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Van Genderen E.,ZINC Inc | Adams W.,Rio Tinto Alcan | Dwyer R.,International Copper Association | Garman E.,Nickel Producers Environmental Research Association | Gorsuch J.,Copper Development Association Inc
Environmental Toxicology and Chemistry | Year: 2015

The fate and biological effects of chemical mixtures in the environment are receiving increased attention from the scientific and regulatory communities. Understanding the behavior and toxicity of metal mixtures poses unique challenges for incorporating metal-specific concepts and approaches, such as bioavailability and metal speciation, in multiple-metal exposures. To avoid the use of oversimplified approaches to assess the toxicity of metal mixtures, a collaborative 2-yr research project and multistakeholder group workshop were conducted to examine and evaluate available higher-tiered chemical speciation-based metal mixtures modeling approaches. The Metal Mixture Modeling Evaluation project and workshop achieved 3 important objectives related to modeling and interpretation of biological effects of metal mixtures: 1) bioavailability models calibrated for single-metal exposures can be integrated to assess mixture scenarios; 2) the available modeling approaches perform consistently well for various metal combinations, organisms, and endpoints; and 3) several technical advancements have been identified that should be incorporated into speciation models and environmental risk assessments for metals. © 2015 SETAC.

Schlekat C.E.,Nickel Producers Environmental Research Association | Van Genderen E.,Parametrix Inc. | De Schamphelaere K.A.C.,Ghent University | Antunes P.M.C.,Consulting Inc. | And 2 more authors.
Science of the Total Environment | Year: 2010

The use of Biotic Ligand Models (BLMs) to normalize metal ecotoxicity data and predict effects in non-BLM organisms should be supported by quantitative evidence. This study determined the ability of chronic nickel BLMs developed for the cladocera Daphnia magna and Ceriodaphnia dubia to predict chronic nickel toxicity to three invertebrates for which no specific BLMs were developed. Those invertebrates were the snail Lymnaea stagnalis, the insect Chironomus tentans, and the rotifer Brachionus calyciflorus. Similarly, we also determined the ability of chronic nickel BLMs developed for the alga Pseudokirchneriella subcapitata and the terrestrial vascular plant Hordeum vulgare to predict chronic nickel toxicity to the aquatic vascular plant Lemna minor. Chronic nickel toxicity to the three invertebrates and the aquatic plant were measured in five natural waters that varied in pH, Ca, Mg, and dissolved organic carbon (DOC), which are known to affect chronic nickel toxicity and are the important input variables for the chronic nickel BLMs. Nickel toxicity to the three invertebrates varied considerably among the test waters, i.e., a 14-fold variation of EC50s in L. stagnalis, a 3-fold variation in EC20s in C. tentans, and a 10-fold variation in EC20s in B. calyciflorus, but the cladoceran BLMs were able to predict nickel effect concentrations within a factor of two. Nickel toxicity (EC50s) to L. minor varied by 6-fold among the test waters. Although the P. subcapitata and H. vulgare BLMs offered reasonable predictions of nickel EC50s to L. minor, the D. magna and C. dubia BLM showed better predictions. Our results confirm the influence of site-specific pH, hardness, and DOC on chronic nickel toxicity to aquatic organisms, and support the use of chronic nickel BLMs to manage this influence through normalizations of ecotoxicity data. © 2010 Elsevier B.V.

Hughson G.W.,Institute of Occupational Medicine | Hughson G.W.,University of Aberdeen | Galea K.S.,Institute of Occupational Medicine | Heim K.E.,Nickel Producers Environmental Research Association
Annals of Occupational Hygiene | Year: 2010

