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Groundwater quality in the Madera and Chowchilla subbasins of the San Joaquin Valley, California

Groundwater provides more than 40 percent of California’s drinking water. To protect this vital resource, the State of California created the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The Priority Basin Project of the GAMA Program provides a comprehensive assessment of the State’s untreated groundwater quality and increases public access to groundwater-quality information. The Madera and Chowchilla subbasins of the San Joaquin Valley constitute one of the study units being evaluated. The Madera-Chowchilla study unit is about 860 square miles and consists of the Madera and Chowchilla groundwater subbasins of the San Joaquin Valley Basin (California Department of Water Resources, 2003; Shelton and others, 2009). The study unit has hot, dry summers and cool, moist winters. Average annual rainfall ranges from 11 to 15 inches, most of which occurs between November and February. The main surface-water features in the study unit are the San Joaquin, Fresno, and Chowchilla Rivers, and the Madera and Chowchilla canals. Land use in the study unit is about 69 percent (%) agricultural, 28% natural (mainly grasslands), and 3% urban. The primary crops are orchards and vineyards. The largest urban area is the city of Madera. The primary aquifer system is defined as those parts of the aquifer corresponding to the perforated intervals of wells listed in the California Department of Public Health (CDPH) database. In the Madera-Chowchilla study unit, these wells typically are drilled to depths between 200 and 800 feet, consist of a solid casing from land surface to a depth of about 140 to 400 feet, and are perforated below the solid casing. Water quality in the primary aquifer system may differ from that in the shallower and deeper parts of the aquifer system. The primary aquifer system in the study unit consists of Quaternary-age alluvial-fan and fluvial deposits that were formed by the rivers draining the Sierra Nevada. Sediments consist of gravels, sands, silts, and clays and generally are coarser closest to the Sierra Nevada and become finer towards the center of the basin. The structure and composition of the deposits in the Madera-Chowchilla study unit are different from those in other parts of the eastern San Joaquin Valley because the Fresno and Chowchilla Rivers primarily drain the Sierra Nevada foothills, whereas the larger rivers drain higher elevations with greater sediment supply. These differences in the sources of sediments are important because they may affect the groundwater chemistry and the physical structure of the sedimentary deposits. Some of the clay layers are lacustrine deposits, the most extensive of which, the Corcoran Clay, underlies the western part of the study unit and divides the primary aquifer system into an unconfined to semi-confined upper system and a largely confined lower system. Regional lateral flow of groundwater is southwest towards the valley trough. Irrigation return flows are the major source of groundwater recharge, and groundwater pumping is the major source of discharge. Groundwater on a lateral flow path may be repeatedly extracted by pumping wells and reapplied at the surface multiple times before reaching the valley trough, resulting in a substantial component of downward vertical flow (Burow and others, 2004; Phillips and others, 2007; Faunt, 2009). This flow pattern enhances movement of water from shallow depths to the primary aquifer system.

California

Pesticides and amphibian declines in California, USA

Several species of anuran amphibians have undergone drastic population declines in the western United States over the last 10 to 15 years. In California, the most severe declines are in the Sierra Mountains east of the Central Valley and downwind of the intensely agricultural San Joaquin Valley. In contrast, coastal and more northern populations across from the less agrarian Sacramento Valley are stable or declining less precipitously. In this article, we provide evidence that pesticides are instrumental in declines of these species. Using Hyla regilla as a sentinel species, we found that cholinesterase (ChE) activity in tadpoles was depressed in mountainous areas east of the Central Valley compared with sites along the coast or north of the Valley. Cholinesterase was also lower in areas where ranid population status was poor or moderate compared with areas with good ranid status. Up to 50% of the sampled population in areas with reduced ChE had detectable organophosphorus residues, with concentrations as high as 190 ppb wet weight. In addition, up to 86% of some populations had measurable endosulfan concentrations and 40% had detectable 4,4′-dichlorodiphenyldichloroethylene, 4,4′-DDT, and 2,4′-DDT residues.

