A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

A comparison of sediment quality guidelines for toxicity assessment in the Sunderban wetlands (Bay of Bengal, India)

The aim of this paper was to obtain the first screening ecotoxicological risk evaluation in the Sunderban wetlands, the largest prograding delta in the estuarine phase of the River Ganges. The characterization of exposure was conducted by means of an extensive survey of several persistent organic pollutants (PAHs, PCBs, DDTs, PBDEs, HCHs, HCB) measured in seven core sediments from the Sunderban wetlands, obtaining a dataset with more than 2200 analyses. The pollutant effects were assessed by the use of three different sediment quality guidelines (SQGs) previously developed in the literature to evaluate toxicity induced in sediment-dwelling organisms. The three different approaches chosen for risk assessment of the Sunderban were the consensus SQGs obtained by TEC (threshold effect concentration), PEC (probable effect concentration) and EEC (extreme effect concentration), the threshold/probable effect level (TEL/PEL) approach and, finally, the ERL-ERM guidelines, including the m-ERM-Q (mean ERM quotient). The evaluation of the toxicity induced by a mixture of the target pollutants indicated the importance of gamma-HCH contamination in the Sunderban sediments despite the very low concentrations measured in core sediments. A different sensitivity for toxicity assessment due to quality guidelines was obtained, as the consensus SQGs based on TEC were less conservative and protective than the TEL and ERL approaches, while the use of m-ERM-Q seems to be the most powerful tool to predict the toxicity related to a contaminant mixture.     

Assessment of toxicant activity in sediments by the ECHA biocide monitor

The ECHA Biocide Monitor, a dipstick procedure originally designed to test the effectiveness of in situ biocides, was evaluated as a possible environmental toxicity assessment procedure. The dipstick procedure was applied to 94 sediment extracts which were also tested by three well documented toxicant screening procedures; Microtox, Daphnia magna and Spirillum volutans. In these samples the Daphnia magna test proved to be the most sensitive indication of toxicant activity (63 of 94) with the ECHA Biocide Monitor easily being the second most sensitive procedure with 27 of 94 sediments indicating the presence of toxic substances. Results of the investigation are detailed.     

The combined use of chemical and biochemical markers to assess water quality along the Ebro River

Carp (Cyprinus carpio) and barbel (Barbus graellsii) were collected from five sites along the Ebro River. The study was designed to assess levels of persistent organic pollutants and metals bioaccumulated by fish, and some biochemical responses (cytochrome P450 system, phase II activities, and metallothioneins) against those pollutants. The highest levels of PCBs and DDTs were detected in carp from industrialised areas, which also showed high levels of mercury and cadmium in the liver, and high levels of nonylphenol in bile. Significant alterations in some biochemical markers were observed and associated to combined exposure to pollutants. The activity 7-ethoxyresorufin O-deethylase ranged from 69 pmol/min/mg protein in carp from the reference site to 415 pmol/min/mg protein in those from polluted sites. Carp from the Ebro Delta, an agricultural area, had depressed acetylcholinesterase in muscle tissue. Metallothionein concentrations were positively correlated with copper residues, but no significant differences among sampling points were observed.     

Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

Levels and distribution of DDT in the Cinca River (Spain).

The evolution over time of the levels and distribution of dichlorodiphenyltrichloroethane (DDT) in water, surface sediments, and fish from the River Cinca (Spain), a tributary of the River Ebro, during the period 1999 to 2004, was investigated by means of gas chromatography coupled with mass spectrometry. The sampling site corresponded to a point downstream from Monzón, a heavily industrialized town with drainage into the river. This river has historically been a source of emissions of DDT and its metabolites. The highest levels were found in 1999 and 2000, although the concentrations of organic compounds in sediments and fish have decreased since then. The levels of DDT in water were below the quantification limit during the period of study. The average composition of DDT isomers measured in sediments and fish showed the prevalence of p,p'-DDE, the product of aerobic degradation of p,p'-DDT. Concentrations in fish were compared with sediment samples, and high quotients indicate that they are highly bioavailable.     

