Response of surface water chemistry to reduced levels of acid precipitation: comparison of trends in two regions of New York,USA

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984–2001 and 1992–2001) and surface water chemistry (1992–2001) were determined in two of the most acid‐sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO₄^2?), nitrate (NO₃^?), and base cation (C_B) concentrations and increasing pH during 1984–2001, but few significant trends during 1992–2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO₄^2? concentrations at all sites, and decreasing trends in NO₃^?, C_B, and H⁺ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid‐neutralizing capacity (ANC) increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO₄^2? trends, but it caused several significant non‐flow‐corrected trends in NO₃^? and ANC to become non‐significant, suggesting that trend results for flow‐sensitive constituents are affected by flow‐related climate variation. SO₄^2? concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation–surface water comparisons, reflecting a strong link between S emissions, precipitation SO₄^2? concentrations, and the processes that affect S cycling within these regions. NO₃^? and H⁺ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation–surface water comparisons, indicating that variation in local‐scale processes driven by factors such as climate are affecting trends in acid–base chemistry in these two regions. Copyright © 2005 John Wiley & Sons, Ltd.     

Groundwater dating with 3H and SF6 in relation to mixing patterns,transport modelling and hydrochemistry

A comprehensive study of a sandy aquifer of deltaic origin in southern Poland included water chemistry, isotopes, dissolved trace gases and transport modelling. Tritium, sulphur hexafluoride (SF₆) and freons (F‐11, F‐12 and F‐113) showed the presence of modern waters in the recharge areas and shallow confined parts of the aquifer. The presence of older Holocene waters farther from the recharge areas was indicated by lack of ³H, SF₆ contents ≤0·02 fmol l⁻¹ and relatively low ¹⁴C values. The discharge from the system is by upward seepage in the valley of a major river. Pre‐Holocene waters of a cooler climate, identified on the basis of δ¹⁸O, δ²H, ¹⁴C, Ne and Ar data, were found in some distant wells. Concentrations of N₂, Ne and Ar determined by gas chromatography were used for calculating the noble gas temperatures, air excess needed for correction of SF₆, and nitrogen content released by denitrification process. The time series of ³H content available for some wells supplied quantitative information on age distributions and the total mean ages of flow through the unsaturated and saturated zones. The derived ³H age distributions turned out to be very wide, with mean values in the range of about 30 to 160 years. For each well with determined ³H age, the SF₆ data showed either a lower age range or the possibility of a lower age as expected due to shorter travel times of SF₆ through the unsaturated zone, which most probably also resulted in different types of age distributions of these tracers. Freons appeared to be of little use for individual age determinations. A quantitative estimation of two‐component mixing from SF₆ ³H relations is not possible unless the travel time of ³H through the unsaturated zone is comparable to that of SF₆. The ratio of integrals of the response function over the age range with tracer and the whole response function yields the ratio of water with tracer to total flow of water. That ratio is a tracer‐dependent function of time. Transport modelling of SF₆ tracer done with MT3D code yielded initially large discrepancies between calculated and measured tracer concentrations. Some discrepancies remained even after calibration of the transport model with SF₆. Simulation of tritium contents with a calibrated transport model yielded reasonable agreement with measured contents in some wells and indicated a need for further investigations, particularly in the eastern part of the aquifer. The existence of distinct hydrochemical zones is consistent with the tracer data; young waters with measurable ³H and SF₆ contents are aerobic and of HCO₃ Ca or HCO₃ SO₄ Ca types. Slightly elevated Na and Cl contents, as well as the highest concentrations of SO₄ and NO₃ within this zone are due to anthropogenic influences. Anaerobic conditions prevail in the far field, under the confining cover, where pre‐bomb era Holocene waters dominate. In that zone, dissolved oxygen, NO₃ and U contents are reduced, and Fe, Mn and NH₄ contents increase. In the third zone, early Holocene and glacial waters occur. They are of HCO₃ Ca Na or HCO₃ Na types, with TDS values higher than 1 g l⁻¹ and Na content higher than 200 mg l⁻¹, due to either small admixtures of ascending or diffusing older water or freshening of marine sediments, a process that is probably occurring till the present time. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrochemical Analyses and Evaluation of Groundwater Resources of North Jordan

