乌龙茶和绿茶成分分析标准物质复研制

杨榕; 顾铁新; 潘含江; 刘妹; 赵凯

doi:10.15898/j.cnki.11-2131/td.202202180025

乌龙茶和绿茶成分分析标准物质复研制

中国地质科学院地球物理地球化学勘查研究所，河北廊坊 065000

基金项目:
中央财政科研项目“6个生物成分分析标准物质复制” (JY201908); 中国地质调查局地质调查项目“全国土地质量调查监测与成果集成”(DD20221770)

详细信息

作者简介: 杨榕, 硕士, 工程师, 地球化学专业。E-mail: yangrong0516@163.com

通讯作者: 潘含江, 博士, 高级工程师, 地球化学专业。E-mail: 121006999@qq.com

中图分类号: O657.31

收稿日期: 2022-02-18

修回日期: 2022-05-16

录用日期: 2022-05-23

刊出日期: 2023-03-28

Redevelopment of Oolong Tea and Green Tea Component Analysis Reference Materials

Institute of Geophysical and Geochemical Exploration, Chinese Academy of Geological Sciences

More Information

Corresponding author: PAN Hanjiang, 121006999@qq.com

Received Date: 18 February 2022

Revised Date: 16 May 2022

Accepted Date: 23 May 2022

Publish Date: 28 March 2023

摘要

摘要:
20世纪80年代至今，中国已研制了9种茶叶成分标准物质。中国地质调查局于2004年下达中国地质科学院地球物理地球化学勘查研究所研制的一套适用于覆盖区农业生态地球化学评价的生物地球化学系列标准物质，其中包括两种茶叶标准物质，定值组分60余项，包括植物营养元素、有毒、有害元素和重金属污染元素以及人们关心的一些微量营养元素等，满足了相关食品卫生安全及生物样品成分检验分析的需要，取得了显著的社会效益。随着农业生态地质调查工作全面部署和展开，对生物样品的分析测试任务加大，对相应地球化学标准物质的需求也随之增加。本文复制了GBW10016a和GBW10052a两种茶叶标准物质，候选物分别为福建武夷山乌龙茶和江西上饶市婺源绿茶。研制过程严格按照JJG 1006—1994、JJF 1343—2012和JJF1646—2017等相关规范要求，侯选物经粗碎、干燥、细碎、过筛、混匀等步骤制备而成，经统计学检验，样品均匀，稳定性良好，定值采用多家实验室合作定值的方式进行，优选国内技术实力较强、仪器设备先进、且有相关标准物质定值测试经验的11家实验室，采用电感耦合等离子体质谱/发射光谱法（ICP-MS/OES）、原子荧光光谱法（AFS）等准确可靠的方法共分析61项指标。GBW10016a最终给出认定值54项，参考值3项；GBW10052a定值57项，参考值3项。本次研制的茶叶标准物质定值成分多样、量值准确可靠，符合国家一级标准物质的要求。与原批次标准物质相比，GBW10016a定值指标增加了Ag和Sn，Ge和Tl由原批次的参考值升级为标准值；GBW10052a增加了Al、Ag、Cl、I、N、S、Sb、Sc、Si及Sn由原批次的参考值升级为标准值。本次复研制的标准物质，在同类型中占据重要地位，研制过程严格按照相关规范执行，测试方法经典可靠，定值结果准确度高，于2019年被审批为国家一级标准物质，能够有效支撑农业生态环境地球化学调查与评价、生物样品的分析及食品与农产品分析测试的需要。
- 茶叶 /
- 标准物质 /
- 定值元素 /
- 电感耦合等离子体质谱/发射光谱法 /
- 质量控制
Abstract: BACKGROUND
With the comprehensive development of the agricultural ecological geological survey and the improvement of people's attention to the ecological environment in our country, the demand for biogeochemical reference materials in biological analysis food analysis and agricultural products analysis is increasing. The existing biogeochemical reference materials are in short supply, and there is an urgent need to develop new reference materials. With the full deployment and development of agro-ecological geological surveys, the demand for biogeochemical reference materials is increasing.
OBJECTIVES
To reproduce tea composition reference materials (GBW10016a & GBW10052a) to take the place of old tea composition reference materials (GBW10016 & GBW10052).
METHODS
According to the development needs of geological surveys, the focus of this paper is on the preparation of two tea reference materials, GBW10016a and GBW10052a. The progress includes sampling, processing and preparation, particle size test, uniformity test, stability test, content test, and calculation of identification value and uncertainty.

