Application of quantitative mineralogy to determine sources of airborne particles at a European copper smelter.

Copper processing operations, such as smelters and refineries, can produce airborne particles that may impact the health of workers. At these operations, worker exposure to chemicals are regularly monitored to ensure that regulatory compliance with occupational exposure limit values (OELVs) are maintained. Determining the type of airborne particles present is important for characterizing the composition of dust exposures and better understanding the relationship between worker exposure and health. Routine methods of analysis (e.g., chemical assay) are unable to differentiate between phases containing the same elements and may result in ambiguity. A novel approach of a combination of Quantitative Evaluation of Materials by Scanning Electron Microscope (QEMSCAN) and chemical characterization was used here to evaluate airborne and settled dust collected at key locations throughout a copper smelter in Europe. The copper (Cu) phases present in the airborne dust are indicative of the activities performed at specific locations. In the batch preparation area where Cu concentrate is received, significant amounts of Cu were carried in sulfidic minerals (chalcocite, chalcopyrite/bornite, >40%), whereas near the anode and electric furnace, the majority of Cu in dust was carried in metallic and oxidic phases (60-70%). Particle size analysis of the settled dust indicates that the sulfidic and oxidic Cu minerals are more likely to become airborne over metallic Cu. Furthermore, overall Cu concentrations decreased with particle size where metallic and oxidic Cu dominate, which suggests that differences in the proportion of Cu forms present in the dust will impact how much Cu ends up in the respirable fraction. These results highlight the need to understand the characterization of Cu in dust in order to set better OELVs.

Is assuming additivity of single-metal toxicity thresholds a conservative approach to assessing risk of ecotoxicity from elevated soil concentrations of cobalt, copper, and nickel at contaminated sites?

Multiple metal-impacted soils are often realistic scenarios for risk assessments, but tools to address these are currently lacking. The objective of this work was to evaluate whether assuming concentration addition (CA) of metal mixture effects was conservative for prospective risk assessment of soils that were elevated mainly in Ni and Cu and somewhat with Co, Pb, or As. Observed whole mixture toxicity for field soils with aged metal mixtures was compared to the expected whole mixture toxicity, assuming additivity of prospective single-metal thresholds ("toxic units") for the mixture components. Bioavailability-adjusted single-metal toxicity thresholds expected for those field soils were the median hazard concentration affecting 5% of species (HC5-50) from the predicted no-effect concentration (PNEC) calculator and calculated from the species-specific dose-response multiple linear relationships (MLRs), all from the European Union Registration, Evaluation, Authorisation and Restriction of Chemicals (EU REACH) dossiers for metals. Generic single-metal toxicity thresholds were based on Canadian Council of Ministers of the Environment soil quality guidelines (CCME SQGs) for agricultural soils. Observed toxicity thresholds were from the community-based risk assessments conducted for Port Colborne and Sudbury, Ontario, Canada. Mostly, prospective single-metal toxicity thresholds were protective relative to the observed toxicity, although that was species or ecological process dependent. The bioavailability-adjusted single-metal thresholds were less conservative than the CCME SQG method, even though the former is based on site-specific EC10 values, and the latter is based on generic EC25 values. When within-site variability in soil properties was used to calculate the 5th and 95th CI for the HC5 sum of toxic units (∑TUs), CA was conservative for far fewer endpoints. In addition, the prospective ∑TUs were more conservative predictions of the observed whole mixture toxicities for Port Colborne soils than for Sudbury soils. The most appropriate balance of accuracy and conservatism for identifying low-level risk of the whole mixtures in these soils appeared to be the bioavailability-adjusted HC5-50, which was applicable to many endpoints and 2 quite different exposure concentration ratios. Integr Environ Assess Manag 2021;17:753-766. © 2020 SETAC.

Long-term spatial and temporal trends, and source apportionment of polycyclic aromatic compounds in the Athabasca Oil Sands Region.

