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USGS2006

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (222Rn, 223,224,226,228Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5??mg L- 1) close to zero salinity and increased several-fold (??? 18??mg L- 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet. Surface water-column 222Rn activities were most elevated (> 28??dpm L- 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (223,224,226,228Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess 226Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 ?? 105??m3 d- 1 (20-74??L m- 2 d- 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH4+ and PO4- 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5????mol m- 2 d- 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates. ?? 2006 Elsevier B.V. All rights reserved.

Marine Chemistry↗

USGS2007

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in Tampa Bay, Florida

A suite of naturally occurring radionuclides in the U/Th decay series ( 222 Rn, 223,224,226,228 Ra) were studied during wet and dry conditions in Tampa Bay, Florida, to evaluate their utility as groundwater discharge tracers, both within the bay proper and within the Alafia River/estuary — a prominent free-flowing river that empties into the bay. In Tampa Bay, almost 30% of the combined riverine inputs still remain ungauged. Consequently, groundwater/surface water (hyporheic) exchange in the discharging coastal rivers, as well as submarine groundwater discharge (SGD) within the bay, are still unresolved components of this system's water and material budgets. Based on known inputs and sinks, there exists an excess of 226 Ra in the water column of Tampa Bay, which can be evaluated in terms of a submarine groundwater contribution to the bay proper. Submarine groundwater discharge rates calculated using a mass balance of excess 226 Ra ranged from 2.2 to 14.5 L m − 2 day − 1 , depending on whether the estuarine residence time was calculated using 224 Ra/xs 228 Ra isotope ratios, or whether a long term, averaged model-derived estuarine residence time was used. When extrapolated to the total shoreline length of the bay, such SGD rates ranged from 1.6 to 10.3 m 3 m − 1 day − 1 . Activities of 222 Rn were also elevated in surface water and shallow groundwater of the bay, as well as in the Alafia River estuary, where upstream activities as high as 250 dpm L − 1 indicate enhanced groundwater/surface water exchange, facilitated by an active spring vent. From average nutrient concentrations of 39 shallow, brackish, groundwater samples, rates of nutrient loading into Tampa Bay by SGD rates were estimated, and these ranged from 0.2 to 1.4 × 10 5 mol day − 1 (PO 4 3− ), 0.9–6.2 × 10 5 mol day − 1 (SiO 4 − ), 0.7–5.0 × 10 5 mol day − 1 (dissolved organic nitrogen, DON), and 0.2–1.4 × 10 6 mol day − 1 (total dissolved nitrogen, TDN). Such nutrient loading estimates, when compared to average river discharge estimates (e.g., TDN = 6.9 × 10 5 mol day − 1 ), suggest that SGD-derived nutrient fluxes to Tampa Bay are indeed important components to the overall nutrient economy of these coastal waters.

Florida↗

USGS2021

Complexity of groundwater age mixing near a seawater intrusion zone based on multiple tracers and Bayesian inference

Aquifer flow systems near seawater interfaces can be complicated by density-driven flows and the formation of stagnation zones, which inevitably introduces uncertainty into groundwater age-dating. While age-dating has proved effective to understand the seawater intrusion and aquifer salinization process in coastal aquifers, further efforts are needed to propagate model and data uncertainty to the uncertainty associated with the inferred age distributions. This study was performed in a coastal aquifer located close to the Yellow Sea, South Korea, where there is a decreasing trend of groundwater levels due to recent heavy exploitation, raising a warning of induced seawater intrusion. We inferred the groundwater age distributions in wells around the intrusion zone and estimated the uncertainty associated with the inference based on multiple age tracers including 3 H, tritiogenic 3 He, radiogenic 4 He, CFC-11, CFC-12 and CFC-113 using Bayesian inference. We examined various models representing the age distributions including traditional parametric Lumped Parameter Models (LPMs) and two non-parametric “shape-free” models. The results showed that the mean ages at the study site ranged from 10.9 to 522.5 y. Complex, multimodal distributions of ages occurred near a seawater intrusion area and upland recharge zones, implying converging paths of a wide range of different ages in those regions. In particular, the age distributions estimated near the seawater intrusion interface were characterized by heavy-tailed mixing structures with elevated concentrations of 4 He. This likely indicates density-driven upward flow at the seawater intrusion interface, forcing old groundwater rich in 4 He into the shallow aquifer. The Bayesian inference estimated large uncertainties particularly for the old age distributions, which was attributed partly to the gradual accumulation of 4 He in groundwater. The Bayesian inference improved understanding of flow dynamics at a complex seawater interface and identified opportunities to further reduce uncertainty of old water age estimates that characterize upwelling groundwater near the interface.

