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葡萄酒中稀土元素的测定

食品重金属及有害元素检测

  • 葡萄酒中稀土元素的测定



    摘要:选用三种典型葡萄酒(红葡萄酒、白葡萄酒和起泡酒),采用湿法消解进行样品前处理,用ICP-MS对其中的稀土元素进行测定,各元素的检出限分别为La 0.0028 μg/L、Ce0.0034μg/L、Y 0.0018 μg/L、Pr 0.0010 μg/L、Nd 0.0037 μg/L、Sm 0.0026 μg/L、Eu 0.0009 μg/L、Gd 0.0019 μg/L、Tb 0.0004 μg/L、Dy 0.0011 μg/L、Ho 0.0003 μg/L、Er 0.0012 μg/L、Tm 0.0003 μg/L、Yb 0.0010 μg/L、Lu 0.0003 μg/L、Ge 0.0065 μg/L、Sc 0.2431 μg/L,三类葡萄酒样品进行三个水平添加回收率在92.0%-106.3%之间;相对标准偏差在0.49%-8.60%之间。本方法快速准确,可用于葡萄酒稀土元素的测定。
    关键词:葡萄酒稀土 ICP-MS
    稀土元素是指元素周期表中原子序数57-71的15种元素以及钪(Sc)和钇(Y)共17种元素。我国是稀土储藏、生产及应用大国,葡萄种植土壤中会有一定量的稀土元素,同时由于稀土元素对植物的生长具有促进作用,被广泛运用到种植业,通过植物迁移作用,进入到植物体内,葡萄酒通过葡萄酿制而成,酿酒葡萄受到品种、土壤、气候以及所施肥料的影响,其元素特性会迁入到葡萄酒中,再加上葡萄酒的酿制过程需要用到硅藻土等,也会带进无机元素,有研究表明葡萄酒中稀土元素含量具有表征其地理标志的作用。
    随着电感耦合等离子体质谱仪不断迅速发展,凭借其背景低,灵敏度高的特点,样品经直接消解进入检测系统,不需要富集分离就可达到ppd级的检出限,在稀土元素的检测中独居鳌头,难以替代。我们在葡萄酒的检测过程中研究建立了葡萄酒稀土检测的电感耦合等离子体质谱法,不仅能为葡萄酒中影响人体健康的稀土元素含量提供有效的检测结果,同时检测结果还可以为葡萄酒地理标志乃至于甄别其真假提供数据依据。
    实验部分
    1、 实验材料
    1.1 葡萄酒样品 市售红葡萄酒、白葡萄酒、起泡酒
    1.2 试剂:硝酸(优级纯);
    稀土元素标准溶液(100mg/L)(加拿大SCP分公司)
    铑元素标准储备液(1000mg/L)(加拿大SCP分公司)
    1.3 仪器:电感耦合等离子体质谱仪ELAN DRC-e美国PE公司
    2方法的建立
    2.1前处理方法的选择及优化
    2.1.1消解方式的选择
    参考相关葡萄酒元素测定以及植物性食品稀土元素检测的样品处理方式,针对葡萄酒含有酒精和其他有机质的特点,主要是从消除酒精,消化有机质两方面重点切入。参照葡萄酒中元素检测的前处理方法(GB/T15038-2006 葡萄酒、果酒通用分析方法中铜、铁测定的处理方法,直接稀释法和酸消解法,通过实验我们发现由于葡萄酒基质的影响,直接酸稀释法检测结果不稳定,加标回收率也不理想,如果采用基质匹配法配制标准溶液,难以找到合适的基质,特别是其中的有机质容易在锥上积碳影响仪器的使用寿命和检测的稳定性,选用酸消解法进行样品前处理,结果非常理想,基本消除了基质的影响。(见表1)。
    表1 直接酸稀释进样检测和酸消解进样检测结果

    直接酸稀释进样检测

    元素

    1

    2

    3

    4

    5

    平均值

    回收率%

    RSD%

    La

    9.15

    8.78

    9.04

    8.35

    8.92

    8.85

    83.33

    3.5

    Ce

    9.78

    9.54

    9.77

    8.92

    9.74

    9.55

    85.21

    3.83

    Y

    10.37

    11.12

    11.50

    11.57

    11.39

    11.19

    100.4

    3.35

    Pr

    8.70

    8.56

    8.82

    8.03

    8.70

    8.56

    84.49

    3.65

    Nd

    9.16

    8.94

    9.04

    8.58

    9.27

    9.00

    85.19

    2.94

    Sm

    9.13

    8.82

    9.06

    8.23

    8.74

    8.79

    85.42

    4.05

    Eu

    8.64

    8.70

    8.72

    8.16

    8.71

    8.51

    85.07

    2.79

    Gd

    9.29

    8.37

    9.18

    8.61

    9.33

    9.05

    89.12

    3.47

    Tb

    9.20

    8.96

    9.18

    8.43

    9.17

    8.99

    89.74

    3.61

    Dy

    9.01

    8.84

    9.21

    8.37

    9.21

    8.93

    87.94

    3.90

    Ho

    9.16

    9.13

    9.26

    8.51

    9.28

    9.07

    90.43

    3.51

    Er

    9.76

    9.32

    9.64

    8.89

    9.54

    9.28

    92.84

    3.23

    Tm

    9.34

    9.15

    9.38

    8.66

    9.43

    9.16

    91.56

    3.32

    Yb

    9.61

    9.31

    9.37

    8.73

    9.47

    9.13

    91.29

    3.32

    Lu

    9.44

    9.22

    9.29

    8.81

    9.41

    9.19

    91.88

    2.47

    Ge

    12.01

    11.67

    12.05

    11.05

    11.59

    11.47

    114.71

    3.38

    Sc

    64.6

    64.01

    62.67

    57.32

    61.71

    10.13

    101.33

    28.46

    酸消解进样检测

    元素

    1

    2

    3

    4

    5

    平均值

    回收率%

    RSD%

    La

    9.93

    10.27

    10.62

    10.37

    10.36

    10.31

    95.74

    2.41

    Ce

    11.03

    11.24

    10.51

    11.37

    10.95

    11.02

    95.43

    2.97

    Y

    10.98

    11.21

    11.03

    11.28

    11.38

    11.18

    99.82

    1.51

    Pr

    9.90

    9.94

    10.11

    10.13

    10.25

    10.06

    98.95

    1.44

    Nd

    9.85

    10.29

    10.23

    10.16

    10.31

    10.13

    95.28

    1.83

    Sm

    9.81

    10.12

    10.31

    10.20

    10.14

    10.17

    98.85

    1.84

    Eu

    9.67

    9.97

    9.85

    10.00

    9.56

    9.81

    97.49

    1.92

    Gd

    9.75

    10.15

    10.11

    10.32

    9.99

    10.06

    98.90

    2.11

    Tb

    9.86

    10.28

    10.26

    9.92

    10.08

    10.08

    100.46

    1.88

    Dy

    10.33

    10.48

    10.31

    10.12

    10.20

    10.29

    101.17

    0.135

    Ho

    9.68

    10.22

    10.13

    10.04

    9.84

    9.98

    99.44

    2.22

    Er

    9.83

    10.39

    9.96

    10.02

    10.13

    10.07

    99.27

    2.10

    Tm

    9.84

    10.04

    10.04

    9.97

    10.00

    9.98

    99.55

    0.85

    Yb

    9.36

    9.88

    9.84

    9.92

    10.02

    9.80

    96.52

    2.61

    Lu

    9.80

    10.06

    10.08

    10.09

    10.04

    10.01

    99.85

    1.24

    Ge

    9.31

    9.40

    9.80

    9.56

    9.50

    9.51

    95.00

    1.94

    Sc

    8.91

    9.74

    9.84

    9.15

    9.30

    9.39

    93.88

    4.19


    2.1.2消解试剂的选择
    参照GB 5009.94-2012 植物性食品中稀土元素的测定中样品处理方法,结合葡萄酒的特殊性,如果直接用酸进行消解,由于酒精的存在,会使反应异常剧烈,因此我们选择在100℃(酒精沸点78.3℃)进行低温加热挥发,待溶液挥发三分之二后,冷却加酸消解。
    硝酸是一种强氧化性酸,为食品无机分析最主要的消解试剂,可以有效的分解大多数食品样品,目前成为较好的食品消解试剂,同时,由于其产生的质谱干扰小,被认为是ICP-MS分析最好的酸介质,因此,我们选取硝酸作为消解酸。检测中未发现酸介质干扰。
    2.4 消解试剂用量的选择
    我们本着保证完全消解样品,尽量减少消解试剂用量的原则,结合其他方法选用的试剂用量,分别选取0mL、3mL、5mL、8mL和10mL对添加量10μg/L的样品进行进行实验,结果见表2。
    表2 硝酸用量对检测的影响

    元素

    硝酸用量

    红葡萄酒

    白葡萄酒

    起泡酒

    含量(μg/L)

    回收率

    含量(μg/L)

    回收率

    含量(μg/L)

