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USGS2020

Legacy and contaminants of emerging concern (CECs) in tree swallows along an agricultural to industrial gradient: Maumee River, OH

Exposure to multiple classes of contaminants, both legacy and contaminants of emerging concern (CECs), were assessed in tree swallow ( Tachycineta bicolor ) tissue and diet samples from 6 sites along the Maumee River, Ohio, USA, to understand both exposure and possible effects of exposure to those CECs for which there are little avian data. The 6 sites represented a gradient from intensive agriculture upstream to highly urbanized and industrial landscapes downstream; 1 or 2 remote Wisconsin lakes were assessed for comparative purposes. Cytochrome P450 induction, DNA damage, and thyroid function were also assessed relative to contaminant exposure. Bioaccumulative CECs, such as polybrominated diphenyl ethers (PBDEs) and perfluorinated substances, did not follow any upstream to downstream gradient; but both had significantly greater concentrations along the Maumee River than at the remote lake sites. Greater exposure to PBDEs was apparent in swallows at or near wastewater‐treatment facilities than at other sites. Total polychlorinated biphenyl and total polycyclic aromatic hydrocarbon concentrations were greater in swallows at downstream locations compared to upstream sites and were associated with higher ethoxyresorufin‐ O ‐dealkylase activity. Few herbicides or nonorganochlorine insecticides were detected in swallow tissues or their food, except for atrazine and its metabolite desethylatrazine. Few pharmaceuticals and personal care products were detected except for DEET and iopamidol. Both were detected in most liver samples but not in eggs, as well as detected at the remote lake sites. This is one of the most comprehensive assessments to date of exposure and effects of a wide variety of CECs in birds.

Ohio↗

USGS1970

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from activities of man. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural fresh water. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position: of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken all together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in composition of moving water and the effects of particulate suspended material. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, most probable forms of elements and ions in solution, solubility controls, expected concentration ranges and other chemical factors. Concentrations of elements that are commonly present in amounts less than a few tens of micrograms per liter cannot always be easily explained, but present information suggests many are controlled by solubility of hydroxide or carbonate or by sorption on solid particles. Chemical analyses may be grouped and statistically evaluated by averages, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among waters, probable sources of solutes, areal water-quality regimen, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrologic parameters, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 75 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also utilized in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Activities of man may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of sea water in ground-water aquifiers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural water composition is required for rational management of water quality.

Water Supply Paper↗

USGS1959

Study and interpretation of the chemical characteristics of natural water

Water Supply Paper↗

USGS2009

Regression models for explaining and predicting concentrations of organochlorine pesticides in fish from streams in the United States

Empirical regression models were developed for estimating concentrations of dieldrin, total chlordane, and total DDT in whole fish from U.S. streams. Models were based on pesticide concentrations measured in whole fish at 648 stream sites nationwide (1992-2001) as part of the U.S. Geological Survey's National Water Quality Assessment Program. Explanatory variables included fish lipid content, estimates (or surrogates) representing historical agricultural and urban sources, watershed characteristics, and geographic location. Models were developed using Tobit regression methods appropriate for data with censoring. Typically, the models explain approximately 50 to 70% of the variability in pesticide concentrations measured in whole fish. The models were used to predict pesticide concentrations in whole fish for streams nationwide using the U.S. Environmental Protection Agency's River Reach File 1 and to estimate the probability that whole-fish concentrations exceed benchmarks for protection of fish-eating wildlife. Predicted concentrations were highest for dieldrin in the Corn Belt, Texas, and scattered urban areas; for total chlordane in the Corn Belt, Texas, the Southeast, and urbanized Northeast; and for total DDT in the Southeast, Texas, California, and urban areas nationwide. The probability of exceeding wildlife benchmarks for dieldrin and chlordane was predicted to be low for most U.S. streams. The probability of exceeding wildlife benchmarks for total DDT is higher but varies depending on the fish taxon and on the benchmark used. Because the models in the present study are based on fish data collected during the 1990s and organochlorine pesticide residues in the environment continue to decline decades after their uses were discontinued, these models may overestimate present-day pesticide concentrations in fish. ?? 2009 SETAC.

Environmental Toxicology and Chemistry↗

USGS1999

Hydroxyatrazine in soils and sediments

Hydroxyatrazine (HA) is the major metabolite of atrazine in most surface soils. Knowledge of HA sorption to soils, and its pattern of stream water contamination suggest that it is persistent in the environment. Soils with different atrazine use histories were collected from four sites, and sediments were collected from an agricultural watershed. Samples were exhaustively extracted with a mixed—mode extractant, and HA was quantitated using high performance liquid chromatography with UV detection. Atrazine, deethylatrazine (DEA), and deisopropylatrazine (DIA) were also measured in all samples. Concentrations of HA were considerably greater than concentrations of atrazine, DEA, and DIA in all soils and sediments studied. Soil concentrations of HA ranged from 14 to 640 μg/kg with a median concentration of 84 μg/kg. Sediment concentrations of HA ranged from 11 to 96 μg/kg, with a median concentration of 14 μg/kg. Correlations of HA and atrazine concentrations to soil properties indicated that HA levels in soils were controlled by sorption of atrazine. Because atrazine hydrolysis is known to be enhanced by sorption and pH extremes, soils with high organic matter (OM) and clay content and low pH will result in greater atrazine sorption and subsequent hydrolysis. Significant correlation of HA concentrations to OM, pH, and cation exchange capacity of sediments indicated that mixed—mode sorption (i.e., binding by cation exchange and hydrophobic interactions) was the mechanism controlling HA levels in sediment. The presence of HA in soils and stream sediments at the levels observed support existing hypotheses regarding its transport in surface runoff. These results also indicated that persistence of HA in terrestrial and aquatic ecosystems is an additional risk factor associated with atrazine usage.

