Maternal transfer of trace elements to shark eggs and their dietary assimilation efficiencies.

Dogfish (Scyliorhinus canicula) transferred trace elements (110Ag, 109Cd, 54Mn and 75Se) from their diet to eggs, and their components (yolk and embryo, case and jelly) at greatly varying rates. Trace element levels in eggs showed positive linear relationships (p < 0.001; r2-0.83-0.91) with their cumulative rates of maternal ingestion over 61 days (maternal-to-egg transfer rates: mTFs). These mTFs varied by 2-3 orders of magnitude, with 54Mn > 110Ag > 75Se > 109Cd, and their range encompassed those previously measured for 60Co, 65Zn, 241Am and 134Cs. For six of the eight trace elements, their mTFs were significantly influenced (p < 0.05; r2 = 0.72) by both their dietary assimilation efficiency and their location within the egg (case). In contrast, both 110Ag and 54Mn greatly exceeded the mTFs predicted by this multiple regression model by one and 2-3 orders of magnitude, respectively, and were predominantly transferred to the egg case. Among elements, contrasting rates of transfer and percentage distributions in egg components imply differing ecotoxicological and radiological detriments to the developing embryo.

Cadmium-109 Internal Kinetics in Diamond Sturgeon Acipenser gueldenstaedtii are Strongly Influenced by Salinity, Exposure Pathway and History.

Cadmium-109 whole-body and internal biokinetics were experimentally investigated in critically endangered diamond sturgeon Acipenser gueldenstaedtii after uptake from water or food, in fresh (FW) and brackish (BW; 9‰) salinities typical of the Caspian Sea. Whole-body rates of uptake of 109Cd from water and subsequent depuration were quantified over 14 and 28 days, respectively. Uptake was greater in FW than BW by a factor of 2.4, but depuration rates were similar in both salinities. In contrast, for the dietary (chironomid) exposure pathway 109Cd assimilation efficiencies (AEs) were higher in BW (13%) compared to FW (9.5%). Head (including gills) or digestive tract were major repositories of 109Cd following aqueous and dietary exposures, respectively, including both uptake and depuration phases. The point-of-entry of 109Cd into the body was also a major and persistent determiner of its subsequent internal distribution. For aqueous exposures, the internal distributions of 109Cd changed appreciably during depuration with increased activity concentrations in some body components, which again varied with salinity. Increased salinity appreciably enhanced the percentage distributions and activity concentrations of 109Cd in the liver, kidney and digestive tract, which are typically most pathologically altered by elevated Cd exposure. For dietary exposure, increased salinity also enhanced 109Cd activity concentrations in most body components. The results repeatedly indicate the important role of salinity in the whole-body and internal biokinetics of 109Cd in A. gueldenstaedtii, a representative of both a phylogenetically distinct and most endangered family of fishes.

Thallium toxicity to temperate and tropical marine organisms: Derivation of water quality guidelines to protect marine life.

A lack of thallium (Tl) toxicity data for marine organisms has hampered the development of water quality guidelines for protecting marine life and assessing ecological hazard/risk. This study assessed the toxicity (EC10/EC50) of Tl in natural seawater (salinity 34 psu and pH 8.05) to 26 functionally diverse marine organisms (19 phyla from five trophic levels) from a variety of temperate and tropical coastal marine habitats. EC10 values ranged from 3.0 µg/L (copepod, Acartia tranteri) to 489 µg/L (cyanobacterium, Cyanobium sp.), while EC50 values ranged from 9.7 µg/L to 1550 µg/L. Thallium(I) was the dominant (86-99 %) oxidation state in test waters across the range of EC10 and EC50 values. Thallium toxicity (EC10/EC50) did not differ between temperate and tropical marine organisms. New, reliable, long-term Tl water quality guidelines were derived using species sensitivity distributions (with model-averaging) to protect marine life in Australia (e.g., 3.9 µg/L for 95 % species protection).

Internal distributions of a radio-element array in cartilaginous and bony marine fishes: Different and heterogeneous.

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.

Comparative embryo/larval sensitivity of Australian marine bivalves to ten metals: A disjunct between physiology and phylogeny.

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.

Assessing the Toxicity of Mine-Water Mixtures and the Effectiveness of Water Quality Guideline Values in Protecting Local Aquatic Species.

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.

Dataset of genotoxic and cytotoxic effects on the pygmy mussel, Xenostrobus securis, from the highly urbanised Sydney Estuary, Australia: Relationships with metal bioaccumulation.

