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

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 (δ¹³C‐CH₄ and δ²H‐CH₄) 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 δ¹³C‐CH₄ and δ²H‐CH₄ 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 CO₂ 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.     

Hydrocarbon‐Rich Groundwater above Shale‐Gas Formations: A Karoo Basin Case Study

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale‐gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near‐pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre‐industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane‐rich samples were associated with high‐salinity, NaCl‐type groundwater and elevated levels of ethane, ⁴He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ¹³C‐CH₄ and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane‐rich samples record a history of fractionation during gas‐phase migration from source rocks to shallow aquifers. Conversely, methane‐poor samples have a paucity of ethane and ⁴He, near saturation levels of atmospheric noble gases, and more negative δ¹³C‐CH₄; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).     

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

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 δ¹³C_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 δ¹³C_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.     

A Stream‐Based Methane Monitoring Approach for Evaluating Groundwater Impacts Associated with Unconventional Gas Development

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 δ¹³C_CH4 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.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.     

Effect of Different Sampling Methodologies on Measured Methane Concentrations in Groundwater Samples

Analysis of dissolved light hydrocarbon gas concentrations (primarily methane and ethane) in water supply wells is commonly used to establish conditions before and after drilling in areas of shale gas and oil extraction. Several methods are currently used to collect samples for dissolved gas analysis from water supply wells; however, the reliability of results obtained from these methods has not been quantified. This study compares dissolved methane and ethane concentrations measured in groundwater samples collected using three sampling methods employed in pre‐ and post‐drill sampling programs in the Appalachian Basin. These include an open‐system collection method where 40 mL volatile organic analysis (VOA) vials are filled directly while in contact with the atmosphere (Direct‐Fill VOA) and two alternative methods: (1) a semi‐closed system method whereby 40 mL VOA vials are filled while inverted under a head of water (Inverted VOA) and (2) a relatively new (2013) closed system method in which the sample is collected without direct contact with purge water or the atmosphere (IsoFlask^®). This study reveals that, in the absence of effervescence, the difference in methane concentrations between the three sampling methods was relatively small. However, when methane concentrations equaled or exceeded 20 mg/L (the approximate concentration at which effervescence occurs in the study area), IsoFlask^® (closed system) samples yielded significantly higher methane concentrations than Direct‐Fill VOA (open system) samples, and Inverted VOA (semi‐closed system) samples yielded lower concentrations. These results suggest that open and semi‐closed system sample collection methods are adequate for non‐effervescing samples. However, the use of a closed system collection method provides the most accurate means for the measurement of dissolved hydrocarbon gases under all conditions.     

Identification of groundwater recharge sources and processes in a heterogeneous alluvial aquifer: results from multi‐level monitoring of hydrochemistry and environmental isotopes in a riverside agricultural area in Korea

We evaluated sources and pathways of groundwater recharge for a heterogeneous alluvial aquifer beneath an agricultural field, based on multi‐level monitoring of hydrochemistry and environmental isotopes of a riverside groundwater system at Buyeo, Korea. Two distinct groundwater zones were identified with depth: (1) a shallow oxic groundwater zone, characterized by elevated concentrations of NO₃^? and (2) a deeper (>10–14 m from the ground surface) sub‐oxic groundwater zone with high concentrations of dissolved Fe, silica, and HCO₃^?, but little nitrate. The change of redox zones occurred at a depth where the aquifer sediments change from an upper sandy stratum to a silty stratum with mud caps. The δ¹⁸O and δ²H values of groundwater were also different between the two zones. Hydrochemical and δ¹⁸O? δ²H data of oxic groundwater are similar to those of soil water. This illustrates that recharge of oxic groundwater mainly occurs through direct infiltration of rain and irrigation water in the sandy soil area where vegetable cropping with abundant fertilizer use is predominant. Oxic groundwater is therefore severely contaminated by agrochemical pollutants such as nitrate. In contrast, deeper sub‐oxic groundwater contains only small amounts of dissolved oxygen (DO) and NO₃^?. The ³H contents and elevated silica concentrations in sub‐oxic groundwater indicate a somewhat longer mean residence time of groundwater within this part of the aquifer. Sub‐oxic groundwater was also characterized by higher δ¹⁸O and δ²H values and lower d‐excess values, indicating significant evaporation during recharge. We suggest that recharge of sub‐oxic groundwater occurs in the areas of paddy rice fields where standing irrigation and rain water are affected by strong evaporation, and that reducing conditions develop during subsequent sub‐surface infiltration. This study illustrates the existence of two groundwater bodies with different recharge processes within an alluvial aquifer. Copyright © 2009 John Wiley & Sons, Ltd.     