Ecological risk assessment for aquatic species exposed to contaminants in Keelung River, Taiwan

An ecological risk assessment was conducted for Keelung River in northern Taiwan. The objective of this study was to assess the risk to fish, aquatic insects, and benthic macroinvertebrates associated with chemical-of-potential-concern (COPC) in the river and to rank ecological risk for these chemicals. The protection of at least 95% of the species 90% of the time from acute and chronic COPC exposures was the defined assessment endpoint. Nine inorganic and organic contaminants were selected to evaluate the impact to aquatic community in the Keelung River. The quotient method served as screen level estimation of risk. The Aquatic Ecological Risk Assessment model was used to analyze exposure and ecological effects and to estimate community level risk. The logarithmic regression model between probability and lethal concentration was established. The combined risks of multiple chemicals were evaluated under assumption of additive risk. The results indicated that zinc and copper pose higher risk among metals. Ammonia, copper, and zinc posed virtually all of the risk, while organic COPCs posed a negligible risk. Potential ecological risk from ammonia exposure was greatest. The probability of more than 5% of the species being affected by acute or chronic toxicity of COPCs is about 100%. In average (50% of the time), 99% of the species would be affected by acute toxicity of COPCs, and about all the species would be affected by chronic toxicity of COPCs. Uncertainties in this assessment were associated with variability in ecosystem stressors, exposure data, ecological effect data, and risk characterization.     

Ex situ remediation of contaminated sediments using mineral additives: assessment of pollutant bioavailability with the Microtox solid phase test

The aim of this work is to assess the potential ecotoxicological effects of contaminated sediments treated with mineral additives. The Microtox solid phase test was used to evaluate the effect of mineral additives on the toxicity of sediment suspensions. Four Mediterranean port sediments were studied after dredging and bioremediation: Sample A from navy harbor, sample B from commercial port and samples C and D from pleasure ports. Sediment samples were stabilized with three mineral additives: hematite, zero-valent iron and zeolite. Results show that all studied mineral additives can act as stabilizer agent in highly contaminated sediments (A and C) by decreasing dissolved metal concentrations and sediment toxicity level. On the contrary, for the less contaminated samples (B and D) hematite and zeolite can provoke toxic effect towards Vibrio fischeri since additive particles can favor bacteria retention and decrease bioluminescence emission.     

Microtox testing of pentachlorophenol in soil extracts and quantification by capillary electrochromatography (CEC)--a rapid screening approach for contaminated land

An approach to rapid soil testing which involved the use of simple solvent extraction methods was developed. The analytes of interest were priority pollutants of low water solubility which could not be readily removed from the soil using water. Direct toxicity testing of the soil samples by Microtox showed a high background toxicity which prevented realistic toxicity data from being obtained for the contaminants present. A range of different extraction solutions was used in an attempt to extract the contaminants while eliminating the matrix effects of the soil. It was necessary that the solvents selected for extraction of the soil samples were not of significant toxicity, as this could potentially mask the toxic effects of any compounds extracted from the soil. The extraction efficiencies of solvent systems were evaluated using pentachlorophenol (PCP) as a model compound of known toxicity in the Microtox assay. A rapid and cost-effective method was developed in order to determine the amount of PCP recovered from the soil by the extraction solvents employed. This method consisted of a solid phase extraction (SPE) step followed by quantification using capillary electrochromatography (CEC). Recoveries were greater when a higher proportion of organic solvent (methanol) was used in the extraction process, and lowest when water was used. An extraction based on water could provide information on the potential for leaching of contaminants from the soil into nearby water bodies in an environmental setting. An organic solvent extraction method could indicate how much toxicity soil-dependent organisms might be exposed to through ingestion. Extraction based on 50% (v/v) methanol in water was considered to be the most suitable overall extraction solution for soil screening, given that this permitted extraction of the water-insoluble compound PCP at a level which was clearly toxic in the Microtox assay while also retaining the capability to extract water-soluble contaminants.     

Characterization of heavy metal concentrations in the sediments of three freshwater rivers in Huludao City, Northeast China

Wuli River, Cishan River, and Lianshan River are three freshwater rivers flowing through Huludao City, in a region of northeast China strongly affected by industrialization. Contamination assessment has never been conducted in a comprehensive way. For the first time, the contamination of three rivers impacted by different sources in the same city was compared. This work investigated the distribution and sources of Hg, Pb, Cd, Zn and Cu in the surface sediments of Wuli River, Cishan River, and Lianshan River, and assessed heavy metal toxicity risk with the application of two different sets of Sediment Quality Guideline (SQG) indices (effect range low/effect range median values, ERL/ERM; and threshold effect level/probable effect level, TEL/PEL). Furthermore, this study used a toxic unit approach to compare and gauge the individual and combined metal contamination for Hg, Pb, Cd, Zn and Cu. Results showed that Hg contamination in the sediments of Wuli River originated from previous sediment contamination of the chlor-alkali producing industry, and Pb, Cd, Zn and Cu contamination was mainly derived from atmospheric deposition and unknown small pollution sources. Heavy metal contamination to Cishan River sediments was mainly derived from Huludao Zinc Plant, while atmospheric deposition, sewage wastewater and unknown small pollution were the primary sources for Lianshan River. The potential acute toxicity in sediment of Wuli River may be primarily due to Hg contamination. Hg is the major toxicity contributor, accounting for 53.3-93.2%, 7.9-54.9% to total toxicity in Wuli River and Lianshan River, respectively, followed by Cd. In Cishan River, Cd is the major sediment toxicity contributor, however, accounting for 63.2-66.9% of total toxicity.     

