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Antimicrobial residues in animal waste and water resources proximal to large-scale swine and poultry feeding operations

Expansion and intensification of large-scale animal feeding operations (AFOs) in the United States has resulted in concern about environmental contamination and its potential public health impacts. The objective of this investigation was to obtain background data on a broad profile of antimicrobial residues in animal wastes and surface water and groundwater proximal to large-scale swine and poultry operations. The samples were measured for antimicrobial compounds using both radioimmunoassay and liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) techniques. Multiple classes of antimicrobial compounds (commonly at concentrations of >100 μg/l) were detected in swine waste storage lagoons. In addition, multiple classes of antimicrobial compounds were detected in surface and groundwater samples collected proximal to the swine and poultry farms. This information indicates that animal waste used as fertilizer for crops may serve as a source of antimicrobial residues for the environment. Further research is required to determine if the levels of antimicrobials detected in this study are of consequence to human and/or environmental ecosystems. A comparison of the radioimmunoassay and LC/ESI-MS analytical methods documented that radioimmunoassay techniques were only appropriate for measuring residues in animal waste samples likely to contain high levels of antimicrobials. More sensitive LC/ESI-MS techniques are required in environmental samples, where low levels of antimicrobial residues are more likely.

Science of the Total Environment

Detection of hepatitis E virus and other livestock-related pathogens in Iowa streams

Manure application is a source of pathogens to the environment. Through overland runoff and tile drainage, zoonotic pathogens can contaminate surface water and streambed sediment and could affect both wildlife and human health. This study examined the environmental occurrence of gene markers for livestock-related bacterial, protozoan, and viral pathogens and antibiotic resistance in surface waters within the South Fork Iowa River basin before and after periods of swine manure application on agricultural land. Increased concentrations of indicator bacteria after manure application exceeding Iowa's state bacteria water quality standards suggest that swine manure contributes to diminished water quality and may pose a risk to human health. Additionally, the occurrence of HEV and numerous bacterial pathogen genes for Escherichia coli , Enterococcus spp., Salmonella sp., and Staphylococcus aureus in both manure samples and in corresponding surface water following periods of manure application suggests a potential role for swine in the spreading of zoonotic pathogens to the surrounding environment. During this study, several zoonotic pathogens were detected including Shiga-toxin producing E. coli , Campylobacter jejuni , pathogenic enterococci, and S. aureus ; all of which can pose mild to serious health risks to swine, humans, and other wildlife. This research provides the foundational understanding required for future assessment of the risk to environmental health from livestock-related zoonotic pathogen exposures in this region. This information could also be important for maintaining swine herd biosecurity and protecting the health of wildlife near swine facilities.

Iowa

Poultry litter as potential source of pathogens and other contaminants in groundwater and surface water proximal to large-scale confined poultry feeding operations

Manure from livestock production has been associated with the contamination of water resources. To date, research has primarily focused on runoff of these contaminants from animal operations into surface water, and the introduction of poultry-derived pathogenic zoonoses and other contaminants into groundwater is under-investigated. We characterized pathogens and other microbial and chemical contaminants in poultry litter, groundwater, and surface water near confined poultry feeding operations (chicken layer, turkey) at 9 locations in Iowa and one in Wisconsin from May and June 2016. Results indicate that poultry litter from large-scale poultry confined feeding operations is a likely source of environmental contamination and that groundwater is also susceptible to such poultry-derived contamination. Poultry litter, groundwater, and surface water samples had detections of viable bacteria growth (Salmonella spp., enterococci, staphylococci, lactobacilli), multi-drug resistant Salmonella DT104 flost and int genes, F+ RNA coliphage (group I and IV), antibiotic resistance genes (ARGs; blaDHA, blaOXA-48, blaTEM, blaCMY-2, tetM), phytoestrogens (biochanin A, daidzein, formononetin), and a progestin (progesterone). In addition, mcr-1 (a colistin ARG), was detected in a groundwater sample and in another groundwater sample, antibiotic resistant isolates were positive for Brevibacterium spp., a potential signature of poultry in the environment. Detectable estrogenicity was not measured in poultry litter, but was observed in 67% of the surface water samples and 22% were above the U.S. Environmental Protection Agency trigger level of 1 ng/L. The transport of microbial pathogens to groundwater was significantly greater (p < 0.001) than the transport of trace organic contaminants to groundwater in this study. In addition to viable pathogens, several clinically important ARGs were detected in litter, groundwater, and surface water, highlighting the need for additional research on sources of these contaminants in livestock dominated areas.

