Peters R W
Energy Systems Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA.
J Hazard Mater. 1999 Apr 23;66(1-2):151-210. doi: 10.1016/s0304-3894(99)00010-2.
The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique.
已探讨了使用螯合剂提取重金属污染物的当前技术水平。给出了针对阿伯丁试验场J区作为最坏情况和代表性土壤进行的可处理性研究结果,以提取铜(Cu)、铅(Pb)和锌(Zn)。通过比重计测试确定的土壤粒度分布特征约为60%砂、30%粉砂和10%黏土。对“原样”土壤(最坏情况和代表性土壤)进行了连续萃取,以确定金属形态的种类。该技术将重金属分布分为易提取(可交换)形态、碳酸盐、可还原氧化物、有机结合态和残留态。结果表明,大多数金属处于适合土壤冲洗的形态(即可交换态+碳酸盐态+可还原氧化物态)。金属铜、铅、锌和铬有超过70%的分布形态适合土壤冲洗技术,而镉、锰和铁对使用螯合剂萃取进行土壤冲洗的适用性稍差。然而,受污染土壤中镉和锰的浓度较低。从批量螯合剂萃取研究来看,乙二胺四乙酸(EDTA)、柠檬酸和次氮基三乙酸(NTA)在从J区土壤中去除铜、铅和锌方面均有效。由于NTA是II类致癌物,不建议用于修复受污染土壤。EDTA和柠檬酸似乎作为螯合剂在冲洗阿伯丁试验场土壤方面具有最大潜力。研究的其他螯合剂(葡萄糖酸盐、草酸盐、Citranox、醋酸铵和磷酸,以及调节pH值的水)通常在从土壤中 mobilizing 重金属方面无效。螯合剂溶液同时去除重金属(镉、铜、铅、锌、铁、铬、砷和汞)。使用多阶段批量萃取,土壤成功通过了毒性特性浸出程序(TCLP)和美国环保署总可提取金属限值。最终残留铅浓度约为300 mg/kg,相应的TCLP为1.5 mg/l。在第一萃取阶段实现了铜和锌可交换态和碳酸盐态部分的去除,而铅的相同部分则需要两个萃取阶段。第四至第五阶段萃取之间实现了以可交换态、碳酸盐态和可还原氧化物态存在的铅、铜和锌的去除。多阶段冲洗对铜、铅和锌的总体去除率分别为98.9%、98.9%和97.2%。土壤冲洗萃取的浓度和操作条件不一定经过优化。如果条件经过优化并使用更具代表性的铅浓度(约12000 mg/kg),很可能在两到三次萃取内达到TCLP和残留重金属土壤浓度要求。结果表明,使用土壤冲洗技术可以成功处理J区受污染土壤。 (注:原文中“mobilizing”这个词在这个语境下似乎不太准确,可能是“去除”之类的意思,但按照要求未做修改。)