In the sampling process, the sample collection locations are Wuyishan City, Fujian Province and Wuyuan County, Shangrao City, Jiangxi Province. The candidates are oolong tea and green tea. The tea samples both weigh 400kg.

In the processing and preparation, the samples were cleaned, freeze-dried, heated and dried, ball milled, screened, sub-packed and inactivated. In the particle size test, the BT-9000s laser particle size distributor was used to test the particle size of the samples. The particle size of GBW10016a & GBW10052a centrally distributed in the range of 75μm to 200μm, and the cumulative distribution content reached 98% in the range of 175μm to 200μm.

In the uniformity testing process, 15 bottles of samples were randomly selected for analysis of more than 30 elements. The analysis results show that the relative standard deviation of the elements is less than 7%, the measured values F in the variance test are less than the critical value F. It shows that the uniformity of the samples is acceptable.

In the stability testing process, the short-term and long- term stability of the samples are good according to the analysis and testing in different time periods.

In the content testing process, a total of 61 indicators were analyzed by accurate and reliable methods such as inductively coupled plasma-mass spectrometry/optical emission spectrometry (ICP-MS/OES) and atomic fluorescence spectrometry (AFS) in multiple laboratories.

In the process of calculation of identification value and uncertainty, the Grubbs algorithm and the Dixon algorithm were carried out to check and exclude individual out-group data in the group at the first step. The Cochrane algorithm was used to carry out precision testing at the second step. The Shapiro-Wilk algorithm was used to complete the data normality test.

The whole preparation process of the tea reference materials follow three specifications: Technical Norm of Primary Reference Materials (JJG 1006—1994), General and Statistical Principles for Characterization of Reference Materials (JJF 1343—2012) and The Production of Reference Materials for Geoanalysis(JJF 1646—2017).
RESULTS
GBW10016a (GSB-7a) and GBW10052a (GSB-30a) tea reference materials are successfully reproduced, and have been approved as national first-class reference materials. The GBW10016a (GSB-7a) and GBW10052a (GSB-30a) are characterized by strong representativeness, multi-component planting, and accurate and reliable customization results. A total of 61 indicators are involved in this reproduction: Ag, Al, As, B, Ba, Be, Bi, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, N, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, S, Sb, Sc, Se, Si, Sm, Sn, Sr, Tb, Th, Ti, Tl, Tm, U, V, Y, Yb, Zn. GBW10016a (GSB-7a) contains 54 elements with certified values and uncertainties, and 3 elements with reference values. GBW10052a (GSB-30a) contains 57 elements with certified values and uncertainties, and 3 elements with reference values. For GBW10016a (GSB-7a), Ag and Sn are added, and Ge and Tl are upgraded from the reference values of the original batch (GBW10016) to the certified values. For GBW10052a, Al, Ag, Cl, I, N, S, Sb, Sc, Si and Sn are upgraded from the reference values of the original batch (GBW10052) to the certified values. Due to the current level of analysis technology and objective conditions, the elements of Hf and Nb cannot be given reference values.
CONCLUSIONS
The reference materials effectively support the needs of geochemical investigation and evaluation of the agricultural ecological environment, analysis of biological samples and food and agricultural products. With the development of ecological environmental research and food safety and hygiene inspection, people pay more and more attention to the characteristic elements, and the requirements are increasing. Problems still exists in the analysis of biological samples, such as discrete analysis results of the same method between laboratories and systematic errors among the main analysis methods of individual elements. There are technical difficulties in the analysis of some elements. Analysis and testing technology needs to be continuously improved to cope with the characteristics of a special biological sample matrix, low composition content and difficult testing.
- tea /
- reference material /
- certified value elements /
- inductively coupled plasma-mass spectrometry/atomic emission spectrometry /
- quality control

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图 1 候选物制备流程示意图

Figure 1.

