Predicting the aquatic risk of realistic pesticide mixtures to species assemblages in Portuguese river basins

Although pesticide regulatory tools are mainly based on individual substances, aquatic ecosystems are usually exposed to multiple pesticides from their use on the variety of crops within the catchment of a river. This study estimated the impact of measured pesticide mixtures in surface waters from 2002 and 2008 within three important Portuguese river basins(‘Mondego', ‘Sado' and ‘Tejo') on primary producers, arthropods and fish by toxic pressure calculation. Species sensitivity distributions(SSDs), in combination with mixture toxicity models, were applied. Considering the differences in the responses of the taxonomic groups as well as in the pesticide exposures that these organisms experience, variable acute multi-substance potentially affected fractions(ms PAFs) were obtained. The median msP AF for primary producers and arthropods in surface waters of all river basins exceeded 5%, the cut-off value used in the prospective SSD approach for deriving individual environmental quality standards. A ranking procedure identified various photosystem II inhibiting herbicides, with oxadiazon having the relatively largest toxic effects on primary producers, while the organophosphorus insecticides, chlorfenvinphos and chlorpyrifos, and the organochloride endosulfan had the largest effects on arthropods and fish, respectively. These results ensure compliance with European legislation with regard to ecological risk assessment and management of pesticides in surface waters.     

Predicting the aquatic risk of realistic pesticide mixtures to species assemblages in Portuguese river basins

Although pesticide regulatory tools are mainly based on individual substances, aquatic ecosystems are usually exposed to multiple pesticides from their use on the variety of crops within the catchment of a river. This study estimated the impact of measured pesticide mixtures in surface waters from 2002 and 2008 within three important Portuguese river basins (‘Mondego’, ‘Sado’ and ‘Tejo’) on primary producers, arthropods and fish by toxic pressure calculation. Species sensitivity distributions (SSDs), in combination with mixture toxicity models, were applied. Considering the differences in the responses of the taxonomic groups as well as in the pesticide exposures that these organisms experience, variable acute multi-substance potentially affected fractions (msPAFs) were obtained. The median msPAF for primary producers and arthropods in surface waters of all river basins exceeded 5%, the cut-off value used in the prospective SSD approach for deriving individual environmental quality standards. A ranking procedure identified various photosystem II inhibiting herbicides, with oxadiazon having the relatively largest toxic effects on primary producers, while the organophosphorus insecticides, chlorfenvinphos and chlorpyrifos, and the organochloride endosulfan had the largest effects on arthropods and fish, respectively. These results ensure compliance with European legislation with regard to ecological risk assessment and management of pesticides in surface waters.     

Entry and toxicity of organic pesticides and copper in vineyard streams: Erosion rills jeopardise the efficiency of riparian buffer strips

The present study was performed to characterise in-stream pesticide exposure within the Palatinate vineyard region in south-west Germany, evaluate the influence of buffer strip widths and identify mitigation measures for the relevant entry pathways. In-stream water and sediment samples that were taken at nine sampling sites of different buffer widths following intense rainfall, and edge-of-field runoff that were sampled in erosion rills were analysed regarding 28 active ingredients of pesticides including copper. In-stream samples contained a mix of 8 ± 4 pesticide compounds, resulting in total pesticide concentrations of 1.4-8.9 μg l⁻¹ for water and 16-670 μg kg⁻¹ dw for sediment. Following an exceptional rainfall event with a previous 34-day drought period, pesticide concentrations reached 7.0-83.4 μg l⁻¹. Fungicides were the most important pesticides found and were significantly correlated with the pesticide application frequency and rate. The calculated toxicity values per sample (TU_max) indicated that both organic pesticides and copper concentrations likely cause ecotoxicological effects in the field. The buffer strip width was of little importance for pesticide in-stream concentrations because pesticide entry occurred mainly via the field path network and erosion rills. Pesticide in-stream concentrations were significantly and positively correlated with the concentrations detected in erosion rills (R² = 0.56). As possible risk mitigation measures, we suggest the implementation of grassed field paths and vegetated ditches or wetlands.     

