多杀菌素、阿维菌素乳油和高效氯氰菊酯3种农药对环境生物的安全性评价

防治同一类病虫害的农药种类很多,在保证药效的前提下,选择对施药环境中其他生物安全的农药是非常必要的。通过毒性试验,比较了25 g·L^-1多杀菌素悬浮剂、1.8%阿维菌素乳油和4.5%高效氯氰菊酯水乳剂对环境生物蜜蜂、家蚕、赤眼蜂、大型溞和斑马鱼的风险。结果表明,25 g·L^-1多杀菌素悬浮剂对蜜蜂为高毒,对家蚕为剧毒,对赤眼蜂为高风险,对斑马鱼和大型溞为低毒;1.8%阿维菌素乳油对蜜蜂为高毒,对家蚕为剧毒,对赤眼蜂为高风险,对斑马鱼和大型溞为剧毒;4.5%高效氯氰菊酯水乳剂对蜜蜂为高毒,对家蚕为剧毒,对赤眼蜂为高风险,对斑马鱼和大型溞为剧毒。3种农药对家蚕、蜜蜂、赤眼蜂均为高风险,但与阿维菌素和高效氯氰菊酯相比多杀菌素对水生生物更安全。     

有机磷农药对蛋白核小球藻的毒性相互作用研究

水体中农药复合污染产生的毒性效应具有潜在风险。为系统考察有机磷农药(OPs)混合物对淡水生态系统中绿藻的联合毒性效应,以马拉硫磷(MIT)、敌敌畏(DDVP)、敌百虫(TRC)、乐果(DIT)和氧乐果(OMT)等5种OPs作为混合物组分,运用直接均分射线法设计9组二元混合物体系共45条混合物射线。利用96孔微板测定5种OPs及其二元混合物对蛋白核小球藻(C. pyrenoidosa)的生长抑制毒性,通过基于置信区间的组合指数法分析混合物的联合毒性及毒性相互作用。结果表明,以p EC50为毒性指标,5种OPs对C. pyrenoidosa的毒性大小顺序为:TRCMITDDVPOMTDIT,OPs对C. pyrenoidosa的毒性大小受其中心磷原子的电正性影响;因混合组分的不同,部分OPs混合物对C. pyrenoidosa的联合毒性依赖于组分浓度比; OPs混合物对C. pyrenoidosa的毒性相互作用以加和为主,部分发生拮抗作用,发生拮抗作用的混合体系具有低效应区域呈加和作用,高效应区域呈拮抗作用的规律;与MIT混合的体系均有发生拮抗作用,且依赖于MIT浓度,MIT浓度比例越高,拮抗作用越强,OPs混合物的毒性相互作用与组分浓度比相关; OPs混合物的毒性相互作用组分浓度比依赖性与其联合毒性的组分浓度比依赖性规律不相关。     

Impact of malathion on the biochemical parameters of gobiid fish, Glossogobius giuris (Ham)

There is a dearth of information regarding the changes in heart muscle metabolites induced by pesticides. In the present study, the gobiid fish, Glossogobius giuris, was exposed to sub lethal concentrations of (0.05, 0.25 and 0.5 ppm) organophosphorus pesticide, malathion for short duration (24 to 96 hr). The cardiac muscles showed maximum depletion of glycogen and cholesterol content during 72 and 96 hr after treatment with 0.5 ppm malathion. Whereas a slight fluctuation of protein and glycogen content was observed in low concentration (0.05 ppm) of malathion. The levels of protein showed a significant decrease at high concentration (0.5 ppm) when treated for longer duration (96 hr). The present study reports metabolic dysfunction in response to malathion toxicity in the fish.     

Organophosphate Residues in Grasshoppers from Sprayed Rangelands

Grasshoppers (Orthoptera) were collected in pastures that had been sprayed with malathion and acephate to estimate the secondary exposure of insectivorous birds to those pesticides. Residues of malathion were below 3 ppm at 30 and 54 hours after spraying and no malaoxon was detected. In contrast, acephate was found at 8 and 9 ppm 4 hours after spray; 3-5 ppm of the toxic metabolite methamidophos were also detected at that time. By 53 hours postspray, acephate levels declined to 2 ppm and methamidophos to less than 1 ppm. These results suggest that although malathion may not be a hazard to insectivorous species, acephate may be hazardous through metabolic transformation to methamidophos.     

