空气中有机氯农药在不同粒径颗粒物上的分布

采用 DFJ-1型五段分级采样装置,对呼和浩特市冬夏两季空气中不同粒径(分别为≥7.0μ m,7.0-3.3μm,3.3-2.0μm,2.0-1.1μm,≤1.1μm)颗粒物上有机氯农药的残留量进行分析.测定结果表明:在空气颗粒物分级样品中,均检出有机氯农药(HCH-666 和p,p'-DDE)残留量;空气颗粒物中HCH-666冬季均值为0.502ng·m -3,夏季为1.070ng·m-3,而p,p'-DDE在冬季为0.0 85ng·m-3,夏季为0.108ng·m-3;呼和浩特市空气中有机氯农药残留量夏季均高于冬季,不同粒径空气颗粒物中有机氯农药的分布规律为:冬季主要富集在细小颗粒 (≤1.1μm)上,在30.6%-70.5%之间,在夏季有机氯农药的残留分散吸附在五个不同粒径级上.     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

Mercaptobenzothiazole-on-gold organic phase biosensor systems: 1. Enhanced organosphosphate pesticide determination

This paper reports the construction of the gold/mercaptobenzothiazole/polyaniline/acetylcholinesterase/polyvinylacetate (Au/ MBT/PANI/AChE/PVAc) thick-film biosensor for the determination of certain organophosphate pesticide solutions in selected aqueous organic solvent solutions. The Au/MBT/PANI/AChE/PVAc electrocatalytic biosensor device was constructed by encapsulating acetylcholinesterase (AChE) enzyme in the PANI polymer composite, followed by the coating of poly(vinyl acetate) (PVAc) on top to secure the biosensor film from disintegration in the organic solvents evaluated. The electroactive substrate called acetylthiocholine (ATCh) was employed to provide the movement of electrons in the amperometric biosensor. The voltammetric results have shown that the current shifts more anodically as the Au/MBT/PANI/AChE/PVAc biosensor responded to successive acetylthiocholine (ATCh) substrate addition under anaerobic conditions in 0.1 M phosphate buffer, KCl (pH 7.2) solution and aqueous organic solvent solutions. For the Au/MBT/PANI/AChE/PVAc biosensor, various performance and stability parameters were evaluated. These factors include the optimal enzyme loading, effect of pH, long-term stability of the biosensor, temperature stability of the biosensor, the effect of polar organic solvents, and the effect of non-polar organic solvents on the amperometric behavior of the biosensor. The biosensor was then applied to detect a series of 5 organophosphorous pesticides in aqueous organic solvents and the pesticides studied were parathion-methyl, malathion and chlorpyrifos. The results obtained have shown that the detection limit values for the individual pesticides were 1.332 nM (parathion-methyl), 0.189 nM (malathion), 0.018 nM (chlorpyrifos).     

Organohalogen compounds in blubber of Indo-Pacific bottlenose dolphin (Tursiops aduncus) and spinner dolphin (Stenella longirostris) from Zanzibar, Tanzania

Blubber samples of Indo-Pacific bottlenose (Tursiops aduncus) and spinner (Stenella longirostris) dolphins from Zanzibar, East Africa, were analyzed for a wide range of organohalogen compounds. Methoxylated polybrominated diphenyl ethers (MeO-BDEs), presumably biogenic, were found at higher concentrations than anthropogenic organochlorine pesticides (OCPs). Only traces of industrial pollutants, such as polychlorinated biphenyls, were detected. The OCP levels found off Zanzibar were lower than those reported from other regions while MeO-BDE levels were higher. The relative composition of the OCPs indicated recent use of lindane (γ-hexachlorocyclohexane) and aged residues of DDT and technical HCH. Placental transfer was estimated to 2.5% and 0.5% of the total burden of OCPs and MeO-BDEs, respectively. Overall transfer from mother to calf in Indo-Pacific bottlenose dolphins was estimated to 72% and 85% for the OCPs and MeO-BDEs burdens, respectively. Health effects of MeO-BDEs are not known, but structural similarities with well-known environmental toxins are cause for concern.     

