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Six tropical freshwater species were used to assess the toxicity of mine waters from a uranium mine adjacent to a World Heritage area in northern Australia. Key contaminants of potential concern for the mine were U, Mg, Mn, and total ammonia nitrogen (TAN). Direct toxicity assessments were carried out to assess whether the established site-specific guideline values for individual contaminants would be protective with the contaminants occurring as mixtures. Metal speciation was calculated for contaminants to determine which were the major contributors of toxicity, with 84 to 96% of Mg predicted in the free-ion form as Mg2+ , and 76 to 92% of Mn predicted as Mn2+ . Uranium, Al, and Cu were predicted to be strongly bound to fulvic acid. Uranium, Mg, Mn, and Cu were incorporated into concentration addition or independent action mixture toxicity models to compare the observed toxicity in each of the waters with predicted toxicity. For >90% of the data, mine-water toxicity was less than predicted by the concentration addition model. Instances where toxicity was greater than predicted were accompanied by exceedances of individual metal guideline values in all but one case (i.e., a Mg concentration within 10% of the guideline value). This indicates that existing individual water quality guideline values for U, Mg, Mn, and TAN would adequately protect ecosystems downstream of the mine. Environ Toxicol Chem 2021;40:2334-2346. © 2021 Commonwealth of Australia. Environmental Toxicology and Chemistry © 2021 SETAC.

This experimental study determined internal distributions of an array of radio-elements (54Mn, 60Co, 65Zn, 134Cs, 241Am, 109Cd, 110mAg, 75Se and 51Cr) accumulated from seawater by three chondrichthyan fish species (Scyliorhinus canicula (dogfish), Raja undulata (undulate ray) and Torpedo marmorata (spotted torpedo)) and three teleost species (Scophthalmus maximus (turbot), Sparus aurata (seabream) and Dicentrarchus labrax (seabass)). The study tested the hypothesis that the chondrichthyan (cartilaginous) fish taxon and teleost (bony) fish taxon have different patterns of bioaccumulation of these radio-elements in six body components (head, digestive tract, liver, kidneys, skin and muscle), consistent with their long period of evolutionary divergence. Comparisons of body component CFs between the two taxa for each radio-element and the full array of radio-elements showed highly significant differences (p ≤ 0.001) between cartilaginous and bony fishes in each body component, confirming the existence of a strong and pervasive phylogenetic signal; however, the subset of radio-elements most determinant of these differences were unique for each body component. Partitioning between the three individual bony species and the three individual cartilaginous species also occurred repeatedly among their body components, particularly for bony fishes. Distributions of these radio-elements among body components were typically highly heterogeneous for both fish taxa.

Metal contamination within the urbanized coastal zon is one threat linked to a decline in the abundance, distribution and/or species diversity of wild marine bivalve populations. This study determined the 48-h embryo/larval sensitivity (no-effect concentration (NEC) and median-effect concentration (EC50)) of ten marine bivalve species (nine endemic to Australia) to aluminium (Al), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), nickel (Ni) and zinc (Zn), key metal contaminants impacting urbanized coastal zones in south-eastern Australia, in natural seawater (20-22 °C, 30‰ salinity, pH 7.8-7.9, 1.2 mg/L dissolved organic carbon). For all metals, except Fe, the order of sensitivity was oysters > mussels ≥ scallops ≥ cockles ≥ clams, where the economically-important oysters, Magallana gigas and Saccostrea glomerata, were 2.6 (Al) to 4.2 (Cd) times more sensitive than the least sensitive clam species. For all bivalve species, the order of metal sensitivity was Cu > Pb > Zn = Ni > Co > Cd > Al > Cr(VI) > Mn ≥ Fe(III), where Cu was eight times more toxic than Zn or Ni, 28 times more toxic than Cd, 220 times more toxic than Cr(VI) and 570 times more toxic than Fe(III). Iron, unlike the other nine soluble metals, occurred as particulate Fe(III) oxyhydroxide, where EC50 values decreased with increasing exposure time as the larval (D-veliger) stage. There was no significant (p > 0.05) effect of embryo/larval mass, or surface area/volume, on metal sensitivity. Further, there was no significant (p > 0.05) relationship between metal sensitivity and phylogeny (genetic distance). Divalent metal sensitivity was positively related (r2 = 0.87) to cell surface metal-binding affinity. The current Australian marine water quality guideline for Ni is not protective of the ten bivalve species (NECs were 2-6-fold below the guideline), while the guideline for Zn is not protective of oysters.

Freshwater mussels (Bivalvia: Unionida) are among the most threatened freshwater faunal groups worldwide. Metal contamination is one threat that has been linked to declining mussel population distribution and abundance. This study determined the sensitivity (valve closure) of the glochidia (larvae) of six species of Australian freshwater mussels to cadmium (Cd), cobalt (Co), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn), key metal contaminants impacting urbanized coastal rivers in south-eastern Australia (home to ~50% of the population), in a soft reconstituted freshwater (hardness 42mgCaCO3L-1; alkalinity 22mgCaCO3L-1 and pH7.0) over 72h. The sensitivity of each mussel species to each metal increased 2.5-fold with increasing exposure time from 24 to 72h. The most sensitive mussel species (Cucumerunio novaehollandiae), across all metals and exposure times, was ~60% more sensitive than the least sensitive species (Velesunio ambiguus). The relative sensitivity of glochidia to the six selected metals, across all mussel species and exposure times, was: Cu>Cd>Pb>Co=Ni>Zn. Glochidia were most sensitive to Cu and least sensitive to Zn. Quantitatively, the toxicity of Cu was 3-fold more than Cd, 8-fold more than Pb, 14-fold more than Co or Ni and 16-fold more than Zn. The cell surface binding affinities (conditional log K values) of Cd (range 6.65-6.94), Co (6.04-6.29), Cu (7.17-7.46), Ni (6.02-6.29), Pb (6.24-6.53) or Zn (5.96-6.23), pooled for all mussel species after 72h exposure, were positively related to metal sensitivity. The chronic no effect concentrations (NECs) of Cu, Ni and Zn were below (i.e. glochidia were more sensitive than) their national freshwater guideline values, indicating that freshwater mussels may not be adequately protected for these metals in urbanized coastal rivers within south-eastern Australia.

This article contains general physico-chemical data (salinity, pH, redox potential, temperature, dissolved oxygen, suspended particulate matter (SPM), dissolved organic carbon and chlorophyll a concentrations) for surface waters at 15 near-pristine sites in the Hawkesbury Estuary and 24 sites (encompassing a wide range of metal contamination) in the highly urbanized Sydney Estuary, south-eastern Australia. Data on concentrations of five key metals (cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb) and zinc (Zn)) in filtered (0.2 μm) and surface sediments (

There is a lack of good quality data and mechanistic understanding on the effects of true water hardness (calcium (Ca) and magnesium (Mg)) on the bioavailability and toxicity of uranium (U) to freshwater biota. This study determined the effect of true water hardness (20, 75, 150, 275 and 400 mg CaCO(3) L(-1)) on the cell surface binding affinity (log K), accumulation and toxicity (growth inhibition) of U in a submerged, rootless, macrophyte (Ceratophyllum demersum) in a synthetic freshwater with constant alkalinity (13 mg CaCO(3) L(-1)) and pH (6.2) over 7 days. A 20-fold increase in water hardness resulted in a 4-fold decrease in U toxicity (median effect concentration (EC50)=134 μg L(-1)U at 20 mg CaCO(3 )L(-1) hardness, increasing to 547 μg L(-1) U at 400 mg CaCO(3) L(-1) hardness), cell surface binding affinity (log K=6.25 at 20 mg CaCO(3) L(-1) hardness, decreasing to log K=5.64 at 400 mg CaCO(3) L(-1) hardness) and accumulation (the concentration factor decreased from 63 at 20 mg CaCO(3) L(-1) hardness to 15 at 400 mg CaCO(3) L(-1) hardness) of U. Calcium provided a 4-fold greater protective effect against U accumulation and toxicity compared to Mg. Speciation calculations indicated negligible differences in the percentages of key U species (UO(2)(2+), UO(2)OH(+), UO(2)(OH)(2)) over the range of water hardness tested. The inhibition of U binding at the cell surface, and subsequent uptake, by C. demersum, with increasing Ca and/or Mg concentration, may be explained in terms of (i) competition between Ca(2+)/Mg(2+) and UO(2)(2+) (and/or UO(2)OH(+)) for physiologically active sites at the cell surface, and/or (ii) reduced negative charge (electrical potential) at the cell surface, resulting in a decrease in the activity of UO(2)(2+) (and/or UO(2)OH(+)) at the plant/water interface (boundary layer), and consequently, less U bound to physiologically active cell surface sites. In the absence of a biotic ligand model for U, the results of this study (together with previous work) reinforce the need for a more flexible, hardness-dependent, U guideline for the protection of selected freshwater biota.

