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Anthropogenic vs. natural pollution: An environmental study of an industrial site under remediation (Naples, Italy)

Heavy metal concentrations and Pb isotopic composition were determined in the soils, slags, scums and landfill materials from a shut down industrial (brownfield) site. This was the second largest integrated steelworks in Italy, and is now under remediation by a Government project. It is located in the outskirts of Napoli on the Bagnoli-Fuorigrotta plain (BFP), which is part of the Campi Flegrei (CF) volcanic caldera, where many spas and geothermal springs occur. The purpose of this work is to distinguish the natural (geogenic) component, originated by hydrothermal activity, from anthropogenic contamination owing to industrial activity. 'In-situ sediments' (soils), slags, scums and landfill materials from 20 drill-cores were selected from a network of 197 drills carried out on a 100 ?? 100 m grid, covering the entire brownfield site. In general, heavy metal enrichments in the upper 3 m of the cores strongly suggest mixing between natural (geogenic) and anthropogenic components. Pb isotopic data are suggestive of three potential end members, and confirm the existence of a strong natural component in addition to contamination from anthropogenic activities. The slags, scums and landfill materials have been proved, through mineralogy and leachate experiments, to be geochemically stable; this shows that metal pollutants are not bio-available and, hence, do not pose a risk to future developments on this site. The natural contribution of hydrothermal fluids to soil pollution, in addition to the non-bio-availability of metal pollutants from industrial materials, indicate that heavy metal remediation of soils in this area would be of little use. Continuous discharge from mineralized hydrothermal solutions would cancel out any remediation effort.

Geochemistry: Exploration, Environment, Analysis

Contaminated-sediment database development and assessment in Boston Harbor

Bottom sediments have been regarded as memory banks for contaminant inputs to urban waterways. Bottom sediments accumulate by the addition of particles that enter the waterway from many sources (U.S. National Research Council, 1989). Sediments include solid contaminants, as well as contaminants from the water column that are adsorbed on organic matter or soil (rock) particles. Sediments from Boston Harbor and adjacent parts of Massachusetts Bay are now among the most intensively studied in the Nation in terms of chemical composition. Scientists at the U.S. Geological Survey (USGS), Woods Hole, Mass., undertook a pioneering effort to assemble a database from all available sources of information on chemicals in sediments of the Boston Harbor study area. The database was created to help understand the distribution of sediment contaminants and their sources, transport, and other processes and to support environmental management. The work involved collaboration with the U.S. Environmental Protection Agency (USEPA), the U.S. Army Corps of Engineers (USACOE), the Massachusetts Water Resources Authority, and other organizations. More than 100,000 sediment measurements from more than 3,000 samples were gleaned from 1,500 references. New approaches were developed to scientifically edit and validate data from heterogeneous sources. The compiled data included inorganic and organic chemical information and physical parameters like sediment texture (grain size), as well as documentation to minimize a userđs need to track down hard-to-find reports.

Massachusetts

Pesticide residues in Hemlock and Canadice Lakes and their tributaries in western New York, 1997-98

In 1997, the U.S.Geological Survey (USGS) and the City of Rochester began a cooperative program to study the presence of pesticides (herbicides and insecticides) that occur at trace levels in Hemlock and Canadice Lakes and their tributaries. The most frequently detected pesticides in streamflow and lake-water samples were herbicides commonly used in agriculture — atrazine, metolachlor, and simazine. None of the concentrations of these compounds in the samples exceeded Federal or State water-quality standards. Differences in the concentrations among stream samples can be attributed to land use and streamflow, and the timing of rainfall in relation to herbicide application. The north (lower) end of Hemlock Lake can receive pesticides in agricultural runoff from northern parts of its watershed and Canadice Creek. These pesticide inputs bypass most of the lake and could periodically affect the water quality periodically affect the water quality at the City of Rochester intake. Pesticide concentrations in samples from the intake during this study, however, were about 100 times less than current Federal and State standards for drinking water. Residues of DDT, dieldrin, and mirex are present in low concentrations in the bottom sediments of both lakes, but none were detected in water samples. The use of these insecticides was banned in 1972,and their persistence in the lakebed sediments is probably due to erosion of contaminated soils from agricultural lands.