California

Reduced freshwater mussel juvenile production as a result of agricultural and urban contaminant mixture exposures

Freshwater mussels provide invaluable ecological services but are threatened by habitat alteration, poor water quality, invasive species, climate change, and contaminants, including contaminants of emerging concern (CECs). Contaminants of emerging concerns are well documented in aquatic environments, including the Great Lakes Basin, but limited information is available on how environmentally relevant mixtures affect freshwater mussel biology throughout their varied life stages. Our main goal was to assess mussels' reproductive output in response to exposure to agricultural and urban CEC mixtures during glochidial development through juvenile transformation and excystment focusing on how exposure duration and treatment affect: (1) the number of glochidia prematurely released by brooding females, (2) glochidial transformation through host-fish excystment, and (3) the number of fully metamorphosed juveniles able to continue the lifecycle. Mussels and host fish were exposed to either a control water (CW), control ethanol (CE), agriculture CEC mixture (AM), or urban CEC mixture (UM) for 40 and 100 days. We found no effect from treatment or exposure duration on the number of glochidia prematurely released. Fewer partially and fully metamorphosed AM juveniles were observed during the 100-day exposure, compared with the 40-day. During the 40-day exposure, CW produced more fully metamorphosed individuals compared with CE and UM, but during the 100-day exposure AM produced more fully metamorphosed individuals compared with the CW. There was reduction in fully metamorphosed juveniles compared with partially metamorphosed for CE and UM during the 40-day exposure, as well as in the CW during the 100-day exposure. These results will be important for understanding how mussel populations are affected by CEC exposure. The experiments also yielded many insights for laboratory toxicology exposure studies.

Environmental Toxicology and Chemistry

Toxic effects of boron on mallard reproduction

Boron, a naturally occurring trace element generally considered environmentally innocuous, was documented to severely impair mallard reproduction. Boron is leached from irrigated agricultural soils and transported in drainage water that contaminates wetlands. Until now, only the selenium accumulated in aquatic food chains has been documented to pose a toxic hazard to wildlife in drainage water wetlands. Adult mallard ( Anas platyrhynchos ) ducks were fed diets supplemented with 0, 30, 300 or 1,000 ppm boron (fresh weight; diets contained about 10% moisture). The hatching success of fertile eggs was significantly reduced by 1,000 ppm boron, less than one-third the highest boron concentrations found in plants in California's San Joaquin Valley. Hatching weights, duckling survival and duckling weight gain were also reduced by 1,000 ppm boron. Boron concentrations in mallard egg, liver and brain tissues were dose-related. Boron did not affect adult survival or egg fertility. Management of drainage water-contaminated environments must now also consider the adverse effects of boron, as well as the possible interactions of drainage water contaminants.

Environmental Toxicology and Chemistry

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter

Design and methods of the California stream quality assessment (CSQA), 2017

During 2017, as part of the National Water-Quality Assessment Project, the U.S. Geological Survey conducted the California Stream Quality Assessment to investigate the quality of streams in the Central California Foothills and Coastal Mountains ecoregion, United States. The goal of the California Stream Quality Assessment study was to assess the health of wadeable streams in the region by characterizing multiple water-quality factors that are stressors to aquatic biota and by evaluating the relation between these stressors and biological indicators of stream health. Urbanization, agriculture, and modifications to streamflow are anthropogenic changes that affect water quality in the region; consequently, the study design primarily targeted sites and specific stressors associated with these activities. For the study, 85 stream sites were selected to represent the types and intensity of land use in the watershed; categories of site types were undeveloped, urban (low, medium, high), agriculture (low, high), and mixed (urban and agriculture). Most sites (about 70 percent) represent a gradient of urbanization from undeveloped to 99-percent urbanized. At most of the sites, streamgages or pressure transducers were used to monitor stream discharge and stage, as well as temperature. Water-quality samples were collected routinely at all sites and were analyzed for major ions, organic contaminants, nutrients, and suspended sediment. Sampling frequency varied on the basis of site type and location. Discrete water samples were collected weekly and generally 6 times per site, except for 11 undeveloped sites that were sampled only 4 times (during the last 4 weeks). Water sampling began at sites in the southern part of the study on March 13, 2017, and at sites in the northern part of the study on April 3, 2017. Passive samplers were deployed at most sites for measurement of polar organic contaminants (pesticides and pharmaceuticals). In May 2017, coincident with completion of water-quality sampling, an ecological survey was conducted at each site to assess benthic algal and macroinvertebrate communities and instream habitat. During the ecological surveys, a single composite streambed-sediment sample was collected for chemical analysis and toxicity testing. In addition, a few focused studies were done at subsets of sites, namely, measuring pesticides using small-volume automated samplers, measuring pesticides in biofilms, and sampling suspended sediments using passive samplers. This report describes the various study components and methods of the California Stream Quality Assessment, including measurements of water quality, sediment chemistry, habitat assessments, and ecological surveys, as well as procedures for sample analysis, quality assurance and quality control, and data management.