yDepartment of Sustainability, Environment, Water, Population and Communities, Darwin, Northern Territory, AustraliazAquatic Solutions International, Dundas Valley, New South Wales, Australia§CSIRO Land and Water, Kirrawee, New South Wales, Australia(Submitted 1 February 2012; Returned for Revision 12 April 2012; Accepted 18 July 2012)Abstract—The present study reanalyzed 46 existing uranium (U) chronic toxicity datasets for four freshwater species to generateconsistenttoxicitymeasuresandexplorerelationshipsbetweenUtoxicityandkeyphysicochemicalvariables.Dissolvedorganiccarbon(DOC) was consistently the best predictor of U toxicity based on 10% inhibitory concentration (IC10) and median inhibitoryconcentration (IC50) values, with water hardness also being a significant co-predictor of IC50 concentrations for one species. Theinfluence of DOC on acute and chronic U toxicity was further characterized using existing data for five species, and was found to varydepending on species, DOC source, and exposure duration (acute vs chronic). The slopes of the relationships between DOC and(normalized)acuteandchronicUtoxicityweremodeledusingcumulativeprobabilitydistributions.Fromthese,slopeswereselectedforwhich tocorrect acute orchronic U toxicityvalues orhazard estimates basedon theaquatic DOC concentration.The fifth percentiles ofthesecumulativeprobabilitydistributionsforacuteandchronicexposuredatawere0.064and0.090,respectively,correspondingtoa6.4and 9.0% reduction in U toxicity relative to the toxicity at the base DOC concentration for each 1mg/L increase in DOC concentration(over the DOC range 0–30mg/L). Algorithms were developed to enable the adjustment of U toxicity values and U hazard estimates,depending on DOC concentrations. These algorithms will significantly enhance the environmental relevance of water quality/riskassessments for U in fresh surface waters. Environ. Toxicol. Chem. 2012;31:2606–2614. # 2012 SETACKeywords—Uranium Toxicity Dissolved organic carbon Freshwater Risk assessmentINTRODUCTION

The effects of chronic uranium (U) exposure on larval Northern trout gudgeon, Mogurnda mogurnda, were assessed in two experiments using a newly-developed 28d survival and growth toxicity test. Significant effects were observed in both tests, but toxicity was markedly higher in Test 2 than Test 1. The LC50s for Tests 1 and 2 were 2090microgL(-1) and 1070microgL(-1), respectively. Larval growth IC10s for Tests 1 and 2 were 860microgL(-1) and 660microgL(-1) (dry weight), and 1160microgL(-1) and 850microgL(-1) (length), respectively. Uranium speciation modelling showed that a lower pH in Test 2 (mean of 6.0) compared to Test 1 (mean of 6.7) resulted in a greater proportion of free uranyl ion (UO(2)(2+)), the predominant bioavailable form of U. A higher dissolved organic carbon concentration (DOC) in Test 2 (4.2mgL(-1)) compared to Test 1 (2.1mgL(-1)) resulted in a higher proportion of U-DOC in Test 2, but this was insufficient to counter the effect of pH on the proportion of UO(2)(2+). The difference in U toxicity between the two tests could be explained by normalising for UO(2)(2+); the concentrations of UO(2)(2+) at the LC50s for Tests 1 and 2 were calculated to be 13.3 and 13.7microgL(-1), respectively. Finally, the results of this study, and comparisons with other studies suggest that U toxicity to M. mogurnda appears to be as much, if not more, a function of exposure water quality and feeding regime, as exposure duration.

Cephalopods play a key role in many marine trophic networks and constitute alternative fisheries resources, especially given the ongoing decline in finfish stocks. Along the European coast, the eggs of the cuttlefish Sepia officinalis are characterized by an increasing permeability of the eggshell during development, which leads to selective accumulation of essential and non-essential elements in the embryo. Temperature and pH are two critical factors that affect the metabolism of marine organisms in the coastal shallow waters. In this study, we investigated the effects of pH and temperature through a crossed (3×2; pH 8.1 (pCO2, 400 ppm), 7.85 (900 ppm) and 7.6 (1400 ppm) at 16 and 19°C, respectively) laboratory experiment. Seawater pH showed a strong effect on the egg weight and non-significant impact on the weight of hatchlings at the end of development implying an egg swelling process and embryo growth disturbances. The lower the seawater pH, the more 110 mAg was accumulated in the tissues of hatchlings. The 109Cd concentration factor (CF) decreased with decreasing pH and 65Zn CF reached maximal values pH 7.85, independently of temperature. Our results suggest that pH and temperature affected both the permeability properties of the eggshell and embryonic metabolism. To the best of our knowledge, this is one of the first studies on the consequences of ocean acidification and ocean warming on metal uptake in marine organisms, and our results indicate the need to further evaluate the likely ecotoxicological impact of the global change on the early-life stages of the cuttlefish.

The decommissioned Mount Todd gold mine, located in the wet-dry tropics of northern Australia, consists of a large waste water inventory and an acid rock drainage problem, which has the potential to impact upon freshwater ecosystems of the Edith River catchment. The toxicity of retention pond 1 (RP1) water was determined using six local freshwater species (duckweed, alga, cladoceran, snail, hydra and a fish). RP1 water was very toxic to all species, with the percentage dilution of RP1 water inhibiting 10% of organism response (IC10), or lethal to 5% of individuals (LC5), ranging from 0.007 to 0.088%. The percentage dilution of RP1 water inhibiting 50% of organism response (IC50), or lethal to 50% of individuals (LC50), ranged from 0.051% to 0.58%. Based on chemical analyses and geochemical speciation modelling of the test waters, Cu, Zn and Al were the most likely toxic components at acidic dilutions (i.e. > or =1%), while Cu and Zn were the most likely toxic components at 0.1% RP1 water, where pH was 6.5. Species sensitivity distributions (SSDs) were used to predict dilutions of RP1 water that would protect or unacceptably affect the downstream aquatic ecosystems. A dilution ratio of 1 part RP1 water to 20000 parts Edith River water (0.005% RP1 water) was calculated to be required for the protection of at least 95% of species. This information can be used in conjunction with field chemical and biological data to better predict the ecological risks of RP1 waste water downstream of the Mount Todd mine.

Semaphore crabs (Heloecius cordiformis), soldier crabs (Mictyris platycheles), ghost shrimps (Trypaea australiensis), pygmy mussels (Xenostrobus securis), and polychaetes (Eunice sp.), key benthic prey items of predatory fish commonly found in estuaries throughout southeastern Australia, were exposed to dissolved (109)Cd and (75)Se for 385 h at 30 k Bq/l (uptake phase), followed by exposure to radionuclide-free water for 189 h (loss phase). The whole body uptake rates of (75)Se by pygmy mussels, semaphore crabs and soldier crabs were 1.9, 2.4 and 4.1 times higher than (109)Cd, respectively. There were no significant (P>0.05) differences between the uptake rates of (75)Se and (109)Cd for ghost shrimps and polychaetes. The uptake rates of (109)Cd and (75)Se were highest in pygmy mussels; about six times higher than in soldier crabs for (109)Cd and in polychaetes for (75)Se - the organisms with the lowest uptake rates. The loss rates of (109)Cd and (75)Se were highest in semaphore crabs; about four times higher than in polychaetes for (109)Cd and nine times higher than in ghost shrimps for (75)Se - the organisms with the lowest loss rates. The loss of (109)Cd and (75)Se in all organisms was best described by a two (i.e. short and a longer-lived) compartment model. In the short-lived, or rapidly exchanging, compartment, the biological half-lives of (75)Se (16-39 h) were about three times greater than those of (109)Cd (5-12h). In contrast, the biological half-lives of (109)Cd in the longer-lived, or slowly exchanging compartment(s), were typically greater (1370-5950 h) than those of (75)Se (161-1500 h). Semaphore crabs had the shortest biological half-lives of both radionuclides in the long-lived compartment, whereas polychaetes had the greatest biological half-life for (109)Cd (5950 h), and ghost shrimps had the greatest biological half-life for (75)Se (1500 h). This study provides the first reported data for the biological half-lives of Se in estuarine decapod crustaceans. Moreover, it emphasises the importance of determining metal(loid) accumulation and loss kinetics in keystone prey items, which consequently influences their trophic transfer potential to higher-order predators.

