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Lead in the environment

Anthropogenic uses of lead have probably altered its availability and environmental distribution more than any other toxic element. Consequently, lead concentrations in many living organisms may be approaching thresholds of toxicity for the adverse effects of lead. Such thresholds are difficult to define, as they vary with the chemical and physical form of lead, exposure regime, other elements present and also vary both within and between species. The technological capability to accurately quantify low lead concentrations has increased over the last decade, and physiological and behavioral effects have been measured in wildlife with tissue lead concentrations below those previously considered safe for humans.s.236 Consequently. lead criteria for the protection of wildlife and human health are frequently under review, and 'thresholds' of lead toxicity are being reconsidered. Proposed lead criteria for the protection of natural resources have been reviewed by Eisler. Uptake of lead by plants is limited by its generally low availability in soils and sediments, and toxicity may be limited by storage mechanisms and its apparently limited translocation within most plants. Lead does not generally accumulate within the foliar parts of plants, which limits its transfer to higher trophic levels. Although lead may concentrate in plant and animal tissues, no evidence of biomagnification exists. Acid deposition onto surface waters and soils with low buffering capacity may influence the availability of lead for uptake by plants and animals, and this may merit investigation at susceptible sites. The biological significance of chronic low-level lead exposure to wildlife is sometimes difficult to quantify. Animals living in urban environments or near point sources of lead emission are inevitably subject to greater exposure to lead and enhanced risk of lead poisoning. Increasingly strict controls on lead emissions in many countries have reduced exposure to lead from some sources. and the .reduction of lead in gasoline has resulted in lower tissue lead concentrations in humans and wildlife from many, particularly urban, locations. However, it has been suggested that increasing use of organic lead compounds as catalysts for the production of plastics and as wood preservatives and biocides could adversely affect wildlife. The most significant source of direct wildlife mortality from lead is spent gunshot and fishing sinkers. Elevated mortality from shot ingestion in avian species resulted in the introduction of nontoxic (steel) shot zones along certain flyways in the United States in the mid-1970s and a total ban on the use of lead for waterfowl and coot hunting nationwide by 1992. Several other countries are now following suit and have either banned or are in the process of restricting the use of lead shot for waterfowl hunting. In the United States it has been estimated that since the 1986 hunting season. when the use of nontoxic shot became widespread. over 6 million ducks have not been lost to lead poisoning. Raptors, especially eagles, have also apparently benefited. although lead poisoning from ingestion of bullet fragments remains a problem for the critically threatened California condor. Quantifying reductions in lead mortality rates would be difficult since eagle populations throughout North America are rapidly recovering from other anthropogenic perturbations, especially organochlorine pesticides.

Book chapter↗

Release of elements to natural water from sediments of Lake Roosevelt, Washington, USA

Reservoir sediments from Lake Roosevelt (WA, USA) that were contaminated with smelter waste discharged into the Columbia River (BC, Canada) were examined using three measures of elemental release reflecting varying degrees of physical mixing and time scales. Aqueous concentrations of Cd, Cu, Pb, and Zn in the interstitial water of reservoir sediments, in the gently stirred overlying waters of incubated sediment cores, and in supernatants of aggressively tumbled slurries of reservoir sediments generally were higher than the concentrations from a reference site. When compared to chronic water-quality criteria, all three measures of release suggest that slag-contaminated sediments near the U.S.-Canadian border are potentially toxic as a result of Cu release and Pb release in two of the three measures. All three measures of Cd release suggest potential toxicity for one site farther down the reservoir, probably contaminated as a result of transport and adsorption of Cd from smelter liquid waste. Releases of Zn and As did not appear to be potentially toxic. Carbonate geochemistry indirectly affects the potential toxicity by increasing water hardness.

Washington↗

Assessing the effect of pesticides in agricultural runoff on aquatic life in the Sangamon River near Monticello, Illinois

Stream-water samples collected from a midwest stream, following a thunderstorm during May 1991 were toxic to water fleas (Ceriodaphnia dubia), but not fathead minnows (Pimephales promelas), or a bacterium (Photobacterium phosphoreum) or green alga (Selenastrum capricornutum). It was unlikely that the toxicity to the water fleas was caused by herbicides, but it may have been caused by insecticides.Stream-water samples collected from a midwest stream, following a thunderstorm during May 1991 were toxic to water fleas (Ceriodaphnia dubia), but not fathead minnows (Pimephales promelas), or a bacterium (Photobacterium phosphoreum) or green alga (Selenastrum capricornutum). It was unlikely that the toxicity to the water fleas was caused by herbicides, but it may have been caused by insecticides.

