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Vertical gradients in water chemistry and age in the southern High Plains Aquifer, Texas, 2002

The southern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of New Mexico and Texas. Despite the aquifer's importance to the overall economy of the southern High Plains, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey's National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the southern High Plains aquifer at two locations (Castro and Hale Counties, Texas) were analyzed for field parameters, major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, and dissolved gases to evaluate vertical gradients in water chemistry and age in the aquifer. Tritium measurements indicate that recent (post-1953) recharge was present near the water table and that deeper water was recharged before 1953. Concentrations of dissolved oxygen were largest (2.6 to 5.6 milligrams per liter) at the water table and decreased with depth below the water table. The smallest concentrations were less than 0.5 milligram per liter. The largest major-ion concentrations generally were detected at the water table because of the effects of overlying agricultural activities, as indicated by postbomb tritium concentrations and elevated nitrate and pesticide concentrations at the water table. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions and mixing with water from the underlying aquifer in rocks of Cretaceous age. The concentration increases primarily were accounted for by dissolved sodium, bicarbonate, chloride, and sulfate. Nitrite plus nitrate concentrations at the water table were 2.0 to 6.1 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer to a maximum concentration of 0.55 milligram per liter as nitrogen. Dissolved-gas and nitrogen-isotope data from the deep wells in Castro County indicate that denitrification occurred in the aquifer, removing 74 to more than 97 percent of the nitrate originally present in recharge. There was no evidence of denitrification in the deep part of the aquifer in Hale County. After correcting for denitrification effects, the background concentration of nitrate in water recharged before 1953 ranged from 0.4 to 3.2 milligrams per liter as nitrogen, with an average of 1.6 milligrams per liter as nitrogen. The d15N composition of background nitrate at the time of recharge was estimated to range from 9.6 to 12.3 per mil. Mass-balance models indicate that the decreases in dissolved oxygen and nitrate concentrations and small increases in major-ion concentrations along flow paths can be accounted for by small amounts of silicate-mineral and calcite dissolution; SiO2, goethite, and clay-mineral precipitation; organic-carbon and pyrite oxidation; denitrification; and cation exchange. Mass-balance models for some wells also required mixing with water from the underlying aquifer in rocks of Cretaceous age to achieve mole and isotope balances. Carbon mass transfers identified in the models were used to adjust radiocarbon ages of water samples recharged before 1953. Adjusted radiocarbon ages ranged from less than 1,000 to 9,000 carbon-14 years before present. Radiocarbon ages were more sensitive to uncertainties in the carbon-14 content of recharge than uncertainties in carbon mass transfers, leading to 1-sigma uncertainties of about ?2,000 years in the adjusted ages. Despite these relatively large uncertainties in adjusted radiocarbon ages, it appears that deep water in the aquifer was considerably older (at least 1,000 years) than water near the water table. There was essentially no change in ground-water age with depth in deeper parts of the aquifer, indicating that water in that

Texas

Design and methods of the Pacific Northwest Stream Quality Assessment (PNSQA), 2015

In 2015, the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project conducted the Pacific Northwest Stream Quality Assessment (PNSQA) to investigate stream quality across the western part of the Pacific Northwest. The goal of the PNSQA was to assess the health of streams in the region by characterizing multiple water-quality factors that are stressors to in-stream aquatic life and by evaluating the relation between these stressors and the condition of biological communities. The effects of urbanization and agriculture on stream quality for the Puget Lowland and Willamette Valley Level III Ecoregions were the focus of this regional study. Findings will help inform the public and policymakers about human and environmental factors that are the most critical in affecting stream quality and, thus, provide insights into possible strategies to protect or improve the health of streams in the region. Land-use data were used in the study to identify and select sites within the region that ranged in levels of urban and agricultural development. A total of 88 sites were selected across the region—69 were on streams that explicitly spanned a range of urban land use in their watersheds, 8 were on streams in agricultural watersheds, and 11 were reference sites with little or no development in their watersheds. Depending on the type of land use, sites were sampled for contaminants, nutrients, and sediment for either a 4- or 10-week period during April, May, and June 2015. This water-quality “index period” was immediately followed with an ecological survey of all sites that included stream habitat, benthic algae, benthic macroinvertebrates, and fish. Additionally, streambed sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. This report provides a detailed description of the specific study components and methods of the PNSQA, including (1) surveys of stream habitat and aquatic biota, (2) discrete water sampling, (3) deployment of passive polar organic chemical integrative samplers for pesticides and pharmaceuticals, and (4) sampling of streambed sediment. At selected study sites, toxicity testing of streambed sediment, continuous water-quality monitoring, and daily pesticide sampling also were conducted and are described.

Oregon, Washington

Surface-water and ground-water quality in the Yucaipa area, San Bernardino and Riverside Counties, California, 1996-98

The quality of surface water and ground water in the Yucaipa area was evaluated to determine general chemical characteristics and to identify areas of recent ground-water recharge. Water samples, collected from 8 sites on 3 creeks and from 25 wells, were analyzed for general chemistry, nutrients, tritium, and stable isotopes of hydrogen and oxygen. At one production well (1S/2W-25R4), water samples were collected at discrete depths during pumping and a continuous profile of the vertical flow rate inside the well casing was recorded. In addition to general-chemistry samples, tritium and carbon-14 samples were collected at this well to interpret the age of water at different depths.Results indicate that most water in the Yucaipa area is a calcium-bicarbonate type. The general chemical composition of surface water resembles that of ground water, although the concentration of most constituents is higher in ground water. The chemical composition of most ground-water samples is similar. Elevated concentrations of nitrate in some ground-water samples may indicate recharge from agricultural areas.In surface water that recharges ground water tritium activity ranged from 7 to 18 picocuries per liter. The range of tritium activity found in ground water indicates different times since recharge and possible mixing along ground-water flow paths. The oldest ground-water sample had a tritium activity less than 0.3 picocuries per liter, indicating more than 50 years since recharge. Water samples that had tritium activity greater than 0.3 picocuries per liter indicate that some of the water was recharged since 1952. The youngest ground water (greater than 7 picocuries per liter) was found near the hills and mountains surrounding the Yucaipa area; the oldest ground water (less than 0.3 picocuries per liter) was found in the Western Heights subbasin. Testing of the vertical contribution of ground water to well 1S/2W-25R4 showed that more than one-half of the water flowed into the well between depths of about 450 and 600 feet below land surface; the rest of the water flowed into the well between 600 and about 850 feet below land surface. At a discharge rate of 750 gallons per minute, virtually no water was contributed to the well below a depth of about 850 feet. The water samples collected at this well ranged in age from less than 50 to less than 400 years before present.

