Patricio H. Rodriguez

Biotic ligand model prediction of copper toxicity to daphnids in a range of natural waters in Chile

The objective of this study was to assess the predictive capacity of the biotic ligand model (BLM) for acute copper toxicity to daphnids as applied to a number of freshwaters from Chile and to synthetic laboratory-prepared waters. Thirty-seven freshwater bodies were sampled, chemically characterized, and used to determine the copper concentration associated with the 50% of mortality (LC50) for Daphnia magna, Daphnia pulex, and Daphnia obtusa (native to Chile). The data were then used to run three versions of the acute copper BLM, and the predicted LC50s were compared to the observed ones. The same was done with synthetic assay media at various hardness and dissolved organic carbon (DOC) levels. The BLM versions differed in the affinity constants for some biotic ligand-ion pairs, stability constants for inorganic Cu complexes, and assumptions regarding Cu binding to DOC. All three versions showed a high degree of predictive performance, mostly within a twofold range of observed toxicity values. The D. obtusa data set was used to compare water quality criteria (WQC) derived from the observed toxicity values with those derived from either the BLM or the U.S. Environmental Protection Agency (U.S. EPA) procedure. For most low DOC waters, the three procedures generated similar WQCs. For the high-DOC waters, the EPA-derived criteria were significantly lower, that is, greatly overprotective. The results are also discussed in terms of the validation of the BLM for regulatory use.

Agricultural soils spiked with copper mine wastes and copper concentrate: implications for copper bioavailability and bioaccumulation.

A better understanding of exposure to and effects of copper-rich pollutants in soils is required for accurate environmental risk assessment of copper. A greenhouse experiment was conducted to study copper bioavailability and bioaccumulation in agricultural soils spiked with different types of copper-rich mine solid wastes (copper ore, tailing sand, smelter dust, and smelter slag) and copper concentrate. A copper salt (copper sulfate, CuSO4) that frequently is used to assess soil copper bioavailability and phytotoxicity also was included for comparison. Results showed that smelter dust, tailing sand, and CuSO4 are more likely to be bioavailable and, thus, toxic to plants compared with smelter slag, concentrate, and ore at equivalent total copper concentrations. Differences may be explained by intrinsic differences in copper solubilization from the source materials, but also by their capability to decrease soil pH (confounding effect). The copper toxicity and bioaccumulation in plants also varied according to soil physicochemical characteristics (e.g., pH and total organic carbon) and the available levels of plant nutrients, such as nitrogen, phosphorus, and potassium. Chemistry/mineralogy of mine materials, soil/pore-water chemistry, and plant physiological status thus should be integrated for building adequate models to predict phytotoxicity and environmental risk of copper.

Soil acidification as a confounding factor on metal phytotoxicity in soils spiked with copper‐rich mine wastes

Pollution of soil with mine wastes results in both Cu enrichment and soil acidification. This confounding effect may be very important in terms of phytotoxicity, because pH is a key parameter influencing Cu solubility in soil solution. Laboratory toxicity tests were used to assess the effect of acidification by acidic mine wastes on Cu solubility and on root elongation of barley (Hordeum vulgare L.). Three contrasting substrates (two soils and a commercial sand) and two acidic, Cu-rich mine wastes (oxidized tailings [OxT] and smelter dust [SmD]) were selected as experimental materials. Substrates were spiked with a fixed amount of either SmD or OxT, and the pH of experimental mixtures was then modified in the range of 4.0 to 6.0 and 7.0 using PIPES (piperazine-1,4-bis(2-ethanesulfonic acid)), MES (2-(N-morpholino)ethanesulfonic acid), and MOPS (3-(N-Morpholino)-propanesulfonic acid) buffers. Chemical (pore-water Cu and pH) and toxicological (root length of barley plants) parameters were determined for experimental mixtures. Addition of SmD and OxT to substrates resulted in acidification (0.11-1.16 pH units) and high levels of soluble Cu and Zn. Neutralization of experimental mixtures with MES (pH 6.0) and MOPS (pH 7.0) buffers resulted in a marked decrease in soluble Cu and Zn, but the intensity of the effect was substrate-dependent. Adjustment of soil pH above the range normally considered to be toxic to plants (pH in water extract, > 5.5) significantly reduced metal toxicity in barley, but phytotoxicity was not completely eliminated. The present results stress the importance of considering confounding effects on derivation of toxicity thresholds to plants when using laboratory phytotoxicity tests.

