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Use of chemical analysis and assays of semipermeable membrane devices extracts to assess the response of bioavailable organic pollutants in streams to urbanization in six metropolitan areas of the United States

Studies to assess the effects of urbanization on stream ecosystems are being conducted as part of the U.S. Geological Survey’s National Water-Quality Assessment (NAWQA) Program. The overall objectives of these studies are to (1) determine how hydrologic, geomorphic, water quality, habitat, and biological characteristics respond to land-use changes associated with urbanization in specific environmental settings, and (2) compare these responses across environmental settings. As part of an integrated assessment, semipermeable membrane devices (SPMDs) were deployed in streams along a gradient of urban land-use intensity in and around Atlanta, Georgia; Raleigh-Durham, North Carolina; and Denver-Fort Collins, Colorado, in 2003; and Dallas-Fort Worth, Texas; Milwaukee-Green Bay, Wisconsin; and Portland, Oregon, in 2004. Sites were selected to avoid point-source discharge and to minimize natural variability within each of the six metropolitan areas. In addition to standard chemical analysis for hydrophobic organic contaminants, three assays were used to address mixtures and potential toxicity: (1) Fluoroscan provides an estimate of the total concentration of polycyclic aromatic hydrocarbons (PAHs); (2) the P450RGS assay indicates the presence and levels of aryl hydrocarbon receptor agonists; and (3) Microtox® measures toxicological effects on photo-luminescent bacteria. Of the 140 compounds targeted or identified by gas chromatography/mass spectrometry analysis in this study, 67 were not detected. In terms of numbers and types of compounds, the following were detected: 2 wood preservatives, 6 insecticides (parent compounds), 5 herbicides, 22 polycyclic aromatic hydrocarbons, 2 dibenzofurans, 4 polychlorinated biphenyls, 7 compounds associated with fragrances or personal care products, 4 steroids associated with wastewater, 5 polydibromated diphenyl ethers (flame retardants), 3 plasticizers, 3 antimicrobials/disinfectants, and 3 detergent metabolites. Of the 73 compounds detected and three assays utilized, 29 were detected in 25 percent or more of the streams and were strongly related to increases in urban intensity (defined as having a Spearman’s rho > 0.5 with percent urban land cover) in at least one of the six metropolitan areas investigated. These 29 endpoints included 16 PAHs, a wood preservative (pentachloroanisole), 2 insecticides (chlorpyrifos and chlordane), 3 herbicides (benfluralin, trifluralin, and dacthal), a synthetic musk (hexahydrohexamethylcyclopentabenzopyran, HHCB), 2 furans (methyldibenzofuran and benzo[b]naphtho[2,3-d]furan), and a flame retardant (BDE 47). In addition, the number of compounds detected and results of the Fluoroscan and P450RGS assays were strongly related to urban intensity. Average water concentrations estimated from SPMDs were compared to screening benchmarks for the protection of human health and aquatic life; of the 14 compounds with available benchmarks, 3 compounds (anthracene, dieldrin, and diazinon) exceeded those levels in one or more streams. Both dieldrin and anthracene exceeded their respective benchmarks in seven streams, and diazinon in only one stream. There were more exceedances in Milwaukee-Green Bay and Raleigh-Durham than in the other metropolitan areas, and there were no exceedances in Dallas-Fort Worth. The six metropolitan areas studied differed in the number and types of endpoints related to urban intensity, probably from a combination of factors governing source strength, transport, and fate of hydrophobic compounds. The number of endpoints strongly related to urban intensity ranged from 3 in Dallas-Fort Worth and Portland to 21 in Raleigh-Durham. High frequencies of detection and strong correlations with urban land cover for pyrogenic PAHs (such as unsubstituted 4-ringed PAHs) in all six metropolitan areas indicate that these compounds are an important component of urbanization, regardless of location. Pentachloroanisole, dibenzofurans, and petrogenic PAHs (alkylated PAHs and heterocyclic dibenzothiophenes) were frequently detected and strongly related to urban intensity in Atlanta, Raleigh-Durham, Milwaukee-Green Bay, and Denver-Fort Collins. Two insecticides were related to urban intensity: chlorpyrifos in Atlanta, Raleigh-Durham, and Dallas-Fort Worth; and chlordane in Raleigh-Durham. Three herbicides were strongly related to urban intensity: trifluralin in Atlanta and Raleigh-Durham; benfluralin in Atlanta, and dacthal in Denver-Fort Collins. The detection frequencies for most wastewater indicator compounds were too low to establish relations with urban intensity. Of the wastewater compounds analyzed, HHCB in Raleigh-Durham and Denver-Fort Collins, and BDE 47 in Denver-Fort Collins and Dallas-Forth Worth, had the strongest relations with urban intensity. In addition to pyrogenic PAHs, levels of aryl hydrocarbon receptor agonists (as measured by the P450RGS assay) were strongly related to increasing urban intensity in all six metropolitan areas. PAHs were the only group of aryl hydrocarbon agonists consistently detected and related with urban intensity in all six metropolitan areas. It is unknown which compounds in the SPMDs caused the increased response in the P450RGS assay because the SPMDs likely contained many aryl hydrocarbon receptor agonists not quantified by chemical analysis. It is clear that bioavailable, aryl hydrocarbon receptor agonists increase in streams with increasing urban intensity in the basin. Potential toxicity mediated by this metabolic pathway should be considered in integrated assessments of the response of aquatic biota to urbanization.