Water-Resources Investigations Report

Small watershed studies: Analytical approaches for understanding ecosystem response to environmental change

Biogeochemical studies in small watersheds provide an analytical approach to understand how ecosystems respond to natural climatic variations and human-induced environmental change. Small watersheds, usually less than 5 km2, are small enough to permit characterization and understanding of ecosystem processes within relatively simple, homogeneous biological and physical settings; yet they are large enough to incorporate more complex processes and element cycles than can be studied at plot scales. Watersheds comprise discrete hydrochemical environments allowing quantification of hydrologic, element, and energy budgets. Element budgets, or mass balances, can be quantified as the difference between the mass of a solute that enters a watershed in wet and dry deposition and leaves a watershed in streamflow. Element budgets are primary tools used to investigate biogeochemical processes. Monitoring various aspects of element budgets to assess ecosystem health and stability is analogous to measuring the pulse or blood chemistry of a patient. Monitoring streamwater chemistry, basic climate, soil, and biotic variables provide a means to integrate complex biogeochemical processes and evaluate trends in water quality. Small watershed studies provide a scientific basis to develop predictive models of watershed function. Major emphases of small watershed studies include investigation of hydrologic and chemical responses to natural climate variation, anthropogenic stressors, and alternate forest-management practices. The nature and significance of biogeochemical research in small watersheds is reviewed by Moldan and Cerny (1994). The U.S. Geological Survey, U.S. Department of Agriculture Forest Service, and other federal agencies support several long-term small watershed studies to provide insight into a variety of ecosystem processes. Long-term records are essential to distinguish trends resulting from natural climatic variations or other stressors. The following sites, with noted periods of records, are examples of intensively studied forested watersheds in eastern USA supported by federal agencies: ■ Coweeta Hydrologic Laboratory, North Carolina, (1939-present), Swank and Crossley (1988). ■ Hubbard Brook Experimental Forest, New Hampshire, (1956-present), Bormann and Likens (1979). ■ Sleepers River Research Watershed, Vermont, (1958-present), Shanley et al. (1995). ■ Walker Branch Watershed, Tennessee, (1967-present), Johnson and Van Hook (1989). ■ Catoctin Mountains Research Site, Maryland, (1982-present), Rice and Bricker (1995). ■ Catskill Stream Network, New York, (1983- present), Murdoch and Stoddard (1992). ■ Panola Mountain Research Watershed, Georgia, (1985-present), Huntington et al. (1993). Small watershed studies also provide essential baseline information for understanding variations in water quality and element cycling in "pristine" ecosystems that can be used as benchmarks to evaluate anthropogenic impacts and alternate watershed management practices. This paper provides examples of how analytical tools developed through watershed research provide insight into ecosystem processes and can contribute to the management of watershed resources.

Conference Paper

Orthene® toxicity to little brown bats (Myotis lucifugus): Acetylcholinesterase inhibition, coordination loss, and mortality

The 24-h LD50 of Orthener̀ (active ingredient acephate, acetylphosphoramidothioic acid o,s -dimethyl ester, CAS 30560-19–1) to little brown bats (Myotis lucifugus) was high (> 1,500 mg acephate/kg) and at least several times greater than the LD50 for mice (Mus musculus) (720 mg/kg). Twenty-four hours after dosing, all surviving mice appeared behaviorally normal, but 9 of 30 surviving bats could not right themselves when placed on their backs. When dead and incapacitated bats were combined to calculate an ED50 (median effective dose), the resultant estimate (687 mg/kg) did not differ ( p > 0.05) from the LD50 for mice. Serum cholinesterase (ChE) activity in control bats was 3.2 times greater than in mice. The relationship between this naturally high level of ChE and the relative tolerance of bats to organophosphorus insecticides is unexplained. Toxicity of Orthene was clearly less than that reported elsewhere for methyl parathion (phosphorothioic acid o,o -dimethyl o-[4-nitrophenyl] ester, CAS 298–00-0). This finding may be useful in selection of a chemical for agricultural use, but conclusions about the safety of Orthene to this bat species, or to others, must remain tentative until confirmed by studies under field conditions. Because bats are long-lived with low reproductive rates and slow recruitment, any additional mortality in the wild could be critical to population survival.

Environmental Toxicology and Chemistry

Response of Stream Chemistry During Base Flow to Gradients of Urbanization in Selected Locations Across the Conterminous United States, 2002-04

During 2002-2004, the U.S. Geological Survey's National Water-Quality Assessment Program conducted a study to determine the effects of urbanization on stream water quality and aquatic communities in six environmentally heterogeneous areas of the conterminous United States--Atlanta, Georgia; Raleigh-Durham, North Carolina; Milwaukee-Green Bay, Wisconsin; Dallas-Fort Worth, Texas; Denver, Colorado; and Portland, Oregon. This report compares and contrasts the response of stream chemistry during base flow to urbanization in different environmental settings and examines the relation between the exceedance of water-quality benchmarks and the level of urbanization in these areas. Chemical characteristics studied included concentrations of nutrients, dissolved pesticides, suspended sediment, sulfate, and chloride in base flow. In three study areas where the background land cover in minimally urbanized basins was predominantly forested (Atlanta, Raleigh-Durham, and Portland), urban development was associated with increased concentrations of nitrogen and total herbicides in streams. In Portland, there was evidence of mixed agricultural and urban influences at sites with 20 to 50 percent urban land cover. In two study areas where agriculture was the predominant background land cover (Milwaukee-Green Bay and Dallas-Fort Worth), concentrations of nitrogen and herbicides were flat or decreasing as urbanization increased. In Denver, which had predominantly shrub/grass as background land cover, nitrogen concentrations were only weakly related to urbanization, and total herbicide concentrations did not show any clear pattern relative to land cover - perhaps because of extensive water management in the study area. In contrast, total insecticide concentrations increased with increasing urbanization in all six study areas, likely due to high use of insecticides in urban applications and, for some study areas, the proximity of urban land cover to the sampling sites. Phosphorus concentrations increased with urbanization only in Portland; in Atlanta and Raleigh-Durham, leachate from septic tanks may have increased phosphorus concentrations in basins with minimal urban development. Concentrations of suspended sediment were only weakly associated with urbanization, probably because this study analyzed only base-flow samples, and the bulk of sediment loads to streams is transported in storm runoff rather than base flow. Sulfate and chloride concentrations increased with increasing urbanization in four study areas (Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Portland), likely due to increasing contributions from urban sources of these constituents. The weak relation between sulfate and chloride concentrations and urbanization in Dallas-Fort Worth and Denver was likely due in part to high sulfate and chloride concentrations in ground-water inflow, which would have obscured any pattern of increasing concentration with urbanization. Pesticides often were detected at multiple sites within a study area, so that the pesticide 'signature' for a given study area - the mixtures of pesticides detected, and their relative concentrations, at streams within the study area - tended to show some pesticides as dominant. The type and concentrations of the dominant pesticides varied markedly among sites within a study area. There were differences between pesticide signatures during high and low base-flow conditions in five of the six study areas. Normalization of absolute pesticide concentrations by the pesticide toxicity index (a relative index indicating potential toxicity to aquatic organisms) dramatically changed the pesticide signatures, indicating that the pesticides with the greatest potential to adversely affect cladocerans or fish were not necessarily the pesticides detected at the highest concentrations. In a screening-level assessment, measured contaminant concentrations in individual base-flow water samples were compared with various water-qual

