天然含铁矿物对砷的吸附效果及机制
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摘要
自然界中丰富的含铁矿物作为天然的铁氧化物,可作为一类修复材料用于砷污染水体和土壤稳定化修复.本文通过吸附-解吸附实验对比研究了天然赤铁矿、天然褐铁矿、天然菱铁矿、天然钛铁矿、天然磁铁矿、Fe_2O_3、Fe_3O_4及铁锰双金属材料(FMBO)对砷的吸附-解吸特性,结合光谱学手段研究其作用机制.吸附实验结果表明,9种含铁材料对As(Ⅲ)和As(Ⅴ)的吸附过程更符合准二级动力学方程和Langmuir方程,表明反应机制主要为单层化学吸附作用.其中,FMBO对As的吸附效率和吸附容量远高于其余材料,天然含铁矿物中褐铁矿对As吸附效果表现最好,对As(Ⅲ)和As(Ⅴ)的吸附容量分别为3. 96 mg·g-1和2. 99 mg·g-1.光谱学手段表明天然褐铁矿中含有较为丰富的针铁矿等弱结晶态矿物成分,具有相对丰富的砷吸附位点,是一种具有潜在修复能力的天然材料.
Natural iron-containing minerals present in the geosphere in the form of crystalline minerals can be used as adsorption material for removal of arsenic from wastewater and remediation of arsenic-contaminated soils. In this paper,the adsorption and desorption of arsenic onto different iron-containing materials including hematite,limonite,siderite,ilmenite,magnetite,Fe_2O_3,Fe_3O_4,and Fe-Mn binary oxide( FMBO) were studied in laboratory experiments. The mechanism of arsenic adsorption was analyzed by scanning electron microscopy( SEM),X-ray diffraction( XRD),and fourier transform infrared spectroscopy( FTIR). The results showed that arsenic adsorption is fitted by pseudo-second-order kinetics and the Langmuir isotherm model for almost all adsorbents,suggesting monolayer adsorption of arsenic onto the minerals. The sorption efficiency and capacity of arsenic by FMBO are much higher than those of other materials. Furthermore,limonite has high sorption efficiencies for both As( Ⅲ) and As( Ⅴ) among the natural ironcontaining minerals,and their adsorption capacities are 3. 96 mg·g-1 and 2. 99 mg·g-1,respectively. The XRD results showed that natural limonite contains a large number of weak crystalline mineral components such as goethite,which can provide relatively abundant arsenic adsorption sites. Thus,limonite appears to be the most suitable natural mineral for arsenic adsorption.
Natural iron-containing minerals present in the geosphere in the form of crystalline minerals can be used as adsorption material for removal of arsenic from wastewater and remediation of arsenic-contaminated soils. In this paper,the adsorption and desorption of arsenic onto different iron-containing materials including hematite,limonite,siderite,ilmenite,magnetite,Fe_2O_3,Fe_3O_4,and Fe-Mn binary oxide( FMBO) were studied in laboratory experiments. The mechanism of arsenic adsorption was analyzed by scanning electron microscopy( SEM),X-ray diffraction( XRD),and fourier transform infrared spectroscopy( FTIR). The results showed that arsenic adsorption is fitted by pseudo-second-order kinetics and the Langmuir isotherm model for almost all adsorbents,suggesting monolayer adsorption of arsenic onto the minerals. The sorption efficiency and capacity of arsenic by FMBO are much higher than those of other materials. Furthermore,limonite has high sorption efficiencies for both As( Ⅲ) and As( Ⅴ) among the natural ironcontaining minerals,and their adsorption capacities are 3. 96 mg·g-1 and 2. 99 mg·g-1,respectively. The XRD results showed that natural limonite contains a large number of weak crystalline mineral components such as goethite,which can provide relatively abundant arsenic adsorption sites. Thus,limonite appears to be the most suitable natural mineral for arsenic adsorption.
引文
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[14] Lu A H,Chen J,Shi J X,et al. One-step disposal of Cr(VI)-bearing wastewater by natural pyrrhotite[J]. Chinese Science Bulletin,2000,45(17):1614-1616.