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表 1 国内外茶叶标准物质统计

Table 1. Statistical table of tea reference materials at home and abroad

标准物质名称及编号	研制单位	研制时间	定值元素
茶叶成分分析标准物质(GBW08505)	中国科学院生态环境研究中心	1985年	31项
茶叶成分分析标准物质(GBW07605)	中国地质科学院地球物理地球化学勘查研究所	1990年	52项
生物成分分析标准物质(茶叶) (GBW10016)	中国地质科学院地球物理地球化学勘查研究所	2005年	60项
生物成分分析标准物质(绿茶) (GBW10052)	中国地质科学院地球物理地球化学勘查研究所	2010年	60项
茶叶中氟成分分析标准物质(GBW08516)	浙江省医学科学院	1998年	F
海带—茶叶中碘成分分析标准物质(GBW08519)	浙江省医学科学院	2005年	I
海带—茶叶中碘成分分析标准物质(GBW08518)	浙江省医学科学院	2005年	I
茶叶中锶-90标准物质(GBW04330)	中国疾病预防控制中心辐射防护与核安全医学所	2021年	Sr
茶叶中农药和无机元素成分分析标准物质(GBW10083)	中国计量科学研究院	2013年	14项
茶叶中微量元素的标准物质(CRM7505-a)	NMIJ日本国家计量院计量管理中心	2010年	19项
23号茶叶Ⅱ标准物质(No.23)	国家环境研究所环境测量和分析中心	2009年	14项

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表 2 候选物粒度分布特征统计

Table 2. Statistics of particle size distribution for the candidate materials

粒径 (μm)	BGW10016a (GSB-7a)		BGW10052a (GSB-30a)
粒径 (μm)	区间含量 (%)	累积含量 (%)	区间含量 (%)	累积含量 (%)
10~12	2.66	30.45	2.95	37.41
12~14	2.36	32.81	2.54	39.95
14~17	3.19	36.00	3.29	43.24
17~20	2.92	38.92	2.86	46.12
20~25	4.32	43.24	3.94	50.04
25~30	3.44	46.68	2.91	52.95
30~35	2.62	49.30	2.05	55.23
35~40	3.01	52.31	1.5	56.51
40~45	2.6	54.91	1.23	57.73
45~50	2.4	57.31	2.13	59.86
50~63	4.34	61.65	3.12	62.98
63~75	5.18	66.83	4.35	67.33
75~100	7.24	74.07	7.83	75.16
100~120	5.88	79.95	6.15	81.31
120~140	5.54	85.49	5.53	86.84
140~170	7.25	92.74	6.84	93.68
170~200	5.87	98.61	5.23	98.91
200~250	1.49	100	1.11	100
250~300	0	100	0	100

