A simple headspace equilibration method for measuring dissolved methane

USGS Publications Warehouse

Magen, C; Lapham, L.L.; Pohlman, John W.; Marshall, Kristin N.; Bosman, S.; Casso, Michael; Chanton, J.P.

2014-01-01

Dissolved methane concentrations in the ocean are close to equilibrium with the atmosphere. Because methane is only sparingly soluble in seawater, measuring it without contamination is challenging for samples collected and processed in the presence of air. Several methods for analyzing dissolved methane are described in the literature, yet none has conducted a thorough assessment of the method yield, contamination issues during collection, transport and storage, and the effect of temperature changes and preservative. Previous extraction methods transfer methane from water to gas by either a "sparge and trap" or a "headspace equilibration" technique. The gas is then analyzed for methane by gas chromatography. Here, we revisit the headspace equilibration technique and describe a simple, inexpensive, and reliable method to measure methane in fresh and seawater, regardless of concentration. Within the range of concentrations typically found in surface seawaters (2-1000 nmol L-1), the yield of the method nears 100% of what is expected from solubility calculation following the addition of known amount of methane. In addition to being sensitive (detection limit of 0.1 ppmv, or 0.74 nmol L-1), this method requires less than 10 min per sample, and does not use highly toxic chemicals. It can be conducted with minimum materials and does not require the use of a gas chromatograph at the collection site. It can therefore be used in various remote working environments and conditions.

Distribution and origin of groundwater methane in the Wattenberg oil and gas field of northern Colorado.

PubMed

Li, Huishu; Carlson, Kenneth H

2014-01-01

Public concerns over potential environmental contamination associated with oil and gas well drilling and fracturing in the Wattenberg field in northeast Colorado are increasing. One of the issues of concern is the migration of oil, gas, or produced water to a groundwater aquifer resulting in contamination of drinking water. Since methane is the major component of natural gas and it can be dissolved and transported with groundwater, stray gas in aquifers has elicited attention. The initial step toward understanding the environmental impacts of oil and gas activities, such as well drilling and fracturing, is to determine the occurrence, where it is and where it came from. In this study, groundwater methane data that has been collected in response to a relatively new regulation in Colorado is analyzed. Dissolved methane was detected in 78% of groundwater wells with an average concentration of 4.0 mg/L and a range of 0-37.1 mg/L. Greater than 95% of the methane found in groundwater wells was classified as having a microbial origin, and there was minimal overlap between the C and H isotopic characterization of the produced gas and dissolved methane measured in the aquifer. Neither density of oil/gas wells nor distance to oil/gas wells had a significant impact on methane concentration suggesting other important factors were influencing methane generation and distribution. Thermogenic methane was detected in two aquifer wells indicating a potential contamination pathway from the producing formation, but microbial-origin gas was by far the predominant source of dissolved methane in the Wattenberg field.

Sources and Fluxes of Atmospheric Methane from Lakes in the Alaskan Arctic

NASA Astrophysics Data System (ADS)

Townsend-Small, A.; Akerstrom, F.; Hinkel, K. M.; Arp, C. D.; Beck, R. A.; Grosse, G.; Jones, B. M.; Kim, C.; Lenters, J. D.; Liu, H.; Eisner, W. R.

2014-12-01

Climate warming in the Arctic may result in release of carbon dioxide and/or methane from thawing permafrost soils, resulting in a positive feedback to warming. Permafrost thaw may also result in release of methane from previously trapped natural gas. The Arctic landscape is approximately 50% covered by shallow permafrost lakes, and these environments may serve as bellwethers for climate change - carbon cycle feedbacks, since permafrost thaw is generally deeper under lakes than tundra soils. Since 2011, the Circum-Arctic Lakes Observation Network (CALON) project has documented landscape-scale variability in physical and biogeochemical processes of Arctic lakes in permafrost terrain, including carbon cycle feedbacks to climate warming. Here we present a dataset of concentrations, isotope ratios (13C and 2H), and atmospheric fluxes of methane from lakes in Arctic Alaska. Concentrations of methane in lake water ranged from 0.3 to 43 micrograms per liter, or between 6 and 750 times supersaturated with respect to air. Isotopic measurements of dissolved methane indicated that most of the lakes had methane derived from anaerobic organic matter decomposition, but that some lakes may have a small source of methane from fossil fuel sources such as natural gas or coal beds. Concurrent measurements of methane fluxes and dissolved methane concentrations in summer of 2014 will aid in translating routine dissolved measurements into fluxes, and will also elucidate the relative importance of diffusive versus ebulliative fluxes. It is essential that measurements of methane emissions from Arctic lakes be continued long-term to determine whether methane emissions are on the rise, and whether warming of the lakes leads to increased venting of fossil fuel methane from enhanced thaw of permafrost beneath the lakes.

Variations in Gas and Water Pulses at an Arctic Seep: Fluid Sources and Methane Transport

NASA Astrophysics Data System (ADS)

Hong, W.-L.; Torres, M. E.; Portnov, A.; Waage, M.; Haley, B.; Lepland, A.

2018-05-01

Methane fluxes into the oceans are largely dependent on the methane phase as it migrates upward through the sediments. Here we document decoupled methane transport by gaseous and aqueous phases in Storfjordrenna (offshore Svalbard) and propose a three-stage evolution model for active seepage in the region where gas hydrates are present in the shallow subsurface. In a preactive seepage stage, solute diffusion is the primary transport mechanism for methane in the dissolved phase. Fluids containing dissolved methane have high 87Sr/86Sr ratios due to silicate weathering in the microbial methanogenesis zone. During the active seepage stage, migration of gaseous methane results in near-seafloor gas hydrate formation and vigorous seafloor gas discharge with a thermogenic fingerprint. In the postactive seepage stage, the high concentration of dissolved lithium points to the contribution of a deeper-sourced aqueous fluid, which we postulate advects upward following cessation of gas discharge.

Screening for Dissolved Methane in Groundwater Across Texas Shale Plays

NASA Astrophysics Data System (ADS)

Nicot, J. P.; Mickler, P. J.; Hildenbrand, Z.; Larson, T.; Darvari, R.; Uhlman, K.; Smyth, R. C.; Scanlon, B. R.

2014-12-01

There is considerable interest in methane concentrations in groundwater, particularly as they relate to hydraulic fracturing in shale plays. Recent studies of aquifers in the footprint of several gas plays across the US have shown that (1) dissolved thermogenic methane may or may not be present in the shallow groundwater and (2) shallow thermogenic methane may be naturally occurring and emplaced through mostly vertical migration over geologic time and not necessarily a consequence of recent unconventional gas production. We are currently conducting a large sampling campaign across the state of Texas to characterize shallow methane in fresh-water aquifers overlying shale plays and other tight formations. We collected a total of ~800 water samples, ~500 in the Barnett, ~150 in the Eagle Ford, ~80 in the Haynesville shale plays as well as ~50 in the Delaware Basin of West Texas. Preliminary analytical results suggest that dissolved methane is not widespread in shallow groundwater and that, when present at concentrations exceeding 10 mg/L, it is often of thermogenic origin according to the isotopic signature and to the presence of other light hydrocarbons. The Barnett Shale contains a large methane hotspot (~ 2 miles wide) along the Hood-Parker county line which is likely of natural origin whereas the Eagle Ford and Haynesville shales, neglecting microbial methane, show more distributed methane occurrences. Samples from the Delaware Basin show no methane except close to blowouts.

Methane concentrations in water wells unrelated to proximity to existing oil and gas wells in northeastern Pennsylvania.

PubMed

Siegel, Donald I; Azzolina, Nicholas A; Smith, Bert J; Perry, A Elizabeth; Bothun, Rikka L

2015-04-07

Recent studies in northeastern Pennsylvania report higher concentrations of dissolved methane in domestic water wells associated with proximity to nearby gas-producing wells [ Osborn et al. Proc. Natl. Acad. Sci. U. S. A. 2011 , 108 , 8172 ] and [ Jackson et al. Proc. Natl. Acad. Sci. U. S. A. , 2013 , 110 , 11250 ]. We test this possible association by using Chesapeake Energy's baseline data set of over 11,300 dissolved methane analyses from domestic water wells, densely arrayed in Bradford and nearby counties (Pennsylvania), and near 661 pre-existing oil and gas wells. The majority of these, 92%, were unconventional wells, drilled with horizontal legs and hydraulically fractured. Our data set is hundreds of times larger than data sets used in prior studies. In contrast to prior findings, we found no statistically significant relationship between dissolved methane concentrations in groundwater from domestic water wells and proximity to pre-existing oil or gas wells. Previous analyses used small sample sets compared to the population of domestic wells available, which may explain the difference in prior findings compared to ours.

Stable isotope tracing of anaerobic methane oxidation in the gassy sediments of Eckernfoerde Bay, German Baltic Sea

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

Martens, C.S.; Albert, D.B.; Alperin, M.J.

Methane concentrations in the pore waters of Eckernfoerde Bay in the German Baltic Sea generally reach gas bubble saturation values within the upper meter of the sediment column. The depth at which saturation occurs is controlled by a balance between rates of methane production, consumption (oxidation), and transport. The relative importance of anaerobic methane oxidation (AMO) in controlling dissolved and gas bubble methane distributions in the bay's sediments is indirectly revealed through methane concentration versus depth profiles, depth variations in the stable C and H isotope composition of methane, and the C isotope composition of total dissolved inorganic carbon ({Sigma}CO{submore » 2}). Direct radiotracer measurements indicate that AMO rates of over 15 mM/yr are focused at the base of the sulfate reduction zone. Diagenetic equations that describe the depth destructions of the {delta}{sup 13}C and {delta}D values of methane reproduce isotopic shifts observed throughout the methane oxidation zone and are best fit with kinetic isotope fractionation factors of 1.012 {+-} 0.001 and 1.120 {plus{underscore}minus} 0.020 respectively.« less

Methane Sources and Migration Mechanisms in Shallow Groundwaters in Parker and Hood Counties, Texas-A Heavy Noble Gas Analysis.

PubMed

Wen, Tao; Castro, M Clara; Nicot, Jean-Philippe; Hall, Chris M; Larson, Toti; Mickler, Patrick; Darvari, Roxana

2016-11-01

This study places constraints on the source and transport mechanisms of methane found in groundwater within the Barnett Shale footprint in Texas using dissolved noble gases, with particular emphasis on 84 Kr and 132 Xe. Dissolved methane concentrations are positively correlated with crustal 4 He, 21 Ne, and 40 Ar and suggest that noble gases and methane originate from common sedimentary strata, likely the Strawn Group. In contrast to most samples, four water wells with the highest dissolved methane concentrations unequivocally show strong depletion of all atmospheric noble gases ( 20 Ne, 36 Ar, 84 Kr, 132 Xe) with respect to air-saturated water (ASW). This is consistent with predicted noble gas concentrations in a water phase in contact with a gas phase with initial ASW composition at 18 °C-25 °C and it suggests an in situ, highly localized gas source. All of these four water wells tap into the Strawn Group and it is likely that small gas accumulations known to be present in the shallow subsurface were reached. Additionally, lack of correlation of 84 Kr/ 36 Ar and 132 Xe/ 36 Ar fractionation levels along with 4 He/ 20 Ne with distance to the nearest gas production wells does not support the notion that methane present in these groundwaters migrated from nearby production wells either conventional or using hydraulic fracturing techniques.

Dissolved methane in groundwater, Upper Delaware River Basin, Pennsylvania and New York, 2007-12

USGS Publications Warehouse

Kappel, William M.

2013-01-01

The prospect of natural gas development from the Marcellus and Utica Shales has raised concerns about freshwater aquifers being vulnerable to contamination. Well owners are asking questions about subsurface methane, such as, “Does my well water have methane and is it safe to drink the water?” and “Is my well system at risk of an explosion hazard associated with a combustible gas like methane in groundwater?” This newfound awareness of methane contamination of water wells by stray gas migration is based upon studies such as Molofsky and others (2011) who document the widespread natural occurrence of methane in drinking-water wells in Susquehanna County, Pennsylvania. In the same county, Osborn and others (2011) identified elevated methane concentrations in selected drinking-water wells in the vicinity of Marcellus Shale gas-development activities, although pre-development groundwater samples were not available for comparison. A compilation of dissolved methane concentrations in groundwater for New York State was published by Kappel and Nystrom (2012). Recent work documenting the occurrence and distribution of methane in groundwater was completed in southern Sullivan County, Pennsylvania (Sloto, 2013). Additional work is ongoing with respect to monitoring for stray gases in groundwater (Jackson and others, 2013). These studies and their results indicate the importance of collecting baseline or pre-development data. While such data are being collected in some areas, published data on methane in groundwater are sparse in the Upper Delaware River Basin of Pennsylvania, New York, and New Jersey. To manage drinking-water resources in areas of gas-well drilling and hydraulic fracturing in the Upper Delaware River Basin, the natural occurrence of methane in the tri-state aquifers needs to be documented. The purpose of this report is to present data on dissolved methane concentrations in the groundwater in the Upper Delaware River Basin. The scope is restricted to data for Pennsylvania and New York, no U.S. Geological Survey (USGS) methane analyses are presently available for northwestern New Jersey.

Environmental legacy of an underground gas well blowout: long-term effects of gas and brine leakage on groundwater quality

NASA Astrophysics Data System (ADS)

Schout, Gilian; Hartog, Niels; Majid Hassanizadeh, S.; Griffioen, Jasper

2017-04-01

In 1965, a catastrophic underground blowout occurred during the drilling of a gas well in the village of Sleen, the Netherlands. The blowout led to the uncontrolled release of large amounts of natural gas and saline groundwater. Now, 50 years later, a number of nearby groundwater monitoring have been sampled to study the long term effects of this event on the groundwater composition of the overlying freshwater aquifers. The findings are used as an analogue for studying the potential adverse effects of hydraulic fracturing on groundwater quality. In total, 27 samples were taken and analysed for dissolved gas molecular and isotopic composition, major ion chemistry, water isotopes and stable chlorine isotope ratios. The resulting data show that concentrations of dissolved methane are still strongly elevated compared to background samples in a plume downstream of the blowout location. Isotopic data reveals the thermogenic nature of this plume; all samples with methane concentrations greater than 10 mg/l (n=12) had δC-CH4 values greater than -30‰ (VPDB), characteristic of thermogenic methane. The maximum distance at which thermogenic methane is observed is at approximately 500 meter downstream of the centre of the blowout. The progressive enrichment of both δ13C-CH4 and δ2D-CH4, that is observed with distance from the well and decreasing methane concentrations, presents strong evidence for the role of anaerobic methane oxidation (AOM) in limiting the spread of the dissolved methane plume. Low sulphate and increased Fe(II) and Mn(II) concentrations indeed suggest that multiple AOM pathways are involved in the natural attenuation of the dissolved methane plume. Chlorine concentrations were only elevated in a subset of wells in close proximity to the blowout location, indicating that the present-day effects of brine migration are minimal. Nevertheless, elevated Na/Cl ratio's in multiple wells reveal that freshening of the aquifer is still on-going. In summary, this research sheds new light on the long-term effects of natural gas and brine leakage on groundwater quality, which is considered one of the main environmental hazards related to hydraulic fracturing and unconventional gas production in general. Notably, it shows that the anaerobic oxidation of methane may play a major role in containing the effects of uncontrolled gas migration from reservoirs to shallow aquifers.

Shifts in Rumen Fermentation and Microbiota Are Associated with Dissolved Ruminal Hydrogen Concentrations in Lactating Dairy Cows Fed Different Types of Carbohydrates.

PubMed

Wang, Min; Wang, Rong; Xie, Tian Yu; Janssen, Peter H; Sun, Xue Zhao; Beauchemin, Karen A; Tan, Zhi Liang; Gao, Min

2016-09-01

Different carbohydrates ingested greatly influence rumen fermentation and microbiota and gaseous methane emissions. Dissolved hydrogen concentration is related to rumen fermentation and methane production. We tested the hypothesis that carbohydrates ingested greatly alter the rumen environment in dairy cows, and that dissolved hydrogen concentration is associated with these changes in rumen fermentation and microbiota. Twenty-eight lactating Chinese Holstein dairy cows [aged 4-5 y, body weight 480 ± 37 kg (mean ± SD)] were used in a randomized complete block design to investigate effects of 4 diets differing in forage content (45% compared with 35%) and source (rice straw compared with a mixture of rice straw and corn silage) on feed intake, rumen fermentation, and microbial populations. Feed intake (10.7-12.6 kg/d) and fiber degradation (0.584-0.692) greatly differed (P ≤ 0.05) between cows fed the 4 diets, leading to large differences (P ≤ 0.05) in gaseous methane yield (27.2-37.3 g/kg organic matter digested), dissolved hydrogen (0.258-1.64 μmol/L), rumen fermentation products, and microbiota. Ruminal dissolved hydrogen was negatively correlated (r < -0.40; P < 0.05) with molar proportion of acetate, numbers of fungi, abundance of Fibrobacter succinogenes, and methane yield, but positively correlated (r > 0.40; P < 0.05) with molar proportions of propionate and n-butyrate, numbers of methanogens, and abundance of Selenomonas ruminantium and Prevotella spp. Ruminal dissolved hydrogen was positively correlated (r = 0.93; P < 0.001) with Gibbs free energy changes of reactions producing greater acetate and hydrogen, but not correlated with those reactions producing more propionate without hydrogen. Changes in fermentation pathways from acetate toward propionate production and in microbiota from fibrolytic toward amylolytic species were closely associated with ruminal dissolved hydrogen in lactating dairy cows. An unresolved paradox was that greater dissolved hydrogen was associated with greater numbers of methanogens but with lower gaseous methane emissions. © 2016 American Society for Nutrition.

Seeding hydrate formation in water-saturated sand with dissolved-phase methane obtained from hydrate dissolution: A progress report

USGS Publications Warehouse

Waite, William F.; Osegovic, J.P.; Winters, William J.; Max, M.D.; Mason, David H.

2008-01-01

An isobaric flow loop added to the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) is being investigated as a means of rapidly forming methane hydrate in watersaturated sand from methane dissolved in water. Water circulates through a relatively warm source chamber, dissolving granular methane hydrate that was pre-made from seed ice, then enters a colder hydrate growth chamber where hydrate can precipitate in a water-saturated sand pack. Hydrate dissolution in the source chamber imparts a known methane concentration to the circulating water, and hydrate particles from the source chamber entrained in the circulating water can become nucleation sites to hasten the onset of hydrate formation in the growth chamber. Initial results suggest hydrate grows rapidly near the growth chamber inlet. Techniques for establishing homogeneous hydrate formation throughout the sand pack are being developed.

Fluxes of dissolved methane from the seafloor at the landward limit of the gas hydrate stability zone offshore western Svalbard

NASA Astrophysics Data System (ADS)

Graves, Carolyn; Steinle, Lea; Niemann, Helge; Rehder, Gregor; Fisher, Rebecca; Lowry, Dave; Connelly, Doug; James, Rachael

2015-04-01

Seepage of methane from seafloor sediments offshore Svalbard may partly be driven by destabilization of gas hydrates as a result of bottom water warming. As the world's oceans are expected to continue to warm, in particular in the Arctic, destabilization of hydrate may become an important source of methane to ocean bottom waters and potentially to the overlying atmosphere where it contributes to further warming. In order to quantify the fate of methane from seafloor seeps, we have determined the distribution of dissolved methane in the water column on the upper slope and shelf offshore western Svalbard during three research cruises with RRS James Clark Ross (JR253) in 2011 and R/V Maria S. Merian (MSM21/4) and Heincke (HE387) in 2012. Combining discrete depth profile methane concentration data and surface seawater concentrations from an equilibrator-online system with oxidation rate measurements and atmospheric methane observations allows insight into the fate of methane input from the seafloor, and evaluation of the potential contributions of other methane sources. A simple box model considering oxidation and horizontal and vertical mixing indicates that the majority of seep methane is oxidized at depth. A plume of high methane concentrations is expected to persist more than 100 km downstream of the seepage area in the rapid barotropic West Spitsbergen Current, which flows northward towards the Arctic Ocean. We calculate that the diffusive sea-air flux of methane is largest on the shallow shelf, reaching 36 μmol m-2 day-1. Over the entire western Svalbard region there is a persistent, but small, source of methane from surface seawater to the overlying atmosphere. Measurements of the atmospheric methane carbon isotope signature indicate that the seafloor seeps do not make a significant contribution to atmospheric methane in this region, which is consistent with earlier studies. Observations downstream of the seepage region are necessary to further constrain potential for transport of previously hydrate-bound methane to the atmosphere, which would require a mechanism for enhanced vertical mixing of dissolved methane from bottom waters into the surface mixed layer.

Potential for Methanotroph-Mediated Natural Attenuation of TCE in a Basalt Aquifer

NASA Astrophysics Data System (ADS)

Colwell, F. S.; Newby, D. T.; Reed, D. W.; Igoe, A.; Petzke, L.; Delwiche, M. E.; McKinley, J. P.; Roberto, F. F.; Whiticar, M. J.

2002-12-01

Methanotrophic bacteria are one of the microbial communities believed to be responsible for natural attenuation of a trichloroethylene (TCE) plume in the Snake River Plain Aquifer (SRPA). To better understand the role that indigenous methanotrophs may have in TCE degradation in the aquifer, groundwater was collected from four SRPA wells and analyzed for geochemical properties and methanotroph diversity. Dissolved methane concentrations in the aquifer ranged from 1 to >1000 nM. Stable carbon isotope ratios for dissolved methane suggest a microbial source for the methane (del 13C values of ca. -61 per mil in three wells). The combination of 13C enriched methane and 13C depleted-dissolved inorganic carbon in one of the wells suggests that microbial oxidation of methane occurs. Filtered groundwater yielded microorganisms that were used as inocula for enrichments or were frozen and subsequently extracted for DNA. Primers that target taxonomic (type I and type II 16S rDNA) or functional (mmoX and pmoA methane monooxygenase subunits) genes were used to characterize the indigenous methanotrophs via PCR, cloning, and sequencing. DNA sequencing and alignment results suggest that clones with sequences most similar to Methylocystis sp. (a type II methanotroph) and Methylobacter sp. (a type I methanotroph) are frequently present in filtered groundwater with the former often represented in enrichment cultures as well. Methanotroph genes are detected in the aquifer even in wells having methane concentrations as low as 1 nM. Methanotroph presence and a microbial origin for the dissolved methane indicate that microbial cycling of this key gas may play a role in the destruction of TCE in the aquifer.

Methane Occurrences in Aquifers Overlying the Barnett Shale Play with a Focus on Parker County, Texas.

PubMed

Nicot, Jean-Philippe; Mickler, Patrick; Larson, Toti; Clara Castro, M; Darvari, Roxana; Uhlman, Kristine; Costley, Ruth

2017-07-01

Clusters of elevated methane concentrations in aquifers overlying the Barnett Shale play have been the focus of recent national attention as they relate to impacts of hydraulic fracturing. The objective of this study was to assess the spatial extent of high dissolved methane previously observed on the western edge of the play (Parker County) and to evaluate its most likely source. A total of 509 well water samples from 12 counties (14,500 km 2 ) were analyzed for methane, major ions, and carbon isotopes. Most samples were collected from the regional Trinity Aquifer and show only low levels of dissolved methane (85% of 457 unique locations <0.1 mg/L). Methane, when present is primarily thermogenic (δ 13 C 10th and 90th percentiles of -57.54 and -39.00‰ and C1/C2+C3 ratio 10th, 50th, and 90th percentiles of 5, 15, and 42). High methane concentrations (>20 mg/L) are limited to a few spatial clusters. The Parker County cluster area includes historical vertical oil and gas wells producing from relatively shallow formations and recent horizontal wells producing from the Barnett Shale (depth of ∼1500 m). Lack of correlation with distance to Barnett Shale horizontal wells, with distance to conventional wells, and with well density suggests a natural origin of the dissolved methane. Known commercial very shallow gas accumulations (<200 m in places) and historical instances of water wells reaching gas pockets point to the underlying Strawn Group of Paleozoic age as the main natural source of the dissolved gas. © 2017, National Ground Water Association.

Baseline assessment of groundwater quality in Pike County, Pennsylvania, 2015

USGS Publications Warehouse

Senior, Lisa A.; Cravotta, Charles A.

2017-12-29

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, which have the potential for natural gas development, underlie Pike County and neighboring counties in northeastern Pennsylvania. In 2015, the U.S. Geological Survey, in cooperation with the Pike County Conservation District, conducted a study that expanded on a previous more limited 2012 study to assess baseline shallow groundwater quality in bedrock aquifers in Pike County prior to possible extensive shale-gas development. Seventy-nine water wells ranging in depths from 80 to 610 feet were sampled during June through September 2015 to provide data on the presence of methane and other aspects of existing groundwater quality in the various bedrock geologic units throughout the county, including concentrations of inorganic constituents commonly present at low values in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. All groundwater samples collected in 2015 were analyzed for bacteria, dissolved and total major ions, nutrients, selected dissolved and total inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Additionally, samples from 20 wells distributed throughout the county were analyzed for selected man-made volatile organic compounds, and samples from 13 wells where waters had detectable gross alpha activity were analyzed for radium-226 on the basis of relatively elevated gross alpha-particle activity.Results of the 2015 study show that groundwater quality generally met most drinking-water standards for constituents and properties included in analyses, but groundwater samples from some wells had one or more constituents or properties, including arsenic, iron, manganese, pH, bacteria, sodium, chloride, sulfate, total dissolved solids, and radon-222, that did not meet (commonly termed failed or exceeded) primary or secondary maximum contaminant levels (MCLs) or Health Advisories (HA) for drinking water. Except for iron, dissolved and total concentrations of major ions and most trace constituents generally were similar. Only 1 of 79 well-water samples had any constituent that exceeded a MCL, with an arsenic concentration of about 30 micrograms per liter (µg/L) that was higher than the MCL of 10 µg/L. However, total arsenic concentrations were higher than the HA of 2 µg/L in samples from another 12 of 79 wells (about 15 percent). Secondary maximum contaminant levels (SMCLs) were exceeded most frequently by pH and concentrations of iron and manganese. The pH was outside of the SMCL range of 6.5–8.5 in samples from 24 of 79 wells (30 percent), ranging from 5.5 to 9.2; more samples had pH values less than 6.5 than had pH values greater than 8.5. Total iron concentrations typically were much greater than dissolved iron concentrations, indicating substantial presence of iron in particulate phase, and exceeded the SMCL of 300 µg/L more often [35 of 79 samples (44 percent)] than dissolved iron concentrations [samples from 8 of 79 wells (10 percent)]. Total manganese concentrations exceeded the SMCL of 50 µg/L in samples from 31 of 79 wells (39 percent) and the HA of 300 µg/L in samples from 13 of 79 wells (about 16 percent). A few (1–2) samples had concentrations of sodium, chloride, sulfate, or TDS higher than the SMCLs of 60, 250, 250, and 500 mg/L, respectively. However, dissolved sodium concentrations were higher than the HA of 20 mg/L in samples from 15 of 79 wells (nearly 20 percent). Total coliform bacteria were detected in samples from 25 of 79 wells (32 percent) but Escherichia coli were not detected in any sample. Radon-222 activities ranged from 11 to 5,100 picocuries per liter (pCi/L), with a median of 1,440 pCi/L, and exceeded the proposed and the alternate proposed drinking-water standards of 300 and 4,000 pCi/L, respectively, in samples from 60 of 79 wells (75 percent) and in samples from 2 of 79 wells (3 percent), respectively.Groundwater samples from all wells were analyzed for dissolved methane by one contract laboratory that determined water from 19 of the 79 wells (24 percent) had concentrations of methane greater than the reporting level of 0.010 milligrams per liter (mg/L) with a maximum methane concentration of 2.5 mg/L. Methane concentrations in 18 replicate samples submitted to a second laboratory for dissolved gas and isotopic analysis generally were higher by as much as a factor of 2.7 from those determined by the first laboratory, indicating potential bias related to combined sampling and analytical methods, and therefore, caution needs to be used when comparing methane results determined by different methods. The isotopic composition of methane in 9 of 10 samples with sufficient dissolved methane (about 0.3 mg/L) for isotopic analysis is consistent with values reported for methane of microbial origin produced through carbon dioxide reduction; an isotopic shift in 1 or 2 samples may indicate subsequent methane oxidation. The low concentrations of ethane relative to methane in these samples further indicate that the methane may be of microbial origin. Groundwater samples with relatively elevated methane concentrations (near or greater than 0.3 mg/L) also had chemical compositions that differed in some respects from groundwater with relatively low methane concentrations (less than 0.3 mg/L) by having higher pH (greater than 8) and higher concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide and chloride/bromide ratios indicative of mixing with a small amount of brine of probable natural occurrence.The spatial distribution of groundwater compositions differs by topographic setting and lithology and generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands underlain by the undivided Poplar Gap and Packerton members of the Catskill Formation in southwestern Pike County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes underlain by other members of the Catskill Formation; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can be present in deep wells in uplands but most frequently occur in stream valleys, especially at low altitudes (less than about 1,200 feet above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River in northern and eastern Pike County. Thus, the baseline assessment of groundwater quality in Pike County prior to gas-well development shows that shallow (less than about 1,000 feet deep) groundwater generally meets primary drinking-water standards for inorganic constituents but varies spatially, with methane and some constituents present in high concentrations in brine (and connate waters from gas and oil reservoirs) present at low to moderate concentrations in some parts of Pike County.

Aqueous Mesocosm Techniques Enabling the Real-Time Measurement of the Chemical and Isotopic Kinetics of Dissolved Methane and Carbon Dioxide.

PubMed

Chan, Eric W; Kessler, John D; Shiller, Alan M; Joung, DongJoo; Colombo, Frank

2016-03-15

Previous studies of microbially mediated methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on what factor(s) are limiting in these types of environments. These factors include the availability of methane, O2, trace metals, nutrients, the density of cell population, and the influence that CO2 production may have on pH. To look at this process in its entirety, we developed an automated mesocosm incubation system with a Dissolved Gas Analysis System (DGAS) coupled to a myriad of analytical tools to monitor chemical changes during methane oxidation. Here, we present new high temporal resolution techniques for investigating dissolved methane and carbon dioxide concentrations and stable isotopic dynamics during aqueous mesocosm and pure culture incubations. These techniques enable us to analyze the gases dissolved in solution and are nondestructive to both the liquid media and the analyzed gases enabling the investigation of a mesocosm or pure culture experiment in a completely closed system, if so desired.

Real-time surrogate analysis for potential oil and gas contamination of drinking water resources

NASA Astrophysics Data System (ADS)

Son, Ji-Hee; Carlson, Kenneth H.

2015-09-01

Public concerns related to the fast-growing shale oil and gas industry have increased during recent years. The major concern regarding shale gas production is the potential of fracturing fluids being injected into the well or produced fluids flowing out of the well to contaminate drinking water resources such as surface water and groundwater. Fracturing fluids contain high total dissolved solids (TDS); thus, changes in TDS concentrations in groundwater might indicate influences of fracturing fluids. An increase of methane concentrations in groundwater could also potentially be due to hydraulic fracturing activities. To understand the possible contamination of groundwater by fracturing activities, real-time groundwater monitoring is being implemented in the Denver-Julesburg basin of northeast Colorado. A strategy of monitoring of surrogate parameters was chosen instead of measuring potential contaminants directly, an approach that is not cost effective or operationally practical. Contaminant surrogates of TDS and dissolved methane were proposed in this study, and were tested for correlation and data distribution with laboratory experiments. Correlations between TDS and electrical conductivity (EC), and between methane contamination and oxidation-reduction potential (ORP) were strong at low concentrations of contaminants (1 mg/L TDS and 0.3 mg/L CH4). Dissolved oxygen (DO) was only an effective surrogate at higher methane concentrations (≥2.5 mg/L). The results indicated that EC and ORP are effective surrogates for detecting concentration changes of TDS and methane, respectively, and that a strategy of monitoring for easy to measure parameters can be effective detecting real-time, anomalous behavior relative to a predetermined baseline.

Overview of groundwater quality in the Piceance Basin, western Colorado, 1946--2009

USGS Publications Warehouse

Thomas, J.C.; McMahon, P.B.

2013-01-01

Groundwater-quality data from public and private sources for the period 1946 to 2009 were compiled and put into a common data repository for the Piceance Basin. The data repository is available on the web at http://rmgsc.cr.usgs.gov/cwqdr/Piceance/index.shtml. A subset of groundwater-quality data from the repository was compiled, reviewed, and checked for quality assurance for this report. The resulting dataset consists of the most recently collected sample from 1,545 wells, 1,007 (65 percent) of which were domestic wells. From those samples, the following constituents were selected for presentation in this report: dissolved oxygen, dissolved solids, pH, major ions (chloride, sulfate, fluoride), trace elements (arsenic, barium, iron, manganese, selenium), nitrate, benzene, toluene, ethylbenzene, xylene, methane, and the stable isotopic compositions of water and methane. Some portion of recharge to most of the wells for which data were available was derived from precipitation (most likely snowmelt), as indicated by δ2H [H2O] and δ18O[H2O] values that plot along the Global Meteoric Water Line and near the values for snow samples collected in the study area. Ninety-three percent of the samples were oxic, on the basis of concentrations of dissolved oxygen that were greater than or equal to 0.5 milligrams per liter. Concentration data were compared with primary and secondary drinking-water standards established by the U.S. Environmental Protection Agency. Constituents that exceeded the primary standards were arsenic (13 percent), selenium (9.2 percent), fluoride (8.4 percent), barium (4.1 percent), nitrate (1.6 percent), and benzene (0.6 percent). Concentrations of toluene, xylenes, and ethylbenzene did not exceed standards in any samples. Constituents that exceeded the secondary standard were dissolved solids (72 percent), sulfate (37 percent), manganese (21 percent), iron (16 percent), and chloride (10 percent). Drinking-water standards have not been established for methane, which was detected in 24 percent of samples. Methane concentrations were greater than or equal to 1 milligram per liter in 8.5 percent of samples. Methane isotopic data for samples collected primarily from domestic wells in Garfield County indicate that methane in samples with relative high methane concentrations were derived from both biogenic and thermogenic sources. Many of the constituents that exceeded standards, such as arsenic, fluoride, iron, and manganese, were derived from rock and sediment in aquifers. Elevated nitrate concentrations were most likely derived from human sources such as fertilizer and human or animal waste. Information about the geologic unit or aquifer in which a well was completed generally was not provided by data sources. However, limited data indicate that Quaternary deposits in Garfield and Mesa Counties, the Wasatch Formation in Garfield County, and the Green River Formation in Rio Blanco County had some of the highest median concentrations of selected constituents. Variations in concentration with depth could not be evaluated because of the general lack of well-depth and water-level data. Concentrations of several important constituents, such as arsenic, manganese, methane, and nitrate, were related to concentrations of dissolved oxygen. Concentrations of arsenic, manganese, and methane were significantly higher in groundwater with low dissolved-oxygen concentrations than in groundwater with high dissolved-oxygen concentrations. In contrast, concentrations of nitrate were significantly higher in groundwater with high dissolved-oxygen concentrations than in groundwater with low dissolved-oxygen concentrations. These results indicate that measurements of dissolved oxygen may be a useful indicator of groundwater vulnerability to some human-derived contaminants and enrichment from some natural constituents. Assessing such a large and diverse dataset as the one available through the repository poses unique challenges for reporting on groundwater quality in the study area. The repository contains data from several studies that differed widely in purpose and scope. In addition to this variability in available data, gaps exist spatially, temporally, and analytically in the repository. For example, groundwater-quality data in the repository were not evenly distributed throughout the study area. Several key water-quality constituents or indicators, such as dissolved oxygen, were underrepresented in the repository. Ancillary information, such as well depth, depth to water, and the geologic unit or aquifer in which a well was completed, was missing for more than 50 percent of samples. Future monitoring could avoid several limitations of the repository by making relatively minor changes to sample- collection and data-reporting protocols. Field measurements for dissolved oxygen could be added to sampling protocols, for example. Information on well construction and the geologic unit or aquifer in which a well was completed should be part of the water-quality dataset. Such changes would increase the comparability of data from different monitoring programs and also add value to each program individually and to that of the regional dataset as a whole. Other changes to monitoring programs could require greater resources, such as sampling for a basic set of constituents that is relevant to major water-quality issues in the regional study area. Creation of such a dataset for the regional study area would help to provide the kinds of information needed to characterize background conditions and the spatial and temporal variability in constituent concentrations associated with those conditions. Without such information, it is difficult to identify departures from background that might be associated with human activities.

Evidence of Sulfate-Dependent Anaerobic Methane Oxidation within an Area Impacted by Coalbed Methane-Related Gas Migration

NASA Astrophysics Data System (ADS)

Wolfe, A. L.; Wikin, R. T.

2017-12-01

We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Over a 17-month study period, water samples were obtained from domestic water wells and monitoring wells located within the impacted area, and analyzed for 245 constituents, including organic compounds, nutrients, major and trace elements, dissolved gases, and isotopic tracers for carbon, sulfur, oxygen, and hydrogen. Multiple lines of evidence suggest that sulfate-dependent methane biodegradation, which involves the oxidation of methane (CH4) to carbon dioxide (CO2) using sulfate (SO42-) as the terminal electron acceptor, is occurring: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher molecular weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. Groundwater-methane attenuation is linked to the production of dissolved sulfide, and elevated dissolved sulfide concentrations represent an undesirable secondary water quality impact. The biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic, chromium, cobalt, nickel, and lead, likely due to the microbial production of hydrogen sulfide, which favors stabilization of metals in aquifer solids.

Influence of environmental parameters on the concentration of subsurface dissolved methane in two hydroelectric power plants in Brazil

NASA Astrophysics Data System (ADS)

Silva, M. G.; Marani, L.; Alvala, P. C.

2013-12-01

Methane (CH4) is a trace gas in the atmosphere of great importance for atmospheric chemistry as one of the main greenhouse gases. There are different sources with the largest individual production associated with the degradation of organic matter submerged in flooded areas. The amount of dissolved methane that reaches the surface depends on the production in the sediments and consumption in the water column. Both processes are associated with microbial activity and consequently dependent on the physico-chemical environmental conditions. The construction of hydroelectric dams cause flooding of areas near the river that can change the characteristics of the environment and cause changes in subsurface methane concentration. In this work, we studied two hydroelectric plants located in Brazil: Batalha (17°20'39.52"S, 47°29'34.29"W), under construction when the samples were take, and Itaipu (25°24'45.00"S, 54°35'39.00"W) which has been floated over 30 years ago. The water samples to determine dissolved methane were collected approximately 5 cm near the surface. In each collection point was measured depth, water temperature, pH and redox potential. The range of dissolved methane between the two dams was similar: 0.07-10.33 μg/l (Batalha) and 0.15-10.93 μg/l (Itaipu). However, the Batalha's average (4.04 × 3.43 μg/l; median = 3.66 μg/l) was higher than that observed in Itaipu (2.15 × 1.59 μg/l; median = 2.53 μg/l). The influence of environmental parameters on the concentration of dissolved methane was evaluated by multivariate statistical techniques (Principal Component Analysis - PCA). All of the parameters had some correlation with dissolved methane, however, the greatest contribution in Batalha was associated with pH while in Itaipu was the depth. The pH variation of the various points studied in Batalha may be associated with periods of drought and flooding of the river and hence the incorporation of organic matter in the environment. The organisms responsible for the production and oxidation of methane in water are very susceptible to changes in pH, resulting in variations in the amount of gas that is transported to the surface. In Itaipu, depth variation was shown to have more influence than the other parameters. The increase of the water column results in a longer path through which methane is transported, increasing the oxidation potencial by bacteria in the water, decreasing the amount of CH4 can be emitted to the atmosphere. The comparison between the two dams showed that the environmental parameters influences the the production and consumption of methane in water and the importance of each parameter can vary according to the characteristics of each reservoir.

Dissolved methane occurrences in aquifers in the footprint of Texas shale plays and their controls

NASA Astrophysics Data System (ADS)

Nicot, J. P.; Mickler, P. J.; Larson, T.; Darvari, R.; Smyth, R. C.

2015-12-01

Many constituents typically associated with oil and gas production, such as methane and higher-order hydrocarbons, exist naturally in shallow groundwater. Recent studies of aquifers in the footprint of several gas plays across the US have showed that (1) dissolved thermogenic methane may or may not be present in the shallow subsurface and (2) shallow thermogenic methane could be naturally occurring and emplaced through mostly vertical migration over geologic time and is not necessarily a consequence of gas production from a gas play. A total of 800+ water wells have been sampled across the state of Texas to characterize shallow methane in fresh-water aquifers overlying shale plays and other tight formations (Barnett, Eagle Ford, Haynesville shale areas as well as in the Delaware Basin of West Texas). Analytical results suggest that dissolved methane is not widespread in shallow groundwater and that, when present at concentration greater than 10 mg/L, is often of natural but thermogenic or mixed origin according to the isotopic signature and to the presence of other light hydrocarbons.

Identifying sources, formation pathways and geological controls of methane in shallow groundwater above unconventional natural gas plays in Alberta, Canada

NASA Astrophysics Data System (ADS)

Mayer, B.; Humez, P.; Nightingale, M.; Ing, J.; Kingston, A. W.; Clarkson, C.; Cahill, A.; Parker, B. L.; Cherry, J. A.; Millot, R.; Kloppmann, W.; Osadetz, K.; Lawton, D.

2015-12-01

With the advent of shale gas development facilitated by hydraulic fracturing it has become increasingly important to develop tracer tools to scientifically determine potential impacts of stray gases on shallow aquifers. To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development, it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta (Canada) between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with often low methane concentrations in shallow groundwater, but in 28 samples methane exceeded 10 mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged -69.7 ± 11.1 ‰ in free gas and -65.6 ± 8.9 ‰ in dissolved gas. δ13C values were not found to vary with well depth or lithology indicating that the methane in Alberta groundwater was formed via a similar mechanism. The low δ13C values in concert with average δ2H values of -289 ± 44 ‰ suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by gas dryness parameters typically >500 due to only small amounts of ethane and a lack of propane in most samples. Novel approaches of in-situ concentration and isotope measurements for methane during drilling of a 530 m deep well yielded a mud-gas profile characterizing natural gas occurrences in the intermediate zone. Comparison with mudgas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100-250 meter depths in the Western Canadian Sedimentary Basin and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The assembled data set provides evidence that potential stray gas contamination by isotopically distinct deeper thermogenic gases from the intermediate or from production zones can be effectively detected by suitable monitoring programs.

Biogeochemical cycles at the sulfate-methane transition zone (SMTZ) and geochemical characteristics of the pore fluids offshore southwestern Taiwan

NASA Astrophysics Data System (ADS)

Hu, Ching-Yi; Frank Yang, Tsanyao; Burr, George S.; Chuang, Pei-Chuan; Chen, Hsuan-Wen; Walia, Monika; Chen, Nai-Chen; Huang, Yu-Chun; Lin, Saulwood; Wang, Yunshuen; Chung, San-Hsiung; Huang, Chin-Da; Chen, Cheng-Hong

2017-11-01

In this study, we used pore water dissolved inorganic carbon (DIC), SO42-, Ca2+ and Mg2+ gradients at the sulfate-methane transition zone (SMTZ) to estimate biogeochemical fluxes for cored sediments collected offshore SW Taiwan. Net DIC flux changes (ΔDIC-Prod) were applied to determine the proportion of sulfate consumption by organic matter oxidation (heterotrophic sulfate reduction) and anaerobic oxidation of methane (AOM), and to determine reliable CH4 fluxes at the SMTZ. Our results show that SO42- profiles are mainly controlled by AOM rather than heterotrophic sulfate reduction. Refinement of CH4 flux estimates enhance our understanding of methane abundance from deep carbon reservoirs to the SMTZ. Concentrations of chloride (Cl-), bromide (Br-) and iodide (I-) dissolved in pore water were used to identify potential sources that control fluid compositions and the behavior of dissolved ions. Constant Cl- concentrations throughout ∼30 m sediment suggest no influence of gas hydrates for the compositions within the core. Bromide (Br-) and Iodine (I-) concentrations increase with sediment depth. The I-/Br- ratio appears to reflect organic matter degradation. SO42- concentrations decrease with sediment depth at a constant rate, and sediment depth profiles of Br- and I- concentrations suggests diffusion as the main transport mechanism. Therefore diffusive flux calculations are reasonable. Coring sites with high CH4 fluxes are more common in the accretionary wedge, amongst thrust faults and fractures, than in the passive continental margin offshore southwestern Taiwan. AOM reactions are a major sink for CH4 passing upward through the SMTZ and prevent high methane fluxes in the water column and to the atmosphere.

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

USGS Publications Warehouse

Weinsten, A.; Navarrete, L; Ruppel, Carolyn D.; Weber, T.C.; Leonte, M.; Kellermann, M.; Arrington, E.; Valentine, D.L.; Scranton, M.L; Kessler, John D.

2016-01-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern US Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady-state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6 – 24 kmol methane per day). These analyses suggest this methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH. This article is protected by copyright. All rights reserved.

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability

NASA Astrophysics Data System (ADS)

Weinstein, Alexander; Navarrete, Luis; Ruppel, Carolyn; Weber, Thomas C.; Leonte, Mihai; Kellermann, Matthias Y.; Arrington, Eleanor C.; Valentine, David L.; Scranton, Mary I.; Kessler, John D.

2016-10-01

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6-24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH.

Modeling of Methane Migration in Shallow Aquifers from Shale Gas Well Drilling.

PubMed

Zhang, Liwei; Soeder, Daniel J

2016-05-01

The vertical portion of a shale gas well, known as the "tophole" is often drilled using an air-hammer bit that may introduce pressures as high as 2400 kPa (350 psi) into groundwater while penetrating shallow aquifers. A 3-D TOUGH2 model was used to simulate the flow of groundwater under the high hydraulic heads that may be imposed by such trapped compressed air, based on an observed case in West Virginia (USA) in 2012. The model realizations show that high-pressure air trapped in aquifers may cause groundwater to surge away from the drill site at observable velocities. If dissolved methane is present within the aquifer, the methane can be entrained and transported to a maximum distance of 10.6 m per day. Results from this study suggest that one cause of the reported increase in methane concentrations in groundwater near shale gas production wells may be the transport of pre-existing methane via groundwater surges induced by air drilling, not necessarily direct natural gas leakage from the unconventional gas reservoir. The primary transport mechanisms are advective transport of dissolved methane with water flow, and diffusive transport of dissolved methane. © 2015, National Ground Water Association.

Chemical Variability in Ocean Frontal Areas: Results of a Workshop Conducted 19-22 September 1983

DTIC Science & Technology

1988-07-01

tidal mixing and is separated from the seasonally stratified waters of the Bering Sea Shelf by a front at approximately 50 m. Salinity, temperature...the concentration of dissolved methane at the entrance to Port Moller is seasonably variable, it averages about a factor of 10 above the ambient...coastal levels regardless of season . By fitting the distribution of dissolved methane to a 2-D advection-diffusion model, we estimated a mean velocity

Continuous, Pulsed Export of Methane-Supersaturated Meltwaters from the Bed of the Greenland Ice Sheet

NASA Astrophysics Data System (ADS)

Lamarche-Gagnon, G.; Wadham, J.; Beaton, A.; Fietzek, P.; Stanley, K. M.; Tedstone, A.; Sherwood Lollar, B.; Lacrampe Couloume, G.; Telling, J.; Liz, B.; Hawkings, J.; Kohler, T. J.; Zarsky, J. D.; Stibal, M.; Mowlem, M. C.

2016-12-01

Both past and present ice sheets have been proposed to cap large quantities of methane (CH4), on orders of magnitude significant enough to impact global greenhouse gas concentrations during periods of rapid ice retreat. However, to date most evidence for sub-ice sheet methane has been indirect, derived from calculations of the methanogenic potential of basal-ice microbial communities and biogeochemical models; field-based empirical measurements are lacking from large ice sheet catchments. Here, we present the first continuous, in situ record of dissolved methane export from a large catchment of the Greenland Ice Sheet (GrIS) in South West Greenland from May-July 2015. Our results indicate that glacial runoff was continuously supersaturated with methane over the observation period (dissolved CH4 concentrations of 30-700 nM), with total methane flux rising as subglacial discharge increased. Periodic subglacial drainage events, characterised by rapid changes (i.e. pulses) in meltwater hydrochemistry, also coincided with a rise in methane concentrations. We argue that these are likely indicative of the flushing of subglacial reservoirs of CH4 beneath the ice sheet. Total methane export was relatively modest when compared to global methane budgets, but too high to be explained by previously determined methanogenic rates from Greenland basal ice. Discrepancies between estimated Greenland methane reserves and observed fluxes stress the need to further investigate GrIS methane fluxes and sources, and suggest a more biogeochemically active subglacial environment than previously considered. Results indicate that future warming, and a coincident increase in ice melt rates, would likely make the GrIS, and by extension the Antarctic Ice Sheet, more significant sources of atmospheric methane, consequently acting as a positive feedback to a warming climate.

In search of thermogenic methane in groundwater in the Netherlands, with emphasis on the location of a historic gas well blowout

NASA Astrophysics Data System (ADS)

Schout, G.; Griffioen, J.; Hassanizadeh, S. M.; Hartog, N.

2017-12-01

Similar to the US, the Netherlands has a long history of oil & gas production, with around 2500 onshore hydrocarbon wells drilled since the late 1930s. While conventional reserves are diminishing, a governmental moratorium was put in place on shale gas exploration and production until 2023, in part due to concerns about its effects on groundwater quality. To investigate the industry's historic and potential future impact on groundwater quality in the country, a study was carried out to assess i) baseline methane concentrations and origin ii) the natural connectivity of deeper gas-bearing layers with the shallower groundwater systems. Through datamining, a dataset consisting of 12,200 groundwater analyses with methane concentrations was assembled. Furthermore, 25 additional samples were collected at targeted locations and analysed for dissolved gas molecular and isotopic composition. Methane concentrations are positively skewed with median, mean and maximum concentrations of 0.28, 2.17 and 120 mg/L, respectively. No correlation between methane concentrations and distance to hydrocarbon wells or faults is observed. In general, concentrations cannot be readily explained by factors such as the depth, geographic location, host formation and depositional environment. Thermogenic methane was first encountered at several hundred meters depth, below thick successions of marine Paleogene and Neogene clays that are present throughout the country and impede vertical flow. All methane encountered above these formations was found to be biogenic in origin, with one notable exception - a sample taken at the site of a catastrophic gas well blowout that occurred in 1965 near the village of Sleen. Combined, these findings suggest that thermogenic methane does not naturally occur in Dutch shallow groundwater and its presence can be used as an indicator of anthropogenic gas leakage. The unique Sleen blowout site was selected for a detailed investigation of the long-term effects of uncontrolled gas leakage on groundwater chemistry. Methane concentrations up to 45 mg/L were observed and the distribution pattern suggests on-going leakage, 50 years after the events. Results also show that anaerobic oxidation of methane plays a major role in controlling the spread of dissolved methane.

Sources, extent and history of methane seepage on the continental shelf off northern Norway

NASA Astrophysics Data System (ADS)

Sauer, Simone; Lepland, Aivo; Chand, Shyam; Schubert, Carsten J.; Eichinger, Florian; Knies, Jochen

2014-05-01

Active natural hydrocarbon gas seepage was recently discovered in the Hola area on the continental shelf off Vesterålen, northern Norway. We conducted acoustic and geochemical investigations to assess the modern and past extent, source and pathways of the gas seepage . Water column echosounder surveys showed bubble plumes up to several tens of metres above the seafloor. Analyses of dissolved methane in the water column indicated slightly elevated concentrations (50 nM) close to the seafloor. To identify fluxes and origin of methane in the sediments we analysed sediment pore water chemistry, the isotopic composition of methane and of dissolved inorganic carbon (d13CCH4, d2HCH4, d13CDIC) in three closely spaced (

Patterns and variability in geochemical signatures and microbial activity within and between diverse cold seep habitats along the lower continental slope, Northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Bowles, Marshall; Hunter, Kimberley S.; Samarkin, Vladimir; Joye, Samantha

2016-07-01

We collected 69 sediment cores from distinct ecological and geological settings along the deep slope in the Northern Gulf of Mexico to evaluate whether specific geochemical- or habitat-related factors correlated with rates of microbial processes and geochemical signatures. By collecting replicate cores from distinct habitats across multiple sites, we illustrate and quantify the heterogeneity of cold seep geochemistry and microbial activity. These data also document the factors driving unique aspects of the geochemistry of deep slope gas, oil and brine seeps. Surprisingly little variation was observed between replicate (n=2-5) cores within sites for most analytes (except methane), implying that the common practice of collecting one core for geochemical analysis can capture the signature of a habitat in most cases. Depth-integrated concentrations of methane, dissolved inorganic carbon (DIC), and calcium were the predominant geochemical factors that correlated with a site's ecological or geological settings. Pore fluid methane concentration was related to the phosphate and DIC concentration, as well as to rates of sulfate reduction. While distinctions between seep habitats were identified from geochemical signatures, habitat specific geochemistry varied little across sites. The relative concentration of dissolved inorganic nitrogen versus phosphorus suggests that phosphorus availability limits biomass production at cold seeps. Correlations between calcium, chloride, and phosphate concentrations were indicative of brine-associated phosphate transport, suggesting that in addition to the co-migration of methane, dissolved organic carbon, and ammonium with brine, phosphate delivery is also associated with brine advection.

Impact of an historic underground gas well blowout on the current methane chemistry in a shallow groundwater system

PubMed Central

Schout, Gilian; Hartog, Niels; Hassanizadeh, S. Majid; Griffioen, Jasper

2018-01-01

Blowouts present a small but genuine risk when drilling into the deep subsurface and can have an immediate and significant impact on the surrounding environment. Nevertheless, studies that document their long-term impact are scarce. In 1965, a catastrophic underground blowout occurred during the drilling of a gas well in The Netherlands, which led to the uncontrolled release of large amounts of natural gas from the reservoir to the surface. In this study, the remaining impact on methane chemistry in the overlying aquifers was investigated. Methane concentrations higher than 10 mg/L (n = 12) were all found to have δ13C-CH4 values larger than −30‰, typical of a thermogenic origin. Both δ13C-CH4 and δD-CH4 correspond to the isotopic composition of the gas reservoir. Based on analysis of local groundwater flow conditions, this methane is not a remnant but most likely the result of ongoing leakage from the reservoir as a result of the blowout. Progressive enrichment of both δ13C-CH4 and δD-CH4 is observed with increasing distance and decreasing methane concentrations. The calculated isotopic fractionation factors of εC = 3 and εD = 54 suggest anaerobic methane oxidation is partly responsible for the observed decrease in concentrations. Elevated dissolved iron and manganese concentrations at the fringe of the methane plume show that oxidation is primarily mediated by the reduction of iron and manganese oxides. Combined, the data reveal the long-term impact that underground gas well blowouts may have on groundwater chemistry, as well as the important role of anaerobic oxidation in controlling the fate of dissolved methane. PMID:29279383

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas, Eastern Kentucky.

PubMed

Zhu, Junfeng; Parris, Thomas M; Taylor, Charles J; Webb, Steven E; Davidson, Bart; Smath, Richard; Richardson, Stephen D; Molofsky, Lisa J; Kromann, Jenna S; Smith, Ann P

2018-05-01

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ 13 C-CH 4 and δ 2 H-CH 4 ) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ 13 C-CH 4 and δ 2 H-CH 4 ranged from -84.0‰ to -58.3‰ and from -246.5‰ to -146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO 2 reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region. © 2017, National Ground Water Association.

Baseline groundwater quality from 34 wells in Wayne County, Pennsylvania, 2011 and 2013

USGS Publications Warehouse

Sloto, Ronald A.

2014-01-01

Differences in groundwater chemistry were related to pH. Water with a pH greater than 7.6 generally had low dissolved oxygen concentrations, indicating reducing conditions in the aquifer. These high pH waters also had relatively elevated concentrations of methane, arsenic, boron, bromide, fluoride, lithium, and sodium but low concentrations of copper, nickel, and zinc. Water samples with a pH greater than 7.8 had methane concentrations equal to or greater than 0.04 mg/L.

Dissolved gasesous hydrocarbons in shallow groundwater of Lower Saxony, Germany - Revisited 2016

NASA Astrophysics Data System (ADS)

Schloemer, Stefan; Illing, Christian J.; Blumenberg, Martin; Oest, Johanna; Elbracht, Jörg

2017-04-01

Many concerns arise within the public and government/political institutions over potential groundwater contamination from deep drilling operations. For this reason we initiated a baseline study in 2014 on the distribution of dissolved methane, ethane and propane in shallow groundwater ( 1000 groundwater wells, Schloemer et al., 2016) of Lower Saxony, which includes the major petroleum and natural gas provinces in Germany. We observed a variation of dissolved methane concentration over 7 orders of magnitude (20 nl/l to 60 ml/l [v/v]). Methane delta13C compositions ranged from -110‰ to +25‰ vs VPDB, narrowly clustering around -70‰ at high concentrations but being increasingly more variable at lower concentrations (-40‰ to -80‰)). Most of the data are clearly indicative for methanogenic processes, samples unusually enriched in delta13C can best be explained by secondary methane oxidation. Although some general regional trend can be observed, results are highly variable within short lateral distances or within different aquifers/filter depths. Frequently ethane (27% of samples, median 50nl/l) and occasionally propane (8%, median 23nl/l) has been detected. Lacking the carbon isotope composition of these homologues and thus solely based on the extremely low concentrations and atypical ethane/propane ratios, these have been tentatively interpreted as ubiquitous microbial background. From the original 2014 sample set around 100 wells have been selected for consecutive testing through 2015. In spring 2016 a total number of 1100 wells have been sampled, 700 of which had already been part of the initial study, providing us with the unique opportunity to assess long term variations. The overall comparison of these 700 samples revealed only small relative variations in methane concentrations (mostly < ± 25%), although higher variations are common at concentrations less than 1 µl/l. Correspondingly the carbon isotopic composition of paired samples is quite stable (± 2‰)) for most of the samples ( 60%) but large discrepancies can be observed at low absolute concentrations (> ± 5‰ in 25% of samples). Minor variations could be related to uncertainties in laboratory analysis (± 10% in concentration, ± 0.5‰ delta13C). To which extent the small number of sampled groundwater with unusually high variations are indeed a result of a naturally occurring process (rapidly changing conditions or anthropogenic influence) is currently under investigation. However, applying different sampling conditions/procedures (i.e. different pumps, flow rates) had to be accepted during the course of the project and might be a reason as well. In any case our preliminary results point toward the necessity of repeated sampling (particularly in shallow unconfined aquifers) to account for possible natural variations and of strictly consistent sampling protocols when analyzing "non-conservative" dissolved gases. Reference Schloemer, S., Elbracht, J., Blumenberg, M. and Illing, C.J., 2016. Distribution and origin of dissolved methane, ethane and propane in shallow groundwater of Lower Saxony, Germany. Applied Geochemistry, 67: 118-132.

Controls on Methane Occurrences in Shallow Aquifers Overlying the Haynesville Shale Gas Field, East Texas.

PubMed

Nicot, Jean-Philippe; Larson, Toti; Darvari, Roxana; Mickler, Patrick; Slotten, Michael; Aldridge, Jordan; Uhlman, Kristine; Costley, Ruth

2017-07-01

Understanding the source of dissolved methane in drinking-water aquifers is critical for assessing potential contributions from hydraulic fracturing in shale plays. Shallow groundwater in the Texas portion of the Haynesville Shale area (13,000 km 2 ) was sampled (70 samples) for methane and other dissolved light alkanes. Most samples were derived from the fresh water bearing Wilcox formations and show little methane except in a localized cluster of 12 water wells (17% of total) in a approximately 30 × 30 km 2 area in Southern Panola County with dissolved methane concentrations less than 10 mg/L. This zone of elevated methane is spatially associated with the termination of an active fault system affecting the entire sedimentary section, including the Haynesville Shale at a depth more than 3.5 km, and with shallow lignite seams of Lower Wilcox age at a depth of 100 to 230 m. The lignite spatial extension overlaps with the cluster. Gas wetness and methane isotope compositions suggest a mixed microbial and thermogenic origin with contribution from lignite beds and from deep thermogenic reservoirs that produce condensate in most of the cluster area. The pathway for methane from the lignite and deeper reservoirs is then provided by the fault system. © 2017, National Ground Water Association.

The distribution of methane in groundwater in Alberta (Canada) and associated aqueous geochemistry conditions

NASA Astrophysics Data System (ADS)

Humez, Pauline; Mayer, Bernhard; Nightingale, Michael; Becker, Veith; Kingston, Andrew; Taylor, Stephen; Millot, Romain; Kloppmann, Wolfram

2016-04-01

Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish: (a) natural in-situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. We have conducted a NSERC-ANR co-funded baseline study investigating the occurrence of methane in shallow groundwater of Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. Our objective was to assess the occurrence and sources of methane in shallow groundwaters and to also characterize the hydrochemical environment in which the methane was formed or transformed through redox processes. Ultimately our aim was to determine whether methane was formed in-situ or whether it migrated from deeper formations into shallow aquifers. Combining hydrochemical and dissolved and free geochemical gas data from 372 groundwater samples obtained from 186 monitoring wells of the provincial groundwater observation well network (GOWN) in Alberta, it was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of dissolved biogenic methane (> 0.01 mM or > 0.2 mg/L), characterized by δ13CCH4 values < -55‰, occurred in anoxic Na-Cl, Na-HCO3 and Na-HCO3-Cl type groundwater with negligible concentrations of nitrate and sulfate suggesting that methane was formed in-situ under methanogenic conditions consistent with the redox ladder concept. Despite quite variable gas concentrations and a wide range of δ13CCH4 values in baseline groundwater samples, no conclusive evidence was found for deep thermogenic gas that had migrated in significant amounts into shallow aquifers either naturally or via anthropogenically induced pathways. This study shows that the combined interpretation of aqueous geochemistry data in concert with the chemical and isotopic composition of dissolved and/or free gas can yield unprecedented insights into formation or migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

Sustained in situ measurements of dissolved oxygen, methane and water transport processes in the benthic boundary layer at MC118, northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Martens, Christopher S.; Mendlovitz, Howard P.; Seim, Harvey; Lapham, Laura; D'Emidio, Marco

2016-07-01

Within months of the BP Macondo Wellhead blowout, elevated methane concentrations within the water column revealed a significant retention of light hydrocarbons in deep waters plus corresponding dissolved oxygen (DO) deficits. However, chemical plume tracking efforts were hindered by a lack of in situ monitoring capabilities. Here, we describe results from in situ time-series, lander-based investigations of physical and biogeochemical processes controlling dissolved oxygen, and methane at Mississippi Canyon lease block 118 ( 18 km from the oil spill) conducted shortly after the blowout through April 2012. Multiple sensor arrays plus open-cylinder flux chambers (;chimneys;) deployed from a benthic lander collected oxygen, methane, pressure, and current speed and direction data within one meter of the seafloor. The ROVARD lander system was deployed for an initial 21-day test experiment (9/13/2010-10/04/2010) at 882 m depth before a longer 160-day deployment (10/24/2011-4/01/2012) at 884 m depth. Temporal variability in current directions and velocities and water temperatures revealed strong influences of bathymetrically steered currents and overlying along-shelf flows on local and regional water transport processes. DO concentrations and temperature were inversely correlated as a result of water mass mixing processes. Flux chamber measurements during the 160-day deployment revealed total oxygen utilization (TOU) averaging 11.6 mmol/m2 day. Chimney DO concentrations measured during the 21-day deployment exhibited quasi-daily variations apparently resulting from an interaction between near inertial waves and the steep topography of an elevated scarp immediately adjacent to the 21-day deployment site that modulated currents at the top of the chimney. Variability in dissolved methane concentrations suggested significant temporal variability in gas release from nearby hydrocarbon seeps and/or delivery by local water transport processes. Free-vehicle (lander) monitoring over time scales of months to years utilizing in situ sensors can provide an understanding of processes controlling water transport, respiration and the fate and impacts of accidental and natural gas and oil releases.

Origin of methane and sources of high concentrations in Los Angeles groundwater

USGS Publications Warehouse

Kulongoski, Justin; McMahon, Peter B.; Land, Michael; Wright, Michael; Johnson, Theodore; Landon, Matthew K.

2018-01-01

In 2014, samples from 37 monitoring wells at 17 locations, within or near oil fields, and one site >5 km from oil fields, in the Los Angeles Basin, California, were analyzed for dissolved hydrocarbon gas isotopes and abundances. The wells sample a variety of depths of an aquifer system composed of unconsolidated and semiconsolidated sediments under various conditions of confinement. Concentrations of methane in groundwater samples ranged from 0.002 to 150 mg/L—some of the highest concentrations reported in a densely populated urban area. The δ13C and δ2H of the methane ranged from −80.8 to −45.5 per mil (‰) and −249.8 to −134.9‰, respectively, and, along with oxidation‐reduction processes, helped to identify the origin of methane as microbial methanogenesis and CO2 reduction as its main formation pathway. The distribution of methane concentrations and isotopes is consistent with the high concentrations of methane in Los Angeles Basin groundwater originating from relatively shallow microbial production in anoxic or suboxic conditions. Source of the methane is the aquifer sediments rather than the upward migration or leakage of thermogenic methane associated with oil fields in the basin.

Origin of Methane and Sources of High Concentrations in Los Angeles Groundwater

NASA Astrophysics Data System (ADS)

Kulongoski, J. T.; McMahon, P. B.; Land, M.; Wright, M. T.; Johnson, T. A.; Landon, M. K.

2018-03-01

In 2014, samples from 37 monitoring wells at 17 locations, within or near oil fields, and one site >5 km from oil fields, in the Los Angeles Basin, California, were analyzed for dissolved hydrocarbon gas isotopes and abundances. The wells sample a variety of depths of an aquifer system composed of unconsolidated and semiconsolidated sediments under various conditions of confinement. Concentrations of methane in groundwater samples ranged from 0.002 to 150 mg/L—some of the highest concentrations reported in a densely populated urban area. The δ13C and δ2H of the methane ranged from -80.8 to -45.5 per mil (‰) and -249.8 to -134.9‰, respectively, and, along with oxidation-reduction processes, helped to identify the origin of methane as microbial methanogenesis and CO2 reduction as its main formation pathway. The distribution of methane concentrations and isotopes is consistent with the high concentrations of methane in Los Angeles Basin groundwater originating from relatively shallow microbial production in anoxic or suboxic conditions. Source of the methane is the aquifer sediments rather than the upward migration or leakage of thermogenic methane associated with oil fields in the basin.

High-resolution chemical and hydrologic records identify environmental factors that control coastal anchialine cave ecosystem function

NASA Astrophysics Data System (ADS)

Brankovits, D.; Pohlman, J.; Lapham, L.; Casso, M.; Roth, E.; Lowell, N. S.; Iliffe, T. M.

2015-12-01

Anchialine caves host a coastal aquifer ecosystem occupied by cave-adapted crustaceans that reside within distinct fresh, brackish and marine waters. Our initial investigation of this subsurface ecotone in the Yucatan Peninsula (Mexico) provides stable isotope-based evidence that methane and dissolved organic carbon (DOC) are the primary sources of energy and carbon for the food web. However, the frequency of observations is sparse, leaving us 'in the dark' with respect to the temporal dynamics of the ecosystem function. In this study, we obtained undisturbed vertical profiles of methane, DOC and DIC concentration and isotopic composition with the 'Octopipi' water sampler from an anchialine cave located ~8 km from the coastline. To document the temporal variability of methane availability in the cave, we deployed an osmotically-driven pump (OsmoSampler). Data loggers recorded dissolved oxygen (DO), salinity, temperature and current velocities, and a rain gauge recorded precipitation. A high-methane water mass near the ceiling (up to 7795 nM) contained elevated concentration (900 µM), 13C-depleted (-27.8 to -28.2 ‰) DOC, suggesting terrestrial organic matter input from the overlying soils. Low-methane saline water (36 to 84 nM) had lower concentration DOC (15 to 97 µM) with a similar δ13C (-25.9 to -27.2 ‰), suggesting significant terrestrial organic matter consumption or removal with increasing depth, from fresh to saline water, within the water column. Our 6-month water chemistry record reveals high concentrations of methane in the wet season, especially following rainfall events, and relatively lower methane concentrations in the dry season. These observations suggest rain flushes methane generated in overlying anoxic soils into the cave. DO, water level, and groundwater flow patterns were also linked to the precipitation record. These data provide novel insight into the interconnections between external climate forcing and subterranean anchialine ecosystems within coastal aquifers.

Testing short-range migration of microbial methane as a hydrate formation mechanism: Results from Andaman Sea and Kumano Basin drill sites and global implications

NASA Astrophysics Data System (ADS)

Malinverno, Alberto; Goldberg, David S.

2015-07-01

Methane gas hydrates in marine sediments often concentrate in coarse-grained layers surrounded by fine-grained marine muds that are hydrate-free. Methane in these hydrate deposits is typically microbial, and must have migrated from its source as the coarse-grained sediments contain little or no organic matter. In "long-range" migration, fluid flow through permeable layers transports methane from deeper sources into the gas hydrate stability zone (GHSZ). In "short-range" migration, microbial methane is generated within the GHSZ in fine-grained sediments, where small pore sizes inhibit hydrate formation. Dissolved methane can then diffuse into adjacent sand layers, where pore size does not restrict hydrate formation and hydrates can accumulate. Short-range migration has been used to explain hydrate accumulations in sand layers observed in drill sites on the northern Cascadia margin and in the Gulf of Mexico. Here we test the feasibility of short-range migration in two additional locations, where gas hydrates have been found in coarse-grained volcanic ash layers (Site NGHP-01-17, Andaman Sea, Indian Ocean) and turbidite sand beds (Site IODP-C0002, Kumano forearc basin, Nankai Trough, western Pacific). We apply reaction-transport modeling to calculate dissolved methane concentration and gas hydrate amounts resulting from microbial methane generated within the GHSZ. Model results show that short-range migration of microbial methane can explain the overall amounts of methane hydrate observed at the two sites. Short-range migration has been shown to be feasible in diverse margin environments and is likely to be a widespread methane transport mechanism in gas hydrate systems. It only requires a small amount of organic carbon and sediment sequences consisting of thin coarse-grained layers that can concentrate microbial methane generated within thick fine-grained sediment beds; these conditions are common along continental margins around the globe.

Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

USGS Publications Warehouse

Pohlman, J.W.; Bauer, J.E.; Waite, W.F.; Osburn, C.L.; Chapman, N.R.

2011-01-01

Marine sediments contain about 500-10,000 Gt of methane carbon, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined, but it releases relatively little methane to the ocean and atmosphere. Sedimentary microbes convert most of the dissolved methane to carbon dioxide. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use ??14 C and ??13 C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13 C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000-6,000 year age of dissolved organic carbon in the deep ocean, and provide reduced organic matter and energy to deep-ocean microbial communities. ?? 2011 Macmillan Publishers Limited. All rights reserved.

40 CFR 63.457 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... of methane or n-hexane and air at a concentration of approximately, but less than, 10,000 parts per million by volume methane or n-hexane. (e) Negative pressure procedures. To demonstrate negative pressure... between 6.95 and 7.05. (4) To prepare the 0.1 normality (N) sodium thiosulfate solution, dissolve 25 g of...

Predicting the fate of methane emanating from the seafloor using a marine two-phase gas model in one dimension (M2PG1) - Example from a known Arctic methane seep site offshore Svalbard

NASA Astrophysics Data System (ADS)

Jansson, Pär; Ferré, Benedicte

2017-04-01

Transport of methane in seawater occurs by diffusion and advection in the dissolved phase, and/or as free gas in form of bubbles. The fate of methane in bubbles emitted from the seafloor depends on both bubble size and ambient conditions. Larger bubbles can transport methane higher into the water column, potentially reaching the atmosphere and contributing to greenhouse gas concentrations and impacts. Single bubble or plume models have been used to predict the fate of bubble mediated methane gas emissions. Here, we present a new process based two-phase (free and dissolved) gas model in one dimension, which has the capability to dynamically couple water column properties such as temperature, salinity and dissolved gases with the free gas species contained in bubbles. The marine two-phase gas model in one dimension (M2PG1) uses a spectrum of bubbles and an Eulerian formulation, discretized on a finite-volume grid. It employs the most up-to-date equations for solubility and compressibility of the included gases, nitrogen, oxygen, carbon dioxide and methane. M2PG1 is an extension of PROBE (Omstedt, 2011), which facilitates atmospheric coupling and turbulence closures to realistically predict vertical mixing of all properties, including dissolved methane. This work presents the model's first application in an Arctic Ocean environment at the landward limit of the methane-hydrate stability zone west of Svalbard, where we observe substantial methane bubble release over longer time periods. The research is part of the Centre for Arctic Gas Hydrate, Environment and Climate (CAGE) and is supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259 and UiT. Omstedt, A. (2011). Guide to process based modeling of lakes and coastal seas: Springer.

Methane in aquifers used for public supply in the United States

USGS Publications Warehouse

McMahon, Peter B.; Belitz, Kenneth; Barlow, Jeannie R.; Jurgens, Bryant

2017-01-01

In 2013 to 2015, 833 public supply wells in 15 Principal aquifers in the U.S. were sampled to identify which aquifers contained high methane concentrations (>1 mg/L) and determine the geologic, hydrologic, and geochemical conditions associated with high concentrations. This study represents the first national assessment of methane in aquifers used for public supply in the U.S. and, as such, advances the understanding of the occurrence and distribution of methane in groundwater nationally. Methane concentrations >1 and > 10 mg/L occurred in 6.7 and 1.1% of the samples, respectively. Most high concentrations occurred in aquifers in the Atlantic and Gulf Coastal Plain regions and upper Midwest. High methane concentrations were most commonly associated with Tertiary and younger aquifer sediments, old groundwater (>60 years), and concentrations of oxygen, nitrate-N, and sulfate <0.5 mg/L. Concentrations of methane were also positively correlated (p < 0.05) with dissolved organic carbon and ammonium. Case studies in Florida, Texas, and Iowa were used to explore how regional context from this data set could aid our understanding of local occurrences of methane in groundwater. Regional data for methane, Br/Cl ratios, sulfate, and other parameters helped identify mixing processes involving end members such as wastewater effluent-impacted groundwater, saline formation water, and pore water in glacial till that contributed methane to groundwater in some cases and supported methane oxidation in others.

Supersaturation of Dissolved Hydrogen and Methane in Rumen of Tibetan Sheep

PubMed Central

Wang, Min; Ungerfeld, Emilio M.; Wang, Rong; Zhou, Chuan She; Basang, Zhu Zha; Ao, Si Man; Tan, Zhi Liang

2016-01-01

Hydrogen (H2) is an essential substrate for methanogens to produce methane (CH4), and also influences pathways of volatile fatty acids (VFA) production in the rumen. Dissolved H2 (H2 (aq)) is the form of H2 available to microbes, and dissolved CH4 (CH4 (aq)) is important for indicating methanogens activity. Rumen H2 (aq) concentration has been estimated by assuming equilibrium with headspace gaseous H2 (H2 (g)) concentration using Henry's law, and has also been directly measured in the liquid phase in some in vitro and in vivo experiments. In this in vivo study, H2 (aq) and CH4 (aq) concentration measured directly in rumen fluid and their corresponding concentrations estimated from their gaseous phase concentrations, were compared to investigate the existence of equilibrium between the gas and liquid phases. Twenty-four Tibetan sheep were randomly assigned to two mixed diets containing the same concentrate mixed with oat grass (OG diet) or barley straw (BS diet). Rumen gaseous phase and contents were sampled using rumenocentesis and oral stomach tubing, respectively. Rumen H2 (aq) and CH4 (aq) concentration and VFA profile differed between sheep fed OG and BS diets. Measured H2 (aq) and CH4 (aq) concentration were greater than H2 (aq) and CH4 (aq) concentrations estimated using gas concentrations, indicating lack of equilibrium between gas and liquid phase and supersaturation of H2 and CH4 in rumen fluid. As a consequence, Gibbs energy changes (ΔG) estimated for various metabolic pathways were different when calculated using dissolved gases concentrations directly measured and when using dissolved gases concentrations assuming equilibrium with the gaseous phase. Dissolved CH4, but not CH4 (g), was positively correlated with H2 (aq). Both H2 (aq) and H2 (g) concentrations were positively correlated with the molar percentage of butyrate and negatively correlated with the molar percentage of acetate. In summary, rumen fluid was supersaturated with both H2 and CH4, and H2 (aq) was closely associated with the VFA profile and CH4 (aq) concentration. The assumption of equilibrium between dissolved gases and gaseous phase affected ΔG estimation. PMID:27379028

The Biogeochemistry of Seattle's Urban Streams

NASA Astrophysics Data System (ADS)

Yonemura, R.

2016-12-01

Urban development is underway at an unprecedented pace in the city of Seattle, WA. What were once productive salmon spawning ecosystems are now highly altered ecosystems that reflect the impacts of human land-use change. However, the impact that these changes have had on the carbon biogeochemistry have not been studied. We investigate the biogeochemical properties over time of two urban streams in Seattle; Ravenna Creek, an urban park and closed network, and Thornton Creek, a recently day-lighted and restored stream network. We conducted a longitudinal sampling along each of these creeks from their headwaters down to their confluences with Lake Washington. Our data suggest that these systems are supersaturated in both dissolved carbon dioxide and dissolved methane. Preliminary results reveal that carbon dioxide and methane are both highest at the end of Ravenna Creek located on the surface of a preexisting landfill. The highest carbon dioxide and methane levels on Thornton Creek are located at the uppermost site and the site directly below a golf course. These findings suggest that local land-use has an impact on the concentrations of dissolved gases in the surrounding water bodies with implications for urban streams as localized sources of carbon dioxide and methane to the atmosphere. Additional data on nutrients and stream metabolism will highlight the consistency of these gas concentrations over time, and provide an additional indicator into the health of these urban systems.

Dissolved methane in the residual basins of the Aral Sea

NASA Astrophysics Data System (ADS)

Izhitskaya, Elena; Zavialov, Peter; Egorov, Alexander

2017-04-01

The state of the Aral Sea has changed significantly since the second half of the 20th century. Due to the level decline the present-day sea consists of the several water bodies: the Large Aral Sea, the Small Aral Sea and Lake Tshchebas. Water balance peculiarities of each basin caused the differences in physical, chemical and biological structure of the ecosystem. Severe salinization of the Large Aral resulted in the increase of water stratification and formation of the anoxic conditions in the bottom layer. According to the field survey of 2002 [Zavialov et al., 2003; Friedrich, Oberhansli, 2004], hydrogen sulfide was detected in the bottom layer of the Large Aral Sea for the first time. Methane formation is the next reaction after sulfate reduction within process of sequential oxidation of organic matter [Break, 1974]. Thus, methane is an important indicator of biogeochemical processes in natural water environments. Besides due to high greenhouse activity of methane study of its emission to the atmosphere is essential for solution of climatological problems [Bazhin, 2000]. The presented study aims to the evaluation of methane dissolved in waters of the Aral region. Measurements of the gas concentration were carried out on surface and vertical profiles, as well as on point stations in 2012, 2013, 2015 and 2016 years in different parts of the sea. Water samples were analyzed by the head-space method with further gas chromatographic determination of methane concentration [Bolshakov, Egorov, 1987]. According to the obtained data, dissolved methane content in the surface waters of the residual basins of the Aral Sea ranges from 12 to 234 nM/l. One of the main results of the research is detection of intensive methane increase in the lower water layer of the Large Aral to 17014 nM/l in central part and to 147316 nM/l in the Chernyshev Bay.

Three-dimensional numerical simulations of methane gas migration from decommissioned hydrocarbon production wells into shallow aquifers

NASA Astrophysics Data System (ADS)

Roy, N.; Molson, J.; Lemieux, J.-M.; Van Stempvoort, D.; Nowamooz, A.

2016-07-01

Three-dimensional numerical simulations are used to provide insight into the behavior of methane as it migrates from a leaky decommissioned hydrocarbon well into a shallow aquifer. The conceptual model includes gas-phase migration from a leaky well, dissolution into groundwater, advective-dispersive transport and biodegradation of the dissolved methane plume. Gas-phase migration is simulated using the DuMux multiphase simulator, while transport and fate of the dissolved phase is simulated using the BIONAPL/3D reactive transport model. Methane behavior is simulated for two conceptual models: first in a shallow confined aquifer containing a decommissioned leaky well based on a monitored field site near Lindbergh, Alberta, Canada, and secondly on a representative unconfined aquifer based loosely on the Borden, Ontario, field site. The simulations show that the Lindbergh site confined aquifer data are generally consistent with a 2 year methane leak of 2-20 m3/d, assuming anaerobic (sulfate-reducing) methane oxidation and with maximum oxidation rates of 1 × 10-5 to 1 × 10-3 kg/m3/d. Under the highest oxidation rate, dissolved methane decreased from solubility (110 mg/L) to the threshold concentration of 10 mg/L within 5 years. In the unconfined case with the same leakage rate, including both aerobic and anaerobic methane oxidation, the methane plume was less extensive compared to the confined aquifer scenarios. Unconfined aquifers may therefore be less vulnerable to impacts from methane leaks along decommissioned wells. At other potential leakage sites, site-specific data on the natural background geochemistry would be necessary to make reliable predictions on the fate of methane in groundwater.

Methane hydrate-bearing seeps as a source of aged dissolved organic carbon to the oceans

USGS Publications Warehouse

Pohlman, John; Waite, William F.; Bauer, James E.; Osburn, Christopher L.; Chapman, N. Ross

2011-01-01

Marine sediments contain about 500–10,000 Gt of methane carbon1, 2, 3, primarily in gas hydrate. This reservoir is comparable in size to the amount of organic carbon in land biota, terrestrial soils, the atmosphere and sea water combined1, 4, but it releases relatively little methane to the ocean and atmosphere5. Sedimentary microbes convert most of the dissolved methane to carbon dioxide6, 7. Here we show that a significant additional product associated with microbial methane consumption is methane-derived dissolved organic carbon. We use Δ14C and δ13C measurements and isotopic mass-balance calculations to evaluate the contribution of methane-derived carbon to seawater dissolved organic carbon overlying gas hydrate-bearing seeps in the northeastern Pacific Ocean. We show that carbon derived from fossil methane accounts for up to 28% of the dissolved organic carbon. This methane-derived material is much older, and more depleted in 13C, than background dissolved organic carbon. We suggest that fossil methane-derived carbon may contribute significantly to the estimated 4,000–6,000 year age of dissolved organic carbon in the deep ocean8, and provide reduced organic matter and energy to deep-ocean microbial communities.

Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

PubMed

Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

2014-12-01

Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere. Copyright © 2014 Elsevier Ltd. All rights reserved.

Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

DOE PAGES

Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Walter Anthony, K.; ...

2015-08-04

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH 4 cycling.« less

Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

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

Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Walter Anthony, K.

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH 4 cycling.« less

Sources and migration pathways of natural gas in near-surface ground water beneath the Animas River valley, Colorado and New Mexico

USGS Publications Warehouse

Chafin, Daniel T.

1994-01-01

In July 1990, the U.S. Geological Survey began a study of the occurrence of natural gas in near-surface ground water in the Animas River valley in the San Juan Basin between Durango, Colorado, and Aztec, New Mexico. The general purpose of the study was to identify the sources and migration pathways of natural gas in nearsurface ground water in the study area. The purpose of this report is to present interpretive conclusions for the study, primarily based on data collected by the U.S. Geological Survey from August 1990 to May 1991.Seventy of the 205 (34 percent) groundwater samples collected during August-November 1990 had methane concentrations that exceeded the reporting limit of 0.005 milligram per liter. The maximum concentration was 39 milligrams per liter, and the mean concentration was 1.3 milligrams per liter. Samples from wells completed in bedrock have greater mean concentrations of methane than samples from wells completed in alluvium. Correlations indicate weak or nonexistent associations between dissolved-methane concentrations and concentrations of dissolved solids, major ions, bromide, silica, iron, manganese, and carbon dioxide. Dissolved methane was associated with hydrogen sulfide.Soil-gas-methane concentrations were measurable at few of 192 ground-water sites, even at sites at which ground water contained large concentrations of dissolved methane, which indicates that soil-gas surveys are not useful to delineate areas of gas-affected ground water. The reporting limit of 0.005 milligram per liter of gas was equaled or exceeded by 40 percent of soil-gas measurements adjacent to 352 gas-well casings. Concentrations of at least 100 milligrams per liter of gas were measured at 25 (7 percent) of the sites.Potential sources of gases in water, soil, gas-well surface casings, and cathodic-protection wells were determined on the basis of their isotopic and molecular compositions and available information about gas-well construction or leaks. Biogenic and thermogenic sources of gas exist in the near-surface environment of the study area. Biogenic gas is present locally in the near-surface Animas and Nacimiento formations, and biogenic gas has been detected in water wells completed in those rocks. Most gas probably is thermogenic gas from deep reservoirs, including the Dakota Sandstone, Mesaverde Group, Lewis Shale, Pictured Cliffs Sandstone, and coals in the Fruitland Formation. Less important sources include sandstones in the upper Fruitland Formation and the Kirtland Shale.Although migration of gas by diffusion or through natural fractures is possible, manmade conduits probably account for most of the upward migration of gas to the near-surface environment of the study area. Primary migration pathways largely consist of 1) leaking, conventional gas wells and 2) uncemented annuli of conventional gas wells along coals in the Fruitland Formation. Secondary migration pathways are gas-well annuli, cathodic-protection wells, seismic-test holes, and bedrock water wells.

