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Simulations of ground-water flow and particle pathline analysis in the zone of contribution of a public-supply well in Modesto, eastern San Joaquin Valley, California

Shallow ground water in the eastern San Joaquin Valley is affected by high nitrate and uranium concentrations and frequent detections of pesticides and volatile organic compounds (VOC), as a result of ground-water development and intensive agricultural and urban land use. A single public-supply well was selected for intensive study to evaluate the dominant processes affecting the vulnerability of public-supply wells in the Modesto area. A network of 23 monitoring wells was installed, and water and sediment samples were collected within the approximate zone of contribution of the public-supply well, to support a detailed analysis of physical and chemical conditions and processes affecting the water chemistry in the well. A three-dimensional, steady-state local ground-water-flow and transport model was developed to evaluate the age of ground water reaching the well and to evaluate the vulnerability of the well to nonpoint source input of nitrate and uranium. Particle tracking was used to compute pathlines and advective travel times in the ground-water flow model. The simulated ages of particles reaching the public-supply well ranged from 9 to 30,000 years, with a median of 54 years. The age of the ground water contributed to the public-supply well increased with depth below the water table. Measured nitrate concentrations, derived primarily from agricultural fertilizer, were highest (17 milligrams per liter) in shallow ground water and decreased with depth to background concentrations of less than 2 milligrams per liter in the deepest wells. Because the movement of water is predominantly downward as a result of ground-water development, and because geochemical conditions are generally oxic, high nitrate concentrations in shallow ground water are expected to continue moving downward without significant attenuation. Simulated long-term nitrate concentrations indicate that concentrations have peaked and will decrease in the public-supply well during the next 100 years because of the low nitrate concentrations in recharge beneath the urban area and the increasing proportion of urban-derived ground water reaching the well. The apparent lag time between peak input concentrations and peak concentrations in the well is about 20 to 30 years. Measured uranium concentrations were also highest (45 micrograms per liter) in shallow ground water, and decreased with depth to background concentrations of about 0.5 microgram per liter. Naturally-occurring uranium adsorbed to aquifer sediments is mobilized by oxygen-rich, high-alkalinity water. Alkalinity increased in shallow ground water in response to agricultural development. As ground-water pumping increased in the 1940s and 1950s, this alkaline water moved downward through the ground-water flow system, mobilizing the uranium adsorbed to aquifer sediments. Ground water with high alkalinity and high uranium concentrations is expected to continue to move deeper in the system, resulting in increased uranium concentrations with depth in ground water. Because alkalinity (and correspondingly uranium) concentrations were high in shallow ground water beneath both the urban and the agricultural land, long-term uranium concentrations in the public-supply well are expected to increase as the proportion of uranium-affected water contributed to the well increases. Assuming that the alkalinity near the water table remains the same, the simulation of long-term alkalinity in the public-supply well indicates that uranium concentrations in the public-supply well will likely approach the maximum contaminant level; however, the time to reach this level is more than 100 years because of the significant proportion of old, unaffected water at depth that is contributed to the public-supply well.

California

The Pothole Hydrology-Linked Systems Simulator (PHyLiSS)—Development and application of a systems model for prairie-pothole wetlands

The North American Prairie Pothole Region covers about 770,000 square kilometers of the United States and Canada (including parts of 5 States and 3 provinces: North Dakota, South Dakota, Montana, Minnesota, Iowa, Saskatchewan, Manitoba, and Alberta). The Laurentide Ice Sheet shaped the landscape of the region about 12,000 to 14,000 years ago. The retreat of the ice sheet left behind low-permeability glacial till and a landscape dotted with millions of depressions known today as prairie potholes. The wetlands that subsequently formed in these depressions, prairie-pothole wetlands, provide critical migratory-bird habitat and support dynamic aquatic communities. Extensive grasslands and productive agricultural systems surround these wetland ecosystems. In prairie-pothole wetlands, the compositions of plant, invertebrate, and vertebrate communities are highly dependent on hydrogeochemical conditions. Regional climate shifts between wet and dry periods affect the length of time that wetlands contain ponded surface water and the chemistry of that ponded water. Land-use change can exacerbate or reduce the effects of climate on wetland hydrology and water chemistry. A mechanistic understanding of the relation among climate, land use, hydrology, chemistry, and biota in prairie-pothole wetlands is needed to better understand the complex, and often interacting, effects of climate and land use on prairie-pothole wetland systems and to facilitate climate and land-use change adaptation efforts. The Pothole Hydrology-Linked Systems Simulator (PHyLiSS) model was developed to address this need. The model simulates water-surface elevation dynamics in prairie-pothole wetlands and quantifies changes in salinity. The PHyLiSS model is unique among other wetland models because it accommodates differing sizes and morphometries of wetland basins, is not dependent on a priori designations of wetland class, and allows for functional changes associated with dynamic shifts in ecohydrological states. The PHyLiSS model also has the capability to simulate wetland salinity, and potential future iterations will also simulate the effects of changing hydrology and geochemical conditions on biota. This report documents the development of the hydrological and geochemical components of the PHyLiSS model and provides example applications.

