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.     

Behavior of pesticides in sediment/water systems in outdoor mesocosms

The distribution of eight pesticides between sediment and water held in 1-m square outdoor stainless-steel mesocosms was studied, simulating both spring and autumn applications. Pesticide behavior was largely independent of rate of application, chosen in the first three experiments to be 4% or 40% of the normal field rate so as to simulate spray drift or partial overspray. Following application by spray to the water surface, all compounds were uniformly distributed in the 30 cm of overlying water within 24 h. The lipophilic pesticides (chlorpyrifos, pendimethalin, and permethrin) moved into the sediment within 30 d but with little penetration below 2.5 cm depth, and only chlorpyrifos persisted beyond 30 d. The mass balance of these lipophilic pesticides at 1 d was only 26.3% to 61%, with these initial losses attributed to processes such as volatilization. Isoproturon and chlorotoluron persisted for around 120 d, remaining largely in the overlying water with a maximum of 15% in the sediment. Permethrin and difenoconazole were much less persistent in these mesocosms, with very little ever found in the sediment in contrast to previous findings in laboratory-scale stirred systems as used in registration tests. The polar mecoprop remained almost entirely in the water phase and was rapidly degraded. Two further experiments examined also the influence of the submerged plant Lagarosiphon major in the mesocosms, the first experiment simulating a full-rate overspray with chlorpyrifos and linuron and the second a repeat in spring of the earlier main autumn experiment. Both chlorpyrifos and linuron applied in the autumn were quite persistent over the winter period, with about 20% still remaining after 152 d. Uptake into L. major was correlated with pesticide lipophilicity, but was only a small factor compared to uptake by sediment and degradation in these lightly vegetated systems.     

Structural and functional responses of benthic invertebrates to imidacloprid in outdoor stream mesocosms

Structural and functional responses of a benthic macroinvertebrate assemblage to pulses of the insecticide imidacloprid were assessed in outdoor stream mesocosms. Imidacloprid pulses reduced invertebrate abundance and community diversity in imidacloprid-dosed streams compared to control streams. These results correlated well with effects of imidacloprid on leaf litter decomposition and feeding rates of Pteronarcys comstocki, a stonefly, in artificial streams. Reductions in oxygen consumption of stoneflies exposed to imidacloprid were also observed in laboratory experiments. Our findings suggest that leaf litter degradation and single species responses can be sensitive ecotoxicological endpoints that can be used as early warning indicators and biomonitoring tools for pesticide contamination. The data generated illustrates the value of mesocosm experiments in environmental assessment and how the consideration of functional and structural endpoints of natural communities together with in situ single species bioassays can improve the evaluation and prediction of pesticide effects on stream ecosystems.     

Phytotoxicity of atrazine, isoproturon, and diuron to submersed macrophytes in outdoor mesocosms

The submersed macrophytes Elodea canadensis, Myriophyllum spicatum and Potamogeton lucens were constantly exposed over a five-week period to environmentally relevant concentrations of atrazine, isoproturon, diuron, and their mixture in outdoor mesocosms. Effects were evaluated investigating photosynthetic efficiency (PE) of the three macrophytes and growth of M. spicatum and E. canadensis. Adverse effects on PE were observed on days 2 and 5 after application. M. spicatum was found to be the more sensitive macrophyte. E. canadensis and P. lucens were less sensitive to atrazine, diuron and the mixture and insensitive to isoproturon. PE of M. spicatum was similarly affected by the single herbicides and the mixture demonstrating concentration addition. Growth of E. canadensis and M. spicatum was not reduced indicating that herbicide exposure did not impair plant development. Although PE measurements turned out to be a sensitive method to monitor PSII herbicides, plant growth remains the more relevant ecological endpoint in risk assessment.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.     

