通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

Arsenic residue in residential area after cleanup of pesticide illegal dumping sources in Thanh Hoa province,Central Vietnam

In Vietnam, Nicotex's site is perhaps the most infamous case of illegal disposal of toxic pesticides near residential areas. In 2013, affected villagers discovered illegal burials of around 1,000 tons of expired pesticides in the Nicotex factory. Organic pesticides were detected in illegal burial areas (IBAs) around 60 times greater than acceptable levels, but no attention was paid to contamination of metals, metalloids, and other classes of organic contaminants, which could be co-contaminants in pesticide formulation. This study assessed the contaminants remaining in the IBAs and surrounding residential areas two years after the source removal conducted in 2014. Additionally, a preliminary health risk assessment from residual contaminants was performed. Nine classes of chemicals including parental pesticides, inorganic and organic degradation byproducts, and metals and metalloids, comprising 123 chemicals were quantified in soil, sediment, and water samples from Nicotex and surrounding residential areas. Although concentrations of organic pesticides were below acceptable levels, arsenic contamination in the soil in a Nicotex IBA named NCT5 and Nap village (NV) exceeded the acceptable level. The enrichment factor and log-probability plot indicate that arsenic enrichment at NV is not from natural sources but is associated with arsenic contamination in NCT5. Arsenic may be a co-contaminant in pesticide manufacturing or an arsenical pesticide, such as monosodium methanearsonate. Arsenic found in NV was toxic arsenate for which the preliminary risk assessment yielded an unacceptable excess carcinogenic risk (1 × 10^?4). While all attention was paid to investigate and treat contamination of organic pesticides, it turns out that arsenic is the major existing threat which poses an unacceptable cancer risk in good agreement with the high cancer rate claimed by villagers near Nicotex. This justifies the need for further investigation of the extent of the arsenic contamination and restoration of the contaminated land.     

Human milk contamination by nine organochlorine pesticide residues (OCPs)

Abstract

Organochlorine pesticides (OCPs) are widely used around the world as insecticides, herbicides, fungicides, nematicides, and rodenticides. Despite banned in Brazil, the usage remains occurring in many countries. The persistence and extreme mobility of OCPs contribute to the contamination of the environment and the human body. The OCPs bioaccumulation in adipose tissue triggers the excretion into human milk during breastfeeding. Hence, the present study determined eighteen OCPs residues in the breast milk of mothers from the Western Region of Bahia State, Brazil. Nine different residue species were found, including beta-Hexachlorocyclohexane (9.24?±?0.00?ng g^?1 fat), delta- Hexachlorocyclohexane (22.15?±?10.48?ng g^?1 fat), Heptachlor (58.08?±?74.13?ng g^?1 fat), Aldrin (142.65?±?50.65?ng g^?1 fat), Dieldrin (774.62?±?472.68?ng g^?1 fat), Endosulfan I (408.44?±?245.51?ng g^?1 fat), Dichloro-diphenyl-dichloro-ethylene (29.17?±?22.42?ng g^?1 fat), Dichloro-diphenyl-trichloro-ethane (28.87?±?0.00?ng g^?1 fat) and Methoxychlor (1699.67?±?797.43?ng g^?1 fat). The Methoxychlor presence in all samples may reveal a recent exposure, while Dieldrin and Endosulfan I analyses can point to distant past exposure.     

内循环活性炭生物流化床处理农药生产废水的试验研究

采用内循环活性炭生物流化床反应器处理某农药厂生产废水,通过试验研究了该反应器在室温条件下处理农药生产废水的性能.结果表明:当进水pH值控制在7.0～7.5、水力停留时间为6h、曝气量控制在使活性炭处于流化状态时,CODcr的去除率为50％,总氮的去除率为32.33％,同时可生化性明显提高,生物毒性有所降低.     