Methane fluxes from tropical coastal lagoons surrounded bymangroves, Yucatán, Mexico

USGS Publications Warehouse

Chuang, Pei-Chuan; Young, Megan B.; Dale, Andrew W.; Miller, Laurence G.; Herrera-Silveira, Jorge A; Paytan, Adina

2017-01-01

Methane concentrations in the water column and emissions to the atmosphere were determined for three tropical coastal lagoons surrounded by mangrove forests on the Yucatán Peninsula, Mexico. Surface water dissolved methane was sampled at different seasons over a period of 2 years in areas representing a wide range of salinities and anthropogenic impacts. The highest surface water methane concentrations (up to 8378 nM) were measured in a polluted canal associated with Terminos Lagoon. In Chelem Lagoon, methane concentrations were typically lower, except in the polluted harbor area (1796 nM). In the relatively pristine Celestún Lagoon, surface water methane concentrations ranged from 41 to 2551 nM. Methane concentrations were negatively correlated with salinity in Celestún, while in Chelem and Terminos high methane concentrations were associated with areas of known pollution inputs, irrespective of salinity. The diffusive methane flux from surface lagoon water to the atmosphere ranged from 0.0023 to 15 mmol CH4 m−2 d−1. Flux chamber measurements revealed that direct methane release as ebullition was up to 3 orders of magnitude greater than measured diffusive flux. Coastal mangrove lagoons may therefore be an important natural source of methane to the atmosphere despite their relatively high salinity. Pollution inputs are likely to substantially enhance this flux. Additional statistically rigorous data collected globally are needed to better consider methane fluxes from mangrove-surrounded coastal areas in response to sea level changes and anthropogenic pollution in order to refine projections of future atmospheric methane budgets.

Methane fluxes from tropical coastal lagoons surrounded by mangroves, Yucatán, Mexico

NASA Astrophysics Data System (ADS)

Chuang, P.-C.; Young, M. B.; Dale, A. W.; Miller, L. G.; Herrera-Silveira, J. A.; Paytan, A.

2017-05-01

Methane concentrations in the water column and emissions to the atmosphere were determined for three tropical coastal lagoons surrounded by mangrove forests on the Yucatán Peninsula, Mexico. Surface water dissolved methane was sampled at different seasons over a period of 2 years in areas representing a wide range of salinities and anthropogenic impacts. The highest surface water methane concentrations (up to 8378 nM) were measured in a polluted canal associated with Terminos Lagoon. In Chelem Lagoon, methane concentrations were typically lower, except in the polluted harbor area (1796 nM). In the relatively pristine Celestún Lagoon, surface water methane concentrations ranged from 41 to 2551 nM. Methane concentrations were negatively correlated with salinity in Celestún, while in Chelem and Terminos high methane concentrations were associated with areas of known pollution inputs, irrespective of salinity. The diffusive methane flux from surface lagoon water to the atmosphere ranged from 0.0023 to 15 mmol CH4 m-2 d-1. Flux chamber measurements revealed that direct methane release as ebullition was up to 3 orders of magnitude greater than measured diffusive flux. Coastal mangrove lagoons may therefore be an important natural source of methane to the atmosphere despite their relatively high salinity. Pollution inputs are likely to substantially enhance this flux. Additional statistically rigorous data collected globally are needed to better consider methane fluxes from mangrove-surrounded coastal areas in response to sea level changes and anthropogenic pollution in order to refine projections of future atmospheric methane budgets.

40 CFR 63.457 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... volume of hydrocarbon in air); and (ii) A mixture of methane or n-hexane and air at a concentration of approximately, but less than, 10,000 parts per million by volume methane or n-hexane. (e) Negative pressure... between 6.95 and 7.05. (4) To prepare the 0.1 normality (N) sodium thiosulfate solution, dissolve 25 g of...

High-resolution passive sampling of dissolved methane in the water column of lakes in Greenland

NASA Astrophysics Data System (ADS)

Goldman, A. E.; Cadieux, S. B.; White, J. R.; Pratt, L. M.

2013-12-01

Arctic lakes are important participants in the global carbon cycle, releasing methane in a warming climate and contributing to a positive feedback to climate change. In order to yield detailed methane budgets and understand the implications of warming on methane dynamics, high-resolution profiles revealing methane behavior within the water column need to be obtained. Single day sampling using disruptive techniques has the potential to result in biases. In order to obtain high-resolution, undisturbed profiles of methane concentration and isotopic composition, this study evaluates a passive sampling method over a multi-day equilibration period. Selected for this study were two small lakes (<1km2) within a narrow valley stretching between Russells Glacier and Søndre Strømfjord in southwestern Greenland, which are part of an ongoing study of a series of seven lakes. Commercially available, 150 mL, polyethylene Passive Diffusion Bags (PDB's) were deployed in July 2013 for five days at 0.5-meter depth intervals. PDB samples were compared to samples collected with a submersible, electric pump taken immediately before PBD deployment. Preliminary CH4 concentrations and carbon isotopes for one lake were obtained in the field using a Los Gatos Research Methane Carbon Isotope Analyzer. PDB sampling and pump sampling resulted in statistically similar concentrations (R2=0.89), ranging from 0.85 to 135 uM from PDB and 0.74 to 143 uM from pump sampling. In anoxic waters of the lake, where concentrations were high enough to yield robust isotopic results on the LGR MCIA, δ13C were also similar between the two methods, yielding -73‰ from PDB and -74‰ from pump sampling. Further investigation will produce results for a second lake and methane carbon and hydrogen isotopic composition for both lakes. Preliminary results for this passive sampling method are promising. We envision the use of this technique in future studies of dissolved methane and expect that it will provide a more finely resolved vertical profile, allowing for a more complete understanding of lacustrine methane dynamics.

Enhanced methane emissions from oil and gas exploration areas to the atmosphere--the central Bohai Sea.

PubMed

Zhang, Yong; Zhao, Hua-de; Zhai, Wei-dong; Zang, Kun-peng; Wang, Ju-ying

2014-04-15

The distributions of dissolved methane in the central Bohai Sea were investigated in November 2011, May 2012, July 2012, and August 2012. Methane concentration in surface seawater, determined using an underway measurement system combined with wavelength-scanned cavity ring-down spectroscopy, showed marked spatiotemporal variations with saturation ratio from 107% to 1193%. The central Bohai Sea was thus a source of atmospheric methane during the survey periods. Several episodic oil and gas spill events increased surface methane concentration by up to 4.7 times and raised the local methane outgassing rate by up to 14.6 times. This study demonstrated a method to detect seafloor CH4 leakages at the sea surface, which may have applicability in many shallow sea areas with oil and gas exploration activities around the world. Copyright © 2014 Elsevier Ltd. All rights reserved.

Methane-oxidizing seawater microbial communities from an Arctic shelf

NASA Astrophysics Data System (ADS)

Uhlig, Christiane; Kirkpatrick, John B.; D'Hondt, Steven; Loose, Brice

2018-06-01

Marine microbial communities can consume dissolved methane before it can escape to the atmosphere and contribute to global warming. Seawater over the shallow Arctic shelf is characterized by excess methane compared to atmospheric equilibrium. This methane originates in sediment, permafrost, and hydrate. Particularly high concentrations are found beneath sea ice. We studied the structure and methane oxidation potential of the microbial communities from seawater collected close to Utqiagvik, Alaska, in April 2016. The in situ methane concentrations were 16.3 ± 7.2 nmol L-1, approximately 4.8 times oversaturated relative to atmospheric equilibrium. The group of methane-oxidizing bacteria (MOB) in the natural seawater and incubated seawater was > 97 % dominated by Methylococcales (γ-Proteobacteria). Incubations of seawater under a range of methane concentrations led to loss of diversity in the bacterial community. The abundance of MOB was low with maximal fractions of 2.5 % at 200 times elevated methane concentration, while sequence reads of non-MOB methylotrophs were 4 times more abundant than MOB in most incubations. The abundances of MOB as well as non-MOB methylotroph sequences correlated tightly with the rate constant (kox) for methane oxidation, indicating that non-MOB methylotrophs might be coupled to MOB and involved in community methane oxidation. In sea ice, where methane concentrations of 82 ± 35.8 nmol kg-1 were found, Methylobacterium (α-Proteobacteria) was the dominant MOB with a relative abundance of 80 %. Total MOB abundances were very low in sea ice, with maximal fractions found at the ice-snow interface (0.1 %), while non-MOB methylotrophs were present in abundances similar to natural seawater communities. The dissimilarities in MOB taxa, methane concentrations, and stable isotope ratios between the sea ice and water column point toward different methane dynamics in the two environments.

Innovations in Sampling Pore Fluids From Deep-Sea Hydrate Sites

NASA Astrophysics Data System (ADS)

Lapham, L. L.; Chanton, J. P.; Martens, C. S.; Schaefer, H.; Chapman, N. R.; Pohlman, J. W.

2003-12-01

We have developed a sea-floor probe capable of collecting and returning undecompressed pore water samples at in situ pressures for determination of dissolved gas concentrations and isotopic values in deep-sea sediments. In the summer of 2003, we tested this instrument in sediments containing gas hydrates off Vancouver Island, Cascadia Margin from ROPOS (a remotely operated vehicle) and in the Gulf of Mexico from Johnson-Sea-Link I (a manned submersible). Sediment push cores were collected alongside the probe to compare methane concentrations and stable carbon isotope compositions in decompressed samples vs. in situ samples obtained by probe. When sufficient gas was available, ethane and propane concentrations and isotopes were also compared. Preliminary data show maximum concentrations of dissolved methane to be 5mM at the Cascadia Margin Fish Boat site (850m water depth) and 12mM in the Gulf of Mexico Bush Hill hydrate site (550m water depth). Methane concentrations were, on average, five times as high in probe samples as in the cores. Carbon isotopic values show a thermogenic input and oxidative effects approaching the sediment-water interface at both sites. This novel data set will provide information that is critical to the understanding of the in situ processes and environmental conditions controlling gas hydrate occurrences in sediments.

Statistical Exposé of a Multiple-Compartment Anaerobic Reactor Treating Domestic Wastewater.

PubMed

Pfluger, Andrew R; Hahn, Martha J; Hering, Amanda S; Munakata-Marr, Junko; Figueroa, Linda

2018-06-01

  Mainstream anaerobic treatment of domestic wastewater is a promising energy-generating treatment strategy; however, such reactors operated in colder regions are not well characterized. Performance data from a pilot-scale, multiple-compartment anaerobic reactor taken over 786 days were subjected to comprehensive statistical analyses. Results suggest that chemical oxygen demand (COD) was a poor proxy for organics in anaerobic systems as oxygen demand from dissolved inorganic material, dissolved methane, and colloidal material influence dissolved and particulate COD measurements. Additionally, univariate and functional boxplots were useful in visualizing variability in contaminant concentrations and identifying statistical outliers. Further, significantly different dissolved organic removal and methane production was observed between operational years, suggesting that anaerobic reactor systems may not achieve steady-state performance within one year. Last, modeling multiple-compartment reactor systems will require data collected over at least two years to capture seasonal variations of the major anaerobic microbial functions occurring within each reactor compartment.

Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico

USGS Publications Warehouse

Pohlman, J.W.; Ruppel, C.; Hutchinson, D.R.; Downer, R.; Coffin, R.B.

2008-01-01

Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum ??13C dissolved inorganic carbon (DIC) values of -55.9??? to -64.8??? at the sulfate-methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the ??13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.

Enhancement of organic matter degradation and methane gas production of anaerobic granular sludge by degasification of dissolved hydrogen gas.

PubMed

Satoh, Hisashi; Bandara, Wasala M K R T W; Sasakawa, Manabu; Nakahara, Yoshihito; Takahashi, Masahiro; Okabe, Satoshi

2017-11-01

A hollow fiber degassing membrane (DM) was applied to enhance organic matter degradation and methane gas production of anaerobic granular sludge process by reducing the dissolved hydrogen gas (D-H 2 ) concentration in the liquid phase. DM was installed in the bench-scale anaerobic granular sludge reactors and D-H 2 was removed through DM using a vacuum pump. Degasification improved the organic matter degradation efficiency to 79% while the efficiency was 62% without degasification at 12,000mgL -1 of the influent T-COD concentration. Measurement of D-H 2 concentrations in the liquid phase confirmed that D-H 2 was removed by degasification. Furthermore, the effect of acetate concentrations on the organic matter degradation efficiency was investigated. At acetate concentrations above 3gL -1 , organic matter degradation deteriorated. Degasification enhanced the propionate and acetate degradation. These results suggest that degasification reduced D-H 2 concentration and volatile fatty acids concentrations, prevented pH drop, and subsequent enhanced organic matter degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Assessing Distribution and Origin of Methane in Shallow Groundwater in Horizontal Oil and Gas Play Areas, Eastern Kentucky

NASA Astrophysics Data System (ADS)

Zhu, J.; Parris, T. M.; Taylor, C. J.; Webb, S. E.; Davidson, B.; Smath, R.; Richardson, S. D.; Molofsky, L.; Kromann, J. S.

2016-12-01

Rapid implementation of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations across the country has increased public concern about possible impact on the environment, especially on shallow drinking-water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Upper Devonian Berea Sandstone in recent years. Although production in the Berea Sandstone is at a relatively small scale, the Rogersville Shale, a deeper, thicker, and more spatially extensive organic-rich shale, is projected to become a major shale play in eastern Kentucky. This has necessitated a better understanding of groundwater quality, especially the occurrence of dissolved methane, in aquifers overlying the Berea and Rogersville plays to help address the public's environmental concerns and protect groundwater resources. To assess baseline groundwater chemistry and evaluate distribution and origin of methane detected in the groundwater, 51 water wells in Greenup, Carter, Boyd, Lawrence, Johnson, and Elliott Counties were sampled and analyzed for major cations and anions, metals, and dissolved light hydrocarbon gases including methane. Twenty-six wells were identified as having methane concentrations greater than 1 mg/L and were further analyzed for carbon and hydrogen isotopes. The results indicate that methane is a relatively common constituent in shallow groundwater in eastern Kentucky. Correlation of methane distribution with water chemistry data shows that elevated methane concentrations were more common in sodium bicarbonate type water and in low-nitrate, low-sulfate redox conditions. Carbon and hydrogen isotope analysis suggests that the methane detected in groundwater is derived primarily from bacterial sources from the CO2 reduction pathway.

The effects of acid deposition on sulfate reduction and methane production in peatlands

NASA Technical Reports Server (NTRS)

Murray, Georgia L.; Hines, Mark E.; Bayley, Suzanne E.

1992-01-01

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Impact of anaerobic oxidation of methane on the geochemical cycle of redox-sensitive elements at cold-seep sites of the northern South China Sea

NASA Astrophysics Data System (ADS)

Hu, Yu; Feng, Dong; Liang, Qianyong; Xia, Zhen; Chen, Linying; Chen, Duofu

2015-12-01

Cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide. However, little is known about the impact of seeping fluids on the geochemical cycle of redox-sensitive elements. Pore waters from four gravity cores (D-8, D-5, D-7, and D-F) collected from cold-seep sites of the northern South China Sea were analyzed for SO42-, Mg2+, Ca2+, Sr2+, dissolved inorganic carbon (DIC), δ13CDIC, dissolved Fe, Mn, and trace elements (e.g. Mo, U). The sulfate concentration-depth profiles, δ13CDIC values and (ΔDIC+ΔCa2++ΔMg2+)/ΔSO42- ratios suggest that organoclastic sulfate reduction (OSR) is the dominant process in D-8 core. Besides OSR, anaerobic oxidation of methane (AOM) is partially responsible for depletion of sulfate at D-5 and D-7 cores. The sulfate consumption at D-F core is predominantly caused by AOM. The depth of sulfate-methane interface (SMI) and methane diffusive flux of D-F core are calculated to be ~7 m and 0.035 mol m-2 yr-1, respectively. The relatively shallow SMI and high methane flux at D-F core suggest the activity of gas seepage in this region. The concentrations of dissolved uranium (U) were inferred to decrease significantly within the iron reduction zone. It seems that AOM has limited influence on the U geochemical cycling. In contrast, a good correlation between the consumption of sulfate and the removal of molybdenum (Mo) suggests that AOM has a significantly influence on the geochemical cycle of Mo at cold seeps. Accordingly, cold seep environments may serve as an important potential sink in the marine geochemical cycle of Mo.

Mechanism of Methane Transport from the Rhizosphere to the Atmosphere through Rice Plants 1

PubMed Central

Nouchi, Isamu; Mariko, Shigeru; Aoki, Kazuyuki

1990-01-01

To clarify the mechanisms of methane transport from the rhizosphere into the atmosphere through rice plants (Oryza sativa L.), the methane emission rate was measured from a shoot whose roots had been kept in a culture solution with a high methane concentration or exposed to methane gas in the gas phase by using a cylindrical chamber. No clear correlation was observed between change in the transpiration rate and that in the methane emission rate. Methane was mostly released from the culm, which is an aggregation of leaf sheaths, but not from the leaf blade. Micropores which are different from stomata were newly found at the abaxial epidermis of the leaf sheath by scanning electron microscopy. The measured methane emission rate was much higher than the calculated methane emission rate that would result from transpiration and the methane concentration in the culture solution. Rice roots could absorb methane gas in the gas phase without water uptake. These results suggest that methane dissolved in the soil water surrounding the roots diffuses into the cell-wall water of the root cells, gasifies in the root cortex, and then is mostly released through the micropores in the leaf sheaths. Images Figure 7 PMID:16667719

Annual variability and regulation of methane and sulfate fluxes in Baltic Sea estuarine sediments

NASA Astrophysics Data System (ADS)

Sawicka, Joanna E.; Brüchert, Volker

2017-01-01

Marine methane emissions originate largely from near-shore coastal systems, but emission estimates are often not based on temporally well-resolved data or sufficient understanding of the variability of methane consumption and production processes in the underlying sediment. The objectives of our investigation were to explore the effects of seasonal temperature, changes in benthic oxygen concentration, and historical eutrophication on sediment methane concentrations and benthic fluxes at two type localities for open-water coastal versus eutrophic, estuarine sediment in the Baltic Sea. Benthic fluxes of methane and oxygen and sediment pore-water concentrations of dissolved sulfate, methane, and 35S-sulfate reduction rates were obtained over a 12-month period from April 2012 to April 2013. Benthic methane fluxes varied by factors of 5 and 12 at the offshore coastal site and the eutrophic estuarine station, respectively, ranging from 0.1 mmol m-2 d-1 in winter at an open coastal site to 2.6 mmol m-2 d-1 in late summer in the inner eutrophic estuary. Total oxygen uptake (TOU) and 35S-sulfate reduction rates (SRRs) correlated with methane fluxes showing low rates in the winter and high rates in the summer. The highest pore-water methane concentrations also varied by factors of 6 and 10 over the sampling period with the lowest values in the winter and highest values in late summer-early autumn. The highest pore-water methane concentrations were 5.7 mM a few centimeters below the sediment surface, but they never exceeded the in situ saturation concentration. Of the total sulfate reduction, 21-24 % was coupled to anaerobic methane oxidation, lowering methane concentrations below the sediment surface far below the saturation concentration. The data imply that bubble emission likely plays no or only a minor role in methane emissions in these sediments. The changes in pore-water methane concentrations over the observation period were too large to be explained by temporal changes in methane formation and methane oxidation rates due to temperature alone. Additional factors such as regional and local hydrostatic pressure changes and coastal submarine groundwater flow may also affect the vertical and lateral transport of methane.

Measuring Concentrations of Dissolved Methane and Ethane and the 13 C of Methane in Shale and Till.

PubMed

Hendry, M Jim; Barbour, S Lee; Schmeling, Erin E; Mundle, Scott O C

2017-01-01

Baseline characterization of concentrations and isotopic values of dissolved natural gases is needed to identify contamination caused by the leakage of fugitive gases from oil and gas activities. Methods to collect and analyze baseline concentration-depth profiles of dissolved CH 4 and C 2 H 6 and δ 13 C-CH 4 in shales and Quaternary clayey tills were assessed at two sites in the Williston Basin, Canada. Core and cuttings samples were stored in Isojars ® in a low O 2 headspace prior to analysis. Measurements and multiphase diffusion modeling show that the gas concentrations in core samples yield well-defined and reproducible depth profiles after 31-d equilibration. No measurable oxidative loss or production during core sample storage was observed. Concentrations from cuttings and mud gas logging (including IsoTubes ® ) were much lower than from cores, but correlated well. Simulations suggest the lower concentrations from cuttings can be attributed to drilling time, and therefore their use to define gas concentration profiles may have inherent limitations. Calculations based on mud gas logging show the method can provide estimates of core concentrations if operational parameters for the mud gas capture cylinder are quantified. The δ 13 C-CH 4 measured from mud gas, IsoTubes ® , cuttings, and core samples are consistent, exhibiting slight variations that should not alter the implications of the results in identifying the sources of the gases. This study shows core and mud gas techniques and, to a lesser extent, cuttings, can generate high-resolution depth profiles of dissolved hydrocarbon gas concentrations and their isotopes. © 2016, National Ground Water Association.

TRACE GAS CONCENTRATIONS IN SMALL STREAMS OF THE GEORGIA PIEDMONT

EPA Science Inventory

Seventeen headwater watersheds within the SFBR watershed ranging from 0.5 to 3.4 km2 were selected. We have been monitoring concentrations of the trace gases nitrous oxide, methane, and carbon dioxide, and other parameters (T, conductivity, dissolved oxygen, pH, nutrients, flow r...

Bedrock, Borehole, and Water-Quality Characterization of a Methane-Producing Water Well in Wolfeboro, New Hampshire

USGS Publications Warehouse

Degnan, James R.; Walsh, Gregory J.; Flanagan, Sarah M.; Burruss, Robert A.

2008-01-01

In August 2004, a commercial drill rig was destroyed by ignition of an explosive gas released during the drilling of a domestic well in granitic bedrock in Tyngsborough, MA. This accident prompted the Massachusetts Department of Environmental Protection (MassDEP) to sample the well water for dissolved methane - a possible explosive fuel. Water samples collected from the Tyngsborough domestic well in 2004 by the MassDEP contained low levels of methane gas (Pierce and others, 2007). When the U.S. Geological Survey (USGS) sampled this well in 2006, there was no measurable amount of methane remaining in the well water (Pierce and others, 2007). Other deep water wells in nearby south-central New Hampshire have been determined to have high concentrations of naturally occurring methane (David Wunsch, New Hampshire State Geologist, 2004, written commun.). Studying additional wells in New England crystalline bedrock aquifers that produce methane may help to understand the origin of methane in crystalline bedrock. Domestic well NH-WRW-37 was chosen for this study because it is a relatively deep well completed in crystalline bedrock, it is not affected by known anthropogenic sources of methane, and it had the highest known natural methane concentration (15.5 mg/L, U.S. Geological Survey, 2007) measured in a study described by Robinson and others (2004). This well has been in use since it was drilled in 1997, and it was originally selected for study in 2000 as part of a 30 well network, major-aquifer study by the USGS' New England Coastal Basins (NECB) study unit of the National Water-Quality Assessment (NAWQA) Program. Dissolved methane in drinking water is not considered an ingestion health hazard, although the occurrence in ground water is a concern because, as a gas, its buildup in confined spaces can cause asphyxiation, fire, or explosion hazards (Mathes and White, 2006). Methane occurrence in the fractured crystalline bedrock is not widely reported or well understood. Borehole-geophysical surveys, bedrock outcrop observations, and water-quality analyses were used to define the geologic and hydrologic characteristics of NH-WRW-37. Collection of additional information on the hydraulic and geologic characteristics of the fractured bedrock and on water quality was initiated in an attempt to understand the setting where methane gas occurs in the bedrock ground water. The origin of dissolved methane in this and other wells in New Hampshire is the subject of ongoing investigations by the State of New Hampshire, the New Hampshire Geological Survey and the USGS.

Measuring temporal variability in pore-fluid chemistry to assess gas hydrate stability: development of a continuous pore-fluid array.

PubMed

Lapham, Laura L; Chanton, Jeffrey P; Martens, Christopher S; Higley, Paul D; Jannasch, Hans W; Woolsey, J Robert

2008-10-01

A specialized pore-fluid array (PFA) sampler was designed to collect and store pore fluids to monitor temporal changes of ions and gases in gas hydrate bearing sediments. We tested the hypothesis that pore-fluid chemistry records hydrate formation or decomposition events and reflects local seismic activity. The PFA is a seafloor probe that consists of an interchangeable instrument package that houses OsmoSamplers, long-term pore-fluid samplers, a specialized low-dead volume fluid coupler, and eight sample ports along a 10 m sediment probe shaft. The PFA was deployed at Mississippi Canyon 118, a Gulf of Mexico hydrate site. A 170 day record was acquired from the overlying water and 1.3 m below seafloor (mbsf). Fluids were measured for dissolved chloride, sulfate, and methane concentrations and dissolved inorganic carbon and methane stable carbon and deuterium isotope ratios. Chloride and sulfate did not change significantly over time, suggesting the absence of gas hydrate formation or decomposition events. Over the temporal record, methane concentrations averaged 4 mM at 1.3 mbsf, and methane was thermogenic in origin (delta13C-CH4 = -32.4 +/- 3.4 per thousand). The timing of an anomalous 14 mM methane spike coincided with a nearby earthquake (Mw = 5.8), consistent with the hypothesis that pore-fluid chemistry reflects seismic events.

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing

PubMed Central

Osborn, Stephen G.; Vengosh, Avner; Warner, Nathaniel R.; Jackson, Robert B.

2011-01-01

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH4 L-1 (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L-1 (P < 0.05; n = 34). Average δ13C-CH4 values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ13C-CH4 data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ2H-CH4 values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and—possibly—regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use. PMID:21555547

Modeling the formation of methane hydrate-bearing intervals in fine-grained sediments

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

Malinverno, Alberto; Cook, Ann; Daigle, Hugh

Sediment grain size exerts a fundamental control on how methane hydrates are distributed within the pore space. Fine-grained muds are the predominant sediments in continental margins, and hydrates in these sediments have often been observed in semi-vertical veins and fractures. In several instances, these hydrate veins/fractures are found in discrete depth intervals a few tens meters thick within the gas hydrate stability zone (GHSZ) surrounded by hydrate-free sediments above and below. As they are not obviously connected with free gas occurring beneath the base of the GHSZ, these isolated hydrate-bearing intervals have been interpreted as formed by microbial methane generatedmore » in situ. To investigate further the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, solute diffusion, and microbial methane generation. The microbial methane generation term depends on the amount of metabolizable organic carbon deposited at the seafloor, which is degraded at a prescribed rate resulting in methane formation beneath the sulfate reduction zone. In the model, methane hydrate precipitates once the dissolved methane concentration is greater than solubility, or hydrate dissolves if concentration goes below solubility. If the deposition of organic carbon at the seafloor is kept constant in time, we found that the predicted amounts of hydrate formed in discrete intervals within the GHSZ are much less than those estimated from observations. We then investigated the effect of temporal variations in the deposition of organic carbon. If greater amounts of organic carbon are deposited during some time interval, methane generation is enhanced during burial in the corresponding sediment interval. With variations in organic carbon deposition that are consistent with observations in continental margin sediments, we were able to reproduce the methane hydrate contents estimated in discrete depth intervals. Our results support the suggestion that in situ microbial methane generation is the source for hydrates within fine-grained sediments.« less

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.

Occurrence of methane in groundwater of south-central New York State, 2012-systematic evaluation of a glaciated region by hydrogeologic setting

USGS Publications Warehouse

Heisig, Paul M.; Scott, Tia-Marie

2013-01-01

A survey of methane in groundwater was undertaken to document methane occurrence on the basis hydrogeologic setting within a glaciated 1,810-square-mile area of south-central New York along the Pennsylvania border. Sixty-six wells were sampled during the summer of 2012. All wells were at least 1 mile from any known gas well (active, exploratory, or abandoned). Results indicate strong positive and negative associations between hydrogeologic settings and methane occurrence. The hydrogeologic setting classes are based on topographic position (valley and upland), confinement or non-confinement of groundwater by glacial deposits, well completion in fractured bedrock or sand and gravel, and hydrogeologic subcategories. Only domestic wells and similar purposed supply wells with well-construction and log information were selected for classification. Field water-quality characteristics (pH, specific conductance, dissolved oxygen, and temperature) were measured at each well, and samples were collected and analyzed for dissolved gases, including methane and short-chain hydrocarbons. Carbon and hydrogen isotopic ratios of methane were measured in 21 samples that had at least 0.3 milligram per liter (mg/L) of methane. Results of sampling indicate that occurrence of methane in groundwater of the region is common—greater than or equal to 0.001 mg/L in 78 percent of the groundwater samples. Concentrations of methane ranged over five orders of magnitude. Methane concentrations at which monitoring or mitigation are indicated (greater than or equal to 10 mg/L) were measured in 15 percent of the samples. Methane concentrations greater than 0.1 mg/L were associated with specific hydrogeologic settings. Wells completed in bedrock within valleys and under confined groundwater conditions were most closely associated with the highest methane concentrations. Fifty-seven percent of valley wells had greater than or equal to 0.1 mg/L of methane, whereas only 10 percent of upland wells equaled or exceeded that concentration. Isotopic signatures differed between these groups as well. Methane in valley wells was predominantly thermogenic in origin, likely as a result of close vertical proximity to underlying methane-bearing saline groundwater and brine and possibly as a result of enhanced bedrock fracture permeability beneath valleys that provides an avenue for upward gas migration. Isotopic signatures of methane from four upland well samples indicated a microbial origin (carbon-dioxide reduction) with one sample possibly altered by microbial methane oxidation. Water samples from wells in a valley setting that indicate a mix of thermogenic and microbial methane reflect the close proximity of regional groundwater flow and underlying saline water and brine in valley areas. The microbial methane is likely produced by bacteria that utilize carbon dioxide or formational organic matter in highly reducing environments within the subregional groundwater flow system. This characterization of groundwater methane shows the importance of subsurface information (hydrogeology, well construction) in understanding methane occurrence and provides an initial conceptual framework that can be utilized in investigation of stray gas in south-central New York.

High resolution spatial and temporal evolution of dissolved gases in groundwater during a controlled natural gas release experiment.

PubMed

Cahill, Aaron G; Parker, Beth L; Mayer, Bernhard; Mayer, K Ulrich; Cherry, John A

2018-05-01

Fugitive gas comprised primarily of methane (CH 4 ) with traces of ethane and propane (collectively termed C 1-3 ) may negatively impact shallow groundwater when unintentionally released from oil and natural gas wells. Currently, knowledge of fugitive gas migration, subsurface source identification and oxidation potential in groundwater is limited. To advance understanding, a controlled release experiment was performed at the Borden Research Aquifer, Canada, whereby 51m 3 of natural gas was injected into an unconfined sand aquifer over 72days with dissolved gases monitored over 323days. During active gas injection, a dispersed plume of dissolved C 1-3 evolved in a depth discrete and spatially complex manner. Evolution of the dissolved gas plume was driven by free-phase gas migration controlled by small-scale sediment layering and anisotropy. Upon cessation of gas injection, C 1-3 concentrations increased to the greatest levels observed, particularly at 2 and 6m depths, reaching up to 31.5, 1.5 and 0.1mg/L respectively before stabilizing and persisting. At no time did groundwater become fully saturated with natural gas at the scale of sampling undertaken. Throughout the experiment the isotopic composition of injected methane (δ 13 C of -42.2‰) and the wetness parameter (i.e. the ratio of C 1 to C 2+ ) constituted excellent tracers for the presence of fugitive gas at concentrations >2mg/L. At discrete times C 1-3 concentrations varied by up to 4 orders of magnitude over 8m of aquifer thickness (e.g. from <0.01 to 30mg/L for CH 4 ), while some groundwater samples lacked evidence of fugitive gas, despite being within 10m of the injection zone. Meanwhile, carbon isotope ratios of dissolved CH 4 showed no evidence of oxidation. Our results show that while impacts to aquifers from a fugitive gas event are readily detectable at discrete depths, they are spatially and temporally variable and dissolved methane has propensity to persist. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

PubMed

Lomond, Jasmine S; Tong, Anthony Z

2011-01-01

Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

Effect of cobalt supplementation and fractionation on the biological response in the biomethanization of Olive Mill Solid Waste.

PubMed

Pinto-Ibieta, F; Serrano, A; Jeison, D; Borja, R; Fermoso, F G

2016-07-01

Due to the low trace metals concentration in the Olive Mill Solid Waste (OMSW), a proposed strategy to improve its biomethanization is the supplementation of key metals to enhance the microorganism activity. Among essential trace metals, cobalt has been reported to have a crucial role in anaerobic degradation. This study evaluates the effect of cobalt supplementation to OMSW, focusing on the connection between fractionation of cobalt in the system and the biological response. The highest biological responses was found in a range from 0.018 to 0.035mg/L of dissolved cobalt (0.24-0.65mg total cobalt/L), reaching improvements up to 23% and 30% in the methane production rate and the methane yield coefficient, respectively. It was found that the dissolved cobalt fraction is more accurately related with the biological response than the total cobalt. The total cobalt is distorted by the contribution of dissolved and non-dissolved inert fractions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Root-Associated Methane Oxidation and Methanogenesis: Key Determinants of Wetland Methane Emissions

NASA Technical Reports Server (NTRS)

King, G. M.

1997-01-01

During the award period, we have assessed the extent and controls of methane oxidation in north temperate wetlands. It is evident that wetlands have been a major global source of atmospheric methane in the past, and are so at present. It is also evident that microbial methane oxidation consumes a variable fraction of total wetland methane production, perhaps 10%-90%. Methane oxidation is thus a potentially important control of wetland methane emission. Our efforts have been designed to determine the extent of the process, its controls, and possible relationships to changes that might be expected in wetlands as a consequence of anthropogenic or climate-related disturbances. Current work, has emphasized controls of methane oxidation associated with rooted aquatic plants. As for the sediment-water interface, we have observed that oxygen availability is a primary limiting factor. Our conclusion is based on several different lines of evidence obtained from in vitro and in situ analyses. First, we have measured the kinetics of methane oxidation by intact plant roots harboring methane-oxidizing bacteria, as well as the kinetics of the methanotrophs themselves. Values for the half-saturation constant (apparent K(sub m)) are approximately 5 microns. These values are roughly equivalent to, or much less than porewater methane concentrations, indicating that uptake is likely saturated with respect to methane, and that some other parameter must limit activity. Methane concentrations in the lacunar spaces at the base of plant stems are also comparable to the half-saturation constants (when expressed as equivalent dissolved concentrations), providing further support for limitation of uptake by parameters other than methane.

A laboratory study of anaerobic oxidation of methane in the presence of methane hydrate

NASA Astrophysics Data System (ADS)

Solem, R.; Bartlett, D.; Kastner, M.; Valentine, D.

2003-12-01

In order to mimic and study the process of anaerobic methane oxidation in methane hydrate regions we developed four high-pressure anaerobic bioreactors, designed to incubate environmental sediment samples, and enrich for populations of microbes associated with anaerobic methane oxidation (AMO). We obtained sediment inocula from a bacterial mat at the southern Hydrate Ridge, Cascadia, having cell counts approaching 1010 cells/cc. Ultimately, our goal is to produce an enriched culture of these microbes for characterization of the biochemical processes and chemical fluxes involved, as well as the unique adaptations required for, AMO. Molecular phylogenetic information along with results from fluorescent in situ hybridization indicate that consortia of Archaea and Bacteria are present which are related to those previously described for marine sediment AMO environments. Using a medium of enriched seawater and sediment in a 3:1 ratio, the system was incubated at 4° C under 43 atm of methane pressure; the temperature and pressure were kept constant. We have followed the reactions for seven months, particularly the vigorous consumption rates of dissolved sulfate and alkalinity production, as well as increases in HS-, and decreases in Ca concentrations. We also monitored the dissolved inorganic C (DIC) δ 13C values. The data were reproduced, and indicated that the process is extremely sensitive to changes in methane pressure. The rates of decrease in sulfate and increase in alkalinity concentrations were complimentary and showed considerable linearity with time. When the pressure in the reactor was decreased below the methane hydrate stability field, following the methane hydrate dissociation, sulfate reduction abruptly decreased. When the pressure was restored all the reactions returned to their previous rates. Much of the methane oxidation activity in the reactor is believed to occur in association with the methane hydrate. Upon the completion of one of the experiments, the chamber methane hydrate, liquid phase, and sediment were separated. FISH analyses of the dissociated hydrate fluid indicate a significant presence of Archaea in or on the hydrate. The cell densities in the bioreactor medium liquid phase were 7.2 x 107 cells/cc, and with the methane hydrate, 2.8 x 108 cells/cc.

Spatial variations of community structures and methane cycling across a transect of Lei-Gong-Hou mud volcanoes in eastern Taiwan.

PubMed

Wang, Pei-Ling; Chiu, Yi-Ping; Cheng, Ting-Wen; Chang, Yung-Hsin; Tu, Wei-Xain; Lin, Li-Hung

2014-01-01

This study analyzed cored sediments retrieved from sites distributed across a transect of the Lei-Gong-Hou mud volcanoes in eastern Taiwan to uncover the spatial distributions of biogeochemical processes and community assemblages involved in methane cycling. The profiles of methane concentration and carbon isotopic composition revealed various orders of the predominance of specific methane-related metabolisms along depth. At a site proximal to the bubbling pool, the methanogenic zone was sandwiched by the anaerobic methanotrophic zones. For two sites distributed toward the topographic depression, the methanogenic zone overlaid the anaerobic methanotrophic zone. The predominance of anaerobic methanotrophy at specific depth intervals is supported by the enhanced copy numbers of the ANME-2a 16S rRNA gene and coincides with high dissolved Fe/Mn concentrations and copy numbers of the Desulfuromonas/Pelobacter 16S rRNA gene. Assemblages of 16S rRNA and mcrA genes revealed that methanogenesis was mediated by Methanococcoides and Methanosarcina. pmoA genes and a few 16S rRNA genes related to aerobic methanotrophs were detected in limited numbers of subsurface samples. While dissolved Fe/Mn signifies the presence of anaerobic metabolisms near the surface, the correlations between geochemical characteristics and gene abundances, and the absence of aerobic methanotrophs in top sediments suggest that anaerobic methanotrophy is potentially dependent on iron/manganese reduction and dominates over aerobic methanotrophy for the removal of methane produced in situ or from a deep source. Near-surface methanogenesis contributes to the methane emissions from mud platform. The alternating arrangements of methanogenic and methanotrophic zones at different sites suggest that the interactions between mud deposition, evaporation, oxidation and fluid transport modulate the assemblages of microbial communities and methane cycling in different compartments of terrestrial mud volcanoes.

Development of a pre-concentration system and auto-analyzer for dissolved methane, ethane, propane, and butane concentration measurements with a GC-FID

NASA Astrophysics Data System (ADS)

Chepigin, A.; Leonte, M.; Colombo, F.; Kessler, J. D.

2014-12-01

Dissolved methane, ethane, propane, and butane concentrations in natural waters are traditionally measured using a headspace equilibration technique and gas chromatograph with flame ionization detector (GC-FID). While a relatively simple technique, headspace equilibration suffers from slow equilibration times and loss of sensitivity due to concentration dilution with the pure gas headspace. Here we present a newly developed pre-concentration system and auto-analyzer for use with a GC-FID. This system decreases the time required for each analysis by eliminating the headspace equilibration time, increases the sensitivity and precision with a rapid pre-concentration step, and minimized operator time with an autoanalyzer. In this method, samples are collected from Niskin bottles in newly developed 1 L plastic sample bags rather than glass vials. Immediately following sample collection, the sample bags are placed in an incubator and individually connected to a multiport sampling valve. Water is pumped automatically from the desired sample bag through a small (6.5 mL) Liqui-Cel® membrane contactor where the dissolved gas is vacuum extracted and directly flushed into the GC sample loop. The gases of interest are preferentially extracted with the Liqui-Cel and thus a natural pre-concentration effect is obtained. Daily method calibration is achieved in the field with a five-point calibration curve that is created by analyzing gas standard-spiked water stored in 5 L gas-impermeable bags. Our system has been shown to substantially pre-concentrate the dissolved gases of interest and produce a highly linear response of peak areas to dissolved gas concentration. The system retains the high accuracy, precision, and wide range of measurable concentrations of the headspace equilibration method while simultaneously increasing the sensitivity due to the pre-concentration step. The time and labor involved in the headspace equilibration method is eliminated and replaced with the immediate and automatic analysis of a maximum of 13 sequential samples. The elapsed time between sample collection and analysis is reduced from approximately 12 hrs to < 10 min, enabling dynamic and highly resolved sampling plans.

Dissolved methane in the Beaufort Sea and the Arctic Ocean, 1992-2009; sources and atmospheric flux

USGS Publications Warehouse

Lorenson, Thomas D.; Greinert, Jens; Coffin, Richard B.

2016-01-01

Methane concentration and isotopic composition was measured in ice-covered and ice-free waters of the Arctic Ocean during eleven surveys spanning the years of 1992-1995 and 2009. During ice-free periods, methane flux from the Beaufort shelf varies from 0.14 to 0.43 mg CH4 m-2 day-1. Maximum fluxes from localized areas of high methane concentration are up to 1.52 mg CH4 m-2 day-1. Seasonal buildup of methane under ice can produce short-term fluxes of methane from the Beaufort shelf that varies from 0.28 to 1.01 to mg CH4 m-2 day-1. Scaled-up estimates of minimum methane flux from the Beaufort Sea and pan-Arctic shelf for both ice-free and ice-covered periods range from 0.02 Tg CH4 yr-1 and 0.30 Tg CH4 yr-1 respectively to maximum fluxes of 0.18 Tg CH4 yr-1 and 2.2 Tg CH4 yr-1 respectively. A methane flux of 0.36 Tg CH4 yr-1from the deep Arctic Ocean was estimated using data from 1993-94. The flux can be as much as 2.35 Tg CH4 yr-1 estimated from maximum methane concentrations and wind speeds of 12 m/s, representing only 0.42% of the annual atmospheric methane budget of ~560 Tg CH4 yr-1. There were no significant changes in methane fluxes during the time period of this study. Microbial methane sources predominate with minor influxes from thermogenic methane offshore Prudhoe Bay and the Mackenzie River delta and may include methane from gas hydrate. Methane oxidation is locally important on the shelf and is a methane sink in the deep Arctic Ocean.

Estimation of methane concentrations and loads in groundwater discharge to Sugar Run, Lycoming County, Pennsylvania

USGS Publications Warehouse

Heilweil, Victor M.; Risser, Dennis W.; Conger, Randall W.; Grieve, Paul L.; Hynek, Scott A.

2014-01-01

A stream-sampling study was conducted to estimate methane concentrations and loads in groundwater discharge to a small stream in an active shale-gas development area of northeastern Pennsylvania. Grab samples collected from 15 streams in Bradford, Lycoming, Susquehanna, and Tioga Counties, Pa., during a reconnaissance survey in May and June 2013 contained dissolved methane concentrations ranging from less than the minimum reporting limit (1.0) to 68.5 micrograms per liter (µg/L). The stream-reach mass-balance method of estimating concentrations and loads of methane in groundwater discharge was applied to a 4-kilometer (km) reach of Sugar Run in Lycoming County, one of the four streams with methane concentrations greater than or equal to 5 µg/L. Three synoptic surveys of stream discharge and methane concentrations were conducted during base-flow periods in May, June, and November 2013. Stream discharge at the lower end of the reach was about 0.10, 0.04, and 0.02 cubic meters per second, respectively, and peak stream methane concentrations were about 20, 67, and 29 µg/L. In order to refine estimated amounts of groundwater discharge and locations where groundwater with methane discharges to the stream, the lower part of the study reach was targeted more precisely during the successive studies, with approximate spacing between stream sampling sites of 800 meters (m), 400 m, and 200 m, in May, June, and November, respectively. Samples collected from shallow piezometers and a seep near the location of the peak methane concentration measured in streamwater had groundwater methane concentrations of 2,300 to 4,600 µg/L. These field data, combined with one-dimensional stream-methane transport modeling, indicate groundwater methane loads of 1.8 ±0.8, 0.7 ±0.3, and 0.7 ±0.2 kilograms per day, respectively, discharging to Sugar Run. Estimated groundwater methane concentrations, based on the transport modeling, ranged from 100 to 3,200 µg/L. Although total methane load and the uncertainty in calculated loads both decreased with lower streamflow conditions and finer-resolution sampling in June and November, the higher loads during May could indicate seasonal variability in base flow. This is consistent with flowmeter measurements indicating that there was less inflow occurring at lower streamflow conditions during June and November.

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.

Investigating the emission, dissolution, and oxidation of CH4 within and around a seep bubble plume in the Gulf of Mexico.

NASA Astrophysics Data System (ADS)

Leonte, M.; Kessler, J. D.; Socolofsky, S. A.

2016-02-01

One of the largest carbon reservoirs on the planet is stored as methane (CH4) in and below the seafloor. However, a large discrepancy exists between estimated fluxes of CH4 into the water column and CH4 fluxes from the sea surface to the atmosphere, suggesting that a significant fraction of CH4 released from seafloor seeps is dissolved and potentially removed through microbial oxidation. Here we present data investigating the fate of CH4 released from the Sleeping Dragon seep site in the Gulf of Mexico. The bubble plume was followed from the seafloor until it fully dissolved using a remotely operated vehicle (ROV). Water samples were collected by the ROV at different depths as well as lateral transects through the bubble plume. These samples were analyzed for dissolved concentrations of methane, ethane, propane, and butane as well as the 13C isotopic ratio of methane. Furthermore, seep bubbles from the seafloor were also collected and analyzed for the same properties. Based on these chemical data, the rate of CH4 emission from the seafloor, oxidation in the water column, and dissolution are investigated.

Methane and hydrogen sulfide emissions in UASB reactors treating domestic wastewater.

PubMed

Souza, C L; Chernicharo, C A L; Melo, G C B

2012-01-01

The release of CH(4) and H(2)S in UASB reactors was evaluated with the aim to quantify the emissions from the liquid surfaces (three-phase separator and settler compartment) and also from the reactor's discharge hydraulic structures. The studies were carried out in two pilot- (360 L) and one demo-scale (14 m(3)) UASB reactors treating domestic wastewater. As expected, the release rates were much higher across the gas/liquid interfaces of the three-phase separators (5.4-9.7 kg CH(4) m(-2) d(-1) and 23.0-35.8 g S m(-2) d(-1)) as compared with the quiescent settler surfaces (11.0-17.8 g CH(4) m(-2) d(-1) and 0.21 to 0.37 g S m(-2) d(-1)). The decrease of dissolved methane and dissolved hydrogen sulfide was very large in the discharging hydraulic structures very close to the reactor (>60 and >80%, respectively), largely due to the loss to the atmosphere, indicating that the concentration of these compounds will probably fall to values close to zero in the near downstream structures. The emission factors due to the release of dissolved methane in the discharge structure amounted to around 0.040 g CH(4) g COD(infl)(-1) and 0.060 g CH(4) g COD(rem)(-1), representing around 60% of the methane collected in the three-phase separator.

Controls of Methane Dynamics and Emissions in an Arctic Warming Experiment

NASA Astrophysics Data System (ADS)

Nielsen, C. S.; Elberling, B.; Michelsen, A.; Strobel, B. W.; Wulff, K.; Banyasz, I.

2015-12-01

Climatic changes have resulted in increasing air temperatures across the Arctic. This may increase anaerobic decomposition of soil organic matter to methane (CH4) in wetlands and increase plant growth and thereby production of substrate. Little is known about how seasonal variations in dissolved CH4 in soil water, substrate availability, and the effect of warming affect arctic wetland dynamics of CH4 production and emission. In 2013 we established two experiments in a fen at Disko Island, W Greenland; one with year round warming by open-top chambers and removal of shrubs, and one with removal of the aerenchymatous sedge Carex aquatilis ssp. stans. Throughout the growing season 2014 we measured how the treatments affected CH4 emissions, dissolved CH4 in the soil water, and substrate availability. Ecosystem CH4 emissions peaked at August 5th 2014 (7.5 μmol m-2 h-1) without coinciding with time of highest concentrations of dissolved CH4 or acetate indicating a decoupling between production and emission of CH4. The peak in dissolved CH4 concentration, at ten cm depth (1368 ppm, September 18th 2014), followed the peak in concentration of acetate in the same depth (0.30 ppm, August 30th 2014) highlighting the importance of this substance as a substrate for methanogenesis. C. aquatilis ssp. stans accounted for 60% and 77% of the ecosystem CH4 emissions in areas of the fen with water table above and below soil surface showing the importance of the presence of this species to serve as a pipe for CH4 emission which is bypassing the upper soil zone and potential methane oxidation. Throughout the season, warming increased the air temperature at soil surface by on average 0.89°C and occasionally warming and shrub removal increased soil temperature in 2 and 5 cm depth, but there was no effect of the treatments on the CH4 emissions indicating that this wetland is quite resilient towards future climate change.

Illuminating Geochemical Controls of Methane Oxidation Along a Gradient of Permafrost Thaw

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N.; McCalley, C. K.; Malhotra, A.; Giesler, R.; Varner, R.

2017-12-01

Increases in annual mean temperature in the subarctic have accelerated the thaw of organic-rich permafrost peatlands, exacerbating methane (CH4) production from microbial decomposition of peat deposits and subsequent CH4 emissions. Methanotrophic bacteria may oxidize/consume upwards of 90% of produced CH4 in some settings, pending substrate availability and environmental conditions. Redox chemistry may also control the rate of CH4 oxidation in thawing permafrost areas, particularly redox potential (Eh) and the availability of oxygen (O2) and other terminal electron receptors. We investigated potential CH4 oxidation rates across a permafrost thaw gradient in Stordalen Mire (68°21'N,18°49'E) near Abisko, Sweden. Methane oxidation rates for sites from thawing and collapsed palsa, semi-wet Sphagnum, and open-water sedge sites were determined through laboratory incubations. Peat cores were extracted from two depths at each site and incubated at in situ temperatures and CH4 concentrations. Headspace samples were collected over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Dissolved O2, Eh, and dissolved CH4 were measured in sites with porewater. Oxidation rates ranged from <0.1 to 19 μg of CH4 per gram of dry biomass per day. Eh remained positive (41.6 to 316.8 mV) with available dissolved O2 (0.3 - 5.2 mg/L) in all measurement locations down to 20cm, indicating in situ aerobic CH4 oxidation is viable across these environments. Potential CH4 oxidation rates increased with increasing dissolved CH4 concentration. Highest potential CH4 oxidation rates were found in open-water sedge sites. Eh and dissolved O2 were lowest at these sites, suggesting that methanotrophs with low-O2 demand may populate sedge areas. Furthermore, potential CH4 oxidation rates were higher at depth than at the surface in thawing palsa, suggesting CH4 oxidation may mitigate CH4 production triggered by warming in these actively thawing environments. Forthcoming elemental analyses of peat and pore water will further elucidate trends and geochemical controls of CH4 oxidation rates in thawing permafrost areas.

Quantifying the Movement and Dissolution of Fugitive Methane in Shallow Aquifers: Visualization Experiments

NASA Astrophysics Data System (ADS)

Van De Ven, C. J. C.; Mumford, K. G.

2016-12-01

The environmental impact and potential human health implications, specifically from the contamination of groundwater sources, has sparked controversy around shale gas extraction in North America. It is clear that understanding the effects of hydraulic fracturing on shallow fresh water aquifers is of great importance, including the threat of stray gas (also referred to as fugitive methane) on groundwater quality. Faulty wells provide a preferential pathway for free gas phase (mostly methane) to migrate from deeper gas-bearing formations of natural gas to shallow aquifers, followed by its dissolution into the surrounding groundwater. An increased understanding of the fate of fugitive methane in shallow aquifers is required to assess the potential risks associated with current and future operations, as well as to better link gas migration, dissolution and the deterioration of groundwater quality. In this study, a series of laboratory experiments were performed using carbon dioxide (CO2) gas as a surrogate for methane to improve our understanding of gas dissolution in groundwater systems. Using CO2, a novel laboratory technique was developed that allows the measurement of dissolved CO2 concentrations using image analysis alongside visualization of free gas mobilization. The technique is based on the acidification of water during CO2 dissolution, which causes a colour change in an indicator dye. The colour change is recorded using a visual light transmission technique, in which digital images are used to track dissolved concentrations at high spatial (1 mm) and temporal (5 s) resolutions in a two-dimensional (25 × 25 × 1 cm3) flow cell. The experiments were completed in both homogeneous sand packs and sand packs containing layered heterogeneities to investigate the dissolution of both gas fingers and gas pools. The results demonstrate the potential of this novel technique for investigating gas dissolution, and showed significant tailing of dissolved CO2 and persistence of other gas phase components. This technique will aid in the development of conceptual models to link fugitive methane to groundwater contamination and provide detailed data required for the validation of numerical models that account for gas-water mass transfer; both of which are required for the development of sound monitoring techniques.

Impact of methane flow through deformable lake sediments on atmospheric release

NASA Astrophysics Data System (ADS)

Scandella, B.; Juanes, R.

2010-12-01

Methane is a potent greenhouse gas that is generated geothermally and biologically in lake and ocean sediments. Free gas bubbles may escape oxidative traps and contribute more to the atmospheric source than dissolved methane, but the details of the methane release depend on the interactions between the multiple fluid phases and the deformable porous medium. We present a model and supporting laboratory experiments of methane release through “breathing” dynamic flow conduits that open in response to drops in the hydrostatic load on lake sediments, which has been validated against a high-resolution record of free gas flux and hydrostatic pressure in Upper Mystic Lake, MA. In contrast to previous linear elastic fracture mechanics analysis of gassy sediments, the evolution of gas transport in a deformable compliant sediment is presented within the framework of multiphase poroplasticity. Experiments address how strongly the mode and rate of gas flow, captured by our model, impacts the size of bubbles released into the water column. A bubble's size in turn determines how efficiently it transports methane to the atmosphere, and integrating this effect will be critical to improving estimates of the atmospheric methane source from lakes. Cross-sectional schematic of lake sediments showing two venting sites: one open at left and one closed at right. The vertical release of gas bubbles (red) at the open venting site creates a local pressure drop, which drives both bubble formation from the methane-rich pore water (higher concentrations shaded darker red) and lateral advection of dissolved methane (purple arrows). Even as bubbles in the open site escape, those at the closed site remain trapped.

ORGANIC WASTE CONTAMINATION INDICATORS IN SMALL GEORGIA PIEDMONT STREAMS

EPA Science Inventory

We monitored concentrations of nitrous oxide, methane, carbon dioxide, nutrients and other parameters (T, conductivity, dissolved oxygen, alkalinity, pH, DOC, DON, flow rate) in 17 headwater streams (watershed sizes from 0.5 to 3.4 kilometers) of the South Fork Broad River waters...

Rapid, Real-time Methane Detection in Ground Water Using a New Gas-Water Equilibrator Design

NASA Astrophysics Data System (ADS)

Ruybal, C. J.; DiGiulio, D. C.; Wilkin, R. T.; Hargrove, K. D.; McCray, J. E.

2014-12-01

Recent increases in unconventional gas development have been accompanied by public concern for methane contamination in drinking water wells near production areas. Although not a regulated pollutant, methane may be a marker contaminant for others that are less mobile in groundwater and thus may be detected later, or at a location closer to the source. In addition, methane poses an explosion hazard if exsolved concentrations reach 5 - 15% volume in air. Methods for determining dissolved gases, such as methane, have evolved over 60 years. However, the response time of these methods is insufficient to monitor trends in methane concentration in real-time. To enable rapid, real-time monitoring of aqueous methane concentrations during ground water purging, a new gas-water equilibrator (GWE) was designed that increases gas-water mass exchange rates of methane for measurement. Monitoring of concentration trends allows a comparison of temporal trends between sampling events and comparison of baseline conditions with potential post-impact conditions. These trends may be a result of removal of stored casing water, pre-purge ambient borehole flow, formation physical and chemical heterogeneity, or flow outside of well casing due to inadequate seals. Real-time information in the field can help focus an investigation, aid in determining when to collect a sample, save money by limiting costs (e.g. analytical, sample transport and storage), and provide an immediate assessment of local methane concentrations. Four domestic water wells, one municipal water well, and one agricultural water well were sampled for traditional laboratory analysis and compared to the field GWE results. Aqueous concentrations measured on the GWE ranged from non-detect to 1,470 μg/L methane. Some trends in aqueous methane concentrations measured on the GWE were observed during purging. Applying a paired t-test comparing the new GWE method and traditional laboratory analysis yielded a p-value 0.383, suggesting no significant difference between the two methods for the current study. Additional field and laboratory experimentation are necessary to justify use beyond screening. However, early GWE use suggests promising results and applications.

Oceanographic Setting Dominates Methane Transport Through the Water Column in the Shallow Area West of Prins Karls Forland, Arctic Ocean

NASA Astrophysics Data System (ADS)

Silyakova, A.; Jansson, P.; Serov, P.; Graves, C. A.; Niemann, H.; Grundger, F.; Ferre, B.; Mienert, J.

2016-02-01

The area west of Prins Karls Forland (PKF, West Spitsbergen) in the Arctic Ocean, restricted to 90 m water depth, is known for a large amount of shallow active gas flares. Gas flares are streams of bubbles that contain mostly methane, which is a potent greenhouse gas. The important questions for many areas with discovered gas flares are: Does this gas reach the atmosphere? What controls the vertical and horizontal distribution of dissolved methane away from the source on the seafloor? Is all dissolved methane detected above gas flares released from those flares or does it partially originate from other areas (eg. Storfjorden, or area of deeper flares on the PKF slope)? The present study is based on two repeated oceanographic surveys conducted in the summers of 2014 and 2015. During the surveys, we sampled 64 CTD stations in a grid above a 30 x 15 km area with active methane flares. Vertical profiles of temperature (T) and salinity (S), as well as TS diagrams indicate very different oceanographic settings during the two surveys. Warm and saline Atlantic waters originating from the West Spitsbergen Current prevailed during the 2014 campaign. In 2015, in contrast, waters were distinctly less saline and cooler. These waters originate from the East-Spitsbergen current that flows northwards over the shelf from the Barents Sea around the southern tip of Spitsbergen. The water mass was furthermore influenced by local sources from the fjords. In both years, we observed strong vertical gradients in the distribution of dissolved methane in the water column above gas flares, with only 4% methane concentrations at the sea surface when compared to bottom waters. However, the circulation of the dominant water masses mainly controlled the horizontal distribution of methane in the water column in the specific year. We discuss oceanographic processes and mechanisms responsible for methane transport and transformation in the study area. This study is funded by CAGE (Centre for Arctic Gas Hydrate, Environment and Climate), Norwegian Research Council grant no. 223259.

Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor

PubMed Central

Chen, Xueming; Liu, Yiwen; Peng, Lai; Yuan, Zhiguo; Ni, Bing-Jie

2016-01-01

In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously. PMID:27112502

Microbial processes in the Kanda Bay, a meromictic water body artifically separated from the White Sea.

PubMed

Savvichev, A S; Demidenko, N A; Krasnova, E D; Kalmatskaya, O V; Kharcheva, A N; Ivanov, M V

2017-05-01

Sings of meromixis are found by means of microbiological and biogeochemical investigations in the southernn part of the Kanda Bay, an artificial water body separated front the White Sea with a railway dam. The concentration of oxygen in the bottom layer attained 1.9 mmol/L, intensity of the process of microbial sulfate reduction, 3.0 μmol of sulfur/(L day). The concentration of dissolved methane, 3.7 μmol/L. Isotopic composition of carbon in methane (δ 13 C (CH 4 ) =-79.2‰) indicates to its microbial genesis. At present, Kanda Bay is a sole in Russia man-made marine water body for which there are data on the rate of microbial processes responsible for formation of bottom water layer containing hydrogen sulfide and methane.

Spatial variations of community structures and methane cycling across a transect of Lei-Gong-Hou mud volcanoes in eastern Taiwan

PubMed Central

Wang, Pei-Ling; Chiu, Yi-Ping; Cheng, Ting-Wen; Chang, Yung-Hsin; Tu, Wei-Xain; Lin, Li-Hung

2014-01-01

This study analyzed cored sediments retrieved from sites distributed across a transect of the Lei-Gong-Hou mud volcanoes in eastern Taiwan to uncover the spatial distributions of biogeochemical processes and community assemblages involved in methane cycling. The profiles of methane concentration and carbon isotopic composition revealed various orders of the predominance of specific methane-related metabolisms along depth. At a site proximal to the bubbling pool, the methanogenic zone was sandwiched by the anaerobic methanotrophic zones. For two sites distributed toward the topographic depression, the methanogenic zone overlaid the anaerobic methanotrophic zone. The predominance of anaerobic methanotrophy at specific depth intervals is supported by the enhanced copy numbers of the ANME-2a 16S rRNA gene and coincides with high dissolved Fe/Mn concentrations and copy numbers of the Desulfuromonas/Pelobacter 16S rRNA gene. Assemblages of 16S rRNA and mcrA genes revealed that methanogenesis was mediated by Methanococcoides and Methanosarcina. pmoA genes and a few 16S rRNA genes related to aerobic methanotrophs were detected in limited numbers of subsurface samples. While dissolved Fe/Mn signifies the presence of anaerobic metabolisms near the surface, the correlations between geochemical characteristics and gene abundances, and the absence of aerobic methanotrophs in top sediments suggest that anaerobic methanotrophy is potentially dependent on iron/manganese reduction and dominates over aerobic methanotrophy for the removal of methane produced in situ or from a deep source. Near-surface methanogenesis contributes to the methane emissions from mud platform. The alternating arrangements of methanogenic and methanotrophic zones at different sites suggest that the interactions between mud deposition, evaporation, oxidation and fluid transport modulate the assemblages of microbial communities and methane cycling in different compartments of terrestrial mud volcanoes. PMID:24723919

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.

Shallow groundwater quality and geochemistry in the Fayetteville Shale gas-production area, north-central Arkansas, 2011

USGS Publications Warehouse

Kresse, Timothy M.; Warner, Nathaniel R.; Hays, Phillip D.; Down, Adrian; Vengosh, Avner; Jackson, Robert B.

2012-01-01

The Mississippian Fayetteville Shale serves as an unconventional gas reservoir across north-central Arkansas, ranging in thickness from approximately 50 to 550 feet and varying in depth from approximately 1,500 to 6,500 feet below the ground surface. Primary permeability in the Fayetteville Shale is severely limited, and successful extraction of the gas reservoir is the result of advances in horizontal drilling techniques and hydraulic fracturing to enhance and develop secondary fracture porosity and permeability. Drilling and production of gas wells began in 2004, with a steady increase in production thereafter. As of April 2012, approximately 4,000 producing wells had been completed in the Fayetteville Shale. In Van Buren and Faulkner Counties, 127 domestic water wells were sampled and analyzed for major ions and trace metals, with a subset of the samples analyzed for methane and carbon isotopes to describe general water quality and geochemistry and to investigate the potential effects of gas-production activities on shallow groundwater in the study area. Water-quality analyses from this study were compared to historical (pregas development) shallow groundwater quality collected in the gas-production area. An additional comparison was made using analyses from this study of groundwater quality in similar geologic and topographic areas for well sites less than and greater than 2 miles from active gas-production wells. Chloride concentrations for the 127 groundwater samples collected for this study ranged from approximately 1.0 milligram per liter (mg/L) to 70 mg/L, with a median concentration of 3.7 mg/L, as compared to maximum and median concentrations for the historical data of 378 mg/L and 20 mg/L, respectively. Statistical analysis of the data sets revealed statistically larger chloride concentrations (p-value <0.001) in the historical data compared to data collected for this study. Chloride serves as an important indicator parameter based on its conservative transport characteristics and relatively elevated concentrations in production waters associated with gas extraction activities. Major ions and trace metals additionally had lower concentrations in data gathered for this study than in the historical analyses. Additionally, no statistical difference existed between chloride concentrations from water-quality data collected for this study from 94 wells located less than 2 miles from a gas-production well and 33 wells located 2 miles or more from a gas-production well; a Wilcoxon rank-sum test showed a p-value of 0.71. Major ion chemistry was investigated to understand the effects of geochemical and reduction-oxidation (redox) processes on the shallow groundwater in the study area along a continuum of increased rock-water interaction represented by increases in dissolved solids concentration. Groundwater in sandstone formations is represented by a low dissolved solids concentration (less than 30 mg/L) and slightly acidic water type. Shallow shale aquifers were represented by dissolved solids concentrations ranging upward to 686 mg/L, and water types evolving from a dominantly mixed-bicarbonate and calcium-bicarbonate to a strongly sodium-bicarbonate water type. Methane concentration and carbon isotopic composition were analyzed in 51 of the 127 samples collected for this study. Methane occurred above a detection limit of 0.0002 mg/L in 32 of the 51 samples, with concentrations ranging upward to 28.5 mg/L. Seven samples had methane concentrations greater than or equal to 0.5 mg/L. The carbon isotopic composition of these higher concentration samples, including the highest concentration of 28.5 mg/L, shows the methane was likely biogenic in origin with carbon isotope ratio values ranging from -57.6 to -74.7 per mil. Methane concentrations increased with increases in dissolved solids concentrations, indicating more strongly reducing conditions with increasing rock-water interaction in the aquifer. As such, groundwater-quality data collected for this study indicate that groundwater chemistry in the shallow aquifer system in the study area is a result of natural processes, beginning with recharge of dilute atmospheric precipitation and evolution of observed groundwater chemistry through rock-water interaction and redox processes.

BIOGEOCHEMICAL INDICATORS OF ORGANIC WASTE CONTAMINATION IN SMALL STREAMS OF THE GEORGIA PIEDMONT

EPA Science Inventory

We monitored concentrations of nitrous oxide, methane, carbon dioxide, nutrients and other parameters (T, conductivity, dissolved oxygen, alkalinity, pH, DOC, DON, flow rate) in 17 headwater streams (watershed sizes from 0.5 to 3.4 km2) of the South Fork Broad River, Georgia wate...

BIOGEOCHEMICAL INDICATORS OF ORGANIC WASTE CONTAMINATION IN GEORGIA PIEDMONT STREAMS

EPA Science Inventory

We monitored concentrations of nitrous oxide, methane, carbon dioxide, nutrients and other parameters (T, conductivity, dissolved oxygen, alkalinity, pH, DOC, DON, flow rate) in 17 headwater streams (watershed sizes from 0.5 to 3.4 km2) of the South Fork Broad River, Georgia wate...

Redox controls on methane formation, migration and fate in shallow aquifers

NASA Astrophysics Data System (ADS)

Humez, Pauline; Mayer, Bernhard; Nightingale, Michael; Becker, Veith; Kingston, Andrew; Taylor, Stephen; Bayegnak, Guy; Millot, Romain; Kloppmann, Wolfram

2016-07-01

Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish (a) natural in situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. This study combines aqueous and gas (dissolved and free) geochemical and isotope data from 372 groundwater samples obtained from 186 monitoring wells of the provincial Groundwater Observation Well Network (GOWN) in Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. We investigated whether methane occurring in shallow groundwater formed in situ, or whether it migrated into the shallow aquifers from elsewhere in the stratigraphic column. It was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of biogenic methane (> 0.01 mM or > 0.2 mgL-1), characterized by δ13CCH4 values < -55 ‰, occurred in anoxic Na-Cl, Na-HCO3, and Na-HCO3-Cl type groundwaters with negligible concentrations of nitrate and sulfate suggesting that methane was formed in situ under methanogenic conditions for 39.1 % of the samples. In only a few cases (3.7 %) was methane of biogenic origin found in more oxidizing shallow aquifer portions suggesting limited upward migration from deeper methanogenic aquifers. Of the samples, 14.1 % contained methane with δ13CCH4 values > -54 ‰, potentially suggesting a thermogenic origin, but aqueous and isotope geochemistry data revealed that the elevated δ13CCH4 values were caused by microbial oxidation of biogenic methane or post-sampling degradation of low CH4 content samples rather than migration of deep thermogenic gas. A significant number of samples (39.2 %) contained methane with predominantly biogenic C isotope ratios (δ13CCH4 < -55 ‰) accompanied by elevated concentrations of ethane and sometimes trace concentrations of propane. These gases, observed in 28.1 % of the samples, bearing both biogenic (δ13C) and thermogenic (presence of C3) characteristics, are most likely derived from shallow coal seams that are prevalent in the Cretaceous Horseshoe Canyon and neighboring formations in which some of the groundwater wells are completed. The remaining 3.7 % of samples were not assigned because of conflicting parameters in the data sets or between replicates samples. Hence, despite quite variable gas concentrations and a wide range of δ13CCH4 values in baseline groundwater samples, we found no conclusive evidence for deep thermogenic gas migration into shallow aquifers either naturally or via anthropogenically induced pathways in this baseline groundwater survey. This study shows that the combined interpretation of aqueous geochemistry data in concert with chemical and isotopic compositions of dissolved and/or free gas can yield unprecedented insights into formation and potential migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

Groundwater-quality characteristics for the Wyoming Groundwater-Quality Monitoring Network, November 2009 through September 2012

USGS Publications Warehouse

Boughton, Gregory K.

2014-01-01

Groundwater samples were collected from 146 shallow (less than or equal to 500 feet deep) wells for the Wyoming Groundwater-Quality Monitoring Network, from November 2009 through September 2012. Groundwater samples were analyzed for physical characteristics, major ions and dissolved solids, trace elements, nutrients and dissolved organic carbon, uranium, stable isotopes of hydrogen and oxygen, volatile organic compounds, and coliform bacteria. Selected samples also were analyzed for gross alpha radioactivity, gross beta radioactivity, radon, tritium, gasoline range organics, diesel range organics, dissolved hydrocarbon gases (methane, ethene, and ethane), and wastewater compounds. Water-quality measurements and concentrations in some samples exceeded numerous U.S. Environmental Protection Agency (EPA) drinking water standards. Physical characteristics and constituents that exceeded EPA Maximum Contaminant Levels (MCLs) in some samples were arsenic, selenium, nitrite, nitrate, gross alpha activity, and uranium. Total coliforms and Escherichia coli in some samples exceeded EPA Maximum Contaminant Level Goals. Measurements of pH and turbidity and concentrations of chloride, sulfate, fluoride, dissolved solids, aluminum, iron, and manganese exceeded EPA Secondary Maximum Contaminant Levels in some samples. Radon concentrations in some samples exceeded the alternative MCL proposed by the EPA. Molybdenum and boron concentrations in some samples exceeded EPA Health Advisory Levels. Water-quality measurements and concentrations also exceeded numerous Wyoming Department of Environmental Quality (WDEQ) groundwater standards. Physical characteristics and constituents that exceeded WDEQ Class I domestic groundwater standards in some samples were measurements of pH and concentrations of chloride, sulfate, dissolved solids, iron, manganese, boron, selenium, nitrite, and nitrate. Measurements of pH and concentrations of chloride, sulfate, dissolved solids, aluminum, iron, manganese, boron, and selenium exceeded WDEQ Class II agriculture groundwater standards in some samples. Measurements of pH and concentrations of sulfate, dissolved solids, aluminum, boron, and selenium exceeded WDEQ Class III livestock groundwater standards in some samples. The concentrations of dissolved solids in two samples exceeded the WDEQ Class IV industry groundwater standard. Measurements of pH and concentrations of dissolved solids, aluminum, iron, manganese, and selenium exceeded WDEQ Class special (A) fish and aquatic life groundwater standards in some samples. Stable isotopes of hydrogen and oxygen measured in water samples were compared to the Global Meteoric Water Line and Local Meteoric Water Lines. Results indicated that recharge to all of the wells was derived from precipitation and that the water has undergone some fractionation, possibly because of evaporation. Concentrations of organic compounds did not exceed any State or Federal water-quality standards. Few volatile organic compounds were detected in samples, whereas gasoline range organics, diesel range organics, and methane were detected most frequently. Concentrations of wastewater compounds did not exceed any State or Federal water-quality standards. The compounds N,N-diethyl-meta-toluamide (DEET), benzophenone, and phenanthrene were detected most frequently. Bacteria samples were collected, processed, incubated, and enumerated in the field or at the U.S. Geological Survey Wyoming-Montana Water Science Center. Total coliforms and Escherichia coli were detected in some samples.

Control of dissolved CH4 in a municipal UASB reactor effluent by means of a desorption - Biofiltration arrangement.

PubMed

Huete, A; de Los Cobos-Vasconcelos, D; Gómez-Borraz, T; Morgan-Sagastume, J M; Noyola, A

2018-06-15

The direct anaerobic treatment of municipal wastewater represents an adapted technology to the conditions of developing countries. In order to get an increased acceptance of this technology, a proper control of dissolved methane in the anaerobic effluents should be considered, as methane is a potent greenhouse gas. In this study, a pilot-scale system was operated for 168 days to recover dissolved methane from an effluent of an upflow anaerobic sludge blanket reactor and then oxidize it in a compost biofilter. The system operated at a constant air (0.9 m 3 /h ±0.09) and two air-to anaerobic effluent ratio (1:1 and 1:2). In both conditions (CH 4 concentration of 2.7 ± 0.87 and 4.3% ± 1.14, respectively) the desorption column recovered 99% of the dissolved CH 4 and approximately 30% ± 8.5 of H 2 S, whose desorption was limited due to the high pH (>8) of the effluent. The biofilter removed 70% ± 8 of the average CH 4 load (60 gCH 4 /m 3 h ± 13) and 100% of the H 2 S load at an empty bed retention time of 23 min. The average temperature inside the biofilter was 42 ± 9 °C due to the CH 4 oxidation reaction, indicating that temperature and moisture control is particularly important for CH 4 removal in compost biofilters. The system may achieve a 54% reduction of greenhouse gas emissions from dissolved CH 4 in this particular case. Copyright © 2017 Elsevier Ltd. All rights reserved.

High soil solution carbon and nitrogen concentrations in a drained Atlantic bog are reduced to natural levels by 10 years of rewetting

NASA Astrophysics Data System (ADS)

Frank, S.; Tiemeyer, B.; Gelbrecht, J.; Freibauer, A.

2014-04-01

Anthropogenic drainage of peatlands releases additional greenhouse gases to the atmosphere, and dissolved carbon (C) and nutrients to downstream ecosystems. Rewetting drained peatlands offers a possibility to reduce nitrogen (N) and C losses. In this study, we investigate the impact of drainage and rewetting on the cycling of dissolved C and N as well as on dissolved gases, over a period of 1 year and a period of 4 months. We chose four sites within one Atlantic bog complex: a near-natural site, two drained grasslands with different mean groundwater levels and a former peat cutting area rewetted 10 years ago. Our results clearly indicate that long-term drainage has increased the concentrations of dissolved organic carbon (DOC), ammonium, nitrate and dissolved organic nitrogen (DON) compared to the near-natural site. DON and ammonium contributed the most to the total dissolved nitrogen. Nitrate concentrations below the mean groundwater table were negligible. The concentrations of DOC and N species increased with drainage depth. In the deeply-drained grassland, with a mean annual water table of 45 cm below surface, DOC concentrations were twice as high as in the partially rewetted grassland with a mean annual water table of 28 cm below surface. The deeply drained grassland had some of the highest-ever observed DOC concentrations of 195.8 ± 77.3 mg L-1 with maximum values of >400 mg L-1. In general, dissolved organic matter (DOM) at the drained sites was enriched in aromatic moieties and showed a higher degradation status (lower DOC to DON ratio) compared to the near-natural site. At the drained sites, the C to N ratios of the uppermost peat layer were the same as of DOM in the peat profile. This suggests that the uppermost degraded peat layer is the main source of DOM. Nearly constant DOM quality through the profile furthermore indicated that DOM moving downwards through the drained sites remained largely biogeochemically unchanged. Unlike DOM concentration, DOM quality and dissolved N species distribution were similar in the two grasslands and thus unaffected by the drainage depth. Methane production during the winter months at the drained sites was limited to the subsoil, which was quasi-permanently water saturated. The recovery of the water table in the winter months led to the production of nitrous oxide around mean water table depth at the drained sites. The rewetted and the near-natural site had comparable DOM quantity and quality (DOC to DON ratio and aromaticity). 10 years after rewetting quasi-pristine biogeochemical conditions have been re-established under continuously water logged conditions in the former peat cut area. Only the elevated dissolved methane and ammonium concentrations reflected the former disturbance by drainage and peat extraction. Rewetting via polder technique seems to be an appropriate way to revitalize peatlands on longer timescales and to improve the water quality of downstream water bodies.

Dissolved methane in New York groundwater, 1999-2011

USGS Publications Warehouse

Kappel, William M.; Nystrom, Elizabeth A.

2012-01-01

New York State is underlain by numerous bedrock formations of Cambrian to Devonian age that produce natural gas and to a lesser extent oil. The first commercial gas well in the United States was dug in the early 1820s in Fredonia, south of Buffalo, New York, and produced methane from Devonian-age black shale. Methane naturally discharges to the land surface at some locations in New York. At Chestnut Ridge County Park in Erie County, just south of Buffalo, N.Y., several surface seeps of natural gas occur from Devonian black shale, including one behind a waterfall. Methane occurs locally in the groundwater of New York; as a result, it may be present in drinking-water wells, in the water produced from those wells, and in the associated water-supply systems (Eltschlager and others, 2001). The natural gas in low-permeability bedrock formations has not been accessible by traditional extraction techniques, which have been used to tap more permeable sandstone and carbonate bedrock reservoirs. However, newly developed techniques involving horizontal drilling and high-volume hydraulic fracturing have made it possible to extract previously inaccessible natural gas from low-permeability bedrock such as the Marcellus and Utica Shales. The use of hydraulic fracturing to release natural gas from these shale formations has raised concerns with water-well owners and water-resource managers across the Marcellus and Utica Shale region (West Virginia, Pennsylvania, New York and parts of several other adjoining States). Molofsky and others (2011) documented the widespread natural occurrence of methane in drinking-water wells in Susquehanna County, Pennsylvania. In the same county, Osborn and others (2011) identified elevated methane concentrations in selected drinking-water wells in the vicinity of Marcellus gas-development activities, although pre-development samples were not available for comparison. In order to manage water resources in areas of gas-well drilling and hydraulic fracturing in New York, the natural occurrence of methane in the State's aquifers needs to be documented. This brief report presents a compilation of data on dissolved methane concentrations in the groundwater of New York available from the U.S. Geological Survey (USGS) National Water Information System (NWIS) (http://waterdata.usgs.gov/nwis).

Effects of low oxygen concentrations on aerobic methane oxidation in seasonally hypoxic coastal waters

NASA Astrophysics Data System (ADS)

Steinle, Lea; Maltby, Johanna; Treude, Tina; Kock, Annette; Bange, Hermann W.; Engbersen, Nadine; Zopfi, Jakob; Lehmann, Moritz F.; Niemann, Helge

2017-03-01

Coastal seas may account for more than 75 % of global oceanic methane emissions. There, methane is mainly produced microbially in anoxic sediments from which it can escape to the overlying water column. Aerobic methane oxidation (MOx) in the water column acts as a biological filter, reducing the amount of methane that eventually evades to the atmosphere. The efficiency of the MOx filter is potentially controlled by the availability of dissolved methane and oxygen, as well as temperature, salinity, and hydrographic dynamics, and all of these factors undergo strong temporal fluctuations in coastal ecosystems. In order to elucidate the key environmental controls, specifically the effect of oxygen availability, on MOx in a seasonally stratified and hypoxic coastal marine setting, we conducted a 2-year time-series study with measurements of MOx and physico-chemical water column parameters in a coastal inlet in the south-western Baltic Sea (Eckernförde Bay). We found that MOx rates generally increased toward the seafloor, but were not directly linked to methane concentrations. MOx exhibited a strong seasonal variability, with maximum rates (up to 11.6 nmol L-1 d-1) during summer stratification when oxygen concentrations were lowest and bottom-water temperatures were highest. Under these conditions, 2.4-19.0 times more methane was oxidized than emitted to the atmosphere, whereas about the same amount was consumed and emitted during the mixed and oxygenated periods. Laboratory experiments with manipulated oxygen concentrations in the range of 0.2-220 µmol L-1 revealed a submicromolar oxygen optimum for MOx at the study site. In contrast, the fraction of methane-carbon incorporation into the bacterial biomass (compared to the total amount of oxidized methane) was up to 38-fold higher at saturated oxygen concentrations, suggesting a different partitioning of catabolic and anabolic processes under oxygen-replete and oxygen-starved conditions, respectively. Our results underscore the importance of MOx in mitigating methane emission from coastal waters and indicate an organism-level adaptation of the water column methanotrophs to hypoxic conditions.

Methane production correlates positively with methanogens, sulfate-reducing bacteria and pore water acetate at an estuarine brackish-marsh landscape scale

NASA Astrophysics Data System (ADS)

Tong, C.; She, C. X.; Jin, Y. F.; Yang, P.; Huang, J. F.

2013-11-01

Methane production is influenced by the abundance of methanogens and the availability of terminal substrates. Sulfate-reducing bacteria (SRB) also play an important role in the anaerobic decomposition of organic matter. However, the relationships between methane production and methanogen populations, pore water terminal substrates in estuarine brackish marshes are poorly characterized, and even to our knowledge, no published research has explored the relationship between methane production rate and abundance of SRB and pore water dimethyl sulfide (DMS) concentration. We investigated methane production rate, abundances of methanogens and SRB, concentrations of pore water terminal substrates and electron acceptors at a brackish marsh landscape dominated by Phragmites australis, Cyperus malaccensis and Spatina alterniflora marshes zones in the Min River estuary. The average rates of methane production at a soil depth of 30 cm in the three marsh zones were 0.142, 0.058 and 0.067 μg g-1 d-1, respectively. The abundance of both methanogens and SRB in the soil of the P. australis marsh with highest soil organic carbon content was higher than in the C. malaccensis and S. alterniflora marshes. The abundance of methanogens and SRB in the three soil layers was statistically indistinguishable. Mean pore water DMS concentrations at a soil depth of 30 cm under the S. alterniflora marsh were higher than those in the C. malaccensis and P. australis marshes. Methane production rate increased with the abundance of both methanogens and SRB across three marsh zones together at the landscape scale, and also increased with the concentration of pore water acetate, but did not correlate with concentrations of pore water DMS and dissolved CO2. Our results suggest that, provided that substrates are available in ample supply, methanogens can continue to produce methane regardless of whether SRB are prevalent in estuarine brackish marshes.

Laboratory formation of non-cementing, methane hydrate-bearing sands

USGS Publications Warehouse

Waite, William F.; Bratton, Peter M.; Mason, David H.

2011-01-01

Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

The Role of Surface Water Flow in Gas Fluxes from a Subtropical Rice Field

NASA Astrophysics Data System (ADS)

Huynh, K. T.; Suvocarev, K.; Reavis, C.; Runkle, B.; Variano, E. A.

2016-12-01

Wetlands are the single largest source of methane emissions, but the underlying processes behind this flux are not yet fully understood. Typically, methane fluxes from wetlands have been attributed to ebullition (bubbling) and to transport through vegetation. However, a third major pathway-hydrodynamic transport-has been seen in a temperate wetland in the Sacramento-San Joaquin Delta. We wish to explore whether this additional pathway is also important to a subtropical rice paddy site where the diel thermal cycle is less pronounced than in the temperate site. Measurements in the surface water of a rice field were collected over two weeks. Specific measurements collected included dissolved and atmospheric methane concentration, surface water velocity, and air and water temperature. These were used to augment a long-term dataset of micrometeorology and gas fluxes. Together, these data demonstrate the role that surface water motions play in the fluxes between soil and atmosphere. Data are analyzed to reveal the fraction of total methane flux that is governed by advective/diffusive transport through surface water, and daily cycles in this behavior. Results will be used to advance predictions of atmospheric methane gas concentrations and could be foundational for developing methane management solutions. Closing this gap in knowledge is key to improving calculations of current global greenhouse gas emissions.

Characterization of Methane Hydrate Growth from Aqueous Solution by Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Chou, I.; Lu, W.; Yuan, S.; Li, J.; Burruss, R. C.

