Melanie A. Trenfield

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.

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.

Manganese toxicity to tropical freshwater species in low hardness water

Elevated manganese (Mn) is a common contaminant issue for mine water discharges, and previous studies have reported that its toxicity is ameliorated by H(+), Ca(2+), and Mg(2+) ions. In the present study, the toxicity of Mn was assessed in a high risk scenario, that is, the slightly acidic, soft waters of Magela Creek, Kakadu National Park, Northern Territory, Australia. Toxicity estimates were derived for 6 tropical freshwater species (Chlorella sp., Lemna aequinoctialis, Amerianna cumingi, Moinodaphnia macleayi, Hydra viridissima, and Mogurnda mogurnda). Low effect chronic inhibition concentration (IC10) and acute lethal concentration (LC05) values ranged between 140 μg L(-1) and 80,000 μg L(-1), with 3 of the species tested (M. macleayi, A. cumingi, and H. viridissima) being more sensitive to Mn than all but 1 species in the international literature (Hyalella azteca). A loss of Mn was observed on the final day for 2 of the H. viridissima toxicity tests, which may be a result of the complex speciation of Mn and biological oxidation. International data from toxicity tests conducted in natural water with a similar physicochemistry to Magela Creek water were combined with the present studys data to increase the sample size to produce a more reliable species sensitivity distribution. A 99% protection guideline value of 73 μg L(-1) (33-466 μg L(-1)) was derived; the low value of this guideline value reflects the higher toxicity of Mn in slightly acidic soft waters.

A chronic toxicity test for the tropical marine snail Nassarius dorsatus to assess the toxicity of copper, aluminium, gallium, and molybdenum

Chronic toxicity test methods for assessing the toxicity of contaminants to tropical marine organisms are generally lacking. A 96-h chronic growth rate toxicity test was developed for the larval stage of the tropical dogwhelk, Nassarius dorsatus. Growth rates of N. dorsatus larvae were assessed following exposures to copper (Cu), aluminium (Al), gallium (Ga), and molybdenum (Mo). Exposure to Cu at 28 °C validated the sensitivity of the test method, with 10% (EC10) and 50% (EC50) effect concentrations of 4.2 μg/L and 7.3 μg/L Cu, respectively. The EC10 and EC50 values for Al (<0.45-μm filtered fraction) at 28 °C were 115 μg/L and 185 μg/L, respectively. The toxicity of Cu and Al was also assessed at 24 °C and 31 °C, representing average year-round water temperatures for subtropical and tropical Australian coastal environments. At 24 °C, the growth rate of control larvae was reduced by 52% compared with the growth rate at 28 °C and there was an increase in sensitivity to Cu (EC50 = 4.7 μg/L) but a similar sensitivity to Al (EC50 = 180 μg/L). At 31 °C the control growth rate increased by 35% from that measured at 28 °C and there was reduced sensitivity to both Cu and Al (EC50s = 8.5 μg/L and 642 μg/L, respectively). There was minimal toxicity resulting from Ga (EC50 = 4560 μg/L) and Mo (no effect at ≤7000 μg/L Mo). Environ Toxicol Chem 2016;35:1788-1795.

Modeling the pH–ammonia toxicity relationship for Hydra viridissima in soft waters with low ionic concentrations

There are limited data concerning the toxicity of ammonia in fresh soft waters. Ammonia toxicity is largely dependent on pH and temperature. The US Environmental Protection Agency (USEPA) has derived equations to adjust species toxicity estimates based on changes in pH and temperature. It has been reported that the pH-ammonia toxicity relationship, derived by the USEPA, may differ in waters with low ionic concentrations because of the absence of potentially ameliorative ionic constituents. The present study aimed to assess the pH-ammonia toxicity relationship for the tropical green hydra, Hydra viridissima, across a range of pH values in a natural water with low ionic content. Ammonia toxicity to H. viridissima was assessed at a pH range between 6.0 and 8.5 and temperature 27.5 ± 1 °C. Test solution pH was maintained using a pH buffer. The resulting median effect concentrations ranged from 9.62 (7.95-11.65) mg L-1 total ammonia nitrogen at pH 6.0 to 0.64 (0.50-0.81) mg L-1 total ammonia nitrogen at pH 7.9. The results indicated that increasing pH increased the sensitivity of H. viridissima to ammonia. The pH dependence equation derived by the USEPA accurately described the relationship between pH and ammonia toxicity for H. viridissima. However, when the model parameters for the generic pooled relationship were used, the fit was less accurate (r2  = 0.66), indicating that the generic pooled pH-dependence equations may not be appropriate for use with this species. Environ Toxicol Chem 2018;37:1189-1196.

Increasing uranium exposure durations to the aquatic snail Amerianna cumingi does not result in lower toxicity estimates.

