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

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 km²) 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 (δ¹³C 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.     

Pre‐drill Groundwater Geochemistry in the Karoo Basin,South Africa

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre‐development assessment of groundwater geochemistry in the critically water‐restricted Karoo Basin, South Africa. Twenty‐two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end‐members: a deep, saline groundwater with a sodium‐chloride composition, an old, deep freshwater with a sodium‐bicarbonate‐chloride composition and a shallow, calcium‐bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water‐rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium‐chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon‐rich saline waters to the surface. This pre‐drill evaluation indicates that the natural migration of methane‐ and salt‐rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.     

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

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 km²) 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 km² 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.     

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.     

A Proposed Method to Estimate In Situ Dissolved Gas Concentrations in Gas‐Saturated Groundwater

Gas‐saturated groundwater forms bubbles when brought to atmospheric pressure, preventing precise determination of its in situ dissolved gas concentrations. To overcome this problem, a modeling approach called the atmospheric sampling method is suggested here to recover the in situ dissolved gas concentrations of groundwater collected ex situ under atmospheric conditions at the Horonobe Underground Research Laboratory, Japan. The results from this method were compared with results measured at the same locations using two special techniques, the sealed sampler and pre‐evacuated vial methods, that have been developed to collect groundwater under its in situ conditions. In gas‐saturated groundwater cases, dissolved methane and inorganic carbon concentrations derived using the atmospheric sampling method were mostly within ±4 and ±10%, respectively, of values from the sealed sampler and pre‐evacuated vial methods. In gas‐unsaturated groundwater, however, the atmospheric sampling method overestimated the in situ dissolved methane concentrations, because the groundwater pressure at which bubbles appear (P_critical) was overestimated. The atmospheric sampling method is recommended for use where gas‐saturated groundwater can be collected only ex situ under atmospheric conditions.     

Isotope Approach to Assess Hydrologic Connections During Marcellus Shale Drilling

Water and gas samples were collected from (1) nine shallow groundwater aquifers overlying Marcellus Shale in north‐central West Virginia before active shale gas drilling, (2) wells producing gas from Upper Devonian sands and Middle Devonian Marcellus Shale in southwestern Pennsylvania, (3) coal‐mine water discharges in southwestern Pennsylvania, and (4) streams in southwestern Pennsylvania and north‐central West Virginia. Our preliminary results demonstrate that the oxygen and hydrogen isotope composition of water, carbon isotope composition of dissolved inorganic carbon, and carbon and hydrogen isotope compositions of methane in Upper Devonian sands and Marcellus Shale are very different compared with shallow groundwater aquifers, coal‐mine waters, and stream waters of the region. Therefore, spatiotemporal stable isotope monitoring of the different sources of water before, during, and after hydraulic fracturing can be used to identify migrations of fluids and gas from deep formations that are coincident with shale gas drilling.     

Trace and rare earth element geochemistry of the black and grey shales of the Calabar Flank,Southeastern Nigeria: constraints on the depositional environment and the degree of metal enrichment

