able to remain anesthetized for 22 hours and awoke normally within 2-3 hours after cessation of anesthesia. The high internal pressures and oxygen levels of the ultrafine bubbles enabled efficient oxygen diffusion across the branchia and permitted the organismal oxygen demands of individual anesthetized fish to be met. Thus, we demonstrated a method for safe, long-duration carbon dioxide anesthesia in living fish under normal water temperatures.

A Novel Method for Analysis of Dissolved Inorganic Carbon Concentration and δ13C by Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Smith, E.; Gonneea, M. E.; Boze, L. G.; Casso, M.; Pohlman, J.

2017-12-01

Dissolved inorganic carbon (DIC) is the largest pool of carbon in the oceans and is where about half of anthropogenic carbon dioxide (CO2) emissions are being sequestered. Determining the concentration and stable carbon isotopic content (δ13C) of DIC allows us to delineate carbon sources that contribute to marine DIC. A simple and reliable method for measuring DIC concentration and δ13C can be used to apportion contributions from external sources and identify effects from biogeochemical reactions that contribute or remove DIC. The U.S. Geological Survey has developed a discrete sample analysis module (DSAM) that interfaces to a Picarro G-2201i cavity ring-down spectrometer (CRDS, Picarro Inc.) to analyze CO2 and methane concentrations and δ13C from discrete gas samples. In this study, we adapted the USGS DSAM-CRDS analysis system to include an AutoMate prep device (Automate FX, Inc.) for analysis of DIC concentration and δ13C from aqueous samples. The Automate prep device was modified to deliver CO2 extracted from DIC to the DSAM, which conditions and transfers the gas to the CRDS. LabVIEW software (National Instruments) triggers the Automate Prep device, controls the DSAM and collects data from the CRDS. CO2 mass concentration data are obtained by numerical integration of the CO2 volumetric concentrations output by the CRDS and subsequent comparison to standard materials. CO2 carbon isotope values from the CRDS (iCO2) are converted to δ13C values using a slope and offset correction calibration procedure. The system design and operation was optimized using sodium bicarbonate (NaHCO3) standards and a certified reference material. Surface water and pore water samples collected from Sage Lot Pond, a salt marsh in Cape Cod MA, have been analyzed for concentration by coulometry and δ13C by isotope ratio mass spectrometry and will be used to validate the DIC-DSAM-CRDS method for field applications.

Impact fracture experiments simulating interstellar grain-grain collisions

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Chang, Sherwood; Dickinson, J. Thomas

1990-01-01

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

NASA Astrophysics Data System (ADS)

Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

2016-04-01

An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

NMR evaluation of total statin content and HMG-CoA reductase inhibition in red yeast rice (Monascus spp.) food supplements

PubMed Central

2012-01-01

Background Red yeast rice (i.e., rice fermented with Monascus spp.), as a food supplement, is claimed to be blood cholesterol-lowering. The red yeast rice constituent monacolin K, also known as lovastatin, is an inhibitor of the hydroxymethylglutaryl-CoA (HMG-CoA) reductase. This article aims to develop a sensitive nuclear magnetic resonance (NMR) method to determine the total statin content of red yeast rice products. Methods The total statin content was determined by a 400 MHz 1H NMR spectroscopic method, based on the integration of the multiplet at δ 5.37-5.32 ppm of a hydrogen at the hexahydronaphthalene moiety in comparison to an external calibration with lovastatin. The activity of HMG-CoA reductase was measured by a commercial spectrophotometric assay kit. Results The NMR detection limit for total statins was 6 mg/L (equivalent to 0.3 mg/capsule, if two capsules are dissolved in 50 mL ethanol). The relative standard deviations were consistently lower than 11%. The total statin concentrations of five red yeast rice supplements were between 1.5 and 25.2 mg per specified daily dose. A dose-dependent inhibition of the HMG-CoA reductase enzyme activity by the red yeast rice products was demonstrated. Conclusion A simple and direct NMR assay was developed to determine the total statin content in red yeast rice. The assay can be applied for the determination of statin content for the regulatory control of red yeast rice products. PMID:22439629

Properties and evolution of dissolved organic matter during co-composting of dairy manure and Chinese herbal residues.

PubMed

Li, Qunliang; Lu, Yanyu; Guo, Xiaobo; Shan, Guangchun; Huang, Junhao

2017-03-01

Composting is an effective method in treating solid organic wastes, in which dissolved organic matter (DOM) plays an important role in transformation of organic matter and microbial activity. Therefore, an understanding of the properties and evolution of DOM during composting is crucial. In this study, DOM was studied using elemental analysis, spectroscopic analysis (UV-vis, FTIR, and pyrolysis-GC/MS), and colloidal analysis during a 120-day composting. Results showed that the content of N and O in DOM increased while C and H content declined progressively over the composting time. Aliphatic C-H stretching, aromatic C=C or C=O stretching of amide groups, and C-O stretch (carbohydrates) showed an obvious decrease, while COO- and C-N groups had a significant increase. The evolution of DOM indicated a gradual decrease of the lipid and polysaccharide fractions, whereas an increase of aromatic and nitrogenous compounds was observed. The DOM also showed a more stable status, and an accumulation of small molecular compounds occurred with composting proceeded. Taken together, these results shed a good insight into the properties and evolution of DOM during a composting process.

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.

Carbonate Mineralization of Volcanic Province Basalts

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

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2010-03-31

Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the United States, India, Iceland, and Canada. As an extension of our previous experiments with Columbia River basalt, basalts from the eastern United States, India, and South Africa were reacted with aqueous dissolved CO2 and aqueous dissolved CO2-H2S mixtures under supercritical CO2 (scCO2) conditions to study the geochemical reactions resulting from injection of CO2 in such formations. The results of these studies are consistent with cation release behavior measured in our previous experiments (in press) for basalt samples tested inmore » single pass flow through dissolution experiments under dilute solution and mildly acidic conditions. Despite the basalt samples having similar bulk chemistry, mineralogy and apparent dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO2-saturated water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic dogtooth spar morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. Examination of polished cross sections of the reacted grains by scanning electron microscopy and energy dispersive x-ray spectroscopy show precipitate overgrowths with varying chemical compositions. Compositional differences in the precipitates suggest changes in fluid chemistry unique to the dissolution behavior of each basalt sample reacted with CO2-saturated water. The Karoo basalt from South Africa appeared the least reactive, with very limited mineralization occurring during the testing with CO2-saturated water. The relative reactivity of different basalt samples were unexpectedly different in the experiments conducted using aqueous dissolved CO2-H2S mixtures versus those reacted with aqueous dissolved CO2 mixtures. For example, the Karoo basalt was highly reactive in the presence of aqueous dissolved CO2-H2S, as evident by small nodules of carbonate coating the basalt grains after 181 days of testing. However the most reactive basalt in CO2-H2O, Newark Basin, formed limited amounts of carbonate precipitates in the presence of aqueous dissolved CO2-H2S mixture. Basalt reactivity in CO2-H2O mixtures appears to be controlled by the composition of the glassy mesostasis, which is the most reactive component in the basalt rock. With the addition of H2S to the CO2-H2O system, basalt reactivity appears to be controlled by precipitation of coatings of insoluble Fe sulfides.« less

Kinetics of CO(2) fluxes outgassing from champagne glasses in tasting conditions: the role of temperature.

PubMed

Liger-Belair, Gérard; Villaume, Sandra; Cilindre, Clara; Jeandet, Philippe

2009-03-11

Measurements of CO(2) fluxes outgassing from a flute poured with a standard Champagne wine initially holding about 11 g L(-1) of dissolved CO(2) were presented, in tasting conditions, all along the first 10 min following the pouring process. Experiments were performed at three sets of temperature, namely, 4 degrees C, 12 degrees C, and 20 degrees C, respectively. It was demonstrated that the lower the champagne temperature, the lower CO(2) volume fluxes outgassing from the flute. Therefore, the lower the champagne temperature, the lower its progressive loss of dissolved CO(2) concentration with time, which constitutes the first analytical proof that low champagne temperatures prolong the drink's chill and helps retains its effervescence. A correlation was also proposed between CO(2) volume fluxes outgassing from the flute poured with champagne and its continuously decreasing dissolved CO(2) concentration. Finally, the contribution of effervescence to the global kinetics of CO(2) release was discussed and modeled by the use of results developed over recent years. The temperature dependence of the champagne viscosity was found to play a major role in the kinetics of CO(2) outgassing from a flute. On the basis of this bubbling model, the theoretical influence of champagne temperature on CO(2) volume fluxes outgassing from a flute was discussed and found to be in quite good accordance with our experimental results.

Unraveling the evolving nature of gaseous and dissolved carbon dioxide in champagne wines: a state-of-the-art review, from the bottle to the tasting glass.

PubMed

Liger-Belair, Gérard; Polidori, Guillaume; Zéninari, Virginie

2012-06-30

In champagne and sparkling wine tasting, the concentration of dissolved CO(2) is indeed an analytical parameter of high importance since it directly impacts the four following sensory properties: (i) the frequency of bubble formation in the glass, (ii) the growth rate of rising bubbles, (iii) the mouth feel, and (iv) the nose of champagne, i.e., its so-called bouquet. In this state-of-the-art review, the evolving nature of the dissolved and gaseous CO(2) found in champagne wines is evidenced, from the bottle to the glass, through various analytical techniques. Results obtained concerning various steps where the CO(2) molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a self-consistent and global overview of how gaseous and dissolved CO(2) impact champagne and sparkling wine science. Copyright © 2011 Elsevier B.V. All rights reserved.

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

USGS Publications Warehouse

Apps, J.A.; Zheng, Lingyun; Spycher, N.; Birkholzer, J.T.; Kharaka, Y.; Thordsen, J.; Kakouros, E.; Trautz, R.

2011-01-01

Food-grade CO2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1-2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca+2-driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO2 dissolution appears to compete for sorption with anionic species such as HAsO4-2, potentially increasing dissolved As levels in groundwater. ?? 2011 Published by Elsevier Ltd.

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.

A comparative study of volatile contents of primitive arc bubble-bearing melt inclusions determined by Raman-spectroscopy and mass-balance versus experimental homogenization methods

NASA Astrophysics Data System (ADS)

Moore, L.; Mironov, N.; Portnyagin, M.; Gazel, E.; Bodnar, R. J.

2016-12-01

Primitive olivine-hosted melt inclusions (MI) are a useful means to estimate the pre-eruptive volatile contents of a volcanic melts but post-entrapment processes complicate this approach. In particular, crystallization of the host phase along the wall of the MI and diffusion of H+ through the host cause CO2 and potentially S or other volatiles to exsolve from the melt to a separate fluid bubble. Recently, experimental rehydration and Raman spectroscopy have become potential methods for restoring the volatile contents of MI by rehomogenization or through mass balance calculations respectively. In order to compare these two approaches, we have studied MI from a single suite of samples from Klyuchevsky volcano (Kamchatka Arc) that have been treated with both experimental rehydration and analyzed using Raman spectroscopy. The maximum MI CO2 contents are in agreement ( 4000 ppm) regardless of the method used to account for CO2 in the bubble, but there is significantly more scatter to lower values using the Raman method which can be attributed to uncertainty related to mass balance calculations and carbonate daughter minerals that have formed at the glass-bubble interface. The presence of S- and C-bearing daughter minerals on the surface of the bubble in unheated melt inclusions indicates that to obtain more confident results with Raman spectroscopy, naturally quenched MIs should be also shortly reheated to dissolve most or all the crystals at the glass-bubble interface. Concerning H2O, MI from the unheated tephra samples contain less H2O than rehydrated MI in lavas. Determining the original H2O content of rehydrated MI is difficult because the H2O concentration in the glass is controlled by the conditions during the rehydration experiment. Thus reconciling the initial H2O content in primitive arc MIs (and degree of H2O loss) still remains a challenging task.

Investigation of the noble gas solubility in H 2O-CO 2 bearing silicate liquids at moderate pressure II: the extended ionic porosity (EIP) model

NASA Astrophysics Data System (ADS)

Nuccio, P. M.; Paonita, A.

2000-12-01

A semi-theoretical model is proposed to predict partitioning of noble gases between any silicate liquid and a H 2O-CO 2 gas phase with noble gas as a minor component, in a large range of pressures (at least up to 300 MPa). The model is based on the relationship between the concentration of dissolved noble gas and ionic porosity of the melt, found by Carroll and Stolper [Geochim. Cosmochim. Acta 57 (1993) 5039-5051] for H 2O-CO 2 free melts. It evaluates the effect of dissolved H 2O and CO 2 on the melt ionic porosity and, consequently on Henry's constants of noble gases. The fugacities of the noble gases in the H 2O-CO 2-noble gas mixtures are also considered in our equilibrium calculations of dissolved gas by using a modified Redlich-Kwong equation of state for the H 2O-CO 2-noble gas system. The formulated model (referred to as the extended ionic porosity model) clearly predicts a positive dependence of noble gas solubility on dissolved H 2O in melt, which becomes negligible when water concentration is higher than 3 wt%. Oppositely, noble gas solubility decreases as a consequence of increasing CO 2 in both basaltic and rhyolitic melts. The increase of noble gas solubility as a consequence of H 2O addition to the melt grows exponentially with the increase of the noble gas atomic size. As a result, although xenon solubility is much lower than the helium solubility in anhydrous melts, they become almost comparable at several percent of dissolved H 2O in the melt. On this basis, an exponential augmentation of the number of large free spaces in silicate liquid can be inferred in relation to increasing dissolved H 2O. Comparison between our predicted values and available experimental data [A. Paonita et al., Earth Planet. Sci. Lett. 181 (2000) 595-604] shows good agreement. At present, the EIP model is the unique tool which predicts how the main volatiles in magmatic systems affect the noble gas solubility in silicate melts, therefore it should be taken into account for future studies of noble gas fractionation in degassing natural magmas.

Increased iron availability resulting from increased CO2 enhances carbon and nitrogen metabolism in the economical marine red macroalga Pyropia haitanensis (Rhodophyta).

PubMed

Chen, Binbin; Zou, Dinghui; Yang, Yufeng

2017-04-01

Ocean acidification caused by rising CO 2 is predicted to increase the concentrations of dissolved species of Fe(II) and Fe(III), leading to the enhanced photosynthetic carbon sequestration in some algal species. In this study, the carbon and nitrogen metabolism in responses to increased iron availability under two CO 2 levels (390 μL L -1 and 1000 μL L -1 ), were investigated in the maricultivated macroalga Pyropia haitanensis (Rhodophyta). The results showed that, elevated CO 2 increased soluble carbonhydrate (SC) contents, resulting from enhanced photosynthesis and photosynthetic pigment synthesis in this algae, but declined its soluble protein (SP) contents, resulting in increased ratio of SC/SP. This enhanced photosynthesis performance and carbon accumulation was more significant under iron enrichment condition in seawater, with higher iron uptake rate at high CO 2 level. As a key essential biogenic element for algae, Fe-replete functionally contributed to P. haitanensis photosynthesis. Increased SC fundamentally provided carbon skeletons for nitrogen assimilation. The significant increase of carbon and nitrogen assimilation finally contributed to enhanced growth in this alga. This was also intuitively reflected by respiration that provided energy for cellular metabolism and algal growth. We propose that, in the predicted scenario of rising atmospheric CO 2 , P. haitanensis is capable to adjust its physiology by increasing its carbon and nitrogen metabolism to acclimate the acidified seawater, at the background of global climate change and simultaneously increased iron concentration due to decreased pH levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

Autocorrelation analysis of the infrared spectra of synthetic and biogenic carbonates along the calcite-dolomite join

NASA Astrophysics Data System (ADS)

Jenkins, David M.; Holmes, Zachary F.; Ishida, Kiyotaka; Manuel, Phillip D.

2018-01-01

Autocorrelation analysis of infrared spectra can provide insights on the strain energy associated with cation substitutions along a solid-solution compositional join which to date has been applied primarily to silicate minerals. In this study, the method is applied to carbonates synthesized at 10 mol% increments along the calcite-dolomite (CaCO3-CaMg(CO3)2) join in the range of 1000-1150 °C and 0.6-2.5 GPa for the purpose of determining how the band broadening in both the far- and mid-infrared ranges, as represented by the autocorrelation parameter δΔCorr, compares with the existing enthalpy of mixing data for this join. It was found that the carbonate internal vibration ν2 (out-of-plane bending) in the mid-infrared range, and the sum of the three internal vibration modes ν4 + ν2 + ν3 most closely matched the enthalpy of mixing data for the synthetic carbonates. Autocorrelation analysis of a series of biogenic carbonates in the mid-infrared range showed only a systematic variation for the ν2 band. Using the biogenic carbonate with the lowest Mg content for reference, the trend in δΔCorr for biogenic carbonates shows a steady increase with increasing Mg content suggesting a steady increase in solubility with Mg content. The results from this study indicate that autocorrelation analysis of carbonates in the mid-infrared range provides an independent and reliable assessment of the crystallographic strain energy of carbonates. In particular, inorganic carbonates in the range of 0-17 mol% MgCO3 experience a minimum in strain energy and a corresponding minimum in the enthalpy of mixing, whereas biogenic carbonates show a steady increase in strain energy with increasing MgCO3 content. In the event of increasing ocean acidification, biogenic carbonates in the range of 0-17 mol% MgCO3 will dissolve more readily than the compositionally equivalent inorganic carbonates.

Autocorrelation analysis of the infrared spectra of synthetic and biogenic carbonates along the calcite-dolomite join

NASA Astrophysics Data System (ADS)

Jenkins, David M.; Holmes, Zachary F.; Ishida, Kiyotaka; Manuel, Phillip D.

2018-06-01

Autocorrelation analysis of infrared spectra can provide insights on the strain energy associated with cation substitutions along a solid-solution compositional join which to date has been applied primarily to silicate minerals. In this study, the method is applied to carbonates synthesized at 10 mol% increments along the calcite-dolomite (CaCO3-CaMg(CO3)2) join in the range of 1000-1150 °C and 0.6-2.5 GPa for the purpose of determining how the band broadening in both the far- and mid-infrared ranges, as represented by the autocorrelation parameter δΔCorr, compares with the existing enthalpy of mixing data for this join. It was found that the carbonate internal vibration ν2 (out-of-plane bending) in the mid-infrared range, and the sum of the three internal vibration modes ν4 + ν2 + ν3 most closely matched the enthalpy of mixing data for the synthetic carbonates. Autocorrelation analysis of a series of biogenic carbonates in the mid-infrared range showed only a systematic variation for the ν2 band. Using the biogenic carbonate with the lowest Mg content for reference, the trend in δΔCorr for biogenic carbonates shows a steady increase with increasing Mg content suggesting a steady increase in solubility with Mg content. The results from this study indicate that autocorrelation analysis of carbonates in the mid-infrared range provides an independent and reliable assessment of the crystallographic strain energy of carbonates. In particular, inorganic carbonates in the range of 0-17 mol% MgCO3 experience a minimum in strain energy and a corresponding minimum in the enthalpy of mixing, whereas biogenic carbonates show a steady increase in strain energy with increasing MgCO3 content. In the event of increasing ocean acidification, biogenic carbonates in the range of 0-17 mol% MgCO3 will dissolve more readily than the compositionally equivalent inorganic carbonates.

Constraints on the magnitude and rate of CO2 dissolution at Bravo Dome natural gas field

PubMed Central

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, Martin; Stockli, Daniel F.

2014-01-01

The injection of carbon dioxide (CO2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO2 emissions from fossil fuels. Dissolution of the injected CO2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO2 storage. We use thermochronology to estimate the timing of CO2 emplacement at Bravo Dome, a large natural CO2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraints on the magnitude, mechanisms, and rates of CO2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO2 storage is possible. Integrating geophysical and geochemical data, we estimate that 1.3 Gt CO2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m2y). The similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO2 on the 10-ky timescale typically considered for storage projects. PMID:25313084

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.

Automated determination of the stable carbon isotopic composition (δ13C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

USGS Publications Warehouse

Révész, Kinga M.; Doctor, Daniel H.

2014-01-01

The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ13C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO2) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO2. This configuration provides a fully automated analysis of total carbon mass and δ13C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H3PO4), which allows the carbonate and bicarbonate species in the sample to dissociate to CO2. The CO2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO2 through an infrared CO2 detector and quantifies the CO2. The CO2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na2S2O8) is added, and the hydroxyl radicals oxidize the organics to CO2. Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

The effect of primary versus secondary processes on the volatile content of MORB glasses: An example from the equatorial Mid-Atlantic Ridge (5°N-3°S)

NASA Astrophysics Data System (ADS)

Le Voyer, Marion; Cottrell, Elizabeth; Kelley, Katherine A.; Brounce, Maryjo; Hauri, Erik H.

2015-01-01

We report microanalysis of volatile and trace element compositions, as well as Fe3+/ΣFe ratios, from 45 basaltic glasses from cruise RC2806 along the equatorial Mid-Atlantic Ridge. The along-strike variations in volatiles result from the complex geodynamical setting of the area, including numerous transform faults, variations in ridge depth, melting degree, and source composition. The strongest gradient is centered on 1.7°N and encompasses an increase of H2O, Cl, and F contents as well as high F/Zr ratio spatially coincident with radiogenic isotope anomalies. We interpret these variations as source enrichment due to the influence of the nearby high-μ-type Sierra Leone plume. South of the St. Paul fracture zone, H2O and F contents, as well as H2O/Ce and F/Zr ratios, decrease progressively. This gradient in volatiles is consistent with progressive dilution of an enriched component in a heterogeneous mantle due to the progressive increase in the degree of melting. These two large-scale gradients are interrupted by small-scale anomalies in volatile contents attributed to (1) low-degree melts preferentially sampling enriched heterogeneities near transform faults and (2) local assimilation of hydrothermal fluids in four samples from dredge 16D. Finally, 20 RC2806 samples described as "popping rocks" during collection do not show any difference in volatile content dissolved in the glass or in vesicularity when compared to the RC2806 "nonpopping" samples. Our observations lead us to question the interpretation of the CO2 content in the highly vesicular 2πD43 "popping rock" as being representative of the CO2 content of undegassed mid-ocean ridge basalt.

Light–dark O2 dynamics in submerged leaves of C3 and C4 halophytes under increased dissolved CO2: clues for saltmarsh response to climate change

PubMed Central

Duarte, B.; Santos, D.; Silva, H.; Marques, J. C.; Caçador, I.; Sleimi, N.

2014-01-01

Waterlogging and submergence are the major constraints to which wetland plants are subjected, with inevitable impacts on their physiology and productivity. Global warming and climate change, as driving forces of sea level rise, tend to increase such submersion periods and also modify the carbonate chemistry of the water column due to the increased concentration of CO2 in the atmosphere. In the present work, the underwater O2 fluxes in the leaves of two abundant Mediterranean halophytes were evaluated at different levels of dissolved CO2. Photosynthetic enhancement due to increased dissolved CO2 was confirmed for both Halimione portulacoides and Spartina maritima, probably due to high tissue porosity, formation of leaf gas films and reduction of the oxygenase activity of Rubisco. Enhancement of the photosynthetic rates in H. portulacoides and S. maritima was concomitant with an increase in energy trapping and transfer, mostly due to enhancement of the carboxylation reaction of Rubisco, leading to a reduction of the energy costs for carbon fixation. Transposing these findings to the ecosystem, and assuming increased dissolved CO2 concentration scenarios, the halophyte community displays a new ecosystem function, increasing the water column oxygenation and thus reinforcing their role as principal primary producers of the estuarine system. PMID:25381259

Fundamental Study on the Dynamics of Heterogeneity-Enhanced CO2 Gas Evolution in the Shallow Subsurface During Possible Leakage from Deep Geologic Storage Sites

NASA Astrophysics Data System (ADS)

Plampin, M. R.; Lassen, R. N.; Sakaki, T.; Pawar, R.; Jensen, K.; Illangasekare, T. H.

2013-12-01

A concern for geologic carbon sequestration is the potential for CO2 stored in deep geologic formations to leak upward into shallow freshwater aquifers where it can have potentially detrimental impacts to the environment and human health. Understanding the mechanisms of CO2 exsolution, migration and accumulation (collectively referred to as 'gas evolution') in the shallow subsurface is critical to predict and mitigate the environmental impacts. During leakage, CO2 can move either as free-phase or as a dissolved component of formation brine. CO2 dissolved in brine may travel upward into shallow freshwater systems, and the gas may be released from solution. In the shallow aquifer, the exsolved gas may accumulate near interfaces between soil types, and/or create flow paths that allow the gas to escape through the vadose zone to the atmosphere. The process of gas evolution in the shallow subsurface is controlled by various factors, including temperature, dissolved CO2 concentration, water pressure, background water flow rate, and geologic heterogeneity. However, the conditions under which heterogeneity controls gas phase evolution have not yet been precisely defined and can therefore not yet be incorporated into models used for environmental risk assessment. The primary goal of this study is to conduct controlled laboratory experiments to help fill this knowledge gap. With this as a goal, a series of intermediate-scale laboratory experiments were conducted to observe CO2 gas evolution in porous media at multiple scales. Deionized water was saturated with dissolved CO2 gas under a specified pressure (the saturation pressure) before being injected at a constant volumetric flow rate into the bottom of a 1.7 meter-tall by 5.7 centimeter-diameter column or a 2.4 meter-tall by 40 centimeter-wide column that were both filled with sand in various heterogeneous packing configurations. Both test systems were initially saturated with fresh water and instrumented with soil moisture sensors to monitor the evolution of gas phase through time by measuring the average water content in small sampling volumes of soil. Tensiometers allowed for observation of water pressure through space and time in the test systems, and a computer-interfaced electronic scale continuously monitored the outflow of water from the top of the two test columns. Several packing configurations with five different types of sands were used in order to test the effects of various pore size contrasts and interface shapes on the evolution of the gas phase near soil texture transitions in the heterogeneous packings. Results indicate that: (1) heterogeneity affects gas phase evolution patterns within a predictable range of conditions quantified by the newly introduced term 'oversaturation,' (2) soil transition interfaces where less permeable material overlies more permeable material have a much more pronounced effect on gas evolution than interfaces with opposite orientations, and (3) anticlines (or stratigraphic traps) cause significantly greater gas accumulation than horizontal interfaces. Further work is underway to apply these findings to more realistic, two-dimensional scenarios, and to assess how well existing numerical models can capture these processes.

[Interactions of straw, nitrogen fertilizer and bacterivorous nematodes on soil labile carbon and nitrogen and greenhouse gas emissions].

PubMed

Zhang, Teng-Hao; Wang, Nan; Liu, Man-Qiang; Li, Fang-Hui; Zhu, Kang-Li; Li, Hui-Xin; Hu, Feng

2014-11-01

A 3 x 2 factorial design of microcosm experiment was conducted to investigate the interactive effects of straw, nitrogen fertilizer and bacterivorous nematodes on soil microbial biomass carbon (C(mic)) and nitrogen (N(mic)), dissolved organic carbon (DOC) and nitrogen (DON), mineral nitrogen (NH(4+)-N and NO(3-)-N), and greenhouse gas (CO2, N2O and CH4) emissions. Results showed that straw amendment remarkably increased the numbers of bacterivorous nematodes and the contents of Cmic and Nmic, but Cmic and Nmic decreased with the increasing dose of nitrogen fertilization. The effects of bacterivorous nematodes strongly depended on either straw or nitrogen fertilization. The interactions of straw, nitrogen fertilization and bacterivorous nematodes on soil DOC, DON and mineral nitrogen were strong. Straw and nitrogen fertilization increased DOC and mineral nitrogen contents, but their influences on DON depended on the bacterivorous nematodes. The DOC and mineral nitrogen were negatively and positively influenced by the bacterivorous nematodes, re- spectively. Straw significantly promoted CO2 and N2O emissions but inhibited CH4 emission, while interactions between nematodes and nitrogen fertilization on emissions of greenhouse gases were obvious. In the presence of straw, nematodes increased cumulative CO2 emissions with low nitrogen fertilization, but decreased CO2 and N2O emissions with high nitrogen fertilization on the 56th day after incubation. In summary, mechanical understanding the soil ecological process would inevitably needs to consider the roles of soil microfauna.

Oxygen fugacity and piston cylinder capsule assemblies

NASA Astrophysics Data System (ADS)

Jakobsson, S.

2011-12-01

A double capsule assembly designed to control oxygen fugacity in piston cylinder experiments has been tested at 1200 °C and 10 kbar. The assembly consists of an outer Pt-capsule containing a solid buffer (Ni-NiO or Co-CoO plus H2O) and an inner AuPd-capsule containing the sample, H2O and a Pt-wire. To prevent direct contact with the buffer phases the AuPd-capsule is embedded in finely ground Al2O3 along with some coarser, fractured Al2O3 facilitating fluid inclusion formation. No water loss is observed in the sample even after 48 hrs but a slight increase in water content is observed in longer duration runs due to oxygen and hydrogen diffusion into the AuPd-capsule. Carbon from the furnace also diffuses through the outer Pt-capsule but reacts with H2O in the outer capsule to form CO2 and never reaches the inner capsule. Oxygen fugacity of runs in equilibrium with the Ni-NiO and Co-CoO buffers was measured by analyzing the Fe content of the Pt-wire in the sample1 and by analyzing Fe dissolved in the AuPd capsule2. The second method gives values that are in good agreement with established buffer whereas results from the first method are one half to one log units higher than the established values. References 1. E. Medard, C. A. McCammon, J. A. Barr, T. L. Grove, Am. Mineral. 93, 1838 (2008). 2. J. Barr, T. Grove, Contrib. Mineral. Petrol. 160, 631 (2010)

Evaluating sensitivity of complex electrical methods for monitoring CO2 intrusion into a shallow groundwater system and associated geochemical transformations

NASA Astrophysics Data System (ADS)

Dafflon, B.; Wu, Y.; Hubbard, S. S.; Birkholzer, J. T.; Daley, T. M.; Pugh, J. D.; Peterson, J.; Trautz, R. C.

2011-12-01

A risk factor of CO2 storage in deep geological formations includes its potential to leak into shallow formations and impact groundwater geochemistry and quality. In particular, CO2 decreases groundwater pH, which can potentially mobilize naturally occurring trace metals and ions commonly absorbed to or contained in sediments. Here, geophysical studies (primarily complex electrical method) are being carried out at both laboratory and field scales to evaluate the sensitivity of geophysical methods for monitoring dissolved CO2 distribution and geochemical transformations that may impact water quality. Our research is performed in association with a field test that is exploring the effects of dissolved CO2 intrusion on groundwater geochemistry. Laboratory experiments using site sediments (silica sand and some fraction of clay minerals) and groundwater were initially conducted under field relevant CO2 partial pressures (pCO2). A significant pH drop was observed with inline sensors with concurrent changes in fluid conductivity caused by CO2 dissolution. Electrical resistivity and electrical phase responses correlated well with the CO2 dissolution process at various pCO2. Specifically, resistivity decreased initially at low pCO2 condition resulting from CO2 dissolution followed by a slight rebound because of the transition of bicarbonate into non-dissociated carbonic acid at lower pH slightly reducing the total concentration of dissociated species. Continuous electrical phase decreases were also observed, which are interpreted to be driven by the decrease of surface charge density (due to the decrease of pH, which approaches the PZC of the sediments). In general, laboratory experiments revealed the sensitivity of electrical signals to CO2 intrusion into groundwater formations and can be used to guide field data interpretation. Cross well complex electrical data are currently being collected periodically throughout a field experiment involving the controlled release of dissolved CO2 into groundwater. The objective of the geophysical cross well monitoring effort is to evaluate the sensitivity of complex electrical methods to dissolved CO2 at the field scale. Here, we report on the ability to translate laboratory-based petrophysical information from lab to field scales, and on the potential of field complex electrical methods for remotely monitoring CO2-induced geochemical transformations.

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.

An experimental study of basaltic glass-H2O-CO2 interaction at 22 and 50 ° C: Implications for subsurface storage of CO2

NASA Astrophysics Data System (ADS)

Galeczka, Iwona; Wolff-Boenisch, Domenik; Oelkers, Eric H.; Gislason, Sigurdur R.

2014-05-01

A novel high pressure column flow reactor (HPCFR) was used to investigate the evolution of fluid chemistry along a 2.3 meter flow path during 37-104 days of pure water- and CO2-charged water- (0.3 M CO2(aq)) basaltic glass interaction experiments at 22 and 50 ° C. The scale of the HPCFR, the ability to sample a reactive fluid at discrete spatial intervals under pressure and the possibility to measure the dissolved inorganic carbon and pH in situ all render the HPCFR unique in comparison with other reactors constructed for studies of CO2-charged water-rock interaction. During the pure water-basaltic glass interaction experiment, the pH of the injected water evolved rapidly from 6.7 to 9-9.5 and most of the dissolved iron was consumed by secondary mineral formation, similar to natural basaltic groundwater systems. In contrast to natural systems, however, the dissolved aluminium concentration remained relatively high along the entire flow path. The reactive fluid was undersaturated with respect to basaltic glass and carbonate minerals, but supersaturated with respect to zeolites, clays, and Fe hydroxides. Basaltic glass dissolution in the CO2-charged water was closer to stoichiometry than in pure water. The mobility of metals increased significantly in the reactive fluid and the concentration of some metals, including Mn, Fe, Cr, Al, and As exceeded the WHO (World Health Organisation) allowable drinking water limits. Iron was mobile and the aqueous Fe2+/Fe3+ ratio increased along the flow path. Basaltic glass dissolution in the CO2-charged water did not overcome the pH buffer capacity of the fluid. The pH rose only from an initial pH of 3.4 to 4.5 along the first 18.5 cm of the column, then remained constant during the remaining 2.1 meters of the flow path. Increasing the temperature of the CO2-charged fluid from 22 to 50 ° C increased the relative amount of dissolved divalent iron along the flow path. After a significant initial increase along the first metre of the column, the dissolved aluminium concentration decreased consistent with its incorporation into secondary minerals. The dissolved chromium concentration evolution mimicked that of Al at 50 ° C, suggesting substitution of trivalent Cr for Al in secondary phases. According to PHREEQC calculations, the CO2-charged fluid was always undersaturated with respect to carbonate minerals within the column, but supersaturated with respect to clays and Fe hydroxides at 22 ° C and with respect to clays and Al hydroxides at 50 ° C. Substantial differences were found between modelled and measured dissolved element concentrations in the fluids during the experiments. These differences underscore the need to improve computational models before they can be used to predict with confidence the fate and consequences of carbon dioxide injected into the subsurface.

Linking carbon and hydrologic fluxes in the critical zone: Observations from high-frequency monitoring of a weathered bedrock vadose zone

NASA Astrophysics Data System (ADS)

Tune, A. K.; Druhan, J. L.; Wang, J.; Cargill, S.; Murphy, C.; Rempe, D. M.

2017-12-01

A principle challenge in quantifying feedbacks between continental weathering and atmospheric CO2 is to improve understanding of how biogeochemical processes in the critical zone influence the distribution and mobility of organic and inorganic carbon. In particular, in landscapes characterized by thin soils and heterogeneous weathered and fractured bedrock, little data exist to inform and constrain predictive models for carbon dynamics. Here, we present the results of an intensive water and gas sampling campaign across an 18 m thick, variably saturated argillite weathering profile in the Eel River CZO. We monitor water content in situ and regularly collect samples of freely-draining water, tightly-held water, and gas through wet and dry seasons using a novel Vadose-zone Monitoring System (VMS) consisting of sensors and samplers distributed across a 20 m long inclined borehole. This novel approach facilitates the interception of gas and water during transport across the entire variably saturated weathering profile. The data demonstrate that seasonal changes in saturation control the vertical distribution and mobility of carbon in the fractured critical zone. Concentrations of gaseous CO2, O2, and dissolved organic and inorganic carbon fluctuate significantly and repeatably with seasonal additions of water infiltrating the weathered bedrock. A persistent vertical structure in the concentrations of dissolved phases and gas concentrations broadly corresponds to depths associated with unsaturated, seasonally saturated, and chronically saturated zones. Associated variations in the vertical structure of mineralogy and elemental composition, including solid phase organic carbon content, are observed in core obtained during drilling. Together, our observations indicate significant respiration of organic carbon at depths greater than the base of the soil, and thus motivate further investigation of the role of heterogeneous weathered, bedrock environments, which are needed to improve quantitative models for feedbacks between terrestrial and atmospheric CO2.

Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature.

PubMed

Jacquemet, Nicolas; Pironon, Jacques; Saint-Marc, Jérémie

2008-01-01

The reactivity of a crushed well cement in contact with (1) a brine with dissolved H2S-CO2; (2) a dry H2S-CO2 supercritical phase; (3) a two-phase fluid associating a brine with dissolved H2S-CO2 and a H2S-CO2 supercritical phase was investigated in batch experiments at 500 bar and 120, 200 degrees C. All of the experiments showed that following 15-60 days cement carbonation occurred. The H2S reactivity with cement is limited since it only transformed the ferrites (minor phases) by sulfidation. It appeared that the primary parameter controlling the degree of carbonation (i.e., the rate of calcium carbonates precipitation and CSH (Calcium Silicate Hydrates) decalcification) is the physical state of the fluid phase contacting the minerals. The carbonation degree is complete when the minerals contact at least the dry H2S-CO2 supercritical phase and partial when they contactthe brine with dissolved H2S-CO2. Aragonite (calcium carbonate polymorph) precipitated specifically within the dry H2S-CO2 supercritical phase. CSH cristallinity is improved by partial carbonation while CSH are amorphized by complete carbonation. However, the features evidenced in this study cannot be directly related to effective features of cement as a monolith. Further studies involving cement as a monolith are necessary to ascertain textural, petrophysical, and mechanical evolution of cement.

Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO 2 exposure

DOE PAGES

Smith, Megan M.; Sholokhova, Yelena; Hao, Yue; ...

2012-07-25

Characterization and geochemical data are presented from a core-flooding experiment on a sample from the Three Fingers evaporite unit forming the lower extent of caprock at the Weyburn-Midale reservoir, Canada. This low-permeability sample was characterized in detail using X-ray computed microtomography before and after exposure to CO 2-acidified brine, allowing mineral phase and voidspace distributions to be quantified in three dimensions. Solution chemistry indicated that CO 2-acidified brine preferentially dissolved dolomite until saturation was attained, while anhydrite remained unreactive. Dolomite dissolution contributed to increases in bulk permeability through the formation of a localized channel, guided by microfractures as well asmore » porosity and reactive phase distributions aligned with depositional bedding. An indirect effect of carbonate mineral reactivity with CO 2-acidified solution is voidspace generation through physical transport of anhydrite freed from the rock matrix following dissolution of dolomite. The development of high permeability fast pathways in this experiment highlights the role of carbonate content and potential fracture orientations in evaporite caprock formations considered for both geologic carbon sequestration and CO 2-enhanced oil recovery operations.« less

Near-infrared spectroscopic investigation of water in supercritical CO2 and the effect of CaCl2

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

Wang, Zheming; Felmy, Andrew R.; Thompson, Christopher J.

2013-01-01

Near-infrared (NIR) spectroscopy was applied to investigate the dissolution and chemical interaction of water dissolved into supercritical carbon dioxide (scCO2) and the influence of CaCl2 in the co-existing aqueous phase at fo empe e : 40 50 75 nd 100 C at 90 atm. Consistent with the trend of the vapor pressure of water, the solubility of pure water in scCO2 inc e ed f om 40 °C (0.32 mole%) o 100 °C (1.61 mole%). The presence of CaCl2 negatively affects the solubility of water in scCO2: at a given temperature and pressure the solubility of water decreased as themore » concentration of CaCl2 in the aqueous phase increased, following the trend of the activity of water. A 40 °C, the water concentration in scCO2 in contact with saturated CaCl2 aqueous solution was only 0.16 mole%, a drop of more than 50% as compared to pure water while that a 100 °C was 1.12 mole%, a drop of over 30% as compared to pure water, under otherwise the same conditions. Analysis of the spectral profiles suggested that water dissolved into scCO2 exists in the monomeric form under the evaluated temperature and pressure conditions, for both neat water and CaCl2 solutions. However, its rotational degrees of freedom decrease at lower temperatures due to higher fluid densities, leading to formation of weak H2O:CO2 Lewis acid-base complexes. Similarly, the nearly invariant spectral profiles of dissolved water in the presence and absence of saturated CaCl2 under the same experimental conditions was taken as evidence that CaCl2 dissolution in scCO2 was limited as the dissolved Ca2+/CaCl2 would likely be highly hydrated and would alter the overall spectra of waters in the scCO2 phase.« less

Effects of Dissolved Organic Matter Properties on Formation and Composition of Mineral-Organic Co-Precipitates at the Nanometer Scale

NASA Astrophysics Data System (ADS)

Possinger, A. R.; Zachman, M.; Lehmann, J.

2016-12-01

An important, yet largely overlooked case of soil organic carbon (SOC) stabilization through mineral-organic associations is the co-precipitation of dissolved organic matter (DOM) into mineral precipitates as they form. The contribution of co-precipitated DOM to the mineral-stabilized SOC pool is expected to be greatest in soil environments with frequent mineral dissolution and precipitation processes. Compared to surface adsorption, properties of mineral-organic co-precipitates are expected to differ at both the particle scale (e.g., total carbon (C) content and composition) and the molecular scale (e.g., impurities in mineral structure), with potential implications for stability and C turnover; additionally, these properties vary across C sources, amounts, and forms. Consequently, high-resolution visualization and characterization combined with bulk chemical measurements is needed to provide a more complete understanding of co-precipitate formation processes and properties, especially as a function of C co-precipitant characteristics. In this study, we evaluate the effect of model C compound and DOM chemical properties (e.g., iron-binding affinity) on the formation, structure, and chemical properties of ferrihydrite (Fh) (Fe3+3O2 •0.5H2O) co-precipitates. Salicylic acid (SA), sucrose and water-extractable DOM from coniferous or deciduous-dominated organic soils were either adsorbed to pre-formed Fh or co-precipitated with Fh. At a C/Fe ratio 10, the amount of co-precipitated C differed among all organic compounds, and for DOM, was more than 2X greater for co-precipitation than adsorption, suggesting a greater capacity for C retention. To probe the molecular-scale C spatial distribution of Fh-SA particles, we obtained Scanning Transmission Electron Microscopy with Electron Energy Loss Spectroscopy (STEM-EELS) maps at a nanometer-scale spatial pixel resolution. Additionally, we will present chemical characteristics of organic-Fh co-precipitates and adsorption complexes investigated in bulk using C Near-Edge X-ray Absorption Fine Structure (NEXAFS) and Fourier Transform Infrared (FT-IR) spectroscopy. Ultimately, these observations of model co-precipitation systems will be used to better interpret observations of putative co-precipitated OM in natural soils.

Processes of nickel and cobalt uptake by a manganese oxide forming sediment in Pinal Creek, Globe mining district, Arizona

USGS Publications Warehouse

Kay, J.T.; Conklin, M.H.; Fuller, C.C.; O'Day, P. A.

2001-01-01

A series of column experiments was conducted using manganese oxide coated sediments collected from the hyporheic zone in Pinal Creek (AZ), a metal-contaminated stream, to study the uptake and retention of Mn, Ni, and Co. Experimental variables included the absence (abiotic) and presence (biotic) of active Mn-oxidizing bacteria, the absence and presence of dissolved Mn, and sediment manganese oxide content. Uptake of Mn under biotic conditions was between 8 and 39% higher than under abiotic conditions. Continuous uptake of Mn due to biotic oxidation was evident from extraction of column sediments. Manganese uptake is hypothesized to initially occur as adsorption, which led to subsequent surface and/or microbial oxidation. Complete breakthrough of Ni within 100 pore volumes indicated no process of continuous uptake and was modeled as an equilibrium adsorption process. Nickel uptake in the presence of dissolved Mn was 67-100% reversible. Sediment extractions suggest that Ni uptake occurred through weak and strong adsorption. Continuous uptake of cobalt increased with sediment manganese oxide content, and Co uptake was up to 75% greater under biotic than abiotic conditions. Cobalt uptake was controlled by both existing and newly formed manganese oxides. Only a small amount of Co uptake was reversible (10-25%). XANES spectral analysis indicated that most Co(II) was oxidized to Co(III) and probably incorporated structurally into manganese oxides. Although manganese oxides were the primary phase controlling uptake and retention of Mn, Ni, and Co, the mechanisms varied among the metals.

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

NASA Astrophysics Data System (ADS)

Aguilera, E.; Chiodini, G.; Cioni, R.; Guidi, M.; Marini, L.; Raco, B.

2000-04-01

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (˜14 m) oxic epilimnion overlying a ˜200 m-thick anoxic hypolimnion. Dissolved CO2 concentrations reached 1000 mg/kg in the lower stratum. Loss of CO2 from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification. The Cl, SO4 and HCO3 contents of Lake Quilotoa are intermediate between those of acid-SO4-Cl Crater lakes and those of neutral-HCO3 Crater lakes, indicating that Lake Quilotoa has a 'memory' of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid-SO4-Cl Crater lakes. The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by ˜4°C or providing heat to hypolimnetic waters or by seismic activity. Although Quilotoa lake contains a huge amount of dissolved CO2(˜3×1011 g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO2-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.

Enhanced production of green tide algal biomass through additional carbon supply.

PubMed

de Paula Silva, Pedro H; Paul, Nicholas A; de Nys, Rocky; Mata, Leonardo

2013-01-01

Intensive algal cultivation usually requires a high flux of dissolved inorganic carbon (Ci) to support productivity, particularly for high density algal cultures. Carbon dioxide (CO2) enrichment can be used to overcome Ci limitation and enhance productivity of algae in intensive culture, however, it is unclear whether algal species with the ability to utilise bicarbonate (HCO3 (-)) as a carbon source for photosynthesis will benefit from CO2 enrichment. This study quantified the HCO3 (-) affinity of three green tide algal species, Cladophora coelothrix, Cladophora patentiramea and Chaetomorpha linum, targeted for biomass and bioenergy production. Subsequently, we quantified productivity and carbon, nitrogen and ash content in response to CO2 enrichment. All three species had similar high pH compensation points (9.7-9.9), and grew at similar rates up to pH 9, demonstrating HCO3 (-) utilization. Algal cultures enriched with CO2 as a carbon source had 30% more total Ci available, supplying twenty five times more CO2 than the control. This higher Ci significantly enhanced the productivity of Cladophora coelothrix (26%), Chaetomorpha linum (24%) and to a lesser extent for Cladophora patentiramea (11%), compared to controls. We demonstrated that supplying carbon as CO2 can enhance the productivity of targeted green tide algal species under intensive culture, despite their clear ability to utilise HCO3 (-).

Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

2014-05-01

Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared to the non reactive one. On the basis of a reaction-diffusion-convection model, we classify the various possible cases and show that the difference between the solutal expansion coefficients of the reactant and of the product governs the type of density profile building up in the aqueous solution and thus the stability of the system. By contrast to non reactive density profiles, reactive density profiles can feature a minimum that induces a delay of the buoyancy-driven convection. This work identifies the parameters that could influence the dissolution-driven convection in the aquifers, and thus impact the safety of the sequestration. In other words, this theoretical study shows that it is crucial to analyse the composition and reactivity of potential storage sites to choose those that will be most efficient for long-term CO2 sequestration.

Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

PubMed

Sujith, K S; Ramachandran, C N

2016-02-07

The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

In vitro genotoxicity of asbestos substitutes induced by coupled stimulation of dissolved high-valence ions and oxide radicals.

PubMed

Huo, Tingting; Dong, Faqin; Deng, Jianjun; Zhang, Qingbi; Ye, Wei; Zhang, Wei; Wang, Pingping; Sun, Dongping

2017-08-01

The wide use of asbestos and its substitutes has given rise to studies on their possible harmful effects on human health and environment. However, their toxic effects remain unclear. The present study was aimed to disclose the coupled effects of dissolved high-valence ions and oxide radicals using the in vitro cytotoxicity and genotoxicity of chrysotile (CA), nano-SiO 2 (NS), ceramic fiber (CF), glass fiber (GF), and rock wool (RW) on Chinese hamster lung cells V79. All samples induced cell mortality correlated well with the chemical SiO 2 content of asbestos substitutes and the amount of dissolved Si. Alkali or alkaline earth metal elements relieved mortality of V79 cells; Al 2 O 3 reinforced toxicity of materials. Asbestos substitutes generated lasting, increasing amount of acellular ·OH which formed at the fiber surface at sites with loose/unsaturated bonds, as well as by catalytic reaction through dissolved iron. Accumulated mechanical and radical stimulation induced the intracellular reactive oxygen species (ROS) elevation, morphology change, and deviating trans-membrane ion flux. The cellular ROS appeared as NS > GF > CF ≈ CA > RW, consistent with cell mortality rather than with acellular ·OH generation. Chromosomal and DNA lesions in V79 cells were not directly associated with the cellular ROS, while influenced by dissolved high-valence irons in the co-culture medium. In conclusion, ions from short-time dissolution of dust samples and the generation of extracellular ·OH presented combined effects in the elevation of intracellular ROS, which further synergistically induced cytotoxicity and genotoxicity.

Biogeochemical Carbon Cycling in Ultrabasic Reducing Springs in Sonoma County, CA

NASA Astrophysics Data System (ADS)

Cotton, J. M.; Morrill, P.; Johnson, O.; Nealson, K. H.; Sherwood Lollar, B.; Eigenbrode, J.; Fogel, M.

2006-12-01

Dissolved gases in the ultrabasic spring waters from The Cedars in Sonoma County, CA were analyzed for concentrations and carbon and hydrogen isotopic ratios in order to determine the geobiological processes occurring in this extreme environment of unknown biological activity. The ultrabasic, highly reducing conditions unique to these springs result from local serpentinization. Gases bubbling from the springs are mainly composed of methane, hydrogen, and nitrogen. Serpentinization is a process characteristic of early Earth, Mars and Titan that is thought to produce abiogenic hydrocarbons as well as provide geochemical energy for chemolithotrophic life. Methane, CO2, hydrogen and nitrogen were detected in the aqueous phases. Earlier work indicated that the primary source of the methane in the free gases bubbling from the springs was associated with microbial fermentation a suspected source of the dissolved methane. Here we report, a negative, linear correlation between concentrations of CO2 and methane that is an indicator of microbial anaerobic methane oxidation taking place in the ultrabasic waters. Furthermore, as the concentrations of methane decrease, the concentration of CO2 increases and both reactant and product become 13C-enriched. These observations are consistent with microbial oxidation of methane, suggesting a biogeochemical carbon cycle exists in these springs. We hypothesize that one group of microbes is breaking down organic matter by a process of fermentation to produce methane and CO2. The CO2 dissolves in the basic springs, while most of the methane escapes solution. The residual dissolved methane undergoes a conversion to CO2 by anaerobic methane oxidation.

Constraints on the magnitude and rate of CO 2 dissolution at Bravo Dome natural gas field

DOE PAGES

Sathaye, Kiran J.; Hesse, Marc A.; Cassidy, M.; ...

2014-10-13

The injection of carbon dioxide (CO 2) captured at large point sources into deep saline aquifers can significantly reduce anthropogenic CO 2 emissions from fossil fuels. Dissolution of the injected CO 2 into the formation brine is a trapping mechanism that helps to ensure the long-term security of geological CO 2 storage. We use thermochronology to estimate the timing of CO 2 emplacement at Bravo Dome, a large natural CO 2 field at a depth of 700 m in New Mexico. Together with estimates of the total mass loss from the field we present, to our knowledge, the first constraintsmore » on the magnitude, mechanisms, and rates of CO 2 dissolution on millennial timescales. Apatite (U-Th)/He thermochronology records heating of the Bravo Dome reservoir due to the emplacement of hot volcanic gases 1.2–1.5 Ma. The CO 2 accumulation is therefore significantly older than previous estimates of 10 ka, which demonstrates that safe long-term geological CO 2 storage is possible. Here, integrating geophysical and geochemical data, we estimate that 1.3 Gt CO 2 are currently stored at Bravo Dome, but that only 22% of the emplaced CO 2 has dissolved into the brine over 1.2 My. Roughly 40% of the dissolution occurred during the emplacement. The CO 2 dissolved after emplacement exceeds the amount expected from diffusion and provides field evidence for convective dissolution with a rate of 0.1 g/(m 2y). Finally, the similarity between Bravo Dome and major US saline aquifers suggests that significant amounts of CO 2 are likely to dissolve during injection at US storage sites, but that convective dissolution is unlikely to trap all injected CO 2 on the 10-ky timescale typically considered for storage projects.« less

Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

NASA Astrophysics Data System (ADS)

Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard

2014-05-01

Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such systematic knowledge of the extent of oxygen isotope fractionation between H2O and CO2 can help to reconstruct equilibration times, fluid-CO2 ratios as well as temperature and salinity conditions. Isotope results from systematic laboratory studies and the information they provide for assessing in situ reservoir conditions can be transferred to field applications concerning integrity of CO2 reservoirs. They can also apply to natural systems and other industrial uses that involve monitoring of gases in the subsurface under similar pressure and temperature conditions. Reference: Myrttinen, A., Becker, V., Barth, J.A.C., 2012. A review of methods used for equilibrium isotope fractionation investigations between dissolved inorganic carbon and CO2. Earth-Science Reviews, 115(3): 192-199.

Coupled oxygen-carbon dioxide modelling to partition potential external contribution to stream carbon dioxide concentrations.

NASA Astrophysics Data System (ADS)

Butman, D. E.; Holtgrieve, G. W.

2017-12-01

Recent modelling studies in large catchments have estimated that in excess of 74% of the dissolved carbon dioxide found in first and second order streams originate from allochthonous sources. Stable isotopes of carbon-13 in carbon dioxide have been used to identify ground water seeps in stream systems, where decreases in δ13CO2 occur along gaining stream reaches, suggesting that carbon dioxide in ground water is more depleted than what is found in surface water due to fractionation of CO2 during emissions across the air water interface. Although isotopes represent a chemical tracer in stream systems for potential groundwater contribution, the temporal resolution of discrete samples make partitioning allochthonous versus autochthonous sources of CO2 difficult on hydrologically relevant time scales. Here we show results of field deployments of high frequent dissolved CO2, O2, PAR, Temperature and pH from the Thornton Creek Watershed, the largest urban watershed in Seattle, WA. We present an exploration into using high resolution time series of dissolved oxygen and carbon dioxide in a dual gas approach to separate the contribution of in stream respiration from external sources. We extend upon previous efforts to model stream metabolism across diel cycles by incorporating simultaneous direct measurements of dissolved oxygen, PCO2, and pH within an inverse modeling framework and Bayesian parameter estimation. With an initial assumption of a stoichiometric ratio of 1:1 for O2 and CO2 for autochthonous driven metabolism, we investigate positive or negative departures from this ratio as an indicator of external CO2 to the stream (terrestrial or atmospheric) and factors contributing to this flux.

[Study on the content and carbon isotopic composition of water dissolved inorganic carbon from rivers around Xi'an City].

PubMed

Guo, Wei; Li, Xiang-Zhong; Liu, Wei-Guo

2013-04-01

In this study, the content and isotopic compositions of water dissolved inorganic carbon (DIC) from four typical rivers (Chanhe, Bahe, Laohe and Heihe) around Xi'an City were studied to trace the possible sources of DIC. The results of this study showed that the content of DIC in the four rivers varied from 0.34 to 5.66 mmol x L(-1) with an average value of 1.23 mmol x L(-1). In general, the content of DIC increased from the headstream to the river mouth. The delta13C(DIC) of four rivers ranged from -13.3 per thousand to -7.2 per thousand, with an average value of -10.1 per thousand. The delta13C(DIC) values of river water were all negative (average value of -12.6 per thousand) at the headstream of four rivers, but the delta13C(DIC) values of downstream water were more positive (with an average value of -9.4 per thousand). In addition, delta13C(DIC) of river water showed relatively negative values (the average value of delta13C(DIC) was -10.5 per thousand) near the estuary of the rivers. The variation of the DIC content and its carbon isotope suggested that the DIC sources of the rivers varied from the headstream to the river mouth. The negative delta13C(DIC) value indicated that the DIC may originate from the soil CO2 at the headstream of the rivers. On the other hand, the delta13C(DIC) values of river water at the middle and lower reaches of rivers were more positive, and it showed that soil CO2 produced by respiration of the C4 plants (like corn) and soil carbonates with positive delta13C values may be imported into river water. Meanwhile, the input of pollutants with low delta13C(DIC) values may result in a decrease of delta13C(DIC) values in the rivers. The study indicated that the DIC content and carbon isotope may be used to trace the sources of DIC in rivers around Xi'an City. Our study may provide some basic information for tracing the sources of DIC of rivers in the small watershed area in the Loess Plateau of China.

Non-Boussinesq Dissolution-Driven Convection in Porous Media

NASA Astrophysics Data System (ADS)

Amooie, M. A.; Soltanian, M. R.; Moortgat, J.

2017-12-01

Geological carbon dioxide (CO2) sequestration in deep saline aquifers has been increasingly recognized as a feasible technology to stabilize the atmospheric carbon concentrations and subsequently mitigate the global warming. Solubility trapping is one of the most effective storage mechanisms, which is associated initially with diffusion-driven slow dissolution of gaseous CO2 into the aqueous phase, followed by density-driven convective mixing of CO2 throughout the aquifer. The convection includes both diffusion and fast advective transport of the dissolved CO2. We study the fluid dynamics of CO2 convection in the underlying single aqueous-phase region. Two modeling approaches are employed to define the system: (i) a constant-concentration condition for CO2 in aqueous phase at the top boundary, and (ii) a sufficiently low, constant injection-rate for CO2 from top boundary. The latter allows for thermodynamically consistent evolution of the CO2 composition and the aqueous phase density against the rate at which the dissolved CO2 convects. Here we accurately model the full nonlinear phase behavior of brine-CO2 mixture in a confined domain altered by dissolution and compressibility, while relaxing the common Boussinesq approximation. We discover new flow regimes and present quantitative scaling relations for global characters of spreading, mixing, and dissolution flux in two- and three-dimensional media for the both model types. We then revisit the universal Sherwood-Rayleigh scaling that is under debate for porous media convective flows. Our findings confirm the sublinear scaling for the constant-concentration case, while reconciling the classical linear scaling for the constant-injection model problem. The results provide a detailed perspective into how the available modeling strategies affect the prediction ability for the total amount of CO2 dissolved in the long term within saline aquifers of different permeabilities.

Inorganic carbon speciation and fluxes in the Congo River

NASA Astrophysics Data System (ADS)

Wang, Zhaohui Aleck; Bienvenu, Dinga Jean; Mann, Paul J.; Hoering, Katherine A.; Poulsen, John R.; Spencer, Robert G. M.; Holmes, Robert M.

2013-02-01

Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11-61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m-2 yr-1. The basin-wide DIC yield was ~8.84 × 104 mol km-2 yr-1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr-1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers.

Strategies for characterizing compositions of industrial pulp and paper sludge

NASA Astrophysics Data System (ADS)

Aslanzadeh, Solmaz; Kemal, Rahmat A.; Pribowo, Amadeus Y.

2018-01-01

The large quantities of waste sludge produced by the pulp and paper industry present significant environmental challenges. In order to minimize the amounts of waste, the pulp sludge should be utilized for productive applications. In order to find feasible solutions, the sludge need to be characterized. In this study, the potential of using acid pretreatment and ashing method to determine the chemical compositions of the sludge is investigated. This study shows that acid pretreatment could be used to dissolve and determine the composition of CaCO3 in the pulp sludge. CaCO3 removal also facilitates the measurement of fiber and ash (clay) contents by using the ashing method. The optimum acid concentration used to completely dissolve CaCO3 was determined using a titration method. Using this method, the measurement of the chemical composition of the sludge sample revealed that it consisted primarily of CaCO3 (55% w/w), clay (25%, w/w), and fibers (18%, w/w). Based on these chemical compositions, potential utilization for the sludge could be determined.

Nitrate and Ammonium Induced Photosynthetic Suppression in N-Limited Selenastrum minutum: II. Effects of NO(3) and NH(4) Addition to CO(2) Efflux in the Light.

PubMed

Birch, D G; Elrifi, I R; Turpin, D H

1986-11-01

The effects of nitrate and ammonium addition on net and gross photosynthesis, CO(2) efflux and the dissolved inorganic carbon compensation point of nitrogen-limited Selenastrum minutum Naeg. Collins (Chlorophyta) were studied. Cultures pulsed with nitrate or ammonium exhibited a marked decrease in both net and gross photosynthetic carbon fixation. During this period of suppression the specific activity of exogenous dissolved inorganic carbon decreased rapidly in comparison to control cells indicating an increase in the rate of CO(2) efflux in the light. The nitrate and ammmonium induced rates of CO(2) efflux were 31.0 and 33.8 micromoles CO(2) per milligram chlorophyll per hour, respectively, and represented 49 and 48% of the rate of gross photosynthesis. Nitrate addition to cells at dissolved inorganic carbon compensation point caused an increase in compensation point while ammonium had no effect. In the presence of the tricarboxylic acid cycle inhibitor fluoroacetate, the nitrate-induced change in compensation point was greatly reduced suggesting the source of this CO(2) was the tricarboxylic acid cycle. These results are consistent with the mechanism of N-induced photosynthetic suppression outlined by Elrifi and Turpin (1986 Plant Physiol 81: 273-279).

Feasibility of Autonomous Monitoring of CO2 Leakage in Aquifers: Results From Controlled Laboratory Experiments

NASA Astrophysics Data System (ADS)

Versteeg, R.; Leger, E.; Dafflon, B.

2016-12-01

Geologic sequestration of CO2 is one of the primary proposed approaches for reducing total atmospheric CO2 concentrations. MVAA (Monitoring, Verification, Accounting and Assessment) of CO2 sequestration is an essential part of the geologic CO2 sequestration cycle. MVAA activities need to meet multiple operational, regulatory and environmental objectives, including ensuring the protection of underground sources of drinking water. Anticipated negative consequences of CO2 leakage into groundwater, besides possible brine contamination and release of gaseous CO2, include a significant increase of dissolved CO2 into shallow groundwater systems, which will decrease groundwater pH and can potentially mobilize naturally occurring trace metals and ions that are commonly absorbed to or contained in sediments. Autonomous electrical geophysical monitoring in aquifers has the potential of allowing for rapid and automated detection of CO2 leakage. However, while the feasibility of such monitoring has been demonstrated by a number of different field experiments, automated interpretation of complex electrical resistivity data requires the development of quantitative relationships between complex electrical resistivity signatures and dissolved CO2 in the aquifer resulting from leakage Under a DOE SBIR funded effort we performed multiple tank scale experiments in which we investigated complex electrical resistivity signatures associated with dissolved CO2 plumes in saturated sediments. We also investigated the feasibility of distinguishing CO2 leakage signatures from signatures associated with other processes such as salt water movement, temperature variations and other variations in chemical or physical conditions. In addition to these experiments we also numerically modeled the tank experiments. These experiments showed that (a) we can distinguish CO2 leakage signatures from other signatures, (b) CO2 leakage signatures have a consistent characteristic, (c) laboratory experiments are in agreement with field results, and (d) we can numerically simulate the main characteristics of CO2 leakage and associated electrical geophysical signatures.

Enhanced convective dissolution of CO2 in reactive systems

NASA Astrophysics Data System (ADS)

de Wit, Anne; Thomas, Carelle; Loodts, Vanessa; Knaepen, Bernard; Rongy, Laurence

2017-11-01

To decrease the atmospheric concentration of CO2, sequestration techniques whereby this greenhouse gas is injected in saline aquifers present in soils are considered. Upon contact with the aquifer, the CO2 can dissolve in it and subsequently be mineralized via reactions with minerals like carbonates for instance. We investigate both experimentally and theoretically the influence of such reactions on the convective dissolution of CO2. Experiments analyze convective patterns developing when gaseous CO2 is put in contact with aqueous solutions of reactants in a confined vertical Hele-Shaw geometry. We show that the reactions can enhance convection and modify the nonlinear dynamics of density fingering. Numerical simulations further show that reactions can increase the flux of dissolving CO2, inducing a more efficient sequestration. Emphasis will be put on the control of the convective pattern properties by varying the very nature of the chemicals. Implications on the choice of optimal sequestration sites will be discussed.

Study on CO2/ N2 separation: the effect of rubbery polymer coating on PVDF membrane

NASA Astrophysics Data System (ADS)

Zuwairi, M. Z.; Rahman, S. A.

2017-06-01

The emission of harmful gases such as carbon dioxide (CO2) via gas processing plant and daily human activities gave negative impacts to the environment and global inhabitant. Flat sheet asymmetric membranes were produced from homogenous solution of Poly(vinylideneflouride) (PVDF) via phase inversion method using N-methyl-2-pyrrolidone (NMP) as the solvent. While the poly ether b-amide (PEBAX) was dissolve by using of (70 ethanol and 30 water) as a solvent and and lithium chloride as a additives. The morphology and cross section of the produced membranes were observed by Scanning Electron Microscope (SEM). Then, the membranes were tested for chemical analysis to define the presence of PEBAX in the membrane by using Fourier Transform Infrared (FTIR) spectroscopy. The permeation performances of the membranes were evaluated in terms of permeability and selectivity of the membranes by using gas permeation test. Increasing the PEBAX content significantly increased the selectivity of the PVDF membrane to separate the CO2/N2 gases but decreased the amount of the gases that passed through the membrane.

In situ mid-infrared spectroscopic titration of forsterite with water in supercritical CO2: Dependence of mineral carbonation on quantitative water speciation

NASA Astrophysics Data System (ADS)

Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Martin, P.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2011-12-01

Geologic sequestration of carbon dioxide holds promise for helping mitigate CO2 emissions generated from the burning of fossil fuels. Supercritical CO2 (scCO2) plumes containing variable water concentrations (wet scCO2) will displace aqueous solution and dominate the pore space adjacent to caprocks. It is important to understand possible mineral reactions with wet scCO2 to better predict long-term caprock integrity. We introduce novel in situ instrumentation that enables quantitative titrations of reactant minerals with water in scCO2 at temperatures and pressures relevant to target geologic reservoirs. The system includes both transmission and attenuated total reflection mid-infrared optics. Transmission infrared spectroscopy is used to measure concentrations of water dissolved in the scCO2, adsorbed on mineral surfaces, and incorporated into precipitated carbonates. Single-reflection attenuated total reflection infrared spectroscopy is used to monitor water adsorption, mineral dissolution, and carbonate precipitation reactions. Results are presented for the infrared spectroscopic titration of forsterite (Mg2SiO4), a model divalent metal silicate, with water in scCO2 at 100 bar and at both 50 and 75°C. The spectral data demonstrate that the quantitative speciation of water as either dissolved or adsorbed is important for understanding the types, growth rates, and amounts of carbonate precipitates formed. Relationships between dissolved/adsorbed water, water concentrations, and the role of liquid-like adsorbed water are discussed. Our results unify previous in situ studies from our laboratory based on infrared spectroscopy, nuclear magnetic resonance spectroscopy and X-ray diffraction.

Measuring permanence of CO2 storage in saline formations: The Frio experiment

USGS Publications Warehouse

Hovorka, Susan D.; Benson, Sally M.; Doughty, Christine; Freifeild, Barry M.; Sakurai, Shinichi; Daley, Thomas M.; Kharaka, Yousif K.; Holtz, Mark H.; Trautz, Robert C.; Nance, H. Seay; Myer, Larry R.; Knauss, Kevin G.

2006-01-01

If CO2 released from fossil fuel during energy production is returned to the subsurface, will it be retained for periods of time significant enough to benefit the atmosphere? Can trapping be assured in saline formations where there is no history of hydrocarbon accumulation? The Frio experiment in Texas was undertaken to provide answers to these questions.One thousand six hundred metric tons of CO2 were injected into the Frio Formation, which underlies large areas of the United States Gulf Coast. Reservoir characterization and numerical modeling were used to design the experiment, as well as to interpret the results through history matching. Closely spaced measurements in space and time were collected to observe the evolution of immiscible and dissolved CO2 during and after injection. The high-permeability, steeply dipping sandstone allowed updip flow of supercritical CO2 as a result of the density contrast with formation brine and absence of a local structural trap.The front of the CO2 plume moved more quickly than had been modeled. By the end of the 10-day injection, however, the plume geometry in the plane of the observation and injection wells had thickened to a distribution similar to the modeled distribution. As expected, CO2 dissolved rapidly into brine, causing pH to fall and calcite and metals to be dissolved.Postinjection measurements, including time-lapse vertical seismic profiling transects along selected azimuths, cross-well seismic topography, and saturation logs, show that CO2 migration under gravity slowed greatly 2 months after injection, matching model predictions that significant CO2 is trapped as relative permeability decreases.