The hydrochemical analyses of twenty-three springs were used to determine the properties and types of groundwater of the Tertiary-Quaternary Aquifer of northern Jordan. The result shows that the geological formation influences the quality of the investigated groundwater more than the anthropogenic factors. The water of the Quaternary-Tertiary aquifer is enriched in Ca⁺⁺ due to the dissolution of the nearby carbonate rocks. The investigated water has a low EC values with Ca(Na)-HCO₃ water type. Most springs belong to this hydrochemical facies except Malka. Groundwater in the Malka wells has high salinity with NaCl waters and a strong Ca(Mg)-HCO₃ facies (900 to 1000 mg/l TDS). The area long-term hydrochemical data have been also evaluated; general trend of increase of the analyzed ion was observed. Bicarbonate represents the most abundant anion in the studied water, which exceeds the permissible limits. Nitrates (NO ₃ ^? ) also exceed the permissible limit and are the most common contaminant in the investigated water. Data on dissolved major and trace elements (K⁺, Na⁺, Mg²⁺, Ca²⁺, Cl^?, SO ₄ ^2? , Fe, Zn, Cu and Pb) in the investigated water revealed that the concentrations lie within the natural background range. The positive correlation values between various ions indicate that most of ions come from same lithological sources. According to the residual sodium carbonate, and EC values, the studied springs are suitable for agricultural purposes.     

Hydrological flowpaths and nitrate removal rates within a riparian floodplain along a fourth‐order stream in Brittany (France)

Three main reservoirs were identified that contribute to the shallow subsurface flow regime of a valley drained by a fourth‐order stream in Brittany (western France). (i) An upland flow that supplied a wetland area, mainly during the high‐water period. It has high N‐NO₃^? and average Cl^? concentrations. (ii) A deep confined aquifer characterized by low nitrate and low chloride concentrations that supplied the floodplain via flow upwelling. (iii) An unconfined aquifer under the riparian zone with high Cl^? and low N‐NO₃^? concentrations where biological processes removed groundwater nitrate. This aquifer collected the upland flow and supplied a relict channel that controlled drainage from the whole riparian zone. Patterns of N‐NO₃^? and Cl^? concentrations along riparian transects, together with calculated high nitrate removal, indicate that removal occurred mainly at the hillslope–riparian zone interface (i.e. first few metres of wetland), whereas dilution occurred in lower parts of the transects, especially during low‐water periods and at the beginning of recharge periods. Stream flow was modelled as a mixture of water from the three reservoirs. An estimation of these contributions revealed that the deep aquifer contribution to stream flow averaged 37% throughout the study period, while the contribution of the unconfined reservoir below the riparian zone and hillslope flow was more variable (from ca 6 to 85%) relative to rainfall events and the level of the riparian water table. At the entire riparian zone scale, NO₃^? removal (probably from denitrification) appeared most effective in winter, despite higher estimated upland NO₃^? fluxes entering the riparian zone during this period. Copyright © 2003 John Wiley & Sons, Ltd.     

Natural Attenuation of Perchlorate in Denitrified Groundwater

Monitoring of a well‐defined septic system groundwater plume and groundwater discharging to two urban streams located in southern Ontario, Canada, provided evidence of natural attenuation of background low level (ng/L) perchlorate (ClO₄^?) under denitrifying conditions in the field. The septic system site at Long Point contains ClO₄^? from a mix of waste water, atmospheric deposition, and periodic use of fireworks, while the nitrate plume indicates active denitrification. Plume nitrate (NO₃^?‐N) concentrations of up to 103 mg/L declined with depth and downgradient of the tile bed due to denitrification and anammox activity, and the plume was almost completely denitrified beyond 35 m from the tile bed. The ClO₄^? natural attenuation occurs at the site only when NO₃^?‐N concentrations are <0.3 mg/L, after which ClO₄^? concentrations decline abruptly from 187 ± 202 to 11 ± 15 ng/L. A similar pattern between NO₃^?‐N and ClO₄^? was found in groundwater discharging to the two urban streams. These findings suggest that natural attenuation (i.e., biodegradation) of ClO₄^? may be commonplace in denitrified aquifers with appropriate electron donors present, and thus, should be considered as a remediation option for ClO₄^? contaminated groundwater.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Evaluation of Methane Sources in Groundwater in Northeastern Pennsylvania