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表 3 候选物均匀性检验结果

Table 3. Homogeneity test results of the candidate materials

组分	单位	GBW10016a(GSB-7a)				GBW10052a(GSB-30a)
组分	单位	平均值(X)	RSD(%)	F_实测值	U_bb	平均值(X)	RSD(%)	F_实测值	U_bb
Al	%	0.239	0.79	1.36	0.0007	0.121	3.92	1.27	0.0016
B	μg/g	12.6	6.81	1.04	0.11	11.3	4.52	1.7	0.26
Ba	μg/g	31.3	4.68	1.31	0.54	31.6	3.93	1.38	0.5
Be	ng/g	49.6	4.38	1.81	1.17	11.6	4.42	1.23	0.17
Bi	ng/g	12.9	5.29	1.41	0.28	31.3	3.71	1.64	0.57
Br	μg/g	2.2	4.26	1.14	0.02	3.07	5.03	1.23	0.05
Ca	%	0.465	0.41	2.6	0.0013	0.354	1	2.54	0.002
Cd	ng/g	45.8	4.35	1.87	1.1	207	2.97	1.41	2.54
Ce	μg/g	1.34	4.48	1.25	0.02	0.502	3.41	1.63	0.008
Co	μg/g	0.28	4.33	1.37	0.005	0.23	3.2	2.19	0.005
Cr	μg/g	0.779	4.75	1.51	0.017	0.577	3.87	1.73	0.012
Cs	μg/g	0.193	4	1.67	0.004	0.414	2.9	1.06	0.002
Cu	μg/g	8.46	2.47	1.04	0.03	13	2.39	1.82	0.17
Fe	μg/g	149	2.89	1.03	0.55	162	5.89	1.54	4.43
Ge	ng/g	13.3	5.46	1.05	0.12	7.61	5.65	1.83	0.23
K	%	1.46	0.22	2.06	0.0019	1.33	0.25	1.82	0.0018
La	μg/g	0.996	4.26	1.07	0.008	0.34531	3.24	1.34	0.004
Li	μg/g	0.253	4.89	1.08	0.002	0.198	4.07	1.22	0.003
Mg	%	0.175	0.48	1.27	0.0003	0.152	2.35	1.01	0.0003
Mn	%	0.127	0.33	1.4	0.0002	0.117	0.38	2.11	0.0003
Mo	μg/g	0.034	6.92	1.81	0.0013	0.055	5.52	2.12	0.0018
Na	μg/g	20.4	6.9	1.02	0.14	14.8	5.06	1.58	0.35
Ni	μg/g	3.63	3.81	1.35	0.05	4.31	3.61	1.72	0.08
P	%	0.235	0.32	1.31	0.0003	0.266	1.01	1.51	0.0012
Pb	μg/g	1.09	10.2	1.29	0.04	1.52	3.89	1.29	0.02
Rb	μg/g	45.98	4.42	1.29	0.73	83.1	1.27	1.34	0.4
S	%	0.262	0.25	1.13	0.0002	0.237	0.31	1.08	0.0001
Sb	ng/g	0.052	7.92	1.08	0.0008	56.5	5.67	2.09	1.91
Si	%	0.044	3.05	1.27	0.0005	0.078	5.08	1.6	0.0019
Sr	μg/g	13.9	4.37	1.18	0.18	14	4.14	1.38	0.23
Y	μg/g	2.02	3.76	1.55	0.04	0.508	4.65	1.61	0.012
Yb	ng/g	95.6	3.99	1.01	0.29	34.8	3.83	1.41	0.55
Zn	μg/g	25.5	4.1	1.34	0.4	26.6	2.8	1.79	0.4
注：RSD为相对标准偏差；U_bb为均匀性引起的不确定度分量。

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表 4 候选物(两种茶叶)短期稳定性检验结果

Table 4. Short-term stability test results of the candidate materials

组分	单位	GBW10016a (GSB-7a)			GBW10052a (GSB-30a)
组分	单位	平均值(X)	β₁	t_0.05×s(β₁)	平均值(X)	β₁	t_0.05×s(β₁)
Al	%	0.241	0.0003	0.002	0.127	0.0003	0.0007
B	μg/g	12.5	0.015	0.328	11.6	0.001	0.0700
Ba	μg/g	22.8	0.049	0.186	31.4	0.050	0.4201
Bi	ng/g	13.1	-0.076	0.093	31.5	-0.072	0.5995
Ca	%	0.464	0.0002	0.002	0.368	0.000	0.0031
Cd	ng/g	44.5	-0.118	0.238	214	0.234	1.2013
Ce	μg/g	1.38	0.006	0.019	0.506	-0.001	0.0053
Co	μg/g	0.280	0.0002	0.003	0.232	0.0002	0.0020
Cr	μg/g	0.786	-0.001	0.005	0.598	-0.0001	0.0063
Cs	μg/g	0.189	0.0004	0.001	0.419	-0.0003	0.0016
Cu	μg/g	8.1	0.017	0.086	13.5	0.001	0.1132
Fe	μg/g	150	-0.962	1.595	173	0.733	1.1041
Ge	ng/g	9.55	-0.024	0.215	8.22	-0.012	0.0986
K	%	1.45	-0.001	0.006	1.34	-0.001	0.0102
La	μg/g	1.02	0.0002	0.009	0.345	-0.0004	0.0044
Li	μg/g	0.255	0.001	0.002	0.207	0.001	0.0030
Mg	%	0.173	-0.0002	0.001	0.151	-0.0003	0.0010
Mn	%	0.128	-0.00003	0.001	0.118	-0.0001	0.0013
Mo	μg/g	0.043	-0.0001	0.002	0.057	0.00003	0.0009
Na	μg/g	20.4	-0.134	0.669	14.7	0.044	0.2413
Ni	μg/g	3.68	0.002	0.014	4.39	0.015	0.0558
P	%	0.236	0.0000	0.001	0.273	-0.0003	0.0019
Pb	μg/g	1.13	0.007	0.015	1.48	0.008	0.0198
S	%	0.264	0.0001	0.002	0.235	0.0003	0.0023
Sr	μg/g	13.6	-0.019	0.049	13.5	0.012	0.2929
Y	μg/g	1.97	0.006	0.009	0.510	0.001	0.0068
Yb	ng/g	86.1	0.042	0.459	34.4	0.137	0.5951
Zn	μg/g	26.8	0.0002	0.527	26.3	-0.019	0.2064
注：β₁为直线的斜率；t_0.05×s(β₁)为自由度95%的学生分布列表值。