Scientific Investigations Report

Biological water-quality assessment of selected streams in the Milwaukee Metropolitan Sewerage District Planning Area of Wisconsin, 2007

Changes in the water quality of stream ecosystems in an urban area may manifest in conspicuous ways, such as in murky or smelly streamwater, or in less conspicuous ways, such as fewer native or pollution-sensitive organisms. In 2004, and again in 2007, the U.S. Geological Survey sampled stream organisms—algae, invertebrates, and fish—in 14 Milwaukee area streams to assess water quality as part of the ongoing Milwaukee Metropolitan Sewerage District (MMSD) Corridor Study. In addition, passive-sampling devices (SPMDs, “semipermeable membrane devices”) were deployed at a subset of sites in order to evaluate the potential exposure of stream organisms to certain toxic chemicals. Results of the 2007 sampling effort are the focus of this report. Results of sampling from 2007 are compared with results from 2004. The water quality of sampled streams was assessed by evaluating biological-assemblage data, metrics computed from assemblage data, and an aggregate bioassessment ranking method that combined data for algae, invertebrates, and fish. These data contain information about the abundance (number) of different species in each group of stream organisms and the balance between species that can or cannot tolerate polluted or disturbed conditions. In 2007, the highest numbers of algal, invertebrate, and fish species were found at the Milwaukee River at Milwaukee, the largest sampled site. Algal results indicated water quality concerns at 10 of the 14 sampled sites due to the occurrence of nuisance algae or low percentages of pollution-sensitive algae. When compared to 2004, total algal biovolume was higher in 2007 at 12 of 14 sites, due mostly to more nuisance green algae from unknown causes. Results of several metrics, including the Hilsenhoff Biotic Index (HBI-10), suggest that invertebrate assemblages in the Little Menomonee River, Underwood Creek, and Honey Creek were poorer quality in 2007 compared to 2004. Six sites received “very poor” quality ratings for fish in 2007, mostly because inadequate numbers of fish were collected at five sites to allow computation of an Index of Biotic Integrity (IBI); this resulted in three additional sites receiving “very poor” ratings compared to 2004. Some signs of potential improvement in the fish assemblage were evident at Lincoln Creek, possibly reflecting delayed effects of the restoration of stream habitat, completed in 2002; however, algae and invertebrates did not show signs of improvement. Aggregate bioassessment rankings across all groups of organisms for 2004 and 2007 indicated that water quality at the two Milwaukee River main stem sites (at Milwaukee and near Cedarburg), Jewel Creek, and the Menomonee River at Menomonee Falls was the least-degraded among all sampled sites. Rankings for Oak Creek and Little Menomonee suggested water quality was worse in 2007 compared to 2004 and placed these two sites together with Kinnickinnic River and Underwood Creek, two concrete-line sites, indicating the most-degraded water quality among all sampled sites. The aggregate ranking for Lincoln Creek in 2007 would have placed it in the most-degraded category but for the positive influence of the fish ranking when compared to poor algal and invertebrate rankings. Potential toxicity due to certain manmade chemicals, such as polycyclic aromatic hydrocarbons (PAHs), was found at all six sites where SPMDs were deployed. As was found in 2004, the highest potential toxicity in 2007 was observed at Lincoln Creek where chemical screening in 2007 also showed the highest total PAHs of all six sites; however, potential toxicity at Little Menomonee River, Honey Creek, and Kinnickinnic River was relatively high compared to Milwaukee River near Cedarburg. Although toxicity and chemical results in 2007 did not agree with aggregate rankings for Lincoln Creek because of fish, nor for Honey Creek, the results did agree with aggregate rankings at four of the six sites. In addition to toxicological and chemical influences, the more urbanized sites have high percentages of impervious surface area, resulting in frequent high stream flows that can adversely affect algal, invertebrate, and fish assemblages. Assessments of the ecological status of different groups of organisms and of potential chemical and physical stressors to organisms are important tools in evaluating streamwater quality.