[15]林娜,宋昕,郭亮,等.天然磁铁矿和商用Fe3O4修复Hg(Ⅱ)污染地下水的模拟研究[J].土壤,2017,49(1):118-128.Lin N, Song X, Guo L, et al. Simulating remediation of Hg(Ⅱ)-contaminated groundwater using natural magnetite and commercial Fe3O4[J]. Soils,2017,49(1):118-128.
[16]费杨,阎秀兰,廖晓勇,等.不同水分条件下铁基氧化物对土壤砷的稳定化效应研究[J].环境科学学报,2015,35(10):3252-3260.Fei Y,Yan X L,Liao X Y,et al. Effects of iron-based oxides on arsenic stabilization in soils of different water contents[J]. Acta Scientiae Circumstantiae,2015,35(10):3252-3260.
[17] Caporale A G,Pigna M,Azam S M G G,et al. Effect of competing ligands on the sorption/desorption of arsenite on/from Mg-Fe layered double hydroxides(Mg-Fe-LDH)[J]. Chemical Engineering Journal,2013,225:704-709.
[18] Zhang G S,Qu J H,Liu H J,et al. Removal mechanism of As(Ⅲ)by a novel Fe-Mn binary oxide adsorbent:oxidation and sorption[J]. Environmental Science&Technology,2007,41(13):4613-4619.
[19]刘辉利,梁美娜,朱义年,等.氢氧化铁对砷的吸附与沉淀机理[J].环境科学学报,2009,29(5):1011-1020.Liu H L,Liang M N,Zhu Y N,et al. The adsorption of arsenic by ferric hydroxide and its precipitation mechanism[J]. Acta Scientiae Circumstantiae,2009,29(5):1011-1020.
[20] Zhang G S,Liu H J,Liu R P,et al. Adsorption behavior and mechanism of arsenate at Fe-Mn binary oxide/water interface[J]. Journal of Hazardous Materials,2009,168(2-3):820-825.
[21] Jia Y F,Xu L Y,Wang X,et al. Infrared spectroscopic and Xray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite[J]. Geochimica et Cosmochimica Acta,2007,71(7):1643-1654.
[22] Goldberg S,Johnston C T. Mechanisms of arsenic adsorption on amorphous oxides evaluated using macroscopic measurements,vibrational spectroscopy,and surface complexation modeling[J].Journal of Colloid and Interface Science,2001,234(1):204-216.
[23]杨智,谢先军,皮坤福.砷酸盐在针铁矿上的界面作用过程及磷酸盐竞争吸附影响的试验和模拟研究[J].安全与环境工程,2017,24(6):62-69.Yang Z, Xie X J, Pi K F. Interfacial interactions between arsenate and goethite under the influence of competitive adsorption of phosphate[J]. Safety and Environmental Engineering,2017,24(6):62-69.
[24] Voegelin A,Hug S J. Catalyzed oxidation of arsenic(Ⅲ)by hydrogen peroxide on the surface of ferrihydrite:an in situ ATRFTIR study[J]. Environmental Science&Technology,2003,37(5):972-978.
[25]杜晓丽.典型含铁锰矿矿物学和表面化学及对砷的吸附研究[D].武汉:华中农业大学,2017. 59-60.Du X L. Mineralogical,surface chemical and arsenic removing characterization of typical ferrous manganese ores[D]. Wuhan:Huazhong Agricultural University,2017. 59-60.
[26] Sherman D M,Randall S R. Surface complexation of arsenic(V)to iron(III)(hydr)oxides:structural mechanism from ab initio molecular geometries and EXAFS spectroscopy[J]. Geochimica et Cosmochimica Acta,2003,67(22):4223-4230.
[27] Hiemstra T, Van Riemsdijk W H. Surface structural ion adsorption modeling of competitive binding of oxyanions by metal(Hydr)oxides[J]. Journal of Colloid and Interface Science,1999,210(1):182-193.
[28] Boparai H K, Joseph M, O'Carroll D M. Kinetics and thermodynamics of cadmium ion removal by adsorption onto Nano zerovalent iron particles[J]. Journal of Hazardous Materials,2011,186(1):458-465.
[29] Waychunas G A,Rea B A,Fuller C C,et al. Surface chemistry of ferrihydrite:Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate[J]. Geochimica et Cosmochimica Acta,1993,57(10):2251-2269.