Water Science and Technology↗

Simazine and other s-triazine compounds as aquatic herbicides in fish habitats

This investigation studied simazine (2-chloro-4,6-bis(ethylamino)- s -triazine), atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), propazine (2-chloro-4,6-bis(isopropylamino)- s -triazine), and prometone (2-methoxy-4,6-bis(isopropylamino)- s -triazine). Preemergence applications of granular formulations of simazine on attaclay or calcium sulfate of simazine at 1 to 2 ppmw controlled Potamogeton , Najas , Ceratophyllum , Heteranthera and Zannichelli a. Higher rates were required to control filamentous algae ( Cladophora and Pithophora ) and chara ( Chara vulgaris ). Early postemergence applications of wettable powder to submersed aquatics and filamentous algae were often effective. Atrazine gave similar results. Concentrations of 0.5 to 1.0 were effective in controlling Cladophora and Pithophora and three species of Potamogeton in pond applications. Spray applications, generally, were more effective than broadcasting granular atrazine. Propazine and prometone did not control submersed species in concentrations up to 3 ppmw. Simazine had a relatively high margin of safety with respect to acute toxicity to fish. It was less toxic than propazine, prometone or atrazine. Granular forms were less toxic than wettable powder or emulsifiable concentrates. Laboratory tests on bottom organisms gave an acute LD 50 toxic dosage of 28 ppmw. Field observations did not demonstrate a serious reduction in the production of bottom organisms. However, the control of aquatic vegetation brought about ecological changes affecting bottom dwelling and weed clinging organisms. These changes would affect certain fishes with special food habits.

Weeds↗

Contaminants of emerging concern in the Great Lakes: Science to inform management practices for protecting the health and integrity of wildlife populations from adverse effects: GLRI action plan I, focus area 1, goal 5

Executive Summary: Under Action Plan I (2010-2014) of the Great Lakes Restoration Initiative (GLRI), Federal and Academic partners began an investigation of the presence and distribution of contaminants of emerging concern (CECs) in the Great Lakes and potential impacts on fish and wildlife. The term CECs is applied to a broad range of chemicals that are currently in use but for which we currently lack good understanding of whether fish, wildlife, or humans are being exposed and/or whether negative health or environmental effects are expected if exposure occurs. Pharmaceuticals, personal care products, flame retardants, many current use pesticides, and poly- and perfluorinated chemicals are some well-known groups of CECs, but there is no definitive or comprehensive list that can be used to support the management of CECs to reduce impacts on the Great Lakes ecosystem. Four overarching goals were identified for this collaborative investigation: 1. Evaluate the sources, occurrence, and distribution of CECs across the Great Lakes Basin. 2. Examine associations between the distribution of CECs and land-use patterns. 3. Review both scientific literature and field-generated data to determine the potential for CECs to cause adverse effects on Great Lakes fish and wildlife populations. 4. Develop efficient strategies to survey and/or monitor for threats that CECs may pose in order to take effective management actions before those threats evolve into large scale impacts on Great Lakes ecosystems or the services they provide. Achievement of these goals ensures progress towards Focus Area 1: Toxic Substances and Areas of Concern from GLRI Action Plan I, Goal 5: “ The health and integrity of wildlife populations and habitat are protected from adverse chemical and biological effects associated with the presence of toxic substances in the Great Lakes Basin ”. This large-scale research effort was comprised of individual and collaborative projects from multiple federal agencies and academic institutions, involving over 85 investigators, and overseen by the U.S. Environmental Protection Agency (EPA) Region 5, Great Lakes National Program Office. Partners include the United States Geological Survey, the National Oceanic and Atmospheric Administration, U.S. Fish and Wildlife Service, Saint Cloud State University, the U.S. EPA Office of Research and Development, and the U.S. Army Corps of Engineers. Key findings: 1. Contaminants of emerging concern were found throughout the monitored Great Lakes tributaries, but types and concentrations vary in association with regional land use. CECs were detected in nearly all samples collected. The type and concentration of the specific contaminants detected varied considerably among field sites and in association with land use type, such as urban, agricultural, wetland, 2 or forest. Contaminants were detected in the water column, sediment, and tissues of all species surveyed in the current work (mussels, aquatic insects, fish, and insect-eating birds). 2. There were over 20 contaminants for which CEC concentrations approached or exceeded those reported to cause toxicity in laboratory experiments. This was based on detection in water, sediments and or biota at one or more field sites. These contaminants represent compounds that warrant further investigation and monitoring with respect to potential impacts in certain areas of the Great Lakes basin. Based on the present investigation, compounds of greatest concern include: polycyclic aromatic hydrocarbons, associated with oil-based products and combustion of organic matter; atrazine, an herbicide; dichlorvos, an insecticide; and ibuprofen and venlafaxine, both pharmaceuticals. 3. Results suggest that mixtures of CECs presently found in most Great Lakes tributary locations surveyed may elicit subtle biological effects, but likely are not, alone, causing obvious detriment to current communities of fish and wildlife. CECs detected in the Great Lakes were associated with subtle biological effects like changes in gene expression, altered circulating glucose, etc. in both wild-caught and laboratory-reared organisms. These effects were generally not indicative of reproductive failure or mortality. However, the effects may have more serious implications when combined with other sources of stress like habitat degradation, changing climate conditions, and competition with invasive species. Due to limited historical data, it is unknown whether severe CEC-related impacts have already affected aquatic communities in waterbodies that have received long-term inputs of these contaminants. Likewise, under Action Plan I, biological effects were not necessarily evaluated at the sites where CEC concentrations exceeding laboratory toxicity thresholds were detected. As a result, strategic, ongoing surveillance and monitoring of CECs is warranted. This collaborative investigation resulted in new tools, approaches, and data that can be used to inform and support the management of CECs to reduce their impacts on Great Lakes natural resources. The following products of this research effort are available through https://communities.geoplatform.gov/glri/ or by contacting the investigators (see technical chapters found in Appendices A-F): 1. Database of CEC occurrence and concentrations in US tributary streams. The database includes CEC detections in water, sediment, and fish and wildlife tissues, and represents the most comprehensive survey of CECs in the Great Lakes Region. 2. Synopses of results and key findings. Integrated summaries of results, conclusions, and management implications of the CEC research are available through reports, topical fact sheets, and presentations. 3. Technical publications: This collaborative research effort has resulted in over 50 peer-reviewed publications, agency reports, and data releases that can be of use to resource managers, the scientific community, and members of the public. 4. Innovative tools. Innovative monitoring devices, sampling equipment, conceptual frameworks, and software applications were developed over the course of this 3 research. These tools are transferable to stakeholders via internet accessibility or via specifications, instructions, and demonstration detailed in technical publications. Hypotheses to guide CECs research under Action Plan II. Findings from 2010-2014 were used to guide further research in 2015-2018 for basin-wide surveillance of CECs and for sites warranting further study of potential biological impacts of CECs. Additional surveillance included both evaluation of additional classes of contaminants and expanded lists for chemical classes shown to be of greatest concern. Mixtures of some of the most frequently detected contaminants were also tested in laboratory studies to understand whether long term exposures to multiple contaminants may result in effects not evident from uncontrolled, short-term field experiments.

