Bicarbonate alone does not totally explain the toxicity from major ions of coal bed derived waters to freshwater invertebrates.

Concentrations of major ions in coal mine discharge waters and unconventional hydrocarbon produced waters derived from coal bed methane (CBM) production, are potentially harmful to freshwater ecosystems. Bicarbonate is a major constituent of produced waters from CBM and coal mining. However, little is known about the relative toxicity of differing ionic proportions, especially bicarbonate, found in these CBM waters. As all freshwater invertebrates tested are more acutely sensitive to sodium bicarbonate (NaHCO3) than sodium chloride (NaCl) or synthetic sea water, we tested the hypotheses that toxicity of CBM waters are driven by bicarbonate concentration, and waters containing a higher proportion of bicarbonate are more toxic to freshwater invertebrates than those with less bicarbonate. We compared the acute (96 h) lethal toxicity to six freshwater invertebrate species of NaHCO3 and two synthetic CBM waters, with ionic proportions representative of water from CBM wells across New South Wales (NSW) and Queensland (Qld), in Australia. The ranking of LC50 values expressed as total salinity was consistent with the hypotheses. However, when toxicity was expressed as bicarbonate concentration, the hypothesis that the toxicity of coal bed waters would be explained by bicarbonate concentration was not well supported, and other ionic components were either ameliorating or exacerbating the NaHCO3 toxicity. Our findings showed NaHCO3 was more toxic than NaCl and that the NaHCO3 proportion of synthetic CBM waters drives toxicity, however other ions are altering the toxicity of bicarbonate.

Do magnesium and chloride ameliorate high sodium bicarbonate concentrations? A comparison between laboratory and mesocosm toxicity experiments.

Increasing salinity is a concern for biodiversity in many freshwater ecosystems globally. Single species laboratory toxicity tests show major differences in freshwater organism survival depending on the specific ions that comprise salinity types and/or their ion ratios. Toxicity has been shown to be reduced by altering ionic composition, despite increasing (total) salinity. For insistence, single species tests show the toxicity of sodium bicarbonate (NaHCO3, which commonly is a large proportion of the salts from coalbeds) to freshwater invertebrates is reduced by adding magnesium (Mg2+) or chloride (Cl-). However, it is uncertain whether reductions in mortality observed in single-species laboratory tests predict effects within populations, communities and to ecosystem processes in more complex multi-species systems both natural and semi-natural. Here we report the results of an outdoor multi-species mesocosm experiment to determine if the effects of NaHCO3 are reduced by increasing the concentrations of Mg2+ or Cl- on: a) stream macroinvertebrate populations and communities; b) benthic chlorophyll-a and; c) the ecosystem process of leaf litter decomposition. We found a large effect of a high NaHCO3 concentration (≈4.45 mS/cm) with reduced abundances of multiple taxa, reduced emergence of adult insects and reduced species richness, altered community structure and increased leaf litter breakdown rates but no effect on benthic chlorophyll-a. However, despite predictions based on laboratory findings, we found no evidence that the addition of either Mg2+ or Cl- altered the effect of NaHCO3. In semi-natural environments such as mesocosms, and natural environments, organisms are subject to varying temperature and habitat factors, while also interacting with other species and trophic levels (e.g. predation, competition, facilitation), which are absent in single species laboratory tests. Thus, it should not be assumed single-species tests are good predictors of the effects of changing ionic compositions on stream biota in more natural environments.

Secondary vitellogenesis persists despite disrupted fecundity in amphipods maintained on metal-contaminated sediment: X-ray fluorescence assessment of oocyte metal content.

