Research on the Chemical Pretreatment for Mo Isotope Analysis of Special Geological Samples
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摘要: Mo同位素的研究在地学领域应用广泛，它可以示踪Mo的全球循环、古海洋氧化还原条件、成矿过程、天体演化过程等。应用多接收电感耦合等离子体质谱法（MC-ICP-MS）分析Mo同位素比值前需对样品进行分离纯化，以富集Mo和去除Zr、Ru、Fe、Mn等干扰元素。处理某些Fe含量特别高且Ca含量也高的特殊地质样品（如含大量黄铁矿的钙质泥岩、钙质页岩等），若根据传统的阴阳离子交换树脂双柱法，需多次使用阳离子交换树脂分离Fe，步骤较繁琐且Mo回收率也会降低，而根据传统的阴离子交换树脂单柱法，使用1mol/L氢氟酸-0.5mol/L盐酸介质会产生较多CaF2沉淀影响分离纯化效果。针对此类特殊地质样品，本实验使用同一阴离子树脂柱（AG1-X8，100~200目）对样品进行两次淋洗，第一次使用6mol/L盐酸，第二次使用1mol/L氢氟酸-0.1mol/L盐酸和6mol/L盐酸。结果表明Mo的回收率>96%，干扰元素的去除效果好，尤其是Ru的去除率接近100%，比原方法提高了约12%。对实际样品进行实验的结果也显示，Mo的回收率和干扰元素的去除都符合要求，δ98/95Mo测定值与文献报道值一致。改进后的阴离子交换树脂单柱-二次淋洗法适用于Fe、Ca含量较高的特殊样品，降低了分析成本，也适用于绝大多数地质样品。Abstract:
BACKGROUNDMo isotopes have been widely used in the field of geosciences. They can be used to trace the global cycle of Mo, paleoocean redox conditions, mineralization processes, and astronomical evolution. Before the analysis of Mo isotope by multi-collector inductivity coupled plasma-mass spectrometry (MC-ICP-MS), the samples must be pretreated to enrich Mo and remove the interference elements (Zr, Ru, Fe and Mn). According to the traditional anion-cation exchange resin double-column method, it is necessary to use a cation-exchange resin multiple times to separate Fe. The steps are more complicated and the Mo recovery will be reduced. According to the traditional anion-exchange resin single-column method, 1mol/L hydrofluoride acid-0.5mol/L hydrochloric acid medium will produce more CaF2 precipitation and affect the separation and purification results. OBJECTIVESTo develop a new method for managing Ca-bearing geological samples with high Fe content before Mo isotope analysis. METHODSFor such special geological samples, the same anionic resin column (AG1-X8, 100-200 mesh) was used to rinse the sample twice, the first time using 6mol/L hydrochloric acid, and the second time using 1mol/L hydrofluoride acid-0.1mol/L hydrochloric acid and 6mol/L hydrochloric acid. RESULTSResults showed that Mo recovery was better than 96%, and the removal of the interference elements was good, especially the Ru removal rate, which was higher than the previous methods by 12%, up to 100%. The results of experiments on actual samples also showed that the recovery of Mo and the removal of interfering elements meet the requirements, and the measured values of δ98/95Mo were consistent with those reported in the literature. CONCLUSIONSThe improved anion exchange resin single-column elution method is suitable for special samples with high Fe and Ca content, which reduces the analysis cost and is applicable to most geological samples. -
