The bioconcentration factor (BCF) and bioaccumulation factor (BAF) are used as the criteria for bioaccumulation in the context of identifying and classifying substances that are hazardous to the aquatic environment. The BCF/BAF criteria, while developed as surrogates for chronic toxicity and/or biomagnification of anthropogenic organic substances, are applied to all substances including metals. This work examines the theoretical and experimental basis for the use of BCF/BAF in the hazard assessment of Zn, Cd, Cu, Pb, Ni, and Ag. As well, BCF/BAFs for Hg (methyl and inorganic forms) and hexachlorobenzene (HCB) were evaluated. The BCF/BAF data for Zn, Cd, Cu, Pb, Ni, and Ag were characterized by extreme variability in mean BCF/BAF values and a clear inverse relationship between BCF/BAF and aqueous exposure. The high variability persisted when even when data were limited to an exposure range where chronic toxicity would be expected. Mean BCF/BAF values for Hg were also variable, but the inverse relationship was equivocal, in contrast with HCB, which conformed to the BCF model. This study illustrates that the BCF/BAF criteria, as currently applied, are inappropriate for the hazard identification and classification of metals. Furthermore, using BCF and BAF data leads to conclusions that are inconsistent with the toxicological data, as values are highest (indicating hazard) at low exposure concentrations and are lowest (indicating no hazard) at high exposure concentrations, where impacts are likely. Bioconcentration and bioaccumulation factors do not distinguish between essential mineral nutrient, normal background metal bioaccumulation, the adaptive capabilities of animals to vary uptake and elimination within the spectrum of exposure regimes, nor the specific ability to sequester, detoxify, and store internalized metal from metal uptake that results in adverse effect. An alternative to BCF, the accumulation factor (ACF), for metals was assessed and, while providing an improvement, it did not provide a complete solution. A bioaccumulation criterion for the hazard identification of metals is required, and work directed at linking chronic toxicity and bioaccumulation may provide some solutions.
The bioconcentration factor (BCF) and bioaccumulation factor (BAF) are used as the criteria for bioaccumulation in the context of identifying and classifying substances that are hazardous to the aquatic environment. The BCF/BAF criteria, while developed as surrogates for chronic toxicity and/or biomagnification of anthropogenic organic substances, are applied to all substances including metals. This work examines the theoretical and experimental basis for the use of BCF/BAF in the hazard assessment of Zn, Cd, Cu, Pb, Ni, and Ag. As well, BCF/BAFs for Hg (methyl and inorganic forms) and hexachlorobenzene (HCB) were evaluated. The BCF/BAF data for Zn, Cd, Cu, Pb, Ni, and Ag were characterized by extreme variability in mean BCF/BAF values and a clear inverse relationship between BCF/BAF and aqueous exposure. The high variability persisted when even when data were limited to an exposure range where chronic toxicity would be expected. Mean BCF/BAF values for Hg were also variable, but the inverse relationship was equivocal, in contrast with HCB, which conformed to the BCF model. This study illustrates that the BCF/BAF criteria, as currently applied, are inappropriate for the hazard identification and classification of metals. Furthermore, using BCF and BAF data leads to conclusions that are inconsistent with the toxicological data, as values are highest (indicating hazard) at low exposure concentrations and are lowest (indicating no hazard) at high exposure concentrations, where impacts are likely. Bioconcentration and bioaccumulation factors do not distinguish between essential mineral nutrient, normal background metal bioaccumulation, the adaptive capabilities of animals to vary uptake and elimination within the spectrum of exposure regimes, nor the specific ability to sequester, detoxify, and store internalized metal from metal uptake that results in adverse effect. An alternative to BCF, the accumulation factor (ACF), for metals was assessed and, while providing an improvement, it did not provide a complete solution. A bioaccumulation criterion for the hazard identification of metals is required, and work directed at linking chronic toxicity and bioaccumulation may provide some solutions.
