水体沉积物毒性鉴别与评价研究进展

综述了水体沉积物毒性鉴别与评价的主流方法以及研究进展,指出毒性测试和致毒因子鉴别方法是限制水体沉积物污染生态风险评价的关键因素,认为发展和应用以生物标记物和生物效应为导向,尤其是各种具有污染专一性指示作用的生物效应标志测试方法的建立和应用,并结合具有选择性的样品分级技术和先进的仪器进行定性定量分析,将是以生物效应为导向、以化学分析为基础的复杂水体沉积物毒性鉴别与评价的重要发展方向.     

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.     

Microscale Toxicity Identification Evaluation (TIE) for interstitial water of estuarine sediments affected by multiple sources of pollution

Estuaries in the world are affected by different contamination sources related to urbanisation and port/industrial activities. Identifying the substances responsible for the environmental toxicity in estuaries is challenging due to the multitude of stressors, both natural and anthropogenic. The Toxicity Identification and Evaluation (TIE) is a suitable way of determining causes of toxicity of sediments, but it poses difficulties since its application is labour intensive and time consuming. The aim of this study is to evaluate the diagnosis provided by a TIE based on microscale embryotoxicity tests with interstitial water (IW) to identify toxicants in estuarine sediments affected by multiple stressors. TIE showed toxicity due to different combinations of metals, apolar organic compounds, ammonia and sulphides, depending on the contamination source closest to the sampling station. The microscale TIE was able to discern different toxicants on sites subject to different contamination sources. There is good agreement between the results indicated in the TIE and the chemical analyses in whole sediment, although there are some disagreements, either due to the sensitivity of the test used, or due to the particularities of the use of interstitial water to assess the sediment toxicity. The improvement of TIE methods focused on identifying toxicants in multiple-stressed estuarine areas are crucial to discern contamination sources and subsidise management strategies.

     

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.     

Effects of two diluents in the Microtox toxicity bioassay with marine sediments

This paper compares the use of two different diluents, EPA synthetic seawater (salinity 31 per thousand ) and NaCl standard diluent (salinity 35 per thousand ), in the Microtox toxicity bioassay performed on elutriate and solid phase derived from marine sediments. The study was performed comparing three series of data obtained by the use of the two diluents.In the first series the intensity of the natural light output of Vibrio fischeri was considered; in the second series pH value, sulphite and ammonia present in the control and in the diluent after the treatment with the sediment samples; in the last series, the measured toxicity in marine sediments was considered. The light output intensity measured with respect to time, gives information about the bacterial activity due to the different osmotic conditions. pH values joint with ammonia and sulphite content, give information about the effect of the bacterial metabolic activities and of the different interaction between each diluent with the sediment sample. At last, the comparison of the two diluents on real samples show how the different osmotic and hydrogenionic conditions determine different toxicity responses. The results show that the EPA diluent allows more suitable environment for the metabolic activities of bacteria depending on lower stressing conditions than those present when the standard diluent is used. Moreover, the use of EPA diluent reduces the risk of false positive response in the execution of the toxicity bioassay.     

Potential impacts of water injection dredging on water quality and ecotoxicity in Limehouse Basin, River Thames, SE England, UK

The use of water injection dredging (WID) is increasing in the UK's inland waterways and marinas. Jets of water are injected under low pressure directly into bottom sediment creating a turbulent water-sediment mixture that flows under the influence of gravity. Many of these sediments are highly contaminated and little is known of the effects of contaminant release on water quality or the risk to biota living in both the sediment and the water column. Sediment cores were collected from Limehouse Basin, a proposed WID site in SE England and current sediment toxicity was assessed using a number of techniques. Comparison of metal data to US sediment quality guidelines indicated intermediate levels of toxicity while, calculation of acid volatile sulphide to simultaneously extracted metal ratios underestimated the potential toxicity to sediment dwelling organisms. In contrast, porewater ammonia concentrations were in excess of all published ecotoxicological guidelines and indicate serious risk to biota. Re-suspension experiments were used to mimic the effects of WID on overlying water quality and ecotoxicity tests were carried out on elutriates using Daphnia magna to examine the impacts on biota. Concentrations of a range of metals in the elutriates predict that adverse biological effects would be observed during WID, however only 10% of the elutriate samples caused an adverse effect on Daphnia. Limehouse Basin is a complex aquatic environment receiving predominantly fresh waters while the sediments have high porewater chloride concentrations reminiscent of previous tidal inputs to the basin, making the choice of test organism problematic.     