2009-12-01

We observed the growth of methane hydrate from aqueous solution in fused silica capillaries near room temperature (RT) in two different experiments. In the first, we sealed methane together with ~2 wt% Na2SO4 solution in a fused silica capillary (0.3x0.3 mm cross-section with 0.05x0.05 mm cavity, and ~6 cm long), using the method of Chou et al. (2008, Geochim. Cosmochim. Acta, 72, 2517). The hydrate, liquid, and vapor coexist at ~23 °C and ~36.5 MPa. The behavior of two methane bubbles, one of which was enclosed by a hydrate crystal and the other near a small hydrate crystal, was monitored. These two bubbles are the only methane sources near the hydrate crystals. The system was slowly cooled to RT (~21 °C), and images were recorded continuously for a period of ~1.5 hours, together with temperature and time information. The images show the exposed bubble decreased in size, while both of the hydrate crystals increased in size, which was caused by the transfer of methane in solution. According to our previous report (Fig. 8 of Lu et al., 2008, Geochim. Cosmochim. Acta, 72, 412), the concentrations of methane in the solution near the exposed bubble are higher than those near the hydrate crystals. Most of the dissolved methane, transferred down the concentration gradient, was consumed and encaged in the nearby crystal, with only a small fraction of methane being consumed by the more distant crystal. Eventually, the exposed vapor bubble was totally consumed, but the bubble shielded by the hydrate crystal remained. This shows hydrate can grow from dissolved methane in the solution far away from free gas. In the 2nd experiment, we sealed methane, together with pure H2O and glass beads (0.04 to 0.07 mm in dia.), in a fused silica capillary (0.3 mm OD, 0.1 mm ID, and ~6 cm long) using the method cited above. We separated the vapor phase from the solution and glass beads by centrifuging the sealed capsule, then imposed a T gradient to the sample by cooling the solution end of the capsule to ~0 °C. It is difficult to recognize the nucleation and growth of hydrate crystals under a microscope, but Raman spectroscopy was used to identify and map the distribution of hydrate crystals along the capsule. Near the original vapor-aqueous phase boundary (V-A B), Raman signals show 100% methane hydrate. However, the lack of dissolved methane in the solution further away from the V-A B limited the growth of hydrate, as indicated by the increase in water/hydrate ratio when the Raman spectrum, which combines signals from both water and hydrate, was collected further away from the V-A B. We are investigating other possible ways to map the distribution of hydrate crystals around the glass beads, including x-ray computed tomography, to understand the nature of methane hydrate crystals that grow around grains in marine sediments from pore water. These observations will improve our ability to interpret the geophysical responses (e.g., electric and acoustic signals) obtained from hydrate-bearing sediments in the field.

Production waters associated with the Ferron coalbed methane fields, central Utah: Chemical and isotopic composition and volumes

USGS Publications Warehouse

Rice, C.A.

2003-01-01

This study investigated the composition of water co-produced with coalbed methane (CBM) from the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in east-central Utah to better understand coalbed methane reservoirs. The Ferron coalbed methane play currently has more than 600 wells producing an average of 240 bbl/day/well water. Water samples collected from 28 wellheads in three fields (Buzzards Bench, Drunkards Wash, and Helper State) of the northeast-southwest trending play were analyzed for chemical and stable isotopic composition.Water produced from coalbed methane wells is a Na-Cl-HCO3 type. Water from the Drunkards Wash field has the lowest total dissolved solids (TDS) (6300 mg/l) increasing in value to the southeast and northeast. In the Helper State field, about 6 miles northeast, water has the highest total dissolved solids (43,000 mg/l), and major ion abundance indicates the possible influence of evaporite dissolution or mixing with a saline brine. In the southern Buzzards Bench field, water has variable total dissolved solids that are not correlated with depth or spatial distance. Significant differences in the relative compositions are present between the three fields implying varying origins of solutes and/or different water-rock interactions along multiple flow paths.Stable isotopic values of water from the Ferron range from +0.9??? to -11.4??? ?? 18O and -32??? to -90??? ?? 2H and plot below the global meteoric water line (GMWL) on a line near, but above values of present-day meteoric water. Isotopic values of Ferron water are consistent with modification of meteoric water along a flow path by mixing with an evolved seawater brine and/or interaction with carbonate minerals. Analysis of isotopic values versus chloride (conservative element) and total dissolved solids concentrations indicates that recharge water in the Buzzards Bench area is distinct from recharge water in Drunkards Wash and is about 3 ??C warmer. These variations in isotopes along with compositional variations imply that the Ferron reservoir is heterogeneous and compartmentalized, and that multiple flow paths may exist. ?? 2003 Published by Elsevier B.V. All rights reserved.

Methane seepage along the Hikurangi Margin offshore New Zealand: 6 years of multidisciplinary studies

NASA Astrophysics Data System (ADS)

Greinert, J.; Bialas, J.; Klaucke, I.; Crutchley, G.; Dale, A.; Linke, P.; Sommer, S.; Bowden, D.; Rowden, A.; de Haas, H.; de Stigter, H.; Faure, K.

2012-12-01

Detailed studies in 2006, 2007 and 2011 along the east coast of New Zealand's North Island highlighted the close link of sub-bottom fluid pathways and seafloor expressions of methane seepage such as clam fields, carbonate build-ups, tubeworms, bacterial mats and methane release (Marine Geology 272). Prior to our studies, only accidental observations of hydroacoustic anomalies, recoveries of calyptogena shells and methane-derived carbonate chimneys indicated active seepage. Wide areas of the sub-seafloor show BSR structures, gas migration pathways, gas chimneys and blanking zones, which are closely linked to actual seep sites. Sidescan surveys showed four prominent seep areas at Omakere Ridge in 1120m water depth, three of them perfectly matching the shapes and locations of faults seen in high resolution 3D-seismic surveys. The fourth seep, Bear's Paw, on its western side represents an old seep which developed into a cold water coral habitat. At the actively seeping eastern part, gas hydrates could be retrieved and bubble release was observed hydroacoustically and confirmed by high dissolved methane values (380nM). No strong microbial oxidation effects could be found in δ13C values plotting along a mixing curve between pure seep (-70 ‰PDB) and atmospheric methane (-47 ‰PDB). Lander deployments show a tide-influenced gas discharge with sometimes eruptive bubble release with possible plume development transporting methane-charged water higher up into the water column. Rock Garden, with just above 600m water depth at its top outside the gas hydrate stability zone, hosts two main seep areas. ROV observations at Faure Site document eruptive releases of free gas from decimeter-wide craters at the seafloor. Flux estimates show peak releases of 420ml/min with bubbles up to 9mm in diameter. Concentrations of dissolved methane reach up to 3500nM close to the bottom, but higher concentrations are limited to below 400m of water depth; here, methane is transported towards the sea surface or even into the mixed layer. Faure site is just at the limit of the gas hydrate phase boundary, where relatively high-permeable sediment layers act as preferred pathway for fluids from below a shallow BSR. Seismic studies at the seep site LM-3 show gas chimneys as main fluid migration pathways in the sub-seafloor. Opouawe Bank has the densest occurrence of seeps. In water depths between 800 and 1200m, seeps of different ages and appearances exist in close proximity. North and South Tower resemble old structures with massive aragonitic carbonate blocks paving the seafloor, tube worms, bacterial mats, clams and beds of ampharetid polychaetes. These patchy polychaetes habitats have a very high total oxygen uptake of up to 83.7 mmol m^-2 day^-1) feeding from organic carbon generated via aerobic methane oxidation. Hydroacoustic flares at the 1200m deep Towers rise more than 600m into the water column above, which the dissolved gas concentrations quickly drop to background. In contrast, the isolated Takahe seep only 2 miles away shows no carbonates at the seafloor surface despite a well developed acoustic gas chimney and surface-near gas hydrates. This seep represents a much younger seep which highlights the great spatial and temporal variability in seep occurrences and activity, which can also be found in fossil seeps on land.

DISSOLVED OXYGEN AND METHANE IN WATER BY A GC HEADSPACE EQUILIBRATION TECHNIQUE

EPA Science Inventory

An analytical procedure is described for the determination of dissolved oxygen and methane in groundwater samples. The method consists of generating a helium gas headspace in a water filled bottle, and analysis of the headspace by gas chromatography. Other permanent gases such as...

Natural Gas Evolution in a Gas Hydrate Melt: Effect of Thermodynamic Hydrate Inhibitors.

PubMed

Sujith, K S; Ramachandran, C N

2017-01-12

Natural gas extraction from gas hydrate sediments by injection of hydrate inhibitors involves the decomposition of hydrates. The evolution of dissolved gas from the hydrate melt is an important step in the extraction process. Using classical molecular dynamics simulations, we study the evolution of dissolved methane from its hydrate melt in the presence of two thermodynamic hydrate inhibitors, NaCl and CH 3 OH. An increase in the concentration of hydrate inhibitors is found to promote the nucleation of methane nanobubbles in the hydrate melt. Whereas NaCl promotes bubble formation by enhancing the hydrophobic interaction between aqueous CH 4 molecules, CH 3 OH molecules assist bubble formation by stabilizing CH 4 bubble nuclei formed in the solution. The CH 3 OH molecules accumulate around the nuclei leading to a decrease in the surface tension at their interface with water. The nanobubbles formed are found to be highly dynamic with frequent exchange of CH 4 molecules between the bubble and the surrounding liquid. A quantitative analysis of the dynamic behavior of the bubble is performed by introducing a unit step function whose value depends on the location of CH 4 molecules with respect to the bubble. It is observed that an increase in the concentration of thermodynamic hydrate inhibitors reduces the exchange process, making the bubble less dynamic. It is also found that for a given concentration of the inhibitor, larger bubbles are less dynamic compared to smaller ones. The dependence of the dynamic nature of nanobubbles on bubble size and inhibitor concentration is correlated with the solubility of CH 4 and the Laplace pressure within the bubble. The effect of CO 2 on the formation of nanobubble in the CH 4 -CO 2 mixed gas hydrate melt in the presence of inhibitors is also examined. The simulations show that the presence of CO 2 molecules significantly reduces the induction time for methane nanobubble nucleation. The role of CO 2 in the early nucleation of bubble is explained based on the interaction between the bubble and the dissolved CO 2 molecules.

Methane and Carbon Dioxide Concentrations and Fluxes in Amazon Floodplains

NASA Astrophysics Data System (ADS)

Melack, J. M.; MacIntyre, S.; Forsberg, B.; Barbosa, P.; Amaral, J. H.

2016-12-01

Field studies on the central Amazon floodplain in representative aquatic habitats (open water, flooded forests, floating macrophytes) combine measurements of methane and carbon dioxide concentrations and fluxes to the atmosphere over diel and seasonal times with deployment of meteorological sensors and high-resolution thermistors and dissolved oxygen sondes. A cavity ringdown spectrometer is used to determine gas concentrations, and floating chambers and bubble collectors are used to measure fluxes. To further understand fluxes, we measured turbulence as rate of dissipation of turbulent kinetic energy based on microstructure profiling. These results allow calculations of vertical mixing within the water column and of air-water exchanges using surface renewal models. Methane and carbon dioxide fluxes varied as a function of season, habitat and water depth. High CO2 fluxes at high water are related to high pCO2; low pCO2 levels at low water result from increased phytoplankton uptake. CO2 fluxes are highest at turbulent open water sites, and pCO2 is highest in macrophyte beds. Fluxes and pCH4 are high in macrophyte beds.

The potential for biologically catalyzed anaerobic methane oxidation on ancient Mars.

PubMed

Marlow, Jeffrey J; Larowe, Douglas E; Ehlmann, Bethany L; Amend, Jan P; Orphan, Victoria J

2014-04-01

This study examines the potential for the biologically mediated anaerobic oxidation of methane (AOM) coupled to sulfate reduction on ancient Mars. Seven distinct fluids representative of putative martian groundwater were used to calculate Gibbs energy values in the presence of dissolved methane under a range of atmospheric CO2 partial pressures. In all scenarios, AOM is exergonic, ranging from -31 to -135 kJ/mol CH4. A reaction transport model was constructed to examine how environmentally relevant parameters such as advection velocity, reactant concentrations, and biomass production rate affect the spatial and temporal dependences of AOM reaction rates. Two geologically supported models for ancient martian AOM are presented: a sulfate-rich groundwater with methane produced from serpentinization by-products, and acid-sulfate fluids with methane from basalt alteration. The simulations presented in this study indicate that AOM could have been a feasible metabolism on ancient Mars, and fossil or isotopic evidence of this metabolic pathway may persist beneath the surface and in surface exposures of eroded ancient terrains.

ANALYSIS OF DISSOLVED METHANE, ETHANE, AND ETHYLENE IN GROUND WATER BY A STANDARD GAS CHROMATOGRAPHIC TECHNIQUE

EPA Science Inventory

The measurement of dissolved gases such as methane, ethane, and ethylene in ground water is important in determining whether intrinsic bioremediation is occurring in a fuel- or solvent-contaminated aquifer. A simple procedure is described for the collection and subsequent analys...

High soil solution carbon und nitrogen concentrations in a drained Atlantic bog are reduced to natural levels by 10 yr of rewetting

NASA Astrophysics Data System (ADS)

Frank, S.; Tiemeyer, B.; Gelbrecht, J.; Freibauer, A.

2013-10-01

Artificial drainage of peatlands causes dramatic changes in the release of greenhouse gases and in the export of dissolved carbon (C) and nutrients to downstream ecosystems. Rewetting anthropogenically altered peatlands offers a possibility to reduce nitrogen (N) and C losses. In this study, we investigate the impact of drainage and rewetting on the cycling of dissolved C and N as well as on dissolved gases over a period of 1 yr and 4 month, respectively. The peeper technique was used to receive a high vertical sampling resolution. Within one Atlantic bog complex a near natural site, two drained grasslands sites with different mean water table positions, and a former peat cutting area rewetted 10 yr ago were chosen. Our results clearly indicate that drainage increased the concentration of dissolved organic carbon (DOC), ammonia, nitrate and dissolved organic nitrogen (DON) compared to the near natural site. Drainage depth further determined the release and therefore the concentration level of DOC and N species, but the biochemical cycling and therefore dissolved organic matter (DOM) quality and N species composition were unaffected. Thus, especially deep drainage can cause high DOC losses. In general, DOM at drained sites was enriched in aromatic moieties as indicated by SUVA280 and showed a higher degradation status (lower DOC to DON ratio) compared to the near natural site. At the drained sites, equal C to N ratios of uppermost peat layer and DOC to DON ratio of DOM in soil solution suggest that the uppermost degraded peat layer is the main source of DOM. Nearly constant DOC to DON ratios and SUVA280 values with depth furthermore indicated that DOM moving downwards through the drained sites remained largely unchanged. DON and ammonia contributed most to the total dissolved nitrogen (TN). The subsoil concentrations of nitrate were negligible due to strong decline in nitrate around mean water table depth. Methane production during the winter months at the drained sites moved downwards to areas which were mostly water saturated over the whole year (>40 cm). Above these depths, the recovery of the water table in winter months led to the production of nitrous oxide around mean water table depth at drained sites. 10 yr after rewetting, the DOM quality (DOC to DON ratio and SUVA280) and quantity were comparable to the near natural site, indicating the re-establishment of mostly pristine biochemical processes under continuously water logged conditions. The only differences occur in elevated dissolved methane and ammonia concentrations reflecting the former disturbance by drainage and peat extraction. Rewetting via polder technique seems to be an appropriate way to revitalize peatlands on longer timescales and to improve the water quality of downstream water bodies.

Modeling the Interaction of H2 on Root Exudate Degradation and Methanogenesis in Wetland Sediments

NASA Astrophysics Data System (ADS)

Pal, D. S.; Jaffe, P. R.

2014-12-01

CH4 is produced in wetland sediments from the microbial degradation of organic carbon through multiple fermentation steps and methanogenesis pathways. There are many potential sources of carbon for methananogenesis; in vegetated wetland sediments, microbial communities consume root exudates as a major source of organic carbon. In many methane models propionate is used as a model carbon molecule. This simple sugar is fermented into acetate and H2, acetate is transformed to methane and CO2 while the H2 and CO2 is synthesized to form an additional CH4 molecule. The hydrogenotrophic pathway involves the equilibrium of two dissolved gases, CH4 and H2. In an effort to limit CH4 emissions from wetlands, there has been growing interest in finding ways to limit plant transport of soil gases through root systems. While this may decrease the direct emissions of methane, there is little understanding about how H2 dynamics may feedback into overall methane production. Since H2 is used in methane production and produced in propionate fermentation, increased subsurface H2 concentrations can simultaneously inhibit propionate fermentation and acetate production and enhance hydrogenotrophic methanogenesis. For this study, we incubated soil samples from vegetated wetland sediments with propionate or acetate and four different hydrogen concentrations. The headspaces from these incubations were simultaneously analyzed for H2 and CH4 at multiple time points over two months. The comparison of methane production between different hydrogen concentrations and different carbon sources can indicate which process is most affected by increased hydrogen concentrations. The results from this study were combined with a newly formulated steady-state model of propionate degradation and formation of methane, that also accounts for the venting off both gases via plants. The resulting model indicates how methane production and emissions would be affected by plant volatilization.

Methane in the Baltic and North Seas and a reassessment of the marine emissions of methane

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

Bange, H.W.; Bartell, U.H.; Rapsomanikis, S.

During three measurement campaigns on the Baltic and North Seas, atmospheric and dissolved methane was determined with an automated gas chromatographic system. Area-weighted mean saturation values in the sea surface waters were 113{+-}5% and 395{+-}82% and 126{+-}8%. On the bases of our data and a compilation of literature data the global oceanic emissions of methane were reassessed by introducing a concept of regional gas transfer coefficients. Our estimates computed with two different air-sea exchange models lie in the range of 11-18 Tg CH{sub 4} yr{sup -1}. Despite the fact that shelf areas and estuaries only represent a small part ofmore » the world`s ocean they contribute about 75% to the global oceanic emissions. We applied a simple, coupled, three-layer model to evaluate the time dependent variation of the oceanic flux to the atmosphere. The model calculations indicate that even with increasing tropospheric methane concentration, the ocean will remain a source of atmospheric methane. 72 refs., 7 figs., 7 tabs.« less

Exceptional summer warming leads to contrasting outcomes for methane cycling in small Arctic lakes of Greenland

NASA Astrophysics Data System (ADS)

Cadieux, Sarah B.; White, Jeffrey R.; Pratt, Lisa M.

2017-02-01

In thermally stratified lakes, the greatest annual methane emissions typically occur during thermal overturn events. In July of 2012, Greenland experienced significant warming that resulted in substantial melting of the Greenland Ice Sheet and enhanced runoff events. This unusual climate phenomenon provided an opportunity to examine the effects of short-term natural heating on lake thermal structure and methane dynamics and compare these observations with those from the following year, when temperatures were normal. Here, we focus on methane concentrations within the water column of five adjacent small lakes on the ice-free margin of southwestern Greenland under open-water and ice-covered conditions from 2012-2014. Enhanced warming of the epilimnion in the lakes under open-water conditions in 2012 led to strong thermal stability and the development of anoxic hypolimnia in each of the lakes. As a result, during open-water conditions, mean dissolved methane concentrations in the water column were significantly (p < 0.0001) greater in 2012 than in 2013. In all of the lakes, mean methane concentrations under ice-covered conditions were significantly (p < 0.0001) greater than under open-water conditions, suggesting spring overturn is currently the largest annual methane flux to the atmosphere. As the climate continues to warm, shorter ice cover durations are expected, which may reduce the winter inventory of methane and lead to a decrease in total methane flux during ice melt. Under open-water conditions, greater heat income and warming of lake surface waters will lead to increased thermal stratification and hypolimnetic anoxia, which will consequently result in increased water column inventories of methane. This stored methane will be susceptible to emissions during fall overturn, which may result in a shift in greatest annual efflux of methane from spring melt to fall overturn. The results of this study suggest that interannual variation in ground-level air temperatures may be the primary driver of changes in methane dynamics because it controls both the duration of ice cover and the strength of thermal stratification.

Subtropical freshwater storages: a major source of nitrous oxide and methane?

NASA Astrophysics Data System (ADS)

Sturm, Katrin; Grinham, Alistair; Yuan, Zhiguo

2013-04-01

Studies of greenhouse gas cycling in subtropical water bodies, particularly in the Southern Hemisphere, are very limited. This represents an important gap in our understanding of global emissions as the higher temperatures experienced in the subtropics will likely accelerate greenhouse gas production and consumption. Critical to understanding the net impact of these accelerated rates are detailed studies of representative systems within this region. In this paper we present a model artificial freshwater storage: Gold Creek Dam in South East Queensland, Australia. Freshwater storages are commonplace for drinking water and irrigation purposes in Australia as unpredictable rainfall patterns make river and ground water sources unreliable. Over 85 % of Australian rivers are modified with weirs and dams providing permanent inundation of previously terrestrial environments. The higher temperatures experienced at these latitudes drive thermal stratification of these systems as well as rapidly deoxygenate bottom waters. High organic matter availability in the sediment zone as well as the anoxic overlying water provide ideal conditions for reduced products (including methane and ammonia) from microbial processing to be formed and diffuse into bottom waters. A mid-water metalimnion is generally associated with large gradients in dissolved oxygen availability and reduced metabolites undergo oxidation prior to their emission from water surface. An intensive field study was undertaken to improve understanding of production and transformation rates of methane and nitrous oxide from the sediments, through the water column and to the atmosphere. Sediment nutrient (ammonia, nitrite/nitrate and filterable reactive phosphorus) and greenhouse gas (methane and nitrous oxide) porewater samples were collected at selected sites. To determine the magnitude of the benthic sediment contribution of methane and nitrous oxide to the water column sediment incubations were conducted in the laboratory. To determine the likely atmospheric flux from this water body surface floating chambers were used to collect gas. Results showed maximum methane concentrations in the sediment porewaters and deeper water column, both anoxic environments. However, nitrous oxide had highest concentrations at the oxycline zone of the water column. Sediment incubations showed clear methane efflux demonstrating the sediments to be a consistent source of methane. Sediments were either a source or sink of nitrous oxide depending on overlying dissolved oxygen concentration. Floating chamber incubations clearly demonstrated Gold Creek Dam was a source of both methane and nitrous oxide with methane an order of magnitude higher expressed as CO2 equivalents. Diffusive atmospheric fluxes of methane ranged from 20 to 450 mg m-2 d-1 and were comparable to tropical reservoirs rather than temperate reservoirs (LOUIS et al., 2000). Results are likely to be globally relevant as an increasing number of large dams are being constructed to meet growing water demand and under a warming climate process occurring in subtropical systems can give insights into future changes likely to occur in temperate systems.

Metabolic activity of subterranean microbial communities in deep granitic groundwater supplemented with methane and H2

PubMed Central

Pedersen, Karsten

2013-01-01

It was previously concluded that opposing gradients of sulphate and methane, observations of 16S ribosomal DNA sequences displaying great similarity to those of anaerobic methane-oxidizing Archaea and a peak in sulphide concentration in groundwater from a depth of 250–350 m in Olkiluoto, Finland, indicated proper conditions for methane oxidation with sulphate. In the present research, pressure-resistant, gas-tight circulating systems were constructed to enable the investigation of attached and unattached anaerobic microbial populations from a depth of 327 m in Olkiluoto under in situ pressure (2.4 MPa), diversity, dissolved gas and chemistry conditions. Three parallel flow cell cabinets were configured to allow observation of the influence on microbial metabolic activity of 11 mℳ methane, 11 mℳ methane plus 10 mℳ H2 or 2.1 mℳ O2 plus 7.9 mℳ N2 (that is, air). The concentrations of these gases and of organic acids and carbon, sulphur chemistry, pH and Eh, ATP, numbers of cultivable micro-organisms, and total numbers of cells and bacteriophages were subsequently recorded under batch conditions for 105 days. The system containing H2 and methane displayed microbial reduction of 0.7 mℳ sulphate to sulphide, whereas the system containing only methane resulted in 0.2 mℳ reduced sulphate. The system containing added air became inhibited and displayed no signs of microbial activity. Added H2 and methane induced increasing numbers of lysogenic bacteriophages per cell. It appears likely that a microbial anaerobic methane-oxidizing process coupled to acetate formation and sulphate reduction may be ongoing in aquifers at a depth of 250–350 m in Olkiluoto. PMID:23235288

Stable thermophilic anaerobic digestion of dissolved air flotation (DAF) sludge by co-digestion with swine manure.

PubMed

Creamer, K S; Chen, Y; Williams, C M; Cheng, J J

2010-05-01

Environmentally sound treatment of by-products in a value-adding process is an ongoing challenge in animal agriculture. The sludge produced as a result of the dissolved air flotation (DAF) wastewater treatment process in swine processing facilities is one such low-value residue. The objective of this study was to determine the fundamental performance parameters for thermophilic anaerobic digestion of DAF sludge. Testing in a semi-continuous stirred tank reactor and in batch reactors was conducted to determine the kinetics of degradation and biogas yield. Stable operation could not be achieved using pure DAF sludge as a substrate, possibly due to inhibition by long-chain fatty acids or to nutrient deficiencies. However, in a 1:1 ratio (w/w, dry basis) with swine manure, operation was both stable and productive. In the semi-continuous stirred reactor at 54.5 degrees Celsius, a hydraulic residence time of 10 days, and an organic loading rate of 4.68 gVS/day/L, the methane production rate was 2.19 L/L/day and the specific methane production rate was 0.47 L/gVS (fed). Maximum specific methanogenic activity (SMA) in batch testing was 0.15 mmoles CH(4) h(-1) gVS(-1) at a substrate concentration of 6.9 gVS L(-1). Higher substrate concentrations cause an initial lag in methane production, possibly due to long-chain fatty acid or nitrogen inhibition. Copyright 2009 Elsevier Ltd. All rights reserved.

Testing and Validation Studies of the NSMII-Benthic Sediment Diagenesis Module

DTIC Science & Technology

2016-07-01

NSMII analytical vs. numerical solutions of sediment methane ............................ 27 3.2.4 Comparisons of the diagenesis rates of three sediment...26 Figure 12. Comparisons of NSMII analytical vs. numerical solutions of sediment methane : (a) layer 2’s CH4, (b...oxygen demand mg-O2 L-1 0-10 CH4 Methane mg-O2 L-1 On/Off HxS Total dissolved sulfides mg-O2 L-1 On/Off DO Dissolved oxygen mg-O2 L-1 On BSi

Methane Occurrence in a Drinking Water Aquifer Before and During Natural Gas Production from the Marcellus Shale

NASA Astrophysics Data System (ADS)

Saiers, J. E.; Barth-Naftilan, E.

2017-12-01

More than 4,000 thousand wells have punctured aquifers of Pennsylvania's northern tier to siphon natural gas from the underlying Marcellus Shale. As drilling and hydraulic fracturing ramped up a decade ago, homeowner reports of well water contamination by methane and other contaminants began to emerge. Although made infrequently compared to the number of gas wells drilled, these reports were troubling and motivated our two-year, prospective study of groundwater quality within the Marcellus Shale Play. We installed multi-level sampling wells within a bedrock aquifer of a 25 km2 area that was targeted for shale gas development. These wells were sampled on a monthly basis before, during, and after seven shale gas wells were drilled, hydraulically fractured, and placed into production. The groundwater samples, together with surface water samples collected from nearby streams, were analyzed for hydrocarbons, trace metals, major ions, and the isotopic compositions of methane, ethane, water, strontium, and dissolved inorganic carbon. With regard to methane in particular, concentrations ranged from under 0.1 to over 60 mg/L, generally increased with aquifer depth, and, at some sites, exhibited considerable temporal variability. The isotopic composition of methane and hydrocarbon ratios also spanned a large range, suggesting that methane origins are diverse and, notably, shift on the time scale of this study. We will present inferences on factors governing methane occurrence across our study area by interpreting time-series data on methane concentrations and isotopic composition in context of local hydrologic variation, companion measurements of groundwater chemistry, and the known timing of key stages of natural gas extraction.

Treatment of domestic wastewater with an anaerobic ceramic membrane bioreactor (AnCMBR).

PubMed

Yue, Xiaodi; Koh, Yoong Keat Kelvin; Ng, How Yong

2015-01-01

In this study, a ceramic membrane with a pore size of 80 nm was incorporated into an anaerobic membrane bioreactor for excellent stability and integrity. Chemical oxygen demand (COD) removal efficiencies by biodegradation reached 78.6 ± 6.0% with mixed liquor suspended solids (MLSS) of 12.8 ± 1.2 g/L. Even though the total methane generated was 0.3 ± 0.03 L/g CODutilized, around 67.4% of it dissolved in permeate and was lost beyond collection. As a result, dissolved methane was 2.7 times of the theoretical saturating concentration calculated from Henry's law. When transmembrane pressure (TMP) of the ceramic membrane reached 30 kPa after 25.3 d, 95.2% of the total resistance was attributed to the cake layer, which made it the major contributor to membrane fouling. Compared to the mixed liquor, cake layer was rich in colloids and soluble products that could bind the solids to form a dense cake layer. The Methanosarcinaceae family preferred to attach to the ceramic membranes.

Tree-mediated methane emissions from tropical and temperate peatlands.

NASA Astrophysics Data System (ADS)

Pangala, S. R.; Gauci, V.; Hornibrook, E. R. C.; Gowing, D. J.

2012-04-01

Methane production and transport processes in peatlands are fairly well understood, but growing evidence for emission of methane through trees has highlighted the need to revisit methane transport processes. In wetland trees, morphological adaptations such as development of hypertrophied lenticels, aerenchyma and adventitious roots in response to soil anoxia mediates gas transport, transporting both oxygen from the atmosphere to oxygen-deprived roots and soil-produced methane from the root-zone to the atmosphere. Although, tree-mediated methane emissions from temperate tree species have been confirmed, methane emissions from tropical tree species and processes that control tree-mediated methane emissions remain unclear. This study explains the role of trees in transporting soil-produced methane to the atmosphere and uncovers the principal mechanisms of tree-mediated methane emissions. Methane emissions from eight tropical tree species and two temperate tree species were studied in situ. The mechanisms and controls on tree-mediated methane emissions were investigated using three year old common alder (Alnus glutinosa; 50 trees) grown under two artificially controlled water-table positions. Methane fluxes from whole mesocosms, the soil surface and tree stems were measured using static closed chambers. Both temperate and tropical tree species released significant quantities of methane, with tropical trees dominating ecosystem level methane fluxes. In temperate peatlands, both the methane gas transport mechanism and quantity of methane emitted from stems is tree-species dependent. In Alnus glutinosa, no correlations were observed between stomatal behaviour and tree-mediated methane emissions, however, stem methane emissions were positively correlated with both stem lenticel density and dissolved soil methane concentration. In Alnus glutinosa, no emissions were observed from leaf surfaces. The results demonstrate that exclusion of tree-mediated methane emissions from flux measurement campaigns in forested peatlands will lead to an underestimation of ecosystem-wide methane emissions.

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play, South Texas.

PubMed

Nicot, Jean-Philippe; Larson, Toti; Darvari, Roxana; Mickler, Patrick; Uhlman, Kristine; Costley, Ruth

2017-07-01

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo-Wilcox Aquifer (250-1200 m depth range) and Queen City-Sparta Aquifer (150-900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ 13 C methane (>-55‰) and δD methane (>-180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ 13 C methane and δD methane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs. © 2017, National Ground Water Association.

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.

Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

NASA Astrophysics Data System (ADS)

Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

2015-12-01

Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and/or abundance of key microbial populations. Together, the data provide an explanation for the seasonal decrease in methane oxidation: rates of oxygen consumption increase over the season, which decreases the amount of oxygen dissolved in porewater at the peatland surface and reduces rates of methane oxidation.

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.

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

USGS Publications Warehouse

Chapelle, Francis H.; Haack, Sheridan K.; Adriaens, Peter; Henry, Mark A.; Bradley, Paul M.

1996-01-01

Measurements of oxidation-reduction potential (Eh) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. Eh measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured Eh and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1-4 nM) and Fe(III)-reducing (H2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than Ehmeasurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

Metagenomic and Clumped Isotopologue Evidence for Microbial Methanogenesis in the Zambales Ophiolite

NASA Astrophysics Data System (ADS)

Woycheese, K. M.; Meyer-Dombard, D. R.; Cardace, D.; Arcilla, C. A.; Ono, S.

2017-12-01

Active serpentinization occurring in the Zambales Ophiolite Range in the Philippines results in ultrabasic (pH > 10) fluid springs high in dissolved hydrogen and methane. Concentrations of dissolved gases varies between the springs; H2 ranges from 16-20% and CH4 by 8-12% by volume. Hydrogen gas is generated by serpentinization, but the provenance of methane is unknown and thought to be thermogenically derived based on a previously-reported δDCH4 values from the Los Fuegos Eternos gas seep1. Here, we present metagenomic and 13CH3D clumped isotopologue evidence for hydrogenotropic and acetoclastic methanogenesis in fluid springs and sediments collected from Manleluag Spring Protected Landscape, Mangatarem, Pangasinan, the Philippines. Methane gas collected from two springs was analyzed on a tunable infrared laser direct absorption spectroscopy (TILDAS) at the Massachusetts Institute of Technology to determine the equilibration temperature of methane. Stable isotope analysis of methane C and H indicate δ13C vs. PDB ratios near -14‰ and δD vs. SMOW ratios near -367‰. The Δ13CH3D approximately -1.0‰ vs. stochastic distribution, which is "anticlumped" (i.e. values <0‰, at which temperature cannot be expressed) and indicative of microbial methanogenesis2. Shotgun metagenomic sequencing analysis of fluids and sediments from Manleluag reveals an abundance of methanogenesis-related genes. Universal methanogenesis genes encoding methyl-coenzyme M reductase (mcr) and heterodisulfide reductase (hdr) are detected in spring fluids and sediments. Genes encoding key steps of both hydrogenotrophic and acetoclastic methanogenesis are present. Universal methane oxidation genes methanol dehydrogenase (mdh) and methane monooxygenase (mmo) are present but less abundant than methanogenesis genes, and not found in all sampling locations. Carbon assimilation genes detected in fluid and sediment metagenomes indicate that the ribulose monophosphate pathway is the predominant methane oxidation mechanism utilized by methanotrophs. This work indicates that the source of microbial methane in Zambales may be very complex and likely involves multiple metabolic pathways. 1. Abrajano et al. (1988). Chem. Geol. 71: 211-222. 2. Wang et al. (2015). Science. 348(6233): 428-431.

A New Method for Carbon Isotopic Analysis of Nanogram Quantities of Carbon from Dissolved Chitin Using A Spooling-wire Microcombustion Interface

NASA Astrophysics Data System (ADS)

Zhao, Y.; Nelson, D. M.; Clegg, B. F.; Berry, J.; Hu, F.

2016-12-01

δ13C analysis of specific taxa or compounds is commonly used for investigating past environmental change, including methane dynamics in lakes. However, most analytical methods require large sample sizes, prohibiting routine analysis of fossils of individual taxa found in sediment deposits. For example, 10-100 individual head capsules of fossil midges are required for δ13C analysis using an elemental analyzer (EA) interfaced with an isotope-ratio mass spectrometer (IRMS). Here we present a new method that uses a spooling-wire microcombustion (SWiM) device interfaced with an IRMS for measuring δ13C values of carbon dissolved from individual head capsules of chitinous aquatic zooplankton. We extracted chitin (a major biochemical component of insect exoskeleton) from modern midge material obtained from four commercial suppliers. We first assessed the effects of sample treatments on carbon yields and δ13C values of dissolved chitin by varying the concentration of HCl used for dissolution, the duration of reaction in HCl, and the temperature of dissolution. We then investigated potential fractionation of carbon isotopes associated with chitin dissolution, by comparing δ13C values of dissolved chitin obtained via SWiM-IRMS with those from untreated head capsules obtained via a EA-IRMS. The average δ13C values of untreated head capsules varied between -25.1 and -30.1‰. Higher acid concentrations and temperatures, as well as longer reaction times, increased dissolution of carbon from the head capsules and the precision of δ13C values. For example, carbon yields from reaction of head capsules with 6N HCl at 25°C increased from 1 to 3 Vs as reaction times increased from 1 to 24 hours. Acid concentration and reaction time had the greatest influence on carbon yields and isotopic precision. The δ13C values of dissolved chitin mirrored the δ13C values of untreated head capsules with minimal offset of absolute values, which suggests no systematic fractionation associated with dissolution. Overall, these results indicate that carbon isotopic analysis of dissolved chitin using the SWiM-IRMS system offers a reliable new method to determine taxa-specific δ13C values for chitinous aquatic zooplankton. In ongoing work, we are applying this tool to reconstruct past methane dynamics in Arctic lakes during the Holocene.

Work Plan for Three-Dimensional Time-Varying, Hydrodynamic and Water Quality Model of Chesapeake Bay

DTIC Science & Technology

1988-08-01

successfully calibrated: a. Dissolved oxygen b. Anmonium c. Nitrate d . Dissolved inorganic phosphorus e. Silica f. Methane g. Sulfide Fluxes of dissolved...oxygen, amonium , nitrate , methane, and sulfide can be related to the rate of diagenesis. A less mechanistic, more empirical approach may be required...CLASSc;CA’ ON A ’I.ORITV 3 D.S1R RUT ON AVA LABMLTY OF REPORT ’b D LASPCTO1,DONGRANG C ED, kApproved for public rele~ise; distribution 2b DC~ASFAT.N

Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulfidic marine sediments

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

Glass, DR. Jennifer; Yu, DR. Hang; Steele, Joshua

Microbes have obligate requirements for trace metals in metalloenzymes that catalyze important biogeochemical reactions. In anoxic methane- and sulfide-rich environments, microbes may have unique adaptations for metal acquisition and utilization due to decreased bioavailability as a result of metal sulfide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulfidic (>1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5-270 nM), cobalt (0.5-6 nM), molybdenum (10-5,600 nM) and tungsten (0.3-8 nM) in Hydrate Ridge sedimentmore » porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalyzing anaerobic oxidation of methane utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrotolerant microorganisms. Finally, our data suggest that chemical speciation of metals in highly sulfidic porewaters may exert a stronger influence on microbial bioavailability than total concentration« less

Methane emissions to the atmosphere through aquatic plants

NASA Technical Reports Server (NTRS)

Sebacher, D. I.; Harriss, R. C.; Bartlett, K. B.

1985-01-01

The movement of methane (CH4) from anaerobic sediments through the leaves, stems, and flowers of aquatic plants and into the atmosphere was found to provide a significant pathway for the emission of CH4 from the aquatic substrates of flooded wetlands. Methane concentrations well above the surrounding ambient air levels were found in the mesophyll of 16 varies of aquatic plants and are attributed to transpiration, diffusion, and pressure-induced flow of gaseous CH4 from the roots when they are embedded in CH4-saturated anaerobic sediments. Methane emissions from the emergent parts of aquatic plants were measured using floating chamber techniques and by enclosing the plants in polyethylene bags of known volume. Concentration changes were monitored in the trapped air using syringes and gas chromatographic techniques. Vertical profiles of dissolved CH4 in sediment pore water surrounding the aquatic plants' rhizomes were obtained using an interstitial sampling technique. Methane emissions from the aquatic plants studied varied from 14.8 mg CH4/d to levels too low to be detectable. Rooted and unrooted freshwater aquatic plants were studied as well as saltwater and brackish water plants. Included in the experiment is detailed set of measurements on CH4 emissions from the common cattail (Typha latifolia). This paper illustrates that aquatic plants play an important gas exchange role in the C cycle between wetlands and the atmosphere.

Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

NASA Astrophysics Data System (ADS)

Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

2013-12-01

Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other pollutants. Finally, the system was deployed shipboard, and field deployment data will also be presented.

Fiber optic gas detection system for health monitoring of oil-filled transformer

NASA Astrophysics Data System (ADS)

Ho, H. L.; Ju, J.; Jin, W.

2009-10-01

This paper reports the development of a fiber-optic gas detection system capable of detecting three types of dissolved fault gases in oil-filled power transformers or equipment. The system is based on absorption spectroscopy and the target gases include acetylene (C2H2), methane (CH4) and ethylene (C2H4). Low-cost multi-pass sensor heads using fiber coupled micro-optic cells are employed for which the interaction length is up to 4m. Also, reference gas cells made of photonic bandgap (PBG) fiber are implemented. The minimum detectable gas concentrations for methane, acetylene and ethylene are 5ppm, 2ppm and 50ppm respectively.

Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

USGS Publications Warehouse

Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

2007-01-01

The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

Biogeochemistry of dissolved methane and hydrogen in basement fluids of the sediment-buried Juan de Fuca Ridge flank at Boreholes (CORKs) 1301A, 1362A and 1362B: methane isotopic compositions

NASA Astrophysics Data System (ADS)

Lin, H.; Cowen, J. P.; Olson, E. J.; Lilley, M. D.; Jungbluth, S.; Rappe, M. S.

2013-12-01

The ocean crust is the largest aquifer system on Earth. Within the sediment-buried 3.5 Myr basaltic crust of the eastern Juan de Fuca Ridge (JFR) flank, the circulating basement fluids have moderate temperature (~65°C) and potentially harbor a substantial subseafloor biosphere. With dissolved oxygen and nitrate exhausted, sulfate may serve as the major electron acceptor in this environment. This study aims to evaluate the availability and the biogeochemistry of two important electron donors, methane and hydrogen, for the subseafloor biosphere. Basement fluids were collected via stainless steel and ethylene-tetrafluoroethylene fluoropolymer (ETFE) fluid delivery lines associated with Integrated Ocean Drilling Program (IODP) Circulation Obviation Retrofit Kits (CORKs) that extend from basement depths to outlet ports at the seafloor. Three CORKs were visited; 1301A, 1362A and 1362B lie within 200 to 500 m of each other, and their fluid intakes lie at ~30, ~60, and ~50 m below the sediment-basement interface (mbs), respectively. In addition, CORK 1362A contains a second intake at a deep (~200 mbs) horizon. The basement fluids from the three CORKs contained significantly higher concentrations of methane (1.5-13μM) and hydrogen (0.05-1.1 μM) than in bottom seawater (0.002 and 0.0004, respectively), indicating that prevalence and availability of both methane and hydrogen as electron donors for the subseafloor biosphere. Thermodynamic calculations show that sulfate reduction coupled with either methane or hydrogen oxidation is energy yielding in the oceanic basement. The δ13C values of methane ranged from -43×1‰ to -58×0.3‰; the δ2H values of methane in CORKs 1301A, 1362A and 1362B fluids were 57×5‰, -262×2‰, -209×2‰, respectively. The isotopic compositions suggest that methane in the basement fluid is of biogenic origin. Interestingly, the δ2H value of methane in the CORK 1301A fluids is far more positive than that in other marine environments investigated so far (Martens et al., 1999; Kessler et al., 2006; Kessler et al., 2008). The positive δ2H value of methane is best explained by partial microbial oxidation of biogenic methane, which has an initial isotopic composition similar to that from CORK 1362A and 1362B borehole fluid. High-throughput sequencing of the small subunit ribosomal RNA gene indicates the presence of methanogenic Euryarchaeota (e.g. Methanobacteria) in each of the borehole fluid samples described here. On average, fluid samples from boreholes 1362A and 1362B possessed a relatively higher abundance of known methanogens compared to borehole 1301A, consistent with higher methane concentration in 1362A and 1362B relative to 1301A fluids. Methane-oxidizing bacterial lineages from the phyla Proteobacteria and Verrucomicrobia were also detected; however, these groups were less abundant relative to the putative methane-producing groups. In conclusion, our study shows that methane and hydrogen are available electron donors and that methane is produced and potentially consumed by microorganisms in the oceanic basement. The data presented will guide incubation experiments using basement fluid in order to better understand the methane production/utilization processes within the oceanic basement.

Impact of sulfate pollution on anaerobic biogeochemical cycles in a wetland sediment.

PubMed

Baldwin, Darren S; Mitchell, Alison

2012-03-15

The impact of sulfate pollution is increasingly being seen as an issue in the management of inland aquatic ecosystems. In this study we use sediment slurry experiments to explore the addition of sulfate, with or without added carbon, on the anaerobic biogeochemical cycles in a wetland sediment that previously had not been exposed to high levels of sulfate. Specifically we looked at the cycling of S (sulfate, dissolved and particulate sulfide--the latter measured as acid volatile sulfide; AVS), C (carbon dioxide, bicarbonate, methane and the short chain volatile fatty acids formate, acetate, butyrate and propionate), N (dinitrogen, ammonium, nitrate and nitrite) and redox active metals (Fe(II) and Mn(II)). Sulfate had the largest effects on the cycling of S and C. All the added S at lower loadings were converted to AVS over the course of the experiment (30 days). At the highest loading (8 mmol) less than 50% of consumed S was converted to AVS, however this is believed to be a kinetic effect. Although sulfate reduction was occurring in sediments with added sulfate, dissolved sulfide concentrations remained low throughout the study. Sulfate addition affected methanogenesis. In the absence of added carbon, addition of sulfate, even at a loading of 1 mmol, resulted in a halving of methane formation. The initial rate of formation of methane was not affected by sulfate if additional carbon was added to the sediment. However, there was evidence for anaerobic methane oxidation in those sediments with added sulfate and carbon, but not in those sediments treated only with carbon. Surprisingly, sulfate addition had little apparent impact on N dynamics; previous studies have shown that sulfide can inhibit denitrification and stimulate dissimilatory nitrate reduction to ammonia. We propose that because most of the reduced sulfur was in particulate form, levels of dissolved sulfide were too low to interfere with the N cycle. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Assessment of Surface Water Contamination from Coalbed Methane Fracturing-Derived Volatile Contaminants in Sullivan County, Indiana, USA.

PubMed

Meszaros, Nicholas; Subedi, Bikram; Stamets, Tristan; Shifa, Naima

2017-09-01

There is a growing concern over the contamination of surface water and the associated environmental and public health consequences from the recent proliferation of hydraulic fracturing in the USA. Petroleum hydrocarbon-derived contaminants of concern [benzene, toluene, ethylbenzene, and xylenes (BTEX)] and various dissolved cations and anions were spatially determined in surface waters around 15 coalbed methane fracking wells in Sullivan County, IN, USA. At least one BTEX compound was detected in 69% of sampling sites (n = 13) and 23% of sampling sites were found to be contaminated with all of the BTEX compounds. Toluene was the most common BTEX compound detected across all sampling sites, both upstream and downstream from coalbed methane fracking wells. The average concentration of toluene at a reservoir and its outlet nearby the fracking wells was ~2× higher than other downstream sites. However, one of the upstream sites was found to be contaminated with BTEX at similar concentrations as in a reservoir site nearby the fracking well. Calcium (~60 ppm) and sulfates (~175 ppm) were the dominant cations and anions, respectively, in surface water around the fracking sites. This study represents the first report of BTEX contamination in surface water from coalbed methane hydraulic fracturing wells.

Simulation of ground-water flow and solute transport in the Glen Canyon aquifer, East-Central Utah

USGS Publications Warehouse

Freethey, Geoffrey W.; Stolp, Bernard J.

2010-01-01

The extraction of methane from coal beds in the Ferron coal trend in central Utah started in the mid-1980s. Beginning in 1994, water from the extraction process was pressure injected into the Glen Canyon aquifer. The lateral extent of the aquifer that could be affected by injection is about 7,600 square miles. To address regional-scale effects of injection over a decadal time frame, a conceptual model of ground-water movement and transport of dissolved solids was formulated. A numerical model that incorporates aquifer concepts was then constructed and used to simulate injection.The Glen Canyon aquifer within the study area is conceptualized in two parts—an active area of ground-water flow and solute transport that exists between recharge areas in the San Rafael Swell and Desert, Waterpocket Fold, and Henry Mountains and discharge locations along the Muddy, Dirty Devil, San Rafael, and Green Rivers. An area of little or negligible ground-water flow exists north of Price, Utah, and beneath the Wasatch Plateau. Pressurized injection of coal-bed methane production water occurs in this area where dissolved-solids concentrations can be more than 100,000 milligrams per liter. Injection has the potential to increase hydrologic interaction with the active flow area, where dissolved-solids concentrations are generally less than 3,000 milligrams per liter.Pressurized injection of coal-bed methane production water in 1994 initiated a net addition of flow and mass of solutes into the Glen Canyon aquifer. To better understand the regional scale hydrologic interaction between the two areas of the Glen Canyon aquifer, pressurized injection was numerically simulated. Data constraints precluded development of a fully calibrated simulation; instead, an uncalibrated model was constructed that is a plausible representation of the conceptual flow and solute-transport processes. The amount of injected water over the 36-year simulation period is about 25,000 acre-feet. As a result, simulated water levels in the injection areas increased by 50 feet and dissolved-solids concentrations increased by 100 milligrams per liter or more. These increases are accrued into aquifer storage and do not extend to the rivers during the 36-year simulation period. The amount of change in simulated discharge and solute load to the rivers is less than the resolution accuracy of the numerical simulation and is interpreted as no significant change over the considered time period.

Stimulation of methane generation from nonproductive coal by addition of nutrients or a microbial consortium

USGS Publications Warehouse

Jones, Elizabeth J.P.; Voytek, Mary A.; Corum, Margo D.; Orem, William H.

2010-01-01

Biogenic formation of methane from coal is of great interest as an underexploited source of clean energy. The goal of some coal bed producers is to extend coal bed methane productivity and to utilize hydrocarbon wastes such as coal slurry to generate new methane. However, the process and factors controlling the process, and thus ways to stimulate it, are poorly understood. Subbituminous coal from a nonproductive well in south Texas was stimulated to produce methane in microcosms when the native population was supplemented with nutrients (biostimulation) or when nutrients and a consortium of bacteria and methanogens enriched from wetland sediment were added (bioaugmentation). The native population enriched by nutrient addition included Pseudomonas spp., Veillonellaceae, and Methanosarcina barkeri. The bioaugmented microcosm generated methane more rapidly and to a higher concentration than the biostimulated microcosm. Dissolved organics, including long-chain fatty acids, single-ring aromatics, and long-chain alkanes accumulated in the first 39 days of the bioaugmented microcosm and were then degraded, accompanied by generation of methane. The bioaugmented microcosm was dominated by Geobacter sp., and most of the methane generation was associated with growth of Methanosaeta concilii. The ability of the bioaugmentation culture to produce methane from coal intermediates was confirmed in incubations of culture with representative organic compounds. This study indicates that methane production could be stimulated at the nonproductive field site and that low microbial biomass may be limiting in situ methane generation. In addition, the microcosm study suggests that the pathway for generating methane from coal involves complex microbial partnerships.

Bioconversion of Coal: Hydrologic indicators of the extent of coal biodegradation under different redox conditions and coal maturity, Velenje Basin case study, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Grassa, Fausto; Lazar, Jerneja; Jamnikar, Sergej; Zavšek, Simon; McIntosh, Jennifer

2014-05-01

Underground mining of coal and coal combustion for energy has significant environmental impacts. In order to reduce greenhouse gas emissions, other lower -carbon energy sources must be utilized. Coalbed methane (CBM) is an important source of relatively low-carbon energy. Approximately 20% of world's coalbed methane is microbial in origin (Bates et al., 2011). Interest in microbial CBM has increased recently due to the possibility of stimulating methanogenesis. Despite increasing interest, the hydrogeochemical conditions and mechanisms for biodegradation of coal and microbial methane production are poorly understood. This project aims to examine geochemical characteristics of coalbed groundwater and coalbed gases in order to constrain biogeochemical processes to better understand the entire process of coal biodegradation of coal to coalbed gases. A better understanding of geochemical processes in CBM areas may potentially lead to sustainable stimulation of microbial methanogenesis at economical rates. Natural analogue studies of carbon dioxide occurring in the subsurface have the potential to yield insights into mechanisms of carbon dioxide storage over geological time scales (Li et al., 2013). In order to explore redox processes related to methanogenesis and determine ideal conditions under which microbial degradation of coal is likely to occur, this study utilizes groundwater and coalbed gas samples from Velenje Basin. Determination of the concentrations of methane, carbondioxide, nitrogen, oxygen, argon was performed with homemade NIER mass spectrometer. Isotopic composition of carbon dioxide, isotopic composition of methane, isotopic composition of deuterium in methane was determined with Europa-Scientific IRMS with an ANCA-TG preparation module and Thermo Delta XP GC-TC/CF-IRMS coupled to a TRACE GC analyzer. Total alkalinity of groundwater was measured by Gran titration. Major cations were analyzed by ICP-OES and anions by IC method. Isotopic composition of dissolved inorganic carbon was determined by MultiflowBio preparation module. The stable isotope composition of sulphur was determined with a Europa Scientific 20-20 continuous flow IRMS ANCA-SL preparation module. Concentrations of tritium were determined with the electrolytic enrichment method. PHREEQC for Windows was used to perform thermodynamic modelling. The average coalbed gas composition in the coalbed seam is approximately carbon dioxide: methane > 2:1, where a high proportion of CO2 is adsorbed on the lignite structure, while methane is present free in coal fractures. It can be concluded that isotopic composition of carbon in methane from -70.4‰ to -50.0‰ is generated via acetate fermentation and via reduction of carbon dioxide, while isotopic composition of carbon in methane values range from -50.0‰ to -18.8‰, thermogenic methane can be explained by secondary processes, causing enrichment of residual methane with the heavier carbon isotope. Isotopic composition of deuterium in methane range from -343.9‰ to -223.1‰. Isotopic composition of carbon in carbon dioxide values at excavation fields range from -11.0‰ to +5‰ and are endogenic and microbial in origin. The major ion chemistry, redox conditions, stable isotopes and tritium measured in groundwater from the Velenje Basin, suggest that the Pliocene and Triassic aquifers contain distinct water bodies. Groundwater in the Triassic aquifer is dominated by hydrogen carbonate, calcium, magnesium and isotopic composition of dissolved inorganic carbon indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has isotopic composition of oxygen and isotopic composition of deuterium values which plot near surface waters on the local and global meteoric water lines and detectable tritium reflects recent recharge. In contrast, groundwater in the Pliocene aquifers is enriched in magnesium, sodium, calcium, potassium, and silica and has alkalinity and isotopic composition of dissolved inorganic carbon values with low sulphate and nitrate concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and magnesium-rich clay minerals. Pliocene aquifer waters are also depleted in heavier oxygen isotope and heavier deuterium isotope and have tritium concentrations near the detection limit, suggesting these waters are older. References Bates, B.L., McIntosh J.C., Lohse K.A., Brooks P.D. 2011: Influence of groundwater flowpaths, residence times, and nutrients on the extent of microbial methanogenesis in coal beds: Powder River Basin, USA, Chemical geology, 284, 45-61. Li, W., Cheng Y., Wang L., Zhou H., Wang H., Wang L. 2013: Evaluating the security of geological coalbed sequestration of supercritical CO2 reservoirs: The Haishiwan coalfield, China as a natural analogue, International Journal of Greenhouse Gas Control, 13, 102-111.

Time-series measurements of methane (CH4) distribution during open water and ice-cover in lakes throughout the Mackenzie River Delta (Canada)

NASA Astrophysics Data System (ADS)

McIntosh, H.; Lapham, L.; Orcutt, B.; Wheat, C. G.; Lesack, L.; Bergstresser, M.; Dallimore, S. R.; MacLeod, R.; Cote, M.

2016-12-01

Arctic lakes are known to emit large amounts of methane to the atmosphere and their importance to the global methane (CH4) cycle has been recognized. It is well known CH4 builds up in Arctic lakes during ice-cover, but the amount of and when the CH4 is released to the atmosphere is not well known. Our preliminary results suggest the largest flux of CH4 from lakes to the atmosphere occurs slightly before complete ice-out; while others have shown the largest flux occurs when lakes overturn in the spring. During ice-out, CH4 can also be oxidized by methane oxidizing bacteria before it can efflux to the atmosphere from the surface water. In order to elucidate the processes contributing to Arctic lake CH4 emissions, continuous, long-term and large scale spatial sampling is required; however it is difficult to achieve in these remote locations. We address this problem using two sampling techniques. 1) We deployed osmotically powered pumps (OsmoSamplers), which were able to autonomously and continuously collect lake bottom water over the course of a year from multiple lakes in the Mackenzie River Delta. OsmoSamplers were placed in four lakes in the mid Delta near Inuvik, Northwest Territories, Canada, two lakes in the outer Delta, and two coastal lakes on Richard's Island in 2015. The dissolved CH4 concentration, stable isotope content of CH4 (δ13C-CH4), and dissolved sulfate concentrations in bottom water from these lakes will be presented to better understand methane dynamics under the ice and over time. 2) Along with the time-series data, we will also present data from discrete samples collected from 40 lakes in the mid Delta during key time periods, before and immediately after the spring ice-out. By determining the CH4 dynamics throughout the year we hope to improve predictions of how CH4 emissions may change in a warming Arctic environment.

Dissolved Organic Carbon: Nitrate Ratios as a Driver of Methane Fluxes in Stream Ecosystems

NASA Astrophysics Data System (ADS)

Sullivan, B. W.; Wymore, A.; Schade, J. D.; McDowell, W. H.

2016-12-01

Fluvial ecosystems are poorly understood components of the global methane (CH4) budget because the ecology of CH4 fluxes in streams has yet to be sufficiently elucidated. Both CH4 production and uptake via oxidation are microbially mediated processes, but it is unclear where in the fluvial environment are the sources and sinks of CH4 and what role terrestrial inputs of carbon (C) and nutrients have on the magnitude and direction of CH4 flux. To address these uncertainties, we measured CH4 fluxes in a laboratory incubation from two temperate headwater streams that differed in ambient dissolved organic carbon (DOC) and nitrate (NO3-) concentrations. We amended stream water and sediment microcosms from each site with labile DOC from senesced leaf litter to assess how DOC concentration and the DOC:NO3- ratio affect proximate controls on CH4 flux. Lastly, we manipulated sediment and water column ratios (0-100%) to estimate sources and fates of CH4 flux within the ecosystem. We measured CH4 fluxes for the first 120 minutes of the incubation to simulate short-term, in stream processes. Initially, streams were a source of methane, but switched to a sink within 120 minutes. Methane fluxes were statistically similar in both stream sediment and water, suggesting that microbial processing of CH4 has similar directionality and magnitude in each environment. Both CH4 oxidation and production were significantly correlated with the DOC: NO3- ratio over the course of the incubation. Early in the incubation, increasing DOC: NO3- increased CH4 flux, but late in the incubation, increasing DOC: NO3- increased CH4 oxidation. Together, our results challenge existing paradigms of CH4 flux in the fluvial environment and identify the DOC:NO3- ratio as a possible mechanism that can explain spatial and temporal CH4 flux patterns in streams.

Formation of carbonate concretions in deep-sea sediment below the CCD and above an active gas hydrate system

NASA Astrophysics Data System (ADS)

Dicus, C. M.; Snyder, G. T.; Dickens, G. R.

2004-12-01

Site 1230 of the Ocean Drilling Program targeted the chemistry and microbiology of an active deep-water gas hydrate system in the Peru Trench. The site is noteworthy because, at nearly 6000 m water depth, it lies well below the carbonate compensation depth and the sediments comprise mostly terrigenous clays and biogenic silica. Shipboard work at this site delineated a prominent sulfate-methane transition (SMT) at 8-10 m below seafloor (mbsf) as well as some carbonate horizons. In this study, we present calcium and strontium data for pore waters and sediments at this site, including across the SMT. Concentration profiles show that dissolved Ca2+ diffuses downward from the seafloor toward the SMT, where a sharp inflection indicates consumption of Ca2+ into an authigenic phase. Dissolved Sr2+, on the other hand, diffuses upward from depth toward the SMT. Again, however, a prominent inflection suggests removal of Sr2+ to sediment. The inferences from pore water profiles are borne out by sediment chemistry. Large peaks in the calcium and strontium content of sediment mark the SMT. The calcium and strontium fronts reach ˜2700 and ˜5 mmol/kg, respectively, at 9 mbsf, which are much greater than average background values of ˜10 and ˜1 mmol/kg. These authigenic fronts are primarily composed of carbonate minerals, as determined by acetic acid extractions and x-ray diffraction. Because the calcium and strontium fronts coincide with both the SMT and changes in dissolved chemistry, it is proposed that the carbonates are currently forming as follows: methane rising from the underlying gas hydrate system reacts with dissolved sulfate through anaerobic oxidation of methane which releases HCO3- and alkalinity and causes carbonate precipitation. The overall process has been observed elsewhere; the Peru Trench is interesting, however, because the process leads to carbonate in sediments otherwise devoid of carbonate.

Methane occurrence in groundwater of south-central New York State, 2012: summary of findings

USGS Publications Warehouse

Heisig, Paul M.; Scott, Tia-Marie

2013-01-01

A survey of methane in groundwater was undertaken to document methane occurrence on the basis of hydrogeologic setting within a glaciated 1,810-square-mile area of south-central New York that has not seen shale-gas resource development. The adjacent region in northeastern Pennsylvania has undergone shale-gas resource development from the Marcellus Shale. Well construction and subsurface data were required for each well sampled so that the local hydrogeologic setting could be classified. All wells were also at least 1 mile from any known gas well (active, exploratory, or abandoned). Sixty-six domestic wells and similar purposed supply wells were sampled during summer 2012. Field water-quality characteristics (pH, specific conductance, dissolved oxygen, and temperature) were measured at each well, and samples were collected and analyzed for dissolved gases, including methane and short-chain hydrocarbons. Carbon and hydrogen isotopic ratios of methane were measured in 21 samples that had at least 0.3 milligram per liter (mg/L) methane.

Performance Evaluation and Dissolved Oxygen Effect in Deep-bed Denitrification Filter: a Full-scale Plant Case Study

NASA Astrophysics Data System (ADS)

Hu, Xiang; Hu, Jie; Wu, Ke; Hou, Hongxun

2018-01-01

The aims of this study were twofold. Firstly, the denitrificaion performance in deep-bed denitrificaiton filter (DBDF), serving as the advanced total nitrogen (TN) and total phosphorus (TP) removal technology, was evaluated. Secondly, the effect of dissolved oxygen (DO) into the DBDF on both the denitrificaion performance and the external carbon source addition was investigated. The operational results over eight months demonstrated good TN removal efficiency (87.8%) in the studied full-scale plant, in which 70.7% and 17.1% of TN were removed in the pre-denitrifation in oxidation ditch and post-denitrifation in DBDF, respectively. The DO concentration was inversely related to both the external carbon source dosage and the nitrate removed in DBDF. A dose of 3.60Kg methane (97%) was required to remove 1Kg nitrate, with approximately 26.2% of methane dosed was depleted by the DO in DBDF influent. It is suggested to take some measures to eliminate or mitigate the waterfall reoxygenation at process configurations before the DBDF, which is expected to save the cost of external carbon source.

Groundwater quality in Geauga County, Ohio: status, including detection frequency of methane in water wells, 2009, and changes during 1978-2009

USGS Publications Warehouse

Jagucki, Martha L.; Kula, Stephanie P.; Mailot, Brian E.

2015-01-01

To evaluate whether constituent concentrations consistently increased or decreased over time, the strength of the association between sampling year (time) and constituent concentration was statistically evaluated for 116 water-quality samples collected by the USGS in 1978, 1980, 1986, 1999, and 2009 from a total of 65 wells across the county (generally domestic wells or wells serving small businesses or churches). Results indicate that many of the constituents that have been analyzed for decades exhibited no consistent temporal trends at a statistically significant level (p-value less than 0.05); fluctuations in concentrations of these constituents represent natural variation in groundwater quality. Dissolved oxygen, calcium, and sulfate concentrations and chloride:bromide ratios increased over time in one or more aquifers, while pH and concentrations of bromide and dissolved organic carbon decreased over time. Detections of total coliform bacteria and nitrate did not become more frequent from 1986 to 2009, even though potential sources of these constituents, such as number of septic systems (linked to population) and percent developed land in the county, increased during this period.

Rumen protozoa and methanogenesis: not a simple cause-effect relationship.

PubMed

Morgavi, Diego P; Martin, Cécile; Jouany, Jean-Pierre; Ranilla, Maria José

2012-02-01

Understanding the interactions between hydrogen producers and consumers in the rumen ecosystem is important for ruminant production and methane mitigation. The present study explored the relationships between rumen protozoa, methanogens and fermentation characteristics. A total of six donor sheep harbouring (F, faunated) or not (D, defaunated) protozoa in their rumens (D animals were kept without protozoa for a period of a few months (D - ) or for more than 2 years (D+)) were used in in vitro and in vivo experiments. In vitro the absence of protozoa decreased NH3 and butyrate production and had no effect on methane. In contrast, the liquid-associated bacterial and methanogens fraction of D+ inocula produced more methane than D -  and F inoculum (P < 0·05). In vivo fermentation parameters of donor animals showed the same trend on NH3 and butyrate and showed that D+ animals were high methane emitters, while D -  were the lowest ( - 35 %). The concentration of dissolved dihydrogen measured after feeding followed the opposite trend. Methane emissions did not correlate with the relative abundance of methanogens in the rumen measured by quantitative PCR, but there was a trend for higher methanogens concentration in the solid-associated population of D+ animals compared with D -  animals. In contrast, PCR-denaturing gradient gel electrophoresis profiles of methanogens' methyl coenzyme-M reductase A gene showed a clear clustering in liquid-associated fractions for all three groups of donors but fewer differences in solid-associated fractions. These results show that the absence of protozoa may affect differently the methanogen community and methane emissions in wethers.

Constraints of gas venting activity for the interstitial water geochemistry at the shallow gas hydrate site, eastern margin of the Japan Sea; results from high resolution time-series fluid sampling by OsmoSampler

NASA Astrophysics Data System (ADS)

Owari, S.; Tomaru, H.; Matsumoto, R.

2016-12-01

We have conducted ROV researches in the eastern margin of the Japan Sea where active gas venting and outcropping of gas hydrates were observed near the seafloor and have found the strength and location of venting had changed within a few days. These observations indicate the seafloor environments with the shallow gas hydrate system could have changed for short period compared to a geological time scale. We have applied a long-term osmotic fluid sampling system "OsmoSampler" on the active gas hydrate system for one year in order to document how the gas venting and gas hydrate activity have changed the geochemical environments near the seafloor. All the major ion concentrations in the interstitial water show synchronous increase and decrease repeatedly in three to five days, reflecting the incorporation and release of fresh water in gas hydrates in response to the gas concentration change near the sampling site. Dissolved methane concentration increases rapidly and excessively (over several mM) in the first 40 days corresponding to the active gas venting. The increases of methane concentration are often associated with high ion concentration during high water pressure period, indicating excess gas release from shallow gas pockets. Contrarily, enhanced gas hydrate growth may plug the fluid-gas paths in shallow sediment, reducing gas hydrate formation due to the decrease of methane flux. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

Modeling sulfate reduction in methane hydrate-bearing continental margin sediments: Does a sulfate-methane transition require anaerobic oxidation of methane?

USGS Publications Warehouse

Malinverno, A.; Pohlman, J.W.

2011-01-01

The sulfate-methane transition (SMT), a biogeochemical zone where sulfate and methane are metabolized, is commonly observed at shallow depths (1-30 mbsf) in methane-bearing marine sediments. Two processes consume sulfate at and above the SMT, anaerobic oxidation of methane (AOM) and organoclastic sulfate reduction (OSR). Differentiating the relative contribution of each process is critical to estimate methane flux into the SMT, which, in turn, is necessary to predict deeper occurrences of gas hydrates in continental margin sediments. To evaluate the relative importance of these two sulfate reduction pathways, we developed a diagenetic model to compute the pore water concentrations of sulfate, methane, and dissolved inorganic carbon (DIC). By separately tracking DIC containing 12C and 13C, the model also computes ??13C-DIC values. The model reproduces common observations from methane-rich sediments: a well-defined SMT with no methane above and no sulfate below and a ??13C-DIC minimum at the SMT. The model also highlights the role of upward diffusing 13C-enriched DIC in contributing to the carbon isotope mass balance of DIC. A combination of OSR and AOM, each consuming similar amounts of sulfate, matches observations from Site U1325 (Integrated Ocean Drilling Program Expedition 311, northern Cascadia margin). Without AOM, methane diffuses above the SMT, which contradicts existing field data. The modeling results are generalized with a dimensional analysis to the range of SMT depths and sedimentation rates typical of continental margins. The modeling shows that AOM must be active to establish an SMT wherein methane is quantitatively consumed and the ??13C-DIC minimum occurs. The presence of an SMT generally requires active AOM. Copyright 2011 by the American Geophysical Union.

Methane hydrate - A major reservoir of carbon in the shallow geosphere?

USGS Publications Warehouse

Kvenvolden, K.A.

1988-01-01

Methane hydrates are solids composed of rigid cages of water molecules that enclose methane. Sediment containing methane hydrates is found within specific pressure-temperature conditions that occur in regions of permafrost and beneath the sea in outer continental margins. Because methane hydrates are globally widespread and concentrate methane within the gas-hydrate structure, the potential amount of methane present in the shallow geosphere at subsurface depths of < ???2000 m is very large. However, estimates of the amount are speculative and range over about three orders of magnitude, from 2 ?? 103 to 4 ?? 106 Gt (gigatons = 1015 g) of carbon, depending on the assumptions made. The estimate I favor is ??? 1 ?? 104 Gt of carbon. The estimated amount of organic carbon in the methane-hydrate reservoir greatly exceeds that in many other reservoirs of the global carbon cycle - for example, the atmosphere (3.6 Gt); terrestrial biota (830 Gt); terrestrial soil, detritus and peat (1960 Gt); marine biota (3 Gt); and marine dissolved materials (980 Gt). In fact, the amount of carbon may exceed that in all fossil fuel deposits (5 ?? 103 Gt). Because methane hydrates contain so much methane and occur in the shallow geosphere, they are of interest as a potential resource of natural gas and as a possible source of atmospheric methane released by global warming. As a potential resource, methane hydrates pose both engineering and production problems. As a contributor to a changing global climate, destabilized methane hydrates, particularly those in shallow, nearshore regions of the Arctic Ocean, may have some effect, but this effect will probably be minimal, at least during the next 100 years. ?? 1988.

Numbers, biomass and cultivable diversity of microbial populations relate to depth and borehole-specific conditions in groundwater from depths of 4-450 m in Olkiluoto, Finland.

PubMed

Pedersen, Karsten; Arlinger, Johanna; Eriksson, Sara; Hallbeck, Anna; Hallbeck, Lotta; Johansson, Jessica

2008-07-01

Microbiology, chemistry and dissolved gas in groundwater from Olkiluoto, Finland, were analysed over 3 years; samples came from 16 shallow observation tubes and boreholes from depths of 3.9-16.2 m and 14 deep boreholes from depths of 35-742 m. The average total number of cells (TNC) was 3.9 x 10(5) cells per ml in the shallow groundwater and 5.7 x 10(4) cells per ml in the deep groundwater. There was a significant correlation between the amount of biomass, analysed as ATP concentration, and TNC. ATP concentration also correlated with the stacked output of anaerobic most probable number cultivations of nitrate-, iron-, manganese- and sulphate-reducing bacteria, and acetogenic bacteria and methanogens. The numbers and biomass varied at most by approximately three orders of magnitude between boreholes, and TNC and ATP were positively related to the concentration of dissolved organic carbon. Two depth zones were found where the numbers, biomass and diversity of the microbial populations peaked. Shallow groundwater down to a depth of 16.2 m on average contained more biomass and cultivable microorganisms than did deep groundwater, except in a zone at a depth of approximately 300 m where the average biomass and number of cultivable microorganisms approached those of shallow groundwater. Starting at a depth of approximately 300 m, there were steep gradients of decreasing sulphate and increasing methane concentrations with depth; together with the peaks in biomass and sulphide concentration at this depth, these suggest that anaerobic methane oxidation may be a significant process at depth in Olkiluoto.

Methane Release and Pingo-Like Feature Across the South kara Sea Shels, an Area of Thawing Offshore Permafrost

NASA Astrophysics Data System (ADS)

Serov, P.; Portnov, A.; Mienert, J.

2015-12-01

Thawing subsea permafrost controls methane release from the Russian Arctic shelf having a considerable impact on the climate-sensitive Arctic environment. Our recent studies revealed extensive gas release over an area of at least 7500 km2and presence of pingo-like features (PLFs), showing severe methane leakage, in the South Kara Sea in water depths >20m (Serov et al., 2015). Specifically, we detected shallow methane ebullition sites expressed in water column acoustic anomalies (gas flares and gas fronts) and areas of increased dissolved methane concentrations in bottom water, which might be sufficient sources of carbon for seawater-atmosphere exchange. A study of nature and source of leaking gas was focused on two PLFs, which are acoustically transparent circular mounds towering 5-9 m above the surrounding seafloor. One PLF (PLF 2) connects to biogenic gas from deeper sources, which is reflected in δ13CCH4 values ranging from -55,1‰ to -88,0‰ and δDCH4values varied from -175‰ to -246‰. Low organic matter content (0.52-1.69%) of seafloor sediments restricts extensive in situ methane production. The formation of PLF 2 is directly linked to the thawing of subsea permafrost and, possibly, decomposition of permafrost related gas hydrates. High accumulations of biogenic methane create the necessary forces to push the remaining frozen layers upwards and, therefore, form a topographic feature. We speculate that PLF 1, which shows ubiquitously low methane concentrations, is either a relict submerged terrestrial pingo, or a PLF lacking the necessary underlying methane accumulations. Our model of glacial-interglacial permafrost evolution supports a scenario in which subsea permafrost tapers seaward and pinches out at 20m isobaths, controlling observed methane emissions and development of PLFs. Serov. P., A. Portnov, J. Mienert, P. Semenov, and P. Ilatovskaya (2015), Methane release from pingo-like features across the South Kara Sea shelf, an area of thawnig offshore permafrost, J. Geophys. Res. Earth Surf.,120,doi:10.1002/2015JF003467

Methanotrophic bacteria.

PubMed Central

Hanson, R S; Hanson, T E

1996-01-01

Methane-utilizing bacteria (methanotrophs) are a diverse group of gram-negative bacteria that are related to other members of the Proteobacteria. These bacteria are classified into three groups based on the pathways used for assimilation of formaldehyde, the major source of cell carbon, and other physiological and morphological features. The type I and type X methanotrophs are found within the gamma subdivision of the Proteobacteria and employ the ribulose monophosphate pathway for formaldehyde assimilation, whereas type II methanotrophs, which employ the serine pathway for formaldehyde assimilation, form a coherent cluster within the beta subdivision of the Proteobacteria. Methanotrophic bacteria are ubiquitous. The growth of type II bacteria appears to be favored in environments that contain relatively high levels of methane, low levels of dissolved oxygen, and limiting concentrations of combined nitrogen and/or copper. Type I methanotrophs appear to be dominant in environments in which methane is limiting and combined nitrogen and copper levels are relatively high. These bacteria serve as biofilters for the oxidation of methane produced in anaerobic environments, and when oxygen is present in soils, atmospheric methane is oxidized. Their activities in nature are greatly influenced by agricultural practices and other human activities. Recent evidence indicates that naturally occurring, uncultured methanotrophs represent new genera. Methanotrophs that are capable of oxidizing methane at atmospheric levels exhibit methane oxidation kinetics different from those of methanotrophs available in pure cultures. A limited number of methanotrophs have the genetic capacity to synthesize a soluble methane monooxygenase which catalyzes the rapid oxidation of environmental pollutants including trichloroethylene. PMID:8801441

Hydrogeology, ground-water quality, and source of ground water causing water-quality changes in the Davis well field at Memphis, Tennessee

USGS Publications Warehouse

Parks, William S.; Mirecki, June E.; Kingsbury, James A.

1995-01-01

NETPATH geochemical model code was used to mix waters from the alluvial aquifer with water from the Memphis aquifer using chloride as a conservative tracer. The resulting models indicated that a mixture containing 3 percent alluvial aquifer water mixed with 97 percent unaffected Memphis aquifer water would produce the chloride concentration measured in water from the Memphis aquifer well most affected by water-quality changes. NETPATH also was used to calculate mixing percentages of alluvial and Memphis aquifer Abstract waters based on changes in the concentrations of selected dissolved major inorganic and trace element constituents that define the dominant reactions that occur during mixing. These models indicated that a mixture containing 18 percent alluvial aquifer water and 82 percent unaffected Memphis aquifer water would produce the major constituent and trace element concentrations measured in water from the Memphis aquifer well most affected by water-quality changes. However, these model simulations predicted higher dissolved methane concentrations than were measured in water samples from the Memphis aquifer wells.

Porewater biogeochemistry and soil metabolism in dwarf red mangrove habitats (Twin Cays, Belize)

USGS Publications Warehouse

Lee, R.Y.; Porubsky, W.P.; Feller, Ilka C.; McKee, K.L.; Joye, S.B.

2008-01-01

Seasonal variability in biogeochemical signatures was used to elucidate the dominant pathways of soil microbial metabolism and elemental cycling in an oligotrophic mangrove system. Three interior dwarf mangrove habitats (Twin Cays, Belize) where surface soils were overlain by microbial mats were sampled during wet and dry periods of the year. Porewater equilibration meters and standard biogeochemical methods provided steady-state porewater profiles of pH, chloride, sulfate, sulfide, ammonium, nitrate/nitrite, phosphate, dissolved organic carbon, nitrogen, and phosphorus, reduced iron and manganese, dissolved inorganic carbon, methane and nitrous oxide. During the wet season, the salinity of overlying pond water and shallow porewaters decreased. Increased rainwater infiltration through soils combined with higher tidal heights appeared to result in increased organic carbon inventories and more reducing soil porewaters. During the dry season, evaporation increased both surface water and porewater salinities, while lower tidal heights resulted in less reduced soil porewaters. Rainfall strongly influenced inventories of dissolved organic carbon and nitrogen, possibly due to more rapid decay of mangrove litter during the wet season. During both times of year, high concentrations of reduced metabolites accumulated at depth, indicating substantial rates of organic matter mineralization coupled primarily to sulfate reduction. Nitrous oxide and methane concentrations were supersaturated indicating considerable rates of nitrification and/or incomplete denitrification and methanogenesis, respectively. More reducing soil conditions during the wet season promoted the production of reduced manganese. Contemporaneous activity of sulfate reduction and methanogenesis was likely fueled by the presence of noncompetitive substrates. The findings indicate that these interior dwarf areas are unique sites of nutrient and energy regeneration and may be critical to the overall persistence and productivity of mangrove-dominated islands in oligotrophic settings. ?? 2008 Springer Science+Business Media B.V.

Baseline assessment of groundwater quality in Wayne County, Pennsylvania, 2014

USGS Publications Warehouse

Senior, Lisa A.; Cravotta, III, Charles A.; Sloto, Ronald A.

2016-06-30

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, geologic formations which have potential for natural gas development, underlie Wayne County and neighboring counties in northeastern Pennsylvania. In 2014, the U.S. Geological Survey, in cooperation with the Wayne Conservation District, conducted a study to assess baseline shallow groundwater quality in bedrock aquifers in Wayne County prior to potential extensive shale-gas development. The 2014 study expanded on previous, more limited studies that included sampling of groundwater from 2 wells in 2011 and 32 wells in 2013 in Wayne County. Eighty-nine water wells were sampled in summer 2014 to provide data on the presence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. Depths of sampled wells ranged from 85 to 1,300 feet (ft) with a median of 291 ft. All of the groundwater samples collected in 2014 were analyzed for bacteria, major ions, nutrients, selected inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, selected man-made organic compounds (including volatile organic compounds and glycols), dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane.Results of the 2014 study show that groundwater quality generally met most drinking-water standards, but some well-water samples had one or more constituents or properties, including arsenic, iron, pH, bacteria, and radon-222, that exceeded primary or secondary maximum contaminant levels (MCLs). Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 4 of 89 samples (4.5 percent) with concentrations as high as 20 µg/L; arsenic concentrations were higher than the Health Advisory level of 2 µg/L in 27 of 89 samples (30 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 µg/L in 9 of 89 samples (10 percent). The pH ranged from 5.4 to 9.3 and did not meet the SMCL range of greater than 6.5 to less than 8.5 in 27 samples (30 percent); 22 samples had pH values less than 6.5, and 5 samples had pH values greater than 8.5. Total coliform bacteria were detected in 22 of 89 samples (25 percent); Escherichia coli were detected in only 2 of those 22 samples. Radon-222 activities ranged from 25 to 7,400 picocuries per liter (pCi/L), with a median of 2,120 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 86 of 89 samples (97 percent); radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 12 of 89 samples (13.5 percent).Water from 8 of the 89 wells (9 percent) had concentrations of methane greater than the reporting level of 0.24 milligrams per liter (mg/L) with the detectable methane concentrations ranging from 0.74 to 9.6 mg/L. Of 16 replicate samples submitted to another laboratory with a lower reporting level of 0.0002 mg/L, 15 samples had detectable methane concentrations that ranged from 0.0011 to 9.7 mg/L. Of these 15 samples, low levels of ethane (0.00032 to 0.0017 mg/L) were detected in 6 of 7 samples with methane concentrations greater than 0.75 mg/L. The isotopic composition of methane in 6 of 8 samples with sufficient dissolved methane (about 1 mg/L) for isotopic analysis is consistent with a predominantly thermogenic methane source (sample carbon isotopic ratio δ13CCH4 values ranging from -56.36 to -45.97 parts per thousand (‰) and hydrogen isotopic ratio δDCH4 values ranging from -233.1 to -141.1 ‰). However, the low levels of ethane relative to methane indicate that the methane may be of microbial origin and subsequently underwent oxidation. Isotopic compositions indicated a possibly mixed thermogenic and microbial source (carbon dioxide reduction process) for the methane in 1 of the 8 samples (δ13CCH4 of -63.72 and δDCH4 of -192.3 ‰) and potential oxidation of microbial and (or) thermogenic methane in the remaining sample (δ13CCH4 of -46.56 and δDCH4 of -79.7 ‰).Groundwater samples with relatively elevated methane concentrations (near or greater than 1 mg/L) had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with relatively low methane concentrations (less than 0.75 mg/L). The seven well-water samples with the highest methane concentrations (from about 1 to 9.6 mg/L) also had among the highest pH values (8.1 to 9.3, respectively) and the highest concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane.Groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less, by volume) similar in composition to that reported for gas and oil well brines in Pennsylvania. Most other samples with low methane concentrations (less than about 1 mg/L) had chloride/bromide ratios that indicate predominantly man-made sources of chloride, such as road salt, septic systems, and (or) animal waste. Although naturally occurring brines may originate from deeper parts of the aquifer system, the man-made sources are likely to affect shallow groundwater.Geochemical modeling showed that the water chemistry of samples with elevated pH, sodium, lithium, bromide, and alkalinity could result from dissolution of calcite (calcium carbonate) combined with cation exchange and mixing with a small amount of brine. Through cation exchange reactions (which are equivalent to processes in a water softener) calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. The spatial distribution of groundwater compositions generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands along the western border of Wayne County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can occur in deep wells in uplands but most frequently occur in stream valleys, especially at low elevations (less than about 1,200 ft above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River. Thus, the baseline assessment of groundwater quality in Wayne County prior to gas-well development shows that shallow (less than about 1,000 ft deep) groundwater is generally of good quality, but methane and some constituents present in high concentrations in brine (and produced waters from gas and oil wells) may be present at low to moderate concentrations in some parts of Wayne County.

[Key pathway of methane production and characteristics of stable carbon isotope of the Tuojia River waterbody.

PubMed

Zhao, Qiang; Lyu, Cheng Wen; Qin, Xiao Bo; Wu, Hong Bao; Wan, Yun Fan; Liao, Yu Lin; Lu, Yan Hong; Wang, Bin; Li, Yong

2018-05-01

This study aimed at exploring the key pathway of methane production and clarifying the composition and distribution of carbon (C) isotopes in the Tuojia River waterbody in Hunan Pro-vince. We estimated CH 4 concentrations and fluxes of four reaches (S 1 , S 2 , S 3 and S 4 ) by a two-layer diffusion model and gas chromatography. The spatial and temporal distribution of CH 4 flux and its relationship with environmental factors were examined. The key pathway of CH 4 production was investigated by stable C isotope method to analyze the distribution characteristics of 13 C isotope (δ 13 C) of water dissolved CH 4 and seston/benthic organic matter. There was significant seasonal variability in water pH, with mean value of (7.27±0.03). The concentration of dissolved oxygen (DO) showed strong seasonal and spatial variations, with the range of 0.43-13.99 mg·L -1 . The maximum value of DO occurred in S 1 and differed significantly in summer and autumin. In addition, DO differed significantly in winter and other seasons in S 2 , S 3 and S 4 . The concentration of dissolved organic carbon (DOC) showed a gradual increasing trend from source to estuary. The highest concentration of DOC (8.32 mg·L -1 ) was found in S 2 , while the lowest was observed in S 1 (0.34 mg·L -1 ). The electrical conductivity (EC) and oxidation-reduction potential (ORP) of water ranged from 17 to 436 μS·cm -1 and from -52.30 to 674.10 mV, respectively, which were significantly different among the four reaches (P＜0.05). Water ammonium nitrogen (NH 4 + -N) and nitrate nitrogen (NO 3 - -N) concentrations were in the ranges of 0.30-1.35 (averaged 0.90±0.10) mg·L -1 and 0.82-2.45 (averaged 1.62±0.16) mg·L -1 , respectively. The dissolved concentration and diffusion flux of CH 4 ranged from 0 to 5.28 μmol·L -1 and from -0.34 to 619.72 μg C·m -2 ·h -1 , respectively, with significant temporal and spatial variations. They showed a similar trend among reaches. Their values were highest in spring, followed by in winter and lowest in summer and autumn. Spatially, the CH 4 concentration and flux followed the order of S 2 >S 3 >S 4 >S 1 . The correlation analysis showed that CH 4 flux was positively correlated with NH 4 + -N and DOC. The pathway of CH 4 production of all reaches was dominated by acetic acid fermentation, while there were obvious differences among the four reaches. The contribution of CH 4 from acetic acid fermentation was greatest (87%) in S 1 , followed by S 4 (81%), S 2 (78%) and S 3 (76%). The mean value of the δ 13 C for dissolved CH 4 , seston organic matter and benthic organic matter was -41.64‰±1.91‰, -14.07‰±1.06‰ and -26.20‰±1.02‰, respectively. There was a positive correlation between the δ 13 C of dissolved CH 4 and benthic organic matter, whereas the δ 13 C value of dissolved CH 4 was negatively correlated with CH 4 flux.