Iowa, Wisconsin

Natural infrastructure in dryland streams (NIDS) can establish regenerative wetland sinks that reverse desertification and strengthen climate resilience

In this article we describe the natural hydrogeomorphological and biogeochemical cycles of dryland fluvial ecosystems that make them unique, yet vulnerable to land use activities and climate change. We introduce Natural Infrastructure in Dryland Streams (NIDS), which are structures naturally or anthropogenically created from earth, wood, debris, or rock that can restore implicit function of these systems. This manuscript further discusses the capability of and functional similarities between beaver dams and anthropogenic NIDS, documented by decades of scientific study. In addition, we present the novel, evidence-based finding that NIDS can create wetlands in water-scarce riparian zones, with soil organic carbon stock as much as 200 to 1400 Mg C/ha in the top meter of soil. We identify the key restorative action of NIDS, which is to slow the drainage of water from the landscape such that more of it can infiltrate and be used to facilitate natural physical, chemical, and biological processes in fluvial environments. Specifically, we assert that the rapid drainage of water from such environments can be reversed through the restoration of natural infrastructure that once existed. We then explore how NIDS can be used to restore the natural biogeochemical feedback loops in these systems. We provide examples of how NIDS have been used to restore such feedback loops, the lessons learned from installation of NIDS in the dryland streams of the southwestern United States, how such efforts might be scaled up, and what the implications are for mitigating climate change effects. Our synthesis portrays how restoration using NIDS can support adaptation to and protection from climate-related disturbances and stressors such as drought, water shortages, flooding, heatwaves, dust storms, wildfire, biodiversity losses, and food insecurity.

Science of the Total Environment

Drivers of Pb, Sb and As release from spent gunshot in wetlands: Enhancement by organic matter and native microorganisms

In many countries the use of lead-based ammunition is prevalent, and results in exposure and poisoning of waterfowl and other species of birds. In waterfowl hunting areas large quantities of spent shot may be deposited in wetland and terrestrial habitats. These pellets can undergo transformation, which are influenced by various abiotic and biotic factors. In addition to lead (Pb), other elements like antimony (Sb) and arsenic (As) can be leached from Pb shot into the environment. In vitro simulations that included organic matter and microorganisms were utilized to examine elemental leaching from gunshot. We found that leaching efficiency was the greatest in solutions rich in organic matter derived from artificial root exudates (2.69% for Pb, 1.16% for Sb, 1.83% for As), while leaching efficiency was considerably lower in river water (0.04%). In vitro simulations containing native microorganisms also exhibited greater leaching efficiency (0.49% for Pb, 0.52% for Sb, 1.32% for As) than in ultrapure deionized water and river water. Surface alterations in gunshot included the formation of a weathering crust and secondary phases dominated by carbonates. Spent gunshot is a source of Pb, Sb and As in wetlands that could affect aquatic ecosystems.

Science of the Total Environment

Linking fire and the United Nations Sustainable Development Goals

Fire is a ubiquitous natural disturbance that affects 3–4% of the Earth's surface each year. It is a tool used by humans for land clearing and burning of agricultural wastes. The United Nations Sustainable Development Goals (SDGs) do not explicitly mention fire, though many of the Goals are affected by the beneficial and adverse consequences of fires on ecosystem services. There are at least three compelling reasons to include a fire perspective in the implementation of the United Nations Sustainable Development Goals. The first reason relates to the stated vision of the United Nations 2030 Agenda to protect the environment. In order to achieve environmental protection during sustainable development activities, it is necessary to understand and plan for the effects of disturbances, in this case fire, on ecosystem services. The second reason is that fires produce emissions with regional and global impacts on air quality and rainfall patterns. Fires contribute to global warming though the release greenhouse gases, primarily CO 2 , and black carbon, identified as a SLCP (short-lived climate pollutant). The third reason is that fire is one of several complex processes that lead to land degradation across the globe. Opportunities exist to incorporate a fire perspective into sustainable development projects or approaches. Two examples are highlighted here. Transdisciplinary communication and collaboration are needed to address the complex issues related to fire, and to climate and land use change.