New York

Grass buffers for playas in agricultural landscapes: A literature synthesis

We summarize current knowledge about grass buffers for protecting small, isolated wetlands in agricultural contexts, including information relevant to protecting playas from runoff containing sediments, nutrients, pesticides, and other contaminants, and information on how buffers may affect densities and productivity of grassland birds. Land-uses surrounding the approximately 60,000 playas within the Playa Lakes Region (PLR), including intensive agriculture, feedlots, and oil extraction, can contribute to severe degradation of playas. Farming and grazing can lead to significant sedimentation in nearby playas, eliminating their ability to hold water, support the region’s biodiversity, or adequately recharge aquifers. Contaminants further degrade habitats and threaten the water quality of underlying aquifers, including the Ogallala Aquifer. Grass buffers hold promise as a management tool to reduce the amount of sediments and contaminants from agricultural runoff that enters playas. Effective buffer width is determined by acceptable sediment-reduction levels, potential water flow and velocity, landscape and soil variables, buffer species, and vegetation structure. Various models have been developed to predict buffer effectiveness; however, most of these models, including those provided by the Natural Resource Conservation Service (NRCS), remain unvalidated. The majority of buffer-effectiveness literature is based on simulated conditions in experimental trays or plots; no published studies of buffer design or effectiveness specifically address playas. Nonetheless, some general patterns have emerged regarding buffer design/effectiveness. Buffers 10–60 m wide are generally considered adequate for trapping most sediments, although in some cases buffers need to be >200 m. The U.S. Fish and Wildlife Service Partners for Wildlife Program in the Southern High Plains recommend a buffer width of ~33 m planted with a diverse mix of native shortgrasses and mixed grasses as a starting point. Most dissolved contaminants, however, are removed from runoff only when they infiltrate the soil, where microbes or other processes can break down or sequester contaminants. Promoting runoff infiltration requires wider buffers with denser stem densities than those required for filtering sediments, which may result in hydrological changes in playas. Ultimately, the balance between runoff and infiltration determines whether or not water eventually reaches a given basin. Long-term buffer effectiveness requires regular maintenance, including excavation to remove overburdens of sediments, repairing vegetation damage, and removing over-mature vegetation or invasions of noxious weeds. Buffers may not be enough to protect playas; best management practices (BMPs; e.g., conservation tillage, contour tilling, and mulching herbicides into soil after application) that diminish soil erosion and contaminant runoff also may be necessary. Nutrient loads in runoff can be minimized by balancing nutrient input with nutrient requirements for livestock and crops. Pesticide application practices also require careful evaluation. Mowing or grazing rather than use of herbicides offer alternatives for suppressing invasive or undesirable plant species in buffers. Future research should entail multiple-scale approaches at regional, wetland-complex, and individual watershed scales. Information needs include direct measures of buffer effectiveness in ‘real-world’ systems, refinement and field tests of buffer-effectiveness models, how buffers may affect floral and faunal communities of playas, and basic ecological information on playa function and playa wildlife ecology. Understanding how wildlife communities respond to patch size and habitat fragmentation is crucial for addressing questions regarding habitat quality of grass buffers in playa systems.

Open-File Report

Fish health study Ashtabula River natural resource damage assessment

INTRODUCTION The Ashtabula River is located in northeast Ohio, flowing into Lake Erie at Ashtabula, Ohio. Tributaries include Fields Brook, Hubbard Run, Strong Brook, and Ashtabula Creek. The bottom sediments, bank soils and biota of Fields Brook have been severely contaminated by unregulated discharges of hazardous substances. Hazardous substances have migrated downstream from Fields Brook to the Ashtabula River and Harbor, contaminating bottom sediments, fish and wildlife. There are presently more than 1,000,000 cubic yards of contaminated sediment in the Ashtabula River and Harbor, much of which originated from Fields Brook. Contaminants include polychlorinated biphenyls (PCBs), chlorinated benzenes, chlorinated ethenes, hexachlorobutadiene, polyaromatic hydrocarbons (PAHs), other organic chemicals, heavy metals and low level radionuclides. A Preassessment Screen, using existing data, was completed for the Ashtabula River and Harbor on May 18, 2001. Among the findings was that the fish community at Ashtabula contained approximately 45 percent fewer species and 52 percent fewer individuals than the Ohio EPA designated reference area, Conneaut Creek. The Ashtabula River and Conneaut Creek are similar in many respects, with the exception of the presence of contamination at Ashtabula. The difference in the fish communities between the two sites is believed to be at least partially a result of the hazardous substance contamination at Ashtabula. In order to investigate this matter further, the Trustees elected to conduct a study of the status and health of the aquatic biological communities of the Ashtabula River and Conneaut Creek in 2002-2004. The following document contains brief method descriptions (more detail available in attached Appendix A) and a summary of the data used to evaluate the health status of brown bullheads (Ameiurus nebulosus) and largemouth bass (Micropterus salmoides) collected from the above sites.