Pesticide usage in California and the United States

In recent years, pesticide usage in the United States has increased markedly. As measured in 1980 for the U.S.A., there were: (1) more than 45 000 individually products registered; (2) more than 1500 active ingredients involved; and (3) about 2.5 billion pounds of active ingredients used annually. Pesticide usage in agriculture has probably peaked and will probably level off and may even decrease in the 1980's because of public health concerns, environmental concerns, lower dose levels of newer pesticides, and the introduction and use of integrated pest management programs and bio-control programs.     

应用稳态模型计算中国南方地表水的硫沉降临界负荷

为了解我国地表水体对酸沉降的响应情况,应用基于酸度平衡的稳态模型计算我国南方地表水的硫沉降临界负荷.文中根据我国实际情况获得了计算地表水背景硫酸盐浓度的经验公式.结果表明,我国南方绝大部分地表水的硫沉降临界负荷大于2.0 keq·(hm²·a)^-1,对酸沉降不敏感.临界负荷小于2.0 keq·(hm²·a)^-1的水体主要为部分山地水体.除了这部分山地水体外,其余水体的现状S沉降都没有超过临界负荷,表明它们在短期内不会发生酸化.超临界负荷的地区分布和临界负荷类似,均表现为东南沿海的福建、广东和江西3省低于西南和华中地区.对模型结果的不确定性分析表明,只要模型参数的取值在合适的范围内,参数的不确定性对结果造成的误差较小,可以接受.     

邻里效应能否促使稻农施用生物农药?——基于鄂、赣、浙三省农户调查数据的考察

在构建邻里效应对农户生物农药施用行为影响的理论模型基础上,利用鄂、赣、浙三省农户的调研数据,实证检验了邻里效应对农户生物农药施用行为的影响,在此基础上,进一步讨论了邻里效应促使稻农施用生物农药的条件与内在作用机制。结果表明：第一,55.76%的样本农户施用过生物农药,且施用生物农药的农户有较强的邻里关系。第二,邻里效应对农户生物农药施用行为有显著的正向影响,且强邻里效应的农户生物农药平均施用量要显著高于弱邻里效应农户。第三,邻里效应对稻农生物农药施用行为的影响存在条件限制,对高收入农户和规模户而言,邻里效应的影响不显著。第四,邻里效应对农户生物农药施用行为有显著直接作用,也通过降低信息搜寻成本和有效规避农业生产风险两条路径间接影响农户生物农药施用行为。     

Effects of multiple but low pesticide loads on aquatic fungal communities colonizing leaf litter

In the first tier risk assessment (RA) of pesticides, risk for aquatic communities is estimated by using results from standard laboratory tests with algae, daphnids and fish for single pesticides such as herbicides, fungicides, and insecticides. However, fungi as key organisms for nutrient cycling in ecosystems as well as multiple pesticide applications are not considered in the RA. In this study, the effects of multiple low pesticide pulses using regulatory acceptable concentrations (RACs) on the dynamics of non-target aquatic fungi were investigated in a study using pond mesocosm. For that, fungi colonizing black alder (Alnus glutinosa) leaves were exposed to multiple, low pulses of 11 different pesticides over a period of 60 days using a real farmer''s pesticide application protocol for apple cropping. Four pond mesocosms served as treatments and 4 as controls. The composition of fungal communities colonizing the litter material was analyzed using a molecular fingerprinting approach based on the terminal Restriction Fragment Length Polymorphism (t-RFLP) of the fungal Internal Transcribed Spacer (ITS) region of the ribonucleic acid (RNA) gene(s). Our data indicated a clear fluctuation of fungal communities based on the degree of leaf litter degradation. However significant effects of the applied spraying sequence were not observed. Consequently also degradation rates of the litter material were not affected by the treatments. Our results indicate that the nutrient rich environment of the leaf litter material gave fungal communities the possibility to express genes that induce tolerance against the applied pesticides. Thus our data may not be transferred to other fresh water habitats with lower nutrient availability.     

Modeling the fate of paddy field pesticide in surface water and environmental risk assessment

The risk of drinking water is greatly concerned because of the large amount of pesticide applied to paddy field and the contamination of drinking water sources due to the runoff. A mathematical model is developed, based on the mass balance, to predict the fate of paddy field pesticides from application, runoff and mixing in a river, taking account of the physical-chemical properties and processes of volatilization, degradation, adsorption and desorption. The model is applied to a river basin in Japan to estimate the contaminant level of several popularly used pesticides at the water intakes. The health risk in drinking water induced by each pesticide concerned is estimated and evaluated by comparing with the acceptable daily intake values (ADI) and with that induced by trihalomethanes. An index to evaluate the total risk of all pesticides appearing in water is proposed. The methods for risk management are also discussed.     

