不同产区葡萄酒中的微量元素及风险评估
表1 ICP-MS工作参数
Table 1 Working parameter of ICP-MS
参数Parameters | 设定值Value | 参数Parameters | 设定值Value |
射频功率RF power (W) | 1100 | 等离子气流量 Plasma flow (L/min) | 15.0 |
载气流量 Carrier flow (L/min) | 0.940 | 辅助气流量 Auxiliary flow (L/min) | 1.20 |
透镜电压Lens voltage (V) | 5.50 | 雾化室温度 Atomization chamber temperature (℃) | 2.00 |
蠕动泵转速 Speed of peristaltic pump (r/s) | 0.100 | 采样流量 Sampling flow rate (mL/min) | 0.800 |
采样深度Sampling depth (mm) | 8.00 | 重复次数Repetitions | 3.00 |
按照表1设定的仪器条件测定所配制的混合标准溶液,绘制标准曲线并计算相关系数和斜率。连续平行测定11次2%的硝酸空白溶液,依据IUPAC,以3倍标准偏差对应的浓度作为检出限(LOD),以10倍标准偏差对应的浓度作为定量限(LOQ),结果如表2所示。28种微量元素标准曲线的相关系数在0.988~0.999范围内,说明被测元素在各自线性范围内线性关系良好;LOD和LOQ分别在0.001~0.395 μg/L和0.003~1.30 μg/L范围内,表明该方法灵敏度较高。
表2 各元素线性范围及检出限
Table 2 Linear range and detection limit of each element
元素 Element | 线性范围Linear range (μg/L) | 斜率 Slope | 相关系数 R2 | 检出限 LOD (μg/L) | 定量限 LOQ (μg/L) |
197Au | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.008 | 0.998 | 0.011 | 0.035 |
140Ce | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.034 | 0.999 | 0.007 | 0.022 |
133Cs | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.064 | 0.988 | 0.002 | 0.007 |
164Dy | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.014 | 0.999 | 0.004 | 0.013 |
166Er | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.017 | 0.999 | 0.002 | 0.008 |
153Eu | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.026 | 0.999 | 0.002 | 0.008 |
69Ga | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.014 | 0.999 | 0.069 | 0.227 |
158Gd | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.012 | 0.999 | 0.005 | 0.015 |
74Ge | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.005 | 0.999 | 0.058 | 0.192 |
180Hf | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.019 | 0.999 | 0.011 | 0.038 |
165Ho | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.049 | 0.999 | 0.002 | 0.006 |
139La | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.037 | 0.999 | 0.006 | 0.020 |
175Lu | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.051 | 0.999 | 0.002 | 0.006 |
142Nd | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.012 | 0.999 | 0.015 | 0.050 |
192Os | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.018 | 0.999 | 0.010 | 0.033 |
141Pr | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.043 | 0.999 | 0.003 | 0.011 |
195Pt | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.007 | 0.999 | 0.005 | 0.017 |
187Re | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.024 | 0.999 | 0.004 | 0.014 |
103Rh | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.026 | 0.999 | 0.011 | 0.036 |
102Ru | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.009 | 0.999 | 0.395 | 1.30 |
45Sc | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.015 | 0.993 | 0.366 | 1.21 |
152Sm | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.013 | 0.999 | 0.004 | 0.013 |