Ohio

Contaminant baselines and sediment provenance along the Puget Sound Energy Transport Corridor, 2015

The transport of coal and oil can result in contaminated soil, water, and organisms from unintended releases. Trains carrying coal and crude oil regularly pass through Puget Sound, Washington, and an increase in the number of coal and oil trains is expected in the future. This study characterized levels of potentially toxic contaminants in sediment in September 2015: arsenic, metals, and polycyclic aromatic hydrocarbons (PAHs) at four sites with fine-grained sediment (Chuckanut Bay, Padilla Bay, Snohomish River Delta, Nisqually River Delta) adjacent to the Burlington Northern Santa Fe (BNSF) rail line in the Puget Sound region. Arsenic (As) and metals levels were compared to those measured at a fifth site, urban Saltwater State Park, which was expected to show contaminants associated with urbanization but not rail transport of coal and oil because it is not adjacent to the BNSF rail line. Knowledge about current properties of soil and sediment is essential for quantifying impacts of spills and other releases, and for setting remediation or restoration targets. For the sampling effort and timing of this study, all five sites had fine sediment contents of cadmium (Cd), mercury (Hg), lead (Pb), and zinc (Zn) below minimal effects levels. Pb and Zn appeared to be urban sourced. Median As, chromium (Cr), copper (Cu), and nickel (Ni) levels were in the range where adverse biological effects would possibly occur; however, Cr and Ni were geologically sourced and unlikely to be bioavailable to organisms. As, Cu, and antimony (Sb) levels were highly correlated, an association that is characteristic of legacy smelting operations; however, total sediment contents of these three elements, along with Hg and As/Sb ratios, were near natural levels and could indicate river-borne inputs. Median total PAH concentrations were highest at Snohomish River Delta, but were below minimal effects levels at all sites. Diagnostic PAH ratios were indicative of PAHs sourced from petroleum combustion and coal/biomass burning, rather than from spilled petroleum or coal. Rare earth element patterns were distinct among watersheds with Cascade volcanoes, granitic rocks, or non-volcanic sediments, making them promising sediment provenance indicators. Knowledge about sediment sources and contaminant distributions could provide unique insights about sediment-bound contaminant sourcing, delivery, and dispersal in nearshore regions.

Washington

Assessment of mercury in sediments and waters of Grubers Grove Bay, Wisconsin

Mercury is a global contaminant that can be detrimental to wildlife and human health. Anthropogenic emissions and point sources are primarily responsible for elevated mercury concentrations in sediments and waters. Mercury can physically move and chemically transform in the environment, resulting in biomagnification of mercury, in the form of methylmercury, in the food web and causing elevated mercury concentrations in upper trophic levels. The ability to measure total mercury concentrations in the environment has existed for several decades and makes it possible to detect hotspots that might exist because of ongoing or previous anthropogenic activity. However, recent (within the past 15 years) developments in mass spectrometry have made it possible to complete low level stable isotope analysis allowing for the determination of mercury sources—natural and anthropogenic—in the environment through “fingerprinting.” Grubers Grove Bay in Lake Wisconsin, the focus area of this study, was determined to have elevated mercury levels even after multiple remediation efforts, resulting in its listing on the Federal list of impaired waters pursuant to the Clean Water Act. Adjacent to the bay is the former Badger Army Ammunition Plant, which manufactured ammunition for the U.S. Army during the early and middle 20th century, after which it was put on standby before being fully decommissioned. This study assesses mercury concentrations in the sediments and suspended particulate matter of Grubers Grove Bay, Wiegands Bay, and upstream sites, and in adjacent soils on the former Badger Army Ammunition Plant site. This study confirmed that mercury contamination exists in the sediments of Grubers Grove Bay even after dredging attempts by the U.S. Army. Additionally, using isotope ratios and a two-endmember mixing model, it was determined that soil from within Badger Army Ammunition Plant’s former site contributed a substantial amount of mercury to the bay. This result was supported by an observed gradient of high to low mercury concentrations from the innermost (nearest Badger Army Ammunition Plant) to the outermost (farthest from Badger Army Ammunition Plant) part of the bay.