停留时间对滴滴涕农药热处理特性的影响研究

利用高温管式炉研究停留时间对滴滴涕农药热处理特性的影响。结果表明,600℃时ηDDT在15 min内迅速增长,在15 min后稳定在85%上下;900℃时,当停留时间≥15 min,ηDDT≥99%;1 200℃时,各时段的ηDDT≥99.9%。在滴滴涕农药残渣中,DDTs在600℃和900℃时的配比随停留时间的增加变化甚微,在1 200℃时,p,p’-DDD、DDT和o,p’-DDT分别占DDTs总量的比例随时间增加明显降低,p,p’-DDE则大幅增加。在尾气中,DDTs在600℃时的配比随停留时间的增加无明显变化,DDT为主要尾气残留物质,900℃时DDTs在尾气中配比变化混乱,1 200℃时,p,p’-DDE的比例随停留时间的增长迅速增加,并成为尾气中的主要DDTs残留物质。     

有机氯农药污染土壤的Fenton氧化修复研究

研究了Fenton氧化对某实际有机氯农药污染场地土壤的修复效果。结果显示:Fenton氧化能够快速有效地降解污染土壤中的六氯和DDTs。当Fe2+浓度为80 mmol/L,Fe2+与H2O2的摩尔浓度比为1∶5,水土比10∶1时,反应6 h,土壤中六氯和总DDT的去除率分别为:96.7%和78.2%。每方土的修复成本估算为951元。     

南四湖底泥中有机氯农药分布特征

采用GC-ECD对南四湖底泥中的有机氯农药HCHs和DDTs含量进行了定性和定量分析。南四湖8个采用点均有不同程度的HCHs和DDTs检出,其中中部区域含量较高。根据各含量的值推测南四湖部分地区仍然有林丹在使用,基本没有HCHs工业制品在使用,底泥中的HCHs主要为早期残留;南四湖地区没有新的DDTs输入,大部分的DDT在好氧条件下转化成为了DDE并赋存在底泥中。     

养殖鳜鱼体内典型有机氯化合物的检测与人体健康风险评估初探

利用GC-ECD检测了江苏省吴江市某养殖塘内的一批鳜鱼体内有机氯农药（OCPs）和多氯联苯（PCBs）等典型有机氯化合物（OCs）的含量水平,并对其人体健康风险进行了初步评估.结果表明,养殖鳜鱼体内滴滴涕（DDTs）、六六六（HCHs）、六氯苯（HCB）和PCBs的含量范围分别为1.3～4.57、0.13～1.24、0...     

辽宁大伙房水库沉积物中有机氯农药和多氯联苯的分布、来源及风险评价

利用GC-MS测定24个大伙房水库表层沉积物中有机氯农药和多氯联苯含量,主要揭示水库沉积物中有机氯农药和多氯联苯的残留特征.结果表明,HCHs的含量为0.70～3.48 ng.g-1,均值为（1.58±0.71）ng.g-1;DDTs的含量为0.85～4.94ng.g-1,均值为（1.94±0.82）ng.g-1;PCBs的含量为1.46～3.52 ng.g-1,均值为（2.42±0.64）ng.g-1.γ-HCH、β-HCH、DDE、DDT和PCB28百分含量较高.高百分含量γ-HCH和DDT表明目前仍在使用的林丹和工业滴滴涕产品;β-HCH、DDE和PCB28可能来自土壤中农药和多氯联苯残留.水库上游污染物含量明显高于水库下游,同时污染物高值点主要集中在浑河河口,表明水库上游浑河河流搬运是水库沉积物中污染物的主要输入来源,并影响污染物在沉积物中的分布.生态风险评价结果表明,沉积物中DDTs和γ-HCH存在较高的生态风险;沉积物中PCBs残留尚未对周围环境造成不利影响.     

高效木薯渣分解复合菌群RXS的构建及其发酵特性研究

从富含腐烂纤维质的环境中取样,通过以木薯渣及滤纸为碳源的蛋白胨纤维素培养基不断地富集培养,构建了一组高效稳定的纤维质分解复合菌群.考察了该复合菌群对不同纤维质底物的分解性能及其在木薯渣水解过程中主要参数的变化.研究发现该复合菌群对滤纸、脱脂棉、微晶纤维素、麦秸秆和木薯渣等原料均能够进行有效的降解.在该复合菌群应用于木薯渣的水解过程中,监测发现纤维素酶、半纤维素酶、果胶酶等关键酶的酶活力分别在第2～3 d达到最大值34.4、90.5和15.8U;经过10 d的发酵后,木薯渣中的纤维素、半纤维素及木质素分别降解了79.8%、85.9%和19.4%,且木薯渣的失重高达61.5%;此外,代谢产物主要是乙酸、丁酸、己酸和甘油;而溶解性COD、总糖和总挥发酸的变化表明第2 d时木薯渣的水解率最高.上述结果表明,该复合菌群能够有效地水解木薯燃料酒精生产过程中的废弃物木薯渣,并有望用于木薯渣高效沼气发酵的前处理中.