181Ta | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.039 | 0.999 | 0.012 | 0.038 |
159Tb | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.052 | 0.999 | 0.003 | 0.009 |
169Tm | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.052 | 0.999 | 0.001 | 0.003 |
184W | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.011 | 0.999 | 0.018 | 0.059 |
174Yb | 0.250, 0.500, 1.00, 5.00, 10.0, 20.0 | 0.016 | 0.999 | 0.006 | 0.021 |
90Zr | 0.250, 0.500, 1.00, 5.00, 10.0, 50.0 | 0.012 | 0.999 | 0.057 | 0.188 |
表3 不同消解方式的加标回收率
Table 3 Recovery rate of different digestion methods
元素 Element | 加标水平 Added (μg/L) | 微波消解microwave digestion | 湿法消解wet digestion | |||
回收率 Recovery (%) | 精密度 Precision (%) | 回收率 Recovery (%) | 精密度 Precision (%) | |||
197Au | 0.050 | 122* | 6.51 | 92 | 5.33 | |
0.100 | 81 | 5.14 | 80 | 4.12 | ||
0.500 | 87 | 4.73 | 89 | 4.58 | ||
140Ce | 0.100 | 86 | 4.22 | 85 | 2.64 | |
0.200 | 82 | 2.17 | 81 | 4.21 | ||
1.00 | 83* | 1.94 | 88 | 2.06 | ||
133Cs | 0.050 | 85 | 4.89 | 82 | 3.31 | |
0.100 | 101* | 3.67 | 91 | 3.63 | ||
0.500 | 86 | 2.67 | 84 | 3.72 | ||
164Dy | 0.050 | 92* | 3.74 | 84 | 2.67 | |
0.100 | 83 | 4.43 | 81 | 2.21 | ||
0.500 | 87* | 2.02 | 77 | 2.43 | ||
166Er | 0.050 | 99* | 3.56 | 89 | 3.11 | |
0.100 | 89* | 4.20 | 79 | 2.20 | ||
0.500 | 88 | 3.43 | 84 | 3.41 | ||
153Eu | 0.050 | 95 | 3.52 | 92 | 4.20 | |
0.100 | 90 | 3.41 | 89 | 2.33 | ||
0.500 | 90* | 1.78 | 79 | 2.44 | ||
69Ga | 1.00 | 100* | 3.11 | 90 | 3.32 | |
5.00 | 92 | 1.41 | 97 | 2.42 | ||
10.0 | 91 | 1.89 | 93 | 1.93 | ||
158Gd | 0.050 | 108* | 4.08 | 98 | 4.27 | |
0.100 | 91 | 5.41 | 89 | 4.37 | ||
0.500 | 90 | 1.78 | 90 | 1.32 | ||
74Ge | 0.050 | 91 | 1.51 | 87 | 2.45 | |
0.100 | 93* | 2.89 | 83 | 4.44 | ||
0.500 | 89 | 4.39 | 85 | 3.42 | ||
180Hf | 0.100 | 85* | 1.61 | 80 | 2.56 | |
0.200 | 81* | 4.11 | 87 | 4.32 | ||
1.00 | 97* | 3.41 | 82 | 4.42 | ||
165Ho | 0.050 | 97 | 3.89 | 88 | 3.22 | |
0.100 | 83 | 4.38 | 80 | 3.42 | ||
0.500 | 90 | 2.12 | 87 | 3.89 | ||
139La | 0.100 | 91* | 1.78 | 87 | 2.78 | |
0.200 | 96* | 3.13 | 86 | 3.56 | ||
1.00 | 85 | 2.89 | 87 | 3.78 | ||
175Lu | 0.050 | 90 | 5.61 | 88 | 4.43 | |
0.100 | 98* | 4.12 | 88 | 3.61 | ||
0.500 | 88 | 2.11 | 82 | 3.52 | ||
142Nd | 0.050 | 116* | 0.717 | 108 | 1.73 | |
0.100 | 88 | 2.02 | 80 | 4.03 | ||
0.500 | 91* | 2.08 | 89 | 2.89 | ||
192Os | 0.050 | 89* | 5.63 | 76 | 3.43 | |
0.100 | 88* | 3.09 | 79 | 2.14 | ||
0.500 | 82 | 3.52 | 80 | 4.31 | ||
141Pr | 0.050 | 98* | 3.06 | 78 | 3.32 | |
0.100 | 81 | 5.11 | 77 | 4.10 | ||
0.500 | 88 | 2.83 | 76 | 3.80 | ||
195Pt | 0.050 | 99 | 4.22 | 98 | 3.29 | |
0.100 | 83 | 5.21 | 83 | 5.53 | ||
0.500 | 85 | 2.17 | 83 | 2.52 | ||
187Re | 0.050 | 98* | 4.24 | 88 | 5.20 | |
0.100 | 80 | 2.70 | 79 | 3.74 | ||
0.500 | 87* | 1.53 | 80 | 3.51 | ||
103Rh | 0.050 | 109* | 5.45 | 90 | 6.37 | |