Inter-laboratory validation of bioaccessibility testing for metals

Bioelution assays are fast, simple alternatives to in vivo testing. In this study, the intra- and inter-laboratory variability in bioaccessibility data generated by bioelution tests were evaluated in synthetic fluids relevant to oral, inhalation, and dermal exposure. Using one defined protocol, five laboratories measured metal release from cobalt oxide, cobalt powder, copper concentrate, Inconel alloy, leaded brass alloy, and nickel sulfate hexahydrate. Standard deviations of repeatability (sr) and reproducibility (sR) were used to evaluate the intra- and inter-laboratory variability, respectively. Examination of the sR:sr ratios demonstrated that, while gastric and lysosomal fluids had reasonably good reproducibility, other fluids did not show as good concordance between laboratories. Relative standard deviation (RSD) analysis showed more favorable reproducibility outcomes for some data sets; overall results varied more between- than within-laboratories. RSD analysis of sr showed good within-laboratory variability for all conditions except some metals in interstitial fluid. In general, these findings indicate that absolute bioaccessibility results in some biological fluids may vary between different laboratories. However, for most applications, measures of relative bioaccessibility are needed, diminishing the requirement for high inter-laboratory reproducibility in absolute metal releases. The inter-laboratory exercise suggests that the degrees of freedom within the protocol need to be addressed.

Advances in metals classification under the united nations globally harmonized system of classification and labeling

This article shows how regulatory obligations mandated for metal substances can be met with a laboratory-based transformation/dissolution (T/D) method for deriving relevant hazard classification outcomes, which can then be linked to attendant environmental protection management decisions. We report the results of a ring-test at 3 laboratories conducted to determine the interlaboratory precision of the United Nations T/D Protocol (T/DP) in generating data for classifying 4 metal-bearing substances for acute and chronic toxicity under the United Nations Globally Harmonized System of Classification and Labelling (GHS) criteria with respect to the aquatic environment. The test substances were Ni metal powder, cuprous oxide (Cu(2) O) powder, tricobalt tetroxide (Co(3) O(4) ) powder, and cuttings of a NILO K Ni-Co-Fe alloy. Following GHS Annex 10 guidelines, we tested 3 loadings (1, 10, and 100 mg/L) of each substance at pH 6 and 8 for 7 or 28 d to yield T/D data for acute and chronic classification, respectively. We compared the T/DP results (dissolved metal in aqueous media) against acute and chronic ecotoxicity reference values (ERVs) for each substance to assess GHS classification outcomes. For dissolved metal ions, the respective acute and chronic ERVs established at the time of the T/D testing were: 29 and 8 µg/L for Cu; 185 and 1.5 µg/L for Co; and 13.3 and 1.0 mg/L for Fe. The acute ERVs for Ni were pH-dependent: 120 and 68 µg/L at pH 6 and 8, respectively, whereas the chronic ERV for Ni was 2.4 µg/L. The acute classification outcomes were consistent among 3 laboratories: cuprous oxide, Acute 1; Ni metal powder, Acute 3; Co(3) O(4) and the NILO K alloy, no classification. We obtained similar consistent results in chronic classifications: Cu(2) O, Ni metal powder, and Co(3) O(4) , Chronic 4; and the NILO K alloy, no classification. However, we observed equivocal results only in 2 of a possible 48 cases where the coefficient of variation of final T/D concentrations masked clear comparisons with ERVs. Results support the validity and interlaboratory precision of the United Nations T/DP in establishing GHS classification outcomes for metals and metal compounds and support its use in regulatory hazard-based systems. Drawing on T/D data derived from laboratory testing of the metal-bearing substance itself, the T/D approach can be applied to establish scientifically defensible decisions on hazard classification proposals. The resulting decisions can then be incorporated into environmental management measures in such jurisdictions as the European Union.

An Evaluation of the Bioavailability and Aquatic Toxicity Attributed to Ambient Zinc Concentrations in Fresh Surface Waters from Several Parts of the World

