古代玻璃材料LA-ICP-MS组分分析及产源研究

胡志中; 李佩; 蒋璐蔓; 王通洋; 杜谷; 杨波

doi:10.15898/j.cnki.11-2131/td.201909210134

古代玻璃材料LA-ICP-MS组分分析及产源研究

1.
中国地质调查局成都地质调查中心, 四川成都 610081

2.
成都文物考古研究院, 四川成都 610072

详细信息

作者简介: 胡志中, 硕士, 工程师, 从事原位微区分析。E-mail:hzz_pot@aliyun.com

通讯作者: 杨波, 硕士, 高级工程师, 从事同位素分析。E-mail:yangbo@163.com

中图分类号: O657.63

收稿日期: 2019-09-21

修回日期: 2019-11-28

录用日期: 2020-05-13

Application of LA-ICP-MS in the Analysis of Archaeological Glass and Source Discrimination

1.
Chengdu Center of China Geological Survey, Chengdu 610081, China

2.
Chengdu Institute of Cultural Relics and Archaeology, Chengdu 610072, China

More Information

Corresponding author: Bo YANG, yangbo@163.com

Received Date: 21 September 2019

Revised Date: 28 November 2019

Accepted Date: 13 May 2020

摘要

摘要: 古代玻璃及玻璃质材料的定量分析对于研究其制作年代及产地、原料的来源以及制作工艺有着重要的参考意义。与电子探针（EMPA）、能谱扫描-电子显微镜（EDX-SEM）等分析方法相比，LA-ICP-MS能够快速且准确地提供样品主次量及微量元素信息。本文对LA-ICP-MS古代玻璃元素定量分析中的影响因素进行研究认为：在193nm激光下玻璃标准NIST610和康宁玻璃标准之间基体差异造成的影响较小，而采用玻璃标准NIST610为外标结合基体归一化法的校正策略测定康宁标准结果表明，该策略能够准确反映不同类型古代玻璃材料中成分组成；实验中不同剥蚀模式的研究，有助于不同实验条件的建立，从而满足不同研究的需要。本次研究对出土样品进行了分析，为该制品的产源研究提供了数据支持。
- 古代玻璃材料 /
- LA-ICP-MS /
- 标准物质 /
- 基体效应 /
- 校正策略
Abstract: BACKGROUNDQuantitative analysis of ancient glass and vitreous materials has important significance for studying its production time, origin, source of raw materials and production process. Compared with traditional analysis methods (eg. EMPA, EDX-SEM), LA-ICP-MS can be used to analyze the primary, minor and trace elements in samples quickly and accurately. OBJECTIVESTo investigate the composition of archaeological glass and discriminate its sources. METHODSThe element concentration in ancient glass and vitreous materials were determined by LA-ICP-MS. The surface morphologies of pits in glasses were displayed by AFM. RESULTSThe matrix effect among NIST610 and Corning A-D was insignificant under 193nm laser system and this experimental condition. A quantification strategy based on NIST610 and normalization to 100% (w/w) was suitable for analyzing Corning A-D and ancient glass samples. Study on different ablation modes in the experiment is helpful for the establishment of different experimental conditions to meet the requirement of different studies. CONCLUSIONSUnearthed samples were analyzed, which provided data support for the source of the product.
- ancient glass and vitreous materials /
- LA-ICP-MS /
- reference materials /
- matrix effect /
- quantification strategy

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图 1 NIST610和康宁标准A、B、C、D中主要元素氧化物浓度差异

Figure 1.

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图 2 标准物质的元素分馏指数(以Ca为内标)

Figure 2.

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图 3 不同剥蚀条件下NIST610线扫描形貌图

Figure 3.

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图 4 样品中稀土元素配分模式图

Figure 4.

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表 1 LA-ICP-MS仪器工作参数

Table 1. LA-ICP-MS operation conditions

电感耦合等离子体质谱 (ICP-MS)		激光剥蚀系统
ICP-MS	Element 2	激光类型	ArF准分子
分辨率	低分辨(300)	波长	193nm
射频功率	1300W	能量	70mJ
扫描模式	E-scan	频率	5Hz, 10Hz
冷却气(Ar)流速	16.05L/min	样品气(He)流速	0.65L/min
辅助气(Ar)流速	0.75L/min	束斑直径	线扫描：16μm
载气(Ar)流速	0.93L/min		点剥蚀：60μm

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表 2 康宁标准A、B、C、D中主次量元素分析结果

Table 2. Analytical results of major and minor element compositions in Corning reference glass A, B, C and D

