Nickel in freshwater and marine water
Toxicant default guideline values for protecting aquatic ecosystems
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
Nickel can enter the environment naturally through weathering of minerals and rocks and through anthropogenic sources. More than 90% of the nickel in the aquatic environment is associated with particulate mater of sediments (Hart 1982). Nickel is found at low background concentrations in most natural waters (Table 8.3.2 of the ANZECC & ARMCANZ 2000 guidelines). Nickel is an essential trace element for aquatic organisms but may be toxic at higher concentrations.
Bioconcentration factor (BFs) for nickel in seawater range from 370 for oysters and mussels to 1000 for macroalgae (Florence et al. 1994). BFs for microalgae range from 0 to 3000 (Wang & Wood 1984). Optimum accumulation of nickel by microalgae occurs at pH 8. There was no evidence for nickel biomagnification from microalgae to the zooplankton Daphnia magna (Watras et al. 1985). USEPA (1986) did not consider bioconcentration to be a significant problem in the aquatic environment and reported a range of BFs from 0.8 for fish muscle to 193 for a cladoceran.
Summary of factors affecting nickel toxicity
- Nickel toxicity decreases with increased hardness and a hardness algorithm is available (Table 3.4.3 of the ANZECC & ARMCANZ 2000 guidelines).
- Toxicity of nickel increases as pH decreases. This is accounted for in the hardness algorithm.
- Nickel is weakly complexed by dissolved organic matter and is less bioavailable when adsorbed to suspended material.
- Nickel toxicity in seawater increases with decreasing salinity.
- Bioconcentration of nickel is not a significant problem in aquatic environments.
A small number of methods are available for determining the speciation of nickel in water. These include:
- Analytical techniques, such as cathodic stripping voltammetry and ion exchange (van den Berg & Nimmo 1987, Apte & Batley 1995)
- Theoretical techniques, such as geochemical modelling (Florence & Batley 1980, Sadiq 1989, van den Berg et al. 1991, Hawke & Hunter 1992).
Bioassays are typically used to determine metal-organism interactions. These can be used in conjunction with the measured and/or predicted speciation of nickel to define bioavailable nickel species. The current analytical practical quantitation limit (PQL) for nickel is 0.1 µg/L in fresh water and 2 µg/L in marine water (NSW EPA 2000).
Factors that affect the toxicity of nickel
In natural waters, nickel occurs in the +2 valency state. It is generally considered that Ni2+ is the form of nickel primarily responsible for eliciting a toxic response in aquatic organisms.
In seawater, inorganic nickel is usually divided between the free metal ion (Ni2+), carbonate, chloride and nickel–dissolved organic matter (DOM) species (van den Berg et al. 1991, Earth Systems 1996).
There have been surprisingly few studies of nickel complexation by natural DOM in freshwaters. Several recent studies of nickel speciation in estuarine and coastal waters have observed strong complexation by highly specific organic ligands (van den Berg & Nimmo 1987, Nimmo et al. 1989). Typically, 50% of dissolved nickel is organically complexed.
At pH > 6, nickel adsorbs/co-precipitates with iron and manganese (oxy)hydroxides and can also adsorb to suspended organic matter (Rashid 1974, Lee 1975, Richter & Theis 1980). The bioavailability of nickel sorbed to suspended particulate matter was low, compared to dissolved nickel (Klerks & Fraleigh 1997). At pH < 6, sorption is minor and nickel is considered to be highly mobile (CCREM 1987). In aerobic waters, and in the presence of microorganisms, nickel can be remobilised from bottom sediments (Stokes & Szokalo 1977).
Data available for two species indicated that chronic toxicity decreases as hardness increases. The measured chronic concentrations ranged from 15 µg/L for D. magna in soft water to 530 µg/L for fathead minnow Pimephales promelas in hard water (USEPA 1986). Kszos et al. (1992) found that in soft water (40 mg CaCO3/L), 7.5 µg Ni/L was lethal to Ceriodaphnia dubia within 7 days. In hard waters (177 mg CaCO3/L), there was no reduction in survival or fecundity of C. dubia at 7.5 µg Ni/L, although complete death occurred at 15 µg Ni/L. In contrast, concentrations of nickel of 16 mg/L in soft waters did not reduce the survival or growth of the Pimephales promelas.
An exponential, inverse relationship has been demonstrated between water hardness and the uptake and toxicity of nickel. An algorithm has been used to calculate a hardness-modified nickel guideline value for protecting aquatic ecosystems in North America (USEPA 1995a, 1995b).
Toxicity usually increases as the pH decreases (CCREM 1987) but there are exceptions. Schubauer-Berigan et al. (1993) investigated the effect of pH on the toxicity of nickel in hard water to the freshwater species C. dubia, P. promelas, Hyalella azteca and Lumbriculus variegatus. The 48-hour or 96-hour LC50 values for Ni ranged from 13 µg/L for C. dubia to 26 mg/L for Lumbriculus, with toxicity greatest at pH 8.5. The toxicity of nickel to the fathead minnow P. promelas was less dependent on pH, however, as the pH decreased, the nickel toxicity also decreased for all species tested. The maximum accumulation of nickel by microalgae was at pH 8. The presence of cobalt and humic acids decreased uptake of nickel in these algae.