Time-series measurements of bubble plume variability and water column methane distribution above Southern Hydrate Ridge, Oregon

NASA Astrophysics Data System (ADS)

Philip, Brendan T.; Denny, Alden R.; Solomon, Evan A.; Kelley, Deborah S.

2016-03-01

An estimated 500-2500 gigatons of methane carbon is sequestered in gas hydrate at continental margins and some of these deposits are associated with overlying methane seeps. To constrain the impact that seeps have on methane concentrations in overlying ocean waters and to characterize the bubble plumes that transport methane vertically into the ocean, water samples and time-series acoustic images were collected above Southern Hydrate Ridge (SHR), a well-studied hydrate-bearing seep site ˜90 km west of Newport, Oregon. These data were coregistered with robotic vehicle observations to determine the origin of the seeps, the plume rise heights above the seafloor, and the temporal variability in bubble emissions. Results show that the locations of seep activity and bubble release remained unchanged over the 3 year time-series investigation, however, the magnitude of gas release was highly variable on hourly time scales. Bubble plumes were detected to depths of 320-620 m below sea level (mbsl), in several cases exceeding the upper limit of hydrate stability by ˜190 m. For the first time, sustained gas release was imaged at the Pinnacle site and in-between the Pinnacle and the Summit area of venting, indicating that the subseafloor transport of fluid and gas is not restricted to the Summit at SHR, requiring a revision of fluid-flow models. Dissolved methane concentrations above background levels from 100 to 300 mbsl are consistent with long-term seep gas transport into the upper water column, which may lead to the build-up of seep-derived carbon in regional subsurface waters and to increases in associated biological activity.

In Situ Raman Spectroscopic Observations of Gas-Saturated Rising Oil droplets: Simulation with Decane as an Oil-Equivalent Substitute

NASA Astrophysics Data System (ADS)

Peltzer, E. T.; Walz, P. M.; Brewer, P. G.

2016-02-01

Oil droplets rising from the sea floor, whether from seeps or well leakage, contain very large quantities of dissolved gas that profoundly affects their density and critical oil-water interfacial characteristics. The primary dissolved gas is methane which may be up to 30% of the molar volume. This can create a hydrate skin as the methane gas is shed from the oil as it rises through the water column, thus decreasing in pressure and increasing in temperature, and steadily changing the rising droplet buoyancy. We have explored this phenomenon by executing controlled ROV based experiments with a "bubble cup" technique in which a small volume of gas saturated decane (saturated with pure methane, a mix of methane and nitrogen , or a mix of methane and CO2) is interrogated by laser Raman spectroscopy. The use of decane as an oil "substitute" is required since natural oil samples are highly fluorescent due to the presence of polycyclic aromatic hydrocarbons. We have devised Matlab techniques for extracting the spectroscopic dissolved methane signal from the thicket of decane peaks that surround it. We have directly observed the rate at which gases are lost from the "oil" per unit area at depths in the water column that are both within and outside the hydrate forming phase boundary. We have compared the behavior of both a non-hydrate forming dissolved gas (nitrogen) with CO2 where the hydrate phase boundary is at significantly shallower depth. The results indicate complex interfacial behavior and physical chemistry. We did not observe direct gas bubble formation on the decane outer surface but did observe gas bubble formation within the oil droplets as they rose through the water column. Because there are significant energy barriers for homogeneous bubble formation within the decane phase, we took this as evidence of significant gas super-saturation within the oil droplet. The gas loss rates increased significantly in all cases when the hydrate phase boundary was crossed.

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.

The comparison of greenhouse gas emissions in sewage treatment plants with different treatment processes.

PubMed

Masuda, Shuhei; Sano, Itsumi; Hojo, Toshimasa; Li, Yu-You; Nishimura, Osamu

2018-02-01

Greenhouse gas emissions from different sewage treatment plants: oxidation ditch process, double-circulated anoxic-oxic process and anoxic-oxic process were evaluated based on the survey. The methane and nitrous oxide characteristics were discussed based on the gaseous and dissolved gas profiles. As a result, it was found that methane was produced in the sewer pipes and the primary sedimentation tank. Additionally, a ventilation system would promote the gasification of dissolved methane in the first treatment units. Nitrous oxide was produced and emitted in oxic tanks with nitrite accumulation inside the sewage treatment plant. A certain amount of nitrous oxide was also discharged as dissolved gas through the effluent water. If the amount of dissolved nitrous oxide discharge is not included, 7-14% of total nitrous oxide emission would be overlooked. Based on the greenhouse gas calculation, electrical consumption and the N 2 O emission from incineration process were major sources in all the plants. For greenhouse gas reduction, oxidation ditch process has an advantage over the other advanced systems due to lower energy consumption, sludge production, and nitrogen removal without gas stripping. Copyright © 2017 Elsevier Ltd. All rights reserved.

Waste treatment and biogas quality in small-scale agricultural digesters.

PubMed

Lansing, Stephanie; Botero, Raúl Botero; Martin, Jay F

2008-09-01

Seven low-cost digesters in Costa Rica were studied to determine the potential of these systems to treat animal wastewater and produce renewable energy. The effluent water has a significantly lower oxygen demand (COD decreased from 2,968 mg/L to 472 mg/L) and higher dissolved nutrient concentration (NH(4)-N increased by 78.3% to 82.2mg/L) than the influent water, which increases the usefulness of the effluent as an organic fertilizer and decreases its organic loading on surface waters. On average, methane constituted 66% of the produced biogas, which is consistent with industrial digesters. Through principle component analysis, COD, turbidity, NH(4)-N, TKN, and pH were determined to be the most useful parameters to characterize wastewater. The results suggest that the systems have the ability to withstand fluctuations in the influent water quality. This study revealed that small-scale agricultural digesters can produce methane at concentrations useful for cooking, while improving the quality of the livestock wastewater.

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.

2016-04-01

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

Groundwater quality for 75 domestic wells in Lycoming County, Pennsylvania, 2014

USGS Publications Warehouse

Gross, Eliza L.; Cravotta, Charles A.

2017-03-06

Groundwater is a major source of drinking water in Lycoming County and adjacent counties in north-central and northeastern Pennsylvania, which are largely forested and rural and are currently undergoing development for hydrocarbon gases. Water-quality data are needed for assessing the natural characteristics of the groundwater resource and the potential effects from energy and mineral extraction, timber harvesting, agriculture, sewage and septic systems, and other human influences.This report, prepared in cooperation with Lycoming County, presents analytical data for groundwater samples from 75 domestic wells sampled throughout Lycoming County in June, July, and August 2014. The samples were collected using existing pumps and plumbing prior to any treatment and analyzed for physical and chemical characteristics, including nutrients, major ions, metals and trace elements, volatile organic compounds, gross-alpha particle and gross beta-particle activity, uranium, and dissolved gases, including methane and radon-222.Results indicate groundwater quality generally met most drinking-water standards, but that some samples exceeded primary or secondary maximum contaminant levels (MCLs) for arsenic, iron, manganese, total dissolved solids (TDS), chloride, pH, bacteria, or radon-222. Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 9 of the 75 (12 percent) well-water samples, with concentrations as high as 23.6 μg/L; arsenic concentrations were higher than the health advisory level (HAL) of 2 μg/L in 23 samples (31 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 μg/L in 20 of the 75 samples. Total manganese concentrations exceeded the SMCL of 50 μg/L in 20 samples and the HAL of 300 μg/L in 2 of those samples. Three samples had chloride concentrations that exceeded the SMCL of 250 milligrams per liter (mg/L); two of those samples exceeded the SMCL of 500 mg/L for TDS. The pH ranged from 5.3 to 9.15 and did not meet the SMCL range of 6.5 to 8.5 in 22 samples, with 17 samples having a pH less than 6.5 and 8 samples having pH greater than 8.5. Generally, the samples that had elevated TDS, chloride, or arsenic concentrations had high pH.Total coliform bacteria were detected in 39 of 75 samples (52 percent), with Escherichia coli detected in 10 of those 39 samples. Radon-222 activities ranged from non-detect to 7,420 picocuries per liter (pCi/L), with a median of 863 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 50 (67 percent) of the 75 samples; radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 3 samples.Water from 15 of 75 (20 percent) wells had concentrations of methane greater than the reporting level of 0.01 mg/L; detectable methane concentrations ranged from 0.04 to 16.8 mg/L. Two samples had methane concentrations (13.1 and 16.8 mg/L) exceeding the action level of 7 mg/L. Low levels of ethane (up to 0.12 mg/L) were present in the five samples with the highest methane concentrations (near or above 1 mg/L) that were analyzed for hydrocarbon compounds and isotopic composition. The isotopic composition of methane in four of these groundwater samples, from the Catskill and Lock Haven Formations and the Hamilton Group, have sample carbon isotopic ratio delta values (carbon-13/carbon-12) ranging from –42.36 to –36.08 parts per thousand (‰) and hydrogen isotopic ratio delta values (deuterium/protium) ranging from –212.0 to –188.4 ‰, which are consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source of the methane. However, the isotopic composition and ratios of methane to ethane in a fifth sample indicate the methane in that sample may be of microbial origin that subsequently underwent oxidation. The fifth sample had the highest concentration of methane, 16.8 mg/L, with an carbon isotopic ratio delta values of -50.59 ‰ and a hydrogen isotopic ratio delta values of -209.7 ‰.The six well-water samples with the highest methane concentrations also had among the highest pH values (8.25 to 9.15) and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane.Three of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported at undetermined depth below the freshwater aquifer and for gas and oil well brines in Pennsylvania. The sample with the highest methane concentration and most other samples with low methane concentrations (less than about 1 mg/L) have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt, septic systems, and (or) animal waste. Brines that are naturally present may originate from deeper parts of the aquifer system, while anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land-surface.The spatial distribution of groundwater compositions generally indicate that (1) uplands along the western border of Lycoming County usually have dilute, slightly acidic oxygenated, calcium-bicarbonate type waters; (2) intermediate altitudes or areas of carbonate bedrock usually have water of near neutral pH, with highest amounts of hardness (calcium and magnesium); (3) stream valleys, low elevations where groundwater may be discharging, and deep wells in uplands usually have water with pH values greater than 8 and highest arsenic, sodium, lithium, bromide concentrations. Geochemical modeling indicated that for samples with elevated pH, sodium, lithium, bromide, and alkalinity, the water chemistry could have resulted by dissolution of calcite (calcium carbonate) combined with cation-exchange and mixing with a small amount of brine. Through cation-exchange reactions between water and bedrock, which are equivalent to processes in a water softener, calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. Thus, the assessment of groundwater quality in Lycoming County indicates groundwater is generally of good quality, but various parts of Lycoming County can have groundwater with low to moderate concentrations of methane and other constituents that appear in naturally present brine and produced waters from gas and oil wells at high concentrations."

Age of Sulfate Methane Transition Zone Determined by Modelling Barium Sulfate Growth

NASA Astrophysics Data System (ADS)

Lin, S.; Wang, W. C.; Lien, K. L.; Liu, C. C.; Fan, L. F.

2017-12-01

Methane seep to the sediment/water interface could initiate anaerobic methane oxidation (AOM) with subsequent build up of chemosynthetic community, carbonate, pyrite and a number of other authigenic mineral formation. Determination the duration, sequence and time of methane seeps are keys to understand how methane seep to the environment and degree of alteration to the vicinity area. However, limited method existed in defining time of methane seep since there are some known problems involving typical dating methods, i.e. old carbon on C14 of fossil test or authigenic carbonate, thorium from surrounding matrix on U/Th authigenic carbonate dating. In this study, we have employed barium determination method (Dickens, 2001) to model timing of methane seep at two locations in the South China Sea. Our objective is to compare timing of the barium accumulation near the sulfate methane transition zone (SMTZ) on these two different locations and to seek if a similar mechanism driving the methane seep at two locations far apart. Dissolved barium, total sediment barium and aluminum were measured as well as pore water sulfate, and sediment pyrite concentrations. Time for the barium sulfate accumulation is calculated by: T = C/F, C= ∫ I x p x (1-Ø) Our results show that SMTZ is stabilized at each site for a duration of about 4000-5000 years. AOM process have been active at both sites at about the same time. In conjunction, pyrite also accumulated at a depth near the SMTZ as a result of methane oxidation. This result show that AOM could stay at the SMTZ for a relatively long period of time, on a scale of thousands of years.

Biogeochemical and Microbial Survey of Gravity Cores from the Guaymas Basin and Sonora Margin

NASA Astrophysics Data System (ADS)

Buckley, A.; Mckay, L. J.; Chanton, J.; Hensen, C.; Turner, T.; Aiello, I. W.; Ravelo, A. C.; Mortera, C.; Teske, A.

2015-12-01

During the cruise "Guaymas14" with RV El Puma (Oct. 14-25, 2014), 15 sediment cores were obtained from the Guaymas Basin Ridge flanks and the Sonora Margin, to contrast the shallow subsurface sediments of the seafloor set at this spreading center and its adjacent continental margin. Here we present biogeochemical profiles of porewater dissolved gases and stable ions, along with high-throughout 16S rRNA gene sequencing of selected samples. Cores from the NW and SE ends of the Guaymas Basin ridge flanks were not sulfidic, and showed neither sulfate depletion nor methane accumulation. In contrast, samples of compression-impacted Sonora Margin on the NE edge of Guaymas Basin and from the upper Sonora Margin beneath the oxygen minimum zone showed an abundance of sulfide, DIC with sulfate depletion, and accumulation of biogenic methane (δ13C-CH4 ca. -85 to -88 ‰) at supersaturated concentrations below sulfate-replete sediment. Samples from an attenuated off-axis seep site on the NW flank of Guaymas Basin differed from both Sonora Margin and Guaymas Basin. The off-axis seep sediments contained 1 to 1.5 mM methane, with distinct δ13C -isotopic content (δ13C-CH4 near -60 ‰); intermediate to the biogenic methane of the Sonora Margin and the hydrothermally produced methane at Guaymas Basin. Unaltered sulfate and low sulfide concentrations indicate insufficiently reduced conditions, suggesting the methane was not produced in situ. Porewater DIC concentrations in the old seep site and the control site were similar to each other (3-5 mM), and lower than in the Sonora Margin sites (ca. 20-40 mM), indicating low bioremineralization in the old seep site and control sediments. Diverse seafloor habitats are expected to result in distinct microbiota that range from strictly anaerobic seep specialists and methane-cycling archaea in the Sonora Margin to diversified heterotrophic communities in the off-axis ridge flank sediments of Guaymas Basin; high-throughput sequencing should also address potential hydrothermal microbial signature in the attenuated off-axis seep site.

Groundwater quality in central New York, 2012

USGS Publications Warehouse

Reddy, James E.

2014-01-01

Water samples were collected from 14 production wells and 15 private wells in central New York from August through December 2012 in a study conducted by the U.S. Geological Survey in cooperation with the New York State Department of Environmental Conservation. The samples were analyzed to characterize the groundwater quality in unconsolidated and bedrock aquifers in this area. Fifteen of the wells are finished in sand-and-gravel aquifers, and 14 are finished in bedrock aquifers. Six of the 29 wells were sampled in a previous central New York study, which was conducted in 2007. Water samples from the 2012 study were analyzed for 147 physiochemical properties and constituents, including major ions, nutrients, trace elements, radionuclides, pesticides, volatile organic compounds, dissolved gases (argon, carbon dioxide, methane, nitrogen, oxygen), and indicator bacteria. Results of the water-quality analyses are presented in tabular form for individual wells, and summary statistics for specific constituents are presented by aquifer type. The results are compared with Federal and New York State drinking-water standards, which typically are identical. The results indicate that the groundwater generally is of acceptable quality, although for all of the wells sampled, at least one of the following constituents was detected at a concentration that exceeded current or proposed Federal or New York State drinking-water standards: color (2 samples), pH (7 samples), sodium (9 samples), chloride (2 samples), fluoride (2 samples), sulfate (2 samples), dissolved solids (8 samples), aluminum (4 samples), arsenic (1 sample), iron (9 samples), manganese (13 samples), radon-222 (13 samples), total coliform bacteria (6 samples), and heterotrophic bacteria (2 samples). Drinking-water standards for nitrate, nitrite, antimony, barium, beryllium, cadmium, chromium, copper, lead, mercury, selenium, silver, thallium, zinc, gross alpha radioactivity, uranium, fecal coliform, and Escherichia coliwere not exceeded in any of the samples collected. None of the pesticides or volatile organic compounds analyzed exceeded drinking-water standards. Methane was detected in 11 sand-and-gravel wells and 9 bedrock wells. Five of the 14 bedrock wells had water with methane concentrations approaching 10 mg/L; water in one bedrock well had 37 mg/L of methane.

Methane and sulfate dynamics in sediments from mangrove-dominated tropical coastal lagoons, Yucatan, Mexico

USGS Publications Warehouse

Chuang, P. C.; Young, Megan B.; Dale, Andrew W.; Miller, Laurence G.; Herrera-Silveira, Jorge A.; Paytan, Adina

2016-01-01

Porewater profiles in sediment cores from mangrove-dominated coastal lagoons (Celestún and Chelem) on the Yucatán Peninsula, Mexico, reveal the widespread coexistence of dissolved methane and sulfate. This observation is interesting since dissolved methane in porewaters is typically oxidized anaerobically by sulfate. To explain the observations we used a numerical transport-reaction model that was constrained by the field observations. The model suggests that methane in the upper sediments is produced in the sulfate reduction zone at rates ranging between 0.012 and 31 mmol m−2 d−1, concurrent with sulfate reduction rates between 1.1 and 24 mmol SO42− m−2 d−1. These processes are supported by high organic matter content in the sediment and the use of non-competitive substrates by methanogenic microorganisms. Indeed sediment slurry incubation experiments show that non-competitive substrates such as trimethylamine (TMA) and methanol can be utilized for microbial methanogenesis at the study sites. The model also indicates that a significant fraction of methane is transported to the sulfate reduction zone from deeper zones within the sedimentary column by rising bubbles and gas dissolution. The shallow depths of methane production and the fast rising methane gas bubbles reduce the likelihood for oxidation, thereby allowing a large fraction of the methane formed in the sediments to escape to the overlying water column.

A microbial biogeochemistry network for soil carbon and nitrogen cycling and methane flux: model structure and application to Asia

NASA Astrophysics Data System (ADS)

Xu, X.; Song, C.; Wang, Y.; Ricciuto, D. M.; Lipson, D.; Shi, X.; Zona, D.; Song, X.; Yuan, F.; Oechel, W. C.; Thornton, P. E.

2017-12-01

A microbial model is introduced for simulating microbial mechanisms controlling soil carbon and nitrogen biogeochemical cycling and methane fluxes. The model is built within the CN (carbon-nitrogen) framework of Community Land Model 4.5, named as CLM-Microbe to emphasize its explicit representation of microbial mechanisms to biogeochemistry. Based on the CLM4.5, three new pools were added: bacteria, fungi, and dissolved organic matter. It has 11 pools and 34 transitional processes, compared with 8 pools and 9 transitional flow in the CLM4.5. The dissolve organic carbon was linked with a new microbial functional group based methane module to explicitly simulate methane production, oxidation, transport and their microbial controls. Comparing with CLM4.5-CN, the CLM-Microbe model has a number of new features, (1) microbial control on carbon and nitrogen flows between soil carbon/nitrogen pools; (2) an implicit representation of microbial community structure as bacteria and fungi; (3) a microbial functional-group based methane module. The model sensitivity analysis suggests the importance of microbial carbon allocation parameters on soil biogeochemistry and microbial controls on methane dynamics. Preliminary simulations validate the model's capability for simulating carbon and nitrogen dynamics and methane at a number of sites across the globe. The regional application to Asia has verified the model in simulating microbial mechanisms in controlling methane dynamics at multiple scales.

Redox chemistry of shallow permafrost porewaters in western Spitsbergen

NASA Astrophysics Data System (ADS)

Jones, Eleanor; Rogers, Jade; Bak, Ebbe; Finster, Kai; Hodson, Andy; Mallon, Gunnar; Redeker, Kelly; Thornton, Steve; Yde, Jacob

2017-04-01

The western coast of Spitsbergen, located in the zone of continuous permafrost, is kept relatively warm for its latitude by the north Atlantic current. This sensitivity to oceanic and atmospheric warming provides an early warning system for the response of permafrost to climate change. This response includes the release of stored organic carbon and nutrients, which can lead to increased greenhouse gas (GHG) emissions from Arctic wetlands. The aims of this study are to i) develop a methodology to investigate in-situ processes contributing to GHG emissions in shallow permafrost, and ii) correlate the geochemical properties of these permafrost sediments with their potential to support GHG emission. The focus of this project is on three locations within 10 kilometres of Longyearbyen, Western Spitsbergen, Svalbard. All locations were covered by warm-based ice during the Last Glacial Maximum, and so it was only after the deglaciation around 10,000 years ago that permafrost aggraded. After deglaciation, the following depositional environments typical of Svalbard formed and were the subject of this study: i) a sequence of raised beaches, formed due to isostatic rebound, and ii) a prograding delta overlain by aeolian sediments. Ice-wedge polygons and wetlands developed at all study sites. Each location was drilled to a depth of 2 metres. The extracted sediment cores were transported frozen and stored at -18˚ C. Cores were subdivided at 2 centimetre depth resolution and the samples were equilibrated anaerobically with deionised, degassed water in sealed vials. Concentrations of methane and carbon dioxide in the vial headspace, the chemistry of the supernatant, and the initial moisture content of the sediments were determined. Results show a zonation of redox chemistry with depth. Low redox chemistries, indicating anoxia, appear only below 60 cm depth. A correlation of ferrous iron and sulphate is also clear, indicative of the process of sulphide oxidation via reduction of ferrous to ferric iron (below 60 cm). Concentrations of dissolved methane in the porewaters are low (<20 μmol l-1) and concentrations of dissolved carbon dioxide are higher (<4000 μmol l-1). Nitrate concentrations are high throughout (˜ 0.25 mmol l-1). These results point to relatively high redox environments, in which the production of carbon dioxide dominates over the production of methane. This indicates that methanogenesis is limited in these environments by competing anaerobic respiration processes and/or counteracted by anaerobic oxidation of methane, which need to be accounted for in predictions of the future permafrost carbon feedback.

Methane and carbon dioxide concentrations in sediments and diffusive fluxes at the sediment-water interface from three tropical systems in Brazil during the pre-impoundment phase

NASA Astrophysics Data System (ADS)

Abe, D. S.; Sidagis-Galli, C.; Grimberg, D. E.; Blanco, F. D.; Rodrigues-Filho, J. L.; Tundisi, J. G.; Matsumura-Tundisi, T.; Tundisi, J. E.; Cimbleris, A. C.; Damázio, J. M.; Project Balcar

2013-05-01

The concentrations of methane and carbon dioxide in the sediments pore water were quantified by gas chromatography in three hydroelectric reservoirs under construction during the pre-impoundment phase. Sediment sampling was performed in ten to twelve stations in each river by a Kajak-Brinkhurst corer coupled to a 3 m long aluminum rod in four seasons. The theoretical diffusive fluxes of these gases at the sediment-water interface were also calculated using the Fick's first law of diffusion. The mean annual concentration and diffusive flux of methane were highest in the sediments of the Xingu River (12.71 ± 3.03 mmol CH4 m-2 and 3.84 ± 0.91 mmol CH4 m-2 d-1), located in the Amazon, influenced by the presence of organic matter originating from the surrounding forest. The mean annual concentration of carbon dioxide was highest in the São Marcos River (71.36 ± 10.36 mmol CO2 m-2), located in an area of cerrado savanna, while the highest diffusive flux of carbon dioxide was observed in the Madeira River (30.23 ± 2.41 mmol CO2 m-2 d-1), which rises in the Andes Cordillera and has a very high water flow. The mean concentration and diffusive flux of carbon dioxide in the three studied systems were much higher (64-98%) in comparison with the methane, influenced by the oxic condition in these lotic systems. Nevertheless, the present study shows that the sediments of these systems, especially in the Xingu River, have significant amount of methane dissolved in the pore water which is being diffused to the overlying water. The information obtained in this study during the pre-filling phase will be important for the calculation of net flows of greenhouse gases after the impoundment of these future reservoirs. This study is part of the Strategic Project "Monitoring Emissions of Greenhouse Gases in Hydroelectric Reservoirs" - Call 099/2008 of the Brazilian Agency of Electric Energy (ANEEL) and sponsored by ELETRONORTE, FURNAS and CHESF.

Hydrocarbon-fuel/combustion-chamber-liner materials compatibility

NASA Technical Reports Server (NTRS)

Homer, G. David

1991-01-01

The results of dynamic tests using methane and NASA-Z copper test specimen under conditions that simulate those expected in the cooling channels of a regeneratively cooled LOX/hydrocarbon booster engine operating at chamber pressures up to 3000 psi are presented. Methane with less than 0.5 ppm sulfur contamination has little or no effect on cooling channel performance. At higher sulfur concentrations, severe corrosion of the NASA-Z copper alloy occurs and the cuprous sulfide Cu2S, thus formed impedes mass flow rate and heat transfer efficiency. Therefore, it is recommended that the methane specification for this end use set the allowable sulfur content at 0.5 ppm (max). Bulk high purity liquid methane that meets this low sulfur requirement is currently available from only one producer. Pricing, availability, and quality assurance are discussed in detail. Additionally, it was found that dilute sodium cyanide solutions effectively refurbish sulfur corroded cooling channels in only 2 to 5 minutes by completely dissolving all the Cu2S. Sulfur corroded/sodium cyanide refurbished channels are highly roughened and the increased surface roughness leads to significant improvements in heat transfer efficiency with an attendant loss in mass flow rate. Both the sulfur corrosion and refurbishment effects are discussed in detail.

Quantifying the loss of methane through secondary gas mass transport (or 'slip') from a micro-porous membrane contactor applied to biogas upgrading.

PubMed

McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

2013-07-01

Secondary gas transport during the separation of a binary gas with a micro-porous hollow fibre membrane contactor (HMFC) has been studied for biogas upgrading. In this application, the loss or 'slip' of the secondary gas (methane) during separation is a known concern, specifically since methane possesses the intrinsic calorific value. Deionised (DI) water was initially used as the physical solvent. Under these conditions, carbon dioxide (CO2) and methane (CH4) absorption were dependent upon liquid velocity (V(L)). Whilst the highest CO2 flux was recorded at high V(L), selectivity towards CO2 declined due to low residence times and a diminished gas-side partial pressure, and resulted in slip of approximately 5.2% of the inlet methane. Sodium hydroxide was subsequently used as a comparative chemical absorption solvent. Under these conditions, CO2 mass transfer increased by increasing gas velocity (VG) which is attributed to the excess of reactive hydroxide ions present in the solvent, and the fast conversion of dissolved CO2 to carbonate species reinitiating the concentration gradient at the gas-liquid interface. At high gas velocities, CH4 slip was reduced to 0.1% under chemical conditions. Methane slip is therefore dependent upon whether the process is gas phase or liquid phase controlled, since methane mass transport can be adequately described by Henry's law within both physical and chemical solvents. The addition of an electrolyte was found to further retard CH4 absorption via the salting out effect. However, their applicability to physical solvents is limited since electrolytic concentration similarly impinges upon the solvents' capacity for CO2. This study illustrates the significance of secondary gas mass transport, and furthermore demonstrates that gas-phase controlled systems are recommended where greater selectivity is required. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methane and Dissolved Organic Carbon Sustain an Ecosystem within a Density Stratified Coastal Aquifer of the Yucatan Peninsula, Mexico. Evidence for a Subterranean Microbial Loop?

NASA Astrophysics Data System (ADS)

Brankovits, David; Pohlman, John W.; Niemann, Helge; Leigh, Mary Beth; Casso, Michael; Alvarez Noguera, Fernando; Lehmann, Moritz F.; Iliffe, Thomas M.

2016-04-01

In coastal karst terrains, anchialine caves that meander in density stratified aquifers provide an exceptional opportunity for scientists to study in situ biogeochemical processes within the groundwater. The Caribbean coast of Mexico's Yucatan Peninsula contains over 1000 km of mapped cave passages, the densest known accumulation of anchialine caves in the world. A decades-old study based on the simple observation of 13C-depleted biomass in the cave-adapted fauna suggested biogeochemical processes related to methane-linked carbon cycling and/or other chemoautotrophic pathways as a source of energy and carbon. In this study, we utilized cave diving and a novel sampling device (the Octopipi) to obtain cm-scale water column profiles of methane, DOC and DIC concentrations and stable carbon isotope ratios to identify the energy sources and microbial processes that sustain life in these subterranean estuaries. High concentrations (up to 9522 nM) low-δ13C (as low as -67.5 permil) methane near the ceiling of the cave (in the fresh water section of the stratified water column) and evidence for methane oxidation in the brackish water portion of the water column suggest methane availability and consumption. Profiles obtained by the Octopipi demonstrate that virtually all of the methane (˜99%) is oxidized at the interface of anoxic freshwater and hypoxic brackish water masses. The high-methane water mass near the ceiling also contained elevated concentrations of DOC (851 μM) that displayed comparatively high δ13C (-27.8 to -28.2 permil), suggesting terrestrial organic matter input from the overlying soils. Low-methane brackish and saline water was characterized by lower DOC concentration (15 to 97 μM), yet with similar δ13C (-25.9 to -27.2 permil), suggesting significant terrestrial organic matter consumption or removal with increasing depth, from fresh to saline water, within the water column. The presence of 13C-depleted fatty acids (e.g., C16:1ω7c with δ13C-values as low as -54.1 permil) and deuterium-depleted δD values (e.g., as low as δD = -225 permil) from tissues of cave-adapted shrimps suggest that methanotrophic bacteria contributed a substantial fraction of their diet. Molecular microbial community analyses are underway to identify the taxonomic associations and syntrophy effects within a subterranean microbial loop that provides carbon and energy to the anchialine food web. These findings provide novel insight into the carbon cycle and methane dynamics for a largely unknown, yet widespread coastal habitat beneath the Earth's surface.

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

NASA Astrophysics Data System (ADS)

Holmkvist, Lars; Ferdelman, Timothy G.; Jørgensen, Bo Barker

2011-06-01

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe 2+, accumulated in the pore water. Sulfate reduction rates measured by 35S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive "background" concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO 42- cm -3 d -1, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, "potential sulfate reduction" which showed that a physiologically intact community of sulfate reducing bacteria was present. The "background" sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO 2 which is reduced with H 2 to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.

High spatial variability of carbon dioxide and methane emission in three tropical reservoirs

NASA Astrophysics Data System (ADS)

Reinaldo Paranaiba, José; Barros, Nathan O.; Mendonça, Raquel F.; Linkhorst, Annika; Isidorova, Anastasija; Roland, Fabio; Sobek, Sebastian

2017-04-01

In the tropics, many new large hydropower dams are being built, in order to produce renewable energy for economic growth. Most inland waters, such as rivers, lakes and reservoirs, emit greenhouse gases to the atmosphere, and especially tropical reservoirs have been pointed out as strong sources of methane. However, present estimates of greenhouse gas emission from reservoirs are limited by the amount of available data. In particular, the spatial variability of greenhouse gas emission from reservoirs is insufficiently understood. In order to test the hypothesis that the diffusive emission of carbon dioxide (CO2) and methane (CH4) from tropical reservoirs is characterized by strong spatial variability and incorrectly represented by measurements at one site only, we studied three reservoirs situated in different tropical climates, during the dry period. We conducted spatially resolved measurements of surface water concentrations of dissolved carbon dioxide and methane using an on-line equilibration system, as well as of the gas exchange velocity using floating chambers. We found pronounced spatial variability of diffusive CO2 and CH4 emission in all three reservoirs. River inflow areas were more likely to have high concentrations of particularly CH4, but also CO2, than other areas in the reservoirs. Close to the dam, CH4 concentrations were comparatively low in each reservoir. The variability of CH4 concentration was linked to geographical position, which we ascribe to hot spots of methanogenesis at sites of high sediment deposition, such as river inflow areas. The variability of CO2 concentration seemed instead rather to be linked to in-situ metabolism. Also the gas exchange velocity varied pronouncedly in each reservoir, but without any detectable systematic patterns, calling for further studies. We conclude that accurate upscaling of reservoir greenhouse gas emissions requires accounting for within-reservoir spatial variability, and that the anthropogenic increase of sediment flux from catchments to downstream reservoirs may be linked to increased reservoir CH4 emission.

Application of in situ biosparging to remediate a petroleum-hydrocarbon spill site: field and microbial evaluation.

PubMed

Kao, C M; Chen, C Y; Chen, S C; Chien, H Y; Chen, Y L

2008-02-01

In this study, a full-scale biosparging investigation was conducted at a petroleum-hydrocarbon spill site. Field results reveal that natural attenuation was the main cause of the decrease in major contaminants [benzene, toluene, ethylbenzene, and xylenes (BTEX)] concentrations in groundwater before the operation of biosparging system. Evidence of the occurrence of natural attenuation within the BTEX plume includes: (1) decrease of DO, nitrate, sulfate, and redox potential, (2) production of dissolved ferrous iron, sulfide, methane, and CO(2), (3) decreased BTEX concentrations along the transport path, (4) increased microbial populations, and (5) limited spreading of the BTEX plume. Field results also reveal that the operation of biosparging caused the shifting of anaerobic conditions inside the plume to aerobic conditions. This variation can be confirmed by the following field observations inside the plume due to the biosparging process: (1) increase in DO, redox potential, nitrate, and sulfate, (2) decrease dissolved ferrous iron, sulfide, and methane, (3) increased total cultivable heterotrophs, and (4) decreased total cultivable anaerobes as well as methanogens. Results of polymerase chain reaction, denaturing gradient gel electrophoresis, and nucleotide sequence analysis reveal that three BTEX biodegraders (Candidauts magnetobacterium, Flavobacteriales bacterium, and Bacteroidetes bacterium) might exist at this site. Results show that more than 70% of BTEX has been removed through the biosparging system within a 10-month remedial period at an averaged groundwater temperature of 18 degrees C. This indicates that biosparging is a promising technology to remediate BTEX contaminated groundwater.

Carbon and hydrogen isotopic systematics of dissolved methane in small seasonally ice-covered lakes near the margin of the Greenland ice sheet

NASA Astrophysics Data System (ADS)

Cadieux, S. B.; White, J. R.; Pratt, L. M.; Peng, Y.; Young, S. A.

2013-12-01

Northern lakes contribute from 6-16% of annual methane inputs to Earth's atmosphere, yet little is known about the seasonal biogeochemistry of CH4 cycling, particularly for lakes in the Arctic. Studies during ice-free conditions have been conducted in Alaskan, Swedish and Siberian lakes. However, there is little information on CH4 cycling under ice-covered conditions, and few stable isotopic measurements, which can help elucidate production and consumption pathways. In order to better understand methane dynamics of ice-covered Arctic lakes, 4 small lakes (surface area <1 km2) within a narrow valley extending from the Russells Glacier to Søndre Strømfjord in Southwestern Greenland were examined during summer stratification and winter ice-cover. Lakes in the study area are ice-covered from mid-September to mid-June. In both seasons, variations in the concentrations and isotopic composition of methane with depth were related to redox fluctuations. During late winter under~2 m of ice, the entire water column was anoxic with wide variation in methane concentrationsand isotopic composition from lake to lake. In three of the lakes, CH4 concentrations and δ13C were relatively stable over the depth of the water column, averaging from 120 to 480μM, with δ13CH4 values from -56‰ to -66‰, respectively. Methane concentrations in the other lake increased with depth from <1 μM below the ice to 800 μM at the sediment/water interface, while δ13C decreased by 30‰ from -30‰ to -70‰ over this depth. In all the lakes, δ13C of sediment porewater was lighter than the overlying water by at least 10‰. The δD-CH4 in the water column ranged from -370‰ to -50‰, exhibiting covariance with δ13C consistent with significant methanotrophic activity. In the sediment, δD-CH4 values ranged from -330‰ to -275‰, and were inversely correlated with δ13C. We will present detailed information on redox dynamics as a controlling factor in methane cycling, and explore the effects of differing microbial communities and carbon supply. Our study suggests that shallow lakes in continuous permafrost landscapes of the Arctic develop distinct methane cycling dynamics despite their close proximity.

Tidal influence on subtropical estuarine methane emissions

NASA Astrophysics Data System (ADS)

Sturm, Katrin; Grinham, Alistair; Werner, Ursula; Yuan, Zhiguo

2014-05-01

The relatively unstudied subtropical estuaries, particularly in the Southern Hemisphere, represent an important gap in our understanding of global greenhouse gas (GHG) emissions. These systems are likely to form an important component of GHG budgets as they occupy a relatively large surface area, over 38 000 km2 in Australia. Here, we present studies conducted in the Brisbane River estuary, a representative system within the subtropical region of Queensland, Australia. This is a highly modified system typical of 80% of Australia's estuaries. Generally, these systems have undergone channel deepening and straightening for safer shipping access and these modifications have resulted in large increases in tidal reach. The Brisbane River estuary's natural tidal reach was 16 km and this is now 85 km and tidal currents influence double the surface area (9 km2 to 18 km2) in this system. Field studies were undertaken to improve understanding of the driving factors behind methane water-air fluxes. Water-air fluxes in estuaries are usually calculated with the gas exchange coefficient (k) for currents and wind as well as the concentration difference across the water-air interface. Tidal studies in the lower and middle reaches of the estuary were performed to monitor the influence of the tidal stage (a proxy for kcurrent) on methane fluxes. Results for both investigated reaches showed significantly higher methane fluxes during the transition time of tides, the time of greatest tidal currents, than during slack tide periods. At these tidal transition times with highest methane chamber fluxes, lowest methane surface water concentrations were monitored. Modelled fluxes using only wind speed (kwind) were at least one order of magnitude lower than observed from floating chambers, demonstrating that current speed was likely the driving factor of water-air fluxes. An additional study was then conducted sampling the lower, middle and upper reaches during a tidal transition period. Although dissolved methane surface water concentrations were highest in the upper reaches of the estuary, experiencing the lowest tidal currents, fluxes measured using chambers were lower relative to middle and lower reaches. This supports the tidal study findings as higher tidal currents were experienced in the middle and lower reaches. The dominant driver behind estuarine methane water-air fluxes in this system was tidal current speed. Future studies need to take into account flux rates during both transition and slack tide periods to quantify total flux rates.

Methane Sources and Migration Mechanisms in the Shallow Trinity Aquifer in Parker and Hood Counties, Texas - a Noble Gas Analysis

NASA Astrophysics Data System (ADS)

Wen, T.; Castro, C.; Nicot, J. P.; Hall, C. M.; Mickler, P. J.; Darvari, R.

2016-12-01

The presence of elevated methane in groundwaters within the Barnett Shale footprint in Parker and Hood counties, Texas has caused public concern that hydrocarbon production may facilitate migration of natural gas into a critical groundwater resource. This study places constraints on the source of methane in these groundwaters by analyzing water and stray gas data from groundwater wells and gas production wells from both the Barnett Shale and Strawn Group for methane content and noble gases, both of crustal and atmospheric origin. Particular emphasis is given to the atmospheric heavier noble gases 84Kr and 132Xe, which are significantly less affected by the presence of excess air, commonly present in modern Texas groundwaters (e.g., [1]). Dissolved methane concentrations are positively correlated with crustal 4He, 21Ne and 40Ar and suggest that noble gases and methane in these groundwaters originate from a common source, likely the Strawn Group, which the sampled aquifer overlies unconformably. This finding is further supported by the noble gas isotopic signature of stray gas when compared to the gas isotopic signatures of both Barnett Shale and the Strawn Group. In contrast to most samples, four groundwater wells with the highest methane concentrations unequivocally show heavy depletion of the atmospheric noble gases 20Ne, 36Ar, 84Kr and 132Xe with respect to freshwater recharge equilibrated with the atmosphere (ASW). This is consistent with predicted noble gas concentrations in a residual water phase in contact with a gas phase with initial ASW composition at 18°C-25°C, assuming a closed-system and suggest a highly localized gas source. All these four wells, without exception, tap into the Strawn Group and it is likely that shallow gas accumulations, as they are known to exist, were reached. Additionally, lack of correlation between 84Kr/36Ar and 132Xe/36Ar fractionation levels and distance to the nearest production wells does not support the notion that methane present in these groundwater wells migrated from nearby production wells, either conventional or using hydraulic fracturing techniques. Lack of correlation between the latter and 4He/20Ne further supports these findings. [1] Castro et al. (2007) EPSL 257, 170-187.

Dissolved methane concentrations in the water column and surface sediments of Hanna Shoal and Barrow Canyon, Northern Chukchi Sea

NASA Astrophysics Data System (ADS)

Lapham, Laura; Marshall, Kathleen; Magen, Cédric; Lyubchich, Viacheslav; Cooper, Lee W.; Grebmeier, Jacqueline M.

2017-10-01

Current estimates of methane (CH4) flux suggest that Arctic shelves may be a significant source of atmospheric CH4, a potent greenhouse gas. However, little information is known about the CH4 flux from most Arctic shelves, other than the East Siberian Arctic Shelf. We report here dissolved CH4 concentrations in the water column and within surface sediments of the Northern Chukchi Sea. We hypothesized that this area contains high concentrations of CH4 because it receives nutrient rich waters through the Bering Strait, promoting primary production that enhances an organic-rich material flux to the seafloor and eventual microbial methanogenesis in the sediments. In August 2012, as part of the Chukchi Sea Offshore Monitoring in Drilling Area (COMIDA) project, fourteen stations were sampled on Hanna Shoal, a shallow feature on the shelf, and ten stations across the undersea Barrow Canyon. On Hanna Shoal, water column CH4 concentrations ranged from 14 to 74 nM, and surface concentrations were up to 15 times supersaturated in CH4 compared to equilibrium with the average atmospheric concentrations (3 nM). CH4 concentrations at the sediment-water interface were around 1,500 nM, and typically increased with depth in the sediment. At the head of Barrow Canyon, water column CH4 concentrations ranged from 5 to 46 nM, with the highest concentrations in the deepest waters that were sampled (118 m). Overall, the calculated fluxes to the atmosphere ranged from 1 to 80 μmol CH4 m-2 d-1 for Hanna Shoal and 4 to 17 μmol CH4 m-2 d-1 across the Barrow Canyon stations. Although there was a large range in these fluxes, the average atmospheric flux (20 μmol CH4 m-2 d-1) across Hanna Shoal was 12 times lower than the flux reported from the East Siberian Arctic Shelf in summer. We conclude that while there is a positive flux of CH4 to the atmosphere, this part of the Chukchi Sea is not a significant source of atmospheric CH4 compared to the East Siberian Sea shelf.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, July 2015

USGS Publications Warehouse

Huffman, Raegan L.

2016-05-18

In 2015, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all less than 1 milligram per liter; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2015, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were equivalent to the concentrations measured in 2014. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2015 continued to be variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in one of the three wells and in piezometers. Beneath the marsh adjacent to the southern plantation, CVOC concentrations measured in 2015 continued to vary spatially and temporally, and were high. The total CVOC concentration, at what have been historically the most contaminated passive-diffusion sampler sites (S-4 T, S-4B T, and S-5 T), continued elevated trends, as did one of the new sampler sites (S-9 T) installed in 2015. For the intermediate aquifer in 2015, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

A quantitative assessment of methane cycling in Hikurangi Margin sediments (New Zealand) using geophysical imaging and biogeochemical modeling

NASA Astrophysics Data System (ADS)

Luo, Min; Dale, Andrew W.; Haffert, Laura; Haeckel, Matthias; Koch, Stephanie; Crutchley, Gareth; De Stigter, Henko; Chen, Duofu; Greinert, Jens

2016-12-01

Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well-defined subsurface seismic chimney structure ˜80,500 m2 in area. Subseafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction-transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m-2 yr-1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m-2 yr-1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m-2 yr-1, respectively). A seep-wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation, and benthic dissolved methane fluxes of 3.68 × 104 mol yr-1, 73.85 × 104 mol yr-1, and 1.19 × 104 mol yr-1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

PubMed

Li, Huishu; Son, Ji-Hee; Carlson, Kenneth H

2016-01-01

The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport. Copyright © 2015 Elsevier Ltd. All rights reserved.

Impact of reduced water consumption on sulfide and methane production in rising main sewers.

PubMed

Sun, Jing; Hu, Shihu; Sharma, Keshab Raj; Bustamante, Heriberto; Yuan, Zhiguo

2015-05-01

Reduced water consumption (RWC), for water conservation purposes, is expected to change the wastewater composition and flow conditions in sewer networks and affect the in-sewer transformation processes. In this study, the impact of reduced water consumption on sulfide and methane production in rising main sewers was investigated. Two lab-scale rising main sewer systems fed with wastewater of different strength and flow rates were operated to mimic sewers under normal and RWC conditions (water consumption reduced by 40%). Sulfide concentration under the RWC condition increased by 0.7-8.0 mg-S/L, depending on the time of a day. Batch test results showed that the RWC did not change the sulfate-reducing activity of sewer biofilms, the increased sulfide production being mainly due to longer hydraulic retention time (HRT). pH in the RWC system was about 0.2 units lower than that in the normal system, indicating that more sulfide would be in molecular form under the RWC condition, which would result in increased sulfide emission to the atmosphere as confirmed by the model simulation. Model based analysis showed that the cost for chemical dosage for sulfide mitigation would increase significantly per unit volume of sewage, although the total cost would decrease due to a lower sewage flow. The dissolved methane concentration under the RWC condition was over two times higher than that under the normal flow condition and the total methane discharge was about 1.5 times higher, which would potentially result in higher greenhouse gas emissions. Batch tests showed that the methanogenic activity of sewer biofilms increased under the RWC condition, which along with the longer HRT, led to increased methane production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methane- and dissolved organic carbon-fueled microbial loop supports a tropical subterranean estuary ecosystem

USGS Publications Warehouse

Brankovits, D.; Pohlman, John; Niemann, H.; Leigh, M.B.; Leewis, M.C.; Becker, K. W.; Iliffe, T.M.; Alvarez. F.,; Lehmann, M.F.; Phillips, B.

2017-01-01

Subterranean estuaries extend inland into density-stratified coastal carbonate aquifers containing a surprising diversity of endemic animals (mostly crustaceans) within a highly oligotrophic habitat. How complex ecosystems (termed anchialine) thrive in this globally distributed, cryptic environment is poorly understood. Here, we demonstrate that a microbial loop shuttles methane and dissolved organic carbon (DOC) to higher trophic levels of the anchialine food web in the Yucatan Peninsula (Mexico). Methane and DOC production and consumption within the coastal groundwater correspond with a microbial community capable of methanotrophy, heterotrophy, and chemoautotrophy, based on characterization by 16S rRNA gene amplicon sequencing and respiratory quinone composition. Fatty acid and bulk stable carbon isotope values of cave-adapted shrimp suggest that carbon from methanotrophic bacteria comprises 21% of their diet, on average. These findings reveal a heretofore unrecognized subterranean methane sink and contribute to our understanding of the carbon cycle and ecosystem function of karst subterranean estuaries.

Anaerobic Methane Oxidation in Soils - revealed using 13C-labelled methane tracers

NASA Astrophysics Data System (ADS)

Riekie, G. J.; Baggs, E. M.; Killham, K. S.; Smith, J. U.

2008-12-01

In marine sediments, anaerobic methane oxidation is a significant biogeochemical process limiting methane flux from ocean to atmosphere. To date, evidence for anaerobic methane oxidation in terrestrial environments has proved elusive, and its significance is uncertain. In this study, an isotope dilution method specifically designed to detect the process of anaerobic methane oxidation in methanogenic wetland soils is applied. Methane emissions of soils from three contrasting permanently waterlogged sites in Scotland are investigated in strictly anoxic microcosms to which 13C- labelled methane is added, and changes in the concentration and 12C/13C isotope ratios of methane and carbon dioxide are subsequently measured and used to calculate separate the separate components of the methane flux. The method used takes into account the 13C-methane associated with methanogenesis, and the amount of methane dissolved in the soil. The calculations make no prior assumptions about the kinetics of methane production or oxidation. The results indicate that methane oxidation can take place in anoxic soil environments. The clearest evidence for anaerobic methane oxidation is provided by soils from a minerotrophic fen site (pH 6.0) in Bin Forest underlain by ultra-basic and serpentine till. In the fresh soil anoxic microcosms, net consumption methane was observed, and the amount of headspace 13C-CO2 increased at a greater rate than the 12+13C-CO2, further proof of methane oxidation. A net increase in methane was measured in microcosms of soil from Murder Moss, an alkaline site, pH 6.5, with a strong calcareous influence. However, the 13C-CH4 data provided evidence of methane oxidation, both in the disappearance of C- CH4 and appearance of smaller quantities of 13C-CO2. The least alkaline (pH 5.5) microcosms, of Gateside Farm soil - a granitic till - exhibited net methanogenesis and the changes in 13C-CH4 and 13C-CO2 here followed the pattern expected if no methane is consumed. Overall, this study provides good evidence for anaerobic methane oxidation in certain wetland soils, and suggests that models predicting methane flux from wetland soils to the atmosphere could be improved by better understanding of this process.

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.

A gas-tracer injection for evaluating the fate of methane in a coastal plain stream: Degassing versus in-stream oxidation

USGS Publications Warehouse

Heilweil, Victor M.; Solomon, D. Kip; Darrah, Thomas H.; Gilmore, Troy E.; Genereux, David P.

2016-01-01

Methane emissions from streams and rivers have recently been recognized as an important component of global greenhouse budgets. Stream methane is lost as evasion to the atmosphere or in-stream methane oxidation. Previous studies have quantified evasion and oxidation with point-scale measurements. In this study, dissolved gases (methane, krypton) were injected into a coastal plain stream in North Carolina to quantify stream CH4 losses at the watershed scale. Stream-reach modeling yielded gas transfer and oxidation rate constants of 3.2 ± 0.5 and 0.5 ± 1.5 d–1, respectively, indicating a ratio of about 6:1. The resulting evasion and oxidation rates of 2.9 mmol m–2 d–1 and 1,140 nmol L–1 d–1, respectively, lie within ranges of published values. Similarly, the gas transfer velocity (K600) of 2.1 m d–1 is consistent with other gas tracer studies. This study illustrates the utility of dissolved-gas tracers for evaluating stream methane fluxes. In contrast to point measurements, this approach provides a larger watershed-scale perspective. Further work is needed to quantify the magnitude of these fluxes under varying conditions (e.g., stream temperature, nutrient load, gradient, flow rate) at regional and global scales before reliable bottom-up estimates of methane evasion can be determined at global scales.

Methane Dynamics in a Tropical Serpentinizing Environment: The Santa Elena Ophiolite, Costa Rica

PubMed Central

Crespo-Medina, Melitza; Twing, Katrina I.; Sánchez-Murillo, Ricardo; Brazelton, William J.; McCollom, Thomas M.; Schrenk, Matthew O.

2017-01-01

Uplifted ultramafic rocks represent an important vector for the transfer of carbon and reducing power from the deep subsurface into the biosphere and potentially support microbial life through serpentinization. This process has a strong influence upon the production of hydrogen and methane, which can be subsequently consumed by microbial communities. The Santa Elena Ophiolite (SEO) on the northwestern Pacific coast of Costa Rica comprises ~250 km2 of ultramafic rocks and mafic associations. The climatic conditions, consisting of strongly contrasting wet and dry seasons, make the SEO a unique hydrogeological setting, where water-rock reactions are enhanced by large storm events (up to 200 mm in a single storm). Previous work on hyperalkaline spring fluids collected within the SEO has identified the presence of microorganisms potentially involved in hydrogen, methane, and methanol oxidation (such as Hydrogenophaga, Methylobacterium, and Methylibium spp., respectively), as well as the presence of methanogenic Archaea (such as Methanobacterium). Similar organisms have also been documented at other serpentinizing sites, however their functions have not been confirmed. SEO's hyperalkaline springs have elevated methane concentrations, ranging from 145 to 900 μM, in comparison to the background concentrations (<0.3 μM). The presence and potential activity of microorganisms involved in methane cycling in serpentinization-influenced fluids from different sites within the SEO were investigated using molecular, geochemical, and modeling approaches. These results were combined to elucidate the bioenergetically favorable methane production and/or oxidation reactions in this tropical serpentinizing environment. The hyperalkaline springs at SEO contain a greater proportion of Archaea and methanogens than has been detected in any terrestrial serpentinizing system. Archaea involved in methanogenesis and anaerobic methane oxidation accounted from 40 to 90% of total archaeal sequences. Genes involved in methanogenic metabolisms were detected from the metagenome of one of the alkaline springs. Methanogenic activities are likely to be facilitated by the movement of nutrients, including dissolved inorganic carbon (DIC), from surface water and their infiltration into serpentinizing groundwater. These data provide new insight into methane cycle in tropical serpentinizing environments. PMID:28588569

Methane Dynamics in a Tropical Serpentinizing Environment: The Santa Elena Ophiolite, Costa Rica.

PubMed

Crespo-Medina, Melitza; Twing, Katrina I; Sánchez-Murillo, Ricardo; Brazelton, William J; McCollom, Thomas M; Schrenk, Matthew O

2017-01-01

Uplifted ultramafic rocks represent an important vector for the transfer of carbon and reducing power from the deep subsurface into the biosphere and potentially support microbial life through serpentinization. This process has a strong influence upon the production of hydrogen and methane, which can be subsequently consumed by microbial communities. The Santa Elena Ophiolite (SEO) on the northwestern Pacific coast of Costa Rica comprises ~250 km 2 of ultramafic rocks and mafic associations. The climatic conditions, consisting of strongly contrasting wet and dry seasons, make the SEO a unique hydrogeological setting, where water-rock reactions are enhanced by large storm events (up to 200 mm in a single storm). Previous work on hyperalkaline spring fluids collected within the SEO has identified the presence of microorganisms potentially involved in hydrogen, methane, and methanol oxidation (such as Hydrogenophaga, Methylobacterium , and Methylibium spp., respectively), as well as the presence of methanogenic Archaea (such as Methanobacterium ). Similar organisms have also been documented at other serpentinizing sites, however their functions have not been confirmed. SEO's hyperalkaline springs have elevated methane concentrations, ranging from 145 to 900 μM, in comparison to the background concentrations (<0.3 μM). The presence and potential activity of microorganisms involved in methane cycling in serpentinization-influenced fluids from different sites within the SEO were investigated using molecular, geochemical, and modeling approaches. These results were combined to elucidate the bioenergetically favorable methane production and/or oxidation reactions in this tropical serpentinizing environment. The hyperalkaline springs at SEO contain a greater proportion of Archaea and methanogens than has been detected in any terrestrial serpentinizing system. Archaea involved in methanogenesis and anaerobic methane oxidation accounted from 40 to 90% of total archaeal sequences. Genes involved in methanogenic metabolisms were detected from the metagenome of one of the alkaline springs. Methanogenic activities are likely to be facilitated by the movement of nutrients, including dissolved inorganic carbon (DIC), from surface water and their infiltration into serpentinizing groundwater. These data provide new insight into methane cycle in tropical serpentinizing environments.

Flux and distribution of methane (CH4) in the Gunsan Basin of the southeastern Yellow Sea, off the Western Korea.

PubMed

Lee, Jun-Ho; Woo, Han Jun; Son, Seung-Kyu; Kim, Moonkoo; Lee, Dong-Hun; Tsunogai, Urumu; Jeong, Kap-Sik

2018-04-16

The flux and distribution of methane (CH 4 ) was investigated in the seawater column at 14 stations in the Gunsan Basin, the southeastern part of Yellow Sea from 2013 to 2015. Here CH 4 is concentrated 2.4-4.7 (3.4 ± 0.7) nM in the surface and 2.5-7.4 (5.2 ± 1.7) nM in the bottom layer. The CH 4 saturation ratios ranged from 65.5% to 295.5% (162.6 ± 68.7), comprising the mean sea-to-air CH 4 flux of 3.8 to 25.3 (15.6 ± 5.5) µM m -2 d -1 . Methane concentration was largely different in the upper and the lower seawater layers that is separated by the thermocline of which depth is variable (20-60 m) depending on the time of sampling. The concentration of seawater dissolved CH 4 is high between the bottom surface of the thermocline layer and the sea floor. Generally it tends to decrease from the south-westernmost part of the basin toward the west coast of Korea. This distribution pattern of CH 4 seems to result from the CH 4 supply by decomposition of organic matters produced in the upper seawater layer that is superimposed by the larger supply from the underlying sediment layer especially beneath the thermocline. The latter is manifested by ubiquitous CH 4 seeps from the seafloor sediments.

Bacterial Degradation of Phosphonates Bound to High-Molecular-Weight Dissolved Organic Matter Produces Methane and Other Hydrocarbons

NASA Astrophysics Data System (ADS)

Sosa, O.; Ferron Smith, S.; Karl, D. M.; DeLong, E.; Repeta, D.

2016-02-01

The biological degradation of dissolved organic matter (DOM) plays important roles in the carbon cycle and energy balance of the ocean. Yet, the biochemical pathways that drive DOM turnover remain to be fully characterized. In this study, we tested the ability of two open ocean bacterial isolates (a Pseudomonas stutzeri strain (Gammaproteobacteria) and a Sulfitobacter isolate (Alphaproteobacteria)) to degrade DOM phosphonates. Each isolate encoded a complete phosphonate degradation pathway in its genome, and each was able to degrade simple alkyl-phosphonates like methyl phosphonate, releasing methane (or other short chain hydrocarbon gases) as a result. We found that cultures incubated in the presence of HMW DOM polysaccharides also produced methane and other trace gases under aerobic conditions. To demonstrate that phosphonates were the source of these gases, we constructed a P. stutzeri mutant disabled in the phosphonate degradation pathway. Unlike the wild type, the mutant strain was deficient in the production of methane and other gases from HMW DOM-associated phosphonates. These observations support the hypothesis that DOM-bound methyl phosphonates may be a significant source of methane in the water column, and that bacterial degradation of these compounds likely contribute to the subsurface methane maxima observed throughout the world's oceans.

Methane Hydrate Formation in Thick Sand Reservoirs: Long-range Gas Transport or Short-range Methane Diffusion?

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2016-12-01

We developed two 2-D numerical models to simulate hydrate formation by long range methane gas transport and short-range methane diffusion. We interpret that methane hydrates in thick sands are most likely formed by long range gas transport where methane gas is transported upward into the hydrate stability zone (HSZ) under buoyancy and locally forms hydrate to its stability limit. In short-range methane diffusion, methane is generated locally by biodegradation of organic matter in mud and diffused into bounding sands where it forms hydrate. We could not simulate enough methane transport by diffusion to account for its observed concentration in thick sands. In our models, we include the capillary effect on dissolved methane solubility and on the hydrate phase boundary, sedimentation and different compaction in sand and mud, fracture generation as well as the fully coupled multiphase flow and multicomponent transport. We apply our models to a 12 meter-thick hydrate-bearing sand layer at Walker Ridge 313, Northern Gulf of Mexico. With the long-range gas transport, hydrate saturation is greater than 90% and salinity is increased from seawater to about 8 wt.% through the entire sand. With short-range diffusion, hydrate saturation is more than 90% at the sand base and is less than 10% in the overlying section; salinity is close to seawater when sand is deposited to 800 meter below seafloor by short-range methane diffusion. With short-range diffusion, the amount of hydrate formed is much less than that interpreted from the well log data. Two transient gas layers separated by a hydrate layer are formed from short-range diffusion caused by capillary effect. This could be interpreted as a double bottom simulating reflector. This study provides further insights into different hydrate formation mechanisms, and could serve as a base to confirm the hydrate formation mechanism in fields.

Source apportionment of methane using a triple isotope approach - Method development and application in the Baltic Sea

NASA Astrophysics Data System (ADS)

Steinbach, Julia; Holmstrand, Henry; Semiletov, Igor; Shakhova, Natalia; Shcherbakova, Kseniia; Kosmach, Denis; Sapart, Célia J.; Gustafsson, Örjan

2015-04-01

We present a method for measurements of the stable and radiocarbon isotope systems of methane in seawater and sediments. The triple isotope characterization of methane is useful in distinguishing different sources and for improving our understanding of biogeochemical processes affecting methane in the water column. D14C-CH4 is an especially powerful addition to stable isotope analyses in distinguishing between thermogenic and biogenic origins of the methane. Such measurements require large sample sizes, due to low natural abundance of the radiocarbon in CH4. Our system for sample collection, methane extraction and purification builds on the approach by Kessler and Reeburgh (Limn. & Ocean. Meth., 2005). An in-field system extracts methane from 30 -120 l water or 1-2 l sediment (depending on the in-situ methane concentration) by purging the samples with Helium to transfer the dissolved methane to the headspace and circulating it through cryogenically cooled absorbent traps where methane is collected. The in-field preparation eliminates the risks of storage and transport of large seawater quantities and subsequent leakage of sample gas as well as ongoing microbial processes and chemical reactions that may alter the sample composition. In the subsequent shore-based treatment, a laboratory system is used to purify and combust the collected CH4 to AMS-amenable CO2. Subsamples from the methane traps are analyzed for stable isotopes and compared to stable isotope measurements directly measured from small water samples taken in parallel, to correct for any potential fractionation occurring during this process. The system has been successfully tested and used on several shorter shipboard expeditions in the Baltic Sea and on a long summer expedition across the Arctic Ocean. Here we present the details of the method and testing, as well as first triple isotope field data from two cruises to the Landsort Deep area in the Central Baltic Sea.

Treatment of Produced Water From Coal-Bed Methane Production Using Capacitive Deionization Final Report CRADA No. TSV-1380-97

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

Tran, T. D.; Patton, C. C.

The production af Coal-Bed Methane (CBM) is always accompanied by the production of large amounts of water. The produced water is typically too high in dissolved solids and salinity to be suitable for surface disposal.

Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulphidic marine sediments

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

Glass, DR. Jennifer; Yu, DR. Hang; Steele, Joshua

2013-01-01

Microbes have obligate requirements for trace metals in metalloenzymes that catalyse important biogeochemical reactions. In anoxic methane- and sulphiderich environments, microbes may have unique adaptations for metal acquisition and utilization because of decreased bioavailability as a result of metal sulphide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulphidic (> 1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5 270 nM), cobalt (0.5 6 nM), molybdenum (10 5600 nM) and tungsten (0.3 8more » nM) in Hydrate Ridge sediment porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalysing anaerobic oxidation of methane (AOM) utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulphate-reducing bacteria. Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrophilic microorganisms. Overall, our data suggest that AOM consortia use specialized biochemical strategies to overcome the challenges of metal availability in sulphidic environments.« less

Towards Biogeochemical Modeling of Anaerobic Oxidation of Methane: Characterization of Microbial Communities in Methane-bearing North American Continental Margin Sediments

NASA Astrophysics Data System (ADS)

Graw, M. F.; Solomon, E. A.; Chrisler, W.; Krause, S.; Treude, T.; Ruppel, C. D.; Pohlman, J.; Colwell, F. S.

2015-12-01

Methane advecting through continental margin sediments may enter the water column and potentially contribute to ocean acidification and increase atmospheric methane concentrations. Anaerobic oxidation of methane (AOM), mediated by syntrophic consortia of anaerobic methanotrophic archaea and sulfate-reducing bacteria (ANME-SRB), consumes nearly all dissolved methane in methane-bearing sediments before it reaches the sediment-water interface. Despite the significant role ANME-SRB play in carbon cycling, our knowledge of these organisms and their surrounding microbial communities is limited. Our objective is to develop a metabolic model of ANME-SRB within methane-bearing sediments and to couple this to a geochemical reaction-transport model for these margins. As a first step towards this goal, we undertook fluorescent microscopic imaging, 16S rRNA gene deep-sequencing, and shotgun metagenomic sequencing of sediments from the US Pacific (Washington) and northern Atlantic margins where ANME-SRB are present. A successful Illumina MiSeq sequencing run yielded 106,257 bacterial and 857,834 archaeal 16S rRNA gene sequences from 12 communities from the Washington Margin using both universal prokaryotic and archaeal-specific primer sets. Fluorescent microscopy confirmed the presence of cells of the ANME-2c lineage in the sequenced communities. Microbial community characterization was coupled with measurements of sediment physical and geochemical properties and, for samples from the US Atlantic margin, 14C-based measurements of AOM rates and 35S-based measurements of sulfate reduction rates. These findings have the potential to increase understanding of ANME-SRB, their surrounding microbial communities, and their role in carbon cycling within continental margins. In addition, they pave the way for future efforts at developing a metabolic model of ANME-SRB and coupling it to geochemical models of the US Washington and Atlantic margins.

Relationship between anaerobic digestion of biodegradable solid waste and spectral characteristics of the derived liquid digestate.

PubMed

Zheng, Wei; Lü, Fan; Phoungthong, Khamphe; He, Pinjing

2014-06-01

The evolution of spectral properties during anaerobic digestion (AD) of 29 types of biodegradable solid waste was investigated to determine if spectral characteristics could be used for assessment of biological stabilization during AD. Biochemical methane potential tests were conducted and spectral indicators (including the ratio of ultraviolet-visible absorbance at 254nm to dissolved organic carbon concentration (SUVA254), the ratio of ultraviolet-visible absorbance measured at 465nm and 665nm (E4/E6), and the abundance of fluorescence peaks) were measured at different AD phases. Inter-relationship between organic degradation and spectral indicators were analyzed by principle component analysis. The results shows that from methane production phase to the end of methane production phase, SUVA254 increased by 0.16-10.93 times, the abundance of fulvic acid-like compounds fluorescence peak increased by 0.01-0.54 times, the abundance of tyrosine fluorescence peak decreased by 0.03-0.64 times. Therefore, these indicators were useful to judge the course of mixed waste digestion. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

NASA Astrophysics Data System (ADS)

Dale, A. W.; Sommer, S.; Haeckel, M.; Wallmann, K.; Linke, P.; Wegener, G.; Pfannkuche, O.

2010-10-01

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr -1. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m -2 d -1, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m -2 d -1 of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m -2 d -1 of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m -2 d -1 to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m -2 d -1 of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm -3 d -1). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m -2 d -1 or 96 mW m -2 of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m -2 d -1) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m -2 d -1 of CH 4) with a high efficiency of energy expenditure (35 mmol CH 4 kJ -1). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.

Dissolved Methane in the Sills Region of the Gulf of California

EPA Science Inventory

An unusual combination of features make the midriff islands region of the northern Gulf of California (NGC) a strong source of methane to the atmosphere. Oceanographic isolation from the rest of the NGC by a series of sills and islands along with enhanced upward transport of nutr...

Studying methane migration mechanisms at Walker Ridge, Gulf of Mexico, via 3D methane hydrate reservoir modeling

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

Nole, Michael; Daigle, Hugh; Mohanty, Kishore

We have developed a 3D methane hydrate reservoir simulator to model marine methane hydrate systems. Our simulator couples highly nonlinear heat and mass transport equations and includes heterogeneous sedimentation, in-situ microbial methanogenesis, the influence of pore size contrast on solubility gradients, and the impact of salt exclusion from the hydrate phase on dissolved methane equilibrium in pore water. Using environmental parameters from Walker Ridge in the Gulf of Mexico, we first simulate hydrate formation in and around a thin, dipping, planar sand stratum surrounded by clay lithology as it is buried to 295mbsf. We find that with sufficient methane beingmore » supplied by organic methanogenesis in the clays, a 200x pore size contrast between clays and sands allows for a strong enough concentration gradient to significantly drop the concentration of methane hydrate in clays immediately surrounding a thin sand layer, a phenomenon that is observed in well log data. Building upon previous work, our simulations account for the increase in sand-clay solubility contrast with depth from about 1.6% near the top of the sediment column to 8.6% at depth, which leads to a progressive strengthening of the diffusive flux of methane with time. By including an exponentially decaying organic methanogenesis input to the clay lithology with depth, we see a decrease in the aqueous methane supplied to the clays surrounding the sand layer with time, which works to further enhance the contrast in hydrate saturation between the sand and surrounding clays. Significant diffusive methane transport is observed in a clay interval of about 11m above the sand layer and about 4m below it, which matches well log observations. The clay-sand pore size contrast alone is not enough to completely eliminate hydrate (as observed in logs), because the diffusive flux of aqueous methane due to a contrast in pore size occurs slower than the rate at which methane is supplied via organic methanogenesis. Therefore, it is likely that additional mechanisms are at play, notably bound water activity reduction in clays. Three-dimensionality allows for inclusion of lithologic heterogeneities, which focus fluid flow and subsequently allow for heterogeneity in the methane migration mechanisms that dominate in marine sediments at a local scale. Incorporating recently acquired 3D seismic data from Walker Ridge to inform the lithologic structure of our modeled reservoir, we show that even with deep adjective sourcing of methane along highly permeable pathways, local hydrate accumulations can be sourced either by diffusive or advective methane flux; advectively-sourced hydrates accumulate evenly in highly permeable strata, while diffusively-sourced hydrates are characterized by thin strata-bound intervals with high clay-sand pore size contrasts.« less

A reconnaissance spatial and temporal assessment of methane and inorganic constituents in groundwater in bedrock aquifers, Pike County, Pennsylvania, 2012-13

USGS Publications Warehouse

Senior, Lisa A.

2014-01-01

The June 2013 samples were also analyzed for radium-226 and age-dating dissolved gases. Activities of radium-226 ranged from 0.041 to 0.29 pCi/L in water samples from the six wells and were less than the drinking-water standard of 5 pCi/L for combined radium-226 and radium-228. Age-dating of groundwater using a method based on the presence of anthropogenic gases (chlorofluorocarbons and sulfur hexafluoride) released into the atmosphere yielded estimated recharge dates for water from these six wells that ranged from the 1940s to early 2000s. The oldest water was in samples from wells that had the highest methane concentrations and the youngest water was in samples from a continuously pumped 300-foot deep production well.

Microbial mineralization of ethene under sulfate-reducing conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

2002-01-01

A limited investigation of the potential for anaerobic ethylene biodegradation under SO4-reducing conditions was performed. Microorganisms indigenous to a lake-bed sediment completely mineralized [1,2-14C] ethylene to 14CO2 when incubated under SO4-reducing conditions. Reliance on ethylene and/or ethane accumulation as a quantitative indicator of complete reductive dechlorination of chloroethylene contaminants may not be warranted. SO4 addition stimulated SO4 reduction as indicated by decreasing SO4 concentrations (> 40% decrease) and production of dissolved sulfide (880 ??M). SO4 amendment completely suppressed the production of ethane and methane. The concomitant absence of ethane and methane production under SO4-amended conditions was consistent with previous conclusions that reduction of ethylene to ethane occurred under methanogenic conditions. A lack of ethylene accumulation under SO4-reducing conditions may reflect insignificant reductive dechlorination of vinyl chloride or efficient anaerobic mineralization of ethylene to CO2.

Methane Emissions and Microbial Communities as Influenced by Dual Cropping of Azolla along with Early Rice

NASA Astrophysics Data System (ADS)

Liu, Jingna; Xu, Heshui; Jiang, Ying; Zhang, Kai; Hu, Yuegao; Zeng, Zhaohai

2017-01-01

Azolla caroliniana Willd. is widely used as a green manure accompanying rice, but its ecological importance remains unclear, except for its ability to fix nitrogen in association with cyanobacteria. To investigate the impacts of Azolla cultivation on methane emissions and environmental variables in paddy fields, we performed this study on the plain of Dongting Lake, China, in 2014. The results showed that the dual cropping of Azolla significantly suppressed the methane emissions from paddies, likely due to the increase in redox potential in the root region and dissolved oxygen concentration at the soil-water interface. Furthermore, the floodwater pH decreased in association with Azolla cultivation, which is also a factor significantly correlated with the decrease in methane emissions. An increase in methanotrophic bacteria population (pmoA gene copies) and a reduction in methanogenic archaea (16S rRNA gene copies) were observed in association with Azolla growth. During rice cultivation period, dual cropping of Azolla also intensified increasing trend of 1/Simpson of methanogens and significantly decreased species richness (Chao 1) and species diversity (1/Simpson, 1/D) of methanotrophs. These results clearly demonstrate the suppression of CH4 emissions by culturing Azolla and show the environmental and microbial responses in paddy soil under Azolla cultivation.

Methane Emissions and Microbial Communities as Influenced by Dual Cropping of Azolla along with Early Rice.

PubMed

Liu, Jingna; Xu, Heshui; Jiang, Ying; Zhang, Kai; Hu, Yuegao; Zeng, Zhaohai

2017-01-17

Azolla caroliniana Willd. is widely used as a green manure accompanying rice, but its ecological importance remains unclear, except for its ability to fix nitrogen in association with cyanobacteria. To investigate the impacts of Azolla cultivation on methane emissions and environmental variables in paddy fields, we performed this study on the plain of Dongting Lake, China, in 2014. The results showed that the dual cropping of Azolla significantly suppressed the methane emissions from paddies, likely due to the increase in redox potential in the root region and dissolved oxygen concentration at the soil-water interface. Furthermore, the floodwater pH decreased in association with Azolla cultivation, which is also a factor significantly correlated with the decrease in methane emissions. An increase in methanotrophic bacteria population (pmoA gene copies) and a reduction in methanogenic archaea (16S rRNA gene copies) were observed in association with Azolla growth. During rice cultivation period, dual cropping of Azolla also intensified increasing trend of 1/Simpson of methanogens and significantly decreased species richness (Chao 1) and species diversity (1/Simpson, 1/D) of methanotrophs. These results clearly demonstrate the suppression of CH 4 emissions by culturing Azolla and show the environmental and microbial responses in paddy soil under Azolla cultivation.

Methane Emissions and Microbial Communities as Influenced by Dual Cropping of Azolla along with Early Rice

PubMed Central

Liu, Jingna; Xu, Heshui; Jiang, Ying; Zhang, Kai; Hu, Yuegao; Zeng, Zhaohai

2017-01-01

Azolla caroliniana Willd. is widely used as a green manure accompanying rice, but its ecological importance remains unclear, except for its ability to fix nitrogen in association with cyanobacteria. To investigate the impacts of Azolla cultivation on methane emissions and environmental variables in paddy fields, we performed this study on the plain of Dongting Lake, China, in 2014. The results showed that the dual cropping of Azolla significantly suppressed the methane emissions from paddies, likely due to the increase in redox potential in the root region and dissolved oxygen concentration at the soil-water interface. Furthermore, the floodwater pH decreased in association with Azolla cultivation, which is also a factor significantly correlated with the decrease in methane emissions. An increase in methanotrophic bacteria population (pmoA gene copies) and a reduction in methanogenic archaea (16S rRNA gene copies) were observed in association with Azolla growth. During rice cultivation period, dual cropping of Azolla also intensified increasing trend of 1/Simpson of methanogens and significantly decreased species richness (Chao 1) and species diversity (1/Simpson, 1/D) of methanotrophs. These results clearly demonstrate the suppression of CH4 emissions by culturing Azolla and show the environmental and microbial responses in paddy soil under Azolla cultivation. PMID:28094773

Quantification of Methane Gas Flux and Bubble Fate on the Eastern Siberian Arctic Shelf Utilizing Calibrated Split-beam Echosounder Data.

NASA Astrophysics Data System (ADS)

Weidner, E. F.; Mayer, L. A.; Weber, T. C.; Jerram, K.; Jakobsson, M.; Chernykh, D.; Ananiev, R.; Mohammad, R.; Semiletov, I. P.

2016-12-01

On the Eastern Siberian Arctic Shelf (ESAS) subsea permafrost, shallow gas hydrates, and trapped free gas hold an estimated 1400 Gt of methane. Recent observations of methane bubble plumes and high concentrations of dissolved methane in the water column indicate methane release via ebullition. Methane gas released from the shallow ESAS (<50 m average depth) has high potential to be transported to the atmosphere. To directly and quantitatively address the magnitude of methane flux and the fate of rising bubbles in the ESAS, methane seeps were mapped with a broadband split-beam echosounder as part of the Swedish-Russian-US Arctic Ocean Investigation of Climate-Cryosphere-Carbon Interactions program (SWERUS-C3). Acoustic measurements were made over a broad range of frequencies (16 to 29 kHz). The broad bandwidth provided excellent discrimination of individual targets in the water column, allowing for the identification of single bubbles. Absolute bubble target strength values were determined by compensating apparent target strength measurements for beam pattern effects via standard calibration techniques. The bubble size distribution of seeps with individual bubble signatures was determined by exploiting bubble target strength models over the broad range of frequencies. For denser seeps, with potential higher methane flux, bubble size distribution was determined via extrapolation from seeps in similar geomorphological settings. By coupling bubble size distributions with rise velocity measurements, which are made possible by split-beam target tracking, methane gas flux can be estimated. Of the 56 identified seeps in the SWERUS data set, individual bubbles scatterers were identified in more than half (31) of the seeps. Preliminary bubble size distribution results indicate bubble radii range from 0.75 to 3.0 mm, with relatively constant bubble size distribution throughout the water column. Initial rise velocity observations indicate bubble rise velocity increases with decreasing depth, seemingly independent of bubble radius.

Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation.

PubMed

Chen, Ku-Fan; Kao, Chih-Ming; Chen, Chiu-Wen; Surampalli, Rao Y; Lee, Mu-Sheng

2010-01-01

In the first phase of this study, the effectiveness of intrinsic bioremediation on the containment of petroleum hydrocarbons was evaluated at a gasoline spill site. Evidences of the occurrence of intrinsic bioremediation within the BTEX (benzene, toluene, ethylbenzene, and xylenes) plume included (1) decreased BTEX concentrations; (2) depletion of dissolved oxygen (DO), nitrate, and sulfate; (3) production of dissolved ferrous iron, methane, and CO2; (4) deceased pH and redox potential; and (5) increased methanogens, total heterotrophs, and total anaerobes, especially within the highly contaminated areas. In the second phase of this study, enhanced aerobic bioremediation process was applied at site to enhance the BTEX decay rates. Air was injected into the subsurface near the mid-plume area to biostimulate the naturally occurring microorganisms for BTEX biodegradation. Field results showed that enhanced bioremediation process caused the change of BTEX removal mechanisms from anaerobic biodegradation inside the plume to aerobic biodegradation. This variation could be confirmed by the following field observations inside the plume due to the enhanced aerobic bioremediation process: (1) increased in DO, CO2, redox potential, nitrate, and sulfate, (2) decreased in dissolved ferrous iron, sulfide, and methane, (3) increased total heterotrophs and decreased total anaerobes. Field results also showed that the percentage of total BTEX removal increased from 92% to 99%, and the calculated total BTEX first-order natural attenuation rates increased from 0.0092% to 0.0188% per day, respectively, after the application of enhanced bioremediation system from the spill area to the downgradient area (located approximately 300 m from the source area).

In situ Raman-based measurements of high dissolved methane concentrations in hydrate-rich ocean sediments

NASA Astrophysics Data System (ADS)

Zhang, Xin; Hester, Keith C.; Ussler, William; Walz, Peter M.; Peltzer, Edward T.; Brewer, Peter G.

2011-04-01

Ocean sediment dissolved CH4 concentrations are of interest for possible climate-driven venting from sea floor hydrate decomposition, for supporting the large-scale microbial anaerobic oxidation of CH4 that holds the oceanic CH4 budget in balance, and for environmental issues of the oil and gas industry. Analyses of CH4 from recovered cores near vent locations typically show a maximum of ˜1 mM, close to the 1 atmosphere equilibrium value. We show from novel in situ measurement with a Raman-based probe that geochemically coherent profiles of dissolved CH4 occur rising to 30 mM (pCH4 = 3 MPa) or an excess pressure ˜3× greater than CO2 in a bottle of champagne. Normalization of the CH4 Raman ν1 peak to the ubiquitous water ν2 bending peak provides a fundamental internal calibration. Very large losses of CH4 and fractions of other gases (CO2, H2S) must typically occur from recovered cores at gas rich sites. The new data are consistent with observations of microbial biomass and observed CH4 oxidation rates at hydrate rich sites and support estimates of a greatly expanded near surface oceanic pore water CH4 reservoir.

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: Groundwater biogeochemistry

USGS Publications Warehouse

Witt, M.E.; Klecka, G.M.; Lutz, E.J.; Ei, T.A.; Grosso, N.R.; Chapelle, F.H.

2002-01-01

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.

U.S. Geological Survey Noble Gas Laboratory’s standard operating procedures for the measurement of dissolved gas in water samples

USGS Publications Warehouse

Hunt, Andrew G.

2015-08-12

This report addresses the standard operating procedures used by the U.S. Geological Survey’s Noble Gas Laboratory in Denver, Colorado, U.S.A., for the measurement of dissolved gases (methane, nitrogen, oxygen, and carbon dioxide) and noble gas isotopes (helium-3, helium-4, neon-20, neon-21, neon-22, argon-36, argon-38, argon-40, kryton-84, krypton-86, xenon-103, and xenon-132) dissolved in water. A synopsis of the instrumentation used, procedures followed, calibration practices, standards used, and a quality assurance and quality control program is presented. The report outlines the day-to-day operation of the Residual Gas Analyzer Model 200, Mass Analyzer Products Model 215–50, and ultralow vacuum extraction line along with the sample handling procedures, noble gas extraction and purification, instrument measurement procedures, instrumental data acquisition, and calculations for the conversion of raw data from the mass spectrometer into noble gas concentrations per unit mass of water analyzed. Techniques for the preparation of artificial dissolved gas standards are detailed and coupled to a quality assurance and quality control program to present the accuracy of the procedures used in the laboratory.

Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

NASA Astrophysics Data System (ADS)

Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

2017-12-01

Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost same for all models.

Isotopic Composition of Methane and Inferred Methanogenic Substrates Along a Salinity Gradient in a Hypersaline Microbial Mat System

NASA Astrophysics Data System (ADS)

Potter, Elyn G.; Bebout, Brad M.; Kelley, Cheryl A.

2009-05-01

The importance of hypersaline environments over geological time, the discovery of similar habitats on Mars, and the importance of methane as a biosignature gas combine to compel an understanding of the factors important in controlling methane released from hypersaline microbial mat environments. To further this understanding, changes in stable carbon isotopes of methane and possible methanogenic substrates in microbial mat communities were investigated as a function of salinity here on Earth. Microbial mats were sampled from four different field sites located within salterns in Baja California Sur, Mexico. Salinities ranged from 50 to 106 parts per thousand (ppt). Pore water and microbial mat samples were analyzed for the carbon isotopic composition of dissolved methane, dissolved inorganic carbon (DIC), and mat material (particulate organic carbon or POC). The POC δ13C values ranged from -6.7 to -13.5%, and DIC δ13C values ranged from -1.4 to -9.6%. These values were similar to previously reported values. The δ13C values of methane ranged from -49.6 to -74.1%; the methane most enriched in 13C was obtained from the highest salinity area. The apparent fractionation factors between methane and DIC, and between methane and POC, within the mats were also determined and were found to change with salinity. The apparent fractionation factors ranged from 1.042 to 1.077 when calculated using DIC and from 1.038 to 1.068 when calculated using POC. The highest-salinity area showed the least fractionation, the moderate-salinity area showed the highest fractionation, and the lower-salinity sites showed fractionations that were intermediate. These differences in fractionation are most likely due to changes in the dominant methanogenic pathways and substrates used at the different sites because of salinity differences.

Effect of process parameters and operational mode on nitrous oxide emissions from a nitritation reactor treating reject wastewater.

PubMed

Pijuan, Maite; Torà, Josep; Rodríguez-Caballero, Adrián; César, Elvira; Carrera, Julián; Pérez, Julio

2014-02-01

Nitrous oxide (N2O) and methane emissions were monitored in a continuous granular airlift nitritation reactor from ammonium-rich wastewater (reject wastewater). N2O emissions were found to be dependent on dissolved oxygen (DO) concentration in the range of 1-4.5 mg O2/L, increasing within this range when reducing the DO values. At higher DO concentrations, N2O emissions remained constant at 2.2% of the N oxidized to nitrite, suggesting two different mechanisms behind N2O production, one dependent and one independent of DO concentration. Changes on ammonium, nitrite, free ammonia and free nitrous acid concentrations did not have an effect on N2O emissions within the concentration range tested. When operating the reactor in a sequencing batch mode under high DO concentration (>5 mg O2/L), N2O emissions increased one order of magnitude reaching values of 19.3 ± 7.5% of the N oxidized. Moreover, CH4 emissions detected were due to the stripping of the soluble CH4 that remained dissolved in the reject wastewater after anaerobic digestion. Finally, an economical and carbon footprint assessment of a theoretical scaled up of the pilot plant was conducted. Copyright © 2013 Elsevier Ltd. All rights reserved.

Significance of dissolved methane in effluents of anaerobically treated low strength wastewater and potential for recovery as an energy product: A review

EPA Science Inventory

The need for energy efficient Domestic Wastewater (DWW) treatment is increasing annually with population growth and expanding global energy demand. Anaerobic treatment of low strength DWW produces methane which can be used to as an energy product. Temperature sensitivity, low rem...