Great Lakes↗

Hydrogeology, water quality, and ecology of Anderton Branch near the Quail Hollow Landfill, Bedford County, Tennessee, 1995-99

The Quail Hollow Landfill, located in southeastern Bedford County on the Highland Rim overlooking the Central Basin karst region of Tennessee, is constructed on the gravelly, clay-rich residuum of the Fort Payne Formation of Mississippian age. A conceptual hydrologic model of the landfill indicated that Anderton Branch was at risk of being affected by the landfill. Ground water flowing beneath the landfill mixes with percolating rainwater that has passed through the landfill and discharges to the surface from numerous weeps, seeps, and springs present in the area. Anderton Branch, adjacent to the landfill site on the north and east, receives most of the discharge from these weeps, seeps, and springs. Anderton Branch also receives water from the Powell Branch drainage basin to the west and south because of diverted flow of ground water through Harrison Spring Cave. The U.S. Geological Survey, in cooperation with the Bedford County Solid Waste Authority, conducted a study to evaluate the effect of the Quail Hollow Landfill on ground- and surface-water quality. During storm runoff, specific conductance was elevated, and cadmium, iron, manganese, lead, and nickel concentrations in Anderton Branch frequently exceeded maximum contaminant levels for drinking water for the State of Tennessee. High chloride inputs to Anderton Branch were detected at two locations?a barnyard straddling the stream and a tributary draining a pond that receives water directly from the landfill. The chloride inputs probably contribute to chloride load levels that are three times higher for Anderton Branch than for the control stream Anthony Branch. Although toxic volatile organic compounds were detected in water from monitoring wells at the landfill, no organic contaminants were detected in domestic water wells adjacent to the landfill or in Anderton Branch. Sons Spring, a karst spring near the landfill, has been affected by the landfill as indicated by an increase in chloride concentrations from 4 milligrams per liter in 1974 to 59 milligrams per liter in 1996. Analysis of water samples from Sons Spring detected concentrations of nickel that exceeded primary drinking-water standards and Tennessee Department of Environment and Conservation fish and aquatic life chronic standards. Trichloroethene, 1,1-dichloroethene, and 1,1-dichloroethane also were detected at Sons Spring. The presence of these chlorinated solvents imply the landfill origin of the contaminants in Sons Spring. Continuous monitoring at Sons Spring indicated a pattern of decreased specific conductance and lower contaminant concentrations after a storm. Contaminant concentrations increased with specific conductance to pre-storm levels after several days. The benthic macroinvertebrate community in Anderton Branch adjacent to the landfill was not different from the communities at control sites upstream and in Anthony Branch. Sons Spring, however, has low abundance and numbers of benthic macroinvertebrate taxa. Toxicity studies using Ceriodaphnia dubia indicated no toxicity in the base flow or storm water in Anderton Branch or in a tributary draining a pond that receives water from the landfill and Sons Spring; however, water collected from Sons Spring resulted in 100 percent mortality to all organisms within 48 hours. High concentrations of nickel were detected in crayfish tissue from control sites and Anderton Branch. Analysis of sediment samples also indicates nickel concentrations are high at control sites upstream of the landfill. Increased levels of the biomarker metallothionein detected in crayfish from Anderton Branch likely are not caused by nickel or cadmium because the levels present in the tissue are not correlated with metallothionein levels. Despite the high levels of certain metals in Anderton Branch during storm flow, the lack of toxicity and the health of the benthic community imply no detectable negative effect from the landfill to the stream. Sons Spring, howe

