Regional assessment of marine and estuarine sediment toxicity in Southern California, USA

Sediment toxicity was investigated at 222 stations in the Southern California Bight (SCB) during 2008. This represented the first time that assessment methods established by California's new Sediment Quality Objectives program were employed in a survey of this scale. The goal was to determine the extent and magnitude of sediment toxicity in the SCB, how toxicity compared among specific environments, and whether toxicity has changed over the last decade. Two toxicity tests were used: the 10-day amphipod whole sediment survival test with Eohaustorius estuarius and a 48-h embryo development test with the mussel Mytilus galloprovincialis exposed at the sediment–water interface. Less than 1 % of the area of the SCB was found to be toxic to the amphipod test. No toxicity was found in offshore stations, but 14 % of embayment areas were toxic to the amphipods. The mussel test identified 13 % of the embayment areas to be toxic. Estuary and marina locations had the greatest areal extent of toxicity for both tests. The two toxicity methods agreed that sediments were not toxic at over half of the stations tested. The mussel test showed a greater magnitude of response than the amphipod. Sediment toxicity was shown to have declined in both extent and magnitude from levels measured in 1998 and 2003.     

Toxicity of Surficial Sediments from Sydney Harbour and Vicinity, Australia

The toxicological responses of three species to 103 surficial saltwater sediment samples from Sydney Harbour, and coastal lakes and estuaries on the south-east coast of New South Wales, Australia, were tested in a battery of four to six laboratory toxicity tests. This is the first large-scale toxicological study of sediments in Australia, the objective of which is to assess the protective and predictive abilities of North American biological effects-based sediment quality guidelines, recently adopted in Australia. Amphipods were exposed to whole sediments in survival and reburial tests, sea urchin fertilisation and larval development tests were conducted on porewaters, and bacterial bio-luminescence (Microtox) tests were conducted on organic solvent extracts and porewaters. Local indigenous species were used for the amphipod and sea urchin tests (Corophium sp. and Heliocidaris tuberculata, respectively). A wide range of responses, from <25 to 100% of negative controls were observed in all tests. Mean control-adjusted responses ranged from 46 to 96% for all tests. The percentages of highly toxic samples ranged from 11 to 83% in the various tests. The order of test sensitivity was: amphipod survival < Microtox test of porewaters < amphipod reburial < sea urchin larval development < sea urchin fertilisation < Microtox test of solvent extracts. Concordance between toxicity tests in classifying samples as highly toxic or not, ranged from 47 to 79%, indicating some similarities between test results, but not complete equivalence. Combined toxicity test results showed that the incidence of highly toxic responses occurring in the majority of tests (75-100% of tests) was low (5% of samples), but a large percentage of samples had highly toxic results in at least one test (76% of samples). Toxicity was more pervasive in the Sydney region than in coastal lakes and estuaries south of Sydney. The current study demonstrated the utility of indigenous invertebrate species and the Microtox bacterium in a sediment toxicity test battery for Australian saltwater sediments.     

Relationships Between Toxicity and Concentrations of Chemical Contaminants in Sediments from Sydney Harbour, Australia, and Vicinity

Correlation analyses between measures of toxicity and concentrations of chemical contaminants were conducted for 103 surficial sediments from Sydney Harbour, Australia, and vicinity. Toxicity tests consisted of amphipod survival and reburial tests of whole sediments (Corophium colo), sea urchin fertilisation and larval development tests of pore waters (Heliocidaris tuberculata) and microbial bioluminescence (Microtox) tests of solvent extracts and pore waters. Toxicity in most tests correlated with concentrations of metallic contaminants, in particular, zinc, lead and copper. Organic contaminants did not correlate as significantly with toxicity. However, Heliocidaris tuberculata showed relationships with organochlorine compounds in samples with low to moderate metals contamination. Toxicity in the Microtox solvent extract test appeared to be primarily influenced by the presence of sulfur. This study has no precedent in Australia and the results support the validity of using local indigenous species in toxicity tests of field-collected sediments. This toxicity/chemistry dataset may be used in evaluations of sediment quality guidelines recently introduced to Australia.     

