电感耦合等离子体发射光谱法测定地热水中的硫化物
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摘要
地热水中的硫化物(H_2S、HS~-和S~(2-))通常受到硫酸根、亚硫酸根、硫代硫酸根等硫元素的共存干扰,并且硫化物具有热、光、氧不稳定性,在水样保存、前处理、标准溶液配制等环节影响着测试的准确度和精密度。本文在现场采集的地热水水样中加入乙酸锌及氢氧化钠,使硫化物形成硫化锌沉淀而与溶液分离,将此沉淀溶于双氧水和逆王水,使低价态的S2-氧化成稳定的SO_4~(2-),选择易于纯化且性质稳定的硫酸钠配制硫标准储备液,以182.624 nm谱线作为硫元素分析谱线,应用电感耦合等离子体发射光谱法测定出地热水样中的硫化物含量。硫的浓度在0.1~100 mg/L范围内与其发射强度呈线性(相关系数为0.9994);方法检出限为0.009 mg/L,相对标准偏差(n=11)低于1.80%,实际水样中硫化物的加标回收率介于99.0%~103.0%。与前人相关测试方法相比,本方法的技术指标具有优势。
Existing sulfur-containing compounds, such as sulfate, sulfite and thiosulfate, can affect the determination of sulfide( H_2S,HS~- and S~(2-)) in geothermal water. In addition,the detection accuracy and precision may also be influenced by sample treatment processes such as sample collecting,sample pretreatment,and standard solution preparation. Zinc acetate and sodium hydroxide were added to water samples collected at the site in which sulfide would be precipitated as zinc sulfide and separated from water. The precipitation was further dissolved in hydrogen peroxide and Lefort aqua regia in which S~(2-) would be oxidized to SO_4~(2-). The standard stock solution was prepared by using sodium sulfate,which was stable and easily purified. Sulfur content in water was determined by Inductively Coupled Plasma-Optical Emission Spectrometry( ICP-OES) using the spectrum of 182. 624 nm as the sulfur element analysis line. It was found that S~(2-) concentration ranging between 0. 1 and 100mg/L was linearly correlated with emission intensity with a correlation coefficient of 0. 9994. Detection limit of the method was 0. 009 mg/L,relative standard deviation( n = 11) was less than 1. 80%,and standard addition recovery was 99. 0%-103. 0%. The technical indicators in this method are superior to previous analytical methods.
Existing sulfur-containing compounds, such as sulfate, sulfite and thiosulfate, can affect the determination of sulfide( H_2S,HS~- and S~(2-)) in geothermal water. In addition,the detection accuracy and precision may also be influenced by sample treatment processes such as sample collecting,sample pretreatment,and standard solution preparation. Zinc acetate and sodium hydroxide were added to water samples collected at the site in which sulfide would be precipitated as zinc sulfide and separated from water. The precipitation was further dissolved in hydrogen peroxide and Lefort aqua regia in which S~(2-) would be oxidized to SO_4~(2-). The standard stock solution was prepared by using sodium sulfate,which was stable and easily purified. Sulfur content in water was determined by Inductively Coupled Plasma-Optical Emission Spectrometry( ICP-OES) using the spectrum of 182. 624 nm as the sulfur element analysis line. It was found that S~(2-) concentration ranging between 0. 1 and 100mg/L was linearly correlated with emission intensity with a correlation coefficient of 0. 9994. Detection limit of the method was 0. 009 mg/L,relative standard deviation( n = 11) was less than 1. 80%,and standard addition recovery was 99. 0%-103. 0%. The technical indicators in this method are superior to previous analytical methods.
引文
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[8]马锦.采用碘量法测定硫化物中值得注意的几个问题[J].干旱环境监测,2002,16(1):56-57.Ma J.Problems worthy of paid attention to in the determination of sulfide by iodine method[J].Arid Environmental Monitoring,2002,16(1):56-57.
[9]Alizadeh N,Mahjoub M.A comparison between determination of trace amounts of sulfide in the presence and absence of micelle particles in natural waters(Qazvin,Iran):A kinetic spectrophotometric approach[J].Environmental Monitoring&Assessment,2015,187(5):1-14.
