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W. G. Brumbaugh

Publications and source records attributed to W. G. Brumbaugh.

At least 19 recordsLinked to original sources

Improved selenium recovery from tissue with modified sample decomposition

The present paper describes a simple modification of a recently reported decomposition method for determination of selenium in biological tissue by hydride generation atomic absorption. The modified method yielded slightly higher selenium recoveries (3-4%) for selected reference tissues and fish tissue spiked with selenomethionine. Radiotracer experiments indicated that the addition of a small volume of hydrochloric acid to the wet digestate mixture reduced slight losses of selenium as the sample initially went to dryness before ashing. With the modified method, selenium spiked as selenomethionine behaved more like the selenium in reference tissues than did the inorganic spike forms when this digestion modification was used.

Journal of the Association of Official Analytical

Effects of historical lead–zinc mining on riffle-dwelling benthic fish and crayfish in the Big River of southeastern Missouri, USA

The Big River (BGR) drains much of the Old Lead Belt mining district (OLB) in southeastern Missouri, USA, which was historically among the largest producers of lead–zinc (Pb–Zn) ore in the world. We sampled benthic fish and crayfish in riffle habitats at eight sites in the BGR and conducted 56-day in situ exposures to the woodland crayfish (Orconectes hylas) and golden crayfish (Orconectes luteus) in cages at four sites affected to differing degrees by mining. Densities of fish and crayfish, physical habitat and water quality, and the survival and growth of caged crayfish were examined at sites with no known upstream mining activities (i.e., reference sites) and at sites downstream of mining areas (i.e., mining and downstream sites). Lead, zinc, and cadmium were analyzed in surface and pore water, sediment, detritus, fish, crayfish, and other benthic macro-invertebrates. Metals concentrations in all materials analyzed were greater at mining and downstream sites than at reference sites. Ten species of fish and four species of crayfish were collected. Fish and crayfish densities were significantly greater at reference than mining or downstream sites, and densities were greater at downstream than mining sites. Survival of caged crayfish was significantly lower at mining sites than reference sites; downstream sites were not tested. Chronic toxic-unit scores and sediment probable effects quotients indicated significant risk of toxicity to fish and crayfish, and metals concentrations in crayfish were sufficiently high to represent a risk to wildlife at mining and downstream sites. Collectively, the results provided direct evidence that metals associated with historical mining activities in the OLB continue to affect aquatic life in the BGR.

Missouri

Laboratory toxicity and benthic invertebrate field colonization of Upper Columbia River sediments: Finding adverse effects using multiple lines of evidence

From 1930 to 1995, the Upper Columbia River (UCR) of northeast Washington State received approximately 12 million metric tons of smelter slag and associated effluents from a large smelter facility located in Trail, British Columbia, approximately 10 km north of the United States–Canadian border. Studies conducted during the past two decades have demonstrated the presence of toxic concentrations of heavy metals in slag-based sandy sediments, including cadmium, copper, zinc, and lead in the UCR area as well as the downstream reservoir portion of Lake Roosevelt. We conducted standardized whole-sediment toxicity tests with the amphipod Hyalella azteca (28-day) and the midge Chironomus dilutus (10-day) on 11 samples, including both UCR and study-specific reference sediments. Metal concentrations in sediments were modeled for potential toxicity using three approaches: (1) probable effects quotients (PEQs) based on total recoverable metals (TRMs) and simultaneously extracted metals (SEMs); (2) SEMs corrected for acid-volatile sulfides (AVS; i.e., ∑SEM − AVS); and (3) ∑SEM − AVS normalized to the fractional organic carbon (f oc ) (i.e., ∑SEM − AVS/f oc ). The most highly metal-contaminated sample (∑PEQ TRM = 132; ∑PEQ SEM = 54; ∑SEM − AVS = 323; and ∑SEM − AVS/ foc = 64,600 umol/g) from the UCR was dominated by weathered slag sediment particles and resulted in 80% mortality and 94% decrease in biomass of amphipods; in addition, this sample significantly decreased growth of midge by 10%. The traditional ∑AVS – SEM, uncorrected for organic carbon, was the most accurate approach for estimating the effects of metals in the UCR. Treatment of the toxic slag sediment with 20% Resinex SIR-300 metal-chelating resin significantly decreased the toxicity of the sample. Samples ∑SEM − AVS > 244 was not toxic to amphipods or midge in laboratory testing, indicating that this value may be an approximate threshold for effects in the UCR. In situ benthic invertebrate colonization studies in an experimental pond (8-week duration) indicated that two of the most metal-contaminated UCR sediments (dominated by high levels of sand-sized slag particles) exhibited decreased invertebrate colonization compared with sand-based reference sediments. Field-exposed SIR-300 resin samples also exhibited decreased invertebrate colonization numbers compared with reference materials, which may indicate behavioral avoidance of this material under field conditions. Multiple lines of evidence (analytical chemistry, laboratory toxicity, and field colonization results), along with findings from previous studies, indicate that high metal concentrations associated with slag-enriched sediments in the UCR are likely to adversely impact the growth and survival of native benthic invertebrate communities. Additional laboratory toxicity testing, refinement of the applications of sediment benchmarks for metal toxicity, and in situ benthic invertebrate studies will assist in better defining the spatial extent, temporal variations, and ecological impacts of metal-contaminated sediments in the UCR system.