California

Accumulation of pesticides in pacific chorus frogs (Pseudacris regilla) from California's Sierra Nevada Mountains, USA

Pesticides are receiving increasing attention as potential causes of amphibian declines, acting singly or in combination with other stressors, but limited information is available on the accumulation of current-use pesticides in tissue. The authors examined potential exposure and accumulation of currently used pesticides in pond-breeding frogs (Pseudacris regilla) collected from 7 high elevations sites in northern California. All sites sampled are located downwind of California's highly agricultural Central Valley and receive inputs of pesticides through precipitation and/or dry deposition. Whole frog tissue, water, and sediment were analyzed for more than 90 current-use pesticides and pesticide degradates using gas chromatography–mass spectrometry. Two fungicides, pyraclostrobin and tebuconazole, and one herbicide, simazine, were the most frequently detected pesticides in tissue samples. Median pesticide concentration ranged from 13 µg/kg to 235 µg/kg wet weight. Tebuconazole and pyraclostrobin were the only 2 compounds observed frequently in frog tissue and sediment. Significant spatial differences in tissue concentration were observed, which corresponded to pesticide use in the upwind counties. Data generated indicated that amphibians residing in remote locations are exposed to and capable of accumulating current-use pesticides. A comparison of P. regilla tissue concentrations with water and sediment data indicated that the frogs are accumulating pesticides and are potentially a more reliable indicator of exposure to this group of pesticides than either water or sediment.

California

Chlorinated hydrocarbon pesticides and polychlorinated biphenyls in sediment cores from San Francisco Bay

Sediment cores of known chronology from Richardson and San Pablo Bays in San Francisco Bay, CA, were analyzed for a suite of chlorinated hydrocarbon pesticides and polychlorinated biphenyls to reconstruct a historic record of inputs. Total DDTs (DDT = 2,4'- and 4,4'-dichlorodiphenyltrichloroethane and the metabolites, 2,4'- and 4,4'-DDE, -DDD) range in concentration from 4-21 ng/g and constitute a major fraction (> 84%) of the total pesticides in the top 70 cm of Richardson Bay sediment. A subsurface maximum corresponds to a peak deposition date of 1969-1974. The first measurable DDT levels are found in sediment deposited in the late 1930's. The higher DDT inventory in the San Pablo relative to the Richardson Bay core probably reflects the greater proximity of San Pablo Bay to agricultural activities in the watershed of the Sacramento and San Joaquin rivers. Total polychlorinated biphenyls (PCBs) occur at comparable levels in the two Bays (< 1-34 ng/g). PCBs are first detected in sediment deposited during the 1930's in Richardson Bay, about a decade earlier than the onset of detectable levels of DDTs. PCB inventories in San Pablo Bay are about a factor of four higher in the last four decades than in Richardson Bay, suggesting a distribution of inputs not as strongly weighed towards the upper reaches of the estuary as DDTs. The shallower subsurface maximum in PCBs compared to DDT in the San Pablo Bay core is consistent with the imposition of drastic source control measures four these constituents in 1970 and 1977 respectively. The observed decline in DDT and PCB levels towards the surface of both cores is consistent with a dramatic drop in the input of these pollutants once the effect of sediment resuspension and mixing is taken into account.