Inert-Gas Condensed Co-W Nanoclusters: Formation, Structure and Magnetic Properties

NASA Astrophysics Data System (ADS)

Golkar-Fard, Farhad Reza

Rare-earth permanent magnets are used extensively in numerous technical applications, e.g. wind turbines, audio speakers, and hybrid/electric vehicles. The demand and production of rare-earth permanent magnets in the world has in the past decades increased significantly. However, the decrease in export of rare-earth elements from China in recent time has led to a renewed interest in developing rare-earth free permanent magnets. Elements such as Fe and Co have potential, due to their high magnetization, to be used as hosts in rare-earth free permanent magnets but a major challenge is to increase their magnetocrystalline anisotropy constant, K1, which largely drives the coercivity. Theoretical calculations indicate that dissolving the 5d transition metal W in Fe or Co increases the magnetocrystalline anisotropy. The challenge, though, is in creating a solid solution in hcp Co or bcc Fe, which under equilibrium conditions have negligible solubility. In this dissertation, the formation, structure, and magnetic properties of sub-10 nm Co-W clusters with W content ranging from 4 to 24 atomic percent were studied. Co-W alloy clusters with extended solubility of W in hcp Co were produced by inert gas condensation. The different processing conditions such as the cooling scheme and sputtering power were found to control the structural state of the as-deposited Co-W clusters. For clusters formed in the water-cooled formation chamber, the mean size and the fraction crystalline clusters increased with increasing power, while the fraction of crystalline clusters formed in the liquid nitrogen-cooled formation chamber was not as affected by the sputtering power. For the low W content clusters, the structural characterization revealed clusters predominantly single crystalline hcp Co(W) structure, a significant extension of W solubility when compared to the equilibrium solubility, but fcc Co(W) and Co3W structures were observed in very small and large clusters, respectively. At high W content, clusters with hcp Co(W), fcc Co(W) or Co3W structures were observed. The magnetic measurements at 10 K and 300 K revealed that the coercivity, saturation magnetization and magnetocrystalline anisotropy of the clusters formed in the water-cooled formation chamber were higher than for clusters formed in the liquid nitrogen-cooled formation chamber. The coercivity and magnetocrystalline anisotropy of the clusters increased as long as W was dissolved into the hcp Co structure. With increasing fraction of Co3W and fcc Co(W) clusters, as observed in the high-W content sample, the magnetic properties deteriorated significantly. The highest coercivity and magnetocrystalline anisotropy of 893 Oe and 3.9 x 106 ergs/cm3, respectively, was obtained at 10 K for the 5 at.% W clusters sputtered at 150 W in the water-cooled formation chamber.

Mountain respiration: Rates and patterns of fossil organic carbon oxidation revealed using the trace element rhenium

NASA Astrophysics Data System (ADS)

Hilton, R. G.; Gaillardet, J.; Calmels, D.; Birck, J.

2013-12-01

Fossil organic carbon (OCfossil) from sedimentary rocks can contribute to the carbon stock within the deepest part of soil. OCfossil constitutes a vast stock of carbon that was sequestered from the atmosphere in the geological past, containing ~15x106 PgC, which is approximately 25,000 times the carbon content of the pre-industrial atmosphere. Oxidation of OCfossil during chemical weathering at Earth's surface is thought to be a major source of carbon dioxide (CO2) to the atmosphere. It has been proposed that OCfossil oxidation occurs when fresh sedimentary rocks are exposed to oxygenated water, with the rate of CO2 release controlled by the supply of OCfossil to react. As such, mountain belts where high rates of physical erosion provide an abundant supply of OCfossil to the soil critical zone should be locations where this CO2 source is most potent. However, the rates of OCfossil oxidation during weathering remain poorly constrained. Here we use the trace element rhenium (Re) to shed new light on the rates and patterns of OCfossil oxidation across the landscape. Re is known to be associated with organic matter in rocks and following oxidation forms a soluble anion which contributes to the dissolved load of rivers. Rivers can offer an integrated signal of chemical reactions occurring across the landscape, and so by quantifying the dissolved Re flux we are able to estimate the corresponding release of CO2 by OCfossil weathering. Using a set of mountain river catchments in Taiwan, where water and sediment fluxes are well quantified, we estimate that the rates of CO2 output by this process are significant, and encroach on values expected for net biome productivity. We find that OCfossil oxidation rates are strongly linked to physical erosion rate at the catchment-scale. This suggests that changes in the rates of surface processes may alter this CO2 output from deep soils. On longer timescales, our findings suggest that the total CO2 output by OCfossil weathering in Taiwan does not negate estimates of CO2 sequestration by erosion and sedimentary burial of recent organic matter. Our findings suggest that mountain building in the tropic can result in a net sink of organic carbon during erosion and weathering which acts to sequester atmospheric CO2.

Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

USGS Publications Warehouse

Palandri, J.L.; Rosenbauer, R.J.; Kharaka, Y.K.

2005-01-01

Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

Nitrate and Ammonium Induced Photosynthetic Suppression in N-Limited Selenastrum minutum1

PubMed Central

Birch, Douglas G.; Elrifi, Ivor R.; Turpin, David H.

1986-01-01

The effects of nitrate and ammonium addition on net and gross photosynthesis, CO2 efflux and the dissolved inorganic carbon compensation point of nitrogen-limited Selenastrum minutum Naeg. Collins (Chlorophyta) were studied. Cultures pulsed with nitrate or ammonium exhibited a marked decrease in both net and gross photosynthetic carbon fixation. During this period of suppression the specific activity of exogenous dissolved inorganic carbon decreased rapidly in comparison to control cells indicating an increase in the rate of CO2 efflux in the light. The nitrate and ammmonium induced rates of CO2 efflux were 31.0 and 33.8 micromoles CO2 per milligram chlorophyll per hour, respectively, and represented 49 and 48% of the rate of gross photosynthesis. Nitrate addition to cells at dissolved inorganic carbon compensation point caused an increase in compensation point while ammonium had no effect. In the presence of the tricarboxylic acid cycle inhibitor fluoroacetate, the nitrate-induced change in compensation point was greatly reduced suggesting the source of this CO2 was the tricarboxylic acid cycle. These results are consistent with the mechanism of N-induced photosynthetic suppression outlined by Elrifi and Turpin (1986 Plant Physiol 81: 273-279). PMID:16665097

The persistence of natural CO2 accumulations over millennial timescales: Integrating noble gas and reservoir data at Bravo Dome, NM

NASA Astrophysics Data System (ADS)

Akhbari, D.

2017-12-01

Bravo Dome, the largest CO2 reservoir in the US, is a hydrogeologically closed system that has stored a very large amount of CO2 on millennial time scales. The pre-production gas pressures in Bravo Dome indicate that the reservoir is highly under-pressured and is divided into separate pressure compartments that do not communicate hydrologically. Previous studies used the noble gas composition at Bravo Dome to constrain the amount of dissolved CO2 into the brine. This CO2 dissolution into brine plays an important role in the observed under-pressure at the reservoir. However, the dissolution rates and transport mechanisms remain unknown. In this study, we are looking into reservoir pressures and noble gas composition in the northeastern section of the reservoir to constrain timescales of CO2 dissolution. We are interested in northeastern part of the reservoir because the largest amount of CO2 was dissolved into brine in this section. Also, we specifically look into the evolution of the CO2/3He and 20Ne concentration during convective CO2 dissolution at Bravo Dome. 20Ne has atmospheric origin and is initially in the brine, while 3He and CO2 have magmatic sources and were introduced with the gas. CO2/3He decreases as more CO2 dissolves into brine, due to the higher solubility of CO2 compare to that of 3He. However, 20Ne concentration in the gas increases due to exsolution of 20Ne from brine into the gas phase. We present 2D numerical simulation that demonstrate the persistence of CO2 over 1Ma and reproduce the observed reservoir pressures and noble gas compositions. Our results indicate that convection is required to produce observed changes in gas composition. But diffusion makes a significant contribution to mass transport.

High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film.

PubMed

Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

2017-01-05

Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA=1:1), tributylphosphate(TBP, 0.05mL) and PtOEP (5μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I=1.003+2.663[O2] (R(2)=0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

High sensitivity and accuracy dissolved oxygen (DO) detection by using PtOEP/poly(MMA-co-TFEMA) sensing film

NASA Astrophysics Data System (ADS)

Zhang, Ke; Zhang, Honglin; Wang, Ying; Tian, Yanqing; Zhao, Jiupeng; Li, Yao

2017-01-01

Fluorinated acrylate polymer has received great interest in recent years due to its extraordinary characteristics such as high oxygen permeability, good stability, low surface energy and refractive index. In this work, platinum octaethylporphyrin/poly(methylmethacrylate-co-trifluoroethyl methacrylate) (PtOEP/poly(MMA-co-TFEMA)) oxygen sensing film was prepared by the immobilizing of PtOEP in a poly(MMA-co-TFEMA) matrix and the technological readiness of optical properties was established based on the principle of luminescence quenching. It was found that the oxygen-sensing performance could be improved by optimizing the monomer ratio (MMA/TFEMA = 1:1), tributylphosphate(TBP, 0.05 mL) and PtOEP (5 μg) content. Under this condition, the maximum quenching ratio I0/I100 of the oxygen sensing film is obtained to be about 8.16, Stern-Volmer equation is I0/I = 1.003 + 2.663[O2] (R2 = 0.999), exhibiting a linear relationship, good photo-stability, high sensitivity and accuracy. Finally, the synthesized PtOEP/poly(MMA-co-TFEMA) sensing film was used for DO detection in different water samples.

Emissions of Water and Carbon Dioxide from Fossil-Fuel Combustion Contribute Directly to Ocean Mass and Volume Increases

NASA Astrophysics Data System (ADS)

Skuce, A. G.

2014-12-01

The direct, non-climate, contribution of carbon dioxide and water emissions from fossil-fuel (FF) combustion to the volume and mass of the oceans has been omitted from estimates of sea-level rise (SLR) in IPCC reports. Following the method of Gornitz et al. (1997), H2O emissions are estimated using carbon emissions from the Carbon Dioxide Information Analysis Center, along with typical carbon and hydrogen contents of FF. Historic H2O emissions from 1750 to 2010 amount to 430 ±50 PgH2O, equivalent to 1.2 ±0.2 mmSLR. Sometime in this decade the volume of H2O from historic FF combustion will exceed the volume of Lake Erie (480 km3). CO2 dissolved in the ocean increases the seawater volume by 31-33 mL mol-1 CO2. From 1750 to 2010, 370 ±70 PgCO2 from FF combustion has dissolved in the oceans, causing 0.7 ±0.2 mmSLR. Combined H2O+CO2emissions from FF have therefore added 1.9 ±0.4 mm to sea levels in the Industrial Era. Combustion of FF in 2010 resulted in emissions of 32 PgCO2 and 12 ±1 PgH2O. SLR contributions for that year from FF emissions were 0.033 ±0.005 mm from H2O and 0.011±0.003 mm from dissolved CO2, a total rate of 0.044 ±0.008 mm yr-1. Emissions incorporated in socio-economic models underlying the RCP 8.5 and 2.6 scenarios are used along with concentration-driven CMIP5 Earth System Models results to estimate future sea-level rise from FF combustion. From 2010 to 2100, RCP8.5 and 2.6 models respectively produce 9 ±2 mmSLR and 5 ±1 mmSLR from FF H2O+CO2. For perspective, these amounts are larger than the modelled contributions from loss of glaciers in the Andes. The direct contribution of FF emissions to SLR is small (1-2%) relative to current rates and projected estimates under RCP scenarios up to 2100. The magnitude is similar to SLR estimates from other minor sources such as the melting of floating ice, land-use emissions and produced water from oil operations, none of which are currently included in SLR assessments. As uncertainties in observations and contributions are reduced, small contribution factors, hitherto neglected, will become relatively more important in balancing the books. ReferenceGornitz, V., C. Rosenzweig, and D. Hillel, 1997: Effects of anthropogenic intervention in the land hydrological cycle on global sea level rise. Global and Planetary Change, 14, 147-161. DOI: 10.1016/S0921-8181(96)00008-2

Influence of humic acid on the removal of arsenate and arsenic by ferric chloride: effects of pH, As/Fe ratio, initial As concentration, and co-existing solutes.

PubMed

Kong, Yanli; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Fan, Leitao

2017-01-01

The influence of humic acid (HA) on the removal of arsenic by FeCl 3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl 3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl 3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca 2+ or Cd 2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.

Greenhouse gases concentrations and fluxes from subtropical small reservoirs in relation with watershed urbanization

NASA Astrophysics Data System (ADS)

Wang, Xiaofeng; He, Yixin; Yuan, Xingzhong; Chen, Huai; Peng, Changhui; Yue, Junsheng; Zhang, Qiaoyong; Diao, Yuanbin; Liu, Shuangshuang

2017-04-01

Greenhouse gas (GHG) emissions from reservoirs and global urbanization have gained widespread attention, yet the response of GHG emissions to the watershed urbanization is poorly understood. Meanwhile, there are millions of small reservoirs worldwide that receive and accumulate high loads of anthropogenic carbon and nitrogen due to watershed urbanization and can therefore be hotspots of GHG emissions. In this study, we assessed the GHG concentrations and fluxes in sixteen small reservoirs draining urban, agricultural and forested watersheds over a period of one year. The concentrations of pCO2, CH4 and N2O in sampled urban reservoirs that received more sewage input were higher than those in agricultural reservoirs, and were 3, 7 and 10 times higher than those in reservoirs draining in forested areas, respectively. Accordingly, urban reservoirs had the highest estimated GHG flux rate. Regression analysis indicated that dissolved total phosphorus, dissolved organic carbon (DOC) and chlorophyll-a (Chl-a) had great effect on CO2 production, while the nitrogen (N) and phosphorus (P) content of surface water were closely related to CH4 and N2O production. Therefore, these parameters can act as good predictors of GHG emissions in urban watersheds. Given the rapid progress of global urbanization, small urban reservoirs play a crucial role in accounting for regional GHG emissions and cannot be ignored.

Response of the unicellular diazotrophic cyanobacterium Crocosphaera watsonii to iron limitation.

PubMed

Jacq, Violaine; Ridame, Céline; L'Helguen, Stéphane; Kaczmar, Fanny; Saliot, Alain

2014-01-01

Iron (Fe) is widely suspected as a key controlling factor of N2 fixation due to the high Fe content of nitrogenase and photosynthetic enzymes complex, and to its low concentrations in oceanic surface seawaters. The influence of Fe limitation on the recently discovered unicellular diazotrophic cyanobacteria (UCYN) is poorly understood despite their biogeochemical importance in the carbon and nitrogen cycles. To address this knowledge gap, we conducted culture experiments on Crocosphaera watsonii WH8501 growing under a range of dissolved Fe concentrations (from 3.3 to 403 nM). Overall, severe Fe limitation led to significant decreases in growth rate (2.6-fold), C, N and chlorophyll a contents per cell (up to 4.1-fold), N2 and CO2 fixation rates per cell (17- and 7-fold) as well as biovolume (2.2-fold). We highlighted a two phased response depending on the degree of limitation: (i) under a moderate Fe limitation, the biovolume of C. watsonii was strongly reduced, allowing the cells to keep sufficient energy to maintain an optimal growth, volume-normalized contents and N2 and CO2 fixation rates; (ii) with increasing Fe deprivation, biovolume remained unchanged but the entire cell metabolism was affected, as shown by a strong decrease in the growth rate, volume-normalized contents and N2 and CO2 fixation rates. The half-saturation constant for growth of C. watsonii with respect to Fe is twice as low as that of the filamentous Trichodesmium indicating a better adaptation of C. watsonii to poor Fe environments than filamentous diazotrophs. The physiological response of C. watsonii to Fe limitation was different from that previously shown on the UCYN Cyanothece sp, suggesting potential differences in Fe requirements and/or Fe acquisition within the UCYN community. These results contribute to a better understanding of how Fe bioavailability can control the activity of UCYN and explain the biogeography of diverse N2 fixers in ocean.

Nutrient Removal Vis-à-Vis Change in Partial Pressure of CO2 During Post-Monsoon Season in a Tropical Lentic and Lotic Aquatic Body: A Comparative Study

NASA Astrophysics Data System (ADS)

Bhattacharyya, Sourav; Chanda, Abhra; Das, Sourav; Akhand, Anirban; Pattanaik, Suchismita; Choudhury, S. B.; Dutta, Dibyendu; Hazra, Sugata

2018-04-01

The rate of nutrient removal and changes in pCO2 (water) were compared between a lentic aquaculture pond [East Kolkata Wetlands (EKW), India] and a lotic estuarine system [Diamond Harbor (DH) in Hugli Estuary, India] during the post-monsoon season (experiencing a similar tropical climate) by means of ex situ microcosm experiment. Though the DH waters were found to be substantial source of CO2 towards atmosphere and EKW waters to be sink for CO2 (according to the initial concentration of CO2), the eight consecutive days microcosm experiment revealed that the nutrient removal and pCO2 reduction efficiency were significantly higher in DH (ΔpCO2—90%) compared to EKW (ΔpCO2—78%). Among the five nutrients studied [dissolved nitrate-nitrogen (NO3-N), dissolved ammonium nitrogen (NH4-N), silicate, phosphate and iron], dissolved NO3-N followed by NH4-N was the most utilized in both EKW and DH. Except silicate, the other nutrients reduced to 78-91% in EKW and 84-99% in DH samples of their initial concentrations. Chlorophyll-a concentration steadily depleted in EKW ( 68-26 mg m-3) during the experiment indicating intense zooplankton grazing, whereas in DH it increased rapidly ( 3.4-23 mg m-3) with decreasing pCO2 (water). The present observations further indicated that regular flushing of EKW aquaculture ponds is required to avoid stagnation of water column which would enhance the zooplankton grazing and hamper the primary production of an otherwise sink of CO2. In DH, controlled freshwater discharge from Farakka and reduction of untreated organic waste might allow the existing phytoplankton community to enhance their photosynthetic activity.

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

USGS Publications Warehouse

Leenheer, Jerry A.; Reddy, Michael M.

2008-01-01

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Sonochemical reduction of carbon dioxide.

PubMed

Harada, H

1998-06-01

Sonolysis of carbon dioxide dissolved in water was performed from a standpoint of reducing this material in atmosphere. During one hour of sonication, the amount of CO2 decreased to about half at 5 degrees C under CO2-Ar atmosphere. The decreasing rate for CO2 followed the order Ar > He > H2 > N2 and it was down with increasing temperature in the range of 5-45 degrees C. The most favorable concentration for reducing CO2 was 0.03 (mole fraction of CO2 in gas phase). This concentration in gas phase means an equal mixture of CO2 and Ar in water, because CO2 is more soluble than Ar. Since carbon dioxide dissolved in water would be partly ionized, the roles of ions on the sonolysis were also examined. Gaseous reaction products were CO, H2 and a small amount of O2. Carbon monoxide and hydrogen might be obtained from CO2 and H2O by sonolysis, respectively. Both gases are fuel and react each other to C1 compounds such as methanol, and so on. Therefore, irradiation of ultrasonic waves should be an important technique for reducing CO2.

Experimental study of CO2 dissolution a convection phenomenon at high pressure

NASA Astrophysics Data System (ADS)

Ben Salem, Imen; Chevalier, Sylvie; Faisal, Titly Farhana; Abderrahmane, Hamid; Sassi, Mohamed

2016-05-01

The density driven convection phenomenon has a significant role in enhancing the CO2 geological storage capacity. Deep saline aquifers are targeted for large scale geological sequestration. Once the CO2 is injected in saline aquifer, the supercritical CO2 rises up, forms a thin layer of free phase CO2, and the dissolution and molecular diffusion of the dissolved CO2 in brine begins. The CO2 saturated brine is denser than the original brine leading to gravitational convection of CO2 saturated brine. Convection accelerates the dissolution process and thus improves the safety and the efficiency of the sequestration. Laboratory experiments have been previously performed with experimental set-ups allowing the visualization of the phenomenon (1) eventually combined to the measurements of the dissolved CO2 mass transfer (2) as a function of the permeability of the medium. The visualization of the process was possible as Hele-Shaw cells at atmospheric pressure were used. Pressurized cylindrical vessel containing porous media allows measuring mass transfer of CO2 using the pressure decay concept (3) but visualization of the convection/dissolution was not possible for these setups. In this work, we performed experiments in a pressurized transparent cell similar to a Hele-Shaw cell but with bigger aperture. Permeability was varied by changing the size of the glass beads filling the cell. Bromocrysol green was used as a dye to track the pH change due to the presence of dissolved CO2 (1). The phenomenon is captured by a high resolution camera. We studied the effect of the pressure and of the permeability on the fingering pattern, the onset and the timescale of the phenomenon and the quantitative mass transfer of dissolved CO2. Experiments were validated on numerical simulations performed using STOMP (Subsurface Transport Over Multiple Phases) developed by the PNNL (Pacific Northwest National Laboratory) Hydrology group of the Department of Energy, USA. (1) Kneafsey, T.J., Pruess, K., 2010. Laboratory flow experiments for visualizing carbon dioxide-induced density-driven brine convection, Transport in Porous Media 82, 123-139. (2) Faisal, T. F., Chevalier, S., Bernabé, Y., Juanes, R. and M. Sassi. 2015. Quantitative and qualitative study of density driven CO2 mass transfer in a vertical Hele-Shaw cell. International Journal of Heat and Mass Transfer. Vol. 81, 901-914. (3) Farajzadeh, R.; Barati, A.; Delil, H. A.; Bruining, J.; Zitha, P. L. J., Mass transfer of CO2 into water and surfactant solutions, Petroleum Science and Technology 25 (12) (2007) 1493-1511.

In vitro/in vivo evaluation of an optimized fast dissolving oral film containing olanzapine co-amorphous dispersion with selected carboxylic acids.

PubMed

Maher, Eman Magdy; Ali, Ahmed Mahmoud Abdelhaleem; Salem, Heba Farouk; Abdelrahman, Ahmed Abdelbary

2016-10-01

Improvement of water solubility, dissolution rate, oral bioavailability, and reduction of first pass metabolism of OL (OL), were the aims of this research. Co-amorphization of OL carboxylic acid dispersions at various molar ratios was carried out using rapid solvent evaporation. Characterization of the dispersions was performed using differential scanning calorimetry (DSC), Fourier transform infrared spectrometry (FTIR), X-ray diffractometry (XRD), and scanning electron microscopy (SEM). Dispersions with highest equilibrium solubility were formulated as fast dissolving oral films. Modeling and optimization of film formation were undertaken using artificial neural networks (ANNs). The results indicated co-amorphization of OL-ascorbic acid through H-bonding. The co-amorphous dispersions at 1:2 molar ratio showed more than 600-fold increase in solubility of OL. The model optimized fast dissolving film prepared from the dispersion was physically and chemically stable, demonstrated short disintegration time (8.5 s), fast dissolution (97% in 10 min) and optimum tensile strength (4.9 N/cm 2 ). The results of in vivo data indicated high bioavailability (144 ng h/mL) and maximum plasma concentration (14.2 ng/mL) compared with the marketed references. Therefore, the optimized co-amorphous OL-ascorbic acid fast dissolving film could be a valuable solution for enhancing the physicochemical and pharmacokinetic properties of OL.

Controls of streamwater dissolved inorganic carbon dynamics in a forested watershed

USGS Publications Warehouse

Finlay, J.C.

2003-01-01

I investigated controls of stream dissolved inorganic carbon (DIC) sources and cycling along a stream size and productivity gradient in a temperate forested watershed in northern California. Dissolved CO2 (CO2 (aq)) dynamics in heavily shaded streams contrasted strongly with those of larger, open canopied sites. In streams with canopy cover > 97%, CO2 (aq) was highest during baseflow periods (up to 540 ??M) and was negatively related to discharge. Effects of algal photosynthesis on CO2 (aq) were minimal and stream CO2 (aq) was primarily controlled by groundwater CO2 (aq) inputs and degassing losses to the atmosphere. In contrast to the small streams. CO2 (aq) in larger, open-canopied streams was often below atmospheric levels at midday during baseflow and was positively related to discharge. Here, stream CO2 (aq) was strongly influenced by the balance between autotrophic and heterotrophic processes. Dynamics of HCO3- were less complex. HCO3- and Ca2+ were positively correlated, negatively related to discharge, and showed no pattern with stream size. Stable carbon isotope ratios of DIC (i.e. ??13C DIC) increased with stream size and discharge, indicating contrasting sources of DIC to streams and rivers. During summer baseflows, ??13C DIC were 13C-depleted in the smallest streams (minimum of -17.7???) due to the influence of CO2 (aq) derived from microbial respiration and HCO3- derived from carbonate weathering. ??13C DIC were higher (up to -6.6???) in the larger streams and rivers due to invasion of atmospheric CO2 enhanced by algal CO2 (aq) uptake. While small streams were influenced by groundwater inputs, patterns in CO2 (aq) and evidence from stable isotopes demonstrate the strong influence of stream metabolism and CO2 exchange with the atmosphere on stream and river carbon cycles.

Rising CO2 Levels Will Intensify Phytoplankton Blooms in Eutrophic and Hypertrophic Lakes

PubMed Central

Verspagen, Jolanda M. H.; Van de Waal, Dedmer B.; Finke, Jan F.; Visser, Petra M.; Van Donk, Ellen; Huisman, Jef

2014-01-01

Harmful algal blooms threaten the water quality of many eutrophic and hypertrophic lakes and cause severe ecological and economic damage worldwide. Dense blooms often deplete the dissolved CO2 concentration and raise pH. Yet, quantitative prediction of the feedbacks between phytoplankton growth, CO2 drawdown and the inorganic carbon chemistry of aquatic ecosystems has received surprisingly little attention. Here, we develop a mathematical model to predict dynamic changes in dissolved inorganic carbon (DIC), pH and alkalinity during phytoplankton bloom development. We tested the model in chemostat experiments with the freshwater cyanobacterium Microcystis aeruginosa at different CO2 levels. The experiments showed that dense blooms sequestered large amounts of atmospheric CO2, not only by their own biomass production but also by inducing a high pH and alkalinity that enhanced the capacity for DIC storage in the system. We used the model to explore how phytoplankton blooms of eutrophic waters will respond to rising CO2 levels. The model predicts that (1) dense phytoplankton blooms in low- and moderately alkaline waters can deplete the dissolved CO2 concentration to limiting levels and raise the pH over a relatively wide range of atmospheric CO2 conditions, (2) rising atmospheric CO2 levels will enhance phytoplankton blooms in low- and moderately alkaline waters with high nutrient loads, and (3) above some threshold, rising atmospheric CO2 will alleviate phytoplankton blooms from carbon limitation, resulting in less intense CO2 depletion and a lesser increase in pH. Sensitivity analysis indicated that the model predictions were qualitatively robust. Quantitatively, the predictions were sensitive to variation in lake depth, DIC input and CO2 gas transfer across the air-water interface, but relatively robust to variation in the carbon uptake mechanisms of phytoplankton. In total, these findings warn that rising CO2 levels may result in a marked intensification of phytoplankton blooms in eutrophic and hypertrophic waters. PMID:25119996

Chemical and stable isotopic evidence for water/rock interaction and biogenic origin of coalbed methane, Fort Union Formation, Powder River Basin, Wyoming and Montana U.S.A

USGS Publications Warehouse

Rice, C.A.; Flores, R.M.; Stricker, G.D.; Ellis, M.S.

2008-01-01

Significant amounts (> 36??million m3/day) of coalbed methane (CBM) are currently being extracted from coal beds in the Paleocene Fort Union Formation of the Powder River Basin of Wyoming and Montana. Information on processes that generate methane in these coalbed reservoirs is important for developing methods that will stimulate additional production. The chemical and isotopic compositions of gas and ground water from CBM wells throughout the basin reflect generation processes as well as those that affect water/rock interaction. Our study included analyses of water samples collected from 228 CBM wells. Major cations and anions were measured for all samples, ??DH2O and ??18OH2O were measured for 199 of the samples, and ??DCH4 of gas co-produced with water was measured for 100 of the samples. Results show that (1) water from Fort Union Formation coal beds is exclusively Na-HCO3-type water with low dissolved SO4 content (median < 1??mg/L) and little or no dissolved oxygen (< 0.15??mg/L), whereas shallow groundwater (depth generally < 120??m) is a mixed Ca-Mg-Na-SO4-HCO3 type; (2) water/rock interactions, such as cation exchange on clay minerals and precipitation/dissolution of CaCO3 and SO4 minerals, account for the accumulation of dissolved Na and depletion of Ca and Mg; (3) bacterially-mediated oxidation-reduction reactions account for high HCO3 (270-3310??mg/L) and low SO4 (median < 0.15??mg/L) values; (4) fractionation between ??DCH4 (- 283 to - 328 per mil) and ??DH2O (- 121 to - 167 per mil) indicates that the production of methane is primarily by biogenic CO2 reduction; and (5) values of ??DH2O and ??18OH2O (- 16 to - 22 per mil) have a wide range of values and plot near or above the global meteoric water line, indicating that the original meteoric water has been influenced by methanogenesis and by being mixed with surface and shallow groundwater.

Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

2015-12-01

CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

EFFECTS OF SUNLIGHT ON CARBOXYL CONTENT OF DISSOLVED ORGANIC MATTER IN THE SATILLA RIVER OF GEORGIA, UNITED STATES

EPA Science Inventory

A study examined the effect of sunlight-initiated photo-degradation of dissolved organic matter (DOM) on its carboxyl content, and the role of oxygen and iron in this process. Solar-simulated irradiations were performed on 0.2-mm filtered water samples collected from the highly c...

Monitoring a pilot CO2 injection experiment in a shallow aquifer using 3D cross-well electrical resistance tomography

NASA Astrophysics Data System (ADS)

Yang, X.; Lassen, R. N.; Looms, M. C.; Jensen, K. H.

2014-12-01

Three dimensional electrical resistance tomography (ERT) was used to monitor a pilot CO2 injection experiment at Vrøgum, Denmark. The purpose was to evaluate the effectiveness of the ERT method for monitoring the two opposing effects from gas-phase and dissolved CO2 in a shallow unconfined siliciclastic aquifer. Dissolved CO2 increases water electrical conductivity (EC) while gas phase CO2 reduce EC. We injected 45kg of CO2 into a shallow aquifer for 48 hours. ERT data were collected for 50 hours following CO2 injection. Four ERT monitoring boreholes were installed on a 5m by 5m square grid and each borehole had 24 electrodes at 0.5 m electrode spacing at depths from 1.5 m to 13 m. ERT data were inverted using a difference inversion algorithm for bulk EC. 3D ERT successfully detected the CO2 plume distribution and growth in the shallow aquifer. We found that the changes of bulk EC were dominantly positive following CO2 injection, indicating that the effect of dissolved CO2 overwhelmed that of gas phase CO2. The pre-injection baseline resistivity model clearly showed a three-layer structure of the site. The electrically more conductive glacial sand layer in the northeast region are likely more permeable than the overburden and underburden and CO2 plumes were actually confined in this layer. Temporal bulk EC increase from ERT agreed well with water EC and cross-borehole ground penetrating radar data. ERT monitoring offers a competitive advantage over water sampling and GPR methods because it provides 3D high-resolution temporal tomographic images of CO2 distribution and it can also be automated for unattended operation. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344. Lawrence Livermore National Security, LLC. LLNL IM release#: LLNL-PROC-657944.

Carbon cycling and snowball Earth.

PubMed

Goddéris, Yves; Donnadieu, Yannick

2008-12-18

The possibility that Earth witnessed episodes of global glaciation during the latest Precambrian challenges our understanding of the physical processes controlling the Earth's climate. Peltier et al. suggest that a 'hard snowball Earth' state may have been prevented owing to the release of CO(2) from the oxidation of dissolved organic carbon (DOC) in the ocean as the temperature decreased. Here we show that the model of Peltier et al. is not self-consistent as it implies large fluctuations of the ocean alkalinity content without providing any processes to account for it. Our findings suggest that the hard snowball Earth hypothesis is still valid.

Combined effects of dissolved humic acids and tourmaline on the accumulation of 2, 2', 4, 4', 5, 5'- hexabrominated diphenyl ether (BDE-153) in Lactuca sativa.

PubMed

Wang, Cuiping; Ma, Chuanxin; Jia, Weili; Wang, Dong; Sun, Hongwen; Xing, Baoshan

2017-12-01

In order to investigate the effects of dissolved humic acid (DHA) and tourmaline on uptake of 2, 2', 4, 4', 5, 5'- hexabrominated diphenyl ether (BDE-153) by Lactuca sativa, different fractions of DHA, including DHA 1 and DHA 4 , as well as different doses of tourmaline were introduced into BDE-153 contaminated solutions for plant growth. The levels of BDE-153 in L. sativa tissues were positively correlated with the Fe levels (R 2  = 0.9264) in seedings of the treatments with different doses of tourmaline. However, when adding DHA 1 and DHA 4 into the system, the correlation coefficients (R 2 ) decreased to 0.6976 and 0.5451 from 0.9264, respectively. In contrast with the Fe contents, the presence of DHAs didn't affect the R 2 between the levels of BDE-153 and the lipid contents in plant tissues. Our results indicated that both DHA 1 and DHA 4 could severely alter the BDE-153 uptake by L. sativa through reducing the Fe uptake instead of the lipid contents. Additionally, DHA 4 exhibited much stronger abilities to alter the BDE-153 accumulation than DHA 1 . Transmission electron microscopy (TEM) observations indicated that either DHA 1 or tourmaline or co-treatment with DHA and tourmaline had no negative impact on L. sativa at the cellular level. The present study provides important information for the impacts of different fractions of DHA extracted from soil on the BDE-153 migration in plant systems. Moreover, we elucidated the importance of the iron in tourmaline for migration of the polybrominated diphenyl ethers (PBDEs) in plant systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Effects of experimental CO2 leakage on solubility and transport of seven trace metals in seawater and sediment.

PubMed

Ardelan, Murat V; Steinnes, Eiliv; Lierhagen, Syverin; Linde, Sven Ove

2009-12-01

The impact of CO(2) leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), "dissolved" (<0.2 microm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO(2) seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO(2) chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (Me(DGT)) of all metals increased substantially during the first phase of CO(2) seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO(2) chamber than that of in the control chamber. Al(DGT), Cr(DGT), Ni(DGT), and Pb(DGT) continued to increase during the second phase of the experiment. There was no change in Cd(DGT) during the second phase, while Cu(DGT) and Zn(DGT) decreased by 30% and 25%, respectively in the CO(2) chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO(2) chamber. Our results show that CO(2) leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO(2) acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity of the metals to biota.

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site, Bemidji, Minnesota

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler B.; Baedecker, Mary J.; Glynn, Pierre D.

1995-01-01

Stable isotopic ratios of C and H in dissolved CH4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH4production by acetate fermentation with a contemporaneous increase in HCO3−concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L−1 to less than 0.001 mg L−1 along the investigated flow path. Dissolved N2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH4 occurs with distance from the oil body. However, CH4 is partly oxidized to CO2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; theδ13C of the remaining CH4 increases, theδ13C of the CO2 decreases, and the partial pressure of CO2 increases.Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO2 diffusion coefficient.

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

Hydrological and Climate Controls on Hyporheic Contributions to River Net Ecosystem Productivity

NASA Astrophysics Data System (ADS)

Newcomer, M. E.; Hubbard, S. S.; Fleckenstein, J. H.; Maier, U.; Schmidt, C.; Laube, G.; Chen, N.; Ulrich, C.; Dwivedi, D.; Steefel, C. I.; Rubin, Y.

2016-12-01

Hyporheic zone contributions to river net ecosystem productivity (NEP) can represent a substantial source or sink for organic and inorganic carbon (C). Hyporheic zone processes are estimated to vary with network location as a function of river-aquifer interactions as well as with climatic factors supporting riverbed gross primary productivity (GPP) and ecosystem respiration. Even though hyporheic zone NEP is hypothesized to be a significant budgetary component to river-aquifer biogeochemical cycling, models of river NEP often parameterize hyporheic zone contributions as a space-time constant input of CO2 to rivers, leading to overestimation of hyporheic zone NEP and underestimation of C storage. This assumption is problematic during the summer growing season, when GPP is largest and C is stored in surface and subsurface biomass. We investigated the dynamic role of hyporheic zone NEP using the MIN3P flow and reactive transport model with surface water GPP and ecosystem respiration simulated as a function of light, depth, temperature, pH, and atmospheric CO2. We simulated hyporheic zone NEP for low-order and high-order streams, which collectively represent a range of characteristic flow paths and subsurface residence times. Downscaled climate predictions of temperature and atmospheric CO2 representing carbon emission futures were used to force the models and to compare future and current hyporheic zone NEP. Our results show that river-aquifer flow conditions determine the relative role of the river as either a store or sink of C through direct contributions of O2 and dissolved organic content from river GPP. Modeled results show that high discharge, high order rivers are net stores of CO2 from the atmosphere; however this is dependent on perturbation events that allow stored C from summer GPP to be released (i.e. rising water tables during winter storms). Lacking a perturbation event, C remains in pore-water storage as dissolved CO2 and biomass. Conversely, low-discharge mountainous streams with continuous hyporheic zone flow represent a net source of CO2, with future temperature rises stimulating additional heterotrophic activity. Our work contributes to a better understanding of how river and hyporheic zone processes significantly influence biogeochemical cycling under changing climate conditions.

Comparative evolution of oxygen, carbon dioxide, nitrogen, and sulfites during storage of a rosé wine bottled in PET and glass.

PubMed

Toussaint, Marie; Vidal, Jean-Claude; Salmon, Jean-Michel

2014-04-02

The management of dissolved and headspace gases during bottling and the choice of packaging are both key factors for the shelf life of wine. Two kinds of 75 cL polyethylene terephthalate (PET) bottles (with or without recycled PET) were compared to glass bottles filled with a rosé wine, closed with the same screwcaps and stored upright at 20 °C in light or in the dark. Analytical monitoring (aphrometric pressure, headspace volume, O2, N2, CO2, and SO2) was carried out for 372 days. After the consumption of O2 trapped during bottling, the total O2 content in glass bottles remained stable. A substantial decrease of CO2 and SO2 concentration and an increase of O2 concentration were observed in the PET bottles after 6 months because of the considerable gas permeability of monolayer PET. Light accelerated O2 consumption during the early months. Finally, the kinetic monitoring of partial pressures in gas and liquid phases in bottles showed contrasting behavior of O2 and N2 in comparison with CO2.

Superhydrophobic perfluoropolymer/polystyrene blend films induced by nonsolvent

NASA Astrophysics Data System (ADS)

Gengec, Nevin Atalay; Cengiz, Ugur; Erbil, H. Yildirim

2016-10-01

Statistical copolymers of perfluoroalkyl ethyl acrylate (Zonyl-TAN) and methyl methacrylate (MMA) were synthesized in a CO2 polymerization system where a CO2-expanded monomer mixture was formed at 13 MPa, and 80 °C by using AIBN as initiator. Flat and superhydrophobic surfaces were subsequently prepared on glass slides by applying a phase separation process where the synthesized p(TAN-co-MMA) copolymer and polystyrene (PS) were dissolved in THF solvent. Ethanol was added as the non-solvent to introduce superhydrophobicity during film formation. Water contact angle on the flat p(TAN-co-MMA) copolymer was 118° and increased up to 170° with the formation of surface roughness. The ratio of the ethanol non-solvent in the blend solution has an important effect on the magnitude of surface roughness during the phase separation process. Both pits and protrusions of 1-10 μm in size were formed on the surface when non-solvent was used. Surface roughness increased with the increase in the ethanol ratio and the PS content of the blend solution.

Mitigating Local Causes of Ocean Acidification with Existing Laws

EPA Science Inventory

The oceans continue to absorb CO2 in step with the increasing atmospheric concentration of CO2. The dissolved CO2 reacts with seawater to form carbonic acid (H2CO3) and liberate hydrogen ions, causing the pH of the oceans to decrease. Ocean acidification is thus an inevitable a...

Submarine Flood Basalt Eruptions and Flows of Ontong Java Plateau, Nauru Basin and East Mariana Basin

NASA Astrophysics Data System (ADS)

Michael, P. J.; Trowbridge, S. R.; Zhang, J.; Johnson, A. L.

2016-12-01

The preservation of fresh basalt glasses from the submarine Cretaceous Ontong Java Plateau (OJP), Earth's largest LIP, has allowed correlation of precise lava compositions over 100s of km, as well as determination of eruption depths using dissolved H2O and CO2 contents. Low dissolved H2O in glasses shows that H2O in the mantle source is low [1,2], suggesting mantle temperatures are high. Very high dissolved Cl indicates that magmas interacted extensively with brines. The near total absence of vesicles in OJP glasses contrasts sharply with MORB, and suggests that OJP lavas were saturated or undersaturated with CO2 when they were emplaced, in contrast to MORB that are often oversaturated. The lavas likely remained liquid for a longer period of time so that they degassed to equilibrium levels of dissolved CO2 andlost all bubbles. Very precise major and trace element analyses of glasses, uncomplicated by crystals or alteration, show how lavas within and between widely-spaced drill holes could be related. For example, glasses from Sites 1185B and 1186A, which are about 200 km apart, are compositionally identical within precise limits and must have erupted from the same well-mixed magma chamber. They erupted at about the same depth, but 1186A has a corrected basement depth that is >700m deeper. With a slope of 0.3°, this suggests a flow distance >130km. The eruption depths for glasses from East Mariana and Nauru Basins are similar to those of 1185B and 1186A on OJP, even though their reconstructed basement depths are about 2000 m deeper. It suggests that the plateau lavas flowed into the basins. Similarly, eruption depths in Hole 807C are 3040m for Kwaimbaita lavas but are 1110m [1,2] for Singgalo lavas that directly overlie them. It is unlikely that plateau uplift and subsidence accounts for the observed eruption depths. All of these observations are best explained by very large-volume eruptions whose lavas traveled for long distances, up to 100s of km, into deeper water over gentle slopes (0.1-0.5°). The presence of many glass layers within the cores contrasts with continental flood basalts and suggests the flows were covered by a thick, moving, shifting carapace of solidified lava. They may represent an extreme form of inflated pahoehoe flows. 1 Michael, P.J., 1999 G-Cubed 1 (12), GC000025 2 Roberge J., et al., 2005, Geology 33, 501-504

CO2 volume fluxes outgassing from champagne glasses: the impact of champagne ageing.

PubMed

Liger-Belair, Gérard; Villaume, Sandra; Cilindre, Clara; Jeandet, Philippe

2010-02-15

It was demonstrated that CO(2) volume fluxes outgassing from a flute poured with a young champagne (elaborated in 2007) are much higher than those outgassing from the same flute poured with an older champagne (elaborated in the early 1990s). The difference in dissolved-CO(2) concentrations between the two types of champagne samples was found to be a crucial parameter responsible for differences in CO(2) volume fluxes outgassing from one champagne to another. Nevertheless, it was shown that, for a given identical dissolved-CO(2) concentration in both champagne types, the CO(2) volume flux outgassing from the flute poured with the old champagne is, in average, significantly lower than that outgassing from the flute poured with the young one. Therefore, CO(2) seems to "escape" more easily from the young champagne than from the older one. The diffusion coefficient of CO(2) in both champagne types was pointed as a key parameter to thoroughly determine in the future, in order to unravel our experimental observation. Copyright 2009 Elsevier B.V. All rights reserved.

Estimating gas exchange of CO2 and CH4 between headwater systems and the atmosphere in Southwest Sweden

NASA Astrophysics Data System (ADS)

Somlai, Celia; Natchimuthu, Sivakiruthika; Bastviken, David; Lorke, Andreas

2015-04-01

Quantifying the role of inland water systems in terms of carbon sinks and sources and their connection to the terrestrial ecosystems and landscapes is fundamental for improving the balance approach of regional and global carbon budgets. Recent research showed that freshwater bodies emit significant amounts of CO2 and CH4 into the atmosphere. The extent of the emissions from small streams and headwaters, however, remains uncertain due to a limited availability of data. Studies have shown that headwater systems receive most of the terrestrial organic carbon, have the highest dissolved CO2 concentration and the highest gas exchange velocities and cover the largest fractional surface area within fluvial networks. The gas exchange between inland waters and the atmosphere is controlled by two factors: the difference between the dissolved gas concentration and its atmospheric equilibrium concentration, and the gas exchange velocity. The direct measurement of the dissolved gas concentration of greenhouse gases can be measured straightforwardly, for example, by gas chromatography from headspace extraction of water sample. In contrast, direct measurement of gas exchange velocity is more complex and time consuming, as simultaneous measurements with a volatile and nonvolatile inert tracer gas are needed. Here we analyze measurements of gas exchange velocities, concentrations and fluxes of dissolved CO2 and CH4, as well as loads of total organic and inorganic carbon in 10 reaches in headwater streams in Southwest Sweden. We compare the gas exchange velocities measured directly through tracer injections with those estimated through various empirical approaches, which are based on modelled and measured current velocity, stream depth and slope. Furthermore, we estimate the resulting uncertainties of the flux estimates. We also present different time series of dissolved CO2, CH4 and O2 concentration, water temperature, barometric pressure, electro conductivity, and pH values measured during the period of tracer injection.

Enhanced Production of Green Tide Algal Biomass through Additional Carbon Supply

PubMed Central

de Paula Silva, Pedro H.; Paul, Nicholas A.; de Nys, Rocky; Mata, Leonardo

2013-01-01

Intensive algal cultivation usually requires a high flux of dissolved inorganic carbon (Ci) to support productivity, particularly for high density algal cultures. Carbon dioxide (CO2) enrichment can be used to overcome Ci limitation and enhance productivity of algae in intensive culture, however, it is unclear whether algal species with the ability to utilise bicarbonate (HCO3 −) as a carbon source for photosynthesis will benefit from CO2 enrichment. This study quantified the HCO3 − affinity of three green tide algal species, Cladophora coelothrix, Cladophora patentiramea and Chaetomorpha linum, targeted for biomass and bioenergy production. Subsequently, we quantified productivity and carbon, nitrogen and ash content in response to CO2 enrichment. All three species had similar high pH compensation points (9.7–9.9), and grew at similar rates up to pH 9, demonstrating HCO3 − utilization. Algal cultures enriched with CO2 as a carbon source had 30% more total Ci available, supplying twenty five times more CO2 than the control. This higher Ci significantly enhanced the productivity of Cladophora coelothrix (26%), Chaetomorpha linum (24%) and to a lesser extent for Cladophora patentiramea (11%), compared to controls. We demonstrated that supplying carbon as CO2 can enhance the productivity of targeted green tide algal species under intensive culture, despite their clear ability to utilise HCO3 −. PMID:24324672

Chemistry of manganese precipitation in Pinal Creek, Arizona, USA: A laboratory study

USGS Publications Warehouse

Hem, J.D.; Lind, Carol J.

1994-01-01

Groundwater underlying the valley of Pinal Creek downstream from Globe, Arizona, has been contaminated by low-pH metal-enriched wastewater from copper mining and ore processing at Miami, Arizona. At present, the acidity and most of the dissolved metal content, except for Mn, of the wastewater is removed by reactions with carbonate and other solids in the alluvial aquifer before the neutralized contaminated water enters the creek channel and becomes surface flow. Where flow in the creek is perennial, Mn-bearing precipitates are formed in the stream bed and in some places in the subsurface. As an aid to understanding the processes involved and explaining the mineralogy of the precipitates, closely controlled laboratory redox titration experiments were performed on samples of surface flow and groundwater taken near the head of perennial flow in the creek. The high content of dissolved Ca, Mg, Mn and COP2 species in the neutralized contaminated groundwater caused precipitation of some of the Mn as kutnahorite, (Mn, Mg)Ca(CO3)2, when the experimental system was held between pH 8.5 and 9.0 while CO2-free air was bubbled into the solution. Hausmannite and manganite also were precipitated, in somewhat lower amounts. When the concentrations of dissolved CO2 species in the groundwater sample were decreased before the experiment was started, the Mn precipitated was predominantly in the oxides hausmannite and manganite. In some of the experimental titrations clinoenstatite, (MgSiO3), was precipitated. After titrations were stopped the solutions and precipitates were allowed to stand, with limited access to the atmosphere, for several months. During this aging period the degree of oxidation of the precipitated Mn increased and in one precipitate from an experimental solution the Ca + Mn4+ oxides todorokite and takanelite were identified. These oxides also have been identified in streambed precipitates. Some of these precipitates also gave X-ray diffraction reflections for kutnahorite. Thermodynamic feasibilities of eight potential chemical reactions forming solid phases of interest were evaluated by calculating their respective reaction affinities attained during titration and aging. The results are in general agreement with the indications for the presence of these species given by X-ray and electron diffraction. The presence of carbonates in precipitated encrustations formed from groundwater below the land surface and their occurrence in manganese oxide crusts that precipitate from the creek water, also are predicted by these results. ?? 1994.

Humic substances and trace metals associated with Fe and Al oxides deposited in an acidic mountain stream

USGS Publications Warehouse

McKnight, Diane M.; Wershaw, R. L.; Bencala, K.E.; Zellweger, G.W.; Feder, G.L.

1992-01-01

Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Schoonen, M.A.A.; Candela, J.L.

2000-01-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO4/2- in the aerobic zone, and to the reduction of SO4/2- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55 x 10-4 to 48.6 x 10-4 mmol 1-1 yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO4/2- (1.31 x 10-4 to 15 x 10-4 mmol 1-1 yr-1). The overall increase in SO4/2- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO4/2- loss through microbial reduction is exceeded by SO4/2- gain through diffusion from sediments and through the oxidation of FeS2. Geochemichal and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO4/2- -rich zones have localized SO4/2- -reducing zones in which the formation of iron disulfides been depleted by microbial reduction and resulted in decreases dissolved iron concentrations. These localized zones of SO4/2- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling. (C) 2000 Elsevier Science B.V.Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO42- in the aerobic zone, and to the reduction of SO42- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55??10-4 to 48.6??10-4mmol l-1yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO42- (1.31??10-4 to 15??10-4mmol l-1yr-1). The overall increase in SO42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO42- loss through microbial reduction is exceeded by SO42- gain through diffusion from sediments and through the oxidation of FeS2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO42--rich zones have been depleted by microbial reduction and resulted in localized SO42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Landscape-level controls on dissolved carbon flux from diverse catchments of the circumboreal

USGS Publications Warehouse

Tank, Suzanne; Frey, Karen E.; Striegl, Robert G.; Raymond, Peter A.; Holmes, R. Max; McClelland, James W.; Peterson, Bruce J.

2012-01-01

While much of the dissolved organic carbon (DOC) within rivers is destined for mineralization to CO2, a substantial fraction of riverine bicarbonate (HCO3-) flux represents a CO2 sink, as a result of weathering processes that sequester CO2 as HCO3-. We explored landscape-level controls on DOC and HCO3- flux in subcatchments of the boreal, with a specific focus on the effect of permafrost on riverine dissolved C flux. To do this, we undertook a multivariate analysis that partitioned the variance attributable to known, key regulators of dissolved C flux (runoff, lithology, and vegetation) prior to examining the effect of permafrost, using riverine biogeochemistry data from a suite of subcatchments drawn from the Mackenzie, Yukon, East, and West Siberian regions of the circumboreal. Across the diverse catchments that we study, controls on HCO3- flux were near-universal: runoff and an increased carbonate rock contribution to weathering (assessed as riverwater Ca:Na) increased HCO3- yields, while increasing permafrost extent was associated with decreases in HCO3-. In contrast, permafrost had contrasting and region-specific effects on DOC yield, even after the variation caused by other key drivers of its flux had been accounted for. We used ionic ratios and SO4 yields to calculate the potential range of CO2 sequestered via weathering across these boreal subcatchments, and show that decreasing permafrost extent is associated with increases in weathering-mediated CO2 fixation across broad spatial scales, an effect that could counterbalance some of the organic C mineralization that is predicted with declining permafrost.

Solubility of reduced C-O-H volatiles in basalt as a function of fCO: Implications for the early Earth, the moon, and Mars

NASA Astrophysics Data System (ADS)

Armstrong, L. S.; Hirschmann, M. M.

2013-12-01

Magmatic C-O-H volatiles influence the evolution of planetary atmospheres and, when precipitated and stored in solidified mantles, the dynamical evolution of planetary interiors. In the case of the Earth, the fO2 of the mantle near the end of core formation should have been ~IW-2, and subsequently increased to present-day values [1]. In experiments with fO2 ≤ IW, a variety of reduced volatile species have been found dissolved in magmas, including H2, CH4, CO, Fe(CO)5 and possibly Fe(CO)62+. However, there remains significant disagreement regarding the identity and concentrations of these volatiles in natural magmas, as well as their dependencies on intensive variables (T, P, fO2, fCO, fH2)[2-6]. Previous experiments document the importance of CO-related species [2,6], but were conducted over a limited range of fCO and had potentially interfering effects from poorly controlled variations in H2O. We aim to experimentally determine the solubility of C-O-H volatiles in basaltic magmas under reduced, C-saturated conditions while minimizing water content. The relationship between volatile speciation, fO2, and fCO at 1.2 GPa and 1400°C are constrained, laying the groundwork for a more extensive study at a range of conditions relevant to the interiors of the terrestrial planets and the moon. Both MORB and a martian basalt were studied, contained in Pt-C capsules with Fe × Pt × Si metal added to generate reducing conditions and to monitor fO2. A nominal amount of H2O is unavoidable in experimental charges, but was minimized by drying capsules prior to welding. Phase compositions were determined by electron microprobe and volatile concentrations were measured by FTIR spectroscopy. In preliminary experiments with fO2 of IW-0.70 to +1.75 (corresponding to log fCO of 3.3-4.5), H2O and CO2 concentrations as determined by FTIR are 113-13283 and 12-721 ppm, respectively. Most experiments also display a small FTIR peak at 2205 cm-1, whereas the most reduced experiments lack this peak but have peaks at 3370 and/or 1615 cm-1. The 2205 cm-1 peak was previously observed in similar experiments [6], and attributed to a C=O bond, possibly in the Fe-carbonyl Fe(CO)62+ [7]. The normalized intensity of the 2205 cm-1 peak is zero at IW -0.70 and increases with greater fO2 and fCO. This suggests that over a small fO2 and fCO range with the CCO buffer as an upper limit, CO-bearing species account for a portion of the dissolved C in reduced, graphite-saturated magmas. These volatiles could play an important role in martian magmatism, in the early Earth's mantle post-core formation, and in more oxidized regions of the lunar mantle. However, the fO2 during terrestrial core formation would have been too low for CO2 or the CO-bearing species to dissolve in a magma ocean. Ongoing work will extend the study to more reducing conditions and determine total C and H2O concentrations by SIMS. References: [1] Frost et al. (2008) Phil. Trans. R. Soc. A 366, 4315-4337. [2] Wetzel D. et al. (2013) PNAS, doi:10.1073/pnas.1219266110. [3] Dasgupta et al. (2013) GCA 102, 191-212. [4] Hirschmann et al. (2012) EPSL 345, 38-48. [5] Ardia et al. (2013) GCA 114, 52-71. [6] Stanley et al. (in review), GCA. [7] Bley et al. (1997) Inorg. Chem. 36, 158-160.

An effective device for gas-liquid oxygen removal in enclosed microalgae culture.

PubMed

Su, Zhenfeng; Kang, Ruijuan; Shi, Shaoyuan; Cong, Wei; Cai, Zhaoling

2010-01-01

A high-performance gas-liquid transmission device (HPTD) was described in this paper. To investigate the HPTD mass transfer characteristics, the overall volumetric mass transfer coefficients, K(A)(La,CO(2)) for the absorption of gaseous CO(2) and K(A)(La,O(2)) for the desorption of dissolved O(2) were determined, respectively, by titration and dissolved oxygen electrode. The mass transfer capability of carbon dioxide was compared with that of dissolved oxygen in the device, and the operating conditions were optimized to suit for the large-scale enclosed micro-algae cultivation. Based on the effectiveness evaluation of the HPTD applied in one enclosed flat plate Spirulina culture system, it was confirmed that the HPTD can satisfy the demand of the enclosed system for carbon supplement and excessive oxygen removal.

First estimates of the contribution of CaCO3 precipitation to the release of CO2 to the atmosphere during young sea ice growth

NASA Astrophysics Data System (ADS)

Geilfus, N.-X.; Carnat, G.; Dieckmann, G. S.; Halden, N.; Nehrke, G.; Papakyriakou, T.; Tison, J.-L.; Delille, B.

2013-01-01

report measurements of pH, total alkalinity, air-ice CO2 fluxes (chamber method), and CaCO3 content of frost flowers (FF) and thin landfast sea ice. As the temperature decreases, concentration of solutes in the brine skim increases. Along this gradual concentration process, some salts reach their solubility threshold and start precipitating. The precipitation of ikaite (CaCO3.6H2O) was confirmed in the FF and throughout the ice by Raman spectroscopy and X-ray analysis. The amount of ikaite precipitated was estimated to be 25 µmol kg-1 melted FF, in the FF and is shown to decrease from 19 to 15 µmol kg-1 melted ice in the upper part and at the bottom of the ice, respectively. CO2 release due to precipitation of CaCO3 is estimated to be 50 µmol kg-1 melted samples. The dissolved inorganic carbon (DIC) normalized to a salinity of 10 exhibits significant depletion in the upper layer of the ice and in the FF. This DIC loss is estimated to be 2069 µmol kg-1 melted sample and corresponds to a CO2 release from the ice to the atmosphere ranging from 20 to 40 mmol m-2 d-1. This estimate is consistent with flux measurements of air-ice CO2 exchange. Our measurements confirm previous laboratory findings that growing young sea ice acts as a source of CO2 to the atmosphere. CaCO3 precipitation during early ice growth appears to promote the release of CO2 to the atmosphere; however, its contribution to the overall release by newly formed ice is most likely minor.

Modeling CO2 Storage in Fractured Reservoirs: Fracture-Matrix Interactions of Free-Phase and Dissolved CO2

NASA Astrophysics Data System (ADS)

Oldenburg, C. M.; Zhou, Q.; Birkholzer, J. T.

2017-12-01

The injection of supercritical CO2 (scCO2) in fractured reservoirs has been conducted at several storage sites. However, no site-specific dual-continuum modeling for fractured reservoirs has been reported and modeling studies have generally underestimated the fracture-matrix interactions. We developed a conceptual model for enhanced CO2 storage to take into account global scCO2 migration in the fracture continuum, local storage of scCO2 and dissolved CO2 (dsCO2) in the matrix continuum, and driving forces for scCO2 invasion and dsCO2 diffusion from fractures. High-resolution discrete fracture-matrix models were developed for a column of idealized matrix blocks bounded by vertical and horizontal fractures and for a km-scale fractured reservoir. The column-scale simulation results show that equilibrium storage efficiency strongly depends on matrix entry capillary pressure and matrix-matrix connectivity while the time scale to reach equilibrium is sensitive to fracture spacing and matrix flow properties. The reservoir-scale modeling results shows that the preferential migration of scCO2 through fractures is coupled with bulk storage in the rock matrix that in turn retards the fracture scCO2 plume. We also developed unified-form diffusive flux equations to account for dsCO2 storage in brine-filled matrix blocks and found solubility trapping is significant in fractured reservoirs with low-permeability matrix.

A simple high-performance matrix-free biomass molten carbonate fuel cell without CO2 recirculation

PubMed Central

Lan, Rong; Tao, Shanwen

2016-01-01

In previous reports, flowing CO2 at the cathode is essential for either conventional molten carbonate fuel cells (MCFCs) based on molten carbonate/LiAlO2 electrolytes or matrix-free MCFCs. For the first time, we demonstrate a high-performance matrix-free MCFC without CO2 recirculation. At 800°C, power densities of 430 and 410 mW/cm2 are achieved when biomass—bamboo charcoal and wood, respectively–is used as fuel. At 600°C, a stable performance is observed during the measured 90 hours after the initial degradation. In this MCFC, CO2 is produced at the anode when carbon-containing fuels are used. The produced CO2 then dissolves and diffuses to the cathode to react with oxygen in open air, forming the required CO32− or CO42− ions for continuous operation. The dissolved O2− ions may also take part in the cell reactions. This provides a simple new fuel cell technology to directly convert carbon-containing fuels such as carbon and biomass into electricity with high efficiency. PMID:27540588

Kinetic determinations of trace element bioaccumulation in the mussel Mytilus edulis

USGS Publications Warehouse

Wang, W.-X.; Fisher, N.S.; Luoma, S.N.

1996-01-01

Laboratory experiments employing radiotracer methodology were conducted to determine the assimilation efficiencies from ingested natural seston, the influx rates from the dissolved phase and the efflux rates of 6 trace elements (Ag, Am, Cd, Co, Se and Zn) in the mussel Mytilus edulis. A kinetic model was then employed to predict trace element concentration in mussel tissues in 2 locations for which mussel and environmental data are well described: South San Francisco Bay (California, USA) and Long Island Sound (New York, USA). Assimilation efficiencies from natural seston ranged from 5 to 18% for Ag, 0.6 to 1% for Am, 8 to 20% for Cd, 12 to 16% for Co, 28 to 34% for Se, and 32 to 41% for Zn. Differences in chlorophyll a concentration in ingested natural seston did not have significant impact on the assimilation of Am, Co, Se and Zn. The influx rate of elements from the dissolved phase increased with the dissolved concentration, conforming to Freundlich adsorption isotherms. The calculated dissolved uptake rate constant was greatest for Ag, followed by Zn > Am = Cd > Co > Se. The estimated absorption efficiency from the dissolved phase was 1.53% for Ag, 0.34% for Am, 0.31% for Cd, 0.11% for Co, 0.03% for Se and 0.89% for Zn. Salinity had an inverse effect on the influx rate from the dissolved phase and dissolved organic carbon concentration had no significant effect on trace element uptake. The calculated efflux rate constants for all elements ranged from 1.0 to 3.0% d-1. The route of trace element uptake (food vs dissolved) and the duration of exposure to dissolved trace elements (12 h vs 6 d) did not significantly influence trace element efflux rates. A model which used the experimentally determined influx and efflux rates for each of the trace elements, following exposure from ingested food and from water, predicted concentrations of Ag, Cd, Se and Zn in mussels that were directly comparable to actual tissue concentrations independently measured in the 2 reference sites in national monitoring programs. Sensitivity analysis indicated that the total suspended solids load, which can affect mussel feeding activity, assimilation, and trace element concentration in the dissolved and particulate phases, can significantly influence metal bioaccumulation for particle-reactive elements such as Ag and Am. For all metals, concentrations in mussels are proportionately related to total metal load in the water column and their assimilation efficiency from ingested particles. Further, the model predicted that over 96% of Se in mussels is obtained from ingested food, under conditions typical of coastal waters. For Ag, Am, Cd, Co and Zn, the relative contribution from the dissolved phase decreases significantly with increasing trace element partition coefficients for suspended particles and the assimilation efficiency in mussels of ingested trace elements; values range between 33 and 67% for Ag, 5 and 17% for Am, 47 and 82% for Cd, 4 and 30% for Co, and 17 and 51% for Zn.

Silicate Carbonation in Supercritical CO2 Containing Dissolved H2O: An in situ High Pressure X-Ray Diffraction Study

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

Schaef, Herbert T.; Miller, Quin RS; Thompson, Christopher J.

2013-06-30

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring between supercritical CO2 containing water and the silicate minerals forsterite (Mg2SiO4), wollastonite (CaSiO3), and enstatite (MgSiO3). This study utilizes newly developed in situ high pressure x-ray diffraction (HXRD) and in situ infra red (IR) to examine mineralmore » transformation reactions. Forsterite and enstatite were selected as they are important minerals present in igneous and mafic rocks and have been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Wollastonite, classified as a pyroxenoid (similar to a pyroxene), was chosen as a suitably fast reacting proxy for examining silicate carbonation processes associated with a wet scCO2 fluid as related to geologic carbon sequestration. The experiments were conducted under modest pressures (90 to 160 bar), temperatures between 35° to 70° C, and varying concentrations of dissolved water. Under these conditions scCO2 contains up to 3,500 ppm dissolved water.« less

Stable isotope monitoring of ionic trapping of CO2 in deep brines

NASA Astrophysics Data System (ADS)

Myrttinen, A.; Barth, J. A. C.; Becker, V.; Blum, P.; Grathwohl, P.

2009-04-01

CO2 injection into a depleted gas-reservoir is used as a combined method for Enhanced Gas Recovery (EGR) and CO2 storage. In order to safeguard this process, monitoring the degree of dissolution and potential further precipitation and mineral interactions are a necessity. Here a method is introduced, in which stable isotope and geochemical data can be used as a monitoring technique to quantify ionic trapping of injected CO2. Isotope and geochemical data of dissolved inorganic carbon (DIC) can be used to distinguish between already present and to be injected inorganic carbon. Injected CO2, for instance, is formed during combustion of former plant material and is expected to have a different isotope ratio (δ13C value) than the baseline data of the aquifer. This is because combusted CO2 originates from organic material, such as coal and oil with a predominant C3 plant signature. Mixing the injected CO2 with groundwater is therefore expected to change the isotope, as well as the geochemical composition of the groundwater. Mass balance calculations with stable isotope ratios can serve to quantify ionic trapping of CO2 as DIC in groundwater. However, depending on the composition of the aquifer, weathering of carbonate or silicates may occur. Enhanced weathering processes due to CO2 injection can also further influence the isotopic composition. Such interactions between dissolved CO2 and minerals depend on the temperature and pressure regimes applied. Field data, as well as laboratory experiments are planned to quantify isotope ratios of dissolved inorganic carbon as well as oxygen isotope ratios of the water. These are indicative of geochemical processes before, during and after EGR. The isotope method should therefore provide a new tool to quantify the efficiency of ionic trapping under various temperatures and pressures. Keywords: Enhanced Gas Recovery, monitoring of CO2 dissolution, stable isotopes

Contrasting biogeochemical characteristics of the Oubangui River and tributaries (Congo River basin)

PubMed Central

Bouillon, Steven; Yambélé, Athanase; Gillikin, David P.; Teodoru, Cristian; Darchambeau, François; Lambert, Thibault; Borges, Alberto V.

2014-01-01

The Oubangui is a major tributary of the Congo River. We describe the biogeochemistry of contrasting tributaries within its central catchment, with watershed vegetation ranging from wooded savannahs to humid rainforest. Compared to a 2-year monitoring record on the mainstem Oubangui, these tributaries show a wide range of biogeochemical signatures, from highly diluted blackwaters (low turbidity, pH, conductivity, and total alkalinity) in rainforests to those more typical for savannah systems. Spectral analyses of chromophoric dissolved organic matter showed wide temporal variations in the Oubangui compared to spatio-temporal variations in the tributaries, and confirm that different pools of dissolved organic carbon are mobilized during different hydrological stages. δ13C of dissolved inorganic carbon ranged between −28.1‰ and −5.8‰, and was strongly correlated to both partial pressure of CO2 and to the estimated contribution of carbonate weathering to total alkalinity, suggesting an important control of the weathering regime on CO2 fluxes. All tributaries were oversaturated in dissolved greenhouse gases (CH4, N2O, CO2), with highest levels in rivers draining rainforest. The high diversity observed underscores the importance of sampling that covers the variability in subcatchment characteristics, to improve our understanding of biogeochemical cycling in the Congo Basin. PMID:24954525

Divergent biophysical controls of aquatic CO2 and CH4 in the World's two largest rivers.