National and international concern about the health effects and continued use of Pb, Cd, As and Hg as well as other metals has defined a need for improved estimates of the long-term risks to ecosystems and human health from metals released from mining, metallurgical and energy production activities. A research aircraft was used to determine the microphysical and chemical properties of airborne particulate metal emissions from the Nanticoke coal-fired power-generating station located on the north shore of Lake Erie, Ontario, and the Horne copper smelter at Rouyn-Noranda, Quebec. These properties are critical to the determination of the deposition rates of the metals emitted, and hence the potential for these species to have impacts on local or distant ecosystems. An overview of the measurements made during the study is given. The size distributions of particles emitted from the stacks and observed within 5 km of the point of emission are briefly described. After dilution by ambient air, the concentration of particles smaller than 0.135 μm in diameter in the plumes is tens of thousands per cubic centimetre, far exceeding the concentrations found in ambient air. However, in the size range 0.135 to 3 μm diameter the plumes generally contribute about one to four times more particles than present in ambient air.
The criteria persistence (P), bioaccumulation (B), and toxicity (T) are applied by domestic and international regulators and modelers to the hazard identification of chemical substances, including metals and metalloids, that may present harm to the environment. In this paper, we critically examine the literature to determine the weight of evidence for the application of water column partition half-times as a surrogate for the persistence criterion in the aquatic hazard identification of metals and metal compounds. Dissolved metals such as Fe, Mn, Cu, Pb, Co, Cs, Hg, and Zn, as well as the metalloids As and Se, tend to partition from the water column by adsorption onto sinking particulates, with reported and calculated partition half-times in the range 4 to 30 d, with outliers of 0.07 and 280 d. Within freshwater lakes, values of t ½ for the transition metals Cr, Mn, Fe, Co, and Cu averaged about 10 d, while those for the nontransition metals Sr, Zn, Cs, and Hg and the metalloids As and Se varied up to 55 d. These data are consistent with the well-established complexing properties of the transition metals, which are significantly greater compared to the nontransition metals and the metalloids. While the considerable variations in the literature at present preclude the use of metal partition half-times in aquatic hazard identification, the surrogate for the persistence criterion could be the partition half-time of the bioavailable fraction of the total dissolved metal concentration as determined in a laboratory protocol under standardized conditions.
Most of the metals produced for commercial application enter into service as alloys which, together with metals and all other chemicals in commerce, are subject to a hazard identification and classification initiative now being implemented in a number of jurisdictions worldwide, including the European Union Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) initiative, effective 1 June 2007. This initiative has considerable implications for environmental protection and market access. While a method for the hazard identification and classification of metals is available in the recently developed United Nations (UN) guidance document on the Globally Harmonized System of Hazard Classification and Labelling (GHS), an approach for alloys has yet to be formulated. Within the GHS, a transformation/dissolution protocol (T/DP) for metals and sparingly soluble metal compounds is provided as a standard laboratory method for measuring the rate and extent of the release of metals into aqueous media from metal‐bearing substances. By comparison with ecotoxicity reference data, T/D data can be used to derive UN GHS classification proposals. In this study we applied the T/DP for the 1st time to several economically important metals and alloys: iron powder, nickel powder, copper powder, and the alloys Fe‐2Cu‐0.6C (copper =2%, carbon = 0.6%), Fe‐2Ni‐0.6C, Stainless Steel 304, Monel, brass, Inconel, and nickel‐silver. The iron and copper powders and the iron and nickel powders had been sintered to produce the Fe‐2Me‐0.6C (Me = copper or nickel) alloys which made them essentially resistant to reaction with the aqueous media, so they would not classify under the GHS, although their component copper and nickel metal powders would. Forming a protective passivating film, chromium in the Stainless Steel 304 and Inconel alloys protected them from reaction with the aqueous media, so that their metal releases were minimal and would not result in GHS classification. For the other alloys, we developed a new critical surface area‐toxic units (CSA‐TU) approach to derive their GHS classification proposals. The CSA‐TU approach can be readily applied to other multicomponent alloy systems, without the need to arbitrarily select a particular component among several as the determinant of toxicity. This paper shows how regulatory obligations, such as those mandated by REACH, can be met with a laboratory‐based CSA‐TU method for deriving hazard classification proposals for alloys, linking to attendant environmental protection management decisions. Drawing on T/D data derived from laboratory testing of the alloy itself, the CSA‐TU approach can be applied to establish scientifically defensible decisions on hazard classification proposals for an alloy of interest. The resulting decisions can then be incorporated into environmental management measures in such jurisdictions as the European Union. Based on an approach developed specifically for alloys, the hazard classification decisions can be regarded as relevant, credible,...
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