Jaancheon basin↗

USGS2021

Machine learning predictions of nitrate in groundwater used for drinking supply in the conterminous United States

Groundwater is an important source of drinking water supplies in the conterminous United State (CONUS), and presence of high nitrate concentrations may limit usability of groundwater in some areas because of the potential negative health effects. Prediction of locations of high nitrate groundwater is needed to focus mitigation and relief efforts. A three-dimensional extreme gradient boosting (XGB) machine learning model was developed to predict the distribution of nitrate. Nitrate was predicted at a 1 km resolution for two drinking water zones, each of variable depth, one for domestic supply and one for public supply. The model used measured nitrate concentrations from 12,082 wells and included predictor variables representing well characteristics, hydrologic conditions, soil type, geology, land use, climate, and nitrogen inputs. Predictor variables derived from empirical or numerical process-based models were also included to integrate information on controlling processes and conditions. The model provided accurate estimates at national and regional scales: the training (R 2 of 0.83) and hold-out (R 2 of 0.49) data fits compared favorably to previous studies. Predicted nitrate concentrations were less than 1 mg/L across most of the CONUS. Nationally, well depth, soil and climate characteristics, and the absence of developed land use were among the most influential explanatory factors. Only 1% of the area in either water supply zone had predicted nitrate concentrations greater than 10 mg/L; however, about 1.4 M people depend on groundwater for their drinking supplies in those areas. Predicted high concentrations of nitrate were most prevalent in the central CONUS. In areas of predicted high nitrate concentration, applied manure, farm fertilizer , and agricultural land use were influential predictor variables. This work represents the first application of XGB to a three-dimensional national-scale groundwater quality model and provides a significant milestone in the efforts to document nitrate in groundwater across the CONUS.

Science of the Total Environment↗

USGS2022

Effects of imported recharge on fluoride trends in groundwater used for public supply in California

Fluoride is a naturally occurring element in groundwater that supports bone and dental health at low concentrations but can cause health problems at elevated concentrations in drinking water. This study investigates spatial and temporal trends for fluoride concentrations in untreated groundwater from over 20,000 public supply wells in California. The presence of a significant temporal trend in fluoride concentrations in a well was assessed using the Mann-Kendall test and a spatial-weighting approach was used to identify the areal extent of the groundwater resources with significant trends. Less than 2% of the groundwater resources used for public supply in the state have concentrations above the California maximum contaminant level of 2 mg/L. Approximately 14% of the groundwater resource used for public supply show a significant recent trend (2000–2019), with decreasing trends occurring in 10% of the resource. Potential drivers for trends were evaluated in two of the areas in southern California with the greatest prevalence of trends but distinct climate and hydrogeological characteristics. Aquifers in the Mojave and Whitewater River watersheds, located in the desert region, and the Los Angeles Basin, located on the coast, have been replenished with imported and treated water over the last half century to maintain sustainable groundwater levels. The recharge of imported water with different chemistries has altered the geochemical conditions in the aquifers, driving changes in fluoride concentrations.