Potential hepatoprotective effects of vitamin E and Nigella sativa oil on hepatotoxicity induced by chronic exposure to malathion in human and male albino rats

Malathion is an organophosphorus (OP) insecticide and has a wide range of use in agriculture, veterinary medicine, and public health. Malathion and other OP insecticides produce hepatotoxic effects. The objective of the present study was to investigate the protective effects of Nigella sativa oil and α-tocopherol (vitamin E) on the hepatotoxicity induced by malathion on workers involved in the formulation of pesticides, chronically exposed to malathion, and in male albino rats orally administrated malathion. This study was conducted on both human and experimental animals, the human study was conducted on 30 control subjects working as administrators and 45 subjects working in formulation of pesticides and exposed to malathion (≥3 years), all were males with age ranges from 30 to 60 years. The 45 males working in pesticides formulation were classified into three groups; (1) 15 workers exposed to pesticides (2) 15 workers exposed to pesticides and received vitamin (E), in a dose of 10 mg kg?1 day^?1 orally for 60 days, and (3) 15 workers exposed to pesticides and received 100 mg kg^?1 day^?1 of N. sativa oil for 60 days. The animal experiment was conducted on 40 adult male albino rats weighing 150–200 g. They were divided into four groups (10 rats in each group). First group served as the control group, the second group received malathion in a dose of 50 mg kg^?1 orally per day for 60 days, the third group received malathion (in the same dose and route of administration) and vitamin E in a dose of 10 mg kg^?1 day^?1 orally for 60 days, and the fourth group received malathion (in the same dose and route of administration) and N. sativa oil in a dose of 100 mg kg^?1 day^?1 orally for 60 days. Liver function tests (alanine aminotransferase [ALT], aspartate aminotransferase [AST], serum alkaline phosphatase [ALP], albumin, globulin, albumin/globulin ratio, and total proteins), antioxidant enzymes (catalase (CAT), superoxide dismutase (SOD), and total glutathione peroxidase (GPx)), and lipid peroxidation [MDA] were analyzed in both human and animal experiments. The results of both human and animal study revealed that, exposure to malathion produced significant increases in AST, ALT, and lipid peroxidation. There were significant decrease in albumin, albumin/globulin ratio, total protein, and antioxidant enzymes. There was no significant change in ALP. In addition exposed workers showed significant decreases in serum globulin. Nigella sativa oil or vitamin E administration showed significant improvement of liver function tests, lipid peroxidation, and antioxidant enzymes impairment induced by malathion. Thus, dietary supplement, N. sativa oil, or vitamin E may represent a potential therapeutic agent in reducing malathion-induced hepatotoxicity.     

Removal of organophosphorus pesticides from water by electrogenerated Fenton's reagent

Aqueous solutions of organophosphorus pesticides were completely mineralized via in-situ generated hydroxyl radicals (HO^·) by the Electro-Fenton process. Formation of Fenton's reagent (H₂O₂, Fe²⁺) was carried out by simultaneous reduction of O₂ and Fe³⁺ on carbon cathode in acidic medium. The electrochemistry combined with Fenton's reagent provides an excellent way to continuously produce the hydroxyl radical, a powerful oxidant. We demonstrate the efficiency of the Electro-Fenton process to degrade three organophosphorus insecticides: malathion, parathion ethyl and tetra-ethyl-pyrophosphate (TEPP). Degradation kinetics and removals of chemical oxygen demand (COD) have been investigated. Here we show that the mineralization efficiency was over 80% for three organophosphorus pesticides.     

