Rick A. van Dam

Aquatic toxicity of magnesium sulfate, and the influence of calcium, in very low ionic concentration water

The toxicity of magnesium sulfate (MgSO(4)), and the influence of calcium (Ca), were assessed in very soft freshwater (natural Magela Creek water [NMCW]) using six freshwater species (Chlorella sp., Lemna aequinoctialis, Amerianna cumingi, Moinodaphnia macleayi, Hydra viridissima, and Mogurnda mogurnda). The study involved five stages: toxicity of MgSO(4) in NMCW, determination of the toxic ion, influence of Ca on Mg toxicity, toxicity of MgSO(4) at an Mg:Ca mass ratio of 9:1, and derivation of water quality guideline values for Mg. The toxicity of MgSO(4) was higher than previously reported, with chronic median inhibition concentration (IC50)/acute median lethal concentration (LC50) values ranging from 4 to 1,215 mg/L, as Mg. Experiments exposing the 3 most sensitive species (L. aequinoctialis, H. viridissima, and A. cumingi) to Na(2)SO(4) and MgCl(2) confirmed that Mg was the toxic ion. Additionally, Ca was shown to have an ameliorative effect on Mg toxicity. For L. aequinoctialis and H. viridissima, Mg toxicity at the IC50 concentration was eliminated at Mg:Ca (mass) ratios of < or =10:1 and < or =9:1, respectively. For A. cumingi, a 10 to 30% effect persisted at the IC50 concentration at Mg:Ca ratios <9:1. The toxicity of MgSO(4) in NMCW at a constant Mg:Ca ratio of 9:1 was lower than at background Ca, with chronic IC50/acute LC50 values from 96 to 4,054 mg/L, as Mg. Water quality guideline values for Mg (to protect 99% of species) at Mg:Ca mass ratios of >9:1 and < or =9:1 were 0.8 and 2.5 mg/L, respectively. Magnesium can be toxic at concentrations approaching natural background levels, but toxicity is dependent on Ca concentrations, with exposure in very low ionic concentration, Ca-deficient waters posing the greatest risk to aquatic life.

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.

Effects of alumina refinery wastewater and signature metal constituents at the upper thermal tolerance of: 2. The early life stages of the coral Acropora tenuis.

The success of early life history transitions of the coral Acropora tenuis were used as endpoints to evaluate thermal stress and the effects of wastewater discharged to a tropical marine environment. The studies assessed the effects of: (i) temperature; (ii) three signature metals of the wastewater, aluminium (Al), vanadium (V) and gallium (Ga); and (iii) the wastewater (at 27°C and 32°C) on fertilisation and larval metamorphosis. The median inhibition temperatures for fertilisation and metamorphosis were 32.8°C and 33.0°C, respectively. Fertilisation IC(50)s for Al, V and Ga were 2997, 2884 and 3430 μg L(-1), respectively. Metamorphosis IC(50)s for Al, V and Ga were 1945, 675 and 3566 μg L(-1), respectively. The wastewater only affected fertilisation and metamorphosis at moderate concentrations (IC(50)s=63% and 67%, v/v, respectively, at 27°C), posing a low risk to this species in the field. The effects of wastewater and temperature on fertilisation and metamorphosis were additive.

Silica reduces the toxicity of aluminium to a tropical freshwater fish (Mogurnda mogurnda)

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 < 1% 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 > 0.05) difference from the controls. However, speciation modelling again predicted that little (< 3%) 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.

Toxicity and metal speciation characterisation of waste water from an abandoned gold mine in tropical northern Australia

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.

Water quality guidelines for chemicals: learning lessons to deliver meaningful environmental metrics

Many jurisdictions around the globe have well-developed regulatory frameworks for the derivation and implementation of water quality guidelines (WQGs) or their equivalent (e.g. environmental quality standards, criteria, objectives or limits). However, a great many more still do not have such frameworks and are looking to introduce practical methods to manage chemical exposures in aquatic ecosystems. There is a potential opportunity for learning and sharing of data and information between experts from different jurisdictions in order to deliver efficient and effective methods to manage potential aquatic risks, including the considerable reduction in the need for aquatic toxicity testing and the rapid identification of common challenges. This paper reports the outputs of an international workshop with representatives from 14 countries held in Hong Kong in December 2011. The aim of the workshop and this paper was to identify ‘good practice’ in the development of WQGs to deliver to a range of environmental management goals. However, it is important to broaden this consideration to cover often overlooked facets of implementable WQGs, such as demonstrable field validation (i.e. does the WQG protect what it is supposed to?), fit for purpose of monitoring frameworks (often an on-going cost) and finally how are these monitoring data used to support management decisions in a manner that is transparent and understandable to stakeholders. It is clear that regulators and the regulated community have numerous pressures and constraints on their resources. Therefore, the final section of this paper addresses potential areas of collaboration and harmonisation. Such approaches could deliver a consistent foundation from which to assess potential chemical aquatic risks, including, for example, the adoption of bioavailability-based approaches for metals, whilst reducing administrative and technical burdens in jurisdictions.

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.

Toxicity of magnesium pulses to tropical freshwater species and the development of a duration‐based water quality guideline

Six freshwater species (Chlorella sp., Lemna aequinoctialis, Amerianna cumingi, Hydra viridissima, Moinodaphnia macleayi, and Mogurnda mogurnda) were exposed to 4-h, 8-h, and 24-h Mg pulses in natural creek water. Magnesium toxicity to all species increased with exposure duration; however, the extent of increase and the nature of the relationship differed greatly between species. Based on median inhibitory concentrations (IC50s), and compared with continuous exposure data from a previous study, the increase in toxicity with increasing exposure duration from 4 h to continuous (72-144 h) ranged from approximately 2-fold for Chlorella sp. and H. viridissima to greater than 40-fold for A. cumingi. Moreover, the form of the relationship between Mg toxicity and duration ranged from linear or near-linear to exponential for different species. The life-stage at which M. macleayi was exposed was important, with cladocerans pulsed at the onset of reproductive maturity being approximately 4 times more sensitive (based on IC50s) than younger than 6-h-old neonates. Species sensitivity distributions were constructed for the 4-h, 8-h, and 24-h pulse durations, from which 99% species protection guideline values (95% confidence limits [CLs]) of 94 (6.4-1360) mg/L, 14 (0.5-384) mg/L, and 8.0 (0.5-144) mg/L Mg, respectively, were derived. These values were plotted against exposure duration (h) and polynomial interpolation used to derive a guideline value for any pulse duration within the range assessed.