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At least 1,693 records · Page 94Linked to original sources

Evaluating long-term patterns of decreasing groundwater discharge through a lake-bottom permeable reactive barrier

Identifying and quantifying groundwater exchange is critical when considering contaminant fate and transport at the groundwater/surface-water interface. In this paper, areally distributed temperature and point seepage measurements are used to efficiently assess spatial and temporal groundwater discharge patterns through a glacial-kettle lakebed area containing a zero-valent iron permeable reactive barrier (PRB). Concern was that the PRB was becoming less permeable with time owing to biogeochemical processes within the PRB. Patterns of groundwater discharge over an 8-year period were examined using fiber-optic distributed temperature sensing (FO-DTS) and snapshot-in-time point measurements of temperature. The resulting thermal maps show complex and uneven distributions of temperatures across the lakebed and highlight zones of rapid seepage near the shoreline and along the outer boundaries of the PRB. Repeated thermal mapping indicates an increase in lakebed temperatures over time at periods of similar stage and surface-water temperature. Flux rates in six seepage meters permanently installed on the lakebed in the PRB area decreased on average by 0.021 md -1 (or about 4.5 percent) annually between 2004 and 2015. Modeling of diurnal temperature signals from shallow vertical profiles yielded mean flux values ranging from 0.39 to 1.15 md -1 , with stronger fluxes generally related to colder lakebed temperatures. The combination of an increase in lakebed temperatures, declines in direct seepage, and observations of increased cementation of the lakebed surface provide in situ evidence that the permeability of the PRB is declining. The presence of temporally persistent rapid seepage zones is also discussed.

Journal of Environmental Management↗

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM HC ) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM HC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOM HC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Minnesota↗

Nitrate and herbicide loading in two groundwater basins of Illinois' sinkhole plain

This investigation was designed to estimate the mass loading of nitrate (NO3-) and herbicides in spring water discharging from groundwater basins in an agriculturally dominated, mantled karst terrain. The loading was normalized to land use and NO3- and herbicide losses were compared to estimated losses in other agricultural areas of the Midwestern USA. Our study area consisted of two large karst springs that drain two adjoining groundwater basins (total area of 37.7 km2) in southwestern Illinois' sinkhole plain, USA. The springs and stream that they form were monitored for almost 2 years. Nitrate-nitrogen (NO3-N) concentrations at three monitoring sites were almost always above the background concentration (1.9 mg/l). NO3-N concentrations at the two springs ranged from 1.08 to 6.08 with a median concentration of 3.61 mg/l. Atrazine and alachlor concentrations ranged from <0.01 to 34 ??g/l and <0.01 to 0.98 ??g/l, respectively, with median concentrations of 0.48 and 0.12 ??g/l, respectively. Approximately 100,000 kg/yr of NO3-N, 39 kg/yr of atrazine, and 2.8 kg/yr of alachlor were discharged from the two springs. Slightly more than half of the discharged NO3- came from background sources and most of the remainder probably came from fertilizer. This represents a 21-31% loss of fertilizer N from the groundwater basins. The pesticide losses were 3.8-5.8% of the applied atrazine, and 0.05-0.08% of the applied alachlor. The loss of atrazine adsorbed to the suspended solid fraction was about 2 kg/yr, only about 5% of the total mass of atrazine discharged from the springs. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

Inverse approaches with lithologic information for a regional groundwater system in southwest Kansas

Two practical approaches incorporating lithologic information for groundwater modeling calibration are presented to estimate distributed, cell-based hydraulic conductivity. The first approach is to estimate optimal hydraulic conductivities for geological materials by incorporating thickness distribution of materials into inverse modeling. In the second approach, residuals for the groundwater model solution are minimized according to a globalized Newton method with the aid of a Geographic Information System (GIS) to calculate a cell-wise distribution of hydraulic conductivity. Both approaches honor geologic data and were effective in characterizing the heterogeneity of a regional groundwater modeling system in southwest Kansas. ?? 2005 Elsevier Ltd All rights reserved.