[10]Kong M C R,Salin E D.Spectrophotometric determination of aqueous sulfide on a pneumatically enhanced centrifugal microfluidic platform[J].Analytical Chemistry,2012,84(22):10038-10043.
[11]孙登明,阮大文,王丽红.萃取催化光度法间接测定水中痕量硫离子[J].分析化学,2004,32(2):179-182.Sun D M,Ruan D W,Wang L H.Indirect determination of trace sulfide in water by extraction-catalytic kinetic spectrophotometry[J].Chinese Journal of Analytical Chemistry,2004,32(2):179-182.
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[13]张胜海,聂迎春,胡蝶,等.钙黄绿素-铜(Ⅱ)荧光体系测定痕量硫离子[J].分析试验室,2011,30(7):103-106.Zhang S H,Nie Y C,Hu D,et al.Determination of trace sulfide by fluorescence spectroscopy using calceincopper(Ⅱ)system[J].Chinese Journal of Analysis Laboratory,2011,30(7):103-106.
[14]董建芳,李义,冯锐,等.亚甲蓝分光光度法测定地下水中硫化物的水样保存方法[J].岩矿测试,2012,31(5):868-871.Dong J F,Li Y,Feng R,et al.The preservation method of water samples to determine sulfide in groundwater by the methylene blue spectrophotometric method[J].Rock and Mineral Analysis,2012,31(5):868-871.
[15]Baciu A,Ardelean M,Pop A,et al.Simultaneous voltammetric/amperometric determination of sulfide and nitrite in water at BDD electrode[J].Sensors,2015,15(6):14526-14538.
[16]Sun H,Liu Z,Wu C,et al.Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination[J].Scientific Reports,2016,6:30905.
[17]Rahimnejad M,Hassaninejad-Darzi S K,Izadi P,et al.Surfactant modified ZSM-5 nanozeolite in the modification of carbon paste electrode for voltammetric determination of sulfide[J].Analytical&Bioanalytical Electrochemistry,2015,7(3):370-386.
[18]Dilgin Y,Kízílkaya B,Ertek B,et al.Amperometric determination of sulfide based on its electrocatalytic oxidation at a pencil graphite electrode modified with quercetin[J].Talanta,2012,89:490-495.
[19]Liao H,Dasgupta P K.Permeative amine introduction for very weak acid detection in ion chromatography[J].Analytical Chemistry,2016,88(4):2198-2204.
[20]陆克平.紫外光解/气膜扩散-离子色谱法测定废水中总氰和硫化物[J].色谱,2015,33(3):298-303.Lu K P.Determination of total cyanides and sulfides in wastewater using ion chromatography coupled with ultraviolet photo-dissociation/gas-membrane diffusion[J].Chinese Journal of Chromatography,2015,33(3):298-303.
[21]Rembisz Z,Bzdurska D,Obiedzińska J,et al.A derivatization approach using pyrylium salts for the sensitive and simple determination of sulfide in spring water by high performance liquid chromatography[J].Journal of Chromatography,2015,1407:184-192.
[22]王莹,康万利,吴英,等.电感耦合等离子体原子光谱法间接测定油田污水中硫离子[J].分析化学,2008,36(11):1575-1578.Wang Y,Kang W L,Wu Y,et al.Indirect determination of sulfur ions in oilfield sewage by inductively coupled plasma-atomic emission spectrometry[J].Chinese Journal of Analytical Chemistry,2008,36(11):1575-1578.
[23]王哲,付琳,王玉学,等.电感耦合等离子体原子发射光谱法测定水体中硫化物[J].冶金分析,2016,36(10):47-51.Wang Z,Fu L,Wang Y X,et al.Determination of sulfides in water body by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2016,36(10):47-51.
[24]官崎州.温泉水稳定化研究[D].成都:成都理工大学,2014.Guan Q Z.Stabilization of Spring Water[D].Chengdu:Chengdu University of Technology,2014.
[25]王国玲,杨路平,姜颖虹.硫代乙酰胺作为标准溶液测定水中硫化物[J].中国卫生检验杂志,2009,19(10):2310-2312.Wang G L,Yang L P,Jiang Y H.Thioacetamide used as standard in determination of dissolved sulfide in water[J].Chinese Journal of Health Laboratory Technology,2009,19(10):2310-2312.