Trail

Toxicity of sediment cores collected from the Ashtabula River in northeastern Ohio, USA, to the amphipod Hyalella azteca

This study was conducted to support a Natural Resource Damage Assessment and Restoration project associated with the Ashtabula River in Ohio. The objective of the study was to evaluate the chemistry and toxicity of 50 sediment samples obtained from five cores collected from the Ashtabula River (10 samples/core, with each 10-cm-diameter core collected to a total depth of about 150 cm). Effects of chemicals of potential concern (COPCs) measured in the sediment samples were evaluated by measuring whole-sediment chemistry and whole-sediment toxicity in the sediment samples (including polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], organochlorine pesticides, and metals). Effects on the amphipod Hyalella azteca at the end of a 28-day sediment toxicity test were determined by comparing survival or length of amphipods in individual sediment samples in the cores to the range of responses of amphipods exposed to selected reference sediments that were also collected from the cores. Mean survival or length of amphipods was below the lower limit of the reference envelope in 56% of the sediment samples. Concentrations of total PCBs alone in some samples or concentrations of total PAHs alone in other samples were likely high enough to have caused the reduced survival or length of amphipods (i.e., concentrations of PAHs or PCBs exceeded mechanistically based and empirically based sediment quality guidelines). While elevated concentrations of ammonia in pore water may have contributed to the reduced length of amphipods, it is unlikely that the reduced length was caused solely by elevated ammonia (i.e., concentrations of ammonia were not significantly correlated with the concentrations of PCBs or PAHs and concentrations of ammonia were elevated both in the reference sediments and in the test sediments). Results of this study show that PAHs, PCBs, and ammonia are the primary COPCs that are likely causing or substantially contributing to the toxicity to sediment-dwelling organisms. ?? 2009 US Government.

Archives of Environmental Contamination and Toxico

Concentrations of cadmium, Cobalt, Lead, Nickel, and Zinc in Blood and Fillets of Northern Hog Sucker (Hypentelium nigricans) from streams contaminated by lead-Zinc mining: Implications for monitoring