Open-File Report

New studies initiated by the U.S. Geological Survey - Effects of nutrient enrichment on stream ecosystems

In 2001, the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program began an intensive study of nutrient enrichment elevated concentrations of nitrogen and phosphorus in streams in five agricultural basins across the Nation (see map, p. 2). This study is providing nationally consistent and comparable data and analyses of nutrient conditions, including how these conditions vary as a result of natural and human-related factors, and how nutrient conditions affect algae and other biological communities. This information will benefit stakeholders, including the U.S. Environmental Protection Agency (USEPA) and its partners, who are developing nutrient criteria to protect the aquatic health of streams in different geographic regions. Nutrient enrichment is one of five national priority topics addressed by NAWQA in its second decade of studies, which began in 2001. During its first round of assessments in 51 major river basins (referred to as “Study Units”), NAWQA scientists collected data on water chemistry, stream hydrology and habitat, and biological communities; currently, NAWQA is revisiting selected basins and focusing on (1) trends, (2) factors that affect water quality and aquatic health, and (3) national priority water issues related to, for example, the development of nutrient criteria, source-water protection strategies, and stream restoration plans. The nutrient enrichment study has four major objectives that address nutrient conditions, dissolved oxygen, aquatic communities, and geographic and landscape features in agricultural basins (see inset). The focus on agricultural streams is a starting point. As the study progresses, streams draining other land uses, such as those in residential and urban areas, will likely be added.

Fact Sheet

Groundwater movement, recharge, and perchlorate occurrence in a faulted alluvial aquifer in California (USA)

Perchlorate from military, industrial, and legacy agricultural sources is present within an alluvial aquifer in the Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California (USA). The area is extensively faulted, with water-level differences exceeding 60 m across parts of the Rialto-Colton Fault separating the Rialto-Colton and Chino groundwater subbasins. Coupled well-bore flow and depth-dependent water-quality data show decreases in well yield and changes in water chemistry and isotopic composition, reflecting changing aquifer properties and groundwater recharge sources with depth. Perchlorate movement through some wells under unpumped conditions from shallower to deeper layers underlying mapped plumes was as high as 13 kg/year. Water-level maps suggest potential groundwater movement across the Rialto-Colton Fault through an overlying perched aquifer. Upward flow through a well in the Chino subbasin near the Rialto-Colton Fault suggests potential groundwater movement across the fault through permeable layers within partly consolidated deposits at depth. Although potentially important locally, movement of groundwater from the Rialto-Colton subbasin has not resulted in widespread occurrence of perchlorate within the Chino subbasin. Nitrate and perchlorate concentrations at the water table, associated with legacy agricultural fertilizer use, may be underestimated by data from long-screened wells that mix water from different depths within the aquifer.

California

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO 2 - in the environment, but methods for independent isotopic analyses of NO 2 - in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO 2 - can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens , which selectively reduces NO 2 - to N 2 O for isotope ratio mass spectrometry. When calibrated with solutions containing NO 2 - with known isotopic compositions determined independently, reproducible δ 15 N and δ 18 O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ 15 N and ±0.4−1.0‰ for δ 18 O) and moderately enriched 15 N tracer levels (±20−50‰ for δ 15 N near 5000‰) for 5−20 nmol of NO 2 - (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO 2 - and was used for mixed samples containing both NO 2 - and NO 3 - with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO 3 - in the absence of NO 2 - , providing isotopic analyses of NO 2 - and NO 3 - separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO 2 - in a small stream.

Indiana

Mobilization of selenium from the Mancos Shale and associated soils in the lower Uncompahgre River Basin, Colorado

This study investigates processes controlling mobilization of selenium in the lower part of the Uncompahgre River Basin in western Colorado. Selenium occurs naturally in the underlying Mancos Shale and is leached to groundwater and surface water by limited natural runoff, agricultural and domestic irrigation, and leakage from irrigation canals. Soil and sediment samples from the study area were tested using sequential extractions to identify the forms of selenium present in solid phases. Selenium speciation was characterized for nonirrigated and irrigated soils from an agricultural site and sediments from a wetland formed by a leaking canal. In nonirrigated areas, selenium was present in highly soluble sodium salts and gypsum. In irrigated soils, soluble forms of selenium were depleted and most selenium was associated with organic matter that was stable under near-surface weathering conditions. Laboratory leaching experiments and geochemical modeling confirm that selenium primarily is released to groundwater and surface water by dissolution of highly soluble selenium-bearing salts and gypsum present in soils and bedrock. Rates of selenium dissolution determined from column leachate experiments indicate that selenium is released most rapidly when water is applied to previously nonirrigated soils and sediment. High concentrations of extractable nitrate also were found in nonirrigated soils and bedrock that appear to be partially derived from weathered organic matter from the shale rather than from agricultural sources. Once selenium is mobilized, dissolved nitrate derived from natural sources appears to inhibit the reduction of dissolved selenium leading to elevated concentrations of selenium in groundwater. A conceptual model of selenium weathering is presented and used to explain seasonal variations in the surface-water chemistry of Loutzenhizer Arroyo, a major tributary contributor of selenium to the lower Uncompahgre River.