The aim of this study was to measure the levels of nickel in the skin contaminant layer of workers involved in specific processes and tasks within the primary nickel production and primary nickel user industries. Dermal exposure samples were collected using moist wipes to recover surface contamination from defined areas of skin. These were analysed for soluble and insoluble nickel species. Personal samples of inhalable dust were also collected to determine the corresponding inhalable nickel exposures. The air samples were analysed for total inhalable dust and then for soluble, sulfidic, metallic, and oxidic nickel species. The workplace surveys were carried out in five different workplaces, including three nickel refineries, a stainless steel plant, and a powder metallurgy plant, all of which were located in Europe. Nickel refinery workers involved with electrolytic nickel recovery processes had soluble dermal nickel exposure of 0.34 μg cm-2 [geometric mean (GM)] to the hands and forearms. The GM of soluble dermal nickel exposure for workers involved in packing nickel salts (nickel chloride hexahydrate, nickel sulphate hexahydrate, and nickel hydroxycarbonate) was 0.61 μg cm-2. Refinery workers involved in packing nickel metal powders and end-user powder operatives in magnet production had the highest dermal exposure (GM=2.59 μg cm-2 soluble nickel). The hands, forearms, face, and neck of these workers all received greater dermal nickel exposure compared with the other jobs included in this study. The soluble nickel dermal exposures for stainless steel production workers were at or slightly above the limit of detection (0.02 μg cm -2 soluble nickel). The highest inhalable nickel concentrations were observed for the workers involved in nickel powder packing (GM=0.77 mg m -3), although the soluble component comprised only 2% of the total nickel content. The highest airborne soluble nickel exposures were associated with refineries using electrolytic processes for nickel recovery (GM=0.04 mg m-3 total nickel, containing 82% soluble nickel) and those jobs involving contact with soluble nickel compounds (GM=0.02 mg m-3 total nickel content, containing 76% soluble nickel). The stainless steel workers were exposed to low concentrations of relatively insoluble airborne nickel species (GM=0.03 mg m-3 total nickel, containing 1% soluble nickel). A statistically significant correlation was observed between dermal exposures for all anatomical areas across all tasks. In addition, the dermal and inhalable (total) nickel exposures were similarly associated. Overall, dermal exposures to nickel, nickel compounds, and nickel alloys were relatively low. However, exposures were highly variable, which can be explained by the inconsistent use of personal protective equipment, varying working practices, and different standards of automation and engineering controls within each exposure category.

Nguyen L.T.,Ghent University | Burton G.A.,Wright State University | Schlekat C.E.,Nickel Producers Environmental Research Association | Janssen C.R.,Ghent University
Environmental Toxicology and Chemistry | Year: 2011

A field experiment was performed in four freshwater systems to assess the effects of Ni on the benthic macroinvertebrate communities. Sediments were collected from the sites (in Belgium, Germany, and Italy), spiked with Ni, and returned to the respective field sites. The colonization process of the benthic communities was monitored during a nine-month period. Nickel effect on the benthos was also assessed in the context of equilibrium partitioning model based on acid volatile sulfides (AVS) and simultaneously extracted metals (SEM). Benthic communities were not affected at (SEM - AVS) ≤ 0.4 μmol/g, (SEM - AVS)/fraction of organic carbon (f OC) < 21 μmol/g organic carbon (OC). Sediments with (SEM - AVS) > 2 μmol/g, (SEM - AVS)/f OC > 700 μmol/g OC resulted in clear adverse effects. Uncertainty about the presence and absence of Ni toxicity occurred at (SEM - AVS) and (SEM - AVS)/f OC between 0.4 to 2 μmol/g and 21 to 700 μmol/g OC, respectively. The results of our study also indicate that when applying the SEM:AVS concept for predicting metal toxicity in the field study, stressors other than sediment characteristics (e.g., sorption capacity), such as environmental disturbances, should be considered, and the results should be carefully interpreted. Environ. Toxicol. Chem. 2011;30:162-172. © 2010 SETAC.

Meyer J.S.,Colorado School of Mines | Meyer J.S.,Arcadis | Farley K.J.,Manhattan College | Garman E.R.,Nickel Producers Environmental Research Association
Environmental Toxicology and Chemistry | Year: 2015

Despite more than 5 decades of aquatic toxicity tests conducted with metal mixtures, there is still a need to understand how metals interact in mixtures and to predict their toxicity more accurately than what is currently done. The present study provides a background for understanding the terminology, regulatory framework, qualitative and quantitative concepts, experimental approaches, and visualization and data-analysis methods for chemical mixtures, with an emphasis on bioavailability and metal-metal interactions in mixtures of waterborne metals. In addition, a Monte Carlo-type randomization statistical approach to test for nonadditive toxicity is presented, and an example with a binary-metal toxicity data set demonstrates the challenge involved in inferring statistically significant nonadditive toxicity. This background sets the stage for the toxicity results, data analyses, and bioavailability models related to metal mixtures that are described in the remaining articles in this special section from the Metal Mixture Modeling Evaluation project and workshop. It is concluded that although qualitative terminology such as additive and nonadditive toxicity can be useful to convey general concepts, failure to expand beyond that limited perspective could impede progress in understanding and predicting metal mixture toxicity. Instead of focusing on whether a given metal mixture causes additive or nonadditive toxicity, effort should be directed to develop models that can accurately predict the toxicity of metal mixtures. © 2014 SETAC.