Tributyltin partitioning in sediments: effect of aging

The effect of aging on the solid/pore-water partitioning and desorption behaviour of tributyltin (TBT) in sediments was examined. Three sediment samples with contrasting physical and chemical properties were spiked with 10 mg/kg TBT and aged under sterile conditions for periods of time ranging from 1 to 84 days. Aging had a negligible effect on partitioning and desorption behaviour in a sandy sample with very low organic carbon content (0.2% w/w). In contrast, for samples with larger amounts of organic carbon (2.6% and 4.8% w/w), aging caused substantial increases in TBT sorption. For these samples, apparent distribution coefficients (KD,app) obtained from sequential 2 h desorption experiments also exhibited a twofold increase between spiked sediments subjected to aging for 1 day and 84 days. This study demonstrates that aging effects may be an important aspect of TBT fate in contaminated sediments.     

Physico-chemical changes in metal-spiked sediments deployed in the field: implications for the interpretation of in situ studies

Manipulative field studies are useful for investigating cause-effect relationships between contamination and benthic community health. However, there are many challenges for creating environmentally relevant exposures and determining what measurements are necessary to correctly interpret the results. This study describes the physical and chemical changes in the properties of metal-spiked marine sediments deployed in four different locations for up to 11 months. The test sediments lost between 20% and 75% of their volume during the deployment period, with the greatest losses occurring at sites affected by strong hydrodynamic activity. More sediment was lost from clean treatments than those spiked with high metal concentrations and corresponded with differential recruitment of infauna to these treatments. In general, a greater proportion of spiked-metals remained at lower energy sites (48-85%) than at higher energy sites (15-48%). The decreased metal concentrations were attributed mostly to the loss of the metal-spiked sediments (through resuspension) and their dilution with sediments depositing from the surrounding environment. A range of recommendations are made for optimising the information gained from field-based studies using metal-spiked sediments. These include the careful documentation of physico-chemical sediment properties pre- and post-deployment, the use of co-located sediment traps and knowledge of site-specific hydrodynamic processes.     

Nickel partitioning in formulated and natural freshwater sediments

A natural, field-collected sediment high in organic carbon (OC) and low in acid-volatile sulfide (AVS) was used to evaluate nickel (Ni) complexation to organic matter (OM) over a range of pH under anoxic conditions. It was found that OM strongly influenced Ni partitioning and that Ni complexation to OM was significantly influenced by pH, with complexation increasing with increasing pH (from pH 6 to 8). Using an equilibrium partitioning approach incorporating both [SEM(Ni)]-[AVS] and OC content, lethal and non-lethal toxicity test endpoints were calculated (predicted) and compared to observed toxicity test results using the amphipod, Hyalella azteca, exposed to four Ni-spiked natural sediments varying in OC and AVS content. Generally, lethal and non-lethal toxicity test endpoints were reasonably predictable in low AVS sediments. Due to the apparent lack of equilibrium between dissolved pore-water Ni and the pure Ni sulfide (likely the result of additional dissolved metal binding ligands), and the possible competition of liberated Fe2+ with Ni2+ for binding sites on organic matter, toxicity predictions (based on sediment OC and AVS content) overestimated the combined protective effects of AVS and OC in the sediments containing mid to high (27.87-44.05 micromol/g d.w.) AVS concentrations. Overall, it was found that equilibrium partitioning-based sediment quality guidelines can be improved through the incorporation of nickel complexation to sedimentary OM (in addition to AVS), although further research is required to fully describe nickel-OM interaction.     

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically <10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment.     