California↗

USGS2025

Relations of groundwater quality to long-term surface disposal of produced water near the Midway-Sunset and Buena Vista Oil Fields, California, USA

Contamination of groundwater by oil-field fluids in proximity to oil and gas development has been an issue of concern to water users and regulators given long histories of development and legacy disposal practices. A robust set of geochemical tracers including petroleum hydrocarbon compounds, thermogenic gases, inorganic ion concentrations, stable isotopes, radioactive isotopes, and noble gases were used to assess if oil-field fluids mixed with groundwater near the Midway-Sunset and Buena Vista Oil Fields in California, USA. Results show evidence of mixing of oil-field fluids with groundwater within the study area from either anthropogenic or natural processes. Produced water plumes associated with modern surface disposal facilities, used since the late 1950s, extend up to 1.5 km and currently remain within the boundaries of the oil fields. Plumes associated with earlier routing of produced water down natural drainages and in large retention structures (Midway Basin and Sunset Basin) near the Buena Vista Lake Bed are present in groundwater east of the oil fields. Based on geochemical tracer evidence, aerial imagery, and aerial electromagnetic surveys, these legacy plumes reach the western portion of the Central Valley aquifer system, an important groundwater resource for agricultural and domestic supply. The legacy plume associated with Sunset Basin may further be detected downgradient in deeper groundwater beneath the southern extent of the Buena Vista Lake Bed based on the presence of thermogenic gases and petroleum hydrocarbon compounds.

California↗

USGS2018

Minimum energy requirements for desalination of brackish groundwater in the United States with comparison to international datasets

This paper uses chemical and physical data from a large 2017 U.S. Geological Survey groundwater dataset with wells in the U.S. and three smaller international groundwater datasets with wells primarily in Australia and Spain to carry out a comprehensive investigation of brackish groundwater composition in relation to minimum desalination energy costs. First, we compute the site-specific least work required for groundwater desalination. Least work of separation represents a baseline for specific energy consumption of desalination systems. We develop simplified equations based on the U.S. data for least work as a function of water recovery ratio and a proxy variable for composition, either total dissolved solids, specific conductance, molality or ionic strength. We show that the U.S. correlations for total dissolved solids and molality may be applied to the international datasets. We find that total molality can be used to calculate the least work of dilute solutions with very high accuracy. Then, we examine the effects of groundwater solute composition on minimum energy requirements , showing that separation requirements increase from calcium to sodium for cations and from sulfate to bicarbonate to chloride for anions , for any given TDS concentration. We study the geographic distribution of least work, total dissolved solids, and major ions concentration across the U.S. We determine areas with both low least work and high water stress in order to highlight regions holding potential for desalination to decrease the disparity between high water demand and low water supply. Finally, we discuss the implications of the USGS results on water resource planning, by comparing least work to the specific energy consumption of brackish water reverse osmosis plants and showing the scaling propensity of major electrolytes and silica in the U.S. groundwater samples.

Water Research↗

USGS2026

Predictions of anthropogenic background PFAS concentrations in soil and relation to bedrock lithology and groundwater quality

Detectable concentrations of per- and polyfluoroalkyl substances (PFAS) have been observed in soils in remote areas and presumably originate from atmospheric deposition. These anthropogenic background concentrations may enable some PFAS to leach to groundwater at levels that exceed regulatory criteria for drinking water. However, anthropogenic background soil concentrations and their connection to groundwater are not well characterized. We developed a boosted regression tree model to predict perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) concentrations in shallow soils across northern New England. Low soil pH was the most important predictor of elevated anthropogenic PFOS and PFOA concentrations in background soils, rather than potential PFAS sources, land use, or population density. Total organic carbon (TOC) was also an important predictor for PFOS soil concentrations. Model predictions indicate that 73% of the shallow soils within Maine, Vermont, and New Hampshire exceed New Hampshire’s Soil Remediation Standard for PFOS (0.5 ng/g) and 41% exceed the PFOA standard (0.4 ng/g). Analysis of soil model results and groundwater data suggests that areas with high soil pH are associated with higher groundwater detection frequencies, illustrating how areas with less retention in soil are, conversely, also areas with potentially greater groundwater vulnerability. Further analysis indicates that groundwater may be more vulnerable in calcareous lithologies.

