Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States.
Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States; Kennedy Jenks Consultants, San Francisco, California 94118, United States.
Water Res. 2022 Sep 1;223:119019. doi: 10.1016/j.watres.2022.119019. Epub 2022 Aug 23.
This study reports the results of an 8-month pilot study comparing both regenerable and emerging single-use anion exchange resins (AERs) for treatment of per- and polyfluoroalkyl substances (PFASs) at a source zone impacted by historical use of aqueous film-forming foam (AFFF). Two regenerable (Purolite A860 and A520E) and three single-use (Purolite PFA694E, Calgon CalRes 2301, and Dowex PSR2+) AERs were tested in parallel, collecting effluent samples after treatment for 30-sec and 2-min total empty bed contact time (EBCT). Results demonstrate that single-use AERs significantly outperform regenerable resins, particularly for treatment of long-chain perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs). No detectable concentrations of ≥C7 PFCAs or PFSAs were observed within 150,000 bed volumes (BVs) after treatment with the single-use resins (2-min EBCT). Analysis of effluent samples following 30-sec EBCT treatment shows that even the shortest-chain PFSAs do not reach 50% breakthrough within the first 350,000 BVs, though differences in removal of short-chain PFCAs was less dramatic. The regenerable polyacrylic A860 resin performed very poorly compared to all polystyrene resins, with >90% breakthrough of all PFASs occurring within 10,000 BVs. The greater affinity of polystyrene resins is attributed to increased hydrophobic interactions in addition to electrostatic ion exchange. Analysis of breakthrough profiles reveals empirical correlation with ion exchange affinity coefficients (logK) measured in batch experiments. Postmortem analysis of PFASs extracted from spent resins revealed chromatographic elution behavior and competition among PFASs for adsorption to the resins. PFSAs and long-chain PFCAs were preferentially adsorbed to earlier sections in the AER columns, whereas short-chain PFCAs were competitively displaced towards the later sections of the columns and into the effluent, consistent with effluent concentrations of the latter structures exceeding influent values. These results provide insights into the mechanisms that govern PFAS adsorption to AERs in real multisolute groundwater matrices and support findings from other diverse sites regarding PFAS affinity, elution behavior, and competition for exchange sites.
本研究报告了一项为期 8 个月的试点研究结果,该研究比较了可再生和新兴的单用途阴离子交换树脂(AER)在受历史使用水性成膜泡沫(AFFF)影响的源区处理全氟和多氟烷基物质(PFAS)的效果。两种可再生(Purolite A860 和 A520E)和三种单用途(Purolite PFA694E、Calgon CalRes 2301 和 Dowex PSR2+)AER 同时进行了测试,在 30 秒和 2 分钟总空床接触时间(EBCT)后收集处理后的流出物样品。结果表明,单用途 AER 显著优于可再生树脂,特别是对于长链全氟烷基羧酸(PFCAs)和全氟烷基磺酸(PFSAs)的处理。在用单用途树脂(2 分钟 EBCT)处理后,在处理 150,000 床体积(BV)后,未检测到任何浓度的≥C7 PFCAs 或 PFSAs。对 30 秒 EBCT 处理后的流出物样品进行分析表明,即使是最短链的 PFSAs,在最初的 350,000 BV 内也未达到 50%的穿透,尽管短链 PFCAs 的去除差异较小。与所有聚苯乙烯树脂相比,可再生的聚丙烯 A860 树脂的性能非常差,所有 PFASs 的穿透率>90%发生在 10,000 BV 内。聚苯乙烯树脂更高的亲和力归因于除静电离子交换外,还增加了疏水性相互作用。穿透曲线的分析揭示了与批处理实验中测量的离子交换亲和系数(logK)的经验相关性。从用过的树脂中提取的 PFAS 进行的后分析表明,PFAS 在树脂上的吸附存在色谱洗脱行为和竞争。PFSAs 和长链 PFCAs 优先被吸附到 AER 柱的较早部分,而短链 PFCAs 则被竞争性地推到柱的较晚部分并进入流出物中,与后者结构的流出物浓度超过进水值一致。这些结果提供了对实际多溶质地下水中 PFAS 吸附到 AER 机制的深入了解,并支持了其他不同地点关于 PFAS 亲和力、洗脱行为和交换位点竞争的发现。