Guidelines for copper in sediments with varying properties

A major weakness of sediment quality guidelines (SQGs) is their poor ability to predict how toxicity thresholds change for different sediment types. Using species sensitivity distributions (SSDs) of copper effects data, new guidelines were derived for copper in non-sulfidic marine sediments in which organic carbon (OC) and particle size strongly influence copper bioavailability. The derived SQGs varied in a predictable manner with changes in sediment particle size and organic carbon (OC), and were shown to offer a significant improvement on the existing ‘single value’ SQG. Adequate protection for all benthic organisms is expected to be achieved for a OC-normalised copper concentration of 3.5 mg Cu g⁻¹ OC in the <63 μm sediment fraction. For short-term exposures, the equivalent acute guideline is 11 mg < 63 μm Cu g⁻¹ OC. The new SQGs incorporate a high degree of conservatism owing to the use of copper-spiked sediments and laboratory-based bioassays that were expected to result in greater metal exposure of organisms to bioavailable copper than would be expected for field-contaminated sediments with similar total copper concentrations. SQGs that vary with sediment properties were prepared in an easily referenced tabular format.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments.     

A predictive model for copper partitioning to suspended particulate matter in river waters

A chemical equilibrium-based predictive model expressing Cu partitioning as a function of aqueous and solid phase characteristics was developed. The model takes into account only the most important factors that govern Cu partitioning, and therefore results in a relatively simple formulation. It assumes particulate organic carbon (POC) and dissolved organic carbon (DOC) binding sites play the most important role in solid and aqueous phases. The model formulation assumed one-surface site and two dissolved organic matter (DOM) sites, and included the "solids effect". Proton effects were considered for both the particle surface sites and the DOM. The model was calibrated with data for samples collected from the Susquehanna River, and validated with White Clay Creek and Delaware River samples. Copper partitioning in natural water systems with different pH, and concentrations of alkalinity, DOC, POC, total suspended solids (TSS), and total copper was predicted reasonably well.     

Long-term storage of sediments: Implications for sediment toxicity testing

A study using open-top chambers ventilated with ambient or charcoal-filtered air in the vicinity of Lahore, Pakistan, has demonstrated a reduction of 46.7% and 34.8% in the grain yield for two cultivars of winter wheat (Triticum aestivum L.). The 6-h daily mean O(3) concentrations were 25-45 nl litre(-1) and on the basis of experience in North America and Europe, reductions in yield in the present study are substantially greater than might be predicted. The reasons for this discrepancy are discussed, together with implications for the suitability of a simple, relatively cheap, open-top chamber system for developing-country studies on the effects of air pollution on crops.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

铜在沉积物不同稳定性组分上的吸附特征

沉积物中不同成分的稳定性对重金属的迁移转化有重要影响。按照在自然条件下不同成分的稳定性将沉积物分为3个组分(轻组(LF)、腐殖质(HS)、去除HS的重组(HFRHS))。研究了铜在沉积物及其不同组分上的吸附动力学、吸附等温线以及pH对吸附的影响。结果表明,在沉积物中,LF与HS对吸附铜的速率起控制作用,而HFRHS是主要的吸附组分,pH对铜的吸附有较大影响。在自然环境中,控制LF和HS的迁移转化,可以有效降低铜的迁移能力,减小对环境的影响。     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Grain size partitioning of platinum-group elements in road-deposited sediments: implications for anthropogenic flux estimates from autocatalysts

Twelve road-deposited sediment samples were analyzed for platinum-group elements (PGEs) and Pb in the <63 microm fraction of an urban watershed in Hawaii. Three samples were further fractionated into five size classes, from 63-125 microm to 1000-2000 microm, and these were analyzed for PGEs and Pb. Concentrations in the <63 microm fraction reached 174 microg/kg (Pt), 101 microg/kg (Pd), 16 microg/kg (Rh), and 1.3 microg/kg (Ir). Enrichment ratios followed the sequence Rh>Pt=Pd>Ir. Iridium was geogenic in origin, while the remaining PGEs indicated significant anthropogenic contamination. Palladium, Pt and Rh concentrations and enrichment signals were consistent with PGE bivariate ratios and PGE partitioning in three-way catalysts. Size partitioning indicated that the <63 microm fraction had the lowest PGE concentrations and mass loading percentages. These data suggest that autocatalyst PGE flux estimates into the environment will be significantly underestimated if only a fine grain size fraction is analyzed.