Wisconsin

Software for analysis of chemical mixtures--composition, occurrence, distribution, and possible toxicity

The composition, occurrence, distribution, and possible toxicity of chemical mixtures in the environment are research concerns of the U.S. Geological Survey and others. The presence of specific chemical mixtures may serve as indicators of natural phenomena or human-caused events. Chemical mixtures may also have ecological, industrial, geochemical, or toxicological effects. Chemical-mixture occurrences vary by analyte composition and concentration. Four related computer programs have been developed by the National Water-Quality Assessment Program of the U.S. Geological Survey for research of chemical-mixture compositions, occurrences, distributions, and possible toxicities. The compositions and occurrences are identified for the user-supplied data, and therefore the resultant counts are constrained by the user’s choices for the selection of chemicals, reporting limits for the analytical methods, spatial coverage, and time span for the data supplied. The distribution of chemical mixtures may be spatial, temporal, and (or) related to some other variable, such as chemical usage. Possible toxicities optionally are estimated from user-supplied benchmark data. The software for the analysis of chemical mixtures described in this report is designed to work with chemical-analysis data files retrieved from the U.S. Geological Survey National Water Information System but can also be used with appropriately formatted data from other sources. Installation and usage of the mixture software are documented. This mixture software was designed to function with minimal changes on a variety of computer-operating systems. To obtain the software described herein and other U.S. Geological Survey software, visit http://water.usgs.gov/software/.

Scientific Investigations Report

Anthropogenic organic compounds in source water of select community water systems in the United States, 2002-10

Drinking water delivered by community water systems (CWSs) comes from one or both of two sources: surface water and groundwater. Source water is raw, untreated water used by CWSs and is usually treated before distribution to consumers. Beginning in 2002, the U.S. Geological Survey’s (USGS) National Water-Quality Assessment Program initiated Source Water-Quality Assessments (SWQAs) at select CWSs across the United States, primarily to characterize the occurrence of a large number of anthropogenic organic compounds that are predominantly unregulated by the U.S. Environmental Protection Agency. Source-water samples from CWSs were collected during 2002–10 from 20 surface-water sites (river intakes) and during 2002–09 from 448 groundwater sites (supply wells). River intakes were sampled approximately 16 times during a 1-year sampling period, and supply wells were sampled once. Samples were monitored for 265 anthropogenic organic compounds. An additional 3 herbicides and 16 herbicide degradates were monitored in samples collected from 8 river intakes and 118 supply wells in areas where these compounds likely have been used. Thirty-seven compounds have an established U.S. Environmental Protection Agency (EPA) Maximum Contaminant Level (MCL) for drinking water, 123 have USGS Health-Based Screening Levels (HBSLs), and 29 are included on the EPA Contaminant Candidate List 3. All compounds detected in source water were evaluated both with and without an assessment level and were grouped into 13 categories (hereafter termed as “use groups”) based on their primary use or source. The CWS sites were characterized in a national context using an extract of the EPA Safe Drinking Water Information System to develop spatially derived and system-specific ancillary data. Community water system information is contained in the EPA Public Supply Database, which includes 2,016 active river intakes and 112,099 active supply wells. Ancillary variables including population served, watershed size, land use, population density, and recharge were characterized for each of the watersheds for river intakes and contributing areas for supply wells. A total of 313 samples were collected from 20 river intakes. Between the years of 2002 through 2010, samples were collected approximately 16 times over the course of a year. Seventy-one compounds from 12 of the 13 use groups commonly occurred (detected in greater than or equal to 1 percent of samples using an assessment level of 0.05 microgram per liter or when a compound was detected in greater than or equal to 10 percent of samples without an assessment level) indicating a wide variety of sources and pathways to these rivers and highlighting the importance of source-water protection strategies. A total of 448 supply wells were sampled once during 2002–10 as part of 30 independent groundwater studies. About 15 CWS supply wells were sampled for each independent groundwater study. Twenty-eight compounds from 7 of the 13 use groups commonly occurred indicating a wide variety of sources and pathways exist for these compounds to reach these wells and highlighting the importance of wellhead protection strategies. About one-half the 265 compounds monitored (122) were detected in both surface water and groundwater samples. A more diverse suite of compounds were detected in surface water in comparison to groundwater. However, herbicides and herbicide degradates were the most frequent group of compounds detected in both surface water and groundwater. Sixty-five of the most commonly occurring compounds were detected in one or more samples from both surface water and groundwater. Human-health benchmarks (MCLs for regulated compounds and HBSLs for unregulated compounds) were available for more than one-half the compounds (160 of the 265) monitored in this study. Fifty-eight percent (41 of 71) of the commonly occurring compounds in surface water have a human-health benchmark to which concentrations can be compared; 19 have MCLs and 22 have HBSLs. Eighty-three percent (24 of 28) of the most commonly occurring compounds in groundwater have a human-health benchmark for which concentrations can be compared; 14 have MCLs and 10 have HBSLs. To put results from this study into context with the national distribution of river intakes and supply wells used by CWSs, sites were grouped into the respective national population of land-use quartiles. The increase in compound occurrence with increasing urban and agricultural land use in the watershed or contributing area was more evident for rivers than for supply wells. The increase in detection frequency of herbicides and herbicide degradates with increasing agricultural land use was more evident for rivers than for supply wells. The occurrence of solvents did not change substantially with increasing urban land use for rivers or supply wells. Basic co-occurrence analyses were completed with and without an assessment level. Considering all detections in surface water without an assessment level, approximately 86 percent of source-water samples contained 2 or more compounds, and 50 percent of samples contained at least 14 compounds. Considering all detections in groundwater without an assessment level, 50 percent of samples contained at least three compounds. For the most part, the compounds detected most frequently as individual compounds in the environment often composed the most frequent unique mixtures. Five of the 10 most frequently co-occurring unique mixtures in both surface water and groundwater were the same: atrazine and deethylatrazine; atrazine and chloroform; deethylatrazine and simazine; atrazine and simazine; and deethylatrazine, atrazine, and simazine. Because similar mixtures were identified in both surface water and groundwater without an assessment level, future studies could be directed toward better understanding the toxicological importance of these unique mixtures. Summed concentrations of herbicide degradates were compared to concentrations of the parent herbicides in surface-water and groundwater samples collected from 8 river intakes and 118 CWS wells, from which samples were analyzed for an additional 3 herbicides and 16 degradates. The toxicity to humans for many of these degradate products is largely unknown and thus points to the importance of monitoring these compounds (both the parent and degradate) in the environment. This study highlights the importance of anthropogenic organic compounds in source water of select CWSs in the United States by characterizing their occurrence in surface-water and groundwater samples. Compound concentrations and occurrence are summarized and evaluated in a human-health context, when possible. Additionally, compounds found to co-occur as mixtures for both surface water and groundwater highlight the significance of low-level compound co-occurrence.

