A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re–Os isotope systematics

An extensive study of peridotitic sulfide inclusion bearing diamonds and their prospective harzburgitic host rocks from the 53 Ma Panda kimberlite pipe, Ekati Mine, NWT Canada, has been undertaken with the Re–Os system to establish their age and petrogenesis. Diamonds with peridotitic sulfide inclusions have poorly aggregated nitrogen (<30% N as B centers) at N contents of 200–800 ppm which differs from that of chromite and silicate bearing diamonds and indicates residence in the cooler portion of the Slave craton lithospheric mantle. For most of the sulfide inclusions, relatively low Re contents (average 0.457 ppm) and high Os contents (average 339 ppm) lead to extremely low ¹⁸⁷Re/¹⁸⁸Os, typically << 0.05. An age of 3.52 ± 0.17 Ga (MSWD = 0.46) and a precise initial ¹⁸⁷Os/¹⁸⁸Os of 0.1093 ± 0.0001 are given by a single regression of 11 inclusions from five diamonds that individually provide coincident internal isochrons. This initial Os isotopic composition is 6% enriched in ¹⁸⁷Os over 3.5 Ga chondritic or primitive mantle. Sulfide inclusions with less radiogenic initial Os isotopic compositions reflect isotopic heterogeneity in diamond forming fluids. The harzburgites have even lower initial ¹⁸⁷Os/¹⁸⁸Os than the sulfide inclusions, some approaching the isotopic composition of 3.5 Ga chondritic mantle. In several cases isotopically distinct sulfides occur in different growth zones of the same diamond. This supports a model where C–O–H–S fluids carrying a radiogenic Os signature were introduced into depleted harzburgite and produced diamonds containing sulfides conforming to the 3.5 Ga isochron. Reaction of this fluid with harzburgite led to diamonds with less radiogenic inclusions while elevating the Os isotope ratios of some harzburgites. Subduction is a viable way of introducing such fluids. This implies a role for subduction in creating early continental nuclei at 3.5 Ga and generating peridotitic diamonds.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Sulfides in mantle peridotites from Penghu Islands, Taiwan: Melt percolation, PGE fractionation, and the lithospheric evolution of the South China block

Major elements, highly siderophile elements (HSE) and Re-Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Miocene intraplate basalts from the Penghu Islands, Taiwan. The xenoliths represent texturally and compositionally different mantle domains, and the geochemical characteristics of the sulfides show changes in HSE distribution and Re-Os isotope systematics, produced as their host rocks were metasomatised by percolating fluids/melts. In prophyroclastic and partly metasomatised peridotites from the Kueipi (KP) locality, the sulfides have subchondritic to superchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios. Many of these sulfides reflect fluid/melt interaction with residual MSS and/or crystallization of fractionated sulfide melts, which produced high contents of Cu and PPGEs and high Re/Os; inferred melt/rock ratios are low. In contrast, sulfides in equigranular and extensively metasomatised peridotites from the Tungchiyu (TCY) locality are mainly more sulfur-rich Ni-(Co)-rich MSS, with subchondritic to chondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os. These sulfides are interpreted as products of interaction between pre-existing MSS and percolating silicate melts. Melt/rock ratios were high and the percolating melt was less differentiated than the melt that percolated the KP peridotites. Sulfides in a TCY pyroxenite are mainly MSS; they have the lowest HSE contents, subchondritic to superchondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os, and may have precipitated from sulfide melts that segregated from basaltic melts under S-saturated conditions. In most sulfides melt percolation appears to have induced fractionation among the HSEs and disturbed Re-Os isotope compositions. Despite the metasomatic effects, rare residual MSS, sulfides that from crystallised sulfide melts and sulfides modified by addition of Re (with no evidence for Os addition) can still provide useful chronological information. Such sulfides yield T_RD age peaks of 1.9, 1.7-1.6, 1.4-1.3 and 0.9-0.8 Ga, which may record the timing of melt extraction and/or metasomatic events in the mantle. These periods are contemporaneous with the major crustal events recorded by U-Pb dates and Nd and Hf model ages in the overlying crust. This close correspondence indicates that the sulfide T_RD ages reflect the timing of lithosphere-scale tectonothermal events (such as melting and metasomatism) that affected both the lithospheric mantle and the overlying crust. The sulfide T_RD ages, taken together with the crustal data, suggest that most of the Cathaysia block had formed at least by Paleo-Proterozoic time, and that some domains are Archean in age.     