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表 5 候选物(两种茶叶)长期稳定性检验结果

Table 5. Long-term stability test results of the candidate materials

组分	单位	GBW10016a (GSB-7a)				GBW10052a (GSB-30a)
组分	单位	平均值(X)	β₁	t_0.05×s(β₁)	u_s	平均值(X)	β₁	t_0.05×s(β₁)	u_s
Al	%	0.240	0.000	0.000	0.0	0.126	0.0002	0.0004	0.0
B	μg/g	12.4	0.032	0.182	0.1	11.5	-0.018	0.105	0.4
Ba	μg/g	22.6	0.106	0.154	0.6	31.6	0.073	0.223	0.8
Be	ng/g	49.2	-0.030	0.359	1.4	12.3	-0.030	0.151	0.6
Bi	ng/g	13.1	-0.047	0.057	0.2	31.5	0.042	0.323	1.2
Br	μg/g	2.23	0.008	0.020	0.1	3.1	0.002	0.038	0.1
Ca	%	0.466	-0.0002	0.0003	0.0	0.367	-0.0003	0.001	0.0
Cd	ng/g	44.6	0.025	0.367	1.4	214	0.105	1.038	3.9
Ce	μg/g	1.38	0.005	0.010	0.0	0.499	0.001	0.004	0.0
Co	μg/g	0.278	0.001	0.002	0.0	0.229	0.001	0.002	0.0
Cr	μg/g	0.785	0.001	0.005	0.0	0.585	0.002	0.007	0.0
Cs	μg/g	0.187	0.001	0.001	0.0	0.420	0.001	0.003	0.0
Cu	μg/g	8.17	0.023	0.038	0.1	13.3	0.021	0.100	0.4
Fe	μg/g	149.	-0.618	0.991	1.7	172	0.269	0.757	2.9
Ge	ng/g	9.512	-0.007	0.143	0.5	8.1	0.005	0.075	0.3
K	%	1.463	-0.0003	0.0004	0.0	1.33	-0.0002	0.0004	0.0
La	μg/g	1.01	0.002	0.006	0.0	0.345	0.0003	0.003	0.0
Li	μg/g	0.253	0.0004	0.001	0.0	0.207	0.001	0.002	0.0
Mg	%	0.1752	0.00004	0.0001	0.0	0.150	-0.00001	0.0001	0.0
Mn	%	0.127	-0.00001	0.0001	0.0	0.1167	0.00005	0.0001	0.0
Mo	μg/g	0.043	0.000002	0.001	0.0	0.056	0.0001	0.001	0.0
Na	μg/g	20.4	-0.088	0.398	1.5	14.78	0.060	0.104	0.4
Ni	μg/g	3.66	0.0004	0.017	0.1	4.32	0.013	0.032	0.1
P	%	0.235	0.000001	0.0003	0.0	0.275	-0.00002	0.001	0.0
Pb	μg/g	1.12	0.003	0.008	0.0	1.52	-0.010	0.015	0.1
Rb	μg/g	45.7	0.263	0.349	1.3	83.3	-0.034	0.141	0.5
S	%	0.262	-0.00003	0.00009	0.0	0.235	0.001	0.001	0.0
Sb	μg/g	0.055	0.0002	0.001	0.0	56.3	0.132	0.340	1.3
Sr	μg/g	13.4	0.022	0.069	0.3	13.6	0.005	0.151	0.6
Y	μg/g	1.95	0.003	0.007	0.0	0.507	0.002	0.005	0.0
Yb	ng/g	85.9	0.207	0.314	1.2	34.8	0.014	0.222	0.8
Zn	μg/g	26.6	0.038	0.241	0.9	26.3	-0.030	0.158	0.6
注: β₁为直线的斜率；t_0.05×s(β₁)为自由度95%的学生分布列表值；u_s为稳定性引起的不确定度分量。

