高铁酸钾对菠菜中3种有机磷农药残留降解的影响

菠菜(Spinaciao leracea L.)是我国出口的重要蔬菜品种之一,其农药残留是制约我国菠菜出口的重要"技术壁垒".在露地栽培条件下,研究了叶面喷施高铁酸钾水溶液对菠菜中有机磷农药的降解作用,并探讨了高铁酸钾对菠菜相关酶活、MDA含量及品质指标的影响.结果表明,叶面喷施不同浓度的高铁酸钾(200、400、600mg·L-1)可有效降低菠菜中敌敌畏、毒死蜱和乐果等有机磷农药的残留量.随着高铁酸钾喷施浓度的增大,菠菜中敌敌畏、毒死蜱和乐果残留量显著降低;试验浓度下以600mg·L-1高铁酸钾处理的降解效果最好,可使菠菜中敌敌畏、毒死蜱和乐果的降解率达到72.43%、87.15%和75.45%.叶面喷施高铁酸钾对菠菜过氧化物酶(POD)、过氧化氢酶(CAT)活性、MDA含量以及品质指标没有明显影响.试验表明高铁酸钾具有降解有机磷农药残留的作用,在菠菜生产中将高铁酸钾作为有机磷农药残留降解制剂是可行的.     

壳聚糖对菠菜中毒死蜱和乐果的降解作用（Effects of Spraying Chitosan on Degradation of Chlorpyrifos and Dimethoate Residues in Spinach）

在露地栽培条件下,研究了叶面喷施壳聚糖水溶液对菠菜中毒死蜱和乐果的降解作用.结果表明,叶面喷施不同浓度的壳聚糖(50、100、200、400mg·L-1)可有效降低菠菜中毒死蜱和乐果残留量,其中较低浓度壳聚糖能更有效地降低菠菜中毒死蜱、乐果的残留量.50mg·L-1壳聚糖使菠菜中毒死蜱残留量较对照降低40.2%,安全间隔期缩短2.07d;100mg·L-1壳聚糖使菠菜中乐果残留量较对照降低46.9%,安全间隔期缩短0.5d.壳聚糖作为一种有机磷农药降解剂应用于蔬菜生产是可行的.     

长春市主要蔬菜中农药残留分析

采用速测法和气相色谱法研究了长春市市场销售的主要蔬菜中的农药残留问题。2002年秋季对长春市的9个蔬菜批发市场的16种蔬菜进行抽样检测，蔬菜中有机磷类和氨基甲酸酯类农药平均超标率为11．05％，残留的主要农药种类是甲胺磷、氧化乐果和敌敌畏。检测16种蔬菜中有9种超标。2003年春季同样对9个蔬菜市场的17种蔬菜进行抽样检测，农药残留平均超标率为11．0％，残留的农药主要种类是甲基对硫磷、对硫磷、甲拌磷、敌敌畏、氯氰菊酯和氰戊菊酯等，检测的17种蔬菜中有3种严重超标。由此可见蔬菜中农药残留还是很严重的问题，政府与有关部门仍需加强管理。     

夏季蔬菜中有机磷农药残留调查

报道了夏季蔬菜中有机磷农药残留量的调查。结果表明：在西红柿、青椒和豆角中，乐果平均残留量为０．０８１ｍｇ／ｋｇ，甲基对硫磷为０．０１５ｍｇ／ｋｇ，二嗪农为０．００３ｍｇ／ｋｇ，而敌敌畏在这三种蔬菜中均未检出。夏季蔬菜中农药残留量的超标率甲基对硫磷＞乐果＞二嗪农＞敌敌畏。三种蔬菜中，豆角的有机磷农药检出率最高，其次为青椒、西红柿。     

蔬菜中有机磷农药残留的发光菌快速检测

本文建立了一种用发光细菌快速检测蔬菜中有机磷农药残留的方法，以３％ＮａＣｌ（Ｗ／Ｖ）溶液从蔬菜中洗涤出残留的农药，加入定量发光菌溶液，通过其发光量的变化来检测农药的含量。分析了发光菌对蔬菜中六种有机磷农药的响应情况，探讨了检测空心菜中甲胺磷农药残留的最佳参数，实验表明，新建立的方法是检测蔬菜中有机磷农药残留的一种快速有效，价廉的方法。     