An interlaboratory comparison of sediment elutriate preparation and toxicity test methods

Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.     

Spatial Extent of Sediment Toxicity in U.S. Estuaries and Marine Bays

Acute, laboratory toxicity tests were performed by the National Oceanic and Atmospheric Administration (NOAA) on 1543 surficial sediment samples collected during 1991 through 1997 throughout 25 estuaries and marine bays. Selected areas were sampled along the Atlantic, Gulf of Mexico, and Pacific coasts. The toxicity of each sample was determined with 10-day amphipod survival tests performed with solid-phase (bulk) sediments. Collectively, the 1543 samples tested through 1997 represented a total area of approximately 7300 km². Toxicity was observed with the amphipod survival tests in samples that represented approximately 6% of the combined area. Using similar tests conducted on samples collected in different, but overlapping, study areas, the U.S. Environmental Protection Agency (EPA) estimated that approximately 7% of the combined estuarine area sampled was toxic. Generally, toxicity was most severe in northeastern and southwestern estuaries and least prevalent in southeastern and northwestern areas. However, considerable portions of the Pacific coast have not been tested with the same methods. In tests of CYP1A enzyme induction (n=464), samples were toxic that represented about 5% of the combined study areas. Toxicity was much more widespread, however, when the results of two sub-lethal tests were analyzed. Significant results occurred in samples that represented approximately 25% and 39% of the study areas in tests of sea urchin fertilization (n=1309) and microbial bioluminescence (n=1215), respectively.     

Evaluation of a bioassays battery for ecotoxicological screening of marine sediments from Ionian Sea (Mediterranea Sea, Southern Italy)

Sediments are an ecologically important component of the aquatic environment and may play a key role in mediating the exchange of contaminants between particulate, dissolved, and biological phases. For a comprehensive assessment of potential sediment toxicity, the use of a single species may not detect toxicant with a specific mode of action. Therefore it is advisable to carry out ecotoxicological tests on a base-set of taxa utilizing test species belonging to different trophic levels. This paper describes the ecotoxicological evaluation of marine sediments from seven sites of Mar Piccolo estuary (Southern, Italy), four of them were located in the first inlet and three in the second inlet of Mar Piccolo estuary. Sediment samples from a site in Taranto Gulf were used as control sediment. Dunaliella tertiolecta, Tigriopus fulvus, Mytilus galloprovincialis, and Corophium insidiosum, were employed to identify the quality of sediments. The integration of biological tests results showed that all sampling sites located in the first inlet of Mar Piccolo were identified as toxic, according to all tests, while the sites of second inlet were found not toxic. The results obtained in this study indicate that the use of a battery of biological tests have important implications for risk assessment in estuarine e coastal waters.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Biological responses to sediment remediation based on thin layer placement near a former pulp mill in Ward Cove, AK (USA)

In 2001, 28 acres of the bottom of Ward Cove, AK (USA) were remediated using thin layer placement, to enhance the natural recovery of contaminated sediments. The remediated areas were part of an 80-acre area of concern identified offshore from the site of a former sulfite pulp mill. The primary chemicals of concern were those commonly associated with organic enrichment near pulp mills: ammonia and 4-methylphenol. The primary remedial objectives were to reduce the toxicity of the contaminated sediments and to stimulate colonization of the remediated areas by benthic macroinvertebrates. In 2004, the initial monitoring event for the remediated areas was conducted, and included evaluations of physical/chemical sediment variables (i.e., total organic carbon, grain size distribution, ammonia, and 4-methylphenol), sediment toxicity (i.e., using the 10-day amphipod survival test with Eohaustorius estuarius), and in situ benthic macroinvertebrate communities. Results of the monitoring event showed that conditions in the remediated areas had improved considerably in the 3 years since thin layer placement had occurred. At most stations, concentrations of both ammonia and 4-methylphenol were very low, and amphipod survival was >or=90%. In addition, benthic macroinvertebrates appeared to be rapidly colonizing the remediated areas, based on evaluations of several community metrics (i.e., taxa richness, diversity, and dominance), as well as key indicator species of organic enrichment and associated transitional areas (i.e., primarily the polychaetes Capitella capitata and Nephtys cornuta, and the bivalve molluscs Axinopsida serricata and Parvilucina tenuisculpta). In general, colonization was consistent with the patterns identified for areas recovering from organic enrichment on the continental shelf of southern California and elsewhere. Based on these results, thin layer placement was considered successful in enhancing the natural recovery of the remediated sediments in Ward Cove.     