Lead (Pb) and other metals can accumulate in northern hog sucker (Hypentelium nigricans) and other suckers (Catostomidae), which are harvested in large numbers from Ozark streams by recreational fishers. Suckers are also important in the diets of piscivorous wildlife and fishes. Suckers from streams contaminated by historic Pb-zinc (Zn) mining in southeastern Missouri are presently identified in a consumption advisory because of Pb concentrations. We evaluated blood sampling as a potentially nonlethal alternative to fillet sampling for Pb and other metals in northern hog sucker. Scaled, skin-on, bone-in "fillet" and blood samples were obtained from northern hog suckers (n = 75) collected at nine sites representing a wide range of conditions relative to Pb-Zn mining in southeastern Missouri. All samples were analyzed for cadmium (Cd), cobalt (Co), Pb, nickel (Ni), and Zn. Fillets were also analyzed for calcium as an indicator of the amount of bone, skin, and mucus included in the samples. Pb, Cd, Co, and Ni concentrations were typically higher in blood than in fillets, but Zn concentrations were similar in both sample types. Concentrations of all metals except Zn were typically higher at sites located downstream from active and historic Pb-Zn mines and related facilities than at nonmining sites. Blood concentrations of Pb, Cd, and Co were highly correlated with corresponding fillet concentrations; log-log linear regressions between concentrations in the two sample types explained 94% of the variation for Pb, 73-83% of the variation for Co, and 61% of the variation for Cd. In contrast, relations for Ni and Zn explained <12% of the total variation. Fillet Pb and calcium concentrations were correlated (r = 0.83), but only in the 12 fish from the most contaminated site; concentrations were not significantly correlated across all sites. Conversely, fillet Cd and calcium were correlated across the range of sites (r = 0.78), and the inclusion of calcium in the fillet-to-blood relation explained an additional 12% of the total variation in fillet Cd. Collectively, the results indicate that blood sampling could provide reasonably accurate and precise estimates of fillet Pb, Co, and Cd concentrations that would be suitable for identifying contaminated sites and for monitoring, but some fillet sampling might be necessary at contaminated sites for establishing consumption advisories. ?? 2009 US Government.

Archives of Environmental Contamination and Toxico

Distribution of pesticides, PAHs, PCBs, and bioavailable metals in depositional sediments of the lower Missouri River, USA

The lower Missouri River was studied to determine the distribution of selected persistent organic pollutants and bioavailable metals in depositional sediments. Nineteen sites between Omaha, Nebraska and Jefferson City, Missouri were sampled. This stretch of the river receives point-source and non-point-source inputs from industrial, urban, and agricultural activities. As part of an ecological assessment of the river, concentrations of 29 legacy organochlorine pesticides (OC pesticides), including chlordanes, DDTs, and hexachlorocyclohexanes; a select list of current-use pesticides, including trifluralin, diazinon, chlorpyrifos, and permethrin, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), divalent metals (copper, nickel, zinc, cadmium, and lead), and polybrominated diphenyl ethers (PBDEs) were determined. Concentrations (dry weight basis) of OC pesticides in the sediments were less than 1 ng/g, with the exception of the backwater sediment collected from the mouth of the Blue River in the Kansas City metropolitan area, which contained up to 20 ng/g total chlordane, 8.1 ng/g p,p???-DDE, 1.5 ng/g lindane, 4.8 ng/g dieldrin, and 3 ng/g endrin. Concentrations of chlorpyrifos and permethrin ranged from less than 1 ng/g to 5.5 ng/g and 44 ng/g, respectively. Concentrations of PCBs ranged from less than 11 ng/g to 250 ng/g, with the Blue River and Sibley sediments containing 100 and 250 ng/g total PCBs, respectively. Concentrations of total PAHs at 17 of the 19 sites ranged from 250 to 700 ng/g, whereas the Riverfront and Blue River sites in Kansas City contained 1100 ng/g and nearly 4000 ng/g, respectively. Concentrations of the metals did not vary significantly among most sites; however, the Blue River site contained elevated concentrations of zinc (104 ??g/g), cadmium (0.7 ??g/g), and lead (34 ??g/g) compared to the other sites. The moderately high concentrations of acid-volatile sulfide in the sediments suggest a low potential for metal toxicity to benthic organisms along this reach of the Missouri River. The depositional area sediments contained concentrations of the targeted persistent organic chemicals and metals that were below published probable effect level concentrations. ?? 2008 Springer Science+Business Media, LLC.