California

The effects of atmospheric nitrogen deposition in the Rocky Mountains of Colorado and southern Wyoming— A synthesis and critical assessment of published results

The Rocky Mountain region of Colorado and southern Wyoming receives as much as 7 kilograms per hectare per year ((kg/ha)/yr) of atmospheric nitrogen (N) deposition, an amount that may have caused changes in aquatic and terrestrial life in otherwise pristine ecosystems. The Rocky Mountain National Park, in its role of protecting air-quality related values under provisions of the Clean Air Act Amendments of 1977, has provided support for this synthesis and critical assessment of published literature on the effects of atmospheric N deposition. Results from published studies indicate a long-term increase in the rate of atmospheric N deposition during the 20th century, but no region-wide increase during the past 2 decades, although the rate of atmospheric N deposition has increased at three sites east of the Continental Divide in the Front Range region since the mid-1980s. Much of the increase in atmospheric N deposition at all three sites has resulted from an increase in the ammonium concentrations of wet deposition; this suggests an increase in contributions from agricultural areas or from vehicle traffic east of the Rocky Mountains. Lakes at two study sites in the Front Range (Loch Vale and Green Lakes Valley) had NO 3 - concentrations of 30 to 40 micromoles per liter (µmol/L) during early spring snowmelt and remained at 5 to 10 µmol/L during summer. Retention of N in atmospheric wet deposition in some sub-catchments of these lakes was less than 50 percent, which reflects an advanced stage of N saturation. Nitrate concentrations in surface waters west of the Continental Divide were lower—often less than 10 µmol/L during snowmelt and less than 2 µmol/L during summer -- than surface waters east of the Divide, except in areas such as the Mt. Zirkel Wilderness that receive elevated amounts of atmospheric N deposition of 4 to 5 (kg/ha)/yr. Atmospheric N deposition in the Front Range east of the Divide may have altered the composition of alpine tundra-plant communities and lake diatoms, but additional studies would be needed to definitively demonstrate the hypothesized cause-and-effect relations. Rates of N-mineralization and nitrification in soils of the Front Range have increased in response to increased atmospheric N deposition. Projected future population growth and energy use in Colorado and the west increase the likelihood that the subtle effects of atmospheric N deposition now evident in the Front Range will become more pronounced and widespread in the future. The likelihood of future increased N emissions along the Front Range warrants a continuation of existing long-term precipitation and surface-water chemistry monitoring programs, and an expansion of the networks into areas that receive large amounts of atmospheric N deposition, but currently lack adequate monitoring. Long-term study and expanded sampling are needed to address uncertainties about the effects of atmospheric N deposition on terrestrial plant communities, nutrient limitation in lake plankton, shifts of dominant species within diatom communities, and on amphibian response to episodic surface-water acidification.

Colorado, Wyoming

Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry

A method has been developed for the trace analysis of two classes of antimicrobials consisting of six sulfonamides (SAs) and five tetracyclines (TCs), which commonly are used for veterinary purposes and agricultural feed additives and are suspected to leach into ground and surface water. The method used solid-phase extraction and liquid chromatography/mass spectrometry (LC/MS) with positive ion electrospray. The unique combination of a metal chelation agent (Na 2 EDTA) with a macroporous copolymer resulted in quantitative recoveries by solid-phase extraction (mean recovery, 98 ± 12%) at submicrogram-per-liter concentrations. An ammonium formate/formic acid buffer with a methanol/water gradient was used to separate the antimicrobials and to optimize the signal intensity. Mass spectral fragmentation and ionization characteristics were determined for each class of compounds for unequivocal identification. For all SAs, a characteristic m / z 156 ion representing the sulfanilyl fragment was identified. TCs exhibited neutral losses of 17 amu resulting from the loss of ammonia and 35 amu from the subsequent loss of water. Unusual matrix effects were seen only for TCs in this first survey of groundwater and surface water samples from sites around the United States, requiring that TCs be quantitated using the method of standard additions.