Vangheluwe M.L.U.,ARCHE | Verdonck F.A.M.,ARCHE | Besser J.M.,U.S. Geological Survey | Brumbaugh W.G.,U.S. Geological Survey | And 3 more authors.
Environmental Toxicology and Chemistry | Year: 2013

Within the framework of European Union chemical legislations an extensive data set on the chronic toxicity of sediment nickel has been generated. In the initial phase of testing, tests were conducted with 8 taxa of benthic invertebrates in 2 nickel-spiked sediments, including 1 reasonable worst-case sediment with low concentrations of acid-volatile sulfide (AVS) and total organic carbon. The following species were tested: amphipods (Hyalella azteca, Gammarus pseudolimnaeus), mayflies (Hexagenia sp.), oligochaetes (Tubifex tubifex, Lumbriculus variegatus), mussels (Lampsilis siliquoidea), and midges (Chironomus dilutus, Chironomus riparius). In the second phase, tests were conducted with the most sensitive species in 6 additional spiked sediments, thus generating chronic toxicity data for a total of 8 nickel-spiked sediments. A species sensitivity distribution was elaborated based on 10% effective concentrations yielding a threshold value of 94mg Ni/kg dry weight under reasonable worst-case conditions. Data from all sediments were used to model predictive bioavailability relationships between chronic toxicity thresholds (20% effective concentrations) and AVS and Fe, and these models were used to derive site-specific sediment-quality criteria. Normalization of toxicity values reduced the intersediment variability in toxicity values significantly for the amphipod species Hyalella azteca and G. pseudolimnaeus, but these relationships were less clearly defined for the mayfly Hexagenia sp. Application of the models to prevailing local conditions resulted in threshold values ranging from 126mg to 281mg Ni/kg dry weight, based on the AVS model, and 143mg to 265mg Ni/kg dry weight, based on the Fe model. © 2013 SETAC.

Schlekat C.E.,Nickel Producers Environmental Research Association | Garman E.R.,Nickel Producers Environmental Research Association | Vangheluwe M.L.U.,ARCHE | Burton G.A.,University of Michigan
Integrated Environmental Assessment and Management | Year: 2016

To assess nickel (Ni) toxicity and behavior in freshwater sediments, a large-scale laboratory and field sediment testing program was conducted. The program used an integrative testing strategy to generate scientifically based threshold values for Ni in sediments and to develop integrated equilibrium partitioning-based bioavailability models for assessing risks of Ni to benthic ecosystems. The sediment testing program was a multi-institutional collaboration that involved extensive laboratory testing, field validation of laboratory findings, characterization of Ni behavior in natural and laboratory conditions, and examination of solid phase Ni speciation in sediments. The laboratory testing initiative was conducted in 3 phases to satisfy the following objectives: 1) evaluate various methods for spiking sediments with Ni to optimize the relevance of sediment Ni exposures; 2) generate reliable ecotoxicity data by conducting standardized chronic ecotoxicity tests using 9 benthic species in sediments with low and high Ni binding capacity; and, 3) examine sediment bioavailability relationships by conducting chronic ecotoxicity testing in sediments that showed broad ranges of acid volatile sulfides, organic C, and Fe. A subset of 6 Ni-spiked sediments was deployed in the field to examine benthic colonization and community effects. The sediment testing program yielded a broad, high quality data set that was used to develop a Species Sensitivity Distribution for benthic organisms in various sediment types, a reasonable worst case predicted no-effect concentration for Ni in sediment (PNECsediment), and predictive models for bioavailability and toxicity of Ni in freshwater sediments. A bioavailability-based approach was developed using the ecotoxicity data and bioavailability models generated through the research program. The tiered approach can be used to fulfill the outstanding obligations under the European Union (EU) Existing Substances Risk Assessment, EU Registration, Evaluation, Authorisation, and Regulation of Chemicals (REACH), and other global regulatory initiatives. Integr Environ Assess Manag 2016;12:735–746. © 2015 SETAC. © 2015 SETAC