    回收率

    La

    0mL

    9.021

    82.8

    9.211

    83.1

    10.27

    94.4

    3mL

    10.551

    98.1

    11.023

    101.2

    10.87

    100.4

    5mL

    10.362

    96.2

    11.017

    101.2

    10.726

    99.0

    8mL

    10.246

    95.1

    10.989

    100.9

    10.753

    99.2

    10mL

    10.328

    95.9

    10.966

    100.7

    10.733

    99.0

    Ce

    0mL

    10.311

    88.3

    10.16

    79.3

    10.98

    92.2

    3mL

    11.385

    99.1

    12.135

    99.1

    11.373

    96.1

    5mL

    11.274

    97.9

    12.126

    99.0

    11.59

    98.3

    8mL

    11.032

    95.5

    12.093

    98.6

    11.663

    99.0

    10mL

    11.221

    97.4

    12.119

    98.9

    11.594

    98.3

    Y

    0mL

    10.349

    91.6

    12.55

    105.1

    11.72

    101.4

    3mL

    10.922

    97.3

    12.101

    100.6

    11.692

    101.1

    5mL

    10.857

    96.7

    12.028

    99.9

    11.523

    99.4

    8mL

    10.963

    97.7

    12.022

    99.8

    11.533

    99.5

    10mL

    10.951

    97.6

    12.029

    99.9

    11.551

    99.7

    Pr

    0mL

    8.611

    78.7

    8.89

    79.9

    9.77

    95.7

    3mL

    9.090

    83.5

    9.976

    90.8

    10.052

    98.5

    5mL

    10.142

    94.0

    10.017

    91.2

    10.036

    98.4

    8mL

    10.287

    95.5

    10.023

    91.2

    10.044

    98.4

    10mL

    10.203

    94.6

    10.019

    91.2

    10.029

    98.3

    Nd

    0mL

    9.541

    89.2

    9.541

    84.6

    10.217

    93.7

    3mL

    10.444

    98.2

    11.034

    99.5

    10.454

    96.0

    5mL

    10.536

    99.2

    11.062

    99.8

    10.615

    97.7

    8mL

    10.623

    100.0

    11.073

    99.9

    10.739

    98.9

    10mL

    10.579

    99.6

    11.029

    99.5

    10.626

    97.8

    Sm

    0mL

    9.342

    91.1

    9.032

    87.6

    8.891

    86.9

    3mL

    10.521

    102.9

    10.033

    97.6

    9.799

    96.0

    5mL

    10.090

    98.6

    10.124

    98.5

    9.853

    96.5

    8mL

    10.111

    98.8

    10.372

    101.0

    9.692

    94.9

    10mL

    10.185

    99.6

    10.195

    99.3

    9.781

    95.8

    Eu

    0mL

    8.864

    88.0

    8.793

    87.4

    9.581

    92.4

    3mL

    10.020

    99.6

    9.798

    97.5

    10.011

    96.7

    5mL

    10.070

    100.1

    9.664

    96.1

    9.969

    96.3

    8mL

    10.110

    100.5

    9.821

    97.7

    9.953

    96.1

    10mL

    9.560

    95.0

    9.563

    95.1

    9.972

    96.3

    Gd

    0mL

    9.560

    93.8

    9.62

    93.3

    9.38

    91.3

    3mL

    10.230

    100.5

    10.176

    98.9

    10.126

    98.8

    5mL

    10.090

    99.1

    10.126

    98.4

    10.098

    98.5

    8mL

    10.170

    99.9

    10.203

    99.1

    10.158

    99.1

    10mL

    10.380

    102.0

    10.225

    99.4

    10.244

    99.9

    Tb

    0mL

    9.150

    91.2

    8.376

    83.4

    8.011

    79.9

    3mL

    10.270

    102.4

    10.008

    99.7

    9.852

    98.3

    5mL

    10.190

    101.6

    9.793

    97.5

    9.962

    99.4

    8mL

    10.130

    101.0

    9.991

    99.5

    9.754

    97.3

    10mL

    10.050

    100.2

    9.855

    98.2

    9.822

    98.0

    Dy

    0mL

    9.140

    89.7

    9.69

    94.1

    9.25

    90.4

    3mL

    10.570

    104.0

    10.191

    99.1

    10.199

    99.9

    5mL

    10.460

    102.9

    10.232

    99.5

    10.18

    99.7

    8mL

    10.330

    101.6

    10.263

    99.8

    10.262

    100.5

    10mL

    10.450

    102.8

    10.241

    99.6

    10.269

    100.6

    Ho

    0mL

    9.100

    90.6

    9.522

    94.6

    9.181

    91.4

    3mL

    10.210

    101.7

    10.021

    99.6

    10.008

    99.7

    5mL

    10.100

    100.6

    10.173

    101.1

    10.026

    99.9

    8mL

    10.150

    101.1

    10.192

    101.3

    10.031

    99.9

    10mL

    10.060

    100.2

    10.202

    101.4

    10.028

    99.9

    Er

    0mL

    9.150

    90.1

    9.79

    95.5

    9.38

    92.2

    3mL

    10.120

    99.8

    10.185

    99.5

    10.091

    99.3

    5mL

    10.050

    99.1

    10.199

    99.6

    10.122

    99.6

    8mL

    9.870

    97.3

    10.204

    99.6

    10.131

    99.7

    10mL

    10.000

    98.6

    10.115

    98.8

    10.155

    100.0

    Tm

    0mL

    9.110

    90.9

    9.6

    95.7

    9.25

    92.3

    3mL

    10.200

    101.8

    9.973

    99.4

    10.003

    99.8

    5mL

    9.970

    99.5

    10.021

    99.9

    9.945

    99.3

    8mL

    9.880

    98.6

    10.121

    100.9

    9.765

    97.5

    10mL

    9.930

    99.1

    10.104

    100.7

    9.832

    98.1

    Yb

    0mL

    9.020

    88.6

    9.5

    91.8

    9.26

    90.4

    3mL

    10.020

    98.6

    9.983

    96.6

    9.823

    96.0

    5mL

    9.860

    97.0

    10.155

    98.4

    9.996

    97.8

    8mL

    9.950

    97.9

    10.282

    99.6

    10.125

    99.1

    10mL

    9.830

    96.7

    10.102

    97.8

    10.062

    98.4

    Lu

    0mL

    9.216

    91.9

    9.135

    91.0

    9.28

    92.5

    3mL

    9.750

    97.2

    9.936

    99.0

    10.002

    99.7

    5mL

    10.037

    100.1

    9.821

    97.8

    9.933

    99.0

    8mL

    10.063

    100.3

    9.885

    98.5

    9.985

    99.6

    10mL

    10.131

    101.0

    10.011

    99.7

    9.878

    98.5

    Ge

    0mL

    8.943

    89.2

    9.54

    93.8

    9.24

    90.0

    3mL

    9.667

    96.5

    10.083

    99.2

    10.255

    100.2

    5mL

    9.770

    97.5

    9.992

    98.3

    10.236

    100.0

    8mL

    9.823

    98.0

    10.122

    99.6

    10.139

    99.0

    10mL

    9.452

    94.3

    10.093

    99.3

    10.131

    98.9

    Sc

    0mL

    60.230

    基体干扰大

    56.69

    基体干扰大

    61.91

    基体干扰大

    3mL

    9.537

    95.4

    16.047

    110.4

    12.239

    101.4

    5mL

    9.862

    98.6

    15.136

    101.3

    12.011

    99.1

    8mL

    9.655

    96.6

    15.063

    100.5

    12.025

    99.3

    10mL

    9.780

    97.8

    15.069

    100.6

    12.113

    100.1


    从实验中可以看出,不加入酸,检测回收率差于加酸消解,3-10mL硝酸量相对于本实验选取的样品,回收率影响不大,通过本实验结合其他标准方法选取的消解试剂用量,我们选取5mL硝酸作为消解样品消解液的用量。酒精挥发酸消解相对于有文献报道的微波消解方法,我们认为更具安全性,在时效上也不输于微波消解法,是一种更经济适用的样品处理方法。通过实验证明,方法的回收率和稳定性都非常理想。
    3.1仪器测定条件
    按照仪器操作规程用多元素调谐液优化仪器,使其背景值、稳定性、氧化物、双电荷、灵敏度、分辨率等参数达到仪器要求。
    使用稀土标准溶液优化雾化器流量、RF功率。我们使用的仪器分析条件为射频功率1500W;等离子气流量载气流量为0.94L/min;辅助器流量为1.2L/min;等离子气流量为15L/min,;透镜电压5.5V,采样流量0.8mL/min。
    3.2 基体干扰及消除
    机体干扰主要来源于样品的机体,对待测元素产生增强或抑制作用,产生系统偏差。选择适当的内标元素能有效的克服机体效应,内标元素选择我们遵循:样品中不含的元素;不受样品中基体及分析物的干扰;与待测元素质量相近电离能相近原则。在常作为内标元素的元素中我们选取Rh 的质量数为103电离能为719.7与大部分稀土元素质量数和电离能相近,作为内标元素。
    4方法的线性范围、回归方程与定量限
    4.1线性范围和回归方程和方法的定量限
    将仪器调整至最佳状态,分别测定空白溶液、标准系列溶液(0μg/L、0.5μg/L、1.0μg/L、2.0μg/L、5.0μg/L、10.0μg/L、25.0μg/L、50.0μg/L)得到线性方程的相关系数、检出限、定量限。其中检出限为实际流程空白连续测定10次的响应值3倍标准偏差所对应的的浓度值,定量限为10倍标准偏差对应的浓度值(见表3)。
    表3 线性范围、相关系数、检出限