Analytical Chemistry

Reproductive health of bass in the potomac, USA, drainage: Part 2. Seasonal occurrence of persistent and emerging organic contaminants

The seasonal occurrence of organic contaminants, many of which are potential endocrine disruptors, entering the Potomac River, USA, watershed was investigated using a two-pronged approach during the fall of 2005 and spring of 2006. Passive samplers (semipermeable membrane device and polar organic chemical integrative sampler [POCIS]) were deployed in tandem at sites above and below wastewater treatment plant discharges within the watershed. Analysis of the samplers resulted in detection of 84 of 138 targeted chemicals. The agricultural pesticides atrazine and metolachlor had the greatest seasonal changes in water concentrations, with a 3.1 - to 91 -fold increase in the spring compared with the level in the previous fall. Coinciding with the elevated concentrations of atrazine in the spring were increasing concentrations of the atrazine degradation products desethylatrazine and desisopropylatrazine in the fall following spring and summer application of the parent compound. Other targeted chemicals (organochlorine pesticides, polycyclic aromatic hydrocarbons, and organic wastewater chemicals) did not indicate seasonal changes in occurrence or concentration; however, the overall concentrations and number of chemicals present were greater at the sites downstream of wastewater treatment plant discharges. Several fragrances and flame retardants were identified in these downstream sites, which are characteristic of wastewater effluent and human activities. The bioluminescent yeast estrogen screen in vitro assay of the POCIS extracts indicated the presence of chemicals that were capable of producing an estrogenic response at all sampling sites. ?? 2009 SETA.

Environmental Toxicology and Chemistry

Arsenic in New Jersey Coastal Plain streams, sediments, and shallow groundwater: effects from different geologic sources and anthropogenic inputs on biogeochemical and physical mobilization processes

Arsenic (As) concentrations in New Jersey Coastal Plain streams generally exceed the State Surface Water Quality Standard (0.017 micrograms per liter (&micro;g/L)), but concentrations seldom exceed 1 &micro;g/L in filtered stream-water samples, regardless of geologic contributions or anthropogenic inputs. Nevertheless, As concentrations in unfiltered stream water indicate substantial variation because of particle inputs from soils and sediments with differing As contents, and because of discharges from groundwater of widely varying chemistry. In the Inner Coastal Plain, streams draining to lower reaches of the Delaware River traverse As-rich glauconitic sediments of marine origin in which As contents typically are about 20 milligrams per kilogram (mg/kg) or greater. In some of these sedimentary units, As concentrations exceed the New Jersey drinking-water maximum contaminant level (5 &micro;g/L) in shallow groundwater that discharges to streams. Microbes, fueled by organic carbon beneath the streambed, reduce iron (Fe) and As, releasing As and Fe into solution in the shallow groundwater from geologic materials that likely include (in addition to glauconite) other phyllosilicates, apatite, and siderite. When the groundwater discharges to the stream, the dissolved Fe and As are oxidized, the Fe precipitates as a hydroxide, and the As sorbs or co-precipitates with the Fe. Because of the oxidation/precipitation process, dissolved As concentrations measured in filtered stream waters of the Inner Coastal Plain are about 1 &micro;g/L, but the total As concentrations (and loads) are greater, substantially amplified by As-bearing suspended sediment in stormflows. In the Outer Coastal Plain, streams draining to the Atlantic Ocean traverse quartz-rich sediments of mainly deltaic origin where the As content generally is low (<8 mg/kg). In unfiltered and filtered water samples, As concentrations typically are less than 1 &micro;g/L in the acidic stream water and groundwater of the Outer Coastal Plain, but are greater in waters from urban areas. Despite the generally small geologic contributions to Outer Coastal Plain groundwater, where wastewater inputs were indicated, concentrations of As in unfiltered shallow groundwater discharging to small urban streams exceeded the maximum contaminant level. With a history of agriculture in the New Jersey Coastal Plain, anthropogenic inputs of As, such as residues from former pesticide applications in soils, can amplify any geogenic As in runoff. Such inputs contribute to an increased total As load to a stream at high stages of flow. As a result of yet another anthropogenic influence, microbes that reduce and mobilize As beneath the streambeds are stimulated by inputs of dissolved organic carbon (DOC). Although DOC is naturally occurring, anthropogenic contributions from wastewater inputs may deliver increased levels of DOC to subsurface soils and ultimately groundwater. Arsenic concentrations may increase with the increases in pH of groundwater and stream water in developed areas receiving wastewater inputs, as As mobilization caused by pH-controlled sorption and desorption reactions are likely to occur in waters of neutral or alkaline pH (for example, Nimick and others, 1998; Barringer and others, 2007b). Because of the difference in As content of the geologic materials in the two sub-provinces of the Coastal Plain, the amount of As that is mobile in groundwater and stream water is, potentially, substantially greater in the Inner Coastal Plain than in the Outer Coastal Plain. In turn, streams within the Inner and Outer Coastal Plain can receive substantially more As in groundwater discharge from developed areas than from environments where DOC appears to be of natural origin.