Testing of 1701 water wells in northeastern Pennsylvania shows that methane is ubiquitous in groundwater, with higher concentrations observed in valleys vs. upland areas and in association with calcium‐sodium‐bicarbonate, sodium‐bicarbonate, and sodium‐chloride rich waters—indicating that, on a regional scale, methane concentrations are best correlated to topographic and hydrogeologic features, rather than shale‐gas extraction. In addition, our assessment of isotopic and molecular analyses of hydrocarbon gases in the Dimock Township suggest that gases present in local water wells are most consistent with Middle and Upper Devonian gases sampled in the annular spaces of local gas wells, as opposed to Marcellus Production gas. Combined, these findings suggest that the methane concentrations in Susquehanna County water wells can be explained without the migration of Marcellus shale gas through fractures, an observation that has important implications for understanding the nature of risks associated with shale‐gas extraction.     

Evidence for influence of mineral weathering on stream water sulphate in Vermont and New Hampshire (USA)

Mass balance studies in forested catchments in the northeastern USA show that S losses via streamwater SO₄^2? exceed measured atmospheric S inputs. Possible sources of the excess S loss include underestimated dry deposition, mineralization of organic S in soils, desorption of soil sulphate, oxidation of recently formed sulphides and mineral weathering. Evaluating the relative contribution of these sources and processes to SO₄^2? export is important to our understanding of S cycling as well as to policy makers in their evaluation of the efficacy of S emission controls. In order to evaluate the potential for mineral weathering contributions to SO₄^2? export, we measured concentration and isotopic composition (δ³⁴S and δ¹⁸O) of SO₄^2? in stream water, and concentration and δ³⁴S values of four S fractions in bedrock and soil parent material in catchments of varying geological composition. Geological substrates with low S concentrations were represented by catchments underlain by quartzite and granite, whereas geological substrates with high S concentrations were represented by catchments underlain by sulphidic slate, schist and metavolcanic rocks. Catchments with S‐poor bedrock had stream‐water SO₄^2? concentrations <100 µeq L^?1 and isotopic values consistent with those of atmospheric SO₄^2? that had been cycled through the organic soil pool. Catchments with S‐rich bedrock had stream‐water SO₄^2? concentrations ranging from 56 to 229 µeq L^?1. Isotopic values deviated from those of SO₄^2? in atmospheric deposition, clearly indicating a mineral weathering source in some cases, whereas in others spatial variability of mineral δ³⁴S values precluded the isotopic detection of a weathering contribution. These results, along with evidence suggesting formation of secondary sulphate minerals in bedrock weathering rinds, indicate that mineral weathering may be an important source of S in the surface waters of some forested catchments in the northeastern USA. Copyright © 2004 John Wiley & Sons, Ltd.     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Response of deep groundwater to land use change in desert basins of the Trans‐Pecos region,Texas, USA: Effects on infiltration,recharge, and nitrogen fluxes