Melita plumulosa is an epibenthic, detritivorous amphipod found in estuaries along the eastern coast of Australia. It has been utilized as a test organism in rapid ten to thirteen days reproduction toxicity tests for sediment quality assessment. The fecundity of females in the toxicity test has been found to be inhibited by exposure of the amphipods to contaminated sediments enriched with zinc and other metals. This study investigated the proposal that interference in vitellogenesis is the cause of reproductive toxicity of metals in crustaceans. Inspection of the ovaries from amphipods on day 6 of the test either from control or Zn/Pb/Cd/Cu-spiked sediment, that were nearing completion of vitellogenesis, showed that the females in all treatments were producing similar numbers of oocytes undergoing secondary vitellogenesis. The distribution of the Zn, Cu and Pb in the oocytes and ventral caeca of females was examined by X-ray fluorescence microscopy. Elemental mapping revealed a dense accumulation of Zn in primary oocytes and a uniform distribution of Zn and Cu in the secondary oocytes in all treatments. Zn and Cu were also observed to be uniformly distributed in the ventral caeca. Pb was not detected in either of these tissues. The apparent normal morphology and the typical number of oocytes undergoing secondary vitellogenesis suggest that vitellogenesis was not being disrupted by Pb displacing Zn in the metal-binding domain of vitellogenin in amphipods exposed to the contaminated sediment during the test. Alternative mechanisms for the reproductive toxicity of amphipods exposed for six days to metal-contaminated sediment are discussed.

Calibration and field application of Chemcatcher® passive samplers for detecting amitrole residues in agricultural drain waters.

A passive sampler device suitable for monitoring of residues of the hydrophilic ionic herbicide amitrole in irrigation waterways was developed. Uptake of amitrole on styrenedivinylbenzene-reverse phase sulfonated Empore™ disks was linear and proportional to its water concentration over the range of 1-10 µg/L with a sampling rate of 23.1 mL/day under laboratory flow-through conditions. Performance of the sampler was evaluated by deployment in an agricultural irrigation drain for 10 days. The amount of amitrole adsorbed by the passive samplers compared well with the cumulative mean water concentrations calculated from daily spot samplings of the drain water.

Toxicity of the insecticide terbufos, its oxidation metabolites, and the herbicide atrazine in binary mixtures to Ceriodaphnia cf dubia.

The acute toxicity of terbufos and its major metabolites, tested alone, in binary mixtures or in combination with atrazine were evaluated using neonates of the cladoceran Ceriodaphnia cf dubia. Terbufos, terbufos sulfoxide, and terbufos sulfone tested individually were highly toxic to C. cf dubia, with mean 96-h EC(50) values of 0.08, 0.36, and 0.19 µg/l, respectively. The addition of atrazine (10 µg/l) significantly increased the toxicity of terbufos. The toxicity of terbufos sulfone was unaffected by atrazine, whereas the results for terbufos sulfoxide were equivocal. Equitoxic mixtures of the metabolites showed additive toxicity to C. cf dubia. The high toxicities of terbufos and its environmentally persistent oxidative metabolites suggest that contamination of aquatic systems with this insecticide mixture and the coapplied herbicide atrazine might pose a greater hazard to some biota than their individual toxicities.

Morphological abnormalities in frogs from a rice-growing region in NSW, Australia, with investigations into pesticide exposure.

Three frog species (Limnodynastes tasmaniensis, Limnodynastes fletcheri and Litoria raniformis) were surveyed in rice bays of the Coleambally Irrigation Area (CIA), NSW, Australia, during the rice-growing seasons of 2005/2006 and 2006/2007. A total external morphological abnormality index of 7.0% was observed in frogs of the CIA (n=1,209). The types and frequencies of abnormalities were typical of reports from agricultural areas with ectrodactyly being the most common aberration. A relatively low abnormality index of 1.2% was observed in L. raniformis (n=87) compared to indices of 7.1% and 8.2% observed in L. fletcheri (n=694) and L. tasmaniensis (n=428), respectively. No conclusive evidence was found of unnaturally high rates of intersex, gonadal maldevelopment or unbalanced sex ratios in any species. Rice bay surface waters differed significantly in mean pesticide concentrations of atrazine and metolachlor on farms growing rice and corn compared to farms with rice as the sole crop. However, the similar abnormality indices observed in recent metamorphs emerging from these two farm types provided no evidence to suggest a link between larval exposure to the measured pesticides and developmental malformations.

Effects of dietary cadmium exposure on reproduction of saltwater cladoceran Moina monogolica Daday: Implications in water quality criteria.