Environmental Toxicology and Chemistry↗

USGS2010

Pyrethroid insecticide concentrations and toxicity in streambed sediments and loads in surface waters of the San Joaquin Valley, California, USA

Pyrethroid insecticide use in California, USA, is growing, and there is a need to understand the fate of these compounds in the environment. Concentrations and toxicity were assessed in streambed sediment of the San Joaquin Valley of California, one of the most productive agricultural regions of the United States. Concentrations were also measured in the suspended sediment associated with irrigation or storm‐water runoff, and mass loads during storms were calculated. Western valley streambed sediments were frequently toxic to the amphipod, Hyalella azteca , with most of the toxicity attributable to bifenthrin and cyhalothrin. Up to 100% mortality was observed in some locations with concentrations of some pyrethroids up to 20 ng/g. The western San Joaquin Valley streams are mostly small watersheds with clay soils, and sediment‐laden irrigation runoff transports pyrethroid insecticides throughout the growing season. In contrast, eastern tributaries and the San Joaquin River had low bed sediment concentrations (<1 ng/g) and little or no toxicity because of the preponderance of sandy soils and sediments. Bifenthrin, cyhalothrin, and permethrin were the most frequently detected pyrethroids in irrigation and storm water runoff. Esfenvalerate, fenpropathrin, and resmethrin were also detected. All sampled streams contributed to the insecticide load of the San Joaquin River during storms, but some compounds detected in the smaller creeks were not detected in the San Joaquin River. The two smallest streams, Ingram and Hospital Creeks, which had high sediment toxicity during the irrigation season, accounted for less than 5% of the total discharge of the San Joaquin River during storm conditions, and as a result their contribution to the pyrethroid mass load of the larger river was minimal.

California↗

USGS1985

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in the composition of moving water and by the effects of particulate suspended material. Some constituents are unstable and require onsite determination or sample preservation. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, the most probable forms of elements and ions in solution, solubilitycontrols, expected concentration ranges, and other chemical factors. Mechanisms that control concentrations of elements commonly present in amounts less than a few tens of micrograms per liter cannot always be easily ascertained, but present information suggests that many are controlled by solubility of their hydroxides or carbonates or by sorption on solid particles. Many dissolved organic compounds can now be specifically determined. Chemical analyses may be grouped and statistically evaluated by means, medians, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among water, probable sources of solutes, areal water-quality regimen, temporal and spatial variation, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrogeologic characteristics, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 80 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also used in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Human activities may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of seawater in groundwater aquifers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural-water composition is required for rational management of water quality.

Water Supply Paper↗

USGS2026

Multiple-well monitoring site adjacent to the Midway- Sunset and Buena Vista Oil Fields, Kern County, California

Groundwater quality in and around oil fields in the Southern San Joaquin Valley is of interest to many California residents that rely heavily on groundwater for domestic, commercial, and agricultural use. To help assess the effects of historical oil-field activities and natural geologic sources on groundwater near the southwest margins of the Kern County Groundwater Subbasin, a multiple-well monitoring site was installed near the administrative boundary between the Midway-Sunset and Buena Vista Oil Fields in Kern County, California. The installation of the Midway-Sunset Buena Vista multiple-well monitoring site (MSBV) supports regional analysis of the relations of oil and gas sources to groundwater quality by providing information about the geology, hydrology, geophysical properties, and water quality of the alluvial and upper Tulare aquifers in areas where groundwater data were limited. Data collected from the site included drill cuttings, whole core samples, sidewall core samples, mud-gas analysis, borehole geophysical logs, depth to water measurements, and water quality samples. Whole cores were scanned using dual energy computed tomography. Subsamples of selected cores were analyzed for density, porosity, specific retention, and bulk minerology. Thin sections of the subsamples were prepared, photographed, and examined. Two samples were analyzed using scanning electron microscope technology to examine the microporosity of diatomite laden sediment. Instrumentation installed in the wells collect hourly depth to water measurements. Analysis of the data show there is 355 feet of alluvium overlying the Tulare Formation at the well site. The contact between the two formations is an aquitard resulting in a perched aquifer in the alluvium and unconfined aquifer in the Tulare Formation. The alluvium is more heterogenous and finer grained than the Tulare Formation resulting in markedly higher porosity in the alluvium compared to the Tulare Formation. Higher specific retention observed in the alluvium is attributed to the finer grained sediment and greater abundance of reworked diatomite (as represented by opal-CT [cristobalite-tridymite]) compared to the Tulare Formation. Total dissolved solids (TDS) approached or exceeded 10,000 milligrams per liter (mg/L) in the alluvium from approximately 176 to 242 feet below land surface and at the top of the Amnicola clay at approximately 670 feet below land surface within the Tulare Formation. Elevated TDS, chloride, and boron concentrations in the alluvium and on top of the Amnicola clay likely reflect groundwater that is mixed with oil-field water. Water chemistry and modern-aged groundwater in the alluvial monitoring well (MSBV #3) are consistent with the oil-field water in the alluvium being derived from documented historical surface disposal of oil-field water upslope (northwest) of the site. Water chemistry and pre-modern groundwater age in the deeper Tulare monitoring well (MSBV #1) on top of the Amnicola clay are consistent with oil-field fluids derived from upslope natural geologic sources or old oil wells that leak in the subsurface. Shallow groundwater in the Tulare (MSBV #2) is not affected by mixing with oil-field sources.