Scientific Investigations Report

Groundwater and surface-water data from the C-aquifer monitoring program, Northeastern Arizona, 2012–2019

The Coconino aquifer (C aquifer) is a regionally extensive multiple-aquifer system supplying water for municipal, agricultural, and industrial use in northeastern Arizona, northwestern New Mexico, and southeastern Utah. This report focuses on the C aquifer in the arid to semi-arid area between St. Johns, Ariz., and Flagstaff, Ariz., along the Interstate-40 corridor where an increase in groundwater withdrawals coupled with ongoing drought conditions increase the potential for substantial water-level decline within the aquifer. The U.S. Geological Survey (USGS) C-aquifer Monitoring Program began in 2005 to establish baseline groundwater and surface-water conditions and to quantify physical and water-chemistry responses to pumping stresses and climate. This report presents data previously reported in Brown and Macy (2012) that extend back as far as the 1950s, along with new data collected from the USGS C-aquifer Monitoring Program since that publication, from water years 2012 to 2019. Water levels in 17 wells are measured quarterly as part of the C-aquifer Monitoring Program, and five of those are continuously monitored at 15-minute intervals. Water levels in an additional 18 wells in the study area are measured periodically by the USGS or other agencies. The largest historical change in water level in the study area was a decrease of 81.20 feet in Lake Mary 1 Well near Flagstaff between 1962 and 2018. Changes in water levels were greatest around major pumping centers and in the eastern extent of the study area. Surface-water water-quality parameters (pH, water temperature, specific conductance, and dissolved oxygen) and streamflow discharge measurements were collected and analyzed along perennial, groundwater-fed reaches of Clear Creek, Chevelon Creek, and the Little Colorado River during nine baseflow investigations of varying extent between 2005 and 2019. Both Clear Creek and Chevelon Creek gain in flow from the beginning of their perennial reaches to their outflow into the Little Colorado River. The Little Colorado River has relatively steady streamflow in the reach between where the two tributaries enter the river. Chevelon Creek showed an increase in median specific conductance during all baseflow investigations of nearly 4,000 microsiemens per centimeter (μS/cm) from near the headwaters to the confluence with the Little Colorado River; Clear Creek also showed an increase in median specific conductance of almost 5,000 μS/cm from headwaters to confluence. Water temperature, dissolved oxygen, and pH do not show substantial trends along the reaches of Clear Creek, Chevelon Creek, or the Little Colorado River.

Arizona

Efficacy of algal metrics for assessing nutrient and organic enrichment in flowing waters

1. Algal-community metrics were calculated for periphyton samples collected from 976 streams and rivers by the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Programme during 1993–2001 to evaluate national and regional relations with water chemistry and to compare whether algal-metric values differ significantly among undeveloped and developed land-use classifications. 2. Algal metrics with significant positive correlations with nutrient concentrations included indicators of trophic condition, organic enrichment, salinity, motility and taxa richness. The relative abundance of nitrogen-fixing algae was negatively correlated with nitrogen concentrations, and the abundance of diatom species associated with high dissolved oxygen concentrations was negatively correlated with both nitrogen and phosphorus concentrations. Median algal-metric values and nutrient concentrations were significantly lower at undeveloped sites than those draining agricultural or urban catchments. 3. Total algal biovolume did not differ significantly among major river catchments or land-use classifications, and was only weakly correlated with nitrate (positive) and suspended-sediment (negative) concentrations. Estimates of periphyton chlorophyll a indicated an oligotrophic–mesotrophic boundary of about 21 mg m −2 and a mesotrophic–eutrophic boundary of about 55 mg m −2 based on upper and lower quartiles of the biovolume data distribution. 4. Although algal species tolerance to nutrient and organic enrichment is well documented, additional taxonomic and autecological research on sensitive, endemic algal species would further enhance water-quality assessments.

Freshwater Biology

Water quality and landscape processes of four watersheds in eastern Puerto Rico

Humid tropical regions occupy about a quarter of Earth's land surface, yet they contribute a substantially higher fraction of the water, solutes, and sediment discharged to the world's oceans. Nearly half of Earth's population lives in the tropics, and development stresses can potentially harm soil resources, water quality, and water supply and in addition increase landslide and flood hazards. Owing to Puerto Rico's steep topography, low water storage capacity, and dependence on trade-wind precipitation, the island's people, ecosystems, and water supply are vulnerable to extreme weather such as hurricanes, floods, and droughts. Eastern Puerto Rico offers a natural laboratory for separating geologic and land-cover influences from regional- and global-scale influences because of its various bedrock types and the changing land cover surrounding intact, mature forest of the Luquillo Experimental Forest. Accordingly, a multiyear assessment of hydrological and biogeochemical processes was designed to develop an understanding of the effects of these differences on local climate, streamflow, water quality, and ecosystems, and to form the basis for a long-term and event-based program of climate and hydrologic monitoring. Because infrequent, large storms play a major role in this landscape, we focused on high-runoff events, sampling 263 storms, including all major hurricanes from 1991 through 2005. The largest storms have profound geomorphic consequences, such as landslides, debris flows, deep gullying on deforested lands, excavation and suspension of sediment in stream channels, and delivery of a substantial fraction of annual stream sediment load. Large storms sometimes entrain ocean foam and spray causing high concentrations of seasalt-derived constituents in stream waters during the storm. Past deforestation and agricultural activities in the Cayaguás and Canóvanas watersheds accelerated erosion and soil loss, and this material continues to be remobilized during large storms. Nearly 5,000 routine and event samples were analyzed for parameters that allow determination of denudation rates based on suspended and dissolved loads; 860 of these samples were analyzed for a comprehensive suite of chemical constituents. The rivers studied are generally similar in water-quality characteristics, and windward or leeward aspect appears to exert a stronger influence on water quality than geology or land cover. Of samples analyzed for comprehensive chemistry and for sediment, 543 were collected at runoff rates greater than 1 millimeter per hour, 256 at rates exceeding 10 millimeters per hour, and 3 at rates exceeding 90 millimeters per hour. Streams have rarely been sampled during events with such high runoff rates. Rates of physical and chemical weathering are especially high, and physical denudation rates, forested watersheds included, are considerably greater than is expected for a steady-state system. The elevated physical erosion drives an increased particulate organic carbon flux, one that is large, important to the carbon cycle, and sustainable, because soil-carbon regeneration is rapid. The 15-year Water, Energy, and Biogeochemical Budget dataset, which includes discharge, field parameters, suspended sediment, major cations and anions, and nutrients, is available from the U.S. Geological Survey's National Water Information System (http://waterdata.usgs.gov/nwis). The dataset provides a baseline for characterizing future environmental change and will improve our understanding of the interdependencies of land, water, and biological resources and their responses to changes in climate and land use. Because eastern Puerto Rico resembles many tropical regions in terms of geology and patterns of development, implications from this study are transferable to other tropical regions facing deforestation, rapid land-use change, and climate change.