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

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

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

Permeability and porosity of hydrate-bearing sediments in the northern Gulf of Mexico

DOE PAGES

Daigle, Hugh; Cook, Ann; Malinverno, Alberto

2015-10-14

Hydrate-bearing sands are being actively explored because they contain the highest concentrations of hydrate and are the most economically recoverable hydrate resource. However, relatively little is known about the mechanisms or timescales of hydrate formation, which are related to methane supply, fluid flux, and host sediment properties such as permeability. We used logging-while-drilling data from locations in the northern Gulf of Mexico to develop an effective medium theory-based model for predicting permeability based on clay-sized sediment fraction. The model considers permeability varying between sand and clay endpoint permeabilities that are defined from laboratory data. We verified the model using permeabilitymore » measurements on core samples from three boreholes, and then used the model to predict permeability in two wells drilled in Walker Ridge Block 313 during the Gulf of Mexico Gas Hydrate Joint Industry Project Leg II expedition in 2009. We found that the cleanest sands (clay-sized fraction <0.05) had intrinsic (hydrate-free) permeability contrasts of 5-6 orders of magnitude with the surrounding clays, which is sufficient to provide focused hydrate formation due to advection of methane from a deep source or diffusion of microbial methane from nearby clay layers. In sands where the clay-sized fraction exceeds 0.05, the permeability reduces significantly and focused flow is less pronounced. In these cases, diffusion of dissolved microbial methane is most likely the preferred mode of methane supply for hydrate formation. In conclusion, our results provide important constraints on methane supply mechanisms in the Walker Ridge area and have global implications for evaluating rates of methane migration and hydrate formation in hydrate-bearing sands.« less

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Geo- and biogeochemical processes in a heliothermal hypersaline lake

NASA Astrophysics Data System (ADS)

Zachara, John M.; Moran, James J.; Resch, Charles T.; Lindemann, Stephen R.; Felmy, Andrew R.; Bowden, Mark E.; Cory, Alexandra B.; Fredrickson, James K.

2016-05-01

Water chemical variations were investigated over three annual hydrologic cycles in hypersaline, heliothermal, meromictic Hot Lake in north-central Washington State, USA. The lake contains diverse biota with dramatic zonation related to salinity and redox state. Water samples were collected at 10-cm depth intervals through the shallow lake (2.4 m) during 2012-2014, with comprehensive monitoring performed in 2013. Inorganic salt species, dissolved carbon forms (DOC, DIC), oxygen, sulfide, and methane were analyzed in lake water samples. Depth sonde measurements of pH and temperature were also performed to track their seasonal variations. A bathymetric survey of the lake was conducted to enable lake water volume and solute inventory calculations. Sediment cores were collected at low water and analyzed by X-ray diffraction to investigate sediment mineralogy. The primary dissolved salt in Hot Lake water was Mg2+-SO42- whereas sediments were dominated by gypsum (CaSO4·2H2O). Lake water concentrations increased with depth, reaching saturation with epsomite (MgSO4·7H2O) that was exposed at lake bottom. At maximum volume in spring, Hot Lake exhibited a relatively dilute mixolimnion; a lower saline metalimnion with stratified oxygenic and anoxygenic photosynthetic microbiological communities; and a stable, hypersaline monimolimnion, separated from above layers by a chemocline, containing high levels of sulfide and methane. The thickness of the mixolimnion regulates a heliothermal effect that creates temperatures in excess of 60 °C in the underlying metalimnion and monimolimnion. The mixolimnion was dynamic in volume and actively mixed. It displayed large pH variations, in-situ calcium carbonate precipitation, and large evaporative volume losses. The depletion of this layer by fall allowed deeper mixing into the metalimnion, more rapid heat exchange, and lower winter lake temperatures. Solubility calculations indicate seasonal biogenic and thermogenic aragonite precipitation in the mixolimnion and metalimnion, but the absence of calcareous sediments at depth suggests dissolution and recycling during winter months. Dissolved carbon concentrations [dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC)] increased with depth, reaching ∼0.04 mol/L at the metalimnion-monimolimnion boundary. DIC concentrations were seasonally variable in the mixolimnion and metalimnion, and were influenced by calcium carbonate precipitation. DOC concentrations mimicked those of conservative salts (e.g., Na+-Cl-) in the mixolimnion and metalimnion, but decreased in the monimolimnion where mass loss by anaerobic microbial processes is implied. Biogenic reduced solutes originating in monimolimnion (H2S and CH4) were biologically oxidized in the metalimnion as they were not observed in more shallow lake waters. Multi-year solute inventory calculations indicated that Hot Lake is a stable, albeit seasonally and annually dynamic feature, with inorganic solutes cycled between lake waters and sediments depending on annual recharge, temperature, and lake water dilution state. With its extreme geochemical and thermal regime, Hot Lake functions as analog of early earth and extraterrestrial life environments.

Implementation of methane cycling for deep-time global warming simulations with the DCESS Earth system model (version 1.2)

NASA Astrophysics Data System (ADS)

Shaffer, Gary; Fernández Villanueva, Esteban; Rondanelli, Roberto; Olaf Pepke Pedersen, Jens; Malskær Olsen, Steffen; Huber, Matthew

2017-11-01

Geological records reveal a number of ancient, large and rapid negative excursions of the carbon-13 isotope. Such excursions can only be explained by massive injections of depleted carbon to the Earth system over a short duration. These injections may have forced strong global warming events, sometimes accompanied by mass extinctions such as the Triassic-Jurassic and end-Permian extinctions 201 and 252 million years ago, respectively. In many cases, evidence points to methane as the dominant form of injected carbon, whether as thermogenic methane formed by magma intrusions through overlying carbon-rich sediment or from warming-induced dissociation of methane hydrate, a solid compound of methane and water found in ocean sediments. As a consequence of the ubiquity and importance of methane in major Earth events, Earth system models for addressing such events should include a comprehensive treatment of methane cycling but such a treatment has often been lacking. Here we implement methane cycling in the Danish Center for Earth System Science (DCESS) model, a simplified but well-tested Earth system model of intermediate complexity. We use a generic methane input function that allows variation in input type, size, timescale and ocean-atmosphere partition. To be able to treat such massive inputs more correctly, we extend the model to deal with ocean suboxic/anoxic conditions and with radiative forcing and methane lifetimes appropriate for high atmospheric methane concentrations. With this new model version, we carried out an extensive set of simulations for methane inputs of various sizes, timescales and ocean-atmosphere partitions to probe model behavior. We find that larger methane inputs over shorter timescales with more methane dissolving in the ocean lead to ever-increasing ocean anoxia with consequences for ocean life and global carbon cycling. Greater methane input directly to the atmosphere leads to more warming and, for example, greater carbon dioxide release from land soils. Analysis of synthetic sediment cores from the simulations provides guidelines for the interpretation of real sediment cores spanning the warming events. With this improved DCESS model version and paleo-reconstructions, we are now better armed to gauge the amounts, types, timescales and locations of methane injections driving specific, observed deep-time, global warming events.

Pond Hockey on Whitmore Lacus: the Formation of Ponds and Ethane Ice Deposits Following Storm Events on Titan

NASA Astrophysics Data System (ADS)

Steckloff, Jordan; Soderblom, Jason M.

2017-10-01

Cassini ISS observations reveled regions, later identified as topographic low spots (Soderblom et al. 2014, DPS) on Saturn’s moon Titan become significantly darker (lower albedo) following storm events (Turtle et al. 2009, GRL; 2011, Science), suggesting pools of liquid hydrocarbon mixtures (predominantly methane-ethane-nitrogen). However, these dark ponds then significantly brighten (higher albedo relative to pre-storm albedo), before fading to their pre-storm albedos (Barnes et al. 2013 Planet. Sci; Soderblom et al. 2014, DPS). We interpret these data to be the result of ethane ice formation, which cools from evaporation of methane. The formation of ethane ices results from a unique sequence of thermophysical processes. Initially, the methane in the ternary mixture evaporates, cooling the pond. Nitrogen, dissolved primarily in the methane, exsolves, further cooling the liquid. However, because nitrogen is significantly more soluble in cooler methane-hydrocarbon mixtures, the relative concentration of nitrogen in the solution increases as it cools. This increased nitrogen fraction increases the density of the pond, as nitrogen is significantly more dense thane methane or ethane (pure ethane’s density is intermediate to that of methane and nitrogen). At around ~85 K the mixture is as dense as pure liquid ethane. Thus, further evaporative methane loss and cooling at the pond’s surface leads to a chemical stratification, with an increasingly ethane rich epilimnion (surface layer) overlying a methane rich hypolimnion (subsurface layer). Further evaporation of methane from the ethane-rich epilimnion drives its temperature and composition toward the methane-ethane-nitrogen liquidus curve, causing pure ethane ice to precipitate out of solution and settle to the bottom of the pool. This settling would obscure the ethane ice from Cassini VIMS and ISS, which would instead continue to appear as a dark pond on the surface. As the ethane precipitates out completely, a binary methane-nitrogen liquid mixture remains. Eventually, this residual liquid evaporates away, exposing the submerged ethane ice, which Cassini VIMS and ISS would observe as a dramatic brightening of the surface, consistent with observations.

Chamber-Based Estimates of Methane Production in Coastal Estuarine Systems in Southern California

NASA Astrophysics Data System (ADS)

Brigham, B.; Lipson, D.; Lai, C.

2008-12-01

Wetland systems are believed to produce between 100 - 231 Tg CH4 yr-1 which is roughly 20% of global methane emissions. The uncertainty in methane emissions models stem from the lack of detailed information about methane gas production within regional wetland systems. The aim of this study is to report the range of methane fluxes observed along salinity gradients at two San Diego coastal wetland systems, the Tijuana Estuary (Tijuana River National Estuarine Research Reserve) and the Peñasquitos Lagoon (Torrey Pines State Park Reserve). Soil water samples are used to elucidate factors responsible for the observed variation in methane fluxes. Air samples were subsequently collected from the headspace of a static soil chamber and stored in pre- evacuated vials. Methane concentrations were analyzed within hours after collection by gas chromatography in the laboratory. The chemical and physical properties of the soil, including salinity, pH, redox potential and temperature are measured with a hand-held probe nearby soil collars. The biological properties of the soil, including dissolved organic carbon, nitrate, and ammonia levels are measured from soil water samples in the laboratory. We find that saline sites under direct tidal influence produced methane fluxes ranging from -3.10 to 9.10 (mean 2.18) mg CH4 m-2 day-1. We also find that brackish sites (0.6 to 3.2 ppt in salinity) with fresh water input from residential runoff at the Peñasquitos Lagoon produced methane fluxes ranging from 0.53 to 192.10 (mean 33.34) mg CH4 m-2 day-1. Sampling was done over the course of 5 weeks during August-September of 2008. We hypothesize that the contrasting methane fluxes found between the saline and the brackish sites is due primarily to the different salinity, and in turn sulfate levels found at the two sites. The reduction of sulfate to produce energy is more energetically favorable than the reduction of carbon dioxide to produce methane. Thus the presence of sulfate may act as a methanogensis inhibitor resulting in higher methane flux in low salinity conditions such as those found at the brackish sites.

Extraction of soluble substances from organic solid municipal waste to increase methane production.

PubMed

Campuzano, Rosalinda; González-Martínez, Simón

2015-02-01

This work deals with the analysis of the methane production from Mexico City's urban organic wastes after separating soluble from suspended substances. Water was used to extract soluble substances under three different water to waste ratios and after three extraction procedures. Methane production was measured at 35 °C during 21 days using a commercial methane potential testing device. Results indicate that volatile solids extraction increases with dilution rate to a maximum of 40% at 20 °C and to 43% at 93 °C. The extracts methane production increases with the dilution rate as a result of enhanced dissolved solids extraction. The combined (extract and bagasse) methane production reached, in 6 days, 66% of the total methane produced in 21 days. The highest methane production rates were measured during the first six days. Copyright © 2014 Elsevier Ltd. All rights reserved.

Use of Water-Quality Indicators and Environmental Tracers to Determine the Fate and Transport of Recycled Water in Angeles County, California

USGS Publications Warehouse

Anders, Robert A.; Schroeder, Roy A.

2003-01-01

Tertiary-treated municipal wastewater (recycled water) has been used to replenish the Central Basin in Los Angeles County for over 40 years. Therefore, this area provides an excellent location to investigate (1) the fate and transport of wastewater constituents as they travel from the point of recharge to points of withdrawal, and (2) the long-term effects that artificial recharge using recycled water has on the quality of the ground-water basin. The U.S. Geological Survey has been conducting such investigations in this area for about 10 years, beginning in 1992. For this investigation, a variety of inorganic, organic, and isotopic constituents were analyzed in samples from 23 production wells within 500 feet of the San Gabriel and Rio Hondo Coastal Basin Spreading Grounds, and tritium/helium-3, chlorofluorocarbons, dissolved gases, and nitrogen isotopes were analyzed in five multiple-well monitoring sites along a 10-mile flow path extending from just upgradient of the spreading grounds southward through the Central Basin. Spearman rank-order correlation coefficients and level of significance calculated for about 40 water-quality indicators and several physical features show significant correlations between numerous inorganic and organic constituents that indicate the presence of wastewater. On the basis of a simple two-member mixing model, chloride, boron, ultraviolet absorbance at 254 nanometers, and excitation-emission fluorescence yielded the most reasonable estimates of wastewater percentages in the production wells. Tritium/helium-3 age determinations indicated that samples of ground water tested range in age from less than 2 to more than 50 years. Chloride and boron concentrations, along with tritium/helium-3 age determinations, indicate more rapid recharge and (or) displacement of pre-existing ground water at the San Gabriel Coastal Basin Spreading Grounds than at the Rio Hondo Coastal Basin Spreading Grounds. Nitrogen-15 enrichment of the ground-water nitrate and dissolved nitrogen indicates that denitrification, an important process for the removal of nitrate at the shallower depths beneath the spreading grounds, continues to occur at distances of several miles from the spreading grounds and over a period of many years. Analysis of dissolved gases shows that areas that contain recycled water have no detectable methane, whereas methane is present in the native ground water older than 50 years. The absence of methane in the younger ground water suggests that artificial recharge using recycled water has the desirable effect of increasing slightly the redox potential of the ground-water basin. Finally, measured chlorofluorocarbon concentrations and tritium/helium-3 age determinations indicate that chlorofluorocarbon concentrations are markedly elevated above atmosphere-water equilibrium in ground water older than about 20 years but still young enough to contain recycled water.

Big Soda Lake (Nevada). 3. Pelagic methanogenesis and anaerobic methane oxidation

USGS Publications Warehouse

Iversen, Niels; Oremland, Ronald S.; Klug, Michael J.

1987-01-01

In situ rates of methanogenesis and methane oxidation were measured in meromictic Big Soda Lake. Methane production was measured by the accumulation of methane in the headspaces of anaerobically sealed water samples; radiotracer was used to follow methane oxidation. Nearly all the methane oxidation occurred in the anoxic zones of the lake. Rates of anaerobic oxidation exceeded production at all depths studied in both the mixolimnion (2–6 vs. 0.1–1 nmol liter−1 d−1) and monimolimnion (49–85 vs. 1.6–12 nmol liter−1 d−1) of the lake. Thus, a net consumption of methane equivalent to 1.36 mmol m−2 d−1 occurred in the anoxic water column. Anaerobic methane oxidation had a first-order rate constant of 8.1±0.5 × 10−4 d−1, and activity was eliminated by filter sterilization. However, in situ methane oxidation was of insufficient magnitude to cause a noticeable decrease of ambient dissolved methane levels over an incubation period of 97 h.

Analysis of dissolved gas and fluid chemistry in mountainous region of Goaping river watershed in southern Taiwan

NASA Astrophysics Data System (ADS)

Tang, Kai-Wen; Chen, Cheng-Hong; Liu, Tsung-Kwei

2016-04-01

Annual rainfall in Taiwan is up to 2500 mm, about 2.5 times the average value of the world. However due to high topographic relief of the Central Mountain Range in Taiwan, groundwater storage is critical for water supply. Mountain region of the Goaping river watershed in southern Taiwan is one of the potential areas to develop groundwater recharge model. Therefore the target of this study is to understand sources of groundwater and surface water using dissolved gas and fluid chemistry. Four groundwater and 6 surface water samples were collected from watershed, 5 groundwater and 13 surface water samples were collected from downstream. All samples were analyzed for stable isotopes (hydrogen and oxygen), dissolved gases (including nitrogen, oxygen, argon, methane and carbon dioxide), noble gases (helium and radon) and major ions. Hydrogen and oxygen isotopic ratios of surface water and groundwater samples aligned along meteoric water line. For surface water, dissolved gases are abundant in N2 (>80%) and O2 (>10%); helium isotopic ratio is approximately equal to 1 RA (RA is 3He/4He ratio of air); radon-222 concentration is below the detection limit (<200 Bq/m3); and concentrations of major anions and cations are low (Na+ <20 ppm, Ca2+ < 60 ppm, Cl- <2 ppm). All these features indicate that surface waters are predominately recharged by precipitation. For groundwater, helium isotopic ratios (0.9˜0.23 RA) are lower and radon-222 concentrations (300˜6000 Bq/m3) are much higher than the surface water. Some samples have high amounts of dissolved gases, such as CH4 (>20%) or CO2 (>10%), most likely contributed by biogenic or geogenic sources. On the other hand, few samples that have temperature 5° higher than the average of other samples, show significantly high Na+ (>1000 ppm), Ca2+ (>150 ppm) and Cl- (>80 ppm) concentrations. An interaction between such groundwater and local hot springs is inferred. Watershed and downstream samples differ in dissolved gas species and fluid chemistry for groundwater and surface water. The higher hydrogen and oxygen isotopic ratios for surface water from downstream are most probably caused by evaporation. Low radon-222 concentrations of some groundwater from downstream may represent sources from different aquifers. Therefore, we conclude that surface water from downstream are recharged directly from its watershed, but groundwater are influenced by the local geological environment. Keywords: groundwater, dissolved gas, noble gas, radon in water, 3He/4He

Continuous In Situ Measurements of Near Bottom Chemistry and Sediment-Water Fluxes with the Chimney Sampler Array (CSA)

NASA Astrophysics Data System (ADS)

Martens, C. S.; Mendlovitz, H. P.; White, B. L.; Hoer, D.; Sleeper, K.; Chanton, J.; Wilson, R.; Lapham, L.

2011-12-01

The Chimney Sampler Array (CSA) was designed to measure in situ chemical and physical parameters within the benthic boundary layer plus methane and oxygen sediment-water chemical fluxes at upper slope sites in the northern Gulf of Mexico. The CSA can monitor temporal changes plus help to evaluate oceanographic and sub-seafloor processes that can influence the formation and stability of gas hydrates in underlying sediments. The CSA consists of vertical cylinders (chimneys) equipped with internal chemical sensors and with laboratory flume-calibrated washout rates. Chimney washout rates multiplied by chimney mean versus ambient concentrations allow calculation of net O2 and methane sediment-water fluxes. The CSA is emplaced on the seafloor by a ROVARD lander using a ROV for chimney deployments. The CSA presently includes two 30 cm diameter by 90 cm length cylinders that seal against the sediment with lead pellet beanbags; within each chimney cylinder are optode, conductivity and methane sensors. The CSA's data logger platform also includes pressure and turbidity sensors external to the chimneys along with an acoustic Doppler current meter to measure temporal variation in ambient current velocity and direction. The CSA was deployed aboard a ROVARD lander on 9/13/2010 in the northern Gulf of Mexico (Lat. 28 51.28440, Long. 088 29.39421) on biogeochemically active sediments within Block MC-118. A ROV was utilized for chimney deployment away from the ROVARD lander. The CSA monitored temporal changes in water column physical parameters, obtained near-bottom chemical data to compare with pore fluid and sediment core measurements and measured temporal variability in oxygen and methane sediment-water fluxes at two closely spaced stations at MC-118. A continuous, three-week data set was obtained that revealed daily cycles in chemical parameters and episodic flux events. Lower than ambient chimney dissolved O2 concentrations controlled by temporal variability in washout rates were used to calculate sediment O2 demand. Episodic events yielding turbidity spikes produced episodic spikes in chimney methane concentrations and sediment-water fluxes. The robust data set reveals new capabilities for long-term monitoring of near-bottom processes in biogeochemically active, continental margin environments.

Novel applications for biogeophysics: Prospects for detecting key subseafloor geomicrobiological processes or habitats

NASA Astrophysics Data System (ADS)

Colwell, F. S.; Ntarlagiannis, D.

2007-05-01

The new subdiscipline of biogeophysics has focused mostly on the geophysical signatures of microbial processes in contaminated subsurface environments usually undergoing remediation. However, the use of biogeophysics to examine the biogeochemistry of marine sediments has not yet been well-integrated into conceptual models that describe subseafloor processes. Current examples of geophysical measurements that have been used to detect geomicrobiological processes or infer their location in the seafloor include sound surveillance system (SOSUS)-derived data that detect seafloor eruptive events, deep and shallow cross-sectional seismic surveys that determine the presence of hydraulically conductive zones or gas-bearing sediments (e.g., bottom-simulating reflectors or bubble-rich strata), and thermal profiles. One possible area for innovative biogeophysical characterization of the seafloor involves determining the depth of the sulfate-methane interface (SMI) in locations where sulfate diffuses from the seawater and methane emanates from subsurface strata. The SMI demarcates a stratum where microbially-driven anaerobic methane oxidation (AMO) is dependent upon methane as an electron donor and sulfate as an electron acceptor. AMO is carried out by a recently defined, unique consortium of microbes that metabolically temper the flux of methane into the overlying seawater. The depth of the SMI is, respectively, shallow or deep according to whether a high or low rate of methane flux occurs from the deep sediments. Presently, the SMI can only be determined by direct measurements of methane and sulfate concentrations in the interstitial waters or by molecular biological techniques that target the microbes responsible for creating the SMI. Both methods require collection and considerable analysis of sediment samples. Therefore, detection of the SMI by non-destructive methods would be advantageous. As a key biogeochemical threshold in marine sediments, the depth of the SMI defines methane charge in marine sediments, whether it is from dissolved methane or from methane hydrates. As such, a biogeophysical strategy for determining SMI depth would represent an important contribution to assessing methane charge with respect to climate change, sediment stability, or potential energy resources.

High Magnetic Susceptibility in a Highly Saline Sulfate-Rich Aquifer Undergoing Biodegradation of Hydrocarbon Results from Sulfate Reduction.

NASA Astrophysics Data System (ADS)

Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.

2016-12-01

We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH <10 mg/L) and locations with no contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with hydrocarbon, dominance of sulfate reduction as the TEA is responsible for iron cycling and therefore the high MS associated with biodegradation. [AE1]What about sulfate concentrations? And the range in salinity? You need to add these values to the bastrcat

Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

NASA Astrophysics Data System (ADS)

Daigle, H.; Nole, M.; Cook, A.; Malinverno, A.

2017-12-01

In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability ( 1 md in the absence of hydrate). Pore sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.

Investigating the influence of lithologic heterogeneity on gas hydrate formation and methane recycling at the base of the gas hydrate stability zone in channelized systems

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

Daigle, Hugh; Nole, Michael; Cook, Ann

In marine environments, gas hydrate preferentially accumulates in coarse-grained sediments. At the meso- to micro-scale, however, hydrate distribution in these coarse-grained units is often heterogeneous. We employ a methane hydrate reservoir simulator coupling heat and mass transfer as well as capillary effects to investigate how capillary controls on methane solubility affect gas and hydrate accumulations in reservoirs characterized by graded bedding and alternating sequences of coarse-grained sands and fine-grained silt and clay. Simulations bury a channelized reservoir unit encased in homogeneous, fine-grained material characterized by small pores (150 nm) and low permeability (~1 md in the absence of hydrate). Poremore » sizes within each reservoir bed between vary between coarse sand and fine silt. Sands have a median pore size of 35 microns and a lognormal pore size distribution. We also investigate how the amount of labile organic carbon (LOC) affects hydrate growth due to microbial methanogenesis within the sediments. In a diffusion-dominated system, methane movies into reservoir layers along spatial gradients in dissolved methane concentration. Hydrate grows in such a way as to minimize these concentration gradients by accumulating slower in finer-grained reservoir layers and faster in coarser-grained layers. Channelized, fining-upwards sediment bodies accumulate hydrate first along their outer surfaces and thence inward from top to bottom. If LOC is present in thin beds within the channel, higher saturations of hydrate will be distributed more homogeneously throughout the unit. When buried beneath the GHSZ, gas recycling can occur only if enough hydrate is present to form a connected gas phase upon dissociation. Simulations indicate that this is difficult to achieve for diffusion-dominated systems, especially those with thick GHSZs and/or small amounts of LOC. However, capillary-driven fracturing behavior may be more prevalent in settings with thick GHSZs.« less

Formation of methane nano-bubbles during hydrate decomposition and their effect on hydrate growth.

PubMed

Bagherzadeh, S Alireza; Alavi, Saman; Ripmeester, John; Englezos, Peter

2015-06-07

Molecular dynamic simulations are performed to study the conditions for methane nano-bubble formation during methane hydrate dissociation in the presence of water and a methane gas reservoir. Hydrate dissociation leads to the quick release of methane into the liquid phase which can cause methane supersaturation. If the diffusion of methane molecules out of the liquid phase is not fast enough, the methane molecules agglomerate and form bubbles. Under the conditions of our simulations, the methane-rich quasi-spherical bubbles grow to become cylindrical with a radius of ∼11 Å. The nano-bubbles remain stable for about 35 ns until they are gradually and homogeneously dispersed in the liquid phase and finally enter the gas phase reservoirs initially set up in the simulation box. We determined that the minimum mole fraction for the dissolved methane in water to form nano-bubbles is 0.044, corresponding to about 30% of hydrate phase composition (0.148). The importance of nano-bubble formation to the mechanism of methane hydrate formation, growth, and dissociation is discussed.

Use of dissolved and vapor‐phase gases to investigate methanogenic degradation of petroleum hydrocarbon contamination in the subsurface

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich; Bekins, Barbara A.; Delin, Geoffrey N.; Williams, Randi L.

2005-01-01

At many sites contaminated with petroleum hydrocarbons, methanogenesis is a significant degradation pathway. Techniques to estimate CH4 production, consumption, and transport processes are needed to understand the geochemical system, provide a complete carbon mass balance, and quantify the hydrocarbon degradation rate. Dissolved and vapor‐phase gas data collected at a petroleum hydrocarbon contaminated site near Bemidji, Minnesota, demonstrate that naturally occurring nonreactive or relatively inert gases such as Ar and N2 can be effectively used to better understand and quantify physical and chemical processes related to methanogenic activity in the subsurface. In the vadose zone, regions of Ar and N2 depletion and enrichment are indicative of methanogenic and methanotrophic zones, and concentration gradients between the regions suggest that reaction‐induced advection can be an important gas transport process. In the saturated zone, dissolved Ar and N2 concentrations are used to quantify degassing driven by methanogenesis and also suggest that attenuation of methane along the flow path, into the downgradient aquifer, is largely controlled by physical processes. Slight but discernable preferential depletion of N2 over Ar, in both the saturated and unsaturated zones near the free‐phase oil, suggests reactivity of N2 and is consistent with other evidence indicating that nitrogen fixation by microbial activity is taking place at this site.

30 CFR 75.1324 - Methane concentration and tests.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Methane concentration and tests. 75.1324... Methane concentration and tests. (a) No shot shall be fired in an area that contains 1.0 volume percent or more of methane. (b) Immediately before shots are fired, the methane concentration in a working place...

30 CFR 75.1324 - Methane concentration and tests.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Methane concentration and tests. 75.1324... Methane concentration and tests. (a) No shot shall be fired in an area that contains 1.0 volume percent or more of methane. (b) Immediately before shots are fired, the methane concentration in a working place...

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

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

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

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

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

DOE PAGES

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

2015-12-22

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

Technical note: In vitro total gas and methane production measurements from closed or vented rumen batch culture systems.

PubMed

Cattani, M; Tagliapietra, F; Maccarana, L; Hansen, H H; Bailoni, L; Schiavon, S

2014-03-01

This study compared measured gas production (GP) and computed CH4 production values provided by closed or vented bottles connected to gas collection bags. Two forages and 3 concentrates were incubated. Two incubations were conducted, where the 5 feeds were tested in 3 replicates in closed or vented bottles, plus 4 blanks, for a total of 64 bottles. Half of the bottles were not vented, and the others were vented at a fixed pressure (6.8 kPa) and gas was collected into one gas collection bag connected to each bottle. Each bottle (317 mL) was filled with 0.4000 ± 0.0010 g of feed sample and 60 mL of buffered rumen fluid (headspace volume = 257 mL) and incubated at 39.0°C for 24 h. At 24 h, gas samples were collected from the headspace of closed bottles or from headspace and bags of vented bottles and analyzed for CH4 concentration. Volumes of GP at 24 h were corrected for the gas dissolved in the fermentation fluid, according to Henry's law of gas solubility. Methane concentration (mL/100mL of GP) was measured and CH4 production (mL/g of incubated DM) was computed using corrected or uncorrected GP values. Data were analyzed for the effect of venting technique (T), feed (F), interaction between venting technique and feed (T × F), and incubation run as a random factor. Closed bottles provided lower uncorrected GP (-18%) compared with vented bottles, especially for concentrates. Correction for dissolved gas reduced but did not remove differences between techniques, and closed bottles (+25 mL of gas/g of incubated DM) had a greater magnitude of variation than did vented bottles (+1 mL of gas/g of incubated DM). Feeds differed in uncorrected and corrected GP, but the ranking was the same for the 2 techniques. The T × F interaction influenced uncorrected GP values, but this effect disappeared after correction. Closed bottles provided uncorrected CH4 concentrations 23% greater than that of vented bottles. Correction reduced but did not remove this difference. Methane concentration was influenced by feed but not by the T × F interaction. Corrected CH4 production was influenced by feed, but not by venting technique or the T × F interaction. Closed bottles provide good measurements of CH4 production but not of GP. Venting of bottles at low pressure permits a reliable evaluation of total GP and CH4 production. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Widespread methane seepage along the continental margin off Svalbard - from Bjørnøya to Kongsfjorden

PubMed Central

Mau, S.; Römer, M.; Torres, M. E.; Bussmann, I.; Pape, T.; Damm, E.; Geprägs, P.; Wintersteller, P.; Hsu, C.-W.; Loher, M.; Bohrmann, G.

2017-01-01

Numerous articles have recently reported on gas seepage offshore Svalbard, because the gas emission from these Arctic sediments was thought to result from gas hydrate dissociation, possibly triggered by anthropogenic ocean warming. We report on findings of a much broader seepage area, extending from 74° to 79°, where more than a thousand gas discharge sites were imaged as acoustic flares. The gas discharge occurs in water depths at and shallower than the upper edge of the gas hydrate stability zone and generates a dissolved methane plume that is hundreds of kilometer in length. Data collected in the summer of 2015 revealed that 0.02–7.7% of the dissolved methane was aerobically oxidized by microbes and a minor fraction (0.07%) was transferred to the atmosphere during periods of low wind speeds. Most flares were detected in the vicinity of the Hornsund Fracture Zone, leading us to postulate that the gas ascends along this fracture zone. The methane discharges on bathymetric highs characterized by sonic hard grounds, whereas glaciomarine and Holocene sediments in the troughs apparently limit seepage. The large scale seepage reported here is not caused by anthropogenic warming. PMID:28230189

Microbial production and oxidation of methane in deep subsurface

NASA Astrophysics Data System (ADS)

Kotelnikova, Svetlana

2002-10-01

The goal of this review is to summarize present studies on microbial production and oxidation of methane in the deep subterranean environments. Methane is a long-living gas causing the "greenhouse" effect in the planet's atmosphere. Earlier, the deep "organic carbon poor" subsurface was not considered as a source of "biogenic" methane. Evidence of active methanogenesis and presence of viable methanogens including autotrophic organisms were obtained for some subsurface environments including water-flooded oil-fields, deep sandy aquifers, deep sea hydrothermal vents, the deep sediments and granitic groundwater at depths of 10 to 2000 m below sea level. As a rule, the deep subterranean microbial populations dwell at more or less oligotrophic conditions. Molecular hydrogen has been found in a variety of subsurface environments, where its concentrations were significantly higher than in the tested surface aquatic environments. Chemolithoautotrophic microorganisms from deep aquifers that could grow on hydrogen and carbon dioxide can act as primary producers of organic carbon, initiating heterotrophic food chains in the deep subterranean environments independent of photosynthesis. "Biogenic" methane has been found all over the world. On the basis of documented occurrences, gases in reservoirs and older sediments are similar and have the isotopic character of methane derived from CO 2 reduction. Groundwater representing the methanogenic end member are characterized by a relative depletion of dissolved organic carbon (DOC) in combination with an enrichment in 13C in inorganic carbon, which is consistent with the preferential reduction of 12CO 2 by autotrophic methanogens or acetogens. The isotopic composition of methane formed via CO 2 reduction is controlled by the δ13C of the original CO 2 substrate. Literature data shows that CH 4 as heavy as -40‰ or -50‰ can be produced by the microbial reduction of isotopically heavy CO 2. Produced methane may be oxidized microbially to carbon dioxide. Microbial methane oxidation is a biogeochemical process that limits the release of methane, a greenhouse gas from anaerobic environments. Anaerobic methane oxidation plays an important role in marine sediments. Similar processes may take place in deep subsurface and thus fuel the deep microbial community. Organisms or consortia responsible for anaerobic methane oxidation have not yet been cultured, although diverse aerobic methanotrophs have been isolated from a variety of underground niches. The presence of aerobic methanotrophs in the anoxic subsurface remains to be explained. The presence of methane in the deep subsurface have been shown all over the world. The flux of gases between the deep subsurface and the atmosphere is driven by the concentration gradient from depth to the atmosphere. However, methane is consumed by methanotrophs on the way of its evolution in oxidized environments and is transformed to organic form, available for further microbial processing. When the impact of subsurface environments to global warming is estimated, it is necessary to take into account the activity of methane-producing Archaea and methane-oxidizing biofilters in groundwater. Microbial production and oxidation of methane is involved in the carbon cycle in the deep subsurface environments.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands.

PubMed

Dalcin Martins, Paula; Hoyt, David W; Bansal, Sheel; Mills, Christopher T; Tfaily, Malak; Tangen, Brian A; Finocchiaro, Raymond G; Johnston, Michael D; McAdams, Brandon C; Solensky, Matthew J; Smith, Garrett J; Chin, Yu-Ping; Wilkins, Michael J

2017-08-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions. © 2017 John Wiley & Sons Ltd.

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

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

Dalcin Martins, Paula; Hoyt, David W.; Bansal, Sheel

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxesmore » to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR, and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations, or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield non-competitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.« less

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

USGS Publications Warehouse

Martins, Paula; Hoyt, David W.; Bansal, Sheel; Mills, Christopher T.; Tfaily, Malak; Tangen, Brian; Finocchiaro, Raymond; Johnston, Michael D.; McAdams, Brandon C.; Solensky, Matthew J.; Smith, Garrett J.; Chin, Yu-Ping; Wilkins, Michael J.

2017-01-01

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

Biogeochemical evolution of a landfill leachate plume, Norman, Oklahoma

USGS Publications Warehouse

Cozzarelli, Isabelle M.; Böhlke, John Karl; Masoner, Jason R.; Breit, George N.; Lorah, Michelle M.; Tuttle, Michele L.W.; Jaeschke, Jeanne B.

2011-01-01

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifer's geologic and hydrodynamic framework.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2011

USGS Publications Warehouse

Huffman, Raegan L.; Frans, L.M.

2012-01-01

Previous investigations indicate that concentrations of chlorinated volatile organic compounds are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with ongoing natural attenuation processes was the preferred remedy selected by the U.S. Navy, as specified in the Record of Decision for the site. The U.S. Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated volatile organic compounds in shallow groundwater. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. This report presents groundwater geochemical and selected volatile organic compound data collected at Operable Unit 1 by the U.S. Geological Survey during June 20-22, 2011, in support of long-term monitoring for natural attenuation. In 2011, groundwater samples were collected from 13 wells and 9 piezometers. Samples from all wells and piezometers were analyzed for redox sensitive constituents and dissolved gases, and samples from 5 of 13 wells and all piezometers also were analyzed for chlorinated volatile organic compounds. Concentrations of redox sensitive constituents measured in 2011 were consistent with previous years, with dissolved oxygen concentrations all at 0.4 milligram per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. The reductive declorination byproducts - methane, ethane, and ethene - were either not detected in samples collected from the upgradient wells in the landfill and the upper aquifer beneath the northern phytoremediation plantation or were detected at concentrations less than those measured in 2010. Chlorinated volatile organic compound concentrations in 2011 at most piezometers were similar to or slightly less than chlorinated volatile organic compound concentrations measured in previous years. For the upper aquifer beneath the southern phytoremediation plantation, chlorinated volatile organic compound concentrations in 2011 in groundwater from the piezometers were extremely high and continued to vary considerably over space and between years. At piezometer P1-9, the total chlorinated volatile organic compound concentrations increased from 9,500 micrograms per liter in 2010 to more than 44,000 micrograms per liter in 2011. Total chlorinated volatile organic compound concentrations decreased at piezometers P1-6, P1-7, and P1-10 compared to the concentrations measured in 2010. One or both of the reductive dechlorination byproducts ethane and ethene were detected at all piezometers and three of the four wells in the southern plantation. For the intermediate aquifer, concentrations of redox sensitive constituents and chlorinated volatile organic compounds in 2011 were consistent with concentrations measured in previous years, with the exception of notable decreases in sulfate and chloride concentrations at well MW1-28. Concentrations of the reductive dechlorination byproducts ethane and ethene decreased at wells MW1-25 and MW1-28 compared to previously measured concentrations.

The phase transition of methane caused by pressure change during its seeping up from seepage, revealed by video observation and acoustic reflection data

NASA Astrophysics Data System (ADS)

Aoyama, C.

2017-12-01

Methane plumes often exist in the vicinity sea area where shallow type methane hydrates are extracted and they are observed as images displayed on monitors of multi-beam sonar and echo sounder onboard, where methane hydrates are expected at sea bottom on ROV observation data. The hydrates are generally considered to be generated in shallow depths below the sea floor. In this study, author examined annual amount of methane dissolving into seawater by measuring the amount of plume in order to make a quantification of dissolving methane from seafloor. Measurement procedure is plume exploration using multi-beam and quantitative echo sounder , submerge ROV to gushing point at seafloor , calculate the rising speed of methane plumes and examine the phases by monitoring seeping plumes from seafloor with high-definition camera. Components of seeping plumes were defined as methane hydrate particles based on the result by measuring water temperature. From this procedure, it can be concluded that the minimum rising speed of methane hydrate particles from gushing point is 1.6×10-1(m/s) and the maximum of 2.0×10-1(m/s) indicating a difference of more than ten times the gaseous theoretical value of 2.74(m/s). This speed is theoretically closer to the solid speed of the material with physical property similar to hydrates, which is 3.05×10-1 (m/s). Therefore, it can be determined that those particles are in the solid state, immediately above seafloor. To measure the amount of plumes seeping from gushing points funnel-shaped instruments with 20cm diameter opening were used to collect methane plumes in this sea area. This was performed in three different gushing points. As a result, 300ml of methane plume was collected in 643 seconds. Assuming that gushing points exist evenly in the sea area, the annual amount of methane gas seeping from these points will be 7.7×105m3 /per m2. Result shows a large quantity of methane seeping from seafloor into the water. This data is an important factor when considering carbon cycle and future development the shallow methane hydrate resources.

Isotopic composition of methane and inferred methanogenic substrates along a salinity gradient in a hypersaline microbial mat system.

PubMed

Potter, Elyn G; Bebout, Brad M; Kelley, Cheryl A

2009-05-01

The importance of hypersaline environments over geological time, the discovery of similar habitats on Mars, and the importance of methane as a biosignature gas combine to compel an understanding of the factors important in controlling methane released from hypersaline microbial mat environments. To further this understanding, changes in stable carbon isotopes of methane and possible methanogenic substrates in microbial mat communities were investigated as a function of salinity here on Earth. Microbial mats were sampled from four different field sites located within salterns in Baja California Sur, Mexico. Salinities ranged from 50 to 106 parts per thousand (ppt). Pore water and microbial mat samples were analyzed for the carbon isotopic composition of dissolved methane, dissolved inorganic carbon (DIC), and mat material (particulate organic carbon or POC). The POC delta(13)C values ranged from -6.7 to -13.5 per thousand, and DIC delta(13)C values ranged from -1.4 to -9.6 per thousand. These values were similar to previously reported values. The delta(13)C values of methane ranged from -49.6 to -74.1 per thousand; the methane most enriched in (13)C was obtained from the highest salinity area. The apparent fractionation factors between methane and DIC, and between methane and POC, within the mats were also determined and were found to change with salinity. The apparent fractionation factors ranged from 1.042 to 1.077 when calculated using DIC and from 1.038 to 1.068 when calculated using POC. The highest-salinity area showed the least fractionation, the moderate-salinity area showed the highest fractionation, and the lower-salinity sites showed fractionations that were intermediate. These differences in fractionation are most likely due to changes in the dominant methanogenic pathways and substrates used at the different sites because of salinity differences.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2009

USGS Publications Warehouse

Huffman, R.L.; Dinicola, R.S.

2011-01-01

Previous investigations indicate that natural attenuation and biodegradation of chlorinated volatile organic compounds (VOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with ongoing natural attenuation processes was the preferred remedy selected by the U.S. Navy, as specified in the Record of Decision for the site. The U.S. Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated VOCs in shallow groundwater. The U.S. Geological Survey (USGS) has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. This report presents groundwater geochemical and selected VOC data collected at OU 1 by the USGS during June 15-17, 2009, in support of long-term monitoring for natural attenuation. For 2009, groundwater samples were collected from 13 wells and 9 piezometers. Samples from all wells and piezometers were analyzed for redox sensitive constituents, and samples from 10 of 18 upper-aquifer wells and piezometers and 3 of 4 intermediate-aquifer wells also were analyzed for chlorinated VOCs. Concentrations of redox sensitive constituents measured in 2009 were consistent with previous years, with dissolved hydrogen (H2) concentrations ranging from less than 0.1 to 1.8 nanomolar (nM), dissolved oxygen concentrations all at 0.6 milligram per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. The reductive declorination byproducts-methane, ethane, and ethene-were not detected in samples collected from the upgradient wells in the landfill or the upper aquifer beneath the northern phytoremediation plantation. Chlorinated VOC concentrations in 2009 at most piezometers were similar to or slightly less than chlorinated VOC concentrations measured in previous years. In 2009, concentrations of reductive dechlorination byproducts ethane and ethene were less than those measured in 2008 at most northern plantation wells and piezometers. For the upper aquifer beneath the southern phytoremediation plantation, chlorinated VOC concentrations in 2009 at the piezometers were extremely high and continued to vary considerably over space and between years. At piezometer P1-9, the total chlorinated VOC concentration increased from 25,000 micrograms per liter in 2008 to more than 172,000 micrograms per liter in 2009. At piezometer P1-7 in 2009, the concentrations of trichloroethene and cis-1,2-dichloroethene (cis-DCE) were the highest to date. The reductive dechlorination byproducts ethane and ethene were detected at all wells and piezometers in the southern plantation with the exception of piezometer P1-8, although the measured concentrations were not consistently high. For the intermediate aquifer, concentrations of redox sensitive constituents and VOCs in 2009 at wells MW1-25, MW1-28, and MW1-39 were consistent with concentrations measured in previous years. Concentrations of the reductive dechlorination byproducts ethane and ethene at wells MW1-25 and MW1-28 were equal to or greater than previously measured concentrations.

Sulfur and carbon isotope biogeochemistry of a rewetted brackish fen

NASA Astrophysics Data System (ADS)

Koebsch, Franziska; Gehre, Matthias; Winkel, Matthias; Koehler, Stefan; Koch, Marian; Jurasinski, Gerald; Spitzy, Alejandro; Liebner, Susanne; Sachs, Torsten; Schmiedinger, Iris; Kretzschmann, Lisett; Saborowski, Anke; Böttcher, Michael E.

2015-04-01

Coastal wetlands are at the interface between terrestrial freshwater and marine and exhibit very specific biogeochemical conditions. Intermittent sea water intrusion affects metabolic pathways, i. e. anaerobic carbon metabolism is progressively dominated by sulfate reduction with lower contribution of methanogenesis whilst methane production is increasingly shifted from acetoclastic to hydrogenotrophic. Due to expanding anthropogenic impact a large proportion of coastal ecosystems is degraded with severe implications for the biogeochemical processes. We use concentration patterns and stable isotope signatures of water, sulfate, dissolved carbonate, and methane (δ2H, δ13C, δ18O, δ34S) to investigate the S and C metabolic cycle in a rewetted fen close to the southern Baltic Sea border. Such studies are crucial to better predict dynamic ecosystem feedback to global change like organic matter (OM) decomposition or greenhouse gas emissions. Yet, little is known about the metabolic pathways in such environments. The study site is part of the TERENO Observatory "Northeastern German Lowlands' and measurements of methane emissions have run since 2009. High methane fluxes up to 800 mg m-2 hr-1 indicate that methanogenesis is the dominant C metabolism pathway despite of high sulfate concentrations (up to 37 mM). The presented data are part of a comprehensive biogeochemical investigation that we conducted in autumn 2014 and that comprises 4 pore water profiles and sediment samples within a transect of 300-1500 m distance to the Baltic Sea. Depth of organic layers ranged from 25 to 140 cm with high OM contents (up to 90 dwt.%). Sulfate/chloride ratios in the pore waters were lower than in the Baltic Sea for most sites and sediment depths indicated a substantial net sulfate loss. Sulfide concentrations were negligible at the top and increased parallel to the sulfate concentrations with depth to values of up to 0.3 mM. One pore water profiles situated 1150 m from the Baltic Sea coast line exhibited a significant excess of sulfate. Preliminary sulfur isotope analysis of pore water sulfate from a location nearest to this profile revealed an enrichment in 34S (24.9 to 41.8o ) in comparison to Baltic Sea sulfate (21o ). This confirms high degrees of net sulfate reduction. Considering the yet high sulfate concentrations we hypothesize that local processes might supply additional sulfate and that the sulfide produced from sulfate reduction might either be lost by upwards diffusion towards the atmosphere or converted into other S compounds such as pyrite or organic compounds. The isotopic signatures of methane (δ13C: -68 to -57o and δ2H: -133 to -157o respectively) indicated acetoclastic methanogenesis to be the most dominant methane production pathway. However, estimated fractionation factors are comparatively high (1.050-1.065). Enrichment of heavy 13C in methane at the top of the sediment was either caused by methane oxidation or variation in substrate availability (e. g. due to peat degradation). The interpretation of our data in the light of further results will provide deeper insights into metabolic pathways and possible interactions between both coupled element cycles for coastal ecosystems.

Mapping the impact of river regulation on carbon dynamics using coupled field surveys and remotely-sensed optical properties

NASA Astrophysics Data System (ADS)

Kuhn, C.; Butman, D. E.

2016-12-01

Many river-reservoir networks are already managed for ecological targets such as stream temperature regulation, but less is known about how management choices alter the quantity and composition of dissolved organic carbon as well as the concentration of dissolved carbon gases. Understanding these ecological impacts is critical to informing water resources management, especially in light of the global hydropower boom and the increased interest in dam removal in the United States. Here we present results from a field survey and remote sensing imagery analysis quantifying a suite of water quality variables. With this approach, we evaluate spatial differences in carbon signals above, and below eight mainstem dams located on the Columbia and Snake Rivers. Dissolved methane and carbon dioxide concentrations were in excess of atmospheric levels with occasional carbon dioxide undersaturation being observed in the Snake River. CH4 and CO2 δ13C values shifted between the mainstem and the tributaries reflecting changes in carbon sources and processes. Satellite-retrieved estimates of CDOM and chlorophyll-a were compared to in situ measurements to enable surface mapping of concentrations at broader spatial scales. Our technical approach blends cloud-based data fusion techniques and machine learning to link ground-collected observations to remote sensing imagery in order to produce spatially-explicit, cross-scale estimates of carbon dynamics in a large, highly regulated river system. These findings test the feasibility of coupling remote sensing with field-based measurements to observe the complex impacts of run-of-the river impoundments to aquatic carbon cycling.

Methane Concentrations and Biogeochemistry in Lake Sediments from Stordalen Mire, Sub-Arctic Sweden

NASA Astrophysics Data System (ADS)

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

2013-12-01

Lake sediments are an important global carbon sink of both allochthonous and autochthonous inputs. However, lakes are also known to emit carbon in gaseous form, most often as methane (CH4) or carbon dioxide (CO2), which are potent greenhouse gases. As northern latitudes warm, it is increasingly important to understand these gases and the sediments that store them. In July of 2013 we took 48 cores at 16 sites throughout three lakes surrounding a mire underlain by degrading permafrost in sub-arctic Sweden. The goal was to characterize the sedimentology and geochemistry of the lake sediments to better understand the production, distribution, and flux of CO2 and CH4 from these lakes. Villasjön is a shallow lake less than 1.5 meters deep, Mellan Harrsjön has a maximum depth of 7 meters and is stream-fed, and Inre Harrsjön has a maximum depth of 5 meters and is connected to Mellan Harrsjön. Published radiocarbon dates suggest that all three lakes formed approximately 3400 years ago. At each sample site, we retrieved 2 to 4 cores from the lake bottom, approximately 40-80 cm in length. The cores were sub-sampled for measurements of bulk TOC, TC, TN, TS, and CaCO3 (by difference) using a CHNS Elemental Analyzer, and grain size using a laser particle size analyzer. Headspace CO2 and CH4 by gas chromatography and infrared gas analysis (IRGA) yielded production rates and CH4 sediment concentrations. Dissolved inorganic carbon (DIC) from porewater extractions were analyzed using IRGA and stable carbon isotopes of DIC were analyzed via a Quantum Cascade Laser. The recovered sediments in the cores from all three lakes were composed of three layers: an upper layer of organic rich sediment (30-40 cm thick), a middle transition layer of mixed organic and lithogenic materials (5-10 cm thick), and a deep layer of grey lithogenic clay with less organic carbon (of variable thickness). Preliminary results from the 12 Villasjön sites indicate that CH4 is present and produced from the organic-rich layer in the upper 20-40 cm of the sediment. TOC values in this lake range from <1 to 44 wt. %. The TOC maximum (approximately 20-40 wt. %) consistently occurred at the same depth as the methane maximum, centered at ~20 cm. A TOC minimum zone (approximately 0-5 wt. %) occurs from 35-80 cm. Particle size distributions in this lake are dominated by silt and sand size fractions (>4 um). Calcium carbonate (CaCO3) concentrations varied, but the maximum always occurred in the upper 20 cm of the core. Core sites with known high lake surface methane fluxes from bubble trap measurements also show high methane concentrations in the sediment, high DIC concentrations in the pore fluids, and δ 13C signatures of CO2 ranging from 0 to 10, consistent with methanogenesis. Similar results are expected from the integration of pending sediment methane profiles with these data from the other two lakes: Mellan Harrsjön and Inre Harrsjön. Future work, including 14C dating, microbial community profiling, and δ13C signatures of CH4 will yield more insight into the biogeochemical mechanisms that regulate sediment methane distributions. 13C isotopes of methane and DIC should indicate if methane consumption through AOM or diffusion is controlling its distribution.

Changing concentrations of CO, CH(4), C(5)H(8), CH(3)Br, CH(3)I, and dimethyl sulfide during the Southern Ocean Iron Enrichment Experiments.

PubMed

Wingenter, Oliver W; Haase, Karl B; Strutton, Peter; Friederich, Gernot; Meinardi, Simone; Blake, Donald R; Rowland, F Sherwood

2004-06-08

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO(2)) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH(4)), isoprene (C(5)H(8)), methyl bromide (CH(3)Br), dimethyl sulfide, and oxygen (O(2)), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH(3)I), and CO(2) observed during the Southern Ocean Iron Enrichment Experiments.

A stream-based methane monitoring approach for evaluating groundwater impacts associated with unconventional gas development.

PubMed

Heilweil, Victor M; Stolp, Bert J; Kimball, Briant A; Susong, David D; Marston, Thomas M; Gardner, Philip M

2013-01-01

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point-specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH4 ) along such streams. This paper describes a method for using stream CH4 concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1-D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH4 persistence in a stream, a combined bromide (Br) and CH4 tracer injection was conducted on Nine-Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH4 resulted in a fivefold increase in stream CH4 immediately below the injection site. CH4 and δ(13) CCH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1-D stream transport model simulating the decline in CH4 yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH4 in Nine-Mile Creek (prior to CH4 injection) in order to evaluate groundwater CH4 contributions. The total estimated CH4 load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream-gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH4 leakage from gas reservoirs into groundwater and surface water. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

[In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation].

PubMed

Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei

2011-06-01

Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

Widespread methane seepage along the continental margin off Svalbard - from Bjørnøya to Kongsfjorden

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

Mau, S.; Romer, M.; Torres, M. E.

Numerous articles have recently reported on gas seepage offshore Svalbard, because the gas emission from these Arctic sediments was thought to result from gas hydrate dissociation, possibly triggered by anthropogenic ocean warming. We report on findings of a much broader seepage area, extending from 74° to 79°, where more than a thousand gas discharge sites were imaged as acoustic flares. The gas discharge occurs in water depths at and shallower than the upper edge of the gas hydrate stability zone and generates a dissolved methane plume that is hundreds of kilometer in length. Data collected in the summer of 2015more » revealed that 0.02–7.7% of the dissolved methane was aerobically oxidized by microbes and a minor fraction (0.07%) was transferred to the atmosphere during periods of low wind speeds. Most flares were detected in the vicinity of the Hornsund Fracture Zone, leading us to postulate that the gas ascends along this fracture zone. The methane discharges on bathymetric highs characterized by sonic hard grounds, whereas glaciomarine and Holocene sediments in the troughs apparently limit seepage. The large scale seepage reported here is not caused by anthropogenic warming.« less

Headspace gas chromatography with flame ionization detection (HS-GC-FID) for the determination of dissolved methane in wastewater.

PubMed

Beale, D J; Tjandraatmadja, G; Toifl, M; Goodman, N

2014-01-01

There is currently a need for a simple, accurate and reproducible method that quantifies the amount of dissolved methane in wastewater in order to realize the potential methane that can be recovered and account for any emissions. This paper presents such a method, using gas chromatography with flame ionization detection fitted with a GS-Gas PRO column coupled with a headspace auto sampler. A practical limit of detection for methane of 0.9 mg L(-1), with a retention time of 1.24 min, was obtained. It was found that the reproducibility and accuracy of the method increased significantly when samples were collected using an in-house constructed bailer sampling device and with the addition of 100 μL hydrochloric acid (HCl) and 25% sodium chloride (NaCl) and sonication for 30 min prior to analysis. Analysis of wastewater samples and wastewater sludge collected from a treatment facility were observed to range from 12.51 to 15.79 mg L(-1) (relative standard deviation (RSD) 8.1%) and 17.56 to 18.67 mg L(-1) (RSD 3.4%) respectively. The performance of this method was validated by repeatedly measuring a mid-level standard (n=8; 10 mg L(-1)), with an observed RSD of 4.6%.

Widespread methane seepage along the continental margin off Svalbard - from Bjørnøya to Kongsfjorden

DOE PAGES

Mau, S.; Romer, M.; Torres, M. E.; ...

2017-02-23

Numerous articles have recently reported on gas seepage offshore Svalbard, because the gas emission from these Arctic sediments was thought to result from gas hydrate dissociation, possibly triggered by anthropogenic ocean warming. We report on findings of a much broader seepage area, extending from 74° to 79°, where more than a thousand gas discharge sites were imaged as acoustic flares. The gas discharge occurs in water depths at and shallower than the upper edge of the gas hydrate stability zone and generates a dissolved methane plume that is hundreds of kilometer in length. Data collected in the summer of 2015more » revealed that 0.02–7.7% of the dissolved methane was aerobically oxidized by microbes and a minor fraction (0.07%) was transferred to the atmosphere during periods of low wind speeds. Most flares were detected in the vicinity of the Hornsund Fracture Zone, leading us to postulate that the gas ascends along this fracture zone. The methane discharges on bathymetric highs characterized by sonic hard grounds, whereas glaciomarine and Holocene sediments in the troughs apparently limit seepage. The large scale seepage reported here is not caused by anthropogenic warming.« less

When Organic-Rich Turbidites Reach 5000 m: "Cold-Seep Like" Life in the Congo Deep-Sea Fan

NASA Astrophysics Data System (ADS)

Pastor, L.; Toffin, L.; Cathalot, C.; Olu, K.; Brandily, C.; Bessette, S.; Lesongeur, F.; Godfroy, A.; Khripounoff, A.; Decker, C.; Taillefert, M.; Rabouille, C.

2016-12-01

The Congo canyon, located on the west coast of Africa, is a unique example of a canyon directly connected to a major river (The Congo River). Turbidites are responsible for a large input of terrestrial organic matter at depths up to 5000 m. These high inputs led to global high organic matter mineralization rates, with very localized hot spots that were visually observed and specifically sampled with a ROV. These hot spots, featuring substantial concentration of reduced compounds, mainly methane and sulfides, were recognizable in surface by the presence of reduced sediment patches, bacterial mats, and/or vesicomyid bivalves that host bacterial endosymbionts able to process H2S. In this paper we present geochemical sediment profiles of sulfate, methane, sulfide and dissolved iron together with phylogenetic diversity of 16S rRNA communities. This will give a first understanding of biogeochemical processes occurring in this peculiar ecosystem, mainly sulfate reduction, methanogenesis and subsequent anaerobic oxidation of methane with bacterial and archaeal assemblages similar to cold seeps environments. Iron also seems to play a major role in this system and iron/sulfur interactions as a sink for H2S can probably compete with H2S consumption by chemosynthetic bivalves, estimated at one site by vesicomyds gills incubations in a sulfide-rich solution.

A Laughing Gas Greenhouse for the Proterozoic?

NASA Astrophysics Data System (ADS)

Roberson, A. L.; Roadt, J.; Halevy, I.; Kasting, J. F.

2010-12-01

An anoxic, sulfidic ‘Canfield ocean’ during the Proterozoic (0.75-2.3 Ga) would have had limited trace metal abundances because of the low solubility of metal sulfides. The limitation on copper, specifically, would have had a significant impact on marine denitrification. Copper is needed for the enzyme that controls the final step of denitrification, from N2O to N2. Today, only about 5-6 percent of denitrification results in release of N2O. If all denitrification stopped at N2O during the Proterozoic, the N2O flux could have been 15-20 times higher than today. Other parts of the nitrogen cycle should have been able to operate at rates comparable to today, as catalysts for these reactions should have existed. The high N2O flux should have created higher atmospheric N2O concentrations; although this effect may have been offset by faster rates of N2O photolysis if O2 concentrations were lower than today. N2O concentrations of 0.3 to 30 ppmv, along with methane levels of 30-100 ppm, could have kept the surface warm during the Proterozoic without necessitating high CO2 levels. The high methane concentrations were a consequence of lack of dissolved O2 and sulfate in the deep ocean, which should have led to a high CH4 flux from marine sediments. A second oxygenation event at the end of the Proterozoic would have resulted in a shift to a more modern ocean and, consequently, more modern concentrations of atmospheric N2O and CH4.

Methane in Sediments From Three Tropical, Coastal Lagoons on the Yucatan Peninsula, Mexico

NASA Astrophysics Data System (ADS)

Young, B.; Paytan, A.; Miller, L.; Herrera-Silveira, J.

2002-12-01

Tropical wetlands are significant sources of methane (CH4) to the atmosphere, and the majority of research on methane flux and cycling in the tropics has been conducted in fresh-water wetlands and lakes. However, several previous studies have shown that tropical coastal ecosystems can produce significant methane flux to the atmosphere despite the presence of moderate to marine salinities. Information regarding methane cycling within the sediments is crucial to understanding how natural and anthropogenic changes may influence these systems. We measured methane concentrations in sediments from two tropical coastal lagoons during different seasons, as well as in a third, heavily polluted, lagoon (Terminos) during the rainy season. These three lagoons, Celestun, Chelem, and Terminos, have similar vegetation, seasonal temperature and rainfall patterns, and substrate geology, but very different levels of ground water discharge and pollution. Methane concentrations in Celestun and Terminos lagoon showed high spatial variability(> 0.001 to 5 mmol kg-1 wet sediment), while sediments in Chelem Lagoon, which has near marine salinities and little sewage discharge, showed much lower variability of methane concentrations. Methane concentrations in Celestun sediments displayed two predominant patterns: some profiles contained a peak in methane concentration (1 to 2 mmole methane kg-1 wet sediment) between 5 and 15 cm below the surface while the other sediment profiles instead displayed a steady or monotonic increase in methane concentration with depth to approximately 0.025-0.080 mmol kg-1 at 10-15cm below surface followed by stable methane concentrations to the bottom of the cores (20-45 cm below the surface). A subsurface peak in methane concentrations was also found in some locations in Chelem, however, the concentrations were much lower than those measured in Celestun. Previous studies have shown that sewage pollution may drastically increase methane production in tropical coastal ecosystems. Laboratory experiments using sediment from the upper 20 cm in Celestun lagoon resulted in high rates of biogenic production of methane from the addition of trimethylamine, hydrogen, and, while additions of formate and acetate stimulated methane production to a lesser extent. This indicates that methane production in these sediments may be highly responsive to natural or anthropogenic changes in substrate availability. By synthesizing laboratory data and extensive field measurements from the lagoons, we hope to shed light on the factors controlling methane cycling in these sediments, and to better estimate methane flux to the atmosphere from these ecosystems.

Hydrothermal Synthesis of Various Hierarchical ZnO Nanostructures and Their Methane Sensing Properties

PubMed Central

Zhou, Qu; Chen, Weigen; Xu, Lingna; Peng, Shudi

2013-01-01

Hierarchical flower-like ZnO nanorods, net-like ZnO nanofibers and ZnO nanobulks have been successfully synthesized via a surfactant assisted hydrothemal method. The synthesized products were characterized by X-ray powder diffraction and field emission scanning electron microscopy, respectively. A possible growth mechanism of the various hierarchical ZnO nanostructures is discussed in detail. Gas sensors based on the as-prepared ZnO nanostructures were fabricated by screen-printing on a flat ceramic substrate. Furthermore, their gas sensing characteristics towards methane were systematically investigated. Methane is an important characteristic hydrocarbon contaminant found dissolved in power transformer oil as a result of faults. We find that the hierarchical flower-like ZnO nanorods and net-like ZnO nanofibers samples show higher gas response and lower operating temperature with rapid response-recovery time compared to those of sensors based on ZnO nanobulks. These results present a feasible way of exploring high performance sensing materials for on-site detection of characteristic fault gases dissolved in transformer oil. PMID:23666136

Chlorofluorocarbons, sulfur hexafluoride, and dissolved permanent gases in ground water from selected sites in and near the Idaho National Engineering and Environmental Laboratory, Idaho, 1994-97

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel; Bartholomay, Roy C.; Wayland, Julian E.

1998-01-01

From July 1994 through May 1997, the U.S. Geological Survey in cooperation with the Department of Energy, sampled 86 wells completed in the Snake River Plain aquifer at and near the Idaho N ationa1 Engineering and Environmental Laboratory (INEEL). The wells were sampled for a variety of constituents including one- and two-carbon halocarbons. Concentrations of dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11) and trichlorotrifluororoethane (CFC-113) were determined. The samples for halocarbon analysis were collected in 62-milliliter flame sealed borosilicate glass ampoules in the field. The data will be used to evaluate the ages of ground waters at INEEL. The ages of the ground water will be used to determine recharge rates, residence time, and travel time of water in the Snake River Plain aquifer in and near INEEL. The chromatograms of 139 ground waters are presented showing a large number of halomethanes, haloethanes, and haloethenes present in the ground waters underlying the INEEL. The chromatograms can be used to qualitatively evaluate a large number of contaminants at parts per trillion to parts per billion concentrations. The data can be used to study temporal and spatial distribution of contaminants in the Snake River Plain aquifer. Representative compressed chromatograms for all ground waters sampled in this study are available on two 3.5-inch high density computer disks. The data and the program required to decompress the data can be obtained from the U.S. Geological Survey office at Idaho Falls, Idaho. Sulfur hexafluoride (SF6) concentrations were measured in selected wells to determine the feasibility of using this environmental tracer as an age dating tool of ground water. Concentrations of dissolved nitrogen, argon, carbon dioxide, oxygen, and methane were measured in 79 ground waters. Concentrations of dissolved permanent gases are tabulated and will be used to evaluate the temperature of recharge of ground water in and near the INEEL.

Characterizing Dissolved Gases in Cryogenic Liquid Fuels

NASA Astrophysics Data System (ADS)

Richardson, Ian A.

Pressure-Density-Temperature-Composition (PrhoT-x) measurements of cryogenic fuel mixtures are a historical challenge due to the difficulties of maintaining cryogenic temperatures and precision isolation of a mixture sample. For decades NASA has used helium to pressurize liquid hydrogen propellant tanks to maintain tank pressure and reduce boil off. This process causes helium gas to dissolve into liquid hydrogen creating a cryogenic mixture with thermodynamic properties that vary from pure liquid hydrogen. This can lead to inefficiencies in fuel storage and instabilities in fluid flow. As NASA plans for longer missions to Mars and beyond, small inefficiencies such as dissolved helium in liquid propellant become significant. Traditional NASA models are unable to account for dissolved helium due to a lack of fundamental property measurements necessary for the development of a mixture Equation Of State (EOS). The first PrhoT-x measurements of helium-hydrogen mixtures using a retrofitted single-sinker densimeter, magnetic suspension microbalance, and calibrated gas chromatograph are presented in this research. These measurements were used to develop the first multi-phase EOS for helium-hydrogen mixtures which was implemented into NASA's Generalized Fluid System Simulation Program (GFSSP) to determine the significance of mixture non-idealities. It was revealed that having dissolved helium in the propellant does not have a significant effect on the tank pressurization rate but does affect the rate at which the propellant temperature rises. PrhoT-x measurements are conducted on methane-ethane mixtures with dissolved nitrogen gas to simulate the conditions of the hydrocarbon seas of Saturn's moon Titan. Titan is the only known celestial body in the solar system besides Earth with stable liquid seas accessible on the surface. The PrhoT-x measurements are used to develop solubility models to aid in the design of the Titan Submarine. NASA is currently designing the submarine to explore the depths of Titan's methane-ethane seas to study the evolution of hydrocarbons in the universe and provide a pathfinder for future submersible designs. In addition, effervescence and freezing liquid line measurements on various liquid methane-ethane compositions with dissolved gaseous nitrogen are presented from 1.5 bar to 4.5 bar and temperatures from 92 K to 96 K to improve simulations of the conditions of the seas. These measurements will be used to validate sea property and bubble incipience models for the Titan Submarine design.

Distribution and Emission of Methane in Nakdong Estuary

NASA Astrophysics Data System (ADS)

Ryu, J.; An, S.

2014-12-01

Despite a small area, coastal areas contribute most to the oceanic methane flux. A wide range of methane fluxes have been reported in the coastal areas, but limited data were presented for Korean coastal areas. The air and surface water was sampled in Nakdong Estuary where the barrage had been constructed, and methane concentrations were measured using Gas Chromatography. To see the influence of the barrage, surface water was sampled outside and inside the barrage respectively. In the expectation that methane distribution would be different depending on the tides, surface water outside the barrage was collected at high and low tide respectively. Headspace technique and Membrane Inlet Mass Spectrometry were also used. The average atmospheric concentration (1.82ppm) was lower than the global average concentration expected from the IPCC scenario. The concentrations of water inside the barrage (average 173nM) were similar to those measured in other rivers but in the lower side. The average concentrations outside the barrage (52nM at high tide, 85nM at low tide) were lower than those measured in other coastal areas, but of the same order of magnitude as the European tidal estuaries. Methane concentrations in Nakdong estuary were higher than the methane concentration equilibrated with the atmosphere. The spatial variability of methane concentration in Nakdong estuary seems to be the result of the fresh (high methane) and sea (low methane) water mixing. Meanwhile large tidal flat area in Nakdong estuary should play a major role in methane dynamics and methane flux measurements during sediment incubation were conducted to evaluate the immersion/emersion cycle and photosynthesis by MPB (micro phyto benthos) effect.

Changes in Ground-Water Quality near Two Granular-Iron Permeable Reactive Barriers in a Sand and Gravel Aquifer, Cape Cod, Massachusetts, 1997-2000

USGS Publications Warehouse

Savoie, Jennifer G.; Kent, Douglas B.; Smith, Richard L.; LeBlanc, Denis R.; Hubble, David W.

2004-01-01

Two experimental permeable reactive barriers (PRBs) of granular zero-valent iron were emplaced in the path of a tetrachloroethene plume (the Chemical Spill-10 plume) at the Massachusetts Military Reservation, Cape Cod, Massachusetts, in June 1998. The goal of the field experiment was to achieve emplacement of a granular-iron PRB deeper than attempted before. The PRBs were expected to create a reducing environment and degrade the tetrachloroethene by reductive dechlorination. The goal of the work presented in this report was to observe temporary and sustained changes to the ground-water chemistry downgradient from the PRBs. A hydraulic-fracturing method involving injection of the granular iron with a guar-biopolymer and enzyme slurry was used to install the parallel 30- to 33-foot-wide wall-shaped barriers at a depth of 82 to 113 feet below land surface. An acetic acid and enzyme mixture was subsequently injected in wells near the barriers to degrade the guar biopolymer. Prior to the emplacement, tetrachloroethene concentrations in the Chemical Spill-10 plume at the study area were as high as 250 micrograms per liter. Other water properties in the plume generally were similar to the properties of uncontaminated ground water in the area, which typically has dissolved oxygen concentrations of 250 to 375 micromoles per liter, pH of 5.5 to 6.0, and specific conductance of 60 to 90 microsiemens per centimeter. Water-quality samples were collected periodically from monitoring wells near the PRBs to determine how the emplacement of the granular-iron walls altered the ground-water quality. In addition, an automated well-sampling device measured temperature, specific conductance, pH, and dissolved oxygen every 1?4 days for 16 months in a well downgradient from the two parallel PRBs. Temporary increases (lasting about 5 to 6 months) in specific conductance were observed downgradient from the PRBs as a result of the sodium chloride, potassium carbonate, and other salts included in the slurry and the acetic acid and enzyme mixture that was subsequently injected to degrade the guar biopolymer. Temporary increases in the concentrations of major cations (sodium, potassium, magnesium, and calcium) were observed downgradient from the PRBs, as were temporary but substantial increases in the dissolved and total organic carbon concentrations. Methane was detected, sulfate concentrations decreased temporarily, and concentrations of dissolved inorganic carbon increased in samples from wells downgradient from the PRBs. A sustained (longer than 12 months) reducing environment, in which dissolved oxygen concentrations decreased to zero, the pH increased to about 6.8, and dissolved iron concentrations increased substantially, developed as a result of the oxidation (corrosion) of the granular iron; this zone persisted at least 65 feet downgradient from the PRBs. The pH and dissolved iron concentrations increased with distance from the granular-iron walls. Concentrations of arsenic, cobalt, manganese, and phosphorus increased, and nitrate concentrations were reduced to below the detection limit downgradient from the walls. A sustained decrease of tetrachloroethene concentrations was not observed; however, reductive dechlorination products were observed at wells downgradient from the PRBs during several rounds of sampling. The emplacement of zero-valent iron in the aquifer to remove tetrachloroethene from the ground water caused changes in the water chemistry that persisted farther downgradient from the PRBs than has been observed at other sites because of the low chemical reactivity of the quartz-dominated aquifer sediments and the low ambient dissolved chemical concentrations in the ground water. The small transverse dispersion in the aquifer and the probable long-term persistence of the iron indicate that the chemically altered zone probably will extend a substantial distance downgradient from the PRBs for a substantial period of time (years); fur

Importance of the autumn overturn and anoxic conditions in the hypolimnion for the annual methane emissions from a temperate lake.

PubMed

Encinas Fernández, Jorge; Peeters, Frank; Hofmann, Hilmar

2014-07-01

Changes in the budget of dissolved methane measured in a small temperate lake over 1 year indicate that anoxic conditions in the hypolimnion and the autumn overturn period represent key factors for the overall annual methane emissions from lakes. During periods of stable stratification, large amounts of methane accumulate in anoxic deep waters. Approximately 46% of the stored methane was emitted during the autumn overturn, contributing ∼80% of the annual diffusive methane emissions to the atmosphere. After the overturn period, the entire water column was oxic, and only 1% of the original quantity of methane remained in the water column. Current estimates of global methane emissions assume that all of the stored methane is released, whereas several studies of individual lakes have suggested that a major fraction of the stored methane is oxidized during overturns. Our results provide evidence that not all of the stored methane is released to the atmosphere during the overturn period. However, the fraction of stored methane emitted to the atmosphere during overturn may be substantially larger and the fraction of stored methane oxidized may be smaller than in the previous studies suggesting high oxidation losses of methane. The development or change in the vertical extent and duration of the anoxic hypolimnion, which can represent the main source of annual methane emissions from small lakes, may be an important aspect to consider for impact assessments of climate warming on the methane emissions from lakes.

Consumption of methane by soils.

PubMed

Dueñas, C; Fernández, M C; Carretero, J; Pérez, M; Liger, E

1994-05-01

Measurements of the methane flux and methane concentration profiles in soil air are presented. The flux of methane from the soil is calculated by two methods: a) Direct by placing a static open chamber at the soil surface. b) Indirect, using the (222)Rn concentrations profile and the (222)Rn flux in the soil surface in parallel with the methane concentration ((222)Rn calibrated fluxes). The methane flux has been determined in two kinds of soils (sandy and loamy) in the surroundings of Málaga (SPAIN). The directly measured methane fluxes at all investigated sites is higher than methane fluxes derived from "Rn calibrated fluxes". Atmospheric methane is consumed by soils, mean direct flux to the atmosphere were - 0.33 g m(-2)yr-1. The direct methane flux is the same within the measuring error in sandy and loamy soils. The influence of the soil parameters on the methane flux indicates that microbial decomposition of methane is primarily controlled by the transport of methane.

Hydrogeologic Framework of the Yakima River Basin Aquifer System, Washington

USGS Publications Warehouse

Vaccaro, J.J.; Jones, M.A.; Ely, D.M.; Keys, M.E.; Olsen, T.D.; Welch, W.B.; Cox, S.E.

2009-01-01

The Yakima River basin aquifer system underlies about 6,200 square miles in south-central Washington. The aquifer system consists of basin-fill deposits occurring in six structural-sedimentary basins, the Columbia River Basalt Group (CRBG), and generally older bedrock. The basin-fill deposits were divided into 19 hydrogeologic units, the CRBG was divided into three units separated by two interbed units, and the bedrock was divided into four units (the Paleozoic, the Mesozoic, the Tertiary, and the Quaternary bedrock units). The thickness of the basin-fill units and the depth to the top of each unit and interbed of the CRBG were mapped. Only the surficial extent of the bedrock units was mapped due to insufficient data. Average mapped thickness of the different units ranged from 10 to 600 feet. Lateral hydraulic conductivity (Kh) of the units varies widely indicating the heterogeneity of the aquifer system. Average or effective Kh values of the water-producing zones of the basin-fill units are on the order of 1 to 800 ft/d and are about 1 to 10 ft/d for the CRBG units as a whole. Effective or average Kh values for the different rock types of the Paleozoic, Mesozoic, and Tertiary units appear to be about 0.0001 to 3 ft/d. The more permeable Quaternary bedrock unit may have Kh values that range from 1 to 7,000 ft/d. Vertical hydraulic conductivity (Kv) of the units is largely unknown. Kv values have been estimated to range from about 0.009 to 2 ft/d for the basin-fill units and Kv values for the clay-to-shale parts of the units may be as small as 10-10 to 10-7 ft/d. Reported Kv values for the CRBG units ranged from 4x10-7 to 4 ft/d. Variations in the concentrations of geochemical solutes and the concentrations and ratios of the isotopes of hydrogen, oxygen, and carbon in groundwater provided information on the hydrogeologic framework and groundwater movement. Stable isotope ratios of water (deuterium and oxygen-18) indicated dispersed sources of groundwater recharge to the CRBG and basin-fill units and that the source of surface and groundwater is derived from atmospheric precipitation. The concentrations of dissolved methane were larger than could be attributable to atmospheric sources in more than 80 percent of wells with measured methane concentrations. The concentrations of the stable isotope of carbon-13 of methane were indicative of a thermogenic source of methane. Most of the occurrences of methane were at locations several miles distant from mapped structural fault features, suggesting the upward vertical movement of thermogenic methane from the underlying bedrock may be more widespread than previously assumed or there may be a more general occurrence of unmapped (buried) fault structures. Carbon and tritium isotope data and the concentrations of dissolved constituents indicate a complex groundwater flow system with multiple contributing zones to groundwater wells and relative groundwater residence time on the order of a few tens to many thousands of years. Potential mean annual recharge for water years 1950-2003 was estimated to be about 15.6 in. or 7,149 ft3/s (5.2 million acre-ft) and includes affects of human activities such as irrigation of croplands. If there had been no human activities (predevelopment conditions) during that time period, estimated recharge would have been about 11.9 in. or 5,450 ft3/s (3.9 million acre-ft). Estimated mean annual recharge ranges from virtually zero in the dry parts of the lower basin to more than 100 in. in the humid uplands, where annual precipitation is more than 120 in. Groundwater in the different hydrogeologic units occurs under perched, unconfined, semiconfined, and confined conditions. Groundwater moves from topographic highs in the uplands to topographic low areas along the streams. The flow system in the basin-fill units is compartmentalized due to topography and geologic structure. The flow system also is compartmentalized for the CRBG units but not to as large

Gas hydrate dissociation off Svalbard induced by isostatic rebound rather than global warming.

PubMed

Wallmann, Klaus; Riedel, M; Hong, W L; Patton, H; Hubbard, A; Pape, T; Hsu, C W; Schmidt, C; Johnson, J E; Torres, M E; Andreassen, K; Berndt, C; Bohrmann, G

2018-01-08

Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

Methane Fluxes and Consumption in an Oil Sands Tailings End Pit Lake

NASA Astrophysics Data System (ADS)

Slater, G. F.; Goad, C.; Arriaga, D.; Risacher, F.; Morris, P.; Lindsay, M. B.; Mumford, K. G.; Warren, L. A.

2017-12-01

End pit lakes are engineered freshwater lakes designed to reclaim land impacted by surface mining activities via establishment of a functioning ecosystem where biogeochemical cycling mitigates release of hazardous components either by stabilization or biodegradation. End pit lakes provide unique opportunities to gain insight into microbial nutrient cycling under extreme levels of impact that can be applicable to a range of levels of anthropogenic impacts and issues. This study focuses on microbial CH4 cycling in the underlying fluid fine tailings (FFT) and surface waters of Base Mine Lake (BML), the first full demonstration of end pit lake reclamation in the Athabasca Oil Sands Region (AOSR) of northern Alberta, Canada. Over two field seasons (2015 and 2016) BML was thermally stratified, turning over in spring and fall. Oxygen concentrations in the epilimnion (70 to 80 % saturation) decreased steeply through the metalimnion to 3% saturation in the hypolimnion. Conversely, CH4 concentrations were highest in the hypolimnion of BML (25 to 140 µM) with the highest values being observed at the FFT/Water interface. Concentrations decreased to 1-2 µM at the metalimnion and further decreased to < 0.5 µM in the epilimnion. CH4 δ13C in FFT porewater indicated production via fermentative pathways. FFT settlement and dewatering of 0.73 to 1.0 m/yr results in advection of an estimated 1x107 to 2x107 moles/yr CH4 into the surface water, circa an order of magnitude greater than the 3x106 moles/year estimated for molecular diffusion. Calculated fluxes of dissolved CH4 from the FFT into the hypolimnion were 4 orders of magnitude higher than those from the hypolimnion to the metalimnion, indicating a significant sink for CH4 within the hypolimnion limiting upward dissolved CH4 transport. Dissolution of CH4 from bubbles released from the FFT may be contributing to the observed epilimnion concentrations. CH4 δ13C in the hypolimnion showed only minimal enrichment with decreasing concentrations. However, phospholipid fatty acids of bacteria in the hypolimnion were significantly δ13C depleted indicating CH4 consumption was a primary carbon source for the microbial community in the hypolimnion. Ongoing analyses of samples from 2017 will further elucidate the development of methane biogeochemical cycling in BML.

Feasibility of atmospheric methane removal using methanotrophic biotrickling filters.

PubMed

Yoon, Sukhwan; Carey, Jeffrey N; Semrau, Jeremy D

2009-07-01

Methane is a potent greenhouse gas with a global warming potential ~23 times that of carbon dioxide. Here, we describe the modeling of a biotrickling filtration system composed of methane-consuming bacteria, i.e., methanotrophs, to assess the utility of these systems in removing methane from the atmosphere. Model results indicate that assuming the global average atmospheric concentration of methane, 1.7 ppmv, methane removal is ineffective using these methanotrophic biofilters as the methane concentration is too low to enable cell survival. If the concentration is increased to 500-6,000 ppmv, however, similar to that found above landfills and in concentrated animal feeding operations (factory farms), 4.98-35.7 tons of methane can be removed per biofilter per year assuming biotrickling filters of typical size (3.66 m in diameter and 11.5 m in height). Using reported ranges of capital, operational, and maintenance costs, the cost of the equivalent ton of CO(2) removal using these systems is $90-$910 ($2,070-$20,900 per ton of methane), depending on the influent concentration of methane and if heating is required. The use of methanotrophic biofilters for controlling methane emissions is technically feasible and, provided that either the costs of biofilter construction and operation are reduced or the value of CO(2) credits is increased, can also be economically attractive.

Quantification of methane fluxes from industrial sites using a combination of a tracer release method and a Gaussian model

NASA Astrophysics Data System (ADS)

Ars, S.; Broquet, G.; Yver-Kwok, C.; Wu, L.; Bousquet, P.; Roustan, Y.

2015-12-01

Greenhouse gas (GHG) concentrations keep on increasing in the atmosphere since industrial revolution. Methane (CH4) is the second most important anthropogenic GHG after carbon dioxide (CO2). Its sources and sinks are nowadays well identified however their relative contributions remain uncertain. The industries and the waste treatment emit an important part of the anthropogenic methane that is difficult to quantify because the sources are fugitive and discontinuous. A better estimation of methane emissions could help industries to adapt their mitigation's politic and encourage them to install methane recovery systems in order to reduce their emissions while saving money. Different methods exist to quantify methane emissions. Among them is the tracer release method consisting in releasing a tracer gas near the methane source at a well-known rate and measuring both their concentrations in the emission plume. The methane rate is calculated using the ratio of methane and tracer concentrations and the emission rate of the tracer. A good estimation of the methane emissions requires a good differentiation between the methane actually emitted by the site and the methane from the background concentration level, but also a good knowledge of the sources distribution over the site. For this purpose, a Gaussian plume model is used in addition to the tracer release method to assess the emission rates calculated. In a first step, the data obtained for the tracer during a field campaign are used to tune the model. Different model's parameterizations have been tested to find the best representation of the atmospheric dispersion conditions. Once these parameters are set, methane emissions are estimated thanks to the methane concentrations measured and a Bayesian inversion. This enables to adjust the position and the emission rate of the different methane sources of the site and remove the methane background concentration.

Methane source identification in Boston, Massachusetts using isotopic and ethane measurements

NASA Astrophysics Data System (ADS)

Down, A.; Jackson, R. B.; Plata, D.; McKain, K.; Wofsy, S. C.; Rella, C.; Crosson, E.; Phillips, N. G.

2012-12-01

Methane has substantial greenhouse warming potential and is the principle component of natural gas. Fugitive natural gas emissions could be a significant source of methane to the atmosphere. However, the cumulative magnitude of natural gas leaks is not yet well constrained. We used a combination of point source measurements and ambient monitoring to characterize the methane sources in the Boston urban area. We developed distinct fingerprints for natural gas and multiple biogenic methane sources based on hydrocarbon concentration and isotopic composition. We combine these data with periodic measurements of atmospheric methane and ethane concentration to estimate the fractional contribution of natural gas and biogenic methane sources to the cumulative urban methane flux in Boston. These results are used to inform an inverse model of urban methane concentration and emissions.

Quantification of Concentration of Microalgae Anabaena Cylindrica, Coal-bed Methane Water Isolates Nannochloropsis Gaditana and PW-95 in Aquatic Solutions through Hyperspectral Reflectance Measurement and Analytical Model Establishment

NASA Astrophysics Data System (ADS)

Zhou, Z.; Zhou, X.; Apple, M. E.; Spangler, L.

