酚类抗氧化剂及其代谢产物对鱼类的毒性研究进展

简述了水环境中合成酚类抗氧化剂(SPAs)及其代谢产物,SPAs对鱼类的急性毒性效应、发育毒性效应及机制、内分泌干扰毒性效应和机制,以及代谢过程和产物毒性预测。指出,为准确实现对SPAs及其代谢物的化学品管理及生态风险评估,未来研究应聚焦于对合成酚类抗氧化剂及其代谢物在水生生物体内的分布及浓度检测,为该类化合物的生物富集和生物转化研究提供更多的背景资料;开展对SPAs潜在毒性分子机制的研究,并建立起分子水平上的毒理学效应与个体乃至种群水平上的不良后果之间的联系;探究并完善SPAs的代谢机制,并对现已明确的代谢产物（如BHT-Q）开展毒性效应评价。     

Monitoring and risk assessment of pesticides in a tropical river of an agricultural watershed in northern Thailand

The increasing application of pesticides in the uplands of northern Thailand has increased the transfer of pesticides to surface water. To assess the risk of pesticide use for stream water quality, we monitored the concentrations of seven pesticides (atrazine, dichlorvos, chlorpyrifos, dimethoate, chlorothalonil, (α-, β-) endosulfan, cypermethrin) frequently used in the Mae Sa watershed (77 km²) in water and sediment samples over a period of one and a half years (2007–2008). All investigated pesticides were recorded in the river. Chlorpyrifos was detected most often in water samples (75 % at the headwater station), while cypermethrin was most often found in riverbed (86 %) and in all suspended sediment samples. The highest concentrations of the pesticides were detected during the rainy season. About 0.002 to 4.1 % by mass of the applied pesticides was lost to surface water. The risk assessment was based on the risk characterization ratio (RCR). The RCRs of dichlorvos in water, (α-, β-) endosulfan, and cypermethrin in water and sediments were higher than unity indicating that they are likely to pose a threat to aquatic ecosystem. Finally, we discuss the role of sampling design on ecotoxicological risk assessment. Our study shows that pesticide contamination of surface waters is an environmental issue in the Mae Sa watershed and that measures need to be undertaken to reduce the loss of pesticides from soil to surface waters.     

Toxicity of a complex mixture of atmospherically transported pesticides to Ceriodaphnia dubia

The presence of several anthropogenic chemicals has been documented in the atmosphere of the Canadian prairies. The deposition of these chemicals as a mixture is of importancesince little is known of the combined effects of these chemicalson aquatic organisms. This study was designed to evaluate theacute and chronic toxicity of a complex mixture of nineatmospherically transported pesticides to Ceriodaphniadubia. The nine selected pesticides (bromoxynil, dicamba, 2,4-D,MCPA, triallate, trifluralin, pentachlorophenol, lindane, and4,4-DDT) were detected in appreciable quantities in dryatmospheric deposits. The concentration of each pesticide in themixture was based on maximum measured daily dry deposition ratesfor central Canada, except for pentachlorophenol, which wasestimated based on atmospheric concentrations. The 48-h LC50estimate for C. dubia exposed to the pesticide mixture was174.60 g L^-1 (340 times the measured total dry deposition concentration). The estimated NOEC and LOEC for bothsurvival and reproduction, as determined in the 7-d chronic toxicity test, were 51.3 (100 times) and 154 g L^-1 (300 times), respectively. A basic risk assessment, using the toxic unit approach, suggested that the toxicity of the pesticide mixture was mainly due to 4,4-DDT. Overall, this atmospherically transported complex mixture of pesticides appearsto pose a negligible toxicological risk to non-target aquatic invertebrates such as zooplankton.     