Scientific Investigations Report↗

Sediment quality in the north coastal basin of Massachusetts, 2003

The U.S. Geological Survey, in cooperation with the Massachusetts Department of Environmental Protection, completed a reconnaissance-level study of bottom-sediment quality in selected lakes, rivers, and estuaries in the North Coastal Basin of Massachusetts. Bottom-sediment grab samples were collected from 20 sites in the North River, Lake Quannapowitt, Saugus River, Mill River, Shute Brook, Sea Plane Basin, Pines River, and Bear Creek. The samples were tested for various types of potentially harmful contaminants? including 33 elements, 17 polyaromatic hydrocarbons (PAHs), 22 organochlorine pesticides, and 7 polychlorinated biphenyl (PCB) mixtures (Aroclors)?to benthic organisms (bottom-dwelling) and humans. The results were compared among sampling sites, to background concentrations, and to concen-trations measured in other urban rivers, and sediment-quality guidelines were used to predict toxicity at the sampling sites to benthic organisms and humans. Because there are no standards for human toxicity for aquatic sediment, standards for contaminated upland soil were used. Contaminant concentrations measured in sediment collected from the North Coastal Basin generally were equal to or greater than concentrations in sediment from uncontaminated rivers throughout New England. Contaminants in North Coastal Basin sediment with elevated concentrations (above back-ground levels) included arsenic, chromium, copper, lead, nickel, and zinc, some of the PAHs, dichlorodiphenyltrichloro-ethane (DDT) and its metabolites, and dieldrin. No PCBs were measured above the detection limits. Measured concentrations of arsenic, chromium, and lead were also generally greater than those measured in other urban rivers throughout the conter-minous United States. With one exception (arsenic), local con-centrations measured in sediment samples collected from the North Coastal Basin were lower than concentrations measured in sediment collected from two of three urban rivers draining to Boston Harbor. The probable toxicity to benthic organisms ranged from about 33 to 91 percent across the study area. Of the elements analyzed, antimony, arsenic, beryllium, and lead exceeded the soil standards for risk to human health. Of the PAHs analyzed, four also exceeded soil standards. Organochlorine pesticide concentrations, however, were not high enough relative to the soil standards to pose a risk to human health. Some trace element and some organic compound concentrations in bottom sediment may be toxic to aquatic organisms and may pose a risk to human health.

Scientific Investigations Report↗

An Assessment of the Potential Effects of Aquifer Storage and Recovery on Mercury Cycling in South Florida

Mercury contamination in the environment is a global concern, especially in areas with abundant wetlands, such as south Florida. As the causal factors of this concern improve, scientists find that many factors that do not necessarily affect mercury concentrations, such as flooding and drying cycles, or changes to carbon and sulfate loading, can profoundly affect net mercury toxicity. Especially important are ecological factors that alter the conversion of mercury to methylmercury, which is the most bioaccumulative and toxic form of mercury in the environment. Resource managers, therefore, need to be aware of possible deleterious affects to mercury toxicity that could result from land and water management decisions. Several aspects of the Comprehensive Everglades Restoration Plan (CERP), including the planned Aquifer Storage and Recovery (ASR) program, have the potential to affect the abundance of methylmercury. In response to these concerns, the U.S. Geological Survey and U.S. Army Corps of Engineers collaborated on a study to evaluate how the proposed ASR program may affect mercury cycling and toxicity. This project was conducted as an initial assessment of the possible effects of the CERP ASR program on mercury in the south Florida environment. A twofold approach was employed: field sampling and controlled laboratory benchmark experiments. The field sampling survey collected ground-water samples from the Floridan and surficial aquifer systems for the ASR program to determine existing levels of mercury and methylmercury. Laboratory experiments, on the other hand, were designed to determine how the injected surface water would interact with the aquifer during storage periods. Overall, very low levels of mercury and methylmercury (mean values of 0.41 and 0.07 nanograms per liter, respectively) were observed in ground-water samples collected from the Floridan and surficial aquifer systems. These results indicate that 'recovered water' from the CERP ASR program would not represent a significant additional direct load of mercury and methyl-mercury to ASR 'receiving waters'. Net production of methylmercury, however, can result from additions of sulfate or natural organic carbon. Thus, because the Upper Floridan aquifer generally has elevated concentrations of sulfate (relative to ambient Everglades conditions) and surface waters near Lake Okeechobee (the assumed target for ASR receiving waters) are elevated in organic carbon and sulfate, at least some potential for increased methylmercury production might arise from the release of recovered ASR water to locations in or near the Everglades.

Scientific Investigations Report↗

Biological pathways of exposure and ecotoxicity values for uranium and associated radionuclides: Chapter D in Hydrological, geological, and biological site characterization of breccia pipe uranium deposits in Northern Arizona