2017-12-01

Three species of microalgae, Anabaena cylindrica (UTEX # 1611), coal-bed methane water isolates Nannochloropsis gaditana and PW-95 were cultured for the measurements of their hyperspectral profiles in different concentrations. The hyperspectral data were measured by an Analytical Spectral Devices (ASD) spectroradiomter with the spectral resolution of 1 nanometer over the wavelength ranges from 350nm to 1050 nm for samples of microalgae of different concentration. Concentration of microalgae was measured using a Hemocytometer under microscope. The objective of this study is to establish the relation between spectral reflectance and micro-algal concentration so that microalgae concentration can be measured remotely by space- or airborne hyperspectral or multispectral sensors. Two types of analytical models, linear reflectance-concentration model and Lamber-Beer reflectance-concentration model, were established for each species. For linear modeling, the wavelength with the maximum correlation coefficient between the reflectance and concentrations of algae was located and then selected for each species of algae. The results of the linear models for each species are shown in Fig.1(a), in which Refl_1, Refl_2, and Refl_3 represent the reflectance of Anabaena, N. Gaditana, and PW-95 respectively. C1, C2, and C3 represent the Concentrations of Anabaena, N. Gaditana, and PW-95 respectively. The Lamber-Beer models were based on the Lambert-Beer Law, which states that the intensity of light propagating in a substance dissolved in a fully transmitting solvent is directly proportional to the concentration of the substance and the path length of the light through the solution. Thus, for the Lamber-Beer modeling, a wavelength with large absorption in red band was selected for each species. The results of Lambert-Beer models for each species are shown in Fig.1(b). Based on the Lamber-Beer models, the absorption coefficient for the three different species will be quantified.

Polarized electrode enhances biological direct interspecies electron transfer for methane production in upflow anaerobic bioelectrochemical reactor.

PubMed

Feng, Qing; Song, Young-Chae; Yoo, Kyuseon; Kuppanan, Nanthakumar; Subudhi, Sanjukta; Lal, Banwari

2018-08-01

The influence of polarized electrodes on the methane production, which depends on the sludge concentration, was investigated in upflow anaerobic bioelectrochemical (UABE) reactor. When the polarized electrode was placed in the bottom zone with a high sludge concentration, the methane production was 5.34 L/L.d, which was 53% higher than upflow anaerobic sludge blanket (UASB) reactor. However, the methane production was reduced to 4.34 L/L.d by placing the electrode in the upper zone of the UABE reactor with lower sludge concentration. In the UABE reactor, the methane production was mainly improved by the enhanced biological direct interspecies electron transfer (bDIET) pathway, and the methane production via the electrode was a minor fraction of less than 4% of total methane production. The polarized electrodes that placed in the bottom zone with a high sludge concentration enhance the bDIET for methane production in the UABE reactor and greatly improve the methane production. Copyright © 2018. Published by Elsevier Ltd.

Seasonal and interannual variability in wetland methane emissions simulated by CLM4Me' and CAM-chem and comparisons to observations of concentrations

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

Meng, L.; Paudel, R.; Hess, P. G. M.

Understanding the temporal and spatial variation of wetland methane emissions is essential to the estimation of the global methane budget. Our goal for this study is three-fold: (i) to evaluate the wetland methane fluxes simulated in two versions of the Community Land Model, the Carbon-Nitrogen (CN; i.e., CLM4.0) and the Biogeochemistry (BGC; i.e., CLM4.5) versions using the methane emission model CLM4Me' so as to determine the sensitivity of the emissions to the underlying carbon model; (ii) to compare the simulated atmospheric methane concentrations to observations, including latitudinal gradients and interannual variability so as to determine the extent to which themore » atmospheric observations constrain the emissions; (iii) to understand the drivers of seasonal and interannual variability in atmospheric methane concentrations. Simulations of the transport and removal of methane use the Community Atmosphere Model with chemistry (CAM-chem) model in conjunction with CLM4Me' methane emissions from both CN and BGC simulations and other methane emission sources from literature. In each case we compare model-simulated atmospheric methane concentration with observations. In addition, we simulate the atmospheric concentrations based on the TransCom wetland and rice paddy emissions derived from a different terrestrial ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT). Our analysis indicates CN wetland methane emissions are higher in the tropics and lower at high latitudes than emissions from BGC. In CN, methane emissions decrease from 1993 to 2004 while this trend does not appear in the BGC version. In the CN version, methane emission variations follow satellite-derived inundation wetlands closely. However, they are dissimilar in BGC due to its different carbon cycle. CAM-chem simulations with CLM4Me' methane emissions suggest that both prescribed anthropogenic and predicted wetlands methane emissions contribute substantially to seasonal and interannual variability in atmospheric methane concentration. Simulated atmospheric CH 4 concentrations in CAM-chem are highly correlated with observations at most of the 14 measurement stations evaluated with an average correlation between 0.71 and 0.80 depending on the simulation (for the period of 1993–2004 for most stations based on data availability). Our results suggest that different spatial patterns of wetland emissions can have significant impacts on Northern and Southern hemisphere (N–S) atmospheric CH 4 concentration gradients and growth rates. In conclusion, this study suggests that both anthropogenic and wetland emissions have significant contributions to seasonal and interannual variations in atmospheric CH 4 concentrations. However, our analysis also indicates the existence of large uncertainties in terms of spatial patterns and magnitude of global wetland methane budgets, and that substantial uncertainty comes from the carbon model underlying the methane flux modules.« less

Seasonal and interannual variability in wetland methane emissions simulated by CLM4Me' and CAM-chem and comparisons to observations of concentrations

DOE PAGES

Meng, L.; Paudel, R.; Hess, P. G. M.; ...

2015-07-03

Understanding the temporal and spatial variation of wetland methane emissions is essential to the estimation of the global methane budget. Our goal for this study is three-fold: (i) to evaluate the wetland methane fluxes simulated in two versions of the Community Land Model, the Carbon-Nitrogen (CN; i.e., CLM4.0) and the Biogeochemistry (BGC; i.e., CLM4.5) versions using the methane emission model CLM4Me' so as to determine the sensitivity of the emissions to the underlying carbon model; (ii) to compare the simulated atmospheric methane concentrations to observations, including latitudinal gradients and interannual variability so as to determine the extent to which themore » atmospheric observations constrain the emissions; (iii) to understand the drivers of seasonal and interannual variability in atmospheric methane concentrations. Simulations of the transport and removal of methane use the Community Atmosphere Model with chemistry (CAM-chem) model in conjunction with CLM4Me' methane emissions from both CN and BGC simulations and other methane emission sources from literature. In each case we compare model-simulated atmospheric methane concentration with observations. In addition, we simulate the atmospheric concentrations based on the TransCom wetland and rice paddy emissions derived from a different terrestrial ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT). Our analysis indicates CN wetland methane emissions are higher in the tropics and lower at high latitudes than emissions from BGC. In CN, methane emissions decrease from 1993 to 2004 while this trend does not appear in the BGC version. In the CN version, methane emission variations follow satellite-derived inundation wetlands closely. However, they are dissimilar in BGC due to its different carbon cycle. CAM-chem simulations with CLM4Me' methane emissions suggest that both prescribed anthropogenic and predicted wetlands methane emissions contribute substantially to seasonal and interannual variability in atmospheric methane concentration. Simulated atmospheric CH 4 concentrations in CAM-chem are highly correlated with observations at most of the 14 measurement stations evaluated with an average correlation between 0.71 and 0.80 depending on the simulation (for the period of 1993–2004 for most stations based on data availability). Our results suggest that different spatial patterns of wetland emissions can have significant impacts on Northern and Southern hemisphere (N–S) atmospheric CH 4 concentration gradients and growth rates. In conclusion, this study suggests that both anthropogenic and wetland emissions have significant contributions to seasonal and interannual variations in atmospheric CH 4 concentrations. However, our analysis also indicates the existence of large uncertainties in terms of spatial patterns and magnitude of global wetland methane budgets, and that substantial uncertainty comes from the carbon model underlying the methane flux modules.« less

Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

NASA Astrophysics Data System (ADS)

Stern, L. A.; Peltzer, E. T.; Durham, W. B.; Kirby, S. H.; Brewer, P. G.; Circone, S.; Rehder, G.

2002-12-01

We compare dissolution rates of pure, porous, compacted, and oil-contaminated sI methane hydrate and sII methane-ethane hydrate to rates measured previously on pure, compacted, sI methane hydrate and sI carbon dioxide hydrate (Rehder et al., Fall AGU 2001). Laboratory-synthesized test specimens were used in both studies, allowing characterization of test materials prior to their transport and exposure to seawater at 1030-meter depth on the Monterey Canyon seafloor, off coastal Moss Landing, CA. Although pressure and temperature (P-T) conditions at this site are within the nominal P-T equilibrium fields of all gas hydrates tested here, the seawater is undersaturated with respect to the hydrate-forming gas species. Hence, samples dissolve with time, at a rate dependent on water current flow. Four samples were deployed in this second experiment: (1) pure, 30% porous methane hydrate; (2) pure, compacted methane hydrate; (3) pure methane hydrate compacted and then contaminated with a low-T mineral oil; and (4) pure, compacted sII methane-ethane hydrate with methane:ethane molar ratio 0.72. Samples were transferred by pressure vessel at 0 ° C and 15 MPa to the seafloor observatory via the MBARI remotely operated vehicle Ventana. Samples were then exposed to the deep ocean environment and monitored by HDTV camera for several hours at the beginning and end of a 25-hour period. Local current speed and direction were also measured throughout the experiment. Those samples that did not undergo complete dissolution after 25 h were successfully recovered to the laboratory for subsequent analysis by scanning electron microscopy (SEM). Previously, video analysis showed dissolution rates corresponding to 4.0 +/- 0.5 mmole CO2/m2 s for compacted CO2 hydrate samples, and 0.37 +/- 0.03 mmole CH4/m2s for compacted methane hydrate samples (Rehder et al, AGU 2001). The ratio of dissolution rates fits a simple diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

Pressurant requirements for discharge of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank under both static and slosh conditions

NASA Technical Reports Server (NTRS)

Dewitt, R. L.; Mcintire, T. O.

1974-01-01

Pressurized expulsion tests were conducted to determine the effect of various physical parameters on the pressurant gas (methane, helium, hydrogen, and nitrogen) requirements during the expulsion of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank and to compare results with those predicted by an analytical program. Also studied were the effects on methane, helium, and hydrogen pressurant requirements of various slosh excitation frequencies and amplitudes, both with and without slosh suppressing baffles in the tank. The experimental results when using gaseous methane, helium, and hydrogen show that the predictions of the analytical program agreed well with the actual pressurant requirements for static tank expulsions. The analytical program could not be used for gaseous nitrogen expulsions because of the large quantities of nitrogen which can dissolve in liquid methane. Under slosh conditions, a pronounced increase in gaseous methane requirements was observed relative to results obtained for the static tank expulsions. Slight decreases in the helium and hydrogen requirements were noted under similar test conditions.

New insights into the transport processes controlling the sulfate-methane-transition-zone near methane vents.

PubMed

Sultan, Nabil; Garziglia, Sébastien; Ruffine, Livio

2016-05-27

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria's coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.

Low methane concentrations in sediment along the continental slope north of Siberia: Inference from pore water geochemistry

NASA Astrophysics Data System (ADS)

Miller, C.; Dickens, G. R.; Jakobsson, M.; Koshurnikov, A.

2016-12-01

The Eastern Siberian Margin (ESM), a vast region of the Arctic, potentially holds large amounts of methane in sediments as gas hydrate and free gas. Although this CH4 has become a topic of discussion, primarily because of rapid regional climate change, the ESM remains sparingly explored. Here we present pore water chemistry results from 32 cores taken during Leg 2 of the 2014 SWERUS-C3 expedition. The cores come from depth transects across the continental slope of the ESM between Wrangel Island and the New Siberian Islands. Upward CH4 flux towards the seafloor, as inferred from profiles of dissolved sulfate (SO42-), alkalinity, and the δ13C-dissolved inorganic Carbon (DIC), is negligible at all stations east of where the Lomonosov Ridge abuts the ESM at about 143°E. In the upper eight meters of these cores, downward sulfate flux never exceeds 9.2 mol/m2-kyr, the upward alkalinity flux never exceeds 6.8 mol/m2-kyr, and δ13C-DIC only slowly decreases with depth (-3.6‰/m on average). Additionally, dissolved H2S was not detected in these cores, and nutrient and metal profiles reveal that metal oxide reduction by organic carbon dominates the geochemical environment. A single core on Lomonosov Ridge differs, as diffusive fluxes for SO42- and alkalinity were 13.9 and 11.3 mol/m2-kyr, respectively, the δ13C-DIC gradient was 5.6‰/m, and Mn2+ reduction terminated within 1.3 m of the seafloor. These are among the first pore water results generated from this vast climatically sensitive region, and they imply that significant quantities of CH4, including gas hydrates, do not exist in any of our investigated depth transects spread out along much of the ESM continental slope. This contradicts previous assumptions and hypothetical models and discussion, which generally have assumed the presence of substantial CH4.

Hydrate kinetics study in the presence of nonaqueous liquid by nuclear magnetic resonance spectroscopy and imaging.

PubMed

Susilo, Robin; Moudrakovski, Igor L; Ripmeester, John A; Englezos, Peter

2006-12-28

The dynamics of methane hydrate growth and decomposition were studied by nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI). Three well-known large molecule guest substances (LMGS) were used as structure H hydrate formers: 2,2-dimethylbutane (NH), methylcyclohexane (MCH), tert-butyl methyl ether (TBME). In addition, the impact of a non-hydrate former (n-heptane/nC7) was studied. The methane diffusion and hydrate growth were monitored by recording the 2H NMR spectra at 253 K and approximately 4.5 MPa for 20 h. The results revealed that methane diffuses faster in TBME and NH, slower in nC7, and slowest in MCH. The TBME system gives the fastest hydrate formation kinetics followed by NH, MCH, and nC7. The conversion of water into hydrate was also observed. The imaging study showed that TBME has a strong affinity toward ice, which is not the case for the NH and MCH systems. The degree of ice packing was also found to affect the LMGS distribution between ice particles. Highly packed ice increases the mass transfer resistance and hence limits the contact between LMGS and ice. It was also found that "temperature ramping" above the ice point improves the conversion significantly. Finally, hydrates were found to dissociate quickly within the first hour at atmospheric pressure and subsequently at a much slower rate. Methane dissolved in LMGS was also seen. The residual methane in hydrate phase and dissolved in LMGS phase explain the faster kinetics during hydrate re-formation.

Ferrimagnetic Iron Sulfide Formation and Methane Venting Across the Paleocene-Eocene Thermal Maximum in Shallow Marine Sediments, Ancient West Siberian Sea

NASA Astrophysics Data System (ADS)

Rudmin, Maxim; Roberts, Andrew P.; Horng, Chorng-Shern; Mazurov, Aleksey; Savinova, Olesya; Ruban, Aleksey; Kashapov, Roman; Veklich, Maxim

2018-01-01

Authigenesis of ferrimagnetic iron sulfide minerals (greigite and monoclinic pyrrhotite) occurred across the Paleocene-Eocene Thermal Maximum (PETM) within the Bakchar oolitic ironstone in southeastern Western Siberia. Co-occurrence of these minerals is associated with diagenetic environments that support anaerobic oxidation of methane, which has been validated by methane fluid inclusion analysis in the studied sediments. In modern settings, such ferrimagnetic iron sulfide formation is linked to upward methane diffusion in the presence of minor dissolved sulfide ions. The PETM was the most extreme Cenozoic global warming event and massive methane mobilization has been proposed as a major contributor to the globally observed warming and carbon isotope excursion associated with the PETM. The studied sediments provide rare direct evidence for methane mobilization during the PETM. Magnetic iron sulfide formation associated with methanogenesis in the studied sediments can be explained by enhanced local carbon burial across the PETM. While there is no strong evidence to link local methane venting with more widespread methane mobilization and global warming, the magnetic, petrographic, and geochemical approach used here is applicable to identifying authigenic minerals that provide telltale signatures of methane mobility that can be used to assess methane formation and mobilization through the PETM and other hyperthermal climatic events.

Exhaled methane concentration profiles during exercise on an ergometer

PubMed Central

Szabó, A; Ruzsanyi, V; Unterkofler, K; Mohácsi, Á; Tuboly, E; Boros, M; Szabó, G; Hinterhuber, H; Amann, A

2016-01-01

Exhaled methane concentration measurements are extensively used in medical investigation of certain gastrointestinal conditions. However, the dynamics of endogenous methane release is largely unknown. Breath methane profiles during ergometer tests were measured by means of a photoacoustic spectroscopy based sensor. Five methane-producing volunteers (with exhaled methane level being at least 1 ppm higher than room air) were measured. The experimental protocol consisted of 5 min rest—15 min pedalling (at a workload of 75 W)—5 min rest. In addition, hemodynamic and respiratory parameters were determined and compared to the estimated alveolar methane concentration. The alveolar breath methane level decreased considerably, by a factor of 3–4 within 1.5 min, while the estimated ventilation-perfusion ratio increased by a factor of 2–3. Mean pre-exercise and exercise methane concentrations were 11.4 ppm (SD:7.3) and 2.8 ppm (SD:1.9), respectively. The changes can be described by the high sensitivity of exhaled methane to ventilationperfusion ratio and are in line with the Farhi equation. PMID:25749807

Use of ionic liquids as coordination ligands for organometallic catalysts

DOEpatents

Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

2009-11-10

Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

Some seasonal characteristics in atmospheric methane concentration in the beginning of the XXI century

NASA Astrophysics Data System (ADS)

Vinogradova, Anna; Ginzburg, Alexander; Fedorova, Evgeniya

2010-05-01

Global average value of atmospheric methane concentrations have been increasing during the XX century, but this growth nearly stopped with the beginning of the 2000th. Such "stable" situation is the proper time for studying the seasonal cycle and extreme changes of air methane concentration. One of the most interesting periods for such investigations is autumn and winter 2006/07 [1] when a number of weather abnormalities (warm air temperature up to above 0°C, almost permanent cloudiness and absence of snow cover, and so on) in Moscow region created very specific conditions for air methane existence. Temporal variations in air methane concentration within the Moscow city have been studied using the data of observations at 12 stations of Moscow municipal environmental monitoring agency "Mosecomonitoring" in 2004-2008 [2]. It was found that near-surface air concentration of methane was much higher this time than few years before and after. The values of cold season methane concentrations in Moscow region have been compared with similar data measured in the North of Kola Peninsula (at WMO GAW station "Teriberka"), in the Sankt Petersburg region (the two stations of Roshydromet), in Finland and Hungary (the stations of NOAA GMD Carbon Cycle Sampling Network). Winter maxima (more or less) of methane concentrations were revealed almost each year at all these stations, but not everywhere they were simultaneous and as high as those had been found in Moscow. The reasons of winter 2006/07 high methane concentrations in Moscow and other regions of Northern Eurasia may be special weather conditions which could cause both decrease of air methane sinks and increase of methane emissions from natural and anthropogenic sources. Perhaps, the late growth of global atmospheric methane concentration after 2007 [3] was partly produced by those seasonal anomalies in the Northern Hemisphere. References: 1. E. Fedorova, A. Ginzburg, A. Vinogradova. Seasonal variations of atmospheric methane and hot winter 2006-2007 // Geophys. Res. Abstracts, 2007, Vol. 9, SRef-ID: 1607-7962/gra/EDU2007-A-06049. 2. A.A. Vinogradova, E.I. Fedorova, I.B. Belikov, et al. Temporal variations in carbon dioxide and methane concentrations under urban conditions // Izv., Atmospheric and Oceanic Physics, 2007, Vol. 43, No. 5, pp. 599-611. 3. Rigby M., Prinn R.G., Fraser P.J., et al. Renewed growth of atmospheric methane // Geophys. Res. Lett., 2008, Vol. 35. doi: 10,1029/2008GL036037

Modeling of breath methane concentration profiles during exercise on an ergometer*

PubMed Central

Szabó, Anna; Unterkofler, Karl; Mochalski, Pawel; Jandacka, Martin; Ruzsanyi, Vera; Szabó, Gábor; Mohácsi, Árpád; Teschl, Susanne; Teschl, Gerald; King, Julian

2016-01-01

We develop a simple three compartment model based on mass balance equations which quantitatively describes the dynamics of breath methane concentration profiles during exercise on an ergometer. With the help of this model it is possible to estimate the endogenous production rate of methane in the large intestine by measuring breath gas concentrations of methane. PMID:26828421

Temperature, productivity and sediment characteristics as drivers of seasonal and spatial variations of dissolved methane in the near-shore coastal areas (Belgian coastal zone, North Sea)

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Speeckaert, Gaëlle; Champenois, Willy; Scranton, Mary I.; Gypens, Nathalie

2017-04-01

The open ocean is a modest source of CH4 to the atmosphere compared to other natural and anthropogenic CH4 emissions. Coastal regions are more intense sources of CH4 to the atmosphere than open oceanic waters, in particular estuarine zones. The CH4 emission to the atmosphere from coastal areas is sustained by riverine inputs and methanogenesis in the sediments due to high organic matter (OM) deposition. Additionally, natural gas seeps are sources of CH4 to bottom waters leading to high dissolved CH4 concentrations in bottom waters (from tenths of nmol L-1 up to several µmol L-1). We report a data set of dissolved CH4 concentrations obtained at nine fixed stations in the Belgian coastal zone (Southern North Sea), during one yearly cycle, with a bi-monthly frequency in spring, and a monthly frequency during the rest of the year. This is a coastal area with multiple possible sources of CH4 such as from rivers and gassy sediments, and where intense phytoplankton blooms are dominated by the high dimethylsulfoniopropionate (DMSP) producing micro-algae Phaeocystis globosa, leading to DMSP and dimethylsulfide (DMS) concentrations. Furthermore, the BCZ is a site of important OM sedimentation and accumulation unlike the rest of the North Sea. Spatial variations of dissolved CH4 concentrations were very marked with a minimum yearly average of 9 nmol L-1 in one of the most off-shore stations and maximum yearly average of 139 nmol L-1 at one of the most near-shore stations. The spatial variations of dissolved CH4 concentrations were related to the organic matter (OM) content of sediments, although the highest concentrations seemed to also be related to inputs of CH4 from gassy sediments associated to submerged peat. In the near-shore stations with fine sand or muddy sediments with a high OM content, the seasonal cycle of dissolved CH4 concentration closely followed the seasonal cycle of water temperature, suggesting the control of methanogenesis by temperature in these OM replete sediments. In the off-shore stations with permeable sediments with a low OM content, the seasonal cycle of dissolved CH4 concentration showed a yearly peak following the chlorophyll-a spring peak. This suggests that in these OM poor sediments, methanogenesis depended on the delivery to the sediments of freshly produced OM. In both types of sediments, the seasonal cycle of dissolved CH4 concentrations was unrelated the seasonal cycles of DMS, and DMSP, despite the fact that these quantities were very high during the spring Phaeocystis globosa bloom. This suggests that in this shallow coastal environment CH4 production is overwhelmingly related to benthic processes and unrelated to DMS(P) transformations in the water column as recently suggested in several open ocean regions. The annual average CH4 emission was 41 mmol m-2 yr-1 in the most near-shore stations ( 4 km from the coast) and 10 mmol m-2 yr-1 in the most off-shore stations ( 23 km from the coast), 410-100 times higher than the average value in the open ocean (0.1 mmol m-2 yr-1). The strong control of CH4 concentrations by sediment OM content and by temperature suggests that marine coastal CH4 emissions, in particular shallow coastal areas, should respond in future to eutrophication and warming of climate. This is confirmed by the comparison of CH4 concentrations at five stations obtained in March in years 1990 and 2016, showing a decreasing trend consistent with alleviation of eutrophication in the area.

Benthic fluxes of dissolved organic carbon from gas hydrate sediments in the northern South China Sea

PubMed Central

Hung, Chia-Wei; Huang, Kuo-Hao; Shih, Yung-Yen; Lin, Yu-Shih; Chen, Hsin-Hung; Wang, Chau-Chang; Ho, Chuang-Yi; Hung, Chin-Chang; Burdige, David J.

2016-01-01

Hydrocarbon vents have recently been reported to contribute considerable amounts of dissolved organic carbon (DOC) to the oceans. Many such hydrocarbon vents widely exist in the northern South China Sea (NSCS). To investigate if these hydrocarbon vent sites release DOC, we used a real-time video multiple-corer to collect bottom seawater and surface sediments at vent sites. We analyzed concentrations of DOC in these samples and estimated DOC fluxes. Elevated DOC concentrations in the porewaters were found at some sites suggesting that DOC may come from these hydrocarbon vents. Benthic fluxes of DOC from these sediments were 28 to 1264 μmol m−2 d−1 (on average ~321 μmol m−2 d−1) which are several times higher than most DOC fluxes in coastal and continental margin sediments. The results demonstrate that the real-time video multiple-corer can precisely collect samples at vent sites. The estimated benthic DOC flux from the methane venting sites (8.6 × 106 mol y−1), is 24% of the DOC discharge from the Pearl River to the South China Sea, indicating that these sediments make an important contribution to the DOC in deep waters. PMID:27432631

An analytical solubility model for nitrogen-methane-ethane ternary mixtures

NASA Astrophysics Data System (ADS)

Hartwig, Jason; Meyerhofer, Peter; Lorenz, Ralph; Lemmon, Eric

2018-01-01

Saturn's moon Titan has surface liquids of liquid hydrocarbons and a thick, cold, nitrogen atmosphere, and is a target for future exploration. Critical to the design and operation of vehicles for this environment is knowledge of the amount of dissolved nitrogen gas within the cryogenic liquid methane and ethane seas. This paper rigorously reviews experimental data on the vapor-liquid equilibrium of nitrogen/methane/ethane mixtures, noting the possibility for split liquid phases, and presents simple analytical models for conveniently predicting solubility of nitrogen in pure liquid ethane, pure liquid methane, and a mixture of liquid ethane and methane. Model coefficients are fit to three temperature ranges near the critical point, intermediate range, and near the freezing point to permit accurate predictions across the full range of thermodynamic conditions. The models are validated against the consolidated database of 2356 experimental data points, with mean absolute error between data and model less than 8% for both binary nitrogen/methane and nitrogen/ethane systems, and less than 17% for the ternary nitrogen/methane/ethane system. The model can be used to predict the mole fractions of ethane, methane, and nitrogen as a function of location within the Titan seas.

Transport of dissolved gases through unsaturated porous media

NASA Astrophysics Data System (ADS)

Maryshev, B. S.

2017-06-01

The natural porous media (e.g. soil, sand, peat etc.) usually are partially saturated by groundwater. The saturation of soil depends on hydrostatic pressure which is linearly increased with depth. Often some gases (e.g. nitrogen, oxygen, carbon dioxide, methane etc.) are dissolved into the groundwater. The solubility of gases is very small because of that two assumptions is applied: I. The concentration of gas is equal to solubility, II. Solubility depends only on pressure (for isothermal systems). In this way some part of dissolved gas transfers from the solution to the bubble phase. The gas bubbles are immovably trapped in a porous matrix by surface-tension forces and the dominant mechanism of transport of gas mass becomes the diffusion of gas molecules through the liquid. If the value of water content is small then the transport of gas becomes slow and gas accumulates into bubble phase. The presence of bubble phase additionally decreases the water content and slows down the transport. As result the significant mass of gas should be accumulated into the massif of porous media. We derive the transport equations and find the solution which is demonstrated the accumulation of gases. The influence of saturation, porosity and filtration velocity to accumulation process is investigated and discussed.

Nitrogen-assisted Three-phase Equilibrium in Hydrate Systems Composed of Water, Methane, Carbon Dioxide, and Nitrogen

NASA Astrophysics Data System (ADS)

Darnell, K.; Flemings, P. B.; DiCarlo, D. A.

2016-12-01

In June 2016, seawater samples at sediment-seawater interface and sediment samples were collected by the he Jiaolong, China's manned submersible, at four sampling sites located in the Yap Trench. Seawater samples from different depths of the trench were also collected by CTD. Chemical parameters, including pH, alkanility, concentrations of dissolved inorganic carbon, dissolved and total organic carbon, methane, dimethylsulfoniopropionate, nutrients, carbohydrates, and amino acids were analyzed in the seawater samples. Concentrations of total organic carbon, six constant elements and nine trace elements were determined in the sediment samples. All the vertical profiles of the chemical parameters in the seawater have unique characteristics. Our resluts also showed that the carbonate compensation depth (CCD) was between 4500 m and 5000 m in the trench. The hadal sediment at 6500 m depth under the CCD line was siliceous ooze favored for the burial of orgaic carbon, attributed to accumulation of surface sediment by gravity flow. The abyssal sediment at the 4500 m depth was calcareous ooze. Various microfossils, such as discoasters and diatoms, were identified in different sediment layers of the sediment samples.Based on the ratios of Fe/Al and Ti/Al, and the correlation between different elements, the sediment in the Yap Trench were derived from biogenic, terrestrial, volcanic and autogenic sources. The ratios of Ni/Co and V/Cr showed that the deposition environment of the trench should be oxidative, arributed to inflow of the Antractic bottom oxygen-rich seawater.The high concentraiont of Ca in the sediment from the station 371-Yap-S02 below 4 cm depth indicated that there was no large-scale volcanic eruption in the research area and the volcanic materials in the sediment might orginated from the Mariana Volcanic Arc, and the Carolyn Ridge has been slowly sinking on the east side of the trench due to plate subduction. This study is the first systematic study of chemical characteristics in the seawater and sediment of the Yap Trench.

Methane gas seepage - Disregard of significant water column filter processes?

NASA Astrophysics Data System (ADS)

Schneider von Deimling, Jens; Schmale, Oliver

2016-04-01

Marine methane seepage represents a potential contributor for greenhouse gas in the atmosphere and is discussed as a driver for climate change. The ultimate question is how much methane is released from the seafloor on a global scale and what fraction may reach the atmosphere? Dissolved fluxes from methane seepage sites on the seabed were found to be very efficiently reduced by benthic microbial oxidation, whereas transport of free gas bubbles from the seabed is considered to bypass the effective benthic methane filter. Numerical models are available today to predict the fate of such methane gas bubble release to the water column in regard to gas exchange with the ambient water column, respective bubble lifetime and rise height. However, the fate of rising gas bubbles and dissolved methane in the water column is not only governed by dissolution, but is also affected by lateral oceanographic currents and vertical bubble-induced upwelling, microbial oxidation, and physico-chemical processes that remain poorly understood so far. According to this gap of knowledge we present data from two study sites - the anthropogenic North Sea 22/4b Blowout and the natural Coal Oil point seeps - to shed light into two new processes gathered with hydro-acoustic multibeam water column imaging and microbial investigations. The newly discovered processes are hereafter termed Spiral Vortex and Bubble Transport Mechanism. Spiral Vortex describes the evolution of a complex vortical fluid motion of a bubble plume in the wake of an intense gas release site (Blowout, North Sea). It appears very likely that it dramatically changes the dissolution kinetics of the seep gas bubbles. Bubble Transport Mechanism prescribes the transport of sediment-hosted bacteria into the water column via rising gas bubbles. Both processes act as filter mechanisms in regard to vertical transport of seep related methane, but have not been considered before. Spiral Vortex and Bubble Transport Mechanism represent the basis for a follow up research scheduled for August 2016 with the R/V POSEIDON with the aim to better constrain their mechanisms and to quantify their overall importance.

Energy-positive food wastewater treatment using an anaerobic membrane bioreactor (AnMBR).

PubMed

Galib, Mohamed; Elbeshbishy, Elsayed; Reid, Robertson; Hussain, Abid; Lee, Hyung-Sool

2016-11-01

An immersed-membrane anaerobic membrane bioreactor (AnMBR) achieved 88-95% of COD removal for meat-processing wastewater at organic loading rate (OLR) of 0.4-3.2 kgCOD m(-3) d(-1). Membrane flux was stable for low OLR (0.4 and 1.3 kgCOD m(-3) d(-1)), but irrecoverable fouling occurred at high OLR of 3.2 kgCOD m(-3) d(-1). Methane gas yield of 0.13-0.18 LCH4 g(-1)CODremoved was obtained, which accounted for 33-38% of input COD, the most significant electron sink. Dissolved methane was only 3.4-11% of input COD and consistently over-saturated at all OLR conditions. The least accumulation of dissolved methane (25 mg L(-1) and saturation index 1.3) was found for the highest OLR of 3.2 kgCOD m(-3) d(-1) where biogas production rate was the highest. Energy balances showed that AnMBR produced net energy benefit of 0.16-1.82 kWh m(-3), indicating the possibility of energy-positive food wastewater treatment using AnMBRs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Relationship of Hydrogen Bioavailability to Chromate Reduction in Aquifer Sediments

PubMed Central

Marsh, Tamara L.; McInerney, Michael J.

2001-01-01

Biological Cr(VI) reduction was studied in anaerobic sediments from an aquifer in Norman, Okla. Microcosms containing sediment and mineral medium were amended with various electron donors to determine those most important for biological Cr(VI) reduction. Cr(VI) (about 340 μM) was reduced with endogenous substrates (no donor), or acetate was added. The addition of formate, hydrogen, and glucose stimulated Cr(VI) reduction compared with reduction in unamended controls. From these sediments, an anaerobic Cr(VI)-utilizing enrichment was obtained that was dependent upon hydrogen for both growth and Cr(VI) reduction. No methane was produced by the enrichment, which reduced about 750 μM Cr(VI) in less than six days. The dissolved hydrogen concentration was used as an indicator of the terminal electron accepting process occurring in the sediments. Microcosms with sediments, groundwater, and chromate metabolized hydrogen to a concentration below the detection limits of the mercury vapor gas chromatograph. In microcosms without chromate, the hydrogen concentration was about 8 nM, a concentration comparable to that under methanogenic conditions. When these microcosms were amended with 500 μM Cr(VI), the dissolved hydrogen concentration quickly fell below the detection limits. These results showed that the hydrogen concentration under chromate-reducing conditions became very low, as low as that reported under nitrate- and manganese-reducing conditions, a result consistent with the free energy changes for these reactions. The utilization of formate, lactate, hydrogen, and glucose as electron donors for Cr(VI) reduction indicates that increasing the availability of hydrogen results in a greater capacity for Cr(VI) reduction. This conclusion is supported by the existence of an enrichment dependent upon hydrogen for growth and Cr(VI) reduction. PMID:11282599

Factors Controlling Methane in Arctic Lakes of Southwest Greenland.

PubMed

Northington, Robert M; Saros, Jasmine E

2016-01-01

We surveyed 15 lakes during the growing season of 2014 in Arctic lakes of southwest Greenland to determine which factors influence methane concentrations in these systems. Methane averaged 2.5 μmol L-1 in lakes, but varied a great deal across the landscape with lakes on older landscapes farther from the ice sheet margin having some of the highest values of methane reported in lakes in the northern hemisphere (125 μmol L-1). The most important factors influencing methane in Greenland lakes included ionic composition (SO4, Na, Cl) and chlorophyll a in the water column. DOC concentrations were also related to methane, but the short length of the study likely underestimated the influence and timing of DOC on methane concentrations in the region. Atmospheric methane concentrations are increasing globally, with freshwater ecosystems in northern latitudes continuing to serve as potentially large sources in the future. Much less is known about how freshwater lakes in Greenland fit in the global methane budget compared to other, more well-studied areas of the Arctic, hence our work provides essential data for a more complete view of this rapidly changing region.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, July 2013

USGS Publications Warehouse

Huffman, Raegan L.

2014-01-01

Previous investigations indicate that concentrations of chlorinated volatile organic compounds (CVOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision for the site. This report presents groundwater geochemical and selected CVOC data collected at Operable Unit 1 by the U.S. Geological Survey during July 9–18, 2013, in support of longterm monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers and four wells also were analyzed for CVOCs, as were all samples from the passive-diffusion sampling sites. In 2013, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations at all except an upgradient well 0.2 milligrams per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2013, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly lower or the same as concentrations measured in 2012. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2013 continued to be variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in two of the three wells and in all but one piezometer. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2013 continued to vary spatially and temporaly, and also were very high. Total CVOC concentrations, at what have been historically the most contaminated passive-diffusion sampler sites (S-4, S-4B, S-5, and S-5B) remained elevated. For the intermediate aquifer in 2013, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June and September 2014

USGS Publications Warehouse

Huffman, Raegan L.

2015-01-01

Previous investigations indicate that concentrations of chlorinated volatile organic compounds (CVOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation at the site. This report presents groundwater geochemical and selected CVOC data collected at Operable Unit 1 by the U.S. Geological Survey during June 23–25 and September 4, 2014, in support of long-term monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers and four wells also were analyzed for CVOCs, as were all samples from the passive-diffusion sampling sites. In 2014, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all less than 1 milligram per liter; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2014, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly lower or the same as concentrations measured in 2013. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2014 continued to be variable as in previous years, often high, and reductive dechlorination byproducts were detected in one of the three wells and in all but two piezometers. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2014 continued to vary spatially and temporally, and were high. Trends for total CVOC concentration continued to increase at the historically most contaminated passive‑diffusion sampler sites (S-4, S-4B, and S-5). For the intermediate aquifer in 2014, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

PubMed

Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

2015-01-06

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Thermodynamic properties and diffusion of water + methane binary mixtures

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

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

Seasonal Variation in Abundance and Diversity of Bacterial Methanotrophs in Five Temperate Lakes

PubMed Central

Samad, Md Sainur; Bertilsson, Stefan

2017-01-01

Lakes are significant sources of methane (CH4) to the atmosphere. Within these systems, methanotrophs consume CH4 and act as a potential biofilter mitigating the emission of this potent greenhouse gas. However, it is still not well understood how spatial and temporal variation in environmental parameters influence the abundance, diversity, and community structure of methanotrophs in lakes. To address this gap in knowledge, we collected water samples from three depths (surface, middle, and bottom) representing oxic to suboxic or anoxic zones of five different Swedish lakes in winter (ice-covered) and summer. Methanotroph abundance was determined by quantitative real time polymerase chain reaction and a comparison to environmental variables showed that temperature, season as well as depth, phosphate concentration, dissolved oxygen, and CH4 explained the observed variation in methanotroph abundance. Due to minimal differences in methane concentrations (0.19 and 0.29 μM for summer and winter, respectively), only a weak and even negative correlation was observed between CH4 and methanotrophs, which was possibly due to usage of CH4. Methanotrophs were present at concentrations ranging from 105 to 106 copies/l throughout the oxic (surface) and suboxic/anoxic (bottom) water mass of the lakes, but always contributed less than 1.3% to the total microbial community. Relative methanotroph abundance was significantly higher in winter than in summer and consistently increased with depth in the lakes. Phylogenetic analysis of pmoA genes in two clone libraries from two of the ice-covered lakes (Ekoln and Ramsen) separated the methanotrophs into five distinct clusters of Methylobacter sp. (Type I). Terminal restriction fragment length polymorphism analysis of the pmoA gene further revealed significant differences in methanotrophic communities between lakes as well as between winter and summer while there were no significant differences between water layers. The study provides new insights into diversity, abundance, community composition and spatial as well as temporal distribution of freshwater methanotrophs in low-methane dimictic lakes. PMID:28217121

Short-chain alkane cycling in deep Gulf of Mexico cold-seep sediments

NASA Astrophysics Data System (ADS)

Sibert, R.; Joye, S. B.; Hunter, K.

2015-12-01

Mixtures of light hydrocarbon gases are common in deep Gulf of Mexico cold-seep sediments, and are typically dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is usually methane (>80% C1), but ethane (C2) and propane (C3) are nearly always present in trace amounts (<1% total). The processes that control the concentration and isotopic signature of these gases in sediments are well explained for methane, but the controls for C2/C3 cycling are still a relative mystery. Methane production proceeds in deep anoxic sediments by either 1) thermocatalytic cracking of fossil organic matter, or 2) as a direct product of microbial metabolism, i.e. methanogenesis. In surface sediments, it appears that both microbial consumption and chemical deposition of methane (i.e. as methane clathrate) ensures that >95% of the methane produced at depth never reaches the water column. Production of C1 and C2 in deep-sea sediments has been historically attributed only to thermocatalytic processes, though limited data suggests production of C2/C3 compounds through the activity of archaea at depth. Furthermore, carbon isotopic data on ethane and propane from deep cores of Gulf of Mexico sediments suggest alkanogenesis at >3 m depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Additional studies have also isolated microorganisms capable of oxidizing ethane and propane in the laboratory, but field studies of microbial-driven dynamics of C2/C3 gases in cold-seep sediments are rare. Here, we present the results of a series of incubation experiments using sediment slurries culled from surface sediments from one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of alkane oxidation were measured under a variety of conditions to assess the surface-driven microbial controls on C2/C3 cycling in cold-seep environments. Such microbial processes are important in terms of the possible 'oxidative overprinting' of alkane isotopic signatures produced at depth, possibly obscuring typical microbial isotopic signals.

Redirection of Metabolic Hydrogen by Inhibiting Methanogenesis in the Rumen Simulation Technique (RUSITEC)

PubMed Central

Guyader, Jessie; Ungerfeld, Emilio M.; Beauchemin, Karen A.

2017-01-01

A decrease in methanogenesis is expected to improve ruminant performance by allocating rumen metabolic hydrogen ([2H]) to more energy-rendering fermentation pathways for the animal. However, decreases in methane (CH4) emissions of up to 30% are not always linked with greater performance. Therefore, the aim of this study was to understand the fate of [2H] when CH4 production in the rumen is inhibited by known methanogenesis inhibitors (nitrate, NIT; 3-nitrooxypropanol, NOP; anthraquinone, AQ) in comparison with a control treatment (CON) with the Rumen Simulation Technique (RUSITEC). Measurements started after 1 week adaptation. Substrate disappearance was not modified by methanogenesis inhibitors. Nitrate mostly seemed to decrease [2H] availability by acting as an electron acceptor competing with methanogenesis. As a consequence, NIT decreased CH4 production (−75%), dissolved dihydrogen (H2) concentration (−30%) and the percentages of reduced volatile fatty acids (butyrate, isobutyrate, valerate, isovalerate, caproate and heptanoate) except propionate, but increased acetate molar percentage, ethanol concentration and the efficiency of microbial nitrogen synthesis (+14%) without affecting gaseous H2. Nitrooxypropanol decreased methanogenesis (−75%) while increasing both gaseous and dissolved H2 concentrations (+81% and +24%, respectively). Moreover, NOP decreased acetate and isovalerate molar percentages and increased butyrate, valerate, caproate and heptanoate molar percentages as well as n-propanol and ammonium concentrations. Methanogenesis inhibition with AQ (−26%) was associated with higher gaseous H2 production (+70%) but lower dissolved H2 concentration (−76%), evidencing a lack of relationship between the two H2 forms. Anthraquinone increased ammonium concentration, caproate and heptanoate molar percentages but decreased acetate and isobutyrate molar percentages, total microbial nitrogen production and efficiency of microbial protein synthesis (−16%). Overall, NOP and AQ increased the amount of reduced volatile fatty acids, but part of [2H] spared from methanogenesis was lost as gaseous H2. Finally, [2H] recovery was similar among CON, NOP and AQ but was largely lower than 100%. Consequently, further studies are required to discover other so far unidentified [2H] sinks for a better understanding of the metabolic pathways involved in [2H] production and utilization. PMID:28352256

Short-range, overpressure-driven methane migration in coarse-grained gas hydrate reservoirs

DOE PAGES

Nole, Michael; Daigle, Hugh; Cook, Ann E.; ...

2016-08-31

Two methane migration mechanisms have been proposed for coarse-grained gas hydrate reservoirs: short-range diffusive gas migration and long-range advective fluid transport from depth. Herein we demonstrate that short-range fluid flow due to overpressure in marine sediments is a significant additional methane transport mechanism that allows hydrate to precipitate in large quantities in thick, coarse-grained hydrate reservoirs. Two-dimensional simulations demonstrate that this migration mechanism, short-range advective transport, can supply significant amounts of dissolved gas and is unencumbered by limitations of the other two end-member mechanisms. Here, short-range advective migration can increase the amount of methane delivered to sands as compared tomore » the slow process of diffusion, yet it is not necessarily limited by effective porosity reduction as is typical of updip advection from a deep source.« less

Short-range, overpressure-driven methane migration in coarse-grained gas hydrate reservoirs

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

Nole, Michael; Daigle, Hugh; Cook, Ann E.

Two methane migration mechanisms have been proposed for coarse-grained gas hydrate reservoirs: short-range diffusive gas migration and long-range advective fluid transport from depth. Herein we demonstrate that short-range fluid flow due to overpressure in marine sediments is a significant additional methane transport mechanism that allows hydrate to precipitate in large quantities in thick, coarse-grained hydrate reservoirs. Two-dimensional simulations demonstrate that this migration mechanism, short-range advective transport, can supply significant amounts of dissolved gas and is unencumbered by limitations of the other two end-member mechanisms. Here, short-range advective migration can increase the amount of methane delivered to sands as compared tomore » the slow process of diffusion, yet it is not necessarily limited by effective porosity reduction as is typical of updip advection from a deep source.« less

Monitoring Production of Methane from Spills of Gasoline at UST Release Sites (Boston, MA)

EPA Science Inventory

Anaerobic biodegradation of the BTEX compounds can produce substantial concentrations of methane in ground water at gasoline spill sites. This methane can escape the ground water, move through the unsaturated zone and potentially produce explosive concentrations of methane in c...

Groundwater quality in the Mohawk River Basin, New York, 2011

USGS Publications Warehouse

Nystrom, Elizabeth A.; Scott, Tia-Marie

2013-01-01

Water samples were collected from 21 production and domestic wells in the Mohawk River Basin in New York in July 2011 to characterize groundwater quality in the basin. The samples were collected and processed using standard U.S. Geological Survey procedures and were analyzed for 148 physiochemical properties and constituents, including dissolved gases, major ions, nutrients, trace elements, pesticides, volatile organic compounds (VOCs), radionuclides, and indicator bacteria. The Mohawk River Basin covers 3,500 square miles in New York and is underlain by shale, sandstone, carbonate, and crystalline bedrock. The bedrock is overlain by till in much of the basin, but surficial deposits of saturated sand and gravel are present in some areas. Nine of the wells sampled in the Mohawk River Basin are completed in sand and gravel deposits, and 12 are completed in bedrock. Groundwater in the Mohawk River Basin was typically neutral or slightly basic; the water typically was very hard. Bicarbonate, chloride, calcium, and sodium were the major ions with the greatest median concentrations; the dominant nutrient was nitrate. Methane was detected in 15 samples. Strontium, iron, barium, boron, and manganese were the trace elements with the highest median concentrations. Four pesticides, all herbicides or their degradates, were detected in four samples at trace levels; three VOCs, including chloroform and two solvents, were detected in four samples. The greatest radon-222 activity, 2,300 picocuries per liter, was measured in a sample from a bedrock well, but the median radon activity was higher in samples from sand and gravel wells than in samples from bedrock wells. Coliform bacteria were detected in five samples with a maximum of 92 colony-forming units per 100 milliliters. Water quality in the Mohawk River Basin is generally good, but concentrations of some constituents equaled or exceeded current or proposed Federal or New York State drinking-water standards. The standards exceeded are color (1 sample), pH (1 sample), sodium (9 samples), chloride (1 sample), sulfate (2 samples), dissolved solids (7 samples), aluminum (3 samples), iron (8 samples), manganese (6 samples), radon-222 (10 samples), and bacteria (5 samples). Fecal coliform bacteria and Escherichia coli (E. coli) were each detected in one sample. Concentrations of fluoride, nitrate, nitrite, antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, selenium, silver, thallium, zinc, and uranium, and gross alpha activities, did not exceed existing drinking-water standards in any of the samples collected. Methane concentrations in two samples were greater than 28 milligrams per liter, and the maximum measured concentration was 44.3 milligrams per liter.

The role of hydrodynamic transport in greenhouse gas fluxes at a wetland with emergent vegetation

NASA Astrophysics Data System (ADS)

Poindexter, C.; Gilson, E.; Knox, S. H.; Matthes, J. H.; Verfaillie, J. G.; Baldocchi, D. D.; Variano, E. A.

2013-12-01

In wetlands with emergent vegetation, the hydrodynamic transport of dissolved gases is often neglected because emergent plants transport gases directly and limit wind-driven air-water gas exchange by sheltering the water surface. Nevertheless, wetland hydrodynamics, and thermally-driven stirring in particular, have the potential to impact gas fluxes in these environments. We are evaluating the importance of hydrodynamic dissolved gas transport at a re-established marsh on Twitchell Island in the Sacramento-San Joaquin Delta (California, USA). At this marsh, the U.S. Geological Survey has previously observed rapid accumulation of organic material (carbon sequestration) as well as very high methane emissions. To assess the role of hydrodynamics in the marsh's greenhouse gas fluxes, we measured dissolved carbon dioxide and methane in the water column on a bi-weekly basis beginning in July 2012. We employed a model for air-water gas fluxes in wetlands with emergent vegetation that predicts gas transfer velocities from meteorological conditions. Modeled air-water gas fluxes were compared with net gas fluxes measured at the marsh via the eddy covariance technique. This comparison revealed that hydrodynamic transport due to thermal convection was responsible for approximately one third of net carbon dioxide and methane fluxes. The cooling at the water surface driving thermal convection occurred each night and was most pronounced during the warmest months of the year. These finding have implications for the prediction and management of greenhouse gas fluxes at re-established marshes in the Sacramento-San Joaquin Delta and other similar wetlands.

Reductive dechlorination of chlorinated ethenes under oxidation-reduction conditions and potentiometric surfaces in two trichloroethene-contaminated zones at the Double Eagle and Fourth Street Superfund sites in Oklahoma City, Oklahoma

USGS Publications Warehouse

Braun, Christopher L.

2004-01-01

The Double Eagle Refining Superfund site and the Fourth Street Abandoned Refinery Superfund site are in northeast Oklahoma City, Oklahoma, adjacent to one another. The Double Eagle facility became a Superfund site on the basis of contamination from lead and volatile organic compounds; the Fourth Street facility on the basis of volatile organic compounds, pesticides, and acid-base neutral compounds. The study documented in this report was done to investigate whether reductive dechlorination of chlorinated ethenes under oxidation-reduction conditions is occurring in two zones of the Garber-Wellington aquifer (shallow zone 30–60 to 75 feet below land surface, deep zone 75 to 160 feet below land surface) at the sites; and to construct potentiometric surfaces of the two water-yielding zones to determine the directions of groundwater flow at the sites. The presence in some wells of intermediate products of reductive dechlorination, dichloroethene and vinyl chloride, is an indication that reductive dechlorination of trichloroethene is occurring. Dissolved oxygen concentrations (less than 0.5 milligram per liter) indicate that consumption of dissolved oxygen likely had occurred in the oxygen-reducing microbial process associated with reductive dechlorination. Concentrations of nitrate and nitrite nitrogen (generally less than 2.0 and 0.06 milligrams per liter, respectively) indicate that nitrate reduction probably is not a key process in either aquifer zone. Concentrations of ferrous iron greater than 1.00 milligram per liter in the majority of wells sampled indicate that iron reduction is probable. Concentrations of sulfide less than 0.05 milligram per liter in all wells indicate that sulfate reduction probably is not a key process in either zone. The presence of methane in ground water is an indication of strongly reducing conditions that facilitate reductive dechlorination. Methane was detected in all but one well. In the shallow zone in the eastern part of the study area, ground water flowing from the northwest and south coalesces in a potentiometric trough, then moves westward and ultimately northwestward. In the western part of the study area, ground water in the shallow zone flows northwest. In the deep zone in the eastern part of the study area, ground water generally flows northwestward; and in the western part of the study area, ground water in the deep zone generally flows northward.

Effect of Nickel Levels on Hydrogen Partial Pressure and Methane Production in Methanogens

PubMed Central

2016-01-01

Hydrogen (H2) consumption and methane (CH4) production in pure cultures of three different methanogens were investigated during cultivation with 0, 0.2 and 4.21 μM added nickel (Ni). The results showed that the level of dissolved Ni in the anaerobic growth medium did not notably affect CH4 production in the cytochrome-free methanogenic species Methanobacterium bryantii and Methanoculleus bourgensis MAB1, but affected CH4 formation rate in the cytochrome-containing Methanosarcina barkeri grown on H2 and CO2. Methanosarcina barkeri also had the highest amounts of Ni in its cells, indicating that more Ni is needed by cytochrome-containing than by cytochrome-free methanogenic species. The concentration of Ni affected threshold values of H2 partial pressure (pH2) for all three methanogen species studied, with M. bourgensis MAB1 reaching pH2 values as low as 0.1 Pa when Ni was available in amounts used in normal anaerobic growth medium. To our knowledge, this is the lowest pH2 threshold recorded to date in pure methanogen culture, which suggests that M.bourgensis MAB1 have a competitive advantage over other species through its ability to grow at low H2 concentrations. Our study has implications for research on the H2-driven deep subsurface biosphere and biogas reactor performance. PMID:27992585

Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir.

PubMed

McClure, Ryan P; Hamre, Kathleen D; Niederlehner, B R; Munger, Zackary W; Chen, Shengyang; Lofton, Mary E; Schreiber, Madeline E; Carey, Cayelan C

2018-04-30

Metalimnetic oxygen minimum zones (MOMs) commonly develop during the summer stratified period in freshwater reservoirs because of both natural processes and water quality management. While several previous studies have examined the causes of MOMs, much less is known about their effects, especially on reservoir biogeochemistry. MOMs create distinct redox gradients in the water column which may alter the magnitude and vertical distribution of dissolved methane (CH 4 ) and carbon dioxide (CO 2 ). The vertical distribution and diffusive efflux of CH 4 and CO 2 was monitored for two consecutive open-water seasons in a eutrophic reservoir that develops MOMs as a result of the operation of water quality engineering systems. During both summers, elevated concentrations of CH 4 accumulated within the anoxic MOM, reaching a maximum of 120 μM, and elevated concentrations of CO 2 accumulated in the oxic hypolimnion, reaching a maximum of 780 μM. Interestingly, the largest observed diffusive CH 4 effluxes occurred before fall turnover in both years, while peak diffusive CO 2 effluxes occurred both before and during turnover. Our data indicate that MOMs can substantially change the vertical distribution of CH 4 and CO 2 in the water column in reservoirs, resulting in the accumulation of CH 4 in the metalimnion (vs. at the sediments) and CO 2 in the hypolimnion. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Nickel Levels on Hydrogen Partial Pressure and Methane Production in Methanogens.

PubMed

Neubeck, Anna; Sjöberg, Susanne; Price, Alex; Callac, Nolwenn; Schnürer, Anna

2016-01-01

Hydrogen (H2) consumption and methane (CH4) production in pure cultures of three different methanogens were investigated during cultivation with 0, 0.2 and 4.21 μM added nickel (Ni). The results showed that the level of dissolved Ni in the anaerobic growth medium did not notably affect CH4 production in the cytochrome-free methanogenic species Methanobacterium bryantii and Methanoculleus bourgensis MAB1, but affected CH4 formation rate in the cytochrome-containing Methanosarcina barkeri grown on H2 and CO2. Methanosarcina barkeri also had the highest amounts of Ni in its cells, indicating that more Ni is needed by cytochrome-containing than by cytochrome-free methanogenic species. The concentration of Ni affected threshold values of H2 partial pressure (pH2) for all three methanogen species studied, with M. bourgensis MAB1 reaching pH2 values as low as 0.1 Pa when Ni was available in amounts used in normal anaerobic growth medium. To our knowledge, this is the lowest pH2 threshold recorded to date in pure methanogen culture, which suggests that M.bourgensis MAB1 have a competitive advantage over other species through its ability to grow at low H2 concentrations. Our study has implications for research on the H2-driven deep subsurface biosphere and biogas reactor performance.

Inside Story of Gas Processes within Stormwater Biofilters: Does Greenhouse Gas Production Tarnish the Benefits of Nitrogen Removal?

PubMed

Payne, Emily G I; Pham, Tracey; Cook, Perran L M; Deletic, Ana; Hatt, Belinda E; Fletcher, Tim D

2017-04-04

Stormwater biofilters are dynamic environments, supporting diverse processes that act to capture and transform incoming pollutants. However, beneficial water treatment processes can be accompanied by undesirable greenhouse gas production. This study investigated the potential for nitrous oxide (N 2 O) and methane (CH 4 ) generation in dissolved form at the base of laboratory-scale stormwater biofilter columns. The influence of plant presence, species, inflow frequency, and inclusion of a saturated zone and carbon source were studied. Free-draining biofilters remained aerobic with negligible greenhouse gas production during storm events. Designs with a saturated zone were oxygenated at their base by incoming stormwater before anaerobic conditions rapidly re-established, although extended dry periods allowed the reintroduction of oxygen by evapotranspiration. Production of CH 4 and N 2 O in the saturated zone varied significantly in response to plant presence, species, and wetting and drying. Concentrations of N 2 O typically peaked rapidly following stormwater inundation, associated with limited plant root systems and poorer nitrogen removal from biofilter effluent. Production of CH 4 also commenced quickly but continued throughout the anaerobic interevent period and lacked clear relationships with plant characteristics or nitrogen removal performance. Dissolved greenhouse gas concentrations were highly variable, but peak concentrations of N 2 O accounted for <1.5% of the incoming total nitrogen load. While further work is required to measure surface emissions, the potential for substantial release of N 2 O or CH 4 in biofilter effluent appears relatively low.

30 CFR 75.351 - Atmospheric monitoring systems.

Code of Federal Regulations, 2013 CFR

2013-07-01

... methane concentration at any sensor reaches the alert level as specified in § 75.351(i). These signals... carbon monoxide, smoke, or methane concentration at any sensor reaches the alarm level as specified in... methane concentration at any sensor reaches the alarm level as specified in § 75.351(i). These signals...

30 CFR 75.351 - Atmospheric monitoring systems.

Code of Federal Regulations, 2014 CFR

2014-07-01

... methane concentration at any sensor reaches the alert level as specified in § 75.351(i). These signals... carbon monoxide, smoke, or methane concentration at any sensor reaches the alarm level as specified in... methane concentration at any sensor reaches the alarm level as specified in § 75.351(i). These signals...

30 CFR 75.351 - Atmospheric monitoring systems.

Code of Federal Regulations, 2012 CFR

2012-07-01

... methane concentration at any sensor reaches the alert level as specified in § 75.351(i). These signals... carbon monoxide, smoke, or methane concentration at any sensor reaches the alarm level as specified in... methane concentration at any sensor reaches the alarm level as specified in § 75.351(i). These signals...

The design of a PC-based real-time system for monitoring Methane and Oxygen concentration in biogas production

NASA Astrophysics Data System (ADS)

Yantidewi, M.; Muntini, M. S.; Deta, U. A.; Lestari, N. A.

2018-03-01

Limited fossil fuels nowadays trigger the development of alternative energy, one of which is biogas. Biogas is one type of bioenergy in the form of fermented gases of organic materials such as animal waste. The components of gases present in biogas and affect the biogas production are various, such as methane and oxygen. The biogas utilization will be more optimal if both gases concentration (in this case is methane and oxygen concentration) can be monitored. Therefore, this research focused on designing the monitoring system of methane and oxygen concentration in biogas production in real-time. The results showed that the instrument system was capable of monitoring and recording the data of gases (methane and oxygen) concentration in biogas production in every second.

Factors Controlling Methane in Arctic Lakes of Southwest Greenland

PubMed Central

2016-01-01

We surveyed 15 lakes during the growing season of 2014 in Arctic lakes of southwest Greenland to determine which factors influence methane concentrations in these systems. Methane averaged 2.5 μmol L-1 in lakes, but varied a great deal across the landscape with lakes on older landscapes farther from the ice sheet margin having some of the highest values of methane reported in lakes in the northern hemisphere (125 μmol L-1). The most important factors influencing methane in Greenland lakes included ionic composition (SO4, Na, Cl) and chlorophyll a in the water column. DOC concentrations were also related to methane, but the short length of the study likely underestimated the influence and timing of DOC on methane concentrations in the region. Atmospheric methane concentrations are increasing globally, with freshwater ecosystems in northern latitudes continuing to serve as potentially large sources in the future. Much less is known about how freshwater lakes in Greenland fit in the global methane budget compared to other, more well-studied areas of the Arctic, hence our work provides essential data for a more complete view of this rapidly changing region. PMID:27454863

Distribution and Rate of Methane Oxidation in Sediments of the Florida Everglades †

PubMed Central

King, Gary M.; Roslev, Peter; Skovgaard, Henrik

1990-01-01

Rates of methane emission from intact cores were measured during anoxic dark and oxic light and dark incubations. Rates of methane oxidation were calculated on the basis of oxic incubations by using the anoxic emissions as an estimate of the maximum potential flux. This technique indicated that methane oxidation consumed up to 91% of the maximum potential flux in peat sediments but that oxidation was negligible in marl sediments. Oxygen microprofiles determined for intact cores were comparable to profiles measured in situ. Thus, the laboratory incubations appeared to provide a reasonable approximation of in situ activities. This was further supported by the agreement between measured methane fluxes and fluxes predicted on the basis of methane profiles determined by in situ sampling of pore water. Methane emissions from peat sediments, oxygen concentrations and penetration depths, and methane concentration profiles were all sensitive to light-dark shifts as determined by a combination of field and laboratory analyses. Methane emissions were lower and oxygen concentrations and penetration depths were higher under illuminated than under dark conditions; the profiles of methane concentration changed in correspondence to the changes in oxygen profiles, but the estimated flux of methane into the oxic zone changed negligibly. Sediment-free, root-associated methane oxidation showed a pattern similar to that for methane oxidation in the core analyses: no oxidation was detected for roots growing in marl sediment, even for roots of Cladium jamaicense, which had the highest activity for samples from peat sediments. The magnitude of the root-associated oxidation rates indicated that belowground plant surfaces may not markedly increase the total capacity for methane consumption. However, the data collectively support the notion that the distribution and activity of methane oxidation have a major impact on the magnitude of atmospheric fluxes from the Everglades. PMID:16348299

Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

USGS Publications Warehouse

Pohlman, J.W.; Bauer, J.E.; Canuel, E.A.; Grabowski, K.S.; Knies, D.L.; Mitchell, C.S.; Whiticar, Michael J.; Coffin, R.B.

2009-01-01

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (14C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its 14C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (??? 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations. In combination with ??13C- and ??D-methane measurements, we also determine the extent to which the low, but detectable, amounts of 14C (~ 1-2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A 14C mass balance approach using fossil methane and 14C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6??m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.

Redox processes in the rhizosphere of restored peatlands - The impact of vascular plant species on electrochemical properties of dissolved organic matter

NASA Astrophysics Data System (ADS)

Agethen, Svenja; Wolff, Franziska; Knorr, Klaus-Holger

2016-04-01

Restoration of cut over peatlands in Central Europe is challenging in a landscape overused for agriculture. Excess nutrient availability by excess fertilization triggers uncharacteristic vegetation that is one key driver for carbon cycling. Those nutrient rich systems are often dominated by graminoids, and were often found to emit substantial amounts of methane. Plants grown under nutrient rich conditions provide more labile carbon in rhizodeposition and litter that fuels methanogenesis. Such species often have aerenchyma that facilitates direct CH4 emissions to the atmosphere and therefore impair the climate cooling function of bogs. On the other hand, aerenchymatic tissue supplies oxygen to the rhizosphere, which may reduce methanogenesis or stimulate methane oxidation, as methanogenesis is a strictly anaerobic process. Which of the effects prevail is often unclear. Therefore, the aim of this study was to test the impact of different vegetation on rhizospheric redox conditions and methanogenesis, including aerenchymatic vascular plants that are dominant in restored cut over peatlands. As ombrotrophic peat is poor in inorganic electron acceptors (EAs) to suppress methanogenesis, we analyzed the electron acceptor (EACs) and electron donor capacities (EDCs) of dissolved organic matter (DOM) in the rhizosphere to understand the impact of vegetation on anaerobic organic matter degradation. We planted Juncus effusus, Eriophorum vaginatum, Eriophorum angustifolium, Sphagnum (mixture of S. magellanicum, S. papillosum, S. sec. acutifolia, 1/3 each) plus non-vegetated controls; six replicates per batch; in containers with untreated homogenized peat. The plants grow under constant conditions (20° C, 12h diurnal light cycles and 80% RH). Anoxic conditions were achieved by keeping the water table at +10 cm. For monitoring, the rhizosphere is equipped with suction and gas samplers. We measure dissolved CO2 and CH4 concentrations, inorganic EAs (NO3-, Fe(III), and SO42-) and organic EDCs and EACs via mediated electrochemical reduction/oxidation. We also characterize DOM with fluorescence spectroscopy and monitor the growth of above ground biomass as proxy for photosynthetic activity and potential DOM source. Preliminary results showed after initially equal magnitude of EACs and EDCs in all batches an increase in total electron exchange capacity (Σ EAC, EDC) four weeks later, but EACs increased significantly higher for rooted plants (fivefold vs. threefold in Sphagnum and controls). Subsequently, higher CH4 concentrations were found for Sphagnum and the controls. In our ongoing study we will also try to relate the effect of vegetation on rhizosphere redox conditions to root and shoot biomass and photosynthesis. First results indicate that oxidation of organic EAs occurs for all tested graminoid species. The analysis of EACs and EDCs in the rhizosphere of dominant species may improve our understanding under which conditions methane production and emission is stimulated or reduced by presence of vascular, aerenchymatic plants.

Methane distributions and transports in the nocturnal boundary layer at a rural station

NASA Astrophysics Data System (ADS)

Schäfer, Klaus; Zeeman, Matthias; Brosy, Caroline; Münkel, Christoph; Fersch, Benjamin; Mauder, Matthias; Emeis, Stefan

2016-10-01

To investigate the methane distributions and transports, the role of related atmospheric processes by determination of vertical profiles of wind, turbulence, temperature and humidity as well as nocturnal boundary layer (NBL) height and the quantification of methane emissions at local and plot scale the so-called ScaleX-campaign was performed in a pre-alpine observatory in Southern Germany from 01 June until 31 July 2015. The following measurements from the ground up to the free troposphere were performed: layering of the atmosphere by a ceilometer (Vaisala CL51); temperature, wind, turbulence profiles from 50 m up to 500 m by a Radio-Acoustic Sounding System (RASS, Metek GmbH); temperature, humidity profiles in situ by a hexacopter; methane farm emissions by two open-path laser spectrometers (Boreal GasFinder2); methane concentrations in situ (Los Gatos DLT-100) with tubes in 0.3 m agl and 5 sampling heads; and methane soil emissions by a big chamber (10 m length, 2.60 m width, up to 0.61 m height) with a plastic cover. The methane concentrations near the surface show a daily variation with a maximum and a frequent double-peak structure during night-time. Analysis of the variation of the nocturnal methane concentration together with the hexacopter and RASS data indicates that the first peak in the nocturnal methane concentration is probably due to local cooling and stabilization which keeps the methane emissions from the soil near the ground. The second peak seems to be due to advection of methane-enriched air which had formed in the environment of the nearby farm yards. These dairy farm emissions were determined by up-wind and down-wind open-path concentration measurements, turbulence data from an EC station nearby and Backward Lagrangian Simulation (WindTrax software). The methane fluxes at plot scale (big chamber) are characterized by emissions at water saturated grassland patches, by an exponential decrease of these emissions during grassland drying, and by an uptake of methane at dry grassland. Highest methane concentrations are found with lowest NBL heights which were determined from the ceilometer monitoring (correlation coefficient 0.56).

Temporal variation of aerobic methane oxidation over a tidal cycle in a wetland of northern Taiwan.

NASA Astrophysics Data System (ADS)

Lee, T. Y.; Wang, P. L.; Lin, L. H.

2017-12-01

Aerobic methanotrophy plays an important role in controlling methane emitted from wetlands. However, the activity of aerobic methanotrophy regulated by temporal fluctuation of oxygen and methane supply in tidal wetlands is not well known. This study aims to examine the dynamics of methane fluxes and potential aerobic methane consumption rates in a tidal wetland of northern Taiwan, where the variation of environmental characteristics, such as sulfate and methane concentration in pore water has been demonstrated during a tidal cycle. Two field campaigns were carried out in December of 2016 and March of 2017. Fluxes of methane emission, methane concentrations in surface sediments and oxygen profiles were measured at different tidal phases. Besides, batch incubations were conducted on surface sediments in order to quantify potential microbial methane consumption rates and to derive the kinetic parameters for aerobic methanotrophy. Our results demonstrated temporal changes of the surface methane concentration and the methane emission flux during a tidal cycle, while the oxygen flux into the sediment was kept at a similar magnitude. The methane flux was low when the surface was exposed for both shortest and longest periods of time. The potential aerobic methane oxidation rate was high for sample collected from the surface sediments exposed the longest. No correlation could be found between the potential aerobic methane oxidation rate and either the oxygen downward flux or methane emission flux. The decoupled relationships between these observed rates and fluxes suggest that, rather than aerobic methanotrophy, heterotrophic respirations exert a profound control on oxygen flux, and the methane emission is not only been affected by methane consumption but also methane production at depths. The maximum potential rate and the half saturation concentration determined from the batch incubations were high for the surface sediments collected in low tide, suggesting that aerobic methanotrophy could be modulated to reach peak activity once the influence of saline water is reduced to a low level.

Evidence of sulfate-dependent anaerobic methane oxidation ...

EPA Pesticide Factsheets

The rapid development of unconventional gas resources has been accompanied by an increase in public awareness regarding the potential effects of drilling operations on drinking water sources. Incidents have been reported involving blowouts (e.g., Converse County, WY; Lawrence Township, PA; Aliso Canyon, CA) and home/property explosions (e.g., Bainbridge Township, OH; Dimock, PA; Huerfano County, CO) caused by methane migration in the subsurface within areas of natural gas development. We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Results show persistent secondary water quality impacts related to the biodegradation of methane. We identify four distinct characteristics of groundwater methane attenuation in the Poison Canyon aquifer: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher-molecular-weight (C2+) gaseous hydrocarbons, (iii) patterns of 13C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. We also show that the biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic,

Evaluation of the impact of organic material on the anaerobic methane and ammonium removal in a membrane aerated biofilm reactor (MABR) based on the multispecies biofilm modeling.

PubMed

Wu, Jun; Zhang, Yue

2017-01-01

The simultaneous nitrogen and methane removal by the combined nitritation, anaerobic ammonium oxidation (anammox), and nitrite dependent anaerobic methane oxidation (n-damo) processes in the membrane aerated biofilm reactor (MABR) offers clear advantages in term of energy saving and greenhouse gas emission mitigation. The rejected water from sludge digestion usually contained high ammonium, COD, and dissolved methane. The impact of influent COD on the anaerobic methane and ammonium removal in an MABR was evaluated in the model based study. The results indicated that the influent COD did not reduce the methane and ammonium removal efficiency at C/N ratio (influent COD/NH 4 + -N) less than 0.1. At high C/N ratio, the oxygen transfer coefficient needed to be increased to achieve high methane and nitrogen removal. Substrate flux analysis indicated that heterotrophic denitrification in the outside layer of biofilm reduced the impact of influent COD. Heterotrophic growth needed to be limited at the outside layer by using NO 3 - as electron acceptor; otherwise, the heterotrophic bacteria would compete NO 2 - and space with anammox and n-damo bacteria in the inner layers and reduce the nitrogen and methane removal efficiency.

Effect of Greenhouse Gases Dissolved in Seawater

PubMed Central

Matsunaga, Shigeki

2015-01-01

A molecular dynamics simulation has been performed on the greenhouse gases carbon dioxide and methane dissolved in a sodium chloride aqueous solution, as a simple model of seawater. A carbon dioxide molecule is also treated as a hydrogen carbonate ion. The structure, coordination number, diffusion coefficient, shear viscosity, specific heat, and thermal conductivity of the solutions have been discussed. The anomalous behaviors of these properties, especially the negative pressure dependence of thermal conductivity, have been observed in the higher-pressure region. PMID:26729101

Effect of Greenhouse Gases Dissolved in Seawater.

PubMed

Matsunaga, Shigeki

2015-12-30

A molecular dynamics simulation has been performed on the greenhouse gases carbon dioxide and methane dissolved in a sodium chloride aqueous solution, as a simple model of seawater. A carbon dioxide molecule is also treated as a hydrogen carbonate ion. The structure, coordination number, diffusion coefficient, shear viscosity, specific heat, and thermal conductivity of the solutions have been discussed. The anomalous behaviors of these properties, especially the negative pressure dependence of thermal conductivity, have been observed in the higher-pressure region.

Methane oxidation in anoxic lake waters

NASA Astrophysics Data System (ADS)

Su, Guangyi; Zopfi, Jakob; Niemann, Helge; Lehmann, Moritz

2017-04-01

Freshwater habitats such as lakes are important sources of methante (CH4), however, most studies in lacustrine environments so far provided evidence for aerobic methane oxidation only, and little is known about the importance of anaerobic oxidation of CH4 (AOM) in anoxic lake waters. In marine environments, sulfate reduction coupled to AOM by archaea has been recognized as important sinks of CH4. More recently, the discorvery of anaerobic methane oxidizing denitrifying bacteria represents a novel and possible alternative AOM pathway, involving reactive nitrogen species (e.g., nitrate and nitrite) as electron acceptors in the absence of oxygen. We investigate anaerobic methane oxidation in the water column of two hydrochemically contrasting sites in Lake Lugano, Switzerland. The South Basin displays seasonal stratification, the development of a benthic nepheloid layer and anoxia during summer and fall. The North Basin is permanently stratified with anoxic conditions below 115m water depth. Both Basins accumulate seasonally (South Basin) or permanently (North Basin) large amounts of CH4 in the water column below the chemocline, providing ideal conditions for methanotrophic microorganisms. Previous work revealed a high potential for aerobic methane oxidation within the anoxic water column, but no evidence for true AOM. Here, we show depth distribution data of dissolved CH4, methane oxidation rates and nutrients at both sites. In addition, we performed high resolution phylogenetic analyses of microbial community structures and conducted radio-label incubation experiments with concentrated biomass from anoxic waters and potential alternative electron acceptor additions (nitrate, nitrite and sulfate). First results from the unamended experiments revealed maximum activity of methane oxidation below the redoxcline in both basins. While the incubation experiments neither provided clear evidence for NOx- nor sulfate-dependent AOM, the phylogenetic analysis revealed the presence of members of the Methylomirabiliaceae family (NC10 phylum), known to perform AOM with nitrite as terminal electron acceptor. Interestingly, albeit the similarly favorable conditions in both basins, the South Basin showed nearly two-fold higher CH4 oxidation rates, but the Methylomirabiliaceae abundance appeared to be much higher in the meromictic North Basin. Ongoing work will attempt to verify whether the apparent difference in the abundance of Methylomirabiliaceae is a permanent feature. We will further seek to determine the relative contribution of bacterial nitrite-dependent AOM to total methane oxidation, as well as the environmental controls that may explain the differential importance of Methylomirabiliaceae in the two connected lake basins.

Late Holocene methane rise caused by orbitally controlled increase in tropical sources.

PubMed

Singarayer, Joy S; Valdes, Paul J; Friedlingstein, Pierre; Nelson, Sarah; Beerling, David J

2011-02-03

Considerable debate surrounds the source of the apparently 'anomalous' increase of atmospheric methane concentrations since the mid-Holocene (5,000 years ago) compared to previous interglacial periods as recorded in polar ice core records. Proposed mechanisms for the rise in methane concentrations relate either to methane emissions from anthropogenic early rice cultivation or an increase in natural wetland emissions from tropical or boreal sources. Here we show that our climate and wetland simulations of the global methane cycle over the last glacial cycle (the past 130,000 years) recreate the ice core record and capture the late Holocene increase in methane concentrations. Our analyses indicate that the late Holocene increase results from natural changes in the Earth's orbital configuration, with enhanced emissions in the Southern Hemisphere tropics linked to precession-induced modification of seasonal precipitation. Critically, our simulations capture the declining trend in methane concentrations at the end of the last interglacial period (115,000-130,000 years ago) that was used to diagnose the Holocene methane rise as unique. The difference between the two time periods results from differences in the size and rate of regional insolation changes and the lack of glacial inception in the Holocene. Our findings also suggest that no early agricultural sources are required to account for the increase in methane concentrations in the 5,000 years before the industrial era.

Methane oxidation in Saanich Inlet during summer stratification

NASA Technical Reports Server (NTRS)

Ward, B. B.; Kilpatrick, K. A.; Wopat, A. E.; Minnich, E. C.; Lidstrom, M. E.

1989-01-01

Saanich Inlet, British Columbia, an fjord on the southeast coast of Vancouver Island, typically stratifies in summer, leading to the formation of an oxic-anoxic interface in the water column and accumulation of methane in the deep water. The results of methane concentration measurements in the water column of the inlet at various times throughout the summer months in 1983 are presented. Methane gradients and calculated diffusive fluxes across the oxic-anoxic interface increased as the summer progressed. Methane distribution and consumption in Saanich Inlet were studied in more detail during August 1986. At this time, a typical summer stratification with an oxic-anoxic interface around 140 m was present. At the interface, steep gradients in nutrient concentrations, bacterial abundance and methane concentration were observed. Methane oxidation was detected in the aerobic surface waters and in the anaerobic deep layer, but highest rates occurred in a narrow layer at the oxic-anoxic interface. Estimated methane oxidation rates were suffcient to consume 100 percent of the methane provided by diffusive flux from the anoxic layer. Methane oxidation is thus a mechanism whereby atmospheric flux from anoxic waters is minimized.

Evaluating the relative contribution of methane oxidation to methane emissions from young floodplain soils under Alternative Irrigation Management

NASA Astrophysics Data System (ADS)

Pierreux, Sofie; Verhoeven, Elizabeth; Akter, Masuda; Sleutel, Steven; Said-Pullicino, Daniel; Romani, Marco; Boeckx, Pascal

2016-04-01

To keep the pace with a yearly growing demand for rice by 1-2%, future rice production must come primarily from high yielding irrigated rice, putting a pressure on fresh water reserves. In this context, water saving Alternative Irrigation Management (AIM) is progressively applied worldwide. By introducing repeated or mid-seasonal drainage, AIM suppresses emission of CH4, otherwise prevalent in continuously flooded rice. However, little is known about the effect of AIM on the balance of CH4 genesis and oxidation in paddy soils. We studied relevant soil parameters and CH4 emissions in continuously flooded (CF) and alternately wetted and dried (AWD) rice paddies. During a field campaign at the Castello d'Agogna experimental station (Pavia, Italy), we measured in situ CH4 oxidation and emission rates using the closed gas chamber technique with or without application of CH2F2 as a selective inhibitor of CH4 oxidation. In addition, we determined potential CH4 oxidation rates using incubated soil slurries originating from the same experimental plots. The dataset was supplemented with depth differentiated monitoring of redox potential, temperature, moisture content and soil solution parameters (DOC, Fe2+, Mn3+, mineral N and dissolved CH4). Peaks in dissolved CH4 manifested at 5 and 12.5cm depth, with much lower and equal levels at 25, 50 and 80cm depth. Also depth distributions of dissolved Fe and Mn followed this pattern, indicating that methanogenic activity was primarily confounded to the topsoil. Seasonal CH4 emissions were about halved by AWD compared to CF management. After a fast decline of in situ oxidation within the AWD treatment at the beginning of the season, CH4 oxidation percentages in CF and AWD increased until the booting stage (67DAS), reaching peak values of 83% and 69% of produced CH4, respectively. CH4 oxidation thereafter gradually declined to nearly 50% in both treatments after the final drainage (103 DAS). Seasonal trends of potential CH4 oxidation rates were alike between CF and AWD fields, except at 52 DAS, when 5cm and 25cm depth CH4 oxidation capacities from CF soil slurries exceeded those under AWD. This could firstly be explained by higher observed soil solution CH4 concentrations of CF paddies, while in mid-season dissolved CH4 was nearly absent in case of AWD. We hypothesize that a larger methanotrophic biomass was present in the CF fields, explaining the higher CH4 oxidation potential, but this requires verification by qPCR. In addition, higher NH4+ concentrations were measured under CF, which as well might have favored methanotrophic activity. Ongoing analysis of stable isotope ratios (12C/13C) in both atmospheric and subsurface gas samples will complement the specific inhibitor-based CH4 oxidation estimates. Currently, the dataset assembled during this field experiment will be used to fine-tune the biogeochemical model 'rice DNDC' (DeNitrification-DeComposition) with specific attention to DNDC's capability to simulate CH4 oxidation and depth profiles . The model revision will take into account the seasonal and depth differentiated behavior of parameters relevant to the processes of CH4 oxidation, production and emission, and hence contribute to a more precise estimation of methane emissions under AIM.

World-wide increase in tropospheric methane, 1978-1983

NASA Technical Reports Server (NTRS)

Blake, D. R.; Rowland, F. S.

1986-01-01

Techniques used to assess methane concentration in the troposphere are described, and data obtained during the period from 1978 to 1983 are presented in detail. Tropospheric methane concentrations in remote locations averaged a yearly world-wide increase of 0.018 + or - 0.002 parts per million by volume (ppmv). Average world-wide tropospheric concentration of methane in dry air was 1.625 ppmv at the end of 1983 measured against an NBS standard certified as 0.97 ppmv. Contributing to this steady increase in methane concentration are increases in the source strengths from cattle and rice fields, which in turn result from CO, CH4 and HO coupling. Among the physical and chemical effects is an increase in greenhouse warming of about 0.04 C per decade.

Influence of rumen protozoa on methane emission in ruminants: a meta-analysis approach.

PubMed

Guyader, J; Eugène, M; Nozière, P; Morgavi, D P; Doreau, M; Martin, C

2014-11-01

A meta-analysis was conducted to evaluate the effects of protozoa concentration on methane emission from ruminants. A database was built from 59 publications reporting data from 76 in vivo experiments. The experiments included in the database recorded methane production and rumen protozoa concentration measured on the same groups of animals. Quantitative data such as diet chemical composition, rumen fermentation and microbial parameters, and qualitative information such as methane mitigation strategies were also collected. In the database, 31% of the experiments reported a concomitant reduction of both protozoa concentration and methane emission (g/kg dry matter intake). Nearly all of these experiments tested lipids as methane mitigation strategies. By contrast, 21% of the experiments reported a variation in methane emission without changes in protozoa numbers, indicating that methanogenesis is also regulated by other mechanisms not involving protozoa. Experiments that used chemical compounds as an antimethanogenic treatment belonged to this group. The relationship between methane emission and protozoa concentration was studied with a variance-covariance model, with experiment as a fixed effect. The experiments included in the analysis had a within-experiment variation of protozoa concentration higher than 5.3 log10 cells/ml corresponding to the average s.e.m. of the database for this variable. To detect potential interfering factors for the relationship, the influence of several qualitative and quantitative secondary factors was tested. This meta-analysis showed a significant linear relationship between methane emission and protozoa concentration: methane (g/kg dry matter intake)=-30.7+8.14×protozoa (log10 cells/ml) with 28 experiments (91 treatments), residual mean square error=1.94 and adjusted R 2=0.90. The proportion of butyrate in the rumen positively influenced the least square means of this relationship.

Monitoring concentration and isotopic composition of methane in groundwater in the Utica Shale hydraulic fracturing region of Ohio.

PubMed

Claire Botner, E; Townsend-Small, Amy; Nash, David B; Xu, Xiaomei; Schimmelmann, Arndt; Miller, Joshua H

2018-05-03

Degradation of groundwater quality is a primary public concern in rural hydraulic fracturing areas. Previous studies have shown that natural gas methane (CH 4 ) is present in groundwater near shale gas wells in the Marcellus Shale of Pennsylvania, but did not have pre-drilling baseline measurements. Here, we present the results of a free public water testing program in the Utica Shale of Ohio, where we measured CH 4 concentration, CH 4 stable isotopic composition, and pH and conductivity along temporal and spatial gradients of hydraulic fracturing activity. Dissolved CH 4 ranged from 0.2 μg/L to 25 mg/L, and stable isotopic measurements indicated a predominantly biogenic carbonate reduction CH 4 source. Radiocarbon dating of CH 4 in combination with stable isotopic analysis of CH 4 in three samples indicated that fossil C substrates are the source of CH 4 in groundwater, with one 14 C date indicative of modern biogenic carbonate reduction. We found no relationship between CH 4 concentration or source in groundwater and proximity to active gas well sites. No significant changes in CH 4 concentration, CH 4 isotopic composition, pH, or conductivity in water wells were observed during the study period. These data indicate that high levels of biogenic CH 4 can be present in groundwater wells independent of hydraulic fracturing activity and affirm the need for isotopic or other fingerprinting techniques for CH 4 source identification. Continued monitoring of private drinking water wells is critical to ensure that groundwater quality is not altered as hydraulic fracturing activity continues in the region. Graphical abstract A shale gas well in rural Appalachian Ohio. Photo credit: Claire Botner.

Expansion of Phragmites australis alters methane dynamics and methanogen, methanotroph, and sulfate reducing bacteria communities in tidal marsh in Korea

NASA Astrophysics Data System (ADS)

Kim, J.; Lee, J.; Kim, H.; Gauhar, M.; Kang, H.

2016-12-01

Plant invasion is known to change substantially methane dynamics in tidal marshes. However, the exact mechanisms related to methane dynamics change due to plant invasion have not been fully understood. In Suncheon Bay, South Korea, Phragmites australis has invaded the habitat of native species, Suaeda japonica, and becomes dominant vegetation in this area. We measured methane fluxes, soil biogeochemistry, and microbial communities from both vegetation sites throughout a growing season and conducted a chronosequence analysis in order to illustrate the effect of plant invasion on methane dynamics and microbial communities. For analyzing microbial communities, we collected 1m intact soil cores and conducted functional gene-targeted real-time qPCR, T-RFLP, and PLFA. P. australis invasion significantly increased methane emission in a summer season, accompanied by greater dissolved organic carbon and soil water content. Methanogen, methanotroph, and sulfate reducing bacterial communities were gradually changed along with the invasion periods. In particular, abundances ratio of mcrA/pmoA and mcrA/dsrA had a positive correlation with methane emission, which indicates that P. australis invasion reduces methane oxidation by methanotroph, and competitive inhibition between methanogen and sulfate reducing bacteria. In conclusion, P. australis invasion on S. japonica significantly increased methane emission in tidal marsh by altering the microbial communities in a way that C decomposition would be dominated by methanogenesis.