The chronic toxicity of dietary cadmium to the saltwater cladoceran Moina monogolica Daday and its relative toxicity compared with aquatic exposure were investigated in the present study. The microalgae Chlorella pyrenoidosa, exposed to cadmium in growth inhibition tests, had a 96-h median effective concentration (EC50) of 81.2 microg Cd/L (95% confidence intervals [CIs] = 71.9-95.1). C. pyrenoidosa exposed for 96 h to sublethal dissolved cadmium concentrations in the range 4.10 +/- 0.30 to 70.29 +/- 0.31 microg/L resulted in algal cadmium burdens up to 73.86 x 10(-16) g Cd/cell. Cellular cadmium burdens accumulated in a dose-dependent manner, whereas cell densities inversely declined from 670 x 10(4) to 38 x 10(4) cells/ml with exposure to the increasing aqueous cadmium concentrations. C. pyrenoidosa preexposed to cadmium and used as food in a chronic 21-d toxicity test with the cladoceran M. monogolica, containing no added dissolved cadmium, inhibited reproduction. Significant reductions of the net reproduction rate (R(0)) per brood were observed in all broods, and the decline in the number of neonates produced increased with each subsequent brood. The cadmium concentration (4.10 +/- 0.30 microg/L) in the algal culture water that produced the lowest algal cadmium burden (2.85 +/- 0.76 x 10(-16) g Cd/cell) was shown to inhibit M. monogolica reproduction and was compared with the water quality criteria (WQC) of China. This comparison indicated that dietary exposure to cadmium may cause sublethal responses at concentrations below the current cadmium WQC of China for aquaculture.

A low concentration of atrazine does not influence the acute toxicity of the insecticide terbufos or its breakdown products to Chironomus tepperi.

The acute toxicities of the insecticide terbufos and its major breakdown products individually, as binary mixtures, and in combination with the co-applied herbicide atrazine were evaluated using final instar larvae of the midge Chironomus tepperi. Terbufos, terbufos sulfoxide and terbufos sulfone were highly toxic to C. tepperi with mean 96-h EC50 values of 2.13, 3.64 and 2.59 µg/l, respectively. No interaction was observed between atrazine (25 µg/l) and terbufos or its breakdown products while the binary mixture of terbufos sulfoxide and terbufos sulfone exhibited additive toxicity. The high toxicities of terbufos and its environmentally persistent oxidation products suggest that contamination of aquatic systems with this insecticide pose a threat to aquatic organisms whether or not atrazine is also present.

Hormonal induction of spermiation, courting behavior and spawning in the southern bell frog, Litoria raniformis.

We trialled the efficacy of various exogenous hormones to induce spermiation, courtship behavior, and spawning in the "endangered" southern bell frog, Litoria raniformis. Intralymphatic administration of Lucrin(®), a synthetic nonapeptide luteinizing hormone releasing hormone (LHRH), was used successfully to induce courting behaviors and ejaculation of spermatozoa in males. Various hormones, including Lucrin(®), another synthetic LHRH analog ([des-Gly(10), D-Ala(6)]-LHRH), human chorionic gonadotropin, progesterone, and a dopamine receptor antagonist failed to promote oviposition and spawning in females. This and earlier studies indicate that in the efficacy of hormonal induction in amphibians varies between taxa, hormones, and genders. The lack of response in females may limit the use of reproduction technology in the southern bell frog and closely related species of Australian bell frogs.

Development and application of a rapid amphipod reproduction test for sediment-quality assessment.