We investigated the spatio-temporal trends of polycyclic aromatic compounds (PACs) deposition in the Athabasca Oil Sands Region (AOSR) between 2008 and 2017, and applied source apportionment tools to assess sources using snowpacks. Estimated PAC mass deposition was significantly correlated with crude oil production (R2 = 0.48, p = 0.03), and increased between 2008 and 2017. Loadings of alkylated PACs c1-, c2-fluorenes/pyrenes and c1-, c3-benzo[a]anthracenes/chrysenes/triphenylenes significantly increased at mid-field sites (25-50 km from central industrial reference site, AR6) (Mann-Kendall, p < 0.05) reflecting physical expansion of the AOSR. The distance from emission sources was important in the deposition of PACs, including the distance from AR6 (R2 = 0.69-0.91), nearest petcoke storage (R2 = 0.77-0.88), 0.89) and upgrader stack (R2 = 0.56-0.61). Source apportionment PAC distribution profiles of the source materials (petcokes, oil sand ores, road dust) did not show unique matching profiles with the snowpacks. However, the minimal presence of retene in petcokes and an abundance of benzo[ghi]fluoranthene in road dust was observed, and suggests potential for these compounds as chemical markers in distinguishing sources. Furthermore, correlations between PACs and selected metal(loid)s in the AOSR snowpacks were assessed to infer potential common sources. Significant positive (p < 0.05) correlations between metal(loid)s enriched in bitumen (vanadium, molybdenum, nickel) and PACs, at near to mid-field (0-50 km from AR6) sites suggests common sources or similar transfer and fate processes. The results of our study convey data necessary for monitoring studies in the constantly developing AOSR, advance our knowledge of PACs profiles in source materials (including the much less studied alkylated PACs and dibenzothiophenes), which will be valuable for other studies related to oil pollution, urban run-off and forest fires. PACs mass deposition increasing between 2008 and 2017 coincident with crude oil production, and retene and benzo[ghi]fluoranthene show potential in distinguishing AOSR sources.

Towards an exposure narrative for metals and arsenic in historically contaminated Ni refinery soils: Relationships between speciation, bioavailability, and bioaccessibility.

Archived soils contaminated with Ni, Cu, Co, and As from legacy operations of a nickel refinery at Port Colborne, Ontario, Canada were speciated using mineral liberation analysis. Four Ni minerals were identified as fingerprint compounds of the historical refinery emissions. Cu and Co were present in solid solution in these minerals due to their presence in the refinery's feed. The highest concentrations of Ni, Cu, Co, and As in these soils were 18,553, 1915, 196, and 79mg/kg, respectively, these elevated contaminant concentrations attesting to the importance of incidental soil ingestion to the oral exposure pathway in Port Colborne. The in vitro gastric bioaccessibility (BAc) was determined for these contaminants, as was in vivo oral bioavailability (BAv), using a mass balance approach in male Sprague-Dawley rats. In spite of the elevated soil concentrations of Cu, the BAv of this physiologically important metal could not be distinguished from that in commercial rat chow, suggesting low potential for exposure. Co and As also had low apparent BAv (<2%). For Ni, baseline oral BAv of naturally sourced dietary Ni was found to be approximately 2%, as was the oral BAv of Ni from nickel sulfate hexahydrate. The mass balances of NiSO4·6H2O were fully accounted-for in urine and feces after a single gavage dose, indicating little to no organ incorporation from this highly soluble salt. Therefore, the urinary estimates of Ni BAv for these soils were assumed to represent true BAv despite variable fecal recoveries. The high Ni concentrations enabled BAc-BAv relationships to be developed for these contaminated soils. For absolute bioavailability (ABA) and relative bioavailability (RBA) the relationships were: ABA=0.0116(BAc)-0.0479 and RBA=0.5542(BAc)-2.2817. These findings will advance the development of robust exposure narratives for soil metal contamination in Port Colborne and elsewhere.

Validation of site-specific soil Ni toxicity thresholds with independent ecotoxicity and biogeochemistry data for elevated soil Ni.