Unravelling the effects of melt depletion and secondary infiltration on mantle Re-Os isotopes beneath the French Massif Central

Spinel lherzolite xenoliths from Mont Briançon, French Massif Central, retain evidence for multiple episodes of melt depletion and melt/fluid infiltration (metasomatism). Evidence for primary melt depletion is still preserved in the co-variation of bulk-rock major elements (MgO 38.7-46.1 wt.%; CaO 0.9-3.6 wt.%), and many samples yield unradiogenic bulk-rock Os isotope ratios (¹⁸⁷Os/¹⁸⁸Os = 0.11541-0.12626). However, many individual xenoliths contain interstitial glasses and melt inclusions that are not in equilibrium with the major primary minerals. Incompatible trace element mass balance calculations demonstrate that metasomatic components comprise a significant proportion of the bulk-rock budget for these elements in some rocks, ranging to as much as 25% of Nd and 40% of Sr Critically, for Re-Os geochronology, melt/fluid infiltration is accompanied by the mobilisation of sulfide. Consequently, bulk-rock isotope measurements, whether using lithophile (e.g. Rb-Sr, Sm-Nd) or siderophile (Re-Os) based isotope systems, may only yield a perturbed and/or homogenised average of these multiple events.Osmium mass balance calculations demonstrate that bulk-rock Os in peridotite is dominated by contributions from two populations of sulfide grain: (i) interstitial, metasomatic sulfide with low [Os] and radiogenic ¹⁸⁷Os/¹⁸⁸Os, and (ii) primary sulfides with high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os, which have been preserved within host silicate grains and shielded from interaction with transient melts and fluid. The latter can account for >97% of bulk-rock Os and preserve geochronological information of the melt from which they originally precipitated as an immiscible liquid. The Re-depletion model ages of individual primary sulfide grains preserve evidence for melt depletion beneath the Massif Central from at least 1.8 Gyr ago despite the more recent metasomatic event(s).     

Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the “mantle zoo” may contain more reservoirs than previously envisaged.Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic ¹⁸⁷Os/¹⁸⁸Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic ¹⁸⁷Os/¹⁸⁸Os ([Os] typically ? 1-2 ppm, ¹⁸⁷Os/¹⁸⁸Os ? 0.3729; this study). This population is thought to represent metasomatic sulphide.Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ? 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic ¹⁸⁷Os/¹⁸⁸Os signature. Only when sulphides armoured within silicates are exposed to the melt through continued partial melting will enclosed sulphides add their high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os to the aggregate melt. Platinum-group element data for whole rocks are also consistent with this scenario. The sequence of (i) addition of all of the metasomatic sulphide, followed by (ii) the incorporation of small amounts of armoured sulphide can thus account for the range of both [Os] and ¹⁸⁷Os/¹⁸⁸Os of EM-basalts worldwide without the need for contributions from additional silicate mantle reservoirs.     

Granulite sulphides as tracers of lower crustal origin and evolution: An example from the Slave craton, Canada