Reproductive inhibition (egg production) of the aquatic snail Amerianna cumingi over 4 d has been used to derive toxicity estimates for toxicants of concern in tropical Australia. Toxicity estimates from this test have been used as chronic data points in species sensitivity distributions (SSDs) for deriving site-specific guideline values. However, revised guidance for the Australian and New Zealand Water Quality Guidelines advises that test durations for adult macroinvertebrates should be ≥14 d to be considered chronic. Hence, to strengthen the data set underpinning the site-specific guideline value for uranium (U) in Magela Creek, which receives water from the Ranger Uranium Mine in northern Australia, the toxicity of U to A. cumingi was compared after 4 d, 9 d, and 14 d. Daily U concentrations were measured because of expected U loss during testing, providing extensive chemical analyses of the U exposure during the toxicity tests. Comparison of the U concentrations causing 50% reproductive inhibition (IC50) after 4 d, 9 d, and 14 d showed no difference in toxicity (4 d IC50 = 161 μg L-1 , confidence interval = 133-195; 9-d IC50 = 151 μg L-1 , confidence interval = 127-180; 14-d IC50 = 153 μg L-1 , confidence interval = 29-180). The present study provides evidence that test durations of <14 d are suitable for assessing chronic toxicity to U for this species and supports the use of the 4-d toxicity estimate in the SSD for U. Environ Toxicol Chem 2016;35:2851-2858.

Integrating laboratory and field studies to assess impacts of discharge from a uranium mine and validate a water quality guideline value for agnesium

Magnesium (Mg) is a primary contaminant in mine water discharges from the Ranger Uranium Mine (north Australia). Site-specific water quality guideline values (WQGVs) for Mg have been derived from laboratory and field studies. Contaminated groundwater with elevated electrical conductivity and metals (Mg, Mn, U, SO4 , and Ca) was detected flowing from the mine site into adjacent surface waters. This provided an opportunity to investigate the protectiveness of the Mg WQGV by conducting an integrated laboratory and field study. A direct toxicity assessment (DTA) of the groundwater was conducted with local tropical freshwater species: duckweed (Lemna aequinoctialis), green hydra (Hydra viridissima), and the aquatic snail Amerianna cumingi. An in situ toxicity assessment was carried out in the creek receiving diluted groundwater by use of the same species of snail, to aid interpretation of laboratory-derived data. The toxicity of the contaminated groundwater was higher than Mg-only toxicity testing for H. viridissima, with other elevated metals and major ions contributing to toxicity. However, for duckweed and snail, the contaminated groundwater was less toxic than the Mg-only testing. In situ snail monitoring supported laboratory exposures, showing no effect on reproduction of A. cumingi exposed to an average of approximately 5 mg/L Mg; however, a very small effect was noted closer to the groundwater source, probably associated with other contaminants. The minimal toxicity observed for L. aequinoctialis and A. cumingi, despite the elevated Mg, can be explained by the high calcium (Ca) concentration of the water and the potential amelioration of metal toxicity. The extent of Ca amelioration of Mg toxicity was organism dependent. This study affirms the proposed environmental rehabilitation standard of 3 mg/L Mg for surface waters with a Ca concentration typical of water from this mine site. Integr Environ Assess Manag 2019;15:64-76.

Acute ammonia toxicity to the larvae (glochidia) of the tropical Australian freshwater mussel Velesunio spp. Using a modified toxicity test protocol

Ammonia is recognized as a major pollutant worldwide, originating from natural and anthropogenic sources. Studies have reported that freshwater mussels are among the most sensitive taxa to ammonia, but few data are available on ammonia toxicity for the early life stages of freshwater mussels from tropical regions. We report on the modification of a 24-h acute toxicity test protocol for tropical freshwater mussels and application of the test using ammonia. Velesunio spp. from 3 different sites were used to assess the toxicity of ammonia at a targeted pH of 6.0 and a water temperature of 27.5 °C, which were the average annual values for some slightly to moderately acidic, soft water (3-6 mg/L as CaCO3 ) creeks of tropical northern Australia. The valve closure responses of mussel glochidia (larvae) to a sodium chloride solution were used to measure the survival endpoint. Acute toxicity estimates indicate that tropical Velesunio spp. were highly sensitive to ammonia, with 24-h exposures to ammonium sulfate generating median lethal concentration estimates ranging from 6.8 to 14.2 mg/L total ammonia nitrogen, which, when adjusted to pH 7 and 20 °C, were among the highest sensitivities yet reported for any freshwater mussel species, and among the highest in sensitivity for any tropical taxon. These toxicity estimates can contribute to the derivation or refinement of ammonia guideline values for freshwater ecosystems globally. Environ Toxicol Chem 2018;37:2175-2187.

Assessing chronic toxicity of aluminium, gallium and molybdenum in tropical marine waters using a novel bioassay for larvae of the hermit crab Coenobita variabilis

A novel bioassay is presented that allows for the estimation of the chronic toxicity of contaminants in receiving tropical marine environments. Relevant procedures to identify contaminants of concern and evaluate hazards associated with contamination in these environments have long remained inadequate. The 6-day bioassay is conducted using freshly hatched planktonic larvae of the hermit crab Coenobita variabilis and is targeted at generating environmentally relevant, chronic toxicity data. The developmental endpoint demonstrated consistently high control performance and was validated through the use of copper as a reference toxicant. In addition, the biological effects of aluminium, gallium and molybdenum were assessed. The endpoint expressed high sensitivity to copper (EC10 = 24 µg L-1) and moderate sensitivity to aluminium (EC10 = 312 µg L-1), whereas gallium and molybdenum elicited no obvious effects, even at high concentrations (EC10 > 6000 µg L-1), providing valuable information on the toxicity of these elements in tropical marine waters for derivation of water quality guidelines or testing of compliance limits.