New Jersey

Environmental contaminants in Texas, USA, wetland reptiles: Evaluation using blood samples

Four species of reptiles (diamondback water snake [ Nerodia rhombifer ], blotched water snake [ N. erythrogaster ], cottonmouth [ Agkistrodon piscivorus ], and red-eared slider [ Trachemys scripta ]) were collected at two contaminated and three reference sites in Texas, USA. Old River Slough has received intensive applications of agricultural chemicals since the 1950s. Municipal Lake received industrial arsenic wastes continuously from 1940 to 1993. Blood samples were analyzed for organochlorines, potentially toxic elements, genetic damage, and plasma cholinesterase (ChE). Dichlorodiphenyldichloroethylene (DDE) concentrations reached as high as 3.0 ppm (wet weight) in whole blood of a diamondback water snake at Old River Slough, a level probably roughly equivalent to the maximum concentration found in plasma of peregrine falcons ( Falco peregrinus ) in 1978 to 1979 when DDE peaked in this sensitive species. Possible impacts on diamondback water snakes are unknown, but at least one diamondback water snake was gravid when captured, indicating active reproduction. Arsenic was not found in red-eared sliders (only species sampled) from Municipal Lake. Red-eared sliders of both sexes at Old River Slough showed declining levels of ChE with increasing mass, suggesting a life-long decrease of ChE levels. Possible negative population consequences are unknown, but no evidence was found in body condition (mass relative to carapace length) that red-eared sliders at either contaminated site were harmed.

Texas

Ground-water flow and water quality in the Upper Floridan aquifer, southwestern Albany area, Georgia, 1998-2001

During 1997, the Dougherty County Health Department sampled more than 700 wells completed in the Upper Floridan aquifer in Dougherty County, Georgia, and determined that nitrate as nitrogen (hereinafter called nitrate) concentrations were above 10 milligrams per liter (mg/L) in 12 percent of the wells. Ten mg/L is the Georgia primary drinking-water standard. The ground-water flow system is complex and poorly understood in this predominantly agricultural area. Therefore, the U.S. Geological Survey (USGS) - in cooperation with Albany Water, Gas and Light Commission - conducted a study to better define ground-water flow and water quality in the Upper Florida aquifer in the southwestern Albany area, Georgia. Ground-water levels were measured in the southwestern Albany area, Georgia, during May 1998 and March 1999 (spring), and October 1998 and September 1999 (fall). Groundwater levels measured in 75 wells open only to the Upper Floridan aquifer were used to construct potentiometric-surface maps for those four time periods. These maps show that ground water generally flows from northwest to southeast at gradients ranging from about 2 to greater than 10 feet per mile. During spring and fall 1998, ground-water levels were high and mounding of the potentiometric surface occurred in the central part of the study area, indicating a local recharge area. Water levels declined from December through February, and by March 1999 the mound in the potentiometric surface had dissipated. Of the 75 wells in the potentiometric network, 24 were selected for a water-quality network. These 24 wells and 1 spring were sampled during fall 1998 and spring 1999. Samples were analyzed for major chemical constituents, selected minor constituents, selected nutrients, and chlorofluorocarbons (CFC). Water-quality field measurements - such as water temperature, pH, specific conductance (SC), and dissolved oxygen (DO) - were taken at each well. During August 2000, a ground-water sample was collected and analyzed for selected sewage tracers. During March 2001, water samples from selected wells were analyzed for nitrogen and oxygen isotopes. Age-dating analysis using CFCs yield apparent groundwater ages that range from modern to greater than 50 years. The chemistry of ground water in the Upper Floridan aquifer varies widely throughout the southwestern Albany area, Georgia, and in general represents the chemistry commonly found in recharge areas. From fall 1998 through spring 1999, median values of pH, SC, and DO concentration were 7.6 standard units, 266 microsiemens per centimeter at 25 degrees Celsius (uS/cm), and 5.6 mg/L, respectively. The SC is highest (350 - 400 uS/cm) where mounding of the potentiometric surface exists. Specific DO concentrations indicate an area of anoxic ground water in the north-central part of the study area. Water samples indicate that ground water in the study area is dominated by calcium and bicarbonate ions, which is consistent with the limestone lithology of the aquifer. About 25 percent of the samples contained sodium and chloride at ratios similar to those in rainfall, indicating a close proximity to recharge areas. The remaining water samples, however, had sodiumchloride ratios less than 0.90, the ratio in Tift County, Georgia, rainfall samples. These low sodium-chloride ratios are consistent with chloride enrichment. Minor constituent and nutrient concentrations typically are below laboratory reporting limits; however, the maximum nitrate concentration measured during the study period was 12.2 mg/L, and the median concentration for the study period was 3.0 mg/L. Samples collected during 1999 had a higher median nitrate concentration than the 1998 samples. Regression analysis indicated that nitrate concentrations are related exponentially to chloride concentrations. Four distinct groups of ground-water-quality samples, plus four unique samples, were identified using cluster analysis. Water-quality groups I and

