Effect of Groundwater Components on Hydroxyl Radical Production by Fe (Ⅱ) Oxygenation
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摘要: 羟自由基(·OH)是自然环境中氧化活性最强的物种，对物质转化具有重要影响.前期研究发现地下水接触O2可产生·OH，其中Fe2+氧化起主导作用，但地下水化学组成对Fe2+氧化产生·OH的影响尚不清楚.通过室内模拟实验，探究了地下水中常见组分(Ca2+、Mg2+、腐殖酸(HA)和磷酸根)对Fe2+氧化产生·OH的影响.结果表明，pH 6.5时0.357 mM Fe2+在5 h内氧化完全，产生约1.8 μM的·OH；Ca2+(1~6 mM)、Mg2+(1~4 mM)对Fe2+氧化和·OH产生无明显影响；HA(10~30 mg/L)促进Fe2+氧化和·OH产生，促进效果随pH降低而增强；磷酸根(0.01~0.03 mM)抑制Fe2+氧化，对·OH产生的影响为先抑制后促进.Abstract: Hydroxyl radical (·OH) is the most reactive oxidant in nature, which significantly impacts the transformation of substance and contaminants. Previous studies have substantiated that exposure of groundwater to O2 can produce ·OH through Fe2+ oxygenation. However, the effect of groundwater compositions on Fe2+ oxygenation and ·OH production remainsis unclear. Therefore, this study evaluates the influence of groundwater components (Ca2+, Mg2+, humic acid (HA) and phosphate) on Fe2+ oxygenation and resultant ·OH production. Results show that at pH 6.5, 0.357 mM Fe2+ was completely oxidized within 5 h with production of 1.8 μM ·OH. Ca2+ (1-6 mM) and Mg2+ (1-4 mM) had no obvious influence on Fe2+ oxidation and ·OH production. HA (10-30 mg/L) promoted Fe2+ oxidation and ·OH production, and the promotion increased with the decrease in pH. Phosphate (0.01-0.03 mM) inhibited Fe2+ oxidation and ·OH production in initial stage while promoted Fe2+ oxidation and ·OH production later on.
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Key words:
- ferrous iron /
- hydroxyl radical /
- groundwater /
- oxygenation /
- hydrogeochemistry
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图 1 Ca2+对Fe2+氧化(a)和羟自由基产量(b)的影响，Mg2+对Fe2+氧化(c)和羟自由基产量(d)的影响
Fig. 1. Effects of Ca2+ on Fe2+ oxidation (a) and ·OH production (b), and of Mg2+ on Fe2+ oxidation (c) and ·OH production (d)
图 2 HA在pH6.5时对Fe2+氧化(a)和对羟自由基产量(b)的影响
Fig. 2. Effect of HA on Fe2+ oxidation (a) and ·OH production (b) at pH 6.5
图 3 HA在pH6.2时对Fe2+氧化(a)和对羟自由基产量(b)的影响
Fig. 3. Effect of HA on Fe2+ oxidation (a) and ·OH production (b) at pH 6.2
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Baltpurvins, K.A., Burns, R.C., Lawrance, G.A., et al., 1997.Effect of Ca2+, Mg2+, and Anion Type on the Aging of Iron(Ⅲ) Hydroxide Precipitates.Environmental Science & Technology, 31(4):1024-1032.doi: 10.1021/es960498y Chen, Y.M., Chen, Z.H., Yu, K.B., 2016.Heterogeneity and Water Prevention of Karst Water System in Metal Mine Areas in Southern China:A Case Study of Makeng Iron Mine, Fujian Province.Earth Science, 41(4):692-700(in Chinese with English abstract). http://www.en.cnki.com.cn/Article_en/CJFDTotal-DQKX201604015.htm Deng, Y.M., Wang, Y.X., Li, H.J., et al., 2015.Seasonal Variation of Arsenic Speciation in Shallow Groundwater from Endemic Arsenicosis Area in Jianghan Plain.Earth Science, 40(11):1876-1886(in Chinese with