Bacterial degradation of monocrotophos and phyto- and cyto-toxicological evaluation of metabolites

The bacterium Serratia marsescens strain JAS16 was isolated from agricultural soil which had prior exposure to monocrotophos for three years. The strain JAS16 tolerated up to 1200 mg L^–1 monocrotophos and degraded the insecticide (1000 mg L^–1) at a degradation rate constant of 136 d^?1 (DT₅₀ = 3.7 d). In soil, the degradation rate constant was 105 d^?1 (DT₅₀ = 4.8 d). A schematic pathway is being proposed from the degraded products derived from gas chromatography--mass spectrometry (GC-MS). The phytotoxicity of degradation products to Vigna radiata, Vigna unguiculata, and Macrotyloma uniflorum and the genotoxicity to Allium cepa roots were found to be low. A cost-effective powder-based formulation was achieved with the isolate. The isolate remained viable during the storage and also multiplied with a higher colony forming units (CFU) load g^–1 for over a period of seven weeks of storage.     

镉中毒的干预措施与机理分析

镉极易在人体内蓄积且自然排泄缓慢,对人体健康危害严重,因此关于镉毒性的干预措施及机理研究意义重大。系统总结了螯合剂、金属硫蛋白、营养元素(锌、硒、钙、铁和维生素等),以及中药对镉毒性的干预作用及其机理。目前,镉中毒的许多干预措施均是利用与镉具有更高亲和性的一些外加物质,在动物体内与镉形成易于排出体外的复合物,再通过动物正常的生理活动将镉排出,以消除镉对机体内一些必需元素的正常新陈代谢活动的干扰。中药对镉中毒的干预机理可能成为新的研究热点。     

4种新型杀虫剂对黄色羽摇蚊(Chironomus flaviplumus)老熟幼虫的急性毒性

测定了峰升(15%杀单·唑磷乳油)、稻卫(20.2%阿维·唑磷乳油)、蚜螨克星(1.8%阿维·吡乳油)和蔬卫(2.4%高氯·阿维乳油)4种新型杀虫剂对黄色羽摇蚊(Chironomus flaviplumus)老熟幼虫的急性毒性.结果表明:峰升处理黄色羽摇蚊幼虫后24 h,不同浓度间的存活率无显著差异,而在其他时间段(48、72、96 h),随着杀虫剂浓度的增加,存活率逐渐下降.其他3种杀虫剂处理黄色羽摇蚊幼虫4 d,随着杀虫剂浓度的增加,每天的存活率也呈下降趋势.峰升、稻卫、蚜螨克星和蔬卫对黄色羽摇蚊幼虫48 h的LCs0分别为0.1735、0.0249、0.0015和0.0046 mg·L-1.蚜螨克星毒性最高,毒性在同一数量级的还有蔬卫,其次为稻卫.峰升毒性最低,但仍属高毒杀虫剂.     

生石灰对福寿螺的毒性效应研究

通过室内毒性试验,探索了生石灰对不同大小福寿螺的毒性效应。试验中将福寿螺按照壳高（H）分为小螺（5 mm≤H〈15 mm）、中螺（15 mm≤H〈25 mm）、大螺（25 mm≤H〈35 mm）和超大螺（35 mm≤H〈45 mm）,结果表明：（1）生石灰的控螺效应显著,尤其是对中小福寿螺具很强的抑制和杀灭作用;生石灰处理6 d,除了最低质量浓度0.05 g.L-1处理造成35%死亡率,其他处理死亡率均在70%以上,其中0.20、0.50、1.00和2.00 g.L-1处理中超过90%的福寿螺死亡。（2）生石灰对不同大小福寿螺的半抑制质量浓度（24 h）大小顺序为超大螺〉中螺、大螺〉小螺,半致死质量浓度（24 h）大小顺序为超大螺〉大螺〉中螺〉小螺;（3）生石灰对福寿螺的毒性以抑制效应为主,生石灰对福寿螺的平均半抑制质量浓度为0.06～0.22 g.L-1,低于平均半致死质量浓度0.11～1.09 g.L-1;（4）0.50 g.L-1和2.00 g.L-1质量浓度的石灰处理12 h后,福寿螺鰓组织SOD酶活性呈极显著下降,分别为对照的33%和38%。研究表明,生石灰可用于防治入侵生物福寿螺,在实践中可部分替代杀螺剂的使用。     