Scientific Investigations Report

Development of ion-exchange collectors for monitoring atmospheric deposition of inorganic pollutants in Alaska parklands

Between 2010 and 2014, the U.S. Geological Survey completed a series of laboratory and field experiments designed to develop methodology to support the National Park Service’s long-term atmospheric pollutant monitoring efforts in parklands of Arctic Alaska. The goals of this research were to develop passive sampling methods that could be used for long-term monitoring of inorganic pollutants in remote areas of arctic parklands and characterize relations between wet and dry deposition of atmospheric pollutants to that of concentrations accumulated by mosses, specifically the stair-step, splendid feather moss, Hylocomium splendens. Mosses and lichens have been used by National Park Service managers as atmospheric pollutant biomonitors since about 1990; however, additional research is needed to better characterize the dynamics of moss bioaccumulation for various classes of atmospheric pollutants. To meet these research goals, the U.S. Geological Survey investigated the use of passive ionexchange collectors (IECs) that were adapted from the design of Fenn and others (2004). Using a modified IEC configuration, mulitple experiments were completed that included the following: (a) preliminary laboratory and development testing of IECs, (b) pilot-scale validation field studies during 2012 with IECs at sites with instrumental monitoring stations, and (c) deployment of IECs in 2014 at sites in Alaska having known or suspected regional sources of atmospheric pollutants where samples of Hylocomium splendens moss also could be collected for comparison. The targeted substances primarily included ammonium, nitrate, and sulfate ions, and certain toxicologically important trace metals, including cadmium, cobalt, copper, nickel, lead, and zinc. Deposition of atmospheric pollutants is comparatively low throughout most of Alaska; consequently, modifications of the original IEC design were needed. The most notable modification was conversion from a single-stage mixed-bed column to a two-stage arrangement. With the modified IEC design, ammonium, nitrate, and sulfate ions were determined with a precision of between 5 and 10 percent relative standard deviation for the low loads that happen in remote areas of Alaska. Results from 2012 field studies demonstrated that the targeted ions were stable and fully retained on the IEC during field deployment and could be fully recovered by extraction in the laboratory. Importantly, measurements of annual loads determined by combining snowpack and IEC sampling at sites near National Atmospheric Deposition Program monitoring stations was comparable to results obtained by the National Atmospheric Deposition Program. Field studies completed in 2014 included snowpack and IEC samples to measure depositional loads; the results were compared to concentrations of similar substances in co-located moss samples. Analyses of constituents in snow and IECs included ammonium, nitrate, and sulfate ions; and a suite of trace metals. Constituent measurements in Hylocomium splendens moss included total nitrogen, phosphorous, and sulfur, and trace metals. To recover ammonium ions and metal ions from the upper cation-exchange column, a two-step extraction procedure was developed from laboratory spiking experiments. The 2014 studies determined that concentrations of certain metals, nitrogen, and sulfur in tissues of Hylocomium splendens moss reflected differences in presumptive deposition from local atmospheric sources. Moss tissues collected from two sites farthest from urban locales had the lowest levels of total nitrogen and sulfur, whereas tissues collected from three of the urban sites had the greatest concentrations of many of the trace metals. Moss tissue concentrations of three trace metals (cobalt, chromium, and nickel) were strongly (positively) Spearman’s rank correlated ( p <0.05) with annual depositional loads of those metals. In addition, moss sulfur concentrations were positively rank correlated with annual depositional loads of sulfate ( p <0.07). Exploratory models indicated linear uptake of the three metals by Hylocomium splendens moss and nonlinear uptake of sulfur from sulfate. Our results provided useful preliminary models for several of the targeted substances; however, our ability to characterize relations between concentrations in moss and loadings for many of the metals was precluded by several factors. The few test sites, small concentration gradients, and generally low concentrations hampered model developments. In addition, the weather was unusually warm throughout Alaska during the winter of 2013–14, which caused intermittent melting of the snowpack at some of the test sites; consequently, our measurements of overwinter loads based on snowpack samples (obtained in late March) probably underestimated the actual loads. Regardless of these potential limitations, these studies have established a foundation to support further studies that can improve our understanding of how mosses accumulate inorganic substances and ultimately how mosses might be used as biomonitors of atmospheric pollutants; moreover, the successful development and validation of the IECs during this research documents how the methodology can be used for future monitoring efforts in remote regions of Alaska and elsewhere.

