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物探与化探  2023, Vol. 47 Issue (3): 739-746    DOI: 10.11720/wtyht.2023.1315
  方法研究·信息处理·仪器研制 本期目录 | 过刊浏览 | 高级检索 |
微波消解—电感耦合等离子体发射光谱法同时测定生物样品中12种元素的方法
肖细炼1,2(), 刘杰3(), 魏立1, 陈燕波1, 杨小丽1,2, 杨红梅1,2
1.中国地质调查局 武汉地质调查中心(中南地质科技创新中心),湖北 武汉 430205
2.中国地质调查局 花岗岩成岩成矿地质研究中心,湖北 武汉 430205
3.中国地质调查局 长沙自然资源综合调查中心,湖南 长沙 410699
Simultaneous determination of 12 elements in biological samples using microwave digestion and inductively coupled plasma-optical emission spectrometry
XIAO Xi-Lian1,2(), LIU Jie3(), WEI Li1, CHEN Yan-Bo1, YANG Xiao-Li1,2, YANG Hong-Mei1,2
1. Wuhan Geological Survey Center, China Geological Survey (Central South China Innovation Center for Geosciences), Wuhan 430205, China
2. Research Center for Petrogenesis and Mineralization of Granitoid Rocks, China Geological Survey, Wuhan 430205, China
3. Changsha General Survey of Natural Resources Center, China Geological Survey, Changsha 410699, China
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摘要 

针对生物样品的特殊性,本文建立了微波消解—电感耦合等离子体发射光谱同时测定生物样品中铝(Al)、铁(Fe)、镁(Mg)、钙(Ca)、钠(Na)、钾(K)、锰(Mn)、磷(P)、钛(Ti)、钡(Ba)、锶(Sr)、锌(Zn)等12种元素的分析方法。通过对微波消解样品前处理条件进行优化,选择以10 mL逆王水和1 mL双氧水的混合试剂作为消解试剂,并选择合适的微波消解仪实验程序,能保证样品分解完全;选择最优的等离子体激发条件、元素分析谱线及扣背景位置,使得各元素测定的灵敏度高以及谱线无干扰;以国家一级生物成分标准物质作为校准系列绘制校准曲线,使得校准系列与试样基体尽可能一致,且选定方法总稀释倍数为100,消除了基体效应干扰影响。结果表明:该方法检出限为(0.04~4.93)×10-6;方法相对标准偏差(RSD)为1.41%~5.13%,精密度较好;经国家一级生物成分标准物质验证,方法相对误差(RE)均在±10%以内,测定值与标准值相吻合,方法准确可靠,能够满足生物样品分析要求。
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肖细炼
刘杰
魏立
陈燕波
杨小丽
杨红梅
关键词 ： 微波消解,  电感耦合等离子体发射光谱法,  生物样品,  基体效应,  校准曲线    
Abstract：

Given the particularity of biological samples, this study employed microwave digestion and inductively coupled plasma-optical emission spectrometry (ICP-OES) for the simultaneous determination of 12 elements in biological samples, including aluminum (Al), ferrum (Fe), magnesium (Mg), calcium (Ca), sodium (Na), potassium (K), manganese (Mn), phosphorus (P), titanium (Ti), barium (Ba), strontium (Sr), and zinc (Zn). By optimizing the pretreatment conditions of microwave digestion samples, this study selected the mixed reagent of reverse aqua regia (10 mL) and hydrogen peroxide (1 mL) as the digestion reagent, and an appropriate experimental procedure for the microwave digestion system to ensure complete decomposition of samples. Moreover, this study selected the optimal plasma excitation conditions, analytical spectral lines of elements, and background subtraction position to ensure high determination sensitivity of elements and interference-free spectral lines. This study plotted the calibration curve with the national primary reference materials for biological components as the calibration series, making the calibration series consistent with the sample matrix as much as possible. The simultaneous determination method had a total dilution multiple of 100, eliminating the interference of the matrix effect. The results show that this method had a detection limit of (0.04~4.93)×10-6 and a relative standard deviation (RSD) of 1.41%~5.13%, showing high precision. As verified by the national primary reference materials, this method had a relative error (RE) within ±10% and determined values consistent with standard values. Therefore, this method is accurate and reliable, meeting the analysis requirements of biological samples.