Professional Paper

Global methane budget 2000-2020

Understanding and quantifying the global methane (CH 4 ) budget is important for assessing realistic pathways to mitigate climate change. CH 4 is the second most important human-influenced greenhouse gas in terms of climate forcing after carbon dioxide (CO 2 ), and both emissions and atmospheric concentrations of CH 4 have continued to increase since 2007 after a temporary pause. The relative importance of CH 4 emissions compared to those of CO 2 for temperature change is related to its shorter atmospheric lifetime, stronger radiative effect, and acceleration in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in quantifying the factors responsible for the observed atmospheric growth rate arise from diverse, geographically overlapping CH 4 sources and from the uncertain magnitude and temporal change in the destruction of CH 4 by short-lived and highly variable hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to improve, synthesise, and update the global CH 4 budget regularly and to stimulate new research on the methane cycle. Following Saunois et al. (2016, 2020), we present here the third version of the living review paper dedicated to the decadal CH 4 budget, integrating results of top-down CH 4 emission estimates (based on in situ and Greenhouse Gases Observing SATellite (GOSAT) atmospheric observations and an ensemble of atmospheric inverse-model results) and bottom-up estimates (based on process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). We present a budget for the most recent 2010–2019 calendar decade (the latest period for which full data sets are available), for the previous decade of 2000–2009 and for the year 2020. The revision of the bottom-up budget in this 2025 edition benefits from important progress in estimating inland freshwater emissions, with better counting of emissions from lakes and ponds, reservoirs, and streams and rivers. This budget also reduces double counting across freshwater and wetland emissions and, for the first time, includes an estimate of the potential double counting that may exist (average of 23 Tg CH 4 yr −1 ). Bottom-up approaches show that the combined wetland and inland freshwater emissions average 248 [159–369] Tg CH 4 yr −1 for the 2010–2019 decade. Natural fluxes are perturbed by human activities through climate, eutrophication, and land use. In this budget, we also estimate, for the first time, this anthropogenic component contributing to wetland and inland freshwater emissions. Newly available gridded products also allowed us to derive an almost complete latitudinal and regional budget based on bottom-up approaches. For the 2010–2019 decade, global CH 4 emissions are estimated by atmospheric inversions (top-down) to be 575 Tg CH 4 yr −1 (range 553–586, corresponding to the minimum and maximum estimates of the model ensemble). Of this amount, 369 Tg CH 4 yr −1 or ∼ 65 % is attributed to direct anthropogenic sources in the fossil, agriculture, and waste and anthropogenic biomass burning (range 350–391 Tg CH 4 yr −1 or 63 %–68 %). For the 2000–2009 period, the atmospheric inversions give a slightly lower total emission than for 2010–2019, by 32 Tg CH 4 yr −1 (range 9–40). The 2020 emission rate is the highest of the period and reaches 608 Tg CH 4 yr −1 (range 581–627), which is 12 % higher than the average emissions in the 2000s. Since 2012, global direct anthropogenic CH 4 emission trends have been tracking scenarios that assume no or minimal climate mitigation policies proposed by the Intergovernmental Panel on Climate Change (shared socio-economic pathways SSP5 and SSP3). Bottom-up methods suggest 16 % (94 Tg CH 4 yr −1 ) larger global emissions (669 Tg CH 4 yr −1 , range 512–849) than top-down inversion methods for the 2010–2019 period. The discrepancy between the bottom-up and the top-down budgets has been greatly reduced compared to the previous differences (167 and 156 Tg CH 4 yr −1 in Saunois et al. (2016, 2020) respectively), and for the first time uncertainties in bottom-up and top-down budgets overlap. Although differences have been reduced between inversions and bottom-up, the most important source of uncertainty in the global CH 4 budget is still attributable to natural emissions, especially those from wetlands and inland freshwaters. The tropospheric loss of methane, as the main contributor to methane lifetime, has been estimated at 563 [510–663] Tg CH 4 yr −1 based on chemistry–climate models. These values are slightly larger than for 2000–2009 due to the impact of the rise in atmospheric methane and remaining large uncertainty ( ∼ 25 %). The total sink of CH 4 is estimated at 633 [507–796] Tg CH 4 yr −1 by the bottom-up approaches and at 554 [550–567] Tg CH 4 yr −1 by top-down approaches. However, most of the top-down models use the same OH distribution, which introduces less uncertainty to the global budget than is likely justified. For 2010–2019, agriculture and waste contributed an estimated 228 [213–242] Tg CH 4 yr −1 in the top-down budget and 211 [195–231] Tg CH 4 yr −1 in the bottom-up budget. Fossil fuel emissions contributed 115 [100–124] Tg CH 4 yr −1 in the top-down budget and 120 [117–125] Tg CH 4 yr −1 in the bottom-up budget. Biomass and biofuel burning contributed 27 [26–27] Tg CH 4 yr −1 in the top-down budget and 28 [21–39] Tg CH 4 yr −1 in the bottom-up budget. We identify five major priorities for improving the CH 4 budget: (i) producing a global, high-resolution map of water-saturated soils and inundated areas emitting CH 4 based on a robust classification of different types of emitting ecosystems; (ii) further development of process-based models for inland-water emissions; (iii) intensification of CH 4 observations at local (e.g. FLUXNET-CH 4 measurements, urban-scale monitoring, satellite imagery with pointing capabilities) to regional scales (surface networks and global remote sensing measurements from satellites) to constrain both bottom-up models and atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) integration of 3D variational inversion systems using isotopic and/or co-emitted species such as ethane as well as information in the bottom-up inventories on anthropogenic super-emitters detected by remote sensing (mainly oil and gas sector but also coal, agriculture, and landfills) to improve source partitioning.