Georgia

Occurrence of pesticides in Oregon coastal waters

Pesticides are used globally for a wide range of applications including agricultural, forestry, roadsides, freshwater systems, and personal use. While pesticides have ensured efficient crop production, they are frequently transported away from application sites and are found in almost all terrestrial and aquatic environments. Pesticides are frequently detected in watersheds and rivers, but there is limited research on pesticide presence in United States (U.S.) marine environments. To address these data gaps, this study documents pesticide occurrence in U.S. coastal waters, providing new understanding of pesticide contamination in offshore environments. Polar organic chemical integrative samples (POCIS) were deployed at five sites along the Oregon, U.S. coast to examine the occurrence of pesticides. Between two and seven different pesticides were detected at every site, with herbicides diuron, and atrazine, and fungicides carbendazim, propiconazole, and tebuconazole being the most frequently detected at three sites. The prevalence of herbicides and fungicides in coastal waters indicates a connection between terrestrial pesticide practices and marine contamination. These findings provide new insights into the presence of pesticides in coastal nearshore and offshore waters and suggest that a comprehensive monitoring effort could enhance our understanding of sources, transport, and pesticide risks for marine species both nearshore and offshore.

Oregon

Widespread occurrence and potential for biodegradation of bioactive contaminants in Congaree National Park, USA

Organic contaminants with designed molecular bioactivity, such as pesticides and pharmaceuticals, originate from human and agricultural sources, occur frequently in surface waters, and threaten the structure and function of aquatic and terrestrial ecosystems. Congaree National Park in South Carolina (USA) is a vulnerable park unit due to its location downstream of multiple urban and agricultural contaminant sources and its hydrologic setting, being composed almost entirely of floodplain and aquatic environments. Seventy-two water and sediment samples were collected from 16 sites in Congaree National Park during 2013 to 2015, and analyzed for 199 and 81 targeted organic contaminants, respectively. More than half of these water and sediment analytes were not detected or potentially had natural sources. Pharmaceutical contaminants were detected (49 total) frequently in water throughout Congaree National Park, with higher detection frequencies and concentrations at Congaree and Wateree River sites, downstream from major urban areas. Forty-seven organic wastewater indicator chemicals were detected in water, and 36 were detected in sediment, of which approximately half are distinctly anthropogenic. Endogenous sterols and hormones, which may originate from humans or wildlife, were detected in water and sediment samples throughout Congaree National Park, but synthetic hormones were detected only once, suggesting a comparatively low risk of adverse impacts. Assessment of the biodegradation potentials of 8 14 C-radiolabeled model contaminants indicated poor potentials for some contaminants, particularly under anaerobic sediments conditions.