This article contains a dataset of the genotoxic (DNA damage, via the micronucleus frequency test) and cytotoxic (lysosomal membrane stability (cellular integrity), via the neutral red retention test) effects on the pygmy mussel, Xenostrobus securis (Bivalvia: Mytilidae) from variably contaminated sites (primarily from cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb) and zinc (Zn)) in the highly urbanized Sydney Estuary, south-eastern Australia. Data were collected 15 years apart (June 2004 and June 2019) to assess any change in (i) the "health" of mussels (based on the above two toxicity endpoints) and (ii) their metal contaminant status (measured as whole soft tissue concentrations of Cd, Cr, Cu, Pb and Zn). Linear relationships between both toxicity endpoints and metal concentrations in the whole soft tissue were also investigated. Multivariate statistical techniques, including principal components analysis, multidimensional scaling and cluster analysis, were also explored to reduce dimensional data, investigate patterns and assess similarities among study sites with respect to tissue metal concentrations and toxicity effects in X. securis. Enrichment factors were calculated by dividing the mean whole soft tissue metal concentration at each site in the Sydney Estuary, by its mean baseline metal concentration from near-pristine (reference) sites in the adjacent Hawkesbury Estuary. Salinity, pH, temperature, turbidity, dissolved oxygen and chlorophyll a were measured in the surface waters at each site.

Physico-chemical and key metal data for surface waters and sediments of the Sydney and Hawkesbury estuaries, 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) surface water, suspended particulate matter (>0.2 µm) and surface sediments (<2 mm) at each study site are also provided. The concentrations of Cd, Cr, Cu, Pb and Zn in SPM and sediment at each site were normalised for aluminium (Al) concentration (e.g. Cd/Al), to account for natural variation in particle size and mineralogy. Enrichment factors (EFs) were calculated from these data by dividing the mean metal concentration at each site in the Sydney Estuary, for each environmental matrix (i.e., filtered water, SPM and sediment), by its mean baseline metal concentration from near-pristine reference sites in the adjacent Hawkesbury Estuary. A thorough knowledge of the general physico-chemistry and key metal concentrations in surface waters and sediments in the Sydney Estuary provide a baseline to assess anthropogenic change and better manage estuarine/marine ecosystems.

The euryhaline pygmy mussel, Xenostrobus securis, is a useful biomonitor of key metal contamination in the highly urbanised Sydney Estuary, Australia.

This study critically evaluated the native pygmy mussel (Xenostrobus securis) as a biomonitor of the key metal contaminants in the highly urbanised Sydney Estuary, south-eastern Australia. Five metals (Cd, Cr, Cu, Pb and Zn) were identified as key contaminants, based on their enrichment factors (EFs) in the whole soft tissue of X. securis at 24 sampling sites, relative to baseline values from near-pristine reference sites in the adjacent Hawkesbury Estuary. Inverse relationships established between mussel size (dry tissue weight) and tissue concentrations of each metal were used to reduce variance (by 4-fold) among individuals; gender and reproductive status had no significant (p > 0.05) effect on tissue metal concentrations in X. securis. Metal concentrations in three environmental matrices - filtered (<0.2 µm) surface water (operationally defined as the dissolved/colloidal phase), suspended particulate matter (SPM; >0.2 µm) and surface sediment (<2 mm particle size), which are most relevant to a suspension-feeding estuarine bivalve, were also determined at each sampling site. For each of the five metals, highly significant (p < 0.01) positive linear regressions were established between metal EFs for mussel tissue and each environmental matrix. Metals in surface sediment and SPM explained 80-91% and 81-90%, respectively, of the variability in metal concentrations in mussel tissue, with filtered surface water explaining 74-86%. Cumulative mussel tissue EFs of all five metals, when regressed against each environmental matrix, showed that surface sediment concentrations explained 93% of their variability between sites, SPM 94% and filtered surface water 87-90%. Hence, X. securis very closely reflects the metal concentrations in its aquatic environment. The study provides a quality-assured benchmark of key metal contamination in the Sydney Estuary, and an appropriate methodology that may be used to discern any changes in metal contaminant status using X. securis.

Radionuclide biokinetics in the Russian sturgeon and phylogenetic consistencies with cartilaginous and bony marine fishes.

