葡萄酒中稀土元素的测定

鸭梨

2017/07/07

私聊

ICP-MS

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
元素	硝酸用量	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

元素	样品	添加水平
	样品	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
	样品	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
	样品	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