PubMed

Borges, Alberto V; Abril, Gwenaël; Darchambeau, François; Teodoru, Cristian R; Deborde, Jonathan; Vidal, Luciana O; Lambert, Thibault; Bouillon, Steven

2015-10-23

Carbon emissions to the atmosphere from inland waters are globally significant and mainly occur at tropical latitudes. However, processes controlling the intensity of CO2 and CH4 emissions from tropical inland waters remain poorly understood. Here, we report a data-set of concurrent measurements of the partial pressure of CO2 (pCO2) and dissolved CH4 concentrations in the Amazon (n = 136) and the Congo (n = 280) Rivers. The pCO2 values in the Amazon mainstem were significantly higher than in the Congo, contrasting with CH4 concentrations that were higher in the Congo than in the Amazon. Large-scale patterns in pCO2 across different lowland tropical basins can be apprehended with a relatively simple statistical model related to the extent of wetlands within the basin, showing that, in addition to non-flooded vegetation, wetlands also contribute to CO2 in river channels. On the other hand, dynamics of dissolved CH4 in river channels are less straightforward to predict, and are related to the way hydrology modulates the connectivity between wetlands and river channels.

Technical insight on the requirements for CO2-saturated growth of microalgae in photobioreactors.

PubMed

Yuvraj; Padmanabhan, Padmini

2017-06-01

Microalgal cultures are usually sparged with CO 2 -enriched air to preclude CO 2 limitation during photoautotrophic growth. However, the CO 2 vol% specifically required at operating conditions to meet the carbon requirement of algal cells in photobioreactor is never determined and 1-10% v/v CO 2 -enriched air is arbitrarily used. A scheme is proposed and experimentally validated for Chlorella vulgaris that allows computing CO 2 -saturated growth feasible at given CO 2 vol% and volumetric O 2 mass-transfer coefficient (k L a) O . CO 2 sufficiency in an experiment can be theoretically established to adjust conditions for CO 2 -saturated growth. The methodology completely eliminates the requirement of CO 2 electrode for online estimation of dissolved CO 2 to determine critical CO 2 concentration (C crit ), specific CO 2 uptake rate (SCUR), and volumetric CO 2 mass-transfer coefficient (k L a) C required for the governing CO 2 mass-transfer equation. C crit was estimated from specific O 2 production rate (SOPR) measurements at different dissolved CO 2 concentrations. SCUR was calculated from SOPR and photosynthetic quotient (PQ) determined from the balanced stoichiometric equation of growth. Effect of light attenuation and nutrient depletion on biomass estimate is also discussed. Furthermore, a simple design of photosynthetic activity measurement system was used, which minimizes light attenuation by hanging a low depth (ca. 10 mm) culture over the light source.

The interplay between the paracetamol polymorphism and its molecular structures dissolved in supercritical CO2 in contact with the solid phase: In situ vibration spectroscopy and molecular dynamics simulation analysis.

PubMed

Oparin, Roman D; Moreau, Myriam; De Walle, Isabelle; Paolantoni, Marco; Idrissi, Abdenacer; Kiselev, Michael G

2015-09-18

The aim of this paper is to characterize the distribution of paracetamol conformers which are dissolved in a supercritical CO2 phase being in equilibrium with their corresponding crystalline form. The quantum calculations and molecular dynamics simulations were used in order to characterize the structure and analyze the vibration spectra of the paracetamol conformers in vacuum and in a mixture with CO2 at various thermodynamic state parameters (p,T). The metadynamics approach was applied to efficiently sample the various conformers of paracetamol. Furthermore, using in situ IR spectroscopy, the conformers that are dissolved in supercritical CO2 were identified and the evolution of the probability of their presence as a functions of thermodynamic condition was quantified while the change in the crystalline form of paracetamol have been monitored by DSC, micro IR and Raman techniques. The DSC analysis as well as micro IR and Raman spectroscopic studies of the crystalline paracetamol show that the subsequent heating up above the melting temperature of the polymorph I of paracetamol and the cooling down to room temperature in the presence of supercritical CO2 induces the formation of polymorph II. The in situ IR investigation shows that two conformers (Conf. 1 and Conf. 2) are present in the phase of CO2 while conformer 3 (Conf. 3) has a high probability to be present after re-crystallization. Copyright © 2015. Published by Elsevier B.V.

Composition characteristics and regularities of dissolving of hydroxyapatite materials obtained in water solutions with varied content of silicate ions

NASA Astrophysics Data System (ADS)

Solonenko, A. P.

2018-01-01

Research aimed at developing new bioactive materials for the repair of defects in bone tissues, do not lose relevance due to the strengthening of the regenerative approach in medicine. From this point of view, materials based on calcium phosphates, including silicate ions, consider as one of the most promising group of substances. Methods of synthesis and properties of hydroxyapatite doped with various amounts of SiO4 4- ions are described in literature. In the present work synthesis of a solid phase in the systems Ca(NO3)2 - (NH4)2HPO4 - Na2SiO3 - NH4OH - H2O (Cca/CP = 1.70) performed with a wide range of sodium silicate additive concentration (y = CSi/CP = 0 ÷ 5). It is established that under the studied conditions at y ≥ 0.3 highly dispersed poorly crystallized apatite containing isomorphic impurities of CO3 2- and SiO4 4- precipitates in a mixture with calcium hydrosilicate and SiO2. It is shown that the resulting composites can gradually dissolve in physiological solution and initiate passive formation of the mineral component of hard tissues.

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE PAGES

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.; ...

2018-02-09

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

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

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

A Thermodynamic Approach for Modeling H2O-CO2 Solubility in Alkali-rich Mafic Magmas at Mid-crustal Pressures

NASA Astrophysics Data System (ADS)

Allison, C. M.; Roggensack, K.; Clarke, A. B.

2017-12-01

Volatile solubility in magmas is dependent on several factors, including composition and pressure. Mafic (basaltic) magmas with high concentrations of alkali elements (Na and K) are capable of dissolving larger quantities of H2O and CO2 than low-alkali basalt. The exsolution of abundant gases dissolved in alkali-rich mafic magmas can contribute to large explosive eruptions. Existing volatile solubility models for alkali-rich mafic magmas are well calibrated below 200 MPa, but at greater pressures the experimental data is sparse. To allow for accurate interpretation of mafic magmatic systems at higher pressures, we conducted a set of mixed H2O-CO2 volatile solubility experiments between 400 and 600 MPa at 1200 °C in six mafic compositions with variable alkali contents. Compositions include magmas from volcanoes in Italy, Antarctica, and Arizona. Results from our experiments indicate that existing volatile solubility models for alkali-rich mafic magmas, if extrapolated beyond their calibrated range, over-predict CO2 solubility at mid-crustal pressures. Physically, these results suggest that volatile exsolution can occur at deeper levels than what can be resolved from the lower-pressure experimental data. Existing thermodynamic models used to calculate volatile solubility at different pressures require two experimentally derived parameters. These parameters represent the partial molar volume of the condensed volatile species in the melt and its equilibrium constant, both calculated at a standard temperature and pressure. We derived these parameters for each studied composition and the corresponding thermodynamic model shows good agreement with the CO2 solubility data of the experiments. A general alkali basalt solubility model was also constructed by establishing a relationship between magma composition and the thermodynamic parameters. We utilize cation fractions from our six compositions along with four compositions from the experimental literature in a linear regression to generate this compositional relationship. Our revised general model provides a new framework to interpret volcanic data, yielding greater depths for melt inclusion entrapment than previously calculated using other models, and it can be applied to mafic magma compositions for which no experimental data is available.

Method to Estimate the Dissolved Air Content in Hydraulic Fluid

NASA Technical Reports Server (NTRS)

Hauser, Daniel M.

2011-01-01

In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.

CarbFix I: Rapid CO2 mineralization in basalt for permanent carbon storage

NASA Astrophysics Data System (ADS)

Matter, J. M.; Stute, M.; Snæbjörnsdóttir, S.; Gíslason, S. R.; Oelkers, E. H.; Sigfússon, B.; Gunnarsson, I.; Aradottir, E. S.; Gunnlaugsson, E.; Broecker, W. S.

2015-12-01

Carbon dioxide mineralization via CO2-fluid-rock reactions provides the most permanent solution for geologic CO2 storage. Basalts, onshore or offshore, have the potential to store million metric tons of CO2 as (Ca, Mg, Fe) carbonates [1, 2]. However, as of today it was unclear how fast CO2 is converted to carbonate minerals in-situ in a basalt storage reservoir. The CarbFix I project in Iceland was designed to verify in-situ CO2 mineralization in basaltic rocks. Two injection tests were performed at the CarbFix I pilot injection site near the Hellisheidi geothermal power plant in 2012. 175 tons of pure CO2 and 73 tons of a CO2+H2S mixture were injection from January to March 2012 and in June 2013, respectively. The gases were injected fully dissolved in groundwater into a permeable basalt formation between 400 and 800 m depth using a novel CO2 injection system. Using conservative (SF6, SF5CF3) and reactive (14C) tracers, we quantitatively monitor and detect dissolved and chemically transformed CO2. Tracer breakthrough curves obtained from the first monitoring well indicate that the injected solution arrived in a fast short pulse and a late broad peak. Ratios of 14C/SF6, 14C/SF5CF3 or DIC/SF6 and DIC/SF5CF3 are significantly lower in the monitoring well compared to the injection well, indicating that the injected dissolved CO2 reacted. Mass balance calculations using the tracer data reveal that >95% of the injected CO2 has been mineralized over a period of two years. Evidence of carbonate precipitation has been found in core samples that were collected from the storage reservoir using wireline core drilling as well as in and on the submersible pump in the monitoring well. Results from the core analysis will be presented with emphasis on the CO2 mineralization. [1] McGrail et al. (2006) JGR 111, B12201; [2] Goldberg et al. (2008) PNAS 105(29), 9920-9925.

Sediment carbon and nutrient fluxes from cleared and intact temperate mangrove ecosystems and adjacent sandflats.

PubMed

Bulmer, Richard H; Schwendenmann, Luitgard; Lohrer, Andrew M; Lundquist, Carolyn J

2017-12-01

The loss of mangrove ecosystems is associated with numerous impacts on coastal and estuarine function, including sediment carbon and nutrient cycling. In this study we compared in situ fluxes of carbon dioxide (CO 2 ) from the sediment to the atmosphere, and fluxes of dissolved inorganic nutrients and oxygen across the sediment-water interface, in intact and cleared mangrove and sandflat ecosystems in a temperate estuary. Measurements were made 20 and 25months after mangrove clearance, in summer and winter, respectively. Sediment CO 2 efflux was over two-fold higher from cleared than intact mangrove ecosystems at 20 and 25months after mangrove clearance. The higher CO 2 efflux from the cleared site was explained by an increase in respiration of dead root material along with sediment disturbance following mangrove clearance. In contrast, sediment CO 2 efflux from the sandflat site was negligible (≤9.13±1.18mmolm -2 d -1 ), associated with lower sediment organic matter content. The fluxes of inorganic nutrients (NH 4 + , NO x and PO 4 3- ) from intact and cleared mangrove sediments were low (≤20.37±18.66μmolm -2 h - 1 ). The highest NH 4 + fluxes were measured at the sandflat site (69.21±13.49μmolm -2 h - 1 ). Lower inorganic nutrient fluxes within the cleared and intact mangrove sites compared to the sandflat site were associated with lower abundance of larger burrowing macrofauna. Further, a higher fraction of organic matter, silt and clay content in mangrove sediments may have limited nutrient exchange. Copyright © 2017 Elsevier B.V. All rights reserved.

Solubility, Partitioning, and Speciation of Carbon in Shallow Magma Oceans of Terrestrial Planets Constrained by High P-T Experiments

NASA Astrophysics Data System (ADS)

Chi, H.; Dasgupta, R.; Shimizu, N.

2011-12-01

Deep planetary volatile cycles have a critical influence on planetary geodynamics, atmospheres, climate, and habitability. However, the initial conditions that prevailed in the early, largely molten Earth and other terrestrial planets, in terms of distribution of volatiles between various reservoirs - metals, silicates, and atmosphere - remains poorly constrained. Here we investigate the solubility, partitioning, and speciation of carbon-rich volatile species in a shallow magma ocean environment, i.e., in equilibrium with metallic and silicate melts. A series of high pressure-temperature experiments using a piston cylinder apparatus were performed at 1-3 GPa, 1500-1800 °C on synthetic basaltic mixtures + Fe-Ni metal powders contained in graphite capsules. All the experiments produced glassy silicate melt pool in equilibrium with quenched metal melt composed of dendrites of cohenite and kamacite. Major element compositions of the resulting phases and the carbon content of metallic melts were analyzed by EPMA at NASA-JSC. Carbon and hydrogen concentrations of basaltic glasses were determined using Cameca IMS 1280 SIMS at WHOI and speciation of dissolved volatiles was constrained using FTIR and Raman spectroscopy at Rice University. Based on the equilibria - FeO (silicate melt) = Fe (metal alloy melt) + 1/2O2, we estimate the oxygen fugacity of our experiments in the range of ΔIW of -1 to -2. FTIR analysis on doubly polished basaltic glass chips suggests that the concentrations of dissolved CO32- or molecular CO2 are negligible in graphite and metal saturated reduced conditions, whereas the presence of dissolved OH- is evident from the asymmetric peak at 3500 cm-1. Collected Raman spectra of basaltic glasses in the frequency range of 200-4200 cm-1 suggest that hydrogen is present both as dissolved OH- species (band at 3600 cm-1) and as molecular H2 (band near 4150 cm-1) for all of our experiments. Faint peaks near 2915 cm-1 and consistent peaks near 740 cm-1 suggest that possible carbon species in our reduced glasses are likely minor CH4 and Si-C, respectively and are consistent with the recent solubility studies at reduced conditions [1,2]. Carbon solubility (calibrated using 12C/30Si) at graphite saturation in our reduced basaltic glasses is only in the range 20-100 ppm C, with H2O contents in the range of 0.2-0.7 wt.%. In contrast to the low dissolved carbon concentration in the basaltic silicate melts, carbon solubility in quenched metallic melts vary in the range of 5-7 wt.%. Our preliminary work indicates that the solubility of carbon in reduced basaltic melts relevant for early magma conditions may be several orders of magnitude lower compared to the solubility of carbon in modern terrestrial basalts. This coupled with significant solubility of carbon in Fe-Ni metallic melt suggests that most of magma ocean carbon was likely partitioned into deep metallic melts. Further metal-silicate experiments with more depolymerized basaltic melts of variable compositions are underway and will be presented. [1] Kadik et al. JPetrol 45, 1297-1310, 2004; [2] Kadik et al. Geochem Int 44, 33-47, 2006.

Isotopic Clues on Factors Controlling Geochemical Fluxes From Large Watersheds in Eastern Canada

NASA Astrophysics Data System (ADS)

Rosa, E.; Helie, J.; Ghaleb, B.; Hillaire-Marcel, C.; Gaillardet, J.

2008-12-01

A monitoring and monthly sampling program of the Nelson, Ottawa, St. Lawrence, La Grande and Great Whale rivers was started in September 2007. It provides information on the seasonality and sources of geochemical fluxes into the Hudson Bay and the North Atlantic from watersheds covering more than 2.6 106 km2 of the eastern Canadian boreal domain. Measurements of pH and alkalinity, analyses of major ions, strontium and dissolved silica, 2H and 18O of water, concentrations and isotopic properties of dissolved organic and inorganic carbon (13C) and uranium (234U/238U) were performed. Lithology more than latitudinal climatic gradients controls the river geochemistry. Rivers draining silicate terrains show lower dissolved U concentrations but greater 234U/238U disequilibria than rivers draining carbonates (average of 1.38 vs. 1.23). Groundwater supplies might exert some control on these U- isotope signatures. No clear seasonality is observed in 234U/238U ratios, but U concentrations are correlated to dissolved organic carbon (DOC) concentrations in most rivers. Rivers draining carbonates present higher total dissolved carbon concentrations and higher 13C-contents in dissolved inorganic carbon (DIC), in response to the dissolution of soil carbonates. DOC/DIC ratios above 2.4 are observed in rivers draining silicates; their lower 13C-DIC content directly reflects the organic matter oxidation in soils. Total dissolved solids are one order of magnitude or more greater in rivers draining carbonates, showing the strong difference in chemical weathering rates according to the geological setting. The stability in chemical fluxes and water isotopic compositions in the La Grande River, which hosts hydroelectric reservoirs covering more than 12 000 km2, indicates that it is the most buffered hydrological system among the investigated watersheds. Seasonal fluctuations are observed elsewhere, with maximum geochemical fluxes during the spring snowmelt. 2H-18O content of river water appears to be the only parameter presenting a strong latitudinal and climatic gradient (independent of lithology).

Dynamic analysis of CO₂ labeling and cell respiration using membrane-inlet mass spectrometry.

PubMed

Yang, Tae Hoon

2014-01-01

Here, we introduce a mass spectrometry-based analytical method and relevant technical details for dynamic cell respiration and CO2 labeling analysis. Such measurements can be utilized as additional information and constraints for model-based (13)C metabolic flux analysis. Dissolved dynamics of oxygen consumption and CO2 mass isotopomer evolution from (13)C-labeled tracer substrates through different cellular processes can be precisely measured on-line using a miniaturized reactor system equipped with a membrane-inlet mass spectrometer. The corresponding specific rates of physiologically relevant gases and CO2 mass isotopomers can be quantified within a short-term range based on the liquid-phase dynamics of dissolved fermentation gases.

Pulse labelling for carbon turnover measurements with a CRDS for wetlands - challenges and solutions

NASA Astrophysics Data System (ADS)

Strozecki, Marcin; Samson, Mateusz; Chojnicki, Bogdan H.; Leśny, Jacek; Moni, Christophe; Urbaniak, Marek; Olejnik, Janusz; Juszczak, Radosław; Silvennoinnen, Hanna

2016-04-01

Carbon turnover in peatlands has commonly been studied by estimating carbon allocation and decomposition rates by litterbags, assessing changes in carbon stocks and by measuring the biosphere-atmosphere exchange of carbon gases with various chamber methods or by eddy covariance. In addition, C turnover rates have been measured with pulse labelling methods using 13C and 14C (e.g. Bahn et al. 2009). Pulse labeling (PL) studies in wetlands are, however, sparse (e.g. Gao et al. 2015), presumably as descriptive high water table levels and relatively low productivity render successful tracing difficult. Quite low cost fast-gas-analyzers (Cavity Ring Down Spectrometry, CRDS) make PL experiments more cost-worthy, but their applicability at wetland field and further for measuring elevated 13C - levels is challenging. We carried out a PL as a pre-experiment for a larger labelling campaign of the Wetman-project at Rzecin wetland in Poland. We aimed at defining 1) The optimum labeling for the peatland site, 2) The importance of dissolved 13CO2 both for the loss of the pulse label and for the potential bias to respiratory flux, 3) The reliability of the 13CO2 and 13CH4 measurements when using dynamic closed chambers with a factory calibrated CRDS. We labelled the study area by a transparent chamber combined to Picarro CRDS G2201-i (C input during labelling 4.9 μg 13C). After labelling, we monitored the respiratory 13CO2 flux and the 13CO2 content in the peat water over a 10d- period. In addition, we measured the vegetation13C before labelling and 10 days after. Plants assimilated 2.1 μg C of the added 13C. Half of the recovered 13CO2 (3.6 μg C) originated from respiration. Nearly one third of added 13CO2 immediately dissolved in the water, which at the end of the experiment retained 0.5 μg 13C. Finally, 127 % of the added label was recovered. The high recovery was mainly caused by overestimation in the δ13C. The results of our pre-experiment indicate that 1) Measuring dissolved gases is required for correcting the biases to the respiratory flux 2) the Picarro CRDS has to be thoroughly calibrated for linearity and for δ13C at different signatures. As a result, we developed calibration methods suitable for field conditions and for higher labels. The Research was co-founded by the Polish National Centre for Research and Development within the Polish-Norwegian Research Programme within the project WETMAN (Central European Wetland Ecosystem Feedbacks to Changing Climate - Field Scale Manipulation, Project ID: 203258, contract No. Pol-Nor/203258/31/2013 (www.wetman.pl). Bahn, M. et al., 2009. The New phytologist, Gao, J. et al., 2015. Scientific Reports,

Mineral Dissolution and Precipitation due to Carbon Dioxide-Water-Rock Interactions: The Significance of Accessory Minerals in Carbonate Reservoirs (Invited)

NASA Astrophysics Data System (ADS)

Kaszuba, J. P.; Marcon, V.; Chopping, C.

2013-12-01

Accessory minerals in carbonate reservoirs, and in the caprocks that seal these reservoirs, can provide insight into multiphase fluid (CO2 + H2O)-rock interactions and the behavior of CO2 that resides in these water-rock systems. Our program integrates field data, hydrothermal experiments, and geochemical modeling to evaluate CO2-water-rock reactions and processes in a variety of carbonate reservoirs in the Rocky Mountain region of the US. These studies provide insights into a wide range of geologic environments, including natural CO2 reservoirs, geologic carbon sequestration, engineered geothermal systems, enhanced oil and gas recovery, and unconventional hydrocarbon resources. One suite of experiments evaluates the Madison Limestone on the Moxa Arch, Southwest Wyoming, a sulfur-rich natural CO2 reservoir. Mineral textures and geochemical features developed in the experiments suggest that carbonate minerals which constitute the natural reservoir will initially dissolve in response to emplacement of CO2. Euhedral, bladed anhydrite concomitantly precipitates in response to injected CO2. Analogous anhydrite is observed in drill core, suggesting that secondary anhydrite in the natural reservoir may be related to emplacement of CO2 into the Madison Limestone. Carbonate minerals ultimately re-precipitate, and anhydrite dissolves, as the rock buffers the acidity and reasserts geochemical control. Another suite of experiments emulates injection of CO2 for enhanced oil recovery in the Desert Creek Limestone (Paradox Formation), Paradox Basin, Southeast Utah. Euhedral iron oxyhydroxides (hematite) precipitate at pH 4.5 to 5 and low Eh (approximately -0.1 V) as a consequence of water-rock reaction. Injection of CO2 decreases pH to approximately 3.5 and increases Eh by approximately 0.1 V, yielding secondary mineralization of euhedral pyrite instead of iron oxyhydroxides. Carbonate minerals also dissolve and ultimately re-precipitate, as determined by experiments in the Madison Limestone, but pyrite will persist and iron oxyhydroxides will not recrystallize.

Supercritical CO2 foamed polycaprolactone scaffolds for controlled delivery of 5-fluorouracil, nicotinamide and triflusal.

PubMed

Salerno, Aurelio; Saurina, Javier; Domingo, Concepción

2015-12-30

The manufacture of porous polycaprolactone (PCL) scaffolds containing three different drugs, namely 5-fluorouracil, nicotinamide and triflusal, was investigated in this work with the aim of obtaining bioactive systems with controlled drug delivery capabilities. The scaffolds were prepared by means of a supercritical CO2 (scCO2) foaming technique by optimizing the drug loading process. This was achieved by dissolving the drugs in organic solvents miscible with scCO2 and by mixing these drug/solvent solutions with PCL powder. The as prepared mixtures were further compressed to eliminate air bubbles and finally processed by the scCO2 foaming technique. ScCO2 saturation and foaming conditions were optimized to create the porosity within the samples and to allow for the concomitant removal of the organic solvents. Physical and chemical properties of porous scaffolds, as well as drug content and delivery profiles, were studied by HPLC. The results of this study demonstrated that the composition of the starting PCL/drug/solvent mixtures affected polymer crystallization, scaffold morphology and pore structure features. Furthermore, it was found that drug loading efficiency depended on both initial solution composition and drug solubility in scCO2. Nevertheless, in the case of highly scCO2-soluble drugs, such as triflusal, loading efficiency was improved by adding a proper amount of free drug inside of the pressure vessel. The drug delivery study indicated that release profiles depended mainly upon scaffolds composition and pore structure features. Copyright © 2015 Elsevier B.V. All rights reserved.

ELEVATED CARBON DIOXIDE DIFFERENTIALLY ALTERS THE PHOTOPHYSIOLOGY OF THALASSIOSIRA PSEUDONANA (BACILLARIOPHYCEAE) AND EMILIANIA HUXLEYI (HAPTOPHYTA)(1).

PubMed

McCarthy, Avery; Rogers, Susan P; Duffy, Stephen J; Campbell, Douglas A

2012-06-01

Increasing anthropogenic carbon dioxide is causing changes to ocean chemistry, which will continue in a predictable manner. Dissolution of additional atmospheric carbon dioxide leads to increased concentrations of dissolved carbon dioxide and bicarbonate and decreased pH in ocean water. The concomitant effects on phytoplankton ecophysiology, leading potentially to changes in community structure, are now a focus of concern. Therefore, we grew the coccolithophore Emiliania huxleyi (Lohmann) W. W. Hay et H. Mohler and the diatom strains Thalassiosira pseudonana (Hust.) Hasle et Heimdal CCMP 1014 and T. pseudonana CCMP 1335 under low light in turbidostat photobioreactors bubbled with air containing 390 ppmv or 750 ppmv CO2 . Increased pCO2 led to increased growth rates in all three strains. In addition, protein levels of RUBISCO increased in the coastal strains of both species, showing a larger capacity for CO2 assimilation at 750 ppmv CO2 . With increased pCO2 , both T. pseudonana strains displayed an increased susceptibility to PSII photoinactivation and, to compensate, an augmented capacity for PSII repair. Consequently, the cost of maintaining PSII function for the diatoms increased at increased pCO2 . In E. huxleyi, PSII photoinactivation and the counter-acting repair, while both intrinsically larger than in T. pseudonana, did not change between the current and high-pCO2 treatments. The content of the photosynthetic electron transport intermediary cytochrome b6/f complex increased significantly in the diatoms under elevated pCO2 , suggesting changes in electron transport function. © 2012 Phycological Society of America.

Preparation of Si and O co-solution strengthened Ti alloys by using rice husks as SiO2 resource and quantitative descriptions on their strengthening effects

NASA Astrophysics Data System (ADS)

Jia, Lei; Chen, Jiang-xian; Lu, Zhen-lin; Li, Shu-feng; Umeda, Junko; Kondoh, Katsuyoshi

2018-04-01

Ti alloys strengthened by both Si and O solutes were prepared by powder metallurgy method from pure Ti and amorphous SiO2 powder obtained by combusting rice husks. At the same time, Ti alloys singly strengthened by Si or O were also prepared for studying the strengthening effect of Si and O solutes. Results showed that amorphous SiO2 powder originated from rice husks could almost fully dissolve into pure Ti matrix when the content was not higher than 1.0 wt%, while higher content of SiO2 addition resulted in the formation of Ti5Si3 intermetallics. Si and O elements leaded to negative and positive distortion of Ti lattice, and the influencing degrees were ‑0.02 and +0.014 Å/wt% for lattice constant a, while ‑0.05 and +0.046 Å/wt% for constant c, respectively. Solid solution of Si and O would also result in the increase of hardness, which was 98.5 and 209.43 HV/wt%, respectively. When Si and O were co-exsited in Ti matrix, the negative and positive distortion cancelled each other, while the strengthening effect did not cancel but enhance each other.

Investigation of solubility of carbon dioxide in anhydrous milk fat by lab-scale manometric method.

PubMed

Truong, Tuyen; Palmer, Martin; Bansal, Nidhi; Bhandari, Bhesh

2017-12-15

This study aims to examine the solubility of CO 2 in anhydrous milk fat (AMF) as functions of partial pressure, temperature, chemical composition and physical state of AMF. AMF was fractionated at 21°C to obtain stearin and olein fractions. The CO 2 solubility was measured using a home-made experimental apparatus based on changes of CO 2 partial pressures. The apparatus was found to be reliable as the measured and theoretical values based on the ideal gas law were comparable. The dissolved CO 2 concentration in AMF increased with an increase in CO 2 partial pressure (0-101kPa). The apparent CO 2 solubility coefficients (molkg -1 Pa -1 ) in the AMF were 5.75±0.16×10 -7 , 3.9±0.19×10 -7 and 1.19±0.14×10 -7 at 35, 24 and 4°C, respectively. Higher liquid oil proportions resulted in higher CO 2 solubility in the AMF. There was insignificant difference in the dissolved CO 2 concentration among the AMF, stearin and olein fractions in their liquid state at 40°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

A hybrid intelligent method for three-dimensional short-term prediction of dissolved oxygen content in aquaculture.

PubMed

Chen, Yingyi; Yu, Huihui; Cheng, Yanjun; Cheng, Qianqian; Li, Daoliang

2018-01-01

A precise predictive model is important for obtaining a clear understanding of the changes in dissolved oxygen content in crab ponds. Highly accurate interval forecasting of dissolved oxygen content is fundamental to reduce risk, and three-dimensional prediction can provide more accurate results and overall guidance. In this study, a hybrid three-dimensional (3D) dissolved oxygen content prediction model based on a radial basis function (RBF) neural network, K-means and subtractive clustering was developed and named the subtractive clustering (SC)-K-means-RBF model. In this modeling process, K-means and subtractive clustering methods were employed to enhance the hyperparameters required in the RBF neural network model. The comparison of the predicted results of different traditional models validated the effectiveness and accuracy of the proposed hybrid SC-K-means-RBF model for three-dimensional prediction of dissolved oxygen content. Consequently, the proposed model can effectively display the three-dimensional distribution of dissolved oxygen content and serve as a guide for feeding and future studies.

Effects of Formation Heterogeneity in Semi-Confining Shale Layers in Enhancing Mixing and Storage of Dissolved CO2

NASA Astrophysics Data System (ADS)

Illangasekare, T. H.; Agartan Karacaer, E.; Vargas-Johnson, J.; Cihan, A.; Birkholzer, J. T.

2017-12-01

It is expected that heterogeneity of the deep geologic formation to play a key role in both trapping of supercritical CO2 and its mixing in the formation brine. In previously reported research by the authors, a set of laboratory experiments and field-scale simulations were used to show that convective mixing and diffusion controlled trapping are two important mechanisms that contribute to the dissolution trapping in multilayered systems with homogeneous low-permeability zones such as shale. However, these low-permeability layers (e.g. shale) are not always homogeneous due to their composition and texture variations in addition to the presence of faults, fractures and fissures. In this study, we investigated the potential outcomes of heterogeneity present within these semi-confining low-permeability layers in regards to mixing and storage of dissolved CO2. An intermediate-scale laboratory experiment was designed to investigate the contribution of convective mixing, diffusion controlled trapping and back diffusion to long-term storage of dissolved CO2 in multilayered formations with heterogeneous low-permeability layers. The experiment was performed using a surrogate fluid combination to represent dissolved CO2 and brine under ambient pressure and temperature conditions. After verifying the numerical model with the experimental results, different distributions of the same low-permeability materials having similar volume ratios with the experimentally studied scenario were tested numerically. The experiment and modeling results showed that connectivity of higher permeability material within the semi-confining low-permeability layers contributes to mixing through brine leakage between upper and lower aquifers, storage through diffusion, and in the long term, back diffusion of stored mass due to reversed concentration gradient.

Observations of changes in the dissolved CO2 system in the North Sea, in four summers of the 2001-2011 decade

NASA Astrophysics Data System (ADS)

Clargo, Nicola; Salt, Lesley; Thomas, Helmuth; de Baar, Hein

2015-04-01

Since the industrial revolution, atmospheric concentrations of carbon dioxide (CO2) have risen dramatically, largely due to the combustion of fossil fuels, changes in land-use patterns and the production of cement. The oceans have absorbed a large amount of this CO2, with resulting impacts on ocean chemistry. Coastal seas play a significant role in the mitigation of anthropogenic atmospheric CO2 as they contribute approximately 10-30% of global primary productivity despite accounting for only 7% of the surface area. The North Sea is a perfect natural laboratory in which to study the CO2 system as it consists of two biogeochemically distinct regions displaying both oceanic and relatively coastal behaviour. It has also been identified as a continental shelf pump with respect to CO2, transporting it to the deeper waters of the North Atlantic. Large scale forcing has been shown to have a significant impact on the CO2 system over varying time scales, often masking the effects of anthropogenic influence. Here, we present data from the North Sea spanning the 2001-2011 decade. In order to investigate the dynamics of the dissolved CO2 system in this region in the face of climate change, four basin-wide cruises were conducted during the summers of 2001, 2005, 2008 and 2011. The acquired Dissolved Inorganic Carbon (DIC) and alkalinity data were then used to fully resolve the carbon system in order to assess trends over the 2001-2011 decade. We find significant interannual variability, but with a consistent, notable trend in decreasing pH. We found that surface alkalinity remained relatively constant over the decade, whereas DIC increased, indicating that the pH decline is DIC-driven. We also found that the partial pressure of CO2 (pCO2) increased faster than concurrent atmospheric CO2 concentrations, and that the CO2 buffering capacity of the North Sea decreased over the decade, with implications for future CO2 uptake.

Partial reactive crystallization of variable CO2-bearing siliceous MORB-eclogite-derived melt in fertile peridotite and genesis of alkalic basalts with signatures of crustal recycling

NASA Astrophysics Data System (ADS)

Mallik, A.; Dasgupta, R.

2013-12-01

The presence of heterogeneity in the form of recycled altered oceanic crust (MORB-eclogite) has been proposed in the source of HIMU ocean island basalts (OIBs) [1]. Partial melts of recycled oceanic crust, however, are siliceous and Mg-poor and thus do not resemble the major element compositions of alkalic OIBs that are silica-poor and Mg-rich. In an upwelling heterogenous mantle, MORB-eclogite undergoes melting deeper than volatile-free peridotite, hence, andesitic partial melt derived from eclogite will react with subsolidus peridotite. We have examined the effect of such a melt-rock reaction under volatile-free conditions at 1375 °C, 3 GPa by varying the melt-rock ratio from 8 to 50 wt.% [2]. We concluded that the reacted melts reproduce certain major element characteristics of oceanic basanites, but not nephelinites. Also, the melt-rock reaction produces olivine and garnet-bearing websteritic residue. Because presence of CO2 has been invoked in the source of many HIMU ocean islands, the effect of CO2 on such a melt-rock reaction needs to be evaluated. Accordingly, we performed reaction experiments on mixtures of 25% and 33% CO2-bearing andesitic partial melt and peridotite at 1375 °C, 3 GPa by varying the dissolved CO2 content of the reacting melts from 1 to 5 wt.% (bulk CO2 from 0.25 to 1.6 wt.%) [3, this study]. Owing to melt-rock reaction, with increasing CO2 in the bulk mixture, (a) modes of olivine and cpx decrease while melt, opx and garnet increase, (b) reacted melts evolve to greater degree of Si-undersaturation (from andesite through basanite to nephelinite), (c) enhanced crystallization of garnet take place with higher CO2 in the melt, reducing alumina content of the reacted melts, and (d) CaO and MgO content of the reacted melts increase, without affecting FeO* and Na2O contents (indicating greater propensity of Ca2+ and Mg2+ over Fe2+ and Na+ to enter silicate melt as carbonate). For a given melt-MgO, the CO2-bearing reacted melts are a better match for alkalic basalts in terms of SiO2, Al2O3, CaO and CaO/Al2O3 than the CO2-free ones [3]. Using the experimental data, we have further developed an empirical model to predict mineral modes in residue and reacted melt compositions for olivine-opx saturated lithologies as a function of melt:rock ratio and bulk CO2 content. For example, in case of 5 wt.% eclogite melt infiltrating in fertile peridotite, with bulk CO2 from 0 to 2 wt.%, the derivative melts show an increase in CaO and MgO from 11 to 16 wt.%, 15 to 24 wt.%, respectively and decrease in SiO2 and Al2O3 from 45 to 39 wt.% and 14 to 5 wt.%, respectively. From this model, we have created a major element composition space of MORB-eclogite-derived reactive melt mass vs. bulk CO2 and we predict that primary HIMU-type magmas require <5 to 10 wt.% of MORB-eclogite melt input and up to 0.8 wt.% bulk CO2 in their source. Our model also allows determining the residual lithology at the source of alkalic basalts, produced owing to eclogite melt-peridotite reaction with or without CO2. [1] Jackson & Dasgupta (2008) EPSL 276, 175-186. [2] Mallik & Dasgupta (2012) EPSL 329-330, 97-108. [3] Mallik & Dasgupta (in press) JPetrol.

Modelling of the dissolution and reprecipitation of uranium under oxidising conditions in the zone of shallow groundwater circulation.

PubMed

Dutova, Ekaterina M; Nikitenkov, Aleksei N; Pokrovskiy, Vitaly D; Banks, David; Frengstad, Bjørn S; Parnachev, Valerii P

2017-11-01

Generic hydrochemical modelling of a grantoid-groundwater system, using the Russian software "HydroGeo", has been carried out with an emphasis on simulating the accumulation of uranium in the aqueous phase. The baseline model run simulates shallow granitoid aquifers (U content 5 ppm) under conditions broadly representative of southern Norway and southwestern Siberia: i.e. temperature 10 °C, equilibrated with a soil gas partial CO 2 pressure (P CO2 , open system) of 10 -2.5 atm. and a mildly oxidising redox environment (Eh = +50 mV). Modelling indicates that aqueous uranium accumulates in parallel with total dissolved solids (or groundwater mineralisation M - regarded as an indicator of degree of hydrochemical evolution), accumulating most rapidly when M = 550-1000 mg L -1 . Accumulation slows at the onset of saturation and precipitation of secondary uranium minerals at M = c. 1000 mg L -1 (which, under baseline modelling conditions, also corresponds approximately to calcite saturation and transition to Na-HCO 3 hydrofacies). The secondary minerals are typically "black" uranium oxides of mixed oxidation state (e.g. U 3 O 7 and U 4 O 9 ). For rock U content of 5-50 ppm, it is possible to generate a wide variety of aqueous uranium concentrations, up to a maximum of just over 1 mg L -1 , but with typical concentrations of up to 10 μg L -1 for modest degrees of hydrochemical maturity (as indicated by M). These observations correspond extremely well with real groundwater analyses from the Altai-Sayan region of Russia and Norwegian crystalline bedrock aquifers. The timing (with respect to M) and degree of aqueous uranium accumulation are also sensitive to Eh (greater mobilisation at higher Eh), uranium content of rocks (aqueous concentration increases as rock content increases) and P CO2 (low P CO2 favours higher pH, rapid accumulation of aqueous U and earlier saturation with respect to uranium minerals). Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon isotope signature of dissolved inorganic carbon (DIC) in precipitation and atmospheric CO2.

PubMed

Górka, Maciej; Sauer, Peter E; Lewicka-Szczebak, Dominika; Jędrysek, Mariusz-Orion

2011-01-01

This paper describes results of chemical and isotopic analysis of inorganic carbon species in the atmosphere and precipitation for the calendar year 2008 in Wrocław (SW Poland). Atmospheric air samples (collected weekly) and rainwater samples (collected after rain episodes) were analysed for CO2 and dissolved inorganic carbon (DIC) concentrations and for δ13C composition. The values obtained varied in the ranges: atmospheric CO2: 337-448 ppm; δ13CCO2 from -14.4 to -8.4‰; DIC in precipitation: 0.6-5.5 mg dm(-3); δ13CDIC from -22.2 to +0.2‰. No statistical correlation was observed between the concentration and δ13C value of atmospheric CO2 and DIC in precipitation. These observations contradict the commonly held assumption that atmospheric CO2 controls the DIC in precipitation. We infer that DIC is generated in ambient air temperatures, but from other sources than the measured atmospheric CO2. The calculated isotopic composition of a hypothetical CO2 source for DIC forming ranges from -31.4 to -11.0‰, showing significant seasonal variations accordingly to changing anthropogenic impact and atmospheric mixing processes. Copyright © 2010 Elsevier Ltd. All rights reserved.

Implications for carbon processing beneath the Greenland Ice Sheet from dissolved CO2 and CH4 concentrations of subglacial discharge

NASA Astrophysics Data System (ADS)

Pain, A.; Martin, J.; Martin, E. E.

2017-12-01

Subglacial carbon processes are of increasing interest as warming induces ice melting and increases fluxes of glacial meltwater into proglacial rivers and the coastal ocean. Meltwater may serve as an atmospheric source or sink of carbon dioxide (CO2) or methane (CH4), depending on the magnitudes of subglacial organic carbon (OC) remineralization, which produces CO2 and CH4, and mineral weathering reactions, which consume CO2 but not CH4. We report wide variability in dissolved CO2 and CH4 concentrations at the beginning of the melt season (May-June 2017) between three sites draining land-terminating glaciers of the Greenland Ice Sheet. Two sites, located along the Watson River in western Greenland, drain the Isunnguata and Russell Glaciers and contained 1060 and 400 ppm CO2, respectively. In-situ CO2 flux measurements indicated that the Isunnguata was a source of atmospheric CO2, while the Russell was a sink. Both sites had elevated CH4 concentrations, at 325 and 25 ppm CH4, respectively, suggesting active anaerobic OC remineralization beneath the ice sheet. Dissolved CO2 and CH4 reached atmospheric equilibrium within 2.6 and 8.6 km downstream of Isunnguata and Russell discharge sites, respectively. These changes reflect rapid gas exchange with the atmosphere and/or CO2 consumption via instream mineral weathering. The third site, draining the Kiagtut Sermiat in southern Greenland, had about half atmospheric CO2 concentrations (250 ppm), but approximately atmospheric CH4 concentrations (2.1 ppm). Downstream CO2 flux measurements indicated ingassing of CO2 over the entire 10-km length of the proglacial river. CO2 undersaturation may be due to more readily weathered lithologies underlying the Kiagtut Sermiat compared to Watson River sites, but low CH4 concentrations also suggest limited contributions of CO2 and CH4 from OC remineralization. These results suggest that carbon processing beneath the Greenland Ice Sheet may be more variable than previously recognized. Variations control whether discharge is a source or sink of atmospheric CO2 or CH4, but gas concentrations could be further modified by instream reactions. Increased meltwater fluxes should enhance the importance of greenhouse gas fluxes from subglacial discharge, and heighten the need to constrain variability in subglacial carbon processing.

Passive Biobarrier for Treating Co-mingled Perchlorate and RDX in Groundwater at an Active Range

DTIC Science & Technology

2016-05-12

and Groundwater Temperature ............................. 102 6.1.2 Dissolved Oxygen (DO) and Oxidation Reduction Potential (ORP...22 or equivalent). Parameters, including temperature , conductivity, dissolved oxygen , oxidation-reduction potential (ORP), turbidity, and pH were...3% for temperature and specific conductivity, and ᝺% for dissolved oxygen , ORP, and turbidity. When parameters were stable according to the above

Usage of pumice as bulking agent in sewage sludge composting.

PubMed

Wu, Chuandong; Li, Weiguang; Wang, Ke; Li, Yunbei

2015-08-01

In this study, the impacts of reused and sucrose-decorated pumice as bulking agents on the composting of sewage sludge were evaluated in the lab-scale reactor. The variations of temperature, pH, NH3 and CO2 emission rate, moisture content (MC), volatile solid, dissolved organic carbon, C/N and the water absorption characteristics of pumice were detected during the 25days composting. The MC of pumice achieved 65.23% of the 24h water absorptivity within the first 2h at the mass ratio of 0.6:1 (pumice:sewage sludge). Reused pumice increased 23.68% of CO2 production and reduced 21.25% of NH3 emission. The sucrose-decorated pumice reduced 43.37% of nitrogen loss. These results suggested that adding pumice and sucrose-decorated pumice in sludge composting matrix could not only adjust the MC of materials, but also improve the degradation of organic matters and reduce nitrogen loss. Copyright © 2015 Elsevier Ltd. All rights reserved.

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

Management effects on greenhouse gas dynamics in fen ditches.

PubMed

Peacock, Mike; Ridley, Luke M; Evans, Chris D; Gauci, Vincent

2017-02-01

Globally, large areas of peatland have been drained through the digging of ditches, generally to increase agricultural production. By lowering the water table it is often assumed that drainage reduces landscape-scale emissions of methane (CH 4 ) into the atmosphere to negligible levels. However, drainage ditches themselves are known to be sources of CH 4 and other greenhouse gases (GHGs), but emissions data are scarce, particularly for carbon dioxide (CO 2 ) and nitrous oxide (N 2 O), and show high spatial and temporal variability. Here, we report dissolved GHGs and diffusive fluxes of CH 4 and CO 2 from ditches at three UK lowland fens under different management; semi-natural fen, cropland, and cropland restored to low-intensity grassland. Ditches at all three fens emitted GHGs to the atmosphere, but both fluxes and dissolved GHGs showed extensive variation both seasonally and within-site. CH 4 fluxes were particularly large, with medians peaking at all three sites in August at 120-230mgm -2 d -1 . Significant between site differences were detected between the cropland and the other two sites for CO 2 flux and all three dissolved GHGs, suggesting that intensive agriculture has major effects on ditch biogeochemistry. Multiple regression models using environmental and water chemistry data were able to explain 29-59% of observed variation in dissolved GHGs. Annual CH 4 fluxes from the ditches were 37.8, 18.3 and 27.2gCH 4 m -2 yr -1 for the semi-natural, grassland and cropland, and annual CO 2 fluxes were similar (1100 to 1440gCO 2 m -2 yr -1 ) among sites. We suggest that fen ditches are important contributors to landscape-scale GHG emissions, particularly for CH 4 . Ditch emissions should be included in GHG budgets of human modified fens, particularly where drainage has removed the original terrestrial CH 4 source, e.g. agricultural peatlands. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Gilbert, Kimberly; Bennett, Philip C.; Wolfe, Will

Dissolution of CO2 into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO2 entering the atmosphere. Ions in solution partially control the amount of CO2 that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO2 solubility is difficult to predict. In this study, CO2 solubility was experimentally determined in water, NaCl, CaCl2, Na2SO4, and NaHCO3 solutions and a mixed brine similar to the Bravo Dome natural CO2 reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO2 pressuresmore » to 35.5 MPa. Increasing ionic strength decreased CO2 solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO2 solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO2 was strongly correlated (R2 = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO2 solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO2 solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl2 brine and a natural Na+, Ca2+, Cl- type brine with minor amounts of Mg2+, K+, Sr2+ and Br-).« less

Phytoplankton Do Not Produce Carbon-Rich Organic Matter in High CO2 Oceans

NASA Astrophysics Data System (ADS)

Kim, Ja-Myung; Lee, Kitack; Suh, Young-Sang; Han, In-Seong

2018-05-01

The ocean is a substantial sink for atmospheric carbon dioxide (CO2) released as a result of human activities. Over the coming decades the dissolved inorganic C concentration in the surface ocean is predicted to increase, which is expected to have a direct influence on the efficiency of C utilization (consumption and production) by phytoplankton during photosynthesis. Here we evaluated the generality of C-rich organic matter production by examining the elemental C:N ratio of organic matter produced under conditions of varying pCO2. The data used in this analysis were obtained from a series of pelagic in situ pCO2 perturbation studies that were performed in the diverse ocean regions and involved natural phytoplankton assemblages. The C:N ratio of the resulting particulate and dissolved organic matter did not differ across the range of pCO2 conditions tested. In particular, the ratio for particulate organic C and N was found to be 6.58 ± 0.05, close to the theoretical value of 6.6.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

NASA Astrophysics Data System (ADS)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

Hydro-geochemical impact of CO2 leakage from geological storage on shallow potable aquifers: A field scale pilot experiment.

NASA Astrophysics Data System (ADS)

Cahill, A.; Jakobsen, R.

2012-04-01

In order to assess the environmental implications of leakage of CO2 from a geological sequestration site into overlying shallow potable aquifers, a 3 month field release experiment is planned to commence in spring 2012 at Vrøgum plantation, Western Denmark. To test the injection and sampling methodologies and as a study of short term effects, a pilot experiment was conducted at the field site: 45 kg of food grade CO2 was injected at 10 m depth over 48 hours into an unconfined, aeolian/glacial sand aquifer and the effects on water chemistry studied. The CO2 was injected through an inclined well installed with a 1 m length of porous polyethylene well screen (20 µm pore size) initially at a rate of 5 litres per minute increasing to 10 litres per minute after 24 hours. Water samples were taken from a network of multi-level sample points (8, 4 and 2.4m depth) before, during and after the injection and measured for physico-chemical parameters and major/trace element composition. Although the site possesses a relatively high hydraulic conductivity (12-16 m/day), due to the small hydraulic gradient (0.0039) 6 days elapsed before effects of CO2 on the ground water were detected in the first sampling point located 0.5 m down flow from the injection well. The dissolved plume of CO2 was observed only in the 8 m depth sample points and moved with flow (approximately 0.10 - 0.12 m/day). The plume spread laterally to 2m width as little as 1 m from the injection screen after 26 days, indicating that CO2 bubbles change the hydraulics of the medium. Dissolved CO2 was not detected in sample points at 4 or 2.4 m depth at any time during the experiment, suggesting gas could not move into the slightly finer grained upper sand. Effects of CO2 dissolution at 8 m depth were manifest as a clear and stable increase in electrical conductivity (approximately 160 to 300 µS/cm), a relatively small increase in total dissolved ions (approximately 30 to 50 mg/l) and an unstable depression of pH (approximately 5.8 to 4.73). The dissolved CO2 plume evolved with a distinct maximal front observed to pass through sample points followed by a slowly dissipating tail. After 56 days the CO2 plume reached the end of the monitoring network and was at its greatest extent (5 m length by 1 m width) however still appeared to be increasing in size suggesting residual gas phase CO2 trapped within the pore space continuously dissolving. Water quality did not significantly deteriorate and only small increases in major and trace elements were observed. Overall, groundwater chemistry results indicate that for an aquifer composed primarily of slowly reacting silicate sediments, such as Vrøgum, the risks to water resources from a short term leak from CCS into shallow overlying aquifers are minimal. However, a potential accumulation effect within the plume front as it moves through the formation was observed inferring a large scale leak may develop a CO2 charged plume exceeding guideline values for major and trace elements.

The Gelation of CO(2): A Sustainable Route to the Creation of Microcellular Materials.

PubMed

Shi; Huang; Kilic; Xu; Enick; Beckman; Carr; Melendez; Hamilton

1999-11-19

Compounds with strong thermodynamic affinity for carbon dioxide (CO(2)) have been designed and synthesized that dissolve in CO(2), then associate to form gels. Upon removal of the CO(2), these gels produced free-standing foams with cells with an average diameter smaller than 1 micrometer and a bulk density reduction of 97 percent relative to the parent material.

The predominance of young carbon in Arctic whole-lake CH4 and CO2 emissions and implications for Boreal yedoma lakes.

NASA Astrophysics Data System (ADS)

Elder, C.; Xu, X.; Walker, J. C.; Walter Anthony, K. M.; Pohlman, J.; Arp, C. D.; Townsend-Small, A.; Hinkel, K. M.; Czimczik, C. I.

2017-12-01

Lakes in Arctic and Boreal regions are hotspots for atmospheric exchange of the greenhouse gases CO2 and CH4. Thermokarst lakes are a subset of these Northern lakes that may further accelerate climate warming by mobilizing ancient permafrost C (> 11,500 years old) that has been disconnected from the active C cycle for millennia. Northern lakes are thus potentially powerful agents of the permafrost C-climate feedback. While they are critical for projecting the magnitude and timing these feedbacks from the rapidly warming circumpolar region, we lack datasets capturing the diversity of northern lakes, especially regarding their CH4contributions to whole-lake C emissions and their ability to access and mobilize ancient C. We measured the radiocarbon (14C) ages of CH4 and CO2 emitted from 60 understudied lakes and ponds in Arctic and Boreal Alaska during winter and summer to estimate the ages of the C sources yielding these gases. Integrated mean ages for whole-lake emissions were inferred from the 14C-age of dissolved gases sampled beneath seasonal ice. Additionally, we measured concentrations and 14C values of gases emitted by ebullition and diffusion in summer to apportion C emission pathways. Using a multi-sourced mass balance approach, we found that whole-lake CH4 and CO2 emissions were predominantly sourced from relatively young C in most lakes. In Arctic lakes, CH4 originated from 850 14C-year old C on average, whereas dissolved CO2 was sourced from 400 14C-year old C, and represented 99% of total dissolved C flux. Although ancient C had a minimal influence (11% of total emissions), we discovered that lakes in finer-textured aeolian deposits (Yedoma) emitted twice as much ancient C as lakes in sandy regions. In Boreal, yedoma-type lakes, CH4 and CO2 were fueled by significantly older sources, and mass balance results estimated CH4-ebullition to comprise 50-60% of whole-lake CH4 emissions. The mean 14C-age of Boreal emissions was 6,000 14C-years for CH4-C, and 2,400 14C-years for CO2-C. Seasonal differences in dissolved CH4 revealed a clear influence of trapped ebullition dissolving into the water below lake ice in Boreal, but not Arctic lakes. Together, our data demonstrate that regional surficial geology exerts a larger control than climate on C ages and gas emission pathways from lakes.

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

Jennings, Ryan de Montmollin; Moran, James J.; Jay, Zackary J.

Biological fixation of CO 2 is the primary mechanism of C reduction in natural systems, and provides a diverse suite of organic compounds utilized by chemoorganoheterotrophs. The extent and mechanisms of CO 2 fixation were evaluated across a comprehensive set of high-temperature, chemotrophic microbial communities in Yellowstone National Park by combining metagenomic and stable 13C isotope analyses. Fifteen geothermal sites representing three distinct habitat types (iron-oxide mats, anoxic sulfur sediments, and filamentous ‘streamer’ communities) were investigated. Genes of the 3-hydroxypropionate/4-hydroxybutyrate, dicarboxylate/4-hydroxybutyrate, and reverse tricarboxylic acid CO 2 fixation pathways were identified in assembled genome sequence corresponding to the predominant Crenarchaeotamore » and Aquificales observed across this habitat range. Stable 13C analyses of dissolved inorganic and organic C (DIC, DOC), and possible landscape C sources were used to interpret the 13C content of microbial community samples. Isotope mixing models showed that the minimum amounts of autotrophic C in microbial biomass were > 50 % in the majority of communities analyzed, but were also dependent on the amounts of heterotrophy and/or accumulation of landscape C. Furthermore, the significance of CO 2 as a C source in these communities provides a foundation for understanding metabolic linkages among autotrophs and heterotrophs, community assembly and succession, and the likely coevolution of deeply-branching thermophiles.« less

Evaluation of the Giggenbach bottle method using artificial fumarolic gases

NASA Astrophysics Data System (ADS)

Lee, S.; Jeong, H. Y.

2013-12-01

Volcanic eruption is one of the most dangerous natural disasters. Mt. Baekdu, located on the border between North Korea and China, has been recently showing multiple signs of its eruption. The magmatic activity of a volcano strongly affects the composition of volcanic gases, which can provide a useful tool for predicting the eruption. Among various volcanic gas monitoring methods, the Giggenbach bottle method involves the on-site sampling of volcanic gases and the subsequent laboratory analysis, thus making it possible to detect a range of volcanic gases at low levels. In this study, we aim to evaluate the effectiveness of the Giggenbach bottle method and develop the associated analytical tools using artificial fumarolic gases with known compositions. The artificial fumarolic gases are generated by mixing CO2, CO, H2S, SO2, Ar, and H2 gas streams with a N2 stream sparged through an acidic medium containing HCl and HF. The target compositions of the fumarolic gases are selected to cover those reported for various volcanoes under different tectonic environments as follows: CO2 (2-12 mol %), CO (0.3-1 mol %), H2S (0.7-2 mol %), SO2 (0.6-4 mol %), Ar (0.3-0.7 mol %), H2 (0.3-0.7 mol %), HCl (0.2-1 mol %), and HF (< 0.015 mol %). The artificial fumarolic gases are collected into an evacuated bottle partially filled with 4 M NaOH solution containing 0.5 mM Cd(CH3COO)2. While non-condensable components such as CO, Ar, H2, and N2 accumulate in the headspace of the bottle, acidic components including CO2, SO2, HCl, and HF dissolve into the alkaline solution. In case of H2S, it reacts with dissolved Cd2+ to precipitate as CdS(s). The gas accumulated in the headspace can be analyzed for CO, Ar, H2, and N2 on a gas chromatography. The alkaline solution is first separated from yellowish CdS precipitates by filtration, and then pretreated with hydrogen peroxide to oxidize dissolved SO2 (H2SO3) to SO42-. The resultant solution can be analyzed for SO2 as SO42-, HCl as Cl-, and HF as F- on an ion chromatography and CO2 on an ionic carbon analyzer. Also, the amount of H2S can be determined by measuring the remaining dissolved Cd2+ on an inductively coupled plasma-mass spectrometry.

Alteration of rhyolite in CO{sub 2} charged water at 200 and 350{degree}C: The unreactivity of CO{sub 2} at higher temperature

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

Bischoff, J.L.; Rosenbauer, R.J.

1996-10-01

Geochemical and hydrologic modeling indicates that geothermal waters in the T > 270{degrees}C reservoirs beneath Yellowstone National Park have HCO{sub 3} {much_lt} Cl and contrast with waters in reservoirs at lower temperatures which attain HCO{sub 3} about equal to Cl. Experiments reacting rhyolite with 0.5 molal solutions of CO{sub 2} at 200{degrees} and 350{degrees}C were carried out to test the hypothesis of Fournier to explain the chemistry of these springs: that CO{sub 2} is relatively unreactive with volcanic rocks at temperatures >270{degrees}C. The experimental results strongly support this hypothesis. Extent of alteration is twenty-seven times greater at 200{degrees}C than atmore » 350{degrees}C. The dominant process in the experiments appears to be the alteration of the albitic component of the rhyolite by dissolved CO{sub 2} to form a kaolinite-like alteration product plus quartz: 2NaAlSi{sub 3}O{sub 8} + 2CO{sub 2} + 3H{sub 2}O = 2Na{sup +} + 2HCO{sub 3}{sup -} + Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4} + 4SiO{sub 2}. CO{sub 2} reacts with water to form H{sub 2}CO{sub 3} which dissociates to H{sup +} and HCO{sub 3}{sup -}, more so at lower temperatures. Kinetic and thermodynamic considerations suggest that the reactivity of H{sub 2}CO{sub 3} with wallrocks is at its maximum between 150{degrees} and 200{degrees}C, consuming most of the H{sup +} and liberating equivalent amounts of cations and bicarbonate. Wallrocks in higher temperature reservoirs are relatively unreactive to dissolved CO{sub 2} which is eventually lost from the system by boiling. These observations also offer a possible explanation for the change in chemical sediments from chloride-dominated to bicarbonate-dominated salts found in the stratigraphic section at Searles Lake, California, the terminus of the Owens River which derives its dissolved load from hot springs of the Long Valley caldera. 21 refs., 5 figs., 2 tabs.« less

Simultaneous and continuous measurements of dissolved CO2, CH4, N2O and CO in rivers using Fourier-Transform-InfraRed (FTIR) spectrometry

NASA Astrophysics Data System (ADS)

Warneke, Thorsten; Müller, Denise; Caldow, Christopher; Rixen, Tim; Notholt, Justus

2015-04-01

We have coupled a Fourier-Transform InfraRed (FTIR) trace gas analyser to an equilibrator, which allows the simultaneous and continuous measurement of dissolved CO2, CH4, N2O and CO in water. The FTIR-technique has a high precision over a wide range of concentrations, making it very suitable for the measurement of these gases in freshwater systems. We have employed this measurement system on a commercial river barge on the Elbe river (Czech Republic, Germany) and on a fisher boat in the coastal area of Sarawak (Malaysia). In addition we have performed stationary continuous measurements at a small river in Northern Germany over the duration of 3 months. The presentation will outline the advantages and disadvantages of the FTIR-technique for freshwater measurements and will present results from the measurement campaigns.

CO2 solubility and speciation in rhyolitic sediment partial melts at 1.5-3.0 GPa - Implications for carbon flux in subduction zones

NASA Astrophysics Data System (ADS)

Duncan, Megan S.; Dasgupta, Rajdeep

2014-01-01

Partial melts of subducting sediments are thought to be critical agents in carrying trace elements and water to arc basalt source regions. Sediment partial melts may also act as a carrier of CO2. However, the CO2 carrying capacity of natural rhyolitic melts that derive from partial fusion of downgoing sediment at sub-arc depths remains unconstrained. We conducted CO2-solubility experiments on a rhyolitic composition similar to average, low-degree experimental partial melt of pelitic sediments between 1.5 and 3.0 GPa at 1300 °C and containing variable water content. Concentrations of water and carbon dioxide were measured using FTIR. Molecular CO2(CO2mol.) and carbonate anions (CO32-) both appear as equilibrium species in our experimental melts. Estimated total CO2 concentrations (CO2mol.+CO32-) increased with increasing pressure and water content. At 3.0 GPa, the bulk CO2 solubility are in the range of ∼1-2.5 wt.%, for melts with H2O contents between 0.5 and 3.5 wt.%. For melts with low H2O content (∼0.5 wt.%), CO2mol. is the dominant carbon species, while in more H2O-rich melts CO32- becomes dominant. The experimentally determined, speciation-specific CO2 solubilities yielded thermodynamic parameters that control dissolution of CO2 vapor both as CO2mol. and as CO32- in silicate melt for each of our compositions with different water content; CO2vapor ↔CO2melt :lnK0=-15 to -18, ΔV0 = 29 to 14 cm3 mol-1 and CO2vapor +Omelt →CO32-melt :lnK0=-20 to -14, ΔV0 = 9 to 27 cm3 mol-1, with ΔV0 of reaction being larger for formation of CO2mol. in water-poor melts and for formation of CO32- in water-rich melts. Our bulk CO2 solubility data, [CO2] (in wt.%) can be fitted as a function of pressure, P (in GPa) and melt water content, [H2O] (in wt.%) with the following function: [CO2](wt.%)=(-0.01108[H2O]+0.03969)P2+(0.10328[H2O]+0.41165)P. This parameterization suggests that over the range of sub-arc depths of 72-173 km, water-rich sediment partial melt may carry as much as 2.6-5.5 wt.% CO2 to the sub-arc mantle source regions. At saturation, 1.6-3.3 wt.% sediment partial melt relative to the mantle wedge is therefore sufficient to bring up the carbon budget of the mantle wedge to produce primary arc basalts with 0.3 wt.% CO2. Sediment plumes in mantle wedge: Sediment plumes or diapirs may form from the downgoing slab because the sediment layer atop the slab is buoyant relative to the overlying, hanging wall mantle (Currie et al., 2007; Behn et al., 2011). Via this process, sediment layers with carbonates would carry CO2 to the arc source region. Owing to the higher temperature in the mantle wedge, carbonate can breakdown. Behn et al. (2011) suggested that sediment layers as thin as 100 m, appropriate for modern arcs, could form sediment diapirs. They predicted that diapirs would form from the slab in the sub-arc region for most subduction zones today without requiring hydrous melting. H2O-rich fluid driven carbonate breakdown: Hydrous fluid flushing of the slab owing to the breakdown of hydrous minerals could drive carbonate breakdown (Kerrick and Connolly, 2001b; Grove et al., 2002; Gorman et al., 2006). The addition of water would cause decarbonation creating an H2O-CO2-rich fluid that would then flux through the overlying sediment layer, lower the solidus temperature, and trigger melting. Recent geochemical (Cooper et al., 2012) and geodynamic (van Keken, 2003; Syracuse et al., 2010) constraints suggest that the sub-arc slab top temperatures are above the hydrous fluid-present sediment solidus, thus in the presence of excess fluid, both infiltration induced decarbonation and sediment melting may occur. Hot subduction: This is relevant for subduction zones such as Cascadia and Mexico, where slab-surface temperatures are estimated to be higher (Syracuse et al., 2010). A higher temperature could cause carbonate breakdown and sediment partial melting without requiring a hydrous fluid flux. In this case a relatively dry silicate sediment melt will have the opportunity to dissolve and carry CO2. For hot subduction zones, even if sedimentary layer itself does not carry carbonate, CO2 released from basalt-hosted carbonates may be dissolved in sediment partial melt. Experiments conducted on subducted sediment compositions show that the partial melt compositions are generally rhyolitic (Johnson and Plank, 1999; Hermann and Green, 2001; Schmidt et al., 2004; Auzanneau et al., 2006; Hermann and Spandler, 2008; Spandler et al., 2010; Tsuno and Dasgupta, 2011). Therefore, solubility of CO2 in rhyolitic sediment partial melts needs to be known. Previous studies on rhyolitic melts experimentally determined CO2 solubility from 0.05 to 0.66 GPa (Fig. 1; Fogel and Rutherford, 1990; Blank et al., 1993; Tamic et al., 2001). This pressure range is not appropriate for global sub-arc depth range of 72-173 km (Syracuse and Abers, 2006) settings (P = 2-5 GPa). Carbon dioxide solubility experiments at pressures from 1.5 to 3.5 GPa are available but only on simple compositions - i.e., albite, which does not have the chemical complexity of natural sediment partial melts (Fig. 1; Brey, 1976; Mysen, 1976; Mysen et al., 1976; Mysen and Virgo, 1980; Stolper et al., 1987; Brooker et al., 1999). For example, natural rhyolitic melt derived from partial fusion of pelitic sediments contain non-negligible concentrations of Ca2+, Mg2+, Fe2+. Many of these studies were also conducted under mixed-volatile conditions (CO2 + H2O) with H2O contents from 0.06 to 3.3 wt.%. These studies were used in calculating various solubility models: Volatile-Calc (Newman and Lowenstern, 2002), that of Liu et al. (2005), and that of Papale et al. (2006). Volatile-Calc can be used to calculate CO2 solubility only on a generic rhyolite composition up to 0.5 GPa. The model of Liu et al. (2005) is also on a generic rhyolite up to 0.5 GPa, but can calculate mixed volatile concentrations provided the vapor composition is known. The model of Papale et al. (2006) can be used to calculate mixed volatile concentrations for a melt composition of interest, but only up to 1.0 GPa.The literature data show that CO2 solubility increases with increasing pressure and decreases with increasing melt silica content (decreasing NBO/T; e.g., Brooker et al., 2001). The effect of temperature remains somewhat ambiguous, but is thought to be relatively smaller than the pressure or compositional effects, with Mysen (1976) measuring increasing CO2 solubility with temperature for albite melt, Brooker et al. (2001) and Fogel and Rutherford (1990) noticing decreasing CO2 solubility with increasing temperature, and Stolper et al. (1987) concluding that temperature has essentially no effect on total melt CO2 concentration at saturation. The presence of water in the melt also is known to affect CO2 solution (e.g., Mysen, 1976; Eggler and Rosenhauer, 1978), yet quantitative effect of water on CO2 solution in natural rhyolitic melt has only been investigated up to 0.5 GPa (Tamic et al., 2001). In order to determine the CO2 carrying capacity of sediment partial melts, experiments must be conducted at conditions (pressure, temperature, major element compositions, and XH2O) relevant to sub-arc settings.In this study we measured the solubility and speciation of CO2 in rhyolitic sediment partial melts. Experiments were conducted from 1.5 to 3.0 GPa at 1300 °C with variable water contents and synthesized glasses were analyzed for water and carbon speciation using Fourier-transformed infrared spectroscopy. Our measured solubility data allowed us to constrain volume change and equilibrium constant of the CO2 dissolution reactions. Moreover, we parameterize CO2 solubility in sediment partial melt as a function of pressure and melt water content. Our data and empirical model suggest that the CO2 carrying capacity of sediment partial melts is sufficiently high at sub-arc depths and hydrous sediment melt can potentially carry the necessary dose of CO2 to arc mantle source regions.