Archives of Environmental Contamination and Toxico

Effects of acclimation on the toxicity of stream water contaminated with zinc and cadmium to juvenile cutthroat trout

We investigated the influence of acclimation on results of in situ bioassays with cutthroat trout in metal-contaminated streams. Cutthroat trout (Oncorhynchus clarki) were held for 21 days (1) in live containers at a reference or "clean" site having dissolved metals near detection limits (0.01 ??g/L cadmium [Cd] and 2.8 ??g/L zinc [Zn]; hardness 32 mg/L as CaCO3) and (2) at a site in a mining-impacted watershed having moderately increased metals (0.07 ??g/L Cd and 38 to 40 ??g/L Zn; hardness 50 mg/L as CaCO3). The 96-hour survival of each treatment group was then tested in situ at five sites from September 5 to 9, 2002, and each group exhibited a range of metal concentrations (0.44 to 39 ??g/L arsenic [As], 0.01 to 2.2 ??g/L Cd, and 0.49 to 856 ??g/L Zn). Survival was 100% at three sites for both treatments. However, a higher percentage of metal-acclimated fish survived at the site with the second highest concentrations of Cd and Zn (0.90 and 238 ??g/L, respectively) compared with fish acclimated at the reference site (100% vs. 55%, respectively). Survival was 65% for acclimated fish and 0% for metal-nai??ve fish at the site with the largest metal concentrations (2.2 ??g/L Cd and 856 ??g/L Zn). Water collected from the site with the largest concentrations of dissolved metals (on October 30, 2002) was used in a laboratory serial dilution to determine 96-hour LC50 values. The 96-hour LC50 estimates of nai??ve fish during the in situ and laboratory experiments were similar (0.60 ??g Cd/L and 226 ??g Zn/L for in situ and 0.64 ??g Cd/L and 201 ??g Zn/L for laboratory serial dilutions). However, mortality of nai??ve cutthroat trout tested under laboratory conditions was more rapid in dilutions of 100%, 75%, and 38% site water than in situ experiments. ?? 2007 Springer Science+Business Media, LLC.

Archives of Environmental Contamination and Toxico

Chronic toxicity of copper and ammonia to juvenile freshwater mussels (Unionidae)

The objectives of the present study were to develop methods for conducting chronic toxicity tests with juvenile mussels under flow-through conditions and to determine the chronic toxicity of copper and ammonia to juvenile mussels using these methods. In two feeding tests, two-month-old fatmucket (Lampsilis siliquoidea) and rainbow mussel (Villosa iris) were fed various live algae or nonviable algal mixture for 28 d. The algal mixture was the best food resulting in high survival (???90%) and growth. Multiple copper and ammonia toxicity tests were conducted for 28 d starting with two-month-old mussels. Six toxicity tests using the algal mixture were successfully completed with a control survival of 88 to 100%. Among copper tests with rainbow mussel, fatmucket, and oyster mussel (Epioblasma capsaeformis), chronic value ([ChV], geometric mean of the no-observed-effect concentration and the lowest-observed-effect concentration) ranged from 8.5 to 9.8 ??g Cu/L for survival and from 4.6 to 8.5 ??g Cu/L for growth. Among ammonia tests with rainbow mussel, fatmucket, and wavy-rayed lampmussel (L. fasciola), the ChV ranged from 0.37 to 1.2 mg total ammonia N/L for survival and from 0.37 to 0.67 mg N/L for growth. These ChVs were below the U.S. Environmental Protection Agency 1996 chronic water quality criterion (WQC) for copper (15 ??g/L; hardness 170 mg/L) and 1999 WQC for total ammonia (1.26 mg N/L; pH 8.2 and 20??C). Results indicate that toxicity tests with two-month-old mussels can be conducted for 28 d with >80% control survival; growth was frequently a more sensitive endpoint compared to survival; and the 1996 chronic WQC for copper and the 1999 chronic WQC for total ammonia might not be adequately protective of the mussel species tested. However, a recently revised 2007 chronic WQC for copper based on the biotic ligand model may be more protective in the water tested. ?? 2007 SETAC.