Alaska

Relations among rainstorm runoff, streamflow, pH, and metal concentrations, Summitville Mine area, upper Alamosa River basin, southwest Colorado, 1995-97

The upper Alamosa River Basin contains areas that are geochemically altered and have associated secondary sulfide mineralization. Occurring with this sulfide mineralization are copper, gold, and silver deposits that have been mined since the 1870's. Weathering of areas with sulfide mineralization produces runoff with anomalously low pH and high metal concentrations; mining activities exacerbate the condition. Summer rainstorms in the upper Alamosa River Basin produce a characteristic relation between streamflow and pH; streamflow suddenly increases and pH suddenly decreases (commonly by more than 1 pH unit). This report evaluates changes in pH in the upper Alamosa River Basin during July, August, and September 1995, 1996, and 1997 to examine possible adverse environmental effects due to rainstorm runoff. Ninety-three percent of the rainstorms occurring during 1995?97 produced runoff throughout the entire basin. Out of 54 storms, only 3 storms were isolated to the river reach upstream from the streamflow-gaging station Alamosa River above Wightman Fork, and only 1 storm was isolated to the river reach between the streamflow-gaging stations Alamosa River below Jasper and Alamosa River above Terrace Reservoir. Although most rainstorm runoff events occurred throughout the entire basin, pH changes were highest in parts of the basin that receive runoff from hydrothermally altered areas. The three principal altered areas within the basin are the Jasper, Stunner, and Summitville areas. Only limited mining occurred in the Stunner altered area, and yet significant decreases in pH values occur due to runoff from this area. Even after environmental restoration activities are completed at the Summitville Mine, the main stem of the Alamosa River may continue to be adversely affected by runoff from the Stunner and Jasper altered areas. A comparison of measured pH with Federal and State of Colorado water-quality standards and Toxicological Reference Values indicates pH was too low to support aquatic life in many parts of the basin for extended periods of time. Added stresses from sudden decreases in pH due to rainstorm runoff compound the adverse effects. Discharge of effluent from the Summitville Mine impoundment can significantly decrease pH in the Alamosa River downstream to Terrace Reservoir. A release of only 3 cubic feet per second from the impoundment decreased pH by at least 1 standard unit at all downstream sites. Low-flow years may pose a substantial risk to aquatic organisms within and downstream from Terrace Reservoir. During 1996, the basin had a low-flow year, and water storage and pool size of Terrace Reservoir were significantly reduced. The pH of water discharging from Terrace Reservoir was anomalously low during late August and September 1996, possibly due to geochemical interactions between sediment and the water column within the reservoir. In general, an inverse log-log relation exists between pH and the logarithm of dissolved metal concentrations, but the relations generally are not significant enough to confidently predict metal concentrations based upon measured pH values.