Colorado

Synoptic analysis and WRF-Chem model simulation of dust events in the southwestern United States

Dust transported from rangelands of the Southwestern United States (US) to mountain snowpack in the Upper Colorado River Basin during spring (March-May) forces earlier and faster snowmelt, which creates problems for water resources and agriculture. To better understand the drivers of dust events, we investigated large-scale meteorology responsible for organizing two Southwest US dust events from two different dominant geographic locations: (a) the Colorado Plateau and (b) the northern Chihuahuan Desert. High-resolution Weather Research and Forecasting coupled with Chemistry model (WRF-Chem) simulations with the Air Force Weather Agency dust emission scheme incorporating a MODIS albedo-based drag-partition was used to explore land surface-atmosphere interactions driving two dust events. We identified commonalities in their meteorological setups. The meteorological analyses revealed that Polar and Sub-tropical jet stream interaction was a common upper-level meteorological feature before each of the two dust events. When the two jet streams merged, a strong northeast-directed pressure gradient upstream and over the source areas resulted in strong near-surface winds, which lifted available dust into the atmosphere. Concurrently, a strong mid-tropospheric flow developed over the dust source areas, which transported dust to the San Juan Mountains and southern Colorado snowpack. The WRF-Chem simulations reproduced both dust events, indicating that the simulations represented the dust sources that contributed to dust-on-snow events reasonably well. The representativeness of the simulated dust emission and transport in different geographic and meteorological conditions with our use of albedo-based drag partition provides a basis for additional dust-on-snow simulations to assess the hydrologic impact in the Southwest US.

southwestern United States

A benthic-macroinvertebrate index of biotic integrity and assessment of conditions in selected streams in Chester County, Pennsylvania, 1998-2009

The Stream Conditions of Chester County Biological Monitoring Network (Network) was established by the U.S. Geological Survey and the Chester County Water Resources Authority in 1969. Chester County encompasses 760 square miles in southeastern Pennsylvania and has a rapidly expanding population. Land-use change has occurred in response to this continual growth, as open space, agricultural lands, and wooded lands have been converted to residential and commercial lands. In 1998, the Network was modified to include 18 fixed-location sites and 9 flexible-location sites. Sites were sampled annually in the fall (October-November) during base-flow conditions for water chemistry, instream habitat, and benthic macroinvertebrates. A new set of 9 flexible-location sites was selected each year. From 1998 to 2009, 213 samples were collected from the 18 fixed-location sites and 107 samples were collected from the 84 flexible-location sites. Eighteen flexible-location sites were sampled more than once over the 12-year period; 66 sites were sampled only once. Benthic-macroinvertebrate data from samples collected during 1998-2009 were used to establish the Chester County Index of Biotic Integrity (CC-IBI). The CC-IBI was based on the methods and metrics outlined in the Pennsylvania Department of Environmental Protection's "A Benthic Index of Biotic Integrity for Wadeable Freestone Streams in Pennsylvania." The resulting CC-IBI consists of scores for benthic-macroinvertebrate samples collected from sites in the Network that related to reference conditions in Chester County. Mean CC-IBI scores for 18 fixed-location sites ranged from 37.21 to 88.92. Thirty-nine percent of the 213 samples collected at the 18 fixed-location sites had a CC-IBI score less than 50; 33 percent, 50 to 70; 28 percent, greater than 70. CC-IBI scores from the 107 flexible-location samples ranged from 23.48 to 99.96. Twenty-five percent of the 107 samples collected at the flexible-location sites had a CC-IBI score less than 50; 33 percent, 50 to 70; and 42 percent, greater than 70. Factors that were found to affect CC-IBI scores are nutrient concentrations, habitat conditions, and percent of wooded and urban land use. A positive relation was determined between mean CC-IBI scores and mean total habitat scores for the 18 fixed-location sites. CC-IBI scores were most strongly affected by stream bank vegetative protection, embeddedness, riparian zone width, and sediment deposition. The highest CC-IBI scores were associated with sites that had greater than 28 percent wooded-wetland-water land use, less than 5 percent urban land use, and no municipal wastewater discharges within 10 miles upstream from the sampling site. The lowest CC-IBI scores were associated with sites where urban land use was greater than 15 percent or a municipal wastewater discharge was within 10 miles upstream from the sampling reach. The Mann Kendall test for trends was used to determine trends in CC-IBI scores and concentrations of nitrate, orthophosphate, and chloride for the 18 fixed-location sites. A positive trend in CC-IBI was determined for six sites, and a negative trend was determined for one site. Positive trends in nitrate concentrations were determined for 4 of the 18 fixed-location sites, and a negative trend in orthophosphate concentrations was determined for 1 of the 18 fixed-location sites. Positive trends in chloride concentrations were determined for 16 of the 18 fixed-location sites.

Pennsylvania

Transboundary pollution: Persistent organochlorine pesticides in migrant birds of the Southwestern United States and Mexico

The hypothesis that migratory birds accumulate persistent organochlorine pesticides (POPs) during the winter in Latin America has been prevalent for many years, particularly since 1,1,1-trichloro-2,2–bis(p-chlorophenyl)ethane (DDT) was banned in the United States in 1972. It has been suggested that peregrine falcons ( Falco peregrinus ), black-crowned night herons ( Nycticorax nycticorax ), white-faced ibises ( Plegadis chihi ), various migratory waterfowl and shorebirds, and other avian species accumulate higher concentrations of POPs while on migration or on their wintering grounds in Latin America. Nonetheless, the data obtained thus far are limited, and there is no clear pattern to suggest that such accumulation occurs on a widespread basis. In this review wildlife contaminant studies conducted along the U.S.-Mexico border and throughout Mexico are discussed. The results for the most part seem to indicate that no major accumulation of 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene) (DDE), the most persistent organochlorine compound, has occurred or been reported for most parts of Mexico. The majority of the DDE values in birds from Mexico were similar to those reported in birds from the southwestern United States during the same years. More work needs to be done, particularly in those cotton-producing areas of Mexico where DDT was applied heavily in the past (e.g., Chiapas and Michoacan). Because DDT is still used for malaria control and may still be used in agriculture in Chiapas, this state is probably the one where most migrant species would still be at a significant risk of increased accumulation of DDE and DDT.

