The Toxicity of Molybdate to Freshwater and Marine Organisms. III
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Science of the Total Environment 609 (2017) 420–428 Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv The toxicity of molybdate to freshwater and marine organisms. III. Generating additional chronic toxicity data for the refinement of safe environmental exposure concentrations in the US and Europe D.G. Heijerick a,⁎,S.Careyb a ARCHE Consulting, Liefkensstraat 35d, 9032 Gent-Wondelgem, Belgium b International Molybdenum Association, 454–458 Chiswick High Road, London W4 5TT, United Kingdom HIGHLIGHTS GRAPHICAL ABSTRACT • Chronic ecotoxicity data for Mo were generated for a freshwater and marine species. • Data sets meet the US-EPA information requirements for deriving Final Chronic Values. • The US FCV-approach and European SSD-approach result in similar EQS- values for Mo. article info abstract Article history: The freshwater and marine long-term ecotoxicity datasets used in the European REACH registration dossiers for Received 27 March 2017 molybdenum and molybdenum compounds resulted in the derivation of a HC5,50%,freshwater (38.2 mg Mo/L) and Received in revised form 26 June 2017 HC5,50%,marine (5.70 mg Mo/L) by means of the statistical extrapolation method. Both datasets, however, did not Accepted 8 July 2017 meet the US-EPA information requirements for deriving Final Chronic Values (FCV) that were based on chronic Available online xxxx data. US-EPA compliance was achieved by generating chronic no-effect data for the freshwater benthic amphipod fi Editor: Henner Hollert Hyalella azteca and the marine inland silverside sh Menidia beryllina, using sodium molybdate dihydrate as test substance. A 42d-EC10 of 44.6 mg Mo/L for reproduction was determined in a water-only exposure with H. azteca. Keywords: For M. beryllina, a 37d-NOEC of 139 mg mMo/L for standard length and blotted wet weight was found. Other end- Molybdate points (e.g., survival, hatching success) proved to be less sensitive. Data were added to the existing chronic tox- Marine assessment icity datasets, together with new long-term no-effect values that were identified in open literature for brown Freshwater assessment trout Salmo trutta, the marine alga Isochrysis galbana, the marine snail Nassarius dorsatus and the marine barnacle FCV derivation Amphibalanus amphitrite. The updated data sets resulted in a freshwater and marine HC5,50% of 35.7 and PNEC derivation 6.85 mg Mo/L, respectively. The same data sets were also used for the determination of US-EPA FCVs, where the FVCfreshwater was 36.1 mg/L, and the FCVmarine was 3.85 mg Mo/L. As the Final Plant Values for both aquatic environments were higher than their respective FCVs, the Criterion Continuous Concentration (CCC) for molyb- denum is equal to the FCV. © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/). ⁎ Corresponding author at: Liefkensstraat 35 D, B9032 Gent-Wondelgem, Belgium. E-mail address: [email protected] (D.G. Heijerick). http://dx.doi.org/10.1016/j.scitotenv.2017.07.070 0048-9697/© 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). D.G. Heijerick, S. Carey / Science of the Total Environment 609 (2017) 420–428 421 1. Introduction MDR for the freshwater and marine environment and – where possible – allocates the species reported in Heijerick et al. (2012b) to these fami- The introduction of the EU-REACH legislation in 2006 (EC, 2006)re- lies. Based on the data in both tables, which include long-term no- quired the importers and manufacturers of high-tonnage chemicals effect levels for micro-alga, macro-alga and/or higher plants, two data (N1000 t/year) to submit a registration dossier for each of their sub- gaps were identified: a chronic endpoint for a benthic crustacean was stances. Conducting an environmental risk assessment on the basis of lacking for the freshwater environment, whereas the data gap for the mandatory data requirements (e.g. chronic toxicity data) was an inte- marine environment was a chronic endpoint for a second family of gral part of their registration obligation and is documented within the the Phylum “Chordata”. To ensure that water quality standards for Mo Chemical Safety Report (CSR) for each substance. in the United States are based on scientific relevant and robust data, The International Molybdenum Association (IMOA) coordinated the IMOA commissioned chronic toxicity tests for Mo with the freshwater development of such CSRs for eleven different molybdenum com- amphipod Hyalella azteca and the marine fish Menidia beryllina,hereby pounds, and commissioned an extensive research program for the as- addressing the identified data gaps with regard to FCV-derivation based sessment of long-term environmental effects of molybdate in the on chronic data. freshwater and