Modeling the fate of paddy field pesticide in surface water and environmental risk assessment

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我国区域性水体农药污染现状研究分析

以4大流域为基础,较为全面地概述了我国区域性农药污染情况,并对其污染原因进行了分析。结果表明:长江流域有机磷农药、氨基甲酸酯类农药以及部分拟除虫菊酯类农药的的残留量很高;珠江流域农药污染情况较轻,检出量均低于我国地表水环境质量标准;黄淮海流域和松辽流域主要检出农药为酰胺类和三嗪类农药,但具体检出物质存在差异。研究分析表明各流域农药污染与该区域的农作物种类有重要关系。     

Mutagenic and cytotoxic potential of Endosulfan and Lambda-cyhalothrin - In vitro study describing individual and combined effects of pesticides

Excessive use of pesticides poses increased risks to non target species including humans. In the developing countries, lack of proper awareness about the toxic potential of pesticides makes the farmer more vulnerable to pesticide linked toxicities, which could lead to diverse pathological conditions. The toxic potential of a pesticide could be determined by their ability to induce genetic mutations and cytotoxicity. Hence, determination of genetic mutation and cytotoxicity of each pesticide is unavoidable to legislate health and safety appraisal about pesticides. The objective of current investigation was to determine the genotoxic and cytotoxic potential of Endosulfan（EN） and Lambda-cyhalothrin（LC）; individually and in combination. 3-（4,5-Dimethylthiazol-2-yl）-2,5-Diphenyltetrazolium Bromide（MTT） assay was utilized to determine cytotoxicity, while two mutant histidine dependent Salmonella strains（TA98, TA100） were used to determine the mutagenicity of EN and LC.Moreover, mutagenicity assay was conducted with and without S9 to evaluate the effects of metabolic activation on mutagenicity. Even though a dose dependent increase in the number of revertant colonies was detected with EN against both bacterial strains, a highly significant（p 〈 0.05） increase in the mutagenicity was detected in TA98 with S9. In comparison, data obtained from LC revealed less mutagenic potential than EN. Surprisingly,the non-mutagenic individual-concentrations of EN and LC showed dose dependent mutagenicity when combined. Combination of EN and LC synergistically induced mutagenicity both in TA98 and TA100. MTT assay spotlighted comparable dose dependent cytotoxicity effects of both pesticides. Interestingly, the combination of EN and LC produced increased reversion and cytotoxicity at lower doses as compared to each pesticide, concluding that pesticide exposure even at sub-lethal doses can produce cytotoxicity and genetic mutations, which could lead to carcinogenicity.     

Determination of eighty-two pesticides and application to screening pesticides in cannabis growing facilities

Determination of pesticides in cannabis facilities is increasingly important as medicinal and recreational uses of cannabis products expand rapidly. We report a method involving wipe sampling, liquid chromatography separation, and tandem mass spectrometry, which enables determination of 82 pesticides out of the 96 regulated by Health Canada. To demonstrate an application of the method, we sampled and measured pesticides in two cannabis growing facilities, representing a non-certified and a certified site. We detected 41 pesticides in surface wipe samples at the non-certified site and 6 at the certified site. This study provides the first evidence showing pesticide occurrence on common surfaces in cannabis growing facilities and points to a need for routine monitoring and strict control of pesticide use in cannabis facilities.     

典型手性农药的光解研究

文章以汞灯为光源,在对映体水平上考察了六种典型手性农药的光化学降解。丙溴磷、马拉硫磷、稻丰散、三唑酮和甲氰菊酯等五种农药含有1个手性中心,存在两个对映体,对各对映体分别进行光解,结果表明光解速率基本一致,且几种手性农药是手性稳定的,未发现对映体转化现象,几种农药中有机磷农药降解较快,而甲氰菊酯降解最慢,半衰期长达280h。氯氰菊酯含有3个手性中心,存在4个可在非手性硅胶柱上得到拆分的异构体,每个异构体又存在两个对映体,因此共8个对映体。进一步对氯氰菊酯的一个反式异构体所含的一个单一对映体进行光解,结果发现存在一定的异构体转化,氯氰菊酯的另外3个异构体均有生成,按氯氰菊酯各异构体总量计算的光解半衰期为66.7h。     