Wisconsin

An overview of current applications, challenges, and future trends in distributed process-based models in hydrology

Process-based hydrological models have a long history dating back to the 1960s. Criticized by some as over-parameterized, overly complex, and difficult to use, a more nuanced view is that these tools are necessary in many situations and, in a certain class of problems, they are the most appropriate type of hydrological model. This is especially the case in situations where knowledge of flow paths or distributed state variables and/or preservation of physical constraints is important. Examples of this include: spatiotemporal variability of soil moisture, groundwater flow and runoff generation, sediment and contaminant transport, or when feedbacks among various Earth’s system processes or understanding the impacts of climate non-stationarity are of primary concern. These are situations where process-based models excel and other models are unverifiable. This article presents this pragmatic view in the context of existing literature to justify the approach where applicable and necessary. We review how improvements in data availability, computational resources and algorithms have made detailed hydrological simulations a reality. Avenues for the future of process-based hydrological models are presented suggesting their use as virtual laboratories, for design purposes, and with a powerful treatment of uncertainty.

Journal of Hydrology

Nitrogen species in soil, sediment, and ground water at a former sewage-treatment wastewater lagoon: Naval Air Station Whidbey Island, Island County, Washington

The potential for contamination of ground water from remnant sewage sludge in re-graded sediments of a deconstructed sewage-treatment lagoon was evaluated. Ground-water levels were measured in temporary drive-point wells, and ground-water samples were collected and analyzed for nutrients and other water-quality characteristics. Composite soil and sediment samples were collected and analyzed for organic carbon and nitrogen species. Multiple lines of evidence, including lack of appreciable organic matter in sediments of the former lagoon, agronomic analysis of nitrogen, the sequestration of nitrogen in the developing soils at the former lagoon, and likely occurrence of peat deposits within the aquifer material, suggest that the potential for substantial additions of nitrogen to ground water beneath the former sewage lagoon resulting from remnant sewage sludge not removed from the former lagoon are small. Concentrations of nitrogen species measured in ground-water samples were small and did not exceed the established U.S. Environmental Protection Agency’s maximum contaminant levels for nitrate (10 milligrams per liter). Concentrations of nitrate in ground-water samples were less than the laboratory reporting limit of 0.06 milligram per liter. Seventy to 90 percent of the total nitrogen present in ground water was in the ammonia form with a maximum concentration of 7.67 milligrams per liter. Concentrations of total nitrogen in ground water beneath the site, which is the sum of all forms of nitrogen including nitrate, nitrite, ammonia, and organic nitrogen, ranged from 1.15 to 8.44 milligrams per liter. Thus, even if all forms of nitrogen measured in ground water were converted to nitrate, the combined mass would be less than the maximum contaminant level. Oxidation-reduction conditions in ground water beneath the former sewage lagoon were reducing. Given the abundant supply of ambient organic carbon in the subsurface and in ground water at the former lagoon, any nitrate that may leach from residual sludge and be transported to ground water with recharge is expected to be quickly denitrified or transformed to nitrite and ammonia under the strongly reducing geochemical conditions that are present. Concentrations of organic carbon, the primary constituent of sewage sludge, in sediments of the former sewage lagoon were less than 1 percent, indicating a near absence of organic matter. The amount of total nitrogen present in the sediments at the former sewage lagoon was only about 25 percent of the amount typically present in developed agricultural soils. The lack of substantial carbon and nitrogen in sediments of the former sewage lagoon indicates that surficial sediments of the former lagoon are essentially devoid of residual sewage sludge. The largest concentration of total nitrogen measured in soil samples from the former sewage lagoon (330 milligrams per kilogram) was used to calculate an estimate of the amount of nitrogen that might be leached from residual sewage sludge by recharge. During the first two years following deconstruction of the former sewage lagoon, the concentration of total nitrogen in recharge leachate might exceed 10 milligrams per liter but the recharge leachate would not likely result in substantial increases in the nitrate concentration in ground water to concentrations greater than the drinking-water maximum contaminant level of 10 milligrams per liter.