Journal of Hydrology↗

Effects of land cover on water table, soil moisture, evapotranspiration, and groundwater recharge: A Field observation and analysis

The effects of land cover on water table, soil moisture, evapotranspiration, and groundwater recharge were studied with water level measurements collected from two monitoring wells over a period of 122 days. The two wells were installed under similar conditions except that one was drilled on the east side of a creek which was covered with grass, and the other on the west side of the creek which was burned into a bare ground. Substantial differences in water level fluctuations were observed at these two wells. The water level in the east grass (EG) well was generally lower and had much less response to rainfall events than the west no-grass (WNG) well. Grass cover lowered the water table, reduced soil moisture through ET losses, and thus reduced groundwater recharge. The amount of ET by the grass estimated with a water table recession model decreased exponentially from 7.6 mm/day to zero as the water table declined from near the ground surface to 1.42 m below the ground surface in 33 days. More groundwater recharge was received on the WNG side than on the EG side following large rainfall events and by significant slow internal downward drainage which may last many days after rainfall. Because of the decreased ET and increased R, significantly more baseflow and chemical loads may be generated from a bare ground watershed compared to a vegetated watershed. ?? 2005 Elsevier Ltd All rights reserved.

Journal of Hydrology↗

Groundwater-supported evapotranspiration within glaciated watersheds under conditions of climate change

This paper analyzes the effects of geology and geomorphology on surface-water/-groundwater interactions, evapotranspiration, and recharge under conditions of long-term climatic change. Our analysis uses hydrologic data from the glaciated Crow Wing watershed in central Minnesota, USA, combined with a hydrologic model of transient coupled unsaturated/saturated flow (HYDRAT2D). Analysis of historical water-table (1970-1993) and lake-level (1924-2002) records indicates that larger amplitude and longer period fluctuations occur within the upland portions of watersheds due to the response of the aquifer system to relatively short-term climatic fluctuations. Under drought conditions, lake and water-table levels fell by as much as 2-4 m in the uplands but by 1 m in the lowlands. The same pattern can be seen on millennial time scales. Analysis of Holocene lake-core records indicates that Moody Lake, located near the outlet of the Crow Wing watershed, fell by as much as 4 m between about 4400 and 7000 yr BP. During the same time, water levels in Lake Mina, located near the upland watershed divide, fell by about 15 m. Reconstructed Holocene climate as represented by HYDRAT2D gives somewhat larger drops (6 and 24 m for Moody Lake and Lake Mina, respectively). The discrepancy is probably due to the effect of three-dimensional flow. A sensitivity analysis was also carried out to study how aquifer hydraulic conductivity and land-surface topography can influence water-table fluctuations, wetlands formation, and evapotranspiration. The models were run by recycling a wet year (1985, 87 cm annual precipitation) over a 10-year period followed by 20 years of drier and warmer climate (1976, 38 cm precipitation). Model results indicated that groundwater-supported evapotranspiration accounted for as much as 12% (10 cm) of evapotranspiration. The aquifers of highest hydraulic conductivity had the least amount of groundwater-supported evapotranspiration owing to a deep water table. Recharge was even more sensitive to aquifer hydraulic conductivity, especially in the lowland regions. These findings have important implications for paleoclimatic studies, because the hydrologic response of a surface-water body will vary across the watershed to a given climate signal. ?? 2005 Elsevier B.V. All rights reserved.

Conference Paper↗

Maximum likelihood Bayesian model averaging and its predictive analysis for groundwater reactive transport models