Quantifying the effects of anthropogenic processes on groundwater in arid regions can be complicated by thick unsaturated zones with long transit times. Human activities can alter water and nutrient fluxes, but their impact on groundwater is not always clear. This study of basins in the Trans‐Pecos region of Texas links anthropogenic land use and vegetation change with alterations to unsaturated zone fluxes and regional increases in basin groundwater NO₃^? concentrations. Median increases in groundwater NO₃^? (by 0.7–0.9 mg‐N/l over periods ranging from 10 to 50+ years) occurred despite low precipitation (220–360 mm/year), high potential evapotranspiration (~1570 mm/year), and thick unsaturated zones (10–150+ m). Recent model simulations indicate net infiltration and groundwater recharge can occur beneath Trans‐Pecos basin floors, and may have increased due to irrigation and vegetation change. These processes were investigated further with chemical and isotopic data from groundwater and unsaturated zone cores. Some unsaturated zone solute profiles indicate flushing of natural salt accumulations has occurred. Results are consistent with human‐influenced flushing of naturally accumulated unsaturated zone nitrogen as an important source of NO₃^? to the groundwater. Regional mass balance calculations indicate the mass of natural unsaturated zone NO₃^? (122–910 kg‐N/ha) was sufficient to cause the observed groundwater NO₃^? increases, especially if augmented locally with the addition of fertilizer N. Groundwater NO₃^? trends can be explained by small volumes of high NO₃^? modern recharge mixed with larger volumes of older groundwater in wells. This study illustrates the importance of combining long‐term monitoring and targeted process studies to improve understanding of human impacts on recharge and nutrient cycling in arid regions, which are vulnerable to the effects of climate change and increasing human reliance on dryland ecosystems.     

Dynamics of stream nitrate sources and flow pathways during stormflows on urban,forest and agricultural watersheds in central Pennsylvania,USA

Understanding the influence of storm events on nitrate (NO₃^?) dynamics is important for efficiently managing NO₃^? pollution. In this study, five sites representing a downstream progression of forested uplands underlain by resistant sandstone to karst lowlands with agricultural, urban and mixed land‐use were established in Spring Creek, a 201 km² mixed land‐use watershed in central Pennsylvania, USA. At each site, stream water was monitored during six storm events in 2005 to assess changes in stable isotopes of NO₃^? (δ¹⁵N‐NO₃^? and δ¹⁸O‐NO₃^?) and water (δ¹⁸O‐H₂O) from baseflow to peakflow. Peakflow fractions of event NO₃^? and event water were then computed using two‐component mixing models to elucidate NO₃^? flow pathway differences among the five sites. For the forested upland site, storm size appeared to affect NO₃^? sources and flow pathways. During small storms (<35 mm rainfall), greater event NO₃^? fractions than event water fractions indicated the prevalence of atmospheric NO₃^? source contributions at peakflow. During larger storms (>35 mm rainfall), event NO₃^? fractions were less than event water fractions at peakflow suggesting that NO₃^? was flushed from stored sources via shallow subsurface flow pathways. For the urbanized site, wash‐off of atmospheric NO₃^? was an important NO₃^? source at peakflow, especially during short‐duration storms where event water contributions indicated the prevalence of overland flow. In the karst lowlands, very low fractions of event water and even lower fractions of event NO₃^? at peakflow suggested the dominance of ground water flow pathways during storms. These ground water flow pathways likely flushed stored NO₃^? sources into the stream, while deep soils in the karst lowlands also may have promoted NO₃^? assimilation. The results of this study illustrated how NO₃^? isotopes and δ¹⁸O‐H₂O could be combined to show key differences in water and NO₃^? delivery between forested uplands, karst valleys and fully urbanized watersheds. Copyright © 2009 John Wiley & Sons, Ltd.     

Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrogeochemical balance of forest umbrisol profiles (‘Sierra de Gata’, central western Spain)

Three techniques for obtaining soil water solutions (gravitational and matrical waters extracted using both in situ tension lysimeters and in vitro pressure chambers) and their later chemical analysis were performed in order to know the evolution of the soil‐solution composition when water moves down through the soil, from the Ah soil horizon to the BwC‐ or C‐horizons of forest soils located in western Spain. Additionally, ion concentrations and water volumes of input waters to soil (canopy washout) and exported waters (drainage solutions from C‐horizons) were determined to establish the net balance of solutes in order to determine the rates of leaching or retention of ions. A generalized process of sorption or retention of most components (even Cl^?) was observed, from the soil surface to the C‐horizon, in both gravitational and matrical waters, with H₄SiO₄, Mn²⁺, Na⁺, and SO₄^2? being the net exported components from the soil through the groundwater. These results enhance the role of the recycling effect in these forest soils. The net percentages of elements retained in these forest soils, considering the inputs and the outputs balance, were 68% K⁺, 85% Ca²⁺, 58% Mg²⁺, 7% Al³⁺, 5% Fe³⁺, 34% Zn²⁺, 57% Cl^?, and 20% NO₃^?, and about 75% of dissolved organic carbon was mineralized. Copyright © 2007 John Wiley & Sons, Ltd.     