Community air monitoring for pesticides. Part 1: selecting pesticides and a community

The CA Department of Pesticide Regulation (CDPR) developed methods to select pesticides and a community to fulfill criteria for an ambient air monitoring study it conducted as part of the CA Environmental Protection Agency's Environmental Justice Action Plan. Using a scoring system, CDPR evaluated 100 pesticides based on statewide-reported pesticide use, volatility, and priority in CDPR's risk assessment process (indicators of exposure and toxicity) to produce a list of pesticides to consider as candidates for monitoring. The CDPR also evaluated and scored 83 communities based on demographics and health factors, availability of cumulative impacts data, and reported pesticide use to create a list of community candidates. The scores provide relative rankings to distinguish more highly impacted communities from less impacted ones and to identify which pesticides might contribute most to potential adverse health effects. These methods use criteria that can be quantified, validated, and verified in order to provide a transparent and fair selection process. Based on public comments and highest scores, CDPR recommended 40 pesticides (including some of their degradation products) and one community for its yearlong monitoring study. The CDPR then further refined its list of pesticides by soliciting input from local and technical advisory groups. The CDPR plans to use these methods to select pesticides and communities in future monitoring activities.     

A Probabilistic Screening Model for Evaluating Pyrethroid Surface Water Monitoring Data

Synthetic pyrethroids have been detected in recent California surface water monitoring. Filtration is avoided during sample workup because pyrethroids are extremely hydrophobic, tending to sorb to most surfaces. The resultant analytical pyrethroid concentrations reflect both dissolved pyrethroid and pyrethroid associated with suspended sediment in the water column. Such “whole-water” analytical data are not directly comparable to aquatic acute toxicity effect concentrations measured in laboratory sediment-free water. Consequently, any potential aquatic toxicity risk is indeterminate. In this study a simple probabilistic model was developed to allow a screening-level assessment of pyrethroid whole-water monitoring data. The results suggest that water column toxicity of pyrethroids is possible in California's agriculturally-dominated tributaries, and indicate that additional monitoring to better characterize pyrethroid water-column concentrations are warranted. Model refinement will depend on future work that more firmly establishes the relationship between pyrethroid partitioning and bioavailability, and that addresses the potential influence of dissolved organic carbon on pyrethroid sorption and bioavailability.     

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the ??Alentejo?? region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 ??g L^???1) and pesticides-total (0.5 ??g L^???1) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.     

城市黑臭水体整治前后上覆水和孔隙水的生物毒性对比和评价

以常州市典型城市黑臭水体神童浜为对象,采用小球藻和大型溞作为急性毒性测试手段,对整治前、后神童浜4个点位的上覆水和孔隙水的毒性效应进行了对比和评价。结果表明,整治后神童浜上覆水水质明显改善;上覆水在整治前、后对小球藻生长均无抑制作用,反而呈促进作用;对黑臭水体的整治降低了上覆水和孔隙水的生物毒性,但整治后的上覆水仍存在富营养化问题,且孔隙水对水生生物仍具有一定的毒性风险。提出,利用生物毒性测试能反映出黑臭水体整治前、后的毒性变化,可应用于对黑臭水体整治效果的评价。     

1,2-Dichlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on 1,2-dichlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated on effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 26 data for fish, 24 data for invertebrates and 17 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 37 microg/l. All available monitoring data indicate that 1,2-dichlorobenzene levels in estuaries are below 0.1 microg/l. Worst case concentrations in rivers are below 0.45 microg/l. With this value, calculated PEC/PNEC ratios give safety margins of 100 to 300, taking no account of dilution in the sea. 1,2-dichlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Convention for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of 1,2-dichlorobenzene poses no risk to the aquatic environment.     

1,4-Dichlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on 1,4-dichlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programs in large rivers and estuaries in the North Sea area were collected and evaluated on effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 17 data for fish, 9 data for invertebrates and 7 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 20 microg/l. Recent monitoring data indicate that 1,4-dichlorobenzene levels in coastal waters and estuaries are below the determination limit of 0.1 microg/l used in monitoring programs. The worst case value recorded in river water is below 0.45 microg/l. Using these values, calculated PEC/PNEC ratios give safety margins of about 40-200, taking no account of dilution in the sea. Environmental fate and bioaccumulation data indicate that current use of 1,4-dichlorobenzene poses no risk to the aquatic environment.     