While Bayesian model averaging (BMA) has been widely used in groundwater modeling, it is infrequently applied to groundwater reactive transport modeling because of multiple sources of uncertainty in the coupled hydrogeochemical processes and because of the long execution time of each model run. To resolve these problems, this study analyzed different levels of uncertainty in a hierarchical way, and used the maximum likelihood version of BMA, i.e., MLBMA, to improve the computational efficiency. This study demonstrates the applicability of MLBMA to groundwater reactive transport modeling in a synthetic case in which twenty-seven reactive transport models were designed to predict the reactive transport of hexavalent uranium (U(VI)) based on observations at a former uranium mill site near Naturita, CO. These reactive transport models contain three uncertain model components, i.e., parameterization of hydraulic conductivity, configuration of model boundary, and surface complexation reactions that simulate U(VI) adsorption. These uncertain model components were aggregated into the alternative models by integrating a hierarchical structure into MLBMA. The modeling results of the individual models and MLBMA were analyzed to investigate their predictive performance. The predictive logscore results show that MLBMA generally outperforms the best model, suggesting that using MLBMA is a sound strategy to achieve more robust model predictions relative to a single model. MLBMA works best when the alternative models are structurally distinct and have diverse model predictions. When correlation in model structure exists, two strategies were used to improve predictive performance by retaining structurally distinct models or assigning smaller prior model probabilities to correlated models. Since the synthetic models were designed using data from the Naturita site, the results of this study are expected to provide guidance for real-world modeling. Limitations of applying MLBMA to the synthetic study and future real-world modeling are discussed.

California↗

Groundwater recharge assessment at local and episodic scale in a soil mantled perched karst aquifer in southern Italy

Groundwater recharge assessment of karst aquifers, at various spatial and temporal scales, is a major scientific topic of current importance, since these aquifers play an essential role for both socio-economic development and fluvial ecosystems. In this study, groundwater recharge was estimated at local and episodic scales in a representative perched karst aquifer in a region of southern Italy with a Mediterranean climate. The research utilized measurements of precipitation, air temperature, soil water content, and water-table depth, obtained in 2008 at the Acqua della Madonna test area (Terminio Mount karst aquifer, Campania region). At this location the aquifer is overlain by ash-fall pyroclastic soils. The Episodic Master Recession (EMR) method, an improved version of the Water Table Fluctuation (WTF) method, was applied to estimate the amount of recharge generated episodically by individual rainfall events. The method also quantifies the amount of precipitation generating each recharge episode, thus permitting calculation of the Recharge to the Precipitation Ratio (RPR) on a storm-by-storm basis. Depending on the seasonally varying air temperature, evapotranspiration, and precipitation patterns, calculated values of RPR varied between 35% and 97% among the individual episodes. A multiple linear correlation of the RPR with both the average intensity of recharging rainfall events and the antecedent soil water content was calculated. Given the relatively easy measurability of precipitation and soil water content, such an empirical model would have great hydrogeological and practical utility. It would facilitate short-term forecasting of recharge in karst aquifers of the Mediterranean region and other aquifers with similar hydrogeological characteristics. By establishing relationships between the RPR and climate-dependent variables such as average storm intensity, it would facilitate prediction of climate-change effects on groundwater recharge. The EMR methodology could further be applied to other aquifers for evaluating the relationship of recharge to various hydrometeorological and hydrogeological processes.

Journal of Hydrology↗

Regional oxygen reduction and denitrification rates in groundwater from multi-model residence time distributions, San Joaquin Valley, USA

Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary and covary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into the characteristics of residence times and rates of O 2 reduction and denitrification (NO 3 &minus; reduction) by comparing reaction rates using multi-model analytical residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwater age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The RTD approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF 6 , CFCs, 3 H, He from 3 H (tritiogenic He), 14 C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variances than those produced by individual RTD models. The set of multi-model RTDs was used in combination with NO 3 &minus; and dissolved gas data to estimate zero order and first order rates of O 2 reduction and denitrification. Results indicated that O 2 reduction and denitrification rates followed approximately log-normal distributions. Rates of O 2 and NO 3 &minus; reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O 2 reduction rates. Estimated historical NO 3 &minus; trends were similar to historical measurements. Results show that the multi-model approach can improve estimation of age distributions, and that relatively easily measured O 2 rates can provide information about trends in denitrification rates, which are more difficult to estimate.