[26]杜宝中,高晓泽,薛力,等.以硫代乙酰胺为基准电极法测定工业废水中硫化物[J].分析科学学报,2008,24(6):701-703.Du B Z,Gao X Z,Xue L,et al.Determination of sulfide in industrial waste water with sulfide ion selective electrode using thioacetamide as standard solution[J].Journal of Analytical Science,2008,24(6):701-703.
[27]郭春.真空紫外光学薄膜制备及其性能检测技术研究[D].成都:中国科学院光电技术研究所,2014.Guo C.Study on Preparation and Characterization of Optical Coatings for Vacuum Ultraviolet Applications[D].Chengdu:Institute of Optics and Electronics,Chinese Academy of Sciences,2014.
[2]姜贞贞,刘高令,王祝,等.电感耦合等离子体质谱法测定高海拔地区地热水中的微量元素[J].岩矿测试,2016,35(5):475-480.Jiang Z Z,Liu G L,Wang Z,et al.Determination of trace elements in thermomineral water of a high altitude area by inductively coupled plasma-mass spectrometry[J].Rock and Mineral Analysis,2016,35(5):475-480.
[3]庄亚芹,郭清海,刘明亮,等.高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟:以云南腾冲热海水热区为例[J].地球科学,2016,41(9):1499-1510.Zhuang Y Q,Guo Q H,Liu M L,et al.Geochemical simulation of thioarsenic speciation in high-temperature,sulfide-rich hot springs:A case study in the Rehai hydrothermal area,Tengchong,Yunnan[J].Earth Science,2016,41(9):1499-1510.
[4]Stefnsson A,Keller N S,Robin J G,et al.Multiple sulfur isotope systematics of icelandic geothermal fluids and the source and reactions of sulfur in volcanic geothermal systems at divergent plate boundaries[J].Geochimica et Cosmochimica Acta,2015,165:307-323.
[5]冯明扬,宋汉周,杨谦,等.江苏部分地热水的气体成分和微量元素含量特征及其指示意义[J].水文地质工程地质,2016,43(1):164-170.Feng M Y,Song H Z,Yang Q,et al.Characteristics of dissolved gases and trace element in geothermal waters in Jiangsu and their tracing significance[J].Hydrogeology&Engineering Geology,2016,43(1):164-170.
[6]闫佰忠.长白山玄武岩区地热水资源成因机制研究[D].长春:吉林大学,2016.Yan B Z.Study on the Formation Mechanism of Geothermal Water Resource in Changbai Mountain Basalt Area[D].Changchun:Jilin University,2016.
[7]Magro G,Gherardi F,Bayon F E B.Noble and reactive gases of Palinpinon geothermal field(Philippines):Origin,reservoir processes and geodynamic implications[J].Chemical Geology,2013,339(2):4-15.
[8]马锦.采用碘量法测定硫化物中值得注意的几个问题[J].干旱环境监测,2002,16(1):56-57.Ma J.Problems worthy of paid attention to in the determination of sulfide by iodine method[J].Arid Environmental Monitoring,2002,16(1):56-57.
[9]Alizadeh N,Mahjoub M.A comparison between determination of trace amounts of sulfide in the presence and absence of micelle particles in natural waters(Qazvin,Iran):A kinetic spectrophotometric approach[J].Environmental Monitoring&Assessment,2015,187(5):1-14.
[10]Kong M C R,Salin E D.Spectrophotometric determination of aqueous sulfide on a pneumatically enhanced centrifugal microfluidic platform[J].Analytical Chemistry,2012,84(22):10038-10043.
[11]孙登明,阮大文,王丽红.萃取催化光度法间接测定水中痕量硫离子[J].分析化学,2004,32(2):179-182.Sun D M,Ruan D W,Wang L H.Indirect determination of trace sulfide in water by extraction-catalytic kinetic spectrophotometry[J].Chinese Journal of Analytical Chemistry,2004,32(2):179-182.
[12]崔英.流动注射化学发光法测定硫离子[J].理化检验(化学分册),2010,46(6):616-620.Cui Y.FI-chemiluminescence determination of sulfide ion[J].Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2010,46(6):616-620.