Environmental Toxicology and Chemistry

Groundwater quality, age, and susceptibility and vulnerability to nitrate contamination with linkages to land use and groundwater flow, Upper Black Squirrel Creek Basin, Colorado, 2013

The Upper Black Squirrel Creek Basin is located about 25 kilometers east of Colorado Springs, Colorado. The primary aquifer is a productive section of unconsolidated deposits that overlies bedrock units of the Denver Basin and is a critical resource for local water needs, including irrigation, domestic, and commercial use. The primary aquifer also serves an important regional role by the export of water to nearby communities in the Colorado Springs area. Changes in land use and development over the last decade, which includes substantial growth of subdivisions in the Upper Black Squirrel Creek Basin, have led to uncertainty regarding the potential effects to water quality throughout the basin. In response, the U.S. Geological Survey, in cooperation with Cherokee Metropolitan District, El Paso County, Meridian Service Metropolitan District, Mountain View Electric Association, Upper Black Squirrel Creek Groundwater Management District, Woodmen Hills Metropolitan District, Colorado State Land Board, and Colorado Water Conservation Board, and the stakeholders represented in the Groundwater Quality Study Committee of El Paso County conducted an assessment of groundwater quality and groundwater age with an emphasis on characterizing nitrate in the groundwater. Groundwater-quality samples were collected from 50 randomly selected wells between May and June 2013. The samples were analyzed for major ions, nutrients, dissolved gases, tritium ( 3 H), chlorofluorocarbons (CFC-11, CFC-12, and CFC-113), and fuel products (such as benzene, toluene, ethylbenzene, and xylenes). None of the groundwater samples exceeded the U.S. Environmental Protection Agency (EPA) National Primary Drinking Water Regulations for primary maximum contaminant levels (MCL) for major ions. Secondary maximum contaminant levels, which are not health concerns and affect mainly taste, color, or odor of the water, were observed in rare instances for pH (2 samples), chloride (1 sample), iron (3 samples), and manganese (8 samples). The secondary maximum contaminant level for total dissolved solids was also exceeded for two samples. Nitrate (nitrite plus nitrate as nitrogen in groundwater) was elevated above the estimated background concentration of natural recharge waters of 1 milligram per liter (mg/L) in 44 of the 50 wells sampled and showed a median concentration of 5.4 mg/L. Nitrate concentrations were above the MCL of 10 mg/L in 5 of the 50 wells sampled and above half of the EPA MCL (5 mg/L) in 27 of the 50 wells sampled, which included samples above the MCL. Dissolved-oxygen concentrations exceeded 0.5 mg/L in 95 percent of reported values (40 of 42 samples) and exceeded 2.0 mg/L in 90 percent of reported values (38 of 42 samples). The oxidized conditions observed in most areas indicate that nitrate from fertilizers and animal or human waste was geochemically stable and could persist in the groundwater for decades or perhaps longer. A historical analysis of median nitrate concentrations over nearly three decades showed an increase in nitrate of approximately 1 mg/L from 4.3 to 5.4 mg/L, although the increase was not determined to be significantly different using nonparametric statistical methods. Major-ion data indicate that groundwater representative of the primary aquifer was classified as calcium-sodium bicarbonate type water. Other water samples from wells located mainly along the periphery of the primary aquifer had cation-anion compositions consistent with distinct water sources, including groundwater contributions from the underlying bedrock aquifers. The areas with differentiable water sources were located mainly where alluvial deposits were thin and geologic contacts to the underlying bedrock aquifers were relatively shallow. Nitrate concentrations in the groundwater were evaluated for relations to land use. An agricultural region was defined using a sequence of land satellite imagery. Groundwater flow directions interpreted from median water-table elevations measured from 2000 to 2013 were used in conjunction with cropland locations to define the agricultural region boundaries by encompassing potential pathways of nitrate transport in the groundwater from nitrogen-based fertilizers. A statistically significant higher median nitrate concentration was observed for areas inside the agricultural region (6.7 mg/L) compared to areas outside the agricultural region (2.3 mg/L), although median concentrations in both areas were below the MCL (10 mg/L). Median nitrate concentration was also significantly greater in land parcels with septic use (4.9 mg/L) compared to nonseptic parcels (1.7 mg/L). In general, agriculture or septic use was identified as the primary source of nitrate, depending on location, while commercial, county, grazing, and residential land uses were generally secondary sources of nitrate. Apparent groundwater ages were estimated from chlorofluorocarbons (CFC-11, CFC-12, and CFC-113) and tritium ( 3 H) data using models that assumed piston flow and binary mixing (dilution of a young component with old, tracer-free water). The mean and median groundwater ages were about 30 years and the standard deviation was 6 years, indicating that most groundwater in the primary aquifer was “young” water that had recharged to the aquifer over the last few decades (post-1950s). The median fraction of young water was about 71 percent, and the standard deviation was 29 percent. The remaining water predated the 1950s, which may have originated from deeper geologic formations or may represent slow moving groundwater within the primary aquifer. Some of the oldest groundwater ages (older than 30 years) were observed in the upper reaches of the aquifer to the northwest where the primary aquifer is thin and intersects bedrock, supporting the hypothesis of geochemically distinct groundwater entering the primary aquifer from below. Groundwater that had reached the central part of the aquifer from upgradient areas of the basin was variable in age because of differences in flow paths and travel velocities. The groundwater age analysis showed that current (2013) land-use practices could affect water quality over decades to come, and that responses to remedial actions could be slow, especially for constituents, such as nitrate, that are stable under oxidized conditions. Fuel products (including acetone, benzene, diisopropyl ether, ethylbenzene, methyl acetate, methyl tertiary butyl ether (MTBE), methyl tert-pentyl ether, m- + p-xylene, o-xylene, tert-amyl alcohol, tert-butyl alcohol, tert-butyl ethyl ether, and toluene) were analyzed in groundwater from 49 of the 50 wells. Water from seven sites had detections for fuel compounds; all concentrations were below MCL. The results provided assurance of water quality and a valuable baseline to evaluate future trends of fuel constituents as the region is further developed. Probability maps were developed from logistic regression models to examine the likelihood that nitrate concentrations in groundwater exceeded specified levels. Susceptibility analysis examined relations between mid-level (5.0 mg/L) nitrate concentrations and climatic, hydrologic, and geologic variables; the significant variables were identified as depth to groundwater, soil organic matter, and soil water storage to 25-centimeter (cm) depth. The vulnerability assessments included natural factors driving susceptibility but also human factors related to land use and septic use. Vulnerability to low-level (2.5 mg/L) nitrate was related to depth to groundwater, septic zoning, and soil organic matter. The results highlighted that septic zoning affected low-level nitrate concentrations. Vulnerability to mid-level (5.0 mg/L) nitrate was examined using all 50 samples and also with two data outliers removed, which showed relatively high nitrate concentrations but also anomalous water chemistry or were located beyond the primary study area. Vulnerability to mid-level (5.0 mg/L) nitrate using all 50 samples was related to depth to groundwater, land use, septic use within a 500-meter (m) radius, soil water storage to a 25-cm depth, soil organic matter, and whether a location was within the agricultural region. The mid-level (5.0 mg/L) vulnerability model using 48 samples (two outliers removed) produced the best overall fit and was related to the same variables as when using all samples except septic use. The results for mid-level vulnerability provided additional support that septic use was associated with low levels of nitrate in the groundwater. Soil properties and land use were identified as the main drivers of moderate nitrate concentrations. Probabilities of exceeding low-level nitrate concentrations were high in most areas with the lowest probabilities usually to the northwest along thin geologic deposits in the upper part of the basin. The results of this investigation offer the foundational information needed for developing best management practices to mitigate nitrate contamination, basic concepts on water quality to aid public education, and information to guide regulatory measures if policy makers determine this is warranted. Science-based decision making will require continued monitoring and analysis of water quality in the future.

