超声波-蒸汽蒸馏萃取技术富集沉积物样品中的氯代农药和多氯联苯

为方便快速分离沉积物中含氯农药和多氯联苯,将眼声波技术和蒸汽蒸馏萃取技术相结合,萃取沉积物中的微量含氯农药和多氯联苯,所得萃取物不需进一步的净化和浓缩,可直接用于色谱分析。实验表明,在进行蒸汽蒸馏萃取之前,使用辅助的超声波技术台将大部分待测物的回收率提高２０％－３０％,较好地解决了由于沉积物吸附作用而导致的蒸汽蒸馏回收率偏低的缺陷。     

鱼中氯化二苯并二噁(PCDD)和氯化二苯并呋喃(PCDF)的分析

本工作建立了鱼中从四氯到八氯的二苯并二(口恶)(口英)和二苯并呋喃的分析方法。鱼样品经消化后以己烷提取,提取液经两套层析柱净化后,用反相HPLC进一步净化并分为两个级份。采用GC/SIM-MS测定各PCDD和PCDF。     

香港周边海域野生鱼体内DDTs和PCBs的含量分布和食用风险评估

为研究香港周边海域鱼体内持久性有机污染物的污染水平、分布特征及其对当地居民的健康风险评估,采集了香港周边海域中31种野生鱼,分析鱼体中两类典型持久性有机污染物,如滴滴涕（DDTs）和多氯联苯（PCBs）.结果表明,香港周边海域野生鱼类DDTs和PCBs的含量范围分别为0.44~17 ng·g^-1和0.028~6.3 ng·g^-1,与国内外其他地方相比处于中低水平.在空间分布上,大屿山西部的鱼体内DDTs含量最低,而吐露港鱼体中PCBs含量最低.鱼类的生活环境及食性影响其在鱼体内DDTs与PCBs的富集程度.来源分析显示野生鱼体内DDTs来源主要为历史残留,迁徙的鱼类可能受沿海岸河口DDTs污染影响.此外,健康风险评估结果表明,香港青少年和成年人长期食用香港周边海域的鱼类可能会存在潜在的终生致癌风险.因此,香港当地居民应尽量减少对其周边海岸野生鱼类的摄入.     

溶剂调控Pd/C催化多氯联苯高效加氢脱氯

采用沉积沉淀法制备了5% Pd/C催化剂,研究了溶剂体系对其催化4-氯联苯（4-CBP）加氢脱氯的影响,建立了正丁醇-水两相溶剂体系,实现了高浓度电容器油（主要为多氯联苯（PCBs））的高效加氢脱氯降解.结果表明,相对比非质子溶剂,醇类等质子溶剂对加氢脱氯反应更加有利.水的加入对异丙醇-水均相溶剂和有机-水两相溶剂中Pd/C催化4-CBP加氢脱氯均有明显的促进作用,而且在正丁醇-水（1：3,V/V）两相溶剂体系中可以在90min内实现4-CBP加氢脱氯的完全转化,而且催化剂可以重复使用8次以上.在该溶剂体系中,10g/L的含PCBs电容器油在Pd/C催化下可以在360min内完全加氢脱氯生成联苯.     

FeCl_3存在时六六六热解生成PCDD/Fs的研究

在开管体系中,于280℃时研究了六六六无效体在Fe,理体制FeCl_3存在时的热解,以及影响热解产物中PCDD/Fs生成量的因素.PCDD/Fs的生成主要取决于FeCl_3,而Fe的存在并不增加体系中PCDD/Fs的生成量.在封管体系中,研究结果表明PCSS/Fs的生成量随FeCl_3用量、反应时间和反应温度的增加而增加,但温度影响最大.实验还表明,氯苯、氨酚对PCDD/Fs的生成起决定作用.在250─280℃,PCDD/Fs的生成主要在于二者之间的缩合,而单独氯酚间的缩合则居次要地位.氯化对生成PCDD/Fs的种类及量影响很大.250─280℃时,低氯苯、氨酚在FeCl_3作用下氯代成高氯产物,进而缩合成 OCDD/F;但在 350℃以上时,氯酚反应活性增加,故低氯PCDD/Fs生成量增加,OCDD/F生成量相对降低.     