城市湖泊不同水生植被区水体温室气体溶存浓度及其影响因素

为了解城市湖泊不同水生植被区水体温室气体的溶存浓度及其影响因素,于2015年4-11月按每月2次的频率采用顶空平衡法对聊城市铃铛湖典型植被区——菹草区、莲藕区和睡莲区表层水中CO₂、CH₄和N₂O的溶存浓度进行监测,计算水中温室气体的饱和度和排放通量,并测定水温（T）、pH、溶解氧（DO）、叶绿素a及营养盐浓度等理化指标,以探究水体环境因子对温室气体溶存浓度的影响.结果表明,铃铛湖各植被区水体温室气体均处于过饱和状态,是大气温室气体的"源";莲藕区CH₄浓度、饱和度和排放通量均显著高于菹草区,而各植被区N₂O和CO₂均无显著性差异;不同植被区湖水中DO、总氮（TN）、总磷（TP）和硝态氮（NO₃^--N）浓度具有显著差异,其中DO、TN和NO₃^--N浓度均表现为菹草区最高,莲藕区最低,而TP浓度则正好相反;各植被区温室气体浓度和水环境参数间的相关分析和多元回归分析的结果表明,水生植物可通过影响水体的理化性质对温室气体的产生和排放产生显著差异影响,在菹草区亚硝态氮（NO₂^--N）、NO₃^--N、T和DO是控制水体温室气体浓度的主要因子;睡莲区为TP和pH;莲藕区则为pH、NO₂^--N和DO.     

Impacts of Methane on Carbon Dioxide Storage in Brine Formations

In the context of geological carbon sequestration (GCS), carbon dioxide (CO₂) is often injected into deep formations saturated with a brine that may contain dissolved light hydrocarbons, such as methane (CH₄). In this multicomponent multiphase displacement process, CO₂ competes with CH₄ in terms of dissolution, and CH₄ tends to exsolve from the aqueous into a gaseous phase. Because CH₄ has a lower viscosity than injected CO₂, CH₄ is swept up into a ‘bank’ of CH₄‐rich gas ahead of the CO₂ displacement front. On the one hand, this may provide a useful tracer signal of an approaching CO₂ front. On the other hand, the emergence of gaseous CH₄ is undesirable because it poses a leakage risk of a far more potent greenhouse gas than CO₂ if the cap rock is compromised. Open fractures or faults and wells could result in CH₄ contamination of overlying groundwater aquifers as well as surface emissions. We investigate this process through detailed numerical simulations for a large‐scale GCS pilot project (near Cranfield, Mississippi) for which a rich set of field data is available. An accurate cubic‐plus‐association equation‐of‐state is used to describe the non‐linear phase behavior of multiphase brine‐CH₄‐CO₂ mixtures, and breakthrough curves in two observation wells are used to constrain transport processes. Both field data and simulations indeed show the development of an extensive plume of CH₄‐rich (up to 90 mol%) gas as a consequence of CO₂ injection, with important implications for the risk assessment of future GCS projects.     

Structural and Hydrogeological Controls on Hydrocarbon and Brine Migration into Drinking Water Aquifers in Southern New York

Environmental concerns regarding the potential for drinking water contamination in shallow aquifers have accompanied unconventional energy development in the northern Appalachian Basin. These activities have also raised several critical questions about the hydrogeological parameters that control the naturally occurring presence and migration of hydrocarbon gases in shallow aquifers within petroliferous basins. To interrogate these factors, we analyzed the noble gas, dissolved ion, and hydrocarbon gas (molecular and isotopic composition) geochemistry of 98 groundwater samples from south‐central New York. All samples were collected ?1km from unconventional drilling activities and sample locations were intentionally targeted based on their proximity to various types of documented fault systems. In agreement with studies from other petroliferous basins, our results show significant correlations between elevated levels of radiogenic [⁴He], thermogenic [CH₄], and dissolved ions (e.g., Cl, Br, Sr, Ba). In combination, our data suggest that faults have facilitated the transport of exogenous hydrocarbon‐rich brines from Devonian source rocks into overlying Upper Devonian aquifer lithologies over geologic time. These data conflict with previous reports, which conclude that hydrodynamic focusing regulates the occurrence of methane and salt in shallow aquifers and leads to elevated levels of these species in restricted flow zones within valley bottoms. Instead, our data suggest that faults in Paleozoic rocks play a fundamental role in gas and brine transport from depth, regulate the distribution of their occurrence in shallow aquifers, and influence the geochemistry of shallow groundwater in this petroliferous basin.     