Environmental Toxicology and Chemistry

Effects of acid-volatile sulfide on metal bioavailability and toxicity to midge (Chironomus tentans) larvae in black shale sediments

Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been studied intensely in recent years. Few studies, however, have determined the spatial variability of AVS and its interaction with simultaneously extracted metals (SEM) in sediments containing elevated concentrations of metals resulting from natural geochemical processes, such as weathering of black shales. We collected four sediment samples from each of four headwater bedrock streams in northcentral Arkansa (USA; three black shale-draining streams and one limestone-draining stream). We conducted 10-d acute whole-sediment toxicity tests using the midge Chironomus tentans and performed analyses for AVS, total metals, SEMs, and organic carbon. Most of the sediments from shale-draining streams had similar total metal and SEM concentrations but considerable differences in organic carbon and AVS. Zinc was the leading contributor to the SEM molar sum, averaging between 68 and 74%, whereas lead and cadmium contributed less than 3%. The AVS concentration was very low in all but two samples from one of the shale streams, and the sum of the SEM concentrations was in molar excess of AVS for all shale stream sediments. No significant differences in mean AVS concentrations between sediments collected from shale-draining or limestone-draining sites were noted (p > 0.05). Midge survival and growth in black shale-derived sediments were significantly less (p < 0.001) than that of limestone-derived sediments. On the whole, either SEM alone or SEM-AVS explained the total variation in midge survival and growth about equally well. However, survival and growth were significantly greater (p < 0.05) in the two sediment samples that contained measurable AVS compared with the two sediments from the same stream that contained negligible AVS. ?? 2007 SETAC.

Environmental Toxicology and Chemistry

Biomonitoring in the Boulder River watershed, Montana, USA: metal concentrations in biofilm and macroinvertebrates, and relations with macroinvertebrate assemblage

Portions of the Boulder River watershed contain elevated concentrations of arsenic, cadmium, copper, lead, and zinc in water, sediment, and biota. We measured concentrations of As, Cd, Cu, Pb, and Zn in biofilm and macroinvertebrates, and assessed macroinvertebrate assemblage and aquatic habitat with the objective of monitoring planned remediation efforts. Concentrations of metals were generally higher in downstream sites compared with upstream or reference sites, and two sites contained metal concentrations in macroinvertebrates greater than values reported to reduce health and survival of resident trout. Macroinvertebrate assemblage was correlated with metal concentrations in biofilm and macroinvertebrates. However, macroinvertebrate metrics were significantly correlated with a greater number of biofilm metals (8) than metals in invertebrates (4). Lead concentrations in biofilm appeared to have the most significant impact on macroinvertebrate assemblage. Metal concentrations in macroinvertebrates were directly proportional to concentrations in biofilm, indicating biofilm as a potential surrogate for monitoring metal impacts in aquatic systems.

Environmental Monitoring and Assessment

The potential for chromium to affect the fertilization process of Chinook salmon ( Oncorhynchus tshawytscha ) in the Hanford Reach of the Columbia River, Washington, USA

The Hanford Nuclear Reservation in south central Washington was claimed by the federal government as a site for the production of plutonium. During the course of production and operation of the facilities at Hanford, radionuclides and chromium were discharged directly into the river and also contaminated the groundwater. This study was designed to assess the effects of chromium (Cr) on Chinook salmon (Oncorhynchus tshawytscha) fertilization under exposure conditions similar to those of the Hanford Reach of the Columbia River. Chinook salmon gametes were exposed to aqueous Cr concentrations ranging from 0 to 266 μg Cr l−1. The current ambient water-quality criteria (AWQC) established for the protection of aquatic life (United States Environmental Protection Agency [USEPA] 1986) is 11 μg Cr l−1. Cr has been measured in pore water from bottom sediments of the Columbia River at concentrations >600 μg Cr l−1. Under exposure conditions designed to closely mimic events that occur in the river, the fertilization of Chinook salmon eggs was not affected by concentrations of Cr ranging from 11 to 266 μg Cr l−1. Data suggest that the instantaneous nature of fertilization likely limits the potential effects of Cr on fertilization success. As a result, the current AWQC of 11 μg Cr l−1 is most likely protective of Chinook salmon fertilization.