California↗

Anthropogenic and geologic causes of anomalously high uranium concentrations in groundwater used for drinking water supply in the southeastern San Joaquin Valley, CA

Concentrations of uranium (U) >30 µg/L in groundwater are relatively uncommon in drinking water in the United States but can be of concern in those areas where complex interactions of aquifer materials and anthropogenic alterations of the natural flow regime mobilize uranium. High concentrations (>30 µg/L) of U in the southeastern San Joaquin Valley, California, USA, have been detected in 24 percent of 257 domestic, irrigation, and public-supply wells sampled across an approximately 110,000 km2 area. The location of high concentrations depends on the interactions of U sources from fluvial fans that originate in the Sierra Nevada to the east and seepage of irrigation water that contains high concentrations of HCO3 that leaches U from the sediments. In addition, interactions with phosphate (PO4) from fertilized irrigated fields may sequester U in the aquifer. Principal component analysis of the data demonstrates that HCO3 and ions associated with high total dissolved solids in the aquifer and the percentage of agriculture near the well sampled are associated with high U concentrations. Nitrate concentrations do not appear to control release of U to the aquifer. Age dating of the groundwater and generally increasing U concentrations of the past 25 years in resampled wells where irrigation is prevalent suggests that high U concentrations are associated with younger water, indicating that irrigation of fields over the past 100 years has significantly contributed to increasing concentrations and mobilizing U. In some places, the groundwater is supersaturated with uranyl-containing minerals, as would be expected in roll front deposits. In general, the interaction of natural geological sources high in U, the anthropogenically driven addition of HCO3 and possibly phosphate fertilizer, control the location and concentration of U in each individual fluvial fan, but the addition of nitrate in fertilizer does not appear control the location of high U. These geochemical interactions can be used to determine controls on anomalously high U in alluvial aquifers

California↗

The impact of onsite wastewater disposal systems on groundwater in areas inundated by Hurricane Sandy in New York and New Jersey

Coastal onsite wastewater disposal systems (OWDS) were inundated by Hurricane Sandy's storm tide. This study compares the shallow groundwater quality (nutrients, pharmaceuticals, and hormones) downgradient of OWDS before and after Hurricane Sandy, where available, and establishes a baseline for wastewater influence on groundwater in coastal communities inundated by Hurricane Sandy. Nutrients and contaminants of emerging concern (CECs) were detected in shallow groundwater downgradient of OWDS in two settings along the New Jersey and New York coastlines: 1) a single, centralized OWDS in a park; and 2) multiple OWDS (cesspools) in low-density residential and mixed-use/medium density residential areas. The most frequently detected pharmaceuticals were lidocaine (40%), carbamazepine (36%), and fexofenadine, bupropion, desvenlafaxine, meprobamate, and tramadol (24&ndash;32%). Increases in the number and total concentration of pharmaceuticals after Hurricane Sandy may reflect other factors (seasonality, usage) besides inundation, and demonstrate the importance of analyzing for a wide variety of CECs in regional studies.

New Jersey, New York↗

The energy-water nexus: Potential groundwater-quality degradation associated with production of shale gas

Oil and natural gas have been the main sources of primary energy in the USA, providing 63% of the total energy consumption in 2011. Petroleum production, drilling operations, and improperly sealed abandoned wells have caused significant local groundwater contamination in many states, including at the USGS OSPER sites in Oklahoma. The potential for groundwater contamination is higher when producing natural gas and oil from unconventional sources of energy, including shale and tight sandstones. These reservoirs require horizontally-completed wells and massive hydraulic fracturing that injects large volumes (up to 50,000 m3/well) of high-pressured water with added proppant, and toxic organic and inorganic chemicals. Recent results show that flow back and produced waters from Haynesville (Texas) and Marcellus (Pennsylvania) Shale have high salinities (&ge;200,000 mg/L TDS) and high NORMs (up to 10,000 picocuries/L) concentrations. A major research effort is needed worldwide to minimize all potential environmental impacts, especially groundwater contamination and induced seismicity, when producing these extremely important new sources of energy.

