石英岩化学成分分析标准物质研制

刘瑱; 马玲; 时晓露; 查立新

石英岩化学成分分析标准物质研制

安徽省地质实验研究所, 安徽合肥 230001

基金项目: 国土资源公益性行业科研专项(200911044-05)

详细信息

作者简介: 刘瑱, 高级工程师, 主要从事岩矿测试技术研究和管理等工作.E-mail: ahdss001@163.com

中图分类号: P578.494;TQ421.31;O657.31;O657.63

收稿日期: 2014-01-27

修回日期: 2014-10-26

录用日期: 2014-11-15

刊出日期: 2014-06-25

Preparation of Quartzite Reference Materials for Chemical Composition Analysis

Anhui Provincial Institute of Geological Experiment & Research, Hefei 230001, China

Received Date: 27 January 2014

Revised Date: 26 October 2014

Accepted Date: 15 November 2014

Publish Date: 25 June 2014

摘要

摘要:
目前巴西、英国、日本、南非等国研制有一些石英岩类标准物质, SiO₂含量均在96%以上, 含量范围较窄, 定值元素较少。我国尚无石英岩类的标准物质, 无法满足石英岩勘查和实际应用的需要。本文研制了3个石英岩化学成分分析标准物质, 样品采自我国具有代表性的安徽省凤阳县大庙镇老青山、青海省大通县景阳镇和湖北省蕲春县灵虬山三个石英矿区, 利用流化床式气流粉碎机将样品细碎至-45 μm, 解决了纯度较高的石英岩粉碎加工易受污染的难题。因石英岩样品难以压制成型, 均匀性检验未采用压片制样X射线荧光光谱法, 而是采用以电感耦合等离子体发射光谱法和电感耦合等离子体质谱法为主的检验方法。结果表明, 方差检验的F值均小于临界值, 证明其均匀性符合要求。为期两年的长期稳定性8次检验中未发现统计学意义上的明显变化, 在颠震和极端温度条件下所检验的短期稳定性良好。经我国十家实验室使用多种分析方法联合定值, 同时探索采用类似元素比较法获取未进行均匀性和稳定性检验的成分的相应不确定度分量, 给出了36个成分的认定值(或参考值)和相应的不确定度。3个标准物质现已被批准为国家一级标准物质(编号GBW 07835、GBW 07836、GBW 07837), 其主要成分SiO₂的含量相应为92.93%、95.97%、99.18%, 呈梯度分布。此系列标准物质具有样品粒度均匀、粒度分布范围窄(D₂₅~D₇₅在4~16 μm之间), 定值元素种类多, SiO₂含量分布广泛的特点, 可以满足石英岩样品化学成分分析过程中监控的需要。
- 石英岩 /
- 标准物质 /
- 均匀性 /
- 稳定性 /
- 电感耦合等离子体发射光谱法 /
- 电感耦合等离子体质谱法
Abstract:
At present, quartzitic reference materials are prepared by Brazil, England, Japan, and South Africa but are not in series. The SiO₂ contents in these reference materials are generally above 96% and accurate concentration values are determined for only small number of elements. To date, no quartzitic reference material has been prepared in China, which cannot meet the demand of quartzite exploration and practical applications. In this study, three quartzitic reference materials were developed with samples from representative quartz mining areas, namely Damiao Town, Fengyang County, Anhui Province; Jingyang Town, Datong County, Qinghai Province; and Lingqiu mountain, Qichun County, Hubei Province. The samples were finely crushed to -45 μm with a fluidized bed-type airflow crusher to prevent sample contamination. Homogeneity and stability testing was conducted chiefly by inductively coupled plasma emission spectrometry and mass spectrometry rather than X-ray Fluorescence Spectrometry with tablet sample preparation, which results in the quartzite material being difficult to mould. F values for the variance test were less than the threshold, which indicated a good homogeneity. No significant statistical changes were observed in eight two-year stability tests. The short-term stability analysis in the condition of extreme temperatures and vibration were also consistent. Determined values were certified by 10 laboratories in China with multiple methods. For components without homogeneity and stability tests, values and relative uncertainty of 36 components were obtained by comparing similar elements. The three quartzitic reference materials have been approved as National standard reference materials (GBW 07835, GBW 07836 and GBW 07837), with 92.93%, 95.97% and 99.18% of SiO₂, respectively, as a gradient distributed series. This series of reference materials has the characteristics of uniform grading, narrow diameter distribution (D₂₅-D₇₅ ranged between 4-16 μm), multiple value determined elements, and wide-range distribution of SiO₂ content, which should meet the monitoring requirements of chemical composition analysis of quartzite samples.
- quartzite /
- standard reference material /
- homogeneity /
- stability /
- Inductively Coupled Plasma-Atomic Emission Spectrometry /
- Inductively Coupled Plasma-Atomic Emission Spectrometry-Mass Spectrometry