We carried out a detailed study of sulphide minerals, a ubiquitous mineral group in lower crustal mafic to peraluminous granulite xenoliths from the Diavik kimberlites, to assess their use in constraining the origin and tectonothermal evolution of the deep crust, and to obtain additional data on the composition of lower crust beneath ancient continents. Sulphides are overwhelmingly pyrrhotite with minor Ni (0.7-3.9 at.%), Co (0.1-0.7 at.%), and Cu contents (0.4-3.9 at.%). Sulphide modes in mafic granulites range from 0.14 to 0.55 vol%, translating into bulk rock S contents from ∼600 to 2000 ppm, similar to S contents in other mafic igneous rocks and indicating preservation of primary igneous S contents. In mafic granulites, Re and Os abundances in sulphides range from 42.5 to 726 ppb and 3.2 to 180 ppb, respectively, whereas those in peraluminous granulites are distinctly lower (36.1-282 ppb and 1.8-7.2 ppb, respectively), suggestive of Re and Os loss to fractionating sulphides in the more evolved precursors of these rocks.The significant within-sample variability of ¹⁸⁷Os/¹⁸⁸Os and correlation with ¹⁸⁷Re/¹⁸⁸Os indicates the preservation of primary Re-Os isotope systematics and time-integrated decay of the measured ¹⁸⁷Re. Within the large uncertainties inherent in the nature of the samples and technique, sulphides in some granulites may record major tectonothermal events in the central Slave craton spanning several billion years of evolution. Multiple generations of sulphide can occur in a single sample. These data attest to the heterogeneous composition and complex history of the Slave craton lower crust.     

湖南鲁塘石墨矿Re-Os同位素研究

石墨具有较高的Re、Os含量,可望成为理想的Re-Os同位素测年对象,但迄今国内外研究较少,尤其在煤层经变质作用形成石墨过程中,其中Re-Os同位素体系的变化还有待研究。湖南鲁塘石墨矿是我国典型的隐晶质石墨矿床之一,矿体产于二叠系龙潭组煤系地层中。本文采用Carius管逆王水溶解样品,直接蒸馏、微蒸馏分离纯化Os,丙酮萃取法分离富集Re,热表面电离质谱法对鲁塘矿区石墨样品以及外围原煤进行了Re-Os同位素分析。结果表明:鲁塘石墨的Re含量为0.901~9.794 ng/g,Os含量为7.3~189.5 pg/g,Re-Os同位素等时线年龄为155.6±3.6 Ma,该年龄与鲁塘石墨矿东侧骑田岭岩体第二阶段中粒黑云母花岗岩锆石U-Pb年龄153~157 Ma一致,表明了龙潭组煤层受到骑田岭岩体"烘烤"作用,发生热接触变质作用,使得靠近骑田岭岩体原煤变质为石墨,形成石墨矿床。通过对比石墨、原煤和骑田岭岩体Re、Os含量及比值,发现石墨中的Re、Os主要来源于原煤,并根据石墨Re-Os等时线初始(187Os/188Os)i值(0.686±0.032),推测骑田岭岩体在侵入煤系地层过程中,有少量具有较低187Os/188Os值的Os被碳质吸附。     

Microcontinents among the accretionary complexes of the Central Asia Orogenic Belt: In situ Re–Os evidence

Major elements and Re–Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Quaternary intraplate basalts from the Tariat volcanic field, Central Mongolia. The sulfides are dominantly high-temperature (>900 °C) Fe-rich monosulfide solid solution (MSS). Some sulfides with low Ni contents may be residual MSS, whereas other sulfides defining a negative Ni–Cu correlation may be crystallization products of fractionated sulfide melts. The subchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os of some sulfides also indicate they are residual MSS. Os isotope compositions of sulfides reveal the presence of Archean to Proterozoic lithospheric mantle beneath the region. The sulfides have T_RD model ages ranging from 3.0 to 0.2 Ga, with peaks at 1.5–1.3, 1 and 0.7–0.5 Ga. The peak ages are indicative of significant events in the lithospheric mantle at those times. The timing of these events is remarkably consistent with those of the major crust-building events within the Tarvagatay Terrane where the Tariat volcanic field is located. The similarity in the ranges of crustal U–Pb ages and Nd model ages, and our sulfide Os model ages, suggests that the sulfide ages may date metasomatic events in the underlying lithospheric mantle, which were related to tectonothermal events that affected the overlying crust. Radiometric ages from the Tarvagatay Terrane appear to correspond to the Archean model ages from its SCLM counterpart. The last two events (1.1 and 0.7–0.5 Ga) recorded in the Tarvagatay Terrane suggest involvement of the “CAOB mantle” and development of significant juvenile crustal growth in the orogeny.     