Procedia Earth and Planetary Science↗

Changes in the Chemistry of Groundwater Reacted with CO 2 : Comparison of Laboratory Results with the ZERT Field Pilot

As part of the ZERT program, sediments from two wells at the ZERT site, located in Bozeman, Montana, USA were reacted with a solution having the composition of local groundwater. A total of 50 water samples were collected from 7 containers placed for 15 days in a glove box with one atmosphere of CO 2 to investigate detailed changes in the concentrations of major, minor and trace inorganic compounds, and to compare these with changes observed in groundwater at the ZERT site following CO 2 injection. Laboratory results included rapid changes in pH (8.6 to 5.7), alkalinity (243 to 1295 mg/L as HCO 3 ), electrical conductance (539 to 1822 μS/cm), Ca (28 to 297 mg/L), Mg (18 to 63 mg/L), Fe (5 to 43 μg/L) and Mn (2 to 837 μg/L) following CO 2 injection. These chemical changes, which are in general agreement with those obtained from sampling the ZERT monitoring wells, could provide early detection of CO 2 leakage into shallow groundwater. Dissolution of calcite, some dolomite and minor Mn-oxides, and desorption/ion exchange are likely the main geochemical processes responsible for the observed changes.

Procedia Earth and Planetary Science↗

Application of artificial neural networks to assess pesticide contamination in shallow groundwater

In this study, a feed-forward back-propagation neural network (BPNN) was developed and applied to predict pesticide concentrations in groundwater monitoring wells. Pesticide concentration data are challenging to analyze because they tend to be highly censored. Input data to the neural network included the categorical indices of depth to aquifer material, pesticide leaching class, aquifer sensitivity to pesticide contamination, time (month) of sample collection, well depth, depth to water from land surface, and additional travel distance in the saturated zone (i.e., distance from land surface to midpoint of well screen). The output of the neural network was the total pesticide concentration detected in the well. The model prediction results produced good agreements with observed data in terms of correlation coefficient (R = 0.87) and pesticide detection efficiency (E = 89%), as well as good match between the observed and predicted "class" groups. The relative importance of input parameters to pesticide occurrence in groundwater was examined in terms of R, E, mean error (ME), root mean square error (RMSE), and pesticide occurrence "class" groups by eliminating some key input parameters to the model. Well depth and time of sample collection were the most sensitive input parameters for predicting the pesticide contamination potential of a well. This infers that wells tapping shallow aquifers are more vulnerable to pesticide contamination than those wells tapping deeper aquifers. Pesticide occurrences during post-application months (June through October) were found to be 2.5 to 3 times higher than pesticide occurrences during other months (November through April). The BPNN was used to rank the input parameters with highest potential to contaminate groundwater, including two original and five ancillary parameters. The two original parameters are depth to aquifer material and pesticide leaching class. When these two parameters were the only input parameters for the BPNN, they were not able to predict contamination potential. However, when they were used with other parameters, the predictive performance efficiency of the BPNN in terms of R, E, ME, RMSE, and pesticide occurrence "class" groups increased. Ancillary data include data collected during the study such as well depth and time of sample collection. The BPNN indicated that the ancillary data had more predictive power than the original data. The BPNN results will help researchers identify parameters to improve maps of aquifer sensitivity to pesticide contamination. ?? 2006 Elsevier B.V. All rights reserved.

Science of the Total Environment↗

A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States - I) Groundwater

As part of the continuing effort to collect baseline information on the environmental occurrence of pharmaceuticals, and other organic wastewater contaminants (OWCs) in the Nation's water resources, water samples were collected from a network of 47 groundwater sites across 18 states in 2000. All samples collected were analyzed for 65 OWCs representing a wide variety of uses and origins. Site selection focused on areas suspected to be susceptible to contamination from either animal or human wastewaters (i.e. down gradient of a landfill, unsewered residential development, or animal feedlot). Thus, sites sampled were not necessarily used as a source of drinking water but provide a variety of geohydrologic environments with potential sources of OWCs. OWCs were detected in 81% of the sites sampled, with 35 of the 65 OWCs being found at least once. The most frequently detected compounds include N , N -diethyltoluamide (35%, insect repellant), bisphenol A (30%, plasticizer), tri(2-chloroethyl) phosphate (30%, fire retardant), sulfamethoxazole (23%, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19%, detergent metabolite). Although sampling procedures were intended to ensure that all groundwater samples analyzed were indicative of aquifer conditions it is possible that detections of some OWCs could have resulted from leaching of well-construction materials and/or other site-specific conditions related to well construction and materials. Future research will be needed to identify those factors that are most important in determining the occurrence and concentrations of OWCs in groundwater.