Brumbaugh W.G.,U.S. Geological Survey | Hammerschmidt C.R.,Wright State University | Zanella L.,Northwestern University | Rogevich E.,Nickel Producers Environmental Research Association | And 2 more authors.
Environmental Toxicology and Chemistry | Year: 2011

An interlaboratory comparison of acid-volatile sulfide (AVS) and simultaneously extracted nickel (SEM-Ni) measurements of sediments was conducted among five independent laboratories. Relative standard deviations for the seven test samples ranged from 5.6 to 71% (mean=25%) for AVS and from 5.5 to 15% (mean=10%) for SEM-Ni. These results are in stark contrast to a recently published study that indicated AVS and SEM analyses were highly variable among laboratories. © 2011 SETAC.

Besser J.M.,U.S. Geological Survey | Brumbaugh W.G.,U.S. Geological Survey | Ingersoll C.G.,U.S. Geological Survey | Ivey C.D.,U.S. Geological Survey | And 4 more authors.
Environmental Toxicology and Chemistry | Year: 2013

This study evaluated the chronic toxicity of Ni-spiked freshwater sediments to benthic invertebrates. A 2-step spiking procedure (spiking and sediment dilution) and a 2-stage equilibration period (10wk anaerobic and 1wk aerobic) were used to spike 8 freshwater sediments with wide ranges of acid-volatile sulfide (AVS; 0.94-38μmol/g) and total organic carbon (TOC; 0.42-10%). Chronic sediment toxicity tests were conducted with 8 invertebrates (Hyalella azteca, Gammarus pseudolimnaeus, Chironomus riparius, Chironomus dilutus, Hexagenia sp., Lumbriculus variegatus, Tubifex tubifex, and Lampsilis siliquoidea) in 2 spiked sediments. Nickel toxicity thresholds estimated from species-sensitivity distributions were 97μg/g and 752μg/g (total recoverable Ni; dry wt basis) for sediments with low and high concentrations of AVS and TOC, respectively. Sensitive species were tested with 6 additional sediments. The 20% effect concentrations (EC20s) for Hyalella and Gammarus, but not Hexagenia, were consistent with US Environmental Protection Agency benchmarks based on Ni in porewater and in simultaneously extracted metals (SEM) normalized to AVS and TOC. For Hexagenia, sediment EC20s increased at less than an equimolar basis with increased AVS, and toxicity occurred in several sediments with Ni concentrations in SEM less than AVS. The authors hypothesize that circulation of oxygenated water by Hexagenia led to oxidation of AVS in burrows, creating microenvironments with high Ni exposure. Despite these unexpected results, a strong relationship between Hexagenia EC20s and AVS could provide a basis for conservative site-specific sediment quality guidelines for Ni. © 2013 SETAC.

Brumbaugh W.G.,U.S. Geological Survey | Besser J.M.,U.S. Geological Survey | Ingersoll C.G.,U.S. Geological Survey | May T.W.,U.S. Geological Survey | And 3 more authors.
Environmental Toxicology and Chemistry | Year: 2013

Two spiking methods were compared and nickel (Ni) partitioning was evaluated during a series of toxicity tests with 8 different freshwater sediments having a range of physicochemical characteristics. A 2-step spiking approach with immediate pH adjustment by addition of NaOH at a 2:1 molar ratio to the spiked Ni was effective in producing consistent pH and other chemical characteristics across a range of Ni spiking levels. When Ni was spiked into sediment having a high acid-volatile sulfide and organic matter content, a total equilibration period of at least 10 wk was needed to stabilize Ni partitioning. However, highest spiking levels evidently exceeded sediment binding capacities; therefore, a 7-d equilibration in toxicity test chambers and 8 volume-additions/d of aerobic overlying water were used to avoid unrealistic Ni partitioning during toxicity testing. The 7-d pretest equilibration allowed excess spiked Ni and other ions from pH adjustment to diffuse from sediment porewater and promoted development of an environmentally relevant, 0.5- to 1-cm oxic/suboxic sediment layer in the test chambers. Among the 8 different spiked sediments, the logarithm of sediment/porewater distribution coefficient values (logKd) for Ni during the toxicity tests ranged from 3.5 to 4.5. These Kd values closely match the range of values reported for various field Ni-contaminated sediments, indicating that testing conditions with our spiked sediments were environmentally realistic. © 2013 SETAC.

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