Washington

Lead isotopic compositions of common arsenical pesticides used in New England

The three most important arsenical pesticides and herbicides that were extensively used on apple, blueberry, and potato crops in New England from mid-1800s to recent times are lead arsenate, calcium arsenate, and sodium arsenate. Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in lesser amounts. A recent report identified areas in New England where arsenical pesticides were used extensively (Robinson and Ayuso, 2004). On the basis of factor analysis of metal concentrations in stream sediment samples, a positive correlation with pesticide use was shown in regions having stream sediment sample populations that contained concentrations of high arsenic and lead. Lead isotope compositions of stream sediments from areas with heavy use of the pesticides could not be entirely explained by lead originating from rock sulfides and their weathering products. An industrial lead contribution (mostly from atmospheric deposition of lead) was suggested in general to explain the lead isotopic distributions of the stream sediments that could not be accounted for by the natural lead in the environment. We concluded that when agricultural land previously contaminated with arsenical pesticides is urbanized, pesticide residues in the soils and stream sediments could be released into the groundwater. No lead isotopic data characterizing the compositions of pesticides were available for comparison. We have determined the lead isotopic compositions of commonly used pesticides in New England, such as lead arsenate, sodium metaarsenite, and calcium arsenate, in order to assist in future isotopic comparisons and to better establish anthropogenic sources of Pb and As. New data are also presented for copper acetoarsenite (or Paris green), methyl arsonic acid and methane arsonic acid, as well as for arsanilic acid, all of which are used as feed additives to promote swine and poultry growth. The new data characterize these anthropogenic sources. The data show that the arsenical pesticides have similar compositions: 208Pb/207Pb = 2.3839-2.4721, 206Pb/207Pb = 1.1035-1.2010, and 206Pb/204Pb = 17.070-18.759 and, more importantly, that the pesticides overlap the composition of the stream sediments that represent the areas with the most extensive agricultural use. Copper acetoarsenite (Paris green), arsenic oxide, methyl arsonic acid, methane arsonic acid, and arsanilic acid were also analyzed and have lead isotope compositions that range widely. An important source of arsenic and metals to most of the stream sediment samples in New England appears to be weathering products from rocks and industrial lead, but the extensive use of arsenical pesticides and herbicides up to about the 1960s can also be a significant anthropogenic source in agricultural regions.

Open-File Report

Mercury Loads in the South River and Simulation of Mercury Total Maximum Daily Loads (TMDLs) for the South River, South Fork Shenandoah River, and Shenandoah River: Shenandoah Valley, Virginia

Due to elevated levels of methylmercury in fish, three streams in the Shenandoah Valley of Virginia have been placed on the State's 303d list of contaminated waters. These streams, the South River, the South Fork Shenandoah River, and parts of the Shenandoah River, are downstream from the city of Waynesboro, where mercury waste was discharged from 1929-1950 at an industrial site. To evaluate mercury contamination in fish, this total maximum daily load (TMDL) study was performed in a cooperative effort between the U.S. Geological Survey, the Virginia Department of Environmental Quality, and the U.S. Environmental Protection Agency. The investigation focused on the South River watershed, a headwater of the South Fork Shenandoah River, and extrapolated findings to the other affected downstream rivers. A numerical model of the watershed, based on Hydrological Simulation Program-FORTRAN (HSPF) software, was developed to simulate flows of water, sediment, and total mercury. Results from the investigation and numerical model indicate that contaminated flood-plain soils along the riverbank are the largest source of mercury to the river. Mercury associated with sediment accounts for 96 percent of the annual downstream mercury load (181 of 189 kilograms per year) at the mouth of the South River. Atmospherically deposited mercury contributes a smaller load (less than 1 percent) as do point sources, including current discharge from the historic industrial source area. In order to determine how reductions of mercury loading to the stream could reduce methylmercury concentrations in fish tissue below the U.S. Environmental Protection Agency criterion of 0.3 milligrams per kilogram, multiple scenarios were simulated. Bioaccumulation of mercury was expressed with a site-specific exponential relation between aqueous total mercury and methylmercury in smallmouth bass, the indicator fish species. Simulations indicate that if mercury loading were to decrease by 98.9 percent from 189 to 2 kilograms per year, fish tissue methylmercury concentrations would drop below 0.3 milligrams per kilogram. Based on the simulations, the estimated maximum load of total mercury that can enter the South River without causing fish tissue methylmercury concentrations to rise above 0.3 milligrams per kilogram is 2.03 kilograms per year for the South River, and 4.12 and 6.06 kilograms per year for the South Fork Shenandoah River and Shenandoah River, respectively.

