Thomas John E, Ou Li-Tse, All-Agely Abid
University of Florida, Soil and Water Science Deptartment, Gainesville, FL 32611, USA.
Rev Environ Contam Toxicol. 2008;194:55-69. doi: 10.1007/978-0-387-74816-0_3.
DDT and its metabolites, DDD and DDE, have been shown to be recalcitrant to degradation. The parent compound, DDT, was used extensively worldwide starting in 1939 and was banned in the United States in 1973. The daughter compound, DDE, may result from aerobic degradation, abiotic dehydrochlorination, or photochemical decomposition. DDE has also occurred as a contaminant in commercial-grade DDT. The p,p'-DDE isomer is more biologically active than the o,p-DDE, with a reported half-life of -5.7 years. However, when DDT was repeatedly applied to the soil, the DDE concentration may remain unchanged for more than 20 yr. Remediation of DDE-contaminated soil and water may be done by several techniques. Phytoremediation involves translocating DDT, DDD, and DDE from the soil into the plant, although some aquatic species (duckweed > elodea > parrot feather) can transform DDT into predominantly DDD with some DDE being formed. Of all the plants that can uptake DDE, Cucurbita pepo has been the most extensively studied, with translocation values approaching "hyperaccumulation" levels. Soil moisture, temperature, and plant density have all been documented as important factors in the uptake of DDE by Cucurbita pepo. Uptake may also be influenced positively by amendments such as biosurfactants, mycorrhizal inoculants, and low molecular weight organic acids (e.g., citric and oxalic acids). DDE microbial degradation by dehalogenases, dioxygenases, and hydrolases occurs under the proper conditions. Although several aerobic degradation pathways have been proposed, none has been fully verified. Very few aerobic pure cultures are capable of fully degrading DDE to CO2. Cometabolism of DDE by Pseudomonas sp., Alicaligens sp., and Terrabacter sp. grown on biphenyl has been reported; however, not all bacterial species that produce biphenyl dioxygenase degraded DDE. Arsenic and copper inhibit DDE degradation by aerobic microorganisms. Similarly, metal chelates such as EDTA inhibit the breakdown of DDE by the extracellular lignolytic enzymes produced by white rot fungi. The addition of adjutants such as sodium ion, surfactants, and cellulose increased the rate of DDT aerobic or anaerobic degradation but did little to enhance the rate of DDE disappearance under anaerobic conditions. Only in the past decade has it been demonstrated that DDE can undergo reductive dechlorination under methanogenic and sulfidogenic conditions to form the degradation product DDMU, 1-chloro-2,2'-bis-(4'-chlorophenyl)ethane. The only pure culture reported to degrade DDE under anaerobic conditions was the denitrifier Alcaligens denitrificans. The degradation of DDE by this bacterium was enhanced by glucose, whereas biphenyl fumes had no effect. Abiotic remediation by DDE volatilization was enhanced by flooding and irrigation and deepplowing inhibited the volatilization. The use of zero-valent iron and surfactants in flooded soils enhanced DDT degradation but did not significantly alter the rate of DDE removal. Other catalysts (palladized magnesium, palladium on carbon, and nickel/aluminum alloys) degraded DDT and its metabolites, including DDE. However, these systems are often biphasic or involve explosive gases or both. Safer abiotic alternatives use UV light with titanium oxide or visible light with methylene green to degrade DDT, DDD, and DDE in aqueous or mixed solvent systems. Remediation and degradation of DDE in soil and water by phytoextraction, aerobic and anaerobic microorganisms, or abiotic methods can be accomplished. However, success has been limited, and great care must be taken that the method does not transfer the contaminants to another locale (by volatilization, deep plowing, erosion, or runoff) or to another species (by ingestion of accumulating plants or contaminated water). Although the remediation of DDT-, DDD-, and DDE-contaminated soil and water is beset with myriad problems, there remain many open avenues of research.
滴滴涕(DDT)及其代谢产物滴滴滴(DDD)和滴滴伊(DDE)已被证明难以降解。母体化合物滴滴涕自1939年起在全球广泛使用,并于1973年在美国被禁止。子体化合物滴滴伊可能源于好氧降解、非生物脱氯化氢或光化学分解。滴滴伊也曾作为商业级滴滴涕中的污染物出现。p,p'-滴滴伊异构体比o,p-滴滴伊的生物活性更强,其报告的半衰期约为5.7年。然而,当滴滴涕反复施用于土壤时,滴滴伊的浓度可能在20多年内保持不变。受滴滴伊污染的土壤和水体的修复可采用多种技术。植物修复涉及将滴滴涕、滴滴滴和滴滴伊从土壤转移到植物中,不过一些水生物种(浮萍>伊乐藻>细叶满江红)能将滴滴涕主要转化为滴滴滴,并生成一些滴滴伊。在所有能够吸收滴滴伊的植物中,西葫芦受到的研究最为广泛,其转移值接近“超积累”水平。土壤湿度、温度和植物密度均被记录为西葫芦吸收滴滴伊的重要因素。生物表面活性剂、菌根接种剂和低分子量有机酸(如柠檬酸和草酸)等改良剂也可能对吸收产生积极影响。在适当条件下,脱卤酶、双加氧酶和水解酶可实现滴滴伊的微生物降解。虽然已提出了几种好氧降解途径,但均未得到充分验证。能够将滴滴伊完全降解为二氧化碳的好氧纯培养物极少。据报道,假单胞菌属、产碱菌属和地杆菌属在以联苯为生长底物时可对滴滴伊进行共代谢;然而,并非所有产生联苯双加氧酶的细菌物种都能降解滴滴伊。砷和铜会抑制好氧微生物对滴滴伊的降解。同样,金属螯合剂如乙二胺四乙酸(EDTA)会抑制白腐真菌产生的细胞外木质素分解酶对滴滴伊的分解。添加钠离子、表面活性剂和纤维素等助剂可提高滴滴涕的好氧或厌氧降解速率,但在厌氧条件下对提高滴滴伊的消失速率作用不大。直到过去十年,才证明滴滴伊在产甲烷和产硫化物条件下可进行还原脱氯,形成降解产物1-氯-2,2'-双(4'-氯苯基)乙烷(DDMU)。据报道,唯一能在厌氧条件下降解滴滴伊的纯培养物是反硝化产碱菌。葡萄糖可增强这种细菌对滴滴伊的降解,而联苯烟雾则无影响。通过水淹和灌溉可增强滴滴伊挥发的非生物修复作用,深耕则会抑制挥发。在水淹土壤中使用零价铁和表面活性剂可提高滴滴涕的降解,但对滴滴伊的去除速率没有显著影响。其他催化剂(钯化镁、钯碳和镍/铝合金)可降解滴滴涕及其代谢产物,包括滴滴伊。然而,这些系统通常是两相的,或涉及易爆气体,或两者皆有。更安全的非生物替代方法是在水性或混合溶剂系统中,使用紫外线与二氧化钛或可见光与亚甲基绿来降解滴滴涕、滴滴滴和滴滴伊。通过植物提取、好氧和厌氧微生物或非生物方法可实现土壤和水体中滴滴伊的修复和降解。然而,成功案例有限,必须格外小心,确保该方法不会将污染物转移到另一个区域(通过挥发、深耕、侵蚀或径流)或另一个物种(通过摄入积累了污染物的植物或受污染的水)。尽管受滴滴涕、滴滴滴和滴滴伊污染的土壤和水体的修复面临诸多问题,但仍有许多开放的研究途径。