HTML全文

图 1 GRSY-1粒度分布图

Figure 1.

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图 2 GRSY-2粒度分布图

Figure 2.

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图 3 GRSY-3粒度分布图

Figure 3.

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图 4 GBW07106粒度分布图

Figure 4.

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图 5 GBW03112粒度分布图

Figure 5.

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图 6 GBW 03113粒度分布图

Figure 6.

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表 1 GRSY-1~GRSY-3与标准物质GBW 03112、GBW 03113、GBW 07106粒度分布比较

Table 1. Comparison of grain distribution of GRSY-1~GRSY-3 and known standard materials GBW 07106, GBW 03112, GBW 03113

参数(μm)	GRSY-1 (石英岩)	GRSY-2 (石英岩)	GRSY-3 (脉石英)	GBW 03112 (硅质砂岩)	GBW 03113 (硅质砂岩)	GBW 07106 (石英砂岩)
中位粒径	9.66	9.29	8.89	12.46	11.72	9.79
体积平均粒径	10.67	10.17	9.83	19.25	19.59	15.73
面积平均粒径	4.12	4.09	3.91	4.29	3.97	3.41
D₂₅~D₇₅粒径	4.20~15.54	4.08~14.84	3.83~14.33	3.98~28.85	3.43~28.86	2.96~23.44
最大粒径	46	42	42	105	115	96

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表 2 不同细碎方法检测结果比较

Table 2. Comparison of analytical results for samples with different fine crushing methods

元素	含量单位	样品10L787玛瑙球磨法测定值		样品GRSY-3 气流粉碎法测定值		认定值
SiO₂		99.24	99.18	99.16	99.20	99.18
Al₂O₃		0.29	0.27	0.27	0.28	0.29
CaO		0.035	0.038	0.038	0.037	0.036
K₂O	10^-2	0.055	0.056	0.056	0.058	0.050
Na₂O		0.01	0.011	0.011	0.011	0.010
MgO		0.023	0.024	0.024	0.026	0.022
Fe₂O₃		0.17	0.17	0.17	0.16	0.16
Ba		17.4	16.4	16.5	17.3	17.4
Sr		3.0	3.1	3.1	3.1	3.0
V		1.80	1.73	1.84	1.75	1.80
Be		0.10	0.08	0.08	0.08	0.09
Cu		9.03	8.93	8.64	9.09	8.90
Zn		3.81	3.65	3.89	3.79	3.70
Rb	10^-6	3.13	3.07	3.13	3.06	3.00
Cd		0.016	0.017	0.015	0.016	0.015
Sb		0.19	0.20	0.19	0.19	0.20
Ce		1.01	1.03	1.03	0.98	1.10
Pb		32.21	32.76	31.92	32.02	31.7
Bi		0.036	0.035	0.034	0.036	0.034
U		0.11	0.11	0.10	0.09	0.10