    元素

    线性范围(μg/L)

    相关系数

    溶液检出限μg/L

    溶液定量限μg/L

    139La

    0-50

    0.999941

    0.0028

    0.01

    140Ce

    0-50

    0.999986

    0.0034

    0.01

    89Y

    0-50

    0.999931

    0.0018

    0.01

    141Pr

    0-50

    0.999951

    0.0010

    0.01

    142Nd

    0-50

    0.999883

    0.0037

    0.01

    152Sm

    0-50

    0.999739

    0.0026

    0.01

    153Eu

    0-50

    0.999913

    0.0009

    0.01

    158Gd

    0-50

    0.999949

    0.0019

    0.01

    159Tb

    0-50

    0.999899

    0.0004

    0.01

    164Dy

    0-50

    0.999920

    0.0011

    0.01

    165Ho

    0-50

    0.999891

    0.0003

    0.01

    166Er

    0-50

    0.999935

    0.0012

    0.01

    169Tm

    0-50

    0.999923

    0.0003

    0.01

    174Yb

    0-50

    0.999960

    0.0010

    0.01

    175Lu

    0-50

    0.999851

    0.0003

    0.01

    74Ge

    0-50

    0.999899

    0.0065

    0.02

    45Sc

    0-50

    0.999793

    0.2431

    1.00


    方法的定量限由溶液定量限以及样品取样量和最后稀释体积计算得出。
    4.3检测方法精密度和回收率验证
    采用三类样品加标回收来考察方法的准确性,每个加标水平平行测定10次考察方法的精密度,检验结果见表4。三类所有元素三个添加水平的回收率平均值在92.0%-106.3%之间;相对标准偏差在0.49%-8.60%之间。
    表4 -1红葡萄酒加标回收和精密度实验

    0.

    3

    元素

    样品

    添加水平

    1(μg/L)

    10(μg/L)

    40(μg/L)