EarthArXiv↗

USGS2025

Potential for biological effects of per- and polyfluoroalkyl substances in Great Lakes tributaries and associations with land cover and wastewater effluent

Surface water concentrations of per- and polyfluoroalkyl substances (PFAS) and potential for resulting biological effects were estimated in a study using polar organic chemical integrative samplers (POCIS) from 60 tributary sites within 20 watersheds in the Great Lakes Basin in 2018. Sites represented a range of urban to agricultural, forested, and wetland land uses and included a gradient of wastewater treatment effluent from zero to 44% of annual streamflow. Several sites also had airport influence. Twenty-one of 32 targeted PFAS compounds were detected in POCIS samplers, of which, 16 had available POCIS sampling rates, enabling time-weighted water concentration estimates and comparison with available effects data. Estimated water concentrations were compared with published water quality guidelines (available for nine PFAS), effect concentrations reported in primary literature within the ECOTOX Knowledgebase for apical endpoints (10 PFAS) and nonapical endpoints (10 PFAS), and in vitro high-throughput screening data from the U.S. Environmental Protection Agency Toxicity Forecaster (ToxCast; 14 PFAS). Based on a conservative evaluation approach that was also weighted for persistence and limitations in available toxicological information, five individual PFAS, including perfluorooctanesulfonic acid, perfluorohexanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanoic acid, and perfluorononanoic acid were identified as warranting additional investigation. Possible increased potency of PFAS mixtures over individual chemical effects, estimated by summation of exposure-activity ratios (EARs) for chemicals that influence common ToxCast assays and specified gene targets, indicated that EAR values increased up to 5.6-fold over individual chemicals, with up to 14 chemicals contributing to mixture effect predictions. Potential for biological effects from PFAS, as estimated by summed exposure-activity ratios, were correlated with urban land use and the proportion of streamflow contributed by wastewater effluent.

Great Lakes tributaries↗

USGS1996

Monitoring exposure of nestling songbirds to agricultural application of an organophosphorus insecticide using cholinesterase activity

In June 1992 we collected 53 blood plasma samples from nestling red‐winged blackbirds ( Agelaius phoeniceus ), house sparrows ( Passer domesticus ), and brown‐headed cowbirds ( Molothrus ater ) at five study sites in northwestern Minnesota to evaluate the feasibility of using plasma and brain cholinesterase (ChE) activity and reactivation as a means of assessing exposure of nontarget organisms to the operational use of ChE‐ inhibiting insecticides in an agricultural setting. Three sites were adjacent to sugar beet fields that were likely to be treated with chlorpyrifos as Lorsban® (an organophosphorus [OP] insecticide) for control of sugar beet root maggot ( Tetanops myopaeformis ), and two sites were distant from fields likely to be treated (reference sites). Application of chlorpyrifos in fields surrounding study plots was monitored through contact with landowners and direct observations. Cholinesterase activity levels (total cholinesterase [ChE], acetylcholinesterase [AChE], and butyrylcholinesterase [BChE]) in nestling plasma were measured and tested for reactivation (ChE and AChE) in the presence of 2–PAM, an indication of exposure to an organophosphorus insecticide. In addition, 11 nestlings were euthanatized and in these samples we measured brain ChE activity and reactivation, and we analyzed gastrointestinal tracts and carcass washes for chlorpyrifos residues. Total ChE and BChE activity were lowest in similar‐aged nestlings at sites adjacent to treated beet fields (ChE, t = −2.51, d.f. = 21, p = 0.033; BChE, t = −2.56, d.f. = 21, p = 0.043). Nestlings from sites that were near fields where chlorpyrifos was applied were more likely to exhibit plasma AChE reactivation than nestlings from reference sites where OP or carbamate insecticide application was improbable (x 2 = 3.805, d.f. = 1, p ∼ 0.05). The magnitude of plasma ChE reactivation was highest within 1 to 3 d of insecticide application, although significant reactivation was measured up to 11 d after application of chlorpyrifos. Plasma AChE reactivation in the presence of pyridine‐2–aldoxime methochloride (2–PAM) appeared to be a more sensitive indicator of exposure to chlorpyrifos than plasma ChE or BChE activity levels.