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表 6 标准物质元素及定值测试方法

Table 6. Elements and analytical methods of the certified materials

元素	样品前处理方法	定值方法	元素	样品前处理方法	定值方法
Ag	DAC，DFMW	ICP-MS	Mg	DAC，DAMW，DFMW	ICP-AES，ICP-MS
Al	DAC，FU	ICP-AES，ICP-MS	Mn	DAC，DAMW，DFMW	ICP-AES，ICP-MS
As	DAC，DAMW，DFMW，DMA	ICP-MS，AFS，ICP-AES	Mo	DAC，DAMW，DFMW	ICP-MS
B	DAC，DAMW，DFMW	ICP-MS，ICP-AES，ES	N	DA，DAC，DS	VOL
Ba	DAC，DAMW，DFMW	ICP-MS，ICP-AES	Na	DAC，DAMW，DFMW	ICP-AES，ICP-MS
Be	DAC，DAMW，DFMW	ICP-MS	Nb	DAC，DAMW	ICP-MS
Bi	DAC，DFMW，DMA，DP	ICP-MS，XRF	Nd	DAC，DAMW	ICP-MS
Br	DAC，FU	ICP-MS	Ni	DAC，DAMW	ICP-MS
Ca	DAC，DAMW，DFMW	ICP-AES，ICP-MS	P	DAC，DAMW，DFMW	ICP-AES，ICP-MS
Cd	DAC，DAMW，DFMW，DP	ICP-MS，XRF	Pb	DAC，DAMW，DFMW	ICP-MS
Ce	DAC，DAMW	ICP-MS	Pr	DAC，DAMW，DFMW	ICP-MS
Cl	DAC，DP，FU	COL，IC，XRF	Rb	DAC，DAMW，DFMW	ICP-MS
Co	DAC，DAMW，DFMW	ICP-MS	S	DAC，DAMW，DFMW	ICP-AES，ICP-MS
Cr	DAC，DAMW，DFMW	ICP-MS	Sb	DAC，DAMW，DFMW	ICP-MS，AFS
Cs	DAC，DAMW，DFMW	ICP-MS	Sc	DAC，DAMW，DFMW	ICP-MS
Cu	DAC，DAMW，DFMW	ICP-MS，ICP-AES	Se	DAC，DAMW，DMA	AFS，ICPMS
Dy	DAC，DAMW，DFMW	ICP-MS	Si	DAC，DP，FU	ICP-AES，XRF
Er	DAC，DAMW，DFMW	ICP-MS	Sm	DAC，DAMW，DFMW	ICP-MS
Eu	DAC，DAMW，DFMW	ICP-MS	Sn	DAC，DAMW，DFMW	ICP-MS，ES
F	DAC，DS，FU	ISE，COL，IC	Sr	DAC，DAMW，DFMW	ICP-MS，ICP-AES
Fe	DAC，DAMW，DFMW	ICP-AES，ICP-MS	Tb	DAC，DAMW，DFMW	ICP-MS
Gd	DAC，DAMW，DFMW	ICP-MS	Th	DAC，DAMW，DFMW	ICP-MS
Ge	DAC，DAMW，DFMW	ICP-MS	Ti	DAC，DAMW，DFMW	ICP-MS，ICP-AES
Hg	DAC，DAMW，DFMW，DMA	AFS，ICP-MS	Tl	DAC，DAMW，DFMW	ICP-MS
Ho	DAC，DAMW，DFMW	ICP-MS	Tm	DAC，DAMW，DFMW	ICP-MS
I	DAC，DAMW，FU	ICP-MS，COL	U	DAC，DAMW，DFMW	ICP-MS
K	DAC，DAMW，DFMW	ICP-AES，ICP-MS	V	DAC，DAMW，DFMW	ICP-MS
La	DAC，DAMW，DFMW	ICP-MS	Y	DAC，DAMW，DFMW	ICP-MS
Li	DAC，DAMW，DFMW	ICP-MS	Yb	DAC，DAMW，DFMW	ICP-MS
Lu	DAC，DAMW，DFMW	ICP-MS	Zn	DAC，DAMW，DFMW	ICP-MS，ICP-AES
注：样品分解与富集方法：DAC—硝酸加过氧化氢密闭分解，DFMW—硝酸加氢氟酸微波消解，FU—碱熔或艾斯卡熔融，DAMW—硝酸加过氧化氢微波消解，DMA—混合酸分解，DP—粉末压片法，DS—硫酸分解。元素含量测定方法：ICP-MS—电感耦合等离子体质谱法，ICP-OES—电感耦合等离子体发射光谱法，AFS—原子荧光光谱法，XRF—X射线荧光光谱法，COL—分光光度法，VOL—容量法，ES—直流电弧发射光谱法，IC—离子色谱法，ISE—离子选择电极法。