    测定值

    测定值

    回收率

    测定值

    回收率

    测定值

    回收率

    La

    0.725

    1.712

    97.4

    10.576

    98.4

    40.694

    99.9

    0.784

    1.800

    106.2

    11.012

    102.7

    40.704

    99.9

    0.692

    1.756

    101.8

    11.460

    107.2

    41.710

    102.4

    0.676

    1.722

    98.4

    11.371

    106.3

    40.952

    100.5

    0.800

    1.703

    106.5

    11.303

    105.6

    40.167

    98.6

    0.736

    1.795

    105.7

    11.116

    103.7

    41.021

    100.7

    0.729

    1.753

    101.5

    10.940

    102.1

    39.663

    97.3

    0.736

    1.713

    97.5

    10.763

    100.2

    39.434

    96.7

    0.745

    1.783

    104.5

    10.895

    101.5

    39.772

    97.6

    0.755

    1.755

    101.7

    10.722

    99.9

    39.567

    97.1

    平均值

    0.738

    1.789

    102.1

    11.016

    102.8

    40.368

    99.1

    RSD%

    2.28

    2.66

    1.88

    Ce

    1.524

    2.456

    97.6

    11.18

    97.0

    39.872

    96.0

    1.476

    2.552

    107.2

    11.624

    101.4

    38.872

    93.5

    1.384

    2.572

    109.2

    11.912

    104.3

    40.056

    96.4

    1.536

    2.577

    109.7

    11.823

    103.4

    39.962

    96.2

    1.564

    2.473

    99.3

    11.767

    102.9

    39.933

    96.1

    1.502

    2.601

    112.1

    11.441

    99.6

    39.858

    95.9

    1.535

    2.581

    110.1

    11.502

    100.2

    39.776

    95.7

    1.503

    2.532

    105.2

    11.322

    98.4

    39.895

    96.0

    1.428

    2.538

    105.8

    11.531

    100.5

    39.622

    95.4

    1.352

    2.522

    104.2

    11.620

    101.4

    39.599

    95.3

    平均值

    1.480

    2.560

    106.2

    11.572

    100.9

    39.745

    95.7

    RSD%

    2.46

    1.96

    0.85

    Y

    1.272

    2.124

    93.0

    11.116

    99.2

    40.634

    98.6

    1.176

    2.196

    100.2

    11.748

    105.5

    39.632

    96.1

    1.168

    2.336

    114.2

    11.58

    103.9

    40.744

    98.9

    1.160

    2.253

    105.9

    11.597

    104.0

    39.693

    96.2

    1.132

    2.265

    107.1

    11.466

    102.7

    39.701

    96.3

    1.179

    2.167

    97.3

    11.325

    101.3

    40.557

    98.4

    1.236

    2.199

    100.5

    11.202

    100.1

    40.622

    98.6

    1.193

    2.148

    95.4

    11.684

    104.9

    40.456

    98.1

    1.216

    2.235

    104.1

    11.529

    103.3

    39.852

    96.6

    1.203

    2.263

    106.9

    11.561

    103.8

    40.236

    97.6

    平均值

    1.194

    2.219

    102.5

    11.481

    102.9

    40.213

    97.5

    RSD%

    2.88

    1.79

    1.11

    Pr

    0.168

    1.152

    98.4

    9.860

    96.9

    39.264

    97.7

    0.168

    1.208

    104

    10.180

    100.1

    38.396

    95.6

    0.156

    1.252

    108.4

    10.576

    104.1

    39.668

    98.8

    0.180

    1.283

    111.5

    10.366

    102.0

    39.785

    99.0

    0.160

    1.291

    112.3

    10.323

    101.6

    39.996

    99.6

    0.173

    1.188

    102.0

    10.115

    99.5

    40.037

    99.7

    0.179

    1.181

    101.3

    10.173

    100.1

    40.122

    99.9

    0.168

    1.175

    100.7

    10.028

    98.6

    39.237

    97.7

    0.155

    1.163

    99.5

    9.965

    98.0

    39.899

    99.3

    0.168

    1.204

    103.6

    10.205

    100.4

    39.109

    97.4

    平均值

    0.168

    1.210

    104.2

    10.179

    100.1

    39.551

    98.5

    RSD%

    4.07

    2.04

    1.38

    Nd

    0.660

    1.576

    95.5

    10.292

    96.7

    39.016

    96.0

    0.644

    1.56

    93.9

    10.928

    103.1

    38.528

    94.8

    0.624

    1.696

    107.5

    10.872

    102.5

    39.264

    96.6

    0.632

    1.655

    103.4

    10.697

    100.8

    39.736

    97.8

    0.536

    1.693

    107.2

    10.736

    101.2

    39.569

    97.4

    0.622

    1.576

    95.5

    10.885

    102.6

    39.245

    96.6

    0.597

    1.593

    97.2

    10.264

    96.4

    38.994

    95.9

    0.603

    1.498

    87.7

    10.794

    101.7

    39.982

    98.4

    0.647

    1.594

    97.3

    10.362

    97.4

    39.391

    96.9

    0.640

    1.611

    99.0

    10.697

    100.8

    38.936

    95.8

    平均值

    0.621

    1.605

    98.4

    10.653

    100.3

    39.266

    96.6

    RSD%

    3.83

    2.37

    1.08

    Sm

    0.224

    1.224

    99.2

    10.040

    98.1

    38.463

    95.6

    0.236

    1.188

    95.6

    10.352

    101.2

    37.629

    93.5

    0.200

    1.288

    105.6

    10.540

    103.1

    38.794

    96.4

    0.264

    1.233

    100.1

    10.311

    100.8

    39.262

    97.6

    0.252

    1.262

    103.0

    10.326

    100.9

    39.553

    98.3

    0.232

    1.306

    107.4

    10.175

    99.4

    39.765

    98.8

    0.248

    1.119

    88.7

    10.239

    100.1

    39.331

    97.7

    0.217

    1.169

    93.7

    10.463

    102.3

    38.545

    95.8

    0.211

    1.230

    99.8

    10.174

    99.4

    38.465

    95.6

    0.231

    1.233

    100.1

    10.311

    100.8

    38.328

    95.2

    平均值

    0.232

    1.225

    99.3

    10.293

    100.6

    38.814

    96.5

    RSD%

    4.54

    1.41

    1.69

    Eu

    0.072

    1.108

    104.5

    9.736

    96.7

    39.42

    98.4

    0.068

    1.092

    102.9

    10.032

    99.7

    38.852

    97.0

    0.056

    1.120

    105.7

    9.916

    98.5

    39.356

    98.2

    0.056

    1.102

    103.9

    9.895

    98.3

    38.876

    97.0

    0.060

    1.092

    102.9

    9.996

    99.3

    38.667

    96.5

    0.065

    1.085

    102.2

    9.945

    98.8

    38.974

    97.3

    0.063

    1.099

    103.6

    10.009

    99.5

    39.221

    97.9

    0.059

    1.107

    104.4

    10.022

    99.6

    39.376

    98.3

    0.065

    1.111

    104.8

    10.053

    99.9

    39.152

    97.7

    0.070

    1.062

    99.9

    9.798

    97.4

    38.262

    95.5

    平均值

    0.063

    1.098

    103.5

    9.940

    98.8

    39.016

    97.4

    RSD%

    1.48

    1.06

    0.94

    Gd

    0.172

    1.196

    101.6

    9.924

    97.4

    39.168

    97.5

    0.176

    1.204

    102.4

    10.32

    101.4

    38.792

    96.5

    0.156

    1.192

    101.2

    10.288

    101.1

    39.332

    97.9

    0.192

    1.197

    101.7

    10.177

    100.0

    39.097

    97.3

    0.206

    1.189

    100.9

    10.105

    99.3

    39.665

    98.7

    0.195

    1.178

    99.8

    10.112

    99.3

    39.926

    99.4

    0.186

    1.193

    101.3

    10.096

    99.2

    39.453

    98.2

    0.178

    1.165

    98.5

    10.052

    98.7

    39.282

    97.8

    0.169

    1.21

    103.0

    10.136

    99.6

    38.955

    96.9

    0.174

    1.197

    101.7

    10.177

    100.0

    39.097

    97.3

    平均值

    0.180

    1.192

    101.2

    10.139

    99.6

    39.277

    97.7

    RSD%

    1.07

    1.12

    0.86

    Tb

    0.032

    1.016

    98.4

    9.892

    98.6

    39.116

    97.7

    0.036

    1.036

    100.4

    10.312

    102.8

    37.576

    93.8

    0.032

    1.108

    107.6

    10.288

    102.6

    39.492

    98.6

    0.032

    1.042

    101.0

    10.160

    101.3

    38.728

    96.7

    0.028

    1.053

    102.1

    10.055

    100.2

    38.662

    96.6

    0.037

    1.072

    104.0

    10.017

    99.9

    38.451

    96.0

    0.029

    1.044

    101.2

    10.561

    105.3

    38.785

    96.9

    0.035

    1.021

    98.9

    10.688

    106.6

    38.412

    95.9

    0.033

    1.036

    100.4

    10.028

    100.0

    39.262

    98.1

    0.029

    1.102

    107.0

    9.795

    97.6

    38.565

    96.3

    平均值

    0.032

    1.053

    102.1

    10.180

    101.5

    38.705

    96.7

    RSD%

    3.00

    2.80

    1.38

    Dy

    0.148

    1.240

    107.4

    10.504

    103.4

    40.039

    99.7

    0.180

    1.240

    107.4

    10.652

    104.9

    39.672

    98.8

    0.168

    1.248

    108.2

    10.480

    103.1

    39.960

    99.5

    0.192

    1.243

    107.7

    10.535

    103.7

    39.899

    99.3

    0.148

    1.252

    108.6

    10.526

    103.6

    39.388

    98.1

    0.163

    1.251

    108.5

    10.497

    103.3

    39.545

    98.4

    0.156

    1.264

    109.8

    10.433

    102.7

    39.852

    99.2

    0.162

    1.282

    111.6

    10.520

    103.5

    39.876

    99.3

    0.175

    1.236

    107.0

    10.531

    103.7

    39.774

    99.0

    0.172

    1.233

    106.7

    10.62

    104.5

    39.982

    99.5

    平均值

    0.166

    1.249

    108.3

    10.530

    103.6

    39.799

    99.1

    RSD%

    1.18

    0.58

    0.49

    Ho

    0.04

    1.068

    102.7

    9.72

    96.8

    39.904

    99.7

    0.04

    1.06

    101.9

    10.264

    102.2

    38.932

    97.2

    0.04

    1.096

    105.5

    10.172

    101.3

    39.736

    99.2

    0.036

    1.085

    104.4

    10.092

    100.5

    39.224

    98.0

    0.044

    1.08

    103.9

    10.085

    100.4

    39.392

    98.4

    0.042

    1.077

    103.6

    10.117

    100.8

    38.736

    96.7

    0.041

    1.072

    103.1

    10.231

    101.9

    38.958

    97.3

    0.045

    1.064

    102.3

    10.005

    99.6

    39.285

    98.1

    0.041

    1.059

    101.8

    9.956

    99.2

    39.753

    99.3

    0.037

    1.066

    102.5

    9.785

    97.4

    39.262

    98.0

    平均值

    0.041

    1.073

    103.2

    10.043

    100.0

    39.318

    98.2

    RSD%

    1.10

    1.70

    0.93

    Er

    0.128

    1.116

    97.3

    9.968

    98.25

    39.948

    99.5

    0.152

    1.220

    107.7

    10.532

    103.89

    39.612

    98.6

    0.140

    1.180

    103.7

    10.104

    99.61

    39.952

    99.5

    0.140

    1.172

    102.9

    10.201

    100.58

    39.437

    98.2

    0.142

    1.169

    102.6

    10.017

    98.74

    39.342

    98.0

    0.147

    1.165

    102.2

    10.121

    99.78

    38.947

    97.0

    0.147

    1.168

    102.5

    10.136

    99.93

    39.375

    98.1

    0.145

    1.175

    103.2

    10.362

    102.19

    39.221

    97.7

    0.136

    1.106

    96.3

    10.452

    103.09

    38.568

    96.1

    0.150

    1.112

    96.9

    10.111

    99.68

    39.026

    97.2

    平均值

    0.143

    1.158

    101.5

    10.200

    100.6

    39.343

    98.0

    RSD%

    3.11

    1.83

    1.10

    Tm

    0.024

    1.004

    98.0

    9.860

    98.36

    39.624

    99.0

    0.020

    1.044

    102.0

    10.06

    100.36

    38.132

    95.3

    0.020

    1.08

    105.6

    10.068

    100.44

    39.504

    98.7

    0.025

    1.043

    101.9

    9.996

    99.72

    39.087

    97.7

    0.023

    1.026

    100.2

    10.022

    99.98

    38.94

    97.3

    0.022

    1.056

    103.2

    10.056

    100.32

    37.96

    94.8

    0.025

    1.043

    101.9

    10.011

    99.87

    38.81

    97.0

    0.027

    1.031

    100.7

    10.019

    99.95

    39.03

    97.5

    0.025

    1.053

    102.9

    10.035

    100.11

    39.56

    98.8

    0.024

    1.029

    100.5

    10.023

    99.99

    39.25

    98.1

    平均值

    0.024

    1.041

    101.7

    10.015

    99.91

    38.990

    97.4

    RSD%

    1.96

    0.59

    1.46

    Yb

    5

    0.184

    1.184

    102.0

    10.032

    98.7

    38.764

    96.5

    0.148

    1.256

    109.2

    9.992

    98.3

    38.572

    96.0

    0.148

    1.180

    101.6

    9.877

    97.1

    38.596

    96.1

    0.172

    1.166

    100.2

    9.820

    96.6

    38.647

    96.2

    0.165

    1.141

    97.7

    9.955

    97.91

    37.904

    94.4

    0.158

    1.138

    97.4

    9.895

    97.31

    37.771

    94.0

    0.177

    1.133

    96.9

    9.936

    97.72

    38.562

    96.0

    0.162

    1.151

    98.7

    9.977

    98.13

    38.455

    95.7

    0.159

    1.162

    99.8

    9.997

    98.33

    38.326

    95.4

    平均值

    0.164

    1.161

    99.71

    9.900

    97.36

    38.405

    95.6

    RSD%

    3.57

    1.51

    0.84

    Lu

    0.028

    1.032

    100.3

    9.824

    98.0

    38.288

    95.6

    0.028

    1.004

    97.5

    10.092

    100.6

    38.244

    95.5

    0.036

    1.084

    105.5

    10.112

    100.8

    39.344

    98.3

    0.024

    1.040

    101.1

    10.009

    99.8

    38.959

    97.3

    0.032

    1.023

    99.4

    10.005

    99.8

    38.304

    95.7

    0.030

    1.019

    99.0

    9.996

    99.7

    38.566

    96.3

    0.026

    1.028

    99.9

    9.983

    99.5

    38.852

    97.1

    0.029

    1.033

    100.4

    10.052

    100.2

    39.078

    97.6

    0.029

    1.049

    102.0

    10.066

    100.4

    39.263

    98.1

    0.031

    1.052

    102.3

    10.043

    100.1

    39.223

    98.0

    平均值

    0.029

    1.036

    100.7

    10.018

    99.9

    38.812

    97.0

    RSD%

    2.11

    0.80

    1.11

    Ge

    0.012

    0.956

    93.6

    9.324

    93.0

    37.124

    92.8

    0.023

    0.928

    90.8

    9.412

    93.9

    36.400

    91.0

    0.020

    1.040

    102.0

    9.808

    97.9

    36.656

    91.6

    0.024

    0.975

    95.5

    9.598

    95.8

    36.925

    92.3

    0.016

    0.966

    94.6

    9.685

    96.7

    36.706

    91.7

    0.020

    0.973

    95.3

    9.785

    97.7

    36.765

    91.9

    0.021

    0.952

    93.2

    9.803

    97.8

    37.235

    93.0

    0.018

    0.944

    92.4

    9.660

    96.4

    37.126

    92.8

    0.022

    0.948

    92.8

    9.326

    93.1

    36.895

    92.2

    0.021

    0.965

    94.5

    9.455

    94.4

    36.563

    91.4

    平均值

    0.020

    0.965

    94.5

    9.586

    95.7

    36.840

    92.0

    RSD%

    3.12

    2.01

    0.73

    Sc

    ND

    5.012

    100.2

    9.786

    97.9

    38.756

    96.9

    ND

    5.101

    102.0

    9.925

    99.3

    38.962

    97.4

    ND

    5.006

    100.1

    10.011

    100.1

    39.263

    98.2

    ND

    4.956

    99.1

    10.076

    100.8

    38.922

    97.3

    ND

    4.768

    95.4

    10.036

    100.4

    38.757

    96.9

    ND

    4.899

    98.0

    10.267

    102.7

    38.269

    95.7

    ND

    4.929

    98.6

    10.133

    101.3

    39.332

    98.3

    ND

    4.957

    99.1

    10.021

    100.2

    38.926

    97.3

    ND

    5.111

    102.2

    9.995

    100.0

    38.356

    95.9

    ND

    5.286

    105.7

    9.895

    99.0

    38.022

    95.1

    平均值

    ND

    5.003

    100.1

    10.015

    100.1

    38.757

    96.9

    RSD%

    0.14

    0.13

    0.42


    表4 -2白葡萄酒加标回收和精密度实验

    元素

    样品

    添加水平

    1(μg/L)