Environmental Toxicology and Chemistry↗

USGS1993

National water summary 1990-91: Hydrologic events and stream water quality

National Water Summary 1990-91 Hydrologic Events and Stream Water Quality was planned to complement existing Federal-State water-quality reporting to the U.S. Congress that is required by the Clean Water Act of 1972. This act, formally known as the Federal Water Pollution Control Act Amendments of 1972 (Public Law 92-500), and its amendments in 1977,1979,1980,1981,1983, and 1987, is the principal basis for Federal-State cooperation on maintaining and reporting on water quality in the United States. Under section 305(b) of the Clean Water Act, the States must designate uses for waterbodies, biennially assess whether the waterbodies meet designated uses, and report to the U.S. Environmental Protection Agency (EPA), which in turn summarizes the findings of the State assessments in a biennial National Water Quality Inventory report to the Congress. This volume of the National Water Summary uses a nationally consistent data base and methods of statistical analysis to document stream water quality in the United States, Puerto Rico, and the Western Pacific Islands. As a basis for preparation of this report, the U.S. Geological Survey (uses) created a data base of waterquality data from about 2,900 stream water-quality monitoring stations in the United States (Lanfear, 1993). These data, which were extracted primarily from the uses National Water Information System (NWIS) and supplemented with data from the EPA national data base known as STORET, consisted mostly of water-chemistry and physical-sediment data. About 1,400 of these stations met a criterion, used in this volume for trends analysis of data, of having a period of record that began before water year 1980. (A water year is the period from October 1 through September 30 and is identified by the calendar year at the end of the period.) Inasmuch as the determination of trends requires about 10 years of data, few biological data were suitable for trends analysis because biological indicators of water quality were not being collected extensively by water year 1980. Also, because of the lack of long-term data, an assessment of the water quality of lakes and reservoirs is not included in this National Water Summary . Constituent and waterproperty data were selected from this data base and analyzed with statistical techniques that have been used extensively by the uses to summarize conditions and trends in water quality. (Throughout the remainder of this article, the term "constituent" is used also to represent water properties, such as pH and alkalinity.) Selected results from this analysis are presented graphically, both by State and nationally, in this volume. The data base created for preparation of this volume and the resulting nationally consistent statistical analysis of these data provide a unique opportunity to compare and contrast stream water-quality conditions and trends nationally and State by State. Because of the complexity of water quality and the natural seasonal and diurnal variations in the concentrations of waterquality constituents, the determination of trends in water quality requires a relatively long period of record. Trends in constituent concentrations in the State summaries in this volume were calculated for one or more of four periods water years 1970-89,1975-89,1980- 89, and 1982-89. Unfortunately, few water-quality monitoring stations have periods of record of more than 10 or 15 years, and therefore most analyses in the State summaries were done for 8- or 10-year periods. Although interest in water quality has continued to heighten since passage of the Clean Water Act, funds for support of data-collection programs are limited and data records of many of the constituents now of current concern, especially organic constituents, do not exist or are less than 10-years long; consequently only a modest number of organic constituents are presented in this volume. Discussion of conditions and trends in water quality in this National Water Summary also draw upon information about land use, population, water use, application of agricultural chemicals in rural areas, the siting of industrial facilities, and other ancillary information. Because the results of analysis of a restricted number of constituents are presented in this volume, State 305(b) reports also are cited in the discussion of water quality in each State. The following discussion is an overview of the three parts of this 1990-91 National Water Summary - "Hydrologic Conditions and Water-Related Events, Water Years 1990-91," "Hydrologic Perspectives on Water Issues," and "State Summaries of Stream Water Quality."

Water Supply Paper↗

USGS1995

Hydrogeology and water quality at the management systems evaluation area near Piketon, Ohio

