The distribution of metal and petroleum-derived contaminants within sediments around oil and gas infrastructure in the Gippsland Basin, Australia.

As oil and gas infrastructure comes to the end of its working life, a decommissioning decision must be made: should the infrastructure be abandoned in situ, repurposed, partially removed, or fully removed? Environmental contaminants around oil and gas infrastructure could influence these decisions because contaminants in sediments could degrade the value of the infrastructure as habitat, enter the seafood supply if the area is re-opened for commercial and/or recreational fishing, or be made biologically available as sediment is resuspended when the structures are moved. An initial risk hypothesis, however, may postulate that these concerns are only relevant if contaminant concentrations are above screening values that predict the possibility of environmental harm or contaminant bioaccumulation. To determine whether a substantive contaminants-based risk assessment is needed for infrastructure in the Gippsland Basin (South-eastern Australia), we measured the concentration of metals and polycyclic aromatic hydrocarbons (PAHs) in benthic sediments collected around eight platforms earmarked for decommissioning. The measurements were compared to preset screening values and to background contaminant concentrations in reference sites. Lead (Pb), zinc (Zn), PAHs and other contaminants were occasionally measured at concentrations that exceeded reference values, most often within 150 m of the platforms. The exceedance of a few screening values by contaminants at some platforms indicates that these platforms require further analysis to determine the contaminant risks associated with any decommissioning option.

Predicting chronic algal toxicity from 1- to 48-h pulsed exposures to mine site waters using time-averaged concentrations.

Despite concentrations often fluctuating in aquatic systems that receive contaminant inputs, there has only been a relatively small number of studies investigating the toxicity of intermittent exposures. This is particularly the case for industrial and mine effluents that may contain complex mixtures of contaminants and other stressors. The lack of information is impeding the regulation of such contaminant exposures, whose risk is often assessed by comparison to continuous exposures in whole effluent toxicity (direct toxicity assessment) testing. The current study compared the toxicity from continuous (72-h) and pulsed (1- to 48-h) exposures of two neutralised mine waters (NMWs) to the freshwater algae, Chlorella sp. When the algal toxicity of the different exposures was related to the time-averaged concentration (TAC) of contaminants, it was found that the TAC was a good predictor of toxicity in any given test, with variability in toxicity between tests mainly related to differences in contaminant concentrations from the neutralisation of the acidic mine waters. When the data from tests on two samples were combined on a whole-effluent TAC basis, the EC50 values (95% confidence intervals) for the continuous and pulsed exposures were 0.68% (0.36-1.3) and 0.63% (0.38-1.1) respectively, for NMW sample one, while the corresponding EC50 values for NMW sample two were 1.3% (1.0-1.7) and 1.9% (1.6-2.2), respectively. The toxicity of the second water was strongly influenced by the zinc, and probably copper, concentrations, while the toxicity of the first appeared to be related to additive or synergistic toxicity from Al, Cd, Mn and Pb. The findings are discussed in relation to using a contaminant TAC-approach to revise water quality guideline values derived for continuous exposures for application to pulsed exposures, where higher concentrations may be permissible for short durations.

The use of time-averaged concentrations of metals to predict the toxicity of pulsed complex effluent exposures to a freshwater alga.

Intermittent, fluctuating and pulsed contaminant discharges may result in organisms receiving highly variable toxicant exposures. This study investigated the toxicity of continuous and pulsed exposures of a complex, neutralised drainage water (NDW) and dissolved copper-spiked dilute NDW to the green alga, Pseudokirchneriella subcapitata. The effects of single pulses of between 1 and 48 h duration and continuous exposures (72 h) on algal growth rate inhibition were compared on a time-averaged concentration (TAC) basis. Algal growth rates generally recovered to control levels within 24-48 h of the pulse removal. Continuous exposures to NDW resulted in similar or marginally higher toxicity to the algae when compared to pulsed exposures of equivalent TAC (% NDW). The toxicity of the NDW was attributed mostly to the metals, with the major cations potentially causing effects that are both additive (direct toxicity) and antagonistic (lower bioavailability of trace metals). For dissolved copper in dilute NDW, the pulsed exposures caused slightly higher toxicity than continuous exposures of equivalent dissolved copper TAC, with much of the difference explained by differences in labile copper concentrations between treatments. The results indicate that water quality guideline values for toxicants derived from continuous chronic exposures may be relaxed for pulsed exposures by a factor related to the TAC with the intent to provide an adequately protective but not overly-conservative outcome. The study highlights the influence that natural water quality parameters such as water hardness and DOC can have metal speciation and toxicity, and indicates that these parameters are particularly important for site-specific water quality guideline value derivation where, on a TAC basis, pulsed exposures may be more toxic than continuous exposures typically used in guideline value derivation.