Key words： microwave digestion    inductively coupled plasma-optical emission spectrometry    biological sample    matrix effect    calibration curve
收稿日期: 2022-06-16      修回日期: 2022-12-17      出版日期: 2023-06-20
ZTFLH:  O657  
  X830.1  
基金资助:中国地质调查局地质调查项目(DD20221777);中国地质调查局花岗岩成岩成矿地质研究中心开放基金项目(PMGR202012)
通讯作者: 刘杰(1987-),男,助理工程师,硕士,主要从事实验室质量管理工作。Email:527245266@qq.com
作者简介: 肖细炼(1984-),男,高级工程师,硕士,主要从事地球化学分析方面的研究工作。Email: xiaoxilianezhou@126.com
引用本文:   
肖细炼, 刘杰, 魏立, 陈燕波, 杨小丽, 杨红梅. 微波消解—电感耦合等离子体发射光谱法同时测定生物样品中12种元素的方法[J]. 物探与化探, 2023, 47(3): 739-746.
XIAO Xi-Lian, LIU Jie, WEI Li, CHEN Yan-Bo, YANG Xiao-Li, YANG Hong-Mei. Simultaneous determination of 12 elements in biological samples using microwave digestion and inductively coupled plasma-optical emission spectrometry. Geophysical and Geochemical Exploration, 2023, 47(3): 739-746.
链接本文:  
https://www.wutanyuhuatan.com/CN/10.11720/wtyht.2023.1315      或      https://www.wutanyuhuatan.com/CN/Y2023/V47/I3/739
元素 分析线波长/nm 谱线级次 扣背景位置
Al 167.079 502 左、右
Fe 259.940 130 左、右
Mg 279.553 121 左、右
Ca 393.366 86 左、右
Na 588.995 57 左、右
K 766.490 44 左、右
Mn 257.610 131 左、右
P 177.495 490 左、右
Ti 334.941 101 左、右
Ba 455.403 74 左、右
Sr 407.771 83 左、右
Zn 213.856 458 左、右
Table 1  各元素分析谱线
步骤 升温速率/
(℃·min-1)		 温度/℃ 保温时
间/min		 压力/
atm		 发射功
率/W
1 15 100 15 20 1500
2 10 140 25 30 1500
3 5 180 10 40 1500
Table 2  微波消解仪实验程序
元素 标准物质含量/10-6 校准曲线方程 线性相关系数r
GBW10014 GBW10023 GBW07604 GBW07602
Al 166 4900 1040 2140 y=34.19x+5.49 0.9997
Fe 98 1450 274 1020 y=419.96x+0.81 0.9998
Mg 2410 4000 6500 2870 y=439.13x+153.11 0.9996
Ca 700 1530 18100 22200 y=41846.75x+1526.05 0.9997
Na 10900 15500 200 11000 y=1900.91x+3174.82 0.9998
K 15500 33600 13800 8500 y=342.86x-11.92 0.9997
Mn 18.7 68.0 45.0 58.0 y=65343.68x+16.20 0.9999
P 4600 5850 1680 830 y=182.06x+1.42 0.9998
Ti 9.0 92.0 20.4 95.0 y=1605.31x+0.51 0.9995
Ba 12.0 10.4 26.0 19.0 y=28015.95x+122.45 0.9997
Sr 48 24 154 345 y=38969.35x+0.57 1.0000
Zn 26.0 28.0 37.0 20.6 y=14972.49x+39.51 0.9997
Table 3  标准物质各元素含量及校准曲线方程
元素 GBW07603 GBW07605 GBW10015 GBW10020 检出限/
10-6
X ˉ/10-6 RSD/% X ˉ/10-6 RSD/% X ˉ/10-6 RSD/% X ˉ/10-6 RSD/%
Al 2024 4.05 3026 4.69 620.67 2.10 1143 3.62 4.93