Earth System Science Data

Use of high-throughput screening results to prioritize chemicals for potential adverse biological effects within a West Virginia Watershed

Organic chemicals from industrial, agricultural, and residential activities can enter surface waters through regulated and unregulated discharges, combined sewer overflows, stormwater runoff, accidental spills, and leaking septic-conveyance systems on a daily basis. The impact of point and nonpoint contaminant sources can result in adverse biological effects for organisms living in or near surface waters. Assessing the adverse or toxic effects that may result when exposure occurs is complicated by the fact that many commonly used chemicals lack toxicity information or water quality standards. To address these challenges, an exposure-activity ratio (EAR) screening approach was used to prioritize environmental chemistry data in a West Virginia watershed (Wolf Creek). Wolf Creek is a drinking water source and recreation resource with documented water quality impacts from point and nonpoint sources. The EAR screening approach uses high-throughput screening (HTS) data from ToxCast as a method of integrating environmental chemical occurrence and biological effects data. Using water quality schedule 4433, which targets 69 organic waste compounds typically found in domestic and industrial wastewater, chemicals were screened for potential adverse biological affects at multiple sites in the Wolf Creek watershed. Cumulative EAR mixture values were greatest at Sites 2 and 3, where bisphenol A (BPA) and pentachlorophenol exhibited maximum EAR values of 0.05 and 0.002, respectively. Site 2 is downstream of an unconventional oil and gas (UOG) wastewater disposal facility with documented water quality impacts. Low-level organic contaminants were found at all sample sites in Wolf Creek, except Site 10, where Wolf Creek enters the New River. The application of an EAR screening approach allowed our study to extend beyond traditional environmental monitoring methods to identify multiple sites and chemicals that warrant further investigation.

West Virginia

Quality of groundwater in the Denver Basin aquifer system, Colorado, 2003-5

Groundwater resources from alluvial and bedrock aquifers of the Denver Basin are critical for municipal, domestic, and agricultural uses in Colorado along the eastern front of the Rocky Mountains. Rapid and widespread urban development, primarily along the western boundary of the Denver Basin, has approximately doubled the population since about 1970, and much of the population depends on groundwater for water supply. As part of the National Water-Quality Assessment Program, the U.S. Geological Survey conducted groundwater-quality studies during 2003–5 in the Denver Basin aquifer system to characterize water quality of shallow groundwater at the water table and of the bedrock aquifers, which are important drinking-water resources. For the Denver Basin, water-quality constituents of concern for human health or because they might otherwise limit use of water include total dissolved solids, fluoride, sulfate, nitrate, iron, manganese, selenium, radon, uranium, arsenic, pesticides, and volatile organic compounds. For the water-table studies, two monitoring-well networks were installed and sampled beneath agricultural (31 wells) and urban (29 wells) land uses at or just below the water table in either alluvial material or near-surface bedrock. For the bedrock-aquifer studies, domestic- and municipal-supply wells completed in the bedrock aquifers were sampled. The bedrock aquifers, stratigraphically from youngest (shallowest) to oldest (deepest), are the Dawson, Denver, Arapahoe, and Laramie-Fox Hills aquifers. The extensive dataset collected from wells completed in the bedrock aquifers (79 samples) provides the opportunity to evaluate factors and processes affecting water quality and to establish a baseline that can be used to characterize future changes in groundwater quality. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating constituents and tracers. This report discusses spatial and statistical distributions of chemical constituents and evaluates natural and human-related processes that affect water quality. Findings are synthesized to assess the vulnerability of the Denver Basin aquifer system to groundwater contamination. The chemistry of groundwater samples collected from the water-table wells was generally different from that of samples collected from the bedrock-aquifer wells. Samples from the water-table wells tended to have higher concentrations of total dissolved solids and most major ions. Concentrations of several constituents with potential human-health concerns, including nitrate, selenium, uranium, and arsenic, decreased with depth and were highest in samples from the water-table wells. Exceedances of drinking-water standards and water-quality benchmarks were more frequently associated with shallow groundwater samples; concentrations of total dissolved solids and sulfate exceeded water-quality benchmarks for about half or more of samples from the water-table wells. The sediments and rocks of the Denver Basin are natural sources of the trace elements selenium, uranium, and arsenic, which affect their concentrations in groundwater. Detections of organic contaminants, which are typically indicative of human sources of contamination to groundwater, were more frequent in samples from the water-table wells. Pesticide compounds and volatile organic compounds were detected in 33 and 62 percent, respectively, of water-table well samples. Detected organic contaminant concentrations were much less than the associated drinking-water standards. Samples collected from the bedrock aquifers had lower concentrations of total dissolved solids than did samples collected from the water-table wells, although within the bedrock-aquifer samples, concentrations increased from the Dawson to Denver to Arapahoe to Laramie-Fox Hills aquifers. Concentrations of total dissolved solids and many constituents varied spatially and with depth in the bedrock aquifers, likely as a result of ion-exchange and oxidation-reduction reactions, which are important processes affecting water quality. Major-ion chemistry generally evolved from a calcium-bicarbonate to calcium-sulfate composition, with some sodium-bicarbonate and sodium-sulfate facies in the deeper bedrock aquifers, likely resulting from longer residence times and more extensive water-rock interaction. Oxidation-reduction conditions generally evolved from oxic at the water table to anoxic with increasing depth in the bedrock aquifers. Most samples from the bedrock aquifers were anoxic. Exceedances of drinking-water standards and water-quality benchmarks for the bedrock aquifers occurred in 1 percent or less of samples for nitrate, selenium, or arsenic; there were no exceedances for uranium. Exceedances for total dissolved solids, sulfate, manganese, and iron were generally between about 10 and 20 percent for the bedrock-aquifer samples. Radon concentrations, which were only measured in samples collected from two of the bedrock aquifers, exceeded the lower proposed drinking-water standard for more than 90 percent of samples but exceeded the higher alternative standard for less than 5 percent of samples. Pesticide compounds and volatile organic compounds were detected in 3 and 22 percent, respectively, of bedrock-aquifer samples, all at concentrations that were that were much less than drinking-water standards. Water-quality data were synthesized to evaluate factors that affect spatial and depth variability in water quality and to assess aquifer vulnerability to contaminants from geologic materials and those of human origin. The quality of shallow groundwater in the alluvial aquifer and shallow bedrock aquifer system has been adversely affected by development of agricultural and urban areas. Land use has altered the pattern and composition of recharge. Increased recharge from irrigation water has mobilized dissolved constituents and increased concentrations in the shallow groundwater. Concentrations of most constituents associated with poor or degraded water quality in shallow groundwater decreased with depth; many of these constituents are not geochemically conservative and are affected by geochemical reactions such as oxidation-reduction reactions. Groundwater age tracers provide additional insight into aquifer vulnerability and help determine if young groundwater of potentially poor quality has migrated to deeper parts of the bedrock aquifers used for drinking-water supply. Age-tracer results were used to group samples into categories of young, mixed, and old groundwater. Groundwater ages transitioned from mostly young in the water-table wells to mostly mixed in the shallowest bedrock aquifer, the Dawson aquifer, to mostly old in the deeper bedrock aquifers. Although the bedrock aquifers are mostly old groundwater of good water quality, several lines of evidence indicate that young, contaminant-bearing recharge has reached shallow to moderate depths in some areas of the bedrock aquifers. The Dawson aquifer is the most vulnerable of the bedrock aquifers to contamination, but results indicate that the older (deeper) bedrock aquifers are also vulnerable to groundwater contamination and that mixing with young recharge has occurred in some areas. Heavy pumping has caused water-level declines in the bedrock aquifers in some parts of the Denver Basin, which has the potential to enhance the transport of contaminants from overlying units. Results of this study are consistent with the existing conceptual understanding of aquifer processes and groundwater issues in the Denver Basin and add new insight into the vulnerability of the bedrock aquifers to groundwater contamination.