Several nations have adopted hardness-modified copper (Cu) guidelines for protecting freshwater biota. However, there is a lack of good quality data and mechanistic understanding on the effects of true water hardness (calcium (Ca) and magnesium (Mg)) on the bioavailability and toxicity of Cu to freshwater biota, particularly macrophytes. This study determined the effect of true water hardness (35, 90 and 335 mg CaCO(3)/l, added as Ca and Mg chloride in a 1:1 mole ratio) on the cell surface binding affinity (log K), accumulation and toxicity (96 h growth (biomass and stem length) and photosynthetic pigment inhibition) of Cu in the free-floating submerged macrophyte, Ceratophyllum demersum, in a synthetic freshwater with constant alkalinity (16 mg CaCO(3)/l) and pH (7.0). There were no significant (P0.05) differences in the cell surface binding affinity, accumulation or toxicity of Cu in C. demersum with a 10-fold increase in water hardness from 35 to 335 mg CaCO(3)/l. The mean 96 h EC(50) values (and 95% confidence intervals) for biomass, the most sensitive endpoint, were 8.4 (7.6-9.2), 8.9 (8.0-9.8) and 9.9 (9.1-10.7) microg/l Cu for 35, 90 and 335 mg CaCO(3)/l, respectively. Speciation calculations indicated only very small (1-6%) differences in the percentage distribution (i.e. bioavailability) of Cu over the hardness range. These collective results indicate no apparent competition between Cu and Ca/Mg for binding sites on the cell surface. Given that the mechanism of Cu uptake (via Cu-specific and Na-linked transporters) is fundamentally different to that of Cd, Ni, Pb and Zn (via Ca transporters), for which other hardness-dependent algorithms have been developed, it is doubtful whether a hardness-modified Cu guideline value will be sufficiently protective of sensitive freshwater biota, such as C. demersum, particularly in medium-hard fresh surface waters with low levels of dissolved organic carbon. The biotic ligand model offers a more flexible and mechanistic approach for deriving site-specific Cu (metal) guidelines for protecting freshwater biota.

This study determined the condition and reproductive output of a common estuarine toadfish, Tetractenos glaber, in two metal contaminated and two reference estuaries near Sydney, Australia. Female toadfish from metal contaminated estuaries were smaller and younger than in reference estuaries; however, it could not be resolved whether these differences were due to direct effects of metal contamination or differences in nutritional value of prey. Lipid content in liver and gonad tissues was inversely related with levels of As, Pb, Cd and Co in sediment. In contrast, protein content in liver, gonad and muscle tissues was positively related to sediment levels of Ni and Co. Increased levels of Pb in gonads were associated with decreased oocyte diameter and density. This suggests a reduction in egg size and fecundity, which ultimately may lead to a decline in female reproductive output. Changes in fish health and reproduction caused by chemical pollutants may alter fish population and community structure. © 2005 Elsevier Ltd. All rights reserved.

The freshwater green microalgae Chlorella sp. and Pseudokirchneriella subcapitata (P. subcapitata) were chronically (48 and 72 h, respectively) exposed to copper at various pH levels, i.e., pH 6-7.5 and pH 5.9-8.5, respectively. Concentrations resulting in 50% inhibition of exponential growth rate (EC50) were determined as dissolved Cu, estimated chemical activity of the free Cu2+ ion (as pCu = - log{Cu2+ activity as molarity}), and as external (surface-bound) Cu and internal Cu in the algal cells. With increasing pH, EC50dissolved decreased from 30 to 1.1 microg of Cu L(-1) for Chlorella sp. and from 46 to 18 microg of Cu L(-1) for P. subcapitata. The pH effect on copper toxicity was even more obvious when expressed as Cu2+ activity. The EC50pCu increased on average 1.4 pCu unit per pH unit for Chlorella sp. and 1.1 pCu unit per pH unit for P. subcapitata, thus indicating a marked increase of Cu2+ toxicity at higher pH (more than 1 order of magnitude per pH unit). In contrast, it was found that EC50 values expressed as surface bound or external copper (EC50external) and as internal copper (EC50internal) did not vary substantially when pH was increased. External Cu was operationally defined as the Cu fraction removable from the algal cell by short-term contact with ethylenediaminetetraacetic acid; internal copper was defined as the nonremovable fraction. For Chlorella sp. the EC50external varied between 5 and 10 fg of Cu/ cell (factor of 2 difference) and the EC50internal between 25 and 40 fg of Cu/cell (factor of 1.6 difference). For P. subcapitata the EC50external varied between 10 and 28 fg of Cu/cell (factor of 2.8 difference) and the EC50internal between 42 and 71 fg of Cu/cell (factor of 1.7 difference). Because the observed variation in EC50external and EC50internal is much less than the variation in EC50Cu2+, it is concluded that both external and internal copper are better predictors of copper toxicity than Cu2+ when pH is varied. From the perspective of toxicity modeling, this observation is the first step toward considering the use of the cell surface as the algal biotic ligand for Cu in a similar way as fish gills fulfill this role in the biotic ligand model for predicting metal toxicity to fish species.

The concentrations of 15 metals were measured in the osteoderms (dermal bones) of 30 freshwater crocodiles (Crocodylus johnstoni) from a single population in the Lynd River, northeastern Australia (17 degrees 50'S, 144 degrees 20'E), that were well characterised with respect to site fidelity, reproductive status and age. Multiple linear regression analyses were used to determine the effects of crocodile size (snout-vent length, 25-128 cm), age (0.7-62.7 years), gender (male or female) and reproductive status (sexually mature or immature) on osteoderm metal concentrations. Gender and reproductive status were not significant (P > 0.05) co-predictors of the osteoderm concentration of any metal. In contrast, size, age and osteoderm calcium concentration were highly significant (P < 0.001) systematic predictors of the osteoderm concentrations of all metals, except Na and K. Osteoderm metal concentrations were inversely related (P < 0.001) to both size (r(2) = 0.52-0.92) and age (r(2) = 0.52-0.84), but positively related (P < 0.001) to osteoderm calcium concentration (r(2) = 0.67-0.92). Relative to calcium concentration, the rates of metal accumulation in the osteoderms of C. johnstoni were inversely related to the solubility constant (log K(sp)) of the metal as a phosphate; however this relationship was not linear. This finding is consistent with that previously established for the flesh of freshwater bivalves, which like the crocodilian osteoderm, have a calcium phosphate repository in the form of extracellular granules. The constancy of this relationship between rate of metal accumulation and relative solubility for calcium phosphate deposits, despite contrasting Ca accumulation regimes and taxonomic dissimilarity, points to a potential underlying principle that warrants investigation in a greater range of biota. The implications for using the osteoderms of C. johnstoni as an indicator of metal levels in freshwater ecosystems are also discussed.

Body size, age, and gender (male or female) are important variables influencing many aspects of the ecology, physiology, and survival of animals. However, no data are available on the influence of these variables on bivalves exposed to sublethal metal concentrations. This study tested whether the valve movement responses (measured in terms of the duration or frequency of valve opening) of the Australian tropical freshwater unionoid bivalve, Velesunio angasi, exposed to sublethal uranium (U) concentrations in a standard synthetic water (pH, 6.0; hardness and alkalinity, 4 mg/L as CaCO(3)) were influenced by body size (shell length, shell breadth, or dry tissue weight), age, and/or gender. The valve movement responses of V. angasi to U were independent of gender; the sensitivity of males to U was not significantly (p > 0.05) different from that of females. In contrast, the valve movement responses of V. angasi to U were size- and age-dependent; smaller and younger individuals (median shell length = 36.8 mm; median age = 0.7 years) were 22% more sensitive (p