Re-Os isotopic composition of peridotitic sulphide inclusions in diamonds from Ellendale, Australia: Age constraints on Kimberley cratonic lithosphere

Sulphide-bearing diamonds recovered from the ∼20 Ma Ellendale 4 and 9 lamproite pipes in north-western Australia were investigated to determine the nitrogen aggregation state of the diamonds and Re-Os isotope geochemistry of the sulphide inclusions. The majority of diamond studies have been based on diamonds formed in the sub-continental lithospheric mantle (SCLM) below stable cratons, whereas the Ellendale lamproites intrude the King Leopold Orogen, south of the Kimberley craton. The sulphide inclusions consist of pyrrhotite-pentlandite-chalcopyrite assemblages, and can be divided into peridotitic and eclogitic parageneses on the basis of their Ni and Os contents. A lherzolitic paragenesis for the high-Ni sulphide inclusions is suggested from their Re and Os concentrations. Regression analysis of the Re-Os isotope data for the lherzolitic sulphides yields an age of 1426 ± 130 Ma, with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.1042 ± 0.0034. The upper limit of the uncertainty on the ¹⁸⁷Os/¹⁸⁸Os initial ratio gives a Re depletion age of 2.96 Ga, indicating the presence of SCLM beneath Ellendale since at least the Mesoarchaean, with the lherzolitic diamond-forming event much younger and unrelated to the craton keel stabilisation. The nitrogen aggregation state of the diamonds and calculated mantle residence temperatures suggest an origin and storage of the Ellendale diamonds in a stable cratonic SCLM, consistent with the King Leopold Orogen being cratonised by about 1.8 Ga. The diamonds do not show evidence for pervasive deformation or platelet degradation, which suggests that the diamonds had a relatively undisturbed 1.4 billion year mantle storage history.     

滇东南八布杨万铜矿床硫化物Re-Os同位素年龄及其地质意义

滇东南八布地区发育一套晚古生代超镁铁质-镁铁质杂岩,是认识古特提斯分支洋构造演化的重要窗口,而其中以火山岩为赋矿围岩的杨万铜矿床,被视作区域找矿的突破点。目前,对这套超镁铁质-镁铁质杂岩的构造属性及赋存铜矿床的成矿时代及成因联系还存在争议。通过对杨万铜矿床中黄铜矿和黄铁矿进行Re-Os同位素定年,获得Re-Os等时线年龄为269±3 Ma,表明该矿床形成于早中二叠世,与火山岩(～270 Ma)大致同时;而初始187Os/188Os值为0.31±0.17,暗示成矿时存在热液流体与古海水的相互作用。区内玄武岩围岩和其它超镁铁质-镁铁质岩石的地球化学特征对比分析显示,八布超镁铁质-镁铁质杂岩为一套N-MORB型蛇绿岩组合,代表了古特提斯分支洋盆的洋壳残片。杨万铜矿床应划归为与古特提斯分支洋裂解有关的火山成因块状硫化物(VMS)矿床,其周边地区具有较好的找矿潜力。     

Re-Os study of Fe-Ti-V oxide and Fe-Cu-Ni sulfide deposits, Suwałki Anorthosite Massif, northeast Poland