Colorado

Environmental setting of fixed sites in the western Lake Michigan drainages, Michigan and Wisconsin

This report describes selected environmental- setting features for 11 fixed surface-water sites in the Western Lake Michigan Drainages study unit of the National Water-Quality Assessment Pro- gram. The study unit, which includes 10 major river systems draining to Lake Michigan, is bounded on the south by the Illinois State line and extends north to about 31 miles north of Escanaba, Mich. The fixed sites are on the following streams: Peshekee River, Popple River, Menominee River, Pensaukee River, Duck Creek, Tomorrow River, East River, Fox River, North Branch Milwaukee River, Lincoln Creek, and Milwaukee River. Drainage basins above these sites receive runoff from land uses and land covers, bedrock types, and surficial deposits representative of the main types of each of these characteristics in the study unit. Data types collected at the fixed sites include water chemistry; organic compounds and trace elements in streambed sediment and biological tissues; algal, benthic-invertebrate, and fish communities; and aquatic habitat. Field measurements include water temperature, pH, specific conductance, alkalinity, and dissolved oxygen. Results of water- quality field measurements indicate little variation in temperature among the fixed sites. Specific conductance and alkalinity were generally higher at sites underlain by carbonate bedrock than at sites underlain by igneous/metamorphic bedrock. Differences in pH among the fixed sites were less than those for specific conductance and alkalinity, but pH seemed to increase slightly from north to south. Dissolved-oxygen concentration varied more at agricultural sites than at forested and urban sites, perhaps because of higher nutrient inputs at agricultural sites. The information included in this report has been assembled as reference material for ongoing studies at the fixed sites.

Water-Resources Investigations Report

Geochemistry of groundwater in the Beaver and Camas Creek drainage basins, eastern Idaho

The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, is studying the fate and transport of waste solutes in the eastern Snake River Plain (ESRP) aquifer at the Idaho National Laboratory (INL) in eastern Idaho. This effort requires an understanding of the natural and anthropogenic geochemistry of groundwater at the INL and of the important physical and chemical processes controlling the geochemistry. In this study, the USGS applied geochemical modeling to investigate the geochemistry of groundwater in the Beaver and Camas Creek drainage basins, which provide groundwater recharge to the ESRP aquifer underlying the northeastern part of the INL. Data used in this study include petrology and mineralogy from 2 sediment and 3 rock samples, and water-quality analyses from 4 surface-water and 18 groundwater samples. The mineralogy of the sediment and rock samples was analyzed with X-ray diffraction, and the mineralogy and petrology of the rock samples were examined in thin sections. The water samples were analyzed for field parameters, major ions, silica, nutrients, dissolved organic carbon, trace elements, tritium, and the stable isotope ratios of hydrogen, oxygen, carbon, sulfur, and nitrogen. Groundwater geochemistry was influenced by reactions with rocks of the geologic terranes—carbonate rocks, rhyolite, basalt, evaporite deposits, and sediment comprised of all of these rocks. Agricultural practices near and south of Dubois and application of road anti-icing liquids on U.S. Interstate Highway 15 were likely sources of nitrate, chloride, calcium, and magnesium to groundwater. Groundwater geochemistry was successfully modeled in the alluvial aquifer in Camas Meadows and the ESRP fractured basalt aquifer using the geochemical modeling code PHREEQC. The primary geochemical processes appear to be precipitation or dissolution of calcite and dissolution of silicate minerals. Dissolution of evaporite minerals, associated with Pleistocene Lake Terreton, is an important contributor of solutes in the Mud Lake-Dubois area. Oxidation-reduction reactions are important influences on the chemistry of groundwater at Camas Meadows and the Camas National Wildlife Refuge. In addition, mixing of different groundwaters or surface water with groundwater appears to be an important physical process influencing groundwater geochemistry in much of the study area, and evaporation may be an important physical process influencing the groundwater geochemistry of the Camas National Wildlife Refuge. The mass-balance modeling results from this study provide an explanation of the natural geochemistry of groundwater in the ESRP aquifer northeast of the INL, and thus provide a starting point for evaluating the natural and anthropogenic geochemistry of groundwater at the INL.

