工业废水毒性评估方法与应用研究进展

针对中国缺乏规范的工业废水毒性评估体系的现状，系统归纳了国外在毒性检测、毒性评价标准与方法方面的成功经验。在明确了工业废水急性毒性检测的重要性基础上，重点分析了美国全废水毒性测试法（WET）及其在工业废水评价中的应用；并结合对毒性评价标准的阐述，系统总结了发展较成熟的毒性鉴别评价法（TIE）和效应导向分析法（EDA）的流程与应用实例，以期为中国工业废水毒性检测评估和监管提供参考。     

Necessity of Toxicity Assessment in Turkish Industrial Discharges (Examples from Metal and Textile Industry Effluents)

Toxicity of some organic and inorganic chemicals to microorganisms is an important consideration in assessingtheir environmental impact against their economic benefits.Microorganisms play an important role in several environmentalprocesses, both natural and engineered. Some organic and inorganics at toxic levels have been detected in industrial discharges resulting in plant upsets and discharge permit violations. In addition to this, even though in some cases the effluent wastewater does not exceed the discharge limits,the results of toxicity tests show potential toxicity. Toxicityknowledge of effluents can benefit treatment plant operators inoptimising plant operation, setting pre-treatment standards, and protecting receiving water quality and in establishing sewer discharge permits to safeguard the plant. In the Turkish regulations only toxicity dilution factor (TDF) with fish is part of the toxicity monitoring program of permissible wastewater discharge. In various countries, laboratory studiesinvolving the use of different organisms and protocol for toxicity assessment was conducted involving a number of discharges.In this study, it was aimed to investigate the acute toxicity of textile and metal industry wastewaters by traditional and enrichment toxicity tests and emphasize the importance of toxicity tests in wastewater discharge regulations. The enrichment toxicity tests are novel applications and give anidea whether there is potential toxicity or growth limiting and stimulation conditions. Different organisms were used suchas bacteria (Floc and Coliform bacteria) algae (Chlorella sp.), fish (Lepistes sp.) and protozoan (Vorticella sp.) to represent four tropic levels. The textile industry results showed acute toxicity for at least one organism in 8 out of 23 effluent samples. Acute toxicity for at least two organisms in 7 out of 23 effluent sampling was observed for the metal industry. The toxicity test results were assessed with chemical analyses such as COD, BOD, color and heavy metals. It was observed that the toxicity of the effluents could not be explained by using physicochemical analyses in 5 cases for metal and 4 cases for the textile industries. The results clearly showed that the useof bioassay tests produce additional information about the toxicity potential of industrial discharges and effluents.     

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.     

Heavy metal contamination from mining sites in South Morocco: Monitoring metal content and toxicity of soil runoff and groundwater

The aim of the present work is the assessment of metal toxicity in runoff, in their contaminated soils and in the groundwater sampled from two mining areas in the region of Marrakech using a microbial bioassay MetPLATE™. This bioassay is based on the specific inhibition of the β-galactosidase enzyme of a mutant strain of Escherichia coli, by the metallic pollutants. The stream waters from all sampling stations in the two mines were all very toxic and displayed percent enzyme inhibition exceeding 87% except SWA₄ and SWB₁ stations in mine C. Their high concentrations of copper (Cu) and zinc (Zn) confirm the acute toxicity shown by MetPLATE. The pH of stream waters from mine B and C varied between 2.1 and 6.2 and was probably responsible for metal mobilization, suggesting a problem of acid mine drainage in these mining areas. The bioassay MetPLATE™ was also applied to mine tailings and to soils contaminated by the acidic waters. The results show that the high toxicity of these soils and tailings was mainly due to the relatively concentration of soluble Zn and Cu. The use of MetPLATE™ in groundwater toxicity testing shows that, most of the samples exhibited low metal toxicity (2.7–45.5% inhibition) except GW3 of the mine B (95.3% inhibition during the wet season and 82.9% inhibition during the dry season). This high toxicity is attributed to the higher than usual concentrations of Cu (189 μg Cu l⁻¹) and Zn (1505 μg Zn l⁻¹). These results show the potential risk of the contamination of different ecosystems situated to the vicinity of these two metalliferous sites. The general trend observed was an increase in metal toxicity measured by the MetPLATE with increasing total and mobile metal concentrations in the studied matrices. Therefore, the MetPLATE bioassay is a reliable and fast bioassay to estimate the metals toxicity in the aquatic and solids samples.     

Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO₂) to earthworms (Eisenia fetida)

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.     

A novel approach to rapid detection of acute water toxicity and its policy implications for grassroots sustainable environmental monitoring

Unknown chemicals, emerging contaminants, and the resulting reactions among them make early detection and warning of acute water toxicity extremely challenging. The conventional approach using small fish for toxicity monitoring normally requires a designated species of fish and over a week's time to complete, including dilution of the wastewater, a pre-test, and a full test. It often increases chances for error and delays emergency management. This paper reports a novel approach, based on grassroots knowledge and field and lab experience in Jilin, China. This approach uses a combination of different species of aquarium fish to achieve fast and reliable monitoring. It tests the original source water directly without going through the dilution procedure, while paying attention to the time factor. The approach does not require a pre-test and may shorten the time needed for detecting acute toxicity to a few minutes, using a new classification of aquatic toxicity levels. It is inexpensive to use and may be easily adopted by grassroots organizations. The approach is "greener" and more financially and socially sustainable than traditional approaches. The wide use of the approach has the potential to encourage policy innovations for making toxicity monitoring grassroots based and more effective in reducing acute contamination emergencies.     

Application of a toxicity test battery integrated index for a first screening of the ecotoxicological threat posed by ports and harbors in the southern Adriatic Sea (Italy)

Ports and harbors may represent a threat for coastal ecosystems due to pollutant inputs, especially those derived from maritime activities. In this study, we report a first assessment of the ecotoxicological threat posed by six ports and harbors of opposite coastal regions, Apulia and Albania, in the southern Adriatic Sea (Italy). A bioassay battery consisting of four different species representing different trophic levels, algae Dunaliella tertiolecta, bacteria Vibrio fischeri, crustacean Artemia salina, and echinoids Paracentrotus lividus, has been used to assess sediment elutriates, pore waters, and sediment suspensions. Two different approaches of toxicity data integration, worst case and integrated index, have been used to determine the most appropriate procedure for the investigated sites. All sites with the worst case approach showed high toxicity levels. The chronic test with algae was the most sensitive identifying the highest effects in the battery. This effect can be attributable to contaminants derived from antifouling paints. The sediments, evaluated with V. fischeri test, often showed toxicity not found in the aqueous matrices of the same sites and that can be mainly linked to organic compounds. The test battery used in this study allowed us to perform a preliminary screening of the ecotoxicological risk of the studied area. In fact, the species utilized for toxicity tests responded differently to the investigated samples, showing different sensitivity. The test battery integrated index did not allow highlighting the differences among the sites and showed a general high ecotoxicological risk. A larger number of tests with higher sensitivity together with a tailored attribution of weights to endpoints and matrices will improve the final site evaluation.     

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.     

Toxicity Assessment of Treated Wastewater Using Cultured Human Cell Lines

Bioassay using cultured human cell lines was applied to an effluent of a wastewater treatment plant (WWTP) in Sapporo to assess their toxicity, and in order to investigate the fate of toxicity in the WWTP, bioassay of the water samples from several points in WWTP (influent, effluent, return flow from thickener, from dewatering process and from incineration process) was performed. We also applied bioassay to the mixture of the activated sludge from the investigated plant and artificial sewage. These results showed that the toxicity of the effluent was more intensive than the influent, and organic matter released from activated sludge bacteria during their decay process contributed to the increase of toxicity in the effluent.     

Comparative Toxicological Evaluation of Untreated and Treated Tannery Effluent with Nostoc Muscorum L. (Algal Assay) and Microtox Bioassay

The relative sensitivity of tannery effluent before and after treatment was compared by employing Nostoc muscorum and microtox assay in laboratory. The effect on chlorophyll, protein and biomass content of Nostoc muscorum was studied with the luminescent property inhibition of Photobacterium phosphorium and compared with algal bioassay. The results of microtox assay after 5, 15 and 30 min of exposure were compared with data obtained from algal bioassay. It was observed that the luminescent property of Photobacterium phosphorium in microtox assay as well as the chlorophyll content of Nostoc muscorum in algal assay were the most sensitive parameters in toxicity evaluation of tannery effluent. The microtox assay produced notably comparable EC50 values with that of algal bioassay. The microtox assay of toxicity showed that EC50 (%) in 30 min was 3.19 and 63.49 for untreated and treated tannery effluent, respectively while in algal bioassay the EC50 for chlorophyll was in between 0-2.5% and 100%, respectively, in untreated and treated effluent. More than 60% reduction of toxicity was noted in treated tannery effluent in both test system.     

Ecotoxicity monitoring of hydrocarbon-contaminated soil using earthworm (Eisenia foetida)

In order to assess the applicability of an earthworm bioassayas a technique for monitoring the soil flushing process, short-term and long-term toxicity tests were conducted on remediatedsoil using various pore volumes of surfactant solution. Resultsobtained on short-term toxicity testing indicated that biomassincreased as the soil flushing proceeded, and on diesel-contaminated soils this testing showed that the effect of dieselis lethal and that 25 pore volumes of soil surfactant were notsufficient to abrogate the toxic effect of diesel. These short-term tests also showed strong sublethal relationships between the development of biomass, and the concentrations of toxic chemicals in the soil. Although relationships between contaminants and the various bioassay parameters examined werenot significant in long-term testing, an increase in the numberof juveniles was observed over time, which may have been a consequence of a reduction in toxicity associated with the flushing process.     

焦化废水生化处理过程中溶解性有机物及毒性变化规律

焦化废水中的溶解性有机物(DOM)作为废水污染物和毒性的主要来源受到广泛关注。厌氧-缺氧-好氧(A-A-O)生物法联合混凝沉淀工艺在焦化废水处理中被广泛应用。于2018年4,7和11月分别采集4座焦化废水处理厂废水,采用光谱学分析手段和水生生物急性毒性试验对A-A-O联合混凝沉淀处理过程中焦化废水的DOM和毒性变化进行分析。结果表明,焦化废水中含有大量不饱和芳香性物质,其中类色氨酸、络氨酸物质占主导,其次为类溶解性微生物代谢产物、类富里酸物质和类腐殖酸类物质;未经处理的焦化废水对藻类和大型溞的急性毒性等级为中毒至高毒。A-A-O联合混凝沉淀处理可去除90%以上的类色氨酸、络氨酸和类富里酸物质,但对类腐殖酸类物质去除率相对较低,仅为约80%,关键去除段为缺氧段和好氧段;该工艺对焦化废水急性毒性削减率为80.51%~94.30%,关键削减段为厌氧段。Pearson相关性分析结果显示,焦化废水溶解性总有机碳(TOC)、类腐殖酸类物质荧光组分C1和类富里酸类物质荧光组分C4与废水急性毒性存在显著正相关关系,可利用其作为水样急性毒性初筛的指示性指标。可为焦化废水生化处理的效能优化和废水毒性控制及安全评估提供科学支撑。     

Water chemistry influences the toxicity of silver to the green-lipped mussel Perna viridis

The study determined the influence and relative importance of water chemistry parameters (pH, alkalinity, hardness) on the acute toxicity of silver to the green mussel Perna viridis. A preliminary bioassay revealed that 4 mg L^???1 of silver caused 50% mortality (LC₅₀) in 96 h for mussels placed in seawater with pH 8.5, hardness 1,872 mg L^???1, and alkalinity 172 mg L^???1. Mortality of mussels increased with decreasing pH and increasing hardness and alkalinity variables. In contrast the mortality decreased with increasing pH and decreasing hardness and alkalinity values. The water chemistry also affected the concentration of sliver in experimental seawater and bioaccumulation of silver in mussels. The results revealed that the chemical properties of seawater must be considered while conducting toxicity tests with metals like silver. The possible explanations for the influence of water chemistry on silver toxicity to P. viridis are discussed.     

Selecting indicator species to monitor ecological integrity: a review

We review critical issues that must be considered when selectingindicator species for a monitoring program that aims to maintainor restore ecological integrity. First, we examine the pros andcons of different management approaches on which a conservationprogram can be based and conclude that ecosystem management ismost appropriate. We then identify potential indicators ofecological integrity at various levels of the ecosystem, with aparticular emphasis on the species level. We conclude that,although the use of indicator species remains contentious, it canbe useful if (1) many species representing various taxa and lifehistories are included in the monitoring program, (2) theirselection is primarily based on a sound quantitative databasefrom the focal region, and (3) caution is applied wheninterpreting their population trends to distinguish actualsignals from variations that may be unrelated to thedeterioration of ecological integrity. Finally, we present anddiscuss different methods that have been used to select indicatorspecies.     

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.     

An Integrated Approach for Impact Assessment of Water Harvesting Techniques in Dry Areas: The Case of Oued Oum Zessar Watershed (Tunisia)

In the arid regions of Tunisia, considerable investments are being made to maintain the old water harvesting techniques and introduce new ones to capture the scarce amount of rainwater (100 mm to 230 mm annually) for agricultural and domestic purposes. However, no detailed assessment of the multiple effects and the costs and benefits of these techniques have been made so far. This paper summarizes the results of an in depth investigation of the multiple impacts (runoff mobilization, ground water recharge, agro-socio-economic impacts) of the water harvesting works undertaken in the watershed of oued Oum Zessar (southeastern Tunisia). The importance of interdisciplinary and integrated approaches was revealed through this detailed impact assessment and economic evaluation. In fact, the profitability of the water harvesting works depends largely on the criteria chosen. However, further refinements are needed to better include all possible impacts (positive and negative) that occur as a result of the installation of the water harvesting structures.     

Sensitivity of isolated eggs of pond snails: a new method for toxicity assays and risk assessment

The concentration of heavy metals in the environment is normally low. We here address whether using the development of isolated pond snail Radix auricularia eggs would provide a more sensitive endpoint and whether the gelatinous matrix of the egg mass surrounding the eggs indeed protects the snail embryos. In the present study, artificial removal of the gelatinous matrix of egg masses greatly increased the sensitivity of developing eggs to a heavy metal (cadmium). The sensitivity of isolated eggs to cadmium was determined using several convenient endpoints, including mortality, hatching rate, and heart rate, with an acute toxicity test and a subchronic test. In the acute toxicity test, a 96-h LC₅₀ value of 58.26 μg/L cadmium was determined. In the subchronic toxicity test, sublethal effects in terms of a significant reduction in hatching rate could be found in the 25-μg/L treatment, and a significant decrease of heart rate was observed in both treatments (5 and 25 μg/L). The high sensitivity of isolated eggs indicates that such tests can be efficient for toxicity assays and risk assessment, although one needs to keep in mind that the ecologically relevant measure of toxicity will be how eggs are affected when they are still inside the egg mass.     

水样发光细菌急性毒性测试的方式与表征

选取不同类型的环境和污染源水样开展了发光细菌毒性测试,针对不同环境管理目标,探讨了急性毒性定量表征方式。发光细菌急性毒性测试在环境应急监测、水源早期生物预警中,采用绘制毒性预警基线图的方式比较可行。在污染源监督监测中,对于发光抑制率低于60%、无法求出EC50的样品,采用等效毒性参照物的质量浓度表征废水的毒性;对于发光抑制率高于60%,采用稀释因子表示样品的毒性更直观可靠。