This chapter compiles available chemical and radiation toxicity information for plants and animals from the scientific literature on naturally occurring uranium and associated radionuclides. Specifically, chemical and radiation hazards associated with radionuclides in the uranium decay series including uranium, thallium, thorium, bismuth, radium, radon, protactinium, polonium, actinium, and francium were the focus of the literature compilation. In addition, exposure pathways and a food web specific to the segregation areas were developed. Major biological exposure pathways considered were ingestion, inhalation, absorption, and bioaccumulation, and biota categories included microbes, invertebrates, plants, fishes, amphibians, reptiles, birds, and mammals. These data were developed for incorporation into a risk assessment to be conducted as part of an environmental impact statement for the Bureau of Land Management, which would identify representative plants and animals and their relative sensitivities to exposure of uranium and associated radionuclides. This chapter provides pertinent information to aid in the development of such an ecological risk assessment but does not estimate or derive guidance thresholds for radionuclides associated with uranium. Previous studies have not attempted to quantify the risks to biota caused directly by the chemical or radiation releases at uranium mining sites, although some information is available for uranium mill tailings and uranium mine closure activities. Research into the biological impacts of uranium exposure is strongly biased towards human health and exposure related to enriched or depleted uranium associated with the nuclear energy industry rather than naturally occurring uranium associated with uranium mining. Nevertheless, studies have reported that uranium and other radionuclides can affect the survival, growth, and reproduction of plants and animals. Exposure to chemical and radiation hazards is influenced by a plant’s or an animal’s life history and surrounding environment. Various species of plants, invertebrates, fishes, amphibians, reptiles, birds, and mammals found in the segregation areas that are considered species of concern by State and Federal agencies were included in the development of the site-specific food web. The utilization of subterranean habitats (burrows in uranium-rich areas, burrows in waste rock piles or reclaimed mining areas, mine tunnels) in the seasonally variable but consistently hot, arid environment is of particular concern in the segregation areas. Certain species of reptiles, amphibians, birds, and mammals in the segregation areas spend significant amounts of time in burrows where they can inhale or ingest uranium and other radionuclides through digging, eating, preening, and hibernating. Herbivores may also be exposed though the ingestion of radionuclides that have been aerially deposited on vegetation. Measured tissues concentrations of uranium and other radionuclides are not available for any species of concern in the segregation areas. The sensitivity of these animals to uranium exposure is unknown based on the existing scientific literature, and species-specific uranium presumptive effects levels were only available for two endangered fish species known to inhabit the segregation areas. Overall, the chemical toxicity data available for biological receptors of concern were limited, although chemical and radiation toxicity guidance values are available from several sources. However, caution should be used when directly applying these values to northern Arizona given the unique habitat and life history strategies of biological receptors in the segregation areas and the fact that some guidance values are based on models rather than empirical (laboratory or field) data. No chemical toxicity information based on empirical data is available for reptiles, birds, or wild mammals; therefore, the risks associated with uranium and other radionuclides are unknown for these biota.

Arizona↗

Prioritizing pesticide compounds for analytical methods development

The U.S. Geological Survey (USGS) has a periodic need to re-evaluate pesticide compounds in terms of priorities for inclusion in monitoring and studies and, thus, must also assess the current analytical capabilities for pesticide detection. To meet this need, a strategy has been developed to prioritize pesticides and degradates for analytical methods development. Screening procedures were developed to separately prioritize pesticide compounds in water and sediment. The procedures evaluate pesticide compounds in existing USGS analytical methods for water and sediment and compounds for which recent agricultural-use information was available. Measured occurrence (detection frequency and concentrations) in water and sediment, predicted concentrations in water and predicted likelihood of occurrence in sediment, potential toxicity to aquatic life or humans, and priorities of other agencies or organizations, regulatory or otherwise, were considered. Several existing strategies for prioritizing chemicals for various purposes were reviewed, including those that identify and prioritize persistent, bioaccumulative, and toxic compounds, and those that determine candidates for future regulation of drinking-water contaminants. The systematic procedures developed and used in this study rely on concepts common to many previously established strategies. The evaluation of pesticide compounds resulted in the classification of compounds into three groups: Tier 1 for high priority compounds, Tier 2 for moderate priority compounds, and Tier 3 for low priority compounds. For water, a total of 247 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods for monitoring and studies. Of these, about three-quarters are included in some USGS analytical method; however, many of these compounds are included on research methods that are expensive and for which there are few data on environmental samples. The remaining quarter of Tier 1 compounds are high priority as new analytes. The objective for analytical methods development is to design an integrated analytical strategy that includes as many of the Tier 1 pesticide compounds as possible in a relatively few, cost-effective methods. More than 60 percent of the Tier 1 compounds are high priority because they are anticipated to be present at concentrations approaching levels that could be of concern to human health or aquatic life in surface water or groundwater. An additional 17 percent of Tier 1 compounds were frequently detected in monitoring studies, but either were not measured at levels potentially relevant to humans or aquatic organisms, or do not have benchmarks available with which to compare concentrations. The remaining 21 percent are pesticide degradates that were included because their parent pesticides were in Tier 1. Tier 1 pesticide compounds for water span all major pesticide use groups and a diverse range of chemical classes, with herbicides and their degradates composing half of compounds. Many of the high priority pesticide compounds also are in several national regulatory programs for water, including those that are regulated in drinking water by the U.S. Environmental Protection Agency under the Safe Drinking Water Act and those that are on the latest Contaminant Candidate List. For sediment, a total of 175 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods available for monitoring and studies. More than 60 percent of these compounds are included in some USGS analytical method; however, some are spread across several research methods that are expensive to perform, and monitoring data are not extensive for many compounds. The remaining Tier 1 compounds for sediment are high priority as new analytes. The objective for analytical methods development for sediment is to enhance an existing analytical method that currently includes nearly half of the pesticide compounds in Tier 1 by adding as many additional Tier 1 compounds as are analytically compatible. About 35 percent of the Tier 1 compounds for sediment are high priority on the basis of measured occurrence. A total of 74 compounds, or 42 percent, are high priority on the basis of predicted likelihood of occurrence according to physical-chemical properties, and either have potential toxicity to aquatic life, high pesticide useage, or both. The remaining 22 percent of Tier 1 pesticide compounds were either degradates of Tier 1 parent compounds or included for other reasons. As with water, the Tier 1 pesticide compounds for sediment are distributed across the major pesticide-use groups; insecticides and their degradates are the largest fraction, making up 45 percent of Tier 1. In contrast to water, organochlorines, at 17 percent, are the largest chemical class for Tier 1 in sediment, which is to be expected because there is continued widespread detection in sediments of persistent organochlorine pesticides and their degradates at concentrations high enough for potential effects on aquatic life. Compared to water, there are fewer available benchmarks with which to compare contaminant concentrations in sediment, but a total of 19 Tier 1 compounds have at least one sediment benchmark or screening value for aquatic organisms. Of the 175 compounds in Tier 1, 77 percent have high aquatic-life toxicity, as defined for this process. This evaluation of pesticides and degradates resulted in two lists of compounds that are priorities for USGS analytical methods development, one for water and one for sediment. These lists will be used as the basis for redesigning and enhancing USGS analytical capabilities for pesticides in order to capture as many high-priority pesticide compounds as possible using an economically feasible approach.