Science of the Total Environment

Virulence and biodegradation potential of dynamic microbial communities associated with decaying Cladophora in Great Lakes

Cladophora mats that accumulate and decompose along shorelines of the Great Lakes create potential threats to the health of humans and wildlife. The decaying algae create a low oxygen and redox potential environment favoring growth and persistence of anaerobic microbial populations, including Clostridium botulinum , the causal agent of botulism in humans, birds, and other wildlife. In addition to the diverse population of microbes, a dynamic chemical environment is generated, which involves production of numerous organic and inorganic substances, many of which are believed to be toxic to the sand and aquatic biotic communities. In this study, we used 16S-rDNA-based-amplicon sequencing and microfluidic-based quantitative PCR approaches to characterize the bacterial community structure and the abundances of human pathogens associated with Cladophora at different stages (up to 90 days) of algal decay in laboratory microcosms. Oxygen levels were largely depleted after a few hours of incubation. As Cladophora decayed, the algal microbial biodiversity decreased within 24 h, and the mat transitioned from an aerobic to anaerobic environment. There were increasing abundances of enteric and pathogenic bacteria during decomposition of Cladophora , including Acinetobacter , Enterobacter , Kluyvera , Cedecea , and others. In contrast, there were no or very few sequences (< 0.07%) assigned to such groups in fresh Cladophora samples. Principal coordinate analysis indicated that the bacterial community structure was dynamic and changed significantly with decay time. Knowledge of microbial communities and chemical composition of decaying algal mats is critical to our further understanding of the role that Cladophora plays in a beach ecosystem's structure and function, including the algal role in trophic interactions. Based on these findings, public and environmental health concerns should be considered when decaying Cladophora mats accumulate Great Lakes shorelines.

Great Lakes

A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States - I) Groundwater

As part of the continuing effort to collect baseline information on the environmental occurrence of pharmaceuticals, and other organic wastewater contaminants (OWCs) in the Nation's water resources, water samples were collected from a network of 47 groundwater sites across 18 states in 2000. All samples collected were analyzed for 65 OWCs representing a wide variety of uses and origins. Site selection focused on areas suspected to be susceptible to contamination from either animal or human wastewaters (i.e. down gradient of a landfill, unsewered residential development, or animal feedlot). Thus, sites sampled were not necessarily used as a source of drinking water but provide a variety of geohydrologic environments with potential sources of OWCs. OWCs were detected in 81% of the sites sampled, with 35 of the 65 OWCs being found at least once. The most frequently detected compounds include N , N -diethyltoluamide (35%, insect repellant), bisphenol A (30%, plasticizer), tri(2-chloroethyl) phosphate (30%, fire retardant), sulfamethoxazole (23%, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19%, detergent metabolite). Although sampling procedures were intended to ensure that all groundwater samples analyzed were indicative of aquifer conditions it is possible that detections of some OWCs could have resulted from leaching of well-construction materials and/or other site-specific conditions related to well construction and materials. Future research will be needed to identify those factors that are most important in determining the occurrence and concentrations of OWCs in groundwater.

Science of the Total Environment

Complexation of copper by aquatic humic substances from different environments

The copper-complexing properties of aquatic humic substances isolated from eighteen different environments were characterized by potentiometric titration, using a cupric ion selective electrode. Potentiometric data were analyzed using FITEQL, a computer program for the determination of chemical equilibrium constants from experimental data. All the aquatic humic substances could be modelled as having two types of Cu(II)-binding sites: one with K equal to about 10 6 and a concentration of 1.0 ± 0.4 × 10 −6 M(mg C) −1 and another with K equal to about 10 8 and a concentration of 2.6 ± 1.6 × 10 −7 M(mg C) −1 . A method is described for estimating the Cu(II)-binding sites associated with dissolved humic substances in natural water based on a measurement of dissolved organic carbon, which may be helpful in evaluating chemical processes controlling speciation of Cu and bioavailability of Cu to aquatic organisms.