The Suwałki anorthosite massif, located in extreme northeast Poland beneath more than a kilometer of Phanerozoic cover, hosts major Fe-Ti-V deposits. These deposits, discovered in 1962, are contained in Fe and Ti oxide minerals that coexist with subordinate quantities of Fe, Cu, Ni, and Co sulfides in massif-style anorthosites, norites, and gabbronorites. Accessibility and other considerations preclude development of this natural resource in the present economic climate. Detailed work by Polish geologists during the last 35 years provides a sound geologic framework for this Re-Os study of the age and origin of oxide and sulfide deposits associated with a major, but lesser known anorthosite massif. Rhenium and osmium abundances and Os isotopic compositions were measured for nine sulfides and four titanomagnetites from the Suwałki anorthosite massif. The titanomagnetites are over an order of magnitude lower in Re (0.4–1.5 ppb) and Os (0.036–0.144 ppb) concentrations than co-precipitated pyrrhotite, pyrite, and chalcopyrite that yield consistent concentrations for Re (30–55 ppb) and Os (1–6 ppb). Parallel lines connecting co-existing titanomagnetite and sulfides have slopes of ∼1 on Re versus common Os concentration plots, indicating that both Re and Os behave similarly during crystallization in their high preference for any sulfide phase over magnetite. Samples from three deposits within the anorthosite massif were analyzed. An age of 1559 ± 37 Ma (n=10) with an initial ¹⁸⁷Os/¹⁸⁸Os of 1.16 ± 0.06 for the Jezioro Okrągłe and Krzemianka deposits is essentially identical to an age of 1556 ± 94 Ma (n=3) for the Udryń deposit. Udryń, however, yielded a marginally lower initial ¹⁸⁷Os/¹⁸⁸Os of 0.87 ± 0.20. The high initial ¹⁸⁷Os/¹⁸⁸Os combined with the Proterozoic Re-Os age indicates that the source for Suwałki oxides-sulfides is older crust, and hypothetically, could involve Archean rocks. An average crustal value of 50 for ¹⁸⁷Re/¹⁸⁸Os yields a 2777 Ma age for Suwałki source rocks. Widespread Phanerozoic cover severely limits knowledge of basement rocks in Poland, however, and no Archean rocks are known in the immediate region. More likely, ¹⁸⁷Re/¹⁸⁸Os ratios may be higher than average continental crust, reflecting mafic crust in the source, and may move the source age for Suwałki anorthosite and mineral deposits toward younger values that easily include ∼2.0 Ga Proterozoic rocks. This more favorable case also accommodates Paleoproterozoic Nd model ages. Regardless of Archean or Proterozoic source age, the high initial ¹⁸⁷Os/¹⁸⁸Os ratios derived from the Re-Os isochron indicate that the source for the oxide-sulfide mineral deposits is more likely the crust and not the mantle. Given that these deposits are clearly magmatic, the Re-Os results add a new dimension to the long-standing “origin of anorthosite” problem, implying a crustal source for the anorthosite as well. The 1559 Ma Suwałki age is compatible with a well-exposed east-west band of 1530-1660 Ma rapakivi granite-anorthosite magmatism to the immediate north, transecting western Russia, southern Finland, Estonia and Latvia, and central Sweden. In particular, the age and isotopic character of Suwałki are not unlike those of the well-studied Salmi rapakivi granite-anorthosite batholith in western Russia (Karelia). Received: 4 December 1998 / Accepted: 11 November 1999     

Pt-Os and Re-Os systematics of the Sudbury Igneous Complex, Ontario

We measured by negative thermal ionization mass spectrometry (NTIMS) Re, Os and ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os in 26 samples of 18 Ni-Cu sulfide ores from the Falconbridge, McCreedy West, and Strathcona mines at Sudbury, Ontario. At McCreedy West and Falconbridge, the isochron Re-Os ages are 1835 ± 70 Ma and 1827 ± 340 Ma, and the initial ¹⁸⁷Os/¹⁸⁸Os ratios 0.514 ± 0.019 and 0.550 ± 0.024, respectively. The ages agree with the canonical value of 1850 ± 1 Ma for the Sudbury Igneous Complex (SIC). For Hangingwall and Deep Zone ores at Strathcona, the age of 1780 ± 7 Ma may reflect resetting by dyke activity. The high initial ¹⁸⁷Os/¹⁸⁸Os of 0.934 ± 0.005 in these ores is distinct from those at McCreedy West and Falconbridge. Strathcona Deep Copper Zone ores have highly radiogenic Os giving a mean model age of 1883 ± 54 Ma that is similar to ages at McCreedy West and Falconbridge, but distinct from other Strathcona sulfides. Initial ¹⁸⁶Os/¹⁸⁸Os in two Strathcona ores with low ¹⁹⁰Pt/¹⁸⁸Os average 0.119 826 ± 0.000 009 (n = 3) and 0.119 827 ± 0.000 004 (n = 3), respectively, with a grand mean of 0.119 827 ± 0.000 003. This ratio may be slightly lower than the chondritic value at that time. Similar ores at Falconbridge and McCreedy West show more scatter, averaging 0.119 855 ± 0.000 008 (n = 6) and 0.119 867 ± 0.000 020 (n = 3), respectively. These values are substantially suprachondritic. The Re-Os isotope systematics of Sudbury ores are clearly of crustal origin and may be derived from a binary mixture of Superior Province and Huronian metasedimentary rocks, with Strathcona, Falconbridge, and McCreedy West ores containing, respectively, 55%, 16%, and 12% of Os from Superior sediments. The suprachondritic ¹⁸⁶Os/¹⁸⁸Os at McCreedy West and Falconbridge may be due to admixture of Archean or Paleozoic mafic rocks with ¹⁹⁰Pt/¹⁸⁸Os ≈ 0.1. No trace of the asteroid that produced the Sudbury Structure has been reported. At the Whistle mine S-poor olivine melanorite inclusions with high Ni and Os and low ¹⁸⁷Os/¹⁸⁸Os may contain the signature of a magmatically fractionated asteroidal core contributing 1 to 2.5 % metal. The S-poor melanorite Ni and Os data are equally well explained by admixture of ≈40% mantle peridotite, however.     

