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Hazard for aquatic organisms

Freshwater

Hazard assessment conclusion:
PNEC aqua (freshwater)
PNEC value:
17.8 µg/L
Assessment factor:
3
Extrapolation method:
sensitivity distribution

Marine water

Hazard assessment conclusion:
PNEC aqua (marine water)
PNEC value:
2.5 µg/L
Assessment factor:
10

STP

Hazard assessment conclusion:
PNEC STP
PNEC value:
450 µg/L
Assessment factor:
10
Extrapolation method:
assessment factor

Sediment (freshwater)

Hazard assessment conclusion:
PNEC sediment (freshwater)
PNEC value:
563 mg/kg sediment dw
Extrapolation method:
equilibrium partitioning method

Sediment (marine water)

Hazard assessment conclusion:
PNEC sediment (marine water)
PNEC value:
79 mg/kg sediment dw
Extrapolation method:
equilibrium partitioning method

Hazard for air

Air

Hazard assessment conclusion:
no hazard identified

Hazard for terrestrial organisms

Soil

Hazard assessment conclusion:
PNEC soil
PNEC value:
7.2 mg/kg soil dw
Assessment factor:
3
Extrapolation method:
sensitivity distribution

Hazard for predators

Secondary poisoning

Hazard assessment conclusion:
PNEC oral
PNEC value:
0.167 mg/kg food
Assessment factor:
30

Additional information

Vanadium, oxalate complexes is soluble in environmental media. In a standard transformation/dissolution test according to OECD Series No 29 with a loading of 1 mg VO(C2O4)/L, a complete dissolution was observed after 24h resulting in dissolved vanadium levels of 239 μg/L and 231 μg/L at pH 8 and pH 6, respectively. Further, the solubility of vanadium, oxalate complexes is expected to determine its behaviour and fate in the environment, and subsequently its bioavailability and potential for bioaccumulation and ecotoxicity. Vanadium, oxalate complexes at pH 6 and 8, similar to other inorganic vanadium substances, transforms to the higher (V) oxidation state immediately upon dissolution (91-93% (V(V) after 24 hours). The vanadium ion is considered the moiety of ecotoxicological concern since oxalate is ubiquitous in the environment, readily biodegradable and does not have an aquatic hazard potential (oxalic acid [EC 205-634-3], ECHA CLP inventory, 2021). Therefore, a read-across approach is applied based on all information available for different inorganic vanadium substances and the fate of released vanadium ions can be expected to be similar to the common fate of vanadium ions in the environment. Further information on the applied read-across approach is summarized below.

Read-across approach

In the assessment of the environmental fate and behaviour of inorganic vanadium substances, a read-across approach is applied based on all information available for different inorganic vanadium substances. This grouping of vanadium substances for estimating their environmental fate and toxicity is based on the assumption that properties are likely to be similar or follow a similar pattern as a result of the presence of the common vanadium ion. After emission of metal (vanadium) substances into the environment, it is the potentially bioavailable metal ion (vanadium ion) that is liberated (to a greater or lesser extent) upon contact with environmental solutions, including sediment and soil porewater, and that is the moiety of ecotoxicological concern.This assumption can be considered valid when:

i) differences in solubility among V compounds do not affect the results for ecotoxicity,

ii) ecotoxicity is only affected by the vanadium-ion and not by the counter ions, and

iii) there are no important differences in speciation of vanadium in the environment after emissions of the various V compounds.

Reliable ecotoxicity date of soluble vanadium substances were selected, and respective effect concentrations are based on measured (dissolved) vanadium concentrations. In assessing the ecotoxicity of metals in the various environmental compartments (aquatic, terrestrial and sediment), it is assumed that toxicity is not controlled by the total concentration of a metal, but by the bioavailable fraction. For metals, this bioavailable fraction is generally accepted to be the free metal-ion or oxy-anion in solution. Conservatively, it can also be assumed that the total dissolved vanadium fraction is bioavailable.

The reliable ecotoxicity data are based on pentavalent V substances (NaVO3, NH4VO3, Na3VO4, V2O5, Ca3(VO4)2, (NH4)V3O8), except for one avian toxicity study with VOSO4. All counter-ions (Na+, (NH4)+, Ca2+, and (SO4)2-) are abundantly present in natural environments and/or are essential and are therefore not expected to cause any toxic effects at the concentrations tested.

Vanadium can exist in a multitude of different oxidation states from -2 to +5. However, being a first-row transition element, vanadium has the tendency to exist in high oxidation states (+3, +4 and +5), and vanadium ions will form oxy complexes in aqueous solutions (Cotton and Wilkinson, 1988; Crans et al., 1998). The aqueous chemistry of the metal is complex and involves a wide range of oxygenated species for which stabilities depend mainly on the acidity and oxygen level of receiving waters. Under conditions commonly found in oxic fresh waters (i.e., pH between 5 and 9; redox potential [Eh] between 0.5 and 1 V), the pentavalent forms will be the dominant species in solution (Brookins, 1988; Crans et al., 1998; Takeno, 2005, Larsson et al., 2015a). Tetravalent vanadium also may exist under some specific conditions (e.g. pH< 5). Soil organic matter, which strongly adsorbs to tetra- and pentavalent vanadium species, may potentially reduce V(V) to V(IV), therefore lowering its overall bioaccessibility (Reijonen et al., 2016). It is therefore assumed that upon dissolution of inorganic vanadium substances, the environmental conditions control the (redox) speciation of vanadium in water, soil and sediment, independently of the identity of the V substance.

