Seasonal responses of macroinvertebrate assemblages to magnesium in a seasonally flowing stream.

Macroinvertebrates can be highly sensitive to elevated salinity in freshwater environments, and are known to respond to saline discharges. Magnesium (Mg) is a mine-related contaminant and is a potential environmental risk to a seasonally-flowing, receiving water stream in Kakadu National Park, located in the wet-dry tropics of Australia. The macroinvertebrate assemblage in the stream in the was characterised at four hydrographic phases, from early wet season flow to early dry season pools at flow cessation. On each of the four occasions representing the respective phases, individuals from the most abundant macroinvertebrate species present were collected and acutely exposed to a range (up to 19) of Mg concentrations under laboratory conditions. Sensitivity of taxa to Mg ranged between 39 mg/L Mg (Caenidae: Tasmanocoenis spp.) and 4400 mg/L Mg (Dytiscidae: Clypeodytes feryi), based on the 50% Lethal Concentration (LC50). Characterisation of the macroinvertebrate assemblage at each hydrographic phase indicated the seasons when Mg-sensitive species were present. Whilst no statistical differences in measures of seasonal sensitivity were found, the macroinvertebrate assemblages present during the early flow period had higher Mg-sensitivity than the assemblages present during other hydrographic phases. This could be attributed to the greater relative proportions of Mg-sensitive taxa (e.g. Ephemeroptera) present at early flow compared to greater relative proportions of more Mg-tolerant taxa (C. feryi and Hydacarina spp.) present during later hydrograph phases, especially periods of lower, or no, flow.

Resolving ecosystem complexity in ecological risk assessment for mine site rehabilitation.

CONTEXT: Ecological Risk Assessments (ERAs) are important tools for supporting evidence-based decision making. However, most ERA frameworks rarely consider complex ecological feedbacks, which limit their capacity to evaluate risks at community and ecosystem levels of organisation. METHOD: We used qualitative mathematical modelling to add additional perspectives to previously conducted ERAs for the rehabilitation of the Ranger uranium mine (Northern Territory, Australia) and support an assessment of the cumulative risks from the mine site. Using expert elicitation workshops, separate qualitative models and scenarios were developed for aquatic and terrestrial systems. The models developed in the workshops were used to construct Bayes Nets that predicted whole-of-ecosystem outcomes after components were perturbed. RESULTS: The terrestrial model considered the effect of fire and weeds on established native vegetation that will be important for the successful rehabilitation of Ranger. It predicted that a combined intervention that suppresses both weeds and fire intensity gave similar response predictions as for weed control alone, except for lower levels of certainty to tall grasses and fire intensity in models with immature trees or tall grasses. However, this had ambiguous predictions for short grasses and forbs, and tall grasses in models representing mature vegetation. The aquatic model considered the effects of magnesium (Mg), a key solute in current and predicted mine runoff and groundwater egress, which is known to adversely affect many aquatic species. The aquatic models provided support that attached algae and phytoplankton assemblages are the key trophic base for food webs. It predicted that shifts in phytoplankton abundance arising from increase in Mg to receiving waters, may result in cascading effects through the food-chain. CONCLUSION: The qualitative modelling approach was flexible and capable of modelling both gradual (i.e. decadal) processes in the mine-site restoration and the comparatively more rapid (seasonal) processes of the aquatic ecosystem. The modelling also provides a useful decision tool for identifying important ecosystem sub-systems for further research efforts.

Saline mine-water alters the structure and function of prokaryote communities in shallow groundwater below a tropical stream.

Bacteria and archaea (prokaryotes) are vital components for maintaining healthy function of groundwater ecosystems. The prokaryotic community composition and associated putative functional processes were examined in a shallow sandy aquifer in a wet-dry tropical environment. The aquifer had a contaminated gradient of saline mine-water, which primarily consisted of elevated magnesium (Mg2+) and sulfate (SO42-), although other major ions and trace metals were also present. Groundwaters were sampled from piezometers, approximately 2 m in depth, located in the creek channel upstream and downstream of the mine-water influence. Sampling occurred during the dry-season when only subsurface water flow was present. Next generation sequencing was used to analyse the prokaryote assemblages using 16S rDNA and metabolic functions were predicted with FAPROTAX. Significant changes in community composition and functional processes were observed with exposure to mine-waters. Communities in the exposed sites had significantly lower relative abundance of methanotrophs such as Methylococcaceae and methanogens (Methanobacteriaceae), but higher abundance in Nitrososphaeraceae, associated with nitrification, indicating potentially important changes in the biogeochemistry of the exposed sites. The changes were most strongly correlated with concentrations of SO42-, Mg2+ and Na+. This knowledge allows an assessment of the risk of mine-water contamination to groundwater ecosystem function and aids mine-water management.

