高氯酸盐自然衰减的柱实验研究

doi:10.13745/j.esf.2022.1.36

摘要/Abstract

摘要：

高氯酸盐( $ClO 4 -$ )是一种小分子量、有毒的无机络阴离子,普遍存在于环境中。由于其分子大小与碘离子相似,会干扰人体甲状腺的正常功能,因此其环境污染问题引起了广泛的关注。本文选取污染场地的天然河沙为试验材料,主要通过柱实验对地下水中 $ClO 4 -$ 自然衰减过程进行研究,考察了铁氧化物、 $NO 3 -$ 对 $ClO 4 -$ 自然衰减过程产生的影响。结果表明,高氯酸盐自然衰减过程主要由微生物驱动,天然河沙可去除2 mg/L的 $ClO 4 -$ ,但其过程缓慢且还原量有限,长期去除率不超过10%,其限制因素为缺乏电子供体;铁氧化物可以促进 $ClO 4 -$ 自然衰减,但当溶解性铁的浓度低于5.5 mg/L时,衰减过程开始受到影响;地下水中的 $NO 3 -$ 会抑制 $ClO 4 -$ 的降解,当 $NO 3 -$ 低至10 mg/L或以下时, $ClO 4 -$ 才开始明显降解。

关键词: 高氯酸盐, 自然衰减, 微生物降解, 电子供体, 铁氧化物, 硝酸盐

Abstract:

Perchlorate ( $ClO 4 -$ ), a low molecular weight toxic inorganic complex anion is a widespread contaminant in the environment. Perchlorate contamination is a serious environmental problem as perchlorate is known to impact thyroid function by replacing iodine intake due to its similar molecular size with iodine. Column experiments, using river sand from the polluted site as the experimental material, were conducted to stimulate natural attenuation of the target pollutant, perchlorate ( $ClO 4 -$ ). The effects of iron oxides and nitrate ( $NO 3 -$ ) were also evaluated. The results show that $ClO 4 -$ natural attenuation is mainly dependent on microbial degradation in the aquifer, and the groundwater environment is more conducive to microbial activity. Natural river sand can remove 2 mg/L $ClO 4 -$ ; however, the process is slow and the reduction amount is limited. A lack of electron donors was found to result in a long-term removal efficiency of less than 10%. Iron oxides can stimulate natural attenuation of $ClO 4 -$ . In fact, the attenuation process began to be affected when the concentration of dissolved iron was lower than 5.5 mg/L. Nitrate ( $NO 3 -$ ) in groundwater has an inhibitory effect on $ClO 4 -$ reduction. When $NO 3 -$ concentration was less than 10 mg/L, an apparent reduction in $ClO 4 -$ could be initiated.

Key words: perchlorate, natural attenuation, microbial degradation, electron donors, iron oxides, nitrate

中图分类号:

梁凯旋, 刘菲, 张莉. 高氯酸盐自然衰减的柱实验研究[J]. 地学前缘, 2022, 29(3): 207-216.

LIANG Kaixuan, LIU Fei, ZHANG Li. Natural attenuation of perchlorate: A column experiment study[J]. Earth Science Frontiers, 2022, 29(3): 207-216.

图/表 9

图1 柱实验概念图

Fig.1 Schematic diagram of column experiment

表1 地下水进水化学成分

Table 1 Chemical component of groundwater- influent

水样	浓度/(mg·L^-1)										pH	Eh
水样	Cl^-	$SO 4 2 -$	$NO 3 -$	$HCO 3 -$	$ClO 4 -$	K⁺	Na⁺	Ca²⁺	Mg²⁺	Fe(总)	pH	Eh
进水样	58.26	82.85	22.46	181.9	2.01	1.61	18.45	87.14	37.54	未检出	7.51	156

表1 地下水进水化学成分

Table 1 Chemical component of groundwater- influent

水样	浓度/(mg·L^-1)										pH	Eh
水样	Cl^-	$SO 4 2 -$	$NO 3 -$	$HCO 3 -$	$ClO 4 -$	K⁺	Na⁺	Ca²⁺	Mg²⁺	Fe(总)	pH	Eh
进水样	58.26	82.85	22.46	181.9	2.01	1.61	18.45	87.14	37.54	未检出	7.51	156