Time-averaged concentrations are effective for predicting chronic toxicity of varying copper pulse exposures for two freshwater green algae species.

Intermittent, fluctuating and pulsed contaminant discharges may result in organisms receiving highly variable contaminant exposures. This study investigated the effects of dissolved copper pulse concentration and exposure duration on the toxicity to two freshwater green algae species. The effects of single copper pulses of between 1 and 48 h duration and continuous exposures (72 h) on growth rate inhibition of Pseudokirchneriella subcapitata and Chlorella sp. were compared on a time-averaged concentration (TAC) basis. Relationships were then derived between the exposure concentration and duration required to elicit different levels of toxicity expressed as inhibition concentration (IC). Continuous exposure IC50's of 3.0 and 1.9 µg/L were measured on a TAC basis for P. subcapitata and Chlorella sp., respectively. Algal growth rates generally recovered to control levels within 24-48 h of the copper pulse removal, with some treatments exhibiting significantly (p < 0.05) higher rates of cell division than controls in this recovery period. For both algae, when exposed to treatments with equivalent TACs, the continuous exposure elicited similar or slightly greater growth rate inhibition than the pulsed exposures. To elicit equivalent inhibition, the exposure concentration increased as the exposure duration decreased, and power models fitted this relationship reasonably well for both species. Water quality guideline values (WQGVs) are predominantly derived using data from continuous exposure toxicity bioassays, despite intermittent contaminant exposures often occurring in aquatic systems. The results indicate the WQGV for copper may be relaxed for pulsed exposures by a factor less than or equivalent to the TAC and still achieve a protection to these sensitive algae species.

Toxicity of dissolved and precipitated aluminium to marine diatoms.

Localised aluminium contamination can lead to high concentrations in coastal waters, which have the potential for adverse effects on aquatic organisms. This research investigated the toxicity of 72-h exposures of aluminium to three marine diatoms (Ceratoneis closterium (formerly Nitzschia closterium), Minutocellus polymorphus and Phaeodactylum tricornutum) by measuring population growth rate inhibition and cell membrane damage (SYTOX Green) as endpoints. Toxicity was correlated to the time-averaged concentrations of different aluminium size-fractions, operationally defined as <0.025µm filtered, <0.45µm filtered (dissolved) and unfiltered (total) present in solution over the 72-h bioassay. The chronic population growth rate inhibition after aluminium exposure varied between diatom species. C. closterium was the most sensitive species (10% inhibition of growth rate (72-h IC10) of 80 (55-100)µg Al/L (95% confidence limits)) while M. polymorphus (540 (460-600)µg Al/L) and P. tricornutum (2100 (2000-2200)µg Al/L) were less sensitive (based on measured total aluminium). Dissolved aluminium was the primary contributor to toxicity in C. closterium, while a combination of dissolved and precipitated aluminium forms contributed to toxicity in M. polymorphus. In contrast, aluminium toxicity to the most tolerant diatom P. tricornutum was due predominantly to precipitated aluminium. Preliminary investigations revealed the sensitivity of C. closterium and M. polymorphus to aluminium was influenced by initial cell density with aluminium toxicity significantly (p<0.05) increasing with initial cell density from 10(3) to 10(5)cells/mL. No effects on plasma membrane permeability were observed for any of the three diatoms suggesting that mechanisms of aluminium toxicity to diatoms do not involve compromising the plasma membrane. These results indicate that marine diatoms have a broad range in sensitivity to aluminium with toxic mechanisms related to both dissolved and precipitated aluminium.