我国东南地区饮用水源地多种农药的赋存特征及健康风险评估

为阐明我国东南地区典型饮用水源地农药类微污染物的污染特征及生态风险,检测评估了某省7个水库的苯并咪唑类、酰胺类、三唑类和有机磷类等19类共55种常用农药的检出频率、检出浓度以及每种农药对于绿藻、水蚤和鱼类这3种不同营养级生物的风险商.在分析的55种农药中,多菌灵和乙草胺的检出频率为100%,12种农药的检出频率在80%以上.多菌灵的检出浓度最高(77.7 ng·L^-1),其次是乙草胺(51.6 ng·L^-1).风险评估结果显示,大部分农药在目标区域都处于低风险状态.对于3种生物来说,乙草胺是绿藻的风险主导型农药,而多菌灵是鱼类和水蚤的风险主导型农药.     

基于非靶向物种保护的农药水环境基准及排放限值研究

我国农药行业的水污染排放管理长期以来缺乏对特征污染物的控制要求,特征污染物产生、处理和排放的数据基础也非常薄弱.鉴于农药活性成分对作用对象极其敏感但又具有高选择性的特点,可以立足于对敏感作用对象以外的水生生物加以充分保护的思路,建立基于非靶向物种保护的农药水环境急性基准,作为我国现阶段农药排放限值的推导基础.基于对几十种农药活性成分毒性数据的分析,将物种毒性数据敏感度变化最显著的位序点（累积概率在5%~30%之间）作为“靶向物种”与“非靶向物种”累积概率的分割点,提出保护非靶向物种目标的水质基准计算方法,并以毒死蜱为例,应用物种敏感度分布曲线法对特征污染物毒死蜱水质基准值进行示例推导.筛选出无脊椎动物、脊椎动物和植物等9门39科59种共109个急性毒性数据,经计算得出,毒死蜱对我国水生生物的HC_t（靶向物种的危害浓度）为4.35 μg/L,基于HC_t得到的毒死蜱排放限值为20 μg/L,与美国农药工业水污染物排放指南与排放标准中毒死蜱对现源的日最大排放限值（经换算为8 μg/L）较为接近.研究显示,基于非靶向物种保护的农药水环境基准方法推导的排放限值与发达国家排放控制要求接近,通过有效的污染控制技术可以实现,具有可达性.      

Application of Pesticide Sprays to Fresh Produce: A Risk Assessment for Hepatitis A and <Emphasis Type="Italic">Salmonella</Emphasis>

The purpose of this study was to quantify the transfer of viral and bacterial pathogens in water used to dilute pesticides sprayed onto the surfaces of cantaloupe, iceberg lettuce, and bell peppers. The average percent transfer of bacteria was estimated to range from 0.00021 to 9.4%, while average viral transfer ranged from 0.055 to 4.2%, depending on the type of produce. Based on these values the concentrations of hepatitis A virus (HAV) and Salmonella in water necessary to achieve a 1:10,000 annual risk of infection were calculated. Under worst case scenario assumptions, in which a pesticide is applied on the same day that the produce is harvested and when maximum transfer values are used, concentrations of 1.5 × 10⁻³ CFU Salmonella or 2.7 × 10⁻⁷ MPN HAV per 100 ml of the water used for application would result in 1:10,000 annual infection risk to anyone who consumes the fresh produce. If harvesting does not occur until at least 14 days after the application, to produce the same risk of infection, the numbers of Salmonella in 100 ml of water used to dilute the pesticides will be greater by up to five orders of magnitude, while the HAV numbers will have increased by up to two orders of magnitude. Based on the reported concentrations of enteric viruses in surface and ground waters in the United States, a 1:10,000 annual risk of infection could easily be exceeded with some groundwater sources used in the United States. To reduce the risks associated with the consumption of fresh produce, water used to prepare pesticides in spray applications should be evaluated for its microbiological quality.     