This report presents the results of a study by the U.S. Geological Survey, The Ohio State University, and the U.S. Department of Agriculture to describe the hydrology, water quality, and geochemical factors controlling water quality at the Ohio Management Systems Evaluation Area (MSEA). The Ohio MSEA is located on a 650-acre farm in the Scioto River Valley in Pike County, south-central Ohio. The farm is underlain by an incised bedrock valley filled with about 70 feet of sand and gravel outwash deposits that are covered by a veneer of silty clay alluvium and silty loam and sandy loam soils. Outwash sediment are composed predominantly of dolomite, quartz, and calcite, and have a median organic carbon concentration of 0.39 weight percent. Horizontal hydraulic conductivity of the sediment based on results of multiple-well aquifer tests ranges from 400 to 560 feet per day. Ground-water flow is from east to west-southwest at an average velocity of 1.5 to 2.5 feet per day. Ground water and surface water at the site are highly interconnected. Big Beaver Creek recharges the outwash aquifer along the eastern edge of the study area, and ground water discharges to the Scioto River at the western edge of the study area. High-stage events on the Scioto River cause frequent flow reversals in the aquifer that allow streamwater to travel a maximum observed distance of 190 feet inland. A zone of oxidizing waters (characterized by high dissolved oxygen concentration and Eh) is found in shallow ground water for several hundred feet adjacent to Big Beaver Creek and the Scioto River. This zone of oxidizing ground water is caused by the periodic inflow of surface waters to the aquifer. A ground-water budget for the study area indicates that the aquifer received 17.7 inches of recharge during water year 1992; of this amount, 72 percent originated as infiltrating precipitation, 28 percent as infiltration of surface water from Big Beaver Creek, and 0.2 percent as leakage from bedrock. Areal variation in water quality is caused by areal differences in the relative importance of these three recharge sources. The effects of bedrock leakage are evident only in the northeast corner of the study area. Here, deep outwash waters are transitional in composition between the calcium magnesium bicarbonate waters found elsewhere in the outwash aquifer and the calcium sodium chloride waters of the bedrock aquifer. Mixing calculations indicate that these deep outwash waters are composed of as much as 26 percent bedrock water. In the southern part of the MSEA, ground water is diluted by surface water from Big Beaver Creek as it recharges the aquifer through a sand and gravel streambed. At the northeast corner of the MSEA, however, Big Beaver Creek flows across a shale streambed through which no infiltration occurs. Redox reactions in the outwash aquifer control variations in aquifer chemistry with depth. From the water table to about 40 feet below land surface, oxidizing conditions are characterized by the presence of dissolved oxygen and nitrates in ground water, Eh greater than 200 millivolts, ferrihydrite coatings on sediment grains, and the absence of dissolved iron and manganese. From about 40 feet below land surface to the base of the aquifer, reducing conditions are characterized by dissolved oxygen concentrations less than 2 mg/L, Eh less than 200 millivolts, and the presence of dissolved iron and manganese. Denitrification in the reducing zone naturally remediates anthropogenic nitrate contamination of the aquifer while oxidizing pyrite in the aquifer sediment.

Ohio↗

USGS2025

Pesticide concentrations in multiple physical and biological stream matrices are impacted by a bioenergy production facility receiving pesticide coated corn seeds

Insecticide and fungicide seed coatings have become prevalent in conventional agriculture in recent decades. From 2015 to 2021, the AltEn bioenergy plant (Mead, Nebraska, USA) generated ethanol from almost 100% unused/expired treated corn seeds. This use of these seeds for ethanol production resulted in the accumulation of large amounts of contaminated wastewater and solid residue, a portion of which was applied to surrounding farmland. To better understand the potential long-term environmental effects from the processing of treated seeds at this facility, five nearby stream sites were sampled in 2022 after the closure of the plant; these included two sites directly impacted by AltEn, one upstream, and two downstream of the impacted sites. Water and sediment were collected in March through July, and algae and fish samples were collected in July for chemical analysis. Overall, 60 pesticide compounds (parents and transformation products) were detected in one or more matrices, including 23 fungicides, 20 insecticides, 16 herbicides, and 1 bacterial growth inhibitor. Pesticide results (maximum detection frequency, maximum concentration) varied substantially by environmental compartment: water (100% multiple pesticides; 4,600 ng L −1 thiamethoxam transformation product (NOA-407475)), algae (100% multiple pesticides, 190 ng g −1 atrazine), sediment (60% dithiopyr, 2.3 ng g −1 acetochlor) and fish (20% pyraclostrobin, 2.2 ng g −1 atrazine). Pesticides associated with treated corn seeds (e.g., insecticides clothianidin, thiamethoxam; fungicides fluoxastrobin, thiabendazole) were detected at significantly higher concentrations ( p < 0.05) in stream water from sites impacted by the AltEn facility compared to non-impacted sites. Study results indicate that pesticides associated with the AltEn facility continue to be a source of contaminants to aquatic systems after the plant’s closure in 2021.