7种酚类化学物质对活性污泥的呼吸抑制作用

苯酚类化学物质是废水中常见的有机污染物,其对活性污泥的毒性数据对于污水处理厂稳定运行和化学品危害性评估具有重要意义。本研究采用活性污泥呼吸抑制试验(209)测定7种酚类化学物质对活性污泥的呼吸抑制作用。结果显示,2,6-二叔丁基苯酚和对特辛基苯酚对活性污泥未产生明显的毒性效应;2,4-二氯酚、2-苯基苯酚、4-硝基酚、4-氯酚和对甲酚等5种化学物质都对活性污泥呼吸有不同程度的抑制效应,3 h-EC50值分别为49.7、77.6、102、150.1和462 mg·L-1,构效关系分析结果表明-Cl、-NO2等官能团是导致活性污泥呼吸抑制效应增强的关键因素。在化学品生物降解性测试研究中,要确保有毒化学物质的测试浓度低于EC50值的1/10。     

上海市典型污水处理厂污泥浸出液的化学和毒性评价

为了研究污水污泥在海洋环境中释放带来的生态风险,在分析上海7处典型污水处理厂污水污泥浸出液中重金属与溶解性有机碳的基础上,使用黑鲷,卤虫,三角褐指藻,纤细角毛藻和小球藻研究污水污泥浸出液对海洋生物的急性毒性作用和生长抑制作用。化学分析结果表明,所有样点的污水污泥浸出液中重金属总量均低于中国(GB5085.3-2007)与欧盟(EN12457.2-2002)关于危险废弃物的鉴别标准,但溶解性有机碳(DOC)含量超过欧盟标准1个数量级。毒性实验结果表明,黑鲷幼鱼对污水污泥浸出液的敏感性最强,其次是海洋微藻,卤虫无节幼体的敏感性较低;毒性综合分析结果表明,S2和S3点的污水污泥浸出液对海洋生物的综合生物毒性相对最高,而S4,S5的综合生物毒性最低,其中接纳污水为工业污水,且有机质与硫化物含量较低的污水污泥浸出液对海洋生物的综合生物毒性较低。     

Influence of some parameters on adsorption rate and toxicity of cadmium in activated sludge

The influence of pH, competitor ions (NaNO₃) and aerobic and anaerobic stabilization of activated sludge on the cadmium uptake by activated sludge solids was investigated. Above 0.08 mg L^‐1 cadmium in solution, biosorption was found to follow the Freundlich isotherm. Active cellular uptake of soluble cadmium does not appear to be a significant mechanism of the biosorption. In addition, the cadmium uptake is not completely reversible. The adsorption of cadmium by activated sludge seems to involve a physico‐chemical mechanism with especially weak electrostatic interactions with ion‐exchange reaction. The optimum adsorption pH was 7.5. Adsorption is influenced by sodium ion concentrations up to an equivalent conductivity of 10 000 μS cm^‐1. Aerobic and anaerobic stabilization of activated sludge increase systematically the initial adsorption capacities. Respirometric measurements were done to evaluate the inhibitive effects of cadmium on activated sludge. Monod's equation and the equation of non‐competitive inhibition were used to describe the toxicity related to cadmium uptake. These two equations appear to be complementary.     

氯丹和灭蚁灵污染场地土壤对陆生生物的毒性效应

为向污染土壤的监测、生态毒理诊断及修复提供方法和数据,以氯丹、灭蚁灵污染场地土壤为供试土壤,测定了氯丹、灭蚁灵复合污染对蚯蚓的急性毒性效应以及对小麦、小白菜、玉米和水稻4种植物种子发芽率和根伸长抑制率的影响.结果表明,蚯蚓对本场地污染响应十分敏感,处理d 3高浓度组开始出现死亡,此后死亡率随污染物浓度增大而上升,d 14部分高浓度组死亡率达到100%;同一浓度下,氯丹和灭蚁灵对4种植物种子根伸长抑制率均显著大于对种子发芽的抑制率,植物的根生长比种子发芽对有机污染物的毒性更为敏感.4种植物种子对污染场地土壤的敏感性为小麦>小白菜>水稻>玉米.氯丹和灭蚁灵对蚯蚓的毒性要大于对这几种植物的毒性,蚯蚓对氯丹和灭蚁灵的响应更加敏感.因此,蚯蚓作为指示生物,其急性毒性试验可作为氯丹和灭蚁灵污染场地的诊断指标,诊断周期以14 d为宜.     