手性氟虫腈对意大利蜜蜂和稻螟赤眼蜂的急性毒性及安全评价

手性农药多以外消旋体形式用于农业生产和卫生害虫防治中。但手性农药对映体通常具有不同的生物活性和毒性,这种现象在农药环境风险评价过程中往往被忽视。本研究以氟虫腈为例,首先用高效液相色谱-手性固定相(HPLC-CSP)技术拆分出氟虫腈的S型和R型2种对映体,分别采用点滴法和药膜法测定了氟虫腈对映体及外消旋体对意大利蜜蜂(Apis mellifera L.)和稻螟赤眼蜂(Trichogramma japonicum Ashmead)的急性毒性。结果显示,S(+)-氟虫腈、R(-)-氟虫腈和外消旋体对意大利蜜蜂的48h-LD50分别为0.00341、0.00396和0.00383μg·蜂-1,对稻螟赤眼蜂的24h-LR50分别为7.56×10-7、8.06×10-7和7.29×10-7mg·cm-2。研究表明,氟虫腈对意大利蜜蜂具有高毒性风险,对稻螟赤眼蜂有极高毒性风险,且氟虫腈对意大利蜜蜂和稻螟赤眼蜂的急性毒性无明显的对映体选择性。因此,使用氟虫腈单一对映体不会降低其对环境生物的毒害风险。     

有机磷农药的构效关系及其对浮游生物的毒性效应

以定量构效关系理论和实验室内急性毒性试验相结合研究了六种有机磷农药对四尾栅藻（S.quadricanda）和多刺裸腹溞（Moina macrocopa）的生态毒性。有机磷农药的毒性取决于磷原子的电正性,各取代基种类和构象对电荷分布作用显著。根据构效关系原理,磷氧双键（P=O）被磷硫双键（P=S）取代后毒性降低;羟基（-OH）被甲、乙、丙氧基（-CH3O、-CH3CH2O、-CH3CH2CH2O）取代后有机磷农药毒性依次增强;磷氧单键（P-O）毒性高于磷碳单键（P-C）。该实验中毒死蜱、辛硫磷（-CH3CH2O）毒性高于其它四种（-CH3O）,敌敌畏和敌百虫（P=O）毒性高于乐果（P=S）,敌敌畏（P-O）又高于敌百虫（P-C）,甘氨酸异丙胺盐取代羟基（-OH）的草甘膦毒性最低。毒性试验结果表明,毒死蜱、辛硫磷、敌百虫、敌敌畏、乐果、草甘膦异丙胺盐对四尾栅藻的96 h EC50分别为6.34、6.62、59.53、82.12、141.37和7.25 mg.L-1。它们对多刺裸腹溞的48 h LC50分别为0.20、0.12、0.28、0.17、1.12和5.03 mg.L-1。六种有机磷农药对多刺裸腹溞的毒性强度结果与QSAR分析具有较高的一致性,即表征有机磷农药毒性特征的取代基团作用的毒性强弱顺序为：-OH〉=O〉-O;对四尾栅藻毒性试验结果中,由于草甘膦异丙胺盐作用于植物类靶位点的特殊性,导致其对四尾栅藻毒性显著增强。综合以上研究,以构效关系理论和浮游生物毒性试验相结合进行有机磷农药的生态风险评价将更加便捷和准确。     

Analysis of the toxicity of glyphosate and Faena® using the freshwater invertebrates Daphnia magna and Lecane quadridentata

With the present contribution an evaluation of the toxicity of the pure herbicide glyphosate and its commercial formulation Faena® is reported using the cladoceran Daphnia magna Strauss and the rotifer Lecane quadridentata Ehrenberg. LC₅₀, EC₅₀, NOEC, and LOEC values for each toxicant and for both test organisms are obtained. Regarding acute toxicity, Faena was 11-fold more toxic to L. quadridentata than pure glyphosate and slightly more toxic to D. magna (1.7-fold). Inhibition of esterase activity in L. quadridentata by glyphosate was the most sensitive end-point; the EC₅₀ was 1500-fold smaller than the LC₅₀. The implications of these results and their comparison with established international and national limit values for glyphosate are discussed.     