Colorado

Hydrogeologic framework, ground-water geochemistry, and assessment of nitrogen yield from base flow in two agricultural watersheds, Kent County, Maryland

Hydrostratigraphic and geochemical data collected in two adjacent watersheds on the Delmarva Peninsula, in Kent County, Maryland, indicate that shallow subsurface stratigraphy is an important factor that affects the concentrations of nitrogen in ground water discharging as stream base flow. The flux of nitrogen from shallow aquifers can contribute substantially to the eutrophication of streams and estuaries, degrading water quality and aquatic habitats. The information presented in this report includes a hydrostratigraphic framework for the Locust Grove study area, analyses and interpretation of ground-water chemistry, and an analysis of nutrient yields from stream base flow. An understanding of the processes by which ground-water nitrogen discharges to streams is important for optimal management of nutrients in watersheds in which ground-water discharge is an appreciable percentage of total streamflow. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency (USEPA), collected and analyzed hydrostratigraphic and geochemical data in support of ground-water flow modeling by the USEPA. The adjacent watersheds of Morgan Creek and Chesterville Branch have similar topography and land use; however, reported nitrogen concentrations are generally 6 to 10 milligrams per liter in Chesterville Branch but only 2 to 4 milligrams per liter in Morgan Creek. Ground water in the surficial aquifer in the recharge areas of both streams has high concentrations of nitrate (greater than 10 milligrams per liter as N) and dissolved oxygen. One component of the ground water discharging to Morgan Creek typically is anoxic and contains virtually no dissolved nitrate; most of the ground water discharging to Chesterville Branch is oxygenated and contains moderately high concentrations of nitrate. The surficial aquifer in the study area is composed of the deeply weathered sands and gravels of the Pensauken Formation (the Columbia aquifer) and the underlying glauconitic sands of the upper Aquia Formation (the Aquia aquifer). The lower 6 to 9 meters of the Aquia Formation is a low-permeability silt-clay with abundant glauconite. The Aquia confining layer underlies the Columbia-Aquia surficial aquifer throughout the study area. The sediment redox transition, identified in cores, that occurs in the upper 0.5 to 1 meter of the Aquia confining layer is thought to be a site for subsurface denitrification of ground water. The first confined aquifer is composed of the glauconitic sands in the upper 9 to 11 meters of the Hornerstown Formation. The Hornerstown aquifer is underlain by 10 to 15 meters of glauconitic silt-clay at the base of the Hornerstown Formation (the Hornerstown confining layer), and 5 meters of low-permeability clay in the underlying Severn Formation. The Aquia and Hornerstown Formations dip and thicken to the southeast, and the Aquia confining layer subcrops shallowly (within 5 meters of the land surface) in a band that strikes southwest to northeast across the northern edge of the study area. The surficial aquifer is very thin (generally less than 5 meters) north of Morgan Creek, and the alluvial valley of Morgan Creek has incised into the top of the Aquia confining layer. In contrast, the Aquia confining layer lies 22 meters below Chesterville Branch, and the surficial aquifer approaches 30 meters in thickness (away from the creek). Chemically reduced iron sulfides and glauconite in the Aquia confining layer are likely substrates for denitrification of nitrate in ground water. Evidence from the dissolved concentrations of nitrate, sulfate, iron, argon, and nitrogen gas, and stable nitrogen isotopes support the interpretation that ground water flowing near the top of the Aquia confining layer, or through the confined Hornerstown aquifer, has undergone denitrification. This process appears to have the greatest effect on ground-water chemistry north of Morgan Creek, where the surficial aquifer is thin and a greater percentage of the ground water contacts the Aquia confining layer. The base-flow discharges of total nitrogen from the two watersheds are of similar magnitude, although Chesterville Branch has somewhat higher loads (29,000 kilograms of nitrogen per year) than Morgan Creek (20,000 kilograms of nitrogen per year), although Morgan Creek has a larger drainage area and a greater discharge of water. The base-flow yield of nitrogen (load per unit area) in Chesterville Branch (median of 0.058 grams per second per square kilometer at the outlet) is more than twice that of Morgan Creek (median of 0.022 grams per second per square kilometer at the outlet), reflecting the higher concentration of nitrate in ground water discharging to Chesterville Branch. Total nitrogen concentrations tend to decrease downstream in Chesterville Branch and increase downstream in Morgan Creek. The downstream trend in Chesterville Branch may be affected by instream nitrogen uptake and denitrification, and an increasing proportion of older, denitrified ground water in downstream discharge. The downstream trends in Morgan Creek may be affected by inflow from tributaries, downstream changes in the source of discharge water, and downstream changes in the riparian zone, which could affect the processes and degree of denitrification. Although these two watersheds appear to have landscape features (such as topography, land use, and soils) that would produce similar nitrogen discharges, a more detailed examination of landscape features indicates that Chesterville Branch has soils that are slightly better drained, tributary stream outlets at higher altitudes, and a slightly higher percentage of agricultural land. All of these factors have been related to higher nitrogen yields. Nonetheless, most of the data support the interpretation that hydrostratigraphy has the greatest effect in producing the difference in nitrogen yields between the two watersheds.