The toxicity of aluminium (Al) to fish in acidic waters has been well documented. It was therefore expected that Al toxicity would be significant in fish communities in Gadjarrigamarndah (Gadji) Creek, a seasonally flowing stream in tropical northern Australia. This creek receives acidic groundwater containing elevated concentrations of Al from earlier land irrigation of treated mine tailings water from the former Nabarlek uranium mine. It was hypothesised that Al toxicity was reduced by high levels of silica (Si) in the water, and the subsequent formation of Al-silicate complexes. This prompted a laboratory assessment of the toxicity of Gadji Creek water to sac-fry of the native fish, Mogurnda mogurnda, followed by more detailed investigation of the toxicity of Al and the influence of Si in reducing Al toxicity. No mortality of M. mogurnda sac-fry was observed in two toxicity tests using Gadji Creek water collected in August 1997 and September 1998. The majority of Al (80-95%) was calculated to be complexed with humic substances and sulfate, with l1% being complexed with silicate. Assessment of the influence of silica on the acute toxicity of Al in the absence of natural organic complexants (i.e. in reconstituted freshwater, pH 5) revealed that Si reduced Al toxicity. As the molar ratio of Si:Al was increased, the percent survival of M. mogurnda sac-fry increased until there was no significant (P g 0.05) difference from the controls. However, speciation modelling again predicted that little (l3%) Al complexed with silicate, with the speciation and bioavailability of Al remaining constant as the molar ratio of Si:Al increased. Therefore, the original hypothesis that Al-silicate complexes in solution reduced the toxicity of Al to M. mogurnda could not be supported. This potential mechanism, and an alternative hypothesis, that Si competes with Al for binding sites at the fish gill surface, requires further investigation. Crown Copyright (C) 2002 Published by Elsevier Science Ltd. All rights reserved.

Knowledge of the transport pathways of metals into aquatic organisms is paramount in determining the metal's potential mechanism of toxicity. To determine the relative importance of water and food as cadmium (Cd) sources for the cladoceran Daphnia magna grazing on the algae Chlorella vulgaris, we measured cadmium accumulation and toxicity (feeding inhibition and survival) in three genetically different clones of D. magna subsequent to water, food, and water and food exposures. We found that Cd uptake from water and food was independent of source and additive in effect, with D. magna juveniles accumulating twice as much Cd from water than from food (algae). However, the efficiency with which Cd was assimilated by D. magna from its algal diet was much higher (10%) than from water (0.3%). Uptake and toxic responses were inversely related: tolerant clones accumulated more Cd. As a consequence, models based on uptake of metals from the combined routes of water and food may be reliable to predict metal dynamics in the field, but may fail to predict toxic effects since tolerance to metals is not necessarily linked to reduced total uptake of metals.

Freshwater bivalves (Velesunio angasi) were sampled in 1996 from the Finniss River in tropical northern Australia at 10 sites a priori exposed and nonexposed to acid rock drainage (ARD), containing elevated metal concentrations, from the rehabilitated Rum Jungle copper-uranium mine. Secondary ion mass spectrometry (SIMS) was used to measure Cu, Mn, Zn, U, Ni, Co, Pb, and Fe/Ca ratios across the annual shell laminations of the longest-lived bivalves found at each site, with the aim of evaluating the ability of the shells to archive measured annual metal inputs and their temporal patterns. At sites not contaminated by ARD, relatively constant and similar (baseline) SIMS signals were found for all metals in the shell laminations of V. angasi, dating as far back as 1965. At sites contaminated by ARD, relatively constant, but variably elevated, SIMS signals were evident for Cu, Mn, Zn, Ni, and Co in the shell, which extended back to the end of rehabilitation (1986) only. Since rehabilitation, the temporal patterns of Cu, Zn, and Mn observed in the shells at the most contaminated sites reflected those of the measured annual dissolved loads in the surface waters. The average concentrations of Cu, Mn, Zn, Ni, and Co in the shells decreased (3-13-fold) with increasing distance downstream of the mine site, until concentrations characteristic of the noncontaminated sites were reached. This geographic pattern of decline in pollution signal in the shell with increasing distance downstream of the pollution input is consistent with the pattern established for water and sediment chemistry. Overall, the SIMS results support the proposition that the shells of V. angasi can be used as archival indicators of metal pollution in surface waters of the Finniss River over their lifetime.

Whole soft tissue concentrations of Mn, Co, Ni, Cu, Zn, Pb, Cd and U were measured in two species of freshwater (unionid) bivalves (Hyridella depressa and Velesunio ambiguus) from a minimally polluted site in the Hawkesbury-Nepean River, south-eastern Australia. Although the mean concentrations of metals in the tissue were similar for each bivalve species, their patterns of accumulation were dissimilar. For each metal, positive linear relationships between tissue concentration and shell length (r2 = 0.37-0.77; P < or = 0.001) and tissue dry weight (r2 = 0.29-0.51; P < or = 0.01) were found in H. depressa, but not in V. ambiguus. However, for both species, positive linear relationships were found between the tissue concentration of each divalent metal and Ca tissue concentration (r2 = 0.59-0.97; P < or = 0.001). For both bivalve species, the normalised rates of accumulation of the metals relative to increasing Ca concentration and/or size, were U approximately = Cd > or = Pb > or = Mn > Co > or = Zn > Cu > Ni. The differential rates of accumulation of divalent metals are interpreted as being predominantly governed by their varying loss rates, which are controlled by the differing solubilities (log Ksp values) of the metals in the phosphatic extracellular granules, the demonstrated major sites of metal deposition in the tissue of H. depressa and V. ambiguus. The rates of accumulation of Mn, Co, Zn, Cu and Ni were linearly and inversely related (r2 = 0.91-0.97; P < or = 0.001) to their solubilities as hydrogen phosphates, a finding consistent with the bioaccumulation model previously developed for the alkaline-earth metals. However, for U, Cd and Pb, this linear inverse relationship did not continue to hold, i.e. their rates of accumulation did not increase with decreasing solubility. However, these results are still consistent with the model if U, Cd and Pb are so insoluble in the granules of H. depressa and V. ambiguus over their lifetime (up to approx. 50 years) that there is effectively no loss of these metals, and hence, no differential between their rates of accumulation. The present results reaffirm the use of Ca tissue concentration to predict the tissue concentrations of other divalent metals by explaining up to 94 and 97% of the variability between individual bivalves of H. depressa and V. ambiguus, respectively. The use of Ca tissue concentration to effectively minimise the inherent variability between individuals in their metal tissue improves the ability of an investigator to discern smaller spatial and/or temporal differences in the metal tissue concentrations of these bivalves, and thus to detect metal pollution.

The concentrations of Na, K, Ca, Mg, Ba, Sr, Fe, Al, Mn, Zn, Pb, Cu, Ni, Cr, Co, Se, U, and Ti were determined in the flesh and osteoderms of estuarine crocodiles (Crocodylus porosus) captured in three adjacent catchments of Kakadu National Park, within the Alligator Rivers Region of northern Australia. This study provides, for the first-time, baseline concentrations of elements in both flesh and osteoderms of wild crocodiles. Multiple linear regression analyses were used to determine the effects of total crocodile length, estimated age, gender, inferred reproductive status, physical condition, and catchment of capture on element concentrations in both tissues. The Mg concentration (log10) in the flesh and osteoderms of C. porosus significantly (p < or = 0.001) decreased with increasing length (1.7-5.0 m) and estimated age (5-40 years). Similarly, the Ti concentration (log10) in flesh significantly (p < or = 0.01) decreased with increasing length. In contrast, Zn and Se concentration (log10) in flesh significantly (p < or = 0.001) increased with increasing length and/or age, suggesting that these relationships are mediated by biological rather than environmental chemical factors. In flesh, Fe and Na concentrations (log10) significantly (p < or = 0.05) increased as the physical condition of C. porosus deteriorated. No significant (p > 0.05) effects of gender or inferred reproductive status on element concentrations in the flesh and osteoderms were found. The mean concentrations (log10) of Al, Ba, Cr, Ni, and Pb in flesh and Co, Fe, Mg, Mn, and U in the osteoderms were significantly (p < or = 0.01) different between catchments. The significant (p < or = 0.05) effects of catchment on the concentrations of various elements indicate that C. porosus reflects the chemistry of its environmental milieu and therefore has a certain degree of catchment fidelity, even though the catchments are adjacent to one another. Such catchment-specific signals may be useful in the determination of the provenance of itinerant crocodiles. They also point to the utility of crocodiles as long-term biomonitors of their environment.