 

This is confirmed by redox speciation analysis of dissolved vanadium during transformation/dissolution tests for vanadium metal and vanadium substances with different valence states (including V, V2O3, VOSO4, NaVO3, V2O5) according to OECD Series No 29 (2009). The tests were conducted at a loading of 1 mg/L over 28 days in standard OECD test media at pH 6 and pH 8 under a set of standard laboratory conditions representative of those in standard OECD aquatic ecotoxicity tests. The redox speciation of dissolved vanadium was measured by separating V(IV) and V(V) species by HPLC and analysis by ICP- MS. Regardless of the original valency of the vanadium substance, dissolved V at pH 6 and pH 8 is predominantly present in the pentavalent V form (75-97% of all V), with some traces of V(IV). Recovery of total dissolved V by measured V(V) and V(IV) was on average 96% and did not differ significantly among the substances tested.

Similar observations were made in laboratory experiments at pH 6: In a study performed by Larsson et al. (2015a) using natural soils spiked with vanadium (IV) or vanadium (V), pentavalent vanadium predominated in soil extracts after a 10-d equilibration period. Therefore, vanadium speciation in soil solution was independent of the valence state of the added salt. Accordingly, Reijonen et al. (2016) demonstrated that vanadium speciation (and bioavailability) is mainly regulated by soil organic matter (SOM) and soil pH under oxic conditions, whereas the original valence state of the added vanadium substance is negligible for controlling distribution and water solubility. In line with these findings, long-term investigations (26 years) on fate and transformation of vanadium species performed by Larsson et al. (2015b) on vanadium-containing converter lime applied to pine forest soil suggest further that the long-term speciation is governed by soil properties (pH, SOM, metal hydroxides) and less dependent on the initial valence state.

Based on this information, it was concluded that the read-across conditions stated above are met. Therefore, all toxicity data based on soluble V substances (i.e. maximal bioavailability) are used in a read-across approach and results are expressed based on elemental vanadium concentrations.For further information on the applied read-across approach, please refer to the RAAF document "Read-across approach for environmental toxicity of the vanadium category, 2020" attached in IUCLID Section 13.

Conclusion on classification

Acute and chronic reference values for environmental classification are based on standard tests in accordance with Regulation (EC) No 440/2008 on “test methods pursuant to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)”.

Acute and long-term toxicity data for vanadium are available for the three trophic levels. The lowest L(E)C50 for fish, crustacean or algae growth rate is a 96-h LC50 of 0.693 mg V/L (based on dissolved V concentration), observed for the effect of V2O5 flakes in a GLP-conform standard test with Leuciscus idus (Mitterer, 1999). This value is selected as the acute ecotoxicity reference value for classification.

The lowest chronic NOEC or EC10 for freshwater fish, invertebrates or algae from a standard test is the 28-d EC10 of 0.203 mg V/L for the effect of V2O5 on growth (weight) of Pimephales promelas (Kimball, 1978), and this value is selected as chronic reference value for classification. Available chronic NOEC/EC10 values derived in non-standard tests with non-standard species were not applied for classification conclusions as follows:

- The 21-d EC10 of 0.05 mg V/L (based on dissolved V concentration) for the effect of NaVO3 in a 21-day reproduction test with neonate daphnids (Daphnia dentifera) (Schiffer and Liber, 2017): Daphnia dentifera is not a standard daphnia species and tested specimen were field-collected in Canada. The species is considered of lower relevance in European freshwaters compared to standard organisms, and results were therefore not selected for classification.

- The 30-d EC10 of 0.076 mg V/L (based on dissolved V concentration) for the effect of V2O5 in a 30-day growth test with second generation flagfish larvae (Jordanella floridae) originating from exposed fish (Holdway and Sprague, 1979): This non-standard fish species was exposed in a non-standard test.

- The chronic 14-d EC10 of 0.081 mg V/L for the effect of NaVO3 on reproduction of Aeolosoma sp. (Stubblefield, 2017): was derived with a non-standard species in a non-standard test. 

The acute and long-term ecotoxicity reference values of 0.693 and 0.203 mg V/L, respectively, are based on dissolved elemental V concentrations and are applied for the classification of inorganic vanadium substances. Since vanadium is an inorganic element, biodegradation is not relevant.

For the classification of vanadium, oxalate complexes, the acute and long-term ecotoxicity reference values (in mg V/L) are converted based on the possible maximum vanadium content of anhydrous vanadium, oxalate complexes (33% V), resulting in 2.11 and 0.62 mg VO(C2O4)/L, respectively. Based on these ecotoxicity reference values and classification criteria of Regulation (EC) No 1272/2008, Table 4.1.0 (a), vanadium, oxalate complexes does not meet classification criteria of Acute (short-term) aquatic hazard (acute reference value > 1 mg/L). In accordance with Table 4.1.0 (b(i)), vanadium, oxalate complexes as not-rapidly degradable substance meets criteria of “Aquatic Category Chronic 2” (chronic reference value >0.1 and ≤1 mg/L). Thus, vanadium, oxalate complexes is classified as Long-term Aquatic Hazard Category 2 (H 411).