氧化还原动态变化对沉积物砷和氟释放的影响:以河北白洋淀平原为例

doi:10.19657/j.geoscience.1000-8527.2022.006

摘要/Abstract

摘要：

季风性波动引起的降雨、径流和排泄过程会引发浅层地下水系统周期性氧化还原动态变化,从而对地下水系统中有害组分的迁移转化产生影响。为探讨氧化还原动态过程对沉积物中砷(As)和氟(F)释放的影响,本研究选择河北白洋淀地区沉积物样品,利用发酵罐作为反应器,建立氧化还原动态实验体系,并监测动态变化过程中实验体系各组分含量的变化。结果表明,碱性和还原环境均有利于地下水中As、F的富集。还原阶段较高的pH条件有利于溶液中F^-的解吸,且体系中有机物降解会产生大量HC0₃^-和C0₃^2-,与F^-发生竞争吸附而有利于F^-的富集。对于溶液中As的富集,一方面是由于还原条件下体系中的As以As(III)为主,受沉积物的吸附作用较弱,从而有利于As被释放到溶液中;另一方面是因为还原阶段较高的pH也会使反应体系中As和沉积物间的吸附作用被减弱,造成As的解吸附。由于实验所用沉积物砷含量较低,不同S0₄^2-浓度条件对氧化还原动态过程中As、F迁移的影响不明显。总之,氧化还原动态变化过程会强烈影响地下水系统中砷、氟的富集。

关键词: 白洋淀平原, 氧化还原动态, 砷, 氟

Abstract:

Precipitation, discharge and draining caused by seasonal fluctuations would generate redox oscillations in shallow groundwater system, which may shed light on the reactive transport of groundwater components in aquifers. To explore the influence of redox oscillations on the release of arsenic and fluoride in sediments, a sediment sample from the Baiyangdian Plain was collected for this study. Variations in aerobic/anaerobic conditions were controlled automatically. During the redox oscillations, solution composition changes in each experimental system were monitored. Results suggest that the groundwater As-F enrichment was promoted by the alkaline and reducing conditions. The reason may be that the pH is higher under reducing conditions, which is conducive to F^- enrichment. In addition, DOM degradation produced large amount of HC0₃^- and C0₃^2- in solution, which benefits groundwater F^- enrichment via competition. Since As (III) adsorption onto sediments is weaker than that of As (V), the dominant As (III) species in reducing solution would promote As mobility. Furthermore, the higher pH reduces the As adsorption capacity onto sediments, which causes As desorption. We found that the varying S0₄^2- concentrations show no clear effect on the As-F enrichment in the dynamically redox experiments. To conclude, the dynamic redox changes would strongly affect the enrichment of As and F^- in groundwater.

Key words: Baiyangdian Plain, redox oscillation, arsenic, fluoride

中图分类号:

P641.3
X523

曹元元, 郭华明, 高志鹏. 氧化还原动态变化对沉积物砷和氟释放的影响:以河北白洋淀平原为例[J]. 现代地质, 2022, 36(02): 533-542.

CAO Yuanyuan, GUO Huaming, GAO Zhipeng. Redox Dynamic Effect on Fluoride and Arsenic Released from Sediments in the Baiyangdian Plain, Hebei[J]. Geoscience, 2022, 36(02): 533-542.

图/表 12

图1 研究区地理位置图

Fig.1 Location of the study area

表1 沉积物样品BDZK1-222不同元素含量(mg/kg)

Table 1 Background values of different elements in sediment sample BDZK1-222 (mg/kg)

元素	K	Fe	Ca	Ti	Ba	Mn	Sr	Zr	Rb	V	Zn	Cr	Co	Ta	Ni	Pb	Cu	Th	As
含量	21 749	12 496	4 633	1 199	440	245	229	112	67.3	64.9	25.1	18.8	15	15	14	12.5	5	4	3

图2 氧化还原实验装置实物图(a)及简图(b)

Fig.2 Photo (a) and schematic illustration (b) of the experimental setup

图3 反应器中ORP和pH随时间的变化(灰色和白色阴影区域分别表示还原和有氧阶段,乳酸钠添加点用箭头表示) (a) R1, 0.1 mM S O 4 2 -; (b) R2,1 mM S O 4 2 -; (c) R3, 5 mM S O 4 2 -。下文同

Fig.3 Temporal variations of ORP and pH in three experimental systems (grey and white shades denoting anoxic and oxic half-cycles, respectively; arrows showing the timing of sodium lactate addition)