The veracity of the free ion activity model (FIAM) was tested by examining the acute (48 h) valve movement responses (VMR) (measured in terms of the duration of valve opening) of the Australian tropical freshwater unionid bivalve, Velesunio angasi to increasing concentrations of total Mn or U, in a standard synthetic water under conditions of varying pH (5.0-6.0) and/or dissolved organic carbon (model fulvic acid, FA) concentrations (0-8.9 mg l(-1)). Valve movement behaviour, measured using an automated data acquisition system, was shown to be a quantifiable and rapid, real-time endpoint for assessing the toxic effects of Mn and U exposures. For Mn, the VMR of V. angasi were independent (P>0.05) of pH and/or model FA concentration. In contrast, VMR to U exposures were highly dependent (P< or =0.05) on pH and/or model FA concentration; individuals were more sensitive to U at low pH and model FA concentrations. Valve movement responses to Mn were directly proportional to the activity of the free metal ion (Mn(2+)), which is consistent with the FIAM. In contrast, VMR to U were regarded as an 'exception' to the FIAM, since they were a weighted function of the activities of the free metal ion and the 1:1 metal hydroxide species (i.e. 1.86 x UO2(2+) + UO2OH(+)). Additionally, the effect of U on V. angasi demonstrates the importance of examining VMR at more than one pH. At a fixed pH, the results for U were consistent with the FIAM (i.e. response was directly proportional to UO2(2+)); only when pH was altered, were the results inconsistent with the FIAM. The inconsistency in the VMR of V. angasi to U exposures in this study, together with similar examples from other studies using different metals (e.g. Al or Zn), raises questions regarding the veracity of the FIAM. A detailed examination of the conceptual development of the FIAM is required to probe its apparent failure to describe several metal-organism interactions.

Fresh surface waters from the Hawkesbury–Nepean River, the major river supplying water to the Sydney region in south-eastern Australia, were sampled monthly during 1991 and analysed for major ions (Na, K, Ca, Mg, Cl, SO4 and HCO3), nutrients (NO3 and PO4), organic carbon and trace metals (Al, Fe, Cu, Zn, Pb, Cd, Ni, Co and Mn). The chemical composition of the river during 1991 was consistent with other studies of the river from 1977 to 1996. The major ion composition in the river is predominantly influenced by sea-salt aerosols in rainwater (headwaters) and connate sea-salt in groundwater (mid-lower reaches), with a cationic dominance order of Na≫Mg>Ca>K (equivalents) and an anionic order of Cl≫HCO3>SO4. This is typical of the headwaters of other permanent coastal rivers (freshwater) in south-eastern Australia with a similar catchment lithology. These results differ markedly from the most common natural major ion assemblages established for world rivers (i.e. Ca>Mg>Na>K and HCO3>SO4>Cl), which tend to be predominantly influenced by chemical weathering of rocks and minerals. The mean concentrations of major ions, nutrients, organic carbon and trace metals in the freshwater reaches of the Hawkesbury–Nepean River increased by factors of 2.5–4.4, 14–18, 2.2 and 1.6–11, respectively, with increasing distance from the headwaters. Increases in major ion concentrations are attributed mainly to the increasing influence of saline groundwater inflows from regions of Wianamatta shale. Conversely, concentrations of nutrients, organic carbon and trace metals (except Fe and Al) increased as a consequence of anthropogenic inputs, particularly point discharges from sewage treatment plants (i.e. showing distinct, but variable, concentration peaks), as well as diffuse urban and/or agricultural runoff during storm events. The temporal variability of the mean concentrations of all measured parameters in this study was related to variability in water discharge. The mean concentrations of the major ions decreased by a factor of 1.5–3.0 with increasing water discharge, whereas the concentrations of nutrients, organic carbon and trace metals increased by a factor of 2.0–3.0, 1.6 and 1.3–2.0, respectively. This study provides the first survey of trace metal concentrations in the freshwater reaches of a permanent coastal river in Australia using `clean' sampling and handling techniques. The concentrations of Cu, Zn, Pb, Cd and Ni measured in the headwaters of the Hawkesbury–Nepean River were amongst the lowest reported in the literature for riverine (freshwater) systems, and will form a benchmark for assessing the effects of increasing urbanisation in the catchment.

The ultimate aim of ecotoxicological studies is to predict how natural populations respond to contaminant exposure. Thus, it is crucial to understand how genetic and environmental factors in the field modify responses measured in the laboratory. In the present study the authors determine the genetic and environmental components of variability in acute responses among four Daphnia magna clones exposed to both essential (Zn and Cu) and non-essential (Cd and U) metals in waters with varying water hardness. The authors postulate that genotype acute responses to physiologically non-essential metals may be more variable than responses to essential metals and that this may be explained by hypothesizing that acute responses to non-essential substances are subject to intermittent selection (since the substances may not always be present in biologically significant amounts), whereas responses to essential substances are subject to continuous directional selection (since essential substances by definition co-occur with biota in biologically significant amounts). D. magna clones were exposed to single-metal solutions of varying concentration at two or three levels of water hardness (soft, moderate–hard and hard) for periods ranging from 12–96 h (12 h increments). LC50 values for each metal×genotype×water hardness×exposure period combination were determined for (i) total metal concentration and (ii) the free hydrated metal ion concentration (predicted using geochemical speciation modeling) and compared using analysis of covariance with environment (water hardness) and genotype (clone) as fixed factors and exposure time as a covariate. The results showed that Zn–Cd were consistent, but Cu–U inconsistent, with the essentiality hypothesis. In addition, the small, or even non-existent, genotype-environment interaction effect on the inheritance of metal tolerance supports the argument that genetic variability in resistance to trace metals is inherited through single major genes. Implications of these results for the prediction of population tolerance ranges are discussed in relation to the problem of predicting metal speciation and the biological effects of metals in fresh waters with varying hardness.

Adult Silver Perch ( Bidyanus bidyanus ) were exposed to 137 Cs and 85 Sr for 8 weeks to determine radionuclide concentration factors (CFs) for use in a dose assessment model database for sub-tropical and tropical ecosystems. At equilibrium, the fresh weight CFs for 137 Cs and 85 Sr in the flesh of B. bidyanus were 12.6 ± 5.2 kg 1 −1 (mean ± S.E.) and 0.73 ± 0.21 kg 1 −1 , respectively. The mean CFs were considerably lower than those expected for temperate freshwater fish, but were consistent with recently reported values for other sub-tropical and tropical freshwater fish. The results indicate that the use of recommended CFs for radiological dose assessment models, based on temperate freshwater fish, may provide overestimates of dose when applied to sub-tropical and tropical fish. The biological half-lives of 137 Cs (19 ± 2 days) and 85 Sr (5 ± 1 days) in the flesh of B. bidyanus , estimated from a one-compartment exponential uptake model, were lower than reported values for four other species of sub-tropical and tropical freshwater fish. Cesium-137 was distributed in B. bidyanus as follows: flesh (63%) > skin/scales (22%) > bone (15%). Conversely, 85 Sr showed similar activities in the bone and skin/scales that were still increasing after eight weeks, while the levels in the flesh remained relatively low. Analysis of the skin/scales component showed that the majority of 85 Sr (∼ 94%) was located in the scales.

Uranium is the prime potential contaminant in mine waste waters that may be released from the Ranger Uranium Mine (RUM) into the receiving waters of the Magela Creek, Alligator Rivers Region, Northern Australia. The potential ecological impact of the migration of uranium, that would result from an elevation in its concentration above background, in the Magela Creek downstream of the RUM, has been experimentally investigated by integrating biomonitoring with geochemical speciation modelling. The freshwater bivalve Velesunio angasi, abundant throughout the Magela Creek catchment, was exposed to a variety of uranium concentrations in a synthetic Magela Creek water, at four pH levels (5.0, 5.3, 5.5 and 6.0), in the presence (3.05 and 7.50 mg l{sup -1}) and absence of a model fulvic acid (FA), and its behavioural response was measured. Speciation modelling, using the HARPHRQ code, provided evidence that UO{sup 2+}{sub 2} and UO{sub 2}OH{sup +} are the uranium species most responsible (ca. 96%) for eliciting an adverse behavioural response when UO{sup 2+}{sub 2} is assigned twice the toxic effect of UO{sub 2}OH{sup +}. This finding rejects the notion that biota respond specifically to the sum total of inorganic uranyl species. (orig.)