South Carolina

Pesticides in Mississippi air and rain: A comparison between 1995 and 2007

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux.

Mississippi

Water-quality characteristics of quaternary unconsolidated-deposit aquifers and lower tertiary aquifers of the Bighorn Basin, Wyoming and Montana, 1999-2001

As part of the Yellowstone River Basin National Water Quality Assessment study, ground-water samples were collected from Quaternary unconsolidated-deposit and lower Tertiary aquifers in the Bighorn Basin of Wyoming and Montana from 1999 to 2001. Samples from 54 wells were analyzed for physical characteristics, major ions, trace elements, nutrients, dissolved organic carbon, radionuclides, pesticide compounds, and volatile organic compounds (VOCs) to evaluate current water-quality conditions in both aquifers. Water-quality samples indicated that waters generally were suitable for most uses, and that natural conditions, rather than the effects of human activities, were more likely to limit uses of the waters. Waters in both types of aquifers generally were highly mineralized, and total dissolved-solids concentrations frequently exceeded the U.S. Environmental Protection Agency (USEPA) Secondary Maximum Contaminant Level (SMCL) of 500 milligrams per liter (mg/L). Because of generally high mineralization, waters from nearly one-half of the samples from Quaternary aquifers and more than one-half of the samples from lower Tertiary aquifers were not classified as fresh (dissolved-solids concentration were not less than 1,000 mg/L). The anions sulfate, fluoride, and chloride were measured in some ground-water samples at concentrations greater than SMCLs. Most waters from the Quaternary aquifers were classified as very hard (hardness greater than 180 mg/L), but hardness varied much more in waters from the lower Tertiary aquifers and ranged from soft (less than 60 mg/L) to very hard (greater than 180 mg/L). Major-ion chemistry varied with dissolved-solids concentrations. In both types of aquifers, the predominant anion changes from bicarbonate to sulfate with increasing dissolved-solids concentrations. Samples from Quaternary aquifers with fresh waters generally were calcium-bicarbonate, calcium-sodium-bicarbonate, and calcium-sodium-sulfate-bicarbonate type waters, whereas samples with larger concentrations generally were calcium-sodium-sulfate, calcium-sulfate, or sodium-sulfate-type waters. In the lower Tertiary aquifers, samples with fresh waters generally were sodium-bicarbonate or sodium-bicarbonate-sulfate type waters, whereas samples with larger concentrations were sodium-sulfate or calcium-sodium-sulfate types. Concentrations of most trace elements in both types of aquifers generally were small and most were less than applicable USEPA standards. The trace elements that most often did not meet USEPA secondary drinking-water standards were iron and manganese. In fact, the SMCL for manganese was the most frequently exceeded standard; 68 percent of the samples from the Quaternary aquifers and 31 percent of the samples from the lower Tertiary aquifers exceeded the manganese standard. Geochemical conditions may control manganese in both aquifers as concentrations in Quaternary aquifers were negatively correlated with dissolved oxygen concentrations and concentrations in lower Tertiary aquifers decreased with increasing pH. Elevated nitrate concentrations, in addition to detection of pesticides and VOCs in both aquifers, indicated some effects of human activities on ground-water quality. Nitrate concentrations in 36 percent of the wells in Quaternary aquifers and 28 percent of the wells in lower Tertiary aquifers were greater than 1 mg/L, which may indicate ground-water contamination from human sources. The USEPA drinking-water Maximum Contaminant Level (MCL) for nitrate, 10 mg/L, was exceeded in 8 percent of samples collected from Quaternary aquifers and 3 percent from lower Tertiary aquifers. Nitrate concentrations in Quaternary aquifers were positively correlated with the percentage of cropland and other agricultural land (non-cropland), and negatively correlated with rangeland and riparian land. In the lower Tertiary aquifers, nitrate concentrations only were correlated with the percentage of cropland. Concentratio

Scientific Investigations Report