Ultratrace Platinum Group Elements in Geological Samples by Inductively Coupled Plasma-Mass Spectrometry with Nickel Sulfide Fire Assay
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摘要:
铂族元素(PGEs)六项元素钌、铑、钯、锇、铱和铂的物理化学性质相近，在地壳中丰度极低且分布不均匀，且具有明显的粒金效应，长期以来准确测定其含量始终是岩矿测试的难题。镍锍试金取样量大，可定量分离富集铂族元素，通常被应用于PGEs分析，但将其应用于超痕量PGEs分析的关键问题是流程空白高，质谱干扰严重。本文报道了一种同时测定样品中超痕量铂钯铑铱锇和钌的方法。检查全流程试剂空白后，使用镍锍试金富集样品中的PGEs，经杂质分离，利用电感耦合等离子体质谱(ICP-MS)动能歧视模式测定六项元素，有效地降低了质谱干扰。结果表明，方法的空白主要来自盐酸和捕集剂镍粉，选择合适厂家的试剂或对试金配料进行提纯，可降低全流程空白。同时，使用ICP-MS法测定六项元素时，在标准模式下，铂和钯的检出限小于0.2ng/g，铑、铱和锇的检出限小于0.02ng/g，钌的检出限大于0.1ng/g，钌的检出限无法满足超痕量PGEs的测定要求。使用动能歧视模式后，钌的背景等效浓度比标准模式降低近两个数量级，从而消除了镍对钌的质谱干扰，钌的检出限降低至0.005ng/g，使六项元素检出限同时满足超痕量PGEs测定要求。该方法用于分析土壤(GBW07288、GBW07294)、水系沉积物标准物质(GBW07289)，六项元素的结果与标准值符合，相对误差为−10.9%～11.8%，相对标准偏差为3.85%～9.37%，加标回收率为92%～110%。该方法流程较短、操作简便，满足大批量地质样品中超痕量PGEs的检测要求。
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关键词:
- 镍锍试金 /
- 电感耦合等离子体质谱法 /
- 动能歧视模式 /
- 铂族元素；土壤；水系沉积物
Abstract:Pt, Pd, Rh, Ir, Os and Ru are platinum group elements (PGEs) with similar properties. Due to the low abundance as well as the nugget effect, the accurate determination of PGEs has been a challenge for rock and mineral analysis. Fire assay methods with large sample weights were developed to separate and preconcentrate PGEs, however, there are still difficulties to accurately determine ultratrace PGEs because of the high reagent blanks and the matrix effect. A method of nickel sulfide fire assay combined with ICP-MS simultaneous determination of ultratrace PGEs in samples was established. The results showed that the blank mainly comes from hydrochloric acid and nickel collector when using nickel sulfide fire assay to capture PGEs. The intensities of PGEs were detected by ICP-MS in standard mode and kinetic energy discrimination. In standard mode, the detection limits were 0.2ng/g for Pt and Pd, and 0.02ng/g for Rh, Ir and Os, but it couldn’t reach 0.1ng/g for Ru. In kinetic energy discrimination, the background equivalent concentration of Ru was two orders of magnitude lower than that in the standard mode. With the matrix effect of Ni effectively eliminated, the detection limits reached 0.005ng/g for Ru. The detection limits for PGEs required by geochemical exploration were achieved. The certified reference materials of soil (GBW07288, GBW07294) and stream sediment (GBW07289) were analyzed to test the method. The determined values were in good agreement with the certified values. The relative errors were between −10.9% and 11.8%, the relative standard deviations (RSD, n=12) were 3.88%−9.37%, and the spiked recoveries were 92%−110%. This method is simple, rapid and meets the requirements of ultratrace PGEs determination in large quantities of geological samples. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202407180159 . -
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表 1 ICP-MS仪器工作参数
Table 1. Working parameters of ICP-MS instrument
工作参数 设定值 工作参数 设定值 射频功率 1550W 冷却气流速 15L/min 采样深度 8mm 载气流速 1L/min 雾化室温度 2℃ 辅助气流速 1L/min 提取透镜电压 −165V 碰撞气(He)流速 3.6L/min 