Divergent biophysical controls of aquatic CO2 and CH4 in the World’s two largest rivers

PubMed Central

Borges, Alberto V.; Abril, Gwenaël; Darchambeau, François; Teodoru, Cristian R.; Deborde, Jonathan; Vidal, Luciana O.; Lambert, Thibault; Bouillon, Steven

2015-01-01

Carbon emissions to the atmosphere from inland waters are globally significant and mainly occur at tropical latitudes. However, processes controlling the intensity of CO2 and CH4 emissions from tropical inland waters remain poorly understood. Here, we report a data-set of concurrent measurements of the partial pressure of CO2 (pCO2) and dissolved CH4 concentrations in the Amazon (n = 136) and the Congo (n = 280) Rivers. The pCO2 values in the Amazon mainstem were significantly higher than in the Congo, contrasting with CH4 concentrations that were higher in the Congo than in the Amazon. Large-scale patterns in pCO2 across different lowland tropical basins can be apprehended with a relatively simple statistical model related to the extent of wetlands within the basin, showing that, in addition to non-flooded vegetation, wetlands also contribute to CO2 in river channels. On the other hand, dynamics of dissolved CH4 in river channels are less straightforward to predict, and are related to the way hydrology modulates the connectivity between wetlands and river channels. PMID:26494107

A hybrid intelligent method for three-dimensional short-term prediction of dissolved oxygen content in aquaculture

PubMed Central

Yu, Huihui; Cheng, Yanjun; Cheng, Qianqian; Li, Daoliang

2018-01-01

A precise predictive model is important for obtaining a clear understanding of the changes in dissolved oxygen content in crab ponds. Highly accurate interval forecasting of dissolved oxygen content is fundamental to reduce risk, and three-dimensional prediction can provide more accurate results and overall guidance. In this study, a hybrid three-dimensional (3D) dissolved oxygen content prediction model based on a radial basis function (RBF) neural network, K-means and subtractive clustering was developed and named the subtractive clustering (SC)-K-means-RBF model. In this modeling process, K-means and subtractive clustering methods were employed to enhance the hyperparameters required in the RBF neural network model. The comparison of the predicted results of different traditional models validated the effectiveness and accuracy of the proposed hybrid SC-K-means-RBF model for three-dimensional prediction of dissolved oxygen content. Consequently, the proposed model can effectively display the three-dimensional distribution of dissolved oxygen content and serve as a guide for feeding and future studies. PMID:29466394

Integrated Framework for Assessing Impacts of CO₂ Leakage on Groundwater Quality and Monitoring-Network Efficiency: Case Study at a CO₂ Enhanced Oil Recovery Site.

PubMed

Yang, Changbing; Hovorka, Susan D; Treviño, Ramón H; Delgado-Alonso, Jesus

2015-07-21

This study presents a combined use of site characterization, laboratory experiments, single-well push-pull tests (PPTs), and reactive transport modeling to assess potential impacts of CO2 leakage on groundwater quality and leakage-detection ability of a groundwater monitoring network (GMN) in a potable aquifer at a CO2 enhanced oil recovery (CO2 EOR) site. Site characterization indicates that failures of plugged and abandoned wells are possible CO2 leakage pathways. Groundwater chemistry in the shallow aquifer is dominated mainly by silicate mineral weathering, and no CO2 leakage signals have been detected in the shallow aquifer. Results of the laboratory experiments and the field test show no obvious damage to groundwater chemistry should CO2 leakage occur and further were confirmed with a regional-scale reactive transport model (RSRTM) that was built upon the batch experiments and validated with the single-well PPT. Results of the RSRTM indicate that dissolved CO2 as an indicator for CO2 leakage detection works better than dissolved inorganic carbon, pH, and alkalinity at the CO2 EOR site. The detection ability of a GMN was assessed with monitoring efficiency, depending on various factors, including the natural hydraulic gradient, the leakage rate, the number of monitoring wells, the aquifer heterogeneity, and the time for a CO2 plume traveling to the monitoring well.

Chemical and stable isotopic composition of water and gas in the Fort Union Formation of the Powder River Basin, Wyoming and Montana: Evidence for water/rock interaction and the biogenic origin of coalbed natural gas

USGS Publications Warehouse

Rice, Cynthia A.; Flores, Romeo M.; Stricker, Gary D.; Ellis, Margaret S.

2008-01-01

Significant amounts (> 36 million m3/day) of coalbed methane (CBM) are currently being extracted from coal beds in the Paleocene Fort Union Formation of the Powder River Basin of Wyoming and Montana. Information on processes that generate methane in these coalbed reservoirs is important for developing methods that will stimulate additional production. The chemical and isotopic compositions of gas and ground water from CBM wells throughout the basin reflect generation processes as well as those that affect water/rock interaction. Our study included analyses of water samples collected from 228 CBM wells. Major cations and anions were measured for all samples, δDH2O and δ18OH2O were measured for 199 of the samples, and δDCH4 of gas co-produced with water was measured for 100 of the samples. Results show that (1) water from Fort Union Formation coal beds is exclusively Na–HCO3-type water with low dissolved SO4 content (median < 1 mg/L) and little or no dissolved oxygen (< 0.15 mg/L), whereas shallow groundwater (depth generally < 120 m) is a mixed Ca–Mg–Na–SO4–HCO3 type; (2) water/rock interactions, such as cation exchange on clay minerals and precipitation/dissolution of CaCO3 and SO4 minerals, account for the accumulation of dissolved Na and depletion of Ca and Mg; (3) bacterially-mediated oxidation–reduction reactions account for high HCO3 (270–3310 mg/L) and low SO4 (median < 0.15 mg/L) values; (4) fractionation between δDCH4 (− 283 to − 328 per mil) and δDH2O (− 121 to − 167 per mil) indicates that the production of methane is primarily by biogenic CO2 reduction; and (5) values of δDH2O and δ18OH2O (− 16 to − 22 per mil) have a wide range of values and plot near or above the global meteoric water line, indicating that the original meteoric water has been influenced by methanogenesis and by being mixed with surface and shallow groundwater.

Reviews and Syntheses: Ocean acidification and its potential impacts on marine ecosystems

NASA Astrophysics Data System (ADS)

Mostofa, Khan M. G.; Liu, Cong-Qiang; Zhai, WeiDong; Minella, Marco; Vione, Davide; Gao, Kunshan; Minakata, Daisuke; Arakaki, Takemitsu; Yoshioka, Takahito; Hayakawa, Kazuhide; Konohira, Eiichi; Tanoue, Eiichiro; Akhand, Anirban; Chanda, Abhra; Wang, Baoli; Sakugawa, Hiroshi

2016-03-01

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO2 that adds up with dissolved inorganic carbon (dissolved CO2, H2CO3, HCO3-, and CO32-) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO2 itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different timescales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena.

Reviews and Syntheses: Ocean acidification and its potential impacts on marine ecosystems

NASA Astrophysics Data System (ADS)

Mostofa, K. M. G.; Liu, C.-Q.; Zhai, W. D.; Minella, M.; Vione, D.; Gao, K.; Minakata, D.; Arakaki, T.; Yoshioka, T.; Hayakawa, K.; Konohira, E.; Tanoue, E.; Akhand, A.; Chanda, A.; Wang, B.; Sakugawa, H.

2015-07-01

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO2 that adds up with dissolved inorganic carbon (dissolved CO2, H2CO3, HCO3-, and CO32-) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO2 itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different time scales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena.

Dynamics of planktonic prokaryotes and dissolved carbon in a subtropical coastal lake.

PubMed

Fontes, Maria Luiza S; Tonetta, Denise; Dalpaz, Larissa; Antônio, Regina V; Petrucio, Maurício M

2013-01-01

To understand the dynamics of planktonic prokaryotes in a subtropical lake and its relationship with carbon, we conducted water sampling through four 48-h periods in Peri Lake for 1 year. Planktonic prokaryotes were characterized by the abundance and biomass of heterotrophic bacteria (HB) and of cyanobacteria (coccoid and filamentous cells). During all samplings, we measured wind speed, water temperature (WT), pH, dissolved oxygen (DO), precipitation, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and carbon dioxide (CO2). DOC was higher in the summer (average = 465 μM - WT = 27°C) and lower in the winter (average = 235 μM - WT = 17°C), with no significant variability throughout the daily cycles. CO2 concentrations presented a different pattern, with a minimum in the warm waters of the summer period (8.31 μM) and a maximum in the spring (37.13 μM). Daily trends were observed for pH, DO, WT, and CO2. At an annual scale, both biological and physical-chemical controls were important regulators of CO2. HB abundance and biomass were higher in the winter sampling (5.60 × 10(9) cells L(-1) and 20.83 μmol C L(-1)) and lower in the summer (1.87 × 10(9) cells L(-1) and 3.95 μmol C L(-1)). Filamentous cyanobacteria (0.23 × 10(8)-0.68 × 10(8) filaments L(-1)) produced up to 167.16 μmol C L(-1) as biomass (during the warmer period), whereas coccoid cyanobacteria contributed only 0.38 μmol C L(-1). Precipitation, temperature, and the biomass of HB were the main regulators of CO2 concentrations. Temperature had a negative effect on the concentration of CO2, which may be indirectly attributed to high heterotroph activity in the autumn and winter periods. DOC was positively correlated with the abundance of total cyanobacteria and negatively with HB. Thus, planktonic prokaryotes have played an important role in the dynamics of both dissolved inorganic and organic carbon in the lake.

Dynamics of Planktonic Prokaryotes and Dissolved Carbon in a Subtropical Coastal Lake

PubMed Central

Fontes, Maria Luiza S.; Tonetta, Denise; Dalpaz, Larissa; Antônio, Regina V.; Petrucio, Maurício M.

2013-01-01

To understand the dynamics of planktonic prokaryotes in a subtropical lake and its relationship with carbon, we conducted water sampling through four 48-h periods in Peri Lake for 1 year. Planktonic prokaryotes were characterized by the abundance and biomass of heterotrophic bacteria (HB) and of cyanobacteria (coccoid and filamentous cells). During all samplings, we measured wind speed, water temperature (WT), pH, dissolved oxygen (DO), precipitation, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and carbon dioxide (CO2). DOC was higher in the summer (average = 465 μM – WT = 27°C) and lower in the winter (average = 235 μM – WT = 17°C), with no significant variability throughout the daily cycles. CO2 concentrations presented a different pattern, with a minimum in the warm waters of the summer period (8.31 μM) and a maximum in the spring (37.13 μM). Daily trends were observed for pH, DO, WT, and CO2. At an annual scale, both biological and physical-chemical controls were important regulators of CO2. HB abundance and biomass were higher in the winter sampling (5.60 × 109 cells L−1 and 20.83 μmol C L−1) and lower in the summer (1.87 × 109 cells L−1 and 3.95 μmol C L−1). Filamentous cyanobacteria (0.23 × 108–0.68 × 108 filaments L−1) produced up to 167.16 μmol C L−1 as biomass (during the warmer period), whereas coccoid cyanobacteria contributed only 0.38 μmol C L−1. Precipitation, temperature, and the biomass of HB were the main regulators of CO2 concentrations. Temperature had a negative effect on the concentration of CO2, which may be indirectly attributed to high heterotroph activity in the autumn and winter periods. DOC was positively correlated with the abundance of total cyanobacteria and negatively with HB. Thus, planktonic prokaryotes have played an important role in the dynamics of both dissolved inorganic and organic carbon in the lake. PMID:23579926

Combined effects of acidification and hypoxia on the estuarine ctenophore, Mnemiopsis leidyi

EPA Science Inventory

Estuaries are transitive zones which experience large fluctuations in environmental parameters (temperature, dissolved oxygen, pH, etc.). The interactive effects of reduced dissolved oxygen (DO) and elevated pCO2 on estuarine organisms is not currently well understood. Ctenophore...

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Evaluation of CO2 Efflux From Soils: A New Method Using Streamwater CO2 Measurements, Field Data and a Watershed Model

NASA Astrophysics Data System (ADS)

Sullivan, A. B.; Mulholland, P. J.; Jones, J. B.

2001-05-01

Headwater streams are almost always supersaturated with CO2 compared to concentrations expected in equilibrium with atmospheric CO2. Direct measurements of CO2 in two streams in eastern Tennessee with different bedrock lithologies (Walker Branch, Upper Gum Hollow Branch) over a year revealed levels of supersaturation of two to five times atmospheric CO2. Highest levels were generally found during the summer months. Springs discharging into the stream had dissolved CO2 concentration up to an order of magnitude higher than that in streamwater. These levels of supersaturation are a reflection of the high concentrations of CO2 in soil produced by root respiration and organic matter decomposition. The hydrologic connection between soil CO2 and streamwater CO2 forms the basis of our method to determine soil CO2 concentrations and efflux from the soil to the atmosphere. The method starts with streamwater measurements of CO2. Then corrections are made for evasion from the stream surface using injections of a conservative solute tracer and volatile gas, and for instream metabolism using a dissolved oxygen change technique. The approach then works backward along the hydrologic flowpath and evaluates the contribution of bedrock weathering, which consumes CO2, by examining the changes in major ion chemistry between precipitation and the stream. This produces estimates of CO2 concentration in soil water and soil atmosphere, which when coupled with soil porosity, allows estimation of CO2 efflux from soil. The hydrologic integration of CO2 signals from whole watersheds into streamwater allows calculation of soil CO2 efflux at large scales. These estimates are at scales larger than current chamber or tower methods, and can provide broad estimates of soil CO2 efflux with easily collected stream chemistry data.

Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.

1992-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

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.

Photodegradation of fresh terrigenous organic matter contributes to the heterotrophy of boreal aquatic ecosystems in Quebec (Canada)

NASA Astrophysics Data System (ADS)

Plouhinec, J.; Lucotte, M. M.; Ouellet, A.; Gelinas, Y.

2012-12-01

The processes that fuel heterotrophy and thus contribute to CO2 production in lakes and reservoirs of the boreal region in Quebec are still not fully understood. To shed light on some of the factors controlling heterotrophy, we evaluated the importance of photodechemical mineralization of dissolved organic mater relative to other sources of CO2 production in six natural or human-perturbed lakes through logging on their watersheds and two reservoirs of the Quebec boreal forest over a period of 1.5 year. Rates of CO2 production in the water column were measured through incubation/irradiation experiments, using a series of filtrations to isolate the effects of photochemical mineralization, bacterial respiration, and planktonic respiration. Total CO2 fluxes measured in this study compared well to total diffusive fluxes measured through the traditional thin boundary layer method, thus validating our incubation approach. We calculated the daily integrated production of CO2 through photochemical mineralization (DIPMCO2) of dissolved organic matter over the entire water column using the calculation of the spectrum yield (Φλ). DIPMCO2 appeared as a robust indicator strongly correlated to the absorption coefficient of chromophoric dissolved organic matter (CDOM) at 360 nm (R2=0.81, p<0.01). DIPMCO2 accounts for 15% ± 14% of the total diffusive flux of CO2 to the atmosphere, independently of water body type or perturbation level. Our data also suggests that photochemical mineralization and photosynthesis processes are strongly correlated (R2=0.79, p<0.01), which is due to the fact that the strong photosynthetically active radiation (PAR) attenuation derives from a terrestrial organic matter (TOM) input into the water column. Also, the total diffusive fluxes of CO2 towards the atmosphere (fCO2) are correlated to the DIPMCO2 values (R2=0.49, p<0.01). We have evaluated theoretical CO2 fluxes emitted from the photic zone (f°CO2 ) by photochemical mineralization, bacterial respiration and CO2 consumption by phosynthesis based on measurements obtained from incubation/irradiation experiments. Finally, the relationship between fCO2 and the theoretical CO2 fluxes after production and consumption of CO2 considered only in the epilimnitic zone (R2=0.97, p<0.01) shows that, independently of the environmental conditions, the passive CO2 fluxes are approximately equal to 10 mmol.CO2.m-2.d-1.

Ancient low–molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw

USGS Publications Warehouse

Drake, Travis W.; Wickland, Kimberly P.; Spencer, Robert G. M.; McKnight, Diane M.; Striegl, Robert G.

2015-01-01

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high–temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low–molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters.

Ancient low-molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw.

PubMed

Drake, Travis W; Wickland, Kimberly P; Spencer, Robert G M; McKnight, Diane M; Striegl, Robert G

2015-11-10

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high-temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low-molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters.

Ancient low–molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw

PubMed Central

Drake, Travis W.; Wickland, Kimberly P.; Spencer, Robert G. M.; McKnight, Diane M.; Striegl, Robert G.

2015-01-01

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high–temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low–molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters. PMID:26504243

Factors Influencing Greenhouse Gas Emissions from Three Gorges Reservoir of China

NASA Astrophysics Data System (ADS)

Zhao, Y.; Zhao, X.; Wu, B.; Zeng, Y.

2013-05-01

Three gorges reservoir (TGR) of China located in a subtropical climate region. It has attracted tremendous attentions on greenhouse gas (GHG) emissions from TGR, including carbon dioxide (CO2), methane (CH4) and nitrous Oxide (N2O). Results on monthly fluxes and their spatial and seasonal variations have been determined by a static chamber method and have published elsewhere recently. Here we made further discussions on the factors influencing GHG emissions from TGR. We conclude that the hydrodynamic situation was the key parameter controlling the fluxes. TGR was a typical valley-type reservoir and with a complex terrain in the surrounding catchment, where almost 94% of the region was occupied by mountainous, this situation made the reservoir had sufficient allochthonous organic carbon input origin from eroded soil. But no significant relationship between organic carbon (both dissolved and particulate form) and GHG fluxes, we thought that TGR was not a carbon-limited reservoir on the GHG issue. In the mainstream of the reservoir, dissolved CO2 and CH4 were supersaturation in the water, the relative high flow together with the narrow-deep channel result in great disturbance, which would promote more dissolved gas escape into the atmosphere. This could also approved by the differences in CO2 and CH4 fluxes in different reach from up to downstream of the reservoir. In the reservoir tail water, the mainstream remained the high flow rate, both CO2 and CH4 fluxes is relative high, while downwards, the fluxes were gradually dropped, as after the impoundment of the reservoir, flow rate have greatly decreased. Another evidence was the relative higher CO2 and CH4 fluxes in the rainy season. As the rainy season approaches, TGR would empty the storage to prepare for retention and mitigation. The interplay between water inflows and outflows produced marked variations in the water residence times. During the rainy season times, this could be as short as 6 days with higher water flow rate which would also cause higher disturbance, while for other periods of a year, the reservoir would act more like a lake and residence times could exceed 30 days. Meanwhile the manipulate of the reservoir made the water column not only well mixed top to bottom for most of the year, but also the complete water column has high dissolved oxygen concentrations (> 6 mg/L). Only in April and May is there substantial temperature stratification in mainstream and tributaries. The high dissolved oxygen concentrations even in the deepest parts of the TGR storage minimize the scope for sediment anoxia and less GHG was produced, especially for CH4. In the tributaries, the totally different hydrodynamic situation made these regions a different GHG emission dynamics. After the impoundment, water velocity had greatly decreased, these regions showed more Limnology characteristics compared to the mainstream. This made the tributaries prone to algal blooms which would great affect the surface GHG fluxes, especially for CO2, which would consume the dissolved CO2 in water and cause the intake of atmospheric CO2.

A simple high-performance matrix-free biomass molten carbonate fuel cell without CO2 recirculation.

PubMed

Lan, Rong; Tao, Shanwen

2016-08-01

In previous reports, flowing CO2 at the cathode is essential for either conventional molten carbonate fuel cells (MCFCs) based on molten carbonate/LiAlO2 electrolytes or matrix-free MCFCs. For the first time, we demonstrate a high-performance matrix-free MCFC without CO2 recirculation. At 800°C, power densities of 430 and 410 mW/cm(2) are achieved when biomass-bamboo charcoal and wood, respectively-is used as fuel. At 600°C, a stable performance is observed during the measured 90 hours after the initial degradation. In this MCFC, CO2 is produced at the anode when carbon-containing fuels are used. The produced CO2 then dissolves and diffuses to the cathode to react with oxygen in open air, forming the required [Formula: see text] or [Formula: see text] ions for continuous operation. The dissolved [Formula: see text] ions may also take part in the cell reactions. This provides a simple new fuel cell technology to directly convert carbon-containing fuels such as carbon and biomass into electricity with high efficiency.

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

NASA Astrophysics Data System (ADS)

Federico, C.; Aiuppa, A.; Allard, P.; Bellomo, S.; Jean-Baptiste, P.; Parello, F.; Valenza, M.

2002-03-01

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius. Vesuvius groundwaters are dilute (mean TDS ˜ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ 18O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or 18O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO 2-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions. The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both 13C/ 12C and 3He/ 4He measurements indicate the contribution of a magmatic component with a δ 13C ˜ 0‰ and R/R a of ˜2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts. A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO 2 release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO 2 depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.

Carbon dioxide adsorption in Brazilian coals

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

Jose Luciano Soares; Andre L.B. Oberziner; Humberto J. Jose

Carbon dioxide (CO{sub 2}) is one of the most important greenhouse gases. In the period between 1980 and 1998, CO{sub 2} emissions increased more than 21% and projections suggest that the emissions will continue to increase globally by 2.2% between 2000 and 2020 and 3.3% in the developed countries. The sequestration of CO{sub 2} in deep unminable coal beds is one of the more promising of several methods of geological sequestration that are currently being investigated. CO{sub 2} can adsorb onto coal, and there are several studies demonstrating that CO{sub 2} dissolves in coals and swells them. At very lowmore » pressures (P {lt} 1 bar), CO{sub 2} dissolution does not seem to be a problem; however, high pressures are necessary for CO{sub 2} sequestration (P {gt} 50 bar). In this study, we evaluated the kinetics and equilibrium of sorption of CO{sub 2} on Brazilian coals at low pressures. The adsorption equilibrium isotherm at room temperature (30{sup o}C) was measured through the static method. The results showed that the Freundlich model or the Langmuir model is suitable to describe the equilibrium experimental results. The CO{sub 2} adsorption capacity of Brazilian coals are in the range of 0.089-0.186 mmol CO{sub 2}/g, which are typical values for coals with high ash content. The dynamics of adsorption in a fixed-bed column that contains granular coal (particle sizes of 0.8, 2.4, and 4.8 mm) showed that the adsorption rate is fast and a mathematical model was developed to describe the CO{sub 2} dynamics of the adsorption in a fixed-bed column. The linear driving force (LDF) was used to describe the rate of adsorption and the mass-transfer constants of the LDF model (K{sub s}) are in the range of 1.0-2.0 min{sup -1}. 29 refs., 5 figs., 3 tabs.« less

The Effects of Varying Crustal Carbonate Composition on Assimilation and CO2 Degassing at Arc Volcanoes

NASA Astrophysics Data System (ADS)

Carter, L. B.; Holmes, A. K.; Dasgupta, R.; Tumiati, S.

2015-12-01

Magma-crustal carbonate interaction and subsequent decarbonation can provide an additional source of CO2 release to the exogenic system superimposed on mantle-derived CO2. Carbonate assimilation at present day volcanoes is often modeled by limestone consumption experiments [1-4]. Eruptive products, however, do not clearly display the characteristic ultracalcic melt compositions produced during limestone-magma interaction [4]. Yet estimated CO2outflux [5] and composition of volcanics in many volcanic systems may allow ~3-17% limestone- or dolostone-assimilated melt contribution. Crystallization may retain ultracalcic melts in pyroxenite cumulates. To extend our completed study on limestone assimilation, here we explore the effect of varying composition from calcite to dolomite on chemical and thermal decarbonation efficiency of crustal carbonates. Piston cylinder experiments at 0.5 GPa and 900-1200 °C demonstrate that residual mineralogy during interaction with magma shifts from CaTs cpx and anorthite/scapolite in the presence of calcite to Di cpx and Fo-rich olivine with dolomite. Silica-undersaturated melts double in magnesium content, while maintaining high (>30 wt.%) CaO values. At high-T, partial thermal breakdown of dolomite into periclase and CO2 is minimal (<5%) suggesting that in the presence of magma, CO2 is primarily released due to assimilation. Assimilated melts at identical P-T conditions depict similarly high volatile contents (10-20 wt.% by EMPA deficit at 0.5 GPa, 1150 °C with hydrous basalt) with calcite or dolomite. Analysis of the coexisting fluid phase indicates the majority of water is dissolved in the melt, while CO2 released from the carbonate is preferentially partitioned into the vapor. This suggests that although assimilated melts have a higher CO2 solubility, most of the CO2can easily degas from the vapor phase at arc volcanoes, possibly more so at volcanic plumbing systems traversing dolomite [8]. [1]Conte et al 2009 EuJMin (21) 763-782; [2]Iacono-Marziano et al 2008 CMP (155) 719-738; [3]Mollo et al 2010 Lithos (114) 503-514; [4]Carter and Dasgupta 2015 EPSL (427) 202-214; [5]Burton et al 2013 RevMinGeochem (75) 323-254; [6]Balassone et al 2013 Lithos (160-161) 84-97; [7]Di Rocco et al. 2012 JPet (53) 2307-2332; [8]Del Moro et al 2001 JVGR (112) 15-24.

Forsterite [Mg 2 SiO 4 )] Carbonation in Wet Supercritical CO 2 : An in Situ High-Pressure X-ray Diffraction Study

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

Todd Schaef, Herbert; McGrail, Bernard P.; Loring, John L.

2013-01-02

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolutionmore » studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.« less

Potential evaluation of CO2 storage and enhanced oil recovery of tight oil reservoir in the Ordos Basin, China.

PubMed

Tian, Xiaofeng; Cheng, Linsong; Cao, Renyi; Zhang, Miaoyi; Guo, Qiang; Wang, Yimin; Zhang, Jian; Cui, Yu

2015-07-01

Carbon -di-oxide (CO2) is regarded as the most important greenhouse gas to accelerate climate change and ocean acidification. The Chinese government is seeking methods to reduce anthropogenic CO2 gas emission. CO2 capture and geological storage is one of the main methods. In addition, injecting CO2 is also an effective method to replenish formation energy in developing tight oil reservoirs. However, exiting methods to estimate CO2 storage capacity are all based on the material balance theory. This was absolutely correct for normal reservoirs. However, as natural fractures widely exist in tight oil reservoirs and majority of them are vertical ones, tight oil reservoirs are not close. Therefore, material balance theory is not adaptive. In the present study, a new method to calculate CO2 storage capacity is presented. The CO2 effective storage capacity, in this new method, consisted of free CO2, CO2 dissolved in oil and CO2 dissolved in water. Case studies of tight oil reservoir from Ordos Basin was conducted and it was found that due to far lower viscosity of CO2 and larger solubility in oil, CO2 could flow in tight oil reservoirs more easily. As a result, injecting CO2 in tight oil reservoirs could obviously enhance sweep efficiency by 24.5% and oil recovery efficiency by 7.5%. CO2 effective storage capacity of Chang 7 tight oil reservoir in Longdong area was 1.88 x 10(7) t. The Chang 7 tight oil reservoir in Ordos Basin was estimated to be 6.38 x 10(11) t. As tight oil reservoirs were widely distributed in Songliao Basin, Sichuan Basin and so on, geological storage capacity of CO2 in China is potential.

Carbon Fluxes in Dissolved and Gaseous Forms for a Restored Peatland in British Columbia, Canada

NASA Astrophysics Data System (ADS)

D'Acunha, B.; Johnson, M. S.; Lee, S. C.; Christen, A.

2016-12-01

Peatlands are wetlands where gross primary production exceeds organic matter decomposition causing an accumulation of partially decomposed matter, also called peat. These ecosystems can accumulate more carbon than tropical rainforests. However, dissolved and gaseous fluxes of carbon (as dissolved organic carbon (DOC), CO2 and methane (CH4)) must also be considered to determine if these ecosystems are net sinks or sources of greenhouse gases (GHGs) to the atmosphere, which depends in part on the environmental conditions and the state of the ecosystem. We conducted research in Burns Bog, Delta, BC, Canada, a raised domed peat bog located in the Fraser River Delta and one of the largest raised peat bogs on the west coast of the Americas, but which has been heavily impacted by a range of human activities. Currently, ecological restoration efforts are underway by a large-scale ditch blocking program, with the aim to re-establish a high water table. This is approached in partnership with research on the ecosystem services that the bog provides, including its role in a regional GHG inventory. Here we present data on ecosystem-scale fluxes of CO2 and CH4 determined by eddy covariance (EC) on a floating tower platform, and complementary data on (i) evasion fluxes of CO2, CH4 and nitrous oxide (N2O) from the water surface to the atmosphere, and (ii) the flux and composition of dissolved organic carbon in water draining Burns Bog. Concentrations of dissolved CO2, CH4 and N2O were determined by headspace equilibration, and evasion rates from the water surface were quantified and are used to estimate the role of the hydrosphere in the ecosystem-scale measurements. Water samples collected from five saturated areas in the flux tower footprint were analyzed for DOC concentrations and composition. Results indicated that, even though the whole system is a net C sink, the water surface behaved as a source of CO2 and CH4, and a sink for N2O throughout the study period. Drainage waters were high in DOC (> 30 mg L-1). DOC export was found to offset about 20% of the apparent net C uptake determined by EC, indicating that the EC system overestimates carbon accumulation by not accounting for DOC drainage.

A review of the contrasting behavior of two magmatic volatiles: Chlorine and carbon dioxide

USGS Publications Warehouse

Lowenstern, J. B.

2000-01-01

Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts. (C) 2000 Elsevier Science B.V. All rights reserved.Chlorine (Cl) and carbon dioxide (CO2) are common magmatic volatiles with contrasting behaviors. CO2 solubility increases with pressure whereas Cl solubility shows relatively little pressure or temperature effect. CO2 speciation changes with silicate melt composition, dissolving as carbonate in basaltic magmas and molecular CO2 in more silicic compositions. In H2O-bearing systems, the strongly non-ideal behavior of alkali chlorides causes unmixing of the volatile phase to form a H2O-rich vapor and a hydrosaline phase with important implications for the maximum concentration of Cl in magmas. Addition of CO2 to magma hastens immiscibility at crustal pressures (<500 MPa), inducing the formation of CO2-rich vapors and Cl-rich hydrosaline melts.

Sensitivity of chemical weathering and dissolved carbon dynamics to hydrological conditions in a typical karst river

PubMed Central

Zhong, Jun; Li, Si-liang; Tao, Faxiang; Yue, Fujun; Liu, Cong-Qiang

2017-01-01

To better understand the mechanisms that hydrological conditions control chemical weathering and carbon dynamics in the large rivers, we investigated hydrochemistry and carbon isotopic compositions of dissolved inorganic carbon (DIC) based on high-frequency sampling in the Wujiang River draining the carbonate area in southwestern China. Concentrations of major dissolved solute do not strictly follow the dilution process with increasing discharge, and biogeochemical processes lead to variability in the concentration-discharge relationships. Temporal variations of dissolved solutes are closely related to weathering characteristics and hydrological conditions in the rainy seasons. The concentrations of dissolved carbon and the carbon isotopic compositions vary with discharge changes, suggesting that hydrological conditions and biogeochemical processes control dissolved carbon dynamics. Biological CO2 discharge and intense carbonate weathering by soil CO2 should be responsible for the carbon variability under various hydrological conditions during the high-flow season. The concentration of DICbio (DIC from biological sources) derived from a mixing model increases with increasing discharge, indicating that DICbio influx is the main driver of the chemostatic behaviors of riverine DIC in this typical karst river. The study highlights the sensitivity of chemical weathering and carbon dynamics to hydrological conditions in the riverine system. PMID:28220859

Terrestrial C sequestration at elevated CO2 and temperature: the role of dissolved organic N loss

USGS Publications Warehouse

Rastetter, Edward B.; Perakis, Steven S.; Shaver, Gaius R.; Agren, Goran I.

2005-01-01

We used a simple model of carbon–nitrogen (C–N) interactions in terrestrial ecosystems to examine the responses to elevated CO2 and to elevated CO2 plus warming in ecosystems that had the same total nitrogen loss but that differed in the ratio of dissolved organic nitrogen (DON) to dissolved inorganic nitrogen (DIN) loss. We postulate that DIN losses can be curtailed by higher N demand in response to elevated CO2, but that DON losses cannot. We also examined simulations in which DON losses were held constant, were proportional to the amount of soil organic matter, were proportional to the soil C:N ratio, or were proportional to the rate of decomposition. We found that the mode of N loss made little difference to the short‐term (<60 years) rate of carbon sequestration by the ecosystem, but high DON losses resulted in much lower carbon sequestration in the long term than did low DON losses. In the short term, C sequestration was fueled by an internal redistribution of N from soils to vegetation and by increases in the C:N ratio of soils and vegetation. This sequestration was about three times larger with elevated CO2 and warming than with elevated CO2 alone. After year 60, C sequestration was fueled by a net accumulation of N in the ecosystem, and the rate of sequestration was about the same with elevated CO2 and warming as with elevated CO2alone. With high DON losses, the ecosystem either sequestered C slowly after year 60 (when DON losses were constant or proportional to soil organic matter) or lost C (when DON losses were proportional to the soil C:N ratio or to decomposition). We conclude that changes in long‐term C sequestration depend not only on the magnitude of N losses, but also on the form of those losses.

Dissolved oxygen content prediction in crab culture using a hybrid intelligent method

PubMed Central

Yu, Huihui; Chen, Yingyi; Hassan, ShahbazGul; Li, Daoliang

2016-01-01

A precise predictive model is needed to obtain a clear understanding of the changing dissolved oxygen content in outdoor crab ponds, to assess how to reduce risk and to optimize water quality management. The uncertainties in the data from multiple sensors are a significant factor when building a dissolved oxygen content prediction model. To increase prediction accuracy, a new hybrid dissolved oxygen content forecasting model based on the radial basis function neural networks (RBFNN) data fusion method and a least squares support vector machine (LSSVM) with an optimal improved particle swarm optimization(IPSO) is developed. In the modelling process, the RBFNN data fusion method is used to improve information accuracy and provide more trustworthy training samples for the IPSO-LSSVM prediction model. The LSSVM is a powerful tool for achieving nonlinear dissolved oxygen content forecasting. In addition, an improved particle swarm optimization algorithm is developed to determine the optimal parameters for the LSSVM with high accuracy and generalizability. In this study, the comparison of the prediction results of different traditional models validates the effectiveness and accuracy of the proposed hybrid RBFNN-IPSO-LSSVM model for dissolved oxygen content prediction in outdoor crab ponds. PMID:27270206

Dissolved oxygen content prediction in crab culture using a hybrid intelligent method.

PubMed

Yu, Huihui; Chen, Yingyi; Hassan, ShahbazGul; Li, Daoliang

2016-06-08

A precise predictive model is needed to obtain a clear understanding of the changing dissolved oxygen content in outdoor crab ponds, to assess how to reduce risk and to optimize water quality management. The uncertainties in the data from multiple sensors are a significant factor when building a dissolved oxygen content prediction model. To increase prediction accuracy, a new hybrid dissolved oxygen content forecasting model based on the radial basis function neural networks (RBFNN) data fusion method and a least squares support vector machine (LSSVM) with an optimal improved particle swarm optimization(IPSO) is developed. In the modelling process, the RBFNN data fusion method is used to improve information accuracy and provide more trustworthy training samples for the IPSO-LSSVM prediction model. The LSSVM is a powerful tool for achieving nonlinear dissolved oxygen content forecasting. In addition, an improved particle swarm optimization algorithm is developed to determine the optimal parameters for the LSSVM with high accuracy and generalizability. In this study, the comparison of the prediction results of different traditional models validates the effectiveness and accuracy of the proposed hybrid RBFNN-IPSO-LSSVM model for dissolved oxygen content prediction in outdoor crab ponds.

Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

PubMed Central

Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge, J.; Bonneville, S.; Benning, L. G.; Romero-Gonzalez, M. E.; Leake, J. R.; Banwart, S. A.

2015-01-01

Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using 14CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle. PMID:26197714

Oxalate secretion by ectomycorrhizal Paxillus involutus is mineral-specific and controls calcium weathering from minerals

NASA Astrophysics Data System (ADS)

Schmalenberger, A.; Duran, A. L.; Bray, A. W.; Bridge, J.; Bonneville, S.; Benning, L. G.; Romero-Gonzalez, M. E.; Leake, J. R.; Banwart, S. A.

2015-07-01

Trees and their associated rhizosphere organisms play a major role in mineral weathering driving calcium fluxes from the continents to the oceans that ultimately control long-term atmospheric CO2 and climate through the geochemical carbon cycle. Photosynthate allocation to tree roots and their mycorrhizal fungi is hypothesized to fuel the active secretion of protons and organic chelators that enhance calcium dissolution at fungal-mineral interfaces. This was tested using 14CO2 supplied to shoots of Pinus sylvestris ectomycorrhizal with the widespread fungus Paxillus involutus in monoxenic microcosms, revealing preferential allocation by the fungus of plant photoassimilate to weather grains of limestone and silicates each with a combined calcium and magnesium content of over 10 wt.%. Hyphae had acidic surfaces and linear accumulation of weathered calcium with secreted oxalate, increasing significantly in sequence: quartz, granite < basalt, olivine, limestone < gabbro. These findings confirmed the role of mineral-specific oxalate exudation in ectomycorrhizal weathering to dissolve calcium bearing minerals, thus contributing to the geochemical carbon cycle.

Volatile Concentrations in Pyroclastic Obsidian: Two Case Studies

NASA Astrophysics Data System (ADS)

Wearn, K. M.; Cashman, K. V.; Wallace, P. J.

2002-12-01

Pyroclastic obsidian is abundant in fall deposits associated with Mt. Mazama's Cleetwood eruption and South Sister's Rock Mesa eruption. Measured concentrations of H2Ototal and CO2 in >300 obsidian samples from these two eruptions provide important information about both the style of degassing (open- vs. closed-system) and changes in eruptive conditions through the course of both eruptions. Obsidian clasts preserve a range of total H2O contents, with samples from lower stratigraphic levels displaying a wider range of water concentrations than those from the uppermost tephra layer sampled. All samples from the Cleetwood section contain <=1 wt% water, with those from the top of that deposit containing <0.4 wt%. Obsidian from the basal ash layer of the subsequent climactic eruption contains 0.1 - 0.8 wt% water. Obsidian fragments from the Rock Mesa eruption show a broader range in H2Ototal contents (from 0.1 to >3 wt%) than those from the Cleetwood eruption. At Rock Mesa, maximum total water contents generally decrease with increased stratigraphic height. However, this decrease is not strictly monotonic: fluctuations in maximum total water contents correspond to stratigraphic unit boundaries. In addition, the Rock Mesa event produced abundant obsidian with very low H2Ototal concentrations throughout the eruption. Dissolved molecular CO2 levels are below the detection limit in all of the Cleetwood and Mazama samples. This is not surprising, given the low initial CO2 measured in Cleetwood and Mazama melt inclusions by Bacon et al. (1992). CO2 concentrations in the Rock Mesa clasts range from <5 ppm to ~44 ppm, and are positively correlated with H2Ototal concentrations. Fluorine concentrations in Cleetwood and Mazama climactic obsidian clasts vary between ~510 and ~695 ppm, with climactic samples averaging slightly lower concentrations than Cleetwood samples. Fluorine concentrations in Rock Mesa obsidians are uniformly low (~300 to ~510 ppm). Chlorine contents of Cleetwood and Mazama climactic samples range from ~1400 ppm to ~1610 ppm. The Rock Mesa samples all contain less chlorine (~510 to ~1120 ppm) than the Cleetwood and climactic samples, and in the Rock Mesa obsidian, chlorine and total water are positively correlated. Stratigraphic variations in the volatile contents of pyroclastic obsidian support previous work suggesting that obsidian forms along the margins of the volcanic conduit and is eroded from the conduit walls by fragmenting magma. Both the Cleetwood and the Rock Mesa deposits indicate initial evacuation of shallow vanguard magma followed by a rapid increase in fragmentation depth. Both deposits also show a gradual decrease in the fragmentation depth through time, consistent with subsequent effusive activity in both cases. More puzzling is the apparent closed-system degassing trend defined by the H2O-CO2-Cl relations in the Rock Mesa obsidian samples, despite the loss of volatiles required for obsidian formation. This suggests that volatile data may also provide information on the relative time scales of volatile exsolution and loss and obsidian formation.

Effect of the temperature and the CO2 concentration on the behaviour of the citric acid as a scale inhibitor of CaCO3

NASA Astrophysics Data System (ADS)

Blanco, K.; Aponte, H.; Vera, E.

2017-12-01

For all Industrial sector is important to extend the useful life of the materials that they use in their process, the scales of CaCO3 are common in situation where fluids are handled with high concentration of ions and besides this temperatures and CO2 concentration dissolved, that scale generates large annual losses because there is a reduction in the process efficiency or corrosion damage under deposit, among other. In order to find new alternatives to this problem, the citric acid was evaluated as scale of calcium carbonate inhibition in critical condition of temperature and concentration of CO2 dissolved. Once the results are obtained it was carried out the statistical evaluation in order to generate an equation that allow to see that behaviour, giving as result, a good efficiency of inhibition to the conditions evaluated the scales of products obtained were characterized through scanning electron microscopy.

An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2017-06-01

The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink

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

Moon, Gun-Hee; Shin, Yongsoon; Arey, Bruce W.

An eco-friendly and economical method for the formation of uniform-sized carbon spheres by hydrothermal dehydration/condensation of a commercial carbonated beverage at 200 oC is reported. CO2 dissolved in the beverage accelerates the dehydration kinetics of the dissolved sugar molecules leading to production of homogeneous carbon spheres having a diameter less than 850 nm. In the presence of CO2, the rough surface of these carbon spheres likely results from continuous Ostwald ripening of constituent microscopic carbon-containing spheres that are formed by subsequent polymerization of intermediate HMF molecules.

Solubility trapping in formation water as dominant CO(2) sink in natural gas fields.

PubMed

Gilfillan, Stuart M V; Lollar, Barbara Sherwood; Holland, Greg; Blagburn, Dave; Stevens, Scott; Schoell, Martin; Cassidy, Martin; Ding, Zhenju; Zhou, Zheng; Lacrampe-Couloume, Georges; Ballentine, Chris J

2009-04-02

Injecting CO(2) into deep geological strata is proposed as a safe and economically favourable means of storing CO(2) captured from industrial point sources. It is difficult, however, to assess the long-term consequences of CO(2) flooding in the subsurface from decadal observations of existing disposal sites. Both the site design and long-term safety modelling critically depend on how and where CO(2) will be stored in the site over its lifetime. Within a geological storage site, the injected CO(2) can dissolve in solution or precipitate as carbonate minerals. Here we identify and quantify the principal mechanism of CO(2) fluid phase removal in nine natural gas fields in North America, China and Europe, using noble gas and carbon isotope tracers. The natural gas fields investigated in our study are dominated by a CO(2) phase and provide a natural analogue for assessing the geological storage of anthropogenic CO(2) over millennial timescales. We find that in seven gas fields with siliciclastic or carbonate-dominated reservoir lithologies, dissolution in formation water at a pH of 5-5.8 is the sole major sink for CO(2). In two fields with siliciclastic reservoir lithologies, some CO(2) loss through precipitation as carbonate minerals cannot be ruled out, but can account for a maximum of 18 per cent of the loss of emplaced CO(2). In view of our findings that geological mineral fixation is a minor CO(2) trapping mechanism in natural gas fields, we suggest that long-term anthropogenic CO(2) storage models in similar geological systems should focus on the potential mobility of CO(2) dissolved in water.

Evasion of CO2 from streams - the dominant component of the carbon export through the aquatic conduit in a boreal landscape.

PubMed

Wallin, Marcus B; Grabs, Thomas; Buffam, Ishi; Laudon, Hjalmar; Agren, Ånneli; Öquist, Mats G; Bishop, Kevin

2013-03-01

Evasion of gaseous carbon (C) from streams is often poorly quantified in landscape C budgets. Even though the potential importance of the capillary network of streams as C conduits across the land-water-atmosphere interfaces is sometimes mentioned, low-order streams are often left out of budget estimates due to being poorly characterized in terms of gas exchange and even areal surface coverage. We show that evasion of C is greater than all the total dissolved C (both organic and inorganic) exported downstream in the waters of a boreal landscape. In this study evasion of carbon dioxide (CO2 ) from running waters within a 67 km(2) boreal catchment was studied. During a 4 year period (2006-2009) 13 streams were sampled on 104 different occasions for dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). From a locally determined model of gas exchange properties, we estimated the daily CO2 evasion with a high-resolution (5 × 5 m) grid-based stream evasion model comprising the entire ~100 km stream network. Despite the low areal coverage of stream surface, the evasion of CO2 from the stream network constituted 53% (5.0 (±1.8) g C m(-2)  yr(-1) ) of the entire stream C flux (9.6 (±2.4) g C m(-2)  yr(-1) ) (lateral as DIC, DOC, and vertical as CO2 ). In addition, 72% of the total CO2 loss took place already in the first- and second-order streams. This study demonstrates the importance of including CO2 evasion from low-order boreal streams into landscape C budgets as it more than doubled the magnitude of the aquatic conduit for C from this landscape. Neglecting this term will consequently result in an overestimation of the terrestrial C sink strength in the boreal landscape. © 2012 Blackwell Publishing Ltd.

Coral reefs will transition to net dissolving before end of century

NASA Astrophysics Data System (ADS)

Eyre, Bradley D.; Cyronak, Tyler; Drupp, Patrick; De Carlo, Eric Heinen; Sachs, Julian P.; Andersson, Andreas J.

2018-02-01

Ocean acidification refers to the lowering of the ocean’s pH due to the uptake of anthropogenic CO2 from the atmosphere. Coral reef calcification is expected to decrease as the oceans become more acidic. Dissolving calcium carbonate (CaCO3) sands could greatly exacerbate reef loss associated with reduced calcification but is presently poorly constrained. Here we show that CaCO3 dissolution in reef sediments across five globally distributed sites is negatively correlated with the aragonite saturation state (Ωar) of overlying seawater and that CaCO3 sediment dissolution is 10-fold more sensitive to ocean acidification than coral calcification. Consequently, reef sediments globally will transition from net precipitation to net dissolution when seawater Ωar reaches 2.92 ± 0.16 (expected circa 2050 CE). Notably, some reefs are already experiencing net sediment dissolution.

Modeling pulsed soil respiration in an African savanna ecosystem

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

Fan, Zhaosheng; Neff, Jason C.; Hanan, Niall P.

2015-01-01

Savannas cover 60% of the African continent and play an important role in the global carbon (C) emissions from fire and land use. To better characterize the biophysical controls over soil respiration in these settings, half-hourly observations of volumetric soil-water content, temperature, and the concentration of carbon dioxide (CO2) at different soil depths were continually measured from 2005 to 2007 under trees ("sub-canopy") and between trees ("inter-canopy") in a savanna vegetation near Skukuza, Kruger National Park, South Africa. The measured soil climate and CO2 concentration data were assimilated into a process-based model that estimates the CO2 production and flux withmore » coupled dynamics of dissolved organic C (DOC) and microbial biomass C. Our results show that temporal and spatial variations in CO2 flux were strongly influenced by precipitation and vegetation cover, with two times greater CO2 flux in the subcanopy plots (similar to 2421 g CO2 m(-2) yr(-1)) than in the inter-canopy plots (similar to 1290 g CO2 m(-2) yr(-1)). Precipitation influenced soil respiration by changing soil temperature and moisture; however, our modeling analysis suggests that the pulsed response of soil respiration to precipitation events (known as "Birch effect") is a key control on soil fluxes at this site. At this site, "Birch effect" contributed to approximately 50% and 65% of heterotrophic respiration or 20% and 39% of soil respiration in the sub-canopy and inter-canopy plots, respectively. These results suggest that pulsed response of respiration to precipitation events is an important component of the C cycle of savannas and should be considered in both measurement and modeling studies of carbon exchange in similar ecosystems. (C) 2014 Elsevier B.V. All rights reserved.« less

Distribution of dissolved green-house gases (CO2, CH4, N2O) in Lakes Edward and George: Results from the first field cruise of the HIPE project

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Morana, Cédric D. T.; Lambert, Thibault; Okello, William; Bouillon, Steven

2017-04-01

Inland waters (streams, rivers, lakes, reservoirs) are quantitatively important components of the global budgets of atmospheric emissions of long-lived greenhouse gases (GHGs) (CO2, CH4, N2O). Available data indicate that a very large fraction of CO2 and CH4 emissions from rivers and reservoirs occurs at tropical latitudes. Data on GHGs at tropical latitudes from lakes however are much more scarse, and the relative importance of emissions, in particular in Africa, remains to be determined. Large tropical lakes are net autotrophic (hence potentially sinks for atmospheric CO2) due generally low dissolved organic carbon concentrations, seasonally near constant light and temperature conditions, and generally deep water columns favourable for export of organic matter to depth. This sharply contrasts with their much better documented temperate and boreal counterparts, usually considered as CO2 sources to the atmosphere sustained by net heterotrophy. Here, we report a data-set of dissolved CO2, CH4, N2O obtained in October 2016 in Lakes Edward and George and adjacent streams and crater lakes in the frame of Belgian Science Policy (BELSPO) HIPE (Human impacts on ecosystem health and resources of Lake Edward, http://www.co2.ulg.ac.be/hipe/) project. Lake George and part of Lake Edward were sinks for atmospheric CO2 and N2O due to high primary production and denitrification in sediments, respectively, and modest sources of CH4 to the atmosphere. Sampled rivers and streams were oversaturated in CO2 and CH4 and close to atmospheric equilibrium with regards to N2O. Spatial variations within rivers and streams were related to elevation and vegetation characteristics on the catchments (savannah versus forest). Levels of CO2, CH4, and N2O were within the range of those we reported in other African rivers. Crater lakes acted as sinks for atmospheric CO2 and N2O but were extremely over-saturated in CH4, due to intense primary production sustained by cyanobacteria. These CH4 levels were much higher than what we have reported in other lakes and reservoirs elsewhere in Sub-Saharan Africa.

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

USGS Publications Warehouse

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Subsurface capture of carbon dioxide

DOEpatents

Blount, Gerald; Siddal, Alvin A.; Falta, Ronald W.

2014-07-22

A process and apparatus of separating CO.sub.2 gas from industrial off-gas source in which the CO.sub.2 containing off-gas is introduced deep within an injection well. The CO.sub.2 gases are dissolved in the, liquid within the injection well while non-CO.sub.2 gases, typically being insoluble in water or brine, are returned to the surface. Once the CO.sub.2 saturated liquid is present within the injection well, the injection well may be used for long-term geologic storage of CO.sub.2 or the CO.sub.2 saturated liquid can be returned to the surface for capturing a purified CO.sub.2 gas.

Identification of Preferential Paths of Fossil Carbon within Water Resource Recovery Facilities via Radiocarbon Analysis.

PubMed

Tseng, Linda Y; Robinson, Alice K; Zhang, Xiaying; Xu, Xiaomei; Southon, John; Hamilton, Andrew J; Sobhani, Reza; Stenstrom, Michael K; Rosso, Diego

2016-11-15

The Intergovernmental Panel on Climate Change (IPCC) reported that all carbon dioxide (CO 2 ) emissions generated by water resource recovery facilities (WRRFs) during treatment are modern, based on available literature. Therefore, such emissions were omitted from IPCC's greenhouse gas (GHG) accounting procedures. However, a fraction of wastewater's carbon is fossil in origin. We hypothesized that since the fossil carbon entering municipal WRRFs is mostly from soaps and detergents as dissolved organic matter, its fate can be selectively determined during the universally applied separation treatment processes. Analyzing radiocarbon at different treatment points within municipal WRRFs, we verified that the fossil content could amount to 28% in primary influent and showed varying distribution leaving different unit operations. We recorded the highest proportion of fossil carbon leaving the secondary treatment as off-gas and as solid sludge (averaged 2.08 kg fossil-CO 2 -emission-potential m -3 wastewater treated). By including fossil CO 2 , total GHG emission in municipal WRRFs increased 13%, and 23% if an on-site energy recovery system exists although much of the postdigestion fossil carbon remained in biosolids rather than in biogas, offering yet another carbon sequestration opportunity during biosolids handling. In comparison, fossil carbon contribution to GHG emission can span from negligible to substantial in different types of industrial WRRFs. With such a considerable impact, CO 2 should be analyzed for each WRRF and not omitted from GHG accounting.

Carbon and its isotopes in mid-oceanic basaltic glasses

USGS Publications Warehouse

Des Marais, D.J.; Moore, J.G.

1984-01-01

Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO2 is about 3.8??? enriched in 13C, relative to dissolved carbon. Despite this fractionation, ??13CPDB values for all spreading ridge glasses lie within the range -5.6 and -7.5, and the ??13CPDB of mantle carbon likely lies between -5 and -7. The carbon abundances and ??13CPDB values of Kilauea East Rift glasses apparently are influenced by the differentiation and movement of magma within that Hawaiian volcano. Using 3He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 ?? 1013 g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory. ?? 1984.

To Float or Not to Float: How Interactions between Light and Dissolved Inorganic Carbon Species Determine the Buoyancy of Stratiotes aloides

PubMed Central

Harpenslager, Sarah F.; Smolders, Alfons J. P.; Kieskamp, Ariët A. M.; Roelofs, Jan G. M.; Lamers, Leon P. M.

2015-01-01

Structural diversity formed by dense, floating Stratiotes aloides stands, generates hotspots of biodiversity of flora and fauna in wetlands. However, only part of the populations become emergent and provide this important facilitation. Since it has been hypothesised that its buoyancy depends on the rates of underwater photosynthesis, we investigated the role of dissolved CO2 availability and PAR on photosynthesis, biomass production and buoyancy in a controlled greenhouse experiment. Photosynthesis and growth were strongly influenced by both PAR and CO2 availability. At low PAR, plants formed less biomass and produced no emergent leaves, even when CO2 was abundant. At low CO2 levels, S. aloides switched to HCO3 - use, resulting in a lower photosynthetic O2 production, decreased emergent leaf formation and increased CaCO3 precipitation on its leaves, all of which impaired buoyancy. At high PAR, low CO2 availability resulted in slower colonisation of the water layer, whereas CO2 availability did not influence PAR-limited plants. Our study shows that site conditions, rather than the sole abundance of potentially facilitating species, may strongly determine whether or not they form the structure necessary to act as a facilitator for biodiversity in aquatic environments. PMID:25909504

The fate of carbon dioxide in water-rich fluids under extreme conditions

PubMed Central

Pan, Ding; Galli, Giulia

2016-01-01

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures (P) and temperatures (T) approximating the conditions of Earth’s upper mantle. Contrary to popular geochemical models assuming that molecular CO2(aq) is the major carbon species present in water under deep Earth conditions, we found that at 11 GPa and 1000 K, carbon exists almost entirely in the forms of solvated carbonate (CO32−) and bicarbonate (HCO3−) ions and that even carbonic acid [H2CO3(aq)] is more abundant than CO2(aq). Furthermore, our simulations revealed that ion pairing between Na+ and CO32−/HCO3− is greatly affected by P-T conditions, decreasing with increasing pressure at 800 to 1000 K. Our results suggest that in Earth’s upper mantle, water-rich geofluids transport a majority of carbon in the form of rapidly interconverting CO32− and HCO3− ions, not solvated CO2(aq) molecules. PMID:27757424

Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode

PubMed Central

2017-01-01

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today. PMID:28378994

[Difference of Karst Carbon Sink Under Different Land Use and Land Cover Areas in Dry Season].

PubMed

Zhao, Rui-yi; Liang, Zuo-bing; Wang, Zun-bo; Yu, Zheng-liang; Jiang, Ze-li

2015-05-01

In order to identify the distinction of soil CO2 consumed by carbonate rock dissolution, Baishuwan spring, Lanhuagou spring and Hougou spring were selected as objects to monitor the hydrochemistry from November 2013 to May 2014. The results showed that the highest HCO3- concentration was observed in Baishuwan spring which is covered by pine forest, while the lowest HCO3- concentration was observed in Hougou spring which is mainly covered by cultivated land. In Baishuwan spring, HCO3- was mainly derived from carbonic acid dissolving carbonate rock and the molar ratio between Ca(2+) + Mg2+ and HCO3- was close to 0. 5; while the molar ratio between Ca(2+) + Mg2+ and HCO3- exceeded 0.5 because the carbonate rock in Lanhuagou spring and Hougou spring was mainly dissolved by nitric acid and sulfuric acid. Because of the input of litter and the fact that gas-permeability of soil was limited in Baishuwan spring catchment, most of soil CO2 was dissolved in infiltrated water and reacted with bedrock. However, in Lanhuagou spring catchment and Hougou spring catchment, porous soil made soil CO2 easier to return to the atmosphere in the form of soil respiration. Therefore, in order to accurately estimate karst carbon sink, it was required to clarify the distinction of CO2 consumption by carbonate rock dissolution under different land use and land cover areas.

Carbon isotope variations in a solar pond microbial mat: Role of environmental gradients as steering variables

NASA Astrophysics Data System (ADS)

Schidlowski, Manfred; Gorzawski, Hendrik; Dor, Inka

1994-05-01

A biogeochemical traverse is presented for a juvenile benthic mat covering the depth profile of an artificially stratified and eutrophicated hypersaline heliothermal pond with known gradients of temperature, salinity, pH, and light transmission. It can be shown that visual mat development depends primarily on temperature and salinity as main environmental steering variables whose increase with depth goes along with the attenuation and final disappearance of a visible microbial film in the pond's hypolimnic compartment. Recorded biogeochemical parameters (C org content, cell numbers, chlorophyll-a content) evidently reflect, as either biomass- or productivity-related index functions, the visually perceptible growth gradient of the microbial ecosystem along the pond slope. The observed coincidence of maxima in these index functions with maxima in δ13Corg clearly identifies high rates of primary productivity as the agent ultimately responsible for the generation of isotopically heavy ( 13C-enriched) biomass in these and related environments. Extreme demands placed on the local feeder pool of dissolved inorganic carbon by high rates of primary productivity entertained by the mat-forming microbenthos obviously give rise to severe CO 2 limitation, enforcing the operation of a diffusion-(supply-)limited assimilatory pathway with an isotopically indiscriminate metabolization of the available CO 2 resources.

Modelling the 13C and 12C isotopes of inorganic and organic carbon in the Baltic Sea

NASA Astrophysics Data System (ADS)

Gustafsson, Erik; Mörth, Carl-Magnus; Humborg, Christoph; Gustafsson, Bo G.

2015-08-01

In this study, 12C and 13C contents of all carbon containing state variables (dissolved inorganic and organic carbon, detrital carbon, and the carbon content of autotrophs and heterotrophs) have for the first time been explicitly included in a coupled physical-biogeochemical Baltic Sea model. Different processes in the carbon cycling have distinct fractionation values, resulting in specific isotopic fingerprints. Thus, in addition to simulating concentrations of different tracers, our new model formulation improves the possibility to constrain the rates of processes such as CO2 assimilation, mineralization, and air-sea exchange. We demonstrate that phytoplankton production and respiration, and the related air-sea CO2 fluxes, are to a large degree controlling the isotopic composition of organic and inorganic carbon in the system. The isotopic composition is further, but to a lesser extent, influenced by river loads and deep water inflows as well as transformation of terrestrial organic carbon within the system. Changes in the isotopic composition over the 20th century have been dominated by two processes - the preferential release of 12C to the atmosphere in association with fossil fuel burning, and the eutrophication of the Baltic Sea related to increased nutrient loads under the second half of the century.

Effect of co-application of nano-zero valent iron and biochar on the total and freely dissolved polycyclic aromatic hydrocarbons removal and toxicity of contaminated soils.

PubMed

Oleszczuk, Patryk; Kołtowski, Michał

2017-02-01

The aim of this study was to investigate co-application of biochar and nano zero-valent iron (nZVI) in order to increase the degradation of PAHs and reduce the toxicity of soils historically contaminated with these compounds. To performed the experiment biochar, biochar with nZVI (2 g kg -1 or 10 g kg -1 soil), or nZVI alone (2 g kg -1 or 10 g kg -1 soil) were added to the PAHs contaminated soils. The soils alone and soils with amendments were aged by mixing for 7 and 30 days. After that the chemical analysis were carried out and total (C tot ) and C free PAH content in the samples were determined. Moreover, the toxicity of aqueous extracts were investigated using the Microtox ® (Vibrio fischeri) method. Results showed that any of used nZVI dose did not reduce the content of C tot or C free PAHs in contaminated soils, but biochar applied both alone and together with the nZVI significantly reduced C tot and C free PAHs. However, no significant differences in PAH reduction were found between biochar alone and biochar with nZVI addition. This indicates that the observed reduction was mostly associated with the sorption properties of biochar. Moreover, only in the case of co-application of biochar and nZVI reduction of the toxicity of nZVI to V. fischeri was observed. The toxic effect was different and depend on the type of soil and their properties including total organic carbon and black carbon content, which may affect the PAHs reduction efficiency. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantification of octacalcium phosphate, authigenic apatite and detrital apatite in coastal sediments using differential dissolution and standard addition

NASA Astrophysics Data System (ADS)

Oxmann, J. F.; Schwendenmann, L.

2014-06-01

Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In situ relationships between liquid- and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determining particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions, and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP > HAP > CFAP (4.5% CO3) > CFAP (3.4% CO3) > CFAP (2.2% CO3) > FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the coastal sediments analyzed, which supports the hypothesis of apatite formation by an OCP precursor mechanism.

Quantification of octacalcium phosphate, authigenic apatite and detrital apatite in coastal sediments using differential dissolution and standard addition

NASA Astrophysics Data System (ADS)

Oxmann, J. F.; Schwendenmann, L.

2014-01-01

Knowledge of calcium phosphate (Ca-P) solubility is crucial for understanding temporal and spatial variations of phosphorus (P) concentrations in water bodies and sedimentary reservoirs. In-situ relationships between liquid and solid-phase levels cannot be fully explained by dissolved analytes alone and need to be verified by determination of particular sediment P species. Lack of quantification methods for these species limits the knowledge of the P cycle. To address this issue, we (i) optimized a specifically developed conversion-extraction (CONVEX) method for P species quantification using standard additions; and (ii) simultaneously determined solubilities of Ca-P standards by measuring their pH-dependent contents in the sediment matrix. Ca-P minerals including various carbonate fluorapatite (CFAP) specimens from different localities, fluorapatite (FAP), fish bone apatite, synthetic hydroxylapatite (HAP) and octacalcium phosphate (OCP) were characterized by XRD, Raman, FTIR and elemental analysis. Sediment samples were incubated with and without these reference minerals and then sequentially extracted to quantify Ca-P species by their differential dissolution at pH values between 3 and 8. The quantification of solid-phase phosphates at varying pH revealed solubilities in the following order: OCP > HAP > CFAP (4.5% CO3) > CFAP (3.4% CO3) > CFAP (2.2% CO3) > FAP. Thus, CFAP was less soluble in sediment than HAP, and CFAP solubility increased with carbonate content. Unspiked sediment analyses together with standard addition analyses indicated consistent differential dissolution of natural sediment species vs. added reference species and therefore verified the applicability of the CONVEX method in separately determining the most prevalent Ca-P minerals. We found surprisingly high OCP contents in the analyzed coastal sediments which supports the hypothesis of apatite formation by an OCP precursor.

ABIOTIC O{sub 2} LEVELS ON PLANETS AROUND F, G, K, AND M STARS: POSSIBLE FALSE POSITIVES FOR LIFE?

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

Harman, C. E.; Kasting, J. F.; Schwieterman, E. W.

2015-10-20

In the search for life on Earth-like planets around other stars, the first (and likely only) information will come from the spectroscopic characterization of the planet's atmosphere. Of the countless number of chemical species terrestrial life produces, only a few have the distinct spectral features and the necessary atmospheric abundance to be detectable. The easiest of these species to observe in Earth's atmosphere is O{sub 2} (and its photochemical byproduct, O{sub 3}). However, O{sub 2} can also be produced abiotically by photolysis of CO{sub 2}, followed by recombination of O atoms with each other. CO is produced in stoichiometric proportions. Whethermore » O{sub 2} and CO can accumulate to appreciable concentrations depends on the ratio of far-ultraviolet (FUV) to near-ultraviolet (NUV) radiation coming from the planet's parent star and on what happens to these gases when they dissolve in a planet's oceans. Using a one-dimensional photochemical model, we demonstrate that O{sub 2} derived from CO{sub 2} photolysis should not accumulate to measurable concentrations on planets around F- and G-type stars. K-star, and especially M-star planets, however, may build up O{sub 2} because of the low NUV flux from their parent stars, in agreement with some previous studies. On such planets, a “false positive” for life is possible if recombination of dissolved CO and O{sub 2} in the oceans is slow and if other O{sub 2} sinks (e.g., reduced volcanic gases or dissolved ferrous iron) are small. O{sub 3}, on the other hand, could be detectable at UV wavelengths (λ < 300 nm) for a much broader range of boundary conditions and stellar types.« less

Partitioning Carbon Dioxide Emission and Assessing Dissolved Organic Carbon Leaching of a Drained Peatland Cultivated with Pineapple at Saratok, Malaysia

PubMed Central

Lim Kim Choo, Liza Nuriati; Ahmed, Osumanu Haruna

2014-01-01

Pineapples (Ananas comosus (L.) Merr.) cultivation on drained peats could affect the release of carbon dioxide (CO2) into the atmosphere and also the leaching of dissolved organic carbon (DOC). Carbon dioxide emission needs to be partitioned before deciding on whether cultivated peat is net sink or net source of carbon. Partitioning of CO2 emission into root respiration, microbial respiration, and oxidative peat decomposition was achieved using a lysimeter experiment with three treatments: peat soil cultivated with pineapple, bare peat soil, and bare peat soil fumigated with chloroform. Drainage water leached from cultivated peat and bare peat soil was also analyzed for DOC. On a yearly basis, CO2 emissions were higher under bare peat (218.8 t CO2 ha/yr) than under bare peat treated with chloroform (205 t CO2 ha/yr), and they were the lowest (179.6 t CO2 ha/yr) under cultivated peat. Decreasing CO2 emissions under pineapple were attributed to the positive effects of photosynthesis and soil autotrophic activities. An average 235.7 mg/L loss of DOC under bare peat suggests rapid decline of peat organic carbon through heterotrophic respiration and peat decomposition. Soil CO2 emission depended on moderate temperature fluctuations, but it was not affected by soil moisture. PMID:25215335

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

USGS Publications Warehouse

Ravichandran, Mahalingam; Aiken, George R.; Reddy, Michael M.; Ryan, Joseph N.

1998-01-01

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca2+. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pHpzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

Volatile (H2O, CO2) and Halogen (Cl) Systematics of SMAR MORB (44-52.5 ° S)

NASA Astrophysics Data System (ADS)

le Roux, P. J.; le Roex, A. P.; Hauri, E. H.