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表 7 两种茶叶标准物质的认定值与扩展不确定度

Table 7. Certified values and expanded uncertainty of two tea reference materials

样品编号	组分	认定值及不确定度	组分	认定值及不确定度	组分	认定值及不确定度	组分	认定值及不确定度
GBW10016a (GSB-7a)	Ag	0.010±0.002	Cu	8.3±0.5	Mn^*	0.125±0.004	Sn	0.06±0.01
	Al^*	0.25±0.02	Dy^**	130±20	Mo	0.04±0.01	Sr	13.7±0.7
	As	0.10±0.02	Er^**	80±10	N^*	3.4±0.3	Tb^**	21±2
	B	12.6±0.8	Eu^**	27^▲ 25~29	Na	22.6±6.7	Th^**	33.4±7.2
	Ba	32±3	Fe	149±7	Nd	0.66±0.08	Ti	(11.00)
	Be^**	50±8	Gd^**	140±20	P^*	0.24±0.01	Tl^**	47±8
	Bi^**	13±2	Ge^**	13±5	Pb	1.09±0.13	Tm^**	14±2
	Br	(3.00)	Hg^**	8±1	Pr^**	160^▲ 150~180	U^**	13±2
	Ca^*	0.47±0.02	Ho^**	28±4	Rb	45.9±3.3	V	0.3±0.1
	Cd^**	46±5	I	(0.20)	S*	0.26±0.02	Y	2.0±0.2
	Ce	1.3±0.2	K^*	1.45±0.05	Sb	0.05±0.01	Yb^**	100±20
	Cl^*	0.050±0.004	La	1.01±0.08	Sc**	89±17	Zn	27±3
	Co	0.28±0.02	Li	0.25±0.02	Se	0.09±0.04
	Cr	0.79±0.11	Lu^**	16±3	Si^*	0.04±0.01
	Cs	0.19±0.02	Mg^*	0.18±0.01	Sm^**	120±20
GBW10052a (GSB-30a)	Ag	0.008±0.002	Cu	13.2±0.9	Mg^*	0.150±0.005	Se	0.09±0.03
	Al^*	0.12±0.02	Dy^**	54±8	Mn^*	0.117±0.004	Si^*	0.08±0.01
	As	0.16±0.02	Er^**	33±5	Mo	0.053±0.012	Sm^**	54±6
	B	11±2	Eu^**	20±4	N*	3.7±0.3	Sn	0.11±0.02
	Ba	32±3	F	(155.00)	Na	15±4	Sr	14.0±1.3
	Be^**	12±2	Fe	161±18	Nb	(0.15)	Tb^**	9±1
	Bi^**	31±5	Gd^**	58±7	Nd	0.25±0.04	Th^**	25±8
	Br	3.1±0.8	Ge^**	7.5±1.6	Ni	4.4±0.3	Ti	(11.00)
	Ca^*	0.34^▲ 0.32~0.37	Hg^**	7.3±0.7	P^*	0.27±0.02	Tl^**	57±11
	Cd^**	200±20	Ho^**	11±2	Pb	1.6±0.2	Tm^**	5.4±0.9
	Ce	0.51±0.07	I	0.16±0.06	Pr^**	64±7	U^**	8.2±1.5
	Cl^*	0.05±0.01	K^*	1.31±0.05	Rb	81±6	V	0.26±0.03
	Co	0.23±0.02	La	0.34±0.04	S^*	0.23±0.03	Y	0.51±0.05
	Cr	0.6±0.1	Li	0.20±0.03	Sb	0.055±0.007	Yb^**	36±5
	Cs	0.42±0.05	Lu^**	6±1	Sc^**	54±10	Zn	26±3
注：元素含量单位为10^-6，标注“”质量分数为×10^-2, 标注“*”质量分数为×10^-9，带▲的标准值为中位值，其下数据为置信限，括号内数据为参考值。

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