marine aquatic compartment. The outcome of this re- This publication presents the outcome of these additional long-term search program was published by De Schamphelaere et al. (2010) and toxicity tests. These data, together with recently pubished data on Mo- Heijerick et al. (2012a). The statistical extrapolation methodology toxicity in the aquatic compartment (Lucas et al., 2017; Trenfield et al., used in Europe for deriving a safe concentration level for the freshwa- 2015, 2016; Van Dam et al., 2016), were added to the existing data ter/marine environment is based on a Species Sensitivity Distribution sets and used for a) setting freshwater and marine FCVs on one hand, (SSD) of at least 10 organisms covering 8 different taxonomic groups and b) to refine the freshwater and marine PNECs reported by (ECHA, 2008); this methodology was applied on the chronic data sets Heijerick et al. (2012a). for molybdate and resulted in a median 5% Hazardous Concentration (HC5,50%) values of 38.2 and 5.70 mg Mo/L for the freshwater and marine environment, respectively. The United States Environmental Protection 2. Material and methods Agency (US-EPA), however, applies an alternative methodology for the derivation of a safe concentration level, the so-called Final Acute Value The freshwater ampipod Hyalella azteca was selected for the gener- (FAV) and Final Chronic Value (FCV) (Stephen et al., 1985/2010). A ation of chronic ecotoxicity data for a benthic crustacean. This species major difference between both approaches is that the US-EPA calcula- has been widely used in laboratory sediment toxicity tests and bioaccu- tion method only takes into account a) the four lowest values of a mulation tests, and standard testing procedures have been developed dataset, and b) the number of data points in that data set. Typically, a for both sediment and water-only exposures. It has been shown to be FCV is derived by dividing the FAV by a Final Acute-to-Chronic Ratio among the more sensitive organisms when exposed to metal- (FACR). However, depending on the data that are available concerning contaminated sediments (Milani et al., 2003; Phipps et al., 1995). Simi- chronic toxicity to aquatic animals, the FCV can also be calculated in lar sensitivity was noted in water-only exposure, where H. azteca was the same manner as the FAV. In practice, the availability of reliable more sensitive to cadmium and nickel than three other benthic inverte- chronic data is rather limited for most substances, so the approach brates (Chironomus riparius, Hexagenia spp. and Tubifex tubifex)(Milani that uses the FAV as the starting point (i.e. FCV = FAV/FACR) is the et al., 2003). Thus H. azteca is suitable for assessing the long-term toxic- most used methodology for deriving an FCV. ity of molybdate to bentic crustaceans. In order to derive an FCV that is directly based on chronic no-effect The inland silverside Menidia beryillina is one of three species in the levels, the data set should be in line with the minimum data require- atherinid family that are amenable to laboratory culture, and one of four ments (MDRs) that have been set out by US-EPA (Stephen et al., 1985/ atherinid fish species used for chronic toxicity testing; it is recommend- 2010). This requires that the dataset includes at least acceptable chronic ed by US-EPA for assessing the acute and chronic toxicity of e.g. effluents values for the eight families that are also required for setting an FAV. in the estuarine and marine environments (US-EPA, 2002). The species Algal species and higher plants (e.g., green alga, duckweed) are not in- can be found along the North American Atlantic coast from Cape Cod cluded; therefore, no-effect levels for those taxonomic groups should (Massachusetts) all the way to Florida and west to Vera Cruz, Mexico be set aside when deriving the FCV. It should be noted that information (Johnson, 1975). The species tolerates a wide range of temperature for those taxonomic groups is needed when setting a Final Plant Value (2.9–32.5 °C) (Tagatz and Dudley, 1961; Smith, 1971) and salinity (0– (FPV); both FCV and FPV are considered for setting the Criterion Contin- 58‰)(Simmons, 1957; Renfro, 1960). It is an ecologically important uous Concentration (CCC). species that is part of the diet of several commercial species like the Both the freshwater and marine dataset for molybdate used by bluefish Pomatomus saltatrix,themackerelScomber scombrus,and Heijerick et al. (2012b), and likewise in the relevant molybdenum sub- striped bass Morone saxatilis (Bigelow and Schroeder, 1953). All these stances REACH dossiers, did not comply with the US-EPA 8-family factors make M. beryllina a suitable and relevant species for FCV setting guidelines. Consequently, neither a freshwater nor a marine FCV for mo- in the marine environment.