Science of the Total Environment↗

Groundwater quality impacts from the land application of treated municipal wastewater in a large karstic spring basin: Chemical and microbiological indicators

Geochemical and microbiological techniques were used to assess water-quality impacts from the land application of treated municipal wastewater in the karstic Wakulla Springs basin in northern Florida. Nitrate-N concentrations have increased from about 0.2 to as high as 1.1??mg/L (milligrams per liter) during the past 30??years in Wakulla Springs, a regional discharge point for groundwater (mean flow about 11.3??m 3 /s) from the Upper Floridan aquifer (UFA). A major source of nitrate to the UFA is the approximately 64??million L/d (liters per day) of treated municipal wastewater applied at a 774??ha (hectare) sprayfield farming operation. About 260 chemical and microbiological indicators were analyzed in water samples from the sprayfield effluent reservoir, wells upgradient from the sprayfield, and from 21 downgradient wells and springs to assess the movement of contaminants into the UFA. Concentrations of nitrate-N, boron, chloride, were elevated in water samples from the sprayfield effluent reservoir and in monitoring wells at the sprayfield boundary. Mixing of sprayfield effluent water was indicated by a systematic decrease in concentrations of these constituents with distance downgradient from the sprayfield, with about a 10-fold dilution at Wakulla Springs, about 15??km (kilometers) downgradient from the sprayfield. Groundwater with elevated chloride and boron concentrations in wells downgradient from the sprayfield and in Wakulla Springs had similar nitrate isotopic signatures, whereas the nitrate isotopic composition of water from other sites was consistent with inorganic fertilizers or denitrification. The sprayfield operation was highly effective in removing most studied organic wastewater and pharmaceutical compounds and microbial indicators. Carbamazepine (an anti-convulsant drug) was the only pharmaceutical compound detected in groundwater from two sprayfield monitoring wells (1-2??ppt). One other detection of carbamazepine was found in a distant well water sample where enteroviruses also were detected, indicating a likely influence from a nearby septic tank.

Science of the Total Environment↗

Trends in concentrations of nitrate and total dissolved solids in public supply wells of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins, San Bernardino County, California: Influence of legacy land use

Concentrations and temporal changes in concentrations of nitrate and total dissolved solids (TDS) in groundwater of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins of the Upper Santa Ana Valley Groundwater Basin were evaluated to identify trends and factors that may be affecting trends. One hundred, thirty-one public-supply wells were selected for analysis based on the availability of data spanning at least 11 years between the late 1980s and the 2000s. Forty-one of the 131 wells (31%) had a significant (p < 0.10) increase in nitrate and 14 wells (11%) had a significant decrease in nitrate. For TDS, 46 wells (35%) had a significant increase and 8 wells (6%) had a significant decrease. Slopes for the observed significant trends ranged from − 0.44 to 0.91 mg/L/yr for nitrate (as N) and − 8 to 13 mg/L/yr for TDS. Increasing nitrate trends were associated with greater well depth, higher percentage of agricultural land use, and being closer to the distal end of the flow system. Decreasing nitrate trends were associated with the occurrence of volatile organic compounds (VOCs); VOC occurrence decreases with increasing depth. The relations of nitrate trends to depth, lateral position, and VOCs imply that increasing nitrate concentrations are associated with nitrate loading from historical agricultural land use and that more recent urban land use is generally associated with lower nitrate concentrations and greater VOC occurrence. Increasing TDS trends were associated with relatively greater current nitrate concentrations and relatively greater amounts of urban land. Decreasing TDS trends were associated with relatively greater amounts of natural land use. Trends in TDS concentrations were not related to depth, lateral position, or VOC occurrence, reflecting more complex factors affecting TDS than nitrate in the study area.

California↗

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 &mu;g/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 &mu;m). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The &delta;D and &delta; 18 O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.

Maine↗