English abstract). https://www.researchgate.net/publication/288228393_Seasonal_variation_of_arsenic_speciation_in_shallow_groundwater_from_endemic_arsenicosis_area_in_Jianghan_Plain Duan, Y.H., Gan, Y.Q., Guo, X.X., et al., 2014.Water Chemical Characteristics and Arsenic Enrichment Factor Analysis at High Arsenic Groundwater Monitoring Field of Jianghan Plain.Geological Science and Technology Information, 33(2):140-147(in Chinese with English abstract). Goti, M., Musi, S., Popovi, S., et al., 2008.Investigation of Factors Influencing the Precipitation of Iron Oxides from Fe(Ⅱ) Containing Solutions.Croatica Chemica Acta, 81(4):569-578. https://www.researchgate.net/publication/288079329_Investigation_of_factors_influencing_the_precipitation_of_iron_oxides_from_FeII_containing_solutions Hug, S.J., Leupin, O., 2003.Iron-Catalyzed Oxidation of Arsenic(Ⅲ) by Oxygen and by Hydrogen Peroxide:pH-Dependent Formation of Oxidants in the Fenton Reaction.Environmental Science & Technology, 37(12):2734-2742.doi: 10.1021/es026208x Keenan, C.R., Sedlak, D.L., 2008.Ligand-Enhanced Reactive Oxidant Generation by Nanoparticle Zero-Valent Iron and Oxygen.Environmental Science & Technology, 42(18):6936-6941.doi: 10.1021/es801438 Komadel, P., Stucki, J.W., 1988.Quantitative Assay of Minerals for Fe2+ and Fe3+ Using 1.10-Phenathroline:Ⅲ.A Rapid Photochemical Method.Clays and Clay Minerals, 36(4):379-381.doi: 10.1346/CCMN.1988.0360415 Koppenol, W.H., 2001.The Haber-Weiss Cycle-70 Years Later.Redox Report, 6(4):229-234.doi: 10.1179/135100001101536373 Lee, C.H., Keenan, C.R., Sedlak, D.L., 2008.Polyoxometalate-Enhanced Oxidation of Organic Compounds by Nanoparticulate Zero-Valent Iron and Ferrous Ion in the Presence of Oxygen.Environmental Science & Technology, 42(13):4921-4926.doi: 10.1021/es800317j Li, G.B., Liu, C., 1989.Eliminating Iron and Manganese from Groundwater(2nd Edition).China Architecture & Building Press, Beijing (in Chinese). Liang, L.Y., McNabb, J.A., Paulk, J.M., et al., 1993.Kinetics of Iron(Ⅱ) Oxygenation at Low Partial Pressure of Oxygen in the Presence of Natural Organic Matter.Environmental Science & Technology, 27(9):1864-1870.doi: 10.1021/es00046a014 Liao, P., Li, W.L., Wang, D.J., et al., 2017.Effect of Reduced Humic Acid on the Transport of Ferrihydrite Nanoparticles under Anoxic Conditions.Water Research, 109:347-357.doi: 10.1016/j.watres.2016.11.069 Mopper, K., Zhou, X., 1990.Hydroxyl Radical Photoproduction in the Sea and Its Potential Impact on Marine Processes.Science, 250(4981):661-664.doi: 10.1126/science.250.4981.661 Page, S.E., Kling, G.W., Sander, M., et al., 2013.Dark Formation of Hydroxyl Radicals in Arctic Soil and Surface Waters.Environmental Science & Technology, 47(22):12860-12867.doi: 10.1021/es4033265 Page, S.E., Sander, M., Arnold, W.A., et al., 2012.Hydroxyl Radical Formation upon Oxidation of Reduced Humic Acids by Oxygen in the Dark.Environmental Science & Technology, 46(3):1590-1597.doi: 10.1021/es203836f Pang, S.Y., Jiang, J., Ma, J., 2011.Oxidation of Sulfoxides and Arsenic(Ⅲ) in Corrosion of Nanoscale Zero Valent Iron by Oxygen:Evidence against Ferryl Ions (Fe(Ⅳ)) as Active Intermediates in Fenton Reaction.Environmental Science & Technology, 45(1):307-312.doi: 10.1021/es102401d Rose, J., Flank, A.M., Masion, A., et al., 1997.Nucleation and Growth Mechanisms of Fe Oxyhydroxide in the Presence of PO4 Ions.2.P K-Edge EXAFS Study.Langmuir, 13(6):1827-1834.doi: 10.1021/la961039d Rose, J., Manceau, A., Bottero, J.Y., et al., 1996.Nucleation and Growth Mechanisms of Fe Oxyhydroxide in the Presence of PO4 Ions.1.Fe K-Edge EXAFS Study.Langmuir, 12(26):6701-6707.doi: 10.1021/la9606299 Sharma, P., Ofner, J., Kappler, A., 2010.Formation of Binary and Ternary Colloids and Dissolved Complexes of Organic Matter, Fe and As.Environmental Science & Technology, 44(12):4479-4485.doi: 10.1021/es100066s Stumm, W., Sulzburger, B., 1992.The Cycling of Iron in Natural Environments:Considerations Based on Laboratory Studies of Heterogeneous Redox Processes.Geochimica et Cosmochimica Acta, 56(8):3233-3257.doi: 10.1016/0016-7037(92)90301-X Tong, M., Yuan, S.H., Ma, S.C., et al., 2016.Production of Abundant Hydroxyl Radicals from Oxygenation of Subsurface Sediments.Environmental Science & Technology, 50(1):214-221.doi: 10.1021/acs.est.5b04323 Tryk, D.A., Fujishima, A., Honda, K., 2000.Recent Topics in Photoelectrochemistry:Achievements and Future Prospects.Electrochimica Acta, 45(15-16):2363-2376.doi: 10.1016/S0013-4686(00)00337-6 Zhang, N.D., Zheng W., 2001.The Application of Hydroxyl Radical in Wasterwater Treatment.Journal of Harbin University of Commerce (Natural Sciences Edition), 17(3):22-24, 28(in Chinese with English abstract). doi: 10.1080/10643389.2010.507698?queryID=%24%7BresultBean.queryID%7D Zhang, R.Q., Liang, X., Jin, M.G., et al., 2001.General Hydrogeology.6th Edition.Geological Publishing House, Beijing, 64 (in Chinese). Zhu, J., Zhang, P., Yuan, S.H., et al., 2017.Production of Hydroxyl Radicals from Oxygenation of Simulated AMD Due to CaCO3-Induced pH Increase.Water Research, 111:118-126.doi: 10.1016/j.watres.2016.12.048 陈彦美, 陈植华, 於开炳, 2016.南方岩溶金属矿区地下水非均质性及防治水意义:以福建马坑铁矿为例.地球科学, 41(4):692-700. http://www.earth-science.net/WebPage/Article.aspx?id=3286 邓娅敏, 王焰新, 李慧娟, 等, 2015.江汉平原砷中毒病区地下水砷形态季节性变化特征.地球科学, 40(11):1876-1886. http://www.earth-science.net/WebPage/Article.aspx?id=3194 段艳华, 甘义群, 郭欣欣, 等, 2014.江汉平原高砷地下水监测场水化学特征及砷富集影响因素分析.地质科技情报, 33(2):140-147. http://www.cnki.com.cn/Article/CJFDTOTAL-DZKQ201402024.htm 李圭白, 刘超, 1989.地下水除铁除锰(第2版).北京:中国建筑工业出版社. 张乃东, 郑威, 2001.羟自由基·OH在水处理中的应用.哈尔滨商业大学学报(自然科学版), 17(3):22-24, 28. http://www.cnki.com.cn/Article/CJFDTOTAL-HLJS200103006.htm 张人权, 梁杏, 靳孟贵, 等, 2010.水文地质学基础(第六版).北京:地质出版社, 64. -
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