Scientific Investigations Report

Phytotoxicity of floodplain soils contaminated with trace metals along the clark fork river, Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, United States

Concentrations of metals in sediments and soils deposited along the floodplain of the Clark Fork River, within the Grant-Kohrs Ranch National Historic Site, Deer Lodge, Montana, USA, have exceeded maximum background concentrations in the United States for most metals tested. As a result of mining and smelting activities, portions of the Deer Lodge Valley, including the Grant-Kohrs Ranch, have received National Priority List Designation under the Comprehensive Environmental Response, Compensation and Liability Act. Using a series of plant germination tests, pH measurements, and metal analyses, this study investigated the toxicity of soils from floodplain 'slicken' areas, bare spots devoid of vegetation, along the Clark Fork River. The slicken soils collected from the Grant-Kohrs Ranch were toxic to all four plant species tested. The most sensitive endpoint in the germination tests was root length and the least sensitive was emergence. Considering emergence, the most sensitive species was the resident grass species Agrostis gigantea. The sensitivities were reversed when root lengths were examined, with Echinochloa crusgalli showing the greatest sensitivity. Both elevated concentrations of metals and low pH were necessary to produce an acutely phytotoxic response in laboratory seed germination tests using slicken soils. Moreover, pH values on the Grant-Kohrs Ranch appear to be a better predictor of acutely phytotoxic conditions than total metal levels.

Environmental Toxicology and Chemistry

Reducing sedimentation of depressional wetlands in agricultural landscapes

Depressional wetlands in agricultural landscapes are easily degraded by sediments and contaminants accumulated from their watersheds. Several best management practices can reduce transport of sediments into wetlands, including the establishment of vegetative buffers. We summarize the sources, transport dynamics, and effect of sediments, nutrients, and contaminants that threaten wetlands and the current knowledge of design and usefulness of grass buffers for protecting isolated wetlands. Buffer effectiveness is dependent on several factors, including vegetation structure, buffer width, attributes of the surrounding watershed (i.e., area, vegetative cover, slope and topography, soil type and structure, soil moisture, amount of herbicides and pesticides applied), and intensity and duration of rain events. To reduce dissolved contaminants from runoff, the water must infiltrate the soil where microbes or other processes can break down or sequester contaminants. But increasing infiltration also diminishes total water volume entering a wetland, which presents threats to wetland hydrology in semi-arid regions. Buffer effectiveness may be enhanced significantly by implementing other best management practices (e.g., conservation tillage, balancing input with nutrient requirements for livestock and crops, precision application of chemicals) in the surrounding watershed to diminish soil erosion and associated contaminant runoff. Buffers require regular maintenance to remove sediment build-up and replace damaged or over-mature vegetation. Further research is needed to establish guidelines for effective buffer width and structure, and such efforts should entail a coordinated, regional, multi-scale, multidisciplinary approach to evaluate buffer effectiveness and impacts. Direct measures in "real-world" systems and field validations of buffer-effectiveness models are crucial next steps in evaluating how grass buffers will impact the abiotic and biotic variables attributes that characterize small, isolated wetlands. ?? 2008 The Society of Wetland Scientists.

Wetlands

Groundwater quality at Alabama Plating and Vincent Spring, Vincent, Alabama, 2007–2008

