Evolution of subcontinental lithospheric mantle beneath eastern China: Re–Os isotopic evidence from mantle xenoliths in Paleozoic kimberlites and Mesozoic basalts

The ages of subcontinental lithospheric mantle beneath the North China and South China cratons are less well-constrained than the overlying crust. We report Re–Os isotope systematics of mantle xenoliths entrained in Paleozoic kimberlites and Mesozoic basalts from eastern China. Peridotite xenoliths from the Fuxian and Mengyin Paleozoic diamondiferous kimberlites in the North China Craton give Archean Re depletion ages of 2.6–3.2 Ga and melt depletion ages of 2.9–3.4 Ga. No obvious differences in Re and Os abundances, Os isotopic ratios and model ages are observed between spinel-facies and garnet-facies peridotites from both kimberlite localities. The Re–Os isotopic data, together with the PGE concentrations, demonstrate that beneath the Archean continental crust of the eastern North China Craton, Archean lithospheric mantle of spinel- to diamond-facies existed without apparent compositional stratification during the Paleozoic. The Mesozoic and Cenozoic basalt-borne peridotite and pyroxenite xenoliths, on the other hand, show geochemical features indicating metasomatic enrichment, along with a large range of the Re–Os isotopic model ages from Proterozoic to Phanerozoic. These features indicate that lithospheric transformation or refertilization through melt-peridotite interaction could be the primary mechanism for compositional changes during the Phanerozoic, rather than delamination or thermal-mechanical erosion, despite the potential of these latter processes to play an important role for the loss of garnet-facies mantle. A fresh garnet lherzolite xenolith from the Yangtze Block has a Re depletion age of ∼1.04 Ga, much younger than overlying Archean crustal rocks but the same Re depletion ages as spinel lherzolite xenoliths from adjacent Mesozoic basalts, indicating Neoproterozoic resetting of the Re–Os system in the South China Craton.     

利用扫描电镜-电子探针研究四川杨柳坪镍铜硫化物矿床铂钯的赋存状态及沉淀机制

本文利用电子探针和配备能谱分析功能的扫描电镜对四川杨柳坪镍-铜硫化物矿床中铂钯的赋存状态进行了研究。结果表明,铂以独立矿物相砷铂矿和自然铂存在;钯以碲化物、碲铋化物、碲锑化物、锑化物及自然钯独立矿物相存在,也以类质同象形式分布在碲镍矿中(钯含量约10%),另外还以锑铋钯碲矿、六方锑碲钯矿、碲钯矿独立矿物相存,并以类质同象形式分布在Vavrinite(钯含量5%)和砷铂矿(钯含量1%~5%)中。杨柳坪矿床中铂钯元素沉淀与贱金属矿物(BMS)及晚期热液蚀变矿物蛇纹石、方解石密切相关,其沉淀经历了3个阶段:1早期高温阶段(1200~900℃),铂钯元素沉淀并包裹在BMS中;2中期中高温阶段(650~250℃),分离结晶作用使铂钯元素沉淀并分布BMS矿物的边部,同时该阶段热液来源的铂钯元素沉淀于BMS粒间;3晚期热液蚀变阶段(500~300℃),热液蚀变作用引起铂钯元素沉淀在蚀变矿物中或嵌布在BMS裂隙。本文研究成果为认识该矿床及同类型镍-铜硫化物矿床的铂钯成矿过程提供了新的依据。     

Refertilization of serpentinites in the Sulu UHP terrane,Eastern China: constraints from geochronology,mineral composition,geochemistry, and Re–Os isotopes

ABSTRACT

Serpentinites from Junan (JN), Rizhao (RZ), and Rongcheng (RC) in the Sulu ultra-high-pressure (UHP) terrane, China, were analysed for U–Pb zircon geochronology, mineral chemistry, whole-rock major and trace element chemistry (including rare-earth elements (REEs) and platinum-group elements (PGEs)), and Re–Os isotopes, in order to better constrain their petrogenesis and geodynamic process. The serpentinite zircons yield two age groups: 731 ± 10 to 780 ± 10 Ma for relic magmatic zircon cores, which may indicate early crystallization and emplacement of the peridotite in the Yangtze crust, and 209 ± 2 to 218 ± 3 Ma for metamorphic zircon, which coincides with Triassic UHP metamorphism. The spinels in the serpentinites exhibit significant Cr# variation (0.6–0.91) and have undergone multi-stage metamorphism. The serpentinites are characterized by enrichment in incompatible trace elements, low Ni and IPGE concentrations, and high Pd/Ir ratios, and the bulk-rock major elements plot in the ultramafic cumulate region. Their Re and Os concentrations are similar to those of typical orogenic peridotite, but they have high ¹⁸⁷Os/¹⁸⁸Os ratios (0.12433–0.14423). We believe that the serpentinite’s protolith consisted of cumulates from an asthenosphere-derived melt that intruded into the continental crust of the Yangtze craton in the Neoproterozoic. These cumulates were later subducted and metamorphosed during the subduction of the Yangtze craton in the Triassic. The serpentinites underwent melt–rock interactions and fluid enrichment, both prior to and during serpentinization.     

