河北潘家口水库氯霉素类抗生素检测及风险评估

采用固相萃取-高效液相色谱-串联三重四级杆质谱联用法(SPE-HPLC-MS/MS)测定河北潘家口水库中4种氯霉素类抗生素.该方法采用电喷雾电离源、多重反应监测正或(负)离子模式,4种氯霉素类抗生素加标回收率高于90%,相对标准偏差在1.60%~5.43%.方法的检出限在0.06~0.29ng/L,定量限在0.18~0.87ng/L.潘家口水库水样检测氟苯尼考残留量在26.21~233.35ng/L,氟苯尼考胺在0.53~8.18ng/L,所有水样中氯霉素和甲砜霉素均未检出.对潘家口水库氯霉素类抗生素残留的生态风险和人体健康风险评估表明,RQ(风险商)小于1,说明潘家口水体氯霉素类抗生素对浮游生物和人体健康尚不存在明显危害.丰水期成人和儿童的RQ均比平水期大,最大相差2个数量级.这可能由于此时期为网箱养鱼活跃期,或与水库调水有一定相关性.     

六溴环十二烷(HBCD)对斑马鱼发育早期能量代谢及软骨、肌肉和鱼鳍发育的影响

六溴环十二烷(hexabromocyclododecane, HBCDs)是一种添加型阻燃剂,在环境中广泛存在。由于具有持久性、生物蓄积性和毒性等特征,HBCD很可能在水生生物体内富集并对其生长发育产生影响。将斑马鱼胚胎暴露于不同浓度的HBCD(0.1、0.5和1 mg·L^-1),通过油红O和阿尔新蓝染色观察幼鱼发育状况,并通过能量代谢及发育相关基因探讨可能的作用机制。结果表明,HBCD暴露影响了幼鱼对卵黄囊内生脂肪的吸收,并对幼鱼躯干骨骼肌、头部软骨和鱼鳍的发育产生损害。进一步研究发现,暴露组幼鱼体内ATP含量降低,ATP合成酶及电子呼吸链中还原性辅酶Ⅰ(NOX)和细胞色素C氧化酶(COX)等的活性显著降低;同时,早期发育相关基因如骨形成蛋白bmp、肌肉决定因子myod以及sox9a和wnt等基因的转录水平均受到显著抑制(P<0.05)。上述结果表明,HBCD会影响早期发育阶段的斑马鱼对卵黄囊营养物质的吸收,干扰体内能量代谢,导致能量供应不足,并通过bmp-sox9和wnt-myod等信号通路影响软骨组织、鱼鳍和骨骼肌的正常发育。     

邻苯二甲酸丁基苄酯在鼠肝匀浆中的生物降解及代谢产物鉴定

应用HPLC及HPLC MS方法,研究了邻苯二甲酸丁基苄酯在小鼠肝匀浆中的代谢动力学、酶动力学特征并进行了代谢产物鉴定.测得邻苯二甲酸丁基苄酯在雄性小鼠肝匀浆中的t1 2为73 72min,Km为(73 52±24 11)μmol·L-1,Vmax为(2 85±0 62)μmol·g-1·min-1);在小鼠雌性肝匀浆中t1 2为144 37min,Km为(275 02±64 97)μmol·L-1,Vmax为(6 18±2 30)μmol·g-1·min-1).实验鉴定出邻苯二甲酸丁基苄酯在肝脏中的代谢产物为邻苯二甲酸单丁酯及邻苯二甲酸甲丁酯.实验结果表明,邻苯二甲酸丁基苄酯在肝脏中代谢有明显的性别差异.     

代谢产物积累对二氯甲烷生物降解的影响

研究了代谢调节产物(NaCl)浓度积累对生物法降解二氯甲烷效率的影响。试验表明,一定浓度的NaCl对二氯甲烷降解菌(GD11)的生长有不同程度的抑制作用。摇瓶试验中NaCl对二氯甲烷降解菌的抑制浓度为35.1g/L;当空塔气速91.7m/h、二氯甲烷进口浓度2.02g/m3、温度28.5℃、循环液流量0.06m3/h、pH值6.5～7.5时,生物滴滤塔中NaCl对二氯甲烷降解菌的抑制浓度为23.4g/L,两者相比有一定差异。NaCl浓度对生物膜的厚度有一定影响,这从侧面反映了NaCl浓度对微生物活性的影响。     

Degradation of a chiral nonylphenol isomer in two agricultural soils

The degradation of a chiral nonylphenol isomer, 4-(1-ethyl-1,4-dimethylpentyl)phenol (NP₁₁₂), in two agricultural soils from Monheim and Dortmund, Germany has been studied. The degradation of NP₁₁₂ and the formation of a nitro-nonylphenol metabolite were determined by means of GC-MS analysis. The degradation followed bi-exponential order kinetics, with half-life of less than 5 days in both soils. The nitro-metabolite was found at different concentration levels in the two soils. The nitro-metabolite of NP₁₁₂ was more persistent than its parent compound. After 150 days about 13% of the initially applied NP₁₁₂ remained in the Monheim soil as its nitro-metabolite. Results of the E-screen assay revealed that the nitro-NP₁₁₂ has oestrogenic potency of 85% of that of NP₁₁₂. Furthermore, the results of chiral GC-MS analysis revealed that no chiral degradation of NP₁₁₂ occurred in this study.     

