使用ICP-MS测定白酒中16种稀土元素的含量
表1 检出限、定量限结果
次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | LOD | LOQ |
45Sc | 404.01 | 380.01 | 354.01 | 348.01 | 324.01 | 314.01 | 354.01 | 268.00 | 280.00 | 568.13 | 326.01 | 0.026 | 0.088 |
89Y | 282.00 | 258.00 | 280.00 | 278.00 | 310.01 | 236.00 | 276.00 | 280.00 | 236.00 | 280.00 | 240.00 | 0.0012 | 0.0038 |
139La | 906.04 | 868.03 | 904.04 | 880.03 | 876.04 | 854.03 | 916.04 | 898.04 | 818.03 | 864.03 | 970.05 | 0.00066 | 0.0022 |
140Ce | 13207.06 | 14181.17 | 13129.03 | 14227.20 | 13759.70 | 12844.67 | 13000.88 | 13271.11 | 13261.10 | 13509.39 | 13837.96 | 0.0064 | 0.021 |
141Pr | 182.00 | 164.00 | 178.00 | 190.00 | 182.00 | 156.00 | 164.00 | 182.00 | 168.00 | 170.00 | 190.00 | 0.00014 | 0.00048 |
146Nd | 132.00 | 130.00 | 120.00 | 168.00 | 158.00 | 108.00 | 140.00 | 106.00 | 140.00 | 132.00 | 182.00 | 0.0015 | 0.0051 |
147Sm | 38.00 | 28.00 | 30.00 | 38.00 | 26.00 | 18.00 | 24.00 | 28.00 | 22.00 | 16.00 | 22.00 | 0.00053 | 0.0018 |
151Eu | 26.00 | 28.00 | 22.00 | 28.00 | 22.00 | 30.00 | 30.00 | 18.00 | 36.00 | 20.00 | 32.00 | 0.00011 | 0.00038 |
153Eu | 22.00 | 42.00 | 46.00 | 50.00 | 28.00 | 42.00 | 20.00 | 38.00 | 36.00 | 28.00 | 20.00 | 0.00019 | 0.00064 |
157Gd | 56.00 | 36.00 | 56.00 | 48.00 | 54.00 | 38.00 | 36.00 | 48.00 | 38.00 | 30.00 | 42.00 | 0.00044 | 0.0015 |
159Tb | 48.00 | 54.00 | 30.00 | 40.00 | 40.00 | 42.00 | 54.00 | 44.00 | 62.00 | 58.00 | 44.00 | 0.00007 | 0.00025 |
163Dy | 40.00 | 44.00 | 38.00 | 38.00 | 34.00 | 44.00 | 42.00 | 28.00 | 50.00 | 38.00 | 44.00 | 0.00019 | 0.00063 |
165Ho | 58.00 | 60.00 | 38.00 | 54.00 | 50.00 | 30.00 | 48.00 | 52.00 | 52.00 | 56.00 | 24.00 | 0.00009 | 0.00030 |
166Er | 492.01 | 500.01 | 498.02 | 496.01 | 460.01 | 512.01 | 814.22 | 538.02 | 498.01 | 982.37 | 640.03 | 0.0038 | 0.013 |
169Tm | 44.00 | 36.00 | 38.00 | 34.00 | 44.00 | 26.00 | 26.00 | 26.00 | 20.00 | 32.00 | 30.00 | 0.00005 | 0.00018 |
172Yb | 10.00 | 14.00 | 30.00 | 24.00 | 16.00 | 16.00 | 24.00 | 24.00 | 24.00 | 20.00 | 26.00 | 0.00018 | 0.00061 |
175Lu | 30.00 | 18.00 | 38.00 | 24.00 | 30.00 | 48.00 | 30.00 | 46.00 | 30.00 | 24.00 | 38.00 | 0.00009 | 0.00030 |
huangza
第1楼2023/09/02
2.2 精密度
以某白酒为研究对象,取7个平行样进行重复性实验。
表2 检测结果(单位:μg/L)
样品编号 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 平均值 | 相对标准偏差 |
45Sc | 0.1378 | 0.1362 | 0.1384 | 0.1352 | 0.1329 | 0.1354 | 0.1377 | 0.1362 | 1.4 |
89Y | 1.0015 | 1.0131 | 1.0213 | 1.0005 | 1.0058 | 1.0103 | 1.0115 | 1.0091 | 0.72 |