Maryland

Hydrologic and geochemical controls on pesticide and nutrient transport to two streams on the Delmarva Peninsula

Pesticides and nutrients move from application areas through ground water and surface runoff to streams on the Delmarva Peninsula. The relative importance of different transport media to the movement of these compounds in different watersheds is related to locally variable hydrologic and geochemical conditions among areas of regionally similar land use, geology, and soils. Consideration of such local variability is important to land-management efforts or future environmental investigations on the Peninsula. Chemical analyses of samples collected over a multiyear period from two streams on the Delmarva Peninsula were analyzed along with similar available analyses of ground water to document the occurrence of pesticides and nutrients, and illustrate important processes controlling their movement through watersheds to streams. The upper Pocomoke River and Chesterville Branch drain predominantly agricultural watersheds typical of the Delmarva Peninsula. Chesterville Branch drains a watershed of moderate relief, good drainage, and a permeable surficial aquifer that ranges in thickness from about 15 to 25 meters. The upper Pocomoke River Watershed, however, is extremely flat with poorly drained soils and abundant artificial drainage. Influences on the chemistry of water in each stream were determined from seasonal patterns in the concentrations of selected constituents from 1996 through 2001, and relations with streamflow. Nutrients and pesticides are detectable throughout the year in the upper Pocomoke River and Chesterville Branch. Water in both streams is typically dilute, slightly acidic, and well oxygenated, and nitrate and phosphorus concentrations generally exceed estimated natural levels. Pesticide concentrations are generally low, although concentrations of selected metabolites commonly exceed 1 microgram per liter, particularly in Chesterville Branch. Nitrate and metabolites of pesticide compounds are apparently transported to Chesterville Branch preferentially through ground water in the surficial aquifer, although selected pesticide parent compounds and less soluble nutrients move primarily in surface runoff. Conversely, the relative proportion of discharge from surficial and partially confined aquifers is the most important factor controlling the chemistry of water in the upper Pocomoke River. Surface runoff in the larger and predominantly flat upper Pocomoke River Watershed is apparently limited to particularly significant precipitation events. Transport of pesticides in surface runoff becomes important in both watersheds during such events. Instantaneous loads of pesticides in streams typically stabilize or continue to increase with increasing flow even after runoff begins, although in-stream concentrations may decrease due to dilution.