2013-12-01

New SIMS volatile (H2O, CO2) and halogen (Cl) concentration data are presented for fresh MORB glasses (>6wt% MgO) from the slow-spreading southern Mid-Atlantic Ridge (SMAR; 44-52.5 ° S). This data set complements previous data from the faster-spreading northern East Pacific Rise (EPR; 8-10 ° N and 12-14 ° N; le Roux et al., 2006). The selected MORB samples span the previously observed compositional range between enriched and depleted mantle source regions along this section of the SMAR (le Roux et al., 2002b), as well as the range of magma crystallization characteristics (le Roux et al., 2002a). The pre-eruption transit of MORB magmas through the upper oceanic crust can potentially result in compositional contamination through assimilation of e.g. sea-water altered crustal material and/or saline brines. This would most-noticeable through significant addition of sea-water derived Cl to a magma, resulting in excess Cl concentrations and elevated Cl/Nb ratios (>50) in erupted MORB lavas (le Roux et al., 2006; Michael & Cornell, 1998). Dissolved H2O (0.12-0.61wt%) and CO2 (69-230ppm) concentrations in the MORB glass samples provide pressure estimates of eruption initiation, and therefore the final crustal depth at which significant magma compositional modification occurred (Dsat; le Roux et al., 2006). Unlike the northern EPR region, no geophysical data are available for this section of the SMAR. A comparison of Dsat with the depth of imaged magma chambers, similar to results from the northern EPR (le Roux et al., 2006), is therefore not directly possible. However, estimates of the calculated pressures of MORB magma crystallization for these SMAR samples (le Roux et al., 2002a) can be compared with Dsat. The dissolved H2O and CO2 contents of the SMAR basalts are consistent with slow magma ascent allowing degassing to keep pace with decompression (Dsat 0-550m.b.s.l.). Observed Cl contents (15-170ppm) of these SMAR basalts are well-correlated with Nb and indicate the near absence of interaction of the magmas with hydrothermally-altered rocks in the crust (Cl/Nb 5.67-14.2). This may be due to the absence of long-lived hydrothermal systems linked to established sub-ridge magma chambers, as observed at the northern EPR where spreading rates and magma supply are both higher. le Roux et al. (2002a) CMP, 142, 582-602 le Roux et al. (2002b) EPSL, 203, 479-498 le Roux et al. (2006) EPSL, 251, 209-231 Michael; Cornell (1998) JGRes, 103, 18325-18356

Revision of Fontes & Garnier's model for the initial 14C content of dissolved inorganic carbon used in groundwater dating

USGS Publications Warehouse

Han, Liang-Feng; Plummer, Niel

2013-01-01

The widely applied model for groundwater dating using 14C proposed by Fontes and Garnier (F&G) (Fontes and Garnier, 1979) estimates the initial 14C content in waters from carbonate-rock aquifers affected by isotopic exchange. Usually, the model of F&G is applied in one of two ways: (1) using a single 13C fractionation factor of gaseous CO2 with respect to a solid carbonate mineral, εg/s, regardless of whether the carbon isotopic exchange is controlled by soil CO2 in the unsaturated zone, or by solid carbonate mineral in the saturated zone; or (2) using different fractionation factors if the exchange process is dominated by soil CO2 gas as opposed to solid carbonate mineral (typically calcite). An analysis of the F&G model shows an inadequate conceptualization, resulting in underestimation of the initial 14C values (14C0) for groundwater systems that have undergone isotopic exchange. The degree to which the 14C0 is underestimated increases with the extent of isotopic exchange. Examples show that in extreme cases, the error in calculated adjusted initial 14C values can be more than 20% modern carbon (pmc). A model is derived that revises the mass balance method of F&G by using a modified model conceptualization. The derivation yields a “global” model both for carbon isotopic exchange dominated by gaseous CO2 in the unsaturated zone, and for carbon isotopic exchange dominated by solid carbonate mineral in the saturated zone. However, the revised model requires different parameters for exchange dominated by gaseous CO2 as opposed to exchange dominated by solid carbonate minerals. The revised model for exchange dominated by gaseous CO2 is shown to be identical to the model of Mook (Mook, 1976). For groundwater systems where exchange occurs both in the unsaturated zone and saturated zone, the revised model can still be used; however, 14C0 will be slightly underestimated. Finally, in carbonate systems undergoing complex geochemical reactions, such as oxidation of organic carbon, radiocarbon ages are best estimated by inverse geochemical modeling techniques.

Engineering Tough Materials: Biomimetic Eggshell

DTIC Science & Technology

2016-08-29

known that this domain interacts with CO32- ions. Eggshell collagen membrane (Figure 1) was extracted by dissolving the shell of a chicken egg in 1 M...Therefore, an experiment was designed and executed with the aim of trying to elucidate whether the shell membrane has a mechanical role. Eggs 8 were...obtained from the local supermarket and holes were punctured at the equator in order to remove the liquid contents (both yolk and white). Eggs were tested in

Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas.

PubMed

Madeddu, Silvia; Priestnall, Michael; Godoy, Erik; Kumar, R Vasant; Raymahasay, Sugat; Evans, Michael; Wang, Ruofan; Manenye, Seabelo; Kinoshita, Hajime

2015-01-01

The utilisation of Mg(OH)2 to capture exhaust CO2 has been hindered by the limited availability of brucite, the Mg(OH)2 mineral in natural deposits. Our previous study demonstrated that Mg(OH)2 can be obtained from dunite, an ultramafic rock composed of Mg silicate minerals, in highly concentrated NaOH aqueous systems. However, the large quantity of NaOH consumed was considered an obstacle for the implementation of the technology. In the present study, Mg(OH)2 was extracted from dunite reacted in solid systems with NaOH assisted with H2O. The consumption of NaOH was reduced by 97% with respect to the NaOH aqueous systems, maintaining a comparable yield of Mg(OH)2 extraction, i.e. 64.8-66%. The capture of CO2 from a CO2-N2 gas mixture was tested at ambient conditions using a Mg(OH)2 aqueous slurry. Mg(OH)2 almost fully dissolved and reacted with dissolved CO2 by forming Mg(HCO3)2 which remained in equilibrium storing the CO2 in the aqueous solution. The CO2 balance of the process was assessed from the emissions derived from the power consumption for NaOH production and Mg(OH)2 extraction together with the CO2 captured by Mg(OH)2 derived from dunite. The process resulted as carbon neutral when dunite is reacted at 250 °C for durations of 1 and 3 hours and CO2 is captured as Mg(HCO3)2.

Quantitation of dissolved gas content in emulsions and in blood using mass spectrometric detection

PubMed Central

Grimley, Everett; Turner, Nicole; Newell, Clayton; Simpkins, Cuthbert; Rodriguez, Juan

2011-01-01

Quantitation of dissolved gases in blood or in other biological media is essential for understanding the dynamics of metabolic processes. Current detection techniques, while enabling rapid and convenient assessment of dissolved gases, provide only direct information on the partial pressure of gases dissolved in the aqueous fraction of the fluid. The more relevant quantity known as gas content, which refers to the total amount of the gas in all fractions of the sample, can be inferred from those partial pressures, but only indirectly through mathematical modeling. Here we describe a simple mass spectrometric technique for rapid and direct quantitation of gas content for a wide range of gases. The technique is based on a mass spectrometer detector that continuously monitors gases that are rapidly extracted from samples injected into a purge vessel. The accuracy and sample processing speed of the system is demonstrated with experiments that reproduce within minutes literature values for the solubility of various gases in water. The capability of the technique is further demonstrated through accurate determination of O2 content in a lipid emulsion and in whole blood, using as little as 20 μL of sample. The approach to gas content quantitation described here should greatly expand the range of animals and conditions that may be used in studies of metabolic gas exchange, and facilitate the development of artificial oxygen carriers and resuscitation fluids. PMID:21497566

Origin and distribution of carbon dioxide in the unsaturated zone of the southern High Plains of Texas

USGS Publications Warehouse

Wood, Warren W.; Petraitis, Michael J.

1984-01-01

Partial pressures of CO2, O2, N2, and Ar were monitored at two locations in the Ogallala aquifer system on the Southern High Plains of Texas. Samples were collected monthly during parts of 1980–1981 from nine depths ranging from 0.6 to 36 meters below land surface. PCO2 was observed to be greater at depth than in the active soil zone and thus appears to contradict the normal process in which CO2 is generated in the soil zone and diffuses upward to the atmosphere and downward to the water table. The δ13C of the CO2 gas was quite uniform and averaged −17.9 per mil. PO2 declined with depth, suggesting in situ generation of CO2 by the oxidation of carbon. Several hypotheses were considered to explain the origin of the CO2 at depth. It was concluded that the most probable hypothesis was that dissolved and particulate organic carbon introduced by recharging water was oxidized to CO2 by the aerobic microbial community that utilized oxygen diffusing in from the atmosphere. This hypothesis is consistent with the CO2 concentration profile, calculated production profile of CO2, δ13C values of CO2 gas, caliche, soil humic acid fraction, and dissolved carbonate in groundwater. The abundance of CO2, its concentration profile, and its probable origin provide information for evaluating the observed complex sequence of caliche dissolution and precipitation known to occur in the aquifer.

Microbial dissolution of calcite at T = 28 °C and ambient pCO 2

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Wu, Lingling

2009-04-01

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species ( Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO 2 over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH 4+ as an N source, and H 2PO 4- as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H 2O-CO 2-CaCO 3 system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH 4+ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H 2CO 3 generated by dissolution of atmospheric CO 2 (H 2CO 3 + CaCO 3 → Ca 2+ + 2HCO 3-) and H + released during NH 4+ uptake (H + + CaCO 3 → Ca 2+ + HCO 3-). Reaction with H 2CO 3 and H + supplied ˜45% and 55% of the total Ca 2+ and ˜60% and 40% of the total HCO 3-, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH 4+ was ˜2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H 2CO 3. In lactate bearing reactors, most H + generated by NH 4+ uptake reacted with HCO 3- produced by lactate oxidation to yield CO 2 and H 2O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H 2CO 3 at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH 4+ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.

Integration of metagenomic and stable carbon isotope evidence reveals the extent and mechanisms of carbon dioxide fixation in high-temperature microbial communities

DOE PAGES

Jennings, Ryan de Montmollin; Moran, James J.; Jay, Zackary J.; ...

2017-02-03

Biological fixation of CO 2 is the primary mechanism of C reduction in natural systems, and provides a diverse suite of organic compounds utilized by chemoorganoheterotrophs. The extent and mechanisms of CO 2 fixation were evaluated across a comprehensive set of high-temperature, chemotrophic microbial communities in Yellowstone National Park by combining metagenomic and stable 13C isotope analyses. Fifteen geothermal sites representing three distinct habitat types (iron-oxide mats, anoxic sulfur sediments, and filamentous ‘streamer’ communities) were investigated. Genes of the 3-hydroxypropionate/4-hydroxybutyrate, dicarboxylate/4-hydroxybutyrate, and reverse tricarboxylic acid CO 2 fixation pathways were identified in assembled genome sequence corresponding to the predominant Crenarchaeotamore » and Aquificales observed across this habitat range. Stable 13C analyses of dissolved inorganic and organic C (DIC, DOC), and possible landscape C sources were used to interpret the 13C content of microbial community samples. Isotope mixing models showed that the minimum amounts of autotrophic C in microbial biomass were > 50 % in the majority of communities analyzed, but were also dependent on the amounts of heterotrophy and/or accumulation of landscape C. Furthermore, the significance of CO 2 as a C source in these communities provides a foundation for understanding metabolic linkages among autotrophs and heterotrophs, community assembly and succession, and the likely coevolution of deeply-branching thermophiles.« less

Method of controlling injection of oxygen into hydrogen-rich fuel cell feed stream

DOEpatents

Meltser, Mark Alexander; Gutowski, Stanley; Weisbrod, Kirk

2001-01-01

A method of operating a H.sub.2 --O.sub.2 fuel cell fueled by hydrogen-rich fuel stream containing CO. The CO content is reduced to acceptable levels by injecting oxygen into the fuel gas stream. The amount of oxygen injected is controlled in relation to the CO content of the fuel gas, by a control strategy that involves (a) determining the CO content of the fuel stream at a first injection rate, (b) increasing the O.sub.2 injection rate, (c) determining the CO content of the stream at the higher injection rate, (d) further increasing the O.sub.2 injection rate if the second measured CO content is lower than the first measured CO content or reducing the O.sub.2 injection rate if the second measured CO content is greater than the first measured CO content, and (e) repeating steps a-d as needed to optimize CO consumption and minimize H.sub.2 consumption.

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

NASA Astrophysics Data System (ADS)

Brown, C. J.; Schoonen, M. A. A.; Candela, J. L.

2000-11-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O 2 and SO 42- in the aerobic zone, and to the reduction of SO 42- in the anaerobic zone; estimated rates of CO 2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO 2 production calculated from dissolved inorganic carbon mass transfer (2.55×10 -4 to 48.6×10 -4 mmol l -1 yr-1) generally were comparable to the calculated rates of CO 2 production by the combined reduction of O 2, Fe(III) and SO 42- (1.31×10 -4 to 15×10 -4 mmol l -1 yr-1). The overall increase in SO 42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in δ34S values along the flow path indicate that SO 42- loss through microbial reduction is exceeded by SO 42- gain through diffusion from sediments and through the oxidation of FeS 2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO 42--rich zones have been depleted by microbial reduction and resulted in localized SO 42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO 42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Melting mountains of Appalachia: exceptionally high weathering rates in mined watersheds

NASA Astrophysics Data System (ADS)

Ross, M. R.; Nippgen, F.; Hassett, B.; McGlynn, B. L.; Bernhardt, E. S.

2016-12-01

Mountaintop mining operations excavate ridges as deep as 200 m and bury adjacent valleys and streams beneath fractured bedrock and coal residues. Post-mining, landscapes have lower slopes, greatly increased water storage potential, and an abundance of acid-generating pyrite, which is intentionally mixed with neutralizing calcareous bedrock. Together these design features of mountaintop mined lands create ideal conditions for long water residence times and rapid weathering rates, leading to widely documented and substantial increases in streamwater ion concentrations. To date, these concentration changes have not been linked to rates of watershed scale element flux. In a paired catchment study, we documented a 4,000% increase in the export of total dissolved solids from a mined watershed, and estimate that pyrite and carbonate weathering in reclaimed mines can export 9,000 kg ha-1 y-1 of dissolved rock to receiving streams. Such high rates of element flux after a disturbance are not only much higher than other watershed disturbances, but are among the highest rates of weathering ever reported globally. Sulfuric acid weathering of carbonate rock drives these patterns of chemical erosion. This strong acid weathering changes Appalachian geology from a slight net geologic CO2 sink-sequestering 800-1,500 kg CO2 km-2 yr-1 through carbonic acid weathering of carbonates-to a substantial net geologic source of CO2, releasing 170,000 kg CO2 km-2 yr-1. Over the more than 4,000 km2 area of Central Appalachia that has undergone mountaintop mining, this rapid weathering represents 4 million tons of dissolved rock being delivered to the streams of West Virginia, potentially releasing 680,000 tons of CO2 in the process.

Model-Data Fusion to Test Hypothesized Drivers of Lake Carbon Cycling Reveals Importance of Physical Controls

NASA Astrophysics Data System (ADS)

Hararuk, Oleksandra; Zwart, Jacob A.; Jones, Stuart E.; Prairie, Yves; Solomon, Christopher T.

2018-03-01

Formal integration of models and data to test hypotheses about the processes controlling carbon dynamics in lakes is rare, despite the importance of lakes in the carbon cycle. We built a suite of models (n = 102) representing different hypotheses about lake carbon processing, fit these models to data from a north-temperate lake using data assimilation, and identified which processes were essential for adequately describing the observations. The hypotheses that we tested concerned organic matter lability and its variability through time, temperature dependence of biological decay, photooxidation, microbial dynamics, and vertical transport of water via hypolimnetic entrainment and inflowing density currents. The data included epilimnetic and hypolimnetic CO2 and dissolved organic carbon, hydrologic fluxes, carbon loads, gross primary production, temperature, and light conditions at high frequency for one calibration and one validation year. The best models explained 76-81% and 64-67% of the variability in observed epilimnetic CO2 and dissolved organic carbon content in the validation data. Accurately describing C dynamics required accounting for hypolimnetic entrainment and inflowing density currents, in addition to accounting for biological transformations. In contrast, neither photooxidation nor variable organic matter lability improved model performance. The temperature dependence of biological decay (Q10) was estimated at 1.45, significantly lower than the commonly assumed Q10 of 2. By confronting multiple models of lake C dynamics with observations, we identified processes essential for describing C dynamics in a temperate lake at daily to annual scales, while also providing a methodological roadmap for using data assimilation to further improve understanding of lake C cycling.

Monitoring of impact of anthropogenic inputs on water quality of mangrove ecosystem of Uran, Navi Mumbai, west coast of India.

PubMed

Pawar, Prabhakar R

2013-10-15

Surface water samples were collected from substations along Sheva creek and Dharamtar creek mangrove ecosystems of Uran (Raigad), Navi Mumbai, west coast of India. Water samples were collected fortnightly from April 2009 to March 2011 during spring low and high tides and were analyzed for pH, Temperature, Turbidity, Total solids (TS), Total dissolved solids (TDS), Total suspended solids (TSS), Dissolved oxygen (DO), Biochemical oxygen demand (BOD), Carbon dioxide (CO2), Chemical oxygen demand (COD), Salinity, Orthophosphate (O-PO4), Nitrite-nitrogen (NO2-N), Nitrate-nitrogen (NO3-N), and Silicates. Variables like pH, turbidity, TDS, salinity, DO, and BOD show seasonal variations. Higher content of O-PO4, NO3-N, and silicates is recorded due to discharge of domestic wastes and sewage, effluents from industries, oil tanking depots and also from maritime activities of Jawaharlal Nehru Port Trust (JNPT), hectic activities of Container Freight Stations (CFS), and other port wastes. This study reveals that water quality from mangrove ecosystems of Uran is deteriorating due to industrial pollution and that mangrove from Uran is facing the threat due to anthropogenic stress. Copyright © 2013 Elsevier Ltd. All rights reserved.

Arctic catchment releases mostly young aquatic carbon despite complete thawing of old organic-rich permafrost soils during growing season.

NASA Astrophysics Data System (ADS)

Dean, Joshua F.; Billett, Michael F.; Dinsmore, Kerry J.; Garnett, Mark H.; van der Velde, Ype

2017-04-01

Radiocarbon (14C) dating of dissolved organic carbon (DOC) in Arctic freshwaters has been used as a crucial tool for detecting old C mobilised from thawing permafrost, but DO14C in major Arctic rivers is usually quite young. New methods for the collection of both CO2 and CH4 from inland waters allow novel observation of dissolved 14CO2 and 14CH4 alongside DO14C, and provide a more sensitive method than aquatic OC alone - published Arctic freshwater 14C studies to date focus only on DOC, particulate OC, or ebullition CH4/CO2. The mobilisation of old C sourced from deepening permafrost soil active-layers into Arctic freshwaters has the potential to form a significant positive climate feedback. We compare 14C in DOC, dissolved CO2 and dissolved CH4 at five time points over a single growing season from streams, ponds and lakes underlain by continuous permafrost in the western Canadian Arctic. Using age distribution analysis based on atmospheric 14CO2 records, we estimated the age of aquatic C that would otherwise be labelled as "modern" due to the 14C bomb peak. We then calculated the vertical and lateral C fluxes in the study systems, and estimated the proportion derived from old permafrost C. The upper organic-rich soils are the dominant hydrologic pathway, which were completely thawed by late season, and we hypothesised that mobilisation of older, deeper organic soil C would be visible in the aquatic 14C by late in the growing season. Early in the season, median aquatic DO14C and CO2 ages were 65-131 years old (all 14C ages reported here are years before sampling date). By the end of the season, DO14C was 156-271 years old, while CO2 was 113-161 years old, demonstrating that aquatic C ages reflect the mobilisation of thawing older permafrost C. CH4 concentrations were generally low throughout and only two dates were obtained: 202 and 1,970 years old. Overall there was limited evidence of very old permafrost organic C, which comprised 0-10% of vertical and lateral aquatic fluxes. Our results demonstrate that permafrost thaw will result in the mobilisation of old C into the aquatic phase as DOC, CO2 and CH4, but also indicate potential resilience within these systems in response to climate change.

Biogeochemical generation of dissolved inorganic carbon and nitrogen in the North Branch of inner Changjiang Estuary in a dry season

NASA Astrophysics Data System (ADS)

Zhai, Wei-Dong; Yan, Xiu-Li; Qi, Di

2017-10-01

We investigated the surface water carbonate system, nutrients, and relevant hydrochemical parameters in the inner Changjiang (Yangtze River) Estuary in early spring 2009 and 2010. The two surveys were carried out shortly after spring-tide days, and covered both the channel-like South Branch and the freshwater-blocked North Branch. In the North Branch, with a water residence time of approximately one month, we detected remarkable partial pressures of CO2 (pCO2) of 930-1518 μatm with a salinity range of 4.5-17.4, which were substantially higher than the South Branch pCO2 values of 700-1100 μatm at salinities of less than 0.88. The North Branch pCO2 distribution pattern is unique compared with many other estuaries where aquatic pCO2 normally declines with salinity increase. Furthermore, the biogeochemical additions of ammonium (7.4-65.7 μmol kg-1) and alkalinity (196-695 μmol kg-1) were identified in salinities between 4 and 16 in the North Branch. Based on field data analyses and simplified stoichiometric equations, we suggest that the relatively high North Branch pCO2 values and estuarine additions of dissolved inorganic nitrogen/carbon in the mid-salinity area were strongly associated with each other. These signals were primarily controlled by biogeochemical processes in the North Branch, combining biogenic organic matter decomposition (i.e. respiration), ammonia oxidation, CaCO3 dissolution, and CO2 degassing. In the upper reach of the South Branch, notable salinity values of 0.20-0.88 were detected, indicating saltwater spillover from the North Branch. These spillover waters had minor contributions (1.5-6.9%) to the springtime nutrient, dissolved inorganic carbon, and alkalinity export fluxes from Changjiang to the adjacent East China Sea. This is the first attempt to understand the biogeochemical controls of the unique pCO2 distributions in the North Branch, and to evaluate the effects of saltwater spillover from the North Branch on dry-season export fluxes of biogenic elements to the adjacent East China Sea.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Response of soil dissolved organic matter to microplastic addition in Chinese loess soil.

PubMed

Liu, Hongfei; Yang, Xiaomei; Liu, Guobin; Liang, Chutao; Xue, Sha; Chen, Hao; Ritsema, Coen J; Geissen, Violette

2017-10-01

Plastic debris is accumulating in agricultural land due to the increased use of plastic mulches, which is causing serious environmental problems, especially for biochemical and physical properties of the soil. Dissolved organic matter (DOM) plays a central role in driving soil biogeochemistry, but little information is available on the effects of plastic residues, especially microplastic, on soil DOM. We conducted a soil-incubation experiment in a climate-controlled chamber with three levels of microplastic added to loess soil collected from the Loess Plateau in China: 0% (control, CK), 7% (M1) and 28% (M2) (w/w). We analysed the soil contents of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), NH 4 + , NO 3 - , dissolved organic phosphorus (DOP), and PO 4 3- and the activities of fluorescein diacetate hydrolase (FDAse) and phenol oxidase. The higher level of microplastic addition significantly increased the nutrient contents of the DOM solution. The lower level of addition had no significant effect on the DOM solution during the first seven days, but the rate of DOM decomposition decreased in M1 between days 7 and 30, which increased the nutrient contents. The microplastic facilitated the accumulation of high-molecular-weight humic-like material between days 7 and 30. The DOM solutions were mainly comprised of high-molecular-weight humic-like material in CK and M1 and of high-molecular-weight humic-like material and tyrosine-like material in M2. The Microplastic stimulated the activities of both enzymes. Microplastic addition thus stimulated enzymatic activity, activated pools of organic C, N, and P, and was beneficial for the accumulation of dissolved organic C, N and P. Copyright © 2017 Elsevier Ltd. All rights reserved.

Continuous pCO2 time series from Ocean Networks Canada cabled observatories at the northeast Pacific shelf edge and in the sub-tidal Arctic

NASA Astrophysics Data System (ADS)

Juniper, S. Kim; Sastri, Akash; Mihaly, Steven; Duke, Patrick; Else, Brent; Thomas, Helmuth; Miller, Lisa

2017-04-01

Marine pCO2 sensor technology has progressed to the point where months-long time series from remotely-deployed pCO2 sensors can be used to document seasonal and higher frequency variability in pCO2 and its relationship to oceanographic processes. Ocean Networks Canada recently deployed pCO2 sensors on two cabled platforms: a bottom-moored (400 m depth), vertical profiler at the edge of the northeast Pacific continental shelf off Vancouver Island, Canada, and a subtidal seafloor platform in the Canadian High Arctic (69˚ N) at Cambridge Bay, Nunavut. Both platforms streamed continuous data to a shore-based archive from Pro-Oceanus pCO2 sensors and other oceanographic instruments. The vertical profiler time series revealed substantial intrusions of corrosive (high CO2/low O2), saltier, colder water masses during the summertime upwelling season and during winter-time reversals of along-slope currents. Step-wise profiles during the downcast provided the most reliable pCO2 data, permitting the sensor to equilibrate to the broad range of pCO2 concentrations encountered over the 400 metre depth interval. The Arctic pCO2 sensor was deployed in August 2015. Reversing seasonal trends in pCO2 and dissolved oxygen values can be related to the changing balance of photosynthesis and respiration under sea ice, as influenced by irradiance. Correlation of pCO2 and dissolved oxygen sensor data and the collection of calibration samples have permitted evaluation of sensor performance in relation to operational conditions encountered in vertical profiling and lengthy exposure to subzero seawater.

RAPID AND PRECISE METHOD FOR MEASURING STABLE CARBON ISOTOPE RATIOS OF DISSOLVED INORGANIC CARBON

EPA Science Inventory

We describe a method for rapid preparation, concentration and stable isotopic analysis of dissolved inorganic carbon (d13C-DIC). Liberation of CO2 was accomplished by placing 100 ?l phosphoric acid and 0.9 ml water in an evacuated 1.7-ml gas chromatography (GC) injection vial. Fo...

Effects of dissolved oxygen concentration on photosynthetic bacteria wastewater treatment: Pollutants removal, cell growth and pigments production.

PubMed

Meng, Fan; Yang, Anqi; Zhang, Guangming; Wang, Hangyao

2017-10-01

Dissolved oxygen (DO) is an important parameter in photosynthetic bacteria (PSB) wastewater treatment. This study set different DO levels and detected the pollutants removal, PSB growth and pigments production. Results showed that DO significantly influenced the performances of PSB wastewater treatment process. The highest COD (93%) and NH 3 -N removal (83%) was achieved under DO of 4-8mg/L, but DO of 2-4mg/L was recommended considering the aeration cost. PSB biomass reached 1645mg/L under DO of 4-8mg/L with satisfying co-enzyme Q10 content. The biomass yield was relatively stable at all DO levels. For bacteriochlorophyll and carotenoids, DO>1mg/L could satisfy their production. On the other hand, DO<0.5mg/L led to the highest dehydrogenase activity. According to the different purposes, the optimal treatment time was different. The most pigments production occurred at 24h; biomass reached peak at 48h; and the optimal time for pollutants removal was 72h. Copyright © 2017 Elsevier Ltd. All rights reserved.

Understanding the role of soil erosion on co2-c loss using (13)c isotopic signatures in abandoned Mediterranean agricultural land.

PubMed

Novara, Agata; Keesstra, Saskia; Cerdà, Artemio; Pereira, Paulo; Gristina, Luciano

2016-04-15

Understanding soil water erosion processes is essential to evaluate the redistribution of soil organic carbon (SOC) within a landscape and is fundamental to assess the role of soil erosion in the global carbon (C) budget. The main aim of this study was to estimate the C redistribution and losses using (13)C natural abundance. Carbon losses in soil sediment, dissolved organic carbon (DOC) and CO2 emission were determined. Four bounded parallel plots were installed on a 10% slope. In the upper part of the plots, C3soil was replaced with C4soil. The SOC and δ(13)C were measured after 145.2mm rainfall in the upper (2m far from C4strip), middle (4m far from C4strip) lower (6m far from C4strip) trams of the plot and in the sediments collected in the Gerlach collector at the lower part of the plot. A laboratory incubation experiment was performed to evaluate the CO2 emission rate of soils in each area. OC was mainly lost in the sediments as 2.08g(-)(2) of C was lost after 145.2mm rainfall. DOC losses were only 5.61% of off-site OC loss. Three months after the beginning of the experiment, 15.90% of SOC in the upper tram of the plot had a C4 origin. The C4-SOC content decreased along the 6m length of the plot, and in the sediments collected by the Gerlach collector. CO2 emission rate was high in the upper plot tram due to the high SOC content. The discrimination of CO2 in C3 and C4 portion permitted to increase our level of understanding on the stability of SOC and its resilience to decomposition. The transport of sediments along the plot increased SOC mineralization by 43%. Our study underlined the impact of rainfall in C losses in soil and water in abandoned Mediterranean agriculture fields and the consequent implications on the C balance. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetic characteristics and modeling of microalgae Chlorella vulgaris growth and CO2 biofixation considering the coupled effects of light intensity and dissolved inorganic carbon.

PubMed

Chang, Hai-Xing; Huang, Yun; Fu, Qian; Liao, Qiang; Zhu, Xun

2016-04-01

Understanding and optimizing the microalgae growth process is an essential prerequisite for effective CO2 capture using microalgae in photobioreactors. In this study, the kinetic characteristics of microalgae Chlorella vulgaris growth in response to light intensity and dissolved inorganic carbon (DIC) concentration were investigated. The greatest values of maximum biomass concentration (Xmax) and maximum specific growth rate (μmax) were obtained as 2.303 g L(-1) and 0.078 h(-1), respectively, at a light intensity of 120 μmol m(-2) s(-1) and DIC concentration of 17 mM. Based on the results, mathematical models describing the coupled effects of light intensity and DIC concentration on microalgae growth and CO2 biofixation are proposed. The models are able to predict the temporal evolution of C. vulgaris growth and CO2 biofixation rates from lag to stationary phases. Verification experiments confirmed that the model predictions agreed well with the experimental results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental determination of dissolved CO2 content in nominally anhydrous andesitic melts at graphite/diamond saturation - Remobilization of deeply subducted reduced carbon via partial melts of MORB-like eclogite

NASA Astrophysics Data System (ADS)

Eguchi, J.; Dasgupta, R.

2015-12-01

Experimental phase relations of carbonated lithologies [1] and geochemistry of deep diamonds [2] suggest that deep recycling of carbon has likely been efficient for a significant portion of Earth's history. Both carbonates and organic carbon subduct into the mantle, but with gradual decrease of fO2 with depth [3] most carbon in deep mantle rocks including eclogite could be diamond/graphite [4]. Previous studies investigated the transfer of CO2 from subducted eclogite to the ambient mantle by partial melting in the presence of carbonates, i.e., by generation of carbonate-rich melts [5]. However, the transfer of carbon from subducted eclogite to the mantle can also happen, perhaps more commonly, by extraction of silicate partial melt in the presence of reduced carbon; yet, CO2 solubility in eclogite-derived andesitic melt at graphite/diamond saturation remains unconstrained. CO2content of eclogite melts is also critical as geochemistry of many ocean island basalts suggest the presence of C and eclogite in their source regions [6]. In the present study we determine CO2 concentration in a model andesitic melt [7] at graphite/diamond saturation at conditions relevant for partial melting of eclogite in the convecting upper mantle. Piston cylinder and multi anvil experiments were conducted at 1-6 GPa and 1375-1550 °C using Pt/Gr double capsules. Oxygen fugacity was monitored with Pt-Fe sensors in the starting mix. Completed experiments at 1-3 GPa show that CO2 concentration increases with increasing P, T, and fO2 up to ~0.3 wt%. Results were used to develop empirical and thermodynamic models to predict CO2 concentration in partial melts of graphite saturated eclogite. This allowed us to quantify the extent to which CO2 can mobilize from eclogitic heterogeneities at graphite/diamond saturated conditions. With estimates of eclogite contribution to erupted basaltic lavas, the models developed here allow us to put constraints on the flux of CO2 to mantle source regions coming from subducted crust and investigate the possible role this process may play in the deep carbon cycle. [1] Dasgupta (2013) RiMG. [2] Shirey, et al. (2013) RiMG. [3] Frost & McCammon (2008) Ann Rev Earth Plan Sci. [4] Stagno, et al. (2015) CMP. [5] Kiseeva, et al. (2012) JPet. [6] Mallik & Dasgupta (2014) G3. [7] Spandler, et al. (2008) JPet.

Biogeochemistry of a treeline watershed, northwestern Alaska

USGS Publications Warehouse

Stottlemyer, R.

2001-01-01

Since 1950, mean annual temperatures in northwestern Alaska have increased. Change in forest floor and soil temperature or moisture could alter N mineralization rates, production of dissolved organic carbon (DOC) and organic nitrogen (DON), and their export to the aquatic ecosystem. In 1990, we began study of nutrient cycles in the 800-ha Asik watershed, located at treeline in the Noatak National Preserve, northwestern Alaska. This paper summarizes relationships between topographic aspect, soil temperature and moisture, inorganic and organic N pools, C pools, CO2 efflux, growing season net N mineralization rates, and stream water chemistry. Forest floor (O2) C/N ratios, C pools, temperature, and moisture were greater on south aspects. More rapid melt of the soil active layer (zone of annual freeze-thaw) and permafrost accounted for the higher moisture. The O2 C and N content were correlated with moisture, inorganic N pools, CO2 efflux, and inversely with temperature. Inorganic N pools were correlated with temperature and CO2 efflux. Net N mineralization rates were positive in early summer, and correlated with O2 moisture, temperature, and C and N pools. Net nitrification rates were inversely correlated with moisture, total C and N. The CO2 efflux increased with temperature and moisture, and was greater on south aspects. Stream ion concentrations declined and DOC increased with discharge. Stream inorganic nitrogen (DIN) output exceeded input by 70%. Alpine stream water nitrate (NO-3) and DOC concentrations indicated substantial contributions to the watershed DIN and DOC budgets.

Biogeochemistry of a treeline watershed, northwestern Alaska.

PubMed

Stottlemyer, R

2001-01-01

Since 1950, mean annual temperatures in northwestern Alaska have increased. Change in forest floor and soil temperature or moisture could alter N mineralization rates, production of dissolved organic carbon (DOC) and organic nitrogen (DON), and their export to the aquatic ecosystem. In 1990, we began study of nutrient cycles in the 800-ha Asik watershed, located at treeline in the Noatak National Preserve, northwestern Alaska. This paper summarizes relationships between topographic aspect, soil temperature and moisture, inorganic and organic N pools, C pools, CO2 efflux, growing season net N mineralization rates, and stream water chemistry. Forest floor (O2) C/N ratios, C pools, temperature, and moisture were greater on south aspects. More rapid melt of the soil active layer (zone of annual freeze-thaw) and permafrost accounted for the higher moisture. The O2 C and N content were correlated with moisture, inorganic N pools, CO2 efflux, and inversely with temperature. Inorganic N pools were correlated with temperature and CO2 efflux. Net N mineralization rates were positive in early summer, and correlated with O2 moisture, temperature, and C and N pools. Net nitrification rates were inversely correlated with moisture, total C and N. The CO2 efflux increased with temperature and moisture, and was greater on south aspects. Stream ion concentrations declined and DOC increased with discharge. Stream inorganic nitrogen (DIN) output exceeded input by 70%. Alpine stream water nitrate (NO3-) and DOC concentrations indicated substantial contributions to the watershed DIN and DOC budgets.

Chemical modeling of groundwater in the Banat Plain, southwestern Romania, with elevated As content and co-occurring species by combining diagrams and unsupervised multivariate statistical approaches.

PubMed

Butaciu, Sinziana; Senila, Marin; Sarbu, Costel; Ponta, Michaela; Tanaselia, Claudiu; Cadar, Oana; Roman, Marius; Radu, Emil; Sima, Mihaela; Frentiu, Tiberiu

2017-04-01

The study proposes a combined model based on diagrams (Gibbs, Piper, Stuyfzand Hydrogeochemical Classification System) and unsupervised statistical approaches (Cluster Analysis, Principal Component Analysis, Fuzzy Principal Component Analysis, Fuzzy Hierarchical Cross-Clustering) to describe natural enrichment of inorganic arsenic and co-occurring species in groundwater in the Banat Plain, southwestern Romania. Speciation of inorganic As (arsenite, arsenate), ion concentrations (Na + , K + , Ca 2+ , Mg 2+ , HCO 3 - , Cl - , F - , SO 4 2- , PO 4 3- , NO 3 - ), pH, redox potential, conductivity and total dissolved substances were performed. Classical diagrams provided the hydrochemical characterization, while statistical approaches were helpful to establish (i) the mechanism of naturally occurring of As and F - species and the anthropogenic one for NO 3 - , SO 4 2- , PO 4 3- and K + and (ii) classification of groundwater based on content of arsenic species. The HCO 3 - type of local groundwater and alkaline pH (8.31-8.49) were found to be responsible for the enrichment of arsenic species and occurrence of F - but by different paths. The PO 4 3- -AsO 4 3- ion exchange, water-rock interaction (silicates hydrolysis and desorption from clay) were associated to arsenate enrichment in the oxidizing aquifer. Fuzzy Hierarchical Cross-Clustering was the strongest tool for the rapid simultaneous classification of groundwaters as a function of arsenic content and hydrogeochemical characteristics. The approach indicated the Na + -F - -pH cluster as marker for groundwater with naturally elevated As and highlighted which parameters need to be monitored. A chemical conceptual model illustrating the natural and anthropogenic paths and enrichment of As and co-occurring species in the local groundwater supported by mineralogical analysis of rocks was established. Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation of xerogel SiO2 from roasted iron sand under various acidic solution

NASA Astrophysics Data System (ADS)

Ramelan, A. H.; Wahyuningsih, S.; Ismoyo, Y. A.; Pranata, H. P.; Munawaroh, H.

2016-11-01

Xerogel SiO2 had been prepared from roasted iron sand through variation of Na2CO3 addition and sol-gel process under various acidic solution. Roasting treatment was carried out on the compositional variation of iron sand:Na2CO3 = 1:2; 1:1 and 2:1 at 1100 °C. While the sol-gel process was conducted at room temperature and neutralized using HCl 0.1 M and 6 M. The color characteristics of roasted iron sand shown light brown, dark brown and dark gray of the compositional variation of iron sand:Na2CO3 = 1:2; 1:1 and 2:1, respectively. In addition, the levels of thoughness increased by increasing the ratio of sand in the composition of the mixture. The best composition of roasted treatment was at a variety of iron sand:Na2SiO3 = 1:2 with 57.72% had been dissolved in hot water. The addition of Na2CO3 will influence the Na2SiO3 formation, because of the increase of Na2CO3 capable produced the iron sand decomposition product. Na2SiO3 gel had been produced after it was neutralized with certain amount of HCl solution. The neutralization was more effective if using high concentration of HCl because of the formation of gel SiO2 will be easier occurred. The results of SiO2 had been identified by the FTIR spectra, which an absorption spectra of Si-O-Si asymmetric stretching at 1098.51 cm-1, symmetric stretching of Si-O-Si at 804.35 cm-1 and the bending O-Si-O at 469.69 cm'1. The result of SiO2 content by XRF analysis is about 85.15%.

Dissolved carbon dynamics in large boreal rivers from eastern Canada following their impoundment

NASA Astrophysics Data System (ADS)

Helie, J.; Rosa, E.; Lalonde, A.; Hillaire-Marcel, C.

2009-12-01

The carbon cycling in Canadian boreal environments is the focus of a growing number of investigations mainly because of the importance of hydropower and its potential in the area. Here, we document the behaviour of dissolved inorganic and organic carbon as well as particulate organic carbon (DIC-DOC-POC henceforth) in 5 impounded and 2 pristine river systems (respectively: La Grande 3400 m 3s-1, Eastmain 990 m3s-1, St. Lawrence 12 100 m3s-1, Ottawa 1950 m3s-1, Nelson 2370 m3s-1; Great Whales 680 m3s-1 and Koksoak 1895 m3s-1) river systems. These major rivers were sampled monthly at their outlet for one year except at the St. Lawrence River that has been sampled since June of 1997 on a bi-weekly basis. Complementary synoptic surveys were undertaken in August 2008 on the La Grande and Great Whales Rivers. When sampling, water temperature, pH, alkalinity and specific conductivity were measured. Samples were collected for the analysis of i) major ions concentrations; ii) δ13C and concentration of DIC, DOC and POC); iii) δ18O and δ2H of the water molecule; and iv) U series and Sr isotopes. In all the sampled river systems, POC concentrations were at least an order of magnitude smaller than the dissolved forms. Rivers draining carbonates bedrocks (St.Lawrence and Nelson Rivers) present higher concentrations and δ13C-DIC values linked to carbonate dissolution in soils. Conversely, rivers draining silicate-rich watersheds present lower δ13C- DIC values linked to the production of an isotopically light CO2 through oxidation of organic matter in soils and that of soil-derived DOC along river courses. However, isotopic composition of DIC in impounded rivers draining silicate catchments indicate significant CO2 degassing and some isotopic exchange with atmospheric CO2 in reservoirs. A relatively strong relationship is observed between pCO2 and δ13C-DIC across the studied river systems suggesting a continuum between the production of CO2 through DOM oxidation and CO2 degassing. A relationship is also observed between δ13C-DIC values and [DOC]/[DIC] suggesting here that the more DOC is available for degradation, the more it will be oxidized to dissolved CO2. A striking feature of boreal systems is the homogeneity of the isotopic composition of its DOC (-27.4±0.2‰ vs. V-PDB). Moreover, C/N ratios and 14C activities >100% (vs. "modern" carbon) of bulk dissolved organic matter (MOD) measured in the impounded La Grande River also lead to conclude that that this DOC, mostly fresh and young, has a low overall residence time in the catchment basin.

Photosynthates as dominant source of CH4 and CO2 in soil water and CH4 emitted to the atmosphere from paddy fields

NASA Astrophysics Data System (ADS)

Minoda, Tomomi; Kimura, Mamoto; Wada, Eitaro

1996-09-01

Emission rates of CH4 from paddy soil with and without rice straw applications were measured with pot experiments to estimate the contribution of rice straw to the total CH4 emission during the growth period of rice plants. The CH4 derived from rice straw was calculated to be 44% of the total emission. 13CO2 uptake experiments were also carried out four times from June 30 to September 13, 1994, to estimate the contribution of photosynthesized carbon to CH4 emission. The contribution percentages of photosynthesized carbon to the total CH4 emitted to the atmosphere were 3.8% around June 30, 31% around July 25, 30% around August 19, and 14% around September 13 in the treatment with rice straw applications, and 52% around July 25, 28% around August 19, and 15% around September 13 in the treatment without rice straw applications. They were calculated to be 22% and 29% for the entire growth period in the treatments with and without rice straw applications, respectively. The contribution percentages of photosynthesized carbon to the total CH4 and inorganic carbon (Σ CO2) dissolved in soil water were 1.3%, 30%, 29%, and 34% for dissolved CH4 and 3.0%, 36%, 30% and 28% for dissolved inorganic carbon around June 30, July 25, August l9, and September 13, respectively, in the treatment with rice straw applications. They were 70%, 23%, and 32% for dissolved CH4 and 31%, 16%, and 19% for dissolved inorganic carbon around July 25, August 19, and September 13, respectively, in the treatment without rice straw applications.

[FTIR and 13C NMR Analysis of Dissolved Organic Matter (DOM) in the Treatment Process of Tannery Wastewater].

PubMed

Fan, Chun-hui; Zhang, Ying-chao; Tang, Ze-heng; Wang, Jia-hong

2015-05-01

Nowadays, the wastewater quantity discharged yearly from tannery industry is around 0. 2 billion t in China. The contaminants of tannery wastewater include macromolecular organic matters, such as grease, fur scraps and collagen, and the alkaline wastewater appears to be of high content of salt and COD. The quality of tannery wastewater is monitored strictly among all kinds of industry wastewater. In the treatment process of tannery wastewater, the quality of inlet and outlet water is generally analyzed. In fact, the transformation behavior of contaminants should be additionally checked to optimize the treatment conditions. Dissolved organic matter (DOM) is commonly existed in water-bodies and helpful to understand the physicochemical characteristics, while the related work should be further studied on tannery wastewater. The approaches of elemental analysis, thermal gravimetric analysis (TG), Fourier infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C NMR) were used to reveal the characteristics of DOM in the treatment process of tannery wastewater. The results showed the carbon content of DOM samples increased gradually, atomic ratios of H/C increased firstly and then decreased, indicating the organic matters were decomposed into chain structures firstly, finally forming the component hard to degraded. The pyrolysis process of DOM mainly proceeded in the regions of 110~530 °C (aliphatic compound, protein, etc. ) and 530~800 °C (aromatic ring, single bond of C-C, etc. ). The functional groups of DOM included -OH, -NH2, C=O and so on, and the aromatic substances were detected, shown from FTIR figures, in the later period of the reaction, caused by the metabolism effect of micro-organism. The content of alkoxy-C increased to the maximum in the second biochemical pond, and the minimum content of aromatic-C appeared in the second biochemical pond, suggesting the transformation behavior of carbon functional groups. The investigation on DOM in tannery wastewater is significant to understand the purification mechanism of contaminants in tannery wastewater.

Zircon-quartz-calcite segregations in carbonate-alkaline metasomatic rocks of the western Baikal region and their petrogenetic implications

NASA Astrophysics Data System (ADS)

Savelyeva, V. B.; Bazarova, E. P.; Sharygin, V. V.; Karmanov, N. S.

2015-12-01

Fine-grained segregations up to 5 mm in size composed of graphic intergrowths of zircon, quartz, calcite and containing up to 0.8 wt % SrO have been found in albite-riebeckite and dolomite-biotite metasomatic rocks formed after alaskite granite. They contain magnetite, titanomagnetite (25.4 wt % TiO2), cerite-(Ce,Nd), rutile (up to 1.2 wt % Nb2O5), as well as rare micrograins of monazite-(Ce), bastnaesite-(Ce), and barite (up to 5.7 wt % SrO). The fine-grained structure of mineral aggregates suggests a metacolloidal nature. It is assumed that the zircon-quartz-calcite assemblage was formed due to exchange decomposition reaction between the salt phase of hydrothermal solution with predominant Na2CO3, elevated Zr and, to a lesser extent, Fe, Ti, LREE, Nb contents and dissolved calcium and silica compounds of a Na2SiO3 type.

Dynamic analysis of reactive oxygen nitrogen species in plasma-activated culture medium by UV absorption spectroscopy

NASA Astrophysics Data System (ADS)

Brubaker, Timothy R.; Ishikawa, Kenji; Takeda, Keigo; Oh, Jun-Seok; Kondo, Hiroki; Hashizume, Hiroshi; Tanaka, Hiromasa; Knecht, Sean D.; Bilén, Sven G.; Hori, Masaru

2017-12-01

The liquid-phase chemical kinetics of a cell culture basal medium during treatment by an argon-fed, non-equilibrium atmospheric-pressure plasma source were investigated using real-time ultraviolet absorption spectroscopy and colorimetric assays. Depth- and time-resolved NO2- and NO3- concentrations were strongly inhomogeneous and primarily driven by convection during and after plasma-liquid interactions. H2O2 concentrations determined from deconvolved optical depth spectra were found to compensate for the optical depth spectra of excluded reactive species and changes in dissolved gas content. Plasma-activated media remained weakly basic due to NaHCO3 buffering, preventing the H+-catalyzed decomposition of NO2- seen in acidic plasma-activated water. An initial increase in pH may indicate CO2 sparging. Furthermore, the pH-dependency of UV optical depth spectra illustrated the need for pH compensation in the fitting of optical depth data.

Preparation of paclitaxel/chitosan co-assembled core-shell nanofibers for drug-eluting stent

NASA Astrophysics Data System (ADS)

Tang, Jing; Liu, Yongjia; Zhu, Bangshang; Su, Yue; Zhu, Xinyuan

2017-01-01

The paclitaxel/chitosan (PTX/CS) core-shell nanofibers (NFs) are easily prepared by co-assembly of PTX and CS and used in drug-eluting stent. The mixture solution of PTX (dissolved in ethanol) and CS (dissolved in 1% acetic acid water solution) under sonication will make the formation of NFs, in which small molecule PTX co-assembles with biomacromolecular CS through non-covalent interactions. The obtained NFs are tens to hundreds nanometers in diameter and millimeter level in length. Furthermore, the structure of PTX/CS NFs was characterized by confocal laser scanning microscopy (CLSM), zeta potential, X-ray photoelectron spectroscopy (XPS) and nanoscale infra-red (nanoIR), which provided evidences demonstrated that PTX/CS NFs are core-shell structures. The 'shell' of CS wrapped outside of the NFs, while PTX is located in the core. Thus it resulted in high drug loading content (>40 wt.%). The well-controlled drug release, low cytotoxicity and good haemocompatibility were also found in drug carrier system of PTX/CS NFs. In addition, the hydrophilic and flexible properties of NFs make them easily coating and filming on stent to prepare drug-eluting stent (DES). Therefore, this study provides a convenient method to prepare high PTX loaded NFs, which is a promising nano-drug carrier used for DES and other biomedical applications. The possible molecular mechanism of PTX and CS co-assembly and core-shell nanofiber formation is also explored.

Contemporary reliance on bicarbonate acquisition predicts increased growth of seagrass Amphibolis antarctica in a high-CO2 world

PubMed Central

Burnell, Owen W.; Connell, Sean D.; Irving, Andrew D.; Watling, Jennifer R.; Russell, Bayden D.

2014-01-01

Rising atmospheric CO2 is increasing the availability of dissolved CO2 in the ocean relative to HCO3−. Currently, many marine primary producers use HCO3− for photosynthesis, but this is energetically costly. Increasing passive CO2 uptake relative to HCO3− pathways could provide energy savings, leading to increased productivity and growth of marine plants. Inorganic carbon-uptake mechanisms in the seagrass Amphibolis antarctica were determined using the carbonic anhydrase inhibitor acetazolamide (AZ) and the buffer tris(hydroxymethyl)aminomethane (TRIS). Amphibolis antarctica seedlings were also maintained in current and forecasted CO2 concentrations to measure their physiology and growth. Photosynthesis of A. antarctica was significantly reduced by AZ and TRIS, indicating utilization of HCO3−-uptake mechanisms. When acclimated plants were switched between CO2 treatments, the photosynthetic rate was dependent on measurement conditions but not growth conditions, indicating a dynamic response to changes in dissolved CO2 concentration, rather than lasting effects of acclimation. At forecast CO2 concentrations, seedlings had a greater maximum electron transport rate (1.4-fold), photosynthesis (2.1-fold), below-ground biomass (1.7-fold) and increase in leaf number (2-fold) relative to plants in the current CO2 concentration. The greater increase in photosynthesis (measured as O2 production) compared with the electron transport rate at forecasted CO2 concentration suggests that photosynthetic efficiency increased, possibly due to a decrease in photorespiration. Thus, it appears that the photosynthesis and growth of seagrasses reliant on energetically costly HCO3− acquisition, such as A. antarctica, might increase at forecasted CO2 concentrations. Greater growth might enhance the future prosperity and rehabilitation of these important habitat-forming plants, which have experienced declines of global significance. PMID:27293673

Contemporary reliance on bicarbonate acquisition predicts increased growth of seagrass Amphibolis antarctica in a high-CO2 world.

PubMed

Burnell, Owen W; Connell, Sean D; Irving, Andrew D; Watling, Jennifer R; Russell, Bayden D

2014-01-01

Rising atmospheric CO2 is increasing the availability of dissolved CO2 in the ocean relative to HCO3 (-). Currently, many marine primary producers use HCO3 (-) for photosynthesis, but this is energetically costly. Increasing passive CO2 uptake relative to HCO3 (-) pathways could provide energy savings, leading to increased productivity and growth of marine plants. Inorganic carbon-uptake mechanisms in the seagrass Amphibolis antarctica were determined using the carbonic anhydrase inhibitor acetazolamide (AZ) and the buffer tris(hydroxymethyl)aminomethane (TRIS). Amphibolis antarctica seedlings were also maintained in current and forecasted CO2 concentrations to measure their physiology and growth. Photosynthesis of A. antarctica was significantly reduced by AZ and TRIS, indicating utilization of HCO3 (-)-uptake mechanisms. When acclimated plants were switched between CO2 treatments, the photosynthetic rate was dependent on measurement conditions but not growth conditions, indicating a dynamic response to changes in dissolved CO2 concentration, rather than lasting effects of acclimation. At forecast CO2 concentrations, seedlings had a greater maximum electron transport rate (1.4-fold), photosynthesis (2.1-fold), below-ground biomass (1.7-fold) and increase in leaf number (2-fold) relative to plants in the current CO2 concentration. The greater increase in photosynthesis (measured as O2 production) compared with the electron transport rate at forecasted CO2 concentration suggests that photosynthetic efficiency increased, possibly due to a decrease in photorespiration. Thus, it appears that the photosynthesis and growth of seagrasses reliant on energetically costly HCO3 (-) acquisition, such as A. antarctica, might increase at forecasted CO2 concentrations. Greater growth might enhance the future prosperity and rehabilitation of these important habitat-forming plants, which have experienced declines of global significance.

Pressure, O2, and CO2, in aquatic Closed Ecological Systems

NASA Astrophysics Data System (ADS)

Taub, Frieda B.; McLaskey, Anna K.

2013-03-01

Pressure increased during net photosynthetic O2 production in the light and decreased during respiratory O2 uptake during the dark in aquatic Closed Ecological Systems (CESs) with small head gas volumes. Because most CO2 will be in the liquid phase as bicarbonate and carbonate anions, and CO2 is more soluble than O2, volumes of gaseous CO2 and gaseous O2 will not change in a compensatory manner, leading to the development of pressure. Pressure increases were greatest with nutrient rich medium with NaHCO3 as the carbon source. With more dilute media, pressure was greatest with NaHCO3, and less with cellulose or no-added carbon. Without adequate turbulence, pressure measurements lagged dissolved O2 concentrations by several hours and dark respiration would have been especially underestimated in our systems (250-1000 ml). With adequate turbulence (rotary shaker), pressure measurements and dissolved O2 concentrations generally agreed during lights on/off cycles, but O2 measurements provided more detail. At 20 °C, 29.9 times as much O2 will distribute into the gas phase as in the liquid, per unit volume, as a result of the limited solubility of O2 in water and according to Henry's Law. Thus even a small head gas volume can contain more O2 than a larger volume of water. When both dissolved and gaseous O2 and CO2 are summed, the changes in Total O2 and CO2 are in relatively close agreement when NaHCO3 is the carbon source. These findings disprove an assumption made in some of Taub's earlier research that aquatic CESs would remain at approximately atmospheric pressure because approximately equal molar quantities of O2 and CO2 would exchange during photosynthesis and respiration; this assumption neglected the distribution of O2 between water and gas phases. High pressures can occur when NaHCO3 is the carbon source in nutrient rich media and if head-gas volumes are small relative to the liquid volume; e.g., one "worse case" condition developed 800 mm Hg above atmospheric pressure and broke the glass container. Plastic screw cap closures are likely to leak at high pressures and should not be assumed to seal unless tested at appropriate pressures. Pressure can be reduced by having larger head-gas volumes and using less concentrated nutrient solutions. It is important that pressure changes be considered for both safety and closure, and if total O2 is used as the measure of net photosynthesis and respiration, the O2 in the gas phase must be added to the dissolved O2.

Reductive solubilization of arsenic in a mining-impacted river floodplain: Influence of soil properties and temperature.

PubMed

Simmler, Michael; Bommer, Jérôme; Frischknecht, Sarah; Christl, Iso; Kotsev, Tsvetan; Kretzschmar, Ruben

2017-12-01

Mining activities have contaminated many riverine floodplains with arsenic (As). When floodplain soils become anoxic under water-saturated conditions, As can be released from the solid phase. Several microbially-driven As solubilization processes and numerous influential factors were recognized in the past. However, the interplay and relative importance of soil properties and the influence of environmental factors such as temperature remain poorly understood, especially considering the (co)variation of soil properties in a floodplain. We conducted anoxic microcosm experiments at 10, 17.5, and 25 °C using 65 representative soils from the mining-impacted Ogosta River floodplain in Bulgaria. To investigate the processes of As solubilization and its quantitative variation we followed the As and Fe redox dynamics in the solid and the dissolved phase and monitored a range of other solution parameters including pH, Eh, dissolved organic C, and dissolved Mn. We related soil properties to dissolved As observed after 20 days of microcosm incubation to identify key soil properties for As solubilization. Our results evidenced reductive dissolution of As-bearing Fe(III)-oxyhydroxides as the main cause for high solubilization. The availability of nutrients, most likely organic C as the source of energy for microorganisms, was found to limit this process. Following the vertical nutrient gradient common in vegetated soil, we observed several hundred μM dissolved As after 1-2 weeks for some topsoils (0-20 cm), while for subsoils (20-40 cm) with comparable total As levels only minor solubilization was observed. While high Mn contents were found to inhibit As solubilization, the opposite applied for higher temperature (Q 10 2.3-6.1 for range 10-25 °C). Our results suggest that flooding of nutrient-rich surface layers might be more problematic than water-saturation of nutrient-poor subsoil layers, especially in summer floodings when soil temperature is higher than in winter or spring. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sources and Dynamics of Inorganic Carbon within the Upper Reaches of the Xi River Basin, Southwest China

PubMed Central

Zou, Junyu

2016-01-01

The carbon isotopic composition (δ13C) of dissolved and particulate inorganic carbon (DIC; PIC) was used to compare and analyze the origin, dynamics and evolution of inorganic carbon in two headwater tributaries of the Xi River, Southwest China. Carbonate dissolution and soil CO2 were regarded as the primary sources of DIC on the basis of δ13CDIC values which varied along the Nanpan and Beipan Rivers, from −13.9‰ to 8.1‰. Spatial trends in DIC differed between the two rivers (i.e., the tributaries), in part because factors controlling pCO2, which strongly affected carbonate dissolution, differed between the two river basins. Transport of soil CO2 and organic carbon through hydrologic conduits predominately controlled the levels of pCO2 in the Nanpan River. However, pCO2 along the upper reaches of the Nanpan River also was controlled by the extent of urbanization and industrialization relative to agriculture. DIC concentrations in the highly urbanized upper reaches of the Nanpan River were typical higher than in other carbonate-dominated areas of the upper Xi River. Within the Beipan River, the oxidation of organic carbon is the primary process that maintains pCO2 levels. The pCO2 within the Beipan River was more affected by sulfuric acid from coal industries, inputs from a scenic spot, and groundwater than along the Nanpan River. With regards to PIC, the contents and δ13C values in the Nanpan River were generally lower than those in the Beipan River, indicating that chemical and physical weathering contributes more marine carbonate detritus to the PIC along the Beipan River. The CO2 evasion flux from the Nanpan River was higher than that in the Beipan River, and generally higher than along the middle and lower reaches of the Xi River, demonstrating that the Nanpan River is an important net source of atmospheric CO2 in Southwest China. PMID:27513939

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

2017-07-01

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

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.

Greenhouse gases dissolved in soil solution - often ignored, but important?

NASA Astrophysics Data System (ADS)

Weymann, Daniel; Brueggemann, Nicolas; Puetz, Thomas; Vereecken, Harry

2014-05-01

Flux measurements of climate-relevant trace gases from soils are frequently undertaken in contemporary ecosystem studies and substantially contribute to our understanding of greenhouse gas balances of the biosphere. While the great majority of such investigations builds on closed chamber and eddy covariance measurements, where upward gas fluxes to the atmosphere are measured, fewest concurrently consider greenhouse gas dissolution in the seepage and leaching of dissolved gases via the vadose zone to the groundwater. Here we present annual leaching losses of dissolved N2O and CO2 from arable, grassland, and forest lysimeter soils from three sites differing in altitude and climate. We aim to assess their importance in comparison to direct N2O emission, soil respiration, and further leaching parameters of the C- and N cycle. The lysimeters are part of the Germany-wide lysimeter network initiative TERENO-SoilCan, which investigates feedbacks of climate change to the pedosphere on a long-term scale. Soil water samples were collected weekly from different depths of the profiles by means of suction cups. A laboratory pre-experiment proved that no degassing occurred under those sampling conditions. We applied the headspace equilibration technique to determine dissolved gas concentrations by gas chromatography. The seepage water of all lysimeters was consistently supersaturated with N2O and CO2 compared to water equilibrated ambient air. In terms of N2O, leaching losses increased in the ascending order forest, grassland, and arable soils, respectively. In case of the latter soils, we observed a strong variability of N2O, with dissolved concentrations up to 23 μg N L-1. However, since seepage discharge of the arable lysimeters was comparatively small and mostly limited to the hydrological winter season, leached N2O appeared to be less important than direct N2O emissions. In terms of dissolved CO2,our measurements revealed considerable leaching losses from the mountainous forest and grassland soils, based on concentrations up to 24 mg C L-1 and high seepage discharge. Such losses turned out to be similarly important like soil respiration, particularly during winter when temperature-dependent soil respiration declined. In conclusion, the results of the first year of our measurements provide evidence that dissolved greenhouse gases should be considered in studies which aim to assess full greenhouse gas balances, particularly in ecosystems where hydrological conditions favour microbial activity and high leaching losses.

Co(III)EDTA- Reduction by Desulfovibrio vulgaris and Propagation of Reactions Involving Dissolved Sulfide and Polysulfides.

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

Blessing, T.C.; B.W. Wielinga; M.J. Morra

2001-04-15

The migration of 60Co is driven by Co(III)EDTA- complexes. Here we document the bacterial mediated reduction of Co(III) to Co(II)EDTA2- complexes, which are far less mobile within the environment. Additionally, we demonstrate that sulfate promotes reduction via production of reactive polysulfides rather than acting as a competitive electron acceptor.

Behavioral Response of Hermit Crabs (Clibanarius digueti) to Dissolved Carbon Dioxide

NASA Astrophysics Data System (ADS)

Maier, H. J.

2015-12-01

CO2 induced ocean acidification is currently changing the population dynamics of marine organisms. As a result of ocean acidification, marine organisms expend extra energy on modifying behaviors. The current rate of ocean acidification will deplete the marine food chain that much of the world relies on as their major food supply. The purpose of this study was to understand whether and how ocean acidification affects the behavior of hermit crabs Clibanarius digueti. We hypothesized that an increase in carbonic acid would modify grazing and individual movement, because an increase in acidification alters the normal chemical composition of the water and potentially the niche occupancy of C. digueti. A model tidal pool experiment consisting of two tanks (control and treatment) inhabited with seven living C. digueti was set up in the Ocean Biome of Biosphere-2. Each tank was also provided with uninhabited shells: two Turbo fluctuosa and four Cerithium sp. Gaseous CO2 was dissolved into a treatment tank and measured as dissolved CO2 by using a sodium hydroxide titration method. Additionally, water conditions were characterized for UV- light and temperature. Two trials were run in this experiment with tanks and treatments interchanged in each trial. We assessed whether increased CO2 affected hermit crab shell change rate. We found that shell changes only happened among C. digueti placed under increased CO2. The information from this analysis will allow us to assess whether ocean acidification affects basic behavior in hermit crabs, which could later affect population dynamics. Bringing together all of this information will allow us to measure the effects of climate change on the behavior of C.Digueti.

Expansion of mesenchymal stem cells under atmospheric carbon dioxide.

PubMed

Brodsky, Arthur Nathan; Zhang, Jing; Visconti, Richard P; Harcum, Sarah W

2013-01-01

Stem cells are needed for an increasing number of scientific applications, including both fundamental research and clinical disease treatment. To meet this rising demand, improved expansion methods to generate high quantities of high quality stem cells must be developed. Unfortunately, the bicarbonate buffering system - which relies upon an elevated CO2 environment - typically used to maintain pH in stem cell cultures introduces several unnecessary limitations in bioreactor systems. In addition to artificially high dissolved CO2 levels negatively affecting cell growth, but more importantly, the need to sparge CO2 into the system complicates the ability to control culture parameters. This control is especially important for stem cells, whose behavior and phenotype is highly sensitive to changes in culture conditions such as dissolved oxygen and pH. As a first step, this study developed a buffer to support expansion of mesenchymal stem cells (MSC) under an atmospheric CO2 environment in static cultures. MSC expanded under atmospheric CO2 with this buffer achieved equivalent growth rates without adaptation compared to those grown in standard conditions and also maintained a stem cell phenotype, self-renewal properties, and the ability to differentiate into multiple lineages after expansion. © 2013 American Institute of Chemical Engineers.

Reduced gas seepages in serpentinized peridotite complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

NASA Astrophysics Data System (ADS)

Deville, E.; Vacquand, C.; Beaumont, V.; Francois, G.; Sissmann, O.; Pillot, D.; Arcilla, C. A.; Prinzhofer, A.

2017-12-01

A comparative study of reduced gas seepages associated to serpentinized ultrabasic rocks was conducted in the ophiolitic complexes of Oman, the Philippines, Turkey and New Caledonia. This study is based on analyzes of the gas chemical composition, noble gases contents, and stable isotopes of carbon, hydrogen and nitrogen. These gas seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct families of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These families are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich family associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 families. H2-bearing gases are either associated to ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and high pH conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4 (conditions of strong carbon restriction). The N2-rich family is associated with relatively high contents of crustal 4He. In this family N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

Reduced gas seepages in ophiolitic complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

NASA Astrophysics Data System (ADS)

Vacquand, Christèle; Deville, Eric; Beaumont, Valérie; Guyot, François; Sissmann, Olivier; Pillot, Daniel; Arcilla, Carlo; Prinzhofer, Alain

2018-02-01

This paper proposes a comparative study of reduced gas seepages occurring in ultrabasic to basic rocks outcropping in ophiolitic complexes based on the study of seepages from Oman, the Philippines, Turkey and New Caledonia. This study is based on analyses of the gas chemical composition, noble gases contents, stable isotopes of carbon, hydrogen and nitrogen. These seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct types of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These types are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich type, associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 types. H2-bearing gases are either associated with ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and alkaline conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4. The N2-rich type is notably associated with relatively high contents of crustal 4He and in this gas type N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

The influence of headspace and dissolved oxygen level on growth and haemolytic BL enterotoxin production of a psychrotolerant Bacillus weihenstephanensis isolate on potato based ready-to-eat food products.

PubMed

Samapundo, S; Everaert, H; Wandutu, J N; Rajkovic, A; Uyttendaele, M; Devlieghere, F

2011-04-01

The major objective of this study was to determine the influence of the initial headspace and dissolved O(2) level and vacuum packaging on growth and diarrhoeal enterotoxin production by Bacillus weihenstephanensis on potato based ready-to-eat food products. In general, the lower the initial headspace or dissolved O(2) level the slower the maximum growth rate (μ(max), log(10) CFU g(-1) d(-1)), the longer the lag phase duration (λ, d) and the smaller the maximum population density (N(max), log(10) CFU g(-1)) became. The slowest μ(max), the longest λ and the smallest N(max) were generally found for growth under vacuum packaging. This implies shorter shelf-lives will occur at higher initial headspace or dissolved O(2) levels as the growth of B. weihenstephanensis to the infective dose of 10(5) CFU g(-1) in such atmospheres takes a shorter time. Significant consumption of dissolved O(2) only occurred when growth shifted from the lag to the exponential phase and growth generally transitioned from the exponential to the stationary phase when the dissolved O(2) levels fell below ca. 75 ppb. Diarrhoeal enterotoxin production (determined via detection of the L2 component of haemolytic BL) was similar for growth under initial headspace O(2) levels of 1-20.9%, and was only reduced when growth took place under vacuum packaging. The reduction in L2 production when growth took place under vacuum was most probably related to the low final cell densities observed under this condition. Both growth and L2 production were inhibited over a 32-day incubation period at 7 °C by 40% CO(2) irrespective of the headspace or dissolved O(2) levels. The results illustrate the importance of residual O(2) and CO(2) on the shelf-stability and safety of modified atmosphere packaged potato based ready-to-eat food products with regards to B. weihenstephanensis. Copyright © 2010 Elsevier Ltd. All rights reserved.

Evaluation of supercritical CO2 dried cellulose aerogels as nano-biomaterials

NASA Astrophysics Data System (ADS)

Lee, Sinah; Kang, Kyu-Young; Jeong, Myung-Joon; Potthast, Antje; Liebner, Falk

2017-10-01

Cellulose is the renewable, biodegradable and abundant resource and is suggested as an alternative material to silica due to the high price and environmental load of silica. The first step for cellulose aerogel production is to dissolve cellulose, and hydrated calcium thiocyanate molten salt is one of the most effective solvents for preparing porous material. Cellulose aerogels were prepared from dissolved cellulose samples of different degree of polymerization (DP) and drying methods, and tested with shrinkage, density and mechanical strength. Supercritical CO2 dried cellulose aerogels shrank less compared to freeze-dried cellulose aerogels, whereas the densities were increased according to the DP increases in both cellulose aerogels. Furthermore, scanning electron microscope (SEM) images showed that the higher DP cellulose aerogels were more uniform with micro-porous structure. Regarding the mechanical strength of cellulose aerogels, supercritical CO2 dried cellulose aerogels with higher molecular weight were much more solid.

Carbon dioxide dynamics in a lake and a reservoir on a tropical island (Bali, Indonesia).