Maine, New Hampshire, Vermont↗

USGS2018

Elevated manganese concentrations in United States groundwater, role of land surface–soil–aquifer connections

Chemical data from 43 334 wells were used to examine the role of land surface–soil–aquifer connections in producing elevated manganese concentrations (>300 μg/L) in United States (U.S.) groundwater. Elevated concentrations of manganese and dissolved organic carbon (DOC) in groundwater are associated with shallow, anoxic water tables and soils enriched in organic carbon, suggesting soil-derived DOC supports manganese reduction and mobilization in shallow groundwater. Manganese and DOC concentrations are higher near rivers than farther from rivers, suggesting river-derived DOC also supports manganese mobilization. Anthropogenic nitrogen may also affect manganese concentrations in groundwater. In parts of the northeastern U.S. containing poorly buffered soils, ∼40% of the samples with elevated manganese concentrations have pH values < 6 and elevated concentrations of nitrate relative to samples with pH ≥ 6, suggesting acidic recharge produced by the oxidation of ammonium in fertilizer helps mobilize manganese. An estimated 2.6 million people potentially consume groundwater with elevated manganese concentrations, the highest densities of which occur near rivers and in areas with organic carbon rich soil. Results from this study indicate land surface–soil–aquifer connections play an important role in producing elevated manganese concentrations in groundwater used for human consumption.

Environmental Science & Technology↗

USGS2000

In situ stimulation of groundwater denitrification with formate to remediate nitrate contamination

In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.In situ stimulation of denitrification has been proposed as a mechanism to remediate groundwater nitrate contamination. In this study, sodium formate was added to a sand and gravel aquifer on Cape Cod, MA, to test whether formate could serve as a potential electron donor for subsurface denitrification. During 16- and 10-day trials, groundwater from an anoxic nitrate-containing zone (0.5-1.5 mM) was continuously withdrawn, amended with formate and bromide, and pumped back into the aquifer. Concentrations of groundwater constituents were monitored in multilevel samplers after up to 15 m of transport by natural gradient flow. Nitrate and formate concentrations were decreased 80-100% and 60-70%, respectively, with time and subsequent travel distance, while nitrite concentrations inversely increased. The field experiment breakthrough curves were simulated with a two-dimensional site-specific model that included transport, denitrification, and microbial growth. Initial values for model parameters were obtained from laboratory incubations with aquifer core material and then refined to fit field breakthrough curves. The model and the lab results indicated that formate-enhanced nitrite reduction was nearly 4-fold slower than nitrate reduction, but in the lab, nitrite was completely consumed with sufficient exposure time. Results of this study suggest that a long-term injection of formate is necessary to test the remediation potential of this approach for nitrate contamination and that adaptation to nitrite accumulation will be a key determinative factor.

Environmental Science & Technology↗

USGS2002

Migration of wood-preserving chemicals in contaminated groundwater in a sand aquifer at Pensacola, Florida

Operation of a wood-preserving facility for nearly 80 years at Pensacola, FL, contaminated the near-surface groundwater with creosote and pentachlorophenol. The major source of aquifer contamination was unlined surface impoundments that were in direct hydraulic contact with the groundwater. Episodes of overtopping the impoundments and overland flow of treatment liquor and waste were also significant to the migration and contamination of the groundwater. Solutes contaminating the ground-water are mainly naphthalene and substituted phenols. Sorption did not influence retardation of solutes in transport in the groundwater. Phenol and the mono substituted methylphenols appear to be undergoing bio-transformation. Pentachlorophenol (PCP) was not found in significant concentrations in the groundwater possibly because the solubility of PCP is approximately 5 mg/L at pH 6, near the average acidity for the groundwater.

Florida↗

USGS2002

Distribution and mobility of selenium and other trace elements in shallow groundwater of the western San Joaquin Valley, California

Samples of shallow groundwater that underlies much of the irrigated area in the western San Joaquin Valley, CA, were analyzed for various major ions and trace elements, including selenium. Concentrations of the major ions generally were similar for groundwater collected in the two primary geologic zones - the alluvial fan and basin trough. Selenium concentrations are significantly (α = 0.05) higher in the groundwater of the alluvial-fan zone than in that of the basin-trough zone. The concentrations of oxyanion trace elements were significantly correlated (α = 0.05) with groundwater salinity, but the correlations between selenium and salinity and between molybdenum and salinity were significantly different (α = 0.05) in the alluvial-fan geologic zone compared with those in the basin-trough geologic zone. The evidence suggests that the main factors affecting selenium concentrations in the shallow groundwater are the degree of groundwater salinity and the geologic source of the alluvial soil material.