    10(μg/L)

    40(μg/L)

    测定值

    测定值

    回收率

    测定值

    回收率

    测定值

    回收率

    La

    0.906

    1.895

    99.5

    10.889

    99.89

    40.299

    98.5

    0.910

    1.786

    88.6

    10.523

    96.23

    40.383

    98.7

    0.893

    1.908

    100.8

    10.902

    100.02

    40.766

    99.7

    0.881

    1.912

    101.2

    10.789

    98.89

    40.932

    100.1

    0.892

    1.883

    98.3

    10.868

    99.68

    40.263

    98.4

    0.913

    1.896

    99.6

    10.793

    98.93

    40.252

    98.4

    0.915

    1.922

    102.2

    10.045

    91.45

    39.836

    97.3

    0.903

    1.901

    100.1

    10.916

    100.16

    39.966

    97.7

    0.912

    1.91

    101.0

    10.778

    98.78

    39.942

    97.6

    0.877

    1.882

    98.2

    10.862

    99.62

    39.981

    97.7

    平均值

    0.900

    1.890

    99.0

    10.737

    98.4

    40.262

    98.4

    RSD%

    2.04

    2.50

    0.90

    Ce

    2.124

    3.151

    92.2

    11.939

    97.1

    39.872

    94.1

    2.276

    3.233

    100.4

    12.022

    97.9

    39.396

    92.9

    2.384

    3.098

    86.9

    12.152

    99.2

    39.875

    94.1

    2.211

    3.122

    89.3

    12.566

    103.4

    40.013

    94.5

    2.528

    3.306

    107.7

    12.461

    102.3

    40.033

    94.5

    2.088

    3.192

    96.3

    12.066

    98.4

    40.121

    94.7

    2.106

    3.144

    91.5

    12.269

    100.4

    40.172

    94.9

    2.233

    3.258

    102.9

    12.453

    102.2

    39.951

    94.3

    2.159

    3.306

    107.7

    12.373

    101.4

    39.888

    94.1

    2.185

    3.077

    84.8

    12.019

    97.9

    39.792

    93.9

    平均值

    2.229

    3.189

    96.0

    12.232

    100.0

    39.911

    94.2

    RSD%

    2.62

    1.81

    0.54

    Y

    1.983

    2.905

    86.5

    11.993

    99.53

    39.634

    94.0

    2.013

    3.012

    97.2

    12.011

    99.71

    39.866

    94.6

    2.239

    2.897

    85.7

    11.875

    98.35

    39.532

    93.7

    1.966

    2.966

    92.6

    11.962

    99.22

    40.127

    95.2

    1.833

    3.131

    109.1

    12.102

    100.62

    40.059

    95.0

    1.856

    3.152

    111.2

    12.033

    99.93

    40.166

    95.3

    1.974

    3.011

    97.1

    12.041

    100.01

    40.072

    95.1

    2.125

    2.962

    92.2

    11.872

    98.32

    38.252

    90.5

    2.169

    2.989

    94.9

    11.855

    98.15

    39.771

    94.3

    2.231

    2.885

    84.5

    11.922

    98.82

    40.052

    95.0

    平均值

    2.0389

    2.991

    95.1

    11.967

    99.3

    39.753

    94.3

    RSD%

    3.06

    0.70

    1.43

    Pr

    0.219

    1.119

    86.9

    10.091

    98.4

    39.036

    97.0

    0.237

    1.156

    90.6

    10.235

    99.9

    38.396

    95.4

    0.241

    1.323

    107.3

    10.363

    101.1

    38.792

    96.4

    0.301

    1.184

    93.4

    10.161

    99.1

    39.013

    96.9

    0.322

    1.175

    92.5

    10.202

    99.5

    39.265

    97.5

    0.282

    1.372

    112.2

    10.012

    97.6

    38.976

    96.8

    0.209

    1.109

    85.9

    10.173

    99.2

    39.162

    97.3

    0.237

    1.158

    90.8

    10.266

    100.2

    39.214

    97.4

    0.255

    1.223

    97.3

    10.137

    98.9

    39.565

    98.3

    0.218

    1.204

    95.4

    10.159

    99.1

    39.477

    98.1

    平均值

    0.2521

    1.2023

    95.23

    10.1799

    99.3

    39.090

    97.1

    RSD%

    4.07

    2.04

    1.38

    Nd

    0.941

    1.971

    89.1

    10.932

    98.5

    39.145

    95.2

    0.99

    2.034

    95.4

    10.898

    98.2

    39.033

    94.9

    1.053

    2.053

    97.3

    11.108

    100.3

    38.796

    94.3

    1.173

    2.039

    95.9

    10.793

    97.1

    38.665

    94.0

    1.231

    2.172

    109.2

    10.869

    97.9

    39.215

    95.3

    1.265

    2.111

    103.1

    10.532

    94.5

    39.552

    96.2

    0.917

    1.993

    91.3

    10.774

    96.9

    39.368

    95.7

    0.863

    2.105

    102.5

    11.016

    99.4

    40.023

    97.4

    1.126

    2.006

    92.6

    11.053

    99.7

    40.055

    97.4

    1.212

    2.025

    94.5

    11.005

    99.3

    39.757

    96.7

    平均值

    1.077

    2.051

    97.1

    10.898

    98.2

    39.361

    95.7

    RSD%

    3.00

    1.55

    1.23

    Sm

    0.285

    1.211

    94.1

    10.114

    98.44

    38.925

    96.6

    0.273

    1.193

    92.3

    10.236

    99.66

    39.011

    96.9

    0.292

    1.206

    93.6

    10.259

    99.89

    39.254

    97.5

    0.266

    1.239

    96.9

    10.066

    97.96

    39.441

    97.9

    0.238

    1.262

    99.2

    9.758

    94.88

    39.599

    98.3

    0.245

    1.273

    100.3

    10.055

    97.85

    40.102

    99.6

    0.285

    1.282

    101.2

    10.176

    99.06

    40.113

    99.6

    0.251

    1.301

    103.1

    10.836

    105.66

    40.292

    100.1

    0.277

    1.264

    99.4

    9.898

    96.28

    39.735

    98.7

    0.247

    1.197

    92.7

    10.005

    97.35

    38.988

    96.8

    平均值

    0.266

    1.243

    97.3

    10.140

    98.7

    39.546

    98.2

    RSD%

    3.13

    2.84

    1.28

    Eu

    0.066

    1.036

    98.6

    9.665

    96.2

    38.663

    96.5

    0.053

    1.102

    105.2

    9.739

    96.9

    39.787

    99.3

    0.055

    1.093

    104.3

    9.798

    97.5

    39.594

    98.9

    0.046

    1.072

    102.2

    9.856

    98.1

    38.838

    97.0

    0.049

    1.055

    100.5

    9.823

    97.7

    39.271

    98.1

    0.058

    1.042

    99.2

    10.01

    99.6

    39.146

    97.7

    0.061

    1.056

    100.6

    10.023

    99.7

    38.889

    97.1

    0.053

    1.022

    97.2

    10.066

    100.2

    38.564

    96.3

    0.061

    1.037

    98.7

    10.41

    103.6

    38.248

    95.5

    0.045

    1.044

    99.4

    9.892

    98.4

    39.229

    97.9

    平均值

    0.0547

    1.056

    100.6

    9.93

    98.8

    39.023

    97.4

    RSD%

    2.45

    2.14

    1.21

    Gd

    0.273

    1.177

    88.8

    10.033

    97.4

    38.557

    95.7

    0.329

    1.209

    92

    10.135

    98.5

    38.899

    96.5

    0.295

    1.235

    94.6

    10.266

    99.8

    39.263

    97.4

    0.301

    1.293

    100.4

    10.378

    100.9

    39.483

    98.0

    0.266

    1.326

    103.7

    10.352

    100.6

    39.182

    97.2

    0.286

    1.348

    105.9

    10.295

    100.1

    39.736

    98.6

    0.281

    1.198

    90.9

    10.034

    97.4

    39.566

    98.2

    0.305

    1.347

    105.8

    10.052

    97.6

    38.793

    96.3

    0.262

    1.202

    91.3

    10.247

    99.6

    38.866

    96.4

    0.292

    1.363

    107.4

    10.119

    98.3

    39.251

    97.4

    平均值

    0.289

    1.270

    98.08

    10.191

    99.0

    39.160

    97.2

    RSD%

    5.74

    1.30

    0.96

    Tb

    0.039

    1.003

    96.3

    10.125

    100.9

    38.662

    96.6

    0.038

    1.006

    96.6

    10.03

    99.9

    39.263

    98.1

    0.045

    1.105

    106.5

    10.111

    100.7

    39.134

    97.7

    0.043

    1.105

    106.5

    10.056

    100.2

    39.026

    97.5

    0.035

    1.103

    106.3

    10.006

    99.7

    38.775

    96.8

    0.036

    1.002

    96.2

    9.982

    99.4

    38.528

    96.2

    0.033