Evaluation of the state-of-the-art of butyl- and phenyltin compound determinations in freshwater sediment prior to certification of a reference material

In order to control the quality of butyl- and phenyltin compound determinations in sediment, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a freshwater sediment for its contents of a range of organotin compounds (mono-, di- and tributyltin, and mono-, di- and triphenyltin). The first part of this project involved an interlaboratory study which aimed to test the feasibility of preparation of candidate freshwater sediment reference material and to detect and remove most of the pitfalls observed in organotin determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The agreement obtained among laboratories for the six compounds determined was considered to reflect the state-of-the-art and was encouraging enough to decide upon the organisation of a certification campaign, which will be concluded in June 1999.     

城市黑臭河道治理前后沉积物对大型溞的毒性变化监测与评价

以常州市典型城市黑臭水体神童滨为对象,利用大型溞-固定沉积物毒性实验,成功地对治理前、后污染河流沉积物毒性变化进行监测,获得较浸出液毒性实验更灵敏的结果。结果表明,治理前污染河流4个采样点沉积物的毒性均为中毒级,治理后,3个采样点的毒性下降到微毒级,1个点位毒性为无毒级。根据河道整治前、后的沉积物对水生生物的综合毒性变化,评价河道治理前的危害程度和治理后的生态安全性,为采取合理的整治方法以达到可持续治理效果提供科学依据。     

Integrative sediment assessment at Atlantic Spanish harbours by means of chemical and ecotoxicological tools

This study refers to the integrative assessment of sediment quality in three harbour areas at the Spanish Atlantic Coast: Vigo (Northwestern Spain), Bilbao and Pasajes (Northern Spain). At each site, two lines of evidence have been considered: chemical analyses (metal, PAH and PCB concentrations in sediments and ammonia concentration in bioassays) and toxicity tests (Microtox®, Corophium sp. marine amphipod and Paracentrotus lividus sea urchin larvae). Chemical and ecotoxicological results have been integrated by means of a tabular matrix and a multivariate factorial analysis (FA). Highly toxic samples have been characterised in Vigo and Pasajes harbours while Bilbao samples present toxicity levels ranging from non-toxic to moderately toxic. High toxicity is associated with high levels of contaminants whereas confounding factors (ammonia, organic matter and mud) have been identified to be the main cause of low to moderate toxicity. Based on the obtained results, it can be concluded that deriving potential toxicity of sediments based on comparison with Sediment Quality Guidelines (SQGs) is in agreement to toxicity results in areas presenting high levels of contaminants. However, at lower levels of toxicity (low to moderate), the mismatch between the potential toxicity (SQG approach) and the toxicity measured by bioassays is greater, as the former only accounts for chemical concentrations, without considering the interaction between contaminants and the effect of confounding factors. Contrarily, the multivariate analysis seems to be a robust tool for the integration and interpretation of different lines of evidence in areas affected by different sources of contamination.     