0.100 | 82 | 3.67 | 80 | 4.44 | ||
0.500 | 86 | 0.635 | 88 | 2.62 | ||
102Ru | 0.050 | 104* | 3.67 | 84 | 4.78 | |
0.100 | 93* | 4.70 | 76 | 4.34 | ||
0.500 | 87* | 3.51 | 75 | 2.62 | ||
45Sc | 1.00 | 98* | 4.13 | 89 | 4.08 | |
5.00 | 105 | 1.63 | 102 | 3.62 | ||
10.0 | 86* | 3.12 | 96 | 3.07 | ||
152Sm | 0.050 | 126* | 4.14 | 110 | 6.28 | |
0.100 | 97* | 2.33 | 87 | 2.43 | ||
0.500 | 90* | 5.31 | 79 | 4.32 | ||
181Ta | 0.050 | 89* | 2.84 | 79 | 3.67 | |
0.100 | 90* | 4.30 | 74 | 4.51 | ||
0.500 | 87* | 0.515 | 78 | 4.46 | ||
159Tb | 0.050 | 89* | 1.30 | 80 | 3.31 | |
0.100 | 81 | 3.91 | 78 | 3.78 | ||
0.500 | 85* | 0.697 | 75 | 1.52 | ||
169Tm | 0.050 | 91* | 3.30 | 79 | 4.23 | |
0.100 | 80 | 2.89 | 81 | 3.21 | ||
0.500 | 88* | 0.927 | 82 | 2.89 | ||
184W | 0.050 | 108* | 3.60 | 98 | 3.92 | |
0.100 | 96 | 3.04 | 93 | 3.67 | ||
0.500 | 97* | 1.90 | 83 | 2.22 | ||
174Yb | 0.050 | 108* | 3.54 | 99 | 5.16 | |
0.100 | 82 | 3.78 | 79 | 3.59 | ||
0.500 | 89* | 0.633 | 80 | 2.60 | ||
90Zr | 1.00 | 88* | 1.44 | 98 | 2.21 | |
5.00 | 102* | 2.08 | 92 | 2.56 | ||
10.0 | 103* | 1.34 | 93 | 3.28 |
注:上标“*”表示在同一添加水平上微波消解与湿法消解回收率之间的差异达到显著水平(P < 0.05)。
表4 不同产区葡萄酒中各元素质量浓度
Table 4 The concentration of each element in wine from different wine producing regions
元素 Element | 河西走廊 Hexi Corridor (μg/L) | 西南高山 Southwest Highland (μg/L) | 延怀河谷 Yanhuai Valley (μg/L) |
197Au | ND | ND | ND |
140Ce | 0.129 ± 0.099a | 0.141 ± 0.121a | 0.128 ± 0.123a |
133Cs | 0.864 ± 0.351a | 10.8 ± 11.7b | 4.54 ± 2.70ab |
164Dy | 0.023 ± 0.021a | 0.014 ± 0.015a | 0.013 ± 0.015a |
166Er | 0.019 ± 0.013a | 0.011 ± 0.009a | 0.012 ± 0.011a |
153Eu | 0.026 ± 0.010a | 0.028 ± 0.011a | 0.024 ± 0.005a |
69Ga | 2.49 ± 0.918a | 2.83 ± 1.07a | 2.29 ± 0.437a |
158Gd | 0.024 ± 0.024a | 0.016 ± 0.017a | 0.012 ± 0.015a* |
74Ge | ND | ND | ND |
180Hf | 0.029 ± 0.021a* | 0.036 ± 0.038a* | 0.022 ± 0.017a* |
165Ho | 0.006 ± 0.005a | 0.003 ± 0.003a* | 0.003 ± 0.004a* |
139La | 0.147 ± 0.251a | 0.066 ± 0.065a | 0.040 ± 0.040a |
175Lu | 0.005 ± 0.003b* | 0.003 ± 0.002a* | 0.004 ± 0.003ab* |
142Nd | 0.062 ± 0.060a | 0.055 ± 0.061a | 0.036 ± 0.043a* |
192Os | ND | ND | ND |
141Pr | 0.015 ± 0.013a | 0.013 ± 0.015a | 0.009 ± 0.009a* |
195Pt | ND | ND | ND |
187Re | 0.026 ± 0.005c | 0.012 ± 0.007a* | 0.018 ± 0.003b |
103Rh | 0.063 ± 0.014b | 0.042 ± 0.014a | 0.051 ± 0.011ab |
102Ru | ND | ND | ND |
45Sc | 45.7 ± 9.85a | 42.2 ± 14.3a | 48.1 ± 16.1a |
152Sm | 0.050 ± 0.027a | 0.052 ± 0.029a | 0.040 ± 0.012a |
181Ta | ND | ND | ND |
159Tb | 0.004 ± 0.003* | ND | ND |
169Tm | 0.003 ± 0.002a | 0.002 ± 0.002a* | 0.002 ± 0.002a* |
184W | 0.184 ± 0.141a | 0.311 ± 0.203a | 0.194 ± 0.046a |
174Yb | 0.029 ± 0.017b | 0.014 ± 0.010a* | 0.021 ± 0.016ab |
90Zr | 1.69 ± 1.26a | 1.68 ± 0.896a | 1.55 ± 0.839a |
注:(1)表中数据均为平均值 ± 标准偏差,每个产区样品数量n = 10,不同小写字母表示有显著性差异(P < 0.05);(2)ND表示结果低于检测限,没有检出;(3)上标“*”表示结果高于检出限但低于定量限,为估计值。