难降解氯代有机物污染环境的生物修复技术研究进展

氯代有机物是一类在生产和生活中广泛应用并被大量排放到环境中的难降解有机污染物质,一旦进入生态环境,就会在水体、土壤和底质中长期残留,并在食物链中不断积累、富集,从而对生物体产生危害。因此,对受这类难降解有机物污染的环境修复是目前所迫切需要解决的环境问题之一。基于物理和化学修复方法成本较高易造成二次污染,文中探讨了国内外生物修复技术的研究进展,并对难降解氯代有机物污染环境修复的研究方向进行了展望,由于环境中的污染物质复杂多变,联合生物修复技术将成为未来的研究热点。     

Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

快速溶剂萃取—气相色谱法分析土壤中的20种有机氯

采用加速溶剂萃取—气相色谱法对土壤中20种有机氯农药进行了提取测定.通过改变加速溶剂萃取条件,选取了最佳条件参数,减少了组份的损失;通过改变气相色谱条件,使得20种有机氯农药快速分离.该方法具有操作简便、灵敏度高、检出限低、快速、溶剂消耗少等优点,方法检出限为1.23～ 3.11 μg/kg,实际样品的加标回收率为62.3％～119.7％.     

崇明岛土壤中MCCPs的污染水平、组成与来源研究

用GC-ECNI-MS测定了崇明岛土壤中24种中链氯化石蜡(MCCPs)同类物组的含量.目的是了解该地区土壤中MCCPs的污染水平、空间分布、组成特征和来源.结果表明MCCPs在崇明岛土壤中普遍存在,浓度范围为2.56~96.3 ng·g-1,中值为7.32 ng·g-1.聚类分析将所有样品分为两类.大多数土壤样品MCCPs以C14-MCCPs和C15-MCCPs为主要碳同类物组,分别占29.8%和28.9%;Cl5-MCCPs和Cl6-MCCPs为主要氯同类物组,分别占29.9%和23.3%;个别样品中,C14-MCCPs是主要碳同类物组,占68.5%,与CP-52的组成相似.大气沉降和土壤-大气交换可能是崇明岛土壤中MCCPs主要来源,个别点可能受到污水处理厂污泥或其他不明污染源的污染.MCCPs与TOC之间没有显著统计相关性.因子分析表明4种MCCPs的碳同类物组具有相似的来源.与国内外其它研究相比,崇明岛土壤中MCCPs处于较低水平.     

电子鼻预处理装置的开发及适用性研究

针对气敏传感器的信号响应受气体湿度影响较大的问题,开发了一套用于快速检测和实时监测土壤中挥发性氯代烃污染的电子鼻的预处理装置.优选了干燥剂的材质,评价了最适干燥剂的除湿性能和对氯代烃化合物的吸附情况;把预处理装置与电子鼻联用,通过与气相色谱（GC）检测结果的比较,评价了其用于土壤通风净化过程监测的适用情况.结果表明：①以无水氯化钙和卤代烃分离管搭配组合的干燥装置效果最佳,湿度去除率达99%以上,电子鼻各传感器的基线值与对照组接近;②上述干燥剂连续通入湿度为75%的空气,90 min内湿度几乎可完全去除,120 min内湿度去除率保持在95%以上,对传感器的基线影响较小.③预处理装置未造成检测气体的吸附损耗,通入干燥预处理装置前后的挥发性氯代烃气体浓度差异只有3%～5%;④在土壤通风脱附过程的检测中,通气湿度98%以上的情况下,预处理装置在120 min内对湿度去除率达99%以上;电子鼻与GC对四氯乙烯污染物的检测结果线性拟合判定系数R2〉0.99（n=18）,表明配以干燥预处理装置的电子鼻能够较好地适用于土壤修复过程监测.     

Migration behavior and in-situ bioremediation of chlorinated hydrocarbon solvent in vadose zone: a review北大核心CSCD

