Transformation/dissolution characterization of tungsten and tungsten compounds for aquatic hazard classification
The transformation/dissolution protocol (T/DP) for metals and sparingly soluble metal compounds was applied to determine the transformation/dissolution (T/D) characteristics of yellow tungsten trioxide, WO3; blue tungsten oxide, WOx, x taken as 2.9; tungsten disulphide, WS2; tungsten metal, W; 3 samples of tungsten carbide, WC; sodium tungstate, Na2WO4 · 2H2O; ammonium paratungstate (APT), (NH4)10(H2W12O42) · 4H2O; and ammonium metatungstate (AMT) (NH4)6(H2W12O40) · 3H2O. The T/D data were used to derive aquatic hazard classification outcomes under the United Nations Globally Harmonized System of Classification and Labelling of Chemicals (UN GHS) and European Union Classification, Labelling and Packaging of Substances and Mixtures (EU CLP) schemes by comparing the data with selected acute and chronic ecotoxicity reference values (ERVs) of 31 and 3.37 mg W/L, respectively. In addition to the concentration of total dissolved tungsten (W), the T/D solutions were analyzed for the concentration of the tungstate anion, because speciation can be an important factor in establishing the ecotoxicity of dissolved metals. Results show that the tungstate anion was the predominant W‐bearing species in solution for all substances examined at pH 6 and 8.5. It was found that the 100 mg/L loadings of both the yellow WO3 and the blue WOx exceeded the 31 mg/L acute ERV, so they would classify as Acute 3‐Chronic 3 under the UN GHS scheme but they would not classify under the EU CLP. An effect of pH on the reactivity of the W metal was observed with 3% and 16% W dissolution at pH 6 and 8.5, respectively. Tungsten metal would not classify under either the UN GHS or EU CLP schemes nor would the WS2. The WCs were the least reactive in terms of the 1% or less dissolution of the contained W at pH 6. A critical surface area for WC was calculated. The sodium tungstate, APT and the AMT all yielded, at pH 8.5, total dissolved W concentrations that would result in UN GHS Acute 3‐Chronic 3 classifications. Integr Environ Assess Manag 2018;14:498–508. © 2018 Her Majesty the Queen in Right of Canada. Integrated Environmental Assessment and Management © 2018 SETAC
Method Development for Determining the Removal of Metals from the Water Column under Transformation/Dissolution Conditions for Chronic Hazard Classification
An extension of the transformation/dissolution protocol (T/DP) was developed and evaluated as a tool to measure the removal of metals from the water column for chronic aquatic hazard classification. The T/DP extension (T/DP‐E) consists of 2 parts: T/DP‐E part 1, to measure metal removal from the water column via binding of metals to a substrate and subsequent settling, and T/DP‐E part 2, to assess the potential for remobilization of metals following resuspension. The T/DP‐E methodology (672‐h [28‐d] removal period, 1‐h resuspension event, and 96‐h resettling period) was tested using Cu, Co, and Sr solutions in the presence of a substrate. The metal removal rates varied from rapid removal for Cu to slower rates of removal for Co and Sr. The resuspension event did not trigger any increase in dissolved Cu, Co, or Sr. Additional 96‐h experiments were conducted using dissolved Ni, Pb, Zn, and Ag and supported the conclusion that the T/DP‐E is sufficiently robust to distinguish removal rates between metals with a wide range of reactivities. The proposed method provides a means to quantify the rate of metal removal from the water column and evaluate remobilization potential in a standardized and reliable way. Environ Toxicol Chem 2019;38:2032–2042. © 2019 SETAC.
Speciation of antimony for the 21st century: promises and pitfalls
The speciation of both volatile and non-volatile antimony compounds in biota has undergone tremendous improvements during recent years. However, many severe problems such as the preservation of species information, the extractability of Sb, and the availability of Sb standard compounds still hamper the reliable speciation of Sb. Although distinct progress has been made towards the hyphenation of adequate separation devices with powerful element-specific detectors, only limited information can be derived from those experiments. This review highlights the current state-of-the-art of Sb speciation, focusing on hyphenated instrumental techniques as well as on problems encountered. Issues such as biomethylation, biological significance, and occupational and environmental exposure are discussed. The principal limitations, and further directions for research needed to improve Sb speciation procedures are described.