Scientific Investigations Report

Identifying biotic integrity and water chemistry relations in nonwadeable rivers of Wisconsin: Toward the development of nutrient criteria

We sampled 41 sites on 34 nonwadeable rivers that represent the types of rivers in Wisconsin, and the kinds and intensities of nutrient and other anthropogenic stressors upon each river type. Sites covered much of United States Environmental Protection Agency national nutrient ecoregions VII-Mostly Glaciated Dairy Region, and VIII-Nutrient Poor, Largely Glaciated upper Midwest. Fish, macroinvertebrates, and three categories of environmental variables including nutrients, other water chemistry, and watershed features were collected using standard protocols. We summarized fish assemblages by index of biotic integrity (IBI) and its 10 component measures, and macroinvertebrates by 2 organic pollution tolerance and 12 proportional richness measures. All biotic and environmental variables represented a wide range of conditions, with biotic measures ranging from poor to excellent status, despite nutrient concentrations being consistently higher than reference concentrations reported for the regions. Regression tree analyses of nutrients on a suite of biotic measures identified breakpoints in total phosphorus (~0.06 mg/l) and total nitrogen (~0.64 mg/l) concentrations at which biotic assemblages were consistently impaired. Redundancy analyses (RDA) were used to identify the most important variables within each of the three environmental variable categories, which were then used to determine the relative influence of each variable category on the biota. Nutrient measures, suspended chlorophyll a, water clarity, and watershed land cover type (forest or row-crop agriculture) were the most important variables and they explained significant amounts of variation within the macroinvertebrate (R 2 = 60.6%) and fish (R 2 = 43.6%) assemblages. The environmental variables selected in the macroinvertebrate model were correlated to such an extent that partial RDA analyses could not attribute variation explained to individual environmental categories, assigning 89% of the explained variation to interactions among the categories. In contrast, partial RDA attributed much of the explained variation to the nutrient (25%) and other water chemistry (38%) categories for the fish model. Our analyses suggest that it would be beneficial to develop criteria based upon a suite of biotic and nutrient variables simultaneously to deem waters as not meeting their designated uses. ?? 2007 Springer Science+Business Media, LLC.

Environmental Management

Relation of water chemistry of the Edwards aquifer to hydrogeology and land use, San Antonio Region, Texas

Water-chemistry data from the Edwards aquifer for 1976-85, consisting of nearly 1,500 chemical analyses from 280 wells and 3 springs, were used to statistically evaluate relations among ground-water chemistry, hydrogeology, and land use. Five land uses associated with sampled wells were classified on the basis of published information and field surveys. Four major subareas of the aquifer were defined to reflect the relative susceptibility of ground water to contamination originating from human activities using hydrogeologic and tritium data. Water from an agricultural area over the unconfined zone of the aquifer had the largest median concentration of nitrite plus nitrate. Large nitrite plus nitrate concentrations were spatially associated with large tritium concentrations and nitrogen isotopic ratios characteristic of streamflow recharge. Detections of fecal-coliform bacteria were associated mainly with water from wells completed in the unconfined zone. Most of the occurrences of tetrachloroethylene, l,2-(trans)-dichloroethylene, trichlorofluoromethane, 1,1,1-trichloroethane, and 2,4-D in ground water were associated with wells completed in the unconfined zone of the aquifer. Fatty acids detected in water from some wells may commonly be present naturally in ground water. The percentage of samples in which arsenic, barium, lead, and zinc were detected was similar among subareas; the samples were from the freshwater parts of the aquifer. Large lead and zinc concentrations were associated with volumes of pumpage less than 1,000 gallons. In general, the quality of ground water in the freshwater parts of the aquifer (north of the "bad-water" line) is suitable for all uses including human consumption. Two areas that are exceptions are: (1) Northeast of Garner Field in Uvalde, Texas, where PCE (tetrachloroethylene) has been detected in groundwater samples, and (2) north-central Bexar County near the former West Avenue landfill where PCE and benzene have been detected in ground-water samples. Concentrations of these organic compounds in water from many wells in the two areas exceed the maximum contaminant level for human consumption set by the U.S. Environmental Protection Agency.

Water-Resources Investigations Report

Occurrence of Uranium and 222Radon in Glacial and Bedrock Aquifers in the Northern United States, 1993-2003

Water-quality data collected from 1,426 wells during 1993-2003 as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program were evaluated to characterize the water quality in glacial and bedrock aquifers of the northern United States. One of the goals of the NAWQA program is to synthesize data from individual studies across the United States to gain regional- and national-scale information about the behavior of contaminants. This study focused on the regional occurrence and distribution of uranium and 222radon in ground water in the glacial aquifer system of the United States as well as in the Cambrian-Ordovician and the New York and New England crystalline aquifer systems that underlie the glacial aquifer system. The occurrence of uranium and 222radon in ground water has long been a concern throughout the United States. In the glacial aquifers, as well as the Cambrian-Ordovician and the New York and New England crystalline aquifer systems of the United States, concentrations of uranium and 222radon were highly variable. High concentrations of uranium and 222radon affect ground water used for drinking water and for agriculture. A combination of information or data on (1) national-scale ground-water regions, (2) regional-scale glacial depositional models, (3) regional-scale geology, and (4) national-scale terrestrial gamma-ray emissions were used to confirm and(or) refine the regions used in the analysis of the water-chemistry data. Significant differences in the occurrence of uranium and 222radon, based primarily on geologic information were observed and used in this report. In general, uranium was highest in the Columbia Plateau glacial, West-Central glacial, and the New York and New England crystalline aquifer groups (75th percentile concentrations of 22.3, 7.7, and 2.9 micrograms per liter (ug/L), respectively). In the Columbia Plateau glacial and the West-Central glacial aquifer groups, more than 10 percent of wells sampled had concentrations of uranium that exceeded the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level of 30 ug/L; in the New York and New England crystalline aquifer group, 4 percent exceeded 30 ug/L. Ground-water samples with high concentrations of uranium were commonly linked to geologic sources rich in uranium. In eight of nine aquifer groups defined for this study, concentrations of uranium correlated significantly with concentrations of sulfate in ground water (Spearman's rho = 0.20 to 0.56; p < 0.05). In the Columbia Plateau, glacial aquifers were derived in part from basaltic lava flows, some felsic volcanic rocks, and some paleo-lake bed materials that may be rich in uranium. In the Columbia Plateau and West-Central glacial aquifer groups, uranium correlated with total dissolved solids, bicarbonate, boron, lithium, selenium, and strontium. In the West-Central glacial aquifer group, rocks such as Cretaceous marine shales, which are abundant in uranium, probably contribute to the high concentrations in ground water; in the southern part of this group, which extends into Nebraska, the glacial or glacial-related sediment may be interbedded with uranium-rich materials that originated to the north and west and in the Rocky Mountains. In New England, crystalline bedrock that is granitic, such as two-mica granites, as well as other high-grade metamorphic rocks, has abundant uranium that is soluble in the predominantly oxic to sub-oxic geochemical conditions. This appears to contribute to high uranium concentrations in ground water. The highest 222radon concentrations were present in samples from wells completed in the New York and New England crystalline aquifer group; the median value (2,122 picocurries per liter (pCi/L)) was about 10 times the median values of all other aquifer groups. More than 25 percent of the samples from the New York and New England crystalline aquifer group wells had 222radon concentrations that exceeded the USEPA Alternative

