二乙基三胺五乙酸浸取-电感耦合等离子体质谱法测定石灰性土壤中有效态铜锌铁锰
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摘要
采用二乙基三胺五乙酸(DTPA)浸提石灰性土壤样品中有效态Cu、Zn、Fe、Mn后,样品溶液基体盐分较大,此时若直接采用电感耦合等离子体质谱法(ICP-MS)进行测定,极易使仪器的采样锥和截取锥发生堵塞,雾室和炬管积盐,进而影响测定准确性。据此,实验用DTPA浸提样品后,采用对样品溶液稀释10～30倍和在标准溶液系列中加入DTPA溶液进行基体匹配的方法以消除基体干扰,利用氦碰撞模式进行测定以消除多原子离子40 Ar16 O对56Fe的质谱干扰,最终实现了ICP-MS对石灰性土壤中有效态Cu、Zn、Fe、Mn的测定。对氦气流量进行了优化,并确定氦气流量为4.5mL/min。在优化的实验条件下,Cu、Zn的质量浓度为5～200ng/mL、Fe的质量浓度为100～3 000ng/mL、Mn的质量浓度为30～1 000ng/mL时,各元素质量浓度分别与其计数值呈线性关系,相关系数均不小于0.999 8。方法检出限为0.003～0.01mg/kg。按照实验方法测定土壤有效态成分分析标准物质中的有效态Cu、Zn、Fe、Mn,测定值与认定值一致,相对标准偏差(RSD)为1.3%～3.1%。采用实验方法和标准方法 HJ804—2016(电感耦合等离子体原子发射光谱法)进行方法对照试验,二者测定值基本一致。
The available Cu,Zn,Fe and Mn in calcareous soil sample were extracted by diethylenetriaminepentaacetic acid(DTPA).Since the contents of matrix salts in sample solution were high,the sampling cone and skimmer cone of instrument were easily blocked if the sample solution was directly determined by inductively coupled plasma mass spectrometry(ICP-MS).The salification in atomizing chamber and torch tube would influence on the determination accuracy.After leaching sample with DTPA,the sample solution was diluted for 10-30 times.Meanwhile,DPTA solution was added into standard solution series for matrix matching to eliminate the matrix interference.The mass spectrometry interference of polyatomic ion 40 Ar16 O with the determination of 56 Fe was eliminated using helium collision mode.Consequently,the determination of available Cu,Zn,Fe and Mn in calcareous soil by ICP-MS was realized.The flow rate of helium was optimized and the optimum flow rate was 4.5 mL/min.Under the optimized experimental conditions,the mass concentration of elements had linear relationship with the counting value for Cu,Zn(5-200 ng/mL),Fe(100-3 000 ng/mL)and Mn(30-1 000 ng/mL).The correlation coefficients were all not less than 0.999 8.The detection limit was 0.003-0.01 mg/kg.The contents of available Cu,Zn,Fe and Mn in certified reference materials of soil for available composition analysis were determination according to the experimental method.The found results were consistent with the certified values,and the relative standard deviations(RSD)were between 1.3%and 3.1%.The proposed method was compared with the standard method HJ 804-2016(inductively coupled plasma atomic emission spectrometry),and the determination results were basically consistent.
The available Cu,Zn,Fe and Mn in calcareous soil sample were extracted by diethylenetriaminepentaacetic acid(DTPA).Since the contents of matrix salts in sample solution were high,the sampling cone and skimmer cone of instrument were easily blocked if the sample solution was directly determined by inductively coupled plasma mass spectrometry(ICP-MS).The salification in atomizing chamber and torch tube would influence on the determination accuracy.After leaching sample with DTPA,the sample solution was diluted for 10-30 times.Meanwhile,DPTA solution was added into standard solution series for matrix matching to eliminate the matrix interference.The mass spectrometry interference of polyatomic ion 40 Ar16 O with the determination of 56 Fe was eliminated using helium collision mode.Consequently,the determination of available Cu,Zn,Fe and Mn in calcareous soil by ICP-MS was realized.The flow rate of helium was optimized and the optimum flow rate was 4.5 mL/min.Under the optimized experimental conditions,the mass concentration of elements had linear relationship with the counting value for Cu,Zn(5-200 ng/mL),Fe(100-3 000 ng/mL)and Mn(30-1 000 ng/mL).The correlation coefficients were all not less than 0.999 8.The detection limit was 0.003-0.01 mg/kg.The contents of available Cu,Zn,Fe and Mn in certified reference materials of soil for available composition analysis were determination according to the experimental method.The found results were consistent with the certified values,and the relative standard deviations(RSD)were between 1.3%and 3.1%.The proposed method was compared with the standard method HJ 804-2016(inductively coupled plasma atomic emission spectrometry),and the determination results were basically consistent.