Electrophysiological responses of Dendroctonus armandi (Coleoptera: Curculionidae: Scolytinae) to volatiles of Chinese white pine as well as to pure enantiomers and racemates of some monoterpenes

To better understand the attractiveness of host tree, Chinese white pines (Pinus armandi Fr.) to Chinese white pine beetle (Dendroctonus armandi Tsai and Li), the antennal responses of D. armandi to the host volatile, as well as the pure enantiomers and racemates of some monoterpenes, were examined using an electroantennogram (EAG). EAG responses of male and female D. armandi to blended volatiles extracted from the host and some synthetic terpenes (α-phellandrene, (−)-β-pinene, (+)-α-pinene, (−)-α-pinene, (−)-camphene, β-myrcene, (S)-(−)-limonene, (+)-camphene and (R)-(+)-limonene) showed significant variation due to different compound concentrations and sex of the beetles. EAG responses to extracted blended volatiles were significantly greater in females than in males, but the EAG response was not always proportional to the volatile concentration. At lower concentrations, females responded strongly to α-phellandrene and males to (−)-β-pinene, while at higher concentrations, females responded most strongly to α-phellandrene and males to (+)-α-pinene. Females were significantly responsive to (−)-α-pinene, α-phellandrene and (−)-camphene, while males were more responsive to (S)-(−)-limonene, (+)-α-pinene and (R)-(+)-limonene. The EAG responses of the female D. armandi to the volatile oil were significantly higher than that of the males, and the infested pine volatiles could evoke higher EAG response. Most of the test compounds elicited similar responses, which suggested that several of the compounds may be used in combination by D. armandi in habitat and/or host community location at the Qinling forest ecosystem.     

Joint acute toxicity of tributyl phosphate and triphenyl phosphate to Daphnia magna

In this study, the joint acute toxicity of tributyl phosphate (TBP) and triphenyl phosphate (TPP) was investigated using Daphnia magna as the test organism. The median lethal concentrations for TBP and TPP at 24 and 48 h were 5.48 and 0.51 mg/L, 1.17 and 0.089 mg/L, respectively. When mixed at either equal concentration or various toxic unit ratios, TBP and TPP mixtures displayed an additive toxicity after both 24- and 48-h exposure. This work suggests that the joint acute toxicity of TBP and TPP towards D. magna can be predicted by calculating the toxic units of mixtures.     

农药在玻璃表面与正己烷中的光解速率

本文通过测定14种农药在正已烷中和在玻璃表面的光解速率,探讨反应介质对光反应速率的影响,七种拟除虫菊酯农药中,具有α-氰基的五种农药的光解速率明显快于结构上不含α-氰基的二氯苯醚菊酯和联苯菊酯;七种有机磷农药中,具有较大共轭体系的农药光解速率较快,农药在正已烷中与在玻璃表面的光解速率常数之间存在高度相关关系(γ=0.991,n=12),两套数据间的定量关系为y=-3.07×10~(-4)+1.67x。     

马拉硫磷急性暴露对斑马鱼的行为毒性研究

以斑马鱼为受试生物,通过水质毒性生物监测仪记录行为轨迹,研究了亚致死浓度的马拉硫磷急性暴露下斑马鱼游动行为和群体分布等多项行为参数的变化。结果表明:斑马鱼对环境变化响应快速,游动速度短时间内急剧增大,之后下降再调整稳定至一定范围,变化趋势符合环境压力模型。游泳高度不断增大,暴露1 h后斑马鱼几乎全部集中到水箱上部,与暴露前水平差异显著。通讯行为参数平均距离和分散度在暴露后短时间内减小之后恢复到暴露前水平。通过解析斑马鱼的行为变化可以实现水体有机磷农药突发污染的早期预警。     

Feeding deterrent and toxicity effects of apo-fucoxanthinoids and phycotoxins on a marine copepod (Tigriopus californicus)