A theoretical and experimental study was performed to determine the kinetics of 45Ca, 60Co, 210Pb, 54Mn and 109Cd in the whole soft tissue of the unionid bivalve Velesunio angasi. This investigation further tested the hypothesis, developed previously for the alkaline-earth metals, that the biological half-life of a metal in soft tissue is related to its solubility when deposited in the extracellular granules of the bivalve. This hypothesis was tested for the above radionuclides (tracers of the stable metals) by a comparison of (a) a qualitative a priori prediction of their biological half-lives in bivalve tissue, based on critically evaluated log Ksp values for their respective hydrogen phosphate salts, and calibrated to previous experimentally determined rates of loss for 45Ca and 226Ra, with (b) their empirical biological half-lives that were investigated experimentally using the radionuclides 45Ca, 60Co, 210Pb, 54Mn and 109Cd. The results of the experimental investigation showed that the mean values calculated for the biological half-lives of 45Ca and 60Co in the tissue were 106 and 121 days, respectively, but there was no significant (P > 0.05) loss of 210Pb, 54Mn or 109Cd from the soft tissue over 160 days, when bivalves were exposed to radionuclide-free water. A chemical model was developed from first principles that quantitatively explains the kinetic mechanisms that underlie the differential rates of loss of divalent metals from the extracellular granules of V. angasi. The experimental results were consistent with the predictions of the model; however, some investigational limitations were evident, and these are discussed. The uptake of each radionuclide into the bivalve tissue tended to be linear, but the variation in tissue concentration, between individual bivalves, increased with the period of exposure. Significant (P < 0.001) positive correlations were found between tissue concentrations of each radionuclide pairing in both the uptake and loss phases of the experiment, indicating that individual bivalves were internally consistent in the way that they metabolised these radionuclides.

The influence of dissolved organic carbon (DOC), in the form of Suwannee River fulvic acid (SRFA), on uranium (U) toxicity to the unicellular eukaryote, Euglena gracilis (Z strain), was investigated at pH 6. In a background medium without SRFA, exposure of E. gracilis to 57 μg L(-1) U resulted in a 50% reduction in growth (IC(50)). The addition of 20 mg L(-1) DOC (as SRFA), reduced U toxicity 4 to 5-fold (IC(50) increased to 254 μg L(-1) U). This reduction in toxicity was also evident at more sensitive effect levels with a 10% reduction in growth (IC(10)) occurring at 5 μg L(-1) U in the background medium and at 17 μg L(-1) U in the SRFA medium, respectively. This amelioration of toxicity with the addition of SRFA was linked to a decrease in the bioavailability of U, with geochemical speciation modelling predicting 84% of U would be complexed by SRFA. The decrease in bioavailability of U in the presence of SRFA was also evident from the 11-14 fold reduction in the cellular concentration of U compared to that of E. gracilis in the background medium. Stepwise multiple linear regression analyses indicated that UO(2)(2+) alone explained 51% of the variation in measured U toxicity to E. gracilis. Preliminary U exposures to E. gracilis in the presence of a reactive oxygen species probe, suggest exposure to ≥60 μg L(-1) U may induce oxidative stress, but this endpoint was not considered to be a sensitive biological indicator.

Radionuclides in (sub-) tropical freshwater systems generally behave in a predictable manner, based on what is known from lakes and streams in the better studied temperate climes. Within the water column, the fate and behaviour of radionuclides and their stable element analogs are typically governed by key physicochemical variables such as pH, redox potential, the concentrations of dissolved ions and the presence and type of organic matter. The chemical form (or speciation) of a radionuclide or stable element is generally of greater biological importance (i.e. bioavailability) than the total concentration. This concept is currently being integrated into mechanistic frameworks (e.g. biotic ligand and bioaccumulation models) by national regulators for protecting freshwater ecosystems. Given that the volume of fresh surface waters (i.e. rivers and lakes) is relatively small (0.01%) in comparison to seas and oceans, then the biota living within them can also substantially influence the chemistry of a radionuclide, by effectively acting as “large particles” available for surface complexation. For example, wetlands serve as effective biofilters to remove radionuclides from the water column. Once radionuclides have been accumulated by organisms, their behaviours generally reflect their similarities to essential (macro and micro nutrients) and non-essential elements. Metabolic mechanisms tending toward homeostasis typically make internal organism chemistry less dynamic than that in the external water column. Again, this is to be expected and radionuclide biokinetics generally follow the patterns observed for freshwater organisms in temperate climates. This constancy has enabled models to be developed to describe the rate and extent of radionuclide bioaccumulation. These models can be adapted to include various uptake pathways (from water, food or sediment) via gills, skin or gut and modes of excretion or dilution (e.g. diffusion, egestion, moulting and growth) and different parameters can be estimated for each radionuclide and organism. Key biotic factors known to influence radionuclide bioaccumulation are size, age and gender. There are also differences within and between species that reflect the natural variability within any system. Despite the similarities that exist between tropical and temperate freshwater systems, it should be noted that there is still a paucity of data for (sub-) tropical freshwater organisms and systems, and hence there is the chance for exceptions to the consistency to exist. Data are presented that show that the uptake of Sr and Cs by tropical freshwater fishes is much lower than would be expected based on the studies of freshwater temperate fishes. These observations point to the need to undertake additional site- and species- specific investigations on the radioecology of key radionuclides, whenever future nuclear developments in tropical systems are initiated.

A competitive inhibition experimental design, incorporating radiotracer labelling of metals and the geochemical simulation of their speciation at two varying Ca water concentrations, was employed to conclusively demonstrate that the divalent trace metals Pb, Mn, Cd and Co, were absorbed from the aquatic medium as metabolic analogues of Ca by two species of Australian freshwater bivalves (Hyridella depressa and Velesunio ambiguus). Several important implications stem from this mechanistic interpretation of metal uptake by aquatic organisms. Because of the general positive empirical relationship established between metal uptake/accumulation and acute/sub-chronic toxicity, the ameliorative effect of an increased water hardness on metal toxicity most likely results from the competitive binding of Ca ( > Mg) at the Ca channels of the cell membrane. This conclusion is consistent with empirical studies and also with the basic chemical properties of Ca and Mg, that are relevant to their behaviour at the Ca channel. It follows that Ca water concentration, rather than total water hardness, should be utilised in water quality guidelines as the variable that governs the maximum permissible concentration of certain trace metals that can be sustained by freshwater life.

The influence of dissolved organic carbon (DOC) on the toxicity of aluminum (Al) at pH 5 (relevant to acid mine drainage conditions), to the tropical green hydra (Hydra viridissima), green alga (Chlorella sp.), and cladoceran (Moinodaphnia macleayi) was assessed. Two DOC sources, a natural in situ DOC in soft billabong water (SBW) and Suwannee River fulvic acid (SRFA) standard, were compared. The order of sensitivity of the test organisms to dissolved Al (0.1 µm fraction) was Hydra viridissima > Moinodaphnia macleayi > Chlorella sp. with DOC reducing dissolved Al toxicity most for Hydra viridissima. However, colloidal or precipitated Al may contribute indirectly to the toxicity for M. macleayi and Chlorella sp. The toxicity of dissolved Al was up to six times lower in test waters containing 10 mg L−1 DOC (in the form of SRFA), relative to toxicity observed at 1 mg L−1 DOC. In contrast, the toxicity of Al was up to two times lower in SBW containing 10 mg L−1 DOC, relative to water containing 1 mg L−1 DOC. The increased ability of SRFA in reducing Al toxicity was linked to its greater affinity for complexing Al compared with the in situ DOC. This has important implications for studies that use commercial standards of humic substances to predict Al toxicity in local environments. Speciation modeling demonstrated that Al3+ and AlOH2+ provided a strong relationship with toxicity. An empirical relationship is provided for each organism that can be used to predict Al toxicity at a given Al and DOC concentration. Environ. Toxicol. Chem. 2012;31:427–436. © 2011 SETAC

Fulvic acid (FA) from a tropical Australian billabong (lagoon) was isolated with XAD-8 resin and characterized using size exclusion chromatography, solid state cross-polarization magic angle spinning, 13C nuclear magnetic resonance spectroscopy, elemental analysis, and potentiometric acid-base titration. Physicochemical characteristics of the billabong FA were comparable with those of the Suwannee River Fulvic Acid (SRFA) standard. The greater negative charge density of the billabong FA suggested it contained protons that were more weakly bound than those of SRFA, with the potential for billabong water to complex less metal contaminants, such as uranium (U). This may subsequently influence the toxicity of metal contaminants to resident freshwater organisms. The complexation of U with dissolved organic carbon (DOC) (10 mg L(-1)) in billabong water was calculated using the HARPHRQ geochemical speciation model and also measured using flow field-flow fractionation combined with inductively coupled plasma mass-spectroscopy. Agreement between both methods was very good (within 4% as U-DOC). The results suggest that in billabong water at pH 6.0, containing an average DOC of 10 mg L(-1) and a U concentration of 90 μg L(-1), around 10% of U is complexed with DOC.