Environmental Toxicology and Chemistry↗

USGS2015

Hydrology of the middle San Pedro area, southeastern Arizona

In the middle San Pedro Watershed in southeastern Arizona, groundwater is the primary source of water supply for municipal, domestic, industrial, and agricultural use. The watershed comprises two smaller subareas, the Benson subarea and the Narrows-Redington subarea. Early 21st century projections for heavy population growth in the watershed have not yet become a reality, but increased groundwater withdrawals could have undesired consequences - such as decreased base flow to the San Pedro River, and groundwater-level declines - that would lead to the need to deepen existing wells. This report describes the hydrology, hydrochemistry, water quality, and development of a groundwater budget for the middle San Pedro Watershed, focusing primarily on the elements of groundwater movement that could be most useful for the development of a groundwater model Precipitation data from Tombstone, Arizona, and base flow at the stream-gaging station on the San Pedro River at Charleston both show relatively dry periods during the 1960s through the mid-1980s and in the mid-1990s to 2009, and wetter periods from the mid-1980s through the mid-1990s. Water levels in four out of five wells near the mountain fronts show cyclical patterns of recharge, with rates of recharge greatest in the early 1980s through the mid-1990s. Three wells near the San Pedro River recorded their lowest levels during the 1950s to the mid-1960s. The water-level record from one well, completed in the confined part of the coarse-grained lower basin fill, showed a decline of approximately 21 meters. Annual flow of the San Pedro River, measured at the Charleston and Redington gages, has decreased since the 1940s. The median annual streamflow and base flow at the gaging station on the river near Tombstone has decreased by 50 percent between the periods 1968–1986 and 1997–2009. Estimates of streamflow infiltration along the San Pedro River during 1914–2009 have decreased 44 percent, with the largest decreases in the months June–October in the Benson subarea. In the Narrows-Redington subarea, streamflow infiltration has decreased about 65 percent during 1914–2009. The average annual outflow (27.6 hm 3 /year [cubic hectometers per year]) from the Benson subarea aquifer for water years 2001 through 2009 exceeded the inflows (20.0 hm 3 / yr) by 7.60 hm 3 /yr. In the Narrows-Redington subarea for the same period, the average annual outflow (15.7 hm 3 /yr) from the aquifer system exceeded the inflows (13.8 hm 3 /yr) by nearly 2 hm 3 /yr. The largest withdrawals of groundwater in both subareas are for irrigation; these withdrawals peaked in 1973 and have been steadily decreasing since then. Recharge from streamflow infiltration exceeded recharge from the mountain-front and from ephemeral channels in the Benson subarea. In the Narrows-Redington subarea, however, recharge from mountain-front and ephemeral channel recharge exceeded recharge from streamflow infiltration. Evapotranspiration by phreatophytes accounts for the largest outflow of groundwater for both subareas—78 percent of the outflow in the Narrows-Redington subarea and 62 percent of the outflow in the Benson subarea. Precipitation, surface-water, and groundwater chemistry and isotope data indicated the relative age and residence time of groundwater, the amount of interaction between geologic sources and groundwater, and how recharge elevation and season were related to the presence of modern water. The bedrock aquifer receives modern recharge (

Arizona↗

USGS2023

Environmental tracers of groundwater source, age, and geochemical evolution

Hexavalent chromium, Cr(VI), was discharged in cooling wastewater to unlined surface ponds from 1952 to 1964 and reached the underlying unconsolidated aquifer at the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California. A suite of environmental tracers was analyzed in water samples collected from more than 100 wells to characterize the source, age, and geochemical evolution of groundwater within and near the Cr(VI) plume in Hinkley and Water Valleys. This information was used to help determine the extent of Cr(VI) associated with releases from the Hinkley compressor station and to identify Cr(VI) associated with natural sources. The source of water in most wells, indicated by stable oxygen and hydrogen isotope values for water, delta oxygen-18 and delta deuterium, was recharge by infiltration of intermittent surface flows in the Mojave River. With the exception of small flows in 1958, the Mojave River was largely dry between 1952 and 1969. This dry period spans the period of Cr(VI) releases from the Hinkley compressor station; 1952–69 also spans the period of high tritium levels in precipitation resulting from the atmospheric testing of nuclear weapons and, as a consequence, tritium concentrations in groundwater in Hinkley Valley were comparatively low. Groundwater ages (time since recharge) increased downgradient from the Mojave River and with depth. Tritium, measured by helium ingrowth with a study reporting level of 0.05 tritium unit, was detected in water from 51 percent of wells, with detectable tritium as far as 7 miles downgradient from the Mojave River. Tritium concentrations were higher, and tritium/helium-3 groundwater ages younger, in water from wells near the Mojave River and in water from shallower wells downgradient. Agricultural pumping has decreased groundwater levels as much as 60 feet since 1952. As a result of this pumping, some groundwater containing tritium, and presumably anthropogenic Cr(VI), has been removed from the aquifer. The distribution of wells having carbon-14 activities near or greater than 100-percent modern carbon, consistent with post-1952 recharge water, was similar to the distribution of wells containing detectable tritium. Carbon-14 activities as low as 8.9-percent modern carbon, with carbon-14 ages (unadjusted for reactions with aquifer materials) of almost 20,000 years before present (ybp), were sampled in water from some deep wells. Hexavalent chromium concentrations in older groundwater were as high as 11 micrograms per liter but did not exceed 3.6 micrograms per liter in older water from wells completed in “Mojave-type” deposits (composed of felsic Mojave River stream and near-shore lake deposits sourced from the Mojave River); this value may represent an upper limit on Cr(VI) concentrations in groundwater within Mojave-type deposits that likely approximates background Cr(VI) concentrations in the study area. Chlorofluorocarbons were released to the atmosphere and hydrologic cycle as a result of industrial activity beginning in the 1930s. Chlorofluorocarbon data were not generally suitable for groundwater-age dating in Hinkley and Water Valley because of nonatmospheric contributions from local sources. Strontium-87/86 isotope ratios and stable chromium isotopes, delta chromium-53, provide information on the geochemical evolution of groundwater in the aquifer. Highly radiogenic strontium-87/86 ratios greater than 0.71000 were present in water from wells completed in coarse-textured Mojave-type deposits having low chromium concentrations but were not diagnostic of these materials. Nonradiogenic strontium-87/86 ratios less than 0.70950 were diagnostic of weathered materials in the northern subarea of Hinkley and in Water Valley that were eroded from Miocene (23–5 million ybp) deposits east of the study area. Values for delta chromium-53 ranged from near 0 to 2.8 parts per thousand (‰) difference. The extent of reductive fractionation, mixing with native groundwater, and longitudinal dispersion within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume can be estimated on the basis of the delta chromium-53 isotope composition of groundwater within the plume. Reduction of Cr(VI) to trivalent chromium, Cr(III), can occur in the presence of natural reductants in oxic groundwater. Although not diagnostic of anthropogenic chromium at the concentrations of interest near the Q4 2015 regulatory Cr(VI) plume margin, delta chromium-53 data indicate anthropogenic Cr(VI) within the plume is not conservative and has reacted with aquifer materials; these reactions have removed some anthropogenic Cr(VI) from groundwater. Environmental tracers, and the distribution of modern (post-1952) and premodern (pre-1952) groundwater, inform understanding of the extent of anthropogenic and naturally occurring Cr(VI) near the Q4 2015 regulatory Cr(VI) plume and the understanding of geochemical processes occurring in and near the margins of the Cr(VI) plume. The oxygen and hydrogen isotope compositions of water, tritium/helium-3 groundwater-age data, and carbon-14 data were used with mineralogy and chemistry data as part of a summative-scale analysis to determine the Cr(VI) plume extent later in this professional paper (chapter G).