Using the marine harpacticoid copepod Tigriopus californicus, the effects of phytoplankton feeding deterrents and toxins were differentiated and measured. Eight compounds were tested for feeding deterrence and toxicity responses: four apo-fucoxanthinoids (apo-10′-fucoxanthinal, apo-12′-fucoxanthinal, apo-12-fucoxanthinal, and apo-13′-fucoxanthinone) and four well-known phycotoxins (domoic acid, okadaic acid, microcystin-LR, and a mixture of PSP-1 toxins). Since several of these compounds exhibited both feeding deterrence and toxicity, a model was developed to deconvolute the observed toxicity response from the observed feeding deterrence response, and to classify these compounds based on the degree of toxicity and/or feeding deterrence they exhibited towards T. californicus. Microcystin-LR, the PSP-1 toxins, and the four apo-fucoxanthinoids behaved only as feeding deterrents at low concentrations. Okadaic acid exhibited both toxicity and feeding deterrence at low concentrations, with the threshold concentration for feeding deterrence at a lower level than the threshold concentration for toxicity. Domoic acid acted only as a toxin at low concentrations, with all decreases in feeding resulting from the death of the copepod. Received: 4 November 1996 / Accepted: 3 December 1996     

Indoor air pollution: A review∗

Relationships between toxicities of substituted aromatic hydrocarbons to Daphnia magna and to Fathead minnows or Photobacterium phosphoreum were studied based on structure‐activity equations we established. Good relationships between toxicities of chemicals to Daphnia magna and to Fathead minnows, Photobacterium phosphoreum were found for a wide range of chemicals. The toxicity data of fish can be predicted by the toxicity data of Daphnia magna or Photobacterium phosphoreum. It is probable that the toxicities of chemicals to the three organisms are similar.     

Acute/chronic ratios to estimate chronic toxicity from acute data

Acute toxicity of 25 narcotic compounds to D. magna was determined in this paper. Acute/ Chronic Ratios (ACRs), which are often used to estimate chronic toxicity from acute toxicity data, are discussed based on Quantitative Structure‐Activity Relationships (QSARs) of the compounds between both acute and chronic toxicity data and n‐octanol/water partition coefficients, and an improved equation is derived to estimate chronic toxicity data from acute toxicity data. Application of the improved equation and ACRs is illustrated for D. magna and fathead minnow to estimate chronic toxicity from acute toxicity.     

农药类化合物对大型溞的毒性作用模式:与基线毒性化合物比较研究

农药在控制有害生物的同时,对水生生态系统产生较大的毒性效应。本文通过实验获得了25种基线化合物对大型溞的急性毒性数据,并与57种农药类化合物对大型溞的急性毒性数据进行比较研究,同时根据体外浓度LC_(50)、生物富集因子BCF和体内临界浓度CBR的关系,计算了这些化合物在大型溞体内的临界浓度,研究了农药类化合物对大型溞的毒性作用机理。结果表明,基线化合物在大型溞体内的临界浓度log1/CBR值在一个很窄的范围波动,而农药类化合物在大型溞体内的临界浓度log1/CBR值范围广且较高。这说明多数农药类化合物对大型溞为反应性毒性作用模式。其中,除草剂对大型溞的毒性显著低于杀菌剂和杀虫剂对大型溞的毒性。这可能是因为除草剂主要通过干扰植物光合作用、植物激素或植物分子合成发挥毒性效应,从而导致其对大型溞的生理系统难以发生反应性毒性效应。而杀虫剂和杀菌剂主要通过干扰生物神经系统、生殖系统、呼吸作用或大分子合成发挥毒性效应,因此易与大型溞生理系统发生生物化学反应,从而具有较高的毒性效应。本文分别建立了除草剂、杀菌剂和杀虫剂对大型溞的急性毒性QSAR模型。除草剂对大型溞的急性毒性机理较简单,其毒性与化合物疏水性程度和离子化程度有关;而杀菌剂对大型溞的急性毒性主要与化合物的标准生成热和极性表面积有关;杀虫剂对大型溞的急性毒性作用机理较复杂,它们对大型溞的毒性效应与其和生物分子之间的氢键和范德华力有关。     