Risk assessment of water pollutants

The sources of toxic xenobiotics and different factors such as ecological diversity, differences in comparative anatomy, physiology and biochemistry, food chain variation, interrelationship within species and life span, etc., are considered during risk assessment of pollutants, and their impact on aquatic ecotoxicology is identified. A fugacity and multimedia compartment model is suggested, based on toxicodynamic (toxicity of the chemical) and toxicokinetic (metabolism of the chemical) considerations to predict and screen the behaviour of pollutants quantitatively in the aquatic environment. The significance of the risk analysis approach in anticipatory actions and regulation of pollution levels is discussed.     

Dichloromethane Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on dichloromethane was carried out specifically for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1997). The study consists of collection and evaluation of data on effects and environmental concentrations from analytical monitoring programs in large rivers and estuaries in the North Sea area. The risk is indicated by the ratio of 'predicted environmental concentrations' (PEC) to 'predicted no-effect concentrations' (PNEC) for the marine aquatic environment. In total, 23 studies for fish, 17 studies for invertebrates and 6 studies for algae were evaluated. Both acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a PNEC value of 830 microg/l. Most of the available monitoring data apply to rivers and estuaries and were used to calculate PECs. The most recent data (1983--1995) support a typical PEC for dichloromethane lower than 0.2 microg/l and a worst case PEC of 13.6 microg/l. Dichloromethane is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC). The calculated PEC/PNEC ratios give margins of 60 to 4000 between the PNEC and PEC, dilution within the sea would further increase these margins. It can be concluded that the present use of dichloromethane does not present a risk to the marine aquatic environment.     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

Monochlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on monochlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated for effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 27 data for fish, 24 data for invertebrates and 13 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 32 micro/l. Recent monitoring data indicate that monochlorobenzene levels in surface waters are below determination limits of 0.1, 0.2, 0.5 microg/l used in monitoring programs. Assuming that half of the lowest determination (0.1 microg/l) is typical, a PEC of 0.05 microg/l was derived. A worst case of 0.5 microg/l is assumed. PEC/PNEC ratios give safety factors of 60 to over 500, taking no account of dilution in the sea. Monochlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of monochlorobenzene poses no unacceptable risk to the aquatic environment.     

Pesticide occurrence and aquatic benchmark exceedances in urban surface waters and sediments in three urban areas of California, USA, 2008–2011

Urban pesticide use has a direct impact on surface water quality. To determine the extent of pesticide contamination, the California Department of Pesticide Regulation initiated a multi-area urban monitoring program in 2008. Water and sediment samples were collected at sites unaffected by agricultural inputs in three areas: Sacramento (SAC), San Francisco Bay (SFB), and Orange County (OC). Samples were analyzed for up to 64 pesticides or degradates. Multiple detections were common; 50 % of the water samples contained five or more pesticides. Statewide, the most frequently detected insecticides in water were bifenthrin, imidacloprid, fipronil, fipronil sulfone, fipronil desulfinyl, carbaryl, and malathion. Bifenthrin was the most common contaminant in sediment samples. Key differences by area: OC had more pesticides detected than SAC or SFB with higher concentrations of fipronil, whereas SAC had higher concentrations of bifenthrin. The most frequently detected herbicides were 2,4-D, triclopyr, dicamba, diuron, and pendimethalin. Key differences by area: OC and SFB had higher concentrations of triclopyr, whereas SAC had higher concentrations of 2,4-D and dicamba. Detection frequency, number of pesticides per sample, and pesticide concentration increased during rainstorm events. In water samples, all of the bifenthrin, malathion, fipronil, permethrin, and λ-cyhalothrin detections, and most of the fipronil sulfone and cyfluthrin detections were above their lowest US EPA aquatic benchmark. Diuron was the only herbicide that was detected above its lowest benchmark. Based on the number of pesticides and exceedances of aquatic benchmarks or the high number of sediment toxicity units, pesticides are abundant in California surface waters.     

水环境生物监测的发展方向与核心技术

水环境生物监测是环境监测的重要内容,它应重点说清环境胁迫的生物效应。简述了总量管理、流域管理、风险管理、生态管理等环境管理对水环境生物监测有迫切需求,应引入＂生态系统健康＂、＂生物完整性＂、＂环境胁迫＂、＂全排水毒性＂等现代环境生物监测的基本概念,建立水环境生物监测技术发展的理论基础,发展生物完整性、综合毒性等监测与评价核心技术;革新现行监测方法体系,建立包括QA/QC、快速方法等支持系统在内的现代水环境生物监测业务化方法体系;创新评价技术体系,建立水环境生态健康评价及综合毒性评价指标体系、基准及分级管理标准,确立水环境质量管理的生物学目标。     

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.     