Scientific Investigations Report↗

Variability in stream chemistry in relation to urban development and biological condition in seven metropolitan areas of the United States, 1999-2004

Beginning in 1999, the U.S. Geological Survey National Water Quality Assessment Program investigated the effects of urban development on stream ecosystems in nine metropolitan study areas across the United States. In seven of these study areas, stream-chemistry samples were collected every other month for 1 year at 6 to 10 sites. Within a study area, the sites collectively represented a gradient of urban development from minimally to highly developed watersheds, based on the percentage of urban land cover; depending on study area, the land cover before urban development was either forested or agricultural. The stream-chemistry factors measured in the samples were total nitrogen, total phosphorus, chloride, and pesticide toxicity. These data were used to characterize the stream-chemistry factors in four ways (hereafter referred to as characterizations)—seasonal high-flow value, seasonal low-flow value, the median value (representing a single integrated value of the factor over the year), and the standard deviation of values (representing the variation of the factor over the year). Aquatic macroinvertebrate communities were sampled at each site to infer the biological condition of the stream based on the relative sensitivity of the community to environmental stressors. A Spearman correlation analysis was used to evaluate relations between (1) urban development and each characterization of the stream-chemistry factors and (2) the biological condition of a stream and the different characterizations of chloride and pesticide toxicity. Overall, the study areas where the land cover before urban development was primarily forested had a greater number of moderate and strong relations compared with the study areas where the land cover before urban development was primarily agriculture; this was true when urban development was correlated with the stream-chemistry factors (except chloride) and when chloride and pesticide toxicity was correlated with the biological condition. Except for primarily phosphorus in two study areas, stream-chemistry factors generally increased with urban development, and among the different characterizations, the median value typically indicated the strongest relations. The variation in stream-chemistry factors throughout the year generally increased with urban development, indicating that water quality became less consistent as watersheds were developed. In study areas with high annual snow fall, the variation in chloride concentrations throughout the year was particularly strongly related to urban development, likely a result of road salt applications during the winter. The relations of the biological condition to chloride and pesticide toxicity were calculated irrespective of urban development, but the overall results indicated that the relations were still stronger in the study areas that had been forested before urban development. The weaker relations in the study areas that had been agricultural before urban development were likely the results of biological communities having been degraded from agricultural practices in the watersheds. Collectively, these results indicated that, compared with sampling a stream at a single point in time, sampling at regular intervals during a year may provide a more representative measure of water quality, especially in the areas of high urban development where water quality fluctuated more widely between samples. Furthermore, the use of "integrated" values of stream chemistry factors may be more appropriate when assessing relations to the biological condition of a stream because the taxa composition of a biological community typically reflects the water-quality conditions over time.

Scientific Investigations Report↗

Dissolved arsenic concentrations in surface waters within the upper portions of the Klamath River Basin, Oregon and California