Carbon Isotope Biogeochemistry of Methane from Anoxic Sediments

NASA Technical Reports Server (NTRS)

Blair, Neal E.

1993-01-01

The isotopic composition of naturally occurring methane was used to constrain the tropospheric budget of that radiatively active gas. Numerous studies have shown that the isotopic composition is not constant, even for a specific source, and may vary temporally and spatially. The objective was to develop a process-level model that reproduced the seasonal variations in the C-13/C-12 composition of methane observed at the coastal site, Cape Lookout Bight, NC. Details of the mass balance are provided. Experiments and models designed to determine what factors incluence C-13/C-12 ratio of dissolved CO2 are reported. All the factors described were combined in a model that faithfully reproduces the seasonal C-13/C-12 variations observed at Cape Lookout. The model is described.

Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event.

PubMed

Konhauser, Kurt O; Pecoits, Ernesto; Lalonde, Stefan V; Papineau, Dominic; Nisbet, Euan G; Barley, Mark E; Arndt, Nicholas T; Zahnle, Kevin; Kamber, Balz S

2009-04-09

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse, but this explanation is difficult to reconcile with the rock record. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached approximately 400 nM throughout much of the Archaean eon, but dropped below approximately 200 nM by 2.5 Gyr ago and to modern day values ( approximately 9 nM) by approximately 550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.

Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part III - Sulfate- and methane- based microbial processes

NASA Astrophysics Data System (ADS)

Pastor, L.; Toffin, L.; Decker, C.; Olu, K.; Cathalot, C.; Lesongeur, F.; Caprais, J.-C.; Bessette, S.; Brandily, C.; Taillefert, M.; Rabouille, C.

2017-08-01

Geochemical profiles (SO42-, H2S, CH4, δ13CH4) and phylogenetic diversity of Archaea and Bacteria from two oceanographic cruises dedicated to the lobes sediments of the Congo deep-sea fan are presented in this paper. In this area, organic-rich turbidites reach 5000 m and allow the establishment of patchy cold-seep-like habitats including microbial mats, reduced sediments, and vesicomyid bivalves assemblages. These bivalves live in endosymbiosis with sulfur-oxidizing bacteria and use sulfides to perform chemosynthesis. In these habitats, unlike classical abyssal sediments, anoxic processes are dominant. Total oxygen uptake fluxes and methane fluxes measured with benthic chambers are in the same range as those of active cold-seep environments, and oxygen is mainly used for reoxidation of reduced compounds, especially in bacterial mats and reduced sediments. High concentrations of methane and sulfate co-exist in the upper 20 cm of sediments, and evidence indicates that sulfate-reducing microorganisms and methanogens co-occur in the shallow layers of these sediments. Simultaneously, anaerobic oxidation of methane (AOM) with sulfate as the electron acceptor is evidenced by the presence of ANMEs (ANaerobic MEthanotroph). Dissolved sulfide produced through the reduction of sulfate is reoxidized through several pathways depending on the habitat. These pathways include vesicomyid bivalves uptake (adults or juveniles in the bacterial mats habitats), reoxidation by oxygen or iron phases within the reduced sediment, or reoxidation by microbial mats. Sulfide uptake rates by vesicomyids measured in sulfide-rich sea water (90±18 mmol S m-2 d-1) were similar to sulfide production rates obtained by modelling the sulfate profile with different bioirrigation constants, highlighting the major control of vesicomyids on sulfur cycle in their habitats.

Dynamics of submarine groundwater discharge and associated fluxes of dissolved nutrients, carbon, and trace gases to the coastal zone (Okatee River estuary, South Carolina)

USGS Publications Warehouse

Porubsky, W.P.; Weston, N.B.; Moore, W.S.; Ruppel, C.; Joye, S.B.

2014-01-01

Multiple techniques, including thermal infrared aerial remote sensing, geophysical and geological data, geochemical characterization and radium isotopes, were used to evaluate the role of groundwater as a source of dissolved nutrients, carbon, and trace gases to the Okatee River estuary, South Carolina. Thermal infrared aerial remote sensing surveys illustrated the presence of multiple submarine groundwater discharge sites in Okatee headwaters. Significant relationships were observed between groundwater geochemical constituents and 226Ra activity in groundwater with higher 226Ra activity correlated to higher concentrations of organics, dissolved inorganic carbon, nutrients, and trace gases to the Okatee system. A system-level radium mass balance confirmed a substantial submarine groundwater discharge contribution of these constituents to the Okatee River. Diffusive benthic flux measurements and potential denitrification rate assays tracked the fate of constituents in creek bank sediments. Diffusive benthic fluxes were substantially lower than calculated radium-based submarine groundwater discharge inputs, showing that advection of groundwater-derived nutrients dominated fluxes in the system. While a considerable potential for denitrification in tidal creek bank sediments was noted, in situ denitrification rates were nitrate-limited, making intertidal sediments an inefficient nitrogen sink in this system. Groundwater geochemical data indicated significant differences in groundwater chemical composition and radium activity ratios between the eastern and western sides of the river; these likely arose from the distinct hydrological regimes observed in each area. Groundwater from the western side of the Okatee headwaters was characterized by higher concentrations of dissolved organic and inorganic carbon, dissolved organic nitrogen, inorganic nutrients and reduced metabolites and trace gases, i.e. methane and nitrous oxide, than groundwater from the eastern side. Differences in microbial sulfate reduction, organic matter supply, and/or groundwater residence time likely contributed to this pattern. The contrasting features of the east and west sub-marsh zones highlight the need for multiple techniques for characterization of submarine groundwater discharge sources and the impact of biogeochemical processes on the delivery of nutrients and carbon to coastal areas via submarine groundwater discharge.

The Microbial Contribution to Shale Gas: How Much Have They Done, and How Fast Can They Do It?

NASA Astrophysics Data System (ADS)

Martini, A. M.

2014-12-01

Over the past few decades, the importance of microbial contributions to our natural gas supply has been widely recognized, even leading to efforts to enhance the rate of methanogenesis in reservoirs whether the substrate is oil, coal or the organic matter in shale. The identification of biogenic gas was first established with gas compositional and isotopic data. More recently, molecular genomic data has been applied, giving us a glimpse into bacterial and archaeal communities in the subsurface, both in reservoirs where the microbial community was expected by the geochemical signature, but also in flowback waters from formations where there was no indication of anything other than thermogenic gas. With these microbes, it is not so much a question of "build it and they will come", but more that the community lies in wait for conditions to improve and allow them to flourish. Conditions for microbial methanogenesis are well constrained: temperatures up to ~80oC, low sulfate concentration, and chloride concentrations under 2M. However, these are rather expansive boundaries and within each range there lies constant turnover in population density as well specific microbial abundances. In addition, the rates at which these microbes are able convert complex organic matter into methane depend upon environmental conditions. Confounding our evaluation of these subsurface communities is the effect that production incurs. Over the past two decades, wells under production in the Antrim Shale have exhibited changes in the geochemistry of formation fluids, most notably a drop in dissolved inorganic carbon of ~10mM. Gas chemistry has also shifted, with increasing concentrations of carbon dioxide that have also become more enriched in 13C, while the co-produced methane has become more depleted in 13C over the 20 years that these few wells have been monitored. Perhaps not unsurprisingly, the microbial community has also shifted with the water's chemical evolution. Most intriguing is the correlation of the deuterium in the water to the methane, where CO2-reduction seems to remain the dominant methanogenic pathway and the gas composition is responding to changes in the water source. This may signify a relatively high proportion of recently produced methane in the system.

Freezing and hungry? Hydrocarbon degrading microbial communities in Barents Sea sediments around Svalbard

NASA Astrophysics Data System (ADS)

Krueger, Martin; Straaten, Nontje

2017-04-01

The Polar Regions are characterised by varying temperatures and changing ice coverage, so most of the primary production take place in the warmer season. Consequently, sedimentation rates and nutrient input are low. The diversity and metabolic potentials of the microbial communities inhabiting these sediments in the Northern Barents Sea are largely unknown. Recent reports on natural methane seeps as well as the increase in hydrocarbon exploration activities in the Arctic initiated our studies on the potential of indigenous microbial communities to degrade methane and higher hydrocarbons under in situ pressure and temperature conditions. Furthermore, the subseafloor geochemistry in these areas was studied, together with important microbial groups, like methanotrophs, methanogens, metal and sulfate reducers, which may drive seafloor ecosystems in the Northern Barents Sea. Sediment samples were collected in several areas around Svalbard in the years 2013-2016 ranging from shallow (200m) areas on the Svalbard shelf to deep sea areas on the eastern Yermak Plateau (3200m water depths). Shelf sediments showed the highest organic carbon content which decreased with increasing depths. Iron and manganese as potential electron acceptors were found in the porewater especially in the top 50 cm of the cores, while sulfate was always present in substantial amounts in porewater samples down to the end of the up to two metre long cores. Concentrations of dissolved methane and carbon dioxide were low. The potential of the indigenous microorganisms to degrade methane and higher hydrocarbons as well as different oils under in situ temperatures and pressures was widespread in surface sediments. Degradation rates were higher under aerobic than under anaerobic conditions, and decreased with increasing sediment as well as water depths. Similar pattern were found for other metabolic processes, including sulfate, Fe and Mn reduction as well as carbon dioxide and methane production rates. Ongoing molecular biological analyses of original sediments and enrichment cultures indicate the presence of diverse and varying microbial communities.

Geological Characteristics of Active Methane Expulsion In Accretionary Prism Kaoping Slope Off SW Taiwan

NASA Astrophysics Data System (ADS)

Huang, C.; Chien, C.; Yang, T. F.; Lin, S.

2005-12-01

The Kaoping Slope off SW Taiwan represents the syn-collision accretionary prism characterized by active NW-trending folding - thrusting structures and high sedimentation rate favoring the formation of gas hydrate. For an assessment of gas hydrate potential in the Kaoping Slope off SW Taiwan, sedimentology, paleontology and geochemistry in box cores and piston cores were studied. BSRs are commonly found in seismic profiles in 400-600 m below seafloor of water depth 2500-1000 m. Active expulsions of methane were found along active thrust faults where sulfate/methane interface could be as shallow as 30 cm and the methane concentration of dissolved gases in bottom water and in pore-space of drilled core samples could be three-four order higher than the normal marine environments. Occurrences of authigenic carbonate and elongated pyrite tubes are correlated with shallow SMI depth and high methane content in bottom water and pore-space of sediment cores. Authigenic carbonates were found in seafloor surface and in 20-25 meters below seafloor. The authigenic carbonate nodules are characterized by irregular shape, whitish color, no visible microfossil, containing native sulfur, pyrites, gypsum, small open spaces, and very depleted carbon isotope (-54 ~ -43 per mil PDB). Tiny native sulfur and gypsum crystals were commonly found either on surface of foraminiferal tests and elongated pyrite tubes or in the authigenic carbonate nodules. Morphological measurements of elongated pyrite tubes show that they could represent pseudomorphs after three types of Pogonophora tube worm. Foraminifers are commonly filled by rhomboidal pyrites or cemented by pyrite crystals. Normal marine benthic foraminifers predominated by calcareous tests of slope fauna are associated with authigenic carbonate nodules in the study area, suggesting no major geochemistry effect on distribution of benthic foraminifers. Integrating sedimentology, paleontology and geochemistry characters, there could be high potential to have gas hydrate in the accretionary prism off SW Taiwan.

Geochemical and geological factors controlling the spatial distribution of sulfate-methane transition zone in the Ría de Vigo (NW Spain)

NASA Astrophysics Data System (ADS)

Martínez-Carreño, N.; García-Gil, S.; Cartelle, V.; de Blas, E.; Ramírez-Pérez, A. M.; Insua, T. L.

2017-05-01

High-resolution seismic profiles, gravity core analysis and radiocarbon data have been used to identify the factors behind the methane production and free gas accumulation in the Ría de Vigo. Lithological and geochemical parameters (sulfate and methane concentration) from seventeen gravity cores were analyzed to characterize the sediment of the ria. The distribution of methane-charged sediments is mainly controlled by the quantity and quality of organic matter. Geochemical analyses reveal minimum methane concentrations ranging between 1 μM and 1 mM in sediments located outside the acoustic gas field, while gas-bearing sediments, show methane concentrations up to 5 mM. A shallowing of the sulfate-methane transition zone (SMTZ) is observed from the outer to the inner area of the ria. The presence of methane in the sulfate reduction zone (SRZ) likely to reflect the existence of methylotropic methanogenesis and/or migration processes of deeper methane gas in the sediments of the Ría de Vigo. The presence of an 'anomalous' high-sulfate concentration layer below the SMTZ in the inner and middle area of the ria, is attributed to the intrusion of sulfate-rich waters from adjacent areas that could be transported laterally through more porous layers.

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.

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.

A comparison of methane emissions following rice paddies conversion to crab-fish farming wetlands in southeast China.

PubMed

Hu, Zhiqiang; Wu, Shuang; Ji, Cheng; Zou, Jianwen; Zhou, Quansuo; Liu, Shuwei

2016-01-01

Rice paddies and aquaculture wetlands are typical agricultural wetlands that constitute one of the important sources of atmospheric methane (CH4). Traditional transplanted rice paddies have been experiencing conversion to pond aquaculture wetlands for pursuing higher economic benefits over the past decades in southeast China. A parallel field experiment was carried out to compare CH4 emissions from a transplanted rice paddy and its converted crab-fish farming wetland in southeast China. Over the rice-growing season, CH4 fluxes averaged 1.86 mg m(-2) h(-1) from rice paddies, and 1.14 and 0.50 mg m(-2) h(-1) for the treatments with or without aquatic vegetation present in the crab-fish farming wetlands, respectively. When averaged across the treatments, seasonal CH4 emissions from crab-fish framing wetlands were 52% lower than those from rice paddies. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to soil/sediment dissolved organic carbon (DOC) content in crab-fish farming wetlands. Dependence of CH4 fluxes on DO or DOC was intensified by the aquatic vegetation presence. By extrapolating the present CH4 emission rate with the current rice paddy-converted aquaculture cultivation area, the seasonal CH4 emissions from inland aquaculture wetlands during the critical farming stage (20 June to 18 October) were estimated to be 33.6 Gg ha(-1) in southeast China in 2012. Rice paddies conversion to crab-fish farming wetlands might have reduced CH4 emissions by 22-54% in mainland China. Results of this study suggest that the conversion of transplanted rice paddies to crab-fish aquaculture wetlands for higher economic benefits would also lead to a lower ecosystem CH4 release rate.

Coupled hydrology and biogeochemistry of Paleocene–Eocene coal beds, northern Gulf of Mexico

USGS Publications Warehouse

McIntosh, Jennifer C.; Warwick, Peter D.; Martini, Anna M.; Osborn, Stephen G.

2010-01-01

Thirty-six formation waters, gas, and microbial samples were collected and analyzed from natural gas and oil wells producing from the Paleocene to Eocene Wilcox Group coal beds and adjacent sandstones in north-central Louisiana, USA, to investigate the role hydrology plays on the generation and distribution of microbial methane. Major ion chemistry and Cl−Br relations of Wilcox Group formation waters suggest mixing of freshwater with halite-derived brines. High alkalinities (up to 47.8 meq/L), no detectable SO4, and elevated δ13C values of dissolved inorganic carbon (up to 20.5‰ Vienna Peedee belemnite [VPDB]) and CO2 (up to 17.67‰ VPDB) in the Wilcox Group coals and adjacent sandstones indicate the dominance of microbial methanogenesis. The δ13C and δD values of CH4, and carbon isotope fractionation of CO2 and CH4, suggest CO2 reduction is the major methanogenic pathway. Geochemical indicators for methanogenesis drop off significantly at chloride concentrations above ∼1.7 mol/L, suggesting that high salinities inhibit microbial activity at depths greater than ∼1.6 km. Formation waters in the Wilcox Group contain up to 1.6% modern carbon (A14C) to at least 1690 m depth; the covariance of δD values of co-produced H2O and CH4 indicate that the microbial methane was generated in situ with these Late Pleistocene or younger waters. The most enriched carbon isotope values for dissolved inorganic carbon (DIC) and CO2, and highest alkalinities, were detected in Wilcox Group sandstone reservoirs that were CO2 flooded in the 1980s for enhanced oil recovery, leading to the intriguing hypothesis that CO2 sequestration may actually enhance methanogenesis in organic-rich formations.

Quantification of the methane concentration using anaerobic oxidation of methane coupled to extracellular electron transfer.

PubMed

Gao, Yaohuan; Ryu, Hodon; Rittmann, Bruce E; Hussain, Abid; Lee, Hyung-Sool

2017-10-01

A biofilm anode acclimated with growth media containing acetate, then acetate+methane, and finally methane alone produced electrical current in a microbial electrochemical cell (MxC) fed with methane as the sole electron donor. Geobacter was the dominant genus for the bacterial domain (93%) in the biofilm anode, while methanogens (Methanocorpusculum labreanum and Methanosaeta concilii) accounted for 82% of the total archaeal clones in the biofilm. Fluorescence in situ hybridization (FISH) imaging clearly showed a biofilm of mixed bacteria and archaea, suggesting a syntrophic interaction between them for performing anaerobic oxidation of methane (AOM) in the biofilm anode. Measured cumulative coulombs were linearly correlated to the methane-gas concentration in the range of 10-99.97% (R 2 ≥0.99) when the measurement was sustained for at least 50min Thus, cumulative coulombs over 50min could be used to quantify the methane concentration in gas samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of chemical, thermobaric and thermochemical pre-treatment on anaerobic digestion of high-fat cattle slaughterhouse waste.

PubMed

Harris, Peter W; Schmidt, Thomas; McCabe, Bernadette K

2017-11-01

This work aimed to enhance the anaerobic digestion of fat-rich dissolved air flotation (DAF) sludge through chemical, thermobaric, and thermochemical pre-treatment methods. Soluble chemical oxygen demand was enhanced from 16.3% in the control to 20.84% (thermobaric), 40.82% (chemical), and 50.7% (thermochemical). Pre-treatment altered volatile fatty acid concentration by -64% (thermobaric), 127% (chemical) and 228% (thermochemical). Early inhibition was reduced by 20% in the thermochemical group, and 100% in the thermobaric group. Specific methane production was enhanced by 3.28% (chemical), 8.32% (thermobaric), and 8.49% (thermochemical) as a result of pre-treatment. Under batch digestion, thermobaric pre-treatment demonstrated the greatest improvement in methane yield with respect to degree of pre-treatment applied. Thermobaric pre-treatment was also the most viable for implementation at slaughterhouses, with potential for heat-exchange to reduce pre-treatment cost. Further investigation into long-term impact of pre-treatments in semi-continuous digestion experiments will provide additional evaluation of appropriate pre-treatment options for high-fat slaughterhouse wastewater. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

A physical catalyst for the electrolysis of nitrogen to ammonia

PubMed Central

Johnson, Daniel; Peng, Rui; Hensley, Dale K.; Bonnesen, Peter V.; Yang, Fengchang; Zhang, Fei; Tschaplinski, Timothy J.; Engle, Nancy L.; Wu, Zili; Meyer, Harry M.; Sumpter, Bobby G.

2018-01-01

Ammonia synthesis consumes 3 to 5% of the world’s natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at −1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 μg hour−1 cm−2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N2 concentration within the Stern layer. The energy efficiency of the reaction is estimated to be 5.25% at the current FE of 11.56%. PMID:29719860

Fugitive methane emissions from natural, urban, agricultural, and energy-production landscapes of eastern Australia

NASA Astrophysics Data System (ADS)

Kelly, Bryce F. J.; Iverach, Charlotte P.; Lowry, Dave; Fisher, Rebecca E.; France, James L.; Nisbet, Euan G.

2015-04-01

Modern cavity ringdown spectroscopy systems (CRDS) enable the continuous measurement of methane concentration. This allows for improved quantification of greenhouse gas emissions associated with various natural and human landscapes. We present a subset of over 4000 km of continuous methane surveying along the east coast of Australia, made using a Picarro G2301 CRDS, deployed in a utility vehicle with an air inlet above the roof at 2.2 mAGL. Measurements were made every 5 seconds to a precision of <0.5 ppb for CH4. These surveys were undertaken during dry daytime hours and all measurements were moisture corrected. We compare the concentration of methane in the near surface atmosphere adjacent to open-cut coal mines, unconventional gas developments (coal seam gas; CSG), and leaks detected in cities and country towns. In areas of dryland crops the median methane concentration was 1.78 ppm, while in the irrigation districts located on vertisol soils the concentration was as low as 1.76 ppm, which may indicate that these soils are a sink for methane. In the Hunter Valley, New South Wales, open-cut coal mining district we mapped a continuous 50 km interval where the concentration of methane exceeded 1.80 ppm. The median concentration in this interval was 2.02 ppm. Peak readings were beyond the range of the reliable measurement (in excess of 3.00 ppm). This extended plume is an amalgamation of plumes from 17 major pits 1 to 10 km in length. Adjacent to CSG developments in the Surat Basin, southeast Queensland, only small anomalies were detected near the well-heads. Throughout the vast majority of the gas fields the concentration of methane was below 1.80 ppm. The largest source of fugitive methane associated with CSG was off-gassing methane from the co-produced water holding ponds. At one location the down wind plume had a cross section of approximately 1 km where the concentration of methane was above 1.80 ppm. The median concentration within this section was 1.82 ppm, with a peak reading of 2.11 ppm. The ambient air methane concentration was always higher in urban environments compared to the surrounding countryside. Along one major road in Sydney we mapped an interval that extended for 6 km where the concentration was greater than 1.80 ppm. The median concentration in this interval was 1.90 ppm, with a peak reading of 1.97 ppm. This high reading in an urban setting is most likely due to leaks from the domestic gas distribution system. Methane leaks were detected in all country towns. Our measurements show that at the point of resource extraction the methane emission footprint of CSG is smaller than that of open-cut coal mining. However, leaking gas from urban centers must be added to the fugitive emissions of CSG to calculate the total fugitive emission footprint of CSG, which may therefore not be as low as claimed in the national greenhouse gas accounts. Our results highlight the need for additional continuous monitoring of methane emissions from all sectors, and for the full life-cycle of energy resources to be considered.

Gas hydrate and spatial venting variations in the continental margin offshore Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Lin, S.; Lim, Y.; Hsieh, W.; Yang, T.; Wang, Y.

2006-12-01

Strong BSR, high methane contents and rapid sulfate reduction were found in the continental margin sediments offshore southwestern Taiwan. In order to identify the venting phenomena and its relationship with gas hydrate, this research investigate sea floor vent features using WHOI?|s Towcam system as well as piston core in the study region. A total of 10 dives were conducted on board the r/v OR-1. Pore water sulfate, dissolved sulfide, methane, chloride, del O18 ratio, sediment organic carbon, carbonate content and carbonate del C13 ratio, pyrite-S were measured Large spatial variations were found based on pictures obtained from Towcam system and piston cores. Active venting features include bacteria mat, live dense bivalve patches, gas plume, temperature and salinity fluctuations, rapid sulfate reduction and high concentrations of methane in sediments. In addition, vent chimney, pockmark and large authigenic carbonate buildup were also observed in the active venting area. In contrast, in some areas without active venting features, scatter dead chimney, semi- buried carbonate structures, and dead bivalves were found. Total sulfate depletion was found at depth as shallow as 1 meter below sediment water interface in area near active vent whereas almost no sulfate depletion was observed in areas without any vent feature. Stages of carbonate build up existed, with initial phase dominated by small tube, chimney, and later with massive carbonate structures protruding the sea floor. The appearances of massive carbonate buildup structures seemed to indicate the end stage of gas hydrate venting phenomena.

Coalbed methane produced water in China: status and environmental issues.

PubMed

Meng, Yanjun; Tang, Dazhen; Xu, Hao; Li, Yong; Gao, Lijun

2014-01-01

As one of the unconventional natural gas family members, coalbed methane (CBM) receives great attention throughout the world. The major associated problem of CBM production is the management of produced water. In the USA, Canada, and Australia, much research has been done on the effects and management of coalbed methane produced water (CMPW). However, in China, the environmental effects of CMPW were overlooked. The quantity and the quality of CMPW both vary enormously between coal basins or stratigraphic units in China. The unit produced water volume of CBM wells in China ranges from 10 to 271,280 L/well/day, and the concentration of total dissolved solids (TDS) ranges from 691 to 93,898 mg/L. Most pH values of CMPW are more than 7.0, showing the alkaline feature, and the Na-HCO3 and Na-HCO3-Cl are typical types of CMPW in China. Treatment and utilization of CMPW in China lag far behind the USA and Australia, and CMPW is mainly managed by surface impoundments and evaporation. Currently, the core environmental issues associated with CMPW in China are that the potential environmental problems of CMPW have not been given enough attention, and relevant regulations as well as environmental impact assessment (EIA) guidelines for CMPW are still lacking. Other potential issues in China includes (1) water quality monitoring issues for CMPW with special components in special areas, (2) groundwater level decline issues associated with the dewatering process, and (3) potential environmental issues of groundwater pollution associated with hydraulic fracturing.

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.

Carbon isotope fractionation during microbial methane oxidation

NASA Astrophysics Data System (ADS)

Barker, James F.; Fritz, Peter

1981-09-01

Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

Ebullitive methane emissions from oxygenated wetland streams

USGS Publications Warehouse

Crawford, John T.; Stanley, Emily H.; Spawn, Seth A.; Finlay, Jacques C.; Striegl, Robert G.

2014-01-01

Stream and river carbon dioxide emissions are an important component of the global carbon cycle. Methane emissions from streams could also contribute to regional or global greenhouse gas cycling, but there are relatively few data regarding stream and river methane emissions. Furthermore, the available data do not typically include the ebullitive (bubble-mediated) pathway, instead focusing on emission of dissolved methane by diffusion or convection. Here, we show the importance of ebullitive methane emissions from small streams in the regional greenhouse gas balance of a lake and wetland-dominated landscape in temperate North America and identify the origin of the methane emitted from these well-oxygenated streams. Stream methane flux densities from this landscape tended to exceed those of nearby wetland diffusive fluxes as well as average global wetland ebullitive fluxes. Total stream ebullitive methane flux at the regional scale (103 Mg C yr−1; over 6400 km2) was of the same magnitude as diffusive methane flux previously documented at the same scale. Organic-rich stream sediments had the highest rates of bubble release and higher enrichment of methane in bubbles, but glacial sand sediments also exhibited high bubble emissions relative to other studied environments. Our results from a database of groundwater chemistry support the hypothesis that methane in bubbles is produced in anoxic near-stream sediment porewaters, and not in deeper, oxygenated groundwaters. Methane interacts with other key elemental cycles such as nitrogen, oxygen, and sulfur, which has implications for ecosystem changes such as drought and increased nutrient loading. Our results support the contention that streams, particularly those draining wetland landscapes of the northern hemisphere, are an important component of the global methane cycle.

Silicate Weathering and Pervasive Authigenic Carbonate Precipitation Coupled to Methanogenesis in the Krishna-Godavari Basin, Offshore India

NASA Astrophysics Data System (ADS)

Solomon, E. A.; Spivack, A. J.; Kastner, M.; Torres, M. E.

2014-12-01

The cycling of methane in marine sediments has been actively studied for the past several decades, but less attention has been paid to the cycling of CO2 produced in methanogenic sediments. The National Gas Hydrate Program Expedition 01 cored 10 sites with the Joides Resolution drillship in the Krishna-Godavari basin, located on the southeastern margin of India. A comprehensive suite of pore water solute concentrations and isotope ratios were analyzed to investigate the distribution and concentration of gas hydrate along the margin, in situ diagenetic and metabolic reactions, fluid migration and flow pathways, and fluid and gas sources. This represents one of the most comprehensive pore water geochemical datasets collected at a continental margin to date, and provides the necessary tracers to better understand the processes and sinks controlling CO2 in margin sediments. Our results show that the CO2 produced through net microbial methanogenesis is effectively neutralized through silicate weathering throughout the sediment column drilled at each site (~100-300 m), buffering the pH of the sedimentary pore water and generating excess alkalinity through the same reaction sequence as continental silicate weathering. Most of the excess alkalinity produced through silicate weathering in the Krishna-Godavari basin is sequestered in Ca- and Fe-carbonates as a result of ubiquitous calcium release from weathering detrital silicates and Fe-reduction within the methanogenic sediments. Formation of secondary hydrous silicates (e.g. smectite) related to incongruent primary silicate dissolution acts as a significant sink for pore water Mg, K, Li, Rb, and B. The consumption of methane through anaerobic oxidation of methane, sequestration of methane in gas hydrate, and sequestration of dissolved inorganic carbon in authigenic carbonates keeps methanogenesis as a thermodynamically feasible catabolic pathway. Our results combined with previous indications of silicate weathering in anoxic sediments in the Sea of Okhotsk, suggest that silicate weathering coupled to microbial methanogenesis should be occurring in continental margins worldwide, providing a net sink of atmospheric CO2 over geologic timescales.

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June and October 2012

USGS Publications Warehouse

Huffman, R.L.

2013-01-01

Previous investigations indicate that concentrations of chlorinated volatile organic compounds are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision for the site. This report presents groundwater geochemical and selected chlorinated volatile organic compound data collected at Operable Unit 1 by the U.S. Geological Survey during June and October 2012, in support of long-term monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers also were analyzed for chlorinated volatile organic compounds, as were all samples from the passive-diffusion sampling sites. In 2012, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all at 0.4 milligram per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2012, chlorinated volatile organic compound (CVOC) concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly higher or the same as concentrations measured in 2011. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2012 continued to be extremely variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in two of the four wells and in all piezometers. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2012 continued to vary spatially and temporarily, and also were very high. Additionally, CVOC concentrations measured in samplers deployed in access tubes were about two to four times less than those measured in the two samplers buried nearby, beneath the marsh stream. Total CVOC concentration, at what has been historically the most contaminated passive-diffusion sampler site (S-4), continued an increasing trend. For the intermediate aquifer in 2012, concentrations of reductive dechlorination byproducts ethane and ethene were consistent with those measured in previous years.

Aragonite precipitation induced by anaerobic oxidation of methane in shallow-water seeps, Tyrrhenian Sea, Italy

NASA Astrophysics Data System (ADS)

Wiedling, Johanna; Kuhfuß, Hanna; Lott, Christian; Böttcher, Michael E.; Lichtschlag, Anna; Wegener, Gunter; Deusner, Christian; Bach, Wolfgang; Weber, Miriam

2014-05-01

In the shallow-water organic-poor silicate sands off the West coast of Elba, Italy, we found aragonite precipitates within a radius of 10 cm to methane seeps in 20 - 40 cm sediment depth. The shallow seep site was mapped by SCUBA diving and in an area of 100 m2 nine gas emission spots were observed. The gas emission, containing 73 Vol. % methane, was measured to be 0.72 L m-2 d-1. Findings of anaerobic methane oxidizing archea (ANME 1, 2, 2a, 2b) and sulphate reducing bacteria (SRB) as well as in vitro rate measurements of anaerobic oxidation of methane (AOM) with a maximum of 67 ± 7 nmol CH4 cm-3 d-1 led to the hypothesis that carbonate precipitation is coupled to these microbial processes. Porewater analysis showed elevated concentrations of dissolved inorganic carbon (DIC) (up to 15.5 mmol L-1) and hydrogen sulfide (up to 6.6 mmol L-1). The presence of bicarbonate and the ambient temperature (14 - 25 ° C) facilitate the precipitation of needle-shaped aragonite. Oxygen isotope compositions of the mineral are consistent with the ambient temperatures and may indicate a recent diagenetic formation of this mineral. Although precipitation should not be preserved in these sandy permeable sediments, influenced by seasonality, wave action, and fluid flow, we found up to 10-50 cm3 irregular pieces of cemented sand grains, very often encrusting dead seagrass rhizomes. Commonly known carbonate structures, especially from the deep sea, are chimneys, mounds, hardgrounds and nodules. These structures are well known from seep and vent sites, usually showing the same range of stable carbon isotope fractionation as the escaping methane. The permeable sediment at the Elba site possibly allows the gas to frequently change its pathway to the sediment surface and thus precipitation can occure at several spots and more irregular than in the reported sites. Preservation of precipitates, however, requires sufficient authigenic aragonite to be formed before fluid dynamics changed the flow path. The Elba aragonites, showed a carbon isotope signature of -14.9o vs. VPDB, mirroring the isotopic signature of the pore-water DIC at this sediment depth. Similar δ13C-compositions of -15.3o were obtained for the discharging methane, giving room for discussion about the origin of the gas. We suppose that AOM is the main driver for aragonite precipitation in the permeable sands at the shallow-water seeps because of (1) very low organic carbon contents (0.5 mg/g) in the sediment, (2) 13C enrichment in the methane gas, (3) elevated DIC concentrations in the pore-water, and (4) AOM in vitro activity. Thus, aragonite precipitates of the seep site near Elba may represent a unique system to study ongoing abiogenic seep carbonate formation at shallow depth as a modern analogue for seep carbonates occurring in the geological record.

Shallow Gas Migration along Hydrocarbon Wells-An Unconsidered, Anthropogenic Source of Biogenic Methane in the North Sea.

PubMed

Vielstädte, Lisa; Haeckel, Matthias; Karstens, Jens; Linke, Peter; Schmidt, Mark; Steinle, Lea; Wallmann, Klaus

2017-09-05

Shallow gas migration along hydrocarbon wells constitutes a potential methane emission pathway that currently is not recognized in any regulatory framework or greenhouse gas inventory. Recently, the first methane emission measurements at three abandoned offshore wells in the Central North Sea (CNS) were conducted showing that considerable amounts of biogenic methane originating from shallow gas accumulations in the overburden of deep reservoirs were released by the boreholes. Here, we identify numerous wells poking through shallow gas pockets in 3-D seismic data of the CNS indicating that about one-third of the wells may leak, potentially releasing a total of 3-17 kt of methane per year into the North Sea. This poses a significant contribution to the North Sea methane budget. A large fraction of this gas (∼42%) may reach the atmosphere via direct bubble transport (0-2 kt yr -1 ) and via diffusive exchange of methane dissolving in the surface mixed layer (1-5 kt yr -1 ), as indicated by numerical modeling. In the North Sea and in other hydrocarbon-prolific provinces of the world shallow gas pockets are frequently observed in the sedimentary overburden and aggregate leakages along the numerous wells drilled in those areas may be significant.

Biological formation of ethane and propane in the deep marine subsurface.

PubMed

Hinrichs, Kai-Uwe; Hayes, John M; Bach, Wolfgang; Spivack, Arthur J; Hmelo, Laura R; Holm, Nils G; Johnson, Carl G; Sylva, Sean P

2006-10-03

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in (13)C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H(2). Production of C(2) and C(3) hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material.

Biological formation of ethane and propane in the deep marine subsurface

PubMed Central

Hinrichs, Kai-Uwe; Hayes, John M.; Bach, Wolfgang; Spivack, Arthur J.; Hmelo, Laura R.; Holm, Nils G.; Johnson, Carl G.; Sylva, Sean P.

2006-01-01

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in 13C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H2. Production of C2 and C3 hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material. PMID:16990430

Modeling Dissolved Organic Carbon (DOC) Dynamics in Flooded Wetlands

EPA Science Inventory

Wetlands play an important role in the global carbon cycle and are recognized for their considerable potential to sequester carbon. Wetlands contain the largest component (18-30%) of the terrestrial carbon pool and are responsible for about a quarter of the global methane emissi...

Geo- and Biogeochemical Processes in a Heliothermal Hypersaline Lake

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

Zachara, John M.; Moran, James J.; Resch, Charles T.

Water chemical variations were investigated over three annual hydrologic cycles in hypersaline, heliothermal, meromictic Hot Lake in north-central Washington State, USA. The lake, originally studied by Anderson (1958), contains diverse biota with dramatic zonation related to salinity and redox state. Water samples were collected at 10 cm depth intervals through the shallow lake (2.4 m) at a consistent location during 2012-2014, with comprehensive monitoring performed in 2013. Inorganic salt species, total dissolved solids (TDS), dissolved carbon forms (DOC, DIC), oxygen, sulfide, and methane were analyzed in lake water samples. Depth sonde measurements of pH and temperature were also performed tomore » track their seasonal variations. A bathymetric survey of the lake was conducted to enable lake water volume and solute inventory calculations. Sediment cores were collected at low water and analyzed by x-ray diffraction to investigate sediment mineralogy. The primary dissolved salt in Hot Lake water was Mg2+-SO42- while sediments were dominated by gypsum (CaSO4•2H2O). Lake water concentrations increased with depth to reach saturation with epsomite that was exposed at lake bottom. At maximum volume in spring, Hot Lake exhibited a relatively dilute mixolimnion containing phyto- and zooplankton; a lower saline metalimnion with stratified oxygenic and anoxygenic photosynthetic microbiologic communities; and a stable, hypersaline monimolimnion, separated from above layers by a chemocline, containing high levels of sulfide and methane. The thickness of the mixolimnion regulates a heliothermal effect which creates temperatures in excess of 60 oC in the underlying metalimnion and monimolimnion. The mixolimnion was dynamic and actively mixed. It displayed large pH variations, in-situ calcium carbonate precipitation, and large evaporative volume losses. The depletion of this ephemeral layer by fall allowed deeper mixing into the volume-stable lower mixolimnion, more rapid heat exchange, and lower winter lake temperatures. Solubility calculations indicated seasonal biogenic and thermogenic aragonite precipitation in the upper and lower mixolimnion, but the absence of calcareous sediments at depth suggested dissolution and recycling during winter months. Carbon concentrations were high in Hot Lake (e.g., 0 to 450 mg/L for both DOC and DIC) and increased with depth. DIC concentrations were variable and influenced by calcium carbonate precipitation, but DOC concentrations remained constant except in the monimolimnion where mass loss by anaerobic microbial processes was implied. Biogenic reduced solutes originating in monimolimnion (H2S and CH4) appeared to be biologically oxidized in the metalimnion as they were not observed in more shallow lake waters. Multi-year solute inventory calculations indicated that Hot Lake is a stable, albeit seasonally and annually dynamic feature, with inorganic solutes cycled between lake waters and sediments depending on annual recharge, temperature, and lake water dilution state. Hot Lake with its extreme geochemical and thermal regime functions as analogue of early earth and extraterrestrial life environments.« less

Modelling geochemical and microbial consumption of dissolved oxygen after backfilling a high level radiactive waste repository.

PubMed

Yang, Changbing; Samper, Javier; Molinero, Jorge; Bonilla, Mercedes

2007-08-15

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste (HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived from calibration of the REX in situ experiment carried out at the Aspö underground laboratory. The role of geochemical and microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.

Iron-Coupled Anaerobic Oxidation of Methane Performed by a Mixed Bacterial-Archaeal Community Based on Poorly Reactive Minerals.

PubMed

Bar-Or, Itay; Elvert, Marcus; Eckert, Werner; Kushmaro, Ariel; Vigderovich, Hanni; Zhu, Qingzeng; Ben-Dov, Eitan; Sivan, Orit

2017-11-07

Anaerobic oxidation of methane (AOM) was shown to reduce methane emissions by over 50% in freshwater systems, its main natural contributor to the atmosphere. In these environments iron oxides can become main agents for AOM, but the underlying mechanism for this process has remained enigmatic. By conducting anoxic slurry incubations with lake sediments amended with 13 C-labeled methane and naturally abundant iron oxides the process was evidenced by significant 13 C-enrichment of the dissolved inorganic carbon pool and most pronounced when poorly reactive iron minerals such as magnetite and hematite were applied. Methane incorporation into biomass was apparent by strong uptake of 13 C into fatty acids indicative of methanotrophic bacteria, associated with increasing copy numbers of the functional methane monooxygenase pmoA gene. Archaea were not directly involved in full methane oxidation, but their crucial participation, likely being mediators in electron transfer, was indicated by specific inhibition of their activity that fully stopped iron-coupled AOM. By contrast, inhibition of sulfur cycling increased 13 C-methane turnover, pointing to sulfur species involvement in a competing process. Our findings suggest that the mechanism of iron-coupled AOM is accomplished by a complex microbe-mineral reaction network, being likely representative of many similar but hidden interactions sustaining life under highly reducing low energy conditions.

High Concentration of Methane and Magnificent gas Plumes Over gas Hydrate Field in the Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Ishida, Y.; Matsumoto, R.; Hiruta, A.; Aoyama, C.; Tomaru, H.; Hiromatsu, M.

2005-12-01

Gas hydrates and prominent pockmarks have been observed on the Umitaka Spur in the eastern margin of Japan Sea, at the depth of about 900 m.Magnificent methane plumes, 550 to 600 m high, were detected by echo sounder for fish school, and massive gas hydrates were recovered by piston coring during the UT04 cruise of R/V Umitaka-maru (2004). The seawater over this area was collected by CTD and the samples of interstitial waters were extracted from sediment cores by hydraulic squeezer. The ratio of methane to ethane concentration (C1/C2) and the isotopic (δ 13C) composition of methane in the plume sites are less than 103 and from -40 to -50 (‰ PDB) respectively, suggesting that the origin of such gases are mostly thermogenic, whereas the gases in the sediments away from plumes are mostly microbial. The seawater samples demonstrated anomalously high concentration of methane over the plume sites. Maximum concentration is 160nmol/L above the methane plume site. The methane concentration values of most samples ranged from 4 to 6nmol/L. When it compared with the Nankai Trough (1 to 4nmol/L), even the base level methane is quite high. Seawater samples collected at the depth of 200 m exhibit sharp anomalies of 16 to 34nmol/L. With the intension to check the possibility of the inflow from the shelf and river waters, we collected surface waters far away from the Umitaka spur. Methane concentration was only 7nmol/L. Therefore, we conclude that anomalously high concentration at 200 m level over the spur is not likely to be explained by inflow of shelf waters, but also by methane seeps. The temperature of waters are extremely low from 0.25°C to 1.0°C below 300 m, then abruptly increases in shallow waters to about 25°C at surface water. Thus, bottom and intermediate waters are within the stability condition of methane hydrate. Under these conditions, gases from the sea floor would form gas hydrate within bottom water mass. Gas hydrate crystals would float up shallow to the water mass where they dissociate to supply methane at around 300 m due to abrupt temperature increase.

Effects of gas composition in headspace and bicarbonate concentrations in media on gas and methane production, degradability, and rumen fermentation using in vitro gas production techniques.

PubMed

Patra, Amlan Kumar; Yu, Zhongtang

2013-07-01

Headspace gas composition and bicarbonate concentrations in media can affect methane production and other characteristics of rumen fermentation in in vitro gas production systems, but these 2 important factors have not been evaluated systematically. In this study, these 2 factors were investigated with respect to gas and methane production, in vitro digestibility of feed substrate, and volatile fatty acid (VFA) profile using in vitro gas production techniques. Three headspace gas compositions (N2+ CO2+ H2 in the ratio of 90:5:5, CO2, and N2) with 2 substrate types (alfalfa hay only, and alfalfa hay and a concentrate mixture in a 50:50 ratio) in a 3×2 factorial design (experiment 1) and 3 headspace compositions (N2, N2 + CO2 in a 50:50 ratio, and CO2) with 3 bicarbonate concentrations (80, 100, and 120 mM) in a 3×3 factorial design (experiment 2) were evaluated. In experiment 1, total gas production (TGP) and net gas production (NGP) was the lowest for CO2, followed by N2, and then the gas mixture. Methane concentration in headspace gas after fermentation was greater for CO2 than for N2 and the gas mixture, whereas total methane production (TMP) and net methane production (NMP) were the greatest for CO2, followed by the gas mixture, and then N2. Headspace composition did not affect in vitro digestibility or the VFA profile, except molar percentages of propionate, which were greater for CO2 and N2 than for the gas mixture. Methane concentration in headspace gas, TGP, and NGP were affected by the interaction of headspace gas composition and substrate type. In experiment 2, increasing concentrations of CO2 in the headspace decreased TGP and NGP quadratically, but increased the concentrations of methane, NMP, and in vitro fiber digestibility linearly, and TMP quadratically. Fiber digestibility, TGP, and NGP increased linearly with increasing bicarbonate concentrations in the medium. Concentrations of methane and NMP were unaffected by bicarbonate concentration, but TMP tended to increase due to increasing bicarbonate concentration. Although total VFA concentration and molar percentage of butyrate were unchanged, the molar percentage of acetate, and acetate-to-propionate ratio decreased, whereas the molar percentage of propionate increased quadratically with increasing bicarbonate concentration. This study demonstrated for the first time that headspace composition, especially CO2 content, and bicarbonate concentration in media could significantly influence gas and methane production, and rumen fermentation in gas production techniques. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Effects of household detergent on anaerobic fermentation of kitchen wastewater from food waste disposer.

PubMed

Lee, K H; Park, K Y; Khanal, S K; Lee, J W

2013-01-15

This study examines the effects of household detergent on anaerobic methane fermentation of wastewater from food waste disposers (FWDs). Anaerobic toxicity assay (ATA) demonstrated that methane production substantially decreased at a higher detergent concentration. The Gompertz three-parameter model fitted well with the ATA results, and both the extent of methane production (M) and methane production rate (R(m)) obtained from the model were strongly affected by the concentration of the detergent. The 50% inhibitory concentration (IC(50)) of the detergent was 603 mg/L based on R(m). Results from fatty acid methyl esters (FAMEs) analysis of microbial culture revealed that deterioration of methane fermentation was attributed to impaired structure of anaerobic microbial membrane due to detergent. This study suggests that wastewater from FWD could be used for methane production, but it is necessary to reduce the concentration of detergent prior to anaerobic fermentation. Copyright © 2012 Elsevier B.V. All rights reserved.

Methane distribution and oxidation around the Lena Delta in summer 2013

NASA Astrophysics Data System (ADS)

Bussmann, Ingeborg; Hackbusch, Steffen; Schaal, Patrick; Wichels, Antje

2017-11-01

The Lena River is one of the largest Russian rivers draining into the Laptev Sea. The predicted increases in global temperatures are expected to cause the permafrost areas surrounding the Lena Delta to melt at increasing rates. This melting will result in high amounts of methane reaching the waters of the Lena and the adjacent Laptev Sea. The only biological sink that can lower methane concentrations within this system is methane oxidation by methanotrophic bacteria. However, the polar estuary of the Lena River, due to its strong fluctuations in salinity and temperature, is a challenging environment for bacteria. We determined the activity and abundance of aerobic methanotrophic bacteria by a tracer method and by the quantitative polymerase chain reaction. We described the methanotrophic population with a molecular fingerprinting method (monooxygenase intergenic spacer analysis), as well as the methane distribution (via a headspace method) and other abiotic parameters, in the Lena Delta in September 2013. The median methane concentrations were 22 nmol L-1 for riverine water (salinity (S) < 5), 19 nmol L-1 for mixed water (5 < S < 20) and 28 nmol L-1 for polar water (S > 20). The Lena River was not the source of methane in surface water, and the methane concentrations of the bottom water were mainly influenced by the methane concentration in surface sediments. However, the bacterial populations of the riverine and polar waters showed similar methane oxidation rates (0.419 and 0.400 nmol L-1 d-1), despite a higher relative abundance of methanotrophs and a higher estimated diversity in the riverine water than in the polar water. The methane turnover times ranged from 167 days in mixed water and 91 days in riverine water to only 36 days in polar water. The environmental parameters influencing the methane oxidation rate and the methanotrophic population also differed between the water masses. We postulate the presence of a riverine methanotrophic population that is limited by sub-optimal temperatures and substrate concentrations and a polar methanotrophic population that is well adapted to the cold and methane-poor polar environment but limited by a lack of nitrogen. The diffusive methane flux into the atmosphere ranged from 4 to 163 µmol m2 d-1 (median 24). The diffusive methane flux accounted for a loss of 8 % of the total methane inventory of the investigated area, whereas the methanotrophic bacteria consumed only 1 % of this methane inventory. Our results underscore the importance of measuring the methane oxidation activities in polar estuaries, and they indicate a population-level differentiation between riverine and polar water methanotrophs.

Comparison of seven types of thermo-chemical pretreatments on the structural features and anaerobic digestion of sunflower stalks.

PubMed

Monlau, F; Barakat, A; Steyer, J P; Carrere, H

2012-09-01

Sunflower stalks can be used for the production of methane, but their recalcitrant structure requires the use of thermo-chemical pretreatments. Two thermal (55 and 170°C) and five thermo-chemical pretreatments (NaOH, H(2)O(2), Ca(OH)(2), HCl and FeCl(3)) were carried out, followed by anaerobic digestion. The highest methane production (259 ± 6 mL CH(4)g(-1) VS) was achieved after pretreatment at 55°C with 4% NaOH for 24h. Acidic pretreatments at 170°C removed more than 90% of hemicelluloses and uronic acids whereas alkaline and oxidative pretreatments were more effective in dissolving lignin. However, no pretreatment was effective in reducing the crystallinity of cellulose. Methane production rate was positively correlated with the amount of solubilized matter whereas methane potential was negatively correlated with the amount of lignin. Considering that the major challenge is obtaining increased methane potential, alkaline pretreatments can be recommended in order to optimize the anaerobic digestion of lignocellulosic substrates. Copyright © 2012 Elsevier Ltd. All rights reserved.

The Extent of CH4 Emission and Oxidation in Thermogenic and Biogenic Gas Hydrate Environments

NASA Astrophysics Data System (ADS)

Kastner, M.; Solem, C.; Bartlett, D.; MacDonald, I.; Valentine, D.

2003-12-01

The role of methane hydrate in the global methane budget is poorly understood, because relatively little is known about the transport of gaseous and dissolved methane through the seafloor into the ocean, from the water column into the atmosphere, and the extent of water-column methanotrophy that occurs en route. We characterize the transport and consumption of methane in three distinct gas hydrate environments, spanning the spectrum of thermogenic and biogenic methane occurrences: Bush Hill in the Gulf of Mexico, Eel River off the coast of Northern California, and the Noth and South Hydrate Ridges on the Cascadia Oregon margin. At all the sites studied a significant enrichment in δ 13CH4 with distance along isopycnals away from the methane source is observed, indicative of extensive aerobic bacterial methane oxidation in the water column. The effects of this process are principally pronounced in the mostly biogenic methane setting, with δ 13C-CH4 measured as high as -12 permil (PDB) between North and South Hydrate Ridge. The δ 13C-CH4 values ranged from -12 to -67 permil at Hydrate Ridge, -34 to -52 permil at Eel River, and -41 to -49 permil at Bush Hill. The large variation in methane carbon isotope ranges between the sites suggest that major differences exist in both the rates of aerobic methane oxidation and system openness at the studied locations. A mean kinetic isotope fractionation factor is being determined using a closed-system Rayleigh distillation model. An approximate regional methane flux from the ocean into the atmosphere is being estimated for the Gulf of Mexico, by extrapolation of the flux value from the Bush Hill methane plume over 390 plume locations having persistent oil slicks on the ocean surface, mapped by time series satellite data.

Methane Metabolizing Microbial Communities in the Cold Seep Areas in the Northern Continental Shelf of South China Sea

NASA Astrophysics Data System (ADS)

Wang, F.; Liang, Q.

2016-12-01

Marine sediment contains large amount of methane, estimated approximately 500-2500 gigatonnes of dissolved and hydrated methane carbon stored therein, mainly in continental margins. In localized specific areas named cold seeps, hydrocarbon (mainly methane) containing fluids rise to the seafloor, and support oases of ecosystem composed of various microorganisms and faunal assemblages. South China Sea (SCS) is surrounded by passive continental margins in the west and north and convergent margins in the south and east. Thick organic-rich sediments have accumulated in the SCS since the late Mesozoic, which are continuing sources to form gas hydrates in the sediments of SCS. Here, Microbial ecosystems, particularly those involved in methane transformations were investigated in the cold seep areas (Qiongdongnan, Shenhu, and Dongsha) in the northern continental shelf of SCS. Multiple interdisciplinary analytic tools such as stable isotope probing, geochemical analysis, and molecular ecology, were applied for a comprehensive understanding of the microbe mediated methane transformation in this project. A variety of sediments cores have been collected, the geochemical profiles and the associated microbial distribution along the sediment cores were recorded. The major microbial groups involved in the methane transformation in these sediment cores were revealed, known methane producing and oxidizing archaea including Methanosarcinales, anaerobic methane oxidizing groups ANME-1, ANME-2 and their niche preference in the SCS sediments were found. In-depth comparative analysis revealed the presence of SCS-specific archaeal subtypes which probably reflected the evolution and adaptation of these methane metabolizing microbes to the SCS environmental conditions. Our work represents the first comprehensive analysis of the methane metabolizing microbial communities in the cold seep areas along the northern continental shelf of South China Sea, would provide new insight into the mechanisms of methane biotransformation.

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.

Influence of process parameters on the extraction of soluble substances from OFMSW and methane production.

PubMed

Campuzano, Rosalinda; González-Martínez, Simón

2017-04-01

Microorganisms involved in anaerobic digestion require dissolved substrates to transport them through the cell wall to different processing units and finally to be disposed as waste, such as methane and carbon dioxide. In order to increase methane production, this work proposes to separate the soluble substances from OFMSW and analyse methane production from extracts and OFMSW. Using water as solvent, four extraction parameters were proposed: (1) Number of consecutive extractions, (2) Duration of mixing for every consecutive extraction, (3) OFMSW to water mass ratios 1:1, 1:2, and 1:3 and, (4) The influence of temperature on the extraction process. Results indicated that is possible to separate 40% of VS from OFMSW with only three consecutive extraction with mixing of 30min in every extraction using ambient temperature water. For every OFMSW to water combination, the first three consecutive extracts were analysed for biochemical methane potential test during 21days at 35°C; OFMSW was also tested as reference. Methane production from all substrates is highest during the first day and then it slowly decreases to increase again during a second stage. This was identified as diauxic behaviour. Specific methane production at day 21 increased with increasing water content of the extracts where OFMSW methane production was the lowest of all with 535NL/kgVS. These results indicate that it is feasible to rapidly produce methane from extracted substances. Copyright © 2017 Elsevier Ltd. All rights reserved.

Improved methane removal in exhaust gas from biogas upgrading process using immobilized methane-oxidizing bacteria.

PubMed

Sun, Meng-Ting; Yang, Zhi-Man; Fu, Shan-Fei; Fan, Xiao-Lei; Guo, Rong-Bo

2018-05-01

Methane in exhaust gas from biogas upgrading process, which is a greenhouse gas, could cause global warming. The biofilter with immobilized methane-oxidizing bacteria (MOB) is a promising approach for methane removal, and the selections of inoculated MOB culture and support material are vital for the biofilter. In this work, five MOB consortia were enriched at different methane concentrations. The MOB-20 consortium enriched at the methane concentration of 20.0% (v/v) was then immobilized on sponge and two particle sizes of volcanic rock in biofilters to remove methane in exhaust gas from biogas upgrading process. Results showed that the immobilized MOB performed more admirable methane removal capacity than suspended cells. The immobilized MOB on sponge reached the highest methane removal efficiency (RE) of 35%. The rough surface, preferable hydroscopicity, appropriate pore size and particle size of support material might favor the MOB immobilization and accordingly methane removal. Copyright © 2018 Elsevier Ltd. All rights reserved.

Risks of using EDTA as an agent for trace metals dosing in anaerobic digestion of olive mill solid waste.

PubMed

Serrano, A; Pinto-Ibieta, F; Braga, A F M; Jeison, D; Borja, R; Fermoso, F G

2017-12-01

Low concentrations of trace elements in many organic wastes recommend their supplementation in order to avoid potential limitations. Different chelating agents have been used to ensure an adequate trace metal pool in the soluble fraction, by forming dissolved complexes. Ethylenediaminetetraacetic acid (EDTA) is probably the most common, although several negative effects could be associated with its usage. Biomethane potential tests were performed using Olive Mill Solid Waste as the substrate, supplementing different combinations of Fe, Co, Ni, Ba, always under the presence of EDTA. Results show that Ni and Co slightly recovered biodegradability. However, Ba supplementation resulted in worsening the methane yield coefficient in all cases. High concentration of EDTA led to decrease in the activity of anaerobic digestion. High availability of EDTA induces the capture of trace metals like Co or Ni, key trace metals for anaerobic biomass activity. While supplementing trace metals, the addition of Ba and/or EDTA must be carefully considered.

Carbon and hydrogen isotope composition and C-14 concentration in methane from sources and from the atmosphere: Implications for a global methane budget

NASA Technical Reports Server (NTRS)

Wahlen, Martin

1994-01-01

The topics covered include the following: biogenic methane studies; forest soil methane uptake; rice field methane sources; atmospheric measurements; stratospheric samples; Antarctica; California; and Germany.

Methane anomalies in the oxygenated upper waters of the central Baltic Sea associated with zooplankton abundance

NASA Astrophysics Data System (ADS)

Schmale, Oliver; Wäge, Janine; Morholz, Volker; Rehder, Gregor; Wasmund, Norbert; Gräwe, Ulf; Labrenz, Matthias; Loick-Wilde, Natalie

2017-04-01

Apart from the sediment as the dominant source of methane in the aquatic realm the process of methane production in well-oxygenated waters has received considerable attention during the last years. The paradox of methane accumulation in these relatively shallow waters, commonly termed as "oceanic methane paradox", has been sporadically observed in lakes as well as in marine ecosystems like the Gulf of Mexico, the Black Sea, the Baltic Sea, Arctic waters or above the continental shelf off the coast of Spain and Africa. Even if this phenomenon has been described in the literature over the last decades, the potential sources of shallow methane accumulation are still controversially discussed. We report on methane enrichments that were observed during summer in the upper water column of the Gotland Basin, central Baltic Sea. In the eastern part of the basin methane concentrations just below the thermocline (in about 30 m water depth) varied between 15 and 77 nM, in contrast to the western part of the basin where no methane enrichments could be detected. Stable carbon isotope ratios of methane (delta 13C-CH4 of -67.6‰) clearly indicated its in situ biogenic origin. This is supported by clonal sequences from the depth with high methane concentrations in the eastern Gotland Basin, which cluster with the clade Methanomicrobiacea, a family of methanogenic Archaea. Hydroacoustic observation in combination with plankton net tows displayed a seston enrichment (size >100 micro meter) in a layer between 30-50 m depth. The dominant species in the phytoplankton, Dinophysis norvegica, was concentrated at 10-20 m depth, and showed higher concentrations in the eastern Gotland Basin in comparison with the western part of the basin. In contrast to the western Gotland Basin, the zooplankton community in the eastern part was dominated by the copepod species Temora longicornis. Laboratory incubations of a T. longicornis dominated seston fraction (>100 micro meter) sampled in the depth of the subthermocline methane anomaly showed a clear correlation between seston concentration (i.e. abundance of copepods) and methane production rates.

Anaerobic Transformation of Chlorinated Aliphatic Hydrocarbons in a Sand Aquifer Based on Spatial Chemical Distributions

NASA Astrophysics Data System (ADS)

Semprini, Lewis; Kitanidis, Peter K.; Kampbell, Don H.; Wilson, John T.

1995-04-01

We estimated the distribution of chlorinated aliphatic hydrocarbons (CAHs) from groundwater samples collected along three transects in a sand aquifer. Trichloroethylene (TCE) leaked and contaminated the aquifer probably more than a decade before we collected the measurements. The data show significant concentrations of TCE, cis-l,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethene. We attributed DCE, VC, and ethene to the reductive dehalogenation of TCE. The CAH concentrations varied significantly with depth and correlate with sulfate and methane concentrations. Anoxic aquifer conditions exist with methane present at relatively high concentrations at depth. High concentrations of TCE correspond with the absence of methane or low methane concentrations, whereas products of TCE dehalogenation are associated with higher methane concentrations and low sulfate concentrations. Indications are that the dechlorination of TCE and DCE to VC and ethene is associated with sulfate reduction and active methanogenesis. TCE dechlorination to DCE is likely occurring under the less reducing conditions of sulfate reduction, with further reductions to VC and ethene occurring under methanogenic conditions. We estimated that about 20% of TCE has dechlorinated to ethene. The analysis of the data enhanced our knowledge of natural in situ transformation and transport processes of CAHs.

40 CFR 60.565 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... emission control efficiency of a combustion device or the outlet concentration of TOC (minus methane and... performance test period, and (ii) The percent reduction of TOC (minus methane and ethane) achieved by the incinerator, the concentration of TOC (minus methane and ethane) (ppmv, by compound) at the outlet of the...

40 CFR 60.565 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... emission control efficiency of a combustion device or the outlet concentration of TOC (minus methane and... performance test period, and (ii) The percent reduction of TOC (minus methane and ethane) achieved by the incinerator, the concentration of TOC (minus methane and ethane) (ppmv, by compound) at the outlet of the...

40 CFR 60.565 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... emission control efficiency of a combustion device or the outlet concentration of TOC (minus methane and... performance test period, and (ii) The percent reduction of TOC (minus methane and ethane) achieved by the incinerator, the concentration of TOC (minus methane and ethane) (ppmv, by compound) at the outlet of the...

40 CFR 60.565 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... emission control efficiency of a combustion device or the outlet concentration of TOC (minus methane and... performance test period, and (ii) The percent reduction of TOC (minus methane and ethane) achieved by the incinerator, the concentration of TOC (minus methane and ethane) (ppmv, by compound) at the outlet of the...

40 CFR 60.565 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... emission control efficiency of a combustion device or the outlet concentration of TOC (minus methane and... performance test period, and (ii) The percent reduction of TOC (minus methane and ethane) achieved by the incinerator, the concentration of TOC (minus methane and ethane) (ppmv, by compound) at the outlet of the...

30 CFR 75.388 - Boreholes in advance of mining.

Code of Federal Regulations, 2013 CFR

2013-07-01

... more than 1.0 percent methane, less than 19.5 percent oxygen, or harmful concentrations of carbon monoxide, carbon dioxide or other explosive, harmful or noxious gases; (2) Tests for methane, oxygen... and the mine workings; (3) The concentrations of methane, oxygen, carbon monoxide, and carbon dioxide...

30 CFR 75.388 - Boreholes in advance of mining.

Code of Federal Regulations, 2010 CFR

2010-07-01

... more than 1.0 percent methane, less than 19.5 percent oxygen, or harmful concentrations of carbon monoxide, carbon dioxide or other explosive, harmful or noxious gases; (2) Tests for methane, oxygen... and the mine workings; (3) The concentrations of methane, oxygen, carbon monoxide, and carbon dioxide...

30 CFR 75.388 - Boreholes in advance of mining.

Code of Federal Regulations, 2012 CFR

2012-07-01

... more than 1.0 percent methane, less than 19.5 percent oxygen, or harmful concentrations of carbon monoxide, carbon dioxide or other explosive, harmful or noxious gases; (2) Tests for methane, oxygen... and the mine workings; (3) The concentrations of methane, oxygen, carbon monoxide, and carbon dioxide...

30 CFR 75.388 - Boreholes in advance of mining.

Code of Federal Regulations, 2014 CFR

2014-07-01

... more than 1.0 percent methane, less than 19.5 percent oxygen, or harmful concentrations of carbon monoxide, carbon dioxide or other explosive, harmful or noxious gases; (2) Tests for methane, oxygen... and the mine workings; (3) The concentrations of methane, oxygen, carbon monoxide, and carbon dioxide...

30 CFR 75.388 - Boreholes in advance of mining.

Code of Federal Regulations, 2011 CFR

2011-07-01

... more than 1.0 percent methane, less than 19.5 percent oxygen, or harmful concentrations of carbon monoxide, carbon dioxide or other explosive, harmful or noxious gases; (2) Tests for methane, oxygen... and the mine workings; (3) The concentrations of methane, oxygen, carbon monoxide, and carbon dioxide...

Investigation of flame structure and burning intensity of partially premixed methane enrichment of syngas using OH-PLIF and kinetic simulation

NASA Astrophysics Data System (ADS)

Pu, Ge; Huang, Beibei; Zhang, Xun; Du, Jiantai; Zhu, Tuanhui; Chen, Bei

2018-05-01

Various experiments were conducted to study the combustion characteristics of partially premixed methane enrichment of syngas by using the OH-PLIF technique. Experiments were conducted on a co-flow burner, and the methane concentration (XCH4 = CH4/(H2+CO+CH4)) was varied from 0 to 20%, the overall equivalence ratio was varied from 0.4 to 1.2 and the inner equivalence ratio was varied from 1.5 to 3.5. Kinetic simulation was conducted by using OPPDIF module of CHEMKIN-Pro software. Results show that an increase in XCH4 and ϕoverall weakens the OH signal intensity. Adding methane into the fuel greatly increases the height of the inner flame front, and the increase of methane concentration has a negative effect on flame propagation speed. Meanwhile, simulation results remain consistent with the experiments. The main OH radical production reaction changes from R46: H+HO2 = 2OH to R38: H+O2 = O+OH when methane concentration contained in the fuel mixture increases. Sensitivity analysis also indicates that reaction which plays a dominant effect on temperature changes with the increase of methane concentration.

Groundwater quality in the Lake Champlain and Susquehanna River basins, New York, 2014

USGS Publications Warehouse

Scott, Tia-Marie; Nystrom, Elizabeth A.; Reddy, James E.

2016-11-04

In a study conducted by the U.S. Geological Survey in cooperation with the New York State Department of Environmental Conservation, groundwater samples were collected from 6 production wells and 7 domestic wells in the Lake Champlain Basin and from 11 production wells and 9 domestic wells in the Susquehanna River Basin in New York. All samples were collected from June through December 2014 to characterize groundwater quality in these basins. The samples were collected and processed using standard procedures of the U.S. Geological Survey and were analyzed for 148 physiochemical properties and constituents, including dissolved gases, major ions, nutrients, trace elements, pesticides, volatile organic compounds, radionuclides, and indicator bacteria.The Lake Champlain Basin study area covers the 3,050 square miles of the basin in northeastern New York; the remaining part of the basin is in Vermont and Canada. Of the 13 wells sampled in the Lake Champlain Basin, 6 are completed in sand and gravel, and 7 are completed in bedrock. Groundwater in the Lake Champlain Basin was generally of good quality, although properties and concentrations of some constituents— fluoride, iron, manganese, dissolved solids, sodium, radon-222, total coliform bacteria, fecal coliform bacteria, and Escherichia coli bacteria—sometimes equaled or exceeded primary, secondary, or proposed drinking-water standards. The constituent most frequently detected in concentrations exceeding drinking-water standards (5 of 13 samples) was radon-222.The Susquehanna River Basin study area covers the entire 4,522 square miles of the basin in south-central New York; the remaining part of the basin is in Pennsylvania. Of the 20 wells sampled in the Susquehanna River Basin, 11 are completed in sand and gravel, and 9 are completed in bedrock. Groundwater in the Susquehanna River Basin was generally of good quality, although properties and concentrations of some constituents—pH, chloride, sodium, dissolved solids, iron, manganese, aluminum, arsenic, barium, gross-alpha radioactivity, radon-222, methane, total coliform bacteria, and fecal coliform bacteria—sometimes equaled or exceeded primary, secondary, or proposed drinking-water standards. As in the Lake Champlain Basin, the constituent most frequently detected in concentrations exceeding drinking-water standards (13 of 20 samples) was radon-222.

Ground truthing for methane hotspots at Railroad Valley, NV - application to Mars

NASA Astrophysics Data System (ADS)

Detweiler, A. M.; Kelley, C. A.; Bebout, B.; McKay, C. P.; DeMarines, J.; Yates, E. L.; Iraci, L. T.

2011-12-01

During the 2010 Greenhouse gas Observing SATellite (GOSAT) calibration and validation campaign at Railroad Valley (RRV) playa, NV, unexpected methane and carbon dioxide fluctuations were observed at the dry lakebed. Possible sources included the presence of natural gas (thermogenic methane) from oil deposits in the surrounding playa, and/or methane production from microbial activity (biogenic) in the subsurface of the playa. In the summer of 2011, measurements were undertaken to identify potential methane sources at RRV. The biogenicity of the methane was determined based on δ13C values and methane/ethane ratios. Soil gas samples and sediments were collected at different sites in the playa and surrounding areas. The soils of the playa consist of a surface crust layer (upper ~ 10 cm) grading to a dense clay below about 25 cm. Soil gas from the playa, sampled at about 20 and 80 cm depths, reflected atmospheric methane concentrations, ranging from 2 to 2.4 ppm, suggesting that no methane was produced within the playa. Natural springs on the northeast and western border of the playa, detected as methane hotspots from a flyover by the Sensor Integrated Environmental Remote Research Aircraft (SIERRA), were also sampled. Bubbles in these springs had methane concentrations that ranged from 69 to 84% by volume. In addition, ethane was detected at very low concentrations, giving methane/ethane ratios in excess of 100,000, indicating biogenic methane in the springs. Soils and sediments collected at the playa and spring sites were incubated in vials over a period of ~23 days. Methane production was observed in the spring sites (avg. 228.6 ± 49.1 nmol/g/d at Kate Springs), but was not evident for the playa sites. The incubation data, therefore, corroborated in situ methane concentration measurements. Particulate organic carbon (POC) was low for all sites samples (0.05-0.38%), with the exception of Kate Springs, which had a much higher POC concentration of 3.4 ± 0.7%. Temperature and relative humidity sensors were placed in the playa at 5, 20, and 30 cm below the surface. Since the relative humidity neared 100% (down to 20 cm below the surface), high enough to support microbial life, the observed absence of methane production in the playa itself is likely due to the low POC content, compared to other methane-producing environments. The spatial distribution of methane in combination with the spectral reflectance at the RRV dry lakebed makes it a good Mars analog. The ground truthing and satellite calibration work accomplished at RRV is a good exercise in preparation to identifying the origins of methane observed in the atmosphere of Mars during the upcoming 2012 Mars Science Laboratory and 2016 ExoMars Trace Gas Orbiter missions.

Temporal variations in parameters reflecting terminal-electron-accepting processes in an aquifer contaminated with waste fuel and chlorinated solvents

USGS Publications Warehouse

McGuire, Jennifer T.; Smith, Erik W.; Long, David T.; Hyndman, David W.; Haack, Sheridan K.; Klug, Michael J.; Velbel, Michael A.

2000-01-01

A fundamental issue in aquifer biogeochemistry is the means by which solute transport, geochemical processes, and microbiological activity combine to produce spatial and temporal variations in redox zonation. In this paper, we describe the temporal variability of TEAP conditions in shallow groundwater contaminated with both waste fuel and chlorinated solvents. TEAP parameters (including methane, dissolved iron, and dissolved hydrogen) were measured to characterize the contaminant plume over a 3-year period. We observed that concentrations of TEAP parameters changed on different time scales and appear to be related, in part, to recharge events. Changes in all TEAP parameters were observed on short time scales (months), and over a longer 3-year period. The results indicate that (1) interpretations of TEAP conditions in aquifers contaminated with a variety of organic chemicals, such as those with petroleum hydrocarbons and chlorinated solvents, must consider additional hydrogen-consuming reactions (e.g., dehalogenation); (2) interpretations must consider the roles of both in situ (at the sampling point) biogeochemical and solute transport processes; and (3) determinations of microbial communities are often necessary to confirm the interpretations made from geochemical and hydrogeological measurements on these processes.

Groundwater quality in the Upper Hudson River Basin, New York, 2012

USGS Publications Warehouse

Scott, Tia-Marie; Nystrom, Elizabeth A.

2014-01-01

Water samples were collected from 20 production and domestic wells in the Upper Hudson River Basin (north of the Federal Dam at Troy, New York) in New York in August 2012 to characterize groundwater quality in the basin. The samples were collected and processed using standard U.S. Geological Survey procedures and were analyzed for 148 physiochemical properties and constituents, including dissolved gases, major ions, nutrients, trace elements, pesticides, volatile organic compounds (VOCs), radionuclides, and indicator bacteria. The Upper Hudson River Basin covers 4,600 square miles in upstate New York, Vermont, and Massachusetts; the study area encompasses the 4,000 square miles that lie within New York. The basin is underlain by crystalline and sedimentary bedrock, including gneiss, shale, and slate; some sandstone and carbonate rocks are present locally. The bedrock in some areas is overlain by surficial deposits of saturated sand and gravel. Eleven of the wells sampled in the Upper Hudson River Basin are completed in sand and gravel deposits, and nine are completed in bedrock. Groundwater in the Upper Hudson River Basin was typically neutral or slightly basic; the water typically was moderately hard. Bicarbonate, chloride, calcium, and sodium were the major ions with the greatest median concentrations; the dominant nutrient was nitrate. Methane was detected in 7 samples. Strontium, iron, barium, boron, and manganese were the trace elements with the highest median concentrations. Two pesticides, an herbicide degradate and an insecticide degredate, were detected in two samples at trace levels; seven VOCs, including chloroform, four solvents, and the gasoline additive methyl tert-butyl ether (MTBE) were detected in four samples. The greatest radon-222 activity, 2,900 picocuries per liter, was measured in a sample from a bedrock well; the median radon activity was higher in samples from bedrock wells than in samples from sand and gravel wells. Coliform bacteria were detected in one sample with a maximum of 2 colony-forming units per 100 milliliters. Water quality in the Upper Hudson River Basin is generally good, but concentrations of some constituents equaled or exceeded current or proposed Federal or New York State drinking-water standards. The standards exceeded are color (1 sample), pH (3 samples), sodium (3 samples), chloride (1 sample), dissolved solids (1 sample), arsenic (1 sample), iron (2 samples), manganese (2 samples), uranium (1 sample), radon-222 (12 samples), and gross beta activities (3 samples). Total coliform bacteria were each detected in one sample. Concentrations of fluoride, sulfate, nitrate, nitrite, aluminum, antimony, barium, beryllium, cadmium, chromium, copper, lead, mercury, selenium, silver, thallium, zinc, and gross alpha activities did not exceed existing drinking-water standards in any of the samples collected. Methane concentration in one sample was greater than 28 milligrams per liter, with a concentration of 35.1 milligrams per liter.

Third-Year Results from the Circumarctic Lakes Observation Network (CALON) Project

NASA Astrophysics Data System (ADS)

Hinkel, K. M.; Arp, C. D.; Beck, R. A.; Eisner, W. R.; Frey, K. E.; Grosse, G.; Jones, B. M.; Kim, C.; Lenters, J. D.; Liu, H.; Townsend-Small, A.

2014-12-01

Since 2012, 60 lakes in northern Alaska have been instrumented under the auspices of CALON, a project designed to document landscape-scale variability in physical and biogeochemical processes of Arctic lakes in permafrost terrain. The network has ten observation nodes along two latitudinal transects extending from the Arctic Ocean inland some 200 km to the Brooks Range foothills. At each node, a meteorological station is deployed, and six representative lakes of differing area and depth are instrumented and sampled at different intensity levels to collect basic field measurements. In April, sensors measuring water temperature and depth are deployed through the ice in each lake, ice and snow thickness recorded, and water samples are collected. Data are downloaded, lakes re-sampled, and bathymetric surveys are conducted in August. In 2014, the snow cover on inland lakes was thinner than in previous years but thicker on lakes located near the coast. Lake ice was generally thinner near the coast, but the difference diminished inland. Winters (Oct-March) have been progressively warmer over the 3-year period, which partially explains the thinner lake ice that formed in 2013-14. Lakes are typically well-mixed and largely isothermal, with minor thermal stratification occurring in deeper lakes during calm, sunny periods. These regional lake and meteorological data sets, used in conjunction with satellite imagery, supports the wind-driven lake circulation model for the origin of thermokarst lakes. Results of biogeochemical analyses of lake waters generally show notably higher concentrations of cations/anions, chromophoric dissolved organic matter, and chlorophyll-a during April as compared with August. Dissolved methane concentrations are also much higher under ice than in open water during summer, although all lakes are a source of atmospheric methane. Interviews with indigenous elders in Anaktuvuk Pass indicate that mountain lakes are drying up. During the 2014 breakup period, 350 entrants participated in the 2nd Annual Toolik Lake Ice Classic including elementary school children, the general public, and international researchers. Ice off occurred on 23 June, and 11 people correctly guessed this day. All field data is archived at A-CADIS, and further information is at www.arcticlakes.org.

Methane concentration and isotopic composition (δ13C-CH4) in the Nerja Cave system (South Spain)

NASA Astrophysics Data System (ADS)

Vadillo, Iñaki; Etiope, Giuseppe; Benavente, José; Ojeda, Lucia; Liñán, Cristina; Carrasco, Francisco

2016-04-01

Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (δ13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. δ13C increases correspondingly from -47 ‰ to -41 ‰ (VPDB). CH4 is systematically 13C-enriched (δ13C > -45) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of sub-atmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.

Baseline groundwater quality in national park units within the Marcellus and Utica Shale gas plays, New York, Pennsylvania, and West Virginia, 2011

USGS Publications Warehouse

Eckhardt, David A.V.; Sloto, Ronald A.

2012-01-01

Groundwater samples were collected from 15 production wells and 1 spring at 9 national park units in New York, Pennsylvania, and West Virginia in July and August 2011 and analyzed to characterize the quality of these water supplies. The sample sites generally were selected to represent areas of potential effects on water quality by drilling and development of gas wells in Marcellus Shale and Utica Shale areas of the northeastern United States. The groundwater samples were analyzed for 53 constituents, including nutrients, major inorganic constituents, trace elements, chemical oxygen demand, radioactivity, and dissolved gases, including methane and radon-222. Results indicated that the groundwater used for water supply at the selected national park units is generally of acceptable quality, although concentrations of some constituents exceeded at least one drinking-water guideline at several wells. Nine analytes were detected in concentrations that exceeded Federal drinking-water standards, mostly secondary standards that define aesthetic properties of water, such as taste and odor. One sample had an arsenic concentration that exceeded the U.S. Environmental Protection Agency maximum contaminant level (MCL) of 10 micrograms per liter (μg/L). The pH, which is a measure of acidity (hydrogen ion activity), ranged from 4.8 to 8.4, and in 5 of the 16 samples, the pH values were outside the accepted U.S. Environmental Protection Agency secondary maximum contaminant level (SMCL) range of 6.5 to 8.5. The concentration of total dissolved solids exceeded the SMCL of 500 milligrams per liter (mg/L) at four sites. The sulfate concentration exceeded the SMCL of 250 mg/L concentration in one sample, and the fluoride concentration exceeded the SMCL of 2 mg/L in one sample. Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking water health advisory of 60 mg/L at four sites. Iron concentrations exceeded the SMCL of 300 μg/L in two samples, and manganese concentrations exceeded the SMCL of 50 μg/L in five samples. Radon-222 concentrations exceeded the proposed U.S. Environmental Protection Agency MCL of 300 picocuries per liter in eight samples.

Enhanced CO2 uptake at a shallow Arctic Ocean seep field overwhelms the positive warming potential of emitted methane.

PubMed

Pohlman, John W; Greinert, Jens; Ruppel, Carolyn; Silyakova, Anna; Vielstädte, Lisa; Casso, Michael; Mienert, Jürgen; Bünz, Stefan

2017-05-23

Continued warming of the Arctic Ocean in coming decades is projected to trigger the release of teragrams (1 Tg = 10 6 tons) of methane from thawing subsea permafrost on shallow continental shelves and dissociation of methane hydrate on upper continental slopes. On the shallow shelves (<100 m water depth), methane released from the seafloor may reach the atmosphere and potentially amplify global warming. On the other hand, biological uptake of carbon dioxide (CO 2 ) has the potential to offset the positive warming potential of emitted methane, a process that has not received detailed consideration for these settings. Continuous sea-air gas flux data collected over a shallow ebullitive methane seep field on the Svalbard margin reveal atmospheric CO 2 uptake rates (-33,300 ± 7,900 μmol m -2 ⋅d -1 ) twice that of surrounding waters and ∼1,900 times greater than the diffusive sea-air methane efflux (17.3 ± 4.8 μmol m -2 ⋅d -1 ). The negative radiative forcing expected from this CO 2 uptake is up to 231 times greater than the positive radiative forcing from the methane emissions. Surface water characteristics (e.g., high dissolved oxygen, high pH, and enrichment of 13 C in CO 2 ) indicate that upwelling of cold, nutrient-rich water from near the seafloor accompanies methane emissions and stimulates CO 2 consumption by photosynthesizing phytoplankton. These findings challenge the widely held perception that areas characterized by shallow-water methane seeps and/or strongly elevated sea-air methane flux always increase the global atmospheric greenhouse gas burden.

Enhanced CO2 uptake at a shallow Arctic Ocean seep field overwhelms the positive warming potential of emitted methane

PubMed Central

Greinert, Jens; Silyakova, Anna; Vielstädte, Lisa; Casso, Michael; Mienert, Jürgen; Bünz, Stefan

2017-01-01

Continued warming of the Arctic Ocean in coming decades is projected to trigger the release of teragrams (1 Tg = 106 tons) of methane from thawing subsea permafrost on shallow continental shelves and dissociation of methane hydrate on upper continental slopes. On the shallow shelves (<100 m water depth), methane released from the seafloor may reach the atmosphere and potentially amplify global warming. On the other hand, biological uptake of carbon dioxide (CO2) has the potential to offset the positive warming potential of emitted methane, a process that has not received detailed consideration for these settings. Continuous sea−air gas flux data collected over a shallow ebullitive methane seep field on the Svalbard margin reveal atmospheric CO2 uptake rates (−33,300 ± 7,900 μmol m−2⋅d−1) twice that of surrounding waters and ∼1,900 times greater than the diffusive sea−air methane efflux (17.3 ± 4.8 μmol m−2⋅d−1). The negative radiative forcing expected from this CO2 uptake is up to 231 times greater than the positive radiative forcing from the methane emissions. Surface water characteristics (e.g., high dissolved oxygen, high pH, and enrichment of 13C in CO2) indicate that upwelling of cold, nutrient-rich water from near the seafloor accompanies methane emissions and stimulates CO2 consumption by photosynthesizing phytoplankton. These findings challenge the widely held perception that areas characterized by shallow-water methane seeps and/or strongly elevated sea−air methane flux always increase the global atmospheric greenhouse gas burden. PMID:28484018

The influence of tides on biogeochemical dynamics at the mouth of the Amazon River

NASA Astrophysics Data System (ADS)

Ward, N. D.; Sawakuchi, H. O.; Neu, V.; de Matos Valerio, A.; Less, D.; Guedes, V.; Wood, J.; Brito, D. C.; Cunha, A. C.; Kampel, M.; Richey, J. E.

2017-12-01

A major barrier to computing the flux of constituents from the world's largest rivers to the ocean is understanding the dynamic processes that occur along tidally-influenced river reaches. Here, we examine the response of a suite of biogeochemical parameters to tide-induced flow reversals at the mouth of the Amazon River. Continuous measurements of pCO2, pCH4, dissolved O2, pH, turbidity, and fluorescent dissolved organic matter (FDOM) were made throughout tidal cycles while held stationary in the center of the river and during hourly transects for ADCP discharge measurements. Samples were collected hourly from the surface and 50% depth during stationary samplings and from the surface during ADCP transects for analysis of suspended sediment concentrations along with other parameters such as nutrient and mercury concentrations. Suspended sediment and specific components of the suspended phase, such as particulate mercury, concentrations were positively correlated to mean river velocity during both high and low water periods with a more pronounced response at 50% depth than the surface. Tidal variations also influenced the concentration of O2 and CO2 by altering the dynamic balance between photosynthesis, respiration, and gas transfer. CO2 was positively correlated and O2 and pH were negatively correlated with river velocity. The concentration of methane generally increased during low tide (i.e. when river water level was lowest) both in the mainstem and in small side channels. In side channels concentrations increased by several orders of magnitude during low tide with visible bubbling from the sediment, presumably due to a release of hydrostatic pressure. These results suggest that biogeochemical processes are highly dynamic in tidal rivers, and these dynamic variations need to be quantified to better constrain global and regional scale budgets. Understanding these rapid processes may also provide insight into the long-term response of aquatic systems to change.