Abstract Ambient concentrations of metals in surface waters have become an important consideration when establishing water quality criteria and conducting risk assessments. This study sought to estimate amounts of zinc that may be released into freshwater considering ambient concentrations, toxicity thresholds, and bioavailability. Cumulative distribution functions of ambient zinc concentrations were compared statistically for streams and lakes in Europe, North America, and South America to identify differences among mean distribution variables (e.g., slopes, intercepts, and inflection points). Results illustrated that most of the distributions among sites differed significantly. These differences illustrate the variability in ambient zinc concentrations in surface waters because of geographic location, regional geology, and anthropogenic influence. Additionally, water quality data were used to estimate bioavailable zinc concentrations in ambient surface waters (based on predictions using biotic ligand models). The amount of dissolved metal that could be added to surface waters without exceeding toxicity thresholds was calculated by subtracting ambient surface water concentrations from chronic no observable effect concentrations (NOEC; reproduction for Daphnia magna) or 10% effective concentrations (EC10; growth rate for Pseudokirchneriella subcapitata). Because ambient dissolved-zinc concentrations were, on average, below predicted effects thresholds, an average of 57.1 ± 175 μg/L (±SD) of zinc could be added before exceeding the D. magna chronic NOEC or the P. subcapitata chronic EC10. However, numerous sites (17%) were identified as having ambient zinc concentrations in excess of these toxicity thresholds. This article uses existing biotic ligand models for zinc to estimate the potential magnitudes and variabilities of bioavailable zinc concentrations in fresh surface waters from different regions of the world.

Development and application of a biotic ligand model for predicting the chronic toxicity of dissolved and precipitated aluminum to aquatic organisms

Aluminum (Al) toxicity to aquatic organisms is strongly affected by water chemistry. Toxicity-modifying factors such as pH, dissolved organic carbon (DOC), hardness, and temperature have a large impact on the bioavailability and toxicity of Al to aquatic organisms. The importance of water chemistry on the bioavailability and toxicity of Al suggests that interactions between Al and chemical constituents in exposures to aquatic organisms can affect the form and reactivity of Al, thereby altering the extent to which it interacts with biological membranes. These types of interactions have previously been observed in the toxicity data for other metals, which have been well described by the biotic ligand model (BLM) framework. In BLM applications to other metals (including cadmium, cobalt, copper, lead, nickel, silver, and zinc), these interactions have focused on dissolved metal. A review of Al toxicity data shows that concentrations of Al that cause toxicity are frequently in excess of solubility limitations. Aluminum solubility is strongly pH dependent, with a solubility minimum near pH 6 and increasing at both lower and higher pH values. For the Al BLM, the mechanistic framework has been extended to consider toxicity resulting from a combination of dissolved and precipitated Al to recognize the solubility limitation. The resulting model can effectively predict toxicity to fish, invertebrates, and algae over a wide range of conditions. Environ Toxicol Chem 2018;37:70-79.

Effect of Fe (III) on Pseudokirchneriella subcapitata at circumneutral pH in standard laboratory tests is explained by nutrient sequestration

The complex chemistry of iron (Fe) at circumneutral pH in oxygenated waters and the poor correlation between ecotoxicity results in laboratory and natural waters have led to regulatory approaches for iron based on field studies (US Environmental Protection Agency Water Quality Criteria and European Union Water Framework Directive proposal for Fe). The results of the present study account for the observed differences between laboratory and field observations for Fe toxicity to algae (Pseudokirchneriella subcapitata). Results from standard 72-h assays with Fe at pH 6.3 and pH 8 resulted in similar toxicity values measured as algal biomass, with 50% effect concentrations (EC50) of 3.28 mg/L and 4.95 mg/L total Fe(III), respectively. At the end of the 72-h exposure, however, dissolved Fe concentrations were lower than 30 μg/L for all test concentrations, making a direct toxic effect of dissolved iron on algae unlikely. Analysis of nutrient concentrations in the artificial test media detected phosphorus depletion in a dose-dependent manner that correlated well with algal toxicity. Subsequent experiments adding excess phosphorus after Fe precipitation eliminated the toxicity. These results strongly suggest that observed Fe(III) toxicity on algae in laboratory conditions is a secondary effect of phosphorous depletion. Environ Toxicol Chem 2017;36:952-958.

Hazard Assessment of Ores and Concentrates

Abstract Metal ores and concentrates are complex substances, for which the environmental and human health hazard identification and classification present particular challenges. These relate to the great variability of their compositions and the various mitigating effects of their mineralogical, physical structures, and forms. Based on the UN GHS guidelines, industry has developed a framework for consistent assessment of the hazard profiles of metal ores and concentrates, supported by research and data collection to ensure correct hazard classification of these materials. The resulting tiered approach integrates essential information about the chemical and mineralogical properties, bioavailability and toxicity of the known constituents of the ore or concentrate. The UN GHS classification conclusions are routinely used for hazard classification, risk assessment and identification of mitigation measures relevant to transport, handling, and storage of metal ores and concentrates.