The Existing Substances Regulation Risk Assessments by the European Union (EU RA) generated new toxicity data for soil organisms exposed to Ni added to sixteen field-collected soils with low background concentration of metals and varying physico-chemical soil characteristics. Using only effective cation exchange capacity (eCEC) as a bioavailability correction, chronic toxicity of Ni in soils with a wide range of characteristics could be predicted within a factor of two. The objective of the present study was to determine whether this was also the case for three independent data sets of Ni toxicity thresholds. Two of the data sets were from Community Based Risk Assessments in Port Colborne ON, and Sudbury ON (Canada) for soils containing elevated concentrations of Ni, Co and Cu arising from many decades of Ni mining, smelting and refining. The third data set was the Metals in Asia study of soluble Ni added to field soils in China. These data yielded 72 leached and aged EC10/NOEC values for soil Ni, for arthropods, higher plants and woodlot structure and function. These were reduced to nine most sensitive single or geometric mean species/function endpoints, none of which were lower than the HC5 predicted for a soil with an eCEC of 20 cmol/kg. Most of these leached and aged EC10/NOEC values were from soils co-contaminated with Cu, in some cases at its median HC5 as predicted by the EU RA from soil characteristics. We conclude that the EU RA is protective of Ni toxicity to higher-tier ecological endpoints, including in mixture with Cu, before the assessment factor of 2 is applied. We suggest that for prospective risk assessment, the bioavailability based PNEC (HC5/2) be used as a conservative screen, but for retrospective and site-specific risk assessment, the bioavailability based HC5 is sufficient.

Internal versus External Dose for Describing Ternary Metal Mixture (Ni, Cu, Cd) Chronic Toxicity to Lemna minor.

Simultaneous determinations of internal dose ([M]tiss) and external doses ([M]tot, {M2+} in solution) were conducted to study ternary mixture (Ni, Cu, Cd) chronic toxicity to Lemna minor in alkaline solution (pH 8.3). Also, concentration addition (CA) based on internal dose was evaluated as a tool for risk assessment of metal mixture. Multiple regression analysis of dose versus root growth inhibition, as well as saturation binding kinetics, provided insight into interactions. Multiple regressions were simpler for [M]tiss than [M]tot and {M2+}, and along with saturation kinetics to the internal biotic ligand(s) in the cytoplasm, they indicated that Ni-Cu-Cd competed for uptake into plant, but once inside, only Cu-Cd shared a binding site. Copper inorganic complexes (hydroxides, carbonates) played a role in metal bioavailability in single metal exposure but not in mixtures. Regardless of interactions, the current regulatory approach of using CA based on [M]tot can sufficiently predict mixture toxicity (∑TU close to 1), but CA based on [M]tiss was closest to unity across a range of doses. Internal dose integrates all metal-metal interactions in solution and during uptake into the organism, thereby providing a more direct metric describing toxicity.

Effect of liming on nickel bioavailability and toxicity to oat and soybean grown in field soils containing aged emissions from a nickel refinery.

Remediation of soils elevated in trace metals so that the soils may provide ecosystems services is typically achieved through pH adjustment or addition of sorbents. The present study aimed to generate higher-tier in situ toxicity data for elevated nickel (Ni) in soils with and without lime addition and to explore the effect of liming on soil chemistry and bioavailability of Ni to plants. A multiyear study of agronomic yield of field-grown oat and soybean occurred in 3 adjacent fields that had received air emissions from a Ni refinery for 66 yr. The soil Ni concentration in the plots ranged between 1300 mg/kg and 4900 mg/kg, and each field was amended with either 50 Mg/ha, 10 Mg/ha, or 0 Mg/ha (or tonnes/ha) of crushed dolomitic limestone. As expected, liming raised the pH of the soils and subsequently reduced the plant availability of Ni. Toxicity thresholds (effective concentrations causing 50% reduction in growth) for limed soils supported the hypothesis that liming reduces toxicity. Relationships were found between relative yield and soil cation exchange capacity and between relative yield and soil pH, corroborating findings of the European Union Risk Assessments and the Metals in Asia studies, respectively. Higher tier ecotoxicity data such as these are a valuable contribution to risk assessment for Ni in soils. Environ Toxicol Chem 2017;36:1110-1119. © 2016 SETAC.

Root length of aquatic plant, Lemna minor L., as an optimal toxicity endpoint for biomonitoring of mining effluents.