杀虫剂对土壤温室气体排放的影响

在室内培养条件下,研究了在施用尿素的土壤（有效氮质量分数为200 mg·kg^-1）中分别添加不同剂量（在5、10和50 mg·kg^-1）的吡虫啉和毒死蜱2种杀虫剂时,杀虫剂对土壤温室气体CO2、N2O和CH4排放过程的影响。结果表明：和空白相比,施用尿素明显地增加了土壤中温室气体N2O和CO2的排放量,但对CH4的排放无明显影响。当施用5 mg·kg^-1吡虫啉时,土壤中N2O和CO2排放总量和尿素处理相比无明显差异,但吡虫啉用量上升至10和50 mg·kg^-1时则显著降低了温室气体N2O和CO2的排放量（P〈0.05）,N2O排放量分别降低了26.89%和53.10%,CO2排放量分别降低15.14%和13.79%。毒死蜱在5、10和50 mg·kg^-1三种用量时土壤的N2O排放量与尿素处理相比均无明显差异。毒死蜱在5和10 mg·kg^-1用量时则明显抑制了土壤CO2的排放（p〈0.05）,分别比尿素处理降低了19.88%和19.02%;用量上升到50 mg·kg^-1用量时,土壤的CO2排放量与尿素处理相比无差异。吡虫啉和毒死蜱对CH4排放量均没有明显影响。可见,杀虫剂施用明显影响到土壤温室气体的排放,但不同杀虫剂品种及其用量的效应也存在明显差异。     

9种杀虫剂对中华大刀螂幼虫的毒性

螳螂是田间控制害虫种群增加的重要捕食性天敌之一。以中华大刀螂3龄幼虫(Paratenodera sinensis Saussure)为受试生物,利用9种常用杀虫剂配制成不同浓度梯度的药剂,通过喷雾法直接暴露,分别测定了LC50和死亡率来评价不同杀虫剂对中华大刀螂毒性和危害程度的影响。结果显示,9种杀虫剂对中华大刀螂幼虫的毒性(LC50值)差异很大,用药后24h的LC50在0.7182～347.7962mg·L-1之间,LC95在8.8057～1734.5650mg·L-1之间;用药后48h的LC50在0.3564～193.6887mg·L-1之间,LC95在3.8958～1548.3258mg·L-1之间;用药后72h的LC50在0.2232～115.3391mg·L-1之间,LC95在1.7730～530.6462mg·L-1之间。不同杀虫剂对中华大刀螂幼虫的毒性差异最高达到543.46倍。毒性大小依次为,高效氯氟氰菊酯﹥啶虫脒﹥联苯菊酯﹥毒死蜱﹥噻虫嗪﹥茚虫威﹥吡虫啉﹥阿维菌素﹥苏云金杆菌原粉(Bt)。根据田间推荐浓度处理的死亡率判断,毒死蜱、联苯菊酯、啶虫脒、高效氯氟氰菊酯为有害水平,Bt为中度有害水平,吡虫啉、茚虫威、噻虫嗪为微害水平,阿维菌素接近无害水平。根据LC50与田间推荐浓度的比值判断,阿维菌素、吡虫啉对螳螂种群数量不会产生太大影响;Bt、茚虫威和噻虫嗪对螳螂种群数量会产生一定危害;而毒死蜱、啶虫脒、联苯菊酯和高效氯氟氰菊酯将严重影响螳螂种群数量的稳定性。在24～72h范围内,不同杀虫剂LC50和LC95随施药时间的延长而降低,说明暴露时间越长毒性越大,危害程度也越大。建议在中华大刀螂生活范围内减少高效氯氟氰菊酯、联苯菊酯、啶虫脒和毒死蜱的施用,推荐杀虫剂田间使用量时,除考虑对防治对象的防效,还应考虑对天敌种群的危害,提高药剂使用安全性,保护天敌种群的稳定性。     