California↗

USGS2013

Mercury speciation and mobilization in a wastewater-contaminated groundwater plume

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5–1 pM, and aquifer sediments have 0.5–1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg(II) to Hg0 within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone.

Massachusetts↗

USGS2013

Groundwater ages and mixing in the Piceance Basin natural gas province, Colorado

Reliably identifying the effects of energy development on groundwater quality can be difficult because baseline assessments of water quality completed before the onset of energy development are rare and because interactions between hydrocarbon reservoirs and aquifers can be complex, involving both natural and human processes. Groundwater age and mixing data can strengthen interpretations of monitoring data from those areas by providing better understanding of the groundwater flow systems. Chemical, isotopic, and age tracers were used to characterize groundwater ages and mixing with deeper saline water in three areas of the Piceance Basin natural gas province. The data revealed a complex array of groundwater ages (<10 to >50,000 years) and mixing patterns in the basin that helped explain concentrations and sources of methane in groundwater. Age and mixing data also can strengthen the design of monitoring programs by providing information on time scales at which water quality changes in aquifers might be expected to occur. This information could be used to establish maximum allowable distances of monitoring wells from energy development activity and the appropriate duration of monitoring.

Colorado↗

USGS1998

Occurrence of pesticides in shallow groundwater of the United States: initial results from the National Water-Quality Assessment program

The first phase of intensive data collection for the National Water-Quality Assessment (NAWQA) was completed during 1993−1995 in 20 major hydrologic basins of the United States. Groundwater land-use studies, designed to sample recently recharged groundwater (generally within 10 years) beneath specific land-use and hydrogeologic settings, are a major component of the groundwater quality as sessment for NAWQA. Pesticide results from the 41 land-use studies conducted during 1993−1995 indicate that pesticides were commonly detected in shallow groundwater, having been found at 54.4% of the 1034 sites sampled in agricultural and urban settings across the United States. Pesticide concentrations were generally low, with over 95% of the detections at concentrations less than 1 μg/L. Of the 46 pesticide compounds examined, 39 were detected. The compounds detected most frequently were atrazine (38.2%), deethylatrazine (34.2%), simazine (18.0%), metolachlor (14.6%), and prometon (13.9%). Statistically significant relations were observed between frequencies of detection and the use, mobility, and persistence of these compounds. Pesticides were commonly detected in both agricultural (56.4%; 813 sites) and urban (46.6%; 221 sites) settings. Frequent detections of pesticides in urban areas indicate that, as is the case with agricultural pesticide use in agricultural areas, urban and suburban pesticide use significantly contribute to pesticide occurrence in shallow groundwater. Although pesticides were detected in groundwater sampled in urban areas and all nine of the agricultural land-use categories examined, significant variations in occurrence were observed among these categories. Maximum contaminant levels (MCLs) established by the U.S. Environmental Protection Agency for drinking water were exceeded for only one pesticide (atrazine, 3 μg/L) at a single location. However, MCLs have been established for only 25 of the 46 pesticide compounds examined, do not cover pesticide degradates, and, at present, do not take into account additive or synergistic effects of combinations of pesticide compounds or potential effects on nearby aquatic ecosystems.

Environmental Science & Technology↗

USGS1999

Volatile organic compounds in untreated ambient groundwater of the United States, 1985-1995