Water-Resources Investigations Report

Volcanic ash activates the NLRP3 inflammasome in murine and human macrophages

Volcanic ash is a heterogeneous mineral dust that is typically composed of a mixture of amorphous (glass) and crystalline (mineral) fragments. It commonly contains an abundance of the crystalline silica (SiO 2 ) polymorph cristobalite. Inhalation of crystalline silica can induce inflammation by stimulating the NLRP3 inflammasome, a cytosolic receptor complex that plays a critical role in driving inflammatory immune responses. Ingested material results in the assembly of NLRP3, ASC, and caspase-1 with subsequent secretion of the interleukin-1 family cytokine IL-1β. Previous toxicology work suggests that cristobalite-bearing volcanic ash is minimally reactive, calling into question the reactivity of volcanically derived crystalline silica, in general. In this study, we target the NLRP3 inflammasome as a crystalline silica responsive element to clarify volcanic cristobalite reactivity. We expose immortalized bone marrow-derived macrophages of genetically engineered mice and primary human peripheral blood mononuclear cells (PBMCs) to ash from the Soufrière Hills volcano as well as representative, pure-phase samples of its primary componentry (volcanic glass, feldspar, cristobalite) and measure NLRP3 inflammasome activation. We demonstrate that respirable Soufrière Hills volcanic ash induces the activation of caspase-1 with subsequent release of mature IL-1β in a NLRP3 inflammasome-dependent manner. Macrophages deficient in NLRP3 inflammasome components are incapable of secreting IL-1β in response to volcanic ash ingestion. Cellular uptake induces lysosomal destabilization involving cysteine proteases. Furthermore, the response involves activation of mitochondrial stress pathways leading to the generation of reactive oxygen species. Considering ash componentry, cristobalite is the most reactive pure-phase with other components inducing only low-level IL-1β secretion. Inflammasome activation mediated by inhaled ash and its potential relevance in chronic pulmonary disease was further evidenced in PBMC using the NLRP3 small-molecule inhibitor CP-456,773 (CRID3, MCC950). Our data indicate the functional activation of the NLRP3 inflammasome by volcanic ash in murine and human macrophages in vitro . Cristobalite is identified as the apparent driver, thereby contesting previous assertions that chemical and structural imperfections may be sufficient to abrogate the reactivity of volcanically derived cristobalite. This is a novel mechanism for the stimulation of a pro-inflammatory response by volcanic particulate and provides new insight regarding chronic exposure to environmentally occurring particles.

Frontiers in Immunology

The determination of Metals in sediment pore waters and in 1N HCl-extracted sediments by ICP-MS

Concentrations of metals in sediment interstitial water (pore water) and those extractable from sediment with weak acids can provide important information about the bioavailability and toxicological effects of such contaminants. The highly variable nature of metal concentrations in these matrices requires instrumentation with the detection limit capability of graphite furnace atomic absorption and the wide dynamic linear range capability of ICP-OES. These criteria are satisfied with ICP-MS instrumentation. We investigated the performance of ICP-MS in the determination of certain metals from these matrices. The results for three metals were compared to those determined by graphite furnace atomic absorption spectroscopy. It was concluded that ICP-MS was an excellent instrumental approach for the determination of metals in these matrices.

Atomic Spectroscopy

Is sensitivity to anticoagulant rodenticides affected by repeated exposure in hawks?

A seminal question in wildlife toxicology is whether exposure to an environmental contaminant, in particular a second-generation anticoagulant rodenticide, can evoke subtle long lasting effects on body condition, physiological function and survival. Many reports indicate that non-target predators often carry residues of several rodenticides, which is indicative of multiple exposures. An often-cited study in laboratory rats demonstrated that exposure to the second-generation anticoagulant rodenticide brodifacoum prolongs blood clotting time for a few days, but weeks later when rats were re-exposed to the first-generation anticoagulant rodenticide warfarin, coagulopathy was more pronounced in brodifacoum-treated rats than naïve rats exposed to warfarin. To further investigate this phenomenon, American kestrels were fed environmentally realistic doses of chlorophacinone or brodifacoum for a week, and following a week-long recovery period, birds were then challenged with a low-level dietary dose of chlorophacinone. In the present study, neither hematocrit nor clotting time (prothrombin time, Russell’s viper venom time) were differentially affected in sequentially exposed kestrels compared to naïve birds fed low-level dietary dose of chlorophacinone. While the present findings do not reveal lasting effects of anticoagulant exposure on blood clotting ability, findings in laboratory rats and other species have demonstrated such effects on blood clotting, and even other molecular pathways associated with immune function and xenobiotic metabolism. Additional studies using an environmentally realistic route of exposure and dose are underway to further test this hypothesis.