California↗

USGS2003

Geohydrologic Framework of Recharge and Seawater Intrusion in the Pajaro Valley, Santa Cruz and Monterey Counties, California

Pajaro Valley is a coastal watershed of 160 square miles located along Monterey Bay north of Elkhorn Slough and south of the city of Santa Cruz. The valley has been predominantly developed for agriculture since the late 1800s. In 1984 the Pajaro Valley Water Management Agency (PVWMA) was formed and was delegated with the responsibility of the management of the water resources within the Pajaro Valley by the State of California. About 84 percent of the water is used for agriculture and 16 percent is used for industrial and municipal water supply; almost all of the demand is supplied by ground water. Ground-water pumpage varies with seasonal and climatic periods. The alluvial aquifers are composed of Quaternary- and Tertiary-aged sediments that are layered marine and terrestrial coarse-grained deposits separated by extensive fine-grained deposits that potentially restrict vertical movement of ground water and seawater intrusion in the coastal subareas. The coarse-grained deposits, which persist over large areas, control pumpage and related seawater intrusion. The Aromas Sand crops out throughout the north and central parts of the PVWMA area and offshore on the continental shelf and in Monterey submarine canyon. Because many of the wells in the coastal and inland subregions are screened at depths of 200 to 400 feet below land surface, a direct avenue is provided for seawater intrusion through the coarse-grained deposits of the shallower alluvium and Aromas Sand. Geophysical logs from monitoring wells indicate discrete zones of saline water that are related to pumpage and seawater intrusion in the aquifers of the shallower alluvium and upper Aromas Sand in the upper-aquifer system and to deeper saline waters in the lower Aromas Sand within the lower-aquifer system. The precipitation data indicate that there were at least nine dry and nine wet periods that range from 2 to 19 years during the period of record, 1880?1997. The ground-water pumpage, runoff, streamflow and related water quality of streamflow also vary with seasonal and climatic periods. Recharge occurs from deep percolation of precipitation and from infiltration of streamflow. Streamflow originates from local runoff and from outside the valley as inflow from the Pajaro River. Although partly regulated, streamflow in the Pajaro River at Chittenden is less than 200 cubic feet per second 88 percent of the time and is less than 12 cubic feet per second 50 percent of the time. Streamflow water-quality data suggest that there may be several sources of poor-quality water that contribute to elevated chloride, sulfate, and nitrate concentrations in streamflow. The poor water quality occurring during lower streamflows indicates that low flows may be an additional source of salinity for ground-water recharge as streamflow infiltration along the Pajaro River. The geochemical data from this study indicate that the two main sources of recharge are deep percolation of local runoff and streamflow infiltration of Pajaro River water. The geophysical and geochemical data suggest that only the shallow alluvial aquifer and parts of the upper Aromas Sand that constitute the upper-aquifer system are being replenished by recent recharge in the coastal areas of Pajaro Valley and represent the renewable ground-water resources. These data also suggest that there is very little vertical flow through the layered aquifer systems in the coastal regions. The confining aquitards are laterally extensive but may be missing in places owing to fluvial erosion or offsetting by fault movement. Geochemical and geophysical data indicate that the ground water from some parts of the upper and lower Aromas Sand in the coastal regions was recharged thousands of years ago and may, in part, represent nonrenewable ground-water resources. The analysis of major-ion chemistry, in combination with isotope and trace-element/chloride ratios, indicates that the coastal ground-water and surface-water samples