Geochemistry and toxicity of sediment porewater in a salt-impacted urban stormwater detention pond

A comprehensive study was carried out to investigate the impacts of road salts on the benthic compartment of a small urban detention facility, Rouge River Pond. Although the pond is an engineered water body, it is representative of many small urban lakes, ponds and wetlands, which receive road runoff and are probable high impact areas. Specific objectives of the study were to document the porewater chemistry of an aquatic system affected by elevated salt concentrations and to carry out a toxicological assessment of sediment porewater to determine what factors may cause porewater toxicity. The results indicate that the sediment porewater may itself attain high salt concentrations. The computations show that increased chloride levels have important implications on the Cd complexation, augmenting its concentration in porewater. The toxicity tests suggest that the toxicity in porewater is caused by metals or other toxic chemicals, rather than high levels of chloride.     

Effect of sediment turbidity and color on light output measurement for Microtox Basic Solid-Phase Test

In this work, sediment samples collected from several Spanish harbours were tested with two toxicity procedures, designed for solid samples: the Microtox Basic Solid-Phase Test (BSPT) and a modified procedure of the previous test protocol (mBSPT). According to the BSPT procedure, after initial light readings, pure bacteria were exposed to sediment suspension dilutions and light production was directly measured on suspended sediments without any further manipulation. As measurements are likely to be affected by sediment turbidity and color, a variation in initial light measurement has been here suggested, in order to consider the sample effect at all time readings during the test. Firstly, when sediment suspensions at different concentrations were added to bacteria suspension, immediately the initial light output drastically decayed by more than 50% in signal difference, resulting in a false inhibition, as effect of sample turbidity/color. This effect was more evident at high EC50 values, when slightly or not toxic samples were assessed. Secondly, the comparison of the EC50 obtained with both procedures, demonstrated that the mBSPT produced higher EC50 values (less toxic) than those obtained with the standard procedure. The mBSPT procedure resulted rapid and effective and it could be applied simultaneously with BSPT, in order to better evaluate the toxicity.     

城市综合污水处理厂污泥对Daphnia magna 的急性毒性与毒物特征

以城市综合污水处理厂污泥的浸提液对Daphnia magna的24h急性毒性为指标，研究了污泥放置时间与其毒性的关系。结果表明，污泥对Daphnia magna的急性毒性随旋转时间的增加逐渐增大，但在旋转两个月后毒性趋于稳定。对放置3d和84d的污泥，利用TIE（毒性鉴别评价）方法对其浸提液进行了毒物特性鉴别，结果表明，放置3d的污泥，浸提液毒性主要由酸性条件下易挥发的物质引起，放置84d的污泥浸提液中的毒物主要为金属离子和易与酸碱反应的物质。     

Application of the simplified toxicity identification evaluation procedures to a chemical works effluent

Toxicity of a Chemical Works effluent from the Southeast China to the Daphnia magna was compared to determine the most representative aqueous fraction for simplified toxicity identification evaluation (TIE) studies. Toxicity characterization procedures revealed that the primary toxicant(s) was a nonpolar organic compound. Toxicity was recovered through C₁₈ solid-Phase extraction and concentration steps. Gas chromatography-mass spectroscopy of these concentrates revealed the presence of chlorobenzene, nitrobenzene, naphthalene, 1-chloro-3-nitrobenzene, 1-chloro-4-nitrobenzene, 2-naphthol and aniline. The mass balance approach of TIE implicated the seven chemicals as the primary toxicants. The simplified TIE procedures can save our cost and time. The significance of the TIE results may indicate a more widespread problem what chemical(s) has priority to be controlled when being discharged.     

Urease inhibition: a tool for toxicity identification in sediment elutriates

A method for the detection and confirmation of heavy metal toxicants in sediment elutriates based on a urease inhibition assay, ICP-AES analysis and EDTA chelation in the frame of toxicity identification evaluation (TIE) is presented. Zinc was identified as the major toxicant in pHstat elutriates of sediments of the river Saale (Germany). Implications of natural and anthropogenic chelating agents, which are frequently present in environmental samples, on toxicity confirmation of heavy metals based on the toxic unit approach are discussed.     