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表 1 Mo的分离纯化操作流程
Table 1. Elution sequence of the two-step single-column separation for Mo
方法1(使用盐酸、硝酸收集Mo) 步骤 材料和试剂 用量(mL) 操作步骤详细说明 装树脂 AG1-X8树脂 5 - 洗涤 3mol/L硝酸 30 - 洗涤 水 15 - 洗涤 1mol/L盐酸 30 - 平衡 6mol/L盐酸 15 - 样品引入 样品(介质6mol/L盐酸) 5 - 洗涤 6mol/L盐酸 10+10+10 - 收集Mo 1mol/L盐酸 30 将这60mL溶液收集后分析相关元素含量 收集Mo 3mol/L硝酸 30 洗涤 水 10+10+10 为第二次过柱做准备 洗涤 0.1mol/L盐酸 10 为第二次过柱做准备 平衡 1mol/L氢氟酸-0.1mol/L盐酸 15 - 样品引入 样品(介质1mol/L氢氟酸-0.1mol/L盐酸) 5 第二次过柱 洗涤 1mol/L氢氟酸-0.1mol/L盐酸 20 - 洗涤 6mol/L盐酸 10+10 - 收集Mo 1mol/L盐酸 30 每5mL收集为一件样品，共6件样品，分析每件样品的相关元素含量 收集Mo 3mol/L硝酸 30 每5mL收集为一件样品，共6件样品，分析每件样品的相关元素含量 方法2(使用盐酸收集Mo) 步骤 材料和试剂 用量(mL) 操作步骤详细说明 装树脂 AG1-X8树脂 5 - 洗涤 水 15 - 洗涤 1mol/L盐酸 30 - 平衡 6mol/L盐酸 15 - 样品引入 样品(介质6mol/L盐酸) 5 - 洗涤 6mol/L盐酸 10+10+10 - 收集Mo 1mol/L盐酸 40 将这40mL溶液收集后分析相关元素含量 洗涤 水 10+10+10 为第二次过柱做准备 洗涤 0.1mol/L盐酸 10 为第二次过柱做准备 平衡 1mol/L氢氟酸-0.1mol/L盐酸 15 - 样品引入 样品(介质1mol/L氢氟酸-0.1mol/L盐酸) 5 第二次过柱 洗涤 1mol/L氢氟酸-0.1mol/L盐酸 20 - 洗涤 6mol/L盐酸 10+10 - 收集Mo 1mol/L盐酸 40 每5mL收集为一件样品，共8件样品，分析每件样品的相关元素含量 注：“-”表示淋洗的酸液中主要为基质元素，作为废液处理。 
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表 2 质谱分析Mo同位素组成过程中潜在的干扰离子
Table 2. Potential species interfering Mo isotope measured by MC-ICP-MS
被干扰核素 干扰离子(多原子) 干扰离子(单原子) 92Mo 54Fe38Ar+, 56Fe36Ar+, 54Cr38Ar+, 52Cr40Ar+ 92Zr, 184W++, 184Os++ 94Mo 58Fe36Ar+, 56Fe38Ar+, 54Fe40Ar+, 58Ni36Ar+, 54Cr40Ar+ 94Zr, 188Os++ 95Mo 57Fe38Ar+, 55Mn40Ar+, 59Co36Ar+ 190Os++, 190Pt++ 96Mo 56Fe40Ar+, 58Fe38Ar+, 58Ni38Ar+, 60Ni36Ar+ 96Zr, 96Ru, 192Os++, 192Pt++ 97Mo 57Fe40Ar+, 59Co38Ar+, 61Ni36Ar+ 194Pt++ 98Mo 58Fe40Ar+, 58Ni40Ar+, 60Ni38Ar+, 62Ni36Ar+ 98Ru, 196Pt++, 196Hg++ 100Mo 64Ni36Ar+, 64Zn36Ar+, 62Ni38Ar+, 60Ni40Ar 100Ru+, 200Hg++
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表 3 通过离子交换树脂后的洗涤(收集)液的分析结果(方法1)
Table 3. Analysis of the sample purified by the anion resin exchange column (Method 1)