Lemna minor, a free-floating macrophyte, is used for biomonitoring of mine effluent quality under the Metal Mining Effluent Regulations (MMER) of the Environmental Effects Monitoring (EEM) program in Canada and is known to be sensitive to trace metals commonly discharged in mine effluents such as Ni. Environment Canada's standard toxicity testing protocol recommends frond count (FC) and dry weight (DW) as the 2 required toxicity endpoints-this is similar to other major protocols such as those by the US Environmental Protection Agency (USEPA) and the Organisation for Economic Co-operation and Development (OECD)-that both require frond growth or biomass endpoints. However, we suggest that similar to terrestrial plants, average root length (RL) of aquatic plants will be an optimal and relevant endpoint. As expected, results demonstrate that RL is the ideal endpoint based on the 3 criteria: accuracy (i.e., toxicological sensitivity to contaminant), precision (i.e., lowest variance), and ecological relevance (metal mining effluents). Roots are known to play a major role in nutrient uptake in conditions of low nutrient conditions-thus having ecological relevance to freshwater from mining regions. Root length was the most sensitive and precise endpoint in this study where water chemistry varied greatly (pH and varying concentrations of Ca, Mg, Na, K, dissolved organic carbon, and an anthropogenic organic contaminant, sodium isopropyl xanthates) to match mining effluent ranges. Although frond count was a close second, dry weight proved to be an unreliable endpoint. We conclude that toxicity testing for the floating macrophyte should require average RL measurement as a primary endpoint.

Effect of major cations (Ca2+, Mg2+, Na+, K+) and anions (SO4(2-), Cl- , NO3-) on Ni accumulation and toxicity in aquatic plant (Lemna minor L.): implications For Ni risk assessment.

The effect of major cation activity (Ca(2+) , Mg(2+) , Na(+) , K(+) ) on Ni toxicity, with dose expressed as exposure (total dissolved Ni concentration NiTot ) or free Ni ion activity (in solution Ni(2+) ), or as tissue residue (Ni concentration in plant tissue NiTiss ) to the aquatic plant Lemna minor L. was examined. In addition, Ni accumulation kinetics was explored to provide mechanistic insight into current approaches of toxicity modeling, such as the tissue residue approach and the biotic ligand model (BLM), and the implications for plant Ni risk assessment. Major cations did not inhibit Ni accumulation via competitive inhibition as expected by the BLM framework. For example, Ca(2+) and Mg(2+) (sulfate as counter-anion) had an anticompetitive effect on Ni accumulation, suggesting that Ca or Mg forms a ternary complex with Ni-biotic ligand. The counter-anion of the added Ca (sulfate, chloride, or nitrate) affected plant response (percentage of root growth inhibition) to Ni. Generally, sulfate and chloride influenced plant response while nitrate did not, even when compared within the same range of Ca(2+) , which suggests that the anion dominated the observed plant response. Overall, although an effect of major cations on Ni toxicity to L. minor L. was observed at a physiological level, Ni(2+) or NiTot alone modeled plant response, generally within a span of twofold, over a wide range of water chemistry. Thus, consideration of major cation competition for improving Ni toxicity predictions in risk assessment for aquatic plants may not be necessary.

Kinetic speciation of nickel in mining and municipal effluents.

This study presents the results of kinetic speciation of nickel in undiluted mining and municipal effluents and effluents diluted with receiving freshwaters from the surrounding environment. The dilution ratios used for the dilution of the effluents were arbitrarily chosen, but were representative of the prevailing mining practices. The purpose of the this dilution was to mimic dilution with natural waters that result from dilution of the mining and municipal effluents with receiving freshwaters, so that this study would reveal environmental realities that are of concern to the managers and regulators of water resources. Ligand exchange kinetics using the competing ligand exchange method (CLEM) was studied using two independent techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime (DMG) as the competing ligand to determine the percentage of Ni metal released from Ni(II)-DOC complexes and the rate of dissociation of Ni(II)-DOC complexes. Using a sample containing a mixture of 30% Copper Cliff Mine effluent, 40% Sudbury municipal effluent and 30% Vermillion River water, both techniques gave results showing that the dilution of the effluent samples increased the percentage of nickel released from Ni(II)-DOC complexes. This increase in the release of nickel from the Ni(II)-DOC complexes may be of concern to managers and regulators of water resources. Agreement between the results of these two techniques has enhanced the validity of the competing ligand exchange method used by both techniques.