139La | 0.8215 | 0.8272 | 0.8296 | 0.8290 | 0.8299 | 0.8267 | 0.8233 | 0.8267 | 0.39 |
140Ce | 2.6148 | 2.6475 | 2.6629 | 2.6357 | 2.6255 | 2.6425 | 2.6576 | 2.6410 | 0.65 |
141Pr | 0.2102 | 0.2129 | 0.2149 | 0.2134 | 0.2138 | 0.2149 | 0.2128 | 0.2133 | 0.75 |
146Nd | 0.8770 | 0.8884 | 0.8882 | 0.8822 | 0.8790 | 0.8832 | 0.8874 | 0.8836 | 0.52 |
147Sm | 0.1869 | 0.1905 | 0.1886 | 0.1898 | 0.1900 | 0.1892 | 0.1884 | 0.1891 | 0.64 |
151Eu | 0.0423 | 0.0419 | 0.0421 | 0.0422 | 0.0419 | 0.0421 | 0.0421 | 0.0421 | 0.38 |
153Eu | 0.0421 | 0.0425 | 0.0419 | 0.0418 | 0.0424 | 0.0418 | 0.0419 | 0.0421 | 0.70 |
157Gd | 0.2425 | 0.2423 | 0.2455 | 0.2440 | 0.2441 | 0.2451 | 0.2453 | 0.2441 | 0.53 |
159Tb | 0.0296 | 0.0300 | 0.0298 | 0.0298 | 0.0297 | 0.0296 | 0.0298 | 0.0298 | 0.51 |
163Dy | 0.1731 | 0.1752 | 0.1747 | 0.1757 | 0.1726 | 0.1738 | 0.1725 | 0.1739 | 0.73 |
165Ho | 0.0345 | 0.0343 | 0.0347 | 0.0347 | 0.0346 | 0.0346 | 0.0343 | 0.0345 | 0.52 |
166Er | 0.1567 | 0.1573 | 0.1602 | 0.1572 | 0.1568 | 0.1587 | 0.1589 | 0.1580 | 0.85 |
169Tm | 0.0130 | 0.0131 | 0.0131 | 0.0130 | 0.0130 | 0.0130 | 0.0131 | 0.0131 | 0.50 |
172Yb | 0.0850 | 0.0849 | 0.0842 | 0.0846 | 0.0839 | 0.0855 | 0.0854 | 0.0848 | 0.67 |
175Lu | 0.0125 | 0.0124 | 0.0124 | 0.0126 | 0.0125 | 0.0124 | 0.0124 | 0.0125 | 0.72 |
表3 回收率实验结果
元素 | 本底值(μg/L) | 测定值(μg/L) | 加标量(μg/L) | 回收率(%) | 元素 | 本底值(μg/L) | 测定值(μg/L) | 加标量(μg/L) | 回收率(%) |
45Sc | 0.5040 | 1.5877 | 1.0 | 108.4 | 89Y | 4.1499 | 5.2051 | 1.0 | 105.5 |
1.5314 | 102.7 | 5.2367 | 108.7 | ||||||
1.5080 | 100.4 | 5.2026 | 105.3 | ||||||
2.4743 | 2.0 | 98.5 | 6.0648 | 2.0 | 95.7 | ||||
2.4973 | 99.7 | 6.2162 | 103.3 | ||||||
2.5190 | 100.7 | 6.1374 | 99.4 | ||||||
3.5118 | 3.0 | 100.3 | 7.2260 | 3.0 | 102.5 | ||||
3.4534 | 98.3 | 7.3090 | 105.3 | ||||||
3.5716 | 102.3 | 7.3196 | 105.7 | ||||||
139La | 3.3495 | 4.3652 | 1.0 | 101.6 | 140Ce | 8.1489 | 9.1007 | 1.0 | 95.2 |
4.3236 | 97.4 | 9.1386 | 99.0 | ||||||
4.3319 | 98.2 | 9.2251 | 107.6 | ||||||
5.2844 | 2.0 | 96.7 | 10.2171 | 2.0 | 103.4 | ||||
5.3627 | 100.7 | 10.1062 | 97.9 | ||||||
5.2929 | 97.2 | 10.2297 | 104.0 | ||||||
6.3162 | 3.0 | 98.9 | 11.1977 | 3.0 | 101.6 | ||||
6.3615 | 100.4 | 11.3151 | 105.5 | ||||||
6.4473 | 103.3 | 11.2199 | 102.4 | ||||||
141Pr | 0.8634 | 1.8578 | 1.0
| 99.4 | 146Nd | 3.5569 | 4.5271 | 1.0 | 97.0 |
1.8767 | 101.3 | 4.5512 | 99.4 | ||||||
1.8576 | 99.4 | 4.5871 | 103.0 | ||||||