图4 反应器中DOC质量浓度随时间变化

Fig.4 Temporal variations of DOC concentrations in three experimental systems

图5 反应器中F-质量浓度随时间变化

Fig.5 Temporal variations of F- concentrations in three experimental systems

表2 反应器溶液中S O 4 2 -浓度与F-质量浓度对比

Table 2 Comparison of solution S O 4 2 - and F-concentrations in three experimental systems

反应器	R₁	R₂	R₃
S $O 4 2 -$ 浓度/mM	0.1	1	5
F^-质量浓度(最大值)/(mg/L)	14.50	8.98	6.66

表2 反应器溶液中S O 4 2 -浓度与F-质量浓度对比

Table 2 Comparison of solution S O 4 2 - and F-concentrations in three experimental systems

反应器	R₁	R₂	R₃
S $O 4 2 -$ 浓度/mM	0.1	1	5
F^-质量浓度(最大值)/(mg/L)	14.50	8.98	6.66

图6 氧化和还原阶段反应器中pH值及F-质量浓度对比箱型图

Fig.6 Box plots of pH and F- concentrations in three experimental systems in oxic and anoxic stages

图7 反应器溶液中F-与DOC质量浓度的相关性图

Fig.7 Correlation plots for F- vs. DOC concentrations in three experimental systems

图8 反应器中As质量浓度随时间变化

Fig.8 Temporal variations of As (total) concentrations in three experimental systems

图9 反应器中pH值与As质量浓度的相关性分析

Fig.9 Correlation plots of pH vs. As concentrations in three experimental systems

图10 反应器溶液中As与DOC消耗量(ΔDOC)的相关性分析

Fig.10 Correlation plots of As vs. consumed DOC concentrations in three experimental systems