Geochemical weathering at the bed of Haut Glacier d'Arolla,Switzerland—a new model

Waters were sampled from 17 boreholes at Haut Glacier d'Arolla during the 1993 and 1994 ablation seasons. Three types of concentrated subglacial water were identified, based on the relative proportions of Ca²⁺, HCO₃^? and SO₄^2? to Si. Type A waters are the most solute rich and have the lowest relative proportion of Si. They are believed to form in hydrologically inefficient areas of a distributed drainage system. Most solute is obtained from coupled sulphide oxidation and carbonate dissolution (SO–CD). It is possible that there is a subglacial source of O₂, perhaps from gas bubbles released during regelation, because the high SO₄^2? levels found (up to 1200 µeq/L) are greater than could be achieved if sulphides are oxidized by oxygen in saturated water at 0 °C (c.414 µeq/L). A more likely alternative is that sulphide is oxidized by Fe³⁺ in anoxic environments. If this is the case, exchange reactions involving Fe^III and Fe^II from silicates are possible. These have the potential to generate relatively high concentrations of HCO₃^? with respect to SO₄^2?. Formation of secondary weathering products, such as clays, may explain the low Si concentrations of Type A waters. Type B waters were the most frequently sampled subglacial water. They are believed to be representative of waters flowing in more efficient parts of a distributed drainage system. Residence time and reaction kinetics help determine the solute composition of these waters. The initial water–rock reactions are carbonate and silicate hydrolysis, and there is exchange of divalent cations from solution for monovalent cations held on surface exchange sites. Hydrolysis is followed by SO–CD. The SO₄^2? concentrations usually are <414 µeq/L, although some range up to 580 µeq/L, which suggests that elements of the distributed drainage system may become anoxic. Type C waters were the most dilute, yet they were very turbid. Their chemical composition is characterized by low SO₄^2? : HCO₃^? ratios and high pH. Type C waters were usually artefacts of the borehole chemical weathering environment. True Type C waters are believed to flow through sulphide‐poor basal debris, particularly in the channel marginal zone. The composition of bulk runoff was most similar to diluted Type B waters at high discharge, and was similar to a mixture of Type B and C waters at lower discharge. These observations suggest that some supraglacial meltwaters input to the bed are stored temporarily in the channel marginal zone during rising discharge and are released during declining flow. Little of the subglacial chemical weathering we infer is associated with the sequestration of atmospheric CO₂. The progression of reactions is from carbonate and silicate hydrolysis, through sulphide oxidation by first oxygen and then Fe^III, which drives further carbonate and silicate weathering. A crude estimate of the ratio of carbonate to silicate weathering following hydrolysis is 4 : 1. We speculate that microbial oxidation of organic carbon also may occur. Both sulphide oxidation and microbial oxidation of organic carbon are likely to drive the bed towards suboxic conditions. Hence, we believe that subglacial chemical weathering does not sequester significant quantities of atmospheric CO₂ and that one of the key controls on the rate and magnitude of solute acquisition is microbial activity, which catalyses the reduction of Fe^III and the oxidation of FeS₂. Copyright © 2002 John Wiley & Sons, Ltd.     

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.     