Constraining the relationships between anaerobic oxidation of methane and sulfate reduction under in situ methane concentrations

NASA Astrophysics Data System (ADS)

Zhuang, G.; Wegener, G.; Joye, S. B.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important microbial metabolism in the global carbon cycle. In marine methane seeps sediment, this process is mediated by syntrophic consortium that includes anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Stoichiometrically in AOM methane oxidation should be coupled to sulfate reduction (SR) in a 1:1 ratio. However, weak coupling of AOM and SR in seep sediments was frequently observed from the ex situ rate measurements, and the metabolic dynamics of AOM and SR under in situ conditions remain poorly understood. Here we investigated the metabolic activity of AOM and SR with radiotracers by restoring in situ methane concentrations under pressure to constrain the in situ relationships between AOM and SR in the cold seep sediments of Gulf of Mexico as well as the sediment-free AOM enrichments cultivated from cold seep of Italian Island Elba or hydrothermal vent of Guaymas Basin5. Surprisingly, we found that AOM rates strongly exceeded those of SR when high pressures and methane concentrations were applied at seep sites of GC600 and GC767 in Gulf of Mexico. With the addition of molybdate, SR was inhibited but AOM was not affected, suggesting the potential coupling of AOM with other terminal processes. Amendments of nitrate, iron, manganese and AQDS to the SR-inhibited slurries did not stimulate or inhibit the AOM activity, indicating either those electron acceptors were not limiting for AOM in the sediments or AOM was coupled to other process (e.g., organic matter). In the ANME enrichments, higher AOM rates were also observed with the addition of high concentrations of methane (10mM and 50 mM). The tracer transfer of CO2 to methane, i.e., the back reaction of AOM, increased with increasing methane concentrations and accounted for 1%-5% of the AOM rates. AOM rates at 10 mM and 50 mM methane concentration were much higher than the SR rates, suggesting those two processes were not tightly coupled. Collectively, our results provided evidence for the possible decoupling of AOM and SR under in situconditions. This decoupling appears to be widespread in methane-rich marine sediment, motivating a wide variety of future research endeavors.

Feasible metabolisms in high pH springs of the Philippines

PubMed Central

Cardace, Dawn; Meyer-Dombard, D'Arcy R.; Woycheese, Kristin M.; Arcilla, Carlo A.

2015-01-01

A field campaign targeting high pH, H2-, and CH4-emitting serpentinite-associated springs in the Zambales and Palawan Ophiolites of the Philippines was conducted in 2012-2013, and enabled description of several springs sourced in altered pillow basalts, gabbros, and peridotites. We combine field observations of pH, temperature, conductivity, dissolved oxygen, and oxidation-reduction potential with analyses of major ions, dissolved inorganic carbon, dissolved organic carbon, and dissolved gas phases in order to model the activities of selected phases important to microbial metabolism, and to rank feasible metabolic reactions based on energy yield. We document changing geochemical inventories in these springs between sampling years, and examine how the environment supports or prevents the function of certain microbial metabolisms. In all, this geochemistry-based assessment of feasible metabolisms indicates methane cycling, hydrogen oxidation, some iron and sulfur metabolisms, and ammonia oxidation are feasible reactions in this continental site of serpentinization. PMID:25713561

Feasible metabolisms in high pH springs of the Philippines.

PubMed

Cardace, Dawn; Meyer-Dombard, D'Arcy R; Woycheese, Kristin M; Arcilla, Carlo A

2015-01-01

A field campaign targeting high pH, H2-, and CH4-emitting serpentinite-associated springs in the Zambales and Palawan Ophiolites of the Philippines was conducted in 2012-2013, and enabled description of several springs sourced in altered pillow basalts, gabbros, and peridotites. We combine field observations of pH, temperature, conductivity, dissolved oxygen, and oxidation-reduction potential with analyses of major ions, dissolved inorganic carbon, dissolved organic carbon, and dissolved gas phases in order to model the activities of selected phases important to microbial metabolism, and to rank feasible metabolic reactions based on energy yield. We document changing geochemical inventories in these springs between sampling years, and examine how the environment supports or prevents the function of certain microbial metabolisms. In all, this geochemistry-based assessment of feasible metabolisms indicates methane cycling, hydrogen oxidation, some iron and sulfur metabolisms, and ammonia oxidation are feasible reactions in this continental site of serpentinization.

Biochemical methane potential from sewage sludge: Effect of an aerobic pretreatment and fly ash addition as source of trace elements.

PubMed

Huiliñir, César; Pinto-Villegas, Paula; Castillo, Alejandra; Montalvo, Silvio; Guerrero, Lorna

2017-06-01

The effect of aerobic pretreatment and fly ash addition on the production of methane from mixed sludge is studied. Three assays with pretreated and not pretreated mixed sludge in the presence of fly ash (concentrations of 0, 10, 25, 50, 250 and 500mg/L) were run at mesophilic condition. It was found that the combined use of aerobic pretreatment and fly ash addition increases methane production up to 70% when the fly ash concentrations were lower than 50mg/L, while concentrations higher than 250mg/L cause up to 11% decrease of methane production. For the anaerobic treatment of mixed sludge without pretreatment, the fly ash improved methane generation at all the concentrations studied, with a maximum of 56%. The removal of volatile solids does not show an improvement compared to the separate use of an aerobic pre-treatment and fly ash addition. Therefore, the combined use of the aerobic pre-treatment and fly ash addition improves only the production of methane. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multiband infrared inversion for low-concentration methane monitoring in a confined dust-polluted atmosphere.

PubMed

Wang, Wenzheng; Wang, Yanming; Song, Wujun; Li, Xueqin

2017-03-20

A multiband infrared diagnostic (MBID) method for methane emission monitoring in limited underground environments was presented considering the strong optical background of gas/solid attenuation. Based on spatial distribution of aerosols and complex refractive index of dust particles, forward calculations were carried out with/without methane to obtain the spectral transmittance through the participating atmosphere in a mine roadway. Considering the concurrent attenuation and absorption behavior of dust and gases, four infrared wavebands were selected to retrieve the methane concentration combined with a stochastic particle swarm optimization (SPSO) algorithm. Inversion results prove that the presented MBID method is robust and effective in identifying methane at concentrations of 0.1% or even lower with inversed relative error within 10%. Further analyses illustrate that the four selected wavebands are indispensable, and the MBID method is still valid with transmission signal disturbance in a conventional dust-polluted atmosphere under mechanized mining condition. However, the effective detection distance should be limited within 50 m to ensure inversed relative error less than 5% at 1% methane concentration.

Ambient water quality in aquifers used for drinking-water supplies, Gem County, southwestern Idaho, 2015

USGS Publications Warehouse

Bartolino, James R.; Hopkins, Candice B.

2016-12-20

In recent years, the rapid population growth in Gem County, Idaho, has been similar to other counties in southwestern Idaho, increasing about 54 percent from 1990 to 2015. Because the entire population of the study area depends on groundwater for drinking water supply (either from self-supplied domestic, community, or municipal-supply wells), this population growth, along with changes in land use (including potential petroleum exploration and development), indicated to the public and local officials the need to assess the quality of groundwater used for human consumption. To this end, the U.S. Geological Survey, in cooperation with Gem County and the Idaho Department of Environmental Quality, assessed the quality of groundwater from freshwater aquifers used for domestic supply in Gem County. A total of 47 domestic or municipal wells, 1 spring, and 2 surface-water sites on the Payette River were sampled during September 8–November 19, 2015. The sampled water was analyzed for a variety of constituents, including major ions, trace elements, nutrients, bacteria, radionuclides, dissolved gasses, stable isotopes of water and methane, and either volatile organic compounds (VOCs) or pesticides.To better understand analytical results, a conceptual hydrogeologic framework was developed in which three hydrogeologic units were described: Quaternary-Tertiary deposits (QTd), Tertiary Idaho Group rocks (Tig), and Tertiary-Cretaceous igneous rocks (TKi). Water levels were measured in 30 wells during sampling, and a groundwater-level altitude map was constructed for the QTd and Tig units showing groundwater flow toward the Emmett Valley and Payette River.Analytical results indicate that groundwater in Gem County is generally of good quality. Samples collected from two wells contained water with fluoride concentrations greater than the U.S. Environmental Protection Agency (EPA) Maximum Contaminant Level (MCL) of 4 milligrams per liter (mg/L), six wells contained arsenic at concentrations greater than the EPA MCL of 10 micrograms per liter, and a sample from one well exceeded the MCL of 15 picocuries per liter for alpha particles. Although previous samples collected from some wells in Gem County contained nitrate concentrations greater than the MCL of 10 mg/L, the largest concentration detected in the current study was 5.2 mg/L. Total coliform bacteria was detected in four groundwater samples.Three volatile organic compounds (VOCs) were detected in samples collected from five wells, and five compounds of the triazine class of herbicides were detected in samples from five wells; no concentrations were greater than applicable EPA MCLs. Methane was detected in samples from 36 wells, with the concentration in 1 well large enough to be considered an explosion hazard by U.S. Office of Surface Mining guidelines. Stable isotope signatures of methane in six samples suggest that naturally occurring methane in Gem County is probably of both thermogenic and biogenic origin.

Type and amount of organic amendments affect enhanced biogenic methane production from coal and microbial community structure

USGS Publications Warehouse

Davis, Katherine J.; Lu, Shipeng; Barnhart, Elliott P.; Parker, Albert E.; Fields, Matthew W.; Gerlach, Robin

2018-01-01

Slow rates of coal-to-methane conversion limit biogenic methane production from coalbeds. This study demonstrates that rates of coal-to-methane conversion can be increased by the addition of small amounts of organic amendments. Algae, cyanobacteria, yeast cells, and granulated yeast extract were tested at two concentrations (0.1 and 0.5 g/L), and similar increases in total methane produced and methane production rates were observed for all amendments at a given concentration. In 0.1 g/L amended systems, the amount of carbon converted to methane minus the amount produced in coal only systems exceeded the amount of carbon added in the form of amendment, suggesting enhanced coal-to-methane conversion through amendment addition. The amount of methane produced in the 0.5 g/L amended systems did not exceed the amount of carbon added. While the archaeal communities did not vary significantly, the bacterial populations appeared to be strongly influenced by the presence of coal when 0.1 g/L of amendment was added; at an amendment concentration of 0.5 g/L the bacterial community composition appeared to be affected most strongly by the amendment type. Overall, the results suggest that small amounts of amendment are not only sufficient but possibly advantageous if faster in situcoal-to-methane production is to be promoted.

Methane biofiltration using autoclaved aerated concrete as the carrier material.

PubMed

Ganendra, Giovanni; Mercado-Garcia, Daniel; Hernandez-Sanabria, Emma; Boeckx, Pascal; Ho, Adrian; Boon, Nico

2015-09-01

The methane removal capacity of mixed methane-oxidizing bacteria (MOB) culture in a biofilter setup using autoclaved aerated concrete (AAC) as a highly porous carrier material was tested. Batch experiment was performed to optimize MOB immobilization on AAC specimens where optimum methane removal was obtained when calcium chloride was not added during bacterial inoculation step and 10-mm-thick AAC specimens were used. The immobilized MOB could remove methane at low concentration (~1000 ppmv) in a biofilter setup for 127 days at average removal efficiency (RE) of 28.7 %. Unlike a plug flow reactor, increasing the total volume of the filter by adding a biofilter in series did not result in higher total RE. MOB also exhibited a higher abundance at the bottom of the filter, in proximity with the methane gas inlet where a high methane concentration was found. Overall, an efficient methane biofilter performance could be obtained using AAC as the carrier material.

Aerobic methane production in surface waters of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Finke, N.; Crespo-Medina, M.; Schweers, J.; Joye, S. B.

2011-12-01

Near surface water of the global oceans often show elevated methane concentrations compared to the water column below with concentrations in supersaturation in regard to the atmosphere (Lamontagne et al. 1973), resulting in a source of this potent greenhouse gas to the atmosphere. The mechanisms leading to methane supersaturation in surface waters remains unclear. Incubations with Trichodesmium-containing Pacific surface water suggested methylphosphonate as potential methane precursor under phosphate limiting conditions (Karl et al. 2008), whereas in phosphate rich Arctic surface waters, DMSP addition stimulated methane production (Damm et al. 2010). Surface waters of the Gulf of Mexico typically exhibit a methane maximum that is conincident with the deep chlorophyll maximum, below the depths where Trichodesmium is abundant. Addition of methylphosphonate, dimethylsulfoniopropionate (DMSP) or methane thiol (MeSH), the proposed methane precursor in DMSP conversion to methane, to oxic sea water did not affect methane production within the chlorophyll maximum at most stations, whereas methyl phosphonate addition stimulated methane production in the surface water and proposed deep Trichodesmium horizon. Pre-filtration of the water through a 10 μm sieve, which eliminated Trichodesmium, or through a 1.2 μm filter, which eliminated additional cyanobacteria such as Synechococcus, did not reduce methane production. Under dark oxic and dark anoxic conditions, however, methane production was reduced 5 and 7-20 fold, respectively, indicating that anerobic methane production in anoxic microniches is not responsible for the methane production. The reduction of methane production under dark conditions suggests that methane production is, in some yet unrecognized way, linked to phototrophic metabolism. Cyanobacteria are likely not responsible for the observed aerobic methane production in the surface waters of the Gulf of Mexico and while methylphosphonate is a potential precursor in the surface waters, the precursor and methanism of methane production within the coincident deep chlorophyll/methane maximum remains unknown. Lamontagne R, Swinnert J, Linnenbo V, Smith WD (1973) Methane concentrations in various marine environments. Journal of Geophysical Research 78, 5317-5324 Karl DM et al. (2008) Aerobic production of methane in the sea. Nature Geosciences 1, 473-478 Damm E et al. (2010) Methane production in aerobic oligotrophic surface water in the central Arctic Ocean. Biogeosciences 7, 1099-1108

Optical fiber network sensor system for monitoring methane concentration

NASA Astrophysics Data System (ADS)

Zhang, Zhi-wei; Zhang, Ji-long

2011-08-01

With regard to the high accuracy optic-fiber sensor for monitoring methane concentration, the choice of light source depends on methane peak values. Besides, the environment of mine should be considered, that is to say other gas should be considered, such as vapor, CO and CO2 etc, without absorbent spectrum in the decided wavelength. It has been reported that vapor, CO and CO2 have no obvious absorption in 0.85μm, 1.3μm and 1.66μm area, CH4 has no obvious absorption in 0.85μm area. So diode laser with 1.3μm or 1.66μm peak wavelength is chosen as the optic-fiber sensor's light source for detecting methane concentration. On the basis of the principle of optic absorption varied with methane concentration at its characteristic absorbent wavelength, the advantage of optic-fiber sensor technology and the circumstance characteristic of the coal mine. An optic-fiber sensor system is presented for monitoring methane concentration. Space Division Multiple Access Technology (SDMAT) and long optical path absorbent pool technology are combined in the study. Considering the circumstance characteristic of the coal mine, the optic-fiber network sensors for detecting methane concentration from mix gas of vapor, CO, CH4 and CO2 are used. It introduces the principle of an optic-fiber sensor system for monitoring methane concentration in coal mine. It contains the structure block diagram of monitoring system, the system is mainly made up of diode laser for monitoring methane concentration, Y-shaped photo-coupler with coupled rate 50:50, optical switch 1×2, gas absorbent cell, the computer data process and control system and photoelectric transformer. In this study, in order to decrease to the influence of the dark-current of photodiode, intensity in light sources and temperature drifts of processing circuit on the system accuracy in measurement, a beam of light is broken down into two beams in the coupler of Y-shaped coupler, the one acts as the reference optical path, the other is known as the sensing optical path. The experimental result shows that diode laser with 1654.141nm in wavelength is taken as the optic source for detecting methane concentration, the detective limit of the sensor is below 4.274mg/m3 when the optical path of absorbent pool is 20 centimeters, and the prevision and stability could satisfy practical application. The whole instrument can also reach on-line measurement with multiple points on different spot.

Towards quantifying the reaction network around the sulfate–methane-transition-zone in the Ulleung Basin, East Sea, with a kinetic modeling approach

DOE PAGES

Hong, Wei-Li; Torres, Marta E.; Kim, Ji-Hoon; ...

2014-09-01

We present a kinetic model based upon pore water data collected from eight sites drilled during the second Ulleung Basin gas hydrate drilling expedition (UBGH2) in 2010. Three sites were drilled at locations where acoustic chimneys were identified in seismic data, and the rest were drilled on non-chimney (i.e. background) environments. Our model, coupled a comprehensive compositional and isotopic data set, is used to illustrate the different biogeochemical processes at play in those two environments, in terms of reactions around the sulfate-methane-transition-zone (SMTZ). Organic matter decomposition is an important process for production of methane, dissolved inorganic carbon (DIC) and consumptionmore » of sulfate in the non-chimney sites, whereas anaerobic oxidation of methane (AOM) dominates both carbon and sulfur cycles in the chimney environment. Different sources of methane mediate AOM in the two settings. Internally produced methane through CO₂ reduction (CR) and methanogenesis fuels AOM in the non-chimney sites, whereas AOM is sustained by methane from external sources in the chimney sites. We also simulate the system evolution from non-chimney to chimney conditions by increasing the bottom methane supply to a non-chimney setting. We show that the higher CH₄ flux leads to a higher microbial activity of AOM, and more organic matter decomposition through methanogenesis. A higher methanogenesis rate and a smaller CR contribution relative to AOM in the chimney sites is responsible for the isotopically light DIC and heavy methane in this environment, relative to the non-chimney sites.« less

Atmospheric Impacts of Emissions from Oil and Gas Development in the Uintah Basin, Utah, USA

NASA Astrophysics Data System (ADS)

Helmig, D.; Boylan, P. J.; Hueber, J.; Van Dam, B. A.; Mauldin, L.; Parrish, D. D.

2012-12-01

In the Uintah Basin in northeast Utah, USA, surface ozone levels during winter months have approached and on occasion exceeded the US National Ambient Air Quality Standard (NAAQS). Emissions from the extensive oil and gas exploration in this region are suspected to be the cause of these ozone episodes; however emission rates and photochemical processes are uncertain. During February 2012 continuous surface measurements and vertical profiling from a tethered balloon platform at the Horsepool site yielded high resolution boundary layer profile data on ozone and ozone precursor compounds, i.e. nitrogen oxides and volatile organic compounds as well as methane. Findings from this study were: 1. Surface ozone during the study period, which had no snow cover, did not exceed the NAAQS. 2. Nitrogen oxides varied from 1-50 ppbv pointing towards significant emission sources, likely from oil and gas operations. 3. Methane concentrations were elevated, reaching up to ~10 times its Northern Hemisphere (NH) atmospheric background. 3. Light non-methane hydrocarbons (NMHC) constituted the main fraction of volatile organic compounds. NMHC concentrations were highly elevated, exceeding levels seen in urban areas. 4. Ozone, methane, NOx and VOC showed distinct diurnal cycles, with large concentration increases seen at night, except for ozone, which showed the opposite behavior. 5. During nighttime concentrations of NOx, NMHC, and methane built up near the surface to levels that were much higher than their daytime concentrations. 6. Comparing NMHC to methane concentrations indicates a mass flux ratio of ~30% for total VOC/methane emissions for the Uintah Basin.

The future of energy gases

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

Howell, D.G.

1995-04-01

Natural gas, mainly methane, produces lower CO {sub 2}, CO, NO{sub x}, SO {sub 2} and particulate emissions than either oil or coal; thus further substitutions of methane for these fuels could help mitigate air pollution. Methane is, however, a potent greenhouse gas and the domestication of ruminants, cultivation of rice, mining of coal, drilling for oil, and transportation of natural gas have all contributed to a doubling of the amount of atmospheric methane since 1800. Today nearly 300,000 wells yearly produce each 21 trillion cubic feet of methane. Known reserves suggest about a 10 year supply at the abovemore » rates of recovery; and the potential for undiscovered resources is obscured by uncertainty involving price, new technologies, and environmental restrictions stemming from the need to drill an enormous number of wells, many in ecologically sensitive areas. The atomic simplicity of methane, composed of one carbon and four hydrogen atoms, may mask the complexity of this, the most basic of organic molecules. Within the Earth, methane is produced through thermochemical alteration of organic materials, and by biochemical reactions mediated by metabolic processes of archaebacteria; some methane may even be primordial, a residue of planetary accretion. Methane is known to exist in the mantle and lower crust. Near the Earth`s surface, methane occurs in enormous oil and/or gas reservoirs in rock, and is absorbed in coal, dissolved in water, and trapped in a latticework of ice-like material called gas hydrate. Methane also occurs in smaller volumes in landfills, rice paddies, termite complexes, ruminants, and even many humans. As an energy source, methane accounts for roughly 25 percent of current U.S. consumption, but its full energy potential is controversial. Methane is touted by some as a viable bridge to future energy systems, fueled by the sun and uranium and carried by electricity and hydrogen.« less

Selection of associated heterotrophs by methane-oxidizing bacteria at different copper concentrations.

PubMed

van der Ha, David; Vanwonterghem, Inka; Hoefman, Sven; De Vos, Paul; Boon, Nico

2013-03-01

Due to the increasing atmospheric concentration of the greenhouse gas methane, more knowledge is needed on the management of methanotrophic communities. While most studies have focused on the characteristics of the methane-oxidizing bacteria (MOB), less is known about their interactions with the associated heterotrophs. Interpretative tools based on denaturing gradient gel electrophoresis allowed to evaluate the influence of copper-an important enzymatic regulator for MOB-on the activity and composition of the bacterial community. Over 30 days, enrichments with 0.1, 1.0 and 10 μM Cu(2+) respectively, showed comparable methane oxidation activities. The different copper concentrations did not create major shifts in the methanotrophic communities, as a Methylomonas sp. was able to establish dominance at all different copper concentrations by switching between both known methane monooxygenases. The associated heterotrophic communities showed continuous shifts, but over time all cultures evolved to a comparable composition, independent of the copper concentration. This indicates that the MOB selected for certain heterotrophs, possibly fulfilling vital processes such as removal of toxic compounds. The presence of a large heterotrophic food web indirectly depending on methane as sole carbon and energy source was confirmed by a clone library wherein MOB only formed a minority of the identified species.

Effect of silane concentration on the supersonic combustion of a silane/methane mixture

NASA Technical Reports Server (NTRS)

Northam, G. B.; Mclain, A. G.; Pellett, G. L.; Diskin, G. S.

1986-01-01

A series of direct connect combustor tests was conducted to determine the effect of silane concentration on the supersonic combustion characteristics of silane/methane mixtures. Shock tube ignition delay data indicated more than an order of magnitude reduction in ignition delay times for both 10 and 20 percent silane/methane mixtures as compared to methane. The ignition delay time of the 10 percent mixture was only a factor of 2.3 greater than that of the 20 percent mixture. Supersonic combustion tests were conducted with the fuel injected into a model scramjet combustor. The combustor was mounted at the exit of a Mach 2 nozzle and a hydrogen fired heater was used to provide a variation in test gas total temperature. Tests using the 20 percent silane/methane mixture indicated considerable combustion enhancement when compared to methane alone. This mixture had an autoignition total temperature of 1650 R. This autoignition temperature can be contrasted with 2330 R for hydrogen and 1350 R for a 20 percent silane/hydrogen mixture in similar hardware. Methane without the silane additive did not autoignite in this configuration at total temperatures as high as 3900 R, the maximum temperature at which tests were conducted. Supersonic combustion tests with the silane concentration reduced to 10 percent indicated little improvement in combustion performance over pure methane. The addition of 20 percent silane to methane resulted in a pyrophoric fuel with good supersonic combustion performance. Reducing the silane concentration below this level, however, yielded a less pyrophoric fuel that exhibited poor supersonic combustion performance.

Surface-water hydrology and quality, and macroinvertebrate and smallmouth bass populations in four stream basins in southwestern Wisconsin, 1987-90

USGS Publications Warehouse

Graczyk, David J.; Lillie, Richard A.; Schlesser, Roger A.; Mason, John W.; Lyons, John D.; Kerr, Roger A.; Graczyk, David J.

1993-01-01

Low concentrations of dissolved oxygen constituted the most detrimental water-quality problem affecting smallmouth bass populations. Dissolved-oxygen concentrations were occasionally less than 3 milligrams per liter, a dissolved-oxygen concentration that may be detrimental to early-life stages of smallmouth bass in the streams; however, smallmouth bass were apparently able to withstand these low dissolved-oxygen concentrations and seem to have survived in some situations when dissolved-oxygen concentration decreased to1 milligram per liter.

Reactive iron and manganese in estuarine sediments of the Baltic Sea: Impacts of flocculation and redox shuttling

NASA Astrophysics Data System (ADS)

Jilbert, Tom; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Asmala, Eero; Hietanen, Susanna

2016-04-01

Iron (Fe) and manganese (Mn) play important roles in sedimentary carbon cycling in both freshwater and marine systems. Dissimilatory reduction of Fe and Mn oxides is known to be a major pathway of suboxic organic matter remineralization in surface sediments, while recent studies have shown that Fe and Mn oxides may be involved in the anaerobic oxidation of methane deeper in the sediment column (e.g., Egger et al., 2015). Estuaries are transitional environments, characterized by gradients of salinity and redox conditions which impact on the mobility of Fe and Mn. In turn, the distribution of Fe and Mn in estuarine sediments, and the role of the two metals in carbon cycling, is expected to be spatially heterogeneous. However, few studies have attempted to describe the sedimentary distribution of Fe and Mn in the context of processes occurring in the estuarine water column. In particular, salinity-driven flocculation and redox shuttling are two key processes whose relative impacts on sedimentary Fe and Mn have not been clearly demonstrated. In this study we investigated the coupled water column and sedimentary cycling of Fe and Mn along a 60km non-tidal estuarine transect in the Gulf of Finland, Baltic Sea. We show that riverine Fe entering the estuary as colloidal oxides associated with dissolved organic matter (DOM) is quickly flocculated and sedimented within 5 km of the river mouth, despite the shallow lateral salinity gradient. Sediments within this range are enriched in Fe (up to twice the regional average), principally in the form of crystalline Fe oxides as determined by sequential extractions. The high crystallinity implies relative maturity of the oxide mineralogy, likely due to sustained oxic conditions and long residence time in the river catchment. Despite the reducing conditions below the sediment-water interface, Fe is largely retained in the sediments close to the river mouth. In contrast, sedimentary Mn concentrations are highest in a deep silled basin more than 10km downstream. Throughout the estuary, Mn oxides are reductively dissolved shallower in the sediment column than Fe oxides, resulting in strong effluxes of dissolved Mn from the sediments. Subsequent oxidation of bottom water dissolved Mn to particulate oxides and lateral transport ("redox shuttling") account for the sedimentary Mn enrichments in the deep silled basin. Porewater data suggest that the heterogeneity of Fe and Mn availability in the estuarine sediments may influence the relative importance of the two metals for anaerobic oxidation of methane. Egger, M. et al., Environmental Science and Technology 49(1), 277-283, 2015.

Changes in methane emission and microbial community structure in a Phragmites australis-expanding tidal marsh of a temperature region

NASA Astrophysics Data System (ADS)

Kim, J.; Lee, J.; Kang, H.

2017-12-01

Phragmites australis is one of the representative vegetation of coastal wetlands which is distributed in North America, East Asia and European Countries. In North America, P. australis has invaded large areas of coastal wetlands, which causes various ecological problems such as increases in methane emission and reduction in biodiversity. In South Korea, P. australis is rapidly expanded in tidal marshes in Suncheon Bay. The expansion of P. australis enhanced methane emission by increasing dissolved organic carbon and soil moisture, and changing in relative abundances of methanogen, methanotroph, and sulfate reducing bacteria. Microbial community structure might be also shifted and affect methane cycle, but accurate observation on microbial community structure has not been fully illustrated yet. Therefore, we tried to monitor the changing microbial community structure due to P. australis expansion by using Next Generation Sequencing (NGS). NGS results showed that microbial community was substantially changed with the expansion. We also observed seasonal variations and chronosequence of microbial community structures along the expansion of P. australis, which showed distinctive changing patterns. P. australis expansion substantially affected microbial community structure in tidal marsh which may play an important role in methane cycle in tidal marshes.

30 CFR 75.323 - Actions for excessive methane.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Actions for excessive methane. 75.323 Section... excessive methane. (a) Location of tests. Tests for methane concentrations under this section shall be made.... (1) When 1.0 percent or more methane is present in a working place or an intake air course, including...

30 CFR 75.323 - Actions for excessive methane.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Actions for excessive methane. 75.323 Section... excessive methane. (a) Location of tests. Tests for methane concentrations under this section shall be made.... (1) When 1.0 percent or more methane is present in a working place or an intake air course, including...

30 CFR 75.323 - Actions for excessive methane.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Actions for excessive methane. 75.323 Section... excessive methane. (a) Location of tests. Tests for methane concentrations under this section shall be made.... (1) When 1.0 percent or more methane is present in a working place or an intake air course, including...

30 CFR 75.323 - Actions for excessive methane.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Actions for excessive methane. 75.323 Section... excessive methane. (a) Location of tests. Tests for methane concentrations under this section shall be made.... (1) When 1.0 percent or more methane is present in a working place or an intake air course, including...

30 CFR 75.323 - Actions for excessive methane.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Actions for excessive methane. 75.323 Section... excessive methane. (a) Location of tests. Tests for methane concentrations under this section shall be made.... (1) When 1.0 percent or more methane is present in a working place or an intake air course, including...

Archaeal abundance in post-mortem ruminal digesta may help predict methane emissions from beef cattle

NASA Astrophysics Data System (ADS)

Wallace, R. John; Rooke, John A.; Duthie, Carol-Anne; Hyslop, Jimmy J.; Ross, David W.; McKain, Nest; de Souza, Shirley Motta; Snelling, Timothy J.; Waterhouse, Anthony; Roehe, Rainer

2014-07-01

Methane produced from 35 Aberdeen-Angus and 33 Limousin cross steers was measured in respiration chambers. Each group was split to receive either a medium- or high-concentrate diet. Ruminal digesta samples were subsequently removed to investigate correlations between methane emissions and the rumen microbial community, as measured by qPCR of 16S or 18S rRNA genes. Diet had the greatest influence on methane emissions. The high-concentrate diet resulted in lower methane emissions (P < 0.001) than the medium-concentrate diet. Methane was correlated, irrespective of breed, with the abundance of archaea (R = 0.39), bacteria (-0.47), protozoa (0.45), Bacteroidetes (-0.37) and Clostridium Cluster XIVa (-0.35). The archaea:bacteria ratio provided a stronger correlation (0.49). A similar correlation was found with digesta samples taken 2-3 weeks later at slaughter. This finding could help enable greenhouse gas emissions of large animal cohorts to be predicted from samples taken conveniently in the abattoir.

Role of Siderophores in Dissimilatory Iron Reduction in Arctic Soils : Effect of Direct Amendment of Siderophores to Arctic Soil

NASA Astrophysics Data System (ADS)

Srinivas, A. J.; Dinsdale, E. A.; Lipson, D.

2014-12-01

Dissimilatory iron reduction (DIR), where ferric iron (Fe3+) is reduced to ferrous iron (Fe2+) anaerobically, is an important respiratory pathway used by soil bacteria. DIR contributes to carbon dioxide (CO2) efflux from the wet sedge tundra biome in the Arctic Coastal Plain (ACP) in Alaska, and could competitively inhibit the production of methane, a stronger greenhouse gas than CO2, from arctic soils. The occurrence of DIR as a dominant anaerobic process depends on the availability of substantial levels of Fe3+ in soils. Siderophores are metabolites made by microbes to dissolve Fe3+ from soil minerals in iron deficient systems, making Fe3+ soluble for micronutrient uptake. However, as the ACP is not iron deficient, siderophores in arctic soils may play a vital role in anaerobic respiration by dissolving Fe3+ for DIR. We studied the effects of direct siderophore addition to arctic soils through a field study conducted in Barrow, Alaska, and a laboratory incubation study conducted at San Diego State University. In the field experiment, 50μM deferroxamine mesylate (a siderophore), 50μM trisodium nitrilotriacetate (an organic chelator) or an equal volume of water was added to isolated experimental plots, replicated in clusters across the landscape. Fe2+ concentrations were measured in soil pore water samples collected periodically to measure DIR over time in each. In the laboratory experiment, frozen soil samples obtained from drained thaw lake basins in the ACP, were cut into cores and treated with the above-mentioned compounds to the same final concentrations. Along with measuring Fe2+ concentrations, CO2 output was also measured to monitor DIR over time in each core. Experimental addition of siderophores to soils in both the field and laboratory resulted in increased concentrations of soluble Fe3+ and a sustained increase in Fe2+concentrations over time, along with increased respiration rates in siderophore-amended cores. These results show increased DIR in siderophore treated cores compared to the other treatments. From the results of these experiments, we conclude that arctic soil microbes can use siderophores to maintain a pool of dissolved Fe3+ for DIR. This study provides insight into the mechanisms of DIR in this ecosystem, and has relevance for understanding anaerobic soil respiration in the Arctic.

Pasture-scale measurement of methane emissions of grazing cattle

USDA-ARS?s Scientific Manuscript database

Quantifying methane emission of cattle grazing on southern Great Plains pastures using micrometeorology presents several challenges. Cattle are elevated, mobile point sources of methane, so that knowing their location in relation to atmospheric methane concentration measurements becomes critical. St...

Evidence of Titan's Climate History from Evaporite Distribution

NASA Astrophysics Data System (ADS)

MacKenzie, Shannon; Barnes, J. W.; Brown, R.; Sotin, C.; Buratti, B. J.; Clark, R.; Baines, K. H.; Nicholson, P. D.; Le Mouelic, S.; Rodriguez, S.

2013-10-01

5-μm bright material on the surface of Titan has been positively correlated with the shores of RADAR-dark (liquid-filled) and the bottoms of RADAR-bright (empty) lakebeds in the region just south of Ligea Mare by Barnes et al. (2011). This water ice-poor spectral unit was thus proposed to be evaporite, the formerly-dissolved solute deposits left behind when the solvent (here presumably a methane/ethane mixture) evaporates. Because evaporite forms under specific conditions—solute and solvent at or near saturation, no outlets or other means of affecting the solution balance, etc.—the presence of evaporite can shed light on Titan's climate history. Adding to the previously identified cases, we use the breadth of available Cassini VIMS data to comprehensively map new instances of evaporite. In particular, we found new instances of evaporite in the north polar region and the midlatitudes. Our map of the global distribution of Titan's 5-μm-bright deposits can be used to constrain the historical evolution of Titan's surface volatile inventory and may bear on the question of the time variation of the methane concentration in Titan's atmosphere. Furthermore, we explore the implications of the idea that the 5-$\\mu$m-bright areas are indeed mostly evaporitic in nature with respect to the relationship between the regional and global volatile cycles.

Tylosin effect on methanogenesis in an anaerobic biomass from swine wastewater treatment.

PubMed

García-Sánchez, Liliana; Garzón-Zúñiga, Marco Antonio; Buelna, Gerardo; Estrada-Arriaga, Edson Baltazar

2016-01-01

The effect of different concentrations of tylosin on methane production was investigated: first methanogenesis in a biomass without contact with the antibiotic, and later the ability of the sludge to adapt to increasing concentrations of tylosin. Results showed that, for biomass that had no contact with the antibiotic, the presence of tylosin inhibits the generation of methane even at concentrations as small as 0.01 mg L(-1), and samples at concentrations above 0.5 mg L(-1) produced practically no methane, whereas, in the digesters acclimated in the presence of tylosin at a concentration of 0.01 to 0.065 mg L(-1), methanogenesis is not inhibited in the presence of antibiotic and the generation of methane is improved. This behaviour suggests the microorganisms have developed not only resistance to the antibiotic but also an ability to metabolize it.

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.

Mechanisms of the Diffusion of Nonpolar Substances in a Hydrophilic Ionic Liquid

NASA Astrophysics Data System (ADS)

Atamas', N. A.

2018-01-01

The structural-dynamic features of ionic liquid-nonpolar substance systems are studied by means of molecular dynamics using Frenkel's fundamental theory of a liquid and the phonon theory of the thermodynamics of a liquid, in combination with the DL_POLY_4.05 software package. Argon, methane, and benzene molecules serve as the dissolved substances. Model concepts are proposed and analyzed to describe the diffusion of molecules of a dissolved substance in an ionic liquid. It is shown that an increase in the mass of the molecules of a dissolved nonpolar substance correlates with their mobility in a hydrophilic ionic liquid (IL). This determines the diffusion of the components of dmim+/Cl- IL solutions and is responsible for the anomalous behavior of the solubility of nonpolar substances in them.

DISSOLVED METHANE IN THE SILLS AREA, GULF OF CALIFORNIA, MEXICO

EPA Science Inventory

The northern part of the Gulf of California is physically separated from the rest of the Gulf by a series of sills and islands. Its waters are highly productive as several water masses interact with each other at the sills. One of the characteristics in the area is the presence o...

Improved enrichment culture technique for methane-oxidizing bacteria from marine ecosystems: the effect of adhesion material and gas composition.

PubMed

Vekeman, Bram; Dumolin, Charles; De Vos, Paul; Heylen, Kim

2017-02-01

Cultivation of microbial representatives of specific functional guilds from environmental samples depends largely on the suitability of the applied growth conditions. Especially the cultivation of marine methanotrophs has received little attention, resulting in only a limited number of ex situ cultures available. In this study we investigated the effect of adhesion material and headspace composition on the methane oxidation activity in methanotrophic enrichments obtained from marine sediment. Addition of sterilized natural sediment or alternatively the addition of acid-washed silicon dioxide significantly increased methane oxidation. This positive effect was attributed to bacterial adhesion on the particles via extracellular compounds, with a minimum amount of particles required for effect. As a result, the particles were immobilized, thus creating a stratified environment in which a limited diffusive gas gradients could build up and various microniches were formed. Such diffusive gas gradient might necessitate high headspace concentrations of CH 4 and CO 2 for sufficient concentrations to reach the methane-oxidizing bacteria in the enrichment culture technique. Therefore, high concentrations of methane and carbon dioxide, in addition to the addition of adhesion material, were tested and indeed further stimulated methane oxidation. Use of adhesion material in combination with high concentrations of methane and carbon dioxide might thus facilitate the cultivation and subsequent enrichment of environmentally important members of this functional guild. The exact mechanism of the observed positive effects on methane oxidation and the differential effect on methanotrophic diversity still needs to be explored.

Role of Megafauna and Frozen Soil in the Atmospheric CH4 Dynamics

PubMed Central

Zimov, Sergey; Zimov, Nikita

2014-01-01

Modern wetlands are the world’s strongest methane source. But what was the role of this source in the past? An analysis of global 14C data for basal peat combined with modelling of wetland succession allowed us to reconstruct the dynamics of global wetland methane emission through time. These data show that the rise of atmospheric methane concentrations during the Pleistocene-Holocene transition was not connected with wetland expansion, but rather started substantially later, only 9 thousand years ago. Additionally, wetland expansion took place against the background of a decline in atmospheric methane concentration. The isotopic composition of methane varies according to source. Owing to ice sheet drilling programs past dynamics of atmospheric methane isotopic composition is now known. For example over the course of Pleistocene-Holocene transition atmospheric methane became depleted in the deuterium isotope, which indicated that the rise in methane concentrations was not connected with activation of the deuterium-rich gas clathrates. Modelling of the budget of the atmospheric methane and its isotopic composition allowed us to reconstruct the dynamics of all main methane sources. For the late Pleistocene, the largest methane source was megaherbivores, whose total biomass is estimated to have exceeded that of present-day humans and domestic animals. This corresponds with our independent estimates of herbivore density on the pastures of the late Pleistocene based on herbivore skeleton density in the permafrost. During deglaciation, the largest methane emissions originated from degrading frozen soils of the mammoth steppe biome. Methane from this source is unique, as it is depleted of all isotopes. We estimated that over the entire course of deglaciation (15,000 to 6,000 year before present), soils of the mammoth steppe released 300–550 Pg (1015 g) of methane. From current study we conclude that the Late Quaternary Extinction significantly affected the global methane cycle. PMID:24695117

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

NASA Technical Reports Server (NTRS)

Richey, Jeffrey E.; Devol, Allan H.; Wofsy, Steven C.; Victoria, Reynaldo; Riberio, Maria N. G.

1986-01-01

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration.

Spatially Resolved Measurements of CO2 and CH4 Concentration and Gas-Exchange Velocity Highly Influence Carbon-Emission Estimates of Reservoirs

PubMed Central

2017-01-01

The magnitude of diffusive carbon dioxide (CO2) and methane (CH4) emission from man-made reservoirs is uncertain because the spatial variability generally is not well-represented. Here, we examine the spatial variability and its drivers for partial pressure, gas-exchange velocity (k), and diffusive flux of CO2 and CH4 in three tropical reservoirs using spatially resolved measurements of both gas concentrations and k. We observed high spatial variability in CO2 and CH4 concentrations and flux within all three reservoirs, with river inflow areas generally displaying elevated CH4 concentrations. Conversely, areas close to the dam are generally characterized by low concentrations and are therefore not likely to be representative for the whole system. A large share (44–83%) of the within-reservoir variability of gas concentration was explained by dissolved oxygen, pH, chlorophyll, water depth, and within-reservoir location. High spatial variability in k was observed, and kCH4 was persistently higher (on average, 2.5 times more) than kCO2. Not accounting for the within-reservoir variability in concentrations and k may lead to up to 80% underestimation of whole-system diffusive emission of CO2 and CH4. Our findings provide valuable information on how to develop field-sampling strategies to reliably capture the spatial heterogeneity of diffusive carbon fluxes from reservoirs. PMID:29257874

Laser beam methane detector

NASA Technical Reports Server (NTRS)

Hinkley, E. D., Jr.

1981-01-01

Instrument uses infrared absorption to determine methane concentration in liquid natural gas vapor. Two sensors measure intensity of 3.39 mm laser beam after it passes through gas; absorption is proportional to concentration of methane. Instrument is used in modeling spread of LNG clouds and as leak detector on LNG carriers and installations. Unit includes wheels for mobility and is both vertically and horizontally operable.

Fire, Carbon, and Greenhouse Gas Emissions from Aquatic Ecosystems in the Yukon-Kuskokwim River Delta

NASA Astrophysics Data System (ADS)

Schade, J. D.; Kuhn, M. A.; Mann, P. J.; Holmes, R. M.; Natali, S.; Ludwig, S.; Wagner, S.

2016-12-01

Northern latitudes are experiencing rapid changes in climate that are profoundly altering permafrost-dominated ecosystems. Increased permafrost thaw and fire frequency and severity are changing the structure and function of these ecosystems in ways likely to alter greenhouse gas (GHG) emission, leading to feedbacks on climate that may accelerate warming. Our objective was to investigate changes in GHG emissions and carbon and nitrogen dynamics in aquatic ecosystems in response to recent fires in the Yukon-Kuskokwim river delta in western Alaska. In summer 2015, more area in the YK Delta burned then in the previous 74 years combined (726 km2 in 2015 vs. 477 km2 during 1940-2014). In June of 2016, we sampled water and dissolved gases from a variety of aquatic ecosystems, including small upland ponds and wetlands and streams lower in the landscape, in recently burned and control sites near the Kuka Creek 2015 burn scar in the Yukon Delta National Wildlife Refuge. We measured a range of physical parameters, including water temperature, conductivity, dissolved oxygen, and pH. We also estimated fluxes of CO2 and CH4 from surface waters using a floating chamber connected to a Los Gatos Ultraportable gas analyzer. Water samples were analyzed for dissolved organic carbon (DOC) and total dissolved nitrogen (TDN). Results show reduced DOC concentrations in small upland ponds in burned sites and evidence for loss of DOC downslope in control sites. In contrast, TDN concentration was higher in streams draining burned sites, suggesting fire mobilized N in soils, which was then transported to downslope ecosystems. Furthermore, fire generally increased pH, particularly in small ponds. Finally, we observed 3-4 fold higher CO2 and CH4 fluxes from aquatic ecosystems in burned sites as compared with control sites. We hypothesize that this is due to increased thaw depth and increased pH, which combine to increase resource availability and release methane-producing microbes from the constraints of low pH. These results suggest a strong positive feedback on climate from short-term responses of aquatic ecosystems to fire in the Arctic.

Methane baseline concentrations and sources in shallow aquifers from the shale gas-prone region of the St. Lawrence lowlands (Quebec, Canada).

PubMed

Moritz, Anja; Hélie, Jean-Francois; Pinti, Daniele L; Larocque, Marie; Barnetche, Diogo; Retailleau, Sophie; Lefebvre, René; Gélinas, Yves

2015-04-07

Hydraulic fracturing is becoming an important technique worldwide to recover hydrocarbons from unconventional sources such as shale gas. In Quebec (Canada), the Utica Shale has been identified as having unconventional gas production potential. However, there has been a moratorium on shale gas exploration since 2010. The work reported here was aimed at defining baseline concentrations of methane in shallow aquifers of the St. Lawrence Lowlands and its sources using δ(13)C methane signatures. Since this study was performed prior to large-scale fracturing activities, it provides background data prior to the eventual exploitation of shale gas through hydraulic fracturing. Groundwater was sampled from private (n = 81), municipal (n = 34), and observation (n = 15) wells between August 2012 and May 2013. Methane was detected in 80% of the wells with an average concentration of 3.8 ± 8.8 mg/L, and a range of <0.0006 to 45.9 mg/L. Methane concentrations were linked to groundwater chemistry and distance to the major faults in the studied area. The methane δ(1)(3)C signature of 19 samples was > -50‰, indicating a potential thermogenic source. Localized areas of high methane concentrations from predominantly biogenic sources were found throughout the study area. In several samples, mixing, migration, and oxidation processes likely affected the chemical and isotopic composition of the gases, making it difficult to pinpoint their origin. Energy companies should respect a safe distance from major natural faults in the bedrock when planning the localization of hydraulic fracturation activities to minimize the risk of contaminating the surrounding groundwater since natural faults are likely to be a preferential migration pathway for methane.

Chasing Sources and Transports of Methane Plumes in the Northern Gulf of Mexico Using In Situ Sensors on Untethered Landers

NASA Astrophysics Data System (ADS)

Martens, C. S.; Mendlovitz, H.; Seim, H.; Lapham, L.; Magen, C.; Joye, S. B.; MacDonald, I. R.; Asper, V. L.; Diercks, A. R.

2016-02-01

In situ time-series measurements of light hydrocarbons, oxygen, temperature and bottom currents from landers and elevators in the benthic boundary layer (BBL) at multiple sites in the northern Gulf of Mexico reveal spatial and temporal variability in methane concentrations controlled by horizontal advection of methane-rich plumes originating from nearby natural oil and gas seeps. Multi-sensor systems deployed for several weeks within 1m of the seafloor at depths from 882 to 1622m revealed methane concentrations ranging from near atmospheric saturation (<3 nM) to over 4000 nM depending on seep proximity, current speed and direction. Methane concentrations observed in the BBL equal or exceed maximum near-bottom values seen in shipboard water column profiles analyzed by conventional gas chromatography. Continuous laser sensor methane measurements from mini-landers deployed in September 2015 at our Horn Dome and Bush Hill sites featuring numerous gas seeps revealed methane concentrations ranging from <3 to over 300 nM over two-week periods. Net current speeds in the BBL at our six lander sites in blocks GC600, OC26 and MC118 ranged from near zero to over 5 cm/s; instantaneous speeds ranged from near zero to over 30 cm/s. Near real-time acquisition of continuous hydrocarbon concentration and current data within the BBL and friction layer from untethered platforms provides important new opportunities for monitoring the impacts of natural seeps and accidental hydrocarbon releases. The instrumented approaches we have developed to simultaneously monitor methane sources and physical processes controlling plume development and transport will enable more effective responses to further accidental hydrocarbon releases.

Abiotic production of methane in terrestrial planets.

PubMed

Guzmán-Marmolejo, Andrés; Segura, Antígona; Escobar-Briones, Elva

2013-06-01

On Earth, methane is produced mainly by life, and it has been proposed that, under certain conditions, methane detected in an exoplanetary spectrum may be considered a biosignature. Here, we estimate how much methane may be produced in hydrothermal vent systems by serpentinization, its main geological source, using the kinetic properties of the main reactions involved in methane production by serpentinization. Hydrogen production by serpentinization was calculated as a function of the available FeO in the crust, given the current spreading rates. Carbon dioxide is the limiting reactant for methane formation because it is highly depleted in aqueous form in hydrothermal vent systems. We estimated maximum CH4 surface fluxes of 6.8×10(8) and 1.3×10(9) molecules cm(-2) s(-1) for rocky planets with 1 and 5 M⊕, respectively. Using a 1-D photochemical model, we simulated atmospheres with volume mixing ratios of 0.03 and 0.1 CO2 to calculate atmospheric methane concentrations for the maximum production of this compound by serpentinization. The resulting abundances were 2.5 and 2.1 ppmv for 1 M⊕ planets and 4.1 and 3.7 ppmv for 5 M⊕ planets. Therefore, low atmospheric concentrations of methane may be produced by serpentinization. For habitable planets around Sun-like stars with N2-CO2 atmospheres, methane concentrations larger than 10 ppmv may indicate the presence of life.

Ambiguity in the causes for decadal trends in atmospheric methane and hydroxyl

PubMed Central

Turner, Alexander J.; Wennberg, Paul O.; Jacob, Daniel J.

2017-01-01

Methane is the second strongest anthropogenic greenhouse gas and its atmospheric burden has more than doubled since 1850. Methane concentrations stabilized in the early 2000s and began increasing again in 2007. Neither the stabilization nor the recent growth are well understood, as evidenced by multiple competing hypotheses in recent literature. Here we use a multispecies two-box model inversion to jointly constrain 36 y of methane sources and sinks, using ground-based measurements of methane, methyl chloroform, and the C13/C12 ratio in atmospheric methane (δ13CH4) from 1983 through 2015. We find that the problem, as currently formulated, is underdetermined and solutions obtained in previous work are strongly dependent on prior assumptions. Based on our analysis, the mathematically most likely explanation for the renewed growth in atmospheric methane, counterintuitively, involves a 25-Tg/y decrease in methane emissions from 2003 to 2016 that is offset by a 7% decrease in global mean hydroxyl (OH) concentrations, the primary sink for atmospheric methane, over the same period. However, we are still able to fit the observations if we assume that OH concentrations are time invariant (as much of the previous work has assumed) and we then find solutions that are largely consistent with other proposed hypotheses for the renewed growth of atmospheric methane since 2007. We conclude that the current surface observing system does not allow unambiguous attribution of the decadal trends in methane without robust constraints on OH variability, which currently rely purely on methyl chloroform data and its uncertain emissions estimates. PMID:28416668

Specific Conductance and Dissolved-Solids Characteristics for the Green River and Muddy Creek, Wyoming, Water Years 1999-2008

USGS Publications Warehouse

Clark, Melanie L.; Davidson, Seth L.

2009-01-01

Southwestern Wyoming is an area of diverse scenery, wildlife, and natural resources that is actively undergoing energy development. The U.S. Department of the Interior's Wyoming Landscape Conservation Initiative is a long-term science-based effort to assess and enhance aquatic and terrestrial habitats at a landscape scale, while facilitating responsible energy development through local collaboration and partnerships. Water-quality monitoring has been conducted by the U.S. Geological Survey on the Green River near Green River, Wyoming, and Muddy Creek near Baggs, Wyoming. This monitoring, which is being conducted in cooperation with State and other Federal agencies and as part of the Wyoming Landscape Conservation Initiative, is in response to concerns about potentially increased dissolved solids in the Colorado River Basin as a result of energy development. Because of the need to provide real-time dissolved-solids concentrations for the Green River and Muddy Creek on the World Wide Web, the U.S. Geological Survey developed regression equations to estimate dissolved-solids concentrations on the basis of continuous specific conductance using relations between measured specific conductance and dissolved-solids concentrations. Specific conductance and dissolved-solids concentrations were less varied and generally lower for the Green River than for Muddy Creek. The median dissolved-solids concentration for the site on the Green River was 318 milligrams per liter, and the median concentration for the site on Muddy Creek was 943 milligrams per liter. Dissolved-solids concentrations ranged from 187 to 594 milligrams per liter in samples collected from the Green River during water years 1999-2008. Dissolved-solids concentrations ranged from 293 to 2,485 milligrams per liter in samples collected from Muddy Creek during water years 2006-08. The differences in dissolved-solids concentrations in samples collected from the Green River compared to samples collected from Muddy Creek reflect the different basin characteristics. Relations between specific conductance and dissolved-solids concentrations were statistically significant for the Green River (p-value less than 0.001) and Muddy Creek (p-value less than 0.001); therefore, specific conductance can be used to estimate dissolved-solids concentrations. Using continuous specific conductance values to estimate dissolved solids in real-time on the World Wide Web increases the amount and improves the timeliness of data available to water managers for assessing dissolved-solids concentrations in the Colorado River Basin.

Continuous in-situ methane measurements at paddy fields in a rural area of India with poor electric infrastructure, using a low-cost instrument based on open-path near-IR laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hidemori, T.; Matsumi, Y.; Nakayama, T.; Kawasaki, M.; Sasago, H.; Takahashi, K.; Imasu, R.; Takeuchi, W.; Adachi, M.; Machida, T.; Terao, Y.; Nomura, S.; Dhaka, S. K.; Singh, J.

2015-12-01

In southeast and south Asia, the previous satellite observations suggest that the methane emission from rice paddies is significant and important source of methane during rainy season. Since it is difficult to measure methane stably and continuously at rural areas such as the paddy fields in terms of infrastructures and maintenances, there are large uncertainties in quantitative estimation of methane emission in these areas and there are needs for more certification between satellite and ground based measurements. To measure methane concentrations continuously at difficult situations such as the center of paddy fields　and wetlands, we developed the continuous in-situ measurement system, not to look for your lost keys under the streetlight. The methane gas sensor is used an open-path laser based measurement instrument (LaserMethane, ANRITSU CORPORATION), which can quickly and selectively detect average methane concentrations on the optical path of the laser beam. The developed system has the power supply and telecommunication system to run the laser gas sensor in rural areas with poor electricity infrastructure.The methane measurement system was installed at paddy fields of Sonepat, Haryana on the north of Delhi in India and has been operated from the end of 2014. The air sampling along with our measurement has been carried out once a week during daytime to calibrate the laser instrument. We found that the seasonal variation of methane concentrations was different from the satellite observations and there were significant diurnal variations, which it was difficult to detect from occasional air samplings. We will present details of the measurement system and recent results of continuous methane measurements in India.

A 3D Microphysical Model of Titan's Methane Cloud

NASA Astrophysics Data System (ADS)

Xiao, J.; Newman, C.; Inada, A.; Richardson, M.

2006-12-01

A time-dependent idealized 3D microphysical model for Titan's methane cloud is described. This new high resolution microphysical model nests in a Titan WRF GCM model. It assumes the vapor-liquid equilibria of methane-nitrogen mixtures which are based on the recent chemical experiments and thermodynamics models. In particular, the methane is condensed at a given temperature and pressure. Meanwhile nitrogen is dissolved in the methane liquid. The new model first uses the data from the thermodynamic model (Kouvaris et al. 1991), which involves saturation criteria, composition of condensate, and latent heat for a given pressure-temperature profile. For altitudes lower than 14 km, methane is saturated and condensed into liquid phase. However for altitudes from 14 km above to tropopause, methane is changed into supercooled liquid state. Then, we do some testing experiments with 1D model by varying the initial methane vapor mass mixing ratio profile and the initial mole fraction of methane in liquid phase. Based on the steady state results from 1D model, an idealized 3D microphysics model is developed to investigate the convection cloud in Titan's troposphere. Due to lower relative humidity at titan's surface (Samuelson et al. 1997) and the current estimated moist adiabatic lapse rate, convection is hardly to happen without lifting. For this reason, we apply a symmetry cosine ridge in a 100*100 grids box to force the air flow lifted at certain levels, which in turn drives the condensation of methane vapor. In addition to the abundance of methane clouds and its duration provided by the 3D model, our study demonstrates that vertical motion might be likely the major cause of convection clouds in Titan's troposphere. As the future work, we will further investigate size-resolved microphysical scheme to insight into the nature of methane cycle in Titan's atmosphere.

The Application of a Jet Fan for the Control of Air and Methane Streams Mixing at the Excavations Cross - The Results of Numerical Simulation

NASA Astrophysics Data System (ADS)

Wrona, Paweł; Różański, Zenon; Pach, Grzegorz; Domagała, Lech

2016-09-01

The paper presents the results of numerical simulations into the distribution of methane concentration at the intersection of two excavations with a fan (turned on) giving the air stream to the area of the crossing. Assumed case represents emergency situation related to the unexpected flow of methane from an excavation and its mixing with fresh air. It is possible when sudden gas outburst takes place, methane leaks from methane drainage system or gas leaks out the pipelines of underground coal gasification devices. Three options were considered - corresponding to three different speeds of the jet fan. They represent three stages of fan work. First - low air speed is forced by a pneumatic fan, when electricity is cut off after high methane concentration detection. Medium speed can be forced by pneumatic-electric device when methane concentration allows to turn on the electricity. Third, the highest speed is for electric fans. Simulations were carried out in the Fire Dynamics Simulator (FDS) belongs to the group of programs Computational Fluid Dynamics (CFD). The governing equations are being solved in a numerical way. It was shown that proposed solution allows partial dilution of methane in every variant of speed what should allow escape of the miners from hazardous area.

76 FR 37838 - Petitions for Modification of Application of Existing Mandatory Safety Standards

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-28

... may include periodic tests of methane levels and limits on the minimum methane concentrations that may...) Methane monitor(s) will be calibrated on the longwall, continuous mining machine, or cutting machine and... petitioner will test for methane with a hand-held methane detector at least every 10 minutes from the time...

Quantification of the methane concentration using anaerobic oxidation of methane coupled to extracellular electron transfer

EPA Science Inventory

A biofilm anode acclimated with acetate, acetate+methane, and methane growth media for over three years produced a steady current density of 1.6-2.3 mA/m^2 in a microbial electrochemical cell (MxC) fed with methane as the sole electron donor. Geobacter was the dominant genus for...

Biodiesel presence in the source zone hinders aromatic hydrocarbons attenuation in a B20-contaminated groundwater

NASA Astrophysics Data System (ADS)

Ramos, Débora Toledo; Lazzarin, Helen Simone Chiaranda; Alvarez, Pedro J. J.; Vogel, Timothy M.; Fernandes, Marilda; do Rosário, Mário; Corseuil, Henry Xavier

2016-10-01

The behavior of biodiesel blend spills have received limited attention in spite of the increasing and widespread introduction of biodiesel to the transportation fuel matrix. In this work, a controlled field release of biodiesel B20 (100 L of 20:80 v/v soybean biodiesel and diesel) was monitored over 6.2 years to assess the behavior and natural attenuation of constituents of major concern (e.g., BTEX (benzene, toluene, ethyl-benzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons)) in a sandy aquifer material. Biodiesel was preferentially biodegraded compared to diesel aromatic compounds with a concomitant increase in acetate, methane (near saturation limit (≈ 22 mg L- 1)) and dissolved BTEX and PAH concentrations in the source zone during the first 1.5 to 2.0 years after the release. Benzene and benzo(a)pyrene concentrations remained above regulatory limits in the source zone until the end of the experiment (6.2 years after the release). Compared to a previous adjacent 100-L release of ethanol-amended gasoline, biodiesel/diesel blend release resulted in a shorter BTEX plume, but with higher residual dissolved hydrocarbon concentrations near the source zone. This was attributed to greater persistence of viscous (and less mobile) biodiesel than the highly-soluble and mobile ethanol in the source zone. This persistence of biodiesel/diesel NAPL at the source zone slowed BTEX and PAH biodegradation (by the establishment of an anaerobic zone) but reduced the plume length by reducing mobility. This is the first field study to assess biodiesel/diesel blend (B20) behavior in groundwater and its effects on the biodegradation and plume length of priority groundwater pollutants.

Biodiesel presence in the source zone hinders aromatic hydrocarbons attenuation in a B20-contaminated groundwater.

PubMed

Ramos, Débora Toledo; Lazzarin, Helen Simone Chiaranda; Alvarez, Pedro J J; Vogel, Timothy M; Fernandes, Marilda; do Rosário, Mário; Corseuil, Henry Xavier

2016-10-01

The behavior of biodiesel blend spills have received limited attention in spite of the increasing and widespread introduction of biodiesel to the transportation fuel matrix. In this work, a controlled field release of biodiesel B20 (100L of 20:80 v/v soybean biodiesel and diesel) was monitored over 6.2years to assess the behavior and natural attenuation of constituents of major concern (e.g., BTEX (benzene, toluene, ethyl-benzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons)) in a sandy aquifer material. Biodiesel was preferentially biodegraded compared to diesel aromatic compounds with a concomitant increase in acetate, methane (near saturation limit (≈22mgL -1 )) and dissolved BTEX and PAH concentrations in the source zone during the first 1.5 to 2.0years after the release. Benzene and benzo(a)pyrene concentrations remained above regulatory limits in the source zone until the end of the experiment (6.2years after the release). Compared to a previous adjacent 100-L release of ethanol-amended gasoline, biodiesel/diesel blend release resulted in a shorter BTEX plume, but with higher residual dissolved hydrocarbon concentrations near the source zone. This was attributed to greater persistence of viscous (and less mobile) biodiesel than the highly-soluble and mobile ethanol in the source zone. This persistence of biodiesel/diesel NAPL at the source zone slowed BTEX and PAH biodegradation (by the establishment of an anaerobic zone) but reduced the plume length by reducing mobility. This is the first field study to assess biodiesel/diesel blend (B20) behavior in groundwater and its effects on the biodegradation and plume length of priority groundwater pollutants. Copyright © 2016 Elsevier B.V. All rights reserved.

Linking pore-scale and basin-scale effects on diffusive methane transport in hydrate bearing environments through multi-scale reservoir simulations

NASA Astrophysics Data System (ADS)

Nole, M.; Daigle, H.; Cook, A.; Malinverno, A.; Hillman, J. I. T.

2016-12-01

We explore the gas hydrate-generating capacity of diffusive methane transport induced by solubility gradients due to pore size contrasts in lithologically heterogeneous marine sediments. Through the use of 1D, 2D, and 3D reactive transport simulations, we investigate scale-dependent processes in diffusion-dominated gas hydrate systems. These simulations all track a sand body, or series of sands, surrounded by clays as they are buried through the gas hydrate stability zone. Methane is sourced by microbial methanogenesis in the clays surrounding the sand layers. In 1D, simulations performed in a Lagrangian reference frame demonstrate that gas hydrate in thin sands (3.6 m thick) can occur in high saturations (upward of 70%) at the edges of sand bodies within the upper 400 meters below the seafloor. Diffusion of methane toward the center of the sand layer depends on the concentration gradient within the sand: broader sand pore size distributions with smaller median pore sizes enhance diffusive action toward the sand's center. Incorporating downhole log- and laboratory-derived sand pore size distributions, gas hydrate saturations in the center of the sand can reach 20% of the hydrate saturations at the sand's edges. Furthermore, we show that hydrate-free zones exist immediately above and below the sand and are approximately 5 m thick, depending on the sand-clay solubility contrast. A moving reference frame is also adopted in 2D, and the angle of gravity is rotated relative to the grid system to simulate a dipping sand layer. This is important to minimize diffusive edge effects or numerical diffusion that might be associated with a dipping sand in an Eulerian grid system oriented orthogonal to gravity. Two-dimensional simulations demonstrate the tendency for gas hydrate to accumulate downdip in a sand body because of greater methane transport at depth due to larger sand-clay solubility contrasts. In 3D, basin-scale simulations illuminate how convergent sand layers in a multilayered system can compete for diffusion from clays between them, resulting in relatively low hydrate saturations. All simulations suggest that when hydrate present in clays dissociates with burial, the additional dissolved methane is soaked up by nearby sands preserving high hydrate saturations.

Linking pore-scale and basin-scale effects on diffusive methane transport in hydrate bearing environments through multi-scale reservoir simulations

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

Nole, Michael; Daigle, Hugh; Cook, Ann

We explore the gas hydrate-generating capacity of diffusive methane transport induced by solubility gradients due to pore size contrasts in lithologically heterogeneous marine sediments. Through the use of 1D, 2D, and 3D reactive transport simulations, we investigate scale-dependent processes in diffusion-dominated gas hydrate systems. These simulations all track a sand body, or series of sands, surrounded by clays as they are buried through the gas hydrate stability zone. Methane is sourced by microbial methanogenesis in the clays surrounding the sand layers. In 1D, simulations performed in a Lagrangian reference frame demonstrate that gas hydrate in thin sands (3.6 m thick)more » can occur in high saturations (upward of 70%) at the edges of sand bodies within the upper 400 meters below the seafloor. Diffusion of methane toward the center of the sand layer depends on the concentration gradient within the sand: broader sand pore size distributions with smaller median pore sizes enhance diffusive action toward the sand’s center. Incorporating downhole log- and laboratory-derived sand pore size distributions, gas hydrate saturations in the center of the sand can reach 20% of the hydrate saturations at the sand’s edges. Furthermore, we show that hydrate-free zones exist immediately above and below the sand and are approximately 5 m thick, depending on the sand-clay solubility contrast. A moving reference frame is also adopted in 2D, and the angle of gravity is rotated relative to the grid system to simulate a dipping sand layer. This is important to minimize diffusive edge effects or numerical diffusion that might be associated with a dipping sand in an Eulerian grid system oriented orthogonal to gravity. Two-dimensional simulations demonstrate the tendency for gas hydrate to accumulate downdip in a sand body because of greater methane transport at depth due to larger sand-clay solubility contrasts. In 3D, basin-scale simulations illuminate how convergent sand layers in a multilayered system can compete for diffusion from clays between them, resulting in relatively low hydrate saturations. All simulations suggest that when hydrate present in clays dissociates with burial, the additional dissolved methane is soaked up by nearby sands preserving high hydrate saturations.« less

Methods for Finding Legacy Wells in Residential and Commercial Areas

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

Hammack, Richard W.; Veloski, Garret A.

In 1919, the enthusiasm surrounding a short-lived gas play in Versailles Borough, Pennsylvania resulted in the drilling of many needless wells. The legacy of this activity exists today in the form of abandoned, unplugged gas wells that are a continuing source of fugitive methane in the midst of a residential and commercial area. Flammable concentrations of methane have been detected near building foundations, which have forced people from their homes and businesses until methane concentrations decreased. Despite mitigation efforts, methane problems persist and have caused some buildings to be permanently abandoned and demolished. This paper describes the use of magneticmore » and methane sensing methods by the National Energy Technology Laboratory (NETL) to locate abandoned gas wells in Versailles Borough where site access is limited and existing infrastructure can interfere. Here, wells are located between closely spaced houses and beneath buildings and parking lots. Wells are seldom visible, often because wellheads and internal casing strings have been removed, and external casing has been cut off below ground level. The magnetic survey of Versailles Borough identified 53 strong, monopole magnetic anomalies that are presumed to indicate the locations of steel-cased wells. This hypothesis was tested by excavating the location of one strong, monopole magnetic anomaly that was within an area of anomalous methane concentrations. The excavation uncovered an unplugged gas well that was within 0.2 m of the location of the maximum magnetic signal. Truck-mounted methane surveys of Versailles Borough detected numerous methane anomalies that were useful for narrowing search areas. Methane sources identified during truck-mounted surveys included strong methane sources such as sewers and methane mitigation vents. However, inconsistent wind direction and speed, especially between buildings, made locating weaker methane sources (such as leaking wells) difficult. Walking surveys with the methane detector mounted on a cart or wagon were more effective for detecting leaking wells because the instrument’s air inlet was near the ground where: 1) the methane concentration from subsurface sources (including wells) was a maximum, and 2) there was less displacement of methane anomalies from methane sources by air currents. The Versailles Borough survey found 15 methane anomalies that coincided with the location of well-type magnetic anomalies; the methane sources for these anomalies were assumed to be leaking wells. For abandoned well locations where the wellhead and all casing strings have been removed and there is no magnetic anomaly, leaking wellbores can sometimes be detected by methane surveys. Unlike magnetic anomalies, methane anomalies can be: 1) ephemeral, 2) significantly displaced from the well location, and 3) from non-well sources that cannot be discriminated without isotopic analysis. If methane surveys are used for well location, the air inlet to the instrument should be kept as close to the ground as possible to minimize the likelihood of detecting methane from distant, wind-blown sources.« less

Prospecting for Methane in Arabia Terra, Mars - First Results

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Oehler, Dotoyhy Z.; Venechuk, Elizabeth M.

2006-01-01

Methane has been measured in the Martian atmosphere at concentrations of approx. 10 ppb. Since the photochemical lifetime of this gas is approx. 300 years, it is likely that methane is currently being released from the surface. Possible sources for the methane include 1) hydrothermal activity, 2) serpentinization of basalts and other water-rock interactions, 3) thermal maturation of sedimentary organic matter, and 4) metabolism of living bacteria. Any such discovery would revolutionize our understanding of Mars. Longitudinal variations in methane concentration, as measured by the Planetary Fourier Spectrometer (PFS) on Mars Express, show the highest values over Arabia Terra, Elysium Planum, and Arcadia-Memnonia, suggesting localized areas of methane release. We are using orbital data and methodologies derived from petroleum exploration in an attempt to locate these release points.

Hydrological and Geochemical Influences on the Dissolved Silica Concentrations in Natural Water in a Steep Headwater Catchment

NASA Astrophysics Data System (ADS)

Asano, Y.; Uchida, T.; Ohte, N.

2002-12-01

Dissolved silica has been used as a useful indicator of a chemical weathering in many geochemical studies in natural environment. Previous hydrological studies indicated that various hydrological processes affect the dissolution and precipitation of silica in hillslope and transport of this silica to stream; however, information is still limited to link this knowledge to understand geochemical processes. The observations of dissolved silica concentration in groundwater, spring and stream water was conducted at the unchannelled hillslope in the Tanakami Mountains of central Japan; (1) to clarify the effects of preferential flowpaths including lateral and vertical flow in soil layer and flow through bedrock fracture in the variation of dissolved silica concentration in runoff and groundwater, and (2) to isolate the effects of mixing of water from geochemically diverse water sources on the dissolved silica concentration. The mean dissolved silica concentrations in soil water at 40 cm depth and transient groundwater formed in upslope area were relatively constant independent of the variation in the new water ratio. The mean dissolved silica concentrations were similar regardless of the sampling depth in soil although the mean residence times of water increase with depth. These results indicated that dissolved silica concentrations in soil water and transient groundwater were defined almost independent of contact time of water with minerals. While the mean dissolved silica concentration in perennial groundwater, which was recharged by infiltrating water through soil and water emerging from bedrock in a area near to spring, was more than twice that of transient groundwater and the variation was relatively large. The mean dissolved silica concentration increased significantly at downslope from perennial groundwater, spring to the stream and the spring and stream concentrations also showed large variation. The dissolved silica concentrations of those perennial groundwater, the spring and the stream was controlled by the mixing of water from soil and bedrock. Our results demonstrated that in most areas of this headwater catchment, the preferential flowpaths give only small effect on dissolved silica concentrations. While in a small area (less than 10% of the longitudinal axis of the hollow near the spring), the dissolved silica concentration were controlled by the mixing of water from geochemically diverse water sources.

Abiotic vs biological sources and fates of organic compounds in a low temperature continental serpentinizing system

NASA Astrophysics Data System (ADS)

Robinson, K.; Noble, S. M.; Shock, E.

2016-12-01

Serpentinization is likely the most common water-rock reaction in our solar system. During this process ultramafic silicates are hydrated, a calcium hydroxide solution is formed, and H2O is reduced to H2 coupled to the oxidation of Fe2+ to Fe3+. The resulting hyper-alkaline, reduced conditions generate thermodynamic drives for numerous carbon compound reactions, including the precipitation of various carbonate minerals and the reduction of inorganic carbonate to organic carbon. Testing the extent to which these thermodynamic drives lead to observable results led to the present study of the flow and transformations of carbon through the active continental serpentinizing system at the Samail Ophiolite in the Sultanate of Oman. Water samples were collected from shallow groundwater (representing system input), hyper-alkaline seeps (system output), boreholes (system intermediate), and surface fluid mixing zones, and analyzed for concentrations of dissolved inorganic carbon (DIC + δ13C), organic carbon (+ δ13C), formate, acetate, H2, methane (+ δ13C), ethane, and an accompanying suite of other geochemical solutes. These analyses indicate that the vast majority of DIC in these serpentinizing fluids precipitates in the subsurface as carbonate minerals; however, a significant amount of DIC is converted into organic acids and light hydrocarbons and expelled at the surface in hyper-alkaline seeps. Based on thermodynamic calculations, it seems most likely that formate last equilibrated with dolomite (CaMg[CO3]2) in the subsurface, acetate last equilibrated with calcite (CaCO3) near the surface, and methane and ethane last equilibrated in a distinct carbon-limited region of the subsurface. As for the fates of these compounds, energetic calculations reveal that a combination of oxidative, reductive, and fermentative metabolisms are thermodynamically favorable. Indeed, δ13C trends record microbial methane oxidation at the surface and cannot rule out methane as biologically sourced from the subsurface.

Solute concentrations influence microbial methanogenesis in coal-bearing strata of the Cherokee basin, USA

DOE PAGES

Kirk, Matthew F.; Wilson, Brien H.; Marquart, Kyle A.; ...

2015-11-18

In this study, microorganisms have contributed significantly to subsurface energy resources by converting organic matter in hydrocarbon reservoirs into methane, the main component of natural gas. In this study, we consider environmental controls on microbial populations in coal-bearing strata of the Cherokee basin, an unconventional natural gas resource in southeast Kansas, USA. Pennsylvanian-age strata in the basin contain numerous thin (0.4–1.1 m) coalbeds with marginal thermal maturities (0.5–0.7% R o) that are interbedded with shale and sandstone. We collected gas, water, and microbe samples from 16 commercial coalbed methane wells for geochemical and microbiological analysis. The water samples were Na–Clmore » type with total dissolved solids (TDS) content ranging from 34.9 to 91.3 g L –1. Gas dryness values [C 1/(C 2 + C 3)] averaged 2640 and carbon and hydrogen isotope ratios of methane differed from those of carbon dioxide and water, respectively, by an average of 65 and 183‰. These values are thought to be consistent with gas that formed primarily by hydrogenotrophic methanogenesis. Results from cultivation assays and taxonomic analysis of 16S rRNA genes agree with the geochemical results. Cultivable methanogens were present in every sample tested, methanogen sequences dominate the archaeal community in each sample (avg 91%), and few archaeal sequences (avg 4.2%) were classified within Methanosarcinales, an order of methanogens known to contain methylotrophic methanogens. Although hydrogenotrophs appear dominant, geochemical and microbial analyses both indicate that the proportion of methane generated by acetoclastic methanogens increases with the solute content of formation water, a trend that is contrary to existing conceptual models. Consistent with this trend, beta diversity analyses show that archaeal diversity significantly correlates with formation water solute content. In contrast, bacterial diversity more strongly correlates with location than solute content, possibly as a result of spatial variation in the thermal maturity of the coalbeds.« less

Processes and Parameters Controlling the Extent of Methanogenic Conditions in the Unsaturated Zone of a Crude Oil Spill Site

NASA Astrophysics Data System (ADS)

Molins, S.; Mayer, K.

2007-12-01

Gas concentrations measured in the vadose zone at a crude oil spill site near Bemidji, MN, show that a large area near the oil body is currently dominated by methanogenic conditions. Away from the oil body methane concentrations decrease as it is degraded by methanotrophic bacteria under aerobic conditions. Numerical simulations have been conducted to quantify the contributions of the relevant transport and reaction processes to the production and attenuation of methane in the vadose zone. Methane is generated in the vadose zone by anaerobic degradation of oil and is also added by fluxes from the capillary fringe and the saturated zone. Gas diffusion and advection contribute to the transport of methane in the lateral direction and towards the ground surface. Attenuation of methane concentrations occurs through aerobic oxidation in the presence of methanotrophic bacteria. Critical parameters were varied within bounds provided by field data and previous studies. Simulation results confirm that the layered sediment structure present at the site plays a significant role in explaining the observed distribution of gases in the vadose zone. The presence of a low permeability lens in the area upgradient from the source results in higher moisture contents, limiting diffusion of oxygen into the zone of methane production, and contributes to the spread of methane. Diffusion was identified as the most significant transport mechanism for gases in the vadose zone. However, field-observed zones of depleted and enriched N2 and Ar concentrations could only be explained by the development of advective fluxes induced by reactive processes (methanogenesis and methanotrophy). The zones of gas production are characterized by slightly increased total gas pressures and low concentrations of N2 and Ar, while zones of gas consumption show slightly depressed total gas pressures and high concentrations of N2 and Ar. The simulations suggest that the advective flux that develops between these zones contributes up to 15% of the total methane flux.

Temporal variation in methane emissions in a shallow lake at a southern mid latitude during high and low rainfall periods.

PubMed

Fusé, Victoria S; Priano, M Eugenia; Williams, Karen E; Gere, José I; Guzmán, Sergio A; Gratton, Roberto; Juliarena, M Paula

2016-10-01

The global methane (CH 4 ) emission of lakes is estimated at between 6 and 16 % of total natural CH 4 emissions. However, these values have a high uncertainty due to the wide variety of lakes with important differences in their morphological, biological, and physicochemical parameters and the relatively scarse data from southern mid-latitude lakes. For these reasons, we studied CH 4 fluxes and CH 4 dissolved in water in a typical shallow lake in the Pampean Wetland, Argentina, during four periods of consecutive years (April 2011-March 2015) preceded by different rainfall conditions. Other water physicochemical parameters were measured and meteorological data were reported. We identified three different states of the lake throughout the study as the result of the irregular alternation between high and low rainfall periods, with similar water temperature values but with important variations in dissolved oxygen, chemical oxygen demand, water turbidity, electric conductivity, and water level. As a consequence, marked seasonal and interannual variations occurred in CH 4 dissolved in water and CH 4 fluxes from the lake. These temporal variations were best reflected by water temperature and depth of the Secchi disk, as a water turbidity estimation, which had a significant double correlation with CH 4 dissolved in water. The mean CH 4 fluxes values were 0.22 and 4.09 mg/m 2 /h for periods with low and high water turbidity, respectively. This work suggests that water temperature and turbidity measurements could serve as indicator parameters of the state of the lake and, therefore, of its behavior as either a CH 4 source or sink.

Assessing How Water Type, Climate, and Landscape Position Correlate with Variability of Methane in Shallow Groundwater in the Marcellus Region

NASA Astrophysics Data System (ADS)

Campbell, A.; Lautz, L.; Hoke, G. D.

2017-12-01

Prior work shows that spatial differences in naturally-occurring methane concentrations in shallow groundwater in the Marcellus Shale region are correlated with water type (e.g. Ca-HCO3 vs Na-HCO3) and landscape position (e.g. valley vs upland). However, little is known about how naturally-occurring methane in groundwater varies through time, particularly on a seasonal or monthly time scale, and how temporal variability is related to seasonal changes in climate. Extensive development of the Marcellus shale gas play in northeastern Pennsylvania limits opportunities for measuring baseline water quality through time. In contrast, a ban on hydraulic fracturing in NY affords an opportunity for characterizing baseline temporal variability in methane concentrations. The objective of this study is to characterize temporal variability of naturally-occurring methane in shallow groundwater in the Marcellus region, and how such temporal variability is correlated to other well characteristics, such as water type, landscape position, and climatic conditions. We worked with homeowners to sample 11 domestic wells monthly in the Marcellus Shale region of NY for methane concentrations and major ions for a full year. Wells were grouped according to the primary source of methane (e.g. thermogenic vs microbial) based upon δ13C-DIC, δ13C-CH4, and δD-CH4 isotopes. The full dataset and the grouped data were analyzed to assess how well climatic conditions, water type, and landscape position correlate with variability of methane concentrations through time. These data provide information on within year and between year variability of methane, as well as spatial variability between wells, which fills a data gap and can be used to inform policy regulations.

Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Formolo, Michael J.; Lyons, Timothy W.

2013-10-01

Cold seeps in the Gulf of Mexico provide a natural laboratory to study biogeochemical cycling of sulfur, carbon, and oxygen at hydrate- and hydrocarbon-rich deep marine settings with obvious additional relevance to studies of diverse modern and ancient seeps. Of particular interest are the sulfur isotope signatures of microbial sulfate reduction coupled to anaerobic oxidation of methane and other non-methane liquid and gaseous hydrocarbons. Whereas most of the published sulfur isotope data from cold seep systems pertain to pore-water species, our study integrates both solid and dissolved sulfur: acid-volatile sulfides (SAVS), pyrite (Spy), elemental sulfur (S°), dissolved sulfate and ΣH2S. Modeled and 35SO42- reduction rates and δ13C and δ18O data for authigenic carbonates are integrated within this sulfur framework. Our results indicate extreme variability over narrow spatial and temporal scales within short distances (meters) from active seeps. High rates of microbial sulfate reduction can lead to complete consumption of the sulfate within the upper few centimeters of burial, while meters away the sulfate profile shows little depletion. Such small-scale variability must reflect the structure and temporal dynamics of hydrocarbon migration in the presence of low amounts of background organic matter. Our past work demonstrated that electron donors other than methane drive significant levels of microbial activity at these seeps, and very recent work has demonstrated that oxidation of higher chain volatile hydrocarbons can contribute to the high levels of microbial activity. These findings are consistent with our new results. Elevated concentrations of pyrite and diagenetic carbonate relative to background sediments are diagnostic of active seepage, yet the S isotopes tell more complex stories. Low levels of the transient, 'instantaneous' products of S cycling-AVS and S°-show high δ34S values that increase with depth. Most of the pyrite formation, however, seems to be very early as limited by the availability of reactive Fe phases. As such, δ34S values for pyrite at ancient seeps can show consistently low δ34S values that undersell the full intensity of microbial sulfate reduction. Low sedimentation rates, and the resulting low detrital iron fluxes, may in fact limit our ability to recognize seeps in the geologic record using only δ34S compositions for pyrite.

High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

NASA Astrophysics Data System (ADS)

Chan, E. W.; Kessler, J. D.; Redmond, M. C.; Shiller, A. M.; Arrington, E. C.; Valentine, D. L.; Colombo, F.

2015-12-01

Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

Reactive transport model of growth and methane production by high-temperature methanogens in hydrothermal regions of the subseafloor

NASA Astrophysics Data System (ADS)

Stewart, L. C.; Algar, C. K.; Topçuoğlu, B. D.; Fortunato, C. S.; Larson, B. I.; Proskurowski, G. K.; Butterfield, D. A.; Vallino, J. J.; Huber, J. A.; Holden, J. F.

2014-12-01

Hydrogenotrophic methanogens are keystone high-temperature autotrophs in deep-sea hydrothermal vents and tracers of habitability and biogeochemical activity in the hydrothermally active subseafloor. At Axial Seamount, nearly all thermophilic methanogens are Methanothermococcus and Methanocaldococcus species, making this site amenable to modeling through pure culture laboratory experiments coupled with field studies. Based on field microcosm incubations with 1.2 mM, 20 μM, or no hydrogen, the growth of methanogens at 55°C and 80°C is limited primarily by temperature and hydrogen availability, with ammonium amendment showing no consistent effect on total methane output. The Arrhenius constants for methane production by Methanocaldococcus jannaschii (optimum 82°C) and Methanothermococcus thermolithotrophicus (optimum 65°C) were determined in pure culture bottle experiments. The Monod constants for hydrogen concentration were measured by growing both organisms in a 2-liter chemostat at two dilution rates; 55°C, 65°C and 82°C; and variable hydrogen concentrations. M. jannaschii showed higher ks and Vmax constants than M. thermolithotrophicus. In the field, hydrogen and methane concentrations in hydrothermal end-member and low-temperature diffuse fluids were measured, and the concentrations of methanogens that grow at 55°C and 80°C in diffuse fluids were determined using most-probable-number estimates. Methane concentration anomalies in diffuse fluids relative to end-member hydrothermal concentrations and methanogen cell concentrations are being used to constrain a 1-D reactive transport model using the laboratory-determined Arrhenius and Monod constants for methane production by these organisms. By varying flow path length and subseafloor cell concentrations in the model, our goal is to determine solutions for the potential depth of the subseafloor biosphere coupled with the amount of methanogenic biomass it contains.

Changes in deep-sea carbonate-hosted microbial communities associated with high and low methane flux

NASA Astrophysics Data System (ADS)

Case, D. H.; Steele, J. A.; Chadwick, G.; Mendoza, G. F.; Levin, L. A.; Orphan, V. J.

2012-12-01

Methane seeps on continental shelves are rich in authigenic carbonates built of methane-derived carbon. These authigenic carbonates are home to micro- and macroscopic communities whose compositions are thus far poorly constrained but are known to broadly depend on local methane flux. The formation of authigenic carbonates is itself a result of microbial metabolic activity, as associations of anaerobic methane oxidizing archaea (ANME) and sulfate reducing bacteria (SRB) in the sediment subsurface increase both dissolved inorganic carbon (DIC) and alkalinity in pore waters. This 1:1 increase in DIC and alkalinity promotes the precipitation of authigenic carbonates. In this study, we performed in situ manipulations to test the response of micro- and macrofaunal communities to a change in methane flux. Methane-derived authigenic carbonates from two locations at Hydrate Ridge, OR, USA (depth range 595-604 mbsl), were transplanted from "active" cold seep sites (high methane flux) to "inactive" background sites (low methane flux), and vise versa, for one year. Community diversity surveys using T-RFLP and 16S rRNA clone libraries revealed how both bacterial and archaeal assemblages respond to this change in local environment, specifically demonstrating reproducible shifts in different ANME groups (ANME-1 vs. ANME-2). Animal assemblage composition also shifted during transplantation; gastropod representation increased (relative to control rocks) when substrates were moved from inactive to active sites and polychaete, crustacean and echinoderm representation increased when substrates were moved from active to inactive sites. Combined with organic and inorganic carbon δ13C measurements and mineralogy, this unique in situ experiment demonstrates that authigenic carbonates are viable habitats, hosting microbial and macrofaunal communities capable of responding to changes in external environment over relatively short time periods.