图2 批试验中高氯酸盐和氯离子随反应时间的变化

Fig.2 Perchlorate and chloride ion concentration changes in batch tests

图3 不同进水条件下,出水中高氯酸盐的浓度变化

Fig.3 Changes of perchlorate level in effluent with column runtime using two different influents

图4 不同孔隙体积下高氯酸盐浓度随距离的变化进水:高氯酸盐去离子水溶液(a);高氯酸盐地下水溶液(b)。

Fig.4 Change of perchlorate concentration with column distance under6 different pore volumes using effluents of (a) perchloate-deionized water and (b) perchlorate-groundwater solutions

图5 出水中 ClO 4 -、pH值、Eh随孔隙体积的变化

Fig.5 Changes of pH, Eh and perchlorate level in the effluent with column pore volume

图6 沙柱内溶解性铁的最大浓度对 ClO 4 -自然衰减的影响

Fig.6 Effect of the maximum concentration of soluble iron on perchlorate natural attenuation in sand column

图7 溶解性铁和 ClO 4 -相关性分析图

Fig.7 Correlation analysis of dissolved iron and perchlorate

图8 NO 3 -对 ClO 4 -自然衰减产生的影响

Fig.8 Effect of nitrate on perchlorate natural attenuation

参考文献 55

[1]	SHIM Y H, HA S W, YOO E S, et al. Recovery of ammonium perchlorate from obsolete ammunition and its application in synthesis of lithium perchlorate[J]. Propellants Explosives Pyrotechnics, 2021, 46(4): 612-617. DOI URL
[2]	RAJAGOPALAN S, ANDERSON T, COX S, et al. Perchlorate in wet deposition across North America[J]. Environmental Science and Technology, 2009, 43(3): 616-222. DOI URL
[3]	郑雯静, 闻自强, 沈昊宇, 等. 高氯酸盐的来源、危害及其检测方法研究进展[J]. 环境科学与技术, 2018, 41(S1): 103-108.
[4]	张丹, 段慧. 环境中高氯酸盐的污染、分析方法及去除技术的研究进展[J]. 西南农业学报, 2013, 26(6): 2648-2653.
[5]	彭银仙. 高氯酸盐水环境行为特征研究[D]. 镇江: 江苏大学, 2011.
[6]	LYNCH K L, JACKSON W A, REY K, et al. Evidence for biotic perchlorate reduction in naturally perchlorate-rich sediments of pilot valley basin, Utah[J]. Astrobiology, 2019, 19(5): 629-641. DOI URL
[7]	WAGNER H P, SUAREZ F X, PEPICH B V, et al. Challenges encountered in extending the sensitivity of US Environmental Protection Agency Method 314.0 for perchlorate in drinking water[J]. Journal of Chromatography A, 2004, 1039(1/2): 97-104. DOI URL
[8]	KRYNITSKY A J, NIEMANN R A, NORTRUP D A. Determination of perchlorate anion in foods by ion chromatography-tandem mass spectrometry[J]. Analytical Chemistry, 2004, 76(18): 5518-5522. DOI URL
[9]	SANCHEZ C A, KRIEGER R I, KHANDAKER N, et al. Accumulation and perchlorate exposure potential of lettuce produced in the Lower Colorado River region[J]. Journal of Agricultural and Food Chemistry, 2005, 53(13): 5479-5486. DOI URL
[10]	LUO W H, SASAKI K, HIRAJIMA T. Surfactant-modified montmorillonite by benzyloctadecyldimethylammonium chloride for removal of perchlorate[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 481:616-625. DOI URL
[11]	SHI Y L, ZHANG N, GAO J M, et al. Effect of fireworks display on perchlorate in air aerosols during the Spring Festival[J]. Atmospheric Environment, 2011, 45(6): 1323-1327. DOI URL