Significance of ancient sulfide PGE and Re–Os signatures in the mantle beneath Calatrava,Central Spain

Spinel lherzolite and wehrlite xenoliths from the Cenozoic Calatrava volcanic field carry the geochemical imprint of metasomatic agents that have affected the subcontinental lithospheric mantle beneath Central Iberia. Some xenoliths (mainly wehrlites) were enriched in REE, Sr, P, and CO₂ by silicic-carbonate-rich metasomatic melts/fluids, while others record the effects of subduction-related hydrous silicate fluids that have precipitated amphibole and induced high Ti/Eu in primary clinopyroxene. The petrographic observations and geochemical data suggest that interstitial glass in the xenoliths represent the quenched products of Si-rich melts that infiltrated the mantle peridotite shortly before the entrainment of the xenoliths in the host magmas that erupted ca 2 million years ago. During their infiltration, the metasomatic melts reacted with peridotite, resulting in silica enrichment, while remobilizing grains of iron-rich monosulfide solid solution (Fe-rich Mss) initially enclosed in, or intergranular to, primary olivine and pyroxenes. In situ laser ablation inductively coupled plasma-mass spectrometry analysis of single sulfide grains reveals that the Fe-rich Mss in glass shows platinum-group element (PGE) patterns and ¹⁸⁷Os/¹⁸⁸Os compositions identical to the Fe-rich Mss occurring as inclusions in, or at grain boundaries of primary silicates. Moreover, independent of its microstructural position, Fe-rich Mss exhibits PGE and ¹⁸⁷Os/¹⁸⁸Os signatures typical of Mss either residual after partial melting or crystallized directly from sulfide melts. Our findings reveal that young metasomatic melt(s)/fluid(s) may carry remobilized sulfides with PGE and Os-isotopic signatures identical to those of texturally older sulfides in the peridotite xenolith. These sulfides thus still provide useful information about the timing and nature of older magmatic events in the subcontinental mantle.     

石灰岩铼-锇同位素分析方法研究及应用初探

针对石灰岩样品Re-Os同位素分析,在选样和溶样方法上进行了改进,在Carius管封闭前加入HCl与石灰岩反应释放出大量CO2,然后加入氧化剂和稀释剂封闭Carius管溶解样品,大大增加了样品取样量。利用改进的方法对采自青海玉树地区二叠世九十道班组底部的灰黑色微细晶灰岩的Re-Os同位素体系进行了分析测定,得到了精确的沉积年龄(283.1±7.1)Ma(MSWD=0.61,Model1,n=7)。187Os/188Os同位素初始值为0.56±0.12,与二叠纪时海水的187Os/188Os值相一致,反映了石灰岩沉积时海水的187Os/188Os比值。所得石灰岩年龄与其中的生物化石年龄相吻合,并且与区域上岩浆岩锆石年龄相互印证,表明Re-Os同位素体系在该石灰岩中的封闭性较好。通过石灰岩中有机碳含量以及其中Re、Os含量关系研究,得出了Re、Os在灰岩中主要赋存于有机质中的结论。从原理上解释了Re-Os同位素体系在灰岩中的应用具有十分广泛的前景。     