PubMed

Macklin, Paul A; Suryaputra, I Gusti Ngurah Agung; Maher, Damien T; Santos, Isaac R

2018-01-01

Water-to-air carbon dioxide fluxes from tropical lakes and reservoirs (artificial lakes) may be an important but understudied component of global carbon fluxes. Here, we investigate the seasonal dissolved carbon dioxide (CO2) dynamics in a lake and a reservoir on a tropical volcanic island (Bali, Indonesia). Observations were performed over four seasonal surveys in Bali's largest natural lake (Lake Batur) and largest reservoir (Palasari Reservoir). Average CO2 partial pressures in the natural lake and reservoir were 263.7±12.2 μatm and 785.0±283.6 μatm respectively, with the highest area-weighted partial pressures in the wet season for both systems. The strong correlations between seasonal mean values of dissolved oxygen (DO) and pCO2 in the natural lake (r2 = 0.92) suggest that surface water metabolism was an important driver of CO2 dynamics in this deep system. Radon (222Rn, a natural groundwater discharge tracer) explained up to 77% of the variability in pCO2 in the shallow reservoir, suggesting that groundwater seepage was the major CO2 driver in the reservoir. Overall, the natural lake was a sink of atmospheric CO2 (average fluxes of -2.8 mmol m-2 d-1) while the reservoir was a source of CO2 to the atmosphere (average fluxes of 7.3 mmol m-2 d-1). Reservoirs are replacing river valleys and terrestrial ecosystems, particularly throughout developing tropical regions. While the net effect of this conversion on atmospheric CO2 fluxes remains to be resolved, we speculate that reservoir construction will partially offset the CO2 sink provided by deep, volcanic, natural lakes and terrestrial environments.

Export of Dissolved Methane and Carbon Dioxide with Effluents from Municipal Wastewater Treatment Plants.

PubMed

Alshboul, Zeyad; Encinas-Fernández, Jorge; Hofmann, Hilmar; Lorke, Andreas

2016-06-07

Inland waters play an important role for regional and global scale carbon cycling and are significant sources of the atmospheric greenhouse gases methane (CH4) and carbon dioxide (CO2). Although most studies considered the input of terrestrially derived organic and inorganic carbon as the main sources for these emissions, anthropogenic sources have rarely been investigated. Municipal wastewater treatment plants (WWTPs) could be additional sources of carbon by discharging the treated wastewater into the surrounding aquatic ecosystems. Here we analyze seasonally resolved measurements of dissolved CH4 and CO2 concentrations in effluents and receiving streams at nine WWTPs in Germany. We found that effluent addition significantly altered the physicochemical properties of the streamwater. Downstream of the WWTPs, the concentrations of dissolved CH4 and CO2 were enhanced and the atmospheric fluxes of both gases increased by a factor of 1.2 and 8.6, respectively. The CH4 exported with discharged effluent, however, accounted for only a negligible fraction (0.02%) of the estimated total CH4 emissions during the treatment process. The CH4 concentration in the effluent water was linearly related to the organic load of the wastewater, which can provide an empirical basis for future attempts to add WWTPs inputs to regional-scale models for inland water-carbon fluxes.

Compositions for, solutions for, and methods of use of siloxane based aromatic trisureas as viscosifiers

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

Doherty, Mark Daniel; O'Brien, Michael Joseph; Lee, Jason

A compound represented by the following formula is provided: ##STR00001## Also provided is a solution including a compound disclosed herein, a volume of dense carbon dioxide (CO.sub.2), and a co-solvent, where the solution has an increased viscosity greater than the viscosity of dense CO.sub.2. Methods of increasing the viscosity of dense CO.sub.2 and natural gas liquids (NGLs) by, for example, dissolving a compound disclosed herein to form a solution, are also provided.

Constraints on the magnitude and rate of carbon dioxide dissolution at Bravo Dome natural gas field

NASA Astrophysics Data System (ADS)

Sathaye, K.; Hesse, M. A.

2013-12-01

The Bravo Dome field in northeastern New Mexico contains at least 10 trillion cubic feet (tcf) of magmatic CO2. The CO2 has been emplaced in the reservoir for at least 10,000 years, providing a useful analog for geologic CO2 storage. The reservoir is comprised of a CO2 gas layer overlying brine water in a sandstone reservoir. Previous estimates have used differences in the CO2/3He ratio in the gas to infer that locally, half of the CO2 originally emplaced has dissolved into the underlying brine. This study presents the first estimate of the total amount of CO2 dissolved. We incorporate gas pressure, reservoir geometry, and gas layer thickness to show that over 80% of the CO2 originally emplaced is still present in the gas layer. It is generally assumed that the dissolution of CO2 is driven by convective currents in the brine. We present an alternative hypothesis for the spatial differences of the CO2/3He ratio seen in this reservoir. Gas injection theory predicts that as gas displaces a liquid, relatively insoluble gas components will become enriched at the front of the displacement. If the emplacement occurred from west to east this would cause 3He enrichment in the eastern portion of the Bravo Dome field overlying the brine. This effect could be responsible for the spatial differences in the CO2/3He ratio. Mass per area in the gas layer of the reservoir is seen in the 2 right panes. The measured bottom hole pressure data from 1981 is used in combination with CO2/3He measurements to estimate the mass of CO2 originally in place. The water thickness is inversely correlated with the CO2/3He ratio, suggesting that there may be convective dissolution occurring in the eastern part of the reservoir. Present day mass of CO2 is roughly 83% of the original total.

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

NASA Astrophysics Data System (ADS)

Fu, Q.; Socki, R. A.; Niles, P. B.

2010-12-01

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 °C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the δ13C values of CH4 and C2H6 were -50.3‰ and -39.3‰ (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a δ13C value of -19.2‰, which was 3.2‰ heavier than its source, formic acid. The δ13C difference between CO2 and CH4 was 31.1‰, which was higher than the value of 9.4‰ calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1‰) observed in similar experiments previously performed at 400 °C and 50 MPa with longer reaction times. CH4 is 11.0‰ less enriched in 13C than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer-Tropsch-type (FTT) synthesis in a gas phase. The observed increase of δ13C values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, R. A.; Niles, P. B.

2010-01-01

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability.

PubMed

Turner, Andrew; Mawji, Edward

2005-05-01

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.

Effects of different forms of plant-derived organic matter on nitrous oxide emissions.

PubMed

Qiu, Qingyan; Wu, Lanfang; Ouyang, Zhu; Li, Binbin; Xu, Yanyan

2016-07-13

To investigate the impact of different forms of plant-derived organic matter on nitrous oxide (N2O) emissions, an incubation experiment with the same rate of total nitrogen (N) application was carried out at 25 °C for 250 days. Soils were incorporated with maize-derived organic matter (i.e., maize residue-derived dissolved organic matter and maize residues with different C/N ratios) and an inorganic N fertilizer (urea). The pattern and magnitude of nitrous oxide (N2O) emissions were affected by the form of N applied. Single application of maize-derived organic matter resulted in a higher N2O emission than single application of the inorganic N fertilizer or combined application of the inorganic N fertilizer and maize-derived organic matter. The positive effect of maize residue-derived dissolved organic matter (DOM) addition on N2O emissions was relatively short-lived and mainly occurred at the early stage following DOM addition. In contrast, the positive effect induced by maize residue addition was more pronounced and lasted for a longer period. Single application of maize residues resulted in a substantial decrease in soil nitric nitrogen (NO3(-)-N), but it did not affect the production of N2O. No significant relationship between N2O emission and NO3(-)-N and ammonium nitrogen (NH4(+)-N) suggested that the availability of soil N was not limiting the production of N2O in our study. The key factors affecting soil N2O emission were the soil dissolved organic carbon (DOC) content and metabolism quotient (qCO2). Both of them could explain 87% of the variation in cumulative N2O emission. The C/N ratio of maize-derived organic matter was a poor predictor of N2O emission when the soil was not limited by easily available C and the available N content met the microbial N demands for nitrification and denitrification. The results suggested that the magnitude of N2O emission was determined by the impact of organic amendments on soil C availability and microbial activity rather than on soil N availability. In agricultural management practices, if the N inputs from organic and inorganic N fertilizers are equivalent, addition of organic N fertilizers that contain high amounts of available C will result in a higher N2O emission.

Dissolved gases in hydrothermal (phreatic) and geyser eruptions at Yellowstone National Park, USA

USGS Publications Warehouse

Hurwitz, Shaul; Clor, Laura; McCleskey, R. Blaine; Nordstrom, D. Kirk; Hunt, Andrew G.; Evans, William C.

2016-01-01

Multiphase and multicomponent fluid flow in the shallow continental crust plays a significant role in a variety of processes over a broad range of temperatures and pressures. The presence of dissolved gases in aqueous fluids reduces the liquid stability field toward lower temperatures and enhances the explosivity potential with respect to pure water. Therefore, in areas where magma is actively degassing into a hydrothermal system, gas-rich aqueous fluids can exert a major control on geothermal energy production, can be propellants in hazardous hydrothermal (phreatic) eruptions, and can modulate the dynamics of geyser eruptions. We collected pressurized samples of thermal water that preserved dissolved gases in conjunction with precise temperature measurements with depth in research well Y-7 (maximum depth of 70.1 m; casing to 31 m) and five thermal pools (maximum depth of 11.3 m) in the Upper Geyser Basin of Yellowstone National Park, USA. Based on the dissolved gas concentrations, we demonstrate that CO2 mainly derived from magma and N2 from air-saturated meteoric water reduce the near-surface saturation temperature, consistent with some previous observations in geyser conduits. Thermodynamic calculations suggest that the dissolved CO2 and N2 modulate the dynamics of geyser eruptions and are likely triggers of hydrothermal eruptions when recharged into shallow reservoirs at high concentrations. Therefore, monitoring changes in gas emission rate and composition in areas with neutral and alkaline chlorine thermal features could provide important information on the natural resources (geysers) and hazards (eruptions) in these areas.

Dark production of carbon monoxide (CO) from dissolved organic matter in the St. Lawrence estuarine system: Implication for the global coastal and blue water CO budgets

NASA Astrophysics Data System (ADS)

Zhang, Yong; Xie, Huixiang; Fichot, CéDric G.; Chen, Guohua

2008-12-01

We investigated the thermal (dark) production of carbon monoxide (CO) from dissolved organic matter (DOM) in the water column of the St. Lawrence estuarine system in spring 2007. The production rate, Qco, decreased seaward horizontally and downward vertically. Qco exhibited a positive, linear correlation with the abundance of chromophoric dissolved organic matter (CDOM). Terrestrial DOM was more efficient at producing CO than marine DOM. The temperature dependence of Qco can be characterized by the Arrhenius equation with the activation energies of freshwater samples being higher than those of salty samples. Qco remained relatively constant between pH 4-6, increased slowly between pH 6-8 and then rapidly with further rising pH. Ionic strength and iron chemistry had little influence on Qco. An empirical equation, describing Qco as a function of CDOM abundance, temperature, pH, and salinity, was established to evaluate CO dark production in the global coastal waters (depth < 200 m). The total coastal CO dark production from DOM was estimated to be from 0.46 to 1.50 Tg CO-C a-1 (Tg carbon from CO a-1). We speculated the global oceanic (coastal plus open ocean) CO dark production to be in the range from 4.87 to 15.8 Tg CO-C a-1 by extrapolating the coastal water-based results to blue waters (depth > 200 m). Both the coastal and global dark source strengths are significant compared to the corresponding photochemical CO source strengths (coastal: ˜2.9 Tg CO-C a-1; global: ˜50 Tg CO-C a-1). Steady state deepwater CO concentrations inferred from Qco and microbial CO uptake rates are <0.1 nmol L-1.

Lessons Learned From Recent Research on Internal CO2 Transport in Trees. Part II, Recycling of Respired CO2

NASA Astrophysics Data System (ADS)

McGuire, M. A.; Bloemen, J.; Aubrey, D. P.; Steppe, K.; Teskey, R. O.

2016-12-01

It has long been known that photosynthesis in woody tissues can provide substantial contributions to tree carbon economy in species with green bark, for example in the high-latitude species Populus tremuloides and the desert genus Cercidium. In addition, in the last half of the prior century, the capacity to re-assimilate xylem-transported CO2 was shown in leaves and small stems of trees, although little research has been conducted until recently. It is likely that recycling of respired CO2 occurs in leaves and branches of all woody plants and also in large stems of many species. Re-assimilation of respired CO2 may be especially important to the carbon economy of trees during periods of stress because some constraints to carbon gain from the atmosphere are absent in recycling processes; most importantly, acquisition of CO2 is not limited by leaf abscission or stomatal closure as long as respiration continues. The ability to quantify the re-assimilation of xylem-transported CO2 has emerged only in the last decade. Here, we will review newly developed measurement techniques and recent data from several research groups. Factors affecting the re-assimilation capacity of woody plant tissues will be discussed, including light environment, light penetration, chlorophyll content, xylem CO2 concentration, transpiration rate, tissue age, and species. Two main research paths have emerged for measuring re-assimilation of respired CO2: the first involves measuring the fate of isotope-labeled dissolved CO2 in the transpiration stream and the second compares growth of shaded vs. non-shaded woody tissues. Gas exchange measurements have been used to verify both techniques. In experiments on multiple species, isotope labeling has shown that up to 35% of transported CO2 was re-assimilated and shading has shown that up to 30% of carbon needed for stem growth can be provided by woody tissue photosynthesis. We suggest that the role of recycling of xylem-transported respired CO2 in plant carbon dynamics deserves more research attention, especially as related to stress and mortality.

Characterization of a heat-tolerant Chlorella sp. GD mutant with enhanced photosynthetic CO2 fixation efficiency and its implication as lactic acid fermentation feedstock.

PubMed

Lee, Tse-Min; Tseng, Yu-Fei; Cheng, Chieh-Lun; Chen, Yi-Chuan; Lin, Chih-Sheng; Su, Hsiang-Yen; Chow, Te-Jin; Chen, Chun-Yen; Chang, Jo-Shu

2017-01-01

Fermentative production of lactic acid from algae-based carbohydrates devoid of lignin has attracted great attention for its potential as a suitable alternative substrate compared to lignocellulosic biomass. A Chlorella sp. GD mutant with enhanced thermo-tolerance was obtained by mutagenesis using N -methyl- N '-nitro- N -nitrosoguanidine to overcome outdoor high-temperature inhibition and it was used as a feedstock for fermentative lactic acid production. The indoor experiments showed that biomass, reducing sugar content, photosynthetic O 2 evolution rate, photosystem II activity ( F v / F m and F v '/ F m '), and chlorophyll content increased as temperature, light intensity, and CO 2 concentration increased. The mutant showed similar DIC affinity and initial slope of photosynthetic light response curve (α) as that of the wild type but had higher dissolved inorganic carbon (DIC) utilization capacity and maximum photosynthesis rate ( P max ). Moreover, the PSII activity ( F v '/ F m ') in the mutant remained normal without acclimation process after being transferred to photobioreactor. This suggests that efficient utilization of incident high light and enhanced carbon fixation with its subsequent flux to carbohydrates accumulation in the mutant contributes to higher sugar and biomass productivity under enriched CO 2 condition. The mutant was cultured outdoors in a photobioreactor with 6% CO 2 aeration in hot summer season in southern Taiwan. The harvested biomass was subjected to separate hydrolysis and fermentation (SHF) for lactic acid production with carbohydrate concentration equivalent to 20 g/L glucose using the lactic acid-producing bacterium Lactobacillus plantarum 23. The conversion rate and yield of lactic acid were 80% and 0.43 g/g Chlorella biomass, respectively. These results demonstrated that the thermo-tolerant Chlorella mutant with high photosynthetic efficiency and biomass productivity under hot outdoor condition is an efficient fermentative feedstock for large-scale lactic acid production.

Mobility of nutrients and trace metals during weathering in the late Archean

NASA Astrophysics Data System (ADS)

Hao, Jihua; Sverjensky, Dimitri A.; Hazen, Robert M.

2017-08-01

The evolution of the geosphere and biosphere depends on the availability of bio-essential nutrients and trace metals. Consequently, the chemical and isotopic variability of trace elements in the sedimentary record have been widely used to infer the existence of early life and fluctuations in the near-surface environment on the early Earth, particularly fluctuations in the redox state of the atmosphere. In this study, we applied late Archean weathering models (Hao et al., 2017), developed to estimate the behavior of major elements and the composition of late Archean world average river water, to explore the behavior of nutrient and trace metals and their potential for riverine transport. We focused on P, Mn, Cr, and Cu during the weathering of olivine basalt. In our standard late Archean weathering model (pCO2,g = 10-1.5 bars, pH2,g = 10-5.0 bars), crustal apatite was totally dissolved by the acidic rainwater during weathering. Our model quantitatively links the pCO2,g of the atmosphere to phosphate levels transported by rivers. The development of late Archean river water (pH = 6.4) resulted in riverine phosphate of at least 1.7 μmolar, much higher than at the present-day. At the end of the early Proterozoic snowball Earth event when pCO2,g could be 0.01-0.10 bars, river water may have transported up to 70 μmolar phosphate, depending on the availability of apatite, thereby stimulating high levels of oxygenic photosynthesis in the marine environment. Crustal levels of Mn in olivine dissolved completely during weathering, except at large extents of weathering where Mn was stored as a component of a secondary carbonate mineral. The corresponding Mn content of river water, about 1.2 μmolar, is higher than in modern river water. Whiffs of 10-5 mole O2 gas or HNO3 kg-1 H2O resulted in the formation of pyrolusite (MnO2) and abundant hematite and simultaneous dramatic decreases in the concentration of Mn(II) in the river water. Chromite dissolution resulted in negligible dissolved Cr in Archean river water. However, amorphous Cr(OH)3 representing easily-weatherable Cr-bearing minerals dissolved totally during the weathering simulations, resulting in concentrations of Cr(III) in the river water of up to 0.14 μmolar, higher than at the present-day. Late Archean weathering of accessory chalcopyrite produced chalcocite and bornite, and extremely low concentrations of Cu (<10-15 molar) because of the low solubilities of the copper sulfides. However, pulses of either O2,g or HNO3 produced native copper, chalcocite, and bornite, much more hematite, and river water containing levels of dissolved Cu comparable to the present-day. Copper mineralogy predicted by weathering models might provide a new correlation with evidence from studies of copper mineral evolution. Overall, our results implied that the redox state of the atmosphere, the pH of surface waters, and the availability of easily-weatherable minerals are all important factors controlling the dissolution of trace elements in river water. Interpretation of the sedimentary signatures of trace elements should consider not only the redox state but also the pH and availability of accessory minerals.

Elementary pre-service teachers' conceptual understanding of dissolving: a Vygotskian concept development perspective

NASA Astrophysics Data System (ADS)

Harrell, Pamela; Subramaniam, Karthigeyan

2015-09-01

Background and purpose: The purpose of this study was to investigate and identify the nature and the interrelatedness of pre-service teachers' misconceptions and scientific concepts for explaining dissolving before, during, and after a 5E learning cycle lesson on dissolving, the intervention. Sample, design, and methods: Guided by Vygotsky's theory of concept development, the study focused specifically on the spontaneous, and spontaneous pseudo-concepts held by the 61 elementary pre-service teachers during a 15-week science methods course. Data included concept maps, interview transcripts, written artifacts, drawings, and narratives, and were thematically analyzed to classify concepts and interrelatedness. Results: Results of the study showed that spontaneous pseudo-concepts (1) dominated pre-service teachers' understandings about dissolving throughout the study, and (2) were simply associated with scientific concepts during and after the intervention. Conclusion: Collectively, the results indicated that the pre-service teachers' did not acquire a unified system of knowledge about dissolving that could be characterized as abstract, generalizable, and hierarchical. Implications include the need for (1) familiarity with pre-service teachers' prior knowledge about science content; (2) a variety of formative assessments to assess their misconceptions; (3) emphasizing the importance of dialectical method for concept development during instruction; and (4) skillful content instructors.

Effect of pyrolysis temperatures on freely dissolved polycyclic aromatic hydrocarbon (PAH) concentrations in sewage sludge-derived biochars.

PubMed

Zielińska, Anna; Oleszczuk, Patryk

2016-06-01

The aim of this study was to evaluate the effect of sewage sludge pyrolysis on freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) contents in biochars. Four sewage sludges with varying properties and PAH contents were pyrolysed at temperatures of 500 °C, 600 °C or 700 °C. Cfree PAH contents were determined using polyoxymethylene (POM). The contents of Cfree PAHs in the sludges ranged from 262 to 294 ng L(-1). Sewage sludge-derived biochars have from 2.3- to 3.4-times lower Cfree PAH contents comparing to corresponding sewage sludges. The Cfree PAH contents in the biochars ranged between 81 ng L(-1) and 126 ng L(-1). As regards agricultural use of biochar, the lower contents of Cfree PAHs in the biochars compared to the sewage sludges makes biochar a safer material than sewage sludge in terms of PAH contents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Recovery of Minerals in Martian Soils Via Supercritical Fluid Extraction

NASA Astrophysics Data System (ADS)

Debelak, Kenneth A.; Roth, John A.

2001-03-01

We are investigating the use of supercritical fluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercritical fluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercritical fluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercritical fluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2. They reported complete miscibility of TiCl4 with supercritical CO2 (infinite solubility). At 1500 psig, TiCl4 and CO2 form a single liquid phase below 50 C. Tolley et al. also reported on the solubility and thermodynamics of tin tetrachloride in supercritical CO2. Some of their data for TiC14 are shown. Three criteria have been suggested to predict which materials are suitable for supercritical extraction: 1) Hydrocarbons or lipophilic compounds of low molecular weight and polarity are easily extracted with supercritical CO2. 2) Compounds with polar groups are not easily extracted with supercritical CO2. 3) Separation of mixtures is facilitated if components differing mass, vapor pressure, or polarity.

Deepwater Horizon oil in Gulf of Mexico waters after 2 years: transformation into the dissolved organic matter pool.

PubMed

Bianchi, Thomas S; Osburn, Christopher; Shields, Michael R; Yvon-Lewis, Shari; Young, Jordan; Guo, Laodong; Zhou, Zhengzhen

2014-08-19

Recent work has shown the presence of anomalous dissolved organic matter (DOM), with high optical yields, in deep waters 15 months after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico (GOM). Here, we continue to use the fluorescence excitation-emission matrix (EEM) technique coupled with parallel factor analysis (PARAFAC) modeling, measurements of bulk organic carbon, dissolved inorganic carbon (DIC), oil indices, and other optical properties to examine the chemical evolution and transformation of oil components derived from the DWH in the water column of the GOM. Seawater samples were collected from the GOM during July 2012, 2 years after the oil spill. This study shows that, while dissolved organic carbon (DOC) values have decreased since just after the DWH spill, they remain higher at some stations than typical deep-water values for the GOM. Moreover, we continue to observe fluorescent DOM components in deep waters, similar to those of degraded oil observed in lab and field experiments, which suggest that oil-related fluorescence signatures, as part of the DOM pool, have persisted for 2 years in the deep waters. This supports the notion that some oil-derived chromophoric dissolved organic matter (CDOM) components could still be identified in deep waters after 2 years of degradation, which is further supported by the lower DIC and partial pressure of carbon dioxide (pCO2) associated with greater amounts of these oil-derived components in deep waters, assuming microbial activity on DOM in the current water masses is only the controlling factor of DIC and pCO2 concentrations.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

USGS Publications Warehouse

McMahon, Peter B.; Chapelle, Francis H.

1991-01-01

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO2 to respiration CO2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO2 to respiration CO2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

USGS Publications Warehouse

McMahon, Peter B.; Chapelle, Francis H.

1991-01-01

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO2 to respiration CO2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO2 to respiration CO2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

Quantitation of dissolved gas content in emulsions and in blood using mass spectrometric detection.

PubMed

Grimley, Everett; Turner, Nicole; Newell, Clayton; Simpkins, Cuthbert; Rodriguez, Juan

2011-06-01

Quantitation of dissolved gases in blood or in other biological media is essential for understanding the dynamics of metabolic processes. Current detection techniques, while enabling rapid and convenient assessment of dissolved gases, provide only direct information on the partial pressure of gases dissolved in the aqueous fraction of the fluid. The more relevant quantity known as gas content, which refers to the total amount of the gas in all fractions of the sample, can be inferred from those partial pressures, but only indirectly through mathematical modeling. Here we describe a simple mass spectrometric technique for rapid and direct quantitation of gas content for a wide range of gases. The technique is based on a mass spectrometer detector that continuously monitors gases that are rapidly extracted from samples injected into a purge vessel. The accuracy and sample processing speed of the system is demonstrated with experiments that reproduce within minutes literature values for the solubility of various gases in water. The capability of the technique is further demonstrated through accurate determination of O(2) content in a lipid emulsion and in whole blood, using as little as 20 μL of sample. The approach to gas content quantitation described here should greatly expand the range of animals and conditions that may be used in studies of metabolic gas exchange, and facilitate the development of artificial oxygen carriers and resuscitation fluids. Copyright © 2011 Elsevier B.V. All rights reserved.

Influence of low oxygen tensions and sorption to sediment black carbon on biodegradation of pyrene.

PubMed

Ortega-Calvo, José-Julio; Gschwend, Philip M

2010-07-01

Sorption to sediment black carbon (BC) may limit the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in resuspension events and intact sediment beds. We examined this hypothesis experimentally under conditions that were realistic in terms of oxygen concentrations and BC content. A new method, based on synchronous fluorescence observations of (14)C-pyrene, was developed for continuously measuring the uptake of dissolved pyrene by Mycobacterium gilvum VM552, a representative degrader of PAHs. The effect of oxygen and pyrene concentrations on pyrene uptake followed Michaelis-Menten kinetics, resulting in a dissolved oxygen half-saturation constant (K(om)) of 14.1 microM and a dissolved pyrene half-saturation constant (K(pm)) of 6 nM. The fluorescence of (14)C-pyrene in air-saturated suspensions of sediments and induced cells followed time courses that reflected simultaneous desorption and biodegradation of pyrene, ultimately causing a quasi-steady-state concentration of dissolved pyrene balancing desorptive inputs and biodegradation removals. The increasing concentrations of (14)CO(2) in these suspensions, as determined with liquid scintillation, evidenced the strong impact of sorption to BC-rich sediments on the biodegradation rate. Using the best-fit parameter values, we integrated oxygen and sorption effects and showed that oxygen tensions far below saturation levels in water are sufficient to enable significant decreases in the steady-state concentrations of aqueous-phase pyrene. These findings may be relevant for bioaccumulation scenarios that consider the effect of sediment resuspension events on exposure to water column and sediment pore water, as well as the direct uptake of PAHs from sediments.

Accelerated weathering of limestone for CO2 mitigation: Opportunities for the stone and cement industries

USGS Publications Warehouse

Langer, William H.; San, Juan A.; Rau, Greg H.; Caldeira, Ken

2009-01-01

Large amounts of limestone fines co-produced during the processing of crushed limestone may be useful in the sequestration of carbon dioxide (CO2). Accelerated weathering of limestone (AWL) is proposed as a low-tech method to capture and sequester CO2 from fossil fuel-fired power plants and other point sources such as cement manufacturing. AWL reactants are readily available, inexpensive and environmentally benign. Waste CO2 is hydrated with water to produce carbonic acid. This reacts with and is neutralized by limestone fines, thus converting CO2 gas to dissolved calcium bicarbonate.

Reactive Tracer Techniques to Quantitatively Monitor Carbon Dioxide Storage in Geologic Formations

NASA Astrophysics Data System (ADS)

Matter, J. M.; Carson, C.; Stute, M.; Broecker, W. S.

2012-12-01

Injection of CO2 into geologic storage reservoirs induces fluid-rock reactions that may lead to the mineralization of the injected CO2. The long-term safety of geologic CO2 storage is, therefore, determined by in situ CO2-fluid-rock reactions. Currently existing monitoring and verification techniques for CO2 storage are insufficient to characterize the solubility and reactivity of the injected CO2, and to establish a mass balance of the stored CO2. Dissolved and chemically transformed CO2 thus avoid detection. We developed and are testing a new reactive tracer technique for quantitative monitoring and detection of dissolved and chemically transformed CO2 in geologic storage reservoirs. The technique involves tagging the injected carbon with radiocarbon (14C). Carbon-14 is a naturally occurring radioisotope produced by cosmic radiation and made artificially by 14N neutron capture. The ambient concentration is very low with a 14C/12C ratio of 10-12. The concentration of 14C in deep geologic formations and fossil fuels is at least two orders of magnitude lower. This makes 14C an ideal quantitative tracer for tagging underground injections of anthropogenic CO2. We are testing the feasibility of this tracer technique at the CarbFix pilot injection site in Iceland, where approximately 2,000 tons of CO2 dissolved in water are currently injected into a deep basalt aquifer. The injected CO2 is tagged with 14C by dynamically adding calibrated amounts of H14CO3 solution to the injection stream. The target concentration is 12 Bq/kg of injected water, which results in a 14C activity that is 5 times enriched compared to the 1850 background. In addition to 14C as a reactive tracer, trifluormethylsulphur pentafluoride (SF5CF3) and sulfurhexafluoride (SF6) are used as conservative tracers to monitor the transport of the injected CO2 in the subsurface. Fluid samples are collected for tracer analysis from the injection and monitoring wells on a regular basis. Results show a fast reaction of the injected CO2 with the ambient reservoir fluid and rocks. Mixing and in situ CO2-water-rock reactions are detected by changes in the different tracer ratios. The feasibility of 14C as a reactive tracer for geologic CO2 storage also depends on the analytical technique used to measure 14C activities. Currently, 14C is analyzed using Accelerator Mass Spectrometery (AMS), which is expensive and requires centralized facilities. To enable real time online monitoring and verification, we are developing an alternative detection method for radiocarbon. The IntraCavity OptoGalvanic Spectroscopy (ICOGS) system is using a CO2 laser to detect carbon isotope ratios at environmental levels. Results from our prototype of this bench-top technology demonstrate that an ICOGS system can be used in a continuous mode with analysis times of the order of minutes, and can deliver data of similar quality as AMS.

Polyoxymethylene passive samplers to assess the effectiveness of biochar by reducing the content of freely dissolved fipronil and ethiprole.

PubMed

Li, Shasha; Wang, Pingping; Liu, Xingang; Wu, Xiaohu; Dong, Fengshou; Xu, Jun; Zheng, Yongquan

2018-07-15

An equilibrium passive sampler based on polyoxymethylene (POM) was used to determine the freely dissolved concentrations (C free ) of fipronil and ethiprole. The sorption equilibrium times of fipronil and ethiprole in POM were 14.2d and 24.0d, respectively. The POM-water partitioning coefficients (logK POM-water ) were 2.6 for fipronil and 1.4 for ethiprole. The method was further used to evaluate the sorption behavior of biochars which produced by pyrolysis of Magnolia wood (Magnolia denudata) at 300°C, 500°C and 700°C. The amounts of target compounds adsorbed increased with increasing pyrolysis temperature of the biochars. Biochars characterized by a low polarity index had better sorption capacity for the target compounds. The additions of biochars to sediment were effective in reducing C free , and the enhancement was found to be more pronounced with high biochar content. C free in sediment with more organic matter was significantly higher after biochar addition. Increasing the sediment-biochar contact time from 7 to 30d resulted in an increase in sorption of the compounds. We conclude that Magnolia wood biochar effectively reduces the content of freely dissolved fipronil and ethiprole content in sediment. Copyright © 2018. Published by Elsevier B.V.

Pathways and transformations of dissolved methane and dissolved inorganic carbon in Arctic tundra watersheds: Evidence from analysis of stable isotopes

DOE PAGES

Throckmorton, Heather M.; Heikoop, Jeffrey M.; Newman, Brent D.; ...

2015-11-08

Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO 2) and methane (CH 4) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH 4 and CO 2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO 2) and CH 4 in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DICmore » and CH 4 cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH 4 and DIC balance by estimating mechanisms of CH 4 and DIC production and transport pathways and oxidation of subsurface CH 4. We observed a shift from acetoclastic (July) toward hydrogenotropic (September) methanogenesis at sites located toward the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH 4 production mechanism. The majority of subsurface CH 4 was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH 4 oxidation. Thus, surprisingly, CH 4 oxidation only consumed approximately 2.51± 0.82% (July) and 0.79 ± 0.79% (September) of CH 4 produced at the frost table, contributing to <0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. Furthermore, this work highlights the importance of spatial and temporal variability of CH 4 production at the watershed scale and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH 4 and CO 2 production.« less

Element budgets in an Arctic mesocosm CO2 perturbation study

NASA Astrophysics Data System (ADS)

Czerny, J.; Schulz, K. G.; Boxhammer, T.; Bellerby, R. G. J.; Büdenbender, J.; Engel, A.; Krug, S. A.; Ludwig, A.; Nachtigall, K.; Nondal, G.; Niehoff, B.; Siljakova, A.; Riebesell, U.

2012-08-01

Recent studies on the impacts of ocean acidification on pelagic communities have identified changes in carbon to nutrient dynamics with related shifts in elemental stoichiometry. In principle, mesocosm experiments provide the opportunity of determining the temporal dynamics of all relevant carbon and nutrient pools and, thus, calculating elemental budgets. In practice, attempts to budget mesocosm enclosures are often hampered by uncertainties in some of the measured pools and fluxes, in particular due to uncertainties in constraining air/sea gas exchange, particle sinking, and wall growth. In an Arctic mesocosm study on ocean acidification using KOSMOS (Kiel Off-Shore Mesocosms for future Ocean Simulation) all relevant element pools and fluxes of carbon, nitrogen and phosphorus were measured, using an improved experimental design intended to narrow down some of the mentioned uncertainties. Water column concentrations of particulate and dissolved organic and inorganic constituents were determined daily. New approaches for quantitative estimates of material sinking to the bottom of the mesocosms and gas exchange in 48 h temporal resolution, as well as estimates of wall growth were developed to close the gaps in element budgets. Future elevated pCO2 was found to enhance net autotrophic community carbon uptake in 2 of the 3 experimental phases but did not significantly affect particle elemental composition. Enhanced carbon consumption appears to result in accumulation of dissolved organic compounds under nutrient recycling summer conditions. This carbon over-consumption effect becomes evident from budget calculations, but was too small to be resolved by direct measurements of dissolved organics. The out-competing of large diatoms by comparatively small algae in nutrient uptake caused reduced production rates under future ocean CO2 conditions in the end of the experiment. This CO2 induced shift away from diatoms towards smaller phytoplankton and enhanced cycling of dissolved organics was pushing the system towards a retention type food chain with overall negative effects on export potential.

Ikaite solubility in seawater-derived brines at 1 atm and sub-zero temperatures to 265 K

NASA Astrophysics Data System (ADS)

Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

2013-05-01

The concentration-based (stoichiometric) equilibrium solubility product of ikaite (CaCO3·6H2O) in seawater and cryogenic seawater-derived brines was determined at 1 atm total pressure over the temperature range from -1.1 to -7.5 °C and the salinity range from 34 to 124 in temperature-salinity pairs representative of sea ice brines. The solubility measurements were obtained in solutions that were undersaturated and supersaturated with respect to ikaite by equilibration with CO2/N2 gas mixtures of known pCO2 (20-400 μatm). The solutions were then equilibrated with synthetic ikaite (seed) for up to 3 months in a closed system. Arrival of the solid-solution system at a long-term chemical equilibrium was indicated by attainment of constant chemical solution composition with respect to total dissolved calcium, total dissolved inorganic carbon, and total alkalinity. Using these measurements, the stoichiometric equilibrium solubility product of ikaite (Ksp,ikaite∗=[Ca][CO32-], in molkgsolution-2) was determined, with the carbonate ion concentration computed from the measured total alkalinity and total dissolved inorganic carbon concentrations. The computed carbonate ion concentration and, by extension, the Ksp,ikaite∗ are both contingent on solving the system of equations that describe the parameters of the CO2 system in seawater by extrapolation to the experimental salinity and temperature conditions. The results show that the pKsp,ikaite∗=-logKsp,ikaite∗ in seawater of salinity 34 at -1.1 °C was 5.362 ± 0.004 and that the pKsp,ikaite∗ in sea ice at the freezing point of brines of salinity greater than 34 can be described as a function of temperature (T, in K) by the equation, pKsp,ikaite∗=-15489.09608+623443.70216T-1+2355.14596lnT, in the temperature range of 265.15 K < T < 271.15 K (-8 °C < t < -2 °C). Brines of low pCO2 (20 μatm) yielded a much slower (>1 month) approach to chemical equilibrium when incubated without seeding ikaite crystals. Simple modeling indicated that ikaite should not precipitate from sea ice brines evolving under closed system conditions with respect to CO2 exchange. To facilitate ikaite precipitation, brine pCO2 reduction due to photosynthesis or CO2 degassing, or both, is necessary.

Gas Transfer Controls Carbon Limitation During Biomass Production by Marine Microalgae.

PubMed

Tamburic, Bojan; Evenhuis, Christian R; Suggett, David J; Larkum, Anthony W D; Raven, John A; Ralph, Peter J

2015-08-24

This study presents the first in-depth analysis of CO2 limitation on the biomass productivity of the biofuel candidate marine microalga Nannochloropsis oculata. Net photosynthesis decreased by 60% from 125 to 50 μmol O2 L(-1)h(-1) over a 12 h light cycle as a direct result of carbon limitation. Continuous dissolved O2 and pH measurements were used to develop a detailed diurnal mechanism for the interaction between photosynthesis, gas exchange and carbonate chemistry in the photo-bioreactor. Gas exchange determined the degree of carbon limitation experienced by the algae. Carbon limitation was confirmed by delivering more CO2 , which increased net photosynthesis back to its steady-state maximum. This study highlights the importance of maintaining replete carbon concentrations in photo-bioreactors and other culturing facilities, either by constant pH operation or preferably by designing a feedback loop based on the dissolved O2 concentration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of CO2 availability on the growth, iron oxidation and CO2-fixation rates of pure cultures of Leptospirillum ferriphilum and Acidithiobacillus ferrooxidans.

PubMed

Bryan, C G; Davis-Belmar, C S; van Wyk, N; Fraser, M K; Dew, D; Rautenbach, G F; Harrison, S T L

2012-07-01

Understanding how bioleaching systems respond to the availability of CO(2) is essential to developing operating conditions that select for optimum microbial performance. Therefore, the effect of inlet gas and associated dissolved CO(2) concentration on the growth, iron oxidation and CO(2) -fixation rates of pure cultures of Acidithiobacillus ferrooxidans and Leptospirillum ferriphilum was investigated in a batch stirred tank system. The minimum inlet CO(2) concentrations required to promote the growth of At. ferrooxidans and L. ferriphilum were 25 and 70 ppm, respectively, and corresponded to dissolved CO(2) concentrations of 0.71 and 1.57 µM (at 30°C and 37°C, respectively). An actively growing culture of L. ferriphilum was able to maintain growth at inlet CO(2) concentrations less than 30 ppm (0.31-0.45 µM in solution). The highest total new cell production and maximum specific growth rates from the stationary phase inocula were observed with CO(2) inlet concentrations less than that of air. In contrast, the amount of CO(2) fixed per new cell produced increased with increasing inlet CO(2) concentrations above 100 ppm. Where inlet gas CO(2) concentrations were increased above that of air the additional CO(2) was consumed by the organisms but did not lead to increased cell production or significantly increase performance in terms of iron oxidation. It is proposed that At. ferrooxidans has two CO(2) uptake mechanisms, a high affinity system operating at low available CO(2) concentrations, which is subject to substrate inhibition and a low affinity system operating at higher available CO(2) concentrations. L. ferriphilum has a single uptake system characterised by a moderate CO(2) affinity. At. ferrooxidans performed better than L. ferriphilum at lower CO(2) availabilities, and was less affected by CO(2) starvation. Finally, the results demonstrate the limitations of using CO(2) uptake or ferrous iron oxidation data as indirect measures of cell growth and performance across varying physiological conditions. Copyright © 2012 Wiley Periodicals, Inc.

Soil carbon dioxide partial pressure and dissolved inorganic carbonate chemistry under elevated carbon dioxide and ozone

Treesearch

N.J. Karberg; K.S. Pregitzer; J.S. King; A.L. Friend; J.R. Wood

2004-01-01

Global emissions of atmospheric CO2 and tropospheric O3 are rising and expected to impact large areas of the Earth's forests. While CO2 stimulates net primary production, O3 reduces photosynthesis, altering plant C allocation and reducing ecosystem C storage. The effects...

Ultrasonic Monitoring of CO2 Uptake and Release from Sand Packs*

NASA Astrophysics Data System (ADS)

Toffelmier, D. A.; Dufrane, W. L.; Bonner, B. P.; Viani, B. E.; Berge, P. A.

2002-12-01

Sequestration of atmospheric CO2 occurs naturally during the formation of calcite cement in sedimentary rock. Acceleration of this process has been proposed as a means of reducing the atmospheric concentration of CO2, which is a major cause of global warming. Calcite may also be precipitated when highly alkaline waste fluid is introduced into the vadose zone from leaking storage tanks. Seismic methods have potential for monitoring these processes. We devised an experiment, guided by geochemical modeling, to determine how the formation of calcite cement in unsaturated sand affects wave propagation. We used the ultrasonic pulse transmission method to measure compressional (P) and shear (S) wave velocities at ultrasonic frequencies (100-500 kHz) through packs of Ottawa sand containing chemically active pore fluids. The samples were saturated with water containing 0.1mol/L of Ca(OH)2 and 0.1mol/L of NaCl and then drained by flowing water saturated, CO2 free N2 gas, to a residual saturation of ~5%, so that the remaining pore fluid resides mainly in pendular spaces between the sand grains. Ambient air saturated with water and containing atmospheric concentration of CO2 was then passed through the sample to effect the precipitation of calcite. Finally, pure water saturated CO2, was flushed through the sample to dissolve most of the precipitated calcite. Over a three day period, measurable changes in Vp and Vs were observed following water saturation, desaturation, calcite precipitation, and calcite dissolution treatments. Changes in the contents of the pore space require waveforms to be recorded before and after each stage of the experiment so both the short and long range effects can be seen. Wave velocities were slow, as is typical for unconsolidated materials, for the dry sand, with values of 365m/s for Vp and 163m/s for Vs. Compressional velocities increased upon desaturation (443m/s), and again following calcite precipitation (460m/s). The compressional velocity measured following the CO2 flush to dissolve the calcite decreased (451m/s). The shear velocities varied similarly to the compressional velocities except that the dry sand shear velocity was faster than the other shear velocities. These preliminary results suggest that ultrasonics could provide a tool to locate the path of certain types of waste fluid in the vadose zone. *This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract number W-7405-ENG-48 and was supported specifically by the Environmental Management Science Program of the Office of Environmental Management and the Office of Energy Research.

Inhibitory effect of self-generated extracellular dissolved organic carbon on carbon dioxide fixation in sulfur-oxidizing bacteria during a chemoautotrophic cultivation process and its elimination.

PubMed

Wang, Ya-Nan; Tsang, Yiu Fai; Wang, Lei; Fu, Xiaohua; Hu, Jiajun; Li, Huan; Le, Yiquan

2018-03-01

The features of extracellular dissolved organic carbon (EDOC) generation in two typical aerobic sulfur-oxidizing bacteria (Thiobacillus thioparus DSM 505 and Halothiobacillus neapolitanus DSM 15147) and its impact on CO 2 fixation during chemoautotrophic cultivation process were investigated. The results showed that EDOC accumulated in both strains during CO 2 fixation process. Large molecular weight (MW) EDOC derived from cell lysis and decay was dominant during the entire process in DSM 505, whereas small MW EDOC accounted for a large proportion during initial and middle stages of DSM 15147 as its cytoskeleton synthesis rate did not keep up with CO 2 assimilation rate. The self-generated EDOC feedback repressed cbb gene transcription and thus decreased total bacterial cell number and CO 2 fixation yield in both strains, but DSM 505 was more sensitive to this inhibition effect. Moreover, the membrane bioreactor effectively decreased the EDOC/TOC ratio and improved carbon fixation yield of DSM 505. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fiber-optic microsensor for high resolution pCO2 sensing in marine environment.

PubMed

Neurauter, G; Klimant, I; Wolfbeis, O S

2000-03-01

A fast responding fiber-optic microsensor for sensing pCO2 in marine sediments with high spatial resolution is presented. The tip diameter varies typically between 20 and 50 microm. In order to make the pH-indicator 8-hydroxypyrene-1,3,6-trisulfonate soluble in the ethyl cellulose matrix, it was lipophilized with tetraoctylammonium as the counterion [HPTS-(TOA)4]. The microsensor was tuned to sense very low levels of dissolved carbon dioxide which are typically present in marine systems. The detection limit is 0.04 hPa pCO2 which corresponds to 60 ppb CO2 of dissolved carbon dioxide. A soluble Teflon derivative with an extraordinarily high gas permeability was chosen as a protective coating to eliminate interferences by ionic species like chloride or pH. Response times of less than 1 min were observed. The performance of the new microsensor is described with respect to reproducibility of the calibration curves, dynamic range, temperature behavior, long term stability and storage stability. The effect of hydrogen sulfide as an interferent, which is frequently present in anaerobic sediment layers, was studied in detail.

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments.

PubMed

Stoliker, Deborah L; Campbell, Kate M; Fox, Patricia M; Singer, David M; Kaviani, Nazila; Carey, Minna; Peck, Nicole E; Bargar, John R; Kent, Douglas B; Davis, James A

2013-08-20

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

2013-01-01

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

A shell-formation related carbonic anhydrase in Crassostrea gigas modulates intracellular calcium against CO2 exposure: Implication for impacts of ocean acidification on mollusk calcification.

PubMed

Wang, Xiudan; Wang, Mengqiang; Jia, Zhihao; Song, Xiaorui; Wang, Lingling; Song, Linsheng

2017-08-01

Ocean acidification (OA) could decrease the shells and skeletons formation of mollusk by reducing the availability of carbonate ions at calcification sites. Carbonic anhydrases (CAs) convert CO 2 to HCO 3 - and play important roles in biomineralization process from invertebrate to vertebrate. In the present study, a CA (designated as CgCA) was identified and characterized in Pacific oyster C. gigas. The cDNA of CgCA was of 927bp encoding a predicted polypeptide of 308 amino acids with a signal peptide and a CA catalytic function domain. The mRNA transcripts of CgCA were constitutively expressed in all tested tissues with the highest levels in mantle and hemocytes. During the early development period, the mRNA transcripts of CgCA could be detected in all the stages with the highest level in D-veliger larvae. Elevated CO 2 increased the mRNA transcripts of CgCA in muscle, mantle, hepatopancreas, gill and hemocytes significantly (p<0.05) and induced the translocation of CgCA in hemocytes and mantle. Moreover, elevated CO 2 also caused the decrease of intracellular Ca 2+ in hemocytes (p<0.05). The inhibition of CA by acetazolamide and suppression of CgCA gene via RNA interference could increase the intracellular Ca 2+ in hemocytes (p<0.05). Besides, the decrease of intracellular Ca 2+ content caused by Ca 2+ reagent ionomycin could affect localization of CgCA in mantle tissue. The results indicated CgCA played essential roles in calcification and elevated CO 2 accelerated the mutual modulation between calcium and CgCA, implying reduced calcification rate and dissolved shells under OA. Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

NASA Technical Reports Server (NTRS)

Freund, Friedemann

1991-01-01

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Effect of Mineral Dissolution/Precipitation and CO2 Exsolution on CO2 transport in Geological Carbon Storage.

PubMed

Xu, Ruina; Li, Rong; Ma, Jin; He, Di; Jiang, Peixue

2017-09-19

Geological carbon sequestration (GCS) in deep saline aquifers is an effective means for storing carbon dioxide to address global climate change. As the time after injection increases, the safety of storage increases as the CO 2 transforms from a separate phase to CO 2 (aq) and HCO 3 - by dissolution and then to carbonates by mineral dissolution. However, subsequent depressurization could lead to dissolved CO 2 (aq) escaping from the formation water and creating a new separate phase which may reduce the GCS system safety. The mineral dissolution and the CO 2 exsolution and mineral precipitation during depressurization change the morphology, porosity, and permeability of the porous rock medium, which then affects the two-phase flow of the CO 2 and formation water. A better understanding of these effects on the CO 2 -water two-phase flow will improve predictions of the long-term CO 2 storage reliability, especially the impact of depressurization on the long-term stability. In this Account, we summarize our recent work on the effect of CO 2 exsolution and mineral dissolution/precipitation on CO 2 transport in GCS reservoirs. We place emphasis on understanding the behavior and transformation of the carbon components in the reservoir, including CO 2 (sc/g), CO 2 (aq), HCO 3 - , and carbonate minerals (calcite and dolomite), highlight their transport and mobility by coupled geochemical and two-phase flow processes, and consider the implications of these transport mechanisms on estimates of the long-term safety of GCS. We describe experimental and numerical pore- and core-scale methods used in our lab in conjunction with industrial and international partners to investigate these effects. Experimental results show how mineral dissolution affects permeability, capillary pressure, and relative permeability, which are important phenomena affecting the input parameters for reservoir flow modeling. The porosity and the absolute permeability increase when CO 2 dissolved water is continuously injected through the core. The MRI results indicate dissolution of the carbonates during the experiments since the porosity has been increased after the core-flooding experiments. The mineral dissolution changes the pore structure by enlarging the throat diameters and decreasing the pore specific surface areas, resulting in lower CO 2 /water capillary pressures and changes in the relative permeability. When the reservoir pressure decreases, the CO 2 exsolution occurs due to the reduction of solubility. The CO 2 bubbles preferentially grow toward the larger pores instead of toward the throats or the finer pores during the depressurization. After exsolution, the exsolved CO 2 phase shows low mobility due to the highly dispersed pore-scale morphology, and the well dispersed small bubbles tend to merge without interface contact driven by the Ostwald ripening mechanism. During depressurization, the dissolved carbonate could also precipitate as a result of increasing pH. There is increasing formation water flow resistance and low mobility of the CO 2 in the presence of CO 2 exsolution and carbonate precipitation. These effects produce a self-sealing mechanism that may reduce unfavorable CO 2 migration even in the presence of sudden reservoir depressurization.

Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

NASA Astrophysics Data System (ADS)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2013-04-01

Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

Significance of groundwater discharge along the coast of Poland as a source of dissolved metals to the southern Baltic Sea

USGS Publications Warehouse

Szymczycha, Beata; Kroeger, Kevin D.; Pempkowiak, Janusz

2016-01-01

Fluxes of dissolved trace metals (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) via groundwater discharge along the southern Baltic Sea have been assessed for the first time. Dissolved metal concentrations in groundwater samples were less variable than in seawater and were generally one or two orders of magnitude higher: Cd (2.1–2.8 nmol L− 1), Co (8.70–8.76 nmol L− 1), Cr (18.1–18.5 nmol L− 1), Mn (2.4–2.8 μmol L− 1), Pb (1.2–1.5 nmol L− 1), Zn (33.1–34.0 nmol L− 1). Concentrations of Cu (0.5–0.8 nmol L− 1) and Ni (4.9–5.8 nmol L− 1) were, respectively, 32 and 4 times lower, than in seawater. Groundwater-derived trace metal fluxes constitute 93% for Cd, 80% for Co, 91% for Cr, 6% for Cu, 66% for Mn, 4% for Ni, 70% for Pb and 93% for Zn of the total freshwater trace metal flux to the Bay of Puck. Groundwater-seawater mixing, redox conditions and Mn-cycling are the main processes responsible for trace metal distribution in groundwater discharge sites.

Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

DOE PAGES

He, Feng; Zhao, Weirong; Liang, Liyuan; ...

2014-11-11

Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, CO 3 2-, NO 3 -] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h -1) in the presence of bothmore » HCO 3 2- and NO 3 -, whereas HCO 3 2-, NO 3 -, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h -1). Using scavengers and enhancers for singlet oxygen ( 1O 2) and hydroxyl (HO ∙ ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO 3 ∙-) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO 3 ∙- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.« less

"Supergreen" Renewables: Integration of Mineral Weathering Into Renewable Energy Production for Air CO2 Removal and Storage as Ocean Alkalinity

NASA Astrophysics Data System (ADS)

Rau, G. H.; Carroll, S.; Ren, Z. J.

2015-12-01

Excess planetary CO2 and accompanying ocean acidification are naturally mitigated on geologic time scales via mineral weathering. Here, CO2 acidifies the hydrosphere, which then slowly reacts with silicate and carbonate minerals to produce dissolved bicarbonates that are ultimately delivered to the ocean. This alkalinity not only provides long-term sequestration of the excess atmospheric carbon, but it also chemically counters the effects of ocean acidification by stabilizing or raising pH and carbonate saturation state, thus helping rebalance ocean chemistry and preserving marine ecosystems. Recent research has demonstrated ways of greatly accelerating this process by its integration into energy systems. Specifically, it has been shown (1) that some 80% of the CO2 in a waste gas stream can be spontaneously converted to stable, seawater mineral bicarbonate in the presence of a common carbonate mineral - limestone. This can allow removal of CO2 from biomass combustion and bio-energy production while generating beneficial ocean alkalinity, providing a potentially cheaper and more environmentally friendly negative-CO2-emissions alternative to BECCS. It has also been demonstrated that strong acids anodically produced in a standard saline water electrolysis cell in the formation of H2 can be reacted with carbonate or silicate minerals to generate strong base solutions. These solutions are highly absorptive of air CO2, converting it to mineral bicarbonate in solution. When such electrochemical cells are powered by non-fossil energy (e.g. electricity from wind, solar, tidal, biomass, geothermal, etc. energy sources), the system generates H2 that is strongly CO2-emissions-negative, while producing beneficial marine alkalinity (2-4). The preceding systems therefore point the way toward renewable energy production that, when tightly coupled to geochemical mitigation of CO2 and formation of natural ocean "antacids", forms a high capacity, negative-CO2-emissions, "supergreen" source of fuel or electrcity. 1) http://pubs.acs.org/doi/pdf/10.1021/es102671x2) http://pubs.acs.org/doi/full/10.1021/es800366q3) http://www.pnas.org/content/110/25/10095.full.pdf4) http://pubs.acs.org/doi/abs/10.1021/acs.est.5b00875

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.

Greenhouse gases emissions in rivers of the Tibetan Plateau.

PubMed

Qu, Bin; Aho, Kelly Sue; Li, Chaoliu; Kang, Shichang; Sillanpää, Mika; Yan, Fangping; Raymond, Peter A

2017-11-29

Greenhouse gases (GHGs) emissions from streams are important to regional biogeochemical budgets. This study is one of the first to incorporate stream GHGs (CO 2 , CH 4 and N 2 O) concentrations and emissions in rivers of the Tibetan Plateau. With one-time sampling from 32 sites in rivers of the plateau, we found that most of the rivers were supersaturated with CO 2 , CH 4 and N 2 O during the study period. Medians of partial pressures of CO 2 (pCO 2 ), pCH 4 and pN 2 O were presented 864 μatm, 6.3 μatm, and 0.25 μatm respectively. Based on a scaling model of the flux of gas, the calculated fluxes of CO 2 , CH 4 and N 2 O (3,452 mg-C m 2 d -1 , 26.7 mg-C m 2 d -1 and 0.18 mg-N m 2 d -1 , respectively) in rivers of the Tibetan Plateau were found comparable with most other rivers in the world; and it was revealed that the evasion rates of CO 2 and CH 4 in tributaries of the rivers of the plateau were higher than those in the mainstream despite its high altitude. Furthermore, concentrations of GHGs in the studied rivers were related to dissolved carbon and nitrogen, indicating that riverine dissolved components could be used to scale GHGs envision in rivers of the Tibetan Plateau.

Conversion of sustained release omeprazole loaded buccal films into fast dissolving strips using supercritical carbon dioxide (scCO2) processing, for potential paediatric drug delivery.

PubMed

Khan, Sajjad; Trivedi, Vivek; Mitchell, John; Boateng, Joshua S

2016-10-10

This study involves the development of thin oral solvent cast films for the potential delivery of the proton pump inhibitor, omeprazole (OME) via the buccal mucosa for paediatric patients. OME containing films were prepared from ethanolic gels (1% w/w) of metolose (MET) with polyethylene glycol (PEG 400) (0.5% w/w) as plasticiser, and L-arginine (l-arg) (0.2% w/w) as a stabilizer and dried in an oven at 40°C. The blank and drug loaded films were divided into two groups, one group was subjected to supercritical carbon dioxide (scCO2) treatment and the other group untreated. The untreated and scCO2 treated films were then characterised using differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, hydration (swelling), mucoadhesion and in vitro drug dissolution studies. Treatment of the solvent cast films with scCO2 caused significant changes to the functional and physical properties of the MET films. The original drug loaded MET films showed a sustained release of OME (1h), whereas scCO2 treatment of the formulations resulted in fast dissolving films with >90% drug release within 15min. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of a Prototype pCO2 Optical Sensor

NASA Astrophysics Data System (ADS)

Sanborn-Marsh, C.; Sutton, A.; Sabine, C. L.; Lawrence-Salvas, N.; Dietrich, C.

2016-12-01

Anthropogenic greenhouse gas emissions continue to rise, driving climate change and altering the ocean carbonate systems. Carbonate chemistry can be characterized by any two of the four parameters: pH, total alkalinity, dissolved inorganic carbon, and partial pressure of dissolved carbon dioxide gas (pCO2). To fully monitor these dynamic systems, researchers must deploy a more temporally and spatially comprehensive sensor network. Logistical challenges, such as the energy consumption, size, lifetime, depth range, and cost of pCO2 sensors have limited the network's reach so far. NOAA's Pacific Marine Environmental Laboratory has conducted assessment tests of a pCO2 optical sensor (optode), recently developed by Atamanchuk et al (2014). We hope to deploy this optode in the summer of 2017 on high-resolution moored profiler, along with temperature, salinity, and oxygen sensors. While most pCO2 optodes have energy consumptions of 3-10 W, this 36mm-diameter by 86mm-long instrument consumes a mere 7-80 mW. Initial testing showed that its accuracy varied within an absolute range of 2-75 μatm, depending on environmental conditions, including temperature, salinity, response time, and initial calibration. Further research independently examining the effects of each variable on the accuracy of the data will also be presented.

The CarbFix Pilot Project in Iceland - CO2 capture and mineral storage in basaltic rocks

NASA Astrophysics Data System (ADS)

Sigurdardottir, H.; Sigfusson, B.; Aradottir, E. S.; Gunnlaugsson, E.; Gislason, S. R.; Alfredsson, H. A.; Broecker, W. S.; Matter, J. M.; Stute, M.; Oelkers, E.

2010-12-01

The overall objective of the CarbFix project is to develop and optimize a practical and cost-effective technology for capturing CO2 and storing it via in situ mineral carbonation in basaltic rocks, as well as to train young scientist to carry the corresponding knowledge into the future. The project consists of a field injection of CO2 charged water at the Hellisheidi geothermal power plant in SW Iceland, laboratory experiments, numerical reactive transport modeling, tracer tests, natural analogue and cost analysis. The CO2 injection site is situated about 3 km south of the Hellisheidi geothermal power plant. Reykjavik Energy operates the power plant, which currently produces 60,000 tons/year CO2 of magmatic origin. The produced geothermal gas mainly consists of CO2 and H2S. The two gases will be separated in a pilot gas treatment plant, and CO2 will be transported in a pipeline to the injection site. There, CO2 will be fully dissolved in 20 - 25°C water during injection at 25 - 30 bar pressure, resulting in a single fluid phase entering the storage formation, which consists of relatively fresh basaltic lavas. The CO2 charged water is reactive and will dissolve divalent cations from the rock, which will combine with the dissolved carbon to form solid thermodynamically stable carbonate minerals. The injection test is designed to inject 2200 tons of CO2 per year. In the past three years the CarbFix project has been addressing background fluid chemistries at the injection site and characterizing the target reservoir for the planned CO2 injection. Numerous groundwater samples have been collected and analysed. A monitoring and accounting plan has been developed, which integrates surface, subsurface and atmospheric monitoring. A weather station is operating at the injection site for continuous monitoring of atmospheric CO2 and to track all key parameters for the injection. Environmental authorities have granted licenses for the CO2 injection and the use of tracers, based on the monitoring plan. Pipelines, injection and monitoring wells have been installed and equipment test runs are in the final phase. A bailer has been constructed to be used to retrieve samples at reservoir conditions. Hydrological parameters of a three dimensional field model have been calibrated and reactive transport simulations are ongoing. The key risks that the project is currently facing are technical and financial. Until now the project has been facing incidences that have already impacted the time schedule in the CarbFix project. Furthermore the project is facing world-wide exchange rate uncertainty plus the inherited uncertainty that innovative research projects contain. However, the CarbFix group remains optimistic that injection will start in near future.

Coral reefs will transition to net dissolving before end of century.

PubMed

Eyre, Bradley D; Cyronak, Tyler; Drupp, Patrick; De Carlo, Eric Heinen; Sachs, Julian P; Andersson, Andreas J

2018-02-23

Ocean acidification refers to the lowering of the ocean's pH due to the uptake of anthropogenic CO 2 from the atmosphere. Coral reef calcification is expected to decrease as the oceans become more acidic. Dissolving calcium carbonate (CaCO 3 ) sands could greatly exacerbate reef loss associated with reduced calcification but is presently poorly constrained. Here we show that CaCO 3 dissolution in reef sediments across five globally distributed sites is negatively correlated with the aragonite saturation state (Ω ar ) of overlying seawater and that CaCO 3 sediment dissolution is 10-fold more sensitive to ocean acidification than coral calcification. Consequently, reef sediments globally will transition from net precipitation to net dissolution when seawater Ω ar reaches 2.92 ± 0.16 (expected circa 2050 CE). Notably, some reefs are already experiencing net sediment dissolution. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Worldwide Emerging Environmental Issues Affecting the U.S. Military. April 2006 Report

DTIC Science & Technology

2006-04-01

Knowledge and Security Some of the most prominent discussions are as follows: - Dissolving coral reef shells are explained by greater increases in CO2...levels within oceanic waters. Especially vulnerable are cold sea corals and recently discovered planktonic organisms. Increases of CO2 reduce pH...leading to acidification . The panelists at the EGU Assembly suggested that 1/3 of all CO2 is absorbed into oceans and that it has recently been

Effect of CO2 Solubility on Dissolution Rates of Minerals in Porous Media Imbibed with Brine: Actual Efficiency of CO2 Sequestration

NASA Astrophysics Data System (ADS)

Alizadeh Nomeli, M.; Riaz, A.

2016-12-01

A new model is developed for geochemical reactions to access dissolution rate of minerals in saline aquifers with respect to saturated concentration of dissolved CO2 as a function of parameters that are dynamically available during computer program execution such as pressure, temperature, and salinity. A general Arrhenius-type equation, with an explicit dependence on the pH of brine, is employed to determine the rates of mineral dissolution. The amount of dissolved CO2 is determined with the help of an accurate PVTx model for the temperature range of 50-100C and pressures up to 600 bar relevant to the geologic sequestration of CO2. We show how activity coefficients for a given salinity condition alters solubility, pH, and reaction rates. We further evaluate the significance of the pre-exponential factor and the reaction order associated with the modified Arrhenius equation to determine the sensitivity of the reaction rates as a function to the pH of the system. It is found that the model can reasonably reproduce experimental data with new parameters that we obtain from sensitivity studies. Using the new rate equation, we investigate geochemically induced alterations of fracture geometry due to mineral dissolution. Finally, we use our model to evaluate the effects of temperature, pressure, and salinity on the actual efficiency of CO2 storage.

Evaluation of the simultaneous biogas upgrading and treatment of centrates in a high-rate algal pond through C, N and P mass balances.

PubMed

Alcántara, Cynthia; García-Encina, Pedro A; Muñoz, Raúl

2015-01-01

The simultaneous capture of CO2 from biogas and removal of carbon and nutrients from diluted centrates in a 180 L high-rate algal pond (HRAP) interconnected to a 2.5 L absorption column were evaluated using a C, N and P mass balance approach. The experimental set-up was operated indoors at 75 μE/m(2)·s for 24 h/d at 20 days of hydraulic retention time for 2 months of steady state, and supported a C-CO2 removal in the absorption column of 55 ± 6%. Carbon fixation into biomass only accounted for 9 ± 2% of the total C input, which explains the low biomass productivity recorded in the HRAP. In this context, the low impinging light intensity along with the high turbulence in the culture broth entailed a C stripping as CO2 of 49 ± 5% of the total carbon input. Nitrification was the main NH4(+) removal mechanism and accounted for 47 ± 2% of the inlet N-NH4(+), while N removal as biomass represented 14 ± 2% of the total nitrogen input. A luxury P uptake was recorded, which resulted in a P-PO4(-3) biomass content over structural requirements (2.5 ± 0.1%). Phosphorus assimilation corresponded to a 77 ± 2% of the inlet dissolved P-PO4(-3) removed.

Isotope hydrology of voluminous cold springs in fractured rock from an active volcanic region, northeastern California

NASA Astrophysics Data System (ADS)

Roses, Timothy P.; Lee Davisson, M.; Criss, Robert E.

1996-05-01

The more than 1550 km2 (600 mi2) Hat Creek Basin in northeastern California is host to several first magnitude cold springs that emanate from Quaternary basaltic rocks with individual discharge rates ranging from 1.7 to 8.5 m3 s-1 (60-300 ft3 s-1). Stable isotope (δ18O, δD, δ13C) and 14C measurements of surface and groundwater samples were used to identify recharge areas, and to evaluate aquifer residence times and flow paths. Recharge locations were constrained from the regional decrement in meteoric water δ18O values as a function of elevation, determined to be -0.23‰ per 100 m for small springs and creek waters collected along the western Cascade slope of this region. In general, the large-volume springs are lower in (δ18O than surrounding meteoric waters, and are inferred to originate in high-elevation, high-precipitation regions up to 50 km away from their discharge points. Large spring 14C abundances range from 99 to 41 % modern carbon (pmc), and most show evidence of interaction with three distinct carbon isotope reservoirs. These reservoirs are tentatively identified as (1) soil CO2 gas equilibrated under open system conditions with groundwater in the recharge zone [δ13CDIC ≈ -18‰, 14C > 100 pmc], (2) dissolved carbon equilibrated with atmospheric CO2 gas [δ13CDIC ≈ +1‰, 14C > 100 pmc], and (3) dissolved carbon derived from volcanic CO2 gas emissions [δ13CDIC≈0‰, 14C=0 pmc]. Many regional waters show a decrease in 14C abundance with increasing δ13C values, a pattern indicative of interaction with dead carbon originating from volcanic CO2 gas. Several lines of evidence suggest that actual groundwater residence times are too short (⩽ 200 years) to apply radiocarbon dating corrections. In particular, water temperatures measured at springs show that deep groundwater circulation does not occur, which implies an insufficient aquifer volume to account for both the high discharge rates and long residence times suggested by 14C apparent ages. The large springs also exhibit rapid decreases in flow during periods of drought that suggests a high level of aquifer interconnectivity to the recharge area. The estimated amount of volcanic CO2 dissolved in surface and groundwater originating from the Lassen highlands is consistent with the conversion of approximately 10% of the geothermal CO2 flux into dissolved inorganic carbon.

Visualization of gas dissolution following upward gas migration in porous media: Technique and implications for stray gas

NASA Astrophysics Data System (ADS)

Van De Ven, C. J. C.; Mumford, Kevin G.

2018-05-01

The study of gas-water mass transfer in porous media is important in many applications, including unconventional resource extraction, carbon storage, deep geological waste storage, and remediation of contaminated groundwater, all of which rely on an understanding of the fate and transport of free and dissolved gas. The novel visual technique developed in this study provided both quantitative and qualitative observations of gas-water mass transfer. Findings included interaction between free gas architecture and dissolved plume migration, plume geometry and longevity. The technique was applied to the injection of CO2 in source patterns expected for stray gas originating from oil and gas operations to measure dissolved phase concentrations of CO2 at high spatial and temporal resolutions. The data set is the first of its kind to provide high resolution quantification of gas-water dissolution, and will facilitate an improved understanding of the fundamental processes of gas movement and fate in these complex systems.

Microanalysis of dissolved iron and phosphate in pore waters of hypersaline sediment

NASA Technical Reports Server (NTRS)

Haddad, R.; Shaw, T.