Denitrification in a Deep Basalt Aquifer: Implications for Aquifer Storage and Recovery

Aquifer storage and recovery (ASR) can provide a means of storing water for irrigation in agricultural areas where water availability is limited. A concern, however, is that the injected water may lead to a degradation of groundwater quality. In many agricultural areas, nitrate is a limiting factor. In the Umatilla Basin in north central Oregon, shallow alluvial groundwater with elevated nitrate‐nitrogen of <3 mg/L to >9 mg/L is injected into the Columbia River Basalt Group (CRBG), a transmissive confined aquifer(s) with low natural recharge rates. Once recovery of the injected water begins, however, NO₃‐N in the recovered water decreases quickly to <3 mg/L (Eaton et al. 2009), suggesting that NO₃‐N may not persist within the CRBG during ASR storage. In contrast to NO₃‐N, other constituents in the recovered water show little variation, inconsistent with migration or simple mixing as an explanation of the NO₃‐N decrease. Nitrogen isotopic ratios (δ¹⁵N) increase markedly, ranging from +3.5 to > +50, and correlate inversely with NO₃‐N concentrations. This variation occurs in <3 weeks and recovery of <10% of the originally injected volume. TOC is low in the basalt aquifer, averaging <1.5 mg/L, but high in the injected source water, averaging >3.0 mg/L. Similar to nitrate concentrations, TOC drops in the recovered water, consistent with this component contributing to the denitrification of nitrate during storage.     

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

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.     

Factors controlling the acid‐neutralizing capacity of Japanese cedar forest watersheds in stands of various ages and topographic characteristics

Acid‐neutralizing capacity (ANC) is an important index for streamwater acidification caused by external factors (i.e. chronic acid deposition) and internal factors such as soil acidification due to nitrification. In this study, the influence of forest clear‐cutting and subsequent regrowth on internal acidification was investigated in central Japan, where stream pH (near 7·0) and ANC (above 0·1 meq L^?1) are high. pH, the concentrations of major cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺), major anions (NO₃^?, Cl^? and SO₄^2?) and dissolved silica (Si), and ANC were measured in 33 watersheds of various stand ages, during 2002 to 2004. Only NO₃^? concentration decreased with stand age, whereas pH, ANC, and concentrations of the sum of base cations (BC) and Si were negatively correlated with the minimum elevation of the watershed. The correlation between the BC/Si ratio and minimum elevation suggested that factors contributing to acid neutralization changed at 1100 m above sea level. In watersheds at lower elevations (?1100 m), the relatively high contribution of soil water with longer soil contact times should result in higher ANC, and cation exchange reactions should be the dominant process for acid neutralization due to deposition of colluvial soils on the lower slope. In contrast, in higher‐elevation watersheds (≥1100 m), weathered residual soils are thin and the small contribution of deeper groundwater results in lower ANC. These results suggest that the local acid sensitivity is determined by the hydrological and geomorphologic factors generated by steep topography. Copyright © 2008 John Wiley & Sons, Ltd.     

Spatial and temporal variability of groundwater quality of an Algerian aquifer: the case of Soummam Wadi

ABSTRACT

Five-year monitoring of physicochemical parameters was performed with two campaigns in low and high water periods of the Lower Soummam catchment. Data from 18 wells were processed by multivariate statistical tools in order to identify the principal factors influencing groundwater chemistry. Two matrices of 14 and 8 physicochemical parameters with 18 groundwater samples collected in wells were obtained. The correlation matrix showed strong associations between nine variables: K⁺, Ca²⁺, Na⁺, SO₄^2?, Cl^?, Mg²⁺, NO₂^?, Zn²⁺ and Sr²⁺. Principal component analysis and factor analysis showed that the cumulated variance of high and low water periods was of 83.19% and 78.55%, respectively. The variables assigned to the mineralization effect or to pollution indicators were presented by the factor analysis. The bivariate plots confirmed a mineralization model, ascribed to dissolution of geological materials, and to high levels of saline contamination attributed to leakages from sanitary systems. They also showed an increase “upstream to downstream” of the mineralization, visualization of temporal variations, and a dilution process identification of the natural mineralization during the recharge of the aquifer.

EDITOR D. Koutsoyiannis; ASSOCIATE EDITOR X. Chen