Fe 1047 5.13 261.39 2.60 542.42 2.39 463.50 4.20 4.26
Mg 4790 2.44 1734 3.52 5513 2.67 2322 2.80 2.48
Ca 16823 2.24 4248 2.48 6626 2.46 42073 1.41 1.25
Na 19605 1.77 44.02 4.24 15330 2.63 128.03 3.70 1.69
K 9252 2.29 16557 2.40 24666 2.46 7617 2.50 3.55
Mn 61.58 4.54 1252 3.50 42.70 3.99 30.12 4.25 0.14
P 1027 4.80 2817 3.44 3521 3.20 1261 4.69 1.02
Ti 94.67 3.14 24.76 4.29 29.77 2.91 39.03 3.45 0.37
Ba 19.37 5.07 57.65 2.64 8.91 3.51 99.65 2.53 0.11
Sr 243.77 2.16 15.19 3.56 87.39 3.07 169.14 2.84 0.08
Zn 54.73 3.94 26.59 4.34 34.73 2.44 18.82 3.40 0.04
Table 4  方法精密度及检出限
元素 项目 GBW07603 GBW07605 GBW10015 GBW10020 GBW10047 GBW10049
Al 认定值/10-6 2000 3000 610 1150 460 3000
平均值/10-6 2105 3115 614.55 1179 456.85 3125
RE/% 5.25 3.83 0.75 2.52 -0.68 4.17
Fe 认定值/10-6 1070 264 540 480 148 1010
平均值/10-6 1054 265.99 548.57 473.69 145.69 1076
RE/% -1.50 0.75 1.59 -1.31 -1.56 6.53
Mg 认定值/10-6 4800 1700 5520 2340 910 2700
平均值/10-6 4769 1678 5565 2285 904.25 2645
RE/% -0.65 -1.29 0.82 -2.35 -0.63 -2.04
Ca 认定值/10-6 16800 4300 6600 42000 2550 22800
平均值/10-6 17012 4218 6575 41695 2538 22514
RE/% 1.26 -1.91 -0.38 -0.73 -0.47 -1.25
Na 认定值/10-6 19600 44 15000 130 6500 300
平均值/10-6 19328 43.66 14892 128.54 6472 281.65
RE/% -1.39 -0.77 -0.72 -1.12 -0.43 -6.12
K 认定值/10-6 9200 16600 24900 7700 10800 21000
平均值/10-6 9345 16799 24885 7633 10722 20069
RE/% 1.58 1.20 -0.06 -0.87 -0.72 -4.43
Mn 认定值/10-6 61 1240 41 30.5 12.1 173
平均值/10-6 63.25 1295 40.93 31.68 12.65 175.68
RE/% 3.69 4.44 -0.17 3.87 4.55 1.55
P 认定值/10-6 1000 2840 3600 1250 2300 3600
平均值/10-6 1046 2788 3622 1247 2324 3544
RE/% 4.60 -1.83 0.61 -0.24 1.04 -1.56
Ti 认定值/10-6 95 24 28 38 12 62
平均值/10-6 93.52 22.58 27.55 40.25 11.68 63.85
RE/% -1.56 -5.92 -1.61 5.92 -2.67 2.98
Ba 认定值/10-6 18 58 9 98 24 36
平均值/10-6 17.44 56.98 9.28 99.63 23.54 34.44
RE/% -3.11 -1.76 3.11 1.66 -1.92 -4.33
Sr 认定值/10-6 246 15.2 87 170 22 74
平均值/10-6 248.69 16.05 84.69 168.57 22.98 73.22
RE/% 1.09 5.59 -2.66 -0.84 4.45 -1.05
Zn 认定值/10-6 55 26.3 35.3 18 11.2 25
平均值/10-6 53.39 26.58 33.67 17.62 10.86 23.96
RE/% -2.93 1.06 -4.62 -2.11 -3.04 -4.16
Table 5  方法准确度
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