氧化乐果和毒死蜱混剂对大鼠雄性生殖功能的联合毒性

为探讨有机磷农药混合物对生物生殖毒性的影响,以模式动物Sprague- Dawley (SD)大鼠为实验材料,采用亚慢性染毒动物实验,利用3×3析因实验设计方法研究了常见有机磷农药——氧化乐果和毒死蜱的联合雄性生殖毒性效应及机理。结果表明：氧化乐果和毒死蜱联合染毒60 d后,附睾系数增加,精子数量和精子活力降低,联合作用呈现协同效应(p<0.05);混配农药能降低睾丸标志酶乳酸脱氢酶(LDH)、酸性磷酸酶(ACP)、碱性磷酸酶(AKP)、γ-谷氨酰转移酶(γ-GT)的活力,对LDH、ACP、γ-GT的联合作用表现为协同作用(p<0.05);混配农药能增加睾丸中促卵泡生成激素(FSH)含量,降低睾酮(T)含量,联合作用表现为协同作用(p<0.05)。通过组织病理学观察,氧化乐果和毒死蜱混合物能引起曲细精管的萎缩、畸形精子增多、生精细胞坏死、胞浆溶解和线粒体空泡化;支持细胞数量减少,出现坏死,精子从支持细胞上脱落,基底膜脱落等损伤。氧化乐果和毒死蜱对大鼠的联合生殖毒性为协同效应,混合后有明显的增毒作用;对睾丸标志酶(LDH、ACP、γ-GT)活力及睾丸性激素水平(FSH、T)的协同影响,是产生联合生殖毒性的机理之一。以上结果提示,对氧化乐果和毒死蜱进行环境健康风险评价时应考虑这种协同作用。     

蜡状芽孢杆菌不同菌株降解有机磷农药的特性分析

筛选分离降解微生物解决有机磷农药残留给水体和土壤环境带来的污染问题是一项可行的生物修复技术。采用富集培养和定时取样分析有机磷农药残留的方法,分离驯化出三株能够降解有机磷农药的细菌,研究了其形态特征和生理生化特性并对其16SrDNA序列进行了分析,同时比较了三菌株对甲基对硫磷（Methyl－parathion）、毒死蜱（Chlorpyrifos）和_二唑磷（Triazophos）的降解特性。结果表明：通过富集培养得到10菌株具有降解甲基对硫磷和毒死蜱的能力,比较确定HY-1、HY-2和HY-4三菌株作为研究对象,经鉴定为蜡状芽孢杆菌（Bacilluscereus）的不同菌株,三菌株在Genbank上的登录号分别为：eu915687、eu915686和eu915688。在甲基对硫磷质量浓度为50mg·L-1时,三菌株72h的降解率分别为91．7％、87．7％与92．4％．降解率无显著性差异（P〉0．05）,当甲基对硫磷质量浓度增加到100mg·L-1时,三菌株对甲基对硫磷的降解率有所下降,其中HY-2对甲基对硫磷的降解率下降最大达23％,且和其他两菌株有显著性差异（P〈0．05o三菌株72h对100mg·L-1毒死蜱的降解率分别达到64．8％、53．7％和56．5％,在不同的毒死蜱初始质量浓度下,HY-1和HY-4两菌株对毒死蜱的降解率无显著性差异（P〉0．05）,HY-2与HY-1、HY-4两菌株有显著性差异（P〈0．05o三菌株对三唑磷的降解率均较低,其中HY-2对初始质量浓度为100mg·L-1三唑磷的降解率最高仅为20．7％,其余两菌株对三唑磷的降解率比HY-2低且无显著性差异（P〉0．05o可以得出本研究分离得到的蜡状芽孢杆菌不同菌株对有机磷农药的降解存在多态性。     

江汉平原农村食品中农药残留研究

研究了湖北省潜江市农村６类食品中农药的残留情况,采样测定结果表明,在被检食品中有机氯农药污染普遍存在,但残留量均低于最大残留限量（ＭＲＬ）,以植物油残留量为最大;有机磷农药残留只在蔬菜中检出,检出率以根菜类为最大,叶菜类次之,果菜类和花菜类最小;菊酯类农药残留较少;杀菌剂多菌灵残留未检出。     