Melita plumulosa is an epibenthic, detritivorous amphipod native to eastern Australia that has been adopted as a test organism for toxicity evaluations of contaminated estuarine sediments. In the present study, a 13-d amphipod reproduction test was developed that encompasses gametogenesis, fertilization, and embryo development before hatching. The primary endpoints for the test are fecundity (measured as the number of embryos per individual surviving female) and a fecundity index (fecundity multiplied by the stage of embryo development). This new test has been employed to scrutinize the sediments from a metal-contaminated coastal lagoon. Lake Macquarie (NSW, Australia) is a large, saltwater lagoon that has received metal pollution over many decades, leading to a concentration gradient of trace metals, including Pb, Zn, Cd, and Cu, in the sediments. Within one of the northern bays (Warners Bay), the concentrations of these metals either border on or exceed sediment quality guideline values prescribed by Australian and New Zealand Guidelines for Fresh and Marine Water Quality. In trials with the 13-d amphipod reproduction test, Warners Bay sediments significantly reduced fecundity in the test species. Subsequent tests with clean sediments spiked singly with Pb, Zn, or Cu indicated that no single metal was responsible for the observed toxicity in the field sediments. However, sediments spiked with various combinations of Pb, Zn, Cd, and Cu indicated that Zn in combination with one or more of the other metals was responsible for the reproductive toxicity observed in Warners Bay sediments. In all these tests, measured metal concentrations in overlying water and pore water were low, thus confirming that the observed effects on reproduction could be attributed to dietary exposure to metals.

Fatty acid composition of the estuarine amphipod, Melita plumulosa (Zeidler): link between diet and fecundity.

The influence of various diets on the survival, fecundity, and the polyunsaturated fatty acid (PUFA) composition of the benthic estuarine amphipod Melita plumulosa (Zeidler) in laboratory cultures were determined. Apart from a natural silty sediment, six commercial food supplements were examined: an omega-6 PUFA enriched Spirulina-based dry powder, Sera micron; a shrimp-based pellet food; an omega-3 PUFA enriched algal paste, Rotiselco-ALG; an omega-6 PUFA enriched algal dry powder, AlgaMac-ARA (arachidonic acid); flaxseed meal; and an omega-3 PUFA enriched dry powder, Frippak. We have previously established that M. plumulosa cultures perform poorly and eventually decline if provided with silty sediment alone, but will thrive if supplemented with Sera micron. Conversely, if the amphipods are cultured on a nutrient-depleted sand substrate, Sera micron alone does not constitute an adequate feed. The major difference in the fatty acid composition of M. plumulosa cultured on silty sediment compared to amphipods cultured on a sand substrate and both fed Sera micron was an increase in the ratio of omega-3 to omega-6 PUFAs, indicating that the silty sediment provides additional food sources rich in omega-3 PUFAs. Furthermore, amphipods cultured in sand and fed any of the three algal-based foods or the Frippak powder as the sole food source had poor survival rates, although Sera micron maintained the best survival-this was attributed to it containing high amounts of beta-carotene and terpenoids. Melita plumulosa fed a mixture of Sera micron in conjunction with the omega-3 PUFA enriched Rotiselco-ALG and cultured on a silty substrate were found to have good fecundity with low variability.

Distribution of frogs in rice bays within an irrigated agricultural area: links to pesticide usage and farm practices.

In the Coleambally irrigation area (NSW, Australia), the occurrence of four tadpole and frog species in rice bays on farms growing either rice only or both rice and corn was studied over two seasons. In addition to analysis of species occurrence, both gonadal histology and assessment of Batrachochytrium dendrobatidis infection rates were performed. The rice acreage available as potential tadpole habitat was extensively distributed throughout the irrigation area, but more corn was grown in the northern region compared with the southern region. The mean abundance of Litoria raniformis tadpoles was significantly lower in the northern sites compared with the southern sites. In contrast, tadpoles of Limnodynastes fletcheri, Limnodynastes tasmaniensis, and Crinia parinsignifera had a uniform distribution across all study sites. A principal components analysis showed a relationship between farm type and the rice herbicide applied when the crops were initially sown, with sites occupied by Litoria raniformis in the beginning being predominantly rice-only farms. A discriminant analysis showed that low concentrations of the corn herbicide metolachlor and increased pH were the main variables studied that determined site occupation by L. raniformis. This suggested that farms growing only rice (and not corn) with high algal production were the preferred sites. The rates of chytrid infection and gonadal malformations were low across both regions. Histology of the gonads of metamorphs showed that L. raniformis gonadal differentiation is slow compared to that of the two Limnodynastes species. We concluded that farm practices associated with increased corn cropping in the northern region, rather than any direct effect of corn herbicides, determine the reduced presence of Litoria raniformis in the northern region.