引文
[1]侯明,王香桂.土壤有效态钒的浸提剂和浸提条件研究[J].土壤通报,2010,41(5):1241-1245.HOU Ming,WANG Xiang-gui.Study on extraction conditions and extractants for available vanadium in soil[J].Chinese Journal of Soil Science,2010,41(5):1241-1245.
[2]黄昌勇,徐建明.土壤学[M].3版.北京:中国农业出版社,2010.
[3]国家林业局.LY/T 1210~1275—1999森林土壤分析方法[S].北京:中国标准出版社,1999.
[4]中华人民共和国农业部.NY/T 890—2004土壤有效态锌、锰、铁、铜含量的测定二乙三胺五乙酸(DTPA)浸提法[S].北京:中国标准出版社,2004.
[5]环境保护部.HJ 804—2016土壤8种有效态元素的测定二乙烯三胺五乙酸浸提-电感耦合等离子体发射光谱法[S].北京:中国标准出版社,2016.
[6]林光西,徐霞,张静梅.ICP-MS测定土壤样品中的有效锰、铜和锌[J].光谱实验室,2006,23(6):1267-1270.LIN Guang-xi,XU Xia,ZHANG Jing-mei.Determination of available Mn,Cu and Zn in soil by ICP-MS[J].Chinese Journal of Spectroscopy Laboratory,2006,23(6):1267-1270.
[7]农云军,谢继丹,黄名湖,等.超声提取-ICP-MS法测定土壤中有效铅和镉[J].质谱学报,2016,37(1):68-74.NONG Yun-jun,XIE Ji-dan,HUANG Ming-hu,et al.Measurement of available lead and cadmium in soil by ICP-MS with ultrasonic extraction[J].Journal of Chinese Mass Spectrometry Society,2016,37(1):68-74.
[8]季海冰,潘荷芳,李震宇,等.电感耦合等离子质谱法测定土壤中重金属有效态浓度[J].环境污染与防治,2008,30(12):60-62,66.JI Hai-bing,PAN He-fang,LI Zhen-yu,et al.ICP/MS for determination of bio-available heavy metals in soil samples[J].Environmental Pollution&Control,2008,30(12):60-62,66.
[9]王艳泽,施燕支,张华,等.ICP-MS对土壤样品中有效硼的测定[J].光谱学与光谱分析,2006,26(7):1334-1335.WANG Yan-ze,SHI Yan-zhi,ZHANG Hua,et al.Study on the method for the determination of soil available B by ICP-MS[J].Spectroscopy and Spectral Analysis,2006,26(7):1334-1335.
[10]韩张雄,熊英,王龙山,等.DTPA浸提-电感耦合等离子质谱法测定石灰性土壤中的有效态钴和有效态铅[J].岩矿测试,2012,31(6):950-953.HAN Zhang-xiong,XIONG Ying,WANG Long-shan,et al.Rapid determination of available cobalt&lead in calcareous soils by inductively coupled plasma-mass spectrometry with DTPA extraction[J].Rock and Mineral Analysis,2012,31(6):950-953.
[11]杜英秋.土壤中镉、镍、铅全量和有效态的ICP-MS法测定及两者相关性分析[J].中国西部科技,2015,14(12):101-104,84.DU Ying-qiu.Determination for total content and available state of cadmium,nickel,lead in soil by ICP-MS and correlation analysis between the two[J].Science and Technology of West China,2015,14(12):101-104,84.
[12]洪灯,许菲菲,姜士磊,等.ICP-MS法测定硅胶奶嘴中8种可溶性重金属[J].化学研究,2015,26(2):170-174.HONG Deng,XU Fei-fei,JIANG Shi-lei,et al.Determination of eight kinds soluble heavy metals in silicone nipple by ICP-MS[J].Chemical Research,2015,26(2):170-174.
[13]李敏,连晓文,梁旭霞,等.电感耦合等离子质谱法测定水中低浓度铁受钙干扰的消除[J].理化检验:化学分册,2012,48(7):815-817.LI Min,LIAN Xiao-wen,LIANG Xu-xia,et al.On the elimination of interference of calcium in the ICP-MS determination of iron with low concentration in water[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2012,48(7):815-817.'