    1.005

    96.5

    9.917

    98.8

    38.962

    97.3

    0.029

    1.013

    97.3

    9.832

    97.9

    39.261

    98.1

    0.046

    1.021

    98.1

    9.575

    95.4

    38.864

    97.1

    0.052

    1.008

    96.8

    9.874

    98.3

    39.423

    98.5

    平均值

    0.040

    1.037

    99.7

    9.951

    99.1

    38.990

    97.4

    RSD%

    4.50

    1.64

    0.74

    Dy

    0.269

    1.201

    92.1

    10.308

    100.28

    39.569

    98.2

    0.283

    1.218

    93.8

    10.402

    101.22

    39.443

    97.9

    0.267

    1.302

    102.2

    10.451

    101.71

    38.972

    96.7

    0.303

    1.313

    103.3

    10.127

    98.47

    39.122

    97.1

    0.326

    1.209

    92.9

    10.188

    99.08

    39.267

    97.5

    0.291

    1.166

    88.6

    10.263

    99.83

    39.331

    97.6

    0.282

    1.319

    103.9

    10.317

    100.37

    38.698

    96.0

    0.303

    1.306

    102.6

    10.294

    100.14

    38.766

    96.2

    0.262

    1.283

    100.3

    10.311

    100.31

    39.026

    96.9

    0.253

    1.292

    101.2

    10.262

    99.82

    39.138

    97.1

    平均值

    0.284

    1.261

    98.09

    10.292

    100.123

    39.133

    97.1

    RSD%

    4.45

    0.91

    0.72

    Ho

    0.076

    1.092

    103.2

    9.785

    97.25

    39.833

    99.43

    0.072

    1.113

    105.3

    9.893

    98.33

    39.695

    99.09

    0.089

    1.069

    100.9

    9.668

    96.08

    39.748

    99.22

    0.051

    1.053

    99.3

    9.568

    95.08

    39.526

    98.67

    0.065

    1.08

    102

    9.975

    99.15

    38.783

    96.81

    0.046

    1.043

    98.3

    10.063

    100.03

    38.296

    95.59

    0.059

    1.106

    104.6

    10.005

    99.45

    38.565

    96.26

    0.066

    1.037

    97.7

    10.012

    99.52

    38.587

    96.32

    0.062

    1.009

    94.9

    10.126

    100.66

    39.244

    97.96

    0.049

    1.062

    100.2

    10.201

    101.41

    39.369

    98.27

    平均值

    0.064

    1.066

    100.6

    9.930

    98.70

    39.1646

    97.76

    RSD%

    3.05

    2.03

    1.43

    Er

    0.257

    1.143

    90.3

    10.36

    101.2

    39.948

    99.3

    0.245

    1.135

    89.5

    10.256

    100.2

    39.612

    98.4

    0.242

    1.188

    94.8

    10.273

    100.3

    39.952

    99.3

    0.226

    1.236

    99.6

    10.169

    99.3

    39.437

    98.0

    0.213

    1.247

    100.7

    10.179

    99.4

    39.342

    97.8

    0.226

    1.316

    107.6

    10.088

    98.5

    38.947

    96.8

    0.237

    1.126

    88.6

    10.164

    99.2

    39.375

    97.8

    0.241

    1.269

    102.9

    10.295

    100.6

    39.221

    97.5

    0.249

    1.115

    87.5

    10.356

    101.2

    38.568

    95.8

    0.256

    1.217

    97.7

    10.149

    99.1

    39.026

    97.0

    平均值

    0.239

    1.199

    95.9

    10.229

    99.9

    39.343

    97.8

    RSD%

    3.11

    1.83

    1.10

    Tm

    0.027

    1.013

    98.3

    10.023

    99.9

    39.352

    98.3

    0.027

    1.026

    99.6

    10.108

    100.8

    38.966

    97.3

    0.023

    1.029

    99.9

    10.202

    101.7

    38.973

    97.4

    0.039

    1.032

    100.2

    10.026

    100.0

    39.02

    97.5

    0.035

    1.044

    101.4

    10.005

    99.8

    38.794

    96.9

    0.025

    1.035

    100.5

    10.318

    102.9

    38.735

    96.8

    0.032

    1.042

    101.2

    10.201

    101.7

    38.926

    97.2

    0.029

    1.029

    99.9

    10.051

    100.2

    38.783

    96.9

    0.026

    1.017

    98.7

    10.017

    99.9

    39.261

    98.1

    0.026

    1.013

    98.3

    9.893

    98.6

    39.177

    97.9

    平均值

    0.0289

    1.028

    99.8

    10.084

    100.5

    38.999

    97.4

    RSD%

    1.07

    1.23

    0.53

    Yb

    0.326

    1.193

    87.3

    10.423

    101.03

    38.989

    96.67

    0.317

    1.295

    97.5

    10.288

    99.68

    39.562

    98.11

    0.309

    1.196

    87.6

    10.265

    99.45

    39.747

    98.57

    0.341

    1.259

    93.9

    10.427

    101.07

    39.616

    98.24

    0.295

    1.356

    103.6

    10.214

    98.94

    39.56

    98.10

    0.304

    1.402

    108.2

    10.159

    98.39

    38.779

    96.15

    0.327

    1.371

    105.1

    10.365

    100.45

    39.026

    96.77

    0.295

    1.366

    104.6

    10.055

    97.35

    39.149

    97.07

    0.305

    1.251

    93.1

    10.26

    99.4

    39.533

    98.03

    0.339

    1.178

    85.8

    10.047

    97.27

    39.125

    97.01

    平均值

    0.316

    1.287

    96.7

    10.250

    99.3

    39.309

    97.5

    RSD%

    6.47

    1.32

    0.84

    Lu

    0.007

    1.035

    99.5

    9.769

    97.29

    37.986

    94.9

    0.005

    1.052

    101.2

    9.885

    98.45

    38.211

    95.4

    0.006

    1.029

    98.9

    10.005

    99.65

    38.363

    95.8

    0.003

    1.012

    97.2

    10.102

    100.62

    38.569

    96.3

    0.003

    1.035

    99.5

    9.936

    98.96

    38.745

    96.8

    0.003

    1.039

    99.9

    9.925

    98.85

    39.021

    97.5

    0.004

    1.041

    100.1

    9.955

    99.15

    38.155

    95.3

    0.004

    1.037

    99.7

    9.986

    99.46

    38.557

    96.3

    0.004

    1.050

    101

    10.023

    99.83

    39.262

    98.1

    0.002

    1.026

    98.6

    10.011

    99.71

    39.104

    97.7

    平均值

    0.004

    1.036

    99.6

    9.960

    99.2

    38.597

    96.4

    RSD%

    1.12

    0.91

    1.12

    Ge

    0.019

    1.012

    85.2

    10.106

    99.46

    37.351

    92.98

    0.012

    1.010

    85

    10.093

    99.33

    37.467

    93.27

    0.015

    1.131

    97.1

    10.121

    99.61

    37.599

    93.60

    0.010

    1.117

    95.7

    10.098

    99.38

    37.195

    92.59

    0.013

    1.103

    94.3

    10.203

    100.43

    38.026

    94.67

    0.021

    1.261

    110.1

    10.253

    100.93

    38.151

    94.98

    0.026

    1.230

    107

    10.224

    100.64

    37.833

    94.18

    0.019

    1.252

    109.2

    10.175

    100.15

    37.864

    94.26

    0.016

    1.088

    92.8

    10.077

    99.17

    37.566

    93.52

    0.013

    1.023

    86.3

    10.159

    99.99

    38.195

    95.09

    平均值

    0.016

    1.123

    96.3

    10.151

    99.9

    37.725

    93.9

    RSD%

    8.60

    0.60

    0.91

    Sc

    5.026

    10.137

    102.54

    15.017

    100.07

    43.695

    96.71

    5.159

    9.277

    85.34

    15.026

    100.16

    44.122

    97.78

    4.952

    10.174

    103.28

    14.866

    98.56

    43.863

    97.13

    4.895

    10.062

    101.04

    14.753

    97.43

    43.772

    96.91

    5.103

    9.869

    97.18

    14.539

    95.29

    43.919

    97.27

    5.214

    10.023

    100.26

    14.826

    98.16

    44.082

    97.68

    4.826

    10.111

    102.02

    14.838

    98.28

    43.956

    97.37

    4.802

    9.969

    99.18

    15.102

    100.92

    44.269

    98.15

    4.959

    9.653

    92.86

    15.114

    101.04

    43.833

    97.06

    5.142

    10.017

    100.14

    14.377

    93.67

    43.975

    97.41

    平均值

    5.01

    9.929

    98.4

    14.846

    98.36

    43.949

    97.3

    RSD%

    2.76

    1.62

    0.39


    表4 -3起泡酒加标回收和精密度实验

    元素

    样品

    添加水平

    1(μg/L)