The influence of dissolved organic carbon (DOC) on the toxicity of uranium (U) to three Australian tropical freshwater species, the Northern Trout Gudgeon (Mogurnda mogurnda), green hydra (Hydra viridissima) and unicellular green alga (Chlorella sp.) was assessed. Exposures were conducted in synthetic soft water without DOC and with DOC added in the form of standard Suwannee River Fulvic Acid (SRFA). Organisms were exposed to a range of U concentrations at a range of DOC concentrations (0-20 mg L(-1)). U toxicity was up to 20 times less in water containing 20 mg L(-1) DOC, relative to DOC-free test waters. U toxicity was also assessed using natural water from a tropical Australian billabong containing 10 mg L(-1) DOC. U toxicity was up to ten times less in the billabong water, relative to DOC--free test waters. SRFA was twice as effective at reducing U toxicity as the billabong water at equivalent DOC concentrations. Geochemical speciation modeling confirmed the decreased U toxicity that resulted from both DOC sources was primarily due to a decrease in the free uranyl ion (UO2(2+)) through complexation with DOC. A predictive model is presented for each of the organisms that can be used to predict U toxicity at a given U and DOC concentration.

Few data are available on the comparative accumulation of metal(loid)s from water and food in estuarine/marine fish. Smooth toadfish ( Tetractenos glaber ), commonly found in estuaries in south-eastern Australia, were separately exposed to radio-labelled seawater (14 kBq L −1 of 109 Cd and 24 kBq L −1 of 75 Se) and food (ghost shrimps; Trypaea australiensis : 875 Bq g −1 109 Cd and 1130 Bq g −1 75 Se) for 25 days (uptake phase), followed by exposure to radionuclide-free water or food for 30 days (loss phase). Toadfish accumulated 109 Cd predominantly from water (85%) and 75 Se predominantly from food (62%), although the latter was lower than expected. For both the water and food exposures, 109 Cd was predominantly located in the gut lining (60–75%) at the end of the uptake phase, suggesting that the gut may be the primary pathway of 109 Cd uptake. This may be attributed to toadfish drinking large volumes of water to maintain osmoregulation. By the end of the loss phase, 109 Cd had predominantly shifted to the excretory organs – the liver (81%) in toadfish exposed to radio-labelled food, and in the liver, gills and kidney (82%) of toadfish exposed to radio-labelled water. In contrast, 75 Se was predominantly located in the excretory organs (gills, kidneys and liver; 66–76%) at the end of the uptake phase, irrespective of the exposure pathway, with minimal change in percentage distribution (76–83%) after the loss phase. This study emphasises the importance of differentiating accumulation pathways to better understand metal(loid) transfer dynamics and subsequent toxicity, in aquatic biota.

Good quality toxicity data underpins robust hazard and risk assessments in aquatic systems and the derivation of water quality guidelines for ecosystems. Hence, an objective scheme to assess the quality of toxicity data forms an important part of this process. The variation of scores from 2 research papers using the Australasian ecotoxicity database (AED) quality assessment scheme was evaluated by 23 ecotoxicologists. The results showed that the quality class that the assessors gave each paper varied by less than 10% when compared with a quality score agreed a priori between the authors of this study. It was determined that the majority of the variation in each assessment was due to ambiguous or poorly written assessment criteria, information that was difficult to find, or information in the paper that was overlooked by the assessor. This led to refinements of the assessment criteria in the AED, which resulted in a 16% improvement (i.e., reduction) in the mean variation of scores for the 2 papers when compared with the a priori scores. The improvement in consensus among different assessors evaluating the same research papers suggests that the data quality assessment scheme proposed in this article provides a more robust scheme for assessing the quality of aquatic toxicity data than methods currently available.

Copper and zinc toxicity to the freshwater alga Chlorella sp. was determined at a range of pH values (5.5-8.0) in a synthetic softwater (hardness 40-48 mg CaCO(3)/L). The effects of the metals on algal growth (cell division) rate were determined after 48-h exposure at pH 5.5, 6.0, 6.5, 7.0, 7.5, and 8.0. The toxicity of both metals was pH dependent. As pH decreased from 8.0 to 5.5, the copper concentration required to inhibit the algal growth rate by 50% (IC50) increased from 1.0 to 19 microg/L. For zinc, the IC50 increased from 52 to 2,700 microg/L over the same pH range. Changes in solution speciation alone did not explain the increased toxicity observed as the pH increased. Modelled Cu(2+) and Zn(2+) concentrations decreased with increasing pH, whereas toxicity was observed to increase. Measurements of extracellular (cell-bound) metal concentrations support the biotic ligand model (BLM) theory of competition between protons (H(+)) and metals for binding sites at the algal cell surface. Higher extracellular metal concentrations were observed at high pH, indicating reduced competition. Independent of pH, both extracellular and intracellular copper were directly related to growth inhibition in Chlorella sp., whereas zinc toxicity was related to cell-bound zinc only. These findings suggest that the algal cell surface may be considered as the biotic ligand in further development of a chronic BLM with microalgae. Conditional binding constants (log K) were determined experimentally (using measured intracellular metal concentrations) and theoretically (using concentration-response curves) for copper and zinc for Chlorella sp. at selected pH values. Excellent agreement was found indicating the possibility of using concentration-response data to estimate conditional metal-cell binding constants.

The bioaccumulation of selected heavy metals and radionuclides ( 241 Am, 109 Cd, 57 Co, 51 Cr, 134 Cs, 54 Mn and 65 Zn) from seawater was experimentally compared in the Chondrichthyan Scyliorhinus canicula (spotted dogfish) and the Actinopterygian Teleost Psetta maxima (turbot), of comparable size, age and benthic feeding habits. The speciation of these elements in seawater (salinity 38‰, pH 8.1, temperature 16.5 °C) was also calculated to determine their potential bioavailability. The uptake rates, measured over 14 days, varied greatly among isotopes and between species. Concentration factors (CFs) in P. maxima varied 5-fold between ca. 0.2 for 51 Cr and 2.5 for 65 Zn and 134 Cs, whereas in S. canicula they varied by a much greater factor of 350, with CFs for 51 Cr and 241 Am ranging from ca. 0.4 to 140, respectively. With the exception of 134 Cs, all radiotracers were accumulated at a faster rate in S. canicula than in P. maxima , particularly for 241 Am and 65 Zn where the CFs attained during the uptake phase were, two and one order of magnitude greater in S. canicula , respectively. In contrast, 134 Cs reached a CF of about 2.5 in P. maxima, which was 5-fold greater than in S. canicula . Patterns of loss from the experimental depuration phase over 29 days showed greater similarities between species, compared to the uptake phase that highlighted the greater differences between elements. The distributions of these seven radioisotopes among six body components indicated that between the two species the skin of the dogfish displayed a greater bioaccumulation potential, particularly for 241 Am, 57 Co and 65 Zn. However 65 Zn was also distinctive from 241 Am and 57 Co in its pattern of bioaccumulation in dogfish, with its other body components attaining concentrations of 65 Zn that were comparable to the levels found in its skin. The heightened uptake of 134 Cs in turbot was characterised by a more even percentage distribution among its tissues compared to 241 Am and 57 Co, but every tissue of turbot had a higher concentration of 134 Cs, compared to dogfish, particularly the muscle and liver. The elevated uptake rates and higher CFs for most radioisotopes indicate that S. canicula is more susceptible than P. maxima to exposure and contamination by these metals and radionuclides in seawater. These experimentally-determined differences between dogfish and turbot in their bioaccumulation characteristics were assessed against a set of criteria erected to evaluate the working hypothesis that they were taxonomically based. The outcomes of this initial assessment were supportive of this hypothesis that warrants further investigation.

This study determined the metal levels in sediments and tissues of a common estuarine fish, Tetractenos glaber (smooth toadfish), from two metal contaminated and two reference estuaries near Sydney, Australia. Metal levels were highest in sediments and fish from contaminated estuaries. Gonads contained the highest metal levels followed by muscle, gill and liver. Metal accumulation was gender-dependant (e.g. male gonads were >20 times higher in As than females; female gills were >30 times higher than males for Pb). Cadmium, Pb and Ni levels in fish tissues reflected sediment levels, indicating sediment and/or dietary metal uptake. Levels of As, Co, Cd & Pb in gills showed similar patterns to other tissues, suggesting that metals may have been taken up by gills through contaminated water. Similar metal patterns in tissues and sediments suggest more than one uptake pathway. This study indicates that multiple factors influence metal accumulation in fish. © 2005 Elsevier Ltd. All rights reserved.