参考文献 56

[1]	倪萍. 河套盆地含水层沉积物赋存态砷及对地下水砷富集的影响[D]. 北京: 中国地质大学(北京), 2016.
[2]	DUAN Y H, SCHAEFER M V, WANG Y X, et al. Experimental constraints on redox-induced arsenic release and retention from aquifer sediments in the central Yangtze River Basin[J]. Science of the Total Environment, 2019, 649: 629-639.
[3]	FROHNE T, RINKLEBE J, DIAZ-BONE A R, et al. Controlled variation of redox conditions in a floodplain soil: Impact on metal mobilization and biomethylation of arsenic and antimony[J]. Geoderma, 2011, 160: 14-424.
[4]	AYENEW T. The distribution and hydrogeological controls of fluoride in the groundwater of central Ethiopian rift and adjacent highlands[J]. Environmental Geology, 2008, 54(6): 1313-1324.
[5]	CHOWDHURY A, ADAK K M, MUKHERJEE A, et al. A critical review on geochemical and geological aspects of fluoride belts, fluorosis and natural materials and other sources for alternatives to fluoride exposure[J]. Journal of Hydrology, 2019, 574: 333-359.
[6]	Guidelines for Drinking Water Quality[M]. 4th ed. Geneva, World Health Organization, 2011.
[7]	PI K F, WANG Y X, XIE X J, et al. Hydrogeochemistry of co-occurring geogenic arsenic, fluoride and iodine in groundwater at Datong Basin, northern China[J]. Journal of Hazardous Materials, 2015, 300: 652-661.
[8]	LI J X, WANG Y X, XIE X J, et al. Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China[J]. Science of the Total Environment, 2016, 544: 158-167.
[9]	WEN D G, ZHANG F C, ZHANG E Y, et al. Arsenic, fluoride and iodine in groundwater of China[J]. Journal of Geochemical Exploration, 2013, 135: 1-21.
[10]	GUO H M, WEN D G, LIU Z Y, et al. A review of high arsenic groundwater in Mainland and Taiwan, China: Distribution, characteristics and geochemical processes[J]. Applied Geochemistry, 2014, 41:196-217.
[11]	郭华明, 倪萍, 贾永锋, 等. 原生高砷地下水的类型、化学特征及成因[J]. 地学前缘, 2014, 21(4):1-12.
[12]	GUO H M, WANG Y X, SHPEIZER M G, et al. Natural occurrence of arsenic in shallow groundwater, Shanyin, Datong Basin, China[J]. Journal of Environmental Science and Health, 2003, 38(11): 2565-2580.
[13]	GUO H M, YANG S Z, TANG X H, et al. Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia[J]. Science of the Total Environment, 2008, 339(1): 131-144.
[14]	ISLAM S F, GAULT G A, BOOTHMAN C, et al. Role of metal-reducing bacteria in arsenic release from Bengal delta sediments[J]. Nature, 2004, 430: 0028-0836.
[15]	MCARTHUR J M, BANERJEE D M, HUDSON-EDWARDS K A, et al. Natural organic matter in sedimentary basins and its relation to arsenic in anoxic ground water: the example of West Bengal and its worldwide implications[J]. Applied Geochemistry, 2014, 19(8): 1255-1293.
[16]	GUO H M, ZHANG Y, XING L N, et al. Spatial variation in arsenic and fluoride concentrations of shallow groundwater from the town of Shahai in the Hetao basin, Inner Mongolia[J]. Applied Geochemistry, 2012, 27(11): 2187-2196.
[17]	VINSON S D, MCINTOSH C J, DWYER S G, et al. Arsenic and other oxyanion-forming trace elements in an alluvial basin aquifer: Evaluating sources and mobilization by isotopic tracers (Sr, B, S, O, H, Ra)[J]. Applied Geochemistry, 2011, 26(8): 1364-1376.
[18]	JONES W G, PICHLER T. Relationship between pyrite stability and arsenic mobility during aquifer storage and recovery in southwest central Florida[J]. Environmental Science & Technology, 2007, 41(3): 723-730.
[19]	PILI E, TISSERAND D, BUREAU S. Origin, mobility, and temporal evolution of arsenic from a low-contamination catchment in alpine crystalline rocks[J]. Journal of Hazardous Materials, 2017, 262(12): 887-895.
[20]	SHAH T M, DANISHWAR S. Potential fluoride contamination in the drinking water of Naranji area, northwest frontier province, Pakistan[J]. Environmental Geochemistry and Health, 2003, 25(4): 475-481.
[21]	SU C L, WANG Y X, XIE X J, et al. An isotope hydrochemical approach to understand fluoride release into groundwaters of the Datong Basin, northern China[J]. Environmental Science: Processes & Impacts, 2015, 17(4): 791-801.
[22]	MCNAB W W, SINGLETON J M, MORAN E J, et al. Ion exchange and trace element surface complexation reactions associated with applied recharge of low-TDS water in the San Joaquin Valley, California[J]. Applied Geochemistry, 2009, 24(1): 129-137.
[23]	KUMAR M, DAS N, GOSWAMI R, et al. Coupling fractionation and batch desorption to understand arsenic and fluoride co-contamination in the aquifer system[J]. Chemosphere, 2016, 164: 657-667.
[24]	万继涛, 郝奇琛, 巩贵仁, 等. 鲁西南地区高氟水分布规律与成因分析[J]. 现代地质, 2013, 27(2): 448-453.
[25]	WANG Z, GUO H M, XING S P, et al. Hydrogeochemical and geothermal controls on the formation of high fluoride groundwater[J]. Journal of Hydrology, 2021, 598: 126372.
[26]	SCHAEFER V M, YING C S, BENNER G S, et al. Aquifer arsenic cycling induced by seasonal hydrologic changes within the Yangtze River Basin[J]. Environmental Science & Technology, 2016, 50: 3521-3529.