Arsenic toxicity is an environmental health problem. Levels of arsenic in surface waters at some locations in the Klamath River Basin in southern Oregon and northern California can exceed the U.S. Environmental Protection Agency (EPA) standard for drinking water. There are both anthropogenic and natural sources of arsenic. The Klamath River Basin consists primarily of volcanic deposits and contains an underground geothermal system with hot springs and warm water wells, all known natural sources of arsenic. Anthropogenic sources of arsenic are related to the agricultural use of herbicides, fungicides, and insecticides. Surface water arsenic levels can also be affected by fertilizer amendments, evaporative concentration, oxygen-level depletion, and various geochemical transformations that can increase arsenic mobilization. In this study by the U.S. Geological Survey and the Bureau of Reclamation, dissolved concentrations of arsenic, copper, and lead were measured in surface waters at 39 unique sites within the upper portions of the Klamath River Basin between 2018 and 2022. In every year, except 2022, sites were sampled four times between April and November. Surface-water arsenic concentrations varied up to four-orders of magnitude among sites. Median arsenic concentration was lowest at Cherry Creek (0.03 micrograms per liter [μg/L]) and highest at Wood Kimball Spring (36.7 μg/L), two sites located north of Upper Klamath Lake. The highest arsenic concentrations (17.4±4.9 μg/L, n =3) were found in drain sites (defined here as a waterbody returning used irrigation water) while the lowest arsenic concentrations were found in an artesian well (0.8 μg/L, n =1). The elevated arsenic concentrations of the drain sites suggest that arsenic might be concentrated or mobilized by agricultural activities, water re-use practices, and (or) by geochemical processes occurring around water stored in drains (that is, in the water column and across sediment water boundaries). A source of arsenic in drain water in the Klamath Strait Drain area includes water used for irrigation originating from Ady Canal. Other potential sources include groundwater, geothermal water, and local soils and sediments. Seasonal differences in surface-water arsenic concentrations were detected at 13 sites, 10 of which had higher arsenic concentrations in summer than in either spring or fall. The sites sampled around Upper Klamath Lake, the impounded rivers, one of the two canal sites, and 5 of the 14 river sites had higher surface-water arsenic concentrations in the summer than in either spring or fall. Surface-water arsenic concentrations from groundwater sources (that is, springs and in the artesian well) did not vary significantly among seasons (p-values greater than 0.1). Median surface-water concentrations of copper and lead ranged from 0.03 to 3.7 μg/L, and from 0.013 to 0.175 μg/L ( n =2–18), respectively. Dissolved concentrations of both metals were below acute toxicity endpoints reported by the EPA for freshwater animals. Surface-water arsenic concentrations varied independently from corresponding changes in surface-water lead or copper concentrations. However, arsenic concentrations measured in bed-sediment samples collected from a subset of sites located north of Upper Klamath Lake correlated strongly and significantly with the corresponding sedimentary lead concentrations ( p =0.015). Aqueous arsenic speciation measured in a subset of sites in 2019 and 2022 showed that all the arsenic existed as arsenic (V), the most oxidized arsenic species, and presumably, the least toxic. The highest proportions of arsenite (As(III)), the presumably most toxic arsenic species, relative to total arsenic concentrations were found at drain sites. Our assessment of dissolved arsenic concentrations in various surface-water bodies in the Upper Klamath River Basin reveals geographical areas of consistently low (below 2.1 μg/L), moderate (below 10 μg/L) and high (above 10 μg/L) surface-water arsenic concentrations. South of Upper Klamath Lake, surface-water arsenic concentrations were consistently higher than 20 μg/L at two drain sites located in an area of predominant agricultural land use with extensive water re-use practices. North of Upper Klamath Lake, surface-water arsenic concentrations greater than 20 μg/L were consistently measured at sites with limited nearby agricultural activities, suggesting a geogenic source. The consistently high arsenic levels from the Wood River at Jackson F. Kimball State Park, Fort Creek, and Crooked Creek, which are sites located at or near headwater spring sources, suggest a natural background source of arsenic. Water flowing downstream from this area could be a potential source of arsenic to Upper Klamath Lake and the Upper Klamath River.

California, Oregon↗

Priority-pollutant trace elements in streambed sediments of the Cook Inlet basin, Alaska, 1998-2000

Trace element concentrations in 48 streambed sediment samples collected at 47 sites in the Cook Inlet Basin, Alaska, were compared to concentrations from studies in the conterminous United States using identical methods and to Probable Effect Concentrations. Concentrations of arsenic, chromium, mercury, and nickel in the 0.063-mm size fraction of streambed sediments from the Cook Inlet Basin were elevated relative to reference sites in the conterminous United States. Concentrations of cadmium, lead, and zinc were highest at the most urbanized site in Anchorage and at two sites downstream from an ore body in Lake Clark National Park and Preserve. At least 35 percent of the 48 samples collected in the Cook Inlet Basin exceeded the Probable Effect Concentration for arsenic, chromium, or nickel. More than 50 percent of the samples were considered to have low potential toxicity for cadmium, lead, mercury, nickel, selenium, and zinc. A Probable Effect Concentration quotient that reflects the combined toxicity of arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc was exceeded in 44 percent of the samples from the Cook Inlet Basin. The potential toxicity was high in the Denali and Lake Clark National Parks and Preserves where organic carbon concentrations in streambed sediments were low. However, potential toxicity results should be considered in context with the very small amounts of fine-grained sediment present in the streambed sediments of the Cook Inlet Basin.

Water-Resources Investigations Report↗

Detailed study of irrigation drainage in and near wildlife management areas, west-central Nevada, 1987-90; Part B, Effect on biota in Stillwater and Fernley Wildlife Management Areas and other nearby wetlands