The biokinetics of eight radionuclides (241Am, 109Cd, 134Cs, 75Se, 54Mn, 110mAg, 65Zn, 60Co) absorbed from the aquatic medium by juvenile Russian sturgeon (Acipenser gueldenstaedtii) were experimentally determined in fresh (0.42‰) and brackish (9.0‰) waters, of a similar salinity range to the Caspian Sea, and in conjunction with chemical speciation modelling. Uptake and loss rate constants were determined for each radionuclide for a 14 day exposure at each salinity and during 28 days of exposure to radionuclide-free conditions. Whole body (wet): water concentration factors (CF) achieved over 14 days for these eight radionuclides were used in a comparison with the same radionuclide CFs previously determined experimentally for six species of marine teleosts and chondrichthyans, to further test a phylogeny-based model of multi-nuclide bioaccumulation based on marine chordates. Multivariate analyses (multidimensional scaling and hierarchical clustering) identified the relative affinities among these taxa and also those radionuclides which distinguished most between them, in their differing CFs. They consistently showed that sturgeon aggregated as a group, which was also slightly differentiated with salinity. Sturgeon were distinguished from all teleosts and chondrichthyans but were more dissimilar from chondrichthyans than teleosts, in accordance with sturgeon's different periods of divergence from them in evolutionary time. Variable salinity among experiments may also cause changes in radionuclide bioaccumulation due to variations in (i) bioavailability (ii) osmolarity, and (iii) competitive inhibition of a radionuclide's bioaccumulation by its stable analogue or metabolic model. Their potentially confounding effects on these patterns of radionuclide CFs among taxa were critically evaluated for those radionuclides which discriminated most between sturgeon and teleosts or chondrichthyans. Bioavailability, osmolarity and competitive inhibition effects were identified among salinity treatments, however they were not appreciable enough to override the phylogeny-based signal. The results of this study are thus consistent with a phylogeny-based model of radionuclide bioaccumulation by marine chordates being valid for a fish species living in lower salinity regimes.

Sensitivity of the glochidia (larvae) of freshwater mussels (Bivalvia: Unionida: Hyriidae) to cadmium, cobalt, copper, lead, nickel and zinc: Differences between metals, species and exposure time.

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.

Diminished metal accumulation in riverine fishes exposed to acid mine drainage over five decades.

Bony bream (Nematalosa erebi) and black catfish (Neosilurus ater) were sampled from the fresh surface waters of the Finniss River in tropical northern Australia, along a metal pollution gradient draining the Rum Jungle copper/uranium mine, a contaminant source for over five decades. Paradoxically, populations of both fish species exposed to the highest concentrations of mine-related metals (cobalt, copper, lead, manganese, nickel, uranium and zinc) in surface water and sediment had the lowest tissue (bone, liver and muscle) concentrations of these metals. The degree of reduction in tissue concentrations of exposed populations was also specific to each metal and inversely related to its degree of environmental increase above background. Several explanations for diminished metal bioaccumulation in fishes from the contaminated region were evaluated. Geochemical speciation modeling of metal bioavailability in surface water showed no differences between the contaminated region and the control sites. Also, the macro-nutrient (calcium, magnesium and sodium) water concentrations, that may competitively inhibit metal uptake, were not elevated with trace metal contamination. Reduced exposure to contaminants due to avoidance behavior was unlikely due to the absence of refugial water bodies with the requisite metal concentrations lower than the control sites and very reduced connectivity at time of sampling. The most plausible interpretation of these results is that populations of both fish species have modified kinetics within their metal bioaccumulation physiology, via adaptation or tolerance responses, to reduce their body burdens of metals. This hypothesis is consistent with (i) reduced tissue concentrations of calcium, magnesium and sodium (macro-nutrients), in exposed populations of both species, (ii) experimental findings for other fish species from the Finniss River and other contaminated regions, and (iii) the number of generations exposed to likely selection pressure over 50 years.

Water hardness reduces the accumulation and toxicity of uranium in a freshwater macrophyte (Ceratophyllum demersum).

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.

Dissolved organic carbon reduces uranium toxicity to the unicellular eukaryote Euglena gracilis.

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.

Dissolved organic carbon reduces the toxicity of aluminum to three tropical freshwater organisms.

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 Al(3+) and AlOH(2+) 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.

Dissolved organic carbon reduces uranium bioavailability and toxicity. 2. Uranium[VI] speciation and toxicity to three tropical freshwater organisms.

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.

Dissolved organic carbon reduces uranium bioavailability and toxicity. 1. Characterization of an aquatic fulvic acid and its complexation with uranium[VI].

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.

Comparative accumulation of (109)Cd and (75)Se from water and food by an estuarine fish (Tetractenos glaber).

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 (14kBqL(-1) of (109)Cd and 24kBqL(-1) of (75)Se) and food (ghost shrimps; Trypaea australiensis: 875Bqg(-1)(109)Cd and 1130Bqg(-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.

Uptake and loss of dissolved 109Cd and 75Se in estuarine macroinvertebrates.

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.

Non-effect of water hardness on the accumulation and toxicity of copper in a freshwater macrophyte (Ceratophyllum demersum): how useful are hardness-modified copper guidelines for protecting freshwater biota?

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 (P>0.05) 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.