This study focuses on the trace and rare earth elements(REE) geochemistry of the Nkporo and Ekenkpon Shales of the Calabar Flank.The main aim is to infer their depositional environment and the degree of their metal enrichment.The shale samples were analyzed using inductively coupled plasma mass spectrometry.The results indicated that the mean concentrations of K,Na,and Fe in Nkporo and Ekenkpon Shales are 1.45,0.4,and 4.17 wt%,and 1.11,0.44,and 5.42 wt%;respectively.The Nkporo Shale is enriched with the following trace elements;PMn Sr Ba Zn Ce Rb Zr VCr Ni and depleted in the following trace elements;Ta GeSb Bi Cd Ag Te In Hg.While the Ekenkpon Shale is enriched with the following trace elements;P Mn Ba Sr VCe Zr Rb Cr Zn Ni and depleted in;Sb Ge Bi Ag Ce Te InHg.The concentration of redox-sensitive elements such as V,Ni,Mo,U,Cu,Cr,Re,Cd,Sb,Ti,Mn,and their ratio V/Mo and U/Mo in the black and grey shale samples show different patterns.The REE obtained from the Nkporo and Ekenkpon Shales were PAAS normalized.The Nkporo Shale showed a slightly flat light rare-earth element(LREE),middle rare-earth element(MREE),and heavy rare earth element(HREE) pattern enrichment.Ce/Ce*ranges from 0.95 to 1.09 in Nkporo Shale and 0.67 to 1.40 in Ekenkpon Shale.The Ekenkpon Shale showed a slight LREE,MREE enrichment,and depleted HREE patterns.The Mn contents and U/Mo ratio in Nkporo and Ekenkpon Shales suggests a poor oxygen transitional environment.The V/Mo and V/(V+Ni) ratios indicated that the Nkporo shales were deposited in an anoxic to suboxic conditions and Ekenkpon shales were also deposited under an anoxic to suboxic conditions.The V/Ni ratio indicated that the organic matter in the Nkporo shale is terrigenous while that of the Ekenkpon shales are both terrigenous and marine in origin.     

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

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.     

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.     

Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China

Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea.     

Environmental Factors Associated With Natural Methane Occurrence in the Appalachian Basin

The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre‐drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO₃^?] < 0.5 mg/L; [SO₄^2?] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) ‐rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)‐rich waters. For water wells exhibiting Na‐rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors (“Low NO₃^? & SO₄^2?” redox condition, Na‐rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre‐drill monitoring programs and the subsequent evaluation of post‐drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.     

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.     

Geochemical Distribution of Trace Elements in Groundwater from the North Mara Large‐Scale Gold Mining Area of Tanzania

The influence of large‐scale mining operations on groundwater quality was investigated in this study. Trace element concentrations in groundwater samples from the North Mara mining area of northern Tanzania were analyzed. Statistical analyses for relationships between elemental concentrations in the samples and distance of a sampling site from the mine tailings dam were also conducted. Eleven trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were determined, and averages of Fe and Al concentrations were higher than levels accepted by the Tanzanian drinking water guideline. Levels of Pb in three samples were higher than the World Health Organization (WHO) and United States Environmental Protection Agency (USEPA) drinking water guidelines of 10 and 15 µg/L, respectively. One sample contained a higher As level than the WHO and USEPA guideline of 10 µg/L. The correlation between element concentrations and distance from the mine tailings dam was examined using the hierarchical agglomeration cluster analysis method. A significant difference in the elemental concentration existed depending on the distance from the mine tailings dam. Mann–Whitney U‐test post hoc analysis confirmed a relationship between element concentration and distance of a sampling site from the mine tailings dam. This relationship raises concerns about the increased risks of trace elements to people and ecosystem health. A metal pollution index also suggested a relationship between elemental concentrations in the groundwater and the sampling sites’ proximity from the mine tailings dam.     

Use of Chemical and Isotopic Signatures to Distinguish Between Uranium Mill‐Related and Naturally Occurring Groundwater Constituents

Chemical and isotopic signatures were determined in groundwater samples to aid in distinguishing the source of contamination in three desert arroyos and a buried channel (the swale) near Shiprock, New Mexico. The contamination in the swale and one of the arroyos, Many Devils Wash, was previously attributed to a former uranium mill site because of the similar suite of contaminants (nitrate, selenium, sulfate, and uranium) and the close (0.8 km) proximity. The other two arroyos are far removed from the mill site and could not have received contamination from it. Principal component and cluster analysis indicated similarities in groundwater chemistry among the swale and the three arroyos that contrasted with groundwater chemistry at the disposal cell. Disposal cell groundwater is characterized by high uranium and bicarbonate concentrations, whereas that in remaining study areas is characterized by high sodium and sulfate, but lower uranium concentrations. Mancos Shale forms the bedrock in the region and contains elevated concentrations of the same chemical constituents that appear in the swale and arroyo groundwater. Dissolved sulfate in arroyo groundwater was depleted in sulfur‐34, in contrast to mill‐derived sulfate with more enriched sulfur‐34. Uranium‐234 to uranium‐238 activity ratios (ARs) were near the secular equilibrium value of 1 in mill site groundwater, whereas ARs in all arroyo groundwater samples exceeded 2. Elevated tritium activities present in mill site groundwater (49 to 142 pCi/L) are attributed to the mill being operated during atomic bomb testing in the 1950s and 1960s. The combined chemical and isotopic results indicate that groundwater in Many Devils Wash and the swale was likely derived from the Mancos Shale and not from the milling operation.     