3种有机磷农药对水生生物的乙酰胆碱酯酶抑制效应的物种敏感度分析初探

通过筛选敌敌畏、马拉硫磷和对硫磷3种有机磷农药对水生生物的急性毒性数据和乙酰胆碱酯酶抑制效应数据,构建物种敏感度分布曲线进行了比较分析。结果表明,敌敌畏对水生生物的急性毒性和乙酰胆碱酯酶抑制效应的大小顺序为:酶体内抑制效应酶体外抑制效应急性毒性;马拉硫磷和对硫磷的乙酰胆碱酯酶抑制效应数据不足但趋势相似,顺序为:酶体内抑制效应急性毒性酶体外抑制效应。敌敌畏的急性毒性和酶体外抑制效应的5%危害浓度(HC5)分别为2.07μg·L~(-1)和1.53μg·L~(-1),两者相差1.4倍。在水质基准推导中,乙酰胆碱酯酶抑制效应数据对有机磷农药的水生生物基准具有重要的参考价值。     

氯霉素对大型溞的急性和慢性毒性效应研究

氯霉素是一种具有广谱杀菌作用的抗生素,曾在水产养殖中广泛使用,虽然目前已被列入我国渔药禁用清单,但在水环境中仍被大量检出。为探究氯霉素对水生生物的毒性作用,选择大型溞(Daphnia magna)作为受试生物,研究氯霉素对其急性毒性和慢性毒性效应,同时建立了氯霉素的高效液相色谱(HPLC)分析方法,通过实测浓度分析确保实验过程中氯霉素浓度保持在可接受范围内。结果表明:氯霉素对大型溞的48 h半数抑制浓度(EC50)为129.5 mg·L~(-1),95%置信区间为124.4!150.9mg·L~(-1),对溞类的急性毒性为低毒;长期暴露能抑制大型溞的产溞数量,以繁殖量为毒性指标,21 d无可观察效应浓度(NOEC)为1.25 mg·L~(-1),最低可观测效应浓度(LOEC)为2.50 mg·L~(-1);各暴露组实测浓度范围在配制浓度的80%～110%,保证了实验的有效性。同时,利用实验获得的急慢性毒性数据,计算氯霉素对大型溞的急慢性毒性比(ACR),发现利用慢性毒性求得的ACR值比利用急性毒性EC10求得的ACR值更接近推荐值。研究表明氯霉素对大型溞的急性毒性低,但具有慢性毒性效应,其环境风险不容忽视。     

Effects of organochlorines on the ultrastructure of the liver of the damselfish Parma microlepis from reefs in New South Wales, Australia

  Parma microlepis (Günther) were collected from Malabar, an urban location close to the centre of Sydney, Australia, and from Jervis Bay, a reference location 170 km south of the city centre. At each location, fish were collected from two sites separated by 100 to 200 m. The ultrastructure of normal liver tissue is described based on 20 female fish collected from Jervis Bay, where fish are known to be exposed to low levels of organochlorine contaminants. Alterations in the endoplasmic reticulum, mitochondria, lysosomes and nuclei of hepatocytes were identified and quantified in the liver tissue of fish from this location and compared to alterations in 20 female fish collected from Malabar, where fish are exposed to higher concentrations of organochlorine pesticides such as DDT compounds. There were significant differences in the percentage of hepatocytes with swollen mitochondria (F = 124.025, df = 2, 2, P = 0.008) and atypical nuclei (F = 22.198, df = 2, 2, P = 0.043) between sites (100 to 200 m apart), but there were no clear differences between the percentage of structural alterations in the hepatocytes of P. microlepis from Jervis Bay and Malabar. Associations between liver morphology and the organochlorines aldrin, dieldrin, DDE and chlordane were examined using a Pearson correlation matrix. Significant correlations were detected between the percentage of hepatocytes with dilated endoplasmic reticulum and the concentrations of the pesticide aldrin (r = 0.600, df = 11, r _{crit(α = 0.05)} = 0.553). Significant associations were also detected between the percentage of hepatocytes with disorganised endoplasmic reticulum and the concentrations of dieldrin and DDE residues in fish (r = 0.576, r = 0.567, respectively, df = 13, r _{crit (α = 0.05)} = 0.514). However, there was little evidence that ultrastructural alterations in fish responded to increasing concentrations of these pesticides in a consistent dose-response manner. Received: 20 October 1998 / Accepted: 24 November 1999