多氯联苯催化转移氢化脱氯的研究

本文研究了１０％钯／碳存在时，以甲酸铵为氢经予体的多氯联苯（ＰＣＢｓ）脱氯的的摧化转移转氢化方法。在中性介质、低温、常压下，ＰＣＢｓ脱氯效率达９８－１００％。该方法已用于电容器中ＰＣＢｓ的脱氯。     

Tissue distribution of polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) in harbour porpoises (Phocoena phocoena) from Swedish waters

Polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) were analysed in blubber, nuchal fat, liver, muscle, kidney and brain of three male harbour porpoises (Phocoena phocoena) from the west coast of Sweden. To estimate spatial variation, PCNs and non-ortho CBs were analysed in six blubber samples collected at different anatomical sites of each animal. Highest wet weight concentrations of ΣPCNs were detected in the lipid rich tissues (blubber and nuchal fat) and liver (520–730 and 520 pg/g, respectively) and lowest in brain (22 pg/g). TetraCNs were most abundant in muscle, kidney and brain, while the hexaCNs were most abundant in the lipid rich tissues and liver. The highest lipid weight concentration recorded (11 ng/g) was for the hexaCN congeners no. 66/67 in liver. These coeluting hexaCN congeners accounted for 80–100% of total hexaCNs in all tissues examined.

Concentrations of Σnon-ortho CBs were highest in lipid rich tissues (220–280 pg/g wet weight). Non-ortho CB no. 77 and 169 constituted between 62–86% and 4.9–9.3%, respectively, of total Σnon-ortho CBs. No major variation of Σnon-ortho CB concentrations was found between the six different blubber sites but higher ΣPCN concentrations (wet weight) were found dorsally at the peduncle. Toxic equivalent concentrations (TEQs) showed that non-ortho CB no. 126 was the main contributor to total TEQs in all tissues, except liver in which hexaCN congener nos. 66/67 contributed to about 50% of total TEQs.     

超声波处理难降解有机物影响参数研究

考察了多种操作参数对多氯联苯、溴苯超声波降解的影响。结果表明,高频率、高声强、高流速、混合气体可以提高超声反应速率, 358kHz下降解速率比20kHz提高了848%, 34mL/min流速下比4 4mL/min提高了140%,参入Ar比单纯使用O2 提高83% ( +80%Ar)或66% ( +50%Ar)。然而高声强也造成了较多的能量消耗。自由基清除剂的存在则较大地降低了超声反应速率, 200mmol/LCO2- 存在时反应速率下降了79%。     

BAT and BEP as instruments for reducing emissions of unintentionally produced POPs and development of guidelines under the stockholm convention

The 6th Intergovernmental Negotiating Committee (INC 6), under the Stockholm Convention on POPs, gave an expert group the mandate to develop guidelines for the application and implementation of best available techniques (BAT) and best environmental practices (BEP) for the prevention and reduction of unintentionally produced and emitted POPs, including polychlorinated dibenzodioxins/-furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Measures to reduce or eliminate the release of these POPs to the environment can be found in Article 5 of the Convention. BAT and BEP are already being applied as emission reduction instruments in a number of industrialised countries and are elements of other major international treaties, e.g. the UN ECE Protocol on POPs and the Marine Convention's OSPAR and HELCOM, and of the EU Directive for Integrated Pollution Prevention and Control (IPPC Directive). Existing concepts are presented and compared with the requirements of the Stockholm Convention. Consequences, perspectives and questions for the future intersessional work of the above-mentioned Expert Group are discussed.     

多氯联苯复合污染土壤的微生物群落结构多样性变化

土壤微生物群落结构多样性是指示土壤生态系统稳定性及其功能的重要传感器。采用磷脂脂肪酸(Phospholipid fatty acids,PLFAs)方法,对长江三角洲地区某POPs高风险区PCBs长期复合污染土壤的微生物群落结构多样性进行了初步研究。结果表明,PCBs重度污染土壤中格兰氏阴性菌(16:1w9、cy17:0等)和厌氧微生物(18:1w7)的PLFAs组分含量较多,而格兰氏阳性菌(如i15:0、i17:0等)、放线菌(16:0(10Me))及真菌(18:2ω6,9)和好氧性微生物的PLFAs含量较低,表明PCBs污染土壤中微生物群落结构与组成发生了明显变化。这一结果为PCBs降解微生物资源的定向筛选提供了科学依据。