The Use of Atmospheric Dispersion Models in Risk Assessment Decision Support Systems for Pesticides

In the evaluation of potentially adverse effects oforganic chemicals such as pesticides on theenvironment the atmosphere may play an important role.After its release to the atmosphere the chemical willbe transported/dispersed in the atmosphere and finallyit will be removed either by atmospheric-chemicaldestruction or by deposition to the underlying soil orsurface water. In a risk assessment decision supportsystem both ambient concentrations and depositionfluxes must be known to evaluate the risk of directexposure (inhalation) or the risk of soil and watercontamination caused by deposition. This paperdiscusses the use of atmospheric dispersion models insuch risk assessment decision support systems.     

Euro Chlor Risk Assessment for the Marine Environment Osparcom Region: North Sea - Chloroform

This risk assessment on chloroform was carried out specifically for the marine environment, according to the methodology laid down in the EU risk assessment Regulation (1488/94) and the Guidance Document of the EU New and Existing Substances Regulation (TGD, 1997). The study consists of the collection and evaluation of data on effects and environmental concentrations from analytical monitoring programs in large rivers and estuaries in the North Sea area. The risk is indicated by the ratio of the "predicted environmental concentrations" (PEC) and the "predicted no effect concentrations" (PNEC) for the marine aquatic environment. In total, 23 studies for fish, 17 studies for invertebrates and 10 studies for algae have been evaluated. Both acute and chronic toxicity studies have been taken into account and the appropriate assessment factors have been used to define a typical PNEC value of 72 µg/l. Due to limitations of the studies evaluated, a worst PNEC of 1 µg/l could also be used. Most of the available monitoring data apply to rivers and estuaries and were used to calculate PECs. The most recent data (1991-1995) support a typical PEC of 0.2 µg chloroform per litre of water and a worst case PEC of 5 to 11.5 µg chloroform per litre of water. The calculated PEC/PNEC ratios give a safety margin of 6 to 360 between the predicted no effect concentration and the exposure concentrations. A worst case ratio, however, points to a potential risk for sensitive species. Refinement of the assessment is necessary by looking for more data. Additional evaluation of environmental fate and bioaccumulation characteristics showed that no concern is expected for food chain accumulation.     

Toxicity of propargylic alcohols on green alga--Pseudokirchneriella subcapitata

The present study evaluates the toxicity of 34 propargylic alcohols, including primary, primary homo-, secondary, and tertiary alcohols, based on their effects on phytoplankton. A closed-system algal toxicity test was applied because the closed-system technique presents more realistic concentration-response relationships for the above compounds than the conventional batch tests. The green alga, Pseudokirchneriella subcapitata, was the test organism and final yield and growth rate were chosen as the test endpoints. Among all the propargylic alcohols tested, 1-pentyn-3-ol is the most toxic compound with its EC50 equal to 0.50 mg L(-1), which can be classified as a "R50" compound (very toxic to aquatic organisms, EC50/LC50 < 1 mg L(-1)), following the current practice for classification of chemicals in the European Union (EU). There are several other compounds including 2-decyn-1-ol, 3-decyn-1-ol, 1-hexyn-3-ol, 3-butyn-2-ol, and 3-hexyne-2,5-diol, which deserve more attention for their possible adverse impact on the aquatic environment, because these alcohols can be classified as "R51" compounds (toxic to aquatic organisms, EC50/LC50 between 1 and 10 mg L(-1)). Compared to the base-line toxicity relationship (narcosis QSAR) derived previously, tertiary propargylic alcohols can be identified as nonpolar narcotic chemicals, while secondary alcohols and primary alcohols with low molecular weight generally exhibit obvious excess toxicity in relation to the base-line toxicity. Finally, quantitative structure-activity relationships were established for deriving a preliminary estimation of the toxicity of other propargylic alcohols.