    10(μg/L)

    40(μg/L)

    测定值

    测定值

    回收率

    测定值

    回收率

    测定值

    回收率

    La

    0.812

    1.835

    100.5

    10.856

    100.26

    39.569

    96.8

    0.826

    1.802

    97.2

    10.91

    100.8

    39.265

    96.1

    0.836

    1.901

    107.1

    10.743

    99.13

    38.782

    94.9

    0.851

    1.795

    96.5

    10.696

    98.66

    38.963

    95.3

    0.829

    1.833

    100.3

    10.638

    98.08

    39.029

    95.5

    0.864

    1.869

    103.9

    10.655

    98.25

    39.111

    95.7

    0.821

    1.795

    96.5

    10.629

    97.99

    38.785

    94.9

    0.815

    1.802

    97.2

    10.855

    100.25

    38.822

    95.0

    0.809

    1.902

    107.2

    10.796

    99.66

    38.691

    94.7

    0.832

    1.858

    102.8

    10.963

    101.33

    38.462

    94.1

    平均值

    0.830

    1.839

    100.9

    10.774

    99.4

    38.948

    95.3

    RSD%

    2.27

    1.11

    0.81

    Ce

    1.816

    2.801

    104.1

    11.822

    100.6

    39.269

    93.8

    1.812

    2.735

    97.5

    11.834

    100.7

    39.563

    94.5

    1.825

    2.699

    93.9

    11.752

    99.9

    39.925

    95.4

    1.736

    2.783

    102.3

    11.645

    98.9

    39.196

    93.6

    1.739

    2.791

    103.1

    11.483

    97.2

    39.776

    95.0

    1.722

    2.759

    99.9

    11.774

    100.1

    39.206

    93.6

    1.734

    2.739

    97.9

    11.802

    100.4

    39.757

    95.0

    1.729

    2.694

    93.4

    11.836

    100.8

    40.006

    95.6

    1.742

    2.615

    85.5

    11.526

    97.7

    40.236

    96.2

    1.733

    2.703

    94.3

    11.479

    97.2

    40.269

    96.3

    平均值

    1.759

    2.732

    97.2

    11.529

    99.4

    40.157

    94.9

    RSD%

    2.07

    1.29

    1.00

    Y

    1.492

    2.601

    102.1

    11.462

    98.82

    39.561

    95.0

    1.507

    2.593

    101.3

    11.55

    99.7

    39.606

    95.1

    1.563

    2.585

    100.5

    11.399

    98.19

    39.277

    94.2

    1.515

    2.602

    102.2

    11.417

    98.37

    39.751

    95.4

    1.568

    2.499

    91.9

    11.452

    98.72

    39.862

    95.7

    1.602

    2.507

    92.7

    11.462

    98.82

    39.665

    95.2

    1.637

    2.589

    100.9

    11.591

    100.11

    38.269

    91.7

    1.628

    2.575

    99.5

    11.601

    100.21

    38.956

    93.4

    1.611

    2.563

    98.3

    11.482

    99.02

    38.788

    93.0

    1.655

    2.591

    101.1

    11.516

    99.36

    38.769

    93.0

    平均值

    1.5778

    2.5705

    99.05

    11.493

    99.1

    39.250

    94.2

    RSD%

    1.46

    0.60

    1.35

    Pr

    0.222

    1.281

    107.1

    10.113

    99.0

    38.836

    96.6

    0.206

    1.225

    101.5

    10.186

    99.8

    38.748

    96.3

    0.213

    1.267

    105.7

    10.236

    100.3

    38.692

    96.2

    0.202

    1.249

    103.9

    10.161

    99.5

    38.575

    95.9

    0.235

    1.251

    104.1

    10.213

    100.0

    38.626

    96.0

    0.233

    1.206

    99.6

    10.233

    100.2

    39.132

    97.3

    0.206

    1.22

    101

    10.309

    101.0

    39.087

    97.2

    0.201

    1.209

    99.9

    10.321

    101.1

    38.265

    95.1

    0.217

    1.212

    100.2

    10.291

    100.8

    39.117

    97.3

    0.203

    1.231

    102.1

    10.142

    99.3

    39.326

    97.8

    平均值

    0.214

    1.235

    102.5

    10.221

    100.1

    38.840

    96.6

    RSD%

    4.07

    2.04

    1.38

    Nd

    0.846

    1.782

    93.2

    10.663

    98.1

    39.145

    95.7

    0.829

    1.833

    98.3

    10.706

    98.6

    39.033

    95.5

    0.833

    1.901

    105.1

    10.923

    100.7

    38.796

    94.9

    0.857

    1.856

    100.6

    10.976

    101.3

    38.665

    94.5

    0.862

    1.839

    98.9

    10.863

    100.1

    39.215

    95.9

    0.839

    1.792

    94.2

    11.026

    101.8

    39.552

    96.8

    0.849

    1.833

    98.3

    11.134

    102.8

    39.368

    96.3

    0.847

    1.897

    104.7

    11.109

    102.6

    40.023

    97.9

    0.862

    1.877

    102.7

    11.243

    103.9

    40.055

    98.0

    0.859

    1.862

    101.2

    11.036

    101.9

    39.757

    97.3

    平均值

    0.848

    1.847

    99.7

    10.968

    101.2

    39.361

    96.3

    RSD%

    2.16

    1.68

    1.23

    Sm

    0.19

    1.211

    101.1

    10.114

    99.1

    39.112

    97.3

    0.221

    1.206

    100.6

    10.236

    100.4

    39.107

    97.3

    0.209

    1.195

    99.5

    10.259

    100.6

    38.826

    96.6

    0.192

    1.201

    100.1

    10.066

    98.7

    38.937

    96.8

    0.183

    1.245

    104.5

    9.758

    95.6

    38.965

    96.9

    0.189

    1.219

    101.9

    10.055

    98.6

    39.166

    97.4

    0.196

    1.243

    104.3

    10.176

    99.8

    38.526

    95.8

    0.209

    1.226

    102.6

    10.836

    106.4

    38.317

    95.3

    0.201

    1.231

    103.1

    9.898

    97.0

    38.472

    95.7

    0.227

    1.217

    101.7

    10.005

    98.1

    37.269

    92.7

    平均值

    0.202

    1.219

    101.9

    10.140

    99.4

    38.670

    96.2

    RSD%

    1.39

    2.84

    1.48

    Eu

    0.319

    1.402

    106.2

    10.239

    99.0

    39.216

    97.2

    0.327

    1.441

    110.1

    10.217

    98.8

    39.033

    96.7

    0.335

    1.393

    105.3

    10.069

    97.3

    38.935

    96.5

    0.351

    1.385

    104.5

    10.133

    97.9

    38.759

    96.0

    0.355

    1.366

    102.6

    10.275

    99.4

    38.734

    96.0

    0.362

    1.372

    103.2

    10.201

    98.6

    39.262

    97.3

    0.349

    1.347

    100.7

    10.308

    99.7

    38.563

    95.6

    0.333

    1.357

    101.7

    10.325

    99.9

    38.293

    94.9

    0.347

    1.326

    98.6

    10.269

    99.3

    38.445

    95.3

    0.326

    1.328

    98.8

    10.417

    100.8

    38.397

    95.1

    平均值

    0.3404

    1.372

    103.2

    10.25

    99.1

    38.764

    96.1

    RSD%

    2.57

    0.96

    0.88

    Gd

    0.229

    1.206

    95.6

    10.019

    97.7

    38.469

    95.5

    0.242

    1.231

    98.1

    10.139

    98.9

    38.366

    95.3

    0.262

    1.241

    99.1

    10.117

    98.7

    38.201

    94.9

    0.251

    1.229

    97.9

    10.205

    99.6

    38.097

    94.6

    0.266

    1.251

    100.1

    10.146

    99.0

    38.568

    95.8

    0.253

    1.233

    98.3

    10.187

    99.4

    39.252

    97.5

    0.271

    1.239

    98.9

    10.236

    99.9

    39.483

    98.1

    0.236

    1.26

    101

    10.256

    100.1

    38.926

    96.7

    0.238

    1.208

    95.8

    10.195

    99.5

    39.585

    98.3

    0.248

    1.317

    106.7

    10.242

    99.9

    39.776

    98.8

    平均值

    0.250

    1.242

    99.2

    10.174

    99.2

    38.872

    96.6

    RSD%

    2.53

    0.70

    1.58

    Tb

    0.013

    1.013

    99.3

    10.006

    99.9

    38.972

    97.4

    0.016

    1.006

    98.6

    10.009

    99.9

    39.211

    98.0

    0.02

    0.925

    90.5

    9.839

    98.2

    39.265

    98.1

    0.028

    0.984

    96.4

    9.926

    99.1

    39.073

    97.6

    0.019

    0.996

    97.6

    9.667

    96.5

    38.563

    96.4

    0.018

    1.039

    101.9

    9.967

    99.5

    38.726

    96.8

    0.015

    1.026

    100.6

    10.031

    100.1

    38.696

    96.7

    0.024

    1.007

    98.7

    10.042

    100.2

    38.526

    96.3

    0.018

    1.027

    100.7

    10.107

