活化过硫酸盐修复苯胺污染地下水及其环境风险

doi:10.16085/j.issn.1000-6613.2021-0959

摘要/Abstract

摘要：

采用砂柱实验对模拟苯胺（AN）污染地下水进行连续处理，研究了碱（NaOH）活化、铁（Fe²⁺）活化和过氧化氢（H₂O₂）活化三种过硫酸盐（PS）活化方式对AN的去除效果及环境风险。结果表明，H₂O₂活化PS处理对AN去除效果最好，4天内AN累计去除率达到了60%。当H₂O₂浓度递减注射时，4天内AN累计去除率达到了83%，克服了恒定浓度注射时的氧化剂浪费问题。各处理的总有机碳（TOC）矿化率远小于AN去除率，表明大量AN不完全降解。GC/MS分析表明，降解产物主要有对苯醌、偶氮苯和直链烷烃。碱活化显著提升了体系pH，其他反应体系均为中性，反应后pH均下降。H₂O₂活化PS处理的氧化还原电位稳定保持较高水平。处理后的水质急性毒性均高于处理前，主要源于过硫酸钠分解后残留的硫酸盐，使修复后地下水饱和带形成高盐区。因此，采用活化PS原位注射修复时，需对二次污染风险进行严格地评估和防控。

关键词: 活化过硫酸盐, 原位化学氧化, 地下水修复, 生态风险评价, 毒性分析

Abstract:

In this paper, a simulated groundwater polluted by aniline (AN) was treated continuously in a sand column. The removal effect and environmental risks of three persulfate (PS) activation methods on AN were studied. The activators were alkali (NaOH), iron (Fe²⁺) and hydrogen peroxide (H₂O₂). Results showed that H₂O₂ activated PS treatment had the best removal effect on AN. Cumulative removal rate of AN reached 60% within 4 days. When H₂O₂ concentration decreased, the cumulative removal rate of AN reached 83% within 4 days, which could overcome the problem of oxidant waste in constant concentration injection. The total organic carbon (TOC) mineralization rate of each treatment was far less than the AN removal rate, indicating that a lot of AN was not completely degraded. GC/MS analysis showed that the degradation products mainly included p-benzoquinone, azobenzene and straight-chain alkanes. Alkali activation significantly increased the pH of the system, while other reaction systems were all neutral, and pH decreased after reaction. The REDOX potential of PS activated by H₂O₂ was stable and maintained a high level. The acute toxicity of different treatments was higher than before the restoration, which was mainly because the residual sulfate after the decomposition of sodium persulfate made the groundwater saturated zone form a high-salt zone. Therefore, in situ injection of activated persulfate for remediation, the risk of secondary contamination should be strictly assessed and controlled.

Key words: activated persulfate, in situ chemical oxidation, groundwater remediation, ecological risk assessment, toxicity analysis

中图分类号:

X703

李坡, 张珊珊, 施锦秋, 高航, 王明新. 活化过硫酸盐修复苯胺污染地下水及其环境风险[J]. 化工进展, 2022, 41(5): 2753-2760.

LI Po, ZHANG Shanshan, SHI Jinqiu, GAO Hang, WANG Mingxin. Remediation of aniline-contaminated groundwater by activated persulfate and its environmental risks[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2753-2760.

图/表 8

图1 地下水污染模拟装置1—储液桶；2—蠕动泵；3—地下水污染模拟柱；4—石英砂；5—pH/Eh水质传感器；6—集液瓶

表1 氧化剂注射浓度梯度

时间/h	PS浓度/mg·L^-1	H₂O₂浓度/mg·L^-1
0~6	10000	2000
6~12	5000	1000
12~24	2500	500
24~36	1250	250
36~60	625	125
60~96	0	0

图2 不同处理方式AN、TOC浓度和AN累计去除率

图3 不同处理方式下，降解前后AN溶液的GC/MS图

图4 不同反应体系的pH变化

图5 不同反应体系的Eh变化

图6 不同反应体系对发光细菌的相对抑制率

图7 不同反应体系的总盐度变化

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