Oregon

Acute and chronic toxicity of lead in water and diet to the amphipod Hyalella azteca

We evaluated the influence of waterborne and dietary lead (Pb) exposure on the acute and chronic toxicity of Pb to the amphipod Hyalella azteca . Test solutions were generated by a modified diluter with an extended (24‐h) equilibration period. Acute (96‐h) toxicity of Pb varied with water hardness in the range of 71 to 275 mg/L as CaCO 3 , despite similar dissolved Pb concentrations. Acute toxicity was greatest in soft test water, with less than 50% survival at the lowest dissolved Pb concentration (151 μg/L). Survival also was significantly reduced in medium‐hardness water but not in hard test water. In chronic (42‐d) studies, amphipods were exposed to waterborne Pb and fed either a control diet or a diet equilibrated with waterborne Pb levels. For animals fed the control diet, the median lethal concentration (LC50) for Pb was 24 μg/L (as dissolved Pb), and significant reductions in survival occurred at 16 μg/L. Exposure to Pb‐treated diets significantly increased toxicity across a wide range of dissolved Pb concentrations, with a LC50 of 16 μg/L and significant reductions in growth and reproduction at 3.5 μg/L. Significant effects on growth and reproduction occurred at dissolved Pb concentrations close to the current U.S. chronic water‐quality criterion. Our results suggest that both aqueous‐ and dietary‐exposure pathways contribute significantly to chronic Pb exposure and toxic effects in aquatic biota.

Environmental Toxicology and Chemistry

Concentrations of cadmium, lead, and zinc in fish from mining-influenced waters of northeastern Oklahoma: Sampling of blood, carcass, and liver for aquatic biomonitoring

The Tri-States Mining District (TSMD) of Missouri (MO), Kansas (KS), and Oklahoma (OK), USA, was mined for lead (Pb) and zinc (Zn) for more than a century. Mining ceased more than 30 years ago, but wastes remain widely distributed in the region, and there is evidence of surface- and groundwater contamination in the Spring River-Neosho River (SR-NR) system of northeastern OK. In October 2001, we collected a total of 74 fish from six locations in the SR-NR system that included common carp (Cyprinus carpio), channel- and flathead catfish (Ictalurus punctatus and Pylodictis olivaris), largemouth- and spotted bass (Micropterus salmoides and Micropterus punctulatus), and white crappie (Pomoxis annularis). We obtained additional fish from locations in MO that included three reference sites and one site that served as a "positive control" (heavily contaminated by Pb). Blood, carcass (headed, eviscerated, and scaled) and liver (carp only) samples were analyzed for cadmium (Cd), Pb, and Zn. Our objectives were to assess the degree to which fish from the OK portion of the SR-NR system are contaminated by these elements and to evaluate fish blood sampling for biomonitoring. Concentrations of Cd and Pb in carp and catfish from OK sites were elevated and Pb concentrations of some approached those of the highly contaminated site in MO, but concentrations in bass and crappie were relatively low. For Zn, correlations were weak among concentrations in the three tissues and none of the samples appeared to reflect site contamination. Variability was high for Cd in all three tissues of carp; differences between sites were statistically significant (p < 0.05) only for blood even though mean liver concentrations were at least 100-fold greater than those in blood. Blood concentrations of Cd and Pb were positively correlated (r 2 = 0.49 to 0.84) with the concentration of the same element in carp and catfish carcasses or in carp livers, and the corresponding multiple regression models were highly significant (p < 0.001). Our data indicate that potentially nonlethal blood sampling can be useful for monitoring of selected metals in carp, catfish, and perhaps other fishes. ?? 2005 Springer Science+Business Media, Inc.