项目 Mo(μg) Zr(μg) Ru(μg) Fe(μg) Mn(μg) 初始样品 32.9 6.83 11.4 50700 364 60mL Mo收集液(第一次过柱) 32.1 0.252 1.39 49800 1.54 第一次过柱的回收率(%) 97.6 3.69 12.2 98.2 0.42 样品引入+洗涤液(第二次过柱) 0.0626 5.75 0.424 49800 1.54 Mo收集液① 0.0194 < 0.0005 0.0875 < 0.0005 0.0502 Mo收集液② 3.41 < 0.0005 0.0182 < 0.0005 0.137 Mo收集液③ 19.6 < 0.0005 0.0235 < 0.0005 0.124 Mo收集液④ 6.34 < 0.0005 0.0203 < 0.0005 0.132 Mo收集液⑤ 1.20 < 0.0005 0.0213 < 0.0005 0.141 Mo收集液⑥ 0.357 < 0.0005 0.0176 < 0.0005 0.151 盐酸收集液的总量 30.9 - 0.188 - 0.735 盐酸收集液的回收率(相对初始样品，%) 93.9 0 1.65 0 0.20 Mo收集液⑦ 0.163 < 0.0005 0.0227 < 0.0005 0.0774 Mo收集液⑧ 0.540 < 0.0005 0.242 < 0.0005 < 0.0005 Mo收集液⑨ 0.108 < 0.0005 0.367 < 0.0005 < 0.0005 Mo收集液⑩ 0.0527 < 0.0005 0.313 < 0.0005 < 0.0005 Mo收集液B11 0.0321 < 0.0005 0.231 < 0.0005 < 0.0005 Mo收集液B12 0.0174 < 0.0005 0.158 < 0.0005 < 0.0005 硝酸收集液的总量 0.913 - 1.33 - 0.0774 硝酸收集液的回收率(相对初始样品，%) 2.78 0 11.7 0 0.02 总回收率▲(相对初始样品，%) 96.7 0 13.4 0 0.22 注：Mo收集液①~Mo收集液⑥为第二次过柱中依次收集的5mL 1mol/L盐酸收集液，分6次收集，共30mL 1mol/L盐酸收集液；Mo收集液⑦~Mo收集液B12为第二次过柱中依次收集的5mL 3mol/L硝酸收集液，分6次收集，共30mL 3mol/L硝酸收集液。总回收率表示第二次过柱中盐酸收集液与硝酸收集液的总回收率。
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表 4 通过离子交换树脂后的洗涤(收集)液的分析结果(方法2)
Table 4. Analysis of the sample purified by the anion resin exchange column (Method 2)
项目 Mo(μg) Zr(μg) Ru(μg) Fe(μg) Mn(μg) 初始样品 33.0 7.15 10.5 50600 357 40mL Mo收集液(第一次过柱) 32.1 0.281 0.0295 50300 0.230 第一次过柱的回收率(%) 97.3 3.93 0.281 99.4 0.064 样品引入+洗涤液(第二次过柱) - - - - - Mo收集液① 0.0043 0.0005 < 0.0005 0.359 0.0013 Mo收集液② 3.98 0.0027 < 0.0005 0.263 < 0.0005 Mo收集液③ 25.1 0.0077 < 0.0005 0.0551 < 0.0005 Mo收集液④ 2.46 0.0011 < 0.0005 0.265 < 0.0005 Mo收集液⑤ 0.231 0.0007 < 0.0005 0.114 0.0157 Mo收集液⑥ 0.0917 < 0.0005 < 0.0005 0.118 < 0.0005 Mo收集液⑦ 0.0262 < 0.0005 < 0.0005 0.118 < 0.0005 Mo收集液⑧ 0.0165 < 0.0005 < 0.0005 0.049 0.0012 收集液的总量 31.9 0.0127 0 1.34 0.0182 总回收率▲(相对初始样品，%) 96.7 0.178 0 0.003 0.003 注：Mo收集液①~Mo收集液⑧为第二次过柱中依次收集的5mL 1mol/L盐酸收集液，分8次收集，共40 mL 1mol/L盐酸收集液。“▲”总回收率表示第二次过柱中盐酸收集液的总回收率。
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表 5 实际地质样品经阴离子交换树脂单柱-二次淋洗法分离纯化后的Mo同位素分析结果
Table 5. Mo isotope analysis of real geological samples pretreated by the modified separation method of anion exchange resin with single column-double
样品编号 样品性质 δ98/95Mo(‰) 文献 Xiaozhu-01 碳质页岩 -0.21±0.08
-0.22±0.13本研究
文献[44]Wj-4 碳质页岩夹方解石脉 1.65±0.10
1.63±0.12
1.63±0.11本研究
文献[44]
文献[14]Xiaozhu-33 白云岩 1.30±0.12
1.29±0.14本研究
文献[44]GBW07303 水系沉积物标准物质 -0.35±0.10
-0.38±0.16本研究
文献[44]注： ${\delta ^{98/95}}{\rm{Mo}}\left( \right) = [\frac{{{{{(^{98}}{\rm{Mo}}{/^{95}}{\rm{Mo}})}_{样品}}}}{{{{{{\rm{(}}^{98}}{\rm{Mo}}{/^{95}}{\rm{Mo}})}_{{\rm{NIST}}3134}} \times 0.99975}} - 1] \times 1000$ 。
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