The toxicity of nickel to fish, molluscs, crustaceans, fungi and bacteria in marine and estuarine waters decreases with increasing salinity (Hall & Anderson 1995). For example, Bryant et al. (1985b) found that the LC50 value for nickel at 35% salinity for the amphipod Corophium volutator was 34 mg/L, compared to 5.6 mg/L at 5% salinity.
Nickel toxicity for the amphipod C. volutator was found to increase with increasing temperature; the 8-day LC50 varied from 15 mg/L at 5°C to 5.2 mg/L at 10°C (Mance 1987).
Nickel is moderately toxic to freshwater organisms, with acute LC50 values ranging from 510 µg/L for a cladoceran to 43,000 µg/L for fish (ANZECC 1992) at low hardness. The lowest acute toxicity to fish was 2480 µg/L (CCREM 1987). For five species of freshwater green algae, significantly decreased growth was observed at 100 µg Ni/L at pH 7.2 (Spencer & Greene 1981). Reduced growth was noted in several freshwater algae at concentrations as low as 50 µg/L (USEPA 1986). In general, blue-green algae were more tolerant to nickel at pH 7, possibly due to production of extracellular organic compounds that bind nickel outside the cell.
USEPA (1986) reported that the acute toxicity of nickel for 23 marine species in 20 genera ranged from 152 µg/L for juveniles of a mysid Heteromysis formosa (Gentile et al. 1982) to 1100 mg/L for clams. The following low short-term marine toxicity figures were obtained from AQUIRE (1994): diatom (Thalissiosira guillardi 50 to 100 µg/L, 2-day no end-point recorded and EC50), dinoflagellate (Gymnodinium splendens and Glenodinium halli 100 to 200 µg/L, 2-day no end-point recorded and EC50) and bivalve (Villorita cyprinoides 61 µg/L, 4-day LC50 at 3.5 ppt salinity—Abraham et al. 1986). Few data were then available regarding chronic toxicity of nickel in survival and reproduction. The measured acute-chronic ratio was 5.5. One of the more sensitive species included an Australian temperate isolate of the diatom Nitzschia closterium with a 72-hour EC50 of 250 µg/L (Florence et al. 1994). In general, marine invertebrates are more sensitive than vertebrates.
For freshwater guideline derivation, only the chronic nickel data that were linked to pH and hardness measurements were considered and further screened. This reduced the dataset to just 18 data points covering seven species and four taxonomic groups. Geometric means of NOEC equivalents are reported below, after conversion to a uniform hardness of 30 mg/L CaCO3. The pH range was 6.3 to 7.7.
Fish: four species, 13.7 µg/L (Oncorhynchus mykiss) to 151 µg/L, (Micropterus salmoides). The lowest experimental chronic figure, (after hardness correction) was a 28-day LC50 of 18.5 µg/L for O. mykiss.
Amphibian: one species, Ambystoma opacum, 31 µg/L, from 8-day LC50.
Crustacean: one species, D. magna, 13.5 µg/L, from 5 to 30-day EC50. Lowest experimental chronic figure (after hardness correction) was 67 µg/L.
Mollusc: one species, Juga plicifera, 39.5 µg/L. An experimental NOEC of 69 µg/L was reported.
A freshwater high reliability trigger value of 11 µg/L was calculated for nickel using the statistical distribution method at 95% protection. This applies to low hardness waters, 30 mg/L as CaCO3.
Chronic data (34 points) after screening covered five taxonomic groups, as follows (reported as no observed effect concentration [NOEC] equivalents and geometric means of end-points and species). Several low figures (< 200 µg/L) were screened out, mainly because end-points were not reported.
Fish: one species, Fundulus heteroclitus, 30 000 µg/L from 7-day LC50.
Crustaceans: four species, 141 µg/L (36-day chronic mortality, Mysidopsis bahia, Gentile et al. 1982) and 160 µg/L (Portunus pelagicus: from 42-day maximum acceptable toxicant concentration (MATC) growth of 320 µg/L) to 6000 µg/L from 5 to 8-day LC50.
Echinoderm: one species, Asteria forbesi, 2600 µg/L from 7-d LC50.
Mollusc: five species, 240 (Crassostrea virginica; from 12-day LC50 of 1200 µg/L) to 450,000 µg/L from 7 to 12-day LC50.
Annelid: two species, 1540 to 5000 µg/L, from 7-day LC50.
Algae: one species, Nitzschia closterium 50 µg/L, from 5-day EC50 growth (Australian data).
A marine high reliability guideline value of 70 µg/L was derived for nickel using the statistical distribution method at 95% protection. The 99% protection level was 7 µg/L and is recommended for slightly to moderately disturbed marine systems. The 95% protection level does not give sufficient margin of safety from acute toxicity for a juvenile mysid (152 µg/L, Gentile et al. 1982). Low acute toxicity figures, unconfirmed, were also reported for a mollusc (60 µg/L), a diatom (50 to 100 µg/L) and two dinoflagellates (100 µg/L). Hence, the 99% protection level (7 µg/L) is recommended for slightly to moderately disturbed marine systems.
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