1985-01-01

Diurnal fluctuations of reduced iron concentrations, expected to occur in reduced sediments in the photic zone, were studied. Iron concentration was compared to O2-H2S, a microcanalysis of sulfate reduction was performed, as well as an examination of diurnal concentration of dissolved phosphate and changes in interstitial CO2. The iron profiles suggest a strong correlation between iron remobilization and processes occurring in the light. Phosphate profiles suggest the removal of phosphate is strongly correlated with precipitation of oxidized iron in the upper 2 mm to 5 mm of the sediments. Pore water CO2 concentrations and carbon isotope ratios are presented. These data are from the analyses of minisediment cores collected from the 42 per mil salt pond and incubated in the laboratory under light and dark conditions.

Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

DOE PAGES

Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

2014-12-31

Carbon stable isotopes can be used in characterization and monitoring of CO 2 sequestration sites to track the migration of the CO 2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO 2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO 2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport modulemore » of TOUGHREACT was modified to include separate isotopic species of CO 2 gas and dissolved inorganic carbon (CO 2, CO 3 2-, HCO 3 -,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO 2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

Geochemistry of groundwater in parts of Guntur district, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Subba Rao, N.

2002-01-01

Hydrogeochemical investigations, which are significant for the assessment of water quality, have been carried out to study the sources of dissolved ions in groundwaters of some rural areas of Guntur district, Andhra Pradesh, India. Groundwaters in the area are mostly brackish. High contents of SiO2, and Na+ and Cl- ions in groundwater, in comparison with those of seawater, suggests a meteoric origin of groundwater. The high concentration of SiO2 and various geochemical signatures reflect the weathering of minerals. However, the Na++K+ vs Cl- ratio suggests weathering, has occurred only to some extent. The chemistry of groundwater favours the formation of clay minerals (montmorillonite, illite and chlorite), because of evapotranspiration. The positive saturation index of CaCO3 and the high signatures of Ma2+:Ca2+ and Na+:Ca2+ reveals the occurrence of evaporation. The evaporation enhances the concentration of ions (which occurred originally in the water) in the soils during summer. The very high SO{4/2-} and Cl- contents in some groundwaters and the occurrence of kankar (CaCO3) in the area suggest a long history of evaporation. Greater ionic concentration in the groundwaters of post-monsoon compared with pre-monsoon indicates the increasing addition of leachates into the groundwater from the soils in the monsoon and anthropogenic activities, which leads to a deteriorating quality of groundwater. According to the Gibbs' diagrams, rock weathering, to some extent, and evaporation are the dominant phenomena responsible for the higher ionic concentrations found in groundwater. Measures that benefit sustainable management of groundwater quality are suggested in this study.

New Acetylene-Terminated Quinoxaline Oligomers

DTIC Science & Technology

1982-03-01

3󈧭 Br, 20.97 Found: C, 62.88; *H, 3.50; Br, 20.83. ( 2 ) (4-Phenylethynyl- 3 ’- bromo )diphenyl ether (6.98 g, 0.02 mol) was dissolved in 150 ml of...I 2 . Govt Accession No. 3 . Recipient’s Catalog Number AFWAL-TR-82-4006 4. Title (and Subtitle) 5. Type of Report & Period Coverec NEW ACETYLENE...displacement of the nitro group of p-nitrobenzil by treatment with the sodium 3 -ethynylphenolate. 1O-CO-Ar-CO-CO-1 + 2 NH2 ) -- H2 > SNHQ2f \\NH2 NH2

Gas-water-rock interactions in Frio Formation following CO2 injection: Implications for the storage of greenhouse gases in sedimentary basins

USGS Publications Warehouse

Kharaka, Yousif K.; Cole, David R.; Hovorka, Susan D.; Gunter, W.D.; Knauss, Kevin G.; Freifeild, Barry M.

2006-01-01

To investigate the potential for the geologic storage of CO2 in saline sedimentary aquifers, 1600 t of CO2 were injected at 1500 m depth into a 24-m-thick sandstone section of the Frio Formation, a regional brine and oil reservoir in the U.S. Gulf Coast. Fluid samples obtained from the injection and observation wells before CO2 injection showed a Na-Ca-Cl–type brine with 93,000 mg/L total dissolved solids (TDS) at near saturation with CH4 at reservoir conditions. Following CO2 breakthrough, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO3) and Fe (30–1100 mg/L), and significant shifts in the isotopic compositions of H2O, dissolved inorganic carbon (DIC), and CH4. Geochemical modeling indicates that brine pH would have dropped lower but for the buffering by dissolution of carbonate and iron oxyhydroxides. This rapid dissolution of carbonate and other minerals could ultimately create pathways in the rock seals or well cements for CO2 and brine leakage. Dissolution of minerals, especially iron oxyhydroxides, could mobilize toxic trace metals and, where residual oil or suitable organics are present, the injected CO2 could also mobilize toxic organic compounds. Environmental impacts could be major if large brine volumes with mobilized toxic metals and organics migrated into potable groundwater. The δ18O values for brine and CO2 samples indicate that supercritical CO2 comprises ∼50% of pore-fluid volume ∼6 mo after the end of injection. Postinjection sampling, coupled with geochemical modeling, indicates that the brine gradually will return to its preinjection composition.

Implications of elevated CO2 on pelagic carbon fluxes in an Arctic mesocosm study - an elemental mass balance approach

NASA Astrophysics Data System (ADS)

Czerny, J.; Schulz, K. G.; Boxhammer, T.; Bellerby, R. G. J.; Büdenbender, J.; Engel, A.; Krug, S. A.; Ludwig, A.; Nachtigall, K.; Nondal, G.; Niehoff, B.; Silyakova, A.; Riebesell, U.

2013-05-01

Recent studies on the impacts of ocean acidification on pelagic communities have identified changes in carbon to nutrient dynamics with related shifts in elemental stoichiometry. In principle, mesocosm experiments provide the opportunity of determining temporal dynamics of all relevant carbon and nutrient pools and, thus, calculating elemental budgets. In practice, attempts to budget mesocosm enclosures are often hampered by uncertainties in some of the measured pools and fluxes, in particular due to uncertainties in constraining air-sea gas exchange, particle sinking, and wall growth. In an Arctic mesocosm study on ocean acidification applying KOSMOS (Kiel Off-Shore Mesocosms for future Ocean Simulation), all relevant element pools and fluxes of carbon, nitrogen and phosphorus were measured, using an improved experimental design intended to narrow down the mentioned uncertainties. Water-column concentrations of particulate and dissolved organic and inorganic matter were determined daily. New approaches for quantitative estimates of material sinking to the bottom of the mesocosms and gas exchange in 48 h temporal resolution as well as estimates of wall growth were developed to close the gaps in element budgets. However, losses elements from the budgets into a sum of insufficiently determined pools were detected, and are principally unavoidable in mesocosm investigation. The comparison of variability patterns of all single measured datasets revealed analytic precision to be the main issue in determination of budgets. Uncertainties in dissolved organic carbon (DOC), nitrogen (DON) and particulate organic phosphorus (POP) were much higher than the summed error in determination of the same elements in all other pools. With estimates provided for all other major elemental pools, mass balance calculations could be used to infer the temporal development of DOC, DON and POP pools. Future elevated pCO2 was found to enhance net autotrophic community carbon uptake in two of the three experimental phases but did not significantly affect particle elemental composition. Enhanced carbon consumption appears to result in accumulation of dissolved organic carbon under nutrient-recycling summer conditions. This carbon over-consumption effect becomes evident from mass balance calculations, but was too small to be resolved by direct measurements of dissolved organic matter. Faster nutrient uptake by comparatively small algae at high CO2 after nutrient addition resulted in reduced production rates under future ocean CO2 conditions at the end of the experiment. This CO2 mediated shift towards smaller phytoplankton and enhanced cycling of dissolved matter restricted the development of larger phytoplankton, thus pushing the system towards a retention type food chain with overall negative effects on export potential.

Experimental Oxidation of Iron Sulphides from Intertidal Surface Sediments: Stable Isotope Effects (S, O, C)

NASA Astrophysics Data System (ADS)

Ebersbach, F.; Böttcher, M. E.; Al-Raei, A. M.; Segl, M.

2009-04-01

Top intertidal sediments show a pronounced zone of activities of sulphate-reducing bacteria. Iron sulfides may be formed, but a substantial part is reoxidized to sulfate. Microbial or chemical reoxidation can be further enhanced by a resuspension of surface sediments by tidal currents or storms. The rates of the different processes depend on the site-secific sedimentological properties (e.g., grain size, iron and sulphur contents etc.). In the present study 3 different areas of the German Wadden Sea were studied: a mud flat in the Jade Bay, and sandy sediments in the intertidals of Spiekeroog and Sylt islands. The latter site is part of an in-situ lugworm-exclusion experiment. The goal was the experimental and field investigation of the fate of iron sulfides and the formation of sulphate upon resuspension of intertidal surface sediments in oxygenated seawater. All sites were geochemically analyzed for dissolved and solid phase iron, manganese, sulphur and carbon phases/species, and sulphate reduction rates were measured using radiotracers. Dissolved chloride and grain sizes analysis where additionally carried out. TOC, S and metal phase contents were higher in mud compared to sandy sediments. Field results demonstrate gross but only minor net sulphide production and a downcore increases in FeS contents, due to intense sulphide oxidation at the surface. Pyrite, on the other hand, was abundant through the sediments due to continuous sediment reworking. The fate of iron-sulphides and accumulation of sulphate as a function of time was followed in batch experiments using dark suspensions of surface sediments in site-bottom waters at room temperature. During the experiments, each sample was shaken continuously under exposition to oxygen, and sub-samples were taken at the beginning and after discrete time intervalls. A very fast oxidation rate of AVS led to a complete exhaustion within a day, whereas Cr(II)-reducible sulfur was inititially built up and then decreased. This observation can be explained by a formation of S° and FeOOH, followed by the oxidation of pyrite. The dissolved species (SO4/Cl ratios) reflected the continuous accumulation of sulphate as an oxidation product. Dissolved inorganic carbonate (DIC) concentrations decreased upon reaction progress, due to the liberation of protons upon iron sulphide oxidation and degassing of carbon dioxide. The 13C/12C ratio of the residual DIC increased due to the preferential desorption of 12CO2. 34S and 18O contents of dissolved sulphate further show process specific isotope discrimination. The experiments demonstrate the importance of oxidation on the fate of FeS , but less pyrite and the formation of sulphate from resuspended intertidal surface sediments. Acknowledgements: The authors gratefully acknowledge discussions and field advice by N. Volkenborn, and financial support from Deutsche Forschungsgemeinschaft during DFG-SPP ‚BioGeoChemistry of the Wadden Sea' (JO 307/4, BO 1584/4), Max Planck Society, and Leibniz-IO Warnemünde.

Experimental investigation of CO2-brine-rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

USGS Publications Warehouse

Rosenbauer, R.J.; Koksalan, T.; Palandri, J.L.

2005-01-01

Deep-saline aquifers are potential repositories for excess CO2, currently being emitted to the atmosphere from anthropogenic activities, but the reactivity of supercritical CO2 with host aquifer fluids and formation minerals needs to be understood. Experiments reacting supercritical CO2 with natural and synthetic brines in the presence and absence of limestone and plagioclase-rich arkosic sandstone showed that the reaction of CO2-saturated brine with limestone results in compositional, mineralogical, and porosity changes in the aquifer fluid and rock that are dependent on initial brine composition, especially dissolved calcium and sulfate. Experiments reacting CO2-saturated, low-sulfate brine with limestone dissolved 10% of the original calcite and increased rock porosity by 2.6%. Experiments reacting high-sulfate brine with limestone, both in the presence and absence of supercritical CO2, were characterized by the precipitation of anhydrite, dolomitization of the limestone, and a final decrease in porosity of 4.5%. However, based on favorable initial porosity changes of about 15% due to the dissolution of calcite, the combination of CO2 co-injection with other mitigation strategies might help alleviate some of the well-bore scale and formation-plugging problems near the injection zone of a brine disposal well in Paradox Valley, Colorado, as well as provide a repository for CO2. Experiments showed that the solubility of CO2 is enhanced in brine in the presence of limestone by 9% at 25 ??C and 6% at 120 ??C and 200 bar relative to the brine itself. The solubility of CO2 is enhanced also in brine in the presence of arkosic sandstone by 5% at 120 ??C and 300 bar. The storage of CO 2 in limestone aquifers is limited to only ionic and hydraulic trapping. However, brine reacted with supercritical CO2 and arkose yielded fixation and sequestration of CO2 in carbonate mineral phases. Brine desiccation was observed in all experiments containing a discrete CO2 phase, promoting porosity-reducing precipitation reactions in aquifers near saturation with mineral phases. Published by Elsevier B.V.

How Can We Use Carbon Dioxide as a Solvent?

ERIC Educational Resources Information Center

Mohamed, Azmi; Eastoe, Julian

2011-01-01

This article describes the work being undertaken to make more use of supercritical carbon dioxide as a green solvent. It discusses how the use of surfactants can address the limitations of supercritical CO[subscript 2] in dissolving solutes that are polar and of higher molecular weight. The design of appropriate hydrocarbon CO[subscript 2]-philic…

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

The effect of CO2 on the water-saturated solidus of K-poor peridotite between 4 and 6 GPa

NASA Astrophysics Data System (ADS)

Dvir, Omri; Kessel, Ronit

2017-06-01

The effect of various amounts of CO2 on the solidus of H2O-CO2-bearing peridotite was examined by determining the composition of H2O-CO2-bearing fluids and melts in equilibrium with garnet peridotite at 4-6 GPa and 900-1100 °C. Two capsules were placed in a rocking multi-anvil apparatus in each experiment. Both capsules contained a fertile peridotite with 10 wt% H2O, one with 1 (CLZ1) and the other with 5 wt% CO2 (CLZ5). In both capsules a diamond trap was placed on one end of the capsule as a fluid/melt trap. The H2O and CO2 content in the fluid or melt trapped in between the diamonds were measured using the quartz-tube-system technique by releasing the volatiles through infrared gas analyzer. The total dissolved solids in these phases were determined using the cryogenic laser-ablation - inductive couple plasma - mass spectrometry technique. The residual lherzolite consists of olivine, orthopyroxene, ±clinopyroxene, garnet, and ±magnesite as carbonate phase. The solidus of CLZ1 peridotite was located between 900 and 1000 °C at 4 GPa and between 1000 and 1100 °C at 5 and 6 GPa. CLZ5 peridotite melts below 900 °C at 4 GPa and between 900 and 1000 °C at 5 and 6 GPa. The results demonstrate a decrease in melting temperature of hydrous peridotite at pressures between 4 and 6 GPa with increasing amount of CO2. The H2O-CO2-bearing fluids found in this study at 900-1000 °C are similar in composition to low-Mg carbonatitic to silicic high-density fluids found in fluid inclusions in diamonds. With increasing temperature, the melts approach type II kimberlites. We propose that H2O-CO2-induced partial melting of metasomatized garnet lherzolite at 4-6 GPa is a possible origin for group II kimberlites.

First assessment of water and carbon cycles in two tropical coastal rivers of south-west India: an isotopic approach.

PubMed

Tripti, M; Lambs, L; Otto, T; Gurumurthy, G P; Teisserenc, R; Moussa, I; Balakrishna, K; Probst, J L

2013-08-15

The contribution of tropical coastal rivers to the global carbon budget remains unmeasured, despite their high water dynamics, i.e. higher run-off with their basin characteristic of warm temperature. Two rivers draining the western part of the Western Ghats, the Swarna (length 80 km) and Nethravati (147 km) Rivers, were studied for water and carbon cycles. The stable isotope ratios of oxygen (δ(18) O values), hydrogen (δ(2) H values) and carbon (δ(13) C values) were used to understand the water circulation, the weathering processes and the carbon biogeochemical cycle. The river water samples were collected during the dry post-monsoonal season (November 2011). The δ(18) O and δ(2) H values of river water suggested that the monsoonal vapour source and its high recycling have a dominant role because of the orographical and tropical conditions. The absence of calcareous rocks has led to dissolved inorganic carbon (DIC) mainly originating from atmospheric/soil CO2 , via rock-weathering processes, and the low soil organic matter combined with high run-off intensity has led to low riverine dissolved organic carbon (DOC) contents. The δ(13) C values increase from upstream to downstream and decrease with increasing pCO2 . There is a positive relationship between the δ(13) CDIC values and the DOC concentrations in these two rivers that is contrary to that in most of the studied rivers of the world. The higher evapotranspiration supported by tropical conditions suggests that there are higher vapour recycling process in the Swarna and Nethravati basins as studied from the water δ(18) O and δ(2) H values. The basin characteristics of higher rainfall/run-off accompanied by warm temperature suggest that the δ(13) C value of riverine DIC is mainly controlled by the weathering of source rocks (silicates) with variation along the river course by CO2 degassing from the river water to the atmosphere and is less dominated by the oxidation of DOC. Copyright © 2013 John Wiley & Sons, Ltd.

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

Mouzakis, Katherine M.; Navarre-Sitchler, Alexis K.; Rother, Gernot

Carbon capture, utilization, and storage, one proposed method of reducing anthropogenic emissions of CO 2, relies on low permeability formations, such as shales, above injection formations to prevent upward migration of the injected CO 2. Porosity in caprocks evaluated for sealing capacity before injection can be altered by geochemical reactions induced by dissolution of injected CO 2 into pore fluids, impacting long-term sealing capacity. Therefore, long-term performance of CO 2 sequestration sites may be dependent on both initial distribution and connectivity of pores in caprocks, and on changes induced by geochemical reaction after injection of CO 2, which are currentlymore » poorly understood. This paper presents results from an experimental study of changes to caprock porosity and pore network geometry in two caprock formations under conditions relevant to CO 2 sequestration. Pore connectivity and total porosity increased in the Gothic Shale; while total porosity increased but pore connectivity decreased in the Marine Tuscaloosa. Gothic Shale is a carbonate mudstone that contains volumetrically more carbonate minerals than Marine Tuscaloosa. Carbonate minerals dissolved to a greater extent than silicate minerals in Gothic Shale under high CO 2 conditions, leading to increased porosity at length scales <~200 nm that contributed to increased pore connectivity. In contrast, silicate minerals dissolved to a greater extent than carbonate minerals in Marine Tuscaloosa leading to increased porosity at all length scales, and specifically an increase in the number of pores >~1 μm. Mineral reactions also contributed to a decrease in pore connectivity, possibly as a result of precipitation in pore throats or hydration of the high percentage of clays. Finally, this study highlights the role that mineralogy of the caprock can play in geochemical response to CO 2 injection and resulting changes in sealing capacity in long-term CO 2 storage projects.« less

Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production

PubMed Central

Rau, Greg H.; Carroll, Susan A.; Bourcier, William L.; Singleton, Michael J.; Smith, Megan M.; Aines, Roger D.

2013-01-01

We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 105-fold increase in OH− concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH− initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification. PMID:23729814

Pasteurization of fruit juices of different pH values by combined high hydrostatic pressure and carbon dioxide.

PubMed

Li, Wang; Pan, Jian; Xie, Huiming; Yang, Yi; Zhou, Dianfei; Zhu, Zhaona

2012-10-01

The inactivation of the selected vegetative bacteria Escherichia coli, Listeria innocua, and Lactobacillus plantarum by high hydrostatic pressure (HHP) in physiological saline (PS) and in four fruit juices with pHs ranging from 3.4 to 6.3, with or without dissolved CO(2), was investigated. The inactivation effect of HHP on the bacteria was greatly enhanced by dissolved CO(2). Effective inactivation (>7 log) was achieved at 250 MPa for E. coli and 350 MPa for L. innocua and L. plantarum in the presence of 0.2 M CO(2) at room temperature for 15 min in PS, with additional inactivation of more than 4 log for all three bacteria species compared with the results with HHP treatment alone. The combined inactivation by HHP and CO(2) in tomato juice of pH 4.2 and carrot juice of pH 6.3 showed minor differences compared with that in PS. By comparison, the combined effect in orange juice of pH 3.8 was considerably promoted, while the HHP inactivation was enhanced only to a limited extent. In another orange juice with a pH of 3.4, all three strains lost their pressure resistance. HHP alone completely inactivated E. coli at relatively mild pressures of 200 MPa and L. innocua and L. plantarum at 300 MPa. Observations of the survival of the bacteria in treated juices also showed that the combined treatment caused more sublethal injury, which increased further inactivation at a relatively mild pH of 4.2 during storage. The results indicated that the combined treatment of HHP with dissolved CO(2) may provide an effective method for the preservation of low- or medium-acid fruit and vegetable juices at relatively low pressures. HHP alone inactivated bacteria effectively in high-acid fruit juice.

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano, Northern Tanzania

NASA Astrophysics Data System (ADS)

Perova, E. N.; Zaitsev, A. N.

2017-12-01

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na2(CO3), nyerereite Na2Ca(CO3)2, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na2(CO3) · H2O, trona Na3(CO3)(HCO3) · 2H2O, nahcolite Na(HCO3), pirssonite Na2Ca(CO3)2 · 2H2O, calcite Ca(CO3), and shortite Na2Ca2(CO3)3. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H2O and CO2 fugacity, and the ratio of Ca and Na activity in the Na2O-CaO-CO2-H2O system.

Manufacture of dissolving pulps from cornstalk by novel method coupling steam explosion and mechanical carding fractionation.

PubMed

Wang, Ning; Chen, Hong-Zhang

2013-07-01

In order to solve the inhomogeneity of cornstalk as fiber material to manufacture dissolving pulp, a novel method of steam explosion coupling mechanical carding was put forward to fractionate cornstalk long fiber for the production of cornstalk dissolving pulp. The fractionated long fiber had homogeneous structure and low hemicellulose and ash content. The fiber cell content was up to 85% in area, and the hemicellulose and ash content was 8.34% and 1.10% respectively. The α-cellulose content of cornstalk dissolving pulps was up to 93.10-97.10%, the viscosity was 14.37-23.96 mPas, and the yields of cornstalk dissolving pulps were from 10.11% to 12.44%. In addition, the fractionated short fiber was to be hydrolyzed by enzyme to build sugar platform. The constructed method of steam explosion coupling mechanical carding achieved the fractionation of cornstalk into long fiber and short fiber cleanly and effectively, and provided a new way for cornstalk integrated refinery. Copyright © 2013 Elsevier Ltd. All rights reserved.

Photosynthetic diversity meets biodiversity: the C4 plant example.

PubMed

Sage, Rowan F; Stata, Matt

2015-01-01

Physiological diversification reflects adaptation for specific environmental challenges. As the major physiological process that provides plants with carbon and energy, photosynthesis is under strong evolutionary selection that gives rise to variability in nearly all parts of the photosynthetic apparatus. Here, we discuss how plants, notably those using C4 photosynthesis, diversified in response to environmental challenges imposed by declining atmospheric CO2 content in recent geological time. This reduction in atmospheric CO2 increases the rate of photorespiration and reduces photosynthetic efficiency. While plants have evolved numerous mechanisms to compensate for low CO2, the most effective are the carbon concentration mechanisms of C4, C2, and CAM photosynthesis; and the pumping of dissolved inorganic carbon, mainly by algae. C4 photosynthesis enables plants to dominate warm, dry and often salinized habitats, and to colonize areas that are too stressful for most plant groups. Because C4 lineages generally lack arborescence, they cannot form forests. Hence, where they predominate, C4 plants create a different landscape than would occur if C3 plants were to predominate. These landscapes (mostly grasslands and savannahs) present unique selection environments that promoted the diversification of animal guilds able to graze upon the C4 vegetation. Thus, the rise of C4 photosynthesis has made a significant contribution to the origin of numerous biomes in the modern biosphere. Copyright © 2014. Published by Elsevier GmbH.

Enhanced oxidative weathering in glaciated mountain catchments: A stabilising feedback on atmospheric carbon dioxide?

NASA Astrophysics Data System (ADS)

Horan, K.; Hilton, R. G.; Burton, K. W.; Selby, D. S.; Ottley, C. J.

2015-12-01

Mountain belts act as sources of carbon dioxide (CO2) to the atmosphere if physical erosion and exhumation expose rock-derived organic carbon ('petrogenic' organic carbon, OCpetro) to chemical weathering. Estimates suggest 15x1021g of carbon is stored in rocks globally as OCpetro, ~25,000 times the amount of carbon in the pre-industrial atmosphere. Alongside volcanic and metamorphic degassing, OCpetro weathering is thought to be the main source of CO2 to the atmosphere over geological timescales. Erosion in mountain river catchments has been shown to enhance oxidative weathering and CO2 release. However, we still lack studies which quantify this process. In addition, it is not clear how glaciation may impact OCpetro oxidation. In analogy with silicate weathering, large amounts of fine sediment in glacial catchments may enhance oxidative weathering. Here we quantify oxidative weathering in nine catchments draining OCpetro bearing rocks in the western Southern Alps, New Zealand. Using rhenium (Re) as a tracer of oxidative weathering, we develop techniques to precisely measure Re concentration at sub-ppt levels in river waters. Using [Re]water/[Re]rock as a weathering tracer, we estimate that the weathering efficiency in glacial catchments is >4 times that of non-glacial catchments. Combining this with the OCpetro content of rocks and dissolved Re flux, we estimate the CO2 release by OCpetro oxidation. The analysis suggests that non-glacial catchments in the western Southern Alps release similar amounts of CO2 as catchments in Taiwan where erosion rates are comparable. In this mountain belt, the CO2 release does not negate CO2 drawdown by silicate weathering and by riverine transfer of organic matter. Based on our results, we propose that mountain glaciation may greatly enhance OCpetro oxidation rates. Depending on the global fluxes involved, this provides a feedback to damp low atmospheric CO2 levels and global cooling. During glacial periods (low CO2, low global temperatures), increased CO2 emissions by OCpetro oxidation in mountain belts may act to counter global cooling.

Radiocarbon Depression in Aquatic Foodwebs of the Colorado River, USA: Coupling Between Carbonate Weathering and the Biosphere

NASA Astrophysics Data System (ADS)

Sickman, J. O.; Huang, W.; Lucero, D.; Anderson, M.

2012-12-01

The 14C isotopic composition of living organisms is generally considered to be in isotopic equilibrium with atmosphere CO2. During the course of investigations of aquatic foodwebs of the Colorado River, we measured substantial radiocarbon depression of organisms within planktonic and benthic foodwebs of Copper Basin Reservoir, a short residence-time water body at the intake to the Colorado River Aqueduct. All trophic levels had depressed radiocarbon content with inferred "age" of ca. 1,200 radiocarbon years (range: 0.85 to 0.87 fraction modern carbon (fmc)). Additional measurements of the radiocarbon content of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) were made in other major rivers in California (New (near Salton Sea), Santa Ana (near Riverside), San Joaquin (near Fresno) and Salinas (near San Luis Obispo)). In the New River (which is composed primarily of irrigation tailwater derived from the Colorado River), the radiocarbon values for DIC closely matched those found in biota of the Copper Basin Reservoir (0.85 to 0.87 fmc), but radiocarbon values for DOC were slightly higher (0.91 to 0.95 fmc). In the other California rivers, radiocarbon concentrations in DIC were generally below modern and lower than corresponding levels in DOC; in the case of the Santa Ana River, DOC was older than DIC as a result of wastewater inputs from upstream treatment plants. Together these data suggest that the carbonate equilibrium of California rivers is influenced by weathering of carbonate minerals which produces HCO3- with no 14C. We hypothesize that this dead carbon can move into aquatic foodwebs via algae and phytoplankton uptake during photosynthesis, depressing the 14C content of aquatic foodwebs below that of the atmosphere. Based on a simple two-component mixing model incorporating carbonate weathering and atmospheric CO2, we estimate that 15-17% of the carbon in the aquatic foodweb of Copper Basin is derived directly from mineral weathering of carbonate minerals in the Colorado River basin. Worldwide, only a few cases of radiocarbon depression have been reported for aquatic ecosystems. The extent of 14C depression in the Colorado River is much larger than that observed in the Arctic or deep ocean environments.

Predictive modeling of CO2 sequestration in deep saline sandstone reservoirs: Impacts of geochemical kinetics

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

Balashov, Victor N.; Guthrie, George D.; Hakala, J. Alexandra

2013-03-01

One idea for mitigating the increase in fossil-fuel generated CO{sub 2} in the atmosphere is to inject CO{sub 2} into subsurface saline sandstone reservoirs. To decide whether to try such sequestration at a globally significant scale will require the ability to predict the fate of injected CO{sub 2}. Thus, models are needed to predict the rates and extents of subsurface rock-water-gas interactions. Several reactive transport models for CO{sub 2} sequestration created in the last decade predicted sequestration in sandstone reservoirs of ~17 to ~90 kg CO{sub 2} m{sup -3|. To build confidence in such models, a baseline problem including rockmore » + water chemistry is proposed as the basis for future modeling so that both the models and the parameterizations can be compared systematically. In addition, a reactive diffusion model is used to investigate the fate of injected supercritical CO{sub 2} fluid in the proposed baseline reservoir + brine system. In the baseline problem, injected CO{sub 2} is redistributed from the supercritical (SC) free phase by dissolution into pore brine and by formation of carbonates in the sandstone. The numerical transport model incorporates a full kinetic description of mineral-water reactions under the assumption that transport is by diffusion only. Sensitivity tests were also run to understand which mineral kinetics reactions are important for CO{sub 2} trapping. The diffusion transport model shows that for the first ~20 years after CO{sub 2} diffusion initiates, CO{sub 2} is mostly consumed by dissolution into the brine to form CO{sub 2,aq} (solubility trapping). From 20-200 years, both solubility and mineral trapping are important as calcite precipitation is driven by dissolution of oligoclase. From 200 to 1000 years, mineral trapping is the most important sequestration mechanism, as smectite dissolves and calcite precipitates. Beyond 2000 years, most trapping is due to formation of aqueous HCO{sub 3}{sup -}. Ninety-seven percent of the maximum CO{sub 2} sequestration, 34.5 kg CO{sub 2} per m{sup 3} of sandstone, is attained by 4000 years even though the system does not achieve chemical equilibrium until ~25,000 years. This maximum represents about 20% CO{sub 2} dissolved as CO{sub 2},aq, 50% dissolved as HCO{sub 3}{sup -}{sub ,aq}, and 30% precipitated as calcite. The extent of sequestration as HCO{sub 3}{sup -} at equilibrium can be calculated from equilibrium thermodynamics and is roughly equivalent to the amount of Na+ in the initial sandstone in a soluble mineral (here, oligoclase). Similarly, the extent of trapping in calcite is determined by the amount of Ca2+ in the initial oligoclase and smectite. Sensitivity analyses show that the rate of CO{sub 2} sequestration is sensitive to the mineral-water reaction kinetic constants between approximately 10 and 4000 years. The sensitivity of CO{sub 2} sequestration to the rate constants decreases in magnitude respectively from oligoclase to albite to smectite.« less

Chemical characteristics of particulate, colloidal, and dissolved organic material in Loch Vale Watershed, Rocky Mountain National Park

USGS Publications Warehouse

McKnight, Diane M.; Harnish, R.; Wershaw, R. L.; Baron, Jill S.; Schiff, S.

1997-01-01

The chemical relationships among particulate and colloidal organic material and dissolved fulvic acid were examined in an alpine and subalpine lake and two streams in Loch Vale Watershed, Rocky Mountain National Park. The alpine lake, Sky Pond, had the lowest dissolved organic carbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13 mgC/L), and high algal biomass. The watershed of Sky Pond is primarily talus slope, and DOC and POC may be autochthonous. Both Andrews Creek and Icy Brook gain DOC as they flow through wet sedge meadows. The subalpine lake, The Loch, receives additional organic material from the surrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis, stable carbon isotopic compositon, and 13C-NMR characterization showed that: 1) particulate material had relatively high inorganic contents and was heterogeneous in compositon, 2) colloidal material was primarily carbohydrate material with a low inorganic content at all sites; and 3) dissolved fulvic acid varied in compositon among sites. The low concentration and carbohydrate-rich character of the colloidal material suggests that this fraction is labile to microbial degradation and may be turning over more rapidly than particulate fractions or dissolved fulvic acid. Fulvic acid from Andrews Creek had the lowest N content and aromaticity, whereas Sky Pond fulvic acid had a higher N content and lower aromaticity than fulvic acid from The Loch. The UV-visible spectra of the fulvic acids demonstrate that variation in characteristics with sources of organic carbon can explain to some extent the observed nonlinear relationship between UV-B extinction coefficients and DOC concentrations in lakes.

Using melt inclusions to track the evolution of primitive alkalic magmas from Ross Island, Antarctica

NASA Astrophysics Data System (ADS)

Rasmussen, D. J.; Kyle, P. R.; Wallace, P. J.

2013-12-01

Melt inclusions (MI) provide a means for measuring the dissolved volatile (H2O, CO2, S, Cl, F), major and trace element compositions of magmas at depth. Such data are valuable for assessing the physical and chemical conditions within a magmatic system by providing snapshots of magma compositions during ascent and evolution. Here we examine MI in 9 samples of rapidly quenched basanitic ash and hyaloclastite from three locations (Hut Point, Mt. Terror, Mt. Bird) on Ross Island, Antarctica, which radially surround the active, phonolitic Erebus volcano. Ross Island is an intraplate volcanic center located at the southern end of the Terror Rift, an area of active continental extension. Geophysical data show that below the 19-27 km thick crust is a localized region of anomalously hot upwelling mantle. We analyzed volatiles and major elements in 93 olivine-hosted (Fo 78.2-88.3) MI using FTIR spectroscopy and electron microprobe analysis, and all compositions were corrected for the effects of post-entrapment olivine crystallization. Preliminary results show the MI have a range of basanite compositions (SiO2 39.1-45.2 wt.%; Mg# 50.1-66.5). The MI major element trends further suggest the 9 samples are genetically related and may have a common low degree partial melt parental magma. CO2 contents range from ~0.1 to 0.85 wt.%, which are amongst the highest ever measured in MI. H2O contents are ~1 to 1.9 wt.%. The MI also have high concentrations of S, Cl, and F with maximum values of 0.27, 0.22, and 0.14 wt.%, respectively. The H2O and CO2 concentrations require entrapment pressures between ~250 and 600 MPa. Thus, the MI record a magmatic history that begins at near-Moho depths and is exceptionally CO2-rich. Because of its low solubility in magmas CO2 must be the major volatile driving the eruption of these alkalic magmas. More evolved Erebus MI (SiO2 43.4-53.6 wt.%; Mg# 32.9-55.1) from an earlier study [1] have consistently lower H2O concentrations. [1] Oppenheimer et al. (2011) EPSL. 306, 261-271.

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.

Phase equilibria in the Tb-Mg-Co system at 500 °C, crystal structure and hydrogenation properties of selected compounds

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

Shtender, V.V.; Denys, R.V.; Zavaliy, I.Yu., E-mail: zavaliy@ipm.lviv.ua

2015-12-15

The isothermal section of the Tb–Mg–Co phase diagram at 500 °C has been built on the basis of XRD analysis of forty samples prepared by powder metallurgy. The existence of two ternary compounds Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo was confirmed. The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} (0≤x≤0.4) and Tb{sub 1-−x}Mg{sub x}Co{sub 2} (0≤x≤0.6), was found for the first time. It is shown that Tb{sub 5}Mg{sub 24} also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb{sub 4}MgCo and TbMgCo{sub 4} compounds form hydrides (12.7 and 5.3more » at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb{sub 4}MgCoH{sub 12.7} hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb{sub 4}Mg{sub 3}Co{sub 2}H{sub ∼4} and Tb{sub 2}MgCo{sub 9}H{sub 12}, are unstable in air and decompose into the initial compounds. - Highlights: • The phase equilibria at 500 °°C in the Tb–Mg–Co system has been studied. • The existence of two ternary compounds, Tb{sub 4}Mg{sub 3}Co{sub 2} and Tb{sub 4}MgCo, was confirmed. • The formation of two solid solutions, Tb{sub 1−x}Mg{sub x}Co{sub 3} and Tb{sub 1−x}Mg{sub x}Co{sub 2}, was found. • Hydrogen sorption–desorption properties have been studied for the selected alloys.« less

Deep water dissolution in Marine Isotope Stage 3 from the northern South China Sea

NASA Astrophysics Data System (ADS)

Huang, B.

2015-12-01

The production, transport, deposition, and dissolution of carbonate profoundly implicate the global carbon cycle affect the inventory and distribution of dissolved organic carbon (DIC) and alkalinity (ALK), which drive atmospheric CO2 change on glacial-interglacial timescale. the process may provide significant clues for improved understanding of the mechanisms that control the global climate system. In this study, we calculate and analyze the foraminiferal dissolution index (FDX) and the fragmentation ratios of planktonic foraminifera over 60-25 ka based on samples from 17924 and ODP 1144 in the northeastern South China Sea (SCS) to reconstruct the deep water carbonate dissolution during Marine Isotope Stage 3 (MIS 3). Result shows that the dissolution of carbonate increases gradually at 17924 but keeps stable at ODP 1144. The changes of FDX coincidence with that of fragmentation ratios at 17924 and ODP 1144 suggest both indexes can be used as reliable dissolving proxies of planktonic foraminifera. Comparing FDX and fragmentation ratios at both sites, we find the FDX and fragmentation ratios at 17924 are higher than those at 1144, indicating that carbonate dissolution is intenser in 17924 core during MIS 3. The increasing total percentage of both N. dutertrei and G. bulloides during MIS 3 reveals the rising primary productivity that may lead to deep water [CO32-] decrease. The slow down of thermohaline circulation may increase deep water residence time and accelerate carbonate dissolution. In addition, the covering of ice caps, iron supply and increased surface-water stratification also contribute to atmosphere CO2 depletion and [CO32-] decrease in deep water. In the meanwhile, regression result from colder temperature increases the input of ALK and DIC to the deep ocean and deepens the carbonate saturation depth, which makes the deep water [CO32-] rise. In ODP Site 1144, the decrease in [CO32-] caused by more CO2 restored in deep water is equal to the increase in [CO32-] because of regression, so dissolution keeps steady. However, [CO32-] is probably more strongly controlled by regression, the decrease in [CO32-] result from more CO2 restored in deep water overwhelms the increase in [CO32-] due to regression at 17924, so more carbonate dissolved from MIS 3 to the Last Glacial Maximum (LGM).

Evaluation of headspace equilibration methods for quantifying greenhouse gases in groundwater.

PubMed

Jahangir, M M R; Johnston, P; Khalil, M I; Grant, J; Somers, C; Richards, K G

2012-11-30

The objective of the study was to evaluate the different headspace equilibration methods for the quantification of dissolved greenhouse gases in groundwater. Groundwater samples were collected from wells with contrasting hydrogeochemical properties and degassed using the headspace equilibration method. One hundred samples from each well were randomly selected, treatments were applied and headspace gases analysed by gas chromatography. Headspace equilibration treatments varied helium (He):water ratio, shaking time and standing time. Mean groundwater N(2)O, CO(2) and CH(4) concentrations were 0.024 mg N L(-1), 13.71 mg C L(-1) and 1.63 μg C L(-1), respectively. All treatments were found to significantly influence dissolved gas concentrations. Considerable differences in the optimal He:water ratio and standing time were observed between the three gases. For N(2)O, CO(2) and CH(4) the optimum operating points for He:water ratio was 4.4:1, 3:1 and 3.4:1; shaking time was 13, 12 and 13 min; and standing time was 63, 17 and 108 min, respectively. The headspace equilibration method needs to be harmonised to ensure comparability between studies. The experiment reveals that He:water ratio 3:1 and shaking time 13 min give better estimation of dissolved gases than any lower or higher ratios and shaking times. The standing time 63, 17 and 108 min should be applied for N(2)O, CO(2) and CH(4), respectively. Copyright © 2012. Published by Elsevier Ltd.

Stable carbon isotopes of HCO3- in oil-field waters-implications for the origin of CO2

USGS Publications Warehouse

Carothers, W.W.; Kharaka, Y.K.

1980-01-01

The ??13C values of dissolved HCO3- in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO2 of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The ??13C values of total HCO3- indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin. The range of ??13C values for the HCO3- of these waters is -20-28 per mil relative to PDB. This wide range of ??13C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high ??13C values of HCO3- in the shallow production zones where the subsurface temperatures are less than 80??C. The extremely low ??13C values (< -10 per mil) are obtained in waters where concentrations of SO42- are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO42- + CH3COO- ??? 2HCO3- + HS-). The high ??13C values probably result from the degradation of these anions by methanogenic bacteria (CH3COO- + H2O ai HCO3- + CH4). Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO2 and CH4 is probably the major source of CO2 for production zones with subsurface temperatures greater than 80??C. The ??13C values of HCO3- for waters from zones with temperatures greater than 100??C result from isotopic equilibration between CO2 and CH4. At these high temperatures, ??13C values of HCO3- decrease with increasing temperatures and decreasing concentrations of these acid anions. ?? 1980.

Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

NASA Astrophysics Data System (ADS)

da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

2015-03-01

The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

Control of cavitation using dissolved carbon dioxide for damage-free megasonic cleaning of wafers

NASA Astrophysics Data System (ADS)

Kumari, Sangita

This dissertation describes the finding that dissolved carbon dioxide is a potent inhibitor of sonoluminescence and describes the implications of the finding in the development of improved megasonic cleaning formulations. Megasonic cleaning, or the removal of contaminants particles from wafer surfaces using sound-irradiated cleaning fluids, has been traditionally used in the semiconductor industry for cleaning of wafers. A critical challenge in the field is to achieve removal of small particles (22 nm to 200 nm) without causing damage to fine wafer features. The work described here addresses this challenge by identifying sonoluminescence and solution pH as two key factors affecting damage and cleaning efficiency, respectively and establishing novel means to control them using CO2(aq) release compounds in the presence of acids and bases. Sonoluminescence (SL) behavior of the major dissolved gases such as Ar, Air, N2, O2 and CO2 was determined using a newly designed Cavitation Threshold Cell (CT Cell). SL, which is the phenomenon of release of light in sound-irradiated liquids, is a sensitive indicator of cavitation, primarily transient cavitation. It was found that all the tested dissolved gases such as Ar, Air, N2 and O2, generated SL signal efficiently. However, dissolved CO2 was found to be completely incapable of generating SL signal. Based on this interesting result, gradual suppression of SL signal was demonstrated using CO2(aq). It was further demonstrated that CO2(aq) is not only incapable but is also a potent inhibitor of SL. The inhibitory role of CO2(aq) was established using a novel method of controlled in-situ release of CO 2 from NH4HCO3. ~130 ppm CO2(aq) was shown to be necessary and sufficient for complete suppression of SL generation in air saturated DI water. The method however required acidification of solution for significant release of CO2, making it unsuitable for the design of cleaning solutions at high pH. Analysis of the underlying ionic equilibria revealed that the loss of released CO2(aq) upon increase in pH can be compensated by moderate increase in added NH4HCO3. Using this method, simultaneous control of SL and solution pH was demonstrated in two systems, NH4HCO3/HCl and NH4OH/CO2, at two nominal pH values; 5.7 and 7.0. Damage studies were performed on wafer samples with line/space patterns donated by IMEC and FSI International bearing Si/metal/a-Si gate stacks of thickness ~36 nm and Si/Poly-Si gate stacks of thickness ~67 nm, respectively. A single wafer spin cleaning tool MegPieRTM was used for the generation of megasonic energy for inducing damage to the structures. It was demonstrated that CO2 dissolution in DI water suppresses damage to the gate stacks in a dose-dependent manner. Together, these studies establish a systematic and strong correlation between CO2(aq) concentration, SL suppression and damage suppression. Significant damage reduction (~50 % to ~90 %) was observed at [CO2(aq)] > ~300 ppm. It was also demonstrated that CO2(aq) suppresses damage under alkaline pH condition too. This demonstration was made possible by the successful design of two new cleaning systems NH4HCO3/NH4OH and CO2/NH 4OH that could generate CO2(aq) under alkaline conditions. Damage suppressing ability of the newly designed cleaning systems were compared to the standard cleaning system NH4OH at pH 8.2 and it was found that NH4HCO3/NH4OH and CO2/NH 4OH systems were 80 % more efficient in suppressing damage compared to the standard NH4OH cleaning system. Finally, megasonic cleaning studies were conducted in the same single wafer spin cleaning tool MegPieRTM, using SiO2 particles (size 185 nm) deposited on 200 mm oxide Si wafers, as the contaminant. It was found that the standard cleaning chemical, NH4OH, pH 8.2, was effective in achieving > 95 % particle removal for 2 min irradiation of megasonic energy at power densities > 0.7 W/cm2. Based on these results, a new system, NH4HCO3/NH4OH, was designed with an aim to release ~300 ppm CO2 at pH 8.2. It was demonstrated that newly designed system NH4HCO3/NH 4OH, allowed significant suppression of damage in comparison to NH 4OH while maintaining > 90 % cleaning efficiency that was comparable to NH4OH solution, at the same acoustic power densities. Taken together, these studies establish a potent and flexible means for the inhibition of SL generation over a wide pH range and acoustic power densities and demonstrate its use in suppression of wafer damage without compromising megasonic cleaning efficiency. (Abstract shortened by UMI.)

Modeling nonclassical heterogeneous bubble nucleation from cellulose fibers: application to bubbling in carbonated beverages.

PubMed

Liger-Belair, Gérard; Voisin, Cédric; Jeandet, Philippe

2005-08-04

In this paper, the kinetics of CO(2) bubble nucleation from tiny gas pockets trapped inside cellulose fibers immersed in a glass of champagne were investigated, in situ, from high-speed video recordings. Taking into account the diffusion of CO(2)-dissolved molecules from the liquid bulk to the gas pocket, a model was derived which enabled us to connect the kinetics of bubble nucleation with both fiber and liquid parameters. Convection was found to play a major role in this process. The boundary layer around the gas pocket where a gradient of CO(2)-dissolved molecules exists was also indirectly approached and found to be in the order of 10-20 mum. Because most of the particles adsorbed on the wall of a container or vessel free from any particular treatment are also believed to be cellulose fibers coming from the surrounding air, the results of this paper could be indeed extended to the more general field of nonclassical heterogeneous bubble nucleation from supersaturated liquids.

Isotopic insights into sources of acid driving weathering across a mountain-floodplain transition in the Amazon headwaters of Peru

NASA Astrophysics Data System (ADS)

Torres, M. A.; Clark, K.; Paris, G.; Adkins, J. F.; West, A.

2012-12-01

The carbon budget associated with mineral weathering depends on the extent to which weathering is driven by strong acids (e.g., H2SO4, HNO3) as opposed to weak acids derived from atmospheric CO2 (e.g., H2CO3, organic acids). It has remained difficult to accurately partition acid sources associated with carbonate and silicate weathering, presenting an obstacle to quantifying weathering drawdown of CO2. Moreover, little is known about how acid sources change along material pathways from mountains, where rocks are eroded, producing reactive carbonate and silicate minerals, but also sulfides that generate H2SO4, and floodplains, where the resulting sediment is transported, deposited, and chemically reworked. Such mountain-floodplain transitions are increasingly recognized as important weathering reactors, making it important to quantify any associated variation in acid sources. In this study, these questions are addressed using the dissolved major element geochemistry, the carbon isotopic composition of dissolved inorganic carbon (δ13C DIC), and the sulfur isotopic composition of dissolved sulfate (δ34S) of rivers draining the Peruvian Andes and Madre de Dios floodplain. The dissolved major element geochemistry of the Andean headwater catchments suggests inputs of sulfuric acid (from the oxidation of sulfide minerals) but is also consistent with the weathering of sulfate minerals. The δ13C DIC values of river water samples from the Andean catchments provide key constraints and range from -18 to -5 ‰, which is consistent with the mixing of DIC derived from the weathering of silicates by respired CO2 and from the weathering of carbonates by either atmospheric CO2 or sulfuric acid. In order to distinguish between the two possible carbonate weathering agents, we calculated the fraction of carbonate-derived DIC both using an isotope mass balance model and a mineral mass balance model. These results were compared assuming either pure sulfuric acid or atmospheric CO2 weathering. The results of the two models match only if carbonate weathering is driven by sulfuric acid, and if a significant portion of silicate mineral weathering is also driven by sulfuric acid. In the floodplain, low δ13C DIC values in river waters indicate that respired CO2 is the dominant weathering agent of both carbonate and silicate minerals. This indicates that there is a major change in the sources of acidity between the Andes and the Madre de Dios floodplain, which suggests that not only do floodplains promote silicate mineral weathering, as recently identified elsewhere, but this floodplain weathering is also driven to a greater extent by acids derived from CO2, when compared to weathering in the Andes. To further constrain the importance of sulfuric acid weathering in this system, the δ34S of sulfate will be measured and used to determine the source of sulfate and its role in mineral dissolution independently of the major element and δ13C DIC data.

Short term exposure to elevated pCO2 and hypoxia affects the cellular homeostasis of grass shrimp, Palaemonetes pugio

EPA Science Inventory

Estuarine organisms are adapted to frequent changes in temperature, salinity, pH, and dissolved oxygen (DO) levels. The high productivity of an estuary contributes to large changes in environmental conditions, with organismal respiration enhancing hypoxic zones, and elevating pCO...

Synthesis of Zn-In-S Quantum Dots with Tunable Composition and Optical Properties.

PubMed

Wang, Xianliang; Damasco, Jossana; Shao, Wei; Ke, Yujie; Swihart, Mark T

2016-03-03

II-III-VI semiconductors are of interest due to their chemical stability and composition-tunable optical properties. Here, we report a methodology for the synthesis of monodisperse zinc-indium-sulfide (ZIS) alloy quantum dots (QDs, mean diameter from ∼2 to 3.5 nm) with an In content substantially below that of the stoichiometric ZnIn2 S4 compound. The effects of indium incorporation on the size, lattice constant, and optical properties of ZIS QDs are elucidated. In contrast to previous reports, we employ sulfur dissolved in oleic acid as the sulfur donor rather than thioacetamide (TAA). The size of the ZIS QDs and their crystal lattice constant increased with increasing In incorporation, but they maintained the cubic sphalerite phase of ZnS, rather than the hexagonal phase typical of ZnIn2 S4 . The QDs' absorbance onset at UV wavelengths red-shifts with increasing In content and the accompanying increase in NC size. The ZIS NCs and related materials, whose synthesis is enabled by the approach presented here, provide new opportunities to apply II-III-VI semiconductors in solution-processed UV optoelectronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential cobalt limitation of vitamin B12 synthesis in the North Atlantic Ocean

NASA Astrophysics Data System (ADS)

Panzeca, C.; Beck, A. J.; Leblanc, K.; Taylor, G. T.; Hutchins, D. A.; SañUdo-Wilhelmy, S. A.

2008-06-01

While recent studies have confirmed the ecological importance of vitamin B12, it is unclear whether the production of this vitamin could be limited by dissolved Co, a trace metal required for B12 biosynthesis, but found at only subnanomolar concentrations in the open ocean. Herein, we demonstrate that the spatial distribution of dissolved B12 (range: 0.13-5 pmol L-1) in the North Atlantic Ocean follows the abundance of total dissolved Co (range: 15-81 pmol L-1). Similar patterns were observed for bacterial productivity (range: 20-103 pmol 3H leucine L-1 hr-1) and algal biomass (range: 0.4-3.9 μg L-1). In contrast, vitamin B1 concentrations (range: 0.7-30 pM) were decoupled from both Co and B12 concentrations. Cobalt amendment experiments carried out in low-dissolved Co waters (˜20 pmol L-1) enhanced B12 production two-fold over unamended controls. This study provides evidence that B12 synthesis could be limited by the availability of Co in some regions of the world ocean.

The role of iron and reactive oxygen species in the production of CO2 in arctic soil waters

NASA Astrophysics Data System (ADS)

Trusiak, Adrianna; Treibergs, Lija A.; Kling, George W.; Cory, Rose M.

2018-03-01

Hydroxyl radical (radOH) is a highly reactive oxidant of dissolved organic carbon (DOC) in the environment. radOH production in the dark was observed through iron and DOC mediated Fenton reactions in natural environments. Specifically, when dissolved oxygen (O2) was added to low oxygen and anoxic soil waters in arctic Alaska, radOH was produced in proportion to the concentrations of reduced iron (Fe(II)) and DOC. Here we demonstrate that Fe(II) was the main electron donor to O2 to produce radOH. In addition to quantifying radOH production, hydrogen peroxide (H2O2) was detected in soil waters as a likely intermediate in radOH production from oxidation of Fe(II). For the first time in natural systems we detected carbon dioxide (CO2) production from radOH oxidation of DOC. More than half of the arctic soil waters tested showed production of CO2 under conditions conducive for production of radOH. Findings from this study strongly suggest that DOC is the main sink for radOH, and that radOH can oxidize DOC to yield CO2. Thus, this iron-mediated, dark chemical oxidation of DOC may be an important component of the arctic carbon cycle.

Exploring the reversibility of marine climate change impacts in temperature overshoot scenarios

NASA Astrophysics Data System (ADS)

Zickfeld, K.; Li, X.; Tokarska, K.; Kohfeld, K. E.

2017-12-01

Artificial carbon dioxide removal (CDR) from the atmosphere has been proposed as a measure for mitigating climate change and restoring the climate system to a `safe' state after overshoot. Previous studies have demonstrated that the changes in surface air temperature due to anthropogenic CO2 emissions can be reversed through CDR, while some oceanic properties, for example thermosteric sea level rise, show a delay in their response to CDR. This research aims to investigate the reversibility of changes in ocean conditions after implementation of CDR with a focus on ocean biogeochemical properties. To achieve this, we analyze climate model simulations based on two sets of emission scenarios. We first use RCP2.6 and its extension until year 2300 as the reference scenario and design several temperature and cumulative CO2 emissions "overshoot" scenarios based on other RCPs, which represents cases with less ambitious mitigation policies in the near term that temporarily exceed the 2 °C target adopted by the Paris Agreement. In addition, we use a set of emission scenarios with a reference scenario limiting warming to 1.5°C in the long term and two overshoot scenarios. The University of Victoria Earth System Climate Model (UVic ESCM), a climate model of intermediate complexity, is forced with these emission scenarios. We compare the response of select ocean variables (seawater temperature, pH, dissolved oxygen) in the overshoot scenarios to that in the respective reference scenario at the time the same amount of cumulative emissions is achieved. Our results suggest that the overshoot and subsequent return to a reference CO2 cumulative emissions level would leave substantial impacts on the marine environment. Although the changes in global mean sea surface variables (temperature, pH and dissolved oxygen) are largely reversible, global mean ocean temperature, dissolved oxygen and pH differ significantly from those in the reference scenario. Large ocean areas exhibit temperature increase and pH and dissolved oxygen decrease relative to the reference scenario without cumulative CO2 emissions overshoot. Furthermore, our results show that the higher the level of overshoot, the lower the reversibility of changes in the marine environment.

Mitigating climate change through the understanding of Nitrous Oxide (N2O) consumption processes in peat lands

NASA Astrophysics Data System (ADS)

Akrami, N.; Barker, X. Z.; Horwath, W. R.

2017-12-01

Nitrous Oxide (N2O) with global warming potential of 298 over a 100-year horizon is one of the most potent green house gases. In the United States, agriculture share to N2O emissions is over 70%. Peat lands, however, are being considered as both sources and sinks of greenhouse gases. N2O emissions are a product of both production and consumption processes. However, there is still a lack of understanding of N2O consumption processes in soils. In this work, the potential of re-wetted peat lands planted to rice in Sacramento-San Joaquin Delta, California, to act as a potential sink for N2O is being evaluated. Four peat land soils with 1%, 5%, 11% and 23% of organic carbon have been anaerobically incubated with different water contents (15%, 30%, 50%, 75% and 100% of their water holding capacity). 15N-N2O gas has been injected to the headspace of experiment jars and the production and consumption rate of 15N-N2O, 15N-N2 and production rate of Carbon Dioxide (CO2) and Methane (CH4) along with dissolved Nitrate (NO3-), Nitrite (NO2-), Ammonium (NH4+), Iron (II) and Iron (III) concentration has been quantified. Our results show promising N2O consumption rates under high carbon content and relatively high water content treatments. This research introduces organic carbon and water content as two major criteria in N2O consumption processes in peat lands that make it a potential hotspot for climate changes mitigation through adopting effective management practices to decrease greenhouse gas emissions.

Dissolved carbon dioxide determines the productivity of a recombinant hemagglutinin component of an influenza vaccine produced by insect cells.

PubMed

Meghrous, Jamal; Khramtsov, Nikolai; Buckland, Barry C; Cox, Manon M J; Palomares, Laura A; Srivastava, Indresh K

2015-11-01

Dissolved carbon dioxide (dCO2 ) accumulation during cell culture has been recognized as an important parameter that needs to be controlled for successful scale-up of animal cell culture because above a certain concentration there are adverse effects on cell growth performance and protein production. We investigated the effect of accumulation of dCO2 in bioreactor cultures of expresSF+(®) insect cells infected with recombinant baculoviruses expressing recombinant influenza virus hemagglutinins (rHA). Different strategies for bioreactor cultures were used to obtain various ranges of concentrations of dCO2 (<50, 50-100, 100-200, and >200 mmHg) and to determine their effects on recombinant protein production and cell metabolic activity. We show that the accumulation of dCO2 at levels > 100 mmHg resulted in reduced metabolic activity, slowed cell growth, prolonged culture viability after infection, and decreased infection kinetics. The reduced rHA yields were not caused by the decrease in the extracellular pH that resulted from dCO2 accumulation, but were most likely due to the effect of dCO2 accumulation in cells. The results obtained here at the 2 L scale have been used for the design of large-scale processes to manufacture the rHA based recombinant vaccine Flublok™ at the 2500 L scale Biotechnol. Bioeng. 2015;112: 2267-2275. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

The influence of dissolved oxygen on winter habitat selection by largemouth bass: an integration of field biotelemetry studies and laboratory experiments.

PubMed

Hasler, C T; Suski, C D; Hanson, K C; Cooke, S J; Tufts, B L

2009-01-01

In this study, field biotelemetry and laboratory physiology approaches were coupled to allow understanding of the behavioral and physiological responses of fish to winter hypoxia. The biotelemetry study compared dissolved oxygen levels measured throughout the winter period with continually tracked locations of nine adult largemouth bass obtained from a whole-lake submerged telemetry array. Fish habitat usage was compared with habitat availability to assess whether fish were selecting for specific dissolved oxygen concentrations. The laboratory study examined behavioral and physiological responses to progressive hypoxia in juvenile largemouth bass acclimated to winter temperatures. Results from the dissolved oxygen measurements made during the biotelemetry study showed high variance in under-ice dissolved oxygen levels. Avoidance of water with dissolved oxygen <2.0 mg/L by telemetered fish was demonstrated, but significant use of water with intermediate dissolved oxygen levels was also found. Results from the lab experiments showed marked changes in behavior (i.e., yawning and vertical movement) at <2.0 mg/L of dissolved oxygen but no change in tissue lactate, an indicator of anaerobic metabolism. Combined results of the biotelemetry and laboratory studies demonstrate that a dissolved oxygen content of 2.0 mg/L may be a critical threshold that induces behavioral responses by largemouth bass during the winter. In addition, the use by fish of areas with intermediate levels of dissolved oxygen suggests that there are multiple environmental factors influencing winter behavior.

Ocean Acidification: Adaptive Challenge or Extinction Threat?

NASA Astrophysics Data System (ADS)

Caldeira, K.

2012-12-01

Most of the carbon dioxide that we emit to this atmosphere through fossil-fuel burning and deforestation is ultimately absorbed by the oceans. The effects of excess carbon dioxide on the inorganic chemistry of the ocean are largely well understood, but it is less clear what these chemical changes mean for the future of marine biota. Excess dissolved CO2 increases hydrogen-ion concentration (i.e., decreases pH) and decreases carbonate-ion concentrations, affecting the chemical speciation of nutrients and other chemicals dissolved in the ocean, and affecting the ability of organisms to form calcium carbonate shells or skeletons. Some organisms, such as corals, develop shells or skeletons made from aragonite, a particularly soluble form of calcium carbonate. The uptake of O2 and the release of CO2 from the blood of fish are affected by pH, with lower pH leading to a decrease in both O2 uptake and CO2 release. Of these concerns, the effects of excess CO2 on calcification may be the most worrisome. Doubling or quadrupling of atmospheric CO2 content within the space of a few centuries means doubling or quadrupling hydrogen-ion concentrations and halving or quartering the carbonate-ion concentration within a few centuries. Experiments and theory indicate that chemical changes of this magnitude could have important biotic consequences. Changes of this magnitude and rapidity have not occurred on this planet with the possible exception of various paroxysmal extreme events buried deep in Earth history. Most major changes to ocean chemistry occurred over millions of years allowing (i) seawater chemistry to be in approximate equilibrium with respect to riverine and sedimentary fluxes and (ii) marine biota to adapt in evolutionary time. Man's great geochemical experiment will go on at global scale for thousands of years. But experiments can be done in the laboratory in small tanks or in the sea in small enclosures only for limited periods of time. It is difficult to infer from these small scale experiments the potential for adaptation in ecological or evolutionary time. The current evidence points to ocean acidification being catastrophic for at least some organisms and ecosystems (e.g., possibly coral reefs) and likely to lead to the extinction of at least some species. On the other hand, for many organisms and ecosystems (e.g., perhaps some open ocean fish-dominated ecosystems), ocean acidification may represent little more than a minor adaptive challenge. Science can help us to understand the risks, even if some central questions will of necessity remain unanswered. Hopefully, CO2 emissions will be curtailed, and we will never find out which of the more pessimistic or more optimistic projections were correct.

The carbon cycle implications of chemical weathering in retrogressive thaw slump-impacted streams

NASA Astrophysics Data System (ADS)

Zolkos, S.; Tank, S. E.; Kokelj, S. V.

2016-12-01

Permafrost thaw is "unlocking" and exposing significant amounts of sediment, solutes and organic carbon previously maintained in frozen soils to biochemical processing and fluvial transport. While microbial respiration of permafrost organic carbon contributes significantly to CO2 in Arctic headwater streams, chemical weathering of minerals unearthed by thawing permafrost may fix CO2 as bicarbonate (HCO3), thus removing it from the active carbon cycle. However, the degree to which mineral weathering acts to temper CO2 generated during permafrost thaw is largely unknown. During summer 2015, we investigated these dynamics in eight streams (orders 1-3) impacted by retrogressive thaw slumps across the Peel Plateau (NT, Canada), where thaw slumps expose permafrost that is comprised of abundant glacial tills, and glaciofluvial and glaciolacustrine sediments. Thaw slump activity had a discernible signature in all streams: conductivity, pH, dissolved inorgnaic carbon (DIC), and solute concentrations (Ca, Mg, Na, K, SO4, Cl) increased in the downstream (thaw slump-impacted) reach, relative to upstream, while CO2 decreased. This corresponded with an isotopically-enriched DIC pool in impacted streams (mean δ13CDIC = -9.80‰), perhaps indicating the dissolution of carbonate minerals following exposure by thaw slump activity. Despite a general decrease downstream of thaw slumps, CO2 remained supersaturated in impacted streams (mean pCO2 = 915 µatm). However, the highest partial pressures of CO2 were found in thaw slump runoff (mean pCO2 = 4,600 µatm), above the point where runoff entered downstream systems. High pCO2 levels in slump runoff may be derived from microbial respiration of slump-released dissolved organic carbon or, for some slumps, carbonate dissolution (range δ13CDIC = 0.67 - -23.37‰). While this work suggests thaw slumps in the Western Canadian Arctic may act to partially temper CO2 in headwater streams, these stream networks will likely persist as significant sources of CO2 to the atmosphere.

A challenge for green chemistry: designing molecules that readily dissolve in carbon dioxide.

PubMed

Beckman, E J

2004-09-07

Carbon dioxide is a green yet feeble solvent whose full potential won't be realized until we develop a more thorough understanding of its solvent behavior at the molecular level. Fortunately, advances in molecular modeling coupled with experiments are rapidly improving our understanding of CO(2)'s behavior, permitting design of new, more sustainable "CO(2)-philes".

The alteration of rhyolite in CO2 charged water at 200 and 350°C: The unreactivity of CO2 at higher temperature

USGS Publications Warehouse

Bischoff, James L.; Rosenbauer, Robert J.

1996-01-01

These observations also offer a possible explanation for the change in chemical sediments from chloride-dominated to bicarbonate-dominated salts found in the stratigraphic section at Searles Lake, California, the terminus of the Owens River which derives its dissolved load from hot springs of the Long Valley caldera.

The fate of carbon dioxide in water-rich fluids under extreme conditions.

PubMed

Pan, Ding; Galli, Giulia

2016-10-01

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures ( P ) and temperatures ( T ) approximating the conditions of Earth's upper mantle. Contrary to popular geochemical models assuming that molecular CO 2 (aq) is the major carbon species present in water under deep Earth conditions, we found that at 11 GPa and 1000 K, carbon exists almost entirely in the forms of solvated carbonate ([Formula: see text]) and bicarbonate ([Formula: see text]) ions and that even carbonic acid [H 2 CO 3 (aq)] is more abundant than CO 2 (aq). Furthermore, our simulations revealed that ion pairing between Na + and [Formula: see text]/[Formula: see text] is greatly affected by P - T conditions, decreasing with increasing pressure at 800 to 1000 K. Our results suggest that in Earth's upper mantle, water-rich geofluids transport a majority of carbon in the form of rapidly interconverting [Formula: see text] and [Formula: see text] ions, not solvated CO 2 (aq) molecules.

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.

Manufacture of modified milk protein concentrate utilizing injection of carbon dioxide.

PubMed

Marella, Chenchaiah; Salunke, P; Biswas, A C; Kommineni, A; Metzger, L E

2015-06-01

Dried milk protein concentrate is produced from skim milk using a combination of processes such as ultrafiltration (UF), evaporation or nanofiltration, and spray drying. It is well established that dried milk protein concentrate (MPC) that contains 80% (MPC80) and greater protein content (relative to dry matter) can lose solubility during storage as a result of protein-protein interactions and formation of insoluble complexes. Previous studies have shown that partial replacement of calcium with sodium improves MPC80 functionality and prevents the loss in solubility during storage. Those studies have used pH adjustment with the addition of acids, addition of monovalent salts, or ion exchange treatment of UF retentate. The objective of this study was to use carbon dioxide to produce MPC80 with improved functionality. In this study, reduced-calcium MPC80 (RCMPC) was produced from skim milk that was subjected to injection of 2,200 ppm of CO2 before UF, along with additional CO2 injection at a flow rate of 1.5 to 2 L/min during UF. A control MPC80 (CtrlMPC) was also produced from the same lot of skim milk without injection of CO2. The above processes were replicated 3 times, using different lots of skim milk for each replication. All the UF retentates were spray dried using a pilot-scale dryer. Skim milk and UF retentates were tested for ζ-potential (net negative charge), particle size, and viscosity. All the MPC were stored at room (22±1°C) and elevated (40°C) temperatures for 6 mo. Solubility was measured by dissolving the dried MPC in water at 22°C and at 10°C (cold solubility). Injection of CO2 and the resultant solubilization of calcium phosphate had a significant effect on UF performance, resulting in 10 and 20% loss in initial and average flux, respectively. Processing of skim milk with injection of CO2 also resulted in higher irreversible fouling resistances. Compared with control, the reduced-calcium MPC had 28 and 34% less ash and calcium, respectively. Injection of CO2 resulted in a significant decrease in ζ-potential and a significant increase in the size of the casein micelle. Moreover, RCMPC had a significantly higher solubility after storage at room temperature and at elevated temperature. This study demonstrates that MPC80 with a reduced calcium and mineral content can be produced with injection of CO2 before and during UF of skim milk. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Leaching of organic acids from macromolecular organic matter by non-supercritical CO2

NASA Astrophysics Data System (ADS)

Sauer, P.; Glombitza, C.; Kallmeyer, J.