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.     

Relation Between Fracture Stability and Gas Leakage into Deep Aquifers in the North Perth Basin in Western Australia

The Kockatea Shale is a proposed target for unconventional gas development in the North Perth Basin in Western Australia. This research is concerned with correlating the extent of thermogenic gas leakage into deep aquifers overlying the Kockatea Shale with an assessment of how close the formation is to mechanical failure. Data from two petroleum exploration wells located approximately 20 km apart were considered. Both have comparable stratigraphy; however, they differ by their local tectonic setting. The stress regime is strike slip at Arrowsmith 2 well and for an assumed hydrostatic pressure the Kockatea Shale is not close to frictional limits. Minor amounts of methane and trace amounts of short chain alkanes are leaking into deep aquifers pre-development. In contrast, the stress regime is strike slip/normal at Woodada Deep well and the Kockatea Shale is close to frictional limits. Significant volumes of gas including methane and condensate are leaking into deep aquifers. The sealing capacity of the Kockatea Shale as evidenced by the variation in gas concentration in aquifers at the two sites indicates the formation is sensitive to stress. Additionally given the low permeability of the regional Kockatea Shale seal, it is assumed that at both locations gas leakage is via critically stressed faults. Deep aquifers proximal to the shale gas target are low salinity (<5000 ppm NaCl eq.) at Woodada Deep well and are saline at Arrowsmith 2 well. Based on this assessment, it is suggested that hydraulic fracture stimulation at the Woodada Deep well poses a significant environmental risk.     

Trace element and major ion concentrations and dynamics in glacier snow and melt: Eliot Glacier,Oregon Cascades

We present concentrations of environmentally available (unfiltered acidified 2% v/v HNO₃) As, Cu, Cd, Pb, V, Sr, and major ions including Ca²⁺, Cl^?, and SO₄^2? in a July 2005 and a March 2006 shallow snow profile from the lower Eliot Glacier, Mount Hood, Oregon, and its proglacial stream, Eliot Creek. Low enrichment factors (EF) with respect to crustal averages suggests that in fresh March 2006 snow environmentally available elements are derived primarily from lithogenic sources. Soluble salts occurred in lower and less variable concentrations in July 2005 snow than March 2006. Conversely, environmentally available trace elements occurred in greater and more variable concentrations in July 2005 than March 2006 snow. Unlike major solutes, particulate‐associated trace elements are not readily eluted during the melt season. Additionally, elevated surface concentrations suggest that they are likely added throughout the year via dry deposition. In a 1‐h stream sampling, ratios of dissolved (<0·45 µm) V:Cl^?, Sr:Cl^?, and Cu:Cl^? are enriched in the Eliot Stream with respect to their environmentally available trace element to Cl^? ratios in Eliot Glacier snow, suggesting chemical weathering additions in the stream waters. Dissolved Pb:Cl^? is depleted in the Eliot Stream with respect to the ratio of environmentally available Pb to Cl^? in snow, corresponding to greater adsorption onto particles at greater pH values. Copyright © 2009 John Wiley & Sons, Ltd.     