鸭绿江（丹东段）江水中未知有机污染物分析鉴定与有毒有机物名录筛选

采用美国惠普公司MC/GS联用仪,对鸭绿江（丹东段）江水中有机污染物种类、组成进行了分析鉴定,进而采用高压液相色谱法对多环芳烃类进行定量测定与评价,进行了该江段有毒有机物名录筛选,提出由27种有毒有机污染物组成的名单。     

Exposure and Health Effects of Cadmium

The results of a study of photocatalytic degradation of phenol using aqueous oxygenated TiO₂ (anatase) suspensions in a batch Pyrex photoreactor are reported. The influence on the photodegradation rate of various parameters as pH, phenol and TiO₂ content, oxygen partial pressure, anions present in the dispersions was investigated. A complete oxidation of phenol was observed. Intermediate compounds, catechol and quinone, were detected. It was observed that the photodegradation also proceeded with sunlight radiation. A mechanistic and kinetic model, which accounts for the results obtained, is given. Likely reasons for inactivity of the rutile modification for this reaction are also given.     

细颗粒物(PM_(2.5))主要组分模拟溶液对发光细菌的光抑制分析

为明确NH_4~+、 NO_3~-、SO_4~(2-)及金属等组分在水溶性提取液对发光细菌的光抑制过程中所起的作用,参照PM_(2.5)样品提取液浓度,模拟配制与3级以上PM_(2.5)样品提取液中主要组分:硫酸盐、硝酸盐、氨盐相同浓度的溶液,同时选取与PM_(2.5)可溶性提取液发光抑制率相关性较强的铅、锌,配制不同浓度级别模拟溶液,测试各单一组分对发光细菌的发光抑制率及其混合溶液对发光细菌的联合影响效应。基于毒性单位法(TU)、相加指数法(AI)和混合毒性指数法(MTI)评价了混合体系联合影响的作用类型。结果表明,与3~6级PM_(2.5)可溶性提取液中硫酸氨、硫酸氢氨、硝酸氨、硫酸锌和硝酸铅浓度相同的模拟溶液对发光细菌的发光没有抑制作用。不同的评价方法对PM_(2.5)主要组分混合体系联合效应评价结果具有较好的一致性,硫酸氨、硝酸氨、硫酸氢氨混合溶液中,对发光细菌的光抑制均为硫酸氢氨的独立作用,硫酸锌与硝酸铅的混合体系,锌和铅对发光细菌的联合影响效应表现为协同,硫酸氨、硝酸氨、硫酸氢氨与硫酸锌、硝酸铅的多元混合体系呈现协同作用。     

Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes

The aim of this study was to identify the intermediates in clofibric acid degradation under various advanced oxidation processes, namely ultraviolet (UV), UV/H₂O₂, vacuum ultraviolet (VUV), VUV/H₂O₂, and solar/TiO₂ processes, as well as to assess the toxicity of these intermediates. Eleven intermediates have been detected by gas chromatography-mass spectrometer, most of which were reported for the first time to our best knowledge. Combining the evolution of the dissolved organic carbon, Cl^- and specific ultraviolet absorption at 254 nm, it could be deduced that cleavage of aromatic ring followed by dechlorination was the mechanism in solar/TiO₂ process, while dechlorination happened first and accumulation of aromatic intermediates occurred in the other processes. Different transformation pathways were proposed for UV-, VUV-assisted and solar/TiO₂ processes, respectively. The acute toxicity was evaluated by means of Photobacterium phosphoreum T₃ spp. bioassay. It was believed that aromatic intermediates increased the toxicity and the ring-opening pathway in solar/TiO₂ process could relieve the toxicity.     