2.8344 | 2.0 | 98.6 | 5.4833 | 2.0 | 96.3 | ||||
2.8567 | 99.7 | 5.5202 | 98.2 | ||||||
2.8608 | 99.9 | 5.4680 | 95.6 | ||||||
3.8815 | 3.0 | 100.6 | 6.4928 | 3.0 | 97.9 | ||||
3.9084 | 101.5 | 6.5839 | 100.9 | ||||||
3.9409 | 102.6 | 6.5980 | 101.4 | ||||||
147Sm | 0.7827 | 1.7737 | 1.0
| 99.1 | 151Eu | 0.1734 | 1.1918 | 1.0 | 101.8 |
1.7832 | 100.0 | 1.1953 | 102.2 | ||||||
1.7818 | 99.9 | 1.1995 | 102.6 | ||||||
2.7550 | 2.0 | 98.6 | 2.1746 | 2.0 | 100.1 | ||||
2.8129 | 101.5 | 2.2216 | 102.4 | ||||||
2.7695 | 99.3 | 2.1835 | 100.5 | ||||||
3.8148 | 3.0 | 101.1 | 3.2116 | 3.0 | 101.3 | ||||
3.8838 | 103.4 | 3.2431 | 102.3 | ||||||
3.8311 | 101.6 | 3.2142 | 101.4 | ||||||
157Gd | 1.0193 | 1.9974 | 1.0
| 97.8 | 159Tb | 0.1214 | 1.1362 | 1.0 | 101.5 |
2.0314 | 101.2 | 1.1288 | 100.7 | ||||||
2.0643 | 104.5 | 1.1398 | 101.8 | ||||||
3.0021 | 2.0 | 99.1 | 2.1165 | 2.0 | 99.8 | ||||
3.0620 | 102.1 | 2.1221 | 100.0 | ||||||
3.0184 | 100.0 | 2.1075 | 99.3 | ||||||
4.0590 | 3.0 | 101.3 | 3.1041 | 3.0 | 99.4 | ||||
4.0794 | 102.0 | 3.1879 | 102.2 | ||||||
4.0493 | 101.0 | 3.1867 | 102.2 | ||||||
163Dy | 0.7237 | 1.6983 | 1.0
| 97.5 | 165Ho | 0.1417 | 1.1649 | 1.0
| 102.3 |
1.7327 | 100.9 | 1.1629 | 102.1 | ||||||
1.7462 | 102.3 | 1.1806 | 103.9 | ||||||
2.6698 | 2.0
| 97.3 | 2.1324 | 2.0 | 99.5 | ||||
2.7072 | 99.2 | 2.1537 | 100.6 | ||||||
2.7113 | 99.4 | 2.1300 | 99.4 | ||||||
3.7195 | 3.0 | 99.9 | 3.1714 | 3.0 | 101.0 | ||||
3.7522 | 100.9 | 3.1708 | 101.0 | ||||||
3.7200 | 99.9 | 3.1952 | 101.8 | ||||||
166Er | 0.6784 | 1.6994 | 1.0 | 102.1 | 169Tm | 0.0542 | 1.0676 | 1.0 | 101.3 |
1.6888 | 101.0 | 1.0761 | 102.2 | ||||||
1.7050 | 102.7 | 1.0750 | 102.1 | ||||||
2.6670 | 2.0 | 99.4 | 2.0738 | 2.0 | 101.0 | ||||
2.6747 | 99.8 | 2.0504 | 99.8 | ||||||
2.6621 | 99.2 | 2.0500 | 99.8 | ||||||
3.7129 | 3.0 | 101.2 | 3.0672 | 3.0 | 100.4 | ||||
3.7671 | 103.0 | 3.0625 | 100.3 | ||||||
3.7544 | 102.5 | 3.0845 | 101.0 | ||||||
172Yb | 0.3464 | 1.3476 | 1.0 | 100.1 | 175Lu | 0.0504 | 1.0548 | 1.0 | 100.4 |
1.3478 | 100.1 | 1.0488 | 99.8 | ||||||
1.3622 | 101.6 | 1.0652 | 101.5 | ||||||
2.3227 | 2.0 | 98.8 | 2.0492 | 2.0 | 99.9 | ||||
2.2791 | 96.6 | 2.0146 | 98.2 | ||||||
2.3104 | 98.2 | 2.0027 | 97.6 | ||||||
3.2790 | 3.0 | 97.8 | 2.9803 | 3.0 | 97.7 | ||||
3.3513 | 100.2 | 3.0316 | 99.4 | ||||||
3.3770 | 101.0 | 3.0026 | 98.4 |
huangza
第2楼2023/09/02
3. 白酒中稀土元素测定