Endosulfan application to a stream mesocosm: studies on fate, uptake into passive samplers and caged toxicity test with the fish M. ambigua.

A model mesocosm system was used to simulate the effect of endosulfan entering a waterway from episodic events such as accidental overspray or in runoff water containing contaminated sediment following storm events. The fate of technical endosulfan applied to a 24-stream mesocosm was compared in experiments where the pesticide was applied either directly as water contamination or after being pre-bound to sediment. The flow of water through the streams was discontinued for a 10-12 h period following the pesticide application. Following the water application, only approximately 3% of endosulfan remained in the streams after 4 days and then was not detectable after 7 days. In contrast, after application pre-bound to sediment, approximately 33% of the endosulfan remained in the streams after 4 days and 14% after 7 days. Additionally, with the sediment-bound application, the proportion of endosulfan was higher in the substrate (11%) after 7 days than in the overlying water (3%), and approximately 1% was oxidised to the sulphate form. The dissipation of endosulfan in the water column of both experiments followed a two-parameter exponential decay model characterised by a relatively fast first-order single-phase process. In sediment of both experiments and the gravel of the sediment-dosing experiment, the dissipation of endosulfan followed more closely a four-parameter bi-exponential decay model characterised by first-order kinetics of two fractions: the first fraction dissipates quickly, and in the longer term the second fraction dominates the overall dissipation with a slower rate. In the gravel section of the water-dosing experiment, endosulfan dissipation was characterised by relatively very slow two-parameter exponential decay. The overall dissipation rates of the alpha- and beta-endosulfan isomers were significantly higher in the water-dosing than in the sediment-dosing experiment, except in the gravel section of the mesocosm. The uptake of the endosulfan into passive samplers constructed from polyethylene membrane bags containing trimethylpentane solvent (TRIMPS) placed in the overlying water was linear. In contrast, TRIMPS buried in sediment failed to uptake endosulfan from the sediment substrate, indicating that short-term deployment of passive samplers can only be used to determine time-weighted average concentrations of bioavailable chemicals in the water column. A 34-h LC50 of 2.8 microg/l [95% confidence interval (CI) 1.5-4.2 microg/l] for juveniles of the native fish Macquaria ambigua was obtained when exposed during the water-dosing experiment. This study demonstrated that the pulse entry of sediment contaminated with endosulfan into a receiving waterway was more persistent compared with direct aqueous contamination and the endosulfan would be bioavailable to pelagic organisms following a gradual partitioning to the water column.

Genetic and life-history trait variation of the amphipod Melita plumulosa from polluted and unpolluted waterways in eastern Australia.

To monitor genetic diversity and environmental contamination in eastern Australia, toxicity studies have employed the sensitive benthic amphipod Melita plumulosa. The goal of this study was to examine the genetic and life-history variability of natural populations of M. plumulosa from the Parramatta (polluted) and Hawkesbury (unpolluted) Rivers. The underlying genetics of the populations in these distinct waterways was examined at one mitochondrial (cytochrome c oxidase subunit I (COI)) and one nuclear (ribosomal internal transcribed spacer region 1 (ITS1)) locus. Seven unique haplotypes for COI were found amongst animals from the Parramatta River, while animals from the Hawkesbury River showed a complete absence of genetic variation at this locus. At ITS1 a total of two sequence variants were found amongst Parramatta River amphipods and three sequence variants among Hawkesbury River animals, with no common variants across the two river systems. To establish whether genetic differences were associated with organismal responses to toxicant exposure, two life-history trait variables (female head length as an estimator of amphipod size and female fecundity) were analyzed. Life-history trait analyses showed that females from the Hawkesbury River were significantly larger and more fecund. These data have critical implications for toxicity tests, the use of laboratory cultures for testing purposes, and environmental contamination in Sydney Harbor.