A water-quality reconnaissance study during 1986-87 found high concentrations of several potentially toxic elements in water, bottom sediment, and biota in and near Stillwater Wildlife Management Area (WMA). This study prompted the U.S. Department of the Interior to initiate a more detailed study to determine the hydrogeochemical processes that control water quality in the Stillwater WMA, and other nearby wetlands, and the resulting effects on biota, especially migratory birds. Present wetland size is about 10% of historical size; the dissolved- solids load in the water in these now-isolated wetlands has increased only moderately, but the dissolved-solids concentration has increased more than seven-fold. Wetland vegetation has diminished and species composition in flow water has shifted to predominant salt-tolerant species in many areas. Decreased vegetative cover for nesting is implicated in declining waterfowl production. Decreases in numbers or virtual absence of several wildlife species are attributed to degraded water quality. Results of toxicity tests indicate that water in some drains and wetland areas is acutely toxic to some fish and invertebrates. Toxicity is attributed to the combined presence of arsenic, boron, lithium, and molybdenum. Biological pathways are involved in the transport of mercury and selenium from agricultural drains to wetlands. Hatch success of both artificially incubated and field-reared duck eggs was greater than/= 90 percent; no teratogenesis was observed. Mercury in muscle tissue of waterfowl harvested from Carson Lake in October 1987 exceeded the human health criterion six-fold.

Water-Resources Investigations Report↗

Exploration of a piscicide delivery method for invasive Black Carp

A piscicide delivery method was designed to selectively target Black Carp Mylopharyngodon piceus, an invasive fish species in North America, which possesses pharyngeal teeth adapted for crushing mollusk prey. Many North American mollusks exist in small, fragmented populations susceptible to local extirpation. A Black Carp-selective toxic bait deployed properly could be used to protect those populations. Results represent initial efforts to construct an effective single-dose species-selective toxic bait. We prepared a bait by attaching a glass vial containing toxicant (antimycin A) to the exterior of a Corbicula fluminea clam valve. We designed the vial to break from the force of the fish’s pharyngeal teeth when attempting to crush and consume the clam. We tested suitable vial sizes for encapsulating piscicide and two attachment materials, an aquarium epoxy and ultraviolet light-cured attachment material. The aquarium epoxy was rigid and reinforced vials. The ultraviolet light-cured attachment material was softer, resulting in more vials broken at 3- and 24-h post feeding. In a second trial, toxic baits consisting of antimycin A piscicide were administered in pure ethanol and acetone carriers to Black Carp in assembled baits with vials attached to live clam valves at three concentrations (40.0 mg/mL in ethanol, 170.8 mg/mL and 341.5 mg/mL in acetone). We selected aquarium epoxy for assembled baits based on the bond between the epoxy and glass vial, which allowed a greater surface area to be exposed and broken. While Black Carp successfully broke vials containing piscicide, no treatment caused carp mortality. The delivery method was unsuccessful as a single dose antimycin A piscicide bait for Black Carp. Additional considerations for this approach are provided.

Journal of Fish and Wildlife Management↗

A relationship between avian carcasses and living invertebrates in the epizootiology of avian botulism

A survey of the sources of Clostridium botulinum type C toxin possibly utilized as food by aquatic birds in an epizootic area of avian botulism in northern Utah showed that living aquatic and terrestrial invertebrates normally found in close association with dead, decomposing birds commonly carried the toxin. Of 461 samples associated with 21 species of avian carcasses, 198 were toxin-positive. Invertebrate species not normally scavengers of vertebrate tissues were less commonly and less highly toxic, particularly when captured 30 cm or more from a carcass; six of 237 samples of such aquatic invertebrates contained low-level toxin. Of the species tested, blow fly larvae (Calliphoridae) were the most consistently and highly toxic, although others, particularly adult and larval stages of several species of beetles (Coleoptera), contained toxin at levels probably significant in the epizootiology of the disease. An estimated 0.05 to 0.25 g of the most toxic fly larvae or 15 g of the most toxic beetles tested carried a mediam lethal dose for an adult mallard duck. Examination of stomach contents of aquatic birds dead of botulism showed that some had consumed invertebrates.

Utah↗

The susceptibility of the mallard duck (Anas platyrhynchos) to Clostridium botulinum C2 toxin

Most strains of Clostridium botulinum type C, after having lost their capacity to produce their dominant toxin (C 1 ) as a result of being“cured”of their prophages, continue to produce C 2 , a trypsin-activable toxin reported by other investigators. While of relatively low toxicity when administered perorally to the adult mallard duck ( Anas platyrhynchos ), it was highly toxic when given parenterally. By the intravenous route, for example, it was more than 1, 000 times as toxic as C 1 toxin by the same route, when compared on the basis of mouse intraperitoneal toxicity. The cause of death in every instance was massive pulmonary edema and hemorrhage rather than the respiratory paralysis that occurs in C 1 intoxication. 抄録

Japanese Journal of Medical Science and Biology↗

Molecular characteristics versus biological activity

The molecular characteristics of mononitrophenols containing halogens not only play a key role in their biological activity but provide a novel example of selective toxicity among vertebrate animals. It has been reported that efforts to control the parasitic sea lamprey in the Great Lakes are directed at present to the applications of a selective toxicant to streams inhabited by lamprey larvae. Since 1961, the larvicide that has been used almost exclusively in the control program has been 3-trifluoromethyl-4-nitrophenol (TFM). However, this is only one of about 15 closely related compounds, all halogen-containing mononitrophenols, that display a selectively toxic action upon lampreys. Although not all of the halogenated mononitrophenols are selectively toxic to lampreys (in fact, fewer than half of those tested), no other group of related compounds has displayed any useful larvicidal activity except for the substituted nitrosalicylanilides.

Chemistry↗