Alterations in Carbohydrate Metabolism in Selected Tissues of Crab, Oziotelphusa Senex Senex (Fabricius) Under Fenvalerate-Induced Stress

Changes in carbohydrate metabolism in hepatopancreas and muscle of the crab, Oziotelphusa senex senex exposed to a sublethal concentration (0.2 ppm) of fenvalerate, a pyrethroid insecticide, were studied. the glycogen and total carbohydrate levels decreased significantly in the tissues of crab exposed to fenvalerate. an increase in phosphorylase 'a' and decrease in aldolase activity levels suggested increased glycogenolysis, and decreased glycolysis during fenvalerate toxicity. Krebs cycle enzymes such as NAD-isocitrate dehydrogenase, succinate dehydrogenase and malate dehydrogenase were decreased, suggesting reduced mitochondrial oxidative metabolism. Glucose-6-phosphate dehydrogenase activity was increased significantly, indicating enhanced oxidation of glucose through the hexose monophosphate shunt pathway. Lactate dehydrogenase activity was elevated indicating the development of anaerobic conditions at tissue level in the stressed crab. Cytochrome C oxidase and Mg2+ ATPase activity levels were also decreased, indicating the impaired energy synthesis and prevalence of energy crisis. These results suggest that fenvalerate has a profound effect on the glucose metabolism of crab.     

Alterations in Carbohydrate Metabolism in Selected Tissues of Crab,Oziotelphusa Senex Senex (Fabricius) Under Fenvalerate-Induced Stress

Changes in carbohydrate metabolism in hepatopancreas and muscle of the crab, Oziotelphusa senex senex exposed to a sublethal concentration (0.2 ppm) of fenvalerate, a pyrethroid insecticide, were studied. the glycogen and total carbohydrate levels decreased significantly in the tissues of crab exposed to fenvalerate. an increase in phosphorylase ‘a’ and decrease in aldolase activity levels suggested increased glycogenolysis, and decreased glycolysis during fenvalerate toxicity. Krebs cycle enzymes such as NAD-isocitrate dehydrogenase, succinate dehydrogenase and malate dehydrogenase were decreased, suggesting reduced mitochondrial oxidative metabolism. Glucose-6-phosphate dehydrogenase activity was increased significantly, indicating enhanced oxidation of glucose through the hexose monophosphate shunt pathway. Lactate dehydrogenase activity was elevated indicating the development of anaerobic conditions at tissue level in the stressed crab. Cytochrome C oxidase and Mg2+ ATPase activity levels were also decreased, indicating the impaired energy synthesis and prevalence of energy crisis. These results suggest that fenvalerate has a profound effect on the glucose metabolism of crab.     

草甘膦对雄性大鼠睾酮合成的影响

探讨草甘膦亚慢性染毒对雄性大鼠睾酮合成的影响。雄性SD大鼠按体重随机分为对照组(0 mg·kg~(-1))、低剂量组(50 mg·kg~(-1))、中剂量组(200 mg·kg~(-1))和高剂量组(800 mg·kg~(-1)),连续灌胃染毒,第4、8和12周时分别处死一批动物,采集血液和脏器。放射免疫分析法检测大鼠血清中卵泡刺激素(follicle stimulating hormone,FSH)、黄体生成素(luteinizing hormone,LH)、睾酮(testosterone,T)、雌二醇(estradiol,E2)水平; HE染色法(苏木精-伊红染色法)观察睾丸病理学变化;免疫组化法检测3β-羟基类固醇脱氢酶(3beta-hydroxysteroid dehydrogenase,3β-HSD)、类固醇激素合成急性调节蛋白(steroid synthesis of acute regulatory protein,St AR)、细胞色素P450胆固醇侧链裂解酶(cytochrome P450 cholesterol side chain lyase,P450scc)和17β-羟基类固醇脱氢酶(17beta-hydroxysteroid dehydrogenase,17β-HSD)蛋白表达水平。随染毒剂量和时间的增加,大鼠血清FSH和T水平呈下降趋势,第12周高剂量组FSH水平明显低于对照组(P0.05),第8周和第12周高剂量组T水平明显低于对照组(P0.05),LH和E2水平各组间无统计学差异(P0.05)。组织病理学可见中、高剂量组睾丸生精小管、生精细胞、间质区结构被破坏。随草甘膦染毒剂量的增加,St AR和P450scc蛋白表达水平与对照组相比显著下降(P0.05),3β-HSD和17β-HSD蛋白表达水平在各组间无差异(P0.05)。草甘膦能降低血清T水平,抑制T合成相关蛋白St AR和P450scc的表达,干扰T的合成过程,具有雄性生殖毒性作用。     