Biogeochemical processes controlling methane in gassy coastal sediments—Part 2: groundwater flow control of acoustic turbidity in Eckernförde Bay Sediments

To understand the origin of the methane distributions in sediments of Eckernförde Bay, three sites were sampled in May 1994 for determination of methane, sulfate and chloride concentrations in the sediment porewaters. In much of the Bay, bubbles of biogenic methane gas within the sediments lead to widespread ‘acoustic turbidity’ seen in acoustic surveys, masking the sedimentary structure below the gassy horizon. Acoustic windows, where the gas does not appear to be present, occur in several locations in the Bay, often surrounded by acoustically turbid sediments. Pockmarks, shallow depressions in the sediment, are also found in Bay sediments and may show acoustic turbidity at even shallower depths below the interface than surrounding sediments. One site of each type was sampled in this study. The site probably representative of much of the bay below 20 m water depth, revealed methane saturated conditions by about 75 cm depth below the interface, confirming inferences from acoustic scattering data that free gas was present in the sediment. Above this, the methane concentration profile was concave-upward, indicative of methane oxidation in the overlying, sulfate-reducing sediments. These porewaters showed a slightly decreasing chlorinity with depth. At an acoustic window site, methane concentrations rose to a maximum at about 125 cm depth, but did not reach saturation. Below this depth they decreased in a concave-down pattern. Chloride concentrations decreased markedly with depth, indicative of vertical freshwater flow from below. The third site was a pockmark exhibiting very shallow acoustic turbidity at about 25 cm depth. Here methane concentrations rose to exceed saturation within 25 cm depth below the interface and the porewaters became almost fresh by 1.5 m depth, indicative of a stronger flow of freshwater from below. These groundwater flows have competing effects on the methane inventory. They help exclude sulfate from the sediment, allowing the earlier/shallower onset of methanogenesis, but they also aid loss of methane through advection. A diagenetic model that couples the biogeochemistry of sulfate and methane is used to explain the presence or absence of methane gas in these sediments in relation to the flow rate of fresh groundwater from below. Model results indicate that acoustic windows within otherwise acoustically turbid sediments of the bay are likely due to relatively higher rates of vertical advection of fresh groundwater. The gassy pockmark, however, with an even higher vertical advection rate, seems to require the input of additional reactive organic carbon to explain its vertical methane distribution.     

Biogeochemistry of dissolved carbon,major, and trace elements during spring flood periods on the Ob River

Detailed knowledge of the flood period of Arctic rivers remains one of the few factors impeding rigorous prediction of the effect of climate change on carbon and related element fluxes from the land to the Arctic Ocean. In order to test the temporal and spatial variability of element concentration in the Ob River (western Siberia) water during flood period and to quantify the contribution of spring flood period to the annual element export, we sampled the main channel year round in 2014–2017 for dissolved C, major, and trace element concentrations. We revealed high stability (approximately ≤10% relative variation) of dissolved C, major, and trace element concentrations in the Ob River during spring flood period over a 1‐km section of the river channel and over 3 days continuous monitoring (3‐hr frequency). We identified two groups of elements with contrasting relationship to discharge: (a) DIC and soluble elements (Cl, SO₄, Li, B, Na, Mg, Ca, P, V, Cr, Mn, As, Rb, Sr, Mo, Ba, W, and U) negatively correlated (p < 0.05) with discharge and exhibited minimal concentrations during spring flood and autumn high flow and (b) DOC and particle‐reactive elements (Al, Fe, Ti, Y, Zr, Nb, Cs, REEs, Hf, Tl, Pb, and Th), some nutrients (K), and metalloids (Ge, Sb, and Te), positively correlated (p < 0.05) with discharge and showed the highest concentrations during spring flood. We attribute the decreased concentration of soluble elements with discharge to dilution by groundwater feeding and increased concentration of DOC and particle‐reactive metals with discharge to leaching from surface soil, plant litter, and suspended particles. Overall, the present study provides first‐order assessment of fluxes of major and trace elements in the middle course of the Ob River, reveals their high temporal and spatial stability, and characterizes the mechanism of river water chemical composition acquisition.