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.

Rapid tannin profiling of tree fodders using untargeted mid-infrared spectroscopy and partial least squares regression.

BACKGROUND: The presence of condensed tannins (CT) in tree fodders entails a series of productive, health and ecological benefits for ruminant nutrition. Current wet analytical methods employed for full CT characterisation are time and resource-consuming, thus limiting its applicability for silvopastoral systems. The development of quick, safe and robust analytical techniques to monitor CT's full profile is crucial to suitably understand CT variability and biological activity, which would help to develop efficient evidence-based decision-making to maximise CT-derived benefits. The present study investigates the suitability of Fourier-transformed mid-infrared spectroscopy (MIR: 4000-550 cm-1) combined with multivariate analysis to determine CT concentration and structure (mean degree of polymerization-mDP, procyanidins:prodelphidins ratio-PC:PD and cis:trans ratio) in oak, field maple and goat willow foliage, using HCl:Butanol:Acetone:Iron (HBAI) and thiolysis-HPLC as reference methods. RESULTS: The MIR spectra obtained were explored firstly using Principal Component Analysis, whereas multivariate calibration models were developed based on partial least-squares regression. MIR showed an excellent prediction capacity for the determination of PC:PD [coefficient of determination for prediction (R2P) = 0.96; ratio of prediction to deviation (RPD) = 5.26, range error ratio (RER) = 14.1] and cis:trans ratio (R2P = 0.95; RPD = 4.24; RER = 13.3); modest for CT quantification (HBAI: R2P = 0.92; RPD = 3.71; RER = 13.1; Thiolysis: R2P = 0.88; RPD = 2.80; RER = 11.5); and weak for mDP (R2P = 0.66; RPD = 1.86; RER = 7.16). CONCLUSIONS: MIR combined with chemometrics allowed to characterize the full CT profile of tree foliage rapidly, which would help to assess better plant ecology variability and to improve the nutritional management of ruminant livestock.

Elevated Magnesium Concentrations Altered Freshwater Assemblage Structures in a Mesocosm Experiment.

Magnesium (Mg) is a mining-related contaminant in the Alligators Rivers Region of tropical northern Australia. A mesocosm experiment was used to assess Mg toxicity to aquatic freshwater assemblages. Twenty-five 2700-L tubs were arranged, stratified randomly, on the bed of Magela Creek, a seasonally flowing, sandy stream channel in the Alligator Rivers Region of northern Australia. The experiment comprised 5 replicates of 4 nominal Mg treatments, 2.5, 7.5, 23, and 68 mg L-1 , and a control. Phytoplankton biomass, and diatom, zooplankton, and macroinvertebrate assemblages present in the treatment tubs were sampled before and after Mg addition. A significant negative relationship between phytoplankton biomass and Mg was observed 4 wk after Mg addition as measured by chlorophyll a concentrations (r2 = 0.97, p = 0.01). This result was supported by reductions in some major phytoplankton groups in response to increasing Mg concentrations, in the same experiment and from independent field studies. There was a significant negative relationship between zooplankton assemblage similarity (to control) and Mg concentrations (r2 = 0.96, p = 0.002). Seven weeks after Mg addition, macroinvertebrate assemblages were dominated by 3 microcrustacean groups (Ostracoda, Cladocera, and Copepoda), each reaching maximum abundance at intermediate Mg concentrations (i.e., unimodal responses). The responses of phytoplankton and zooplankton were used to derive assemblage effect concentrations (Mg concentrations resulting in x% of the assemblage change [ECx]). Magnesium concentrations resulting in assemblage EC01 values were <3 mg L-1 . Together with candidate guideline values from other laboratory- and field-based lines of evidence, the mesocosm EC01 values were incorporated into a weight-of-evidence framework for a robust regulatory approach to environmental protection. Environ Toxicol Chem 2020;39:1973-1987. © 2020 Commonwealth of Australia. Published by Wiley Periodicals LLC on behalf of SETAC.