[14]刘蜜,仇海旭,郭伟,等.利用电感耦合等离子体质谱仪He碰撞反应模式测定土壤有效钼[J].中国土壤与肥料,2017(6):171-175.LIU Mi,QIU Hai-xu,GUO Wei,et al.Determination of soil available molybdenum using inductively coupled plasma mass spectrometry with He collision model[J].Soil and Fertilizer Sciences in China,2017(6):171-175.
[2]黄昌勇,徐建明.土壤学[M].3版.北京:中国农业出版社,2010.
[3]国家林业局.LY/T 1210~1275—1999森林土壤分析方法[S].北京:中国标准出版社,1999.
[4]中华人民共和国农业部.NY/T 890—2004土壤有效态锌、锰、铁、铜含量的测定二乙三胺五乙酸(DTPA)浸提法[S].北京:中国标准出版社,2004.
[5]环境保护部.HJ 804—2016土壤8种有效态元素的测定二乙烯三胺五乙酸浸提-电感耦合等离子体发射光谱法[S].北京:中国标准出版社,2016.
[6]林光西,徐霞,张静梅.ICP-MS测定土壤样品中的有效锰、铜和锌[J].光谱实验室,2006,23(6):1267-1270.LIN Guang-xi,XU Xia,ZHANG Jing-mei.Determination of available Mn,Cu and Zn in soil by ICP-MS[J].Chinese Journal of Spectroscopy Laboratory,2006,23(6):1267-1270.
[7]农云军,谢继丹,黄名湖,等.超声提取-ICP-MS法测定土壤中有效铅和镉[J].质谱学报,2016,37(1):68-74.NONG Yun-jun,XIE Ji-dan,HUANG Ming-hu,et al.Measurement of available lead and cadmium in soil by ICP-MS with ultrasonic extraction[J].Journal of Chinese Mass Spectrometry Society,2016,37(1):68-74.
[8]季海冰,潘荷芳,李震宇,等.电感耦合等离子质谱法测定土壤中重金属有效态浓度[J].环境污染与防治,2008,30(12):60-62,66.JI Hai-bing,PAN He-fang,LI Zhen-yu,et al.ICP/MS for determination of bio-available heavy metals in soil samples[J].Environmental Pollution&Control,2008,30(12):60-62,66.
[9]王艳泽,施燕支,张华,等.ICP-MS对土壤样品中有效硼的测定[J].光谱学与光谱分析,2006,26(7):1334-1335.WANG Yan-ze,SHI Yan-zhi,ZHANG Hua,et al.Study on the method for the determination of soil available B by ICP-MS[J].Spectroscopy and Spectral Analysis,2006,26(7):1334-1335.
[10]韩张雄,熊英,王龙山,等.DTPA浸提-电感耦合等离子质谱法测定石灰性土壤中的有效态钴和有效态铅[J].岩矿测试,2012,31(6):950-953.HAN Zhang-xiong,XIONG Ying,WANG Long-shan,et al.Rapid determination of available cobalt&lead in calcareous soils by inductively coupled plasma-mass spectrometry with DTPA extraction[J].Rock and Mineral Analysis,2012,31(6):950-953.
[11]杜英秋.土壤中镉、镍、铅全量和有效态的ICP-MS法测定及两者相关性分析[J].中国西部科技,2015,14(12):101-104,84.DU Ying-qiu.Determination for total content and available state of cadmium,nickel,lead in soil by ICP-MS and correlation analysis between the two[J].Science and Technology of West China,2015,14(12):101-104,84.
[12]洪灯,许菲菲,姜士磊,等.ICP-MS法测定硅胶奶嘴中8种可溶性重金属[J].化学研究,2015,26(2):170-174.HONG Deng,XU Fei-fei,JIANG Shi-lei,et al.Determination of eight kinds soluble heavy metals in silicone nipple by ICP-MS[J].Chemical Research,2015,26(2):170-174.
[13]李敏,连晓文,梁旭霞,等.电感耦合等离子质谱法测定水中低浓度铁受钙干扰的消除[J].理化检验:化学分册,2012,48(7):815-817.LI Min,LIAN Xiao-wen,LIANG Xu-xia,et al.On the elimination of interference of calcium in the ICP-MS determination of iron with low concentration in water[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2012,48(7):815-817.'
[14]刘蜜,仇海旭,郭伟,等.利用电感耦合等离子体质谱仪He碰撞反应模式测定土壤有效钼[J].中国土壤与肥料,2017(6):171-175.LIU Mi,QIU Hai-xu,GUO Wei,et al.Determination of soil available molybdenum using inductively coupled plasma mass spectrometry with He collision model[J].Soil and Fertilizer Sciences in China,2017(6):171-175.