岩石样品中低含量铂族元素和锇同位素比值的高精度测量方法

铂族元素（Os,Ir,Pt,Ru,Rh,Pd)具有强亲铁性和强亲铜性，为一组地球化学性质相近的相容元素，铂族元素包含两个同位素衰变体系（^190Pt-^186Os和^187Re-^187Os)。近年来，铂族元素和Re-Os同位素在研究各类不同地持作用过程中，尤其是在地幔岩石的研究中，作用独特，效果显著。由于地幔岩石的铂族元素含量较低，因此高精度，高灵敏度的分析测试方法的研究就显得十分重要。以往的分析方法（如常规的ICP－MS和中子活化分析方法），对含10^-9-10^012级低含量铂族元素的产品分析精度一般较差（＞15％－100％）。所采用的分析流程通常也无法同时获得样品的铂族元素含量和Os同位素比值。本文采用新的熔样方法（HAP－S高温高压釜酸溶法），新的化学流程（溶剂萃取和阴离子交换树脂柱）和新的分析仪器（多接收等离子体质谱MC－ICPMS和负离子热电离质谱N－TIMS）。用同位素稀释法对低含量地幔橄榄岩样品同时测定的铂族元素含量和Os同位素比值，获得了高精度的分析结果。对所分析的地橄榄样品中的铂族元素分配曲线和Os同位素组成的地质意义进行了初步探讨。     

苏鲁超高压变质带仰口蛇纹岩的成因——矿物化学、地球化学和年代学证据

通过矿物化学、全岩主微量元素和铂族元素研究,结合锆石年代学判断苏鲁造山带仰口蛇纹岩的原岩成因和演化历史。蛇纹岩中尖晶石经历了多阶段变质;全岩主量元素具有超基性堆晶岩的性质,代表玄武质组分含量的Ca O+Al_2O_3变化于2.0%~5.83%之间;部分不相容微量元素富集;铂族元素中Ir的含量低(0.64×10~(-9)~1.43×10~(-9)),Pd/Ir值高(1.05~3.42)。蛇纹岩中的锆石一部分为新形成的变质成因锆石(年龄平均为230±3Ma),与高压-超高压变质的年代吻合;另一部分可能是在三叠纪变质阶段古老锆石重结晶形成的。由此认为,仰口蛇纹岩的原岩可能为超基性堆晶岩,三叠纪时随着俯冲的扬子板块发生变质,在发生蛇纹石化作用之前经历了熔体/流体的改造。     

用于铂族元素分析的中外地质标准物质

标准物质作为地质分析的计量标准,在分析质量监控、仪器校准、方法评价和仲裁分析中发挥着重要作用。铂族元素分析一直是地质材料分析中最棘手的任务之一,铂族元素标准物质研制困难,数量少,严重影响了对铂族元素分析方法的评价和分析数据的质量监控,成为铂族金属矿产资源勘查、评价和相关研究工作的瓶颈。收集了中国及国际上现有的34个铂族元素标准物质和52个其他地球化学标准物质中的101个铂族元素定值数据。为便于使用也收集了这些标准物质中其他元素的含量信息,给出了铂族各元素按含量大小排列的信息简表以方便选择。充分利用这些标准物质对促进铂族元素分析方法研究,保证铂族元素分析数据质量,提高中国和世界铂族金属矿产资源勘查、评价及研究水平具有重要意义。     

Efficiency of a re-usable Carius tube for determination of platinum group elements in ultramafic rocks

Digestion with aqua regia in Carius tube is commonly employed for determination of PGEs in geological samples. However, silicates cannot be completely dissolved by aqua regia and PGEs might partially remain in silicate residue. In this study, an ultramafic reference material was used to investigate the efficiencies of a new re-usable Carius tube after digestion at 220 and 240℃, and an autoclave-lined Carius tube at 260 and 280℃. The results show that about 10% of PGEs retained in the silicate residues at 220 and 5% still r℃ emains even digestion temperature increases to 280℃. These results agree with previous works that increasing the digestion pressure and temperature can achieve more effective dissolution. Thus, a modified digestion procedure for determination of PGEs in ultramafic rocks by the re-usable Carius tube was proposed in this study.     