Dioxin-like potencies and extractable organohalogens (EOX) in medical, municipal and domestic waste incinerator ashes in Japan

Ash samples collected from medical, municipal and small-scale domestic incinerators in Japan were tested for dioxin-like activity using bioassay technique (ethoxyresorufin-O-deethylase: EROD assay) and for extractable organohalogens (EOX) using instrumental neutron activation analysis in order to estimate potential toxicity and responsible chemicals in those samples. Crude extracts and fractions cleaned-up for dioxin analysis from the samples were used for the analysis. The ranges of dioxins in the ashes were between 2.23 and 12.29 ng TEQ/g (dry weight). Relative potency ranges estimated by EROD assay in the medical incinerator ashes were 3.8-17.6 times higher than the results of conventional chemical analysis. EOX analysis suggested that ash samples contained plenty of organochlorine compounds apart from chlorinated dioxins. In addition, medical waste incinerator ashes were considered to have relatively higher amount of organoiodine compounds. In the cleaned-up fractions, bioassay potency ranges were lower than those in the crude extracts. However, some samples still exhibited higher potency than expected from chemical analysis. Though some polycyclic aromatic hydrocarbons were found in the fractions, the amounts were relatively low (0.39-10.56 ng/g). The results imply that some bioactive organohalogens that cannot be detected in the conventional chemical analysis might have potential for dioxin-like toxicity, and contribute to higher bioassay activities. The combination of the chemical analysis with the bioassay and EOX provides rough figure of dioxin-like toxicity and suggests types of organohalogen compounds that should be identified as a part of dioxin analysis for control emission from an incineration plant.     

Comparison of test procedures for sediment toxicity evaluation with Vibrio fischeri bacteria

The use of bacterial luminescence assays is particularly effective in the contaminated sediment evaluation. In the present study, a comparison was made of different baterial luminescence assays including acute toxicity of elutriates with Microtox® and LUMIStox®; chronic toxicity of elutriates with LUMIStox®; and, acute toxicity of solvent extracts with both the tests and the Solid Phase test with Microtox. The toxicity assay procedures were utilised for the Po River sediment toxicity evaluation, testing samples with different physical and chemical characteristics. The results evidentiated that each sediment test procedures provided indipendent and complementary ecotoxicological responces usefull for a sediment classification of the most polluted samples.     

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

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

Environmental toxicity assessment in the Paraná river delta (Argentina): simultaneous evaluation of selected pollutants and mortality rates of Corbicula fluminea (Bivalvia) early juveniles

Water and sediment samples were collected in the lower Paraná delta at four sites with different levels of exposure to pollution to evaluate the anthropogenic impact through chemical analyses and mortality bioassays. Individual polychlorinated biphenyls, chlorinated pesticides, aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, and heavy metals were measured in waters, porewaters and sediments. The same three phases were also subjected to toxicity assays with straight-hinged juveniles of Corbicula fluminea. Concentrations of several pollutants were above levels recommended for the protection of aquatic life: in waters, Zn, Cu and Cr were 1.6-4.9 times higher, whereas in the sediments Cr was 1.8-3.6, and benzo(a)pyrene was 2.8-5.6 times higher. Pollutant concentrations followed a clear geographic pattern with highest values in the densely populated area of the Reconquista and Luján rivers, lower levels in the San Antonio, and lowest loadings in the remote Paraná de las Palmas. This gradient was adequately matched by the pattern of mortality rates of C. fluminea early juveniles, which were highest in the Reconquista-Luján (40-93%) and lowest (and not significantly different from the control) in the Paraná (3.3-23%). Mortality rates also increased from surface waters (3.3-53%), to porewaters (12-73%), to sediments (23-93%). Although toxicity was probably mainly due to dissolved contaminants, agreement between chemical and biological evidence of pollution was best for the sediment compartment, whereas porewater and surface water showed a higher degree of variability.     

In situ bioassay chambers and procedures for assessment of sediment toxicity with Chironomus riparius

The purpose of this study was to develop an in situ sediment bioassay chamber and respective procedures, suitable for performing toxicity bioassays with benthic invertebrates, using the midge Chironomus riparius. It was also our objective to compare the responses obtained under controlled conditions (laboratory 10-day larval growth and survival test) with those obtained in situ. Clean sand and a formulated sediment were incorporated in the in situ bioassay, along with local sediments, as a way of minimizing natural variability due to physicochemical differences among sediments or due to interactions with indigenous organisms. Recovery of organisms was good (80-100% in the control and reference site), indicating that the developed chamber and protocol were suitable for exposing and retrieving C. riparius in situ. Results also showed differences between responses obtained with formulated and natural sediment in situ, as well as between laboratory and in situ.     

Testing sediment biological effects with the freshwater amphipod Hyalella azteca: the gap between laboratory and nature

The freshwater amphipod, Hyalella azteca, is widely used in laboratory sediment toxicity and bioaccumulation tests. However, its responses in the laboratory are probably very different from those in the field. A review of the literature indicates that in its natural habitat this species complex is primarily epibenthic, derives little nutrition from the sediments, and responds primarily to contaminants in the overlying water column (including water and food), not sediment or porewater. In laboratory sediment toxicity tests H. azteca is deprived of natural food sources such as algal communities on or above the sediments, and is subjected to constant light without any cover except that afforded by burial into the sediments. Under these constraining laboratory conditions, H. azteca has been reported to respond to sediment or porewater contamination. In nature, contamination of overlying water from sediment is less likely than in the laboratory because of the large, generally non-static sink of natural surface water. H. azteca does not appear to be the most appropriate test species for direct assessments of the bioavailability and toxicity of sediment contaminants, though it is probably appropriate for testing the toxicity of surface waters. Toxic and non-toxic responses will be highly conservative, though the latter are probably the most persuasive given the exposure constraints. Thus H. azteca is probably a suitable surrogate species for determining sediments that are likely not toxic to field populations; however, it is not suitable for determining sediments that are likely toxic to field populations.     

Evaluation of genotoxicity and toxicity of water and sediment samples from a Brazilian stream influenced by tannery industries

This paper reports results of genotoxicity and toxicity studies of water and sediment samples collected from the Estancia Velha stream of southern Brazil, a stream transporting both domestic sewage and effluents from regional factories working in the leather industry. Three sites were selected: in the stream headwaters (Site 1), located downstream of an urban area (Site 2), and near the basin outfall (Site 3). Results obtained with Allium cepa showed no evidence of chromosomal mutation, either in water or in sediment, during winter or summer seasons, but samples collected below Site 1 showed high toxicity. Physical and chemical analyses showed high concentrations of pollutants at these sites. Ecotoxicity tests with Daphnia magna and Ceriodaphnia dubia measured toxicity in water from Sites 2 and 3 in summer 2004. A toxic effect on Hyalella azteca was only found in sediment from Site 3 during winter 2003 and summer 2004. The results suggest that the synergy among different compounds in domestic and industrial sewage discharges can make it difficult to maintain system stability.     

Characterization of dissolved organic matter in fogwater by excitation–emission matrix fluorescence spectroscopy

Dissolved organic matter (DOM) present in fogwater samples collected in southeastern Louisiana and central-eastern China has been characterized using excitation–emission matrix fluorescence spectroscopy. The goal of the study was to illustrate the utility of fluorescence for obtaining information on the large fraction of organic carbon in fogwaters (typically >40% by weight) that defies characterization in terms of specific chemical compounds without the difficulty inherent in obtaining sufficient fogwater volume to isolate DOM for assessment using other spectroscopic and chemical analyses. Based on the findings of previous studies using other characterization methods, it was anticipated that the unidentified organic carbon fraction would have characteristic peaks associated with humic substances and fluorescent amino acids. Both humic- and protein-like fluorophores were observed in the fogwater spectra and fluorescence-derived indices for the fogwater had similar values to those of soil and sediment porewater. Greater biological character was observed in samples with higher organic carbon concentrations. Fogwaters are shown to contain a mixture of terrestrially- and microbially-derived fluorescent organic material, which is expected to be derived from an array of different sources, such as suspended soil and dust particles, biogenic emissions and organic substances generated by atmospheric processes. The fluorescence results indicate that much of the unidentified organic carbon present in fogwater can be represented by humic-like and biologically-derived substances similar to those present in other aquatic systems, though it should be noted that fluorescent signatures representative of DOM produced by atmospheric processing of organic aerosols may be contributing to or masked by humic-like fluorophores.     

Characterisation of potentially genotoxic compounds in sediments collected from United Kingdom estuaries

The mutagenic activity bioassay Mutatox was used to assess the mutagenic activity associated with sediments collected from five UK estuaries. Assays were performed on extracts of sediment pore water and residual particulate material isolated from sediment samples collected from the rivers Tyne, Tees, Mersey, and Thames as well as Southampton Water. No mutagenic activity was associated with the pore water extracts, however, 7 of the 28 organic solvent extracts of sediment particulate material contained potential genotoxins. By using Mutatox in association with bioassay-directed fractionation, attempts were made to identify the mutagenic compounds present in the extracts. The fractionation procedure used normal phase solid phase extraction, C18 reverse phase HPLC and cyano/amino bonded silica normal phase HPLC. GC-MS (EI and NICI) analysis was used to identify polycyclic aromatic hydrocarbons (PAH), alkyl substituted PAH, nitro-polycyclic aromatic compounds (nitro-PACs), polycyclic aromatic ketones, oxygenated-PACs, and other known mutagens contributing to the genotoxicity measured in the samples. Some potentially genotoxic compounds remain unidentified.