Scientific Investigations Report

Design and methods of the Southeast Stream Quality Assessment (SESQA), 2014

During 2014, the U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) assessed stream quality across the Piedmont and southern Appalachian Mountain regions of the southeastern United States. This Southeast Stream Quality Assessment (SESQA) simultaneously characterized watershed and stream-reach water-quality stressors along with instream biological conditions, in order to better understand regional stressor-effects relations. The goal of SESQA is to provide communities and policymakers with information about those human and environmental factors that have the greatest impact on stream quality across the region. The SESQA design focused on hydrologic alteration and urbanization because of their importance as ecological stressors of particular concern to Southeast region resource managers. Streamflow and land-use data were used to identify and select sites representing gradients in urbanization and streamflow alteration across the region. One hundred fifteen sites were selected and sampled for as many as 10 weeks during April, May, and June 2014 for contaminants, nutrients, and sediment. This water-quality &ldquo;index&rdquo; period culminated with an ecological survey of habitat, periphyton, benthic macroinvertebrates, and fish at all sites. Sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. Of the 115 sites, 59 were on streams in watersheds with varying degrees of urban land use, 5 were on streams with multiple confined animal feeding operations, and 13 were reference sites with little or no development in their watersheds. The remaining 38 &ldquo;hydro&rdquo; sites were on streams in watersheds with relatively little agricultural or urban development but with hydrologic alteration, such as a dam or reservoir. This report provides a detailed description of the SESQA study components, including surveys of ecological conditions, routine water sampling, deployment of passive polar organic compound integrative samplers for pesticides and contaminants of emerging concern, and synoptic sediment sampling and toxicity testing at all urban, confined animal feeding operation, and reference sites. Continuous water-quality monitoring and daily pesticide sampling efforts conducted at a subset of urban sites are also described.

Alabama, Georgia, North Carolina, South Carolina,

Application of a multipurpose unequal probability stream survey in the Mid-Atlantic Coastal Plain

A stratified, spatially balanced sample with unequal probability selection was used to design a multipurpose survey of headwater streams in the Mid-Atlantic Coastal Plain. Objectives for the survey include unbiased estimates of regional stream conditions, and adequate coverage of unusual but significant environmental settings to support empirical modeling of the factors affecting those conditions. The design and field application of the survey are discussed in light of these multiple objectives. A probability (random) sample of 175 first-order nontidal streams was selected for synoptic sampling of water chemistry and benthic and riparian ecology during late winter and spring 2000. Twenty-five streams were selected within each of seven hydrogeologic subregions (strata) that were delineated on the basis of physiography and surficial geology. In each subregion, unequal inclusion probabilities were used to provide an approximately even distribution of streams along a gradient of forested to developed (agricultural or urban) land in the contributing watershed. Alternate streams were also selected. Alternates were included in groups of five in each subregion when field reconnaissance demonstrated that primary streams were inaccessible or otherwise unusable. Despite the rejection and replacement of a considerable number of primary streams during reconnaissance (up to 40 percent in one subregion), the desired land use distribution was maintained within each hydrogeologic subregion without sacrificing the probabilistic design.

Journal of the American Water Resources Associatio

Arsenic in the environment: Biology and chemistry

Arsenic (As) distribution and toxicology in the environment is a serious issue, with millions of individuals worldwide being affected by As toxicosis. Sources of As contamination are both natural and anthropogenic and the scale of contamination ranges from local to regional. There are many areas of research that are being actively pursued to address the As contamination problem. These include new methods of screening for As in the field, determining the epidemiology of As in humans, and identifying the risk of As uptake in agriculture. Remediation of As-affected water supplies is important and research includes assessing natural remediation potential as well as phytoremediation. Another area of active research is on the microbially mediated biogeochemical interactions of As in the environment. In 2005, a conference was convened to bring together scientists involved in many of the different areas of As research. In this paper, we present a synthesis of the As issues in the light of long-standing research and with regards to the new findings presented at this conference. This contribution provides a backdrop to the issues raised at the conference together with an overview of contemporary and historical issues of As contamination and health impacts.

Science of the Total Environment