流动注射微柱预富集分离与原子吸收联用测定海水中重金属的研究
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摘要
海水中检测元素的低含量、高背景干扰以及样品处理带来的污染与损失等因素一直是海水样品分析中急需解决的问题。分析前对样品进行分离、富集等前处理是提高原子吸收光谱检测选择性和灵敏度的有效手段。经典的手工样品处理方法费时费力,且在处理过程造成的样品污染不可避免地带来一系列问题,在含有复杂基体且待测物含量极低的样品中尤为突出。流动注射分析(Flow injection analysis,FIA)技术在样品预处理的自动化、微型化和在线化方面引起了革命性变化,不仅极大地提高了整个分析过程的效率、可靠性和分析速度,减小了样品污染概率,也降低了试剂消耗和废液产量,更重要的是使某些难以或无法实现的手工操作成为可能并且效果出众。为此,作者结合项目工作,从海水重金属污染现状、国标检测方法及其存在的弊端等发面出发,对流动注射微柱富集分离技术在原子光谱在线分析中的应用进行了描述。同时,按微柱富集体系填充材料的不同,对近年来基于微柱系统在线预富集新技术进行了讨论,以期为流动注射在线富集技术的深入研究提供参考和借鉴。本文使用的氨基膦酸型螯合树脂具有易于制备、使用寿命长、重现性佳等独特优点。原子吸收光谱法(AAS)是现今较常用的一种元素分析测试手段,具有仪器费用低、线性范围宽、灵敏度高、分析时间快、和易于操作等优点而引人关注。本论文旨在建立一种用于监测海水中铅、镉、铜和锌的海洋行业标准,主要的研究内容如下:
1.用D412螯合树脂微柱富集海水中的Pb(Ⅱ),并与火焰原子吸收光谱法联用测定海水中Pb(Ⅱ)。海水样品在0.2mol·L~(-1)乙酸铵溶液介质中(pH6.0)以3mL·min~(-1)流速进柱,被树脂螯合吸附富集,以0.2mol·L~(-1)乙酸铵溶液淋洗柱体去除干扰物,以硝酸(4mol·L~(-1))为洗脱液,洗脱液接火焰原子吸收光谱仪雾化器,在线检测。当样品进样20mL时,Pb(Ⅱ)测定灵敏度可提高约35倍;检出限1.3μg·L~(-1),相对标准偏差(RSD)为1.2%(n=11,C_(Pb(Ⅱ))=200μg·L~(-1))。讨论了海水中可能存在的共存离子和腐殖酸对于Pb(Ⅱ)测定影响。实际应用于海水样品分析,加标回收率在94%~(-1)05%之间。
2.用3.5%(盐度)人工海水配制标液,D412螯合树脂作微柱填充物,将流动注射在线分离富集系统与石墨炉原子吸收联用,测定海水中Cd(Ⅱ)。优化了Cd(Ⅱ)的酸度条件,进样速度和洗脱条件。在最佳检测条件下当海水样品进样3mL时,Cd(Ⅱ)测检出限0.2*10~(-3)μg·L~(-1),相对标准偏差(RSD)为2.86%(n=11,C_(Cd(Ⅱ))=4μg·L~(-1))。讨论了海水中可能存在的共存物对Cd(Ⅱ)测定的影响。实际应用于杭州湾海水样品分析,加标回收率为94%。
3.采集2011年1月洋山港港口表层海水样品,分别采用火焰原子吸收分光光度法和石墨炉原子吸收分光光度法与流动注射在线富集分离技术联用,测定海水中溶解态Cu、Zn、Pb和Cd和的含量,得出结果(1)表层海水中溶解态Cu、Zn、Pb和Cd和的平均质量浓度分别为11.7μg·L~(-1),18.81μg·L~(-1),4.21μg·L~(-1)和0.91μg·L~(-1),基本达到国家二类海水水质标准;(2)运用此方法测定海水中溶解态Cu、Zn、Pb和Cd,相对标准偏差(RSD)1%-5%,回收率91%-99%,结果较满意。
The factors that low content, high background values and loss in sample treating have been the emerged problems in the heavy metal determination in seawater samples. Sample pretreatment, including separation and concentration, has enhanced the classical analytic method of atomic absorption spectrometry (AAS). Manual pretreatment is not only a long and hard work, but also a way to bring about a series of problems, Especially for the samples with complex matrix and low element contents. Flow injection analysis(FIA) has caused a revolutionary change in areas of automation, miniaturization and online from seawater sample pretreatment. It improves greatly the efficiency, reliability and rate of analysis, reduces sample contamination, and also decrease the amount of material consumption and wastewater discharge. Moreover, it makes some difficult or/even impossible manual operations very efficient and easily implemented. Therefore, with the project implementation, from a perspective of marine heavy metals pollution, State Standard Method of China and its existing problems, the applications of flow injection micro column preconcentration and separation coupling with AAS on-line concentration were discussed. At the same time, the new techniques of on-line preconcentration in recent years were discussed based on micro column system and filling materials, to provide a reference for further research. Amino Methylene Phosphonic Acid Resin (APAR) used in this study is a kind of chelating resins with unique advantages of easy preparation, long lasting life and excellent repeatability. The AAS, with the merits of low cost and fast analysis, high sensitivity, good precision and accuracy, and wide linear range, has been widely applied in trace analysis. The purpose of the present work is to establish a new marine industry standard to monitor copper, zinc, lead and cadmium in seawater. The main research contents are as follows:
1. An analytical method for the determination of Pb(Ⅱ) in sea water based on micro-column pre-concentration coupled with flame atomic absorption spectrometry (FAAS) was established in this study. Pb(Ⅱ) was adsorbed on the micro-column packed with D412 chelating resin in medium of 0.2 mol·L~(-1) ammonium acetate at pH value of 6 and could be eluted with 4mol·L~(-1) nitric acid. The eluent was joined to the nebulizer of the atomic absorption spectrometer for on line determination of Pb. In case of 20mL sea water was injected in analysis, determination sensitivity for Pb(Ⅱ) is increased by about 35 times, with detection limit of 1.3μg·L~(-1), relative standard deviation (RSD) of 1.2% (n = 11, C_(Pb(Ⅱ)) = 200μg·L~(-1)). Effect of concomitants on the Pb(Ⅱ) determination was discussed. The proposed method has been applied to the analysis of real samples taken from Hangzhou Bay.
2. A flow injection separation and preconcentration system coupled to graphite furnace atomic absorption spectrometry (GFAAS) was used to determine the Cd (Ⅱ) in seawater samples. The micro column material was 412 chelating resin. The standard solution was prepared from 3.5% artificial simulated seawater. In experiments, a series of analysis conditions, including acidity, sample flow rate, eluant concentrations and coexisting ions were optimized respectively. Under the optimum conditions, in case of 3mL seawater was injected in the experimental system, the detection limit was 0.2×10~(-3) ug·L~(-1), the relative standard deviation was 2.86% (n=11, C_(Cd(Ⅱ)) = 4μg·L~(-1)). Effect of concomitants on the Cd(Ⅱ) determination was discussed. The proposed method has been applied to the analysis of real samples taken from Hangzhou Bay, the recovery is 94%.
3. Surface seawater samples of Yangshan Port were collected in Jan, 2011. The contents of dissolved copper, zinc, lead and cadmium in seawater were determined by flow injection micro column preconcentration and separation coupled with FAAS and GFAAS respectively. The results were obtained as follows: (1) The mass concentrations of dissolved copper, zinc, lead and cadmium were 11.7μg·L~(-1),18.81μg·L~(-1),4.21μg·L~(-1) and 0.91μg·L~(-1), respectively. The contents of the above heavy metals have reached the national second-class water quality standards. (2)The relative standard deviation (RSD) of experimental results are less than 5%. The recoveries in between 91%~99%.
1.用D412螯合树脂微柱富集海水中的Pb(Ⅱ),并与火焰原子吸收光谱法联用测定海水中Pb(Ⅱ)。海水样品在0.2mol·L~(-1)乙酸铵溶液介质中(pH6.0)以3mL·min~(-1)流速进柱,被树脂螯合吸附富集,以0.2mol·L~(-1)乙酸铵溶液淋洗柱体去除干扰物,以硝酸(4mol·L~(-1))为洗脱液,洗脱液接火焰原子吸收光谱仪雾化器,在线检测。当样品进样20mL时,Pb(Ⅱ)测定灵敏度可提高约35倍;检出限1.3μg·L~(-1),相对标准偏差(RSD)为1.2%(n=11,C_(Pb(Ⅱ))=200μg·L~(-1))。讨论了海水中可能存在的共存离子和腐殖酸对于Pb(Ⅱ)测定影响。实际应用于海水样品分析,加标回收率在94%~(-1)05%之间。
2.用3.5%(盐度)人工海水配制标液,D412螯合树脂作微柱填充物,将流动注射在线分离富集系统与石墨炉原子吸收联用,测定海水中Cd(Ⅱ)。优化了Cd(Ⅱ)的酸度条件,进样速度和洗脱条件。在最佳检测条件下当海水样品进样3mL时,Cd(Ⅱ)测检出限0.2*10~(-3)μg·L~(-1),相对标准偏差(RSD)为2.86%(n=11,C_(Cd(Ⅱ))=4μg·L~(-1))。讨论了海水中可能存在的共存物对Cd(Ⅱ)测定的影响。实际应用于杭州湾海水样品分析,加标回收率为94%。
3.采集2011年1月洋山港港口表层海水样品,分别采用火焰原子吸收分光光度法和石墨炉原子吸收分光光度法与流动注射在线富集分离技术联用,测定海水中溶解态Cu、Zn、Pb和Cd和的含量,得出结果(1)表层海水中溶解态Cu、Zn、Pb和Cd和的平均质量浓度分别为11.7μg·L~(-1),18.81μg·L~(-1),4.21μg·L~(-1)和0.91μg·L~(-1),基本达到国家二类海水水质标准;(2)运用此方法测定海水中溶解态Cu、Zn、Pb和Cd,相对标准偏差(RSD)1%-5%,回收率91%-99%,结果较满意。
The factors that low content, high background values and loss in sample treating have been the emerged problems in the heavy metal determination in seawater samples. Sample pretreatment, including separation and concentration, has enhanced the classical analytic method of atomic absorption spectrometry (AAS). Manual pretreatment is not only a long and hard work, but also a way to bring about a series of problems, Especially for the samples with complex matrix and low element contents. Flow injection analysis(FIA) has caused a revolutionary change in areas of automation, miniaturization and online from seawater sample pretreatment. It improves greatly the efficiency, reliability and rate of