It is of great significance for in-situ bioremediation to clarify the migration behavior and biodegradation laws of chlorinated hydrocarbon solvents (CHS) in the vadose zone. We systematically summarized the phase distribution of CHS, the interaction between different phases, and the migration characteristics and clarified the evolution rules of CHS under different phases in the polluted vadose zone. CHS exists in the vadose zone as the NAPL, dissolved phase, adsorbed phase, gas phase, and other phases, where there are three decay evolution stages: early, middle, and late stages. Phase change and diffusion matrix size are important indicators at different stages; at the same time, gas, solid, liquid and NAPL phase CHS have a variety of interactive relationships in the vadose zone. Subsequently, the characteristics of the three main biological metabolic pathways of CHS in the vadose zone–aerobic co-metabolism, direct oxidation and anaerobic reduction, and dechlorination–and their influencing factors were summarized. Generally speaking, the anaerobic dechlorination capacity decreases with a decrease in the number of chlorine atoms, whereas the aerobic degradation capacity increases with a decrease in the number of chlorine atoms. The current status of in-situ remediation of CHS in the vadose zone was summarized using biostimulation and bioaugmentation methods, indicating that adding nutrient substances and injecting anaerobic dechlorination strains of Dehalococcoides are effective means of remediation. Simultaneously, the factors influencing the biodegradation of CHS in the vadose zone were elaborated to acquire a systematic insight into the significance of redox characteristics (oxygen) on the degradation of CHS. Finally, research on the biodegradation of CHS in the vadose zone is prospected, and it is necessary to carry out research on the interactive relationship between different phases of CHS, the data monitoring of CHS, the structure of the functional bacterial community, and research and development of active strains to provide theoretical guidance for the in-situ remediation of CHS in the vadose zone. © 2022 Science Press. All rights reserved.     

二氧化钛催化下的氯代二苯并-对-二恶英光解反应

本文利用中压汞灯作光源,研究了氯代二苯并-对-二恶英(CDDs,包括CDD,DCDD,PeCDD和OCDD)在二氧化钛催化下的光解反应,并讨论了二氧化钛浓度、pH值、反应温度以及取代氯原子数目等对反应速率的影响.结果表明,二氧化钛能有效地催化CDDs的光降解,在室温下,4h内DCDD,PeCDD,OCDD分别降解了87.2%,84.6%,91.2%,反应温度和二氧化钛浓度是控制该反应的主要因素.     

挥发性氯代烃在干燥土壤中的平衡吸附研究

吸附是挥发性氯代烃（volatile chlorinated hydrocarbons,VCHs）污染土壤的主要机制之一.采集长三角地区3类典型水稻土,用静态平衡吸附实验进行干燥土壤对6种VCHs的平衡吸附研究.结果表明,干燥土壤的平衡吸附等温线难以用Langmuir方程和BET方程描述,但用Dubinin-Astak...     

Validation of a HRGC–ECNI/LRMS method to monitor short-chain chlorinated paraffins in human plasma

Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/serum, mainly due to the difficulty of sample preparation and quantitative analysis. A method using high resolution gas chromatography coupled with electron capture negative ionization low resolution mass spectrometry(HRGC–ECNI/LRMS) was developed and validated to measure SCCPs in human plasma. The pretreatment process included protein denaturation and lipid elimination, liquid–liquid extraction with a mixture of n-hexane/dichloromethane(1:1, V/V), and cleanup on a multilayer silica column. The blank controls, including procedural blank, vacuum blood collection tube blank, and instrumental blank, were the most pivotal points for the reliable analysis of SCCPs. The average value of procedural blanks was 9.0 ng/g; and the method detection limit(MDL), calculated as the sum of the average procedural blank value and 3 times of the standard deviation of the procedural blanks, was 12.6 ng/g plasma. The validated method was applied to measure the concentrations of the total SCCPs(∑ SCCPs) in50 plasma samples from a general population. The measured plasma concentrations of ∑SCCPs ranged from MDL to 203 ng/g wet weight(ww), with an average value of 32.0 ng/g ww.The relative abundance profiles of SCCPs in plasma samples were dominated by C10- and C11-CP congener groups centered on Cl6–7. The developed method can be used for the comprehensive and large-scale investigation of SCCP levels in human plasma.     

微米铁复合生物碳源对地下水中1,2-二氯乙烷的高效去除

1,2-二氯乙烷(1,2-DCA)是一类地下水中常见的难降解饱和氯代烃,为探究厌氧条件下零价铁(ZVI)协同生物作用对其降解规律,采集北京市某氯代烃污染场地地下水及含水层土壤,利用微宇宙实验体系,通过添加由微米级零价铁(mZVI)、生物碳源及营养组成的复合药剂,考察不同条件下1,2-DCA的去除效果,并对地下水理化参数的变化进行长期监测.结果表明:复合药剂添加量为3%时,恒温、避光、匀速振荡的反应条件下,15 d内地下水中的1,2-DCA即可降至低于检出限.中性pH及SO_4~(2-)的存在更有利于1,2-DCA的脱氯降解. 30 d后仅检测到体系中明显的乙烯产生,推测双脱氯消除为1,2-DCA在该体系内的主要降解途径.此外,复合药剂加入后,地下水可长时间维持较低的氧化还原电位(-100～-300 m V)、溶解氧(0. 5 mg·L~(-1))以及适宜的pH值(6. 5～7. 5),利于厌氧微生物活性的维持及脱氯反应的进行.