类球红细菌对敌敌畏暴露中斑马鱼的保护作用

敌敌畏是广泛使用的有机磷农药之一,具有较高的水溶性,对水生动物的危害较大.为探讨敌敌畏降解菌对水体中中毒鱼类的降毒效果,测定了敌敌畏对斑马鱼(Brachydanio rerio)的急性毒性,研究了一株敌敌畏高效降解菌--类球红细菌(Rhodobacter sphaeroides)的解毒作用.结果显示:敌敌畏对斑马鱼24、48、72、96h的LC50分别为42.9、37.5、30.7、25.6mg L-1,安全浓度为2.6mg L-1,属低毒农药;在不同敌敌畏暴露浓度的养鱼水中添加类球红细菌(5×107CFU mL-1)可以显著降低斑马鱼的死亡率,28.3mg L-1和33.6mg L-1敌敌畏暴露浓度下,斑马鱼96h死亡率分别由对照组(不添加类球红细菌)的63.3%和96.7%降低到0;利用液相色谱检测了敌敌畏在添加和不添加类球红细菌的养鱼水中的降解规律,结果表明类球红细菌对斑马鱼的保护作用主要是快速降解水中的敌敌畏,并且没有产生对鱼有毒的降解产物.本研究获得了敌敌畏对斑马鱼的基础毒理学数据,同时为微生物降解水体中的农药残留提供了科学依据.     

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。     

Phytotoxicity and uptake of chlorpyrifos in cabbage

Chinese cabbage, Brassica chinensis L., and cabbage, Brassica oleracea L. var. capitata, are the main daily foliar vegetables of the vast majority of the population of eastern and southern China. Cabbages are also planted and consumed widely in other countries. The insecticide and acaricide chlorpyrifos is registered in many countries. Chlorpyrifos controls a variety of insects in plants and soils, and chlorpyrifos is extensively used in the Chinese market. Food poisoning due to the presence of organophosphorus pesticide residues in vegetables has been reported in China provinces. Plant uptake of pesticide residues in air, water, and soil is a source of pesticide residues in vegetables. Here, phytotoxicity and uptake of chlorpyrifos by Chinese cabbage and cabbage were studied in the laboratory using the batch technique. From 0 to 16 days after chlorpyrifos treatment, vegetables roots, stems, leaves, and culture water samples were collected, and the residues of chlorpyrifos in culture water, plant tissues were analyzed using GC-FPD. The results demonstrate that culture solutions with chlorpyrifos had no significant inhibitory effects on vegetable plant height. However, at 1.0 mg/l, it had significant inhibitory effects on the root length and fresh weight of Chinese cabbage. Then, at 10.0 mg/l, it had only significant inhibitory effects on the root length and fresh weight of cabbage compared to the control treatment. The disappearance rates of chlorpyrifos in solutions were in sequence as: nutrition solution with Chinese cabbage, nutrition solution with cabbage, pond water, nutrition solution. The results showed also that chlorpyrifos can be taken up by roots of Chinese cabbage and cabbage from water and subsequently translocated as a function of time. Uptake dynamics of chlorpyrifos from culture solutions by the two cabbage plants were similar.     

水体和甘蓝及土壤中毒死蜱残留检测方法

研究运用不同的样品前处理方式,在装配火焰光度检测器的气相色谱(GC-FPD)上检测,建立了有机磷杀虫剂毒死蜱在水样、土壤和甘蓝中的残留测定方法.研究表明,不同样品中的毒死蜱残留采用本文中介绍的前处理方法是可行的,用石油醚盐析提取和净化水样中毒死蜱,采用丙酮振荡提取甘蓝中毒死蜱,选用索氏提取法提取土壤中毒死蜱,并经液液分配净化后,采用OV-101大口径毛细管柱(30 m×0.53 mm×1.0μm),在装配火焰光度检测器(FPD和磷滤光片)的气相色谱上测定.该分析方法下,毒死蜱的保留时间为1.74 min,线性范围在1.0×10-11—1.0×10-8g之间,其线性相关系数为0.9998,最小检出量为2.0×10-12g.在设定的较低添加浓度的条件下,毒死蜱在水样、土壤与甘蓝上的添加回收率为80%—120%,变异系数均小于5%.该分析方法灵敏、准确、操作简便,适合水样、甘蓝和土壤中低浓度毒死蜱的残留检测.     

