Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

串联四极杆质谱(GC-QqQ-MS/MS)测定土壤中的有机氯农药和多氯联苯

建立了用加速溶剂萃取仪(ASE)萃取、凝胶渗透色谱(GPC)净化、气相色谱/串联四极杆质谱多反应监测、同时测定土壤中17种有机氯农药和19种多氯联苯的方法.加标浓度在3.3μg/kg时的平均回收率在79.6%～93.2%之间,相对标准偏差在2.9%～13.0%之间,定量限在0.01～0.51μg/kg之间.在检测土壤样品中的有机氯农药和多氯联苯残留方面,Gc-QqQ-MS/MS相对于气相色谱/电子捕获检测器(GC-ECD)和GC-MS的选择离子检测(SIM)模式具有非常明显的优势,尤其是在低浓度水平的定性和定量方面.     

青海省西宁市和天峻县大气颗粒物中有机氯农药和类二噁英多氯联苯的水平与分布

本研究测定了青海省西宁市与海西蒙古族藏族自治州天峻县夏、冬两季大气颗粒物中有机氯农药(OCPs)和类二噁英多氯联苯(DL-PCBs)的浓度水平.结果表明,青海省大气颗粒物中OCPs主要为DDTs、HCHs.西宁市DDTs和HCHs的平均水平分别为:35 pg·m-3、5.9 pg·m-3(夏季)和93 pg·m-3、11 pg·m-3(冬季),天峻县DDTs和HCHs的平均水平分别为:83pg·m-3、6.4 pg·m-3(夏季)和28 pg·m-3、6.7 pg·m-3(冬季).与亚洲其它地区相比,青海省大气颗粒物中OCPs处于较低水平.西宁市大气颗粒物中DL-PCBs的平均水平分别为:0.52 pg·m-3(夏季),0.99 pg·m-3(冬季),天峻县为:0.58 pg·m-3(夏季)、0.52 pg·m-3(冬季).西宁市夏、冬两季OCPs的平均水平均大于天峻县,而两地DL-PCBs的平均水平相当.本研究中高原地区DL-PCBs的分布特点及变化规律与极地地区的研究相比存在一定的相似性,而DDTs和HCHs则存在差异性.     

全二维气相色谱-飞行时间质谱法分离复杂体系中7种指示剂 多氯联苯

采用全二维气相色谱-飞行时间质谱法(GC×GC TOF-MS)分析了混标样品Aroclor 1260、Aroclor 1254、Aroclor 1242中的多氯联苯(PCBs)单体,考察了在复杂体系下对7种PCBs指示剂的分离能力。结果表明,与优化柱系统的分离效果相比,136种单体的混标样品中共分离出121种单体,7种指示剂经一维和二维的保留时间及质谱定性,在121种单体的2D斑点图中清晰可辨。全二维对于复杂体系的PCBs和指示剂的分离表明其强大的分离能力和对于检测复杂体系中指示剂的分辨能力,对该类物质的定性和定量检测具有重要意义。     

气相色谱-质谱法测定沉积物中的有机氯和多氯联苯

采用加速溶剂萃取法提取沉积物中的有机氯和多氯联苯,提取液用凝胶色谱法净化后用气相色谱-质谱法测定。方法在5.00μg/L~200μg/L范围内线性良好,当取样量为10.0 g时,方法检出限为0.03μg/kg~0.37μg/kg,空白样品2个质量比水平的加标回收率为70.8%~121%,测定结果的RSD为2.7%~11.5%。用该方法测定实际样品,结果 12个抽检的沉积物样品中多氯联苯均未检出,9个样品中有机氯检出。     

Chemical dechlorination of polychlorinated biphenyls (PCBs) from dielectric oils

We studied the chemical dechlorination of the polychlorinated biphenyls (PCBs) in some dielectric oils via nucleophilic substitution of the chloro atoms by polyethylene alkoxide. The influence of temperature, ultrasounds, polyethylene glycol (PEG) and base type was investigated. Our findings show that dechlorination of PCBs by chemical treatment is effective at moderate temperature (90–100°C) and is strongly dependent on the nature of matrix oil. Stirring affects the process yield by influencing the homogeneity of the oil/glycol two-phase system. Ultrasounds can improve the process efficiency by making operating conditions less severe. Selected article from the 6th European Meeting on Environmental Chemistry, University of Belgrade, Serbia and Montenegro organized by Prof. Dr. Branimir Jovancicevic ().     

Criteria for the evaluation of dioxins in the environment

In FRG and other countries unequivocal criteria for the limitation of dioxins (PCDD's/PCDF's) in food like vegetables and fruits are lacking. These have to be directly associated with the limitation of dioxins in the soil and the deposition of particulate matter as the two main pathways for plant contamination. Based on recent investigations in the vicinity of cable-waste incinerators in Northrhine-Westphalia with comparatively high contents of dioxins in garden plants and soils and other sources of dioxins, considerations are given for the establishment of the criteria urgently needed.     

Prediction of polychlorinated dibenzofuran congener distribution from gas-phase phenol condensation pathways

A model for predicting the distribution of dibenzofuran and polychlorinated dibenzofuran (PCDF) congeners from a distribution of phenols was developed. The model is based on a simplified chemical mechanism. Relative rate constants and reaction order with respect to phenol precursors were derived from experimental results using single phenols and equal molar mixtures of up to four phenols. For validation, experiments were performed at three temperatures using a distribution of phenol and 19 chlorinated phenols as measured in municipal waste incinerator exhaust gas. Comparison of experimental measurements and model predictions for PCDF isomer distributions and homologue pattern shows agreement within measurement uncertainty. The R-squared correlation coefficient exceeds 0.9 for all PCDF isomer distributions and the distribution of PCDF homologues. These results demonstrate that the distribution of dibenzofuran and the 135 PCDF congeners from gas-phase condensation of phenol and chlorinated phenols can be predicted from measurement of the distribution of phenol and the 19 chlorinated phenol congeners.