On the mechanism of nanoparticulate CeO2 toxicity to freshwater algae.

The factors affecting the chronic (72-h) toxicity of three nanoparticulate (10-34nm) and one micron-sized form of CeO2 to the green alga, Pseudokirchneriella subcapitata were investigated. To characterise transformations in solution, hydrodynamic diameters (HDD) were measured by dynamic light scatter, zeta potential values by electrophoretic mobility, and dissolution by equilibrium dialysis. The protective effects of humic and fulvic dissolved organic carbon (DOC) on toxicity were also assessed. To investigate the mechanisms of algal toxicity, the CytoViva hyperspectral imaging system was used to visualise algal-CeO2 interactions in the presence and absence of DOC, and the role of reactive oxygen species (ROS) was investigated by 'switching off' ROS production using UV-filtered lighting conditions. The nanoparticulate CeO2 immediately aggregated in solution to HDDs measured in the range 113-193nm, whereas the HDD and zeta potential values were significantly lower in the presence of DOC. Negligible CeO2 dissolution over the time course of the bioassay ruled out potential toxicity from dissolved cerium. The nanoparticulate CeO2 concentration that caused 50% inhibition of algal growth rate (IC50) was in the range 7.6-28mg/L compared with 59mg/L for micron-sized ceria, indicating that smaller particles were more toxic. The presence of DOC mitigated toxicity, with IC50s increasing to greater than 100mg/L. Significant ROS were generated in the nanoparticulate CeO2 bioassays under normal light conditions. However, 'switching off' ROS under UV-filtered light conditions resulted in a similar IC50, indicating that ROS generation was not the toxic mechanism. The CytoViva imaging showed negligible sorption of nanoparticulate CeO2 to algal cells in the presence of DOC, and strong sorption in its absence, suggesting that this was the toxic mechanism. The results suggest that DOC in natural waters will coat CeO2 particles and mitigate toxicity to algal cells.

Time-averaged copper concentrations from continuous exposures predicts pulsed exposure toxicity to the marine diatom, Phaeodactylum tricornutum: Importance of uptake and elimination.

Intermittent, fluctuating and pulsed contaminant discharges result in organisms receiving highly variable contaminant exposures. Current water quality guidelines are predominantly derived using data from continuous exposure toxicity tests, and most frequently applied by regulators with the assumption that concentrations from a single sampling event will provide a meaningful approach to assessing potential effects. This study investigated the effect of single and multiple (daily) dissolved copper pulses on the marine diatom, Phaeodactylum tricornutum, including measurements of copper uptake and elimination to investigate the toxic mechanism. Copper pulses of between 0.5 and 24h and continuous exposures with equivalent 72-h time-averaged concentrations (TACs) resulted in similar biomass inhibition of P. tricornutum, with continuous exposures often being marginally more toxic. Rates of cell division generally recovered to control levels within 24h of the copper pulse removal. Upon resuspension in clean seawater, the extracellular copper per cell decreased rapidly, whereas the intracellular copper per cell decreased slowly. Negligible loss of copper from the total algal biomass indicated that P. tricornutum did not have an effective mechanism for eliminating copper from cells, rather the intracellular copper decreased as a result of dilution by cellular division as the algal growth rate recovered. The measurement of copper uptake after 72-h exposure and kinetics of elimination thereafter suggest that continuous exposures are marginally more toxic to P. tricornutum than pulsed copper exposures with equivalent TACs because slow internalization and saturation of algal membrane transport sites results in less copper uptake into pulse-exposed cells than continuously-exposed cells coupled with dilution of internalized copper via cellular division in the post-exposure period. In the case of P. tricornutum, the results indicate that water quality guidelines for copper based on continuous exposure will be conservative when applied to short-term discharges.

Derivation of a water quality guideline for aluminium in marine waters.