analysis, reduces sample contamination, and also decrease the amount of material consumption and wastewater discharge. Moreover, it makes some difficult or/even impossible manual operations very efficient and easily implemented. Therefore, with the project implementation, from a perspective of marine heavy metals pollution, State Standard Method of China and its existing problems, the applications of flow injection micro column preconcentration and separation coupling with AAS on-line concentration were discussed. At the same time, the new techniques of on-line preconcentration in recent years were discussed based on micro column system and filling materials, to provide a reference for further research. Amino Methylene Phosphonic Acid Resin (APAR) used in this study is a kind of chelating resins with unique advantages of easy preparation, long lasting life and excellent repeatability. The AAS, with the merits of low cost and fast analysis, high sensitivity, good precision and accuracy, and wide linear range, has been widely applied in trace analysis. The purpose of the present work is to establish a new marine industry standard to monitor copper, zinc, lead and cadmium in seawater. The main research contents are as follows:
1. An analytical method for the determination of Pb(Ⅱ) in sea water based on micro-column pre-concentration coupled with flame atomic absorption spectrometry (FAAS) was established in this study. Pb(Ⅱ) was adsorbed on the micro-column packed with D412 chelating resin in medium of 0.2 mol·L~(-1) ammonium acetate at pH value of 6 and could be eluted with 4mol·L~(-1) nitric acid. The eluent was joined to the nebulizer of the atomic absorption spectrometer for on line determination of Pb. In case of 20mL sea water was injected in analysis, determination sensitivity for Pb(Ⅱ) is increased by about 35 times, with detection limit of 1.3μg·L~(-1), relative standard deviation (RSD) of 1.2% (n = 11, C_(Pb(Ⅱ)) = 200μg·L~(-1)). Effect of concomitants on the Pb(Ⅱ) determination was discussed. The proposed method has been applied to the analysis of real samples taken from Hangzhou Bay.
2. A flow injection separation and preconcentration system coupled to graphite furnace atomic absorption spectrometry (GFAAS) was used to determine the Cd (Ⅱ) in seawater samples. The micro column material was 412 chelating resin. The standard solution was prepared from 3.5% artificial simulated seawater. In experiments, a series of analysis conditions, including acidity, sample flow rate, eluant concentrations and coexisting ions were optimized respectively. Under the optimum conditions, in case of 3mL seawater was injected in the experimental system, the detection limit was 0.2×10~(-3) ug·L~(-1), the relative standard deviation was 2.86% (n=11, C_(Cd(Ⅱ)) = 4μg·L~(-1)). Effect of concomitants on the Cd(Ⅱ) determination was discussed. The proposed method has been applied to the analysis of real samples taken from Hangzhou Bay, the recovery is 94%.
3. Surface seawater samples of Yangshan Port were collected in Jan, 2011. The contents of dissolved copper, zinc, lead and cadmium in seawater were determined by flow injection micro column preconcentration and separation coupled with FAAS and GFAAS respectively. The results were obtained as follows: (1) The mass concentrations of dissolved copper, zinc, lead and cadmium were 11.7μg·L~(-1),18.81μg·L~(-1),4.21μg·L~(-1) and 0.91μg·L~(-1), respectively. The contents of the above heavy metals have reached the national second-class water quality standards. (2)The relative standard deviation (RSD) of experimental results are less than 5%. The recoveries in between 91%~99%.
引文
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