Toward Sustainable Environmental Quality: Priority Research Questions for Asia.

Environmental and human health challenges are pronounced in Asia, an exceptionally diverse and complex region where influences of global megatrends are extensive and numerous stresses to environmental quality exist. Identifying priorities necessary to engage grand challenges can be facilitated through horizon scanning exercises, and to this end we identified and examined 23 priority research questions needed to advance toward more sustainable environmental quality in Asia, as part of the Global Horizon Scanning Project. Advances in environmental toxicology, environmental chemistry, biological monitoring, and risk-assessment methodologies are necessary to address the adverse impacts of environmental stressors on ecosystem services and biodiversity, with Asia being home to numerous biodiversity hotspots. Intersections of the food-energy-water nexus are profound in Asia; innovative and aggressive technologies are necessary to provide clean water, ensure food safety, and stimulate energy efficiency, while improving ecological integrity and addressing legacy and emerging threats to public health and the environment, particularly with increased aquaculture production. Asia is the largest chemical-producing continent globally. Accordingly, sustainable and green chemistry and engineering present decided opportunities to stimulate innovation and realize a number of the United Nations Sustainable Development Goals. Engaging the priority research questions identified herein will require transdisciplinary coordination through existing and nontraditional partnerships within and among countries and sectors. Answering these questions will not be easy but is necessary to achieve more sustainable environmental quality in Asia. Environ Toxicol Chem 2020;39:1485-1505. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

How Specific Is Site-Specific? A Review and Guidance for Selecting and Evaluating Approaches for Deriving Local Water Quality Benchmarks.

Existing prescriptive guidance on the derivation of local water quality benchmarks (WQBs; e.g., guideline values, criteria, standards) for protecting aquatic ecosystems is limited to only 3 to 4 specific approaches. These approaches do not represent the full suite available for deriving local WQBs for multiple types of water quality-related issues. The general lack of guidance is inconsistent with the need for, and benefits of, local WQBs, and can constrain the appropriate selection and subsequent evaluation of derivation approaches. Consequently, the defensibility of local WQBs may not be commensurate with the nature of the issues for which they are derived. Moreover, where local WQBs are incorporated into regulatory requirements, the lack of guidance presents a potential risk to the derivation of appropriate WQBs and the achievement of desired environmental outcomes. This review addresses the deficiency in guidance by 1) defining local WQBs and outlining initial considerations for deciding if one is required; 2) summarizing the existing regulatory context; 3) summarizing existing guidance and identifying gaps; 4) describing strengths, weaknesses, and potential applications of a range of derivation approaches based on laboratory and/or field data; and 5) presenting a conceptual framework for appropriately selecting and evaluating a derivation approach to best suit the need. The guidance incorporates an existing set of guiding principles for deriving local WQBs and reinforces an existing categorization of site-adapted and site-specific WQBs. The conceptual framework recognizes the need to strike an appropriate balance between effort and ecological risk and, thus, embeds the concept of fit-for-purpose by considering both the significance of the issue being assessed and the extent to which the approach provides confidence that the ecosystem will be appropriately protected. The guidance can be used by industry, regulators, and others for both the a priori selection and the post hoc evaluation of appropriate approaches for deriving local WQBs. Integr Environ Assess Manag 2019;15:683-702. © 2019 The Authors.

Freshwater chronic ammonia toxicity: A tropical-to-temperate comparison.

