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p'!,Y <br />Q' <br />April 2009 <br />Williams and Denholm <br />79 <br />Detection iimits were stated to be between 2 to 5 <br />ng/L. One site, next to an alpine village, showing <br />between 3 to 10 times background (10 to 30 ng/ <br />L), was believed to reflect emissions from over- <br />snow vehicles, chair lifts and fossil fuel emis- <br />sions. The siiver concentratlon in stream runoff <br />was below the detection limit of 1x10'7 g/L <br />(SMHEA 1993). <br />4. TOXICITY OF SIWER ION <br />The toxicity of the silver ion (Ag+) in water to a <br />range of aquatic species has been the subject of <br />a great number of studies reported in the sclen- <br />tific literature. These studies have been compre- <br />hensively reviewed by Eisler (1996), Ratte (1999) <br />and others. <br />4.1 Acute Silver Toxicitv <br />Revfewing the toxicity of Ag` to algae, bacteria <br />and macroinvertebrates, Taylor (cited by Beli and <br />Kramer, 1999) recorded silver cflncentrations in <br />the nanomolar (10 Ng/L) range for threshold ef- <br />fects. More subtle effects were found at concen- <br />trations of 10 to 100 ng/L. <br />Eggs of rainbow trout continuously exposed to <br />silver ions at 0.17 Ng/L had increased embryotox- <br />icity and hatched prematurely. The fry also had a <br />reduced growth rate (Davies et a/. 1978). <br />CICAD 44 notes that aqueous concentrations of <br />silver in the range 1• to 5 Ng/L killed sensitive spe- <br />cies of aquatc organisms including representa- <br />tive species of insects, daphnids, amphipods, <br />trout, flounder and dace. Wood et al. (1996) <br />noted that 96-hr LCm values for freshwater fish <br />generaliy lie in the range 6.5 to 65 Ng/L. <br />In a detailed study of the mechanism of toxicity of <br />silver ion (using silver nitrate), Grosell et al. <br />(2000) found a difference in tolerance to frse sil- <br />ver ion between European eels and rainbow trout <br />of 3 to 4 fold. The 96-hr LCw's ranged from 5 to <br />70 Ng/L. For trout, the sAver fort inhibitsd both <br />sodlum ion and chbride bn inAux whereas for <br />eels only the sodium ion inAux was inhibited. <br />The key target of inhibition in trout and eeis was <br />found to be branchial Na`, K'-ATPase, an en- <br />ryme that drives uptake of Na' needed to <br />counter diffusive loss of Na` to the hypo-osmoac <br />environment. Thia is simifar to the findings of <br />Webb and Wood (1998) and Wood ef al. (1999), <br />who examined physiological responses in rein- <br />bow trout rather than toxicity. in each case the <br />source of the silver ion was siiver nftrate. <br />In the Australian context, acute silver ion toxicity <br />is enerally considered to be of the order of 1 x <br />10' g/L, although the Australian and New Zea- <br />land GuideNnes for Fresh and Marine Water <br />Quality (ANZECC and AMRCANZ 2004) give <br />0.005 Ng/L as a Guideline Trigger Value ("GTV"). <br />The Australian Drinking Water Guldelines <br />(National Heaith and Medical Research Council <br />2004) cite a guidellne valu• of total dissolved <br />siiver of 0.1 mg/L. <br />In the US the EPA has set a guideline of 4.7 Ng <br />total Ag/L in water with a hardness of 120 mg/L <br />as the acute toxic limit. There is no chronic <br />guideline value. <br />Freshwater flsh and amphibians appear to be the <br />most sensitive vertebrates to dissolved silver. <br />The leopard frog, Rana pip/ens, is among the <br />most sensitlve amphibians with an LCso of 10 Ng/ <br />L silver ion. The mast sensitive flsh species are <br />even less tolerant with LC60's befinreen 2.5 and <br />10 Ng/L. <br />The ClCAD 44 monograph has tabutated the <br />range of aquatic species that have been used in <br />toxicity tests with silver lon. The toxic silver con- <br />centraaon for each species is also given in CI- <br />CAD 44. <br />4.2 Chronic Toxicity of Silver lon <br />The importance of exposure pathways in sub- <br />lethal toxicity testing of silver on zooplankton has <br />been examined by Hook and Fisher (2001). <br />In their paper detailing a study on the physiology <br />of silver ion toxicity to freshwater rainbow trout, <br />Wood et al. (1996) note that during chronic expo- <br />sure to 0.5 Nq/l. Ag' (as silver nitrate) the prind- <br />pat sub-lethal effect was a small depression of <br />plaama Na' and CI'. <br />Diamond et al. (1990) canied out a seriea of <br />chronic sitver toxicity tests using a range ot rep- <br />resentative aquatc species including six inverte- <br />brates and three flsh species. Their results sug- <br />gested that some of the invertebrates were more <br />sensitive than the flsh species tested. As a gen- <br />erai $tatemo,t cney concluded tnac for Weter a <br />moderate haMness a chronic value could be ob- <br />- Scientific Papers -