Sediment contamination, bioavailability and toxicity of sediments affected by an acute oil spill: Four years after the sinking of the tanker Prestige (2002)

Sediment contamination and three bioassays were used to determine the sediment quality four years after an oil spill (Prestige, 2002): the Microtox test, a 10-day bioassay using the amphipod Ampelisca brevicornis, and a polychaete 10-day toxicity test with the lugworm Arenicola marina. In addition, bioaccumulation of PAHs was examined in the polychaete after 10 days of exposure. The results obtained from the toxicity tests and bioaccumulation analyses were statistically compared to the sediment chemical data, in order to assess the bioavailability of the contaminants, their effects, and their relationship with the oil spill. The sediments studied were from two areas of the Galician Coast (NW Spain): the Bay of Corme-Laxe and the Cíes Island, located in the Atlantic Island National Park. The results point to a decrease in contamination with respect to previous studies and to the disappearance of the acute toxicity four years after the oil spill. However an important bioaccumulation of PAHs was detected in the organisms exposed to sediments from Corme-Laxe, suggesting that despite the recovery of the environmental quality of the area, effects in the biota might be occurring.     

Indirect effect of nutrient accumulation intensified toxicity risk of metals in sediments from urban river network

The levels of metals in sediments of urban river ecosystems are crucial for aquatic environmental health and pollution assessment. Yet little is known about the interaction of nutrients with metals for environmental risks under contamination accumulation. Here, we combined hierarchical cluster, correlation, and principal component analysis with structural equation model (SEM) to investigate the pollution level, source, toxicity risk, and interaction associated with metals and nutrients in the sediments of a river network in a city area of East China. The results showed that the pollution associated with metals in sediments was rated as moderate degree of contamination load and medium-high toxicity risk in the middle and downstream of urban rivers based on contamination factor, pollution load index, and environmental toxicity quotient. The concentration of mercury (Hg) and zinc (Zn) showed a significant correlation with toxic risks, which had more contribution to toxicity than other metals in the study area. Organic nitrogen and organic pollution index showed heavily polluted sediments in south of the study area. Though correlation analysis indicated that nutrients and metals had different input zones from anthropogenic sources in the urban river network, SEM suggested that nutrient accumulation indirectly intensified toxicity risk of metals by 13.6% in sediments. Therefore, we suggested the combined consideration of metal toxicity risk with nutrient accumulation, which may provide a comprehensive understanding to identify sediment pollution.

Toxicity rate of metals in sediments from urban river network indirectly intensified by nutrients accumulation

     

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.     

Passaic river sediment interstitial water phase I toxicity identification evaluation

A suite of tests was conducted to evaluate and identify the cause or causes of toxicity in Passaic River sediments. Sediment toxicity was measured with three types of bioassays: a whole sediment bioassay with the marine amphipod, Ampelisca abdita, and interstitial water bioassays with A. abdita and the bioluminescent bacterium Vibrio fisheri (Microtox((R))). In addition, a Phase I Toxicity Identification Evaluation (TIE) was conducted to elucidate the cause of observed toxicity. Analytical concentrations of selected residues in whole sediment and interstitial water from the five sampling stations were considered in conjunction with the conclusions drawn from the toxicity tests and Phase I TIE results. Finally, a toxic units approach was used to evaluate the predicted toxicity of measured interstitial water residue concentrations. There was a lack of toxic response in the short-term interstitial water bioassays, indicating that oxidants, soluble forms of metals, and dissolved phase neutral organics were not likely toxicants. However, there was significant toxicity indicated by the whole sediment A. abidita bioassays. After 10 days, there was complete or near complete mortality in amphipods exposed to all of the sediment samples tested. Removal of interstitial water toxicity by filtration was common to all four stations that exhibited measurable initial toxicity. The observed toxicity characteristics are consistent with particle associated neutral organics. This conclusion is supported by toxicity removal via filtration, lack of toxicity in the Microtox((R)) assays, and the fact that whole sediments were more toxic than was interstitial water.     