[30] Wang S,Mulligan C N. Speciation and surface structure of inorganic arsenic in solid phases:a review[J]. Environment International,2008,34(6):867-879.
[31] Zhang W,Singh P,Paling E,et al. Arsenic removal from contaminated water by natural iron ores[J]. Minerals Engineering,2004,17(4):517-524.
[32] Sun X H,Doner H E. An investigation of arsenate and arsenite bonding structures on goethite by FTIR[J]. Soil Science,1996,161(12):865-872.
[2] Smith E, Naidu R, Alston A M. Arsenic in the soil environment:a review[J]. Advances in Agronomy,1998,64:149-195.
[3] Miretzky P,Cirelli A F. Remediation of arsenic-contaminated soils by iron amendments:a review[J]. Critical Reviews in Environmental Science and Technology,2010,40(2):93-115.
[4] Hartley W,Lepp N W. Remediation of arsenic contaminated soils by iron-oxide application, evaluated in terms of plant productivity,arsenic and phytotoxic metal uptake[J]. Science of the Total Environment,2008,390(1):35-44.
[5] Wilkie J A,Hering J G. Adsorption of arsenic onto hydrous ferric oxide:effects of adsorbate/adsorbent ratios and Co-occurring solutes[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,1996,107:97-110.
[6] Chakravarty S,Dureja V,Bhattacharyya G,et al. Removal of arsenic from groundwater using low cost ferruginous manganese ore[J]. Water Research,2002,36(3):625-632.
[7] Ona-Nguema G,Morin G,Juillot F,et al. EXAFS analysis of arsenite adsorption onto two-line ferrihydrite,hematite,goethite,and lepidocrocite[J]. Environmental Science&Technology,2005,39(23):9147-9155.
[8]马玉玲,马杰,陈雅丽,等.水铁矿及其胶体对砷的吸附与吸附形态[J].环境科学,2018,39(1):179-186.Ma Y L,Ma J,Chen Y L,et al. Arsenic adsorption and its species on ferrihydrite and ferrihydrite colloid[J]. Environmental Science,2018,39(1):179-186.
[9] Guo H M,Stüben D,Berner Z. Removal of arsenic from aqueous solution by natural siderite and hematite[J]. Applied Geochemistry,2007,22(5):1039-1051.
[10] Yang X T,Xia L,Li J L,et al. Adsorption of As(Ⅲ)on porous hematite synthesized from goethite concentrate[J].Chemosphere,2017,169:188-193.
[11] Dixit S,Hering J G. Comparison of arsenic(Ⅴ)and arsenic(Ⅲ)sorption onto iron oxide minerals:implications for arsenic mobility[J]. Environmental Science&Technology,2003,37(18):4182-4189.
[12] Giménez J,Martínez M,de Pablo J,et al. Arsenic sorption onto natural hematite, magnetite, and goethite[J]. Journal of Hazardous Materials,2007,141(3):575-580.
[13]刘卓,张小梅,肖才林,等.利用天然磁黄铁矿去除水中As(Ⅴ)的研究[J].环境科学学报,2016,36(10):3701-3708.Liu Z,Zhang X M,Xiao C L,et al. As(Ⅴ)removal from water with natural pyrrhotite[J]. Acta Scientiae Circumstantiae,2016,36(10):3701-3708.
[14] Lu A H,Chen J,Shi J X,et al. One-step disposal of Cr(VI)-bearing wastewater by natural pyrrhotite[J]. Chinese Science Bulletin,2000,45(17):1614-1616.
[15]林娜,宋昕,郭亮,等.天然磁铁矿和商用Fe3O4修复Hg(Ⅱ)污染地下水的模拟研究[J].土壤,2017,49(1):118-128.Lin N, Song X, Guo L, et al. Simulating remediation of Hg(Ⅱ)-contaminated groundwater using natural magnetite and commercial Fe3O4[J]. Soils,2017,49(1):118-128.
[16]费杨,阎秀兰,廖晓勇,等.不同水分条件下铁基氧化物对土壤砷的稳定化效应研究[J].环境科学学报,2015,35(10):3252-3260.Fei Y,Yan X L,Liao X Y,et al. Effects of iron-based oxides on arsenic stabilization in soils of different water contents[J]. Acta Scientiae Circumstantiae,2015,35(10):3252-3260.