唐偲雨等[8]利用包含稀土元素在内的32种矿质元素指纹建立了不同产地的 22个茶叶样品主成分分类模型时发现,稀土元素钇Y、镨Pr、钕Nd、铕Eu、钆Gd、铽Tb、镝Dy、钬Ho、铒Er 和微量元素铁Fe起到主要贡献作用。
采用上述方法对36批白酒中16种稀土元素进行测定,见表4。
表4 白酒中稀土元素测定结果 (μg/L)
元素 | 样品编号 | |||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
钪 | 0.18 | 0.18 | 0.051 | 0.14 | 0.0037 | ND | 0.090 | 0.17 | 0.098 | 0.080 | 0.0079 | 0.13 |
钇 | 0.89 | 0.86 | 0.66 | 0.82 | 0.034 | 0.017 | 0.50 | 1.0 | 0.62 | 0.74 | 0.074 | 0.97 |
镧 | 1.1 | 0.81 | 0.38 | 0.62 | 0.038 | 0.018 | 0.42 | 0.68 | 0.37 | 0.86 | 0.066 | 0.65 |
铈 | 1.4 | 1.6 | 0.70 | 1.2 | 0.078 | 0.041 | 0.88 | 1.2 | 0.69 | 1.8 | 0.13 | 1.1 |
镨 | 0.18 | 0.19 | 0.091 | 0.15 | 0.0087 | 0.0041 | 0.12 | 0.16 | 0.091 | 0.21 | 0.014 | 0.15 |
钕 | 0.73 | 0.79 | 0.40 | 0.66 | 0.051 | 0.029 | 0.50 | 0.65 | 0.40 | 0.84 | 0.075 | 0.64 |
钐 | 0.17 | 0.17 | 0.090 | 0.16 | 0.0071 | 0.0040 | 0.11 | 0.14 | 0.089 | 0.17 | 0.013 | 0.15 |
铕 | 0.036 | 0.038 | 0.021 | 0.036 | 0.0018 | ND | 0.023 | 0.034 | 0.021 | 0.038 | 0.0029 | 0.035 |
钆 | 0.19 | 0.18 | 0.11 | 0.18 | 0.0070 | 0.0046 | 0.11 | 0.17 | 0.11 | 0.17 | 0.015 | 0.17 |
铽 | 0.028 | 0.027 | 0.017 | 0.027 | ND | ND | 0.017 | 0.025 | 0.017 | 0.024 | 0.0021 | 0.025 |
镝 | 0.16 | 0.16 | 0.11 | 0.16 | 0.0065 | 0.0031 | 0.096 | 0.16 | 0.10 | 0.14 | 0.013 | 0.15 |
钬 | 0.032 | 0.031 | 0.023 | 0.030 | 0.0011 | ND | 0.018 | 0.034 | 0.022 | 0.027 | 0.0025 | 0.031 |
铒 | 0.094 | 0.090 | 0.067 | 0.091 | 0.0031 | 0.0019 | 0.051 | 0.099 | 0.067 | 0.077 | 0.0079 | 0.089 |
铥 | 0.012 | 0.012 | 0.0093 | 0.012 | ND | ND | 0.0069 | 0.014 | 0.0089 | 0.0099 | ND | 0.012 |
镱 | 0.083 | 0.079 | 0.062 | 0.074 | 0.0026 | 0.0012 | 0.044 | 0.093 | 0.059 | 0.066 | 0.0063 | 0.076 |
镥 | 0.012 | 0.012 | 0.0095 | 0.011 | ND | ND | 0.0063 | 0.014 | 0.0089 | 0.0084 | ND | 0.011 |
元素 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 |
钪 | 0.037 | 0.036 | 0.0036 | 0.015 | ND | 0.011 | 0.0089 | 0.0091 | 0.0082 | ND | ND | 0.0026 |
钇 | 0.27 | 0.29 | 0.030 | 0.13 | 0.010 | 0.093 | 0.11 | 0.062 | 0.11 | 0.014 | 0.021 | 0.022 |
镧 | 0.36 | 0.35 | 0.084 | 0.18 | 0.018 | 0.066 | 0.092 | 0.051 | 0.084 | 0.11 | 0.039 | 0.035 |
铈 | 0.78 | 0.74 | 0.053 | 0.16 | 0.025 | 0.11 | 0.13 | 0.078 | 0.18 | 0.033 | 0.045 | 0.042 |
镨 | 0.089 | 0.088 | 0.0050 | 0.021 | 0.0023 | 0.014 | 0.019 | 0.010 | 0.020 | 0.0030 | 0.0046 | 0.0043 |
钕 | 0.36 | 0.35 | 0.021 | 0.089 | 0.0090 | 0.060 | 0.076 | 0.053 | 0.081 | 0.012 | 0.019 | 0.029 |
钐 | 0.072 | 0.072 | 0.0047 | 0.021 | 0.0020 | 0.015 | 0.019 | 0.0086 | 0.019 | 0.0025 | 0.0044 | 0.0043 |
