Environmental Engineering Program, Department of Civil Engineering, Auburn University, Auburn, AL 36849, United States.
Water Res. 2010 Apr;44(7):2360-70. doi: 10.1016/j.watres.2009.12.041. Epub 2010 Jan 4.
This study pilot-tested carboxymethyl cellulose (CMC) stabilized zero-valent iron (ZVI) nanoparticles (with a trace amount of Pd catalyst) for in situ destruction of chlorinated ethenes such as perchloroethylene (PCE) and trichloroethylene (TCE) and polychlorinated biphenyls (PCBs) that had been in groundwater for decades. The test site was located in a well-characterized secondary source zone of PCBs and chlorinated ethenes. Four test wells were installed along the groundwater flow direction (spaced 5 ft apart), including one injection well (IW), one up-gradient monitoring well (MW-3) and two down-gradient monitoring wells (MW-1 and MW-2). Stabilized nanoparticle suspension was prepared on-site and injected into the 50-ft deep, unconfined aquifer. Approximately 150 gallons of 0.2 g/L Fe-Pd (CMC = 0.1 wt%, Pd/Fe = 0.1 wt%) was gravity-fed through IW-1 over a 4-h period (Injection #1). One month later, another 150 gallons of 1.0 g/L Fe-Pd (CMC = 0.6 wt%, Pd/Fe = 0.1 wt%) was injected into IW-1 at an injection pressure <5 psi (Injection #2). When benchmarked against the tracer, approximately 37.4% and 70.0% of the injected Fe was detected in MW-1 during injection #1 and #2, respectively, confirming the soil mobility of the nanoparticles through the aquifer, and higher mobility of the particles was observed when the injection was performed under higher pressure. Rapid degradation of PCE and TCE was observed in both MW-1 and MW-2 following each injection, with the maximum degradation being observed during the first week of the injections. The chlorinated ethenes concentrations gradually returned to their pre-injection levels after approximately 2 weeks, indicating exhaustion of the ZVI's reducing power. However, the injection of CMC-stabilized nanoparticle and the abiotic reductive dechlorination process appeared to have boosted a long-term in situ biological dechlorination thereafter, which was evidenced by the fact that PCE and TCE concentrations showed further reduction after two weeks. After 596 days from the first injection, the total chlorinated ethenes concentration decreased by about 40% and 61% in MW-1 and MW-2, respectively. No significant long-term reduction of PCB 1242 was observed in MW-1, but a reduction of 87% was evident in MW-2. During the 596 days of testing, the total concentrations of cis-DCE (dichloroethylene) and VC (vinyl chloride) decreased by 20% and 38% in MW-1 and MW-2, respectively. However, the combined fraction of cis-DCE and VC in the total chlorinated ethenes (PCE, TCE, cis-DCE and VC) increased from 73% to 98% and from 62% to 98%, respectively, which supports the notion that biological dechlorination of PCE and TCE was active. It is proposed that CMC-stabilized ZVI-Pd nanoparticles facilitated the early stage rapid abiotic degradation. Over the long run, the existing biological degradation process was boosted with CMC as the carbon source and hydrogen from the abiotic/biotic processes as the electron donor, resulting in the sustained enhanced destruction of the chlorinated organic chlorinated ethenes in the subsurface.
本研究初步测试了羧甲基纤维素(CMC)稳定的零价铁(ZVI)纳米颗粒(含有微量钯催化剂),用于原位破坏地下水数十年的氯代乙烯(如全氯乙烯(PCE)和三氯乙烯(TCE))和多氯联苯(PCBs)。试验场地位于 PCB 和氯代乙烯的特征明显的次生源区。沿着地下水流动方向安装了四个测试井(间距为 5 英尺),包括一个注入井(IW)、一个上游监测井(MW-3)和两个下游监测井(MW-1 和 MW-2)。在现场制备稳定的纳米颗粒悬浮液并注入 50 英尺深的无约束含水层。在 4 小时内(注射#1)通过 IW-1 重力输送约 150 加仑 0.2 g/L 的 Fe-Pd(CMC=0.1wt%,Pd/Fe=0.1wt%)。一个月后,在 IW-1 中以小于 5 psi 的注入压力再次注入 150 加仑 1.0 g/L 的 Fe-Pd(CMC=0.6wt%,Pd/Fe=0.1wt%)(注射#2)。与示踪剂相比,在注射#1 和#2 期间,MW-1 中分别检测到约 37.4%和 70.0%的注入 Fe,这证实了纳米颗粒通过含水层的土壤迁移性,并且当注入压力较高时,观察到颗粒的迁移性更高。每次注射后,MW-1 和 MW-2 中的 PCE 和 TCE 都迅速降解,在注射的第一周观察到最大降解。氯代乙烯的浓度在大约两周后逐渐恢复到注射前的水平,表明 ZVI 的还原能力已耗尽。然而,CMC 稳定的纳米颗粒的注入和非生物还原脱氯过程似乎在此后促进了长期的原位生物脱氯,这一事实表明,在两周后,PCE 和 TCE 的浓度进一步降低。从第一次注射后 596 天,MW-1 和 MW-2 中的总氯代乙烯浓度分别降低了约 40%和 61%。MW-1 中没有观察到 PCB1242 的明显长期减少,但 MW-2 中减少了 87%。在 596 天的测试期间,MW-1 和 MW-2 中的顺式-DCE(二氯乙烯)和 VC(氯乙烯)的总浓度分别降低了 20%和 38%。然而,氯代乙烯(PCE、TCE、顺式-DCE 和 VC)中的顺式-DCE 和 VC 总浓度从 73%增加到 98%和从 62%增加到 98%,这支持了 PCE 和 TCE 的生物脱氯是活跃的这一观点。据推测,CMC 稳定的 ZVI-Pd 纳米颗粒促进了早期的快速非生物降解。从长远来看,CMC 作为碳源,非生物/生物过程中的氢作为电子供体,促进了现有的生物降解过程,从而持续增强了地下水中氯代有机氯代乙烯的破坏。