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表 3 均匀性检验结果

Table 3. Analytical results of homogeneity test

样品编号	统计项目	SiO₂			Al₂O₃			TiO₂
GRSY-1	含量平均值(10^-2)	92.88			2.40			0.106
	RSD(%)	0.1			0.7			1.0
	F	1.02			1.16			1.26
GRSY-2	含量平均值(10^-2)	95.98			1.36			0.0584
	RSD(%)	0.1			0.7			1.1
	F	1.04			1.12			1.21
GRSY-3	含量平均值(10^-2)	99.13			0.286			0.0125
	RSD(%)	0.1			0.7			2.1
	F	1.07			1.18			1.16
样品编号	统计项目	P₂O₅	Cr₂O₃	Ni	Pb	La	Ce	U	W	Zr	As
GRSY-1	含量平均值(10^-6)	245	77.2	22.1	40	8.61	16.6	0.56	0.49	94.4	0.93
	RSD(%)	2.0	2.5	2.6	2.7	2.0	2.0	2.6	5.8	4.8	4.7
	F	1.32	1.16	1.23	1.09	1.14	1.07	1.39	1.12	1.22	1.29
GRSY-2	含量平均值(10^-6)	178	79.9	24.8	70.1	9.28	19.5	0.47	0.3	54.81	1.4
	RSD(%)	1.7	2.3	1.7	1.6	2.6	2.8	4.1	5.2	6.7	3.2
	F	1.33	1.16	1.62	1.65	1.11	1.08	1.03	1.25	1.09	1.09
GRSY-3	含量平均值(10^-6)	39.7	53.6	15.7	31.5	0.52	1.05	0.092	0.2	2.02	0.43
	RSD(%)	4.9	3.0	2.8	2.6	4.4	4.4	6.4	6.2	8.3	6.7
	F	1.36	1.12	1.44	1.02	1.07	1.09	1.35	1.22	1.16	1.08

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表 4 长期稳定性检验结果

Table 4. Analytical results of long-term stability test

元素	分析方法	参数	GRSY-1	GRSY-2	GRSY-3
As	DAW-AFS	平均值(10^-6)	0.88	1.32	0.46
		b₁	0.0002871	0.0000718	-0.000167
		t_{0.95, 6}×s(b₁)	0.000778	0.0012	0.00107
Co	ICP-MS	平均值(10^-6)	1.87	1.49	1.66
		b₁	0.0000718	-0.0004067	-0.0002392
		t_{0.95, 6}×s(b₁)	0.00108	0.000532	0.00105
Cu	ICP-MS	平均值(10^-6)	14.74	13.38	9.18
		b₁	-0.001268	0.0002871	-0.0039
		t_{0.95, 6}×s(b₁)	0.0062	0.00806	0.00403
La	ICP-MS	平均值(10^-6)	8.63	9.28	0.52
		b₁	0.0004306	-0.0008612	0.0004545
		t_{0.95, 6}×s(b₁)	0.0044	0.0038	0.00069
Ni	ICP-MS	平均值(10^-6)	21.31	22.49	15.38
		b₁	-0.0003828	-0.001412	0.002368
		t_{0.95, 6}×s(b₁)	0.00706	0.0135	0.0039
Pb	ICP-MS	平均值(10^-6)	40.03	69.99	31.26
		b₁	0.01548	0.03574	-0.0219
		t_{0.95, 6}×s(b₁)	0.027	0.038	0.0272
U	ICP-MS	平均值(10^-6)	0.57	0.48	0.105
		b₁	0.0002871	0.0000478	0.0000311
		t_{0.95, 6}×s(b₁)	0.000629	0.00069	0.0011
Zn	ICP-MS	平均值(10^-6)	11.54	7.48	4.05
		b₁	-0.004665	-0.0002321	0.0006699
		t_{0.95, 6}×s(b₁)	0.00782	0.00235	0.0017