Water-Resources Investigations Report↗

USGS2017

Groundwater quality for 75 domestic wells in Lycoming County, Pennsylvania, 2014

Groundwater is a major source of drinking water in Lycoming County and adjacent counties in north-central and northeastern Pennsylvania, which are largely forested and rural and are currently undergoing development for hydrocarbon gases. Water-quality data are needed for assessing the natural characteristics of the groundwater resource and the potential effects from energy and mineral extraction, timber harvesting, agriculture, sewage and septic systems, and other human influences. This report, prepared in cooperation with Lycoming County, presents analytical data for groundwater samples from 75 domestic wells sampled throughout Lycoming County in June, July, and August 2014. The samples were collected using existing pumps and plumbing prior to any treatment and analyzed for physical and chemical characteristics, including nutrients, major ions, metals and trace elements, volatile organic compounds, gross-alpha particle and gross beta-particle activity, uranium, and dissolved gases, including methane and radon-222. Results indicate groundwater quality generally met most drinking-water standards, but that some samples exceeded primary or secondary maximum contaminant levels (MCLs) for arsenic, iron, manganese, total dissolved solids (TDS), chloride, pH, bacteria, or radon-222. Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 9 of the 75 (12 percent) well-water samples, with concentrations as high as 23.6 μg/L; arsenic concentrations were higher than the health advisory level (HAL) of 2 μg/L in 23 samples (31 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 μg/L in 20 of the 75 samples. Total manganese concentrations exceeded the SMCL of 50 μg/L in 20 samples and the HAL of 300 μg/L in 2 of those samples. Three samples had chloride concentrations that exceeded the SMCL of 250 milligrams per liter (mg/L); two of those samples exceeded the SMCL of 500 mg/L for TDS. The pH ranged from 5.3 to 9.15 and did not meet the SMCL range of 6.5 to 8.5 in 22 samples, with 17 samples having a pH less than 6.5 and 8 samples having pH greater than 8.5. Generally, the samples that had elevated TDS, chloride, or arsenic concentrations had high pH. Total coliform bacteria were detected in 39 of 75 samples (52 percent), with Escherichia coli detected in 10 of those 39 samples. Radon-222 activities ranged from non-detect to 7,420 picocuries per liter (pCi/L), with a median of 863 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 50 (67 percent) of the 75 samples; radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 3 samples. Water from 15 of 75 (20 percent) wells had concentrations of methane greater than the reporting level of 0.01 mg/L; detectable methane concentrations ranged from 0.04 to 16.8 mg/L. Two samples had methane concentrations (13.1 and 16.8 mg/L) exceeding the action level of 7 mg/L. Low levels of ethane (up to 0.12 mg/L) were present in the five samples with the highest methane concentrations (near or above 1 mg/L) that were analyzed for hydrocarbon compounds and isotopic composition. The isotopic composition of methane in four of these groundwater samples, from the Catskill and Lock Haven Formations and the Hamilton Group, have sample carbon isotopic ratio delta values (carbon-13/carbon-12) ranging from –42.36 to –36.08 parts per thousand (‰) and hydrogen isotopic ratio delta values (deuterium/protium) ranging from –212.0 to –188.4 ‰, which are consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source of the methane. However, the isotopic composition and ratios of methane to ethane in a fifth sample indicate the methane in that sample may be of microbial origin that subsequently underwent oxidation. The fifth sample had the highest concentration of methane, 16.8 mg/L, with an carbon isotopic ratio delta values of -50.59 ‰ and a hydrogen isotopic ratio delta values of -209.7 ‰. The six well-water samples with the highest methane concentrations also had among the highest pH values (8.25 to 9.15) and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Three of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported at undetermined depth below the freshwater aquifer and for gas and oil well brines in Pennsylvania. The sample with the highest methane concentration and most other samples with low methane concentrations (less than about 1 mg/L) have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt, septic systems, and (or) animal waste. Brines that are naturally present may originate from deeper parts of the aquifer system, while anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land-surface. The spatial distribution of groundwater compositions generally indicate that (1) uplands along the western border of Lycoming County usually have dilute, slightly acidic oxygenated, calcium-bicarbonate type waters; (2) intermediate altitudes or areas of carbonate bedrock usually have water of near neutral pH, with highest amounts of hardness (calcium and magnesium); (3) stream valleys, low elevations where groundwater may be discharging, and deep wells in uplands usually have water with pH values greater than 8 and highest arsenic, sodium, lithium, bromide concentrations. Geochemical modeling indicated that for samples with elevated pH, sodium, lithium, bromide, and alkalinity, the water chemistry could have resulted by dissolution of calcite (calcium carbonate) combined with cation-exchange and mixing with a small amount of brine. Through cation-exchange reactions between water and bedrock, which are equivalent to processes in a water softener, calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. Thus, the assessment of groundwater quality in Lycoming County indicates groundwater is generally of good quality, but various parts of Lycoming County can have groundwater with low to moderate concentrations of methane and other constituents that appear in naturally present brine and produced waters from gas and oil wells at high concentrations."

Pennsylvania↗