[17] Caporale A G,Pigna M,Azam S M G G,et al. Effect of competing ligands on the sorption/desorption of arsenite on/from Mg-Fe layered double hydroxides(Mg-Fe-LDH)[J]. Chemical Engineering Journal,2013,225:704-709.
[18] Zhang G S,Qu J H,Liu H J,et al. Removal mechanism of As(Ⅲ)by a novel Fe-Mn binary oxide adsorbent:oxidation and sorption[J]. Environmental Science&Technology,2007,41(13):4613-4619.
[19]刘辉利,梁美娜,朱义年,等.氢氧化铁对砷的吸附与沉淀机理[J].环境科学学报,2009,29(5):1011-1020.Liu H L,Liang M N,Zhu Y N,et al. The adsorption of arsenic by ferric hydroxide and its precipitation mechanism[J]. Acta Scientiae Circumstantiae,2009,29(5):1011-1020.
[20] Zhang G S,Liu H J,Liu R P,et al. Adsorption behavior and mechanism of arsenate at Fe-Mn binary oxide/water interface[J]. Journal of Hazardous Materials,2009,168(2-3):820-825.
[21] Jia Y F,Xu L Y,Wang X,et al. Infrared spectroscopic and Xray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite[J]. Geochimica et Cosmochimica Acta,2007,71(7):1643-1654.
[22] Goldberg S,Johnston C T. Mechanisms of arsenic adsorption on amorphous oxides evaluated using macroscopic measurements,vibrational spectroscopy,and surface complexation modeling[J].Journal of Colloid and Interface Science,2001,234(1):204-216.
[23]杨智,谢先军,皮坤福.砷酸盐在针铁矿上的界面作用过程及磷酸盐竞争吸附影响的试验和模拟研究[J].安全与环境工程,2017,24(6):62-69.Yang Z, Xie X J, Pi K F. Interfacial interactions between arsenate and goethite under the influence of competitive adsorption of phosphate[J]. Safety and Environmental Engineering,2017,24(6):62-69.
[24] Voegelin A,Hug S J. Catalyzed oxidation of arsenic(Ⅲ)by hydrogen peroxide on the surface of ferrihydrite:an in situ ATRFTIR study[J]. Environmental Science&Technology,2003,37(5):972-978.
[25]杜晓丽.典型含铁锰矿矿物学和表面化学及对砷的吸附研究[D].武汉:华中农业大学,2017. 59-60.Du X L. Mineralogical,surface chemical and arsenic removing characterization of typical ferrous manganese ores[D]. Wuhan:Huazhong Agricultural University,2017. 59-60.
[26] Sherman D M,Randall S R. Surface complexation of arsenic(V)to iron(III)(hydr)oxides:structural mechanism from ab initio molecular geometries and EXAFS spectroscopy[J]. Geochimica et Cosmochimica Acta,2003,67(22):4223-4230.
[27] Hiemstra T, Van Riemsdijk W H. Surface structural ion adsorption modeling of competitive binding of oxyanions by metal(Hydr)oxides[J]. Journal of Colloid and Interface Science,1999,210(1):182-193.
[28] Boparai H K, Joseph M, O'Carroll D M. Kinetics and thermodynamics of cadmium ion removal by adsorption onto Nano zerovalent iron particles[J]. Journal of Hazardous Materials,2011,186(1):458-465.
[29] Waychunas G A,Rea B A,Fuller C C,et al. Surface chemistry of ferrihydrite:Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate[J]. Geochimica et Cosmochimica Acta,1993,57(10):2251-2269.
[30] Wang S,Mulligan C N. Speciation and surface structure of inorganic arsenic in solid phases:a review[J]. Environment International,2008,34(6):867-879.
[31] Zhang W,Singh P,Paling E,et al. Arsenic removal from contaminated water by natural iron ores[J]. Minerals Engineering,2004,17(4):517-524.
[32] Sun X H,Doner H E. An investigation of arsenate and arsenite bonding structures on goethite by FTIR[J]. Soil Science,1996,161(12):865-872.
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