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