Toxicological characterization of sediments from Baie des Anglais on the St. Lawrence Estuary.

The sediments of Baie des Anglais on the St. Lawrence Estuary have a history of environmental contamination, but no information exists relating to their toxicity. The purpose of the present study was to characterize three sites in and near Baie des Anglais, in terms of sediment toxicity and contaminants. Sites 1 and 2 within the Baie des Anglais are relatively close to local industry and municipal sewage discharge points, while Site 3 is outside the bay. Three microscale bioassays, Microtox, echinoderm fertilization and Toxi-ChromoPad, showed that sediments from Site 1 were the most toxic, followed by Site 2. Site 3 was non-toxic. While the solid phase Microtox test did indicate that Site 1 was most toxic, the absolute response was weak. Liver cytochrome P450 1A1 mRNA in American plaice (Hippoglossoides platessoides), captured at Site 1 in the bay was significantly induced compared to the P450 system of plaice captured at Sites 2 and 3. Hepatic metallothionein mRNA levels were not significantly different between plaice captured at all three sites. Sediment chemical analyses revealed a gradient in polycyclic aromatic hydrocarbons, polychlorinated biphenyls and dibenzofurans (PCDF) with the highest levels recorded at Site 1, about 10-fold less at Site 2 and 100-fold less at Site 3. Amongst the organochlorines the PCDF group were deemed the most important due to their prevalence and known toxicity. Heavy metal concentrations were low and representative of background levels for the St. Lawrence Estuary.     

A concurrent neuro-fuzzy inference system for screening the ecological risk in rivers

Purpose  

A conceptual model to assess water quality in river basins was developed here. The model was based on ecological risk assessment principles, and incorporated a novel ranking and scoring system, based on self-organizing maps, to account for the likely ecological hazards posed by the presence of chemical substances in freshwater. This approach was used to study the chemical pollution in the Ebro River basin (Spain), whose currently applied environmental indices must be revised in terms of scientific accuracy.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Total mercury concentrations in an industrialized catchment,the Thur River basin (north-eastern France): geochemical background level and contamination factors

River bottom sediments and soils were collected from the industrialized Thur River basin (north-eastern France) to assess mercury contamination. The regional geochemical background level of total mercury was evaluated to calculate mercury contamination factors (Fc) in soils and river bottom sediments. Our estimate of the mean background mercury levels in river sediments and soils, not affected by human activities, was 232 ng x g(-1) (range: 27-406 ng x g(-1)). Sediments contaminated by the effluent from a chlor-alkali plant yielded the highest contamination factors (Fc=1784). Contamination factors of surficial soils within 1 km of the industrial site range from 6.3 to 43.6. This contamination is attributed to diffuse atmospheric deposition from this local plant. However, even upstream from this industrial area elevated contamination factors were recorded for river bottom sediments (Fc=3.2 to 26.4) and for one alluvial soil profile (Fc=10). This is possibly due to past pollution resulting from waste water discharges. Mercury contamination in the different horizons of alluvial soils is not correlated with soil organic carbon content, but may be the result of occasional accidental pollution arising from the introduction of contaminated suspended particulate matter by the Thur River during periods of flooding.     

The use of Microtox to assess toxicity removal of industrial effluents from the industrial district of Camaçari (BA, Brazil)

The treatment efficiency, as toxicity removal, of complex effluents from the Industrial District of Cama?ari (BA, Brazil), after biological treatment with activated sludge was evaluated using Microtox. Samples of the equalised effluent (EE) were collected prior to treatment together with samples of the treated effluent (TE), which remained 24 h in the treatment plant. Rehydrated colonies of Vibrio fischeri were exposed to sequential dilutions of EE and TE to assess luminosity interference. Values for EC50 were calculated, together with the respective toxicity units. In all, twenty assays of each effluent type were carried out and the mean toxicity removal was 92.71%, while the chemical oxygen demand (COD) presented mean reduction of 83.04%. There was a variability of an order of magnitude between the Microtox results for the two types of effluents. The mean EC50 values were 2.12 for EE and 47.78% for TE. In spite of its weakness in some conditions, the Microtox system demonstrated to work adequately in assessing effluent toxicity removal in this treatment plant and therefore can be used for further toxicity removal programs.