Archives of Environmental Contamination and Toxico

Effects of sediment characteristics on the toxicity of chromium(III) and chromium(VI) to the amphipod, Hyalella azteca

We evaluated the influence of sediment characteristics, acid-volatile sulfide (AVS) and organic matter (OM), on the toxicity of chromium (Cr) in freshwater sediments. We conducted chronic (28-42-d) toxicity tests with the amphipod Hyalella azteca exposed to Cr(VI) and Cr(III) in water and in spiked sediments. Waterborne Cr(VI) caused reduced survival of amphipods with a median lethal concentration (LC50) of 40 ??g/L. Cr(VI) spiked into test sediments with differing levels of AVS resulted in graded decreases in AVS and sediment OM. Only Cr(VI)-spiked sediments with low AVS concentrations (<1 ??mol/g) caused significant amphipod mortality. Waterborne Cr(III) concentrations near solubility limits caused decreased survival of amphipods at pH 7 and pH 8 but not at pH 6. Sediments spiked with high levels of Cr(III) did not affect amphipod survival but had minor effects on growth and inconsistent effects on reproduction. Pore waters of some Cr(III)-spiked sediments contained measurable concentrations of Cr(VI), but observed toxic effects did not correspond closely to Cr concentrations in sediment or pore waters. Our results indicate that risks of Cr toxicity are low in freshwater sediments containing substantial concentrations of AVS.

Environmental Science & Technology

Effects of organic amendments on the toxicity and bioavailability of cadmium and copper in spiked formulated sediments

We evaluated the partitioning and toxicity of cadmium (Cd) and copper (Cu) spiked into formulated sediments containing two types of organic matter (OM), i.e., cellulose and humus. Amendments of cellulose up to 12.5% total organic carbon (TOC) did not affect partitioning of Cd or Cu between sediment and pore water and did not significantly affect the toxicity of spiked sediments in acute toxicity tests with the amphipod Hyalella azteca. In contrast, amendments of natural humus shifted the partitioning of both Cd and Cu toward greater concentrations in sediment and lesser concentrations in pore water and significantly reduced toxic effects of both metals. Thresholds for toxicity, based on measured metal concentrations in whole sediment, were greater for both Cd and Cu in sediments amended with a low level of humus (2.9% TOC) than in sediments without added OM. Amendments with a high level of humus (8.9% TOC) eliminated toxicity at the highest spike concentrations of both metals (sediment concentrations of 12.4 ??g Cd/g and 493 ??g Cu/g). Concentrations of Cd in pore water associated with acute toxicity were similar between sediments with and without humus amendments, suggesting that toxicity of Cd was reduced primarily by sorption to sediment OM. However, toxic effects of Cu in humus treatments were associated with greater pore-water concentrations than in controls, suggesting that toxicity of Cu was reduced both by sorption and by complexation with soluble ligands. Both sorption and complexation by OM tend to make proposed sediment quality guidelines (SQGs) based on total metal concentrations more protective for high-OM sediments. Our results suggest that the predictive ability of SQGs could be improved by models of metal interactions with natural OM in sediment and pore water.

Conference Paper

Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water

A stabilized liquid membrane device (SLMD) is described for potential use as an in situ, passive, integrative sampler for cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in natural waters. The SLMD (patent pending) consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equal mixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagent mixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on sampler configuration, concentration factors of several thousand can be realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow on the sampling rate are currently under investigation.