[27]	HUANG K, LIU Y Y, YANG C, et al. Identification of hydrobiogeochemical processes controlling seasonal variations in arsenic concentrations within a riverbank aquifer at Jianghan Plain, China[J]. Water Resources Research, 2018, 54: 4294-4308.
[28]	FU H Y, ZHANG H, SUI Y, et al. Transformation of uranium species in soil during redox oscillations[J]. Chemosphere, 2018, 208: 846-853.
[29]	THOMASARRIGO K L, MIKUTTA C, LOHMAYER R, et al. Sulfidization of organic freshwater flocs from a minerotrophic peatland: speciation changes of iron, sulfur, and arsenic[J]. Environmental Science & Technology, 2016, 50(7): 3607-3616.
[30]	PARSONS T C, COUTURE R M, OMOREGIE O E, et al. The impact of oscillating redox conditions: arsenic immobilisation in contaminated calcareous floodplain soils[J]. Environmental Pollution, 2013, 178: 254-263.
[31]	COUTURE R M, CHARLET L, MARKELOVA E, et al. On-off mobilization of contaminants in soils during redox oscillations[J]. Environmental Science & Technology, 2015, 49(5): 3015-3023.
[32]	赵振宏. 河北平原深层高氟地下水水文地球化学特征[J]. 工程勘察, 1993(2): 28-31.
[33]	林重阳. 漳卫河流域地下水的水化学特征和高氟地下水的形成[D]. 北京: 中国地质大学(北京), 2020.
[34]	PHAN V, BARDELLI F, PAPE L P, et al. Interplay of S and As in Mekong Delta sediments during redox oscillations[J]. Geoscience Frontiers, 2019, 10(5): 1715-1729.
[35]	高志鹏. 基于一维反应运移模型的河套平原地下水砷富集机理[D]. 北京: 中国地质大学(北京), 2020.
[36]	陈毅. 白洋淀流域平原区地下水-孔隙水的水化学特征和水文地球化学过程[D]. 北京: 中国地质大学(北京), 2018.
[37]	文丽青. 白洋淀水质污染分析及综合治理研究[J]. 河北环境科学, 2001, 9(3):46-48.
[38]	THOMPSON A, CHADWICK A O, RANCOURT G D, et al. Iron-oxide crystallinity increases during soil redox oscillations[J]. Geochimica et Cosmochimica Acta, 2006, 70(7): 1710-1727.
[39]	WANG Y H, PAPE L P, MORIN G, et al. Arsenic speciation in Mekong Delta sediments depends on their depositional environment[J]. Environmental Science & Technology, 2018, 52(6): 3431-3439.
[40]	GHORAI S, PANT K K. Equilibrium, kinetics and breakthrough studies for adsorption of fluoride on activated alumina[J]. Separation and Purification Technology, 2005, 42: 265-271.
[41]	沈照理, 郭华明, 徐刚, 等. 地下水化学异常与地方病[J]. 自然杂志, 2010(2):83-89.
[42]	JACKS G, BHATTACHARYA P, CHAUDHARY V, et al. Controls on the genesis of some high-fluoride groundwaters in India[J]. Applied Geochemistry, 2005, 20(2): 221-228.
[43]	POLOMSKI J, FLUHLER H, BLASER P. Fluoride-induced mobilization and leaching of organic matter, iron, and aluminum[J]. Journal of Environmental Quality, 1982, 11:452-456.
[44]	JESUßEK A, GRANDLE S, DAHMKE A. Impacts of subsurface heat storage on aquifer hydrogeochemistry[J]. Environmental Earth Sciences, 2013, 69(6): 1999-2012.
[45]	BONTE M, BREUKELEN M B, STUYFZAND J P. Temperature-induced impacts on groundwater quality and arsenic mobility in anoxic aquifer sediments used for both drinking water and shallow geothermal energy production[J]. Water Research, 2013, 47(14): 5088-5100.
[46]	MOLINARI A, GUADAGNINI L, MARCACCIO M, et al. Arsenic release from deep natural solid matrices under experimentally controlled redox conditions[J]. Science of the Total Environment, 2013, 444: 231-240.
[47]	SMEDLEY P L, KINNIBURGH D G. A review of the source, behaviour and distribution of arsenic in natural waters[J]. Applied Geochemistry, 2002, 17: 517-568.
[48]	PHAN V, BERNIER-LATMANI R, TISSERAND D, et al. As release under the microbial sulfate reduction during redox oscillations in the Upper Mekong Delta aquifers, Vietnam: A mechanistic study[J]. Science of the Total Environment, 2019, 663: 718-730.
[49]	PEDERSEN D H, POSTMA D, JAKOBSEN R. Release of arsenic associated with the reduction and transformation of iron oxides[J]. Science Direct, 2006, 70: 4116-4129.
[50]	GUO H M, ZHANG B, LI Y, et al. Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia[J]. Environmental Pollution, 2011, 159: 876-883.
[51]	ANAWAR H M, KOMAKI K, AKAI J, et al. Diagenetic control on arsenic partitioning in sediments of the Meghna River delta, Bangladesh[J]. Environmental Geology, 2002, 41(7): 816-825.
[52]	MASSCHELEYN H P, DELAUNE D R, PATRICK H W. Effect of redox potential and pH on arsenic speciation and solubility in a contaminated soil[J]. Environmental Science & Technology, 1991, 25(8): 1414-1419.
[53]	YAMAGUCHIA N, NAKAMURAB T, DONG D, et al. Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution[J]. Chemosphere, 2011, 83: 925-932.
[54]	VAN GEEN A, BOSTICK B C, TRANG P T K, et al. Retardation of arsenic transport through a Pleistocene aquifer[J]. Nature, 2013, 501: 204-207.
[55]	QIAO W, GUO H M, HE C, et al. Molecular evidence of arsenic mobility linked to biodegradable organic matter[J]. Environmental Science & Technology, 2020, 54: 7280-7290.
[56]	邢丽娜. 华北平原典型剖面上地下水化学特征和水文地球化学过程[D]. 北京: 中国地质大学(北京), 2012.