克百威预处理对毒死蜱神经细胞毒性的影响

研究了氨基甲酸酯农药克百威预处理对有机磷农药毒死蜱神经细胞毒性的影响. 采用噻唑蓝(MTT)法测定克百威对原代培养皮层神经细胞存活率的影响,找出无细胞毒性浓度;采用无细胞毒性浓度的克百威对培养细胞进行不同时间的预处理后,加入毒死蜱(克百威仍存在)染毒48 h测定细胞毒性的变化;采用Western blot方法测定克百威不同时间预处理对毒死蜱激活ERK1/2作用的影响. 结果表明:10 μmol/L的克百威处理72 h显示无细胞毒性,10 μmol/L的克百威预处理(2～24 h)可减轻毒死蜱的毒性,其中预处理8 h时作用最强;克百威预处理降低了毒死蜱对ERK1/2的激活作用,抑制ERK1/2激活作用与细胞毒性减轻相关. 克百威预处理时间过短(0～2 h),对毒死蜱的细胞毒性及ERK1/2激活影响很小. 克百威预处理一段时间后可拮抗毒死蜱的细胞毒性,该作用机制与抑制ERK1/2激活有关;但克百威预处理时间过短,则不产生拮抗作用. 提示氨基甲酸酯农药与有机磷农药之间的联合作用模式受二者染毒时间间隔的影响.      

广东省荔枝园土壤农药残留现状研究

荔枝收获完毕后在广东省荔枝主产区采集208个荔枝园土壤样本,检测了9种荔枝常用农药甲霜灵、代森锰锌、多菌灵、溴氰菊酯、氯氰菊酯、三氟氯氰菊酯、敌百虫、乐果和敌敌畏的残留含量.结果表明,农药检出率为氯氰菊酯(59.1%)多菌灵(51.0%)代森锰锌(11.1%)甲霜灵(6.7%)三氟氯氰菊酯(3.4%).乐果和敌敌畏仅在个别果园检出,溴氰菊酯和敌百虫均未检出.土壤同时检出不同种类农药果园的百分数为只检出1种农药(40.4%)同时检出2种(31.3%)未检出(18.8%)同时检出3种(8.2%)同时检出4种(1.4%).检出的7种农药中,代森锰锌残留平均含量最高达39.05μg·kg-1,氯氰菊酯次之为7.83μg·kg-1.其它5种农药平均含量为0.19～1.65μg·kg-1.整体上广东省荔枝园土壤农药残留状况较轻.     

湘江流域土壤中有机氯农药的残留规律

2004年5月采集了湘江流域51个样品,用AES萃取技术,使用GC-MS方法测定了样品中的六氯苯(HCB)、滴滴涕(DDTs)、氯丹、艾氏剂、狄氏剂、异狄氏剂、七氯和灭蚁灵等有机氯农药(OCPs). 结果表明:HCB和DDTs的检出率为100%,氯丹和灭蚁灵的检出率较低,艾氏剂、狄氏剂、异狄氏剂和七氯未检出,说明HCB和DDTs曾在湘江流域广泛施用. w(OCPs)平均值为145.49 μg/kg,其中w(DDTs)占w(OCPs)的90.9%,且有些土壤样品中w(DDT)/w(DDE+DDD)较大,说明DDTs曾作为湘江流域的主要杀虫剂施用过,并且近期仍然有输入. 农药残留量与农药的施用量成正比,农药施用量高的衡阳地区,其土壤中的农药残留量最高. 不同使用功能的土壤中有机氯农药的残留量不同,表现为旱地中的残留量高于水稻地,蔬菜地中以辣椒地的残留量最高.      

中国地表水酸沉降临界负荷的区划

为了解中国地表水体对酸沉降的响应情况,应用基于酸度平衡的稳态法研究中国地表水酸沉降临界负荷区划.结果表明,中国地表水硫沉降临界负荷呈较明显的地带分布.其中,大兴安岭北端水体的硫沉降临界负荷最低,大部分小于2 keq·(hm²·a)^-1,东北北部部分水体和秦岭-淮河以南大部分地区水体的硫沉降临界负荷介于2～10 keq·(hm²·a)^-1之间,其余地区水体硫沉降临界负荷普遍大于10 keq·(hm²·a)^-1.地表水酸度临界负荷的地区分布和数值大小类似于硫沉降临界负荷由于中国地表水酸度临界负荷普遍大于2 keq·(hm²·a)^-1,因此大部分地表水对酸化并不敏感,近期内不易酸化.