氟虫腈对斑马鱼和小菜蛾毒性的手性选择性研究

手性农药分子的不同对映体在环境中的降解速率和对于生物的毒性可能存在很大的差异,因此拆分并使用对靶标生物毒性较高或对非靶标生物毒性较低的单一或浓缩的对映体配方可以有效地降低杀虫剂的环境风险.本文用手性柱拆分了一种广泛使用的手性农药,氟虫腈的两种对映体,研究了这两种对映体和消旋体对靶标生物小菜蛾和非靶标生物斑马鱼的急性毒性.结果表明氟虫腈对受试靶标和非靶标生物的毒性均无手性选择性,说明无法通过对氟虫腈进行手性拆分并使用单一对映体配方来降低氟虫腈的环境风险.这一结论间接支持了农业部新近出台的禁止氟虫腈用于防治农田害虫的政策.     

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。     

氰戊菊酯和锐劲特对原生动物群落的联合毒性试验研究

氰戊菊酯和锐劲特两种农药被广泛用于茶树、果树、水稻、蔬菜等的病虫害防治,它们同时出现在同一环境中的机会非常多,但有关两种农药对生态系统的复合毒性效应却未见有研究报道.与单种生物毒性试验相比,群落级生物毒性试验对毒物胁迫的反映更具环境真实性.以PFU在天然淡水中采集到的原生动物群落为靶生物,研究了氰戊菊酯和锐劲特2种农药对淡水原生动物群落的毒性效应,对于水生生态环境的保护有特殊的意义.研究结果表明,2种农药单独存在时对原生动物群落的48h半数致死浓度分别为15 93mg·L-1和35 83mg·L-1;2种物质以等毒性比(单一LC50的比值)混和,进行联合毒性试验研究,用Marking相加指数法进行评价,其AI值为0 9,表现为协同作用.氰戊菊酯和锐劲特进入水环境后,将使水环境中原生动物群落的结构和组成发生变化,原生动物种类数减少,群落结构变得简单.在所有种类中,纤毛虫受损最大,水生生态系统的物质循环和能量流动将会受到一定程度的影响.     

单克隆抗体间接竞争ELISA测定水体中氟虫腈

制备了氟虫腈单克隆抗体 ,在此基础上建立了水体中氟虫腈测定的间接竞争性酶联免疫吸附测定 (ELISA)法 .在优化条件下 ,氟虫腈测定的线性浓度范围为 1 0 -1 μg·L-1 ～ 1 0 3μg·L-1 ,最低检出浓度 (I1 0 )为 0 0 8μg·L-1 ,检测灵敏度 (I50 )为6 6 8μg·L-1 ;常见的几种与氟虫腈结构类似的农药的交叉反应率均低于 1 % ,不干扰氟虫腈的检测 ;2 0 %丙酮、5 %甲醇、2 %二甲基甲酰胺、2 %乙腈和 2 %乙酸乙酯基本不影响免疫测定 .利用建立的间接竞争性ELISA方法检测不同水样中氟虫腈 ,结果表明不同水样均可直接进行测定 ,方法的精密度和准确度均符合残留测定的要求     

Effect of triazophos,fipronil and their mixture on miRNA expression in adult zebrafish

MicroRNA (miRNA) plays a crucial role in gene expression regulation. However, no data are available on change of miRNA expression of zebrafish (Danio rerio) after treatment with pesticides. We evaluated the effect of fipronil (5-amino-1-[2, 6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl) sulfinyl]-1H-pyrazole-3-carbonitrile) and triazophos (3-(O, O-diethyl)-1-phenyl thiophosphoryl-1, 2, 4-triazol) and their mixture on miRNA expression in zebrafish. MiRNA expression profiles in zebrafish were altered after treatment with these chemicals. An association between these chemicals and the expression of 21 miRNAs was found 96 h after treatment. Among them, 14 miRNAs were differentially expressed due to the treatments with fipronil, triazophos and their mixture; 5 miRNAs showed altered expression level after treatment with formulations of these chemicals; miR-29b and miR-738 were differentially expressed after treatment with adjuvants. MiRNAs might present a novel toxicological response that could be used as a toxicological biomarker and have a different direction for future investigations of their association with miRNAs involved in chemical related diseases.     

D301树脂对水中氟虫腈的吸附去除研究

文章研究D301树脂对水溶液中氟虫腈的吸附行为,考察了吸附剂投加量和溶液pH值对吸附效果的影响,对吸附等温线和吸附动力学进行了探讨,并选择不同模型对吸附曲线进行拟合。结果表明,当氟虫腈溶液初始浓度为2 mg/L,吸附剂投加量为0.5 g/L时,氟虫腈的去除率达到100%;溶液pH值在3⁹范围内变化时,对吸附的影响较小,相对而言pH=7的吸附效果最好;D301树脂对氟虫腈的吸附等温线满足Langmuir吸附等温式和Freundlich吸附等温式,相关系数R2分别为0.994和0.991;吸附动力学符合Lagergren一级反应方程。总体来说,D301树脂对氟虫腈的吸附效果较好。     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

锐劲特对原生动物群落的急性毒性试验

以PFU法采集的淡水原生动物群落为试验对象 ,对锐劲特的急性毒性进行研究 .结果表明 ,锐劲特对原生动物群落的 48h LC50 为 35 83mg·l- 1 ;原生动物群落结构参数和功能参数随加入锐劲特的量而变化 ;在种类组成上 ,虽然鞭毛虫、纤毛虫、肉足虫的种类均随着毒物浓度的增大而下降 ,但是其减少的程度各不相同 ,纤毛虫所受损伤最大 ;在试验浓度范围内 ,功能类群发生显著变化 ,光合作用自养者和食藻者原生动物的物种逐渐消失 ,而一些食菌 碎屑类原生动物具有较高的耐受性 ,随着锐劲特浓度的增加 ,其在群落中的优势度更加明显     

丁烯氟虫腈光降解反应过程及机理

考察了乙腈/水混合溶液中丁烯氟虫腈的光解速率及水体中主要溶解性物质对其光解的影响,通过产物鉴定及模拟计算判定了丁烯氟虫腈光降解反应机理.结果表明,模拟日光下丁烯氟虫腈快速发生光降解,纯水中反应半衰期为17.34 min.腐殖酸通过竞争光吸收来抑制丁烯氟虫腈的光解,NO3-和Cl-对其光解无影响.丁烯氟虫腈光解反应位点位为亚砜基团上的硫原子,主要产物为脱硫化物(MW 442.0),砜化物(MW 506.0)及2种硫化物(MW 473.9和405.8).键级和键长分析也证实丁烯氟虫腈硫原子连接的化学键不稳定,易发生断裂重排反应,生成上述转化产物.