Ultrastructure effects of omethoate and cypermethrin insecticides on maize seedlings

Increasing studies suggest that insecticides are one of the plant stress elements that affect plant growth and productivity by interfering with cell metabolic and biochemical activities. Here, we show that the application of commonly used pesticides omethoate and cypermethrin on maize (Zea mays L. cv. Luyu 9) seedling leaves resulted in adverse effects on leaf ultrastructure changes under laboratory conditions. Electron microscopic studies reveal that the topical application of organophosphorus insecticide omethoate causes direct injury of leaf ultrastructures including cell wall breakdown of abaxial epidermis cells, inner cells, stomata guard cells; degradation of mitochondrial membrane, and chloroplast envelope membrane; and abnormal changes of lamella arrangement of chloroplast. And the topical application of cypermethrin insecticide causes plasmolysis of cells of the adaxial epidermis, mitochondrial cristae are degraded, and loosen arranged lamella of amyloplasts. All these changes indicated that omethoate and cypermethrin are stress factors that caused adverse effects on plant ultrastructures and biochemical molecules.     

In situ enhanced bioremediation of dichlorvos by a phyllosphere Flavobacterium strain

A bacterium capable of degrading dichlorvos was isolated from the rape phyllosphere and designated YD4. The strain was identified as Flavobacterium sp., based on its phenotypic features and 16S rRNA gene sequence. Strain YD4 was able to utilize dichlorvos as the sole source of phosphorus. In situ enhanced bioremediation of dichlorvos by YD4 was hereafter studied. Chlorpyrifos and phoxim could also be degraded by this strain as the sole phosphorus source. A higher degradation rate of dichlorvos was observed after spraying YD4 onto the surface of rape leaves when compared to the sterilized-YD4 and water-treated samples. The results indicated that pesticide-degrading epiphytic bacterium could become a new way for in situ phyllosphere bioremediation where the hostile niche is unsuitable for other pesticide-degrading bacteria isolated from soil and water.     

蔬菜中有机磷农药残留的分光光度法快速检测

以鸡脑为酶源提取乙酰胆碱酯酶,利用酶抑制分光光度法检测蔬菜中有机磷农药残留量.用此方法测定了对硫磷、辛硫磷、氧化乐果三种农药,结果满意,回收率分别达到97%,101%和99%.     

Dichlorvos degradation studied by 31P-NMR

We studied the hydrolysis and TiO₂ photocatalysis of the pesticide dichlorvos at pH 2.6–9 using phosphorus-31 nuclear magnetic resonance (³¹P NMR). We found that the hydrolysis of dichlorvos led to the formation of dimethyl phosphate at pH 5.6–9. On the other hand, TiO₂ photocatalysis decomposed dichlorvos into dimethyl phosphate, which further reacted to form monomethyl phosphate at pH 2.6 and 9. Monomethylphosphate was hydrolysed into phosphate at pH 2.6. ³¹P NMR is therefore a promising tool to study the degradation of organophosphorus pesticides.     

Methylobacterium sp. YAL-2对乙酰甲胺磷的降解特性

从有机磷生产厂家的下水道污泥中分离出一株对高浓度和低浓度乙酰甲胺磷都具有高效降解能力的寡营养菌YAL-2,根据形态、生理生化和16S rRNA基因系统发育分析,将菌株YAL-2鉴定为Methylobacterium sp.降解特性实验表明,菌株YAL-2能利用乙酰甲胺磷为唯一碳源生长和降解;在添加了甲醇的无机盐培养基中,84 h可完全降解300mg L-1乙酰甲胺磷,24 h将50 mg L-1和10 mg L-1乙酰甲胺磷降至非检测水平;4 d能完全去除100 mg L-1甲胺磷,5 d分别降解58.4%和40.6%的100 mg L-1乐果、敌敌畏.小青菜农药残留去除实验显示,菌株YAL-2可在7 d内将乙酰甲胺磷和甲胺磷将至限量水平.结果表明,将菌株YAL-2应用于保证果蔬等食品的食用安全是可行的.