Conference Paper

Antimony in mine wastes: Geochemistry, mineralogy, microbiology

Antimony (Sb) is a valuable mined commodity, used mostly in fire retardants, and considered a critical element. It is also a potential environment hazard classed as a carcinogen. Antimony is concentrated in tailings and waste rock from Sb mines as well as other locations, such as precious metal deposits, where Sb is present in the ore but not recovered. This review covers the aqueous geochemistry, isotope chemistry, mineralogy, and microbiology of Sb in the context of mine waste. The primary minerals stibnite and sulfosalts may release Sb in surface and groundwaters and result in contamination of soils, plants, and river sediments. In some cases, Sb mobility is limited by its adsorption and incorporation into Fe (oxyhydr)oxides. At higher Sb concentrations, precipitation of Sb secondary hosts such as tripuhyite (FeSbO 4 , relatively insoluble) and brandholzite (Mg[Sb(OH) 6 ] 2 · 6H 2 O, highly soluble) influence Sb concentrations in water associated with mine waste. Although Sb is nonessential to organisms, microorganisms are involved in oxidation, reduction, and methylation processes that can drive biogeochemical transformations. Limited toxicological information about Sb makes it challenging to establish regulations or guidelines limiting the concentration of Sb. Antimony is frequently associated with arsenic in mine waste, and remediation design is often based on the assumption that both metalloids behave in a similar way. However, new research suggests that in some environments, this is not the case, and Sb should be considered based on its unique biogeochemical behavior.

Economic Geology

Eggshell thickness and egg morphometrics in five songbird species from the Central Valley, California

Avian eggshell thickness is an important life history metric in birds and has broad applications across disciplines ranging from animal behavior to toxicology. Empirical eggshell thickness values for songbirds (Order Passeriformes) are under-represented in the literature due to the difficulty of measuring smaller eggs using traditional methods. We used a Hall-effect thickness gauge to measure eggs of five focal songbird species from California’s Central Valley: House Wren ( Troglodytes aedon ; n = 567), Tree Swallow ( Tachycineta bicolor ; n = 297), Ash-throated Flycatcher ( Myiarchus cinerascens ; n = 21), Western Bluebird ( Sialia mexicana ; n = 13), and Bewick’s Wren ( Thryomanes bewickii ; n = 5). We compared minimum eggshell thickness measurements at the equator and sharp pole, and we related eggshell thickness to other egg morphometrics and adult body mass. Eggshell thickness at the equator was 5.6% thicker in Ash-throated Flycatchers and 3.5% thinner in Tree Swallows compared with eggshell thickness at the sharp pole. Among species, eggshell thickness at the sharp pole was greater in species with larger eggs, whereas, within species, larger eggs were thinner at the sharp pole. Eggshells were 8% and 11% thinner in late incubation eggs (≥75% of total incubation duration) than early incubation (≤10% of total incubation duration) for House Wren and Tree Swallow eggs, respectively. Whenever possible, it is preferable to use empirical eggshell thickness data that are specific to the species and geographic region being studied, and a relatively new method used in this study allows accurate measurement of small eggs without having to compromise the integrity of preserved eggshell specimens.

Journal of Field Ornithology

Accumulation of lead and organochlorine residues in captive American kestrels fed pine voles from apple orchards

Pine voles (Microtus pinetorum) were collected from pesticide-treated orchards in New York and fed to 3 captive American kestrels (Falco sparverius) for 60 days to evaluate potential hazards from soil-borne persistent insecticides. Three control kestrels were fed uncontaminated laboratory mice (Mus musculus). The pine voles contained an average of 38 ppm lead, 48 ppm DDE and 1.2 ppm dieldrin (dry weight). The kestrels accumulated sublethal amounts of lead (1 ppm lead wet weight) in their livers. In contrast, DDE and dieldrin accumulated in the tissues and brains of kestrels to toxicologically significant concentrations. Control kestrels remained healthy and accumulated insignificant concentrations of the contaminants. The results indicated raptors may not be significantly at risk from lead residues in soil and biota following field applications of lead arsenate. However, sublethal effects may be expected from the level of contamination by organochlorine pesticides. raptors may not be significantly at risk from lead residues in soil and biota following field applications of lead arsenate. However, sublethal effects may be expected from the level of contamination byorganochlorine pesticides. lead wet weight) in their livers.

Journal of Wildlife Diseases

Pentachlorophenol Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Pentachlorophenol (PCP) is now widely used as a wood preservative, and this has contributed to the detection of PCP residues in air, rain, groundwaters, surface waters, fish and aquatic invertebrates, and in human urine, blood, and milk of nursing mothers. This report briefly reviews the technical literature on ecological and toxicological aspects of PCP in the environment, with emphasis on fishery and wildlife resources. Subtopics include sources and uses, chemical properties, fate, background concentrations, lethal and sublethal effects, and current recommendations for resource protection

Contaminant Hazard Reviews

Atrazine Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

The herbicide atrazine (2chloro4ethylamino6isopropylamino1,3,5triazine) is the most heavily used agricultural pesticide in North America. Domestically, more than 50 million kg are applied yearly to more than 25 million ha, primarily to control weeds in corn and sorghum crops. Atrazine residues have been detected in runoff from treated fields in lakes and streams at phytotoxic levels. Birds and mammals were comparatively resistant, with a low probability for atrazine accumulation and retention. Data are lacking on indirect effects of atrazine on wildlife granivores and insectivores. Direct effects to aquatic fauna occur at 94 micrograms/l, and higher; however, indirect effects may occur at 20 micrograms/l, and higher, partly through reduction of the food supply of herbivores, and partly through loss of macrophyte habitat. Ecological and toxicological aspects of atrazine in the environment are briefly reviewed, with special emphasis on fishery and wildlife resources.