Ultrastructural responses and oxidative stress induced by cypermethrin in the liver of Labeo rohita

The present study was conducted to establish the relationship between selected oxidative stress parameters and ultrastructural responses in liver tissue of Labeo rohita fingerlings exposed to cypermethrin. Fish were exposed to lethal (4.0 μg L^?1) and sublethal (0.4 μg L^?1) concentrations of cypermethrin for a period of 24, 48, 72 and 96 h for acute studies and 1, 5, 10 and 15 days for subacute studies, respectively. Results showed increased catalase (CAT) and protease activity, hydrogen peroxide (H₂O₂), malondialdehyde (MDA), protein carbonyls and free amino acid (FAA) levels at both concentrations. This suggests participation of free-radical-induced oxidative cell injury in mediating the hepatotoxicity of cypermethrin. In corroboration of this, ultrastructural lesions witnessed a reduction in the number of cell organelles, swollen, vacuolated and condensed mitochondria, dilated rough endoplasmic reticulum, and reduced numbers of smooth enodplasmic reticulum, peroxisomes and lysosomes at the lethal (4.0 μg L^?1) concentration. At the sublethal (0.4 μg L^?1) concentration, cytoplasmic vacuolation, condensed, vacuolated and swollen mitochondria, dilated rough endoplasmic reticulum and an absence of hepatocyte microvilli were prominent. Ultrastructural changes were exhibited as subcellular responses due to the imbalance in cellular oxidative status by means of oxidative damage.     

Ecotoxicological effects of Trichloroethene upon plankton

A case study in an experimental pond was performed to evaluate the ecotoxic effects of Trichloroethene (TRI) upon the population density and productivity of phyto‐ and zooplankton. TRI was continuously released into two pond enclosures over 11 weeks (mean concentrations 1.5 and 7.5 mg/l). The chronic chemical treatment showed distinctive toxic influences upon the biota. Following the high TRI concentration, the phytoplankton density slightly increased; the productivity per single cells, however, was significantly reduced compared to the controls and the low TRI concentration. Cryptophyceae were the most sensitive algae taxa. The density and reproductivity of Daphniae and Phyllopodae decreased by the high TRI concentration. Most of the Rotatoriae were not negatively influenced. With increasing TRI concentrations two different bacteria forms showed a mass development. Small amounts of Trichloroacetic acid were detected in both enclosures as a conversion product of TRI (～3 μg/l after 80 days treatment).     

四溴双酚A对赤子爱胜蚓的生长和基因表达的影响

试验采用人工土壤法,通过14 d急性毒性试验,研究了不同剂量TBBPA对赤子爱胜蚓(Eisenia fetida)生长、基因表达的影响。在14 d急性毒性试验中,随着暴露时间和浓度的增加,蚯蚓生长受到了显著抑制,未出现死亡现象。超氧化物歧化酶(SOD)的基因表达量在低浓度(50 mg·kg-1)时受到诱导上调;谷胱甘肽转移酶(GST)的基因表达量在400 mg·kg-1染毒组受到明显诱导,是对照组的8.73倍;热休克蛋白(Hsp70)的基因表达量在50、100和200 mg·kg-1染毒组被诱导上调。基因表达量的变化显示,在50、100、200 mg·kg-1浓度条件下,蚯蚓可以利用自身的抗氧化能力维持体内的动态平衡稳定,使得机体免受损伤。但是在超过400 mg·kg-1浓度后,TBBPA的毒性效应超过了机体的应对能力,使机体遭受损伤,外在特征主要表现为蚯蚓身体蜷缩、变细变硬。从生物标志物角度,基因表达量的变化对TBBPA毒性效应的指示作用较生长抑制率更为敏感。