    100.9

    39.225

    98.0

    0.021

    1.036

    101.6

    10.201

    101.8

    39.305

    98.2

    平均值

    0.019

    1.006

    98.6

    9.980

    99.6

    38.447

    97.3

    RSD%

    3.32

    1.47

    0.79

    Dy

    0.205

    1.213

    100.3

    10.166

    99.56

    38.667

    96.1

    0.213

    1.219

    100.9

    10.153

    99.43

    37.953

    94.4

    0.204

    1.206

    99.6

    10.187

    99.77

    37.665

    93.6

    0.189

    1.226

    101.6

    10.251

    100.41

    38.265

    95.1

    0.195

    1.224

    101.4

    10.098

    98.88

    38.196

    95.0

    0.193

    1.251

    104.1

    10.123

    99.13

    38.432

    95.6

    0.217

    1.301

    109.1

    10.202

    99.92

    37.895

    94.2

    0.211

    1.203

    99.3

    10.245

    100.35

    38.066

    94.6

    0.229

    1.213

    100.3

    10.097

    98.87

    39.132

    97.3

    0.225

    1.218

    100.8

    10.088

    98.78

    38.696

    96.2

    平均值

    0.208

    1.227

    101.74

    10.161

    99.510

    38.297

    95.2

    RSD%

    2.37

    0.59

    1.15

    Ho

    0.029

    1.007

    96.7

    9.933

    98.93

    38.863

    97.06

    0.033

    1.002

    96.2

    9.825

    97.85

    38.265

    95.56

    0.042

    1.039

    99.9

    9.965

    99.25

    38.217

    95.44

    0.036

    1.044

    100.4

    10.022

    99.82

    38.225

    95.46

    0.039

    1.041

    100.1

    10.027

    99.87

    39.033

    97.48

    0.045

    1.052

    101.2

    10.019

    99.79

    38.269

    95.57

    0.036

    1.055

    101.5

    10.005

    99.65

    38.137

    95.24

    0.031

    1.049

    100.9

    9.989

    99.49

    37.266

    93.07

    0.042

    1.051

    101.1

    9.978

    99.38

    37.563

    93.81

    0.046

    1.039

    99.9

    9.666

    96.26

    36.989

    92.37

    平均值

    0.038

    1.038

    99.8

    9.943

    99.0

    38.083

    95.1

    RSD%

    1.78

    1.15

    1.70

    Er

    0.146

    1.162

    100.2

    10.112

    99.5

    38.696

    96.3

    0.151

    1.149

    98.9

    10.093

    99.3

    38.753

    96.5

    0.169

    1.144

    98.4

    10.026

    98.7

    38.926

    96.9

    0.155

    1.156

    99.6

    10.044

    98.8

    38.335

    95.4

    0.158

    1.159

    99.9

    10.131

    99.7

    38.269

    95.3

    0.179

    1.171

    101.1

    10.159

    100.0

    37.569

    93.5

    0.151

    1.166

    100.6

    10.009

    98.5

    39.457

    98.2

    0.149

    1.163

    100.3

    10.022

    98.6

    38.745

    96.5

    0.156

    1.182

    102.2

    10.026

    98.7

    38.699

    96.3

    0.157

    1.19

    103

    10.37

    102.1

    39.117

    97.4

    平均值

    0.157

    1.164

    100.4

    10.099

    99.4

    38.657

    96.2

    RSD%

    1.21

    1.07

    1.33

    Tm

    0.015

    1.009

    98.9

    10.003

    99.8

    38.776

    96.9

    0.019

    1.013

    99.3

    10.011

    99.9

    38.632

    96.5

    0.024

    1.03

    101

    9.966

    99.5

    38.921

    97.3

    0.022

    1.026

    100.6

    9.753

    97.3

    39.126

    97.8

    0.017

    1.029

    100.9

    9.851

    98.3

    39.255

    98.1

    0.013

    1.044

    102.4

    9.969

    99.5

    38.751

    96.8

    0.026

    1.051

    103.1

    10.037

    100.2

    38.636

    96.5

    0.023

    1.029

    100.9

    10.021

    100.0

    38.211

    95.5

    0.019

    1.023

    100.3

    10.006

    99.9

    38.736

    96.8

    0.023

    1.045

    102.5

    9.639

    96.2

    38.755

    96.8

    平均值

    0.0201

    1.0299

    100.99

    9.583

    99.1

    38.780

    96.9

    RSD%

    1.32

    1.40

    0.74

    Yb

    0.203

    1.202

    98.2

    10.017

    97.97

    39.011

    96.98

    0.198

    1.217

    99.7

    10.056

    98.36

    39.236

    97.54

    0.211

    1.159

    93.9

    10.106

    98.86

    39.175

    97.39

    0.235

    1.207

    98.7

    10.227

    100.07

    38.688

    96.17

    0.204

    1.301

    108.1

    10.204

    99.84

    38.923

    96.76

    0.239

    1.262

    104.2

    10.139

    99.19

    39.137

    97.29

    0.213

    1.246

    102.6

    10.228

    100.08

    39.206

    97.47

    0.206

    1.253

    103.3

    10.305

    100.85

    38.565

    95.86

    0.219

    1.202

    98.2

    10.416

    101.96

    38.821

    96.50

    0.242

    1.239

    101.9

    10.3

    100.8

    39.02

    97.00

    平均值

    0.217

    1.229

    100.9

    10.200

    99.8

    38.978

    96.9

    RSD%

    3.24

    1.21

    0.58

    Lu

    0.034

    1.029

    99.9

    9.922

    98.92

    38.986

    97.4

    0.033

    1.022

    99.2

    9.956

    99.26

    38.623

    96.5

    0.023

    1.031

    100.1

    9.693

    96.63

    39.112

    97.7

    0.029

    1.039

    100.9

    9.598

    95.68

    38.757

    96.8

    0.026

    1.028

    99.8

    9.775

    97.45

    37.926

    94.7

    0.022

    1.035

    100.5

    9.869

    98.39

    37.969

    94.8

    0.03

    1.042

    101.2

    10.106

    100.76

    38.441

    96.0

    0.032

    1.037

    100.7

    10.063

    100.33

    38.206

    95.4

    0.037

    1.051

    102.1

    10.028

    99.98

    37.83

    94.5

    0.032

    1.066

    103.6

    10.035

    100.05

    37.958

    94.8

    平均值

    0.030

    1.038

    100.8

    9.976

    98.7

    38.381

    95.9

    RSD%

    1.23

    1.70

    1.23

    Ge

    0.175

    1.251

    101.1

    10.233

    99.93

    39.228

    97.47

    0.192

    1.226

    98.6

    10.221

    99.81

    39.314

    97.69

    0.261

    1.263

    102.3

    10.258

    100.18

    39.88

    99.10

    0.24

    1.269

    102.9

    10.3

    100.6

    38.869

    96.57

    0.266

    1.217

    97.7

    10.413

    101.73

    38.785

    96.36

    0.293

    1.309

    106.9

    10.433

    101.93

    39.269

    97.57

    0.225

    1.197

    95.7

    10.396

    101.56

    39.566

    98.32

    0.242

    1.207

    96.7

    10.502

    102.62

    39.476

    98.09

    0.281

    1.305

    106.5

    10.519

    102.79

    39.526

    98.22

    0.264

    1.288

    104.8

    10.447

    102.07

    39.777

    98.84

    平均值

    0.244

    1.253

    101.3

    10.372

    101.3

    39.369

    97.8

    RSD%

    3.23

    1.07

    0.90

    Sc

    2.063

    7.205

    103.9

    12.008

    99.08

    41.088

    97.47

    1.958

    7.175

    103.3

    12.351

    102.51

    39.867

    94.42

    1.866

    7.008

    99.96

    12.201

    101.01

    40.036

    94.84

    2.131

    6.935

    98.5

    12.19

    100.9

    41.937

    99.59

    2.206

    6.984

    99.48

    12.245

    101.45

    42.665

    101.41

    2.093

    6.869

    97.18

    12.306

    102.06

    41.939

    99.60

    2.147

    7.021

    100.22

    12.177

    100.77

    40.086

    94.97

    2.008

    7.032

    100.44

    12.401

    103.01

    39.856

    94.39

    2.317

    7.157

    102.94

    12.473

    103.73

    39.206

    92.77

    2.249

    7.149

    102.78

    12.259

    101.59

    41.572

    98.68

    平均值

    2.10

    7.054

    100.9

    12.261

    101.61

    40.825

    96.8

    RSD%

    1.60

    1.07

    2.84


    结论
    采用低温赶酸,硝酸消解,用ICP-MS测定葡萄酒中的稀土元素,快速准确,可用于葡萄酒的稀土元素检测。
    +关注 私聊
  • huangza

    第1楼2017/07/07

    应助达人

    不错的原创,数据很多啊,佷详细。
    方法的定量限是怎么计算出来的?

0
    +关注 私聊
  • 夏天的雪

    第2楼2017/07/08

    应助达人

    数据很详实,结构也较完整,发表的时候注意一下表格的排版会更方便阅读

0
    +关注 私聊
  • hhciq

    第3楼2017/07/26

    楼主的文章好厉害,制订的标准生效了吧

0
    +关注 私聊
  • yy_0324

    第4楼2017/11/21

    葡萄酒中稀土元素的测定,有助于了解葡萄酒中成分含量!

0
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