The former Alabama Plating site in Vincent, Alabama, includes the location where the Alabama Plating Company operated an electroplating facility from 1956 until 1986. The operation of the facility generated waste containing cyanide, arsenic, cadmium, chromium, copper, lead, zinc, and other heavy metals. Contamination resulting from the site operations was identified in groundwater, soil, and sediment. Vincent Spring, used as a public water supply by the city of Vincent, Alabama, is located about ½ mile southwest of the site. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, conducted an investigation at Vincent Spring and the Alabama Plating site, Vincent, Alabama, during 2007–2008 to evaluate the groundwater quality and evaluate the potential effect of contaminated groundwater on the water quality of Vincent Spring. The results of the investigation will provide scientific data and information on the occurrence, fate, and transport of contaminants in the water resources of the area and aid in the evaluation of the vulnerability of the public water supply to contamination. Samples were analyzed to evaluate the water quality at the former plating site, investigate the presence of possible contaminant indicators at Vincent Spring, and determine the usefulness of stable isotopes and geochemical properties in understanding groundwater flow and contaminant transport in the area. Samples collected from 16 monitor wells near the plating site and Vincent Spring were analyzed for major constituents, trace metals, nutrients, and the stable isotopes for hydrogen ( 2 H/H) and oxygen ( 18 O/ 16 O). Groundwater collected from Vincent Spring was characterized as a calcium-magnesium-bicarbonate water type with total dissolved solids concentrations ranging from 110 to 120 milligrams per liter and pH ranging from about 7.5 to 7.9 units. Groundwater chemistry at the monitor wells at the Alabama Plating site was highly variable by location and depth. Dissolved solids concentrations ranged from 28 to 2,880 milligrams per liter, and the water types varied from calcium-magnesium-bicarbonate-chloride, to calcium-sulfate or calcium-magnesium-sulfate, to sodium-chloride water types. The stable isotope ratios for hydrogen ( 2 H/H) and oxygen ( 18 O/ 16 O) for water from the monitor wells and from Vincent Spring, based on a single sampling event, can be separated into three groups: (1) Vincent Spring, (2) monitor wells MW03 and MW28, and (3) the remaining Alabama Plating monitor wells. The geochemical and stable isotope analyses indicate that water from Vincent Spring is distinct from water from the Alabama Plating monitor wells; however, this evaluation is based on a single sampling event. Although the water from Vincent Spring, for this sampling event, is different and does not seem to be affected by contaminated groundwater from the Alabama Plating site, additional hydrologic and water-quality data are needed to fully identify flow paths, the potential for contaminant transport, and water-quality changes through time.

Alabama

Assessing aquifer contamination risk using immunoassay: Trace analysis of atrazine in unsaturated zone sediments

The vulnerability of a shallow aquifer in south-central Kansas to contamination by atrazine (2-chloro-4-ethylamino-6-isopropylamines-triazine) was assessed by analyzing unsaturated zone soil and sediment samples from about 60 dryland and irrigated sites using an ultrasensitive immunoassay (detection level of 0.02 µg/kg) with verification by gas chromatography/mass spectrometry (GC/MS). Samples were collected at depths of 0 to 1.2 m (i.e., the root zone), 1.2 to 1.8 m, and 1.8 to 3.0 m during two time periods-prior to planting and after harvest of crops. About 75% of the samples contained detectable concentrations of parent atrazine. At the shallow sampling depth, atrazine concentrations ranged from 0.5 to approximately 12 µg/kg. Atrazine concentrations at the intermediate (1.2-1.8 m) depth generally were <1.0 µg/kg, with most of the concentrations <0.10 µg/kg, which suggests substantial degradation of parent atrazine in the root zone. Likewise, atrazine concentrations front the deepest (1.8-3.0 m) depth ranged from <0.02 to 0.33 µg/kg. The metabolite deethylatrazine (2-amino-4-chloro-6- isopropylamine-s-triazine) was detected by GC/MS only in 2 of 60 samples with concentrations of 1.4 and 1.5 µg/kg. The reconnaissance survey shows that, in spite of atrazine use ranging from 1 to 5 or more years, there does not appear to he a significant buildup of parent compound below the root zone. Therefore, the unsaturated zone does not appear to be a major storage compartment of atrazine contamination for the underlying shallow aquifer.

Journal of Environmental Quality

Concentration, distribution, and translocation of mercury and methylmercury in mine-waste, sediment, soil, water, and fish collected near the Abbadia San Salvatore mercury mine, Monte Amiata district, Italy