对饮用水中游离性余氯测定条件的研究

系统研究了反应时间、水温、显色剂的用量及pH对游离性余氯测定的影响,优化选择最佳测定条件为控制水样pH<8,水温25℃,显色剂用量2.5 ml,加入显色剂后立即比色测定游离性余氯。在此条件下,测定3种生活饮用水游离性余氯,回收率为96.7%~99.8%,测定结果与《生活饮用水标准检验法》(GB 5750-85)中37.3滴定法颇为一致。     

有机磷农药废水处理技术

久效磷和亚磷酸三甲酯生产过程中产生的废水经碱解沉淀和超声气浮预处理,可降低其ＣＯＤ和毒性,提高其可生化性,再经以光合细菌为主的生化处理,可使其ＣＯＤ降至２００ｍｇ／Ｌ。     

给水管网中余氯浓度对颗粒物表面细菌附着的影响

为解析余氯浓度对颗粒物表面细菌附着的影响,以给水管网细菌为研究对象,开展其在不同余氯浓度条件下的附着实验.结果表明,低浓度氯(0~0.5 mg·L~(-1))会促进细菌在针铁矿表面的附着,而高浓度氯(0.5~3.0 mg·L~(-1))抑制了细菌的表面附着.通过定量测定及激光共聚焦显微镜的观测发现,当氯浓度为0.5 mg·L~(-1)时,聚集体总细菌数、胞外聚合物(EPS)含量均达到最大.研究结果揭示了余氯浓度调控着细菌EPS的分泌,进而影响细菌在给水管网中颗粒物表面的附着.     

基于环境风险排序的流域优先污染物筛选

在流域生态环境治理中,确定治理水体的优先污染物是首先要考虑的问题.环境风险排序方法可利用污染物的毒性值与该污染的暴露浓度值的比值,快速对流域污染物进行风险排序,确定优先污染物.本文以有多年氟化工生产排放历史的大凌河为研究区域,分季节采集18个样点的水体表层样品,分析全氟辛基磺酸(PFOS)、全氟辛酸(PFOA)以及8种常见重金属,并搜集有关当地物种生态毒性的文献资料,确定其优先污染物.结果发现,2011~2016年间,大凌河水体PFOS和PFOA的中位值浓度分别在0.77~3.57 ng·L~(-1)、82.93~344 ng·L~(-1)之间,参照英国水环境对人体健康的潜在风险值发现其均低于标准限值.重金属和有机氯农药的浓度均低于国家Ⅳ级标准,但Hg和As的最高浓度高于Ⅲ级标准.大凌河环境风险值范围为1.42×10-6~2.3×10-2,环境风险排序结果为CuZnAsp,p'-DDEp,p'-DDTCdPbHgPFOAγ-HCHCrNiα-HCHPFOS.PFOS和PFOA的环境风险排序较为靠后,说明不是该地区需要优先控制的污染物,但长期风险累积不可忽视.Cu是未来大凌河生态环境治理的优先污染物,应重点控制包括造纸厂在内的主要工业企业的生产排放行为.     

基于小波分解与自适应多级残差修正的最小二乘支持向量回归预测模型的PM2.5浓度预测

采用小波分解(WD)将济南市科干所监测站PM_(2.5)浓度的一维时间序列(2013年1月1日—2017年8月15日)分解为高维信息,获得了该监测站附近PM_(2.5)浓度的时频变化特征,重点分析了PM_(2.5)的随机性和趋势性问题.然后构建了基于小波分解的多级残差修正的最小二乘支持向量回归预测模型(AMLRC-WLSSVR),结果发现,该模型能够很好地对济南市PM_(2.5)浓度做出预测,特别是针对重污染天气的预测有很好的精度.为了避免预测结果的不确定性问题,提出了一种基于方差估计给出预测值置信区间上界的方法,同时,有效弥补了单点预测的不稳定性及预测精度不足的缺点,该方法能够为实际空气污染预警提供技术支持.