Idaho

Chemistry of ground water in the Silver Springs basin, Florida, with an emphasis on nitrate

The Silver Springs group, in central Marion County, Florida, has a combined average discharge rate of 796 cubic feet per second and forms the headwaters of the Silver River. The springs support a diverse ecosystem and are an important cultural and economic resource. Concentrations of nitrite-plus-nitrate (nitrate-N) in water from the Main Spring increased from less than 0.5 milligrams per liter (mg/L) in the 1960s to about 1.0 mg/L in 2003. The Upper Floridan aquifer supplies the ground water to support spring discharge. This aquifer is at or near land surface in much of the ground-water basin; nutrients leached at land surface can easily percolate downward into the aquifer. Sources of nitrogen in ground water in the Silver Springs basin include atmospheric deposition, fertilizers used by agricultural and urban activities, and human and animal wastes. During 2000-2001, 56 wells in the area contributing recharge to Silver Springs were sampled for major ions, nutrients, and some trace constituents. Selected wells also were sampled for a suite of organic constituents commonly found in domestic and industrial wastewater and for the ratio of nitrogen isotopes (15N/14N) to better understand the sources of nitrate. Wells were selected to be representative of both confined and unconfined conditions of the Upper Floridan aquifer, as well as a variety of land-use types. Data from this study were compared to data collected from 25 wells in 1989-90. Concentrations of nitrate-N in ground water during this study ranged from less than the detection limit of 0.02 to 12 mg/L, with a median of 1.2 mg/L. For data from 1989-90, the range was from less than 0.02 to 3.6 mg/L, with a median of 1.04 mg/L. Water from wells in agricultural land-use areas had the highest median nitrate-N concentration (1.7 mg/L), although it is uncertain if the 12 mg/L maximum concentration was influenced by land-use activities or proximity to a septic tank. The median value for all urban land-use areas was 1.15 mg/L. Because fewer wells were in rangeland or forested areas, those categories were grouped together. The median concentration for that group was 0.09 mg/L. The ratio of 15N/14N in ground-water samples ranged from -0.5 to 11.5 per mil. The median value for ground-water samples from 35 wells, 4.9 per mil, is near the top of the range that indicates inorganic nitrogen sources. In agricultural areas, the median 15N/14N was 4.8 per mil, indicating mostly inorganic (fertilizer) sources. In urban areas, the median 15N/14N was 5.4 per mil, indicating more influence of organic nitrogen (N) sources. Thus, in both agricultural and urban areas, fertilizer is an important inorganic source of N in ground water (and, therefore, in spring water as well). The influence of organic N is more apparent in urban areas than in agricultural areas. Two distinct 15N/14N values were observed in water from the Main Spring, one indicating an inorganic nitrogen source and the other indicating a mixture of sources with a strong influence of organic nitrogen. Thirty-five wells and three springs of the Silver Springs group (the Main Spring, the Abyss, and the Blue Grotto) were sampled for a suite of 63 compounds common in wastewater. A total of 38 compounds was detected, nearly all in very low concentrations. The most frequently detected compound was the insecticide N,N-diethyl-meta-toluamide (DEET), which was detected in water from 27 wells and all three springs. The presence or absence of DEET in ground-water samples did not seem to be related to land use; however, hydrogeologic conditions at the well sites (confined or unconfined) generally did affect the presence or absence of DEET in the ground water. DEET also appears to be a useful tracer for the presence of reused water. Water samples were collected from the Main Spring and two other springs of the Silver Springs group and analyzed for concentrations of dissolved gasses and for chlorofluorocarbons (CFCs), sulfur hexaflu

Scientific Investigations Report

Factors Affecting Spatial and Temporal Variability in Nutrient and Pesticide Concentrations in the Surficial Aquifer on the Delmarva Peninsula

Water quality in the unconfined, unconsolidated surficial aquifer on the Delmarva Peninsula is influenced by the availability of soluble ions from natural and human sources, and by geochemical factors that affect the mobility and fate of these ions within the aquifer. Ground-water samples were collected from 60 wells completed in the surficial aquifer of the peninsula in 2001 and analyzed for major ions, nutrients, and selected pesticides and degradation products. Analytical results were compared to similar data from a subset of sampled wells in 1988, as well as to land use, soils, geology, depth, and other potential explanatory variables to demonstrate the effects of natural and human factors on water quality in the unconfined surficial aquifer. This study was conducted as part of the National Water-Quality Assessment Program of the U.S. Geological Survey, which is designed (in part) to describe the status and trends in ground-water quality and to provide an understanding of natural and human factors that affect ground-water chemistry in different parts of the United States. Results of this study may be useful for water-resources managers tasked with addressing water-quality issues of local and regional importance because the surficial aquifer on the Delmarva Peninsula is a major source of water for domestic and public supply and provides the majority of flow in local streams. Human impacts are apparent in ground-water quality throughout the surficial aquifer. The surficial aquifer on the Delmarva Peninsula is generally sandy and very permeable with well-oxygenated ground water. Dissolved constituents found throughout various depths of the unconfined aquifer are likely derived from the predominantly agricultural practices on the peninsula, although effects of road salt, mineral dissolution, and other natural and human influences are also apparent in some areas. Nitrate occurred at concentrations exceeding natural levels in many areas, and commonly exceeded 10 milligrams per liter (as nitrogen). In addition to land use in the aquifer recharge area, concentrations of nitrate in ground water are related to regional patterns in soil drainage that affect underlying aquifer redox conditions. Over the peninsula, nitrate concentrations are not related to recharge date of the water, but are positively correlated with depth in shallow wells screened beneath agricultural areas. Nitrate concentrations increased in oxic areas (dissolved oxygen greater than 1 milligram per liter) of the deeper part of the surficial aquifer used for domestic supply by an average of about 2 milligrams per liter between 1988 and 2001, although no changes were apparent in shallower parts of the aquifer over that same period. Water in the surficial aquifer generally flows from land-surface recharge to surface-water discharge areas in less than 30 years. As a result, the entire flow system in the surficial aquifer has likely been affected by human activities on and near the land surface over the past several decades. Pesticide compounds occurred widely at low levels throughout the surficial aquifer. The most commonly used herbicides (metolachlor, alachlor, and atrazine) were the most commonly detected. These pesticides primarily occurred in ground water in the form of degradation products. The widespread occurrence of these and other pesticide compounds reflects their abundant use as well as chemical properties and aquifer characteristics that allow their movement into ground water. Mixtures of pesticides are common. Most samples contained at least 3 different compounds; several samples contained as many as 11. Pesticide concentrations in the surficial aquifer are relatively high beneath recharge areas with well-drained soils in the shallow part of the aquifer and in oxic environments throughout the surficial aquifer. Concentrations are generally below existing drinking-water standards, although standards are not available for all of the pesticide compound

Scientific Investigations Report

Nutrient Enrichment in Estuaries from Discharge of Shallow Ground Water, Mt. Desert Island, Maine