Water, Air, & Soil Pollution

Toxicity assessment of sediments from the Grand Calumet River and Indiana Harbor Canal in northwestern Indiana, USA

The objective of this study was to evaluate the toxicity of sediments from the Grand Calumet River and Indiana Harbor Canal located in northwestern Indiana, USA. Toxicity tests used in this assessment included 10-day sediment exposures with the amphipod Hyalella azteca , 31-day sediment exposures with the oligochaete Lumbriculus variegatus , and the Microtox® Solid-Phase Sediment Toxicity Test. A total of 30 sampling stations were selected in locations that had limited historic matching toxicity and chemistry data. Toxic effects on amphipod survival were observed in 60% of the samples from the assessment area. Results of a toxicity test with oligochaetes indicated that sediments from the assessment area were too toxic to be used in proposed bioaccumulation testing. Measurement of amphipod length after the 10-day exposures did not provide useful information beyond that provided by the survival endpoint. Seven of the 15 samples that were identified as toxic in the amphipod tests were not identified as toxic in the Microtox test, indicating that the 10-day H. azteca test was more sensitive than the Microtox test. Samples that were toxic tended to have the highest concentrations of metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs). The toxic samples often had an excess of simultaneously extracted metals (SEM) relative to acid volatile sulfide (AVS) and had multiple exceedances of probable effect concentrations (PECs). Metals may have contributed to the toxicity of samples that had both an excess molar concentration of SEM relative to AVS and elevated concentrations of metals in pore water. However, of the samples that had an excess of SEM relative to AVS, only 38% of these samples had elevated concentration of metals in pore water. The lack of correspondence between SEM-AVS and pore water metals indicates that there are variables in addition to AVS controlling the concentrations of metals in pore water. A mean PEC quotient of 3.4 (based on concentrations of metals, PAHs, and PCBs) was exceeded in 33% of the sediment samples and a mean quotient of 0.63 was exceeded in 70% of the thirty sediment samples from the assessment area. A 50% incidence of toxicity has been previously reported in a database for sediment tests with H. azteca at a mean quotient of 3.4 in 10-day exposures and at a mean quotient of 0.63 in 28-day exposures. Among the Indiana Harbor samples, most of the samples with a mean PEC quotient above 0.63 ( i.e. , 15 of 21; 71%) and above 3.4 ( i.e. , 10 of 10; 100%) were toxic to amphipods. Results of this study and previous studies demonstrate that sediments from this assessment area are among the most contaminated and toxic that have ever been reported.

Indiana

A passive integrative sampler for mercury vapor in air and neutral mercury species in water

A passive integrative mercury sampler (PIMS) based on a sealed polymeric membrane was effective for the collection and preconcentration of Hg0. Because the Hg is both oxidized and stabilized in the PIMS, sampling intervals of weeks to months are possible. The effective air sampling rate for a 15 x 2.5 cm device was about 21-equivalents/day (0.002 m3/day) and the detection limit for 4-week sampling was about 2 ng/m3 for conventional ICP-MS determination without clean-room preparation. Sampling precision was ??? 5% RSD for laboratory exposures, and 5-10% RSD for field exposures. These results suggest that the PIMS could be useful for screening assessments of Hg contamination and exposure in the environment, the laboratory, and the workplace. The PIMS approach may be particularly useful for applications requiring unattended sampling for extended periods at remote locations. Preliminary results indicate that sampling for dissolved gaseous mercury (DGM) and potentially other neutral mercury species from water is also feasible. Rigorous validation of the sampler performance is currently in progress. (C) 1999 Elsevier Science Ltd.A passive integrative mercury sampler (PIMS) based on a sealed polymeric membrane was effective for the collection and preconcentration of Hg0. Because the Hg is both oxidized and stabilized in the PIMS, sampling intervals of weeks to months are possible. The effective air sampling rate for a 15??2.5 cm device was about 21-equivalents/day (0.002 m3/day) and the detection limit for 4-week sampling was about 2 ng/m3 for conventional ICP-MS determination without clean-room preparation. Sampling precision was ???5% RSD for laboratory exposures, and 5-10% RSD for field exposures. These results suggest that the PIMS could be useful for screening assessments of Hg contamination and exposure in the environment, the laboratory, and the workplace. The PIMS approach may be particularly useful for applications requiring unattended sampling for extended periods at remote locations. Preliminary results indicate that sampling for dissolved gaseous mercury (DGM) and potentially other neutral mercury species from water is also feasible. Rigorous validation of the sampler performance is currently in progress.

Chemosphere - Global Change Science