元素	A			B			C			D
元素	推荐值 (%)	5次测定平均值(%)	RSD (%)	推荐值 (%)	5次测定平均值(%)	RSD (%)	推荐值 (%)	5次测定平均值(%)	RSD (%)	推荐值 (%)	5次测定平均值(%)	RSD (%)
SiO₂	66.56	68.28	0.6	61.55	62.48	0.1	34.87	34.39	1.0	55.24	55.90	0.7
Na₂O	14.30	14.27	1.7	17.00	16.99	0.6	1.07	1.08	1.3	1.20	1.32	2.4
MgO	2.66	2.56	0.9	1.03	0.99	0.6	2.76	2.62	1.1	3.94	3.92	2.1
Al₂O₃	1.00	0.99	1.3	4.36	4.41	0.7	0.87	0.86	1.4	5.30	5.07	1.0
P₂O₅	0.130	0.113	2.0	0.82	0.79	1.1	0.14	0.10	1.5	3.93	3.83	1.7
K₂O	2.87	3.09	1.0	1.00	1.07	0.4	2.84	2.97	1.9	11.30	12.0	1.4
CaO	5.03	5.13	1.5	8.56	8.75	1.1	5.07	5.26	1.2	14.80	15.12	1.5
MnO	1.00	1.11	2.5	0.25	0.26	1.4	0.0011	0.0016	2.1	0.55	0.58	0.6
Fe₂O₃	1.09	1.08	1.9	0.34	0.33	2.2	0.34	0.30	1.4	0.52	0.49	0.6
BaO	0.460	0.489	3.3	0.077	0.078	2.0	11.40	11.19	1.2	0.29	0.30	2.7
PbO	0.073	0.075	2.5	0.61	0.476	2.5	36.70	35.66	1.1	0.24	0.23	1.0
TiO₂	0.79	0.79	1.1	0.089	0.102	1.5	0.79	0.76	1.4	0.38	0.36	1.6
CuO	1.17	1.23	2.0	2.66	2.74	2.2	1.13	1.19	2.7	0.38	0.37	2.4
CoO	0.170	0.173	1.6	0.046	0.044	0.1	0.180	0.173	3.0	0.023	0.018	2.6
B₂O₃	0.20	0.21	2.4	0.035	0.032	1.7	0.20	0.19	3.8	0.10	0.11	2.6
Li₂O	0.01	0.011	5.7	0.003	0.0025	4.2	0.01	0.009	4.6	0.005	0.006	4.2
V₂O₅	0.006	0.007	1.5	0.034	0.034	1.4	0.006	0.007	1.2	0.015	0.017	1.5
Cr₂O₃	0.003	0.004	3.8	0.0096	0.01	3.0	0.0023	0.0035	3.5	0.003	0.004	4.9
NiO	0.02	0.025	2.4	0.100	0.097	1.6	0.020	0.020	0.6	0.050	0.050	2.3
ZnO	0.044	0.050	2.9	0.190	0.204	2.7	0.052	0.069	0.9	0.10	0.10	2.1
Rb₂O	0.010	0.010	3.9	0.001	0.0011	1.5	0.010	0.009	0.4	0.005	0.0046	1.8
SrO	0.10	0.110	3.9	0.019	0.018	1.0	0.29	0.30	0.7	0.057	0.059	2.1
ZrO₂	0.005	0.005	4.6	0.025	0.022	1.5	0.005	0.005	1.6	0.013	0.010	2.4
SnO₂	0.19	0.180	3.7	0.024	0.024	1.8	0.190	0.181	0.4	0.10	0.09	3.1
Bi₂O₃	0.001	0.001	1.6	0.004	0.004	2.8	0.004	0.005	1.2	0.001	0.001	2.1
注：推荐值来自文献[11]。

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表 3 康宁标准A、B、C、D中微量元素分析结果

Table 3. Analytical results of trace element compositions in Corning reference glass A, B, C and D

元素	A			B			C			D
元素	参考值 (μg/g)	5次测定平均值(μg/g)	相对偏差	参考值 (μg/g)	5次测定平均值(μg/g)	相对偏差	参考值 (μg/g)	5次测定平均值(μg/g)	相对偏差	参考值 (μg/g)	5次测定平均值(μg/g)	相对偏差
Y	0.365	0.705	0.037	0.474	0.443	0.020	4.284	8.766	0.095	0.370	0.504	0.012
Cs	0.255	0.240	0.011	0.061	0.057	0.008	0.368	0.256	0.002	0.14	0.13	0.017
Ce	0.236	0.246	0.015	0.164	0.169	0.005	0.046	0.273	0.005	0.256	0.261	0.011
Hf	0.949	0.986	0.061	4.152	3.989	0.185	1.677	0.916	0.026	2.115	1.854	0.101
Ta	0.124	0.116	0.010	0.089	0.084	0.011	0.120	0.095	0.002	0.231	0.192	0.014
Th	0.288	0.273	0.009	0.805	0.776	0.020	0.204	0.183	0.001	0.648	0.555	0.017
U	0.182	0.159	0.010	0.226	0.223	0.010	0.079	0.070	0.004	0.160	0.155	0.014
注：参考值来自文献[23]。

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表 4 古代玻璃材质样品LA-ICP-MS分析结果

Table 4. Analytical results of elements in archaeological glass by LA-ICP-MS

元素	含量单位	样品1 测定值	样品2 测定值
Na₂O	%	0.91	1.84
MgO	%	0.94	0.87
Al₂O₃	%	3.01	3.08
SiO₂	%	73	71
P₂O₅	%	0.45	0.50
K₂O	%	12.15	12.95
CaO	%	4.90	5.54
TiO₂	%	0.22	0.23
MnO	%	0.11	0.15
Fe₂O₃	%	1.43	1.27
Pb	μg/g	163	71
Li	μg/g	39	61
B	μg/g	17	28
V	μg/g	508	284
Cr	μg/g	49	32
Co	μg/g	6.56	6.27
Ni	μg/g	49	47
Cu	μg/g	14981	18650
Zn	μg/g	482	321
Rb	μg/g	128	147
Y	μg/g	17.6	13.1
Zr	μg/g	80	69
Sr	μg/g	310	251
Mo	μg/g	8.51	4.91
Sn	μg/g	265	97
Ba	μg/g	1920	1073
La	μg/g	15.9	14.4
Ce	μg/g	28	25
Pr	μg/g	3.09	2.79
Nd	μg/g	12.7	11.2
Sm	μg/g	2.40	2.00
Eu	μg/g	0.55	0.43
Gd	μg/g	2.25	1.93
Tb	μg/g	0.33	0.29
Dy	μg/g	2.15	1.71
Ho	μg/g	0.49	0.40
Er	μg/g	1.42	1.12
Tm	μg/g	0.20	0.17
Yb	μg/g	1.43	1.10
Lu	μg/g	0.22	0.19
Hf	μg/g	1.96	1.82
Th	μg/g	3.61	3.25
U	μg/g	8.43	3.95

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