Occurrence phase and enrichment mechanism of platinum group elements in the Pacific cobalt-rich crusts
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摘要: 通过选择性化学提取法，对太平洋采薇海山富钴结壳样品中铂族元素进行分级提取实验，利用电感耦合等离子体质谱仪（ICP-MS）测定了铂族元素含量。赋存状态结果显示，富钴结壳中铂族元素在各个化学相态中富集比例从大到小依次为：铁氧化物相、残渣态、锰氧化物相、碳酸盐相、吸附态，未磷酸盐化新壳层和磷酸盐化老壳层中铂族元素都主要赋存于铁氧化物相中，其富集比例为59.26%～82.19%，残渣态中磷酸盐对铂族元素具有一定的富集能力，其富集比例为17.23%～35.37%。不同类型地质体中铂族元素的赋存状态结果，也证实了富钴结壳和海山结核中铂族元素富集主要受到铁氧化物相和残渣态的影响。太平洋海山富钴结壳中铂族元素的富集机理推测为铁氧/氢氧化物胶体粒子的吸附作用，使海水中
${\rm PtCl}_4^{2-} $ 离子被吸附到铁氧化物相中，从而使富钴结壳中铂族元素富集。Abstract: Selective chemical extraction method was utilized to fractionally extract platinum group elements (PGE) in cobalt-rich crusts from Caiwei Seamount in the Pacific, and PGE contents were determined by inductively coupled plasma mass spectrometry (ICP-MS). Occurrence phase analysis results in cobalt-rich crusts show that the PGE enrichments in different phases conform to the following order: iron oxide phase, residual phase, manganese oxide phase, carbonate phase, adsorbed phase. PGE in the new non-phosphate layers and the old phosphate layers are mainly enriched in the iron oxide phase, with the enrichment ratio from 59.26% to 82.19%, and the phosphate in residual phase has certain enrichment ability for PGE, with the enrichment ratio from 17.23% to 35.37%. Meanwhile, occurrence phase analysis results in different geological bodies show that the PGE enrichment in cobalt-rich crusts and seamount nodules is mainly affected by iron oxide phase and residual phase. In addition, the enrichment mechanism of PGE in cobalt-rich crusts is presumed to the iron oxide/iron hydroxides colloid particles adsorption, and the soluble$ {\rm PtCl}_4^{2-}$ in seawater is adsorbed into the iron oxide phase, so PGE are enriched in cobalt-rich crusts. -
图 3 不同类型地质体样品照片
a. 玄武岩，气孔发育，多见白色杏仁体充填；b. 碳酸岩，由有孔虫壳体组成；c. 磷块岩，由微细晶粒或隐晶质矿物组成；d. 海山结核，椭球状结核体
Fig. 3 The photos of different geological bodies
a. Basalt, vesicular structure, filled with secondary minerals；b. carbonate rock, composed of foraminifera shells；c. phosphate rock, composed of fine crystal grains or cryptocrystalline minerals；d. seamount nodules, ellipsoidal nodule bodies
图 4 不同构造层富钴结壳中铂族元素（PGE）赋存状态
Fig. 4 Occurrence phase of platinum group elements (PGE) in different structural layer of cobalt-rich crusts
图 5 不同类型地质体中铂族元素（PGE）赋存状态
Fig. 5 Occurrence phase of platinum group elements (PGE) in different geological bodies
图 6 不同构造层富钴结壳在碳酸盐相、锰氧化物相、铁氧化物相和残渣态中铂族元素配分曲线
Fig. 6 Platinum group elements distribution curves of carbonate phase, manganese oxide phase, iron oxide phase and residual phase in different structural layers of cobalt-rich crusts
表 1 富钴结壳不同构造层样品描述
Tab. 1 Description of different structural layer in cobalt-rich crusts
样品编号 构造层 深度/mm 样品描述 CD16(Ⅰ) 第Ⅰ构造层 0～16 致密，褐黑色，表层葡萄体状突起，以柱状构造为主 CD16(Ⅱ) 第Ⅱ构造层 16～26 致密，黑色，以柱状构造为主 CD16(Ⅲ) 第Ⅲ构造层 26～60 疏松，黄褐色，黏土较多，以树丛状构造为主 CD16(Ⅳ) 第Ⅳ构造层 60～88 致密，黑色，少量磷酸盐脉，以斑杂状构造为主 CD16(Ⅴ) 第Ⅴ构造层 88～98 致密，亮黑色，较多磷酸盐脉，以水平层纹状构造为主 
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表 2 富钴结壳不同构造层样品中铂族元素（PGE）含量
Tab. 2 Platinum group elements (PGE) contents of different structural layer in cobalt-rich crusts
样品 Ru含量/ng·g–1 Pd含量/ng·g–1 Ir含量/ng·g–1 Pt含量/ng·g–1 Rh含量/ng·g–1 Os含量/ng·g–1 PGE含量/ng·g–1 CD16(Ⅰ) 19.00 1.700 4.600 202.4 14.70 0.350 0 242.8 CD16(Ⅱ) 20.60 0.300 0 5.700 247.6 13.20 0.470 0 287.9 CD16(Ⅲ) 10.26 2.350 4.710 380.5 18.95 0.130 0 416.9 CD16(Ⅳ) 15.80 2.700 9.700 866.8 24.90 0.110 0 920.0 CD16(Ⅴ) 9.700 4.200 4.900 470.0 14.40 0.130 0 503.3
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表 3 不同类型地质体中铂族元素（PGE）含量
Tab. 3 Platinum group elements (PGE) contents in different geological bodies
样品 Ru含量/ng·g–1 Pd含量/ng·g–1 Ir含量/ng·g–1 Pt含量/ng·g–1 Rh含量/ng·g–1 Os含量/ng·g–1 PGE含量/ng·g–1 碳酸岩 0.010 0 0.740 0 0.120 0 10.13 0.190 0 0.120 0 11.31 磷块岩 1.360 1.770 0.190 0 33.11 0.260 0 0.110 0 36.80 玄武岩 1.250 3.900 0.340 0 80.49 0.330 0 0.130 0 86.44 海山结核 16.42 2.970 2.290 164.9 0.680 0 0.610 0 187.9 富钴结壳 18.30 4.700 5.400 215.6 15.30 0.200 0 259.5
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