As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, an assessment of 60 volatile organic compounds (VOCs) in untreated, ambient groundwater of the conterminous United States was conducted based on samples collected from 2948 wells between 1985 and 1995. The samples represent urban and rural areas and drinking-water and nondrinking-water wells. A reporting level of 0.2 μg/L was used with the exception of 1,2-dibromo-3-chloropropane, which had a reporting level of 1.0 μg/L. Because ambient groundwater was targeted, areas of known point-source contamination were excluded from this assessment. VOC concentrations generally were low; 56% of the concentrations were less than 1 μg/L. In urban areas, 47% of the sampled wells had at least one VOC, and 29% had two or more VOCs; furthermore, U.S. Environmental Protection Agency drinking-water criteria were exceeded in 6.4% of all sampled wells and in 2.5% of the sampled drinking-water wells. In rural areas, 14% of the sampled wells had at least one VOC; furthermore, drinking-water criteria were exceeded in 1.5% of all sampled wells and in 1.3% of the sampled drinking-water wells. Solvent compounds and the fuel oxygenate methyl tert -butyl ether were among the most frequently detected VOCs in urban and rural areas. It was determined that the probability of finding VOCs in untreated groundwater can be estimated on the basis of a logistic regression model by using population density as an explanatory variable. Although there are limitations to this national scale model, it fit the data from 2354 wells used for model development and adequately estimated the VOC presence in samples from 589 wells used for model validation. Model estimates indicate that 7% (6−9% on the basis of one standard error) of the ambient groundwater resources of the United States probably contain at least one VOC at a reporting level of 0.2 μg/L. Groundwater is used in these areas by 42 million people (35−50 million based on one standard error); however, human exposure to VOCs from this ambient groundwater is uncertain because the quality of the finished drinking water is generally unknown.

Environmental Science & Technology↗

USGS2000

First LC/MS determination of cyanazine amide, cyanazine acid, and cyanazine in groundwater samples

Cyanazine and two of its major metabolites, cyanazine amide and cyanazine acid, were measured at trace levels in groundwater using liquid chromatography/atmospheric pressure chemical ionization/mass spectrometry (LC/APCI/MS). Solid-phase extraction was carried out by passing 20 mL of groundwater sample through a cartridge containing a polymeric phase (PLRP-s), with recoveries ranging from 99 to 108% ( n = 5). Using LC/MS detection in positive ion mode, useful structural information was obtained by increasing the fragmentor voltage, thus permitting the unequivocal identification of these compounds in groundwater samples with low sample volumes. The fragmentation of the amide, carboxylic acid, and cyano group was observed for both metabolites and cyanazine, respectively, leading to a diagnostic ion at m / z 214. Method detection limits were in the range of 0.002−0.005 μg/L for the three compounds. Finally, the newly developed method was evaluated for the analysis of groundwater samples from New York containing the compounds under study and presents evidence that the metabolites, cyanazine acid, and cyanazine amide may leach to groundwater and serve as sources for deisopropylatrazine. The combination of on-line SPE and LC/APCI/MS represents an important advance in environmental analysis of herbicide metabolites in groundwater since it demonstrates that trace amounts of polar metabolites may be determined rapidly. Furthermore, the presence of both cyanazine amide and cyanazine acid indicate that another degradation product, deisopropylatrazine, may be occurring at depth because of the subsequent degradation of cyanazine.

Environmental Science & Technology↗

USGS2001

Catchment-scale variation in the nitrate concentrations of groundwater seeps in the Catskill Mountains, New York, U.S.A.

Forested headwater streams in the Catskill Mountains of New York show significant among-catchment variability in mean annual nitrate (NO3-) concentrations. Large contributions from deep groundwater with high NO3- concentrations have been invoked to explain high NO3- concentrations in stream water during the growing season. To determine whether variable contributions of groundwater could explain among-catchment differences in streamwater, we measured NO3- concentrations in 58 groundwater seeps distributed across six catchments known to have different annual average streamwater concentrations. Seeps were identified based on release from bedrock fractures and bedding planes and had consistently lower temperatures than adjacent streamwaters. Nitrate concentrations in seeps ranged from near detection limits (0.005 mg NO3--N/L) to 0.75 mg NO3--N/L. Within individual catchments, groundwater residence time does not seem to strongly affect NO3- concentrations because in three out of four catchments there were non-significant correlations between seep silica (SiO2) concentrations, a proxy for residence time, and seep NO3- concentrations. Across catchments, there was a significant but weak negative relationship between NO3- and SiO2 concentrations. The large range in NO3- concentrations of seeps across catchments suggests: 1) the principal process generating among-catchment differences in streamwater NO3- concentrations must influence water before it enters the groundwater flow system and 2) this process must act at large spatial scales because among-catchment variability is much greater than intra-catchment variability. Differences in the quantity of groundwater contribution to stream baseflow are not sufficient to account for differences in streamwater NO3- concentrations among catchments in the Catskill Mountains.

Water, Air, & Soil Pollution↗