Methane in shallow cold seeps at Mocha Island off central Chile

We studied for the first time the intertidal and subtidal gas seepage system in Mocha Island off Central Chile. Four main seepage sites were investigated (of which one site included about 150 bubbling points) that release from 150 to 240 tonnes CH₄ into the atmosphere per year. The total amount of methane emitted into the atmosphere is estimated in the order of 800 tonnes per year. The gases emanated from the seeps contain 70% methane, and the stable carbon isotopic composition of methane, δ¹³C-CH₄ averaged −44.4±1.4‰ which indicates a major contribution of thermogenic gas. Adjacent to one of the subtidal seeps, rocky substrates support a diverse community of microbial filaments, macroalgae, and benthic organisms. While stable carbon isotopic compositions of marine benthic organisms indicate a dominant photosynthesis-based food web, those of some hard-substrate invertebrates were in the range −48.8‰ to −36.8‰, suggesting assimilation of methane-derived carbon by some selected taxa. This work highlights the potential subsidy of the trophic web by CH₄-C, and that its emission to the atmosphere justifies the need of evaluating the use of methane to support the energy requirements of the local community.     

Transfer of carbon dioxide and methane through the soil‐water‐atmosphere system at Mer Bleue peatland,Canada

Surface waters associated with peatlands, supersaturated with CO₂ and CH₄ with respect to the atmosphere, act as important pathways linking a large and potentially unstable global repository of C to the atmosphere. Understanding the drivers and mechanisms which control C release from peatland systems to the atmosphere will contribute to better management and modelling of terrestrial C pools. We used non‐dispersive infra‐red (NDIR) CO₂ sensors to continuously measure gas concentrations in a beaver pond at Mer Bleue peatland (Canada); measurements were made between July and August 2007. Concentrations of CO₂ in the surface water (10 cm) reached 13 mg C l^?1 (epCO₂ 72), and 26 mg C l^?1 (epCO₂ 133) at depth (60 cm). The study also showed large diurnal fluctuations in dissolved CO₂ which ranged in amplitude from ～1·6 mg C l^?1 at 10 cm to ～0·2 mg C l^?1 at 60 cm depth. CH₄ concentration and supersaturation (epCH₄) measured using headspace analysis averaged 1·47 mg C l^?1 and 3252, respectively; diurnal cycling was also evident in CH₄ concentrations. Mean estimated evasion rates of CO₂ and CH₄ over the summer period were 44·92 ± 7·86 and 0·44 ± 0·25 µg C m^?2s^?1, respectively. Open water at Mer Bleue is a significant summer hotspot for greenhouse gas emissions within the catchment. Our results suggest that CO₂ concentrations during the summer in beaver ponds at Mer Bleue are strongly influenced by biological processes within the water column involving aquatic plants and algae (in situ photosynthesis and respiration). In terms of carbon cycling, soil‐stream connectivity at this time of year is therefore relatively weak. Copyright © 2008 John Wiley & Sons, Ltd.     

Greenhouse gas emissions (CO2, CH4, and N2O) from several perialpine and alpine hydropower reservoirs by diffusion and loss in turbines

We investigated greenhouse gas emissions (CO₂, CH₄, and N₂O) from reservoirs located across an altitude gradient in Switzerland. These are the first results of greenhouse gas emissions from reservoirs at high elevations in the Alps. Depth profiles were taken in 11 reservoirs located at different altitudes between the years 2003 and 2006. Diffusive trace gas emissions were calculated using surface gas concentrations, wind speeds and transfer velocities. Additionally, methane entering with the inflowing water and methane loss at the turbine was assessed for a subset of the reservoirs. All reservoirs were emitters of carbon dioxide and methane with an average of 970?±?340?mg?m^?2?day^?1 (results only from four lowland and one subalpine reservoir) and 0.20?±?0.15?mg?m^?2?day^?1, respectively. One reservoir (Lake Wohlen) emitted methane at a much higher rate (1.8?±?0.9?mg?m^?2?day^?1) than the other investigated reservoirs. There was no significant difference in methane emissions across the altitude gradient, but average dissolved methane concentrations decreased with increasing elevation. Only lowland reservoirs were sources for N₂O (72?±?22???g?m^?2?day^?1), while the subalpine and alpine reservoirs were in equilibrium with atmospheric concentrations. These results indicate reservoirs from subalpine/alpine regions to be only minor contributors of greenhouse gases to the atmosphere compared to other reservoirs.     