Calibration and field application of a solvent-based cellulose membrane passive sampling device for the monitoring of polar herbicides.

A passive sampler device selective for hydrophilic analytes was constructed from cellulose membrane (40microm thickness) pre-stained with ruthenium red for 96-168h to impede degradation of the cellulose. The sampling device consisted of pre-stained cellulose membrane tubing containing a binary mixture of the solvents 1-dodecanol and 2,2,4-trimethylpentane as the sequestering medium. A laboratory flow-through system was used to investigate the rates of uptake of herbicides into the solvent mixture of the device and their release. The target herbicides were diuron, atrazine, metolachlor and molinate. Uptake of the herbicides into the solvent mixture of the cellulose membrane device was linear for up to 22 days, and daily sampling rates were determined. Release half-lives from the solvent mixture of the sampling device varied from 14 days for diuron, 15 days for atrazine, 84 days for metolachlor and 28 days for molinate. A field study was undertaken to determine if herbicide concentrations in agricultural drainage water derived from the passive sampler devices deployed for periods from 7 to 22 days, using the laboratory-derived sampling rates, would compare closely with time-weighted average herbicide concentrations determined from extractions of daily composite water samples. The concentrations of diuron, atrazine, metolachlor and molinate determined using the cellulose membrane devices were within twofold of the cumulated mean of the daily drainage water extractions.

Species of freshwater invertebrates that are sensitive to one saline water are mostly sensitive to another saline water but an exception exists.

Coal mining and extraction of methane from coal beds generate effluent with elevated salinity or major ion concentrations. If discharged to freshwater systems, these effluents may have adverse environmental effects. There is a growing body of work on freshwater invertebrates that indicates variation in the proportion of major ions can be more important than salinity when determining toxicity. However, it is not known if saline toxicity in a subset of species is representative of toxicity across all freshwater invertebrates. If patterns derived from a subset of species are representative of all freshwater invertebrates, then we would expect a correlation in the relative sensitivity of these species to multiple saline waters. Here, we determine if there is a correlation between the acute (96 h) lethal toxicity in freshwater invertebrates to synthetic marine salts (SMS) and sodium bicarbonate (NaHCO3) added to dechlorinated Sydney tap water. NaHCO3 is a major component of many coal bed effluents. However, most salinization in Australia exhibits ionic composition similar to seawater, which has very little HCO3- Across all eight species tested, NaHCO3 was 2-50 times more toxic than SMS. We also observed strong correlations in the acute toxicity of seven of the tested species to SMS and NaHCO3 The strongest relationship (LC50 r2 = 0.906) was dependent on the exclusion of one species, Paratya australiensis (Decopoda: Atyidae), which was the most sensitive species tested to NaHCO3, but the second-most tolerant of SMS. We conclude that differences in the toxicity of different proportions of major ions can be similar across a wide range of species. Therefore, a small subset of the invertebrate community can be representative of the whole. However, there are some species, which based on the species tested in the current study appear to be a minority, that respond differently to saline effluent and need to be considered separately. We discuss the implications of this study for the management of saline coal bed waters.This article is part of the theme issue 'Salt in freshwaters: causes, ecological consequences and future prospects'.

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC.

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.

Calibration of a passive sampling device for time-integrated sampling of hydrophilic herbicides in aquatic environments.

Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-XC Empore disk) and a styrenedivinylbenzene copolymer sorbent modified with sulfonic acid functional groups (embedded in a SDB-RPS Empore disk), were compared as a receiving phase in a passive sampling device for monitoring polar pesticides. The SDB-XC Empore disk was selected for further evaluation, overlayed with either a polysulfone or a polyethersulfone diffusion membrane. The target herbicides included five nonionized herbicides (simazine, atrazine, diuron, clomazone, and metolachlor) and four phenoxy acid herbicides (dicamba, (2,4-dichlorophenoxy)acetic acid [2,4-D], (4-chloro-2-methylphenoxy)acetic acid [MCPA], and triclopyr) with log octanol/water partition coefficient (log K(OW)) values of less than three in water. Uptake of these herbicides generally was higher into a device constructed of a SDB-XC Empore disk as a receiving phase covered with a polyethersulfone membrane compared to a similar device covered with a polysulfone membrane. Using the device with a SDB-XC Empore disk covered with a polyethersulfone membrane, linear uptake of simazine, atrazine, diuron, clomazone, and metolachlor was observed for up to 21 d, and daily sampling rates of the herbicides from water in a laboratory flow-through system were determined. The uptake rate of each nonionized herbicide by the Empore disk-based passive sampler was linearly proportional to its concentration in the water, and the sampling rate was independent of the water concentrations over the 21-d period. Uptake of the phenoxy acid herbicides (2,4-D, MCPA, and triclopyr) obeyed first-order kinetics and rapidly reached equilibrium in the passive sampler after approximately 12 d of exposure. The Empore disk-based passive sampler displayed isotropic kinetics, with a release half-life for triclopyr of approximately 6 d.

Sensitivities of Australian and New Zealand amphipods to copper and zinc in waters and metal-spiked sediments.

The sensitivities of eight benthic amphipods, Chaetocorophium cf. lucasi, Corophium colo, Grandidierella japonica, Hyale crassicornis, Hyale longicornis, Melita awa, Melita matilda and Melita plumulosa, to copper and zinc in water-only and whole-sediment toxicity tests were compared. Whole-sediment tests used copper- (1300 mg/kg) and zinc- (4000 mg/kg) spiked sediments after equilibration for sufficient time to produce pore water and overlying water concentrations below the lowest observable effect concentrations of water-only exposures. Survival of adults (after 10 d) and juveniles (after 96 h), and the metal concentrations in the body tissues of adults, were determined at the end of the tests. Two epibenthic amphipods from the genus Melita were the most sensitive species to aqueous copper and zinc, with a 96-h LC50 value of 120 microg Cu/l for both M. awa and M. plumulosa juveniles, and a 96-h LC50 value of 640 microg Zn/l for juveniles of M. plumulosa. Juvenile amphipods (7-d old) were more sensitive than adult amphipods (>30-d old) in both water-only and whole-sediment tests, with adult-LC50/juvenile-LC50 ratios in water-only tests ranging from 1.2 to l.5 for copper and 1 to 1.4 for zinc. All species except C. colo, C. cf. lucasi and M. matilda were sensitive to the copper-spiked sediment, with survival between 14% and 74% of controls. Similarly, all species except C. colo and G. japonica, showed a response to the zinc-spiked sediment (26-81% of control survival). The epibenthic amphipods were more sensitive than the infaunal tube-dwelling amphipods and are recommended as test species.

Chronic sublethal sediment toxicity testing using the estuarine amphipod, Melita plumulosa (Zeidler): evaluation using metal-spiked and field-contaminated sediments.

The present study describes the development of a 42-d chronic sublethal sediment toxicity test using the estuarine amphipod Melita plumulosa (Zeilder). This test was shown to predict the toxicity of metal-contaminated sediments previously found to adversely affect benthic community structure. Metals initially were tested individually by spiking reference sediment under conditions that ensured low metal concentrations in pore waters. Fertility was the most sensitive sublethal endpoint for copper- and zinc-spiked sediments, whereas cadmium-spiked sediments were not toxic to M. plumulosa, despite their high bioaccumulation of cadmium. The 42-d chronic sediment test was reproducible; however, variation between reference sediments collected from the same field location over time or from different locations did affect the reproduction of M. plumulosa. Sensitivity of M. plumulosa to metal-spiked sediments suggested that the interim sediment-quality guidelines (ISQGs) were too conservative. However, toxicity testing of sediments collected from field sites known to affect community assemblages significantly (p < 0.001) reduced the fertility of M. plumulosa, reflecting benthic community survey results and supporting the ISQGs. Bioaccumulation of cadmium and copper by M. plumulosa was elevated following chronic exposure to both laboratory and field-contaminated sediments; however, zinc bioaccumulation could be measured only in M. plumulosa exposed to field-contaminated sediments.