Age and sources of the ore at Tharsis and Rio Tinto, Iberian Pyrite Belt, from Re-Os isotopes

Re-Os isotopes were used to constrain the source of the ore-forming elements of the Tharsis and Rio Tinto mines of the Iberian Pyrite Belt, and the timing of mineralization. The pyrite from both mines has simila]r Os and Re concentrations, ranging between 0.05–0.7 and 0.6–66 ppb, respectively. ¹⁸⁷Re/¹⁸⁸Os ratios range from about 14 to 5161. Pyrite-rich ore samples from the massive ore of Tharsis and two samples of stockwork ore from Rio Tinto yield an isochron with an age of 346 ± 26 Ma, and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.69. Five samples from Tharsis yield an age of 353 ± 44 Ma with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.37. A sample of massive sulfide ore from Tharsis and one from Rio Tinto lie well above both isochrons and could represent Re mobilization after mineralization. The pyrite Re-Os ages agree with the paleontological age of 350 Ma of the black shales in which the ores are disseminated. Our data do not permit us to determine whether the Re-Os isochron yields the original age of ore deposition or the age of the Hercynian metamorphism that affected the ores. However, the reasonable Re-Os age reported here indicates that the complex history of the ores that occurred after the severe metamorphic event that affected the Iberian Pyrite Belt massive sulfide deposits did not fundamentally disturb the Re-Os geochronologic system. The highly radiogenic initial Os isotopic ratio agrees with previous Pb isotopic studies. If the initial ratio is recording the initial and not the metamorphic conditions, then the data indicate that the source of the metals was largely crustal. The continental margin sediments that underlie the deposits (phyllite-quartzite group) or the volcanic rocks (volcanogenic-sedimentary complex) in which the ores occur are plausible sources for the ore-forming metals and should constrain the models for the genesis of these deposits. Received: 15 March 1999 / Accepted: 26 July 1999     

Re-Os同位素体系在蛇绿岩应用研究中的进展

Re-Os不同于由亲石元素构成的同位素体系，在原始上地幔（PUN）部分熔融过程中，母体Re是中等不相容元素，优先进入熔体相，子体Os是强相容元素，富集在残留相中，是研究蛇绿岩的极好示踪剂。在蛇绿岩应用研究中已经取得了4个方面的进展：（1）明确了熔体相的Re／Os和^187Os／^188Os比值高，而残留相的低；（2）铬铁矿中铂族元素矿物（PGM）的Re亏损年龄（TRD）证实了蛇绿岩中复杂的超镁铁岩体是多阶段部分熔融的产物；（3）现代大洋橄榄岩和玄武岩的Re-Os同位素研究表明熔体相和残留相的^187Os／^188Os比值在高于亏损地幔值（DMM）的部分是一致的，而低于DMM的存在不一致性，为研究蛇绿岩中熔体相与残留相是否存在“耦合”关系提供了新的制约因素；（4）揭示了蛇绿岩地幔橄榄岩中含有古大陆岩石圈地幔，这是前所未知的。虽然取得了不少进展，但是由于Re-Os同位素体系用于蛇绿岩研究的时间较短，尚存在一些问题，如显生宙蛇绿岩地幔橄榄岩的定年问题，有待进一步深化研究。     

Diamond formation episodes at the southern margin of the Kaapvaal Craton: Re–Os systematics of sulfide inclusions from the Jagersfontein Mine

Sulfide inclusions in diamonds from the 90-Ma Jagersfontein kimberlite, intruded into the southern margin of the Kaapvaal Craton, were analyzed for their Re–Os isotope systematics to constrain the ages and petrogenesis of their host diamonds. The latter have δ¹³C ranging between −3.5 and −9.8‰ and nitrogen aggregation states (from pure Type IaA up to 51% total N as B centers) corresponding to time/temperature history deep within the subcontinental lithospheric mantle. Most sulfides are Ni-poor ([Ni + Co]/Fe = 0.05–0.25 for 15 of 17 inclusions), have elevated Cu/