[12]	张萍, 史亚利, 蔡亚岐, 等. 离子色谱-质谱联用测定瓶装水中的高氯酸盐和溴酸盐[J]. 环境化学, 2007, 26(4): 544-546.
[13]	史亚利, 高健民, 李鑫, 等. 浏阳河水、底泥和土壤中高氯酸盐的污染[J]. 环境化学, 2010, 29(3): 388-391.
[14]	WU Q, ZHANG T, SUN H W, et al. Perchlorate in tap water, groundwater, surface waters, and bottled water from China and its association with other inorganic anions and with disinfection byproducts[J]. Archives of Environmental Contamination and Toxicology, 2010, 58(3): 543-550. DOI URL
[15]	TANG Y L, ZHONG B F, QU B, et al. Occurrence of perchlorate in groundwater, paired farmland soil, lettuce, and rhizosphere soil from Chengdu, China[J]. Environmental Science Processes and Impacts, 2017, 19(5): 752-757. DOI URL
[16]	KUMARATHILAKA P, OZE C, INDRARATNE S P, et al. Perchlorate as an emerging contaminant in soil, water and food[J]. Chemosphere, 2016, 150:667-677. DOI URL
[17]	RAO B, ANDERSON T A, REDDER A, et al. Perchlorate formation by ozone oxidation of aqueous chlorine/oxy-chlorine species: role of cl_xO_y radicals[J]. Environmental Science and Technology, 2010, 44(8): 2961-2967. DOI URL
[18]	闫旭. 我国重点流域及重点地区饮用水中高氯酸盐污染水平调查研究[D]. 北京: 中国疾病预防控制中心, 2020.
[19]	JACKSON W A, BÖHLKE J K, GU B H, et al. Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States[J]. Environmental Science and Technology, 2010, 44(13): 4869-4876. DOI URL
[20]	HU J P, XIAN Y P, WU Y L, et al. Perchlorate occurrence in foodstuffs and water: analytical methods and techniques for removal from water - A review[J]. Food Chemistry, 2021, 360:130146. DOI URL
[21]	李冬桂, 农耀京, 吴凤, 等. 蔬菜水果中高氯酸盐检测及污染情况分析[J]. 食品科技, 2021, 46(2): 315-320.
[22]	陈桂葵, 骆世明, 贺鸿志, 等. 高氯酸盐胁迫对水稻生长发育和养分吸收的影响[J]. 生态学报, 2014, 34(19): 5460-5469.
[23]	方齐乐, 陈宝梁. 新型环境污染物高氯酸盐的环境化学行为、食品安全及健康风险[J]. 科学通报, 2013, 58(26): 2626-2642.
[24]	CHEN Y N, ZHU Z, ZHAO Y, et al. Perchlorate in shellfish from South China Sea and implications for human exposure[J]. Marine Pollution Bulletin, 2021, 170:112672. DOI URL
[25]	田一媚, 宫智勇. 食品中高氯酸盐的污染现状及毒理作用研究进展[J]. 食品科学, 2020, 41(5): 276-281.
[26]	GREER M A, GOODMAN G, PLEUS R C, et al. Health effects assessment for environmental perchlorate contamination: the dose response for inhibition of thyroidal radioiodine uptake in humans[J]. Environmental Health Perspectives, 2002, 110(9): 927-937. DOI URL
[27]	TIKKANEN M W. Development of a drinking water regulation for perchlorate in California[J]. Analytica Chimica Acta, 2006, 567(1): 20-25. DOI URL
[28]	于佳, 唐玄乐, 刘家仁. 高氯酸盐对人体健康影响的研究进展[J]. 环境与健康杂志, 2008, 25(7): 648-650.
[29]	闻自强, 郑雯静, 沈昊宇, 等. 高氯酸盐的危害、水污染现状与去除技术研究进展[J]. 环境化学, 2019, 38(1): 209-216.
[30]	MOTZER W E. Perchlorate: problems, detection, and solutions[J]. Environmental Forensics, 2001, 2(4): 301-311. DOI URL
[31]	SORIAL G A. The perchlorate dilemma in drinking water[J]. Journal of Environmental Engineering, 2004, 130(1): 1-2. DOI URL
[32]	蔡贤雷, 谢寅峰, 刘伟龙, 等. 高氯酸盐污染及修复的研究进展[J]. 生态学报, 2008, 28(11): 5592-5600.