The distribution and translocation of mercury (Hg) was studied in the Paglia River ecosystem, located downstream from the inactive Abbadia San Salvatore mine (ASSM). The ASSM is part of the Monte Amiata Hg district, Southern Tuscany, Italy, which was one of the world’s largest Hg districts. Concentrations of Hg and methyl-Hg were determined in mine-waste calcine (retorted ore), sediment, water, soil, and freshwater fish collected from the ASSM and the downstream Paglia River. Concentrations of Hg in calcine samples ranged from 25 to 1500 μg/g, all of which exceeded the industrial soil contamination level for Hg of 5 μg/g used in Italy. Stream and lake sediment samples collected downstream from the ASSM ranged in Hg concentration from 0.26 to 15 μg/g, of which more than 50% exceeded the probable effect concentration for Hg of 1.06 μg/g, the concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Stream and lake sediment methyl-Hg concentrations showed a significant correlation with TOC indicating considerable methylation and potential bioavailability of Hg. Stream water contained Hg as high as 1400 ng/L, but only one water sample exceeded the 1000 ng/L drinking water Hg standard used in Italy. Concentrations of Hg were elevated in freshwater fish muscle samples and ranged from 0.16 to 1.2 μg/g (wet weight), averaged 0.84 μg/g, and 96% of these exceeded the 0.3 μg/g (methyl-Hg, wet weight) USEPA fish muscle standard recommended to protect human health. Analysis of fish muscle for methyl-Hg confirmed that > 90% of the Hg in these fish is methyl-Hg. Such highly elevated Hg concentrations in fish indicated active methylation, significant bioavailability, and uptake of Hg by fish in the Paglia River ecosystem. Methyl-Hg is highly toxic and the high Hg concentrations in these fish represent a potential pathway of Hg to the human food chain.

Monte Amiata

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

Science support for evaluating natural recovery of polychlorinated biphenyl concentrations in fish from Crab Orchard Lake, Crab Orchard National Wildlife Refuge, Illinois

Introduction Crab Orchard Lake in southern Illinois is one of the largest and most popular recreational lakes in the state. Construction of the nearly 7,000-acre reservoir in the late 1930s created employment opportunities through the Works Progress Administration, and the lake itself was intended to supply water, control flooding, and provide recreational opportunities for local communities (Stall, 1954). In 1942, the Department of War appropriated or purchased more than 20,000 acres of land around Crab Orchard Lake and constructed the Illinois Ordnance Plant, which manufactured bombs and anti-tank mines during World War II. After the war, an Act of Congress transferred the property to the U.S. Department of the Interior. Crab Orchard National Wildlife Refuge was established on August 5, 1947, for the joint purposes of wildlife conservation, agriculture, recreation, and industry. Production of explosives continued, but new industries also moved onsite. More than 200 tenants have held leases with Crab Orchard National Wildlife Refuge and have operated a variety of manufacturing plants (electrical components, plated metal parts, ink, machined parts, painted products, and boats) on-site. Soils, water, and sediments in several areas of the refuge were contaminated with hazardous substances from handling and disposal methods that are no longer acceptable environmental practice (for example, direct discharge to surface water, use of unlined landfills). Polychlorinated biphenyl (PCB) contamination at the refuge was identified in the 1970s, and a PCB-based fish-consumption advisory has been in effect since 1988 for Crab Orchard Lake. The present advisory covers common carp ( Cyprinus carpio ) and channel catfish ( Ictalurus punctatus ); see Illinois Department of Public Health (2017). Some of the most contaminated areas of the refuge were actively remediated, and natural ecosystem recovery processes are expected to further reduce residual PCB concentrations in the lake. The U.S. Fish and Wildlife Service sought technical support to understand environmental drivers of current (2017) PCB residues in fish tissue and patterns in PCB residues through time to inform the fish-consumption advisory for Crab Orchard Lake. This project is planned in two phases (Tasks 1 and 2); the first phase is included in this report. Task 1, reported here, includes a review of existing literature and a brief overview focused on environmental and biochemical/physiological processes that drive PCB residues in fish tissue. This review specifically targets processes that are relevant for freshwater lacustrine environments such as those at Crab Orchard Lake. In addition to discussions of environmental fate, metabolism, and accumulation of PCBs, this review includes a brief scientifically based explanation of approaches used to establish fish-consumption advisories. A planned second task (Task 2) will include a compilation and summary of existing data on PCB residues in fish tissue samples from Crab Orchard Lake. This summary will also place Crab Orchard Lake data in a broader geographic context through a comparison with fish data from other Midwestern lakes. When Task 1 and Task 2 are complete, resource managers will have (a) a synthesis of existing literature that characterizes the processes influencing the fate of residual PCBs remaining in systems such as Crab Orchard Lake, (b) a summary of natural PCB attenuation processes for use in risk communication with the public, and (c) a summary of existing data on PCBs in fish tissues from Crab Orchard Lake, including exploratory plots of tissue residues through time. Overall, this project will provide data to help resource managers better understand the ecological and public health consequences of residual PCBs in Crab Orchard Lake.

Illinois