Science of the Total Environment

Mercury mine drainage and processes that control its environmental impact

Mine drainage from mercury mines in the California Coast Range mercury mineral belt is an environmental concern because of its acidity and high sulfate, mercury, and methylmercury concentrations. Two types of mercury deposits are present in the mineral belt, silica-carbonate and hot-spring type. Mine drainage is associated with both deposit types but more commonly with the silica-carbonate type because of the extensive underground workings present at these mines. Mercury ores consisting primarily of cinnabar were processed in rotary furnaces and retorts and elemental mercury recovered from condensing systems. During the roasting process mercury phases more soluble than cinnabar are formed and concentrated in the mine tailings, commonly termed calcines. Differences in mineralogy and trace metal geochemistry between the two deposit types are reflected in mine drainage composition. Silica-carbonate type deposits have higher iron sulfide content than hot- spring type deposits and mine drainage from these deposits may have extreme acidity and very high concentrations of iron and sulfate. Mercury and methylmercury concentrations in mine drainage are relatively low at the point of discharge from mine workings. The concentration of both mercury species increases significantly in mine drainage that flows through and reacts with calcines. The soluble mercury phases in the calcines are dissolved and sulfate is added such that methylation of mercury by sulfate reducing bacteria is enhanced in calcines that are saturated with mine drainage. Where mercury mine drainage enters and first mixes with stream water, the addition of high concentrations of mercury and sulfate generates a favorable environment for methylation of mercury. Mixing of oxygenated stream water with mine drainage causes oxidation of dissolved iron(II) and precipitation of iron oxyhydroxide that accumulates in the streambed. Both mercury and methylmercury are strongly adsorbed onto iron oxyhydroxide over the pH range of 3.2-7.1 in streams impacted by mine drainage. The dissolved fraction of both mercury species is depleted and concentrated in iron oxyhydroxide such that the amount of iron oxyhydroxide in the water column reflects the concentration of mercury species. In streams impacted by mine drainage, mercury and methylmercury are transported and adsorbed onto particulate phases. During periods of low stream flow, fine-grained iron hydroxide sediment accumulates in the bed load of the stream and adsorbs mercury and methylmercury such that both forms of mercury become highly enriched in the iron oxyhydroxide sediment. During high-flow events, mercury- and methylmercury-enriched iron hydroxide sediment is transported into larger aquatic systems producing a high flux of bioavailable mercury. (C) 2000 Elsevier Science B.V.

Science of the Total Environment

Oil and gas development footprint in the Piceance Basin, western Colorado

Understanding long-term implications of energy development on ecosystem functionrequires establishing regional datasets to quantify past development and determine relationships to predict future development. The Piceance Basin in western Colorado has a history of energy production and development is expected to continue into the foreseeable future due to abundant natural gas resources. To facilitate analyses of regional energy development we digitized all well pads in the Colorado portion of the basin, determined the previous land cover of areas converted to well pads over three time periods (2002–2006, 2007–2011, and 2012–2016), and explored the relationship between number of wells per pad and pad area to model future development. We also calculated the area of pads constructed prior to 2002. Over 21 million m 2 has been converted to well pads with approximately 13 million m 2 converted since 2002. The largest land conversion since 2002 occurred in shrub/scrub (7.9 million m 2 ), evergreen (2.1 million m 2 ), and deciduous (1.3 million m 2 ) forest environments based on National Land Cover Database classifications. Operational practices have transitioned from single well pads to multi-well pads, increasing the average number of wells per pad from 2.5 prior to 2002, to 9.1 between 2012 and 2016. During the same time period the pad area per well has increased from 2030 m 2 to 3504 m 2 . Kernel density estimation was used to model the relationship between the number of wells per pad and pad area, with these curves exhibiting a lognormal distribution. Therefore, either kernel density estimation or lognormal probability distributions may potentially be used to model land use requirements for future development. Digitized well pad locations in the Piceance Basin contribute to a growing body of spatial data on energy infrastructure and, coupled with study results, will facilitate future regional and national studies assessing the spatial and temporal effects of energy development on ecosystem function.

