Johns Adam, Qian Jiajie, Carolan Margaret E, Shaikh Nabil, Peroutka Allison, Seeger Anna, Cerrato José M, Forbes Tori Z, Cwiertny David M
Department of Civil and Environmental Engineering, University of Iowa, 4105 Seamans Center for the Engineering Arts and Sciences, Iowa City, IA 52242.
Department of Civil, Construction & Environmental Engineering, University of New Mexico, Albuquerque, NM 87131.
Environ Sci (Camb). 2020 Mar 1;6(3):622-634. doi: 10.1039/c9ew00834a. Epub 2019 Dec 12.
Uranium (U) contamination of drinking water often affects communities with limited resources, presenting unique technology challenges for U treatment. Here, we develop a suite of chemically functionalized polymer (polyacrylonitrile; PAN) nanofibers for low pressure reactive filtration applications for U removal. Binding agents with either nitrogen-containing or phosphorous-based (e.g., phosphonic acid) functionalities were blended (at 1-3 wt.%) into PAN sol gels used for electrospinning, yielding functionalized nanofiber mats. For comparison, we also functionalized PAN nanofibers with amidoxime (AO) moieties, a group well-recognized for its specificity in U uptake. For optimal N-based (Aliquat® 336 or Aq) and P-containing [hexadecylphosphonic acid (HPDA) and bis(2-ethylhexyl)phosphate (HDEHP)] binding agents, we then explored their use for U removal across a range of pH values (pH 2-7), U concentrations (up to 10 μM), and in flow through systems simulating point of use (POU) water treatment. As expected from the use of quaternary ammonium groups in ion exchange, Aq-containing materials appear to sequester U by electrostatic interactions; while uptake by these materials is limited, it is greatest at circumneutral pH where positively charged N groups bind negatively charged U complexes. In contrast, HDPA and HDEHP perform best at acidic pH representative of mine drainage, where surface complexation of the uranyl cation likely drives uptake. Complexation by AO exhibited the best performance across all pH values, although U uptake via surface precipitation may also occur near circumneutral pH value and at high (10 μM) dissolved U concentrations. In simulated POU treatment studies using a dead-end filtration system, we observed U removal in AO-PAN systems that is insensitive to common co-solutes in groundwater (e.g., hardness and alkalinity). While more research is needed, our results suggest that only 80 g (about 0.2 lbs.) of AO-PAN filter material would be needed to treat an individual's water supply (contaminated at ten-times the U.S. EPA Maximum Contaminant Level for U) for one year.
饮用水中的铀(U)污染常常影响资源有限的社区,给铀处理带来独特的技术挑战。在此,我们开发了一套化学功能化聚合物(聚丙烯腈;PAN)纳米纤维,用于低压反应过滤应用以去除铀。将具有含氮或磷基(如膦酸)官能团的结合剂(以1 - 3 wt.%)混入用于静电纺丝的PAN溶胶凝胶中,得到功能化纳米纤维垫。为作比较,我们还用偕胺肟(AO)基团对PAN纳米纤维进行功能化,该基团因其对铀吸收的特异性而广为人知。对于最佳的基于氮的(Aliquat® 336或Aq)和含磷的[十六烷基膦酸(HPDA)和双(2 - 乙基己基)磷酸酯(HDEHP)]结合剂,我们随后探索了它们在一系列pH值(pH 2 - 7)、铀浓度(高达10 μM)以及模拟使用点(POU)水处理的流通系统中用于去除铀的情况。正如离子交换中使用季铵基团所预期的那样,含Aq的材料似乎通过静电相互作用螯合铀;虽然这些材料对铀的吸收有限,但在中性附近pH值时最大,此时带正电的N基团结合带负电的铀络合物。相比之下,HDPA和HDEHP在代表矿山排水的酸性pH值下表现最佳,此时铀酰阳离子的表面络合可能驱动吸收过程。AO的络合在所有pH值下表现最佳,不过在中性附近pH值以及高(10 μM)溶解铀浓度时,也可能通过表面沉淀发生铀的吸收。在使用死端过滤系统的模拟POU处理研究中,我们观察到AO - PAN系统中对铀的去除对地下水中常见的共溶质(如硬度和碱度)不敏感。虽然还需要更多研究,但我们的结果表明,仅需80克(约0.2磅)的AO - PAN过滤材料就能为一个人处理一年的供水(铀污染程度为美国环境保护局铀最大污染物水平的十倍)。