铕 | 0.016 | 0.016 | 0.0011 | 0.0046 | ND | 0.0032 | 0.0044 | 0.0020 | 0.0043 | ND | ND | ND |
钆 | 0.070 | 0.073 | 0.0058 | 0.025 | 0.0019 | 0.017 | 0.024 | 0.012 | 0.024 | 0.0027 | 0.0048 | 0.0049 |
铽 | 0.0094 | 0.0097 | ND | 0.0035 | ND | 0.0024 | 0.0031 | 0.0016 | 0.0032 | ND | ND | ND |
镝 | 0.054 | 0.056 | 0.0049 | 0.023 | 0.0016 | 0.015 | 0.019 | 0.010 | 0.020 | 0.0021 | 0.0040 | 0.0035 |
钬 | 0.0097 | 0.010 | ND | 0.0043 | ND | 0.0032 | 0.0036 | 0.0019 | 0.0037 | ND | ND | ND |
铒 | 0.030 | 0.028 | 0.0038 | 0.015 | ND | 0.0093 | 0.011 | 0.0063 | 0.010 | 0.0013 | 0.0022 | 0.0019 |
铥 | 0.0034 | 0.0038 | ND | 0.0016 | ND | 0.0011 | 0.0012 | ND | 0.0013 | ND | ND | ND |
镱 | 0.021 | 0.023 | 0.0022 | 0.011 | ND | 0.0074 | 0.0082 | 0.0049 | 0.0082 | ND | 0.0016 | 0.0015 |
镥 | 0.0030 | 0.0032 | 0.0003 | 0.0015 | ND | 0.0010 | 0.0010 | ND | 0.0011 | ND | ND | ND |
元素 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 |
钪 | 0.0015 | 0.0047 | 0.0038 | 0.0029 | 0.0033 | 0.0035 | 0.0028 | 0.0018 | ND | ND | ND | 0.0017 |
钇 | 0.019 | 0.050 | 0.029 | 0.020 | 0.040 | 0.024 | 0.029 | 0.015 | 0.010 | 0.0042 | 0.011 | 0.016 |
镧 | 0.026 | 0.23 | 0.053 | 0.029 | 0.067 | 0.030 | 0.035 | 0.018 | 0.013 | 0.0024 | 0.24 | 0.016 |
铈 | 0.039 | 0.064 | 0.055 | 0.045 | 0.054 | 0.061 | 0.054 | 0.041 | 0.070 | 0.0062 | 0.028 | 0.031 |
镨 | 0.0041 | 0.0081 | 0.0063 | 0.0046 | 0.0063 | 0.0066 | 0.0059 | 0.0036 | 0.0028 | ND | 0.0025 | 0.0033 |
钕 | 0.017 | 0.041 | 0.045 | 0.035 | 0.026 | 0.026 | 0.039 | 0.015 | 0.012 | 0.0025 | 0.0095 | 0.014 |
钐 | 0.0041 | 0.0076 | 0.0056 | 0.0043 | 0.0054 | 0.0050 | 0.0050 | 0.0024 | 0.0019 | ND | 0.0020 | 0.0031 |
铕 | ND | 0.0016 | 0.0013 | ND | 0.0014 | 0.0011 | 0.0012 | ND | ND | ND | ND | ND |
钆 | 0.0048 | 0.0098 | 0.0066 | 0.0049 | 0.0069 | 0.0054 | 0.0058 | 0.0028 | 0.0019 | ND | 0.0020 | 0.0031 |
铽 | ND | 0.0013 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
镝 | 0.0036 | 0.0082 | 0.0052 | 0.0035 | 0.0059 | 0.0045 | 0.0051 | 0.0022 | 0.0017 | ND | 0.0016 | 0.0025 |
钬 | ND | 0.0016 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
铒 | 0.0014 | 0.0042 | 0.0033 | 0.0029 | 0.0038 | 0.0023 | 0.0036 | 0.0024 | 0.0047 | ND | 0.0019 | 0.0018 |
铥 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
镱 | 0.0013 | 0.0038 | 0.0019 | 0.0013 | 0.0029 | 0.0020 | 0.0020 | 0.0013 | ND | ND | ND | 0.0012 |
镥 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |