Vanadium in freshwater and marine water

​Toxicant default guideline values for protecting aquatic ecosystem

October 2000

Extracted from Section 8.3.7 ‘Detailed descriptions of chemicals’ of the ANZECC & ARMCANZ (2000) guidelines.

The default guideline values (previously known as ‘trigger values’) and associated information in this technical brief should be used in accordance with the detailed guidance provided in the Australian and New Zealand Guidelines for Fresh and Marine Water Quality.

Description of chemical

Speciation

Vanadium occurs in the +2, +3, +4 and +5 valency states. However, it appears that in natural waters only the pentavalent [V5+; vanadium (V) or vanadate] state occurs to any significant extent (Lee 1983).

It has been suggested that Ca(VO3)2 controls the solubility of vanadium in seawater and, in general, only monomeric vanadium (V) species are important in oxidising conditions (Sadiq 1988).

A variety of techniques are available for determining the speciation of vanadium in water. These include:

  • analytical techniques, such as ion exchange chromatography and electrophoresis (Takaya & Sawatari 1994, Jen et al. 1997)
  • theoretical techniques, such as geochemical modelling (Stendahl & Sprague 1982, Sadiq 1988, van den Berg et al. 1991).

Bioassays are typically used to ascertain metal-organism interaction. These can be coupled with measured and/or predicted speciation calculations to determine the bioavailability of various vanadium (V) species. The current analytical practical quantitation limit (PQL) for vanadium is 0.05 mg/L in fresh water and 2 mg/L in marine water (NSW EPA 2000).

Factors that affect the toxicity of vanadium

Vanadium (V) is more toxic to aquatic life than vanadium (IV) (Willsky et al. 1984).

Stendahl and Sprague (1982) investigated the toxicity of vanadium (V) to rainbow trout (Oncorhynchus mykiss) as a function of pH, hardness and over the pH range 5.5 to 8.8. The greatest toxicity occurred at pH 7.7 irrespective of the hardness or alkalinity. For example, at a hardness of 360 mg/L as CaCO3 they found a 7-day LC50 of 2.5 mg/L at pH 7.7, which compared to a value of 6.0 mg/L at pH 5.5 and 4.4 mg/L at pH 8.8. Similarly, Giles et al. (1979) found that the toxicity of vanadium to whitefish (Coregonus clupeaformis) was maximum at the intermediate pH of 7.0, in the pH range 6 to 9.

Tarzwell and Henderson (1960) indicated a four-fold decrease in toxicity of vanadium (V) to the fathead minnow (Pimephales promelas) when comparing soft water (20 mg/L as CaCO3) with hard water (400 mg/L as CaCO3). Similarly, Stendahl and Sprague (1982) found that the toxicity of vanadium (V) to rainbow trout decreased with increasing hardness (from low 30 to 355 mg/L as CaCO3), by an average factor of 1.8. However, this trend is disputed and requires further investigation.

Natural DOM does not readily complex aqueous vanadium because it occurs as stable anionic complexes (van den Berg et al. 1991).

In natural surface waters (pH 5 to 9), vanadate can be effectively removed from solution in the presence of colloids (Dzombak & Morel 1990). Since vanadium (V) species are, in general, anionic, sorption is maximised at low pH (pH < 8) and reduces as the pH increases.

Hamilton and Buhl (1990) investigated the acute toxicity of vanadium (V) to chinook salmon (Oncorhynchus tshawytscha) in both fresh and estuarine waters. They found that the toxicity to the salmon was the same in both waters, having a 96-hour LC50 of 17 mg/L, although the age of fish, and hence their weight, tested in the two experiments were significantly different. Conversely, Wilson and Freeburg (1980) found that an increase in salinity reduced the toxicity of vanadium (V) to phytoplankton. For example, the vanadium (V) LC50 for the alga was 1.8 mg/L at a salinity of 14%, whereas it was 24 mg/L at 28%.

Freshwater guideline

Freshwater chronic data (90 points) for vanadium covered three taxonomic groups, as reported below as NOEC equivalents. It was not possible to correct values for hardness at this stage. The pH range was 6.5 to 8.9.

Fish: eight species, 5 to 28-day NOEC (equivalents from LC50), 85 µg/L (P. promelas) to 14,000 µg/L (Salvelinus fontinalis). The lowest measured NOEC was 120 mg/L (P. promelas; 28-day growth).

Crustaceans: one species, Daphnia magna, 5 to 23-day NOEC, 158 to 1600 µg/L (mortality, reproduction).

Algae: one species, Chlorella vulgaris, NOEC, population growth, 1200 to 328,000 µg/L. Although the pH range of this test was very wide (around 2.2 to 8.0), it gives an indication of algal toxicity and its inclusion will only affect the size of the assessment factor (AF) used.

A freshwater low reliability trigger value of 6 µg/L was calculated for vanadium using an AF of 20 (applied to the lowest experimental chronicfigure). This should only be used as an indicative interim working level.

Marine guideline

Only six marine chronic data points were available for vanadium on four taxonomic groups (not including fish). These were as follows (NOEC equivalent figures all calculated from LC50 figures, are reported):

Crustaceans: one species, Carcinus maenas, 9-day NOEC, 7000 µg/L.

Molluscs: one species, Mytilus galloprovincialis, 9-day NOEC, 13,000 µg/L.

Annelids: one species, Nereis diversicolor, 9-day NOEC, 2000 µg/L.

Algae: three species, 13-day NOEC, 100 µg/L (Dunaliella sp.) to 600 µg/L.

A marine high reliability trigger value of 100 µg/L was calculated for vanadium using the statistical distribution method with 95% protection.

References

ANZECC & ARMCANZ 2000. Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Australian and New Zealand Environment and Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand, Canberra.

Dzombak DA & Morel FMM 1990. Surface complexation modeling: Hydrous ferric oxide. John Wiley & Sons, New York.

Giles MA, Klaverkamp JF & Lawrence SG 1979. The acute toxicity of saline groundwater and of vanadium to fish and aquatic invertebrates. Alberta Oil Sands Environmental Research Program Project AF 3.2.1, Report 56, 1–216.

Hamilton SJ & Buhl KJ 1990. Safety assessment of selected inorganic elements to fry of chinook salmon (Orcorhynchus tshawytscha). Ecotoxicology and Environmental Safety 20, 307–324.

Jen J-F, Wu M-H & Yang TC 1997. Simultaneous determination of vanadium(IV) and vanadium(V) as EDTA complexes by capillary zone electrophoresis. Analytica Chimica Acta 339, 251–257.

Lee K 1983. Vanadium in the aquatic ecosystem. In Aquatic toxicology, ed JO Nriagu, John Wiley & Sons, New York, 155–187.

NSW EPA 2000. Analytical Chemistry Section, Table of Trigger Values 20 March 2000, LD33/11, Lidcombe, NSW.

Sadiq M 1988. Thermodynamic solubility relationships of inorganic vanadium in the marine environment. Marine Chemistry 23, 87–96.

Stendahl DH & Sprague JB 1982. Effects of water hardness and pH on vanadium lethality to rainbow trout. Water Research 16, 1479–1488.

Takaya M & Sawatari K 1994. Speciation of vanadium(IV) and vanadium(V) using ion exchange chromatography and ICP-AES. Industrial Health 32, 165–178.

Tarzwell CM & Henderson C 1960. Toxicity of less common metals to fishes. Industrial Wastes 5, 12.

van den Berg CMG, Khan SH, Daly PJ, Riley JP & Turner DR 1991. An electrochemical study of Ni, Sb, Se, Sn, U and V in the estuary of the Tamar. Estuarine Coastal and Shelf Science 33, 309–322.

Willsky GR, Preischel DA & McCabe BC 1984. Metabolism of added orthovanadate to vanadyl and high-molecular-weight vanadates by Saccharomyces cerevisiae. Journal of Biological Chemistry 259, 13273–13281.

Wilson WB & Freeburg LR 1980. Toxicity of metals to marine phytoplankton cultures. Ecological Research Series, United States Environmental Protection Agency, Narragansett.