Colorado

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca 2+ , Mg 2+ , Na + , and Cl − are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na + and Cl − drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

Pennsylvania

Robust projections of future fire probability for the conterminous United States

Globally increasing wildfires have been attributed to anthropogenic climate change. However, providing decision makers with a clear understanding of how future planetary warming could affect fire regimes is complicated by confounding land use factors that influence wildfire and by uncertainty associated with model simulations of climate change. We use an ensemble of statistically downscaled Global Climate Models in combination with the Physical Chemistry Fire Frequency Model (PC2FM) to project changing potential fire probabilities in the conterminous United States for two scenarios representing lower (RCP 4.5) and higher (RCP 8.5) greenhouse gas emission futures. PC2FM is a physically-based and scale-independent model that predicts mean fire return intervals from both fire reactant and reaction variables, which are largely dependent on a locale's climate. Our results overwhelmingly depict increasing potential fire probabilities across the conterminous US for both climate scenarios. The primary mechanism for the projected increases is rising temperatures, reflecting changes in the chemical reaction environment commensurate with enhanced photosynthetic rates and available thermal molecular energy. Existing high risk areas, such as the Cascade Range and the Coastal California Mountains, are projected to experience greater annual fire occurrence probabilities, with relative increases of 122% and 67%, respectively, under RCP 8.5 compared to increases of 63% and 38% under RCP 4.5. Regions not currently associated with frequently occurring wildfires, such as New England and the Great Lakes, are projected to experience a doubling of occurrence probabilities by 2100 under RCP 8.5. This high resolution, continental-scale modeling study of climate change impacts on potential fire probability accounts for shifting background environmental conditions across regions that will interact with topographic drivers to significantly alter future fire probabilities. The ensemble modeling approach presents a useful planning tool for mitigation and adaptation strategies in regions of increasing wildfire risk.

Science of the Total Environment

Geologic sources and well integrity impact methane emissions from orphaned and abandoned oil and gas wells

The 160-year history of oil and gas drilling in the United States has left a legacy of unplugged orphaned and abandoned wells, some of which are leaking methane and other hazardous chemicals into the environment. The locations of around 120,000 documented orphaned wells are currently known with the number of undocumented orphaned wells possibly ranging towards a million. The bulk of methane emissions originate from only 10 % of orphaned and abandoned wells, while the remaining wells have undetectable emissions. Understanding the sources of methane emissions from orphaned wells is key to estimating emission rates and prioritizing plugging. In this article, we identify key studies reporting methane emission measurements from orphaned and abandoned wells in the published literature and analyze previously published isotopic methane data to categorize the sources of methane emissions. Three primary geologic sources provide methane to a leaking well that can migrate from geologic formations into or along the wellbore to contaminate groundwater, the surface environment, and the atmosphere. These geologic sources of methane are petroleum (oil and gas) sourced reservoirs, coal seams, and methanogenesis occurring in and around the wellbore. Thermogenic petroleum gas reservoirs are associated with the highest emission rates measured to date. The next highest rates are from coalbed methane sources, while biogenic sources are the lowest based on the publicly available measured emissions data. Well conditions that could potentially enable methane transport include decay of the wellhead and surface infrastructure, wellbore deterioration from corrosive fluids in the subsurface, delamination of the casing and cement, damage from seismicity, and new fracture networks created by hydraulic fracturing of newly drilled neighboring wells. With an understanding of these geologic sources and well conditions, we can (1) better identify areas where high-emitting wells are likely to be present, (2) improve emission rate estimates from orphaned and abandoned wells, and (3) better prioritize wells for plugging.

Science of the Total Environment

Improvement of the R-SWAT-FME framework to support multiple variables and multi-objective functions

Application of numerical models is a common practice in the environmental field for investigation and prediction of natural and anthropogenic processes. However, process knowledge, parameter identifiability, sensitivity, and uncertainty analyses are still a challenge for large and complex mathematical models such as the hydrological/water quality model, Soil and Water Assessment Tool (SWAT). In this study, the previously developed R program language-SWAT-Flexible Modeling Environment (R-SWAT-FME) was improved to support multiple model variables and objectives at multiple time steps (i.e., daily, monthly, and annually). This expansion is significant because there is usually more than one variable (e.g., water, nutrients, and pesticides) of interest for environmental models like SWAT. To further facilitate its easy use, we also simplified its application requirements without compromising its merits, such as the user-friendly interface. To evaluate the performance of the improved framework, we used a case study focusing on both streamflow and nitrate nitrogen in the Upper Iowa River Basin (above Marengo) in the United States. Results indicated that the R-SWAT-FME performs well and is comparable to the built-in auto-calibration tool in multi-objective model calibration. Overall, the enhanced R-SWAT-FME can be useful for the SWAT community, and the methods we used can also be valuable for wrapping potential R packages with other environmental models.