Winter methane dynamics beneath ice and in snow in a temperate poor fen

The influence of winter on methane (CH₄) stored in pore water and emitted through snow was investigated in a temperate poor fen in New Hampshire over two winters. Methane accumulated beneath ice layers (1 cm) deposited by freezing rain, resulting in snow-pore air mixing ratios as high as 140 ppmv during the first winter and 600 ppmv during the second. An early winter snow crust of 300 kg m^?3 caused no discontinuity in a linear mixing ratio profile and therefore was not observed to retard snowpack emissions. Methane concentration-depth profiles in pore water steepened and concentrations increased by as much as 400 μM at the 10 and 20 cm depths as the ice cover formed. This suggests that the peat-ice cover plays an important part in CH₄ build-up in pore water by limiting the transport of gases between the peat and the atmosphere. Pore water concentrations gradually declined through late winter. The seasonality of dissolved CH₄ in pore water over two winters and one summer showed an average annual amplitude of 1.3 gCH₄m^?2 (25–75cm depth range), with a winter maximum of 4.7gCH₄m^?2. Emissions during the winter with average snowfall accounted for a larger percentage (9.2% in 1993–1994) of total annual emission than the winter with below-average snowfall and warmer air temperature (2% in 1994–1995). Emissions averaged 56 and 26mg m^?2 day^?1 during the first and second winter (December, January and February), respectively.     

Geochemical monitoring of the 2002–2003 eruption at Stromboli volcano (Italy): precursory changes in the carbon and helium isotopic composition of fumarole gases and thermal waters

Significant changes in the helium and carbon isotopic composition of shallow thermal waters vs. gas and a crater fumarolic gas have been recorded at Stromboli prior and during the 2002–2003 eruption. The³He/⁴He ratios corrected for air contamination (Rc/Ra), and δ¹³C of fumarolic gases gradually increased from May to November 2002 before the eruption onset. These variations imply early degassing of a gas-rich magma at depth that likely fed both the intense Strombolian activity and small lava overflows recorded during that period. The lava effusion of late December 2002 was shortly preceded by a marked Rc/Ra decrease both in water and fumarolic gases. Comparison of He/CO₂ and CH₄/CO₂ ratios in dissolved gas and with values rules out the Rc/Ra decrease due to an increasing input of radiogenic⁴He. The Rc/Ra decrease is attributed to the He isotope fractionation during rapid magma ascent and degassing. A new uprising of ³He-rich magma probably occurred in January to February 2003, when Rc/Ra ratios displayed the highest values in dissolved gases ever measured before (4.56 Rc/Ra). The increase in He/CO₂ and CH₄/CO₂ ratios and decrease in δ¹³C of dissolved CO₂ was recorded after the 5 April 2003 explosive paroxysm, likely caused by enhanced gas-water interaction inducing CO₂ dissolution. No anomalous Rc/Ra values were recorded in the same period, when usual Strombolian activity gradually resumed.Editorial responsibility: H Shinohara     

Methane Oxidation in the Water Column of Xiangxi Bay,Three Gorges Reservoir

Four field campaigns are carried out to quantify the methane (CH₄) oxidation rate in Xiangxi Bay (XXB) of the Three Gorges Reservoir (TGR), China. The water depth of the sampling site varied from 13 to 30 m resulting from the water level fluctuation of the TGR. The CH₄ oxidation rates are measured in situ as the decline of dissolved CH₄ concentration versus time in incubated, and those rates. The CH₄ oxidation rates range from 1.18 × 10^?3 to 3.69 × 10^?3 µmol L^?1 h^?1, with higher values and stronger variation during summer. A static floating chamber method is used to measure CH₄ emitted to the atmosphere resulting in an annual mean flux of 4.79 µmol m^?2 h^?1. The CH₄ emission rate is significantly negatively correlated with the water level. The results show that a large fraction of CH₄ is consumed in the water column with a range of 28.97–55.90 µmol m^?2 h^?1, accounting for ≈69–98% of the total CH₄ input into the water column, and more than 90% is consumed outside the summer, when the water level is lowest. Water depth, which is dominated by water level of the TGR, is a potentially important driver for CH₄ oxidation and atmospheric emission in the tributary bay.     