Copper (Cu) and uranium (U) are of potential ecotoxicological concern to tropical freshwater biota in northern Australia, as a result of mining activities. Few data are available on the toxicity of U, and no data are available on the toxic interaction of Cu and U, to freshwater biota. This study determined the toxicity of Cu and U individually, and in combination, to a tropical freshwater macrophyte, Lemna aequinoctialis (duckweed), in a synthetic soft water (27°C; pH, 6.5; hardness, 40 mg CaCO3 l-1, alkalinity, 16 mg CaCO3 l-1), typical of many fresh surface waters in coastal northern Australia. The growth rate of L. aequinoctialis decreased with increasing Cu or U concentrations, with the concentration of Cu inhibiting growth by 50% (EC50) being 16 ± 1.0 μg l-1, with a minimum detectable effect concentration (MDEC) of 3.2 μg l-1. The concentration of U inhibiting growth by 50% (EC50) was 758 ± 35 μg l-1 with a MDEC of 112 μg l-1. The EC50 value for the exposure of L. aequinoctialis to equitoxic mixtures of Cu and U was significantly (P ≤ 0.05) higher than one toxic unit (1.35; 95% confidence interval, 1.18-1.52), indicating that the combined effects of Cu and U are less than additive (antagonistic). Therefore, inhibition of the growth rate of L. aequinoctialis was reduced when Cu and U were present in equitoxic mixtures, relative to individual metal exposures. Since non-additive (e.g. antagonistic) interactions of metal mixtures cannot be predicted using current mixture models, these results have important potential implications for the protection of freshwater ecosystems through the derivation of national water quality guidelines. © 2005 Elsevier Ltd. All rights reserved.

The chronic toxicity (72-h cell division rate) of uranium (U) to the unicellular alga, Chlorella sp., was assessed in natural Magela Creek water (NMCW) to provide data for the derivation of a site-specific water quality trigger value for U in Magela Creek, NT, Australia. In addition, the data were compared to those for Chlorella sp. when tested for U toxicity using synthetic Magela Creek water (SMCW), which simulates the inorganic composition of Magela Creek water and contains no organic component. Based on one rangefinder and four definitive toxicity tests, concentrations causing a 50% inhibition of algal growth after 72 h exposure (72 h IC50s) ranged between 137 and 238 microg/LU, no-observed-effect concentrations (NOECs) from 72 to 157 microg/LU and lowest-observed-effect concentrations (LOECs) from 120 to 187 microg/LU. Based on these data, Chlorella sp. was the second most sensitive organism to U of five local species that have been assessed using NMCW. The U toxicity data for Chlorella sp. were incorporated with existing data for the four other species to derive a site-specific guideline value for Magela Creek that is protective of 99% of species of 6 microg/L. The toxicity of U to Chlorella sp. in NMCW was approximately two to four times lower than in SMCW. Based on geochemical speciation modelling, this difference corresponded to a four-fold decrease in the proportion of free uranyl ion (UO2(2+)) in NMCW compared to SMCW, most likely due to the presence of dissolved organic carbon (DOC) in NMCW. Relatively, large variability in U toxicity across the tests conducted in NMCW was found to be inversely related to DOC concentration (r2 = 0.996, n = 4, P = 0.002). Speciation modelling indicated that the increase in DOC was associated with an increase in the proportion of U complexed with DOC (r2 = 0.986, n = 4, P < 0.001) and a decrease in the proportion of the UO2(2+) (r2 = 0.989, n = 4, P = 0.006). When the proportion of UO2(2+) was regressed against U toxicity, a very strong, positive relationship was observed (r2 = 1, n = 4, P < 0.001). The results indicate that the bioavailability and toxicity of U is highly influenced by dissolved organic matter and that the relationship should be further quantified.

Toxicity testing using a freshwater alga (Chlorella sp.), a bacterium (Erwinnia sp.) and a cladoceran (Ceriodaphnia cf. dubia) exposed to copper in synthetic and natural freshwaters of varying hardness (44-375 mg CaCO3/l), with constant alkalinity, pH and dissolved organic carbon concentration, demonstrated negligible hardness effects in the pH range 6.1-7.8. Therefore, the use of a generic hardness-correction algorithm, developed as part of national water quality guidelines for protecting freshwater biota, is not recommended for assessing the toxicity of copper to these, and other, sensitive freshwater species. Use of the algorithm for these sensitive species will be underprotective because the calculated concentrations of copper in water that cause a toxic effect will be higher.

The extended free ion activity model (FIAM) was developed by integrating concepts from the original FIAM into biological receptor theory, to obtain a conceptual model that more precisely quantifies the interaction of chemical species at biological receptor sites. The extended FIAM was tested by determining the acute (48 h) valve movement behavior (VMB) (measured in terms of the duration of valve opening) of the Australian freshwater bivalve, Hyridella depressa, to increasing concentrations of total Cd or Cu, in a standard synthetic water under conditions of varying pH (6.5-7.5) and/or dissolved organic carbon (as model fulvic acid (FA)) concentrations (0-11.2 mg L(-1)). Valve movement behavior, measured using an automated data acquisition system, was shown to be a quantifiable and rapid, real-time endpoint for assessing the toxic effects of Cd and Cu exposures. The VMB of H. depressa to Cd was independent (p > 0.05) of pH and/or model FA concentration. In contrast, the VMB of H. depressa to Cu was highly dependent (p < 0.001) on pH and/or model FA concentration; individuals were more sensitive to Cu at low pH and model FA concentrations. The VMB of H. depressa was directly proportional to the activity of the free metal ion (Cd2+), for the linear region of the concentration-response curves. In contrast, the VMB of H. depressa was a weighted function of the activities of the free metal ion and the 1:1 metal hydroxide species (i.e. 2.02 x Cu2+ + CuOH+), whereby Cu2+ had a two-fold greater binding affinity than CuOH+ at the cell membrane surface. Moreover, the results for Cd and Cu are consistent with the extended FIAM, as opposed to the original FIAM, where the result for Cu would be regarded as an exception. The extended FIAM explained 98% of the variability in VMB, whereas the original FIAM explained only 63% (i.e. an improvement of 35%). The improved predictability of organism response to Cu is relevant to advancing water quality guidelines for protecting aquatic biota.

Uranium (U) derived from mining activities is of potential ecotoxicological concern to freshwater biota in tropical northern Australia. Few data are available on the effects of water hardness (Ca and/or Mg), which is elevated in U mine wastewaters, on the toxicity and bioavailability of U to freshwater biota, particularly algae. This study determined the effect of water hardness (8, 40, 100 and 400 mg CaCO3 l-1, added as calcium (Ca) and magnesium (Mg) sulphate) on the toxicity (72 h growth rate inhibition) of U to the unicellular green alga, Chlorella sp., in synthetic freshwater, at constant pH (7.0) and alkalinity (8 mg CaCO3 l-1), similar in chemical composition to sandy coastal streams in tropical northern Australia. A 50-fold increase in water hardness resulted in a 5-fold decrease (P≤0.05) in the toxicity of U to Chlorella sp. (i.e. the 72 h EC50 increased from 56 to 270 μg U l-1). Possible explanation for the ameliorative effect of water hardness includes: (i) competition between U and Ca and/or Mg for binding sites on the cell surface; and (ii) a change in U speciation, and hence, bioavailability. Results showed that extracellular (cell-surface) and intracellular U concentrations significantly (P0.05) differences in the predicted speciation (% distribution) of U amongst the four water hardness levels. The reduction in U toxicity with increasing water hardness was most likely due to competition between U and Ca and/or Mg for binding sites on the algal cell surface. The minimum detectable effect concentrations of U were approximately 3 and 24 times higher (at 8 and 400 mg CaCO3 l-1 hardness, respectively) than the national interim U guideline value (0.5 μg l-1) for protecting aquatic ecosystems. Overall, the results reinforce the need for a more flexible U guideline based on a hardness-dependent algorithm, which may allow environmental managers to relax the national guideline for U on a site-specific basis. © 2002 Elsevier Science B.V. All rights reserved.