Metal risk assessment of industrialized harbors and coastal marine waters requires the application of robust water quality guidelines to determine the likelihood of biological impacts. Currently there is no such guideline available for aluminium in marine waters. A water quality guideline of 24 µg total Al/L has been developed for aluminium in marine waters based on chronic 10% inhibition or effect concentrations (IC10 or EC10) and no-observed-effect concentrations (NOECs) from 11 species (2 literature values and 9 species tested including temperate and tropical species) representing 6 taxonomic groups. The 3 most sensitive species tested were a diatom Ceratoneis closterium (formerly Nitzschia closterium; IC10 = 18 µg Al/L, 72-h growth rate inhibition) < mussel Mytilus edulis plannulatus (EC10 = 250 µg Al/L, 72-h embryo development) < oyster Saccostrea echinata (EC10 = 410 µg Al/L, 48-h embryo development). Toxicity to these species was the result of the dissolved aluminium forms of aluminate (Al(OH4 (-) ) and aluminium hydroxide (Al(OH)3 (0) ) although both dissolved, and particulate aluminium contributed to toxicity in the diatom Minutocellus polymorphus and green alga Dunaliella tertiolecta. In contrast, aluminium toxicity to the green flagellate alga Tetraselmis sp. was the result of particulate aluminium only. Four species, a brown macroalga (Hormosira banksii), sea urchin embryo (Heliocidaris tuberculata), and 2 juvenile fish species (Lates calcarifer and Acanthochromis polyacanthus), were not adversely affected at the highest test concentration used.

Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms.

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems.

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag-Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag-PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72h in freshwater (500-600µgL(-1)) and seawater (1300-1500µgL(-1)), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag(+) (1.1, 400 and 0.11µgL(-1), respectively), Ag-Cit (3.0, 2380 and 0.15µgL(-1), respectively) and Ag-PVP (19.5, 3690 and 2.0µgL(-1), respectively) varied widely, with toxicity in the order Ag(+)>Ag-Cit>Ag-PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag(+) or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.

Trace metals associated with deep-sea tailings placement at the Batu Hijau copper-gold mine, Sumbawa, Indonesia.

The Batu Hijau copper-gold mine on the island of Sumbawa, Indonesia operates a deep-sea tailings placement (DSTP) facility to dispose of the tailings within the offshore Senunu Canyon. The concentrations of trace metals in tailings, waters, and sediments from locations in the vicinity of the DSTP were determined during surveys in 2004 and 2009. In coastal and deep seawater samples from Alas Strait and the South Coast of Sumbawa, the dissolved concentrations of Ag, As, Cd, Cr, Hg, Pb and Zn were in the sub µg/L range. Dissolved copper concentrations ranged from 0.05 to 0.65 µg/L for all depths at these sites. Dissolved copper concentrations were the highest in the bottom-water from within the tailings plume inside Senunu Canyon, with up to 6.5 µg Cu/L measured in close proximity to the tailings discharge. In general, the concentrations of dissolved and particulate metals were similar in 2004 and 2009.

Toxicity to Melita plumulosa from intermittent and continuous exposures to dissolved copper.

The concentrations of metal contaminants often fluctuate in estuarine waters; yet we have limited knowledge about the effects of intermittent exposures on estuarine organisms. Using 10-d lethality bioassays with the epibenthic amphipod Melita plumulosa, different combinations of intermittent (pulsed) dissolved Cu exposure were investigated, varying Cu concentration, pulse duration, and time between pulses. Negligible organism mortality was observed immediately after single 12- to 62-h duration pulsed exposures of 100 to 900 µg/L dissolved Cu. However, delayed mortality was observed in the subsequent 96-h nonexposure period, after which negligible additional mortality occurred during the remainder of the 240-h tests. For multiple pulsed exposures, increasing the time between pulses from 0 to 144 h did not result in significantly different mortality rates for 300 and 400 µg/L dissolved copper, indicating that the organisms did not recover between pulses. Organism mortality exhibited a strong relationship with the time-averaged concentration (TAC) resulting from the combination of exposure concentration and duration. The lethal concentration to 50 (LC50), 20 (LC20), and 10% (LC10) (95% confidence interval) of the test population for the combined TAC exposure-survival data were 86 (71-103), 44 (30-64), and 30 (18-49) µg Cu/L, respectively, which were similar to the respective values of 100 (87-114), 55 (43-70), and 39 (28-54) µg Cu/L determined for continuous exposure. The results from the current study support the use of analytical techniques capable of determining the time-averaged concentration of metals, because they will more accurately predict the effects of toxiciants on organisms than single time-point measurements.