Using the Sediment Quality Triad to characterize baseline conditions in the Anacostia River, Washington, DC, USA

The Sediment Quality Triad (SQT) consists of complementary measures of sediment chemistry, benthic community structure, and sediment toxicity. We applied the SQT at 20 stations in the tidal portion of the Anacostia River from Bladensburg, MD to Washington, DC to establish a baseline of conditions to evaluate the effects of management actions. Sediment toxicity was assessed using 10-day survival and growth tests with the freshwater amphipod, Hyalella azteca and the midge, Chironomus dilutus. Triplicate grabs were taken at each station for benthic community analysis and the Benthic Index of Biotic Integrity (B-IBI) was used to interpret the data. Only one station, #92, exhibited toxicity related to sediment contamination. Sediments from this station significantly inhibited growth of both test species, had the highest concentrations of contaminants, and had a degraded benthic community, indicated by a B-IBI of less than 3. Additional sediment from this station was tested and sediment toxicity identification evaluation (TIE) procedures tentatively characterized organic compounds as the cause of toxicity. Overall, forty percent of the stations were classified as degraded by the B-IBI. However, qualitative and quantitative comparisons with sediment quality benchmarks indicated no clear relationship between benthic community health and contaminant concentrations. This study provides a baseline for assessing the effectiveness of management actions in the Anacostia River.     

Seed Clam Growth: An Alternative Sediment Bioassay Developed During EMAP in the Carolinian Province

A new sediment bioassay was developed in conjunction with EMAP studies conducted in the Carolinian Province using juvenile seed clams, Mercenaria mercenaria. This is a sublethal assay, based on growth (total dry weight) after a 7 day incubation period. Seed clam chronic growth assays were significantly more sensitive than amphipod acute toxicity assays. Optimization components include use of hatchery-reared juvenile clams in a rapid growth phase, and size-sieving to ensure a similar size range. Juvenile clam growth was not affected by sediment type, i.e., clams grew well in muddy and sandy sediments. Clams were slightly more sensitive to ammonia than amphipods (NOEC porewater total ammonia 14 - 16 mg/L for clams). Ammonia concentrations above these levels were more common in reference sites, so most of the false positives could be explained by ammonia toxicity. This assay possesses a number of other positive attributes that are desirable for a bioassay, including the requirement for a relatively small sample size (500 ml of sediments), balanced sensitivity, low incremental costs, and high information gained. The seed clam assay is believed to be a valuable tool for EMAP as well as other monitoring efforts for estimating potential chronic toxicity.     

Physicochemical and ecotoxicological based assessment of bottom sediments from the Luján River basin, Buenos Aires, Argentina

The physicochemical analysis of bottom sediments of the Lujan River was done on samples from 14 sites situated along its course and covered grain size and organic matter, total N and P, sulfides, heavy metals, organochlorine, and pyrethroid pesticides. In addition, acute 10-day whole-sediment laboratory toxicity tests were carried with each sample, using the native amphipod Hyalella curvispina as test organism. In order to correlate both types of results, data were assessed by multivariate analysis, including principal component analysis (PCA). The physicochemical profile of samples resulted similar along the river course, though several anomalous data were registered in the middle course of the river, mainly in samples taken downstream a large industrial complex; with a few exceptions in upper basin sites characterized by the dominance of agricultural activities, the pesticides concentration were consistently below the analytical detection limits. Almost 50 % of the samples induced adverse effects on the amphipod when testing sublethal and lethal end points. The toxicity of the samples in terms of survival rate was extremely high in two sites, in particular in samples taken downstream the Pilar industrial complex. The integration of a selection of physicochemical and toxicological parameters of the sediments by PCA allowed discriminating areas of the river basin according the type and intensity of their particular pollution condition.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

Interlaboratory comparability of copper complexation capacity determination in natural waters

The results of a test of interlaboratory comparability for the determination of copper complexation capacity and copper-ligand complex formation constant are presented. Eight water samples comprising, six natural waters, a synthetic ligand solution and a blank solution were analysed by seven laboratories using their own methods of complexation titration. Given the wide variation that might have been possible, relatively good comparability was demonstrated amongst the variety of methods for determining copper complexation capacity. The complexation capacity data largely satisfied the predefined criterion of agreement to within 50%. This provides support for the use of metal speciation criteria in the regulation of copper in the environment. Data for the determination of complex formation constants were of poorer comparability, ranging between 10(7) and 10(12) for the same water.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

River evaluation using ecotoxicological and microbiological procedures

One of the many problems researchers and managers face is to try and interpret data collected from various river studies. There is an underlying awareness of the incompleteness of most data bases due to a variety of problems outside of those concerning sample processing.In this study we have attempted, by using the battery of tests approach (12 tests) and the examination of different types of samples such as water, Milli-Q water extracted sediments, and organic solvent extracted sediments, to explore the implication of spacial and temporal sampling programmes.The results obtained were not unexpected: there were spatial and temporal influences, sometimes so great that it would appear that you were examining samples from different parts of the country. However, data arising from solvent extracted sediments were found to be much less influenced by temporal sampling than by spatial variation. Another interesting and important observation was that sediment composition appeared to have no relationship to toxicant content.In this study, the first field application of the Mutatox test (genotoxicity) was carried out and it was found to be a very responsive test in all three types of samples. This test shows great promise as laboratory studies indicate it is sensitive to many of the chemicals which trigger the Ames test.     

The continuous monitoring of field water samples with a novel multi-channel two-stage mini-bioreactor system

Toxicity monitoring of field water samples was performed using a novel multi-channel two-stage mini-bioreactor system and genetically engineered bioluminescent bacteria for the continuous monitoring and classification of the toxicity present in the samples. The toxicity of various samples spiked with known endocrine disrupting chemicals and phenol was also investigated for system characterization. The field samples used in this study were obtained from two different sites on a monthly basis--from a drinking water treatment plant, referred to as site N, and from a stream near a dam which is currently being constructed, referred to as site T. These samples were either pumped or injected into the second mini-bioreactors to initiate the toxicity test. Most of the samples did not show any specific toxicity. However, one sample showed to have, based upon the detection results, and was deemed toxic. The samples spiked with phenol showed possible responses in the DPD2540 and TV1061 channels, indicating the occurrence of both membrane and protein damage due to phenol. In the tests using an endocrine disrupting chemical, bisphenol A, DNA damage was detected in the DPD2794 channel with a concentration of 2 ppm. Finally, a simple but novel early warning protocol that can be used in a drinking water reservoir and a suspected place where effluents of toxic materials enter the water sourse was suggested with a schematic diagram. In conclusion, this system showed good feasibility for use as a toxicity monitoring system in the field and as an early warning system, indicating if effluents are toxic.     

Investigative monitoring within the European Water Framework Directive: a coastal blast furnace slag disposal, as an example

The European Water Framework Directive (WFD) establishes a framework for the protection of estuarine and coastal waters, with the most important objective being to achieve 'good ecological status' for all waters, by 2015. Hence, Member States are establishing programmes for the monitoring of water quality status, through the assessment of ecological and chemical elements. These monitoring programmes can be of three types: surveillance monitoring; operational monitoring (both undertaken on a routine basis); and investigative monitoring (carried out where the reason of any exceedance for ecological and chemical status is unknown). Until now, nothing has been developed in relation to investigative monitoring and no clear guidance exists for this type of monitoring, as it must be tackled on a 'case-by-case' basis. Consequently, the present study uses slag disposal from a blast furnace, into a coastal area, as a case-study in the implementation of investigative monitoring, according to the WFD.In order to investigate the potential threat of such slags, this contribution includes: a geophysical study, to determine the extent of the disposal area; sediment analysis; a chemical metal analysis; and an ecotoxicological study (including a Microtox test and an amphipod bioassay). The results show that metal concentrations are several times above the background concentration. However, only one of the stations showed toxicity after acute toxicological tests, with the benthic communities being in a good status. The approaches used here show that contaminants are not bioavailable and that no management actions are required with the slags.