In situ destruction of halogenated Superfund contaminants with persulfate-generated radicals

用过硫酸盐产生的自由基原位破坏卤化超级基金污染物

• 批准号: 10349971
• 负责人: David L. Sedlak
• 金额: $ 26.84万
• 依托单位: UNIVERSITY OF CALIFORNIA BERKELEY
• 依托单位国家: 美国
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-04-01 至 2027-06-30
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/10349971
• 关键词: Address; Alcohols; Aldehydes; Ames Assay; Anaerobic Bacteria; Biological Assay; Bioremediations; Carbon; Chemicals; Chronic; Collaborations; Community Health; Complex; Cysteine; Dose; Ecosystem; Engineering; Environment; Estrogens; Ethers; Exhibits; Film; Flushing; Glutathione; Hazardous Waste Sites; Hexachlorobenzene; Histidine; Hydrocarbons; Hydrogen Peroxide; Hydrophobicity; Hydroxyl Radical; In Situ; Ketones; Lysine; Mass Fragmentography; Metabolic Biotransformation; Methods; Modeling; Mutagenicity Tests; Nucleic Acids; Organic solvent product; Oxidants; Oxidation-Reduction; Oxidative Stress; Oxygen; Permeability; Petroleum; Phase; Poison; Polybrominated Biphenyls; Polychlorinated Biphenyls; Predisposition; Process; Production; Property; Pump; Reaction; Reducing Agents; Research; Resistance; Risk; Sampling; Signal Recognition Particle; Site; Soil; Solid; Solvents; Source; Sulfate; Sulfhydryl Compounds; Superfund; System; Techniques; Temperature; Testing; Toxic effect; Water Supply; acute toxicity; aqueous; cold temperature; drinking water; estrogenic activity; experience; ground water; high throughput screening; kinetic model; liquid chromatography mass spectrometry; novel; novel strategies; organic acid; organic contaminant; oxidation; parental monitoring; pollutant; predictive modeling; remediation; screening; superfund site

PROJECT 4: SUMMARY/ABSTRACT After 40 years of research and field experience, the remediation of hazardous waste sites remains a substantial challenge. Over the past three decades, considerable progress has been made in the use of in situ treatment methods, such as bioremediation and permeable reactive barriers. Nonetheless, excavation and off-site disposal remains the most common remedial approach for soil and groundwater extraction (i.e., pump-and-treat) systems are still being employed at numerous Superfund sites. Among the emerging alternatives to these expensive approaches, in situ chemical oxidation (ISCO) has shown substantial potential for providing an effective means of remediating a variety of contaminants, including TCE and petroleum hydrocarbons. Despite its popularity, ISCO has proven difficult to use in the treatment of hydrophobic compounds and compounds that exhibit low reactivity towards hydroxyl radical and sulfate radical—the two strongest oxidants produced during the decomposition of hydrogen peroxide and peroxydisulfate (i.e., persulfate) in the subsurface. Our proposed research aims at developing new in situ chemical remediation techniques capable of treating Superfund contaminants that often require expensive ex-situ methods, (fully halogenated organic solvents, polychlorinated biphenyl (PCBs), polybrominated biphenyl ethers (PBDEs), and per- and polyfluorinated alkyl substances (PFAS)) by employing Anaerobic Radical Treatment (ART). In Aim 1, we propose to develop and optimize anaerobic thermally activated persulfate methods to dehalogenate recalcitrant contaminants. We will develop a kinetic model that will account for temperature, pH, oxidant dose, contaminant concentration, and oxygen concentration. In Aim 2, we will develop a method that employs the use of co-solvent flushing followed by ART. In anaerobic conditions, activated persulfate can react with alcohols to form carbon centered radicals that are able to degrade contaminants. We also predict that persulfate can activate at lower temperature in the presence of solvents, which will allow for more efficient treatment of complex chemical mixtures. This includes aqueous film-forming foams (AFFF) used at sites contaminated with halogenated solvents. Aim 3 is focused on the discovery and fate of stable transformation products formed during ART. In collaboration with Project 3, we will investigate biodegradability of transformation products in microcosm studies. Aim 4 focuses on predicting possible modes of toxicity by utilizing computational toxicity models, screening with biomolecule assays, as well as established bioassay such as the Ames test. The results of Project 4 could provide novel approaches for the remediation of highly halogenated emerging and legacy compounds in the environment, while providing new models and methods for minimizing toxic transformation products.

项目 4：总结/摘要 经过 40 年的研究和现场经验，危险废物的修复 过去三十年来，网站建设仍然是一项重大挑战，取得了长足的进步。 已采用原位处理方法，例如生物修复和渗透性处理 然而，挖掘和场外处置仍然是最常见的障碍。 土壤和地下水抽取（即抽水和处理）系统的补救方法仍然存在 受雇于许多超级基金网站。 昂贵的方法，原位化学氧化（ISCO）已显示出巨大的潜力 提供修复各种污染物的有效方法，包括TCE和 尽管 ISCO 很受欢迎，但事实证明它很难在石油中使用。 疏水性化合物和表现出低反应性的化合物的处理 羟基自由基和硫酸根——氧化过程中产生的两种最强的氧化剂 过氧化氢和过二硫酸盐（即过硫酸盐）在地下的分解。 我们提出的研究旨在开发新的原位化学修复技术 处理通常需要昂贵的异位方法的超级基金污染物，（完全 卤化有机溶剂、多氯联苯（PCB）、多溴联苯醚 （PBDEs），以及全氟和多氟烷基物质（PFAS））通过采用厌氧 根治性治疗（ART）。 在目标 1 中，我们建议开发和优化厌氧热活化过硫酸盐 我们将开发一种动力学模型来去除顽固污染物。 考虑温度、pH、氧化剂剂量、污染物浓度和氧气 在目标 2 中，我们将开发一种使用共溶剂冲洗的方法。 其次是 ART 在厌氧条件下，活化的过硫酸盐可以与醇反应形成。 我们还预测，以碳为中心的自由基能够降解污染物。 可以在溶剂存在的情况下在较低温度下活化，从而提高效率 复杂化学混合物的处理，包括使用水成膜泡沫 (AFFF)。 目标 3 的重点是发现和处理受卤化溶剂污染的场所。 与项目3合作，我们将在ART期间形成稳定的转化产物。 目标 4 的重点是研究微观世界中转化产物的生物降解性。 通过利用计算毒性模型预测可能的毒性模式，筛选 生物分子测定，以及生物建立的测定，例如艾姆斯试验。 项目 4 可以为修复高度卤化的新兴物质提供新方法 和环境中的遗留化合物，同时提供新的模型和方法 有毒转化产物。