Nutrient enrichment from atmospheric deposition, agricultural activities, wildlife, and domestic sources is a concern at Acadia National Park because of the potential problem of water-quality degradation and eutrophication in its estuaries. Water-quality degradation has been observed at the Park?s Bass Harbor Marsh estuary but not in Northeast Creek estuary. Previous studies at Acadia National Park have estimated nutrient inputs to estuaries from atmospheric deposition and surface-water runoff, but the importance of shallow ground water that may contain nutrients derived from domestic or other sources is unknown. Northeast Creek and Bass Harbor Marsh estuaries were studied to (1) identify shallow ground-water seeps, (2) assess the chemistry of the water discharged from selected seeps, and (3) assess the chemistry of ground water in shallow ground-water hyporheic zones. The hyporheic zone is defined here as the region beneath and lateral to a stream bed, where there is mixing of shallow ground water and surface water. This study also provides baseline chemical data for ground water in selected bedrock monitoring wells and domestic wells on Mt. Desert Island. Water samples were analyzed for concentrations of nutrients, wastewater compounds, dissolved organic carbon, pH, dissolved oxygen, temperature and specific conductance. Samples from bedrock monitoring wells also were analyzed for alkalinity, major cations and anions, and trace metals. Shallow ground-water seeps to Northeast Creek and Bass Harbor Marsh estuaries at Acadia National Park were identified and georeferenced using aerial infrared digital imagery. Monitoring included the deployment of continuously recording temperature and specific conductance sensors in the seep discharge zone to access marine or freshwater signatures related to tidal flooding, gradient-driven shallow ground-water flow, or shallow subsurface flow related to precipitation events. Many potential shallow ground-water discharge zones were identified from aerial thermal imagery during flights in May and December 2003 in both estuaries. The occurrence of ground-water seeps was confirmed using continuous and discrete measurements of temperature and specific conductance in selected seeps and in the adjacent estuaries that showed salinity anomalies reflecting the input of freshwater in these complex tidal systems. Analysis of water samples from shallow ground water in the hyporheic zone and from ground-water seeps indicated the presence of elevated concentrations of dissolved nitrogen, compared to concentrations in the adjacent estuaries and surface-water tributaries draining into the estuaries. These findings indicate that shallow ground water is a source of dissolved nitrogen to the estuaries. Orthophosphate levels were low in ground water in the hyporheic zone in Bass Harbor Marsh, but somewhat higher in one hyporheic-zone well in Northeast Creek compared with the concentrations in both estuaries that were at or below detection limits. Household wastewater-related compounds were not detected in ground water in the hyporheic zone. Analysis of water samples from domestic and bedrock monitoring wells developed in fractured bedrock indicated that concentrations of dissolved nitrogen, phosphorus, and household wastewater-related compounds were typically at or below detection, suggesting that the aquifers sampled had not been contaminated from septic sources.

Scientific Investigations Report

Relation of arsenic, iron, and manganese in ground water to aquifer type, bedrock lithogeochemistry, and land use in the New England coastal basins

In a study of arsenic concentrations in public-supply wells in the New England Coastal Basins, concentrations at or above 0.005 mg/L (milligrams per liter) were detected in more samples of water from wells completed in bedrock (25 percent of all samples) than in water from wells completed in stratified drift (7.5 percent of all samples). Iron and manganese were detected (at concentrations of 0.05 and 0.03 mg/L, respectively) at approximately the same frequency in water from wells in both types of aquifers. Concentrations of arsenic in public-supply wells drilled in bedrock (in the National Water-Quality Assessment Program New England Coastal Basins study unit) vary with the bedrock lithology. Broad groups of lithogeochemical units generalized from bedrock lithologic units shown on state geologic maps were used in the statistical analyses. Concentrations of arsenic in water from public-supply wells in metasedimentary bedrock units that contain slightly to moderately calcareous and calcsilicate rocks (lithogeochemical group M c ) were significantly higher than the concentrations in five other groups of bedrock units in the study unit. Arsenic was detected, at or above 0.005 mg/L, in water from 44 percent of the wells in the lithogeochemical group M c and in water from less than 28 percent of wells in the five other groups. Additionally, arsenic concentrations in ground water were the lowest in the metasedimentary rocks that are characterized as variably sulfidic (group M s ). Generally, concentrations of arsenic were low in water from bedrock wells in the felsic igneous rocks (group I f ) though locally some bedrock wells in granitic rocks are known to have ground water with high arsenic concentrations, especially in New Hampshire. The concentrations of arsenic in ground water also correlate with land-use data; significantly higher concentrations are found in areas identified as agricultural land use than in undeveloped areas. There is, however, more agricultural land in areas overlying the metasedimentary rocks of lithogeochemical groups M c and the minimally-deformed clastic sediments of group M md than in areas overlying other lithogeochemical groups. This correlation complicates the interpretation of sources of arsenic to ground water in bedrock. A test of this association revealed that relations between arsenic concentrations and the metasedimentary rocks of group M c are not weakened when data associated with agricultural land use is removed; the reverse is true, however, if the data associated with the group M c are removed from the analysis. The occurrence and variability of arsenic in water from bedrock supply wells could be related to several factors. These include (1) the distribution and chemical form of arsenic in soils and rocks that are part of the ground-water-flow system, (2) the characteristics that influence the solubility and transport of arsenic in ground water, (3) the differing degrees of vulnerability of ground-water supplies to surface contamination, and (4) the spatial associations between land use, geology, and ground-water-flow patterns. Strong relations between agricultural land use and the metasedimentary rocks of group M c complicate the interpretation of arsenic source to water in these bedrock aquifers. This is due in part to the past use of arsenical pesticides; additionally, few whole-rock geochemical data are available for the rock types in the lithogeochemical groups of aquifers that contain ground water with elevated concentrations of arsenic. Without such data, identifying specific bedrock types as arsenic sources is not possible. In southern Maine and south-central New Hampshire, and in northern Massachusetts, the few available whole-rock analyses suggest, at least for these local areas, a connection between known bedrock chemistry and ground-water arsenic levels. Although the lithogeochemical group and land-use category variables individually describe much of the variance in the concentrations of arsenic in ground water, the lithogeochemical relation is statistically stronger than the land-use relation. Low concentrations of arsenic in water from bedrock public-supply wells are associated with the metasedimentary rocks of group M s (characterized as variably sulfidic). This association could reflect a variety of factors and suggests that simple dissolution of arsenic-bearing iron phases, such as sulfides, may not explain concentrations of arsenic in water in this bedrock aquifer group. Whole-rock geochemical data and more complete water-chemistry data, as well as studies of historical variation of arsenic concentrations (time-line studies), and site-specific studies, will be critical in addressing the arsenic source issue.

New England coastal basins