[33]	WANG C Y, DONG J, HU W, et al. Enhanced simultaneous removal of nitrate and perchlorate from groundwater by bioelectrochemical systems (BESs) with cathodic potential regulation[J]. Biochemical Engineering Journal, 2021, 173:108068. DOI URL
[34]	徐碧波. 生物碳及其改性材料对高氯酸盐去除性能及机理研究[D]. 长沙: 湖南大学, 2017.
[35]	张红聘, 刘祥萱, 刘渊, 等. 高氯酸盐废水修复技术研究现状[J]. 化学推进剂与高分子材料, 2013, 11(3): 9-14.
[36]	程丽杰, 高宁博, 楚华, 等. 高氯酸盐还原菌的代谢过程及应用研究进展[J]. 化工进展, 2020, 39(S2): 251-261.
[37]	LIANG S, SHI Q, GAO X Y, et al. Perchlorate removal by autotrophic bacteria associated with zero-valent iron: effect of calcium ions[J]. Journal of Chemical Technology and Biotechnology, 2015, 90(4): 722-729.
[38]	ARTHUR R D, TORLAPATI J, SHIN K H, et al. Process control factors for continuous microbial perchlorate reduction in the presence of zero-valent iron[J]. Frontiers of Environmental Science and Engineering, 2014, 8(3): 386-393. DOI URL
[39]	高孟春, 赵从从, 张健, 等. 硫自养高氯酸盐还原菌培养与驯化[J]. 环境工程学报, 2014, 8(4): 1257-1261.
[40]	邱华, 李佳璐, 龙雨涛, 等. 高氯酸盐高效降解菌的筛选及降解特性[J]. 水处理技术, 2015, 41(4): 58-61.
[41]	吴春笃, 郭静, 许小红. 高氯酸盐降解菌的分离鉴定及特性研究[J]. 生态环境学报, 2010, 19(2): 281-285.
[42]	时琼. 以零价铁为电子供体微生物协同去除地下水中高氯酸盐的研究[D]. 济南: 山东大学, 2012.
[43]	王蕊, 刘菲, 陈鸿汉, 等. 电子供体对地下水中高氯酸盐生物去除的影响研究[J]. 环境科学学报, 2013, 33(11): 3060-3067.
[44]	HAN W Y, FU F L, CHENG Z H, et al. Studies on the optimum conditions using acid-washed zero-valent iron/aluminum mixtures in permeable reactive barriers for the removal of different heavy metal ions from wastewater[J]. Journal of Hazardous Materials, 2016, 302:437-446. DOI URL
[45]	LONDON M R, WAHMAN D G, KATZ L E, et al. Zero-valent iron/biotic treatment system for perchlorate-contaminated water: lab-scale performance, modeling, and full-scale implications[J]. Journal of Environmental Engineering, 2013, 139(11): 1361-1367. DOI URL
[46]	SON A, LEE J, CHIU P C, et al. Microbial reduction of perchlorate with zero-valent iron[J]. Water Research, 2006, 40(10): 2027-2032. DOI URL
[47]	YU X Y, AMRHEIN C, DESHUSSES M A, et al. Perchlorate reduction by autotrophic bacteria in the presence of zero-valent iron[J]. Environmental Science and Technology, 2006, 40(4): 1328-1334. DOI URL
[48]	王小明. 几种亚稳态铁氧化物的结构、形成转化及其表面物理化学特性[D]. 武汉: 华中农业大学, 2015.
[49]	张萌, 郑平. 铁氧化菌的类型、生境及富集培养方法[J]. 科技通报, 2012, 28(11): 72-76,152.
[50]	卢玉琢. 铁锰氧化菌及硫酸盐还原菌在典型水环境中对金属腐蚀的影响研究[D]. 天津: 天津大学, 2011.
[51]	王依依. 地下水高氯酸盐和硝酸盐复合污染的硫自养净化机制[D]. 郑州: 河南工业大学, 2018.
[52]	LIU Y Y, PTACEK C J, BLOWES D W. Treatment of dissolved perchlorate, nitrate, and sulfate using zero-valent iron and organic carbon[J]. Journal of Environmental Quality, 2014, 43(3): 842-850. DOI URL
[53]	谢宇轩. 高氯酸盐及其与硝酸盐氮、氨氮混合污染的微生物降解研究[D]. 北京: 中国地质大学(北京), 2014.
[54]	张波, 蒋霞, 李顺, 等. 零价铝对高氯酸盐污染物的去除[J]. 环境工程学报, 2016, 10(8): 4271-4276.
[55]	谢宇轩, 刘菲, 关翔宇, 等. 基于功能基因表达的高氯酸盐与硝酸盐氮修复[J]. 环境工程学报, 2014, 8(4): 1423-1428.