Carbon and its isotopes in mid-oceanic basaltic glasses

Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO₂ is about 3.8‰ enriched in ¹³C, relative to dissolved carbon. Despite this fractionation, δ¹³C_PDB values for all spreading ridge glasses lie within the range ?5.6 and ?7.5, and the δ¹³C_PDB of mantle carbon likely lies between ?5 and ?7. The carbon abundances and δ¹³C_PDB values of Kilauea East Rift glasses apparently are influenced by the differentiation and movement of magma within that Hawaiian volcano. Using ³He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 × 10¹³ g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory.     

Impact of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology and biogeochemistry

Although riparian zones are well known to reduce nitrogen (N) and phosphorus (P) runoff to streams, they also have the potential to affect greenhouse gas (CO₂, N₂O, and CH₄) fluxes to the atmosphere. Following large storms, soil biogeochemical conditions often become more reduced, especially in oxbow depressions and side channels, which can lead to hot moments of greenhouse gas production. Here, we investigate the impact of the remnants of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology (water table: WT), and biogeochemistry (oxidation‐reduction potential [ORP], dissolved oxygen [DO], NO₃^?, PO₄^3?, CO₂, N₂O, CH₄). Results indicate that large storms have the potential to reset WT levels for weeks to months. Overbank flooding at our site following Irene and Lee led to the infiltration of well‐oxygenated water at depth (higher DO and ORP) while promoting the development of anoxic conditions within soil aggregates near the soil surface (increased N₂O and CH₄ fluxes). A short‐term increase in CO₂ emission was observed following Irene at our site where aerobic respiration was water‐limited. Over a 2‐year period, an oxbow depression exhibited higher WT, higher N₂O and CH₄ fluxes (hot moment), higher CO₂ fluxes (seasonal), and lower NO₃^? concentrations (seasonal) than the rest of the riparian zone. However, neither Irene, nor Lee, nor the oxbow depression significantly impacted PO₄^3?. Dissolved organic carbon, ORP, and DO data illustrate the time‐lag (>20 years) between the creation of an oxbow depression and the development of reducing conditions despite clear differences in riparian zone and oxbow WT dynamics.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.     

Geochemistry of the Submarine Gaseous Emissions of Panarea (Aeolian Islands, Southern Italy): Magmatic vs. Hydrothermal Origin and Implications for Volcanic Surveillance

The marine sector surrounding Panarea Island (Aeolian Islands, South Italy) is affected by widespread submarine emissions of CO₂ -rich gases and thermal water discharges which have been known since the Roman Age. On November 3^rd, 2002 an anomalous degassing event affected the area, probably in response to a submarine explosion. The concentrations of minor reactive gases (CO, CH₄ and H₂) of samples collected in November and December, 2002 show drastic compositional changes when compared to previous samples collected from the same area in the 1980s. In particular the samples collected after the November 3^rd phenomenon display relative increases in H₂ and CO and a strong decrease in the CH₄ contents, while other gas species show no significant change. The interaction of the original gas with seawater explains the variable contents of CO₂, H₂S, N₂, Ar and He which characterize the different samples, but cannot explain the large variations of CO, CH₄ and H₂ which are instead compatible with changes in the redox, temperature and pressure conditions of the system. Two models, both implying an increasing input of magmatic fluids are compatible with the observed variations of minor reactive species. In the first one, the input of magmatic fluids drives the hydrothermal system towards atypical (more oxidizing) redox conditions, slowly pressurizing the system up to a critical state. In the second one, the hydrothermal system is flashed by the rising high-T volcanic fluid, suddenly released by a magmatic body at depth. The two models have different implications for volcanic surveillance and risk assessment: In the first case, the November 3^rd event may represent both the culmination of a relatively slow process which caused the overpressurization of the hydrothermal system and the beginning of a new phase of quiescence. The possible evolution of the second model is unforeseeable because it is mainly related to the thermal, baric and compositional state of the deep magmatic system that is poorly known.