The chronic toxicity of ammonia to tropical freshwater species is understudied, and thus data on temperate species have been used to derive water quality guideline values for tropical regions. Such practices may lead to underprotective guideline values due to differences in toxicities observed between tropical and temperate species. In addition, the presence of ammonia in low-ionic-strength waters may also result in higher toxicity, and studies on this factor are limited. The present study assessed the toxicity of ammonia to 6 tropical freshwater species in low-ionic-strength waters. Because ammonia toxicity varies depending on the pH and temperature, test water pH concentrations were maintained at approximately pH 6.0 ± 0.3 at temperatures between 27.5 and 30 °C. Low-effect chronic inhibition concentrations were derived for the following species: Chlorella sp. 66 mg L-1 ; Lemna aequinoctialis 22 mg L-1 ; Hydra viridissima 1.8 mg L-1 ; Moinodaphnia macleayi 27 mg L-1 ; Amerianna cumingi 17 mg L-1 ; and Mogurnda mogurnda 5.4 mg L-1 total ammonia nitrogen. Two of the species tested (a cnidarian and a fish species) were among the most sensitive reported anywhere within their taxonomic group. Chronic ammonia datasets representing toxicity estimates for temperate and tropical species were plotted and compared using species sensitivity distributions. The results indicate that the differences in chronic toxicity observed between tropical and temperate species were likely due to the low ionic strength of the waters to which tropical species were exposed, rather than any inherent physiological differences between species from tropical and temperate regions. This finding suggests that tropical waters of low ionic strength may be at a higher risk from ammonia compared with other freshwater ecosystems. Environ Toxicol Chem 2019;38:177-189. © 2018 Commonwealth of Australia. Published by Wiley Periodicals, Inc. on behalf of SETAC.

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

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. © 2018 SETAC.

Regime shifts, thresholds and multiple stable states in freshwater ecosystems; a critical appraisal of the evidence.

The concepts of ecosystem regime shifts, thresholds and alternative or multiple stable states are used extensively in the ecological and environmental management literature. When applied to aquatic ecosystems, these terms are used inconsistently reflecting differing levels of supporting evidence among ecosystem types. Although many aquatic ecosystems around the world have become degraded, the magnitude and causes of changes, relative to the range of historical variability, are poorly known. A working group supported by the Australian Centre for Ecological Analysis and Synthesis (ACEAS) reviewed 135 papers on freshwater ecosystems to assess the evidence for pressure-induced non-linear changes in freshwater ecosystems; these papers used terms indicating sudden and non-linear change in their titles and key words, and so was a positively biased sample. We scrutinized papers for study context and methods, ecosystem characteristics and focus, types of pressures and ecological responses considered, and the type of change reported (i.e., gradual, non-linear, hysteretic or irreversible change). There was little empirical evidence for regime shifts and changes between multiple or alternative stable states in these studies although some shifts between turbid phytoplankton-dominated states and clear-water, macrophyte-dominated states were reported in shallow lakes in temperate climates. We found limited understanding of the subtleties of the relevant theoretical concepts and encountered few mechanistic studies that investigated or identified cause-and-effect relationships between ecological responses and nominal pressures. Our results mirror those of reviews for estuarine, nearshore and marine aquatic ecosystems, demonstrating that although the concepts of regime shifts and alternative stable states have become prominent in the scientific and management literature, their empirical underpinning is weak outside of a specific environmental setting. The application of these concepts in future research and management applications should include evidence on the mechanistic links between pressures and consequent ecological change. Explicit consideration should also be given to whether observed temporal dynamics represent variation along a continuum rather than categorically different states.

A study of radium bioaccumulation in freshwater mussels, Velesunio angasi, in the Magela Creek catchment, Northern Territory, Australia.

Freshwater mussels, Velesunio angasi, along Magela Creek in Australia's Northern Territory were examined to study radionuclide activities in mussel flesh and to investigate whether the Ranger Uranium mine is contributing to the radium loads in mussels downstream of the mine. Radium loads in mussels of the same age were highest in Bowerbird Billabong, located 20 km upstream of the mine site. Variations in the ratio of [Ra]:[Ca] in filtered water at the sampling sites accounted for the variations found in mussel radium loads with natural increases in calcium (Ca) in surface waters in a downstream gradient along the Magela Creek catchment gradually reducing radium uptake in mussels. At Mudginberri Billabong, 12 km downstream of the mine, concentration factors for radium have not significantly changed over the past 25 years since the mine commenced operations and this, coupled with a gradual decrease of the (228)Ra/(226)Ra activity ratios observed along the catchment, indicates that the (226)Ra accumulated in mussels is of natural rather than mine origin. The (228)Th/(228)Ra ratio has been used to model radium uptake and a radium biological half-life in mussels of approximately 13 years has been determined. The long biological half-life and the low Ca concentrations in the water account for the high radium concentration factor of 30,000-60,000 measured in mussels from the Magela Creek catchment.

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.