2012-04-01

The storage of CO2 in underground reservoirs is discussed controversly in the scientific literature. The worldwide search for suitable storage formations also considers coal-bearing strata. CO2 is already injected into seams for enhanced recovery of coal bed methane. However, the effects of increased CO2 concentration, especially on organic matter rich formations, are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Huge amounts of low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced by the acidic porewater. Recent investigations outlined the importance of LMWOAs as a feedstock for microbial life in the subsurface [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effect of high concentrations of dissolved CO2 on the release of LMWOAs from coal we developed an inexpensive high-pressure high temperature system that allows manipulating the partial pressure of dissolved gases at pressures and temperatures up to 60 MPa and 120° C, respectively. In a reservoir vessel, gases are added to saturate the extraction medium to the desired level. Inside the extraction vessel hangs a flexible and inert PVDF sleeve (polyvinylidene fluoride, almost impermeable for gases), holding the sample and separating it from the pressure fluid. The flexibility of the sleeve allows for subsampling without loss of pressure. Coal samples from the DEBITS-1 well, Waikato Basin, NZ (R0 = 0.29, TOC = 30%). were extracted at 90° C and 5 MPa, either with pure or CO2-saturated water. Subsamples were taken at different time points during the extraction. The extracted LMWOAs such as formate, acetate and oxalate were analysed by ion chromatography. Yields of LMWOAs were higher with pure water than with CO2-saturated water, revealing a suppressing effect of CO2. Both extractions had higher yields than those reported for soxhlet extraction [2]. LMWOAs found in the extraction fluid may not just result from hydrolysis but also from different secondary reactions. It was suggested that oxalate in aqueous extracts of coals is a result of the decomposition of 1,2-dihydroxy-carboxylic acids [3]. We assume that for oxalate (and maybe for other LMWOAs as well) the extraction yield is not only affected by hydrolysis but also by secondary reactions, which may be inhibited or suppressed in the presence of CO2 in the extraction medium. During soxhlet extraction the sample only gets into contact with freshly distilled water, not with an acidic fluid. This may explain the lower yields.

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.

Nitrous oxide in fresh water systems: An estimate for the yield of atmospheric N2O associated with disposal of human waste

NASA Technical Reports Server (NTRS)

Kaplan, W. A.; Elkins, J. W.; Kolb, C. E.; Mcelroy, M. B.; Wofsy, S. C.; Duran, A. P.

1977-01-01

The N2O content of waters in the Potomac and Merrimack Rivers was measured on a number of occasions over the period April to July 1977. The concentrations of dissolved N2O exceeded those which would apply in equilibrium with air by factors ranging from about 46 in the Potomac to 1.2 in the Merrimack. Highest concentrations of dissolved N2O were associated with sewage discharges from the vicinity of Washington, D. C., and analysis indicates a relatively high yield, 1.3 to 11%, for prompt conversion of waste nitrogen to N2O. Measurements of dissolved N2O in fresh water ponds near Boston demonstrated that aquatic systems provide both strong sources and sinks for atmospheric N2O.

A relationship between dissolved CO2 and the non-volatile chemistry of rainwater.

NASA Astrophysics Data System (ADS)

Durham, Brian; Pfrang, Christian

2016-04-01

Measurements of a volatile acid component in UK rainwater in 2009 implicated CO2, and speculated `a concentrating mechanism (that) could mean that this weakly soluble molecule is recycled at a faster rate than inferred by its Henry's Law constant'. Last year's EGU Presentation 2015-3386 confirmed that the `saturated CO2 content (of UK rainwater) is insignificant, the bulk transport being the volatile component'. However the atmospheric capture mechanism remains enigmatic. For pure water, improved temperature control has discounted the predicted upturn in the Henry coefficient for 450Pa CO2 as the temperature approached freezing point (http://presentations.copernicus.org/EGU2015-3386_presentation.pptx), and the focus has therefore turned to rainwater chemistry. For a mid-range sample the Henry value was: • significantly higher than pure water at 20'C; • but decreasing with lower temperatures. The higher Henry constant might suggest that, as an acid anhydride, CO2 is subject to selective capture where cloud water is alkaline (terrestrial dust or marine aerosol). Analysis has however shown no simple relationship between [CO2]aq and either acidity or conductivity of the carrier water. Seeking therefore a coherent distribution, stripped CO2 was plotted against Δ[H+], from which this paper presents a tight wedge-shaped distribution of 263 UK rain/snow events. The inference is that [CO2]aq is not related directly to [H+], but possibly to Group 1 and 2 cations from marine aerosol that are buffering the cloud water acidity. By contrast, the unexpected decrease in CO2 yield with lower temperatures proved to be an artefact of a progressively slower rate of de-gassing, cooler samples still equilibrating after 100 minutes. An ultrasound stripper is therefore being developed to speed the Henry measurements, and for reproducibility it is proposed to dilute a proprietary `standard Atlantic sea water' to a representative range of conductivities, to be called `standard rainwater'. Any temptation to extrapolate from English results to address the global boundary layer is resisted pending ΔpH values from other stations, which are herewith invited in anticipation of IPCC AR6.

The hydro- and multi-isotope geochemistry of iron-rich ground waters emerging at the southern Baltic Sea coast line

NASA Astrophysics Data System (ADS)

Lipka, Marko; Wu, Zijun; Escher, Peter; Struck, Ulrich; Dellwig, Olaf; Schafmeister, Maria; Böttcher*, Michael E.

2013-04-01

Iron-rich groundwater springs emerging at the shore zone of the southern Baltic Sea (BS; Site Meschendorf) were examined on a seasonal base for a period of about two years. Besides major, minor, and trace elements, stable isotopes of water (H-2, O-18), dissolved inorganic carbon (DIC; C-13), and sulfate (S-34) were analyzed. The stream bed sediment was extracted for the geochemistry of the newly formed precipitates and further characterized via SEM-EDAX. Subsequently, the hydrogeochemical results were subjected to a thermodynamic analysis via the PHREEQC speciation model. The springs emerge from small pits (about 60 cm diameter; up to 15cm depth). Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were stable during the investigation period while the shape of the pits and the stream beds may vary due to wind- and wave-driven forces. Selected measurements of spring yield discharges close to 10 L/min. The H-2 and O-18 contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. The hydrochemistry of the springs was similar and showed some variability in between which indicates that the genetic processes for the ground water before reaching the surface may slightly differ. The springs are characterized by dissolved Ca, Mg, Na, DIC and sulfate, mainly reflecting the interaction with soils and bedrocks in the recharge area that is dominated by marly till. The oxygen-free ground water is rich in Fe, P, and DIC. Iron and dissolved sulfate originate from the oxidation of pyrite, as further confirmed by the 34-S signature of sulfate. The carbon isotope signature of DIC indicates a mixture of biogenic CO2 from the soil zone with some water-rock interaction with carbonate minerals. The streams flow towards the BS and, in contact with the atmosphere, outgas carbon dioxide and takes up oxygen. Upon CO2-degassing, C-12 is preferentially desorbed from the aqueous solution. The changes in the stream composition lead to the formation of iron(oxyhyr)oxide precipitates in the stream bed before the waters pass to underground drainage into a subterranean mixing zone with brackish BS waters. These ochrous precipitates act as a sink for dissolved phosphate and minor calcium. P : Fe ratios and Ca : Fe ratios are about 0.08 and 0.2, respectively, which are caused by P adsorption and a mixture with minor CaCO3 and/or Ca-phosphate. The investigation reveals that the surface precipitation on the beach leads to the formation of SGD essentially free of dissolved iron and strongly depleted in phosphate. Similar iron phases may also be an important part of the subterranean estuary supposed at that coast line, where retention of nutrients and heavy metals by iron(oxyhydr)oxides could influence the release of nutrients into the coastal ecosystem. Fe- and P-rich surface precipitates, however, are transported in suspension into the Baltic Sea during wind-driven flood events. Acknowledgements: This work was partly supported by the BONUS+ project AMBER and the Leibniz IOW.

Multiphase, multicomponent simulations and experiments of reactive flow, relevant for combining geologic CO2 sequestration with geothermal energy capture

NASA Astrophysics Data System (ADS)

Saar, Martin O.

2011-11-01

Understanding the fluid dynamics of supercritical carbon dioxide (CO2) in brine- filled porous media is important for predictions of CO2 flow and brine displacement during geologic CO2 sequestration and during geothermal energy capture using sequestered CO2 as the subsurface heat extraction fluid. We investigate multiphase fluid flow in porous media employing particle image velocimetry experiments and lattice-Boltzmann fluid flow simulations at the pore scale. In particular, we are interested in the motion of a drop (representing a CO2 bubble) through an orifice in a plate, representing a simplified porous medium. In addition, we study single-phase/multicomponent reactive transport experimentally by injecting water with dissolved CO2 into rocks/sediments typically considered for CO2 sequestration to investigate how resultant fluid-mineral reactions modify permeability fields. Finally, we investigate numerically subsurface CO2 and heat transport at the geologic formation scale.

Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

PubMed

Simpson, Stuart L; Vardanega, Christopher R; Jarolimek, Chad; Jolley, Dianne F; Angel, Brad M; Mosley, Luke M

2014-05-01

The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Electron Donor-Acceptor Nature of the Ethanol-CO2 Dimer

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Martin-Drumel, Marie-Aline; McCarthy, Michael A.

2017-08-01

Supercritical CO2 is an appealing nontoxic, environmentally friendly solvent for the industrial extraction of many classes of compounds, from caffeine to natural product drug precursors to petrochemical impurities. Apolar in isolation, the ability of supercritical CO2 to dissolve polar species has been empirically shown to be greatly enhanced by the addition of a small molar percentage of a polar cosolvent, often ethanol. Computational work predicts that the isolated ethanol-CO2 complex can exist either in an electron-donor configuration or through a hydrogen-bonding one; yet, neither has been previously experimentally observed. Here, we demonstrate by rotational spectroscopy that the isolated, gas-phase ethanol-CO2 dimer is an electron donor-acceptor complex.

Chemical composition of dew in Amman, Jordan

NASA Astrophysics Data System (ADS)

Jiries, Anwar

Twenty-six dew samples were collected on a glass surface from an urbanized area in Amman city during the period October 1999 to June 2000. They were analyzed for the major ions (Cl, SO 4, NO 3, Ca, Mg, Na, K and NH 4) in addition to three heavy metals (Pb, Cd and Co). Rain samples were collected for the same period and compared to the chemical constituents of dew. It was found that both rain and dew samples were of almost neutral acidity due to the buffering effect of CaCO 3. Dew composition was mainly from CaSO 4 solution due to conversion of CaCO 3 to CaSO 4 when left exposed to a sulfate-rich atmosphere. The total dissolved solids were higher in dew than rain samples of the same period. This was attributed to higher evaporation effect on dew than rain. The heavy metal content in dew is highest during the cold winter season (December-March) due to excess fossil fuel combustion for heating purposes in this period. The heavy metal content in dew was lower than that for rain during the same period because of the shorter period of dew formation than rainwater.

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

USGS Publications Warehouse

Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

2014-01-01

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Dissolution and storage stability of nanostructured calcium carbonates and phosphates for nutrition

NASA Astrophysics Data System (ADS)

Posavec, Lidija; Knijnenburg, Jesper T. N.; Hilty, Florentine M.; Krumeich, Frank; Pratsinis, Sotiris E.; Zimmermann, Michael B.

2016-10-01

Rapid calcium (Ca) dissolution from nanostructured Ca phosphate and carbonate (CaCO3) powders may allow them to be absorbed in much higher fraction in humans. Nanosized Ca phosphate and CaCO3 made by flame-assisted spray pyrolysis were characterized by nitrogen adsorption, X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. As-prepared nanopowders contained both CaCO3 and CaO, but storing them under ambient conditions over 130 days resulted in a complete transformation into CaCO3, with an increase in both crystal and particle sizes. The small particle size could be stabilized against such aging by cation (Mg, Zn, Sr) and anion (P) doping, with P and Mg being most effective. Calcium phosphate nanopowders made at Ca:P ≤ 1.5 were XRD amorphous and contained γ-Ca2P2O7 with increasing hydroxyapatite content at higher Ca:P. Aging of powders with Ca:P = 1.0 and 1.5 for over 500 days gradually increased particle size (but less than for CaCO3) without a change in phase composition or crystallinity. In 0.01 M H3PO4 calcium phosphate nanopowders dissolved ≈4 times more Ca than micronsized compounds and about twice more Ca than CaCO3 nanopowders, confirming that nanosizing and/or amorphous structuring sharply increases Ca powder dissolution. Because higher Ca solubility in vitro generally leads to greater absorption in vivo, these novel FASP-made Ca nanostructured compounds may prove useful for nutrition applications, including supplementation and/or food fortification.

Influence of Feeding and Controlled Dissolved Oxygen Level on the Production of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) Copolymer by Cupriavidus sp. USMAA2-4 and Its Characterization.

PubMed

Shantini, K; Yahya, A R M; Amirul, A A

2015-07-01

Copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] has been the center of attention in the bio-industrial fields, as it possesses superior mechanical properties compared to poly(3-hydroxybutyrate) [P(3HB)]. The usage of oleic acid and 1-pentanol was exploited as the carbon source for the production of P(3HB-co-3HV) copolymer by using a locally isolated strain Cupriavidus sp. USMAA2-4. In this study, the productivity of polyhydroxyalkanoate (PHA) was improved by varying the frequency of feeding in fed-batch culture. The highest productivity (0.48 g/L/h) that represents 200 % increment was obtained by feeding the carbon source and nitrogen source three times and also by considering the oxygen uptake rate (OUR) and oxygen transfer rate (OTR). A significantly higher P(3HB-co-3HV) concentration of 25.7 g/L and PHA content of 66 wt% were obtained. The 3-hydroxyvalerate (3HV) monomer composition obtained was 24 mol% with the growth of 13.3 g/L. The different frequency of feeding carried out has produced a blend copolymer and has broadened the monomer distribution. In addition, increase in number of granules was also observed as the frequency of feeding increases. In general, the most glaring increment in productivity offer advantage for industrial P(3HB-co-3HV) production, and it is crucial in developing cost-effective processes for commercialization.

Aqueous speciation is likely to control the stable isotopic fractionation of cerium at varying pH

NASA Astrophysics Data System (ADS)

Nakada, Ryoichi; Tanaka, Masato; Tanimizu, Masaharu; Takahashi, Yoshio

2017-12-01

Cerium (Ce) can be used as a plaeoredox proxy as shown by a recent study of stable isotopic fractionation of Ce during adsorption and precipitation. However, the experiments in that study were performed at pH conditions lower than that of natural seawater. In the current study, adsorption and precipitation experiments were performed at pH 6.80, 8.20, and 11.00 with 2.25 mM dissolved carbonate to simulate Ce isotopic fractionation in the natural environment and examine the relationship between isotopic fractionation and Ce speciation in the liquid phase. Mean isotopic fractionation factors between liquid and solid phases (αLq-So) of Ce adsorbed on ferrihydrite did not depend on pH conditions or dissolved Ce species. In the Ce/δ-MnO2 system,αLq-So values decreased from 1.000411 (±0.000079) to 1.000194 (±0.000067) with increasing pH or number of carbonate ions, from Ce3+ to Ce(CO3)2-. In the Ce/precipitation system at pH 8.20 and 11.00 where Ce(CO3)2- is present in solution, the αLq-So values were 0.999821 (±0.000071) and 0.999589 (±0.000074), respectively, meaning that lighter isotope enrichment was observed in the liquid phase, which is the contrary to those of the other systems. Extended X-ray absorption fine structure (EXAFS) analyses were also performed to investigate the coordination structure of the adsorbed or precipitated Ce species that control the isotopic fractionation during adsorption. Even at higher pH, where Ce(CO3)+ or Ce(CO3)2- are the dominant dissolved species, the first coordination sphere of Ce in the solid phase in the Ce/ferrihydrite and Ce/precipitation systems was similar to that observed at pH 5.00 where Ce3+ was the main species in solution. A slight elongation in the Cesbnd O bond length in the solid phase at pH 11.00, where negatively charged dissolved species are dominant in the liquid phase, may cause a decrease in isotopic fractionation in the Ce/δ-MnO2 system. The coordination environment of Ce may not change significantly during the adsorption onto ferrihydrite, because Ce binds to the neutral surface OH group on ferrihydrite at pH below 8.5-8.8 (i.e. the pH of the point of zero charge (PZC) for ferrihydrite), similar to other cations when the metal-O distance was similar in hydrated and adsorbed species. At pH above PZC, Ce bonds to the negatively charged surface OH group, while Ce also bonds with CO32- in dissolved species. The reduced partition functions (ln β) for dissolved species (ln βLq) and adsorbed species (ln βSo) with the same trends canceled each other, because ln β of hydrated cation was reduced by the binding anion, resulting in small isotope fractionations. Thus, isotope fractionations for Ce/ferrihydrite may be quite small at the entire pH conditions in this study. The direction of the isotopic fractionation was estimated based on density functional theory (DFT) calculations, which confirmed that lighter Ce is enriched in the liquid phase when Ce forms a complex with carbonate ions. Therefore, this study indicates that the dissolved species can control stable Ce isotopic fractionation during precipitation reactions.

Temporal biomass dynamics of an Arctic plankton bloom in response to increasing levels of atmospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Schulz, K. G.; Bellerby, R. G. J.; Brussaard, C. P. D.; Büdenbender, J.; Czerny, J.; Engel, A.; Fischer, M.; Koch-Klavsen, S.; Krug, S. A.; Lischka, S.; Ludwig, A.; Meyerhöfer, M.; Nondal, G.; Silyakova, A.; Stuhr, A.; Riebesell, U.

2013-01-01

Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in Kongsfjorden on the west coast of Spitsbergen (Norway), in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 μatm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured as high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2-related shifts in nutrient flow into different phytoplankton groups (mainly dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

Temporal biomass dynamics of an Arctic plankton bloom in response to increasing levels of atmospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Schulz, K. G.; Bellerby, R. G. J.; Brussaard, C. P. D.; Büdenbender, J.; Czerny, J.; Engel, A.; Fischer, M.; Koch-Klavsen, S.; Krug, S. A.; Lischka, S.; Ludwig, A.; Meyerhöfer, M.; Nondal, G.; Silyakova, A.; Stuhr, A.; Riebesell, U.

2012-09-01

Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in 2010, in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 μatm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured at high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2 related shifts in nutrient flow into different phytoplankton groups (mainly diatoms, dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

Nitrogen soil emissions and belowground plant processes in Mediterranean annual pastures are altered by ozone exposure and N-inputs

NASA Astrophysics Data System (ADS)

Sánchez-Martín, L.; Bermejo-Bermejo, V.; García-Torres, L.; Alonso, R.; de la Cruz, A.; Calvete-Sogo, H.; Vallejo, A.

2017-09-01

Increasing tropospheric ozone (O3) and atmospheric nitrogen (N) deposition alter the structure and composition of pastures. These changes could affect N and C compounds in the soil that in turn can influence soil microbial activity and processes involved in the emission of N oxides, methane (CH4) and carbon dioxide (CO2), but these effects have been scarcely studied. Through an open top chamber (OTC) field experiment, the combined effects of both pollutants on soil gas emissions from an annual experimental Mediterranean community were assessed. Four O3 treatments and three different N input levels were considered. Fluxes of nitric (NO) and nitrous (N2O) oxide, CH4 and CO2 were analysed as well as soil mineral N and dissolved organic carbon. Belowground plant parameters like root biomass and root C and N content were also sampled. Ozone strongly increased soil N2O emissions, doubling the cumulative emission through the growing cycle in the highest O3 treatment, while N-inputs enhanced more slightly NO; CH4 and CO2 where not affected. Both N-gases had a clear seasonality, peaking at the start and at the end of the season when pasture physiological activity is minimal; thus, higher microorganism activity occurred when pasture had a low nutrient demand. The O3-induced peak of N2O under low N availability at the end of the growing season was counterbalanced by the high N inputs. These effects were related to the O3 x N significant interaction found for the root-N content in the grass and the enhanced senescence of the community. Results indicate the importance of the belowground processes, where competition between plants and microorganisms for the available soil N is a key factor, for understanding the ecosystem responses to O3 and N.

Solvent composition of one-step self-etch adhesives and dentine wettability.

PubMed

Grégoire, Geneviève; Dabsie, Firas; Dieng-Sarr, Farimata; Akon, Bernadette; Sharrock, Patrick

2011-01-01

Our aim was to determine the wettability of dentine by four commercial self-etch adhesives and evaluate their spreading rate on the dentine surface. Any correlation with chemical composition was sought, particularly with the amount of solvent or HEMA present in the adhesive. The adhesives used were AdheSE One, Optibond All.In.One, Adper Easy Bond and XenoV. Chemical compositions were determined by proton nuclear magnetic resonance (NMR) spectroscopy of the adhesives dissolved in dimethylsulfoxide. Apparent contact angles for sessile drops of adhesives were measured on dentine slices as a function of time for up to 180s. The water contact angles were determined for fully polymerised adhesives. All adhesives were water-based with total solvent contents ranging from 27% to 73% for HEMA-free adhesives, and averaging 45% for HEMA containing adhesives. The contents in hydrophobic groups decreased as water contents increased. No differences were found in the adhesive contact angles after 180s even though the spreading rates were different for the products tested. Water contact angles differed significantly but were not correlated with HEMA or solvent presence. Manufacturers use different approaches to stabilise acid co-monomer ingredients in self-etch adhesives. Co-solvents, HEMA, or acrylamides without co-solvents are used to simultaneously etch and infiltrate dentine. A large proportion of water is necessary for decalcification action. Copyright © 2010 Elsevier Ltd. All rights reserved.

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, Charles A.

2015-01-01

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Dissolved gases in the DOSECC Cajon Pass well: first year results

USGS Publications Warehouse

Evans, William C.; White, L.D.; Kharaka, Y.K.

1988-01-01

Fluid sampled from granitic rock near the 2 km depth in the DOSECC Cajon Pass well contained He, H2, CH4, C2H6, and C2 H4 in concentrations much greater than in air-saturated water. Measured pCO2 values were very low, about 10-5 atm., and the carbon isotopes (??13C = -18.9 per mil) point to an organic source such as plant root respiration for the dissolved carbonate species. No evidence of mantle volatiles was found despite proximity of the well to the San Andreas fault. -from Authors

Is the response of coral calcification to seawater acidification related to nutrient loading?

NASA Astrophysics Data System (ADS)

Chauvin, Anne; Denis, Vianney; Cuet, Pascale

2011-12-01

The effect of decreasing aragonite saturation state (ΩArag) of seawater (elevated pCO2) on calcification rates of Acropora muricata was studied using nubbins prepared from parent colonies located at two sites of La Saline reef (La Réunion Island, western Indian Ocean): a back-reef site (BR) affected by nutrient-enriched groundwater discharge (mainly nitrate), and a reef flat site (RF) with low terrigenous inputs. Protein and chlorophyll a content of the nubbins, as well as zooxanthellae abundance, were lower at RF than BR. Nubbins were incubated at ~27°C over 2 h under sunlight, in filtered seawater manipulated to get differing initial pCO2 (1,440-340 μatm), ΩArag (1.4-4.0), and dissolved inorganic carbon (DIC) concentrations (2,100-1,850 μmol kg-1). Increasing DIC concentrations at constant total alkalinity (AT) resulted in a decrease in ΩArag and an increase in pCO2. AT at the beginning of the incubations was kept at a natural level of 2,193 ± 6 μmol kg-1 (mean ± SD). Net photosynthesis (NP) and calcification were calculated from changes in pH and AT during the incubations. Calcification decrease in response to doubling pCO2 relative to preindustrial level was 22% for RF nubbins. When normalized to surface area of the nubbins, (1) NP and calcification were higher at BR than RF, (2) NP increased in high pCO2 treatments at BR compared to low pCO2 treatments, and (3) calcification was not related to ΩArag at BR. When normalized to NP, calcification was linearly related to ΩArag at both sites, and the slopes of the relationships were not significantly different. The increase in NP at BR in the high pCO2 treatments may have increased calcification and thus masked the negative effect of low ΩArag on calcification. Removing the effect of NP variations at BR showed that calcification declined in a similar manner with decreased ΩArag (increased pCO2) whatever the nutrient loading.

Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts

USGS Publications Warehouse

Sakai, H.; Marais, D.J.D.; Ueda, A.; Moore, J.G.

1984-01-01

Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges,-6.2 ?? 0.2% relative to PDB and +0.2 ?? 0.6 %. relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (??13C = around -24%.) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm, in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). The ??34S values average +0.3 ?? 0.5%. with average fractionation factor between sulfate and sulfide of +7.4 ?? 1.6%.. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt. ?? 1984.

Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts.

PubMed

Sakai, H; Des Marais, D J; Ueda, A; Moore, J G

1984-01-01

Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges, -6.2 +/- 0.2% relative to PDB and +0.2 +/- 0.6% relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (delta 13 C = around -24%) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). the delta 34S values average +0.3 +/- 0.5% with average fractionation factor between sulfate and sulfide of +7.4 +/- 1.6%. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt.

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

NASA Technical Reports Server (NTRS)

Hollander, D. J.; Sinninghe Damste, J. S.; Hayes, J. M.; de Leeuw, J. W.; Huc, A. Y.

1993-01-01

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.

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

PAUL, JOHN H

Oceanic river plumes represent some of the most productive environments on Earth. As major conduits for freshwater and nutrients into the coastal ocean, their impact on water column ecosystems extend for up to a thousand km into oligotrophic oceans. Upon entry into the oceans rivers are tremendous sources of CO2 and dissolved inorganic carbon (DIC). Yet owing to increased light transmissivity from sediment deposition coupled with the influx of nutrients, dramatic CO2 drawdown occurs, and plumes rapidly become sinks for CO2. Using state-of-the-art gene expression technology, we have examined the molecular biodiversity of CO2 fixation in the Mississippi River Plumemore » (MRP; two research cruises) and the Orinoco River Plume (ORP; one cruise). When the MRP extends far into the Gulf because of entrainment with the Loop Current, MRP production (carbon fixation) can account for up to 41% of the surface production in the Gulf of Mexico. Nearer-shore plume stations (“high plume,” salinity< 32 ppt) had tremendous CO2 drawdown that was correlated to heterokont (principally diatom) carbon fixation gene expression. The principal form of nitrogen for this production based upon 15N studies was urea, believed to be from anthropogenic origin (fertilizer) from the MRP watershed. Intermediate plume environments (salinity 34 ppt) were characterized by high levels of Synechococcuus carbon fixation that was fueled by regenerated ammonium. Non-plume stations were characterized by high light Prochlorococcus carbon fixation gene expression that was positively correlated with dissolved CO2 concentrations. Although data from the ORP cruise is still being analyzed, some similarities and striking differences were found between the ORP and MRP. High levels of heterokont carbon fixation gene expression that correlated with CO2 drawdown were observed in the high plume, yet the magnitude of this phenomenon was far below that of the MRP, most likely due to the lower levels of anthropogenic nutrient input. The offshore ORP was characterized by haptophyte and in places Prochlorococcus carbon fixation gene expression in surface water, with greater heterokont rbcL RNA at SCM depths. MODIS satellite chlorophyll-a data implied a plume of high chlorophyll water far into the eastern Caribbean, yet field observations did not support this, most likely because of high levels of colored dissolved organic matter (cDOM) in the ORP. The presence of pelagic nitrogen fixers (Trichodesmium and cyanobacterial diatom endosymbionts) most likely provided N for the offshore MRP production. The results underscore the importance of oceanic river plumes as sinks for CO2 and the need for their incorporation in global carbon models as well as estimates of CO2 sequestration.« less

Use of avoidance response by rainbow trout to carbon dioxide for fish self-transfer between tanks

USGS Publications Warehouse

Clingerman, J.; Bebak, J.; Mazik, P.M.; Summerfelt, S.T.

2007-01-01

Convenient, economical, and reduced labor fish harvest and transfer systems are required to realize operating cost savings that can be achieved with the use of much larger and deeper circular culture tanks. To achieve these goals, we developed a new technology for transferring fish based on their avoidance behavior to elevated concentrations of dissolved carbon dioxide (CO2). We observed this behavioral response during controlled, replicated experiments that showed dissolved CO2 concentrations of 60-120 mg/L induced rainbow trout (Oncorhynchus mykiss) to swim out of their 11 m3 "growout" tank, through a transfer pipe carrying a flow with ???23 mg/L dissolved CO2, into a second 11 m3 "harvest" tank. The research was conducted using separate groups of rainbow trout held at commercially relevant densities (40-60 kg/m3). The average weight of fish ranged from 0.15 to 1.3 kg during the various trials. In all trials that used a constant flow of low CO2 water (???23 mg/L) entering the growout tank from the harvest tank, approximately 80-90% of the fish swam from the growout tank, through the transfer pipe, and into the harvest tank after the CO2 concentration in the growout tank had exceeded 60 mg/L. The fish that remained in the growout tank stayed within the area of relatively low CO2 water at the entrance of the transfer pipe. However, the rate of fish transfer from the growout tank to the harvest tank was more than doubled when the diameter of the transfer pipe was increased from 203 to 406 mm. To consistently achieve fish transfer efficiencies of 99%, water flow rate through the fish transfer pipe had to be reduced to 10-20% of the original flow just before the conclusion of each trial. Reducing the flow of relatively low CO2 water near the end of each fish transfer event, restricted the zone of relatively low CO2 water about the entrance of the fish transfer pipe, and provided the stimulus for all but a few remaining fish to swim out of the growout tank. Results indicate that the CO2 avoidance technique can provide a convenient, efficient, more economical, and reduced labor approach for fish transfer, especially in applications using large and well mixed circular culture tanks. ?? 2007 Elsevier B.V. All rights reserved.

Water geochemistry of the Qiantangjiang River, East China: Chemical weathering and CO2 consumption in a basin affected by severe acid deposition

NASA Astrophysics Data System (ADS)

Liu, Wenjing; Shi, Chao; Xu, Zhifang; Zhao, Tong; Jiang, Hao; Liang, Chongshan; Zhang, Xuan; Zhou, Li; Yu, Chong

2016-09-01

The chemical composition of the Qiantangjiang River, the largest river in Zhejiang province in eastern China, was measured to understand the chemical weathering of rocks and the associated CO2 consumption and anthropogenic influences within a silicate-dominated river basin. The average total dissolved solids (TDS, 113 mg l-1) and total cation concentration (TZ+, 1357 μeq l-1) of the river waters are comparable with those of global major rivers. Ca2+ and HCO3- followed by Na2+ and SO42-, dominate the ionic composition of the river water. There are four major reservoirs (carbonates, silicates, atmospheric and anthropogenic inputs) contributing to the total dissolved load of the investigated rivers. The dissolved loads of the rivers are dominated by both carbonate and silicate weathering, which together account for about 76.3% of the total cationic load origin. The cationic chemical weathering rates of silicate and carbonate for the Qiantangjiang basin are estimated to be approximately 4.9 ton km-2 a-1 and 13.9 ton km-2 a-1, respectively. The calculated CO2 consumption rates with the assumption that all the protons involved in the weathering reaction are provided by carbonic acid are 369 × 103 mol km-2 a-1 and 273 × 103 mol km-2 a-1 by carbonate and silicate weathering, respectively. As one of the most severe impacted area by acid rain in China, H2SO4 from acid precipitation is also an important proton donor in weathering reactions. When H2SO4 is considered, the CO2 consumption rates for the river basin are estimated at 286 × 103 mol km-2 a-1 for carbonate weathering and 211 × 103 mol km-2 a-1 for silicate weathering, respectively. The results highlight that the drawdown effect of CO2 consumption by carbonate and silicate weathering can be largely overestimated if the role of sulfuric acid is ignored, especially in the area heavily impacted by acid deposition like Qiantangjiang basin. The actual CO2 consumption rates (after sulfuric acid weathering effect deduction) is only about 77% of the value calculated with the assumption that carbonic acid donates all the protons involved in the weathering reaction.

A perspective on underwater photosynthesis in submerged terrestrial wetland plants

PubMed Central

Colmer, Timothy D.; Winkel, Anders; Pedersen, Ole

2011-01-01

Background and aims Wetland plants inhabit flood-prone areas and therefore can experience episodes of complete submergence. Submergence impedes exchange of O2 and CO2 between leaves and the environment, and light availability is also reduced. The present review examines limitations to underwater net photosynthesis (PN) by terrestrial (i.e. usually emergent) wetland plants, as compared with submerged aquatic plants, with focus on leaf traits for enhanced CO2 acquisition. Scope Floodwaters are variable in dissolved O2, CO2, light and temperature, and these parameters influence underwater PN and the growth and survival of submerged plants. Aquatic species possess morphological and anatomical leaf traits that reduce diffusion limitations to CO2 uptake and thus aid PN under water. Many aquatic plants also have carbon-concentrating mechanisms to increase CO2 at Rubisco. Terrestrial wetland plants generally lack the numerous beneficial leaf traits possessed by aquatic plants, so submergence markedly reduces PN. Some terrestrial species, however, produce new leaves with a thinner cuticle and higher specific leaf area, whereas others have leaves with hydrophobic surfaces so that gas films are retained when submerged; both improve CO2 entry. Conclusions Submergence inhibits PN by terrestrial wetland plants, but less so in species that produce new leaves under water or in those with leaf gas films. Leaves with a thinner cuticle, or those with gas films, have improved gas diffusion with floodwaters, so that underwater PN is enhanced. Underwater PN provides sugars and O2 to submerged plants. Floodwaters often contain dissolved CO2 above levels in equilibrium with air, enabling at least some PN by terrestrial species when submerged, although rates remain well below those in air. PMID:22476500

Sea Ice as a Sink for CO2 and Biogeochemical Material: a Novel Sampling Method and Astrobiological Applications

NASA Astrophysics Data System (ADS)

Wilner, J.; Hofmann, A.; Hand, K. P.

2017-12-01

Accurately modelling the intensification of greenhouse gas effects in the polar regions ("polar amplification") necessitates a thorough understanding of the geochemical balance between atmospheric, sea ice, and oceanic layers. Sea ice is highly permeable to CO2 and therefore represents a major sink of oceanic CO2 in winter and of atmospheric CO2 in summer, sinks that are typically either poorly constrained in or fully absent from global climate models. We present a novel method for sampling both trapped and dissolved gases (CO2, CH4 and δ13CH4) in sea ice with a Picarro 2132-i Methane Analyzer, taking the following sampling considerations into account: minimization of water and air contamination, full headspace sampling, prevention of inadvertent sample bag double-puncturing, and ease of use. This method involves melting of vacuum-sealed ice cores to evacuate trapped gases to the headspace and sampling the headspace gas with a blunt needle sheathed by a beveled puncturing needle. A gravity catchment tube prevents input of dangerous levels of liquid water to the Picarro cavity. Subsequent ultrasonic degassing allows for dissolved gas measurement. We are in the process of using this method to sample gases trapped and dissolved in Arctic autumn sea ice cores and atmospheric samples collected during the 2016 Polarstern Expedition and during a May 2017 field campaign north of Barrow, Alaska. We additionally employ this method, together with inductively coupled plasma mass spectrometry (ICP-MS), to analyze the transfer of potential biogeochemical signatures of underlying hydrothermal plumes to sea ice. This has particular relevance to Europa and Enceladus, where hypothetical hydrothermal plumes may deliver seafloor chemicals to the overlying ice shell. Hence, we are presently investigating the entrainment of methane and other hydrothermal material in sea ice cores collected along the Gakkel Ridge that may serve as biosignatures of methanogenic organisms in seafloor oases analogous to icy ocean worlds.

The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

NASA Technical Reports Server (NTRS)

Blair, Neal E.; Boehme, Susan E.; Carter, W. Dale, Jr.

1993-01-01

The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO 2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area

DOE PAGES

Mouzakis, Katherine M.; Navarre-Sitchler, Alexis K.; Rother, Gernot; ...

2016-07-18

Carbon capture, utilization, and storage, one proposed method of reducing anthropogenic emissions of CO 2, relies on low permeability formations, such as shales, above injection formations to prevent upward migration of the injected CO 2. Porosity in caprocks evaluated for sealing capacity before injection can be altered by geochemical reactions induced by dissolution of injected CO 2 into pore fluids, impacting long-term sealing capacity. Therefore, long-term performance of CO 2 sequestration sites may be dependent on both initial distribution and connectivity of pores in caprocks, and on changes induced by geochemical reaction after injection of CO 2, which are currentlymore » poorly understood. This paper presents results from an experimental study of changes to caprock porosity and pore network geometry in two caprock formations under conditions relevant to CO 2 sequestration. Pore connectivity and total porosity increased in the Gothic Shale; while total porosity increased but pore connectivity decreased in the Marine Tuscaloosa. Gothic Shale is a carbonate mudstone that contains volumetrically more carbonate minerals than Marine Tuscaloosa. Carbonate minerals dissolved to a greater extent than silicate minerals in Gothic Shale under high CO 2 conditions, leading to increased porosity at length scales <~200 nm that contributed to increased pore connectivity. In contrast, silicate minerals dissolved to a greater extent than carbonate minerals in Marine Tuscaloosa leading to increased porosity at all length scales, and specifically an increase in the number of pores >~1 μm. Mineral reactions also contributed to a decrease in pore connectivity, possibly as a result of precipitation in pore throats or hydration of the high percentage of clays. Finally, this study highlights the role that mineralogy of the caprock can play in geochemical response to CO 2 injection and resulting changes in sealing capacity in long-term CO 2 storage projects.« less

Air-sea CO2 flux pattern along the southern Bay of Bengal waters

NASA Astrophysics Data System (ADS)

Shanthi, R.; Poornima, D.; Naveen, M.; Thangaradjou, T.; Choudhury, S. B.; Rao, K. H.; Dadhwal, V. K.

2016-12-01

Physico-chemical observations made from January 2013 to March 2015 in coastal waters of the southwest Bay of Bengal show pronounced seasonal variation in physico-chemical parameters including total alkalinity (TA: 1927.390-4088.642 μmol kg-1), chlorophyll (0.13-19.41 μg l-1) and also calculated dissolved inorganic carbon (DIC: 1574.219-3790.954 μmol kg-1), partial pressure of carbon dioxide (pCO2: 155.520-1488.607 μatm) and air-sea CO2 flux (FCO2: -4.808 to 11.255 mmol Cm-2 d-1). Most of the physical parameters are at their maximum during summer due to the increased solar radiation at cloud free conditions, less or no riverine inputs, and lack of vertical mixing of water column which leads to the lowest nutrients concentration, dissolved oxygen (DO), biological production, pCO2 and negative flux of CO2 to the atmosphere. Chlorophyll and DO concentrations enhanced due to increased nutrients during premonsoon and monsoon season due to the vertical mixing of water column driven by the strong winds and external inputs at respective seasons. The constant positive loading of nutrients, TA, DIC, chlorophyll, pCO2 and FCO2 against atmospheric temperature (AT), lux, sea surface temperature (SST), pH and salinity observed in principal component analysis (PCA) suggested that physical and biological parameters play vital role in the seasonal distribution of pCO2 along the southwest Bay of Bengal. The annual variability of CO2 flux clearly depicted that the southwest Bay of Bengal switch from sink (2013) to source status in the recent years (2014 and 2015) and it act as significant source of CO2 to the atmosphere with a mean flux of 0.204 ± 1.449 mmol Cm-2 d-1.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

USGS Publications Warehouse

Chapelle, F.H.; McMahon, P.B.

1991-01-01

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO2 production. Although sulfate concentrations are low (approximately 0.05-0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4-20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO2 production (about 10-5 mmoll-1 year-1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2-6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments. ?? 1991.

Soil DIC uptake and fixation in Pinus taeda seedlings and its C contribution to plant tissues and ectomycorrhizal fungi

Treesearch

Chelcy R. Ford; Nina Wurzburger; Ronald L. Henderick; Robert O. Teskey

2007-01-01

Plants can aquaire carbon from sources other than atmospheric carbon dioxide (CO2), including soil-dissolved inorganic carbon (DIC). Although the next flux of CO2 is out of the root, soil DIC can be taken up by the root, transported within the plant, and fixed either photosynthetically or anaplerotically by plant tissues....

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

Lincoln, D.E.

Assay procedures for analysis of four groups of allelochemicals in Artemisia tridentata, big sagebrush, were established. Growth of Artemisia under high and low light at three CO/sub 2/ levels demonstrated that this species also undegoes a ''dilution'' of the leaf nitrogen content and is useful as test species for herbivory response to CO/sub 2/ induced effects. The initiial experiment also showed that high irradiance is a necessary growth condition. Plants from a single population of A. Tridentata were grown at the Duke Phytotron in three CO/sub 2/ regimed and fed to two species of grasshoppers. Sagabrush plants grew more andmore » had lower leaf nitrogen contents as CO/sub 2/ concentration increased. However, the plants had on average lowere leaf carbon as well as lower leaf niitrogen contents with elevated CO/sub 2/. The source of the lower leaf nutritional value does not appear to be solely an increase in carbon content. Grasshopper consumption was greater on leaves from elevated future and from reduced historical CO/sub 2/ regimes, compared to the current concentration. The increased consumption of leaves from elevated CO/sub 2/ is in agreement with previous results. Grasshopper consumption was significantly related to leaf allelochemical content, but not to leaf nitrogen content. The consumption difference among CO/sub 2/ regimes appeared to result from allelochemical differences, which in turn may result from genetic variation or from CO/sub 2/ treatments. 17 refs., 2 figs., 4 tabs.« less

Determination of the δ13C of dissolved inorganic carbon in water; RSIL lab code 1710

USGS Publications Warehouse

Singleton, Glenda L.; Revesz, Kinga; Coplen, Tyler B.

2012-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1710 is to present a method to determine the δ13C of dissolved inorganic carbon (DIC) of water. The DIC of water is precipitated using ammoniacal strontium chloride (SrCl2) solution to form strontium carbonate (SrCO3). The δ13C is analyzed by reacting SrCO3 with 100-percent phosphoric acid (H3PO4) to liberate carbon quantitatively as carbon dioxide (CO2), which is collected, purified by vacuum sublimation, and analyzed by dual inlet isotope-ratio mass spectrometry (DI-IRMS). The DI-IRMS is a DuPont double-focusing mass spectrometer. One ion beam passes through a slit in a forward collector and is collected in the rear collector. The other measurable ion beams are collected in the front collector. By changing the ion-accelerating voltage under computer control, the instrument is capable of measuring mass/charge (m/z) 45 or 46 in the rear collector and m/z 44 and 46 or 44 and 45, respectively, in the front collector. The ion beams from these m/z values are as follows: m/z 44 = CO2 = 12C16O16O, m/z 45 = CO2 = 13C16O16O primarily, and m/z 46 = CO2 = 12C16O18O primarily. The data acquisition and control software calculates δ13C values.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

Tracing oxidative weathering from the Andes to the lowland Amazon Basin using dissoved rhenium

NASA Astrophysics Data System (ADS)

Dellinger, M.; Hilton, R. G.; West, A. J.; Torres, M.; Burton, K. W.; Clark, K. E.; Baronas, J. J.

2016-12-01

Over long timescales (>105 yrs), the abundance of carbon dioxide (CO2) in the atmosphere is determined by the balance of the major carbon sources and sinks. Among the major carbon sources, the oxidation of organic carbon contained within sedimentary rocks ("petrogenic" carbon, or OCpetro) is thought to result in CO2 emission of similar magnitude to that released by volcanism. Rhenium (Re) has been proposed as a proxy for tracing OCpetro oxidation. Here we investigate the source, behavior and flux of dissolved and particulate rhenium (Re) in the Madre de Dios watershed (a major Andean tributary of the Amazon River) and the lowlands, aiming to characterize the behavior of Re in river water and quantify the flux of CO2 released by OCpetro oxidation. Measured Re concentrations in Andean rivers range from 0.07 to 1.55 ppt. In the Andes, Re concentration do not change significantly with water discharge, whereas in the lowlands, Re concentration decrease at high water discharge. Mass balance calculation show that more than 70% of the dissolved Re is sourced from the oxidation of OCpetro the Andes-floodplain system. We calculate dissolved Re flux over a hydrological year to estimate the rates of oxidative weathering, and the associated CO2 release from OCpetro. Rates are high in the Andean headwaters, consistent with estimates from other mountain rivers with similar rates of physical erosion. We find evidence that a significant amount of additional oxidation (Re flux) happens during floodplain transport. These results have important implications for improving our understanding of the source and processes controlling Re in rivers, and allowing us to quantify long-term OCpetro cycling in large river basins.

Diurnal variation of oxygen and carbonate system parameters in Tampa Bay and Florida Bay

USGS Publications Warehouse

Yates, K.K.; Dufore, C.; Smiley, N.; Jackson, C.; Halley, R.B.

2007-01-01

Oxygen and carbonate system parameters were measured, in situ, over diurnal cycles in Tampa Bay and Florida Bay, Florida. All system parameters showed distinct diurnal trends in Tampa Bay with an average range of diurnal variation of 39.1 μmol kg− 1 for total alkalinity, 165.1 μmol kg− 1 for total CO2, 0.22 for pH, 0.093 mmol L− 1 for dissolved oxygen, and 218.1 μatm for pCO2. Average range of diurnal variation for system parameters in Tampa Bay was 73% to 93% of the seasonal range of variability for dissolved oxygen and pH. All system parameters measured in Florida Bay showed distinct variation over diurnal time-scales. However, clear diurnal trends were less evident. The average range of diurnal variability in Florida Bay was 62.8 μmol kg− 1 for total alkalinity, 130.4 μmol kg− 1 for total CO2, 0.13 for pH, 0.053 mmol L− 1 for dissolved oxygen, and 139.8 μatm for pCO2. The average range of diurnal variation was 14% to 102% of the seasonal ranges for these parameters. Diurnal variability in system parameters was most influenced by primary productivity and respiration of benthic communities in Tampa Bay, and by precipitation and dissolution of calcium carbonate in Florida Bay. Our data indicate that use of seasonal data sets without careful consideration of diurnal variability may impart significant error in calculations of annual carbon and oxygen budgets. These observations reinforce the need for higher temporal resolution measurements of oxygen and carbon system parameters in coastal ecosystems.

Investigating ebullition in a sand column using dissolved gas analysis and reactive transport modeling

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich

2006-01-01

Ebullition of gas bubbles through saturated sediments can enhance the migration of gases through the subsurface, affect the rate of biogeochemical processes, and potentially enhance the emission of important greenhouse gases to the atmosphere. To better understand the parameters controlling ebullition, methanogenic conditions were produced in a column experiment and ebullition through the column was monitored and quantified through dissolved gas analysis and reactive transport modeling. Dissolved gas analysis showed rapid transport of CH4 vertically through the column at rates several times faster than the bromide tracer and the more soluble gas CO2, indicating that ebullition was the main transport mechanism for CH4. An empirically derived formulation describing ebullition was integrated into the reactive transport code MIN3P allowing this process to be investigated on the REV scale in a complex geochemical framework. The simulations provided insights into the parameters controlling ebullition and show that, over the duration of the experiment, 36% of the CH4 and 19% of the CO2 produced were transported to the top of the column through ebullition.

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.

Liquid carbon dioxide absorbents, methods of using the same, and related system

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

Perry, Robert James; Soloveichik, Grigorii Lev; Rubinsztajn, Malgorzata Iwona

A carbon dioxide absorbent composition is described, including (i) a liquid, nonaqueous silicon-based material, functionalized with one or more groups that either reversibly react with CO 2 or have a high-affinity for CO 2, and (ii) a hydroxy-containing solvent that is capable of dissolving both the silicon-based material and a reaction product of the silicon-based material and CO 2. The absorbent may be utilized in methods to reduce carbon dioxide in an exhaust gas, and finds particular utility in power plants.

Liquid carbon dioxide absorbents, methods of using the same, and related systems

DOEpatents

O'Brien, Michael Joseph; Perry, Robert James; Lam, Tunchiao Hubert; Soloveichik, Grigorii Lev; Kniajanski, Sergei; Lewis, Larry Neil; Rubinsztajn, Malgorzata Iwona; Hancu, Dan

2016-09-13

A carbon dioxide absorbent composition is described, including (i) a liquid, nonaqueous silicon-based material, functionalized with one or more groups that either reversibly react with CO.sub.2 or have a high-affinity for CO.sub.2; and (ii) a hydroxy-containing solvent that is capable of dissolving both the silicon-based material and a reaction product of the silicon-based material and CO.sub.2. The absorbent may be utilized in methods to reduce carbon dioxide in an exhaust gas, and finds particular utility in power plants.

POISON SPIDER FIELD CHEMICAL FLOOD PROJECT, WYOMING

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

Douglas Arnell; Malcolm Pitts; Jie Qi

2004-11-01

A reservoir engineering and geologic study concluded that approximate 7,852,000 bbls of target oil exits in Poison Spider. Field pore volume, OOIP, and initial oil saturation are defined. Potential injection water has a total dissolved solids content of 1,275 mg/L with no measurable divalent cations. If the Lakota water consistently has no measurable cations, the injection water does not require softening to dissolve alkali. Produced water total dissolved solids were 2,835 mg/L and less than 20 mg/L hardness as the sum of divalent cations. Produced water requires softening to dissolve chemicals. Softened produced water was used to dissolve chemicals inmore » these evaluations. Crude oil API gravity varies across the field from 19.7 to 22.2 degrees with a dead oil viscosity of 95 to 280 cp at 75 F. Interfacial tension reductions of up to 21,025 fold (0.001 dyne/cm) were developed with fifteen alkaline-surfactant combinations at some alkali concentration. An additional three alkaline-surfactant combinations reduced the interfacial tension greater than 5,000 fold. NaOH generally produced the lowest interfacial tension values. Interfacial tension values of less than 0.021 dyne/cm were maintained when the solutions were diluted with produced water to about 60%. Na{sub 2}CO{sub 3} when mixed with surfactants did not reduce interfacial tension values to levels at which incremental oil can be expected. NaOH without surfactant interfacial tension reduction is at a level where some additional oil might be recovered. Most of the alkaline-surfactant-polymer solutions producing ultra low interfacial tension gave type II- phase behavior. Only two solutions produced type III phase behavior. Produced water dilution resulted in maintenance of phase type for a number of solutions at produced water dilutions exceeding 80% dilution. The average loss of phase type occurred at 80% dilution. Linear corefloods were performed to determine relative permeability end points, chemical-rock compatibility, polymer injectivity, dynamic chemical retention by rock, and recommended injected polymer concentration. Average initial oil saturation was 0.796 Vp. Produced water injection recovered 53% OOIP leaving an average residual oil saturation of 0.375 Vp. Poison Spider rock was strongly water-wet with a mobility ratio for produced water displacing the 280 cp crude oil of 8.6. Core was not sensitive to either alkali or surfactant injection. Injectivity increased 60 to 80% with alkali plus surfactant injection. Low and medium molecular weight polyacrylamide polymers (Flopaam 3330S and Flopaam 3430S) dissolved in either an alkaline-surfactant solution or softened produced water injected and flowed through Poison Spider rock. Recommended injected polyacrylamide concentration is 2,100 mg/L for both polymers for a unit mobility ratio. Radial corefloods were performed to evaluate oil recovery efficiency of different chemical solutions. Waterflood oil recovery averaged 46.4 OOIP and alkaline-surfactant-polymer flood oil recovery averaged an additional 18.1% OIP for a total of 64.6% OOIP. Oil cut change due to injection of a 1.5 wt% Na{sub 2}CO{sub 3} plus 0.05 wt% Petrostep B-100 plus 0.05 wt% Stepantan AS1216 plus 2100 mg/L Flopaam 3430S was from 2% to a peak of 23.5%. Additional study might determine the impact on oil recovery of a lower polymer concentration. An alkaline-surfactant-polymer flood field implementation outline report was written.« less

Assessment of tissue blood flow following small artery welding with an intraluminal dissolvable stent.

PubMed

He, F C; Wei, L P; Lanzetta, M; Owen, E R

1999-01-01

Using the technique of radioactive 51Cr-labeled biological microspheres, this study evaluated arterial blood flow following small vessel anastomosis by CO2 laser welding and a dissolvable stent in the lumen. A total of 30 Sprague-Dawley rats were divided into two groups. Group A: 11 rats had their femoral arteries ligated on one side. The contralateral side served as a control, with the artery transected and repaired using conventional microsuturing. Group B: 19 rats had their femoral arteries transected and repaired using CO2 laser welding and an intraluminal dissolvable stent technique. The contralateral side was again used as a control using conventional microsuturing. At 1 hr postoperatively, 51Cr-labeled biological microspheres were injected centripetally into the left common carotid artery and the legs and thighs immediately harvested for measurement of radioactivity. All repaired arteries were patent (30/30 in the microsuturing group and 19/19 in the stented welding group), with no detectable stenosis or dilation at the repaired site. Statistical analysis showed that tissue radioactivity (cpm/g) in the ligated group (3,972 +/- 384 in thighs and 3,142 +/- 742 in legs) was significantly lower than in the microsuturing group (7,132 +/- 1,723 in thighs and 6,557 +/- 1,469 in legs) (P < 0.01). In the ligated group, a significant reduction of blood flow was seen in the legs when compared with the thighs (P < 0.05). There was no significant difference in radioactivity when comparing the microsuturing control with the stented welding group, in both thighs (7,064 +/- 2,599 and 7,006 +/- 2,406, respectively; P > 0.05) and legs (6,386 +/- 1,703 and 6,288 +/- 1,757, respectively; P > 0.05). This study provided evidence that the dissolvable stent placed intraluminally does not impair blood circulation and that when coupled with CO2 laser welding offers a high-quality alternative to conventional small vessel anastomosis.

Autumn photoproduction of carbon monoxide in Jiaozhou Bay, China

NASA Astrophysics Data System (ADS)

Ren, Chunyan; Yang, Guipeng; Lu, Xiaolan

2014-06-01

Carbon monoxide (CO) plays a significant role in global warming and atmospheric chemistry. Global oceans are net natural sources of atmospheric CO. CO at surface ocean is primarily produced from the photochemical degradation of chromophoric dissolved organic matter (CDOM). In this study, the effects of photobleaching, temperature and the origin (terrestrial or marine) of CDOM on the apparent quantum yields (AQY) of CO were studied for seawater samples collected from Jiaozhou Bay. Our results demonstrat that photobleaching, temperature and the origin of CDOM strongly affected the efficiency of CO photoproduction. The concentration, absorbance and fluorescence of CDOM exponentially decreased with increasing light dose. Terrestrial riverine organic matter could be more prone to photodegradation than the marine algae-derived one. The relationships between CO AQY and the dissolved organic carbon-specific absorption coefficient at 254 nm for the photobleaching study were nonlinear, whereas those of the original samples were strongly linear. This suggests that: 1) terrestrial riverine CDOM was more efficient than marine algae-derived CDOM for CO photoproduction; 2) aromatic and olefinic moieties of the CDOM pool were affected more strongly by degradation processes than by aliphatic ones. Water temperature and the origin of CDOM strongly affected the efficiency of CO photoproduction. The photoproduction rate of CO in autumn was estimated to be 31.98 μmol m-2 d-1 and the total DOC photomineralization was equivalent to 3.25%-6.35% of primary production in Jiaozhou Bay. Our results indicate that CO photochemistry in coastal areas is important for oceanic carbon cycle.

A Small Decrease in Rubisco Content by Individual Suppression of RBCS Genes Leads to Improvement of Photosynthesis and Greater Biomass Production in Rice Under Conditions of Elevated CO2.

PubMed

Kanno, Keiichi; Suzuki, Yuji; Makino, Amane

2017-03-01

Rubisco limits photosynthesis at low CO2 concentrations ([CO2]), but does not limit it at elevated [CO2]. This means that the amount of Rubisco is excessive for photosynthesis at elevated [CO2]. Therefore, we examined whether a small decrease in Rubisco content by individual suppression of the RBCS multigene family leads to increases in photosynthesis and biomass production at elevated [CO2] in rice (Oryza sativa L.). Our previous studies indicated that the individual suppression of RBCS decreased Rubisco content in rice by 10-25%. Three lines of BC2F2 progeny were selected from transgenic plants with individual suppression of OsRBCS2, 3 and 5. Rubisco content in the selected lines was 71-90% that of wild-type plants. These three transgenic lines showed lower rates of CO2 assimilation at low [CO2] (28 Pa) but higher rates of CO2 assimilation at elevated [CO2] (120 Pa). Similarly, the biomass production and relative growth rate (RGR) of the two lines were also smaller at low [CO2] but greater than that of wild-type plants at elevated [CO2]. This greater RGR was caused by the higher net assimilation rate (NAR). When the nitrogen use efficiency (NUE) for the NAR was estimated by dividing the NAR by whole-plant leaf N content, the NUE for NAR at elevated [CO2] was higher in these two lines. Thus, a small decrease in Rubisco content leads to improvements of photosynthesis and greater biomass production in rice under conditions of elevated CO2. © The Author 2017. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

The acceleration of dissolved cobalt's ecological stoichiometry due to biological uptake, remineralization, and scavenging in the Atlantic Ocean

NASA Astrophysics Data System (ADS)

Saito, Mak A.; Noble, Abigail E.; Hawco, Nicholas; Twining, Benjamin S.; Ohnemus, Daniel C.; John, Seth G.; Lam, Phoebe; Conway, Tim M.; Johnson, Rod; Moran, Dawn; McIlvin, Matthew

2017-10-01

The stoichiometry of biological components and their influence on dissolved distributions have long been of interest in the study of the oceans. Cobalt has the smallest oceanic inventory of inorganic micronutrients and hence is particularly vulnerable to influence by internal oceanic processes including euphotic zone uptake, remineralization, and scavenging. Here we observe not only large variations in dCo : P stoichiometry but also the acceleration of those dCo : P ratios in the upper water column in response to several environmental processes. The ecological stoichiometry of total dissolved cobalt (dCo) was examined using data from a US North Atlantic GEOTRACES transect and from a zonal South Atlantic GEOTRACES-compliant transect (GA03/3e and GAc01) by Redfieldian analysis of its statistical relationships with the macronutrient phosphate. Trends in the dissolved cobalt to phosphate (dCo : P) stoichiometric relationships were evident in the basin-scale vertical structure of cobalt, with positive dCo : P slopes in the euphotic zone and negative slopes found in the ocean interior and in coastal environments. The euphotic positive slopes were often found to accelerate towards the surface and this was interpreted as being due to the combined influence of depleted phosphate, phosphorus-sparing (conserving) mechanisms, increased alkaline phosphatase metalloenzyme production (a zinc or perhaps cobalt enzyme), and biochemical substitution of Co for depleted Zn. Consistent with this, dissolved Zn (dZn) was found to be drawn down to only 2-fold more than dCo, despite being more than 18-fold more abundant in the ocean interior. Particulate cobalt concentrations increased in abundance from the base of the euphotic zone to become ˜ 10 % of the overall cobalt inventory in the upper euphotic zone with high stoichiometric values of ˜ 400 µmol Co mol-1 P. Metaproteomic results from the Bermuda Atlantic Time-series Study (BATS) station found cyanobacterial isoforms of the alkaline phosphatase enzyme to be prevalent in the upper water column, as well as a sulfolipid biosynthesis protein indicative of P sparing. The negative dCo : P relationships in the ocean interior became increasingly vertical with depth, and were consistent with the sum of scavenging and remineralization processes (as shown by their dCo : P vector sums). Attenuation of the remineralization with depth resulted in the increasingly vertical dCo : P relationships. Analysis of particulate Co with particulate Mn and particulate phosphate also showed positive linear relationships below the euphotic zone, consistent with the presence and increased relative influence of Mn oxide particles involved in scavenging. Visualization of dCo : P slopes across an ocean section revealed hotspots of scavenging and remineralization, such as at the hydrothermal vents and below the oxygen minimum zone (OMZ) region, respectively, while that of an estimate of Co* illustrated stoichiometrically depleted values in the mesopelagic and deep ocean due to scavenging. This study provides insights into the coupling between the dissolved and particulate phase that ultimately creates Redfield stoichiometric ratios, demonstrating that the coupling is not an instantaneous process and is influenced by the element inventory and rate of exchange between phases. Cobalt's small water column inventory and the influence of external factors on its biotic stoichiometry can erode its limited inertia and result in an acceleration of the dissolved stoichiometry towards that of the particulate phase in the upper euphotic zone. As human use of cobalt grows exponentially with widespread adoption of lithium ion batteries, there is a potential to affect the limited biogeochemical inertia of cobalt and its resultant ecology in the oceanic euphotic zone.

Spectral analysis of coniferous foliage and possible links to soil chemistry: are spectral chlorophyll indices related to forest floor dissolved organic C and N?

PubMed

Albrechtova, Jana; Seidl, Zdenek; Aitkenhead-Peterson, Jacqueline; Lhotáková, Zuzana; Rock, Barrett N; Alexander, Jess E; Malenovský, Zbynek; McDowell, William H

2008-10-15

Dissolved organic matter in soils can be predicted from forest floor C:N ratio, which in turn is related to foliar chemistry. Little is known about the linkages between foliar constituents such as chlorophylls, lignin, and cellulose and the concentrations of water-extractable forest floor dissolved organic carbon and dissolved organic nitrogen. Lignin and cellulose are not mobile in foliage and thus may be indicative of growing conditions during prior years, while chlorophylls respond more rapidly to the current physiological status of a tree and reflect nutrient availability. The aim of this study was to examine potential links among spectral foliar data, and the organic C and N of forest soils. Two coniferous species (red spruce and balsam fir) were studied in the White Mountains of New Hampshire, USA. Six trees of each species were sampled at 5 watersheds (2 in the Hubbard Brook Experimental Forest, 3 in the Bartlett Experimental Forest). We hypothesized that in a coniferous forest, chemistry of old foliage would better predict the chemical composition of the forest floor litter layer than younger foliage, which is the more physiologically active and the most likely to be captured by remote sensing of the canopy. Contrary to our expectations, chlorophyll concentration of young needles proved to be most tightly linked to soil properties, in particular water-extractable dissolved organic carbon. Spectral indices related to the chlorophyll content of needles could be used to predict variation in forest floor dissolved organic carbon and dissolved organic nitrogen. Strong correlations were found between optical spectral indices based on chlorophyll absorption and forest floor dissolved organic carbon, with higher foliage chlorophyll content corresponding to lower forest floor dissolved organic carbon. The mechanisms behind these correlations are uncertain and need further investigation. However, the direction of the linkage from soil to tree via nutrient availability is hypothesized based on negative correlations found between foliar N and forest floor dissolved organic carbon.

Whole-plant growth and N utilization in transgenic rice plants with increased or decreased Rubisco content under different CO2 partial pressures.

PubMed

Sudo, Emi; Suzuki, Yuji; Makino, Amane

2014-11-01

Ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) strongly limits photosynthesis at lower CO2 concentration [CO2] whereas [corrected] Rubisco limitation is cancelled by elevated [CO2]. Therefore, increase or reduction in Rubisco content by transformation with a sense or an antisense RBCS construct are expected to alter the biomass production under different CO2 levels. RBCS-sense (125% Rubisco of wild-type) and -antisense (35% Rubisco of wild-type) rice (Oryza sativa L.) plants were grown for 63 days at three different CO2 levels: low [CO2] (28 Pa), normal [CO2] (40 Pa) and elevated [CO2] (120 Pa). The biomass of RBCS-sense plants was 32% and 15% greater at low [CO2] and normal [CO2] than that of the wild-type plants, respectively, but did not differ at elevated [CO2]. Conversely, the biomass of RBCS-antisense plants was the smallest at low [CO2]. Thus, overproduction of Rubisco was effective for biomass production at low [CO2]. Greater biomass production at low [CO2] in RBCS-sense plants was caused by an increase in the net assimilation rate, and associated with an increase in the amount of N uptake. Furthermore, Rubisco overproduction in RBCS-sense plants was also promoted at low [CO2]. Although it seems that low [CO2]-growth additionally stimulates the effect of RBCS overexpression, such a phenomenon observed at low [CO2] was mediated through an increase in total leaf N content. Thus, the dependence of the growth improvement in RBCS-sense rice on growth [CO2] was closely related to the degree of Rubisco overproduction which was accompanied not only by leaf N content but also by whole plant N content. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Hydrochemical Impacts of CO2 Leakage on Fresh Groundwater: a Field Scale Experiment

NASA Astrophysics Data System (ADS)

Lions, J.; Gal, F.; Gombert, P.; Lafortune, S.; Darmoul, Y.; Prevot, F.; Grellier, S.; Squarcioni, P.

2013-12-01

One of the questions related to the emerging technology for Carbon Geological Storage concerns the risk of CO2 migration beyond the geological storage formation. In the event of leakage toward the surface, the CO2 might affect resources in neighbouring formations (geothermal or mineral resources, groundwater) or even represent a hazard for human activities at the surface or in the subsurface. In view of the preservation of the groundwater resources mainly for human consumption, this project studies the potential hydrogeochemical impacts of CO2 leakage on fresh groundwater quality. One of the objectives is to characterize the bio-geochemical mechanisms that may impair the quality of fresh groundwater resources in case of CO2 leakage. To reach the above mentioned objectives, this project proposes a field experiment to characterize in situ the mechanisms that could impact the water quality, the CO2-water-rock interactions and also to improve the monitoring methodology by controlled CO2 leakage in shallow aquifer. The tests were carried out in an experimental site in the chalk formation of the Paris Basin. The site is equipped with an appropriate instrumentation and was previously characterized (8 piezometers, 25 m deep and 4 piezairs 11 m deep). The injection test was preceded by 6 months of monitoring in order to characterize hydrodynamics and geochemical baselines of the site (groundwater, vadose and soil). Leakage into groundwater is simulated via the injection of a small quantity of food-grade CO2 (~20 kg dissolved in 10 m3 of water) in the injection well at a depth of about 20 m. A plume of dissolved CO2 is formed and moves downward according to the direction of groundwater flow and probably by degassing in part to the surface. During the injection test, hydrochemical monitoring of the aquifer is done in situ and by sampling. The parameters monitored in the groundwater are the piezometric head, temperature, pH and electrical conductivity. Analysis on water samples provide chemical elements (major, minor and trace metals), dissolved gases, microbiological diversity and isotopes (13C). The evolution of the composition of the groundwater in terms of major elements, trace elements and isotope signatures is interpreted in terms of geochemical mechanisms, and the water-rock-CO2 interactions are characterized. Modification of the chemical composition of water in the aquifer due to CO2 injection is assessed in term of groundwater quality i.e. metal element release and the possibility of exceeding references and quality of water for human consumption. One outcome of the CIPRES project will be to highlight mechanisms that can impact groundwater quality when a CO2 leakage occurs and to propose recommendations to prevent or/and eliminate negative effects and any risks to the environment and human health. This project is partially funded by the French Research Agency (ANR).

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique.

PubMed

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer.

In Situ Natural Abundance 17 O and 25 Mg NMR Investigation of Aqueous Mg(OH) 2 Dissolution in the Presence of Supercritical CO 2

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

Hu, Mary Y.; Deng, Xuchu; Thanthiriwatte, K. Sahan

We report the development of an in situ high pressure NMR capability that permits natural abundance 17O and 25Mg NMR characterization of dissolved species in aqueous solution and in the presence of supercritical CO 2 fluid (scCO 2). The dissolution of Mg(OH) 2 (brucite) in a multiphase water/scCO 2 fluid at 90 atm pressure and 50 C was studied in situ, with relevance to geological carbon sequestration. 17O NMR spectra allowed identification and distinction of various fluid species including dissolved CO 2 in the H 2O-rich phase, scCO 2, aqueous H 2O, and HCO 3 -. The widely separated spectralmore » peaks for various species can all be observed both dynamically and quantitatively at concentrations of as low as 20 mM. Measurement of the concentrations of these individual species also allows an in situ estimate of the hydrogen ion concentration, or pCH + values, of the reacting solutions. The concentration of Mg 2+ can be observed by natural abundance 25Mg NMR at a concentration as low as 10 mM. Quantum chemistry calculations of the NMR chemical shifts on cluster models aided in the interpretation of the experimental results. Evidence for the formation of polymeric Mg 2+ clusters at high concentrations in the H 2O-rich phase, a possible critical step needed for magnesium carbonate formation, was found. The approach and findings enable insight into metal carbonation reactions associated with geological carbon sequestration that cannot be probed by ex situ methods.« less