Enantioselectivity in toxicity and degradation of dichlorprop-methyl in algal cultures

Enantioselectivity in the toxicity and degradation of the herbicide dichlorprop-methyl (2,4-DCPPM) in algal cultures was studied. Enantioselectivity was clearly observed in the toxicity of racemic 2,4-DCPPM and its two enantiomers. R-2,4-DCPPM showed low toxicity to Chlorella pyrenoidosa and Chlorella vulgaris, but higher toxicity to Scenedesmus obliquus. The observed toxicity was ranked: R-2,4-DCPPM > S-2,4-DCPPM ? Rac-2,4-DCPPM; the toxicity of R-2,4-DCPPM was about 8-fold higher than that of Rac-2,4-DCPPM. Additionally, 2,4-DCPPM was quickly degraded, in the initial 12 h, and different algae cultures had different enantioselectivity for the 2,4-DCPPM enantiomers. There was no significant enantioselectivity for 2,4-DCPPM in Chlorella vulgaris in the initial 7 h. However, racemic 2,4-DCPPM was degraded by Scenedesmus obliquus quickly, in the initial 4 h, much quicker, in fact, than the S- or R-enantiomers (racemate > R- > S-), indicating that the herbicide 2,4-DCPPM was absorbed enantioselectively by Scenedesmus obliquus. The rapid formation of 2,4-DCPP suggested that 2,4-DCPPM adsorbed by algal cells was catalytically hydrolyzed to the free acid, a toxic metabolite. The production rates of 2,4-DCPP were as follows: Scenedesmus obliquus > Chlorella pyrenoidosa > Chlorella vulgaris, consistent with the degradability of 2,4-DCPPM. Scenedesmus obliquus had quick, but different, degradative and uptake abilities for R-, S-, and Rac-2,4-DCPPM. The R- and S- enantiomers were not hydrolyzed in the first 12 h, while both enantiomers were hydrolyzed slowly after that. These results indicate that some physical and chemical properties of compounds are of importance in determining their enantioselective toxicity and degradation. The ester and its metabolite likely played an important role in enantioselective toxicity to the three algae.     

Development of competitive immunoassays to hydroxyl containing fungicide metabolites

This paper describes the isolation of monoclonal antibodies and the development of competitive immunoassays to pesticide metabolites of the fungicides imazalil, carbendazim and thiabendazole. The metabolite specific hydroxyl residues were used as the reactive group with which to link the metabolite to the carrier proteins Keyhole Limpet Haemocyanin (KLH) and Bovine Serum Albumin (BSA). In each case immune responses in mice were raised and monoclonal antibodies were produced. Antibodies were developed into competitive ELISAs to the appropriate metabolite. The antibody raised to a metabolite of imazalil was optimised into a competitive ELISA format which had an assay IC50 of 7.5 μg/L and a limit of detection (LOD) of 1.1 μg/L. A single antibody isolated against the metabolite of carbendazim had assay IC50s of 3.2 and 2.7 μg/L for the metabolites of carbendazim and thiabendazole respectively with an LOD of 0.38 μg/L for both. These sensitive immunoassays may have application in the monitoring of human exposure to these fungicide residues either by occupational or non-occupational routes.     

光照对芦丁稳定性及抑菌活性的影响

黄酮类化合物具有多羟基结构易被氧化,为了解其羟基被氧化后,是否还具有抑菌、抗癌等多种生物学活性,对芦丁光照处理前后的含量、抗氧化活性(清除DPPH.和还原能力)、分子结构以及抑菌活性进行了比较研究.结果表明,随着光照时间的延长,芦丁含量和抗氧化活性均呈下降趋势,降解反应属于一级反应,半衰期为187.3 d.结构鉴定表明,光照处理芦丁母核结构没有降解,只是A环5、7-OH和B环3′、4′-OH氢解离,芦丁在溶液中以负离子或自由基形式存在.芦丁氧化前后的浓度与抑菌效果均成良好的量效关系,其相关系数分别为0.933 2和0.933 0.但氧化芦丁的EC50值(15.58 g/L)与对照(6.34 g/L)相比差异显著(P<0.01).可见,氧化芦丁的抑菌活性明显降低.这进一步表明,芦丁分子结构的细微改变与体外的抗氧化活性和抑菌活性三者之间的构效关系基本一致.     

The effect of multiple soil applications of disulfoton on enhanced microbial degradation in soil and subsequent uptake of insecticidal chemicals by potato plants

Abstract

Potatoes were grown during 1992 in 2 m² plots of loam which had received 1, 2 or 3 annual treatments of Di‐Syston 15G, equivalent to 3.36 kg AI/ha, in furrow at planting. The presence of enhanced degradative activity to the sulfoxide and sulfone metabolites of disulfoton in the soil treated in the previous two years was confirmed by laboratory tests prior to the 1992 treatments. Soil, seed potato and foliage from the three treatments were analyzed for disulfoton and its sulfoxide and sulfone metabolites for 12 wk following planting/treatment. Disulfoton was the major insecticidal component of the soil, a minor component of the seed piece and was not detected (<0.02 ppm) in potato foliage. Disulfoton concentrations in each of the three substrates sampled were similar for the three treatments. Disulfoton sulfoxide and sulfone were the major insecticidal components of the seed piece and foliage. Their maximum concentrations in 1st year soil, seed pieces and foliage were ca. 2x, 2x and 6x, respectively, those measured in the 2nd and 3rd year treatments. The results demonstrate that enhanced microbial degradation of relatively minor insecticidal compounds in the soil can profoundly affect insecticide levels in the plant when these compounds are the major insecticidal components accumulated. The broader implications for crop protection using soil‐applied systemic insecticides are discussed.