Uptake and internalisation of copper by three marine microalgae: comparison of copper-sensitive and copper-tolerant species.

Although it has been well established that different species of marine algae have different sensitivities to metals, our understanding of the physiological and biochemical basis for these differences is limited. This study investigated copper adsorption and internalisation in three algal species with differing sensitivities to copper. The diatom Phaeodactylum tricornutum was particularly sensitive to copper, with a 72-h IC50 (concentration of copper to inhibit growth rate by 50%) of 8.0 microg Cu L(-1), compared to the green algae Tetraselmis sp. (72-h IC50 47 microg Cu L(-1)) and Dunaliella tertiolecta (72-h IC50 530 microg Cu L(-1)). At these IC50 concentrations, Tetraselmis sp. had much higher intracellular copper (1.97+/-0.01 x 10(-13)g Cu cell(-1)) than P. tricornutum (0.23+/-0.19 x 10(-13)g Cu cell(-1)) and D. tertiolecta (0.59+/-0.05 x 10(-13)g Cu cell(-1)), suggesting that Tetraselmis sp. effectively detoxifies copper within the cell. By contrast, at the same external copper concentration (50 microg L(-1)), D. tertiolecta appears to better exclude copper than Tetraselmis sp. by having a slower copper internalisation rate and lower internal copper concentrations at equivalent extracellular concentrations. The results suggest that the use of internal copper concentrations and net uptake rates alone cannot explain differences in species-sensitivity for different algal species. Model prediction of copper toxicity to marine biota and understanding fundamental differences in species-sensitivity will require, not just an understanding of water quality parameters and copper-cell binding, but also further knowledge of cellular detoxification mechanisms.

Metal equilibration in laboratory-contaminated (spiked) sediments used for the development of whole-sediment toxicity tests.

The equilibration and bioavailability of metals in laboratory-contaminated sediments have been investigated in order to provide better guidance on acceptable procedures for spiking sediments with metals for use in the development of whole-sediment toxicity tests. The equilibration rates of Cd, Cu, Ni and Zn spiked into three estuarine surface sediments with varying properties were investigated. Changes to sediment pH, redox potential, porewater and acid-soluble metals, acid-volatile sulfide and bacterial activity during equilibration, effects of temperature and disturbances following equilibration are reported. The addition of metals to sediments caused major decreases in pH and increases in redox potential as metals displaced iron(II) into the porewaters and added metals and iron (following oxidation) were hydrolyzed. The rates of equilibration of metals in porewaters varied considerably and were dependent on sediment and metal properties. For the oxic/sub-oxic sediments studied, metal-spikes of Cd, Cu, Ni and Zn appeared near equilibrium after 25-45, 10-15, 30-70 and 20-40 days, respectively. Acid-soluble metal concentrations decreased during the equilibration period indicating that the metals become more strongly associated with the sediments with time (less bioavailable). Bacterial activity was greatest in the sediment equilibrated at pH 7 and decreased following the addition of metals. During the equilibration period, bacterial activity increased in sediments equilibrated at pH 6, remained low in sediments at pH 8 and varied erratically in sediments at pH 7. Spiked sediments were shown to equilibrate more slowly at lower temperatures resulting in high porewater metal concentrations. Disturbances to equilibrated sediments because of sample manipulation caused significant iron(II) oxidation and losses of metals from porewaters. The importance of documenting spiking and equilibration procedures and carefully measuring and reporting sediment parameters is highlighted so that contaminant bioavailability and exposure pathways can be interpreted and organism sensitivity accurately determined. Recommendations are given for the preparation of metal-spiked sediments for toxicity testing purposes.