Contaminant Hazard Reviews

Molybdenum Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Ecological and toxicological aspects of molybdenum (Mo) in the environment are briefly reviewed, with emphasis on fish and wildlife. Subtopics include sources and uses, chemical properties, mode of action, background concentrations in biological and nonbiological samples, and lethal and sublethal effects on terrestrial plants and invertebrates, aquatic organisms, birds, and mammals. Current recommendations for Mo and the protection of sensitive living resources are presented.

Contaminant Hazard Reviews

Boron Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Ecological and toxicological aspects of boron (B) in the environment are reviewed, with emphasis on natural resources. Subtopics covered include environmental chemistry, background concentrations, effects, and current recommendations for the protection of living resources. Boron is not now considered essential in mammalian nutrition, although low dietary levels protect against fluorosis and bone demineralization. Excessive consumption (i.e., >1,000 mg B/kg diet, >15 mg B/kg body weight daily, >1.0 mg B/L drinking water, or >210 mg B/kg body weight in a single dose) adversely affects growth, survival, or reproduction in sensitive mammals. Boron and its compounds are potent teratogens when applied directly to the mammalian embryo, but there is no evidence of mutagenicity or carcinogenicity. Boron`s unique affinity for cancerous tissues has been exploited in neutron capture radiation therapy of malignant human brain tumors. Current boron criteria recommended for the protection of sensitive species include <0.3 mg B/L in crop irrigation waters, <1.0 mg B/L for aquatic life, <5.0 mg B/L in livestock drinking waters, <30 mg B/kg in waterfowl diets, and <100 mg B/kg in livestock diets.

Contaminant Hazard Reviews

Famphur Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Famphur (phosphorothioic acid, O,(4((dimethylamino)sulfonyl),phenoyl)O,Odimethyl ester), also known as Warbex, is a systemic organophosphorus insecticide used almost exclusively as a veterinary chemical to control parasite in livestock. Only famphur and its oxygen analog, famoxon, were of toxicological significance; other famphur metabolites were 31 to 237 times less toxic, as Judged by acute oraltoxicity tests in the mouse (Mus sp.). Famphur is administered to livestock by intramuscular or subcutaneous injection, through the diet, as a dermal pour-on, or as an oral bolus. Current recommendations include the discontinuance of topical applications of famphur to cattle because of its association with primary and secondary poisoning of birds, and more research on famphur in the three areas of latent effects on treated livestock, fate and effects in aquatic ecosystems, and carcinogenicity evaluation.

Contaminant Hazard Reviews

Planar PCB Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Ecological and toxicological aspects of polychlorinated biphenyls (PCBs) in the environment are reviewed with emphasis on biologically active congeners and fish and wildlife. Subtopics include sources and uses, chemical and biochemical properties, concentrations in field collections, lethal and sublethal effects, and recommendations for the protection of sensitive resources. All production of PCBs in the United States ceased in 1977. Of the 1.2 million tons of PCBs manufactured to date, about 65% are still in use in electrical equipment and 31% in various environmental compartments, and 4% were degraded or incinerated. The 209 PCB congeners and their metabolites show wide differences in biological effects. A significant part of the toxicity associated with commercial PCB mixtures is related to the presence of about 20 planar congeners, i.e., congeners without chlorine substitution in the ortho position. Toxic planar congeners, like other PCB congeners, have been detected in virtually all analyzed samples, regardless of collection locale. Planar PCB concentrations were usually highest in samples from near urban areas and in fat and liver tissues, filter-feeding bivalve mollusks, fish-eating birds, and carnivorous marine mammals. Adverse effects of planar PCBs on growth, survival, and reproduction are highly variable because of numerous biotic and abiotic modifiers, including interaction with other chemicals. In general, embryos and juveniles were the most sensitive stages tested to planar PCBs, and the chinook salmon, domestic chicken, mink, rhesus macaque, and laboratory white rat were among the most sensitive species. for protection of natural resources, most authorities now recommend (1) analyzation of environmental samples for planar and other potentially hazardous congeners; (2) exposure studies with representative species and specific congeners, alone and in combination with other environmental contaminants; (3) clarification of existing structure-induction-metabolism relations; and (4) more research on physiological and biochemical indicators of PCB-stress.

Contaminant Hazard Reviews