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表 6 石英岩标准物质标准值及不确定度

Table 6. Standard value and uncertainty of quartzite standard materials

定值元素	标准值(10^-2)
定值元素	GRSY-1	GRSY-2	GRSY-3
SiO₂	92.93±0.17	95.97±0.22	99.18±0.06
Al₂O₃	2.43±0.11	1.33±0.06	0.29±0.03
TFe₂O₃	0.62±0.02	0.61±0.02	0.16±0.01
CaO	1.20±0.05	0.59±0.02	0.036±0.005
MgO	0.29±0.03	0.15±0.02	0.022±0.003
K₂O	0.60±0.03	0.28±0.01	0.050±0.004
Na₂O	0.28±0.03	0.13±0.02	0.010±0.002
TiO₂	0.10±0.01	0.059±0.004	0.014±0.002
MnO	0.015±0.001	0.0080±0.0004	0.0049±0.0002
P₂O₅	0.025±0.002	0.018±0.002	0.0036±0.0007
Cr₂O₃	0.0077±0.0007	0.0083±0.0008	0.0053±0.0008
LOI	1.35±0.09	0.69±0.05	0.14±0.04
定值元素	标准值(10^-6)
定值元素	GRSY-1	GRSY-2	GRSY-3
As	0.89±0.10	1.3±0.2	0.48±0.10
Ba	84.2±1.6	56.8±1.8	17.4±1.0
Be	0.41±0.03	0.21±0.01	0.09±0.01
Bi	0.036±0.004	0.050±0.004	0.034±0.004
Cd	0.037±0.005	0.025±0.003	0.015±0.003
Ce	16.7±0.7	19.3±0.5	1.1±0.2
Cl	(34)	(38)	(15)
Co	1.8±0.1	1.4±0.1	1.6±0.1
Cu	14.6±0.7	13.4±0.6	8.9±0.4
Hg	(0.003)	(0.002)	(0.002)
La	8.8±0.3	9.3±0.3	0.54±0.06
Li	3.4±0.3	2.7±0.3	2.5±0.3
Mo	1.6±0.1	2.1±0.1	3.8±0.2
Ni	21.5±1.1	23.9±1.2	15.8±0.9
Pb	39.7±2.3	69.4±3.9	31.7±2.2
Rb	16.7±0.7	10.3±0.8	3.0±0.3
Sb	0.20±0.03	0.22±0.03	0.20±0.03
Sr	33.9±1.1	20.0±1.0	3.0±0.4
Th	2.9±0.2	1.8±0.1	0.14±0.03
U	0.58±0.04	0.48±0.05	0.10±0.01
V	11.9±0.7	7.4±0.4	1.8±0.2
W	0.47±0.06	0.27±0.04	0.19±0.03
Zn	11.2±0.6	7.8±0.7	3.7±0.3
Zr	93±6	53±4	(1.7)

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表 5 均匀性、稳定性及定值不确定度比较

Table 5. Comparison of homogeneity, stability and uncertainty

元素	测定不确定度u_c			样品稳定性引入的不确定度u_s			样品均匀性引入的不确定度u_bb
元素	GRSY-1	GRSY-2	GRSY-3	GRSY-1	GRSY-2	GRSY-3	GRSY-1	GRSY-2	GRSY-3
As	0.043	0.057	0.044	0.007	0.011	0.0096	0.013	0.009	0.006
Al₂O₃	0.050	0.021	0.007	-	-	-	0.0044	0.0022	0.0014
Ce	0.289	0.199	0.051	-	-	-	0.060	0.041	0.0095
Co	0.031	0.019	0.042	0.0097	0.0048	0.0095	-	-	-
Cu	0.302	0.259	0.169	0.056	0.072	0.036	-	-	-
Cr₂O₃	0.0003	0.0003	0.0002				0.00005	0.00005	0.00004
La	0.132	0.116	0.026	0.040	0.034	0.006	0.041	0.036	0.004
Ni	0.510	0.540	0.428	0.063	0.12	0.035	0.137	0.082	0.131
P₂O₅	0.001	0.001	0.0003	-	-	-	0.00018	0.00011	0.00008
Pb	1.073	1.913	0.974	0.24	0.34	0.24	0.223	0.560	0.077
SiO₂	0.080	0.103	0.029	-	-	-	0.0094	0.0134	0.0087
TiO₂	0.002	0.002	0.001	-	-	-	0.00034	0.00021	0.00007
U	0.017	0.019	0.005	0.0057	0.006	0.001	0.0058	0.0023	0.0011
W	0.024	0.016	0.011	-	-	-	0.0068	0.0053	0.0033
Zn	0.253	0.311	0.130	0.070	0.021	0.015	-	-	-
Zr	2.570	1.573	0.209	-	-	-	0.657	0.343	0.046

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石英岩化学成分分析标准物质研制

安徽省地质实验研究所, 安徽 合肥 230001

作者简介: 刘瑱, 高级工程师, 主要从事岩矿测试技术研究和管理等工作.E-mail: ahdss001@163.com

Preparation of Quartzite Reference Materials for Chemical Composition Analysis

Anhui Provincial Institute of Geological Experiment & Research, Hefei 230001, China

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安徽省地质实验研究所, 安徽合肥 230001