[13]张胜海,聂迎春,胡蝶,等.钙黄绿素-铜(Ⅱ)荧光体系测定痕量硫离子[J].分析试验室,2011,30(7):103-106.Zhang S H,Nie Y C,Hu D,et al.Determination of trace sulfide by fluorescence spectroscopy using calceincopper(Ⅱ)system[J].Chinese Journal of Analysis Laboratory,2011,30(7):103-106.
[14]董建芳,李义,冯锐,等.亚甲蓝分光光度法测定地下水中硫化物的水样保存方法[J].岩矿测试,2012,31(5):868-871.Dong J F,Li Y,Feng R,et al.The preservation method of water samples to determine sulfide in groundwater by the methylene blue spectrophotometric method[J].Rock and Mineral Analysis,2012,31(5):868-871.
[15]Baciu A,Ardelean M,Pop A,et al.Simultaneous voltammetric/amperometric determination of sulfide and nitrite in water at BDD electrode[J].Sensors,2015,15(6):14526-14538.
[16]Sun H,Liu Z,Wu C,et al.Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination[J].Scientific Reports,2016,6:30905.
[17]Rahimnejad M,Hassaninejad-Darzi S K,Izadi P,et al.Surfactant modified ZSM-5 nanozeolite in the modification of carbon paste electrode for voltammetric determination of sulfide[J].Analytical&Bioanalytical Electrochemistry,2015,7(3):370-386.
[18]Dilgin Y,Kízílkaya B,Ertek B,et al.Amperometric determination of sulfide based on its electrocatalytic oxidation at a pencil graphite electrode modified with quercetin[J].Talanta,2012,89:490-495.
[19]Liao H,Dasgupta P K.Permeative amine introduction for very weak acid detection in ion chromatography[J].Analytical Chemistry,2016,88(4):2198-2204.
[20]陆克平.紫外光解/气膜扩散-离子色谱法测定废水中总氰和硫化物[J].色谱,2015,33(3):298-303.Lu K P.Determination of total cyanides and sulfides in wastewater using ion chromatography coupled with ultraviolet photo-dissociation/gas-membrane diffusion[J].Chinese Journal of Chromatography,2015,33(3):298-303.
[21]Rembisz Z,Bzdurska D,Obiedzińska J,et al.A derivatization approach using pyrylium salts for the sensitive and simple determination of sulfide in spring water by high performance liquid chromatography[J].Journal of Chromatography,2015,1407:184-192.
[22]王莹,康万利,吴英,等.电感耦合等离子体原子光谱法间接测定油田污水中硫离子[J].分析化学,2008,36(11):1575-1578.Wang Y,Kang W L,Wu Y,et al.Indirect determination of sulfur ions in oilfield sewage by inductively coupled plasma-atomic emission spectrometry[J].Chinese Journal of Analytical Chemistry,2008,36(11):1575-1578.
[23]王哲,付琳,王玉学,等.电感耦合等离子体原子发射光谱法测定水体中硫化物[J].冶金分析,2016,36(10):47-51.Wang Z,Fu L,Wang Y X,et al.Determination of sulfides in water body by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2016,36(10):47-51.
[24]官崎州.温泉水稳定化研究[D].成都:成都理工大学,2014.Guan Q Z.Stabilization of Spring Water[D].Chengdu:Chengdu University of Technology,2014.
[25]王国玲,杨路平,姜颖虹.硫代乙酰胺作为标准溶液测定水中硫化物[J].中国卫生检验杂志,2009,19(10):2310-2312.Wang G L,Yang L P,Jiang Y H.Thioacetamide used as standard in determination of dissolved sulfide in water[J].Chinese Journal of Health Laboratory Technology,2009,19(10):2310-2312.
[26]杜宝中,高晓泽,薛力,等.以硫代乙酰胺为基准电极法测定工业废水中硫化物[J].分析科学学报,2008,24(6):701-703.Du B Z,Gao X Z,Xue L,et al.Determination of sulfide in industrial waste water with sulfide ion selective electrode using thioacetamide as standard solution[J].Journal of Analytical Science,2008,24(6):701-703.
[27]郭春.真空紫外光学薄膜制备及其性能检测技术研究[D].成都:中国科学院光电技术研究所,2014.Guo C.Study on Preparation and Characterization of Optical Coatings for Vacuum Ultraviolet Applications[D].Chengdu:Institute of Optics and Electronics,Chinese Academy of Sciences,2014.