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表 2 镍锍试金配料组成
Table 2. Composition of nickel sulfide fire assay ingredients
样品类型 称样量
(g)硫
(g)羰基镍
(g)羰基铁
(g)硼砂
(g)碳酸钠
(g)二氧化硅
(g)面粉
(g)土壤 20 2 1.6 4 25 20 5 1 水系沉积物 20 2 1.6 4 25 20 6 1
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表 3 不同盐酸对应的流程空白
Table 3. Blank values corresponding to different classes of hydrochloric acid
试剂 Ru
(ng/g)Rh
(ng/g)Pd
(ng/g)Os
(ng/g)Ir
(ng/g)Pt
(ng/g)Ⅰ-分析纯 0.0350 0.0003 0.0023 0.0006 ＜0.0001 0.0019 Ⅰ-优级纯 0.0346 0.0004 0.0013 0.0005 ＜0.0001 0.0015 Ⅱ-分析纯 0.0018 0.0001 0.0016 0.0002 ＜0.0001 0.0012 Ⅱ-优级纯 0.0015 0.0002 0.0013 0.0002 ＜0.0001 0.0011
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表 4 不同熔剂用量对应的流程空白
Table 4. Blank values corresponding to different amounts of flux
熔剂用量
(g)Ru
(ng/g)Rh
(ng/g)Pd
(ng/g)Os
(ng/g)Ir
(ng/g)Pt
(ng/g)20 0.390 0.051 0.340 0.010 0.014 0.141 40 0.511 0.076 0.366 0.008 0.008 0.126 60 0.303 0.071 0.361 0.009 0.009 0.125 80 0.414 0.064 0.349 0.010 0.009 0.128
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表 5 不同镍基体的铂族元素含量
Table 5. PGE contents in different Ni matrices
试剂 Ru
(ng/g)Rh
(ng/g)Pd
(ng/g)Os
(ng/g)Ir
(ng/g)Pt
(ng/g)镍粉 0.469 0.095 0.509 4.977 1.962 0.590 硝酸镍 0.779 0.169 0.918 1.107 0.573 0.753 氧化镍 0.560 0.159 0.452 0.480 0.744 0.597 Ⅴ-羰基镍 0.175 0.109 0.096 0.050 0.006 0.120 Ⅵ-羰基镍 0.012 0.010 0.091 0.009 0.009 0.125
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表 6 镍元素对钌元素测定结果的影响
Table 6. Influence of Ni on the determination results of Ru
样品编号 Ru的加入量
(ng/mL)Ni的加入量
(ng/mL)Ru的测定值
(ng/mL)Ru的回收率
(%)1 0.04 500 0.042 105 2 0.04 1000 0.047 116 3 0.04 5000 0.053 133 4 0.04 10000 0.060 150 5 0.04 50000 0.086 214 6 0.04 100000 0.122 304 7 0.04 500000 0.209 521
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表 7 动能歧视模式下铂族元素检出限和测定下限
Table 7. Detection limits and quantification limits for PGEs in kinetic energy discrimination model.
方法参数 Ru
(ng/g)Rh
(ng/g)Pd
(ng/g)Os
(ng/g)Ir
(ng/g)Pt
(ng/g)空白平均值 0.013 0.008 0.155 0.015 0.011 0.112 检出限(3s) 0.005 0.008 0.050 0.012 0.007 0.058 测定下限(10s) 0.015 0.024 0.150 0.036 0.021 0.174
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表 8 标准物质分析结果
Table 8. Analytical results of PGEs in national reference materials
标准物质编号 元素 测定值
(ng/g)RSD
(%)标准值
(ng/g)相对误差
(%)加标量
(ng/g)测定总值
(ng/g)回收率
(%)GBW07288
(土壤)Ru 0.053 7.21 0.05 6.00 0.05 0.101 94 Rh 0.019 7.31 0.017 11.8 0.05 0.068 98 Pd 0.290 9.23 0.26 11.5 0.5 0.750 92 Os 0.055 8.05 0.05 10.0 0.05 0.109 108 Ir 0.035 8.55 0.032 9.38 0.05 0.081 92 Pt 0.280 6.93 0.26 7.69 0.5 0.790 102 GBW07289
(水系沉积物)Ru 0.110 5.38 0.1 10.0 0.1 0.220 110 Rh 0.103 7.08 0.095 8.42 0.1 0.198 95 Pd 2.200 7.66 2.3 −4.35 5 7.660 109 Os 0.066 7.96 0.06 10.0 0.05 0.120 108 Ir 0.054 7.16 0.05 8.00 0.05 0.103 98 Pt 1.700 5.33 1.6 6.25 1 2.790 109 GBW07294
(土壤)Ru 0.588 6.28 0.66 −10.9 0.5 1.051 93 Rh 1.080 5.88 1.1 −1.82 1 2.010 93 Pd 15.100 3.85 15.2 −0.66 10 25.600 105 Os 0.650 9.37 0.64 1.56 0.5 1.170 104 Ir 1.110 3.88 1.2 −7.50 1 2.131 102 Pt 14.100 3.99 14.7 −4.08 10 23.500 94
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