Science of the Total Environment

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis, is beneficial in the prioritization and remediation of mercury-contaminated mine sites. (C) 2000 Elsevier Science B.V.

Science of the Total Environment

Food web contaminant dynamics of a large Atlantic Slope river: Implications for common and imperiled species

Persistent and bioaccumulative contaminants often reach concentrations that threaten aquatic life by causing alterations in organism behavior and development, disruption of biological processes, reproductive abnormalities, and mortality. The objectives of this research were to determine the aquatic food web structure and trophic transfer and accumulation of contaminants within a riverine ecosystem and identify potential stressors to the health of an imperiled fish, the robust redhorse (Moxostoma robustum) and other species of conservation concern in a large Atlantic Slope (USA) river. Trophic position was determined for food web taxa by stable isotope analyses of representative producers, consumers, and organic matter of the Yadkin-Pee Dee River of North Carolina and South Carolina. Contaminant analyses were performed on water, sediment, organic matter, and aquatic biota to assess the prevalence and accumulation of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), current use pesticides (CUPs), polycyclic aromatic hydrocarbons (PAHs), and selected metals. Contaminants were prevalent in the environment and food web components of the river. PCBs were detected in 32% of biotic samples (mean 0.24 μg/g dry weight [DW], range 0.01–3.33 μg/g DW), and DDTs (legacy OCPs and metabolites) were detected in 90% (mean 0.014 μg/g DW, range 0.0004–0.29 μg/g DW). The trace metals manganese and cadmium exceeded published threshold effect concentrations in sediment (460 and 0.99 μg/g DW, respectively). Mercury was detected in all food web samples exhibiting a mean of 0.61 μg/g DW and range 0.006–2.35 μg/g DW (mean 0.13 μg/g wet weight [WW], range 0.001–0.6 μg/g WW). Concentrations exceeded the 0.2 μg/g WW aquatic life criterion for mercury in 38% of fish samples. Fish trophic magnification factors (TMFs; range 0.33–3.75) indicated that contaminant accumulation occurred from both water and dietary sources. The combination of analytical approaches applied here provides new insight into contaminant dynamics with conservation implications.

Science of the Total Environment

Photodegradation of roxarsone in poultry litter leachates

Arsenic compounds have been used extensively in agriculture in the US for applications ranging from cotton herbicides to animal feed supplements. Roxarsone (3-nitro-4-hydroxyphenylarsonic acid), in particular, is used widely in poultry production to control coccidial intestinal parasites. It is excreted unchanged in the manure and introduced into the environment when litter is applied to farmland as fertilizer. Although the toxicity of roxarsone is less than that of inorganic arsenic, roxarsone can degrade, biotically and abiotically, to produce more toxic inorganic forms of arsenic, such as arsenite and arsenate. Experiments were conducted on aqueous litter leachates to test the stability of roxarsone under different conditions. Laboratory experiments have shown that arsenite can be cleaved photolytically from the roxarsone moiety at pH 4-8 and that the degradation rate increases with increasing pH. Furthermore, the rate of photodegradation increases with nitrate and natural organic matter concentration, reactants that are commonly found in poultry-litter-water leachates. Additional photochemical reactions rapidly oxidize the cleaved arsenite to arsenate. The formation of arsenate is not entirely undesirable, because it is less mobile in soil systems and less toxic than arsenite. A possible mechanism for the degradation of roxarsone in poultry litter leachates is proposed. The results suggest that poultry litter storage and field application practices could affect the degradation of roxarsone and subsequent mobilization of inorganic arsenic species. ?? 2002 Elsevier Science B.V. All rights reserved.

Science of the Total Environment