非洲铂族金属矿产资源禀赋特征、成矿潜力及开发利用

铂族元素（Platinum group elements,PGEs）作为地壳最稀缺的一类金属元素,是重要的战略性矿产资源,与金一样,具有经济和科技双重的功能。非洲铂族金属矿产资源丰富且高度集中,占世界资源量> 80 %,主要集中在南非和津巴布韦。本文在前人研究基础上,对非洲PGEs矿床主要成矿类型、时空分布特点和开发利用现状进行了总结,研究认为：（1）非洲大型-超大型PGEs矿床成因类型主要为岩浆型,在时空上与世界级铁质-镁铁质大火成岩省（南非布什维尔德和津巴布韦大岩墙）密切相关,可细化分为脉状铜镍硫化物型、整合接触型铜镍硫化物型、脉状铬铁矿型和钒钛磁铁矿型。依据区域构造演化及其所产出的矿化特征,认为以铁质-镁铁质岩有关的岩浆型矿床仍具有较大的找矿潜力。(2)非洲铂族金属矿产勘查开发程度相对较高,近十年是全球勘查资金投入最多的地区,同时也是世界第一大Pt生产地和第二大Pd生产地。从事勘查开发的主要为世界顶级PGEs矿业寡头。（3）非洲是全球一次性铂族金属矿产品主要供应国,主要出口至美国、日本、中国、德国和英国。加强与南非、津巴布韦等国家之间的合作,保障PGEs资源供应的安全对我国尤为重要。     

雅鲁藏布江缝合带西段达机翁地幔橄榄岩及铬铁矿的铂族元素特征

达机翁蛇绿岩位于雅鲁藏布江缝合带的西段北亚带,该蛇绿岩主要由地幔橄榄岩、玄武岩以及硅质岩组成,其中地幔橄榄岩以方辉橄榄岩为主,同时含有少量的纯橄榄岩,纯橄岩主要呈不规则透镜状或团块状分布于方辉橄榄岩中。在达机翁地幔橄榄岩中产出有3种不同类型的铬铁矿,分别为块状,豆状以及浸染状铬铁矿。文章主要对达机翁地幔橄榄岩的方辉橄榄岩及豆荚状铬铁矿进行了研究,结合岩石的主量元素和铂族元素,对地幔橄榄岩和豆荚状铬铁矿的成因以及雅鲁藏布江缝合带的找矿远景进行了探讨。达机翁地幔橄榄岩具有较高的Mg O含量以及较低的Al2O3和Ca O等含量,这种亏损的全岩成分指示了达机翁地幔橄榄岩经历了较高的部分熔融作用,同时方辉橄榄岩的PGEs的总量为23.68×10-9~31.02×10-9,高于原始地幔的值,Pd和Cu 2个元素的含量较为分散明显偏离部分熔融曲线,指示了达机翁方辉橄榄岩可能遭受了熔体的改造,在熔体-岩石反应的过程中,导致了富含PPGE的硫化物的加入。达机翁豆荚状铬铁矿为高Cr型铬铁矿,具有IPGE和Rh明显富集以及Pt,Pd明显亏损的特征,不同类型的铬铁矿之间具有一致的PGEs的分配模式。雅鲁藏布江缝合带内大量分布的超镁铁岩体在岩石组合、地球化学特征、成因以及形成时代等方面,均具有相似性,是中国铬铁矿找矿的有利远景区。     

中国与世界铂族元素地球化学标准物质评介

铂族元素分析一直是地质材料分析中最棘手的任务之一,是铂族金属矿产资源勘查、评价和相关研究工作的瓶颈。铂族元素标准物质作为铂族元素分析的计量标准,在分析质量监控、分析仪器校准、分析方法评价和仲裁分析中发挥着重要作用。笔者等评介了我国研制的超基性岩和铬铁矿铂族元素标准物质、铂族元素地球化学标准物质、铂族元素矿石标准物质和海山富钴结壳铂族元素标准物质共4个系列21个标准物质,也给出了其他地球化学标准物质中铂族元素的定值数据;并与南非、加拿大、俄罗斯和岩石矿物分析标准国际工作组(GIT-IWG)研制的13个铂族元素标准物质及其他国际地球化学标准物质中铂族元素的数据进行了对比。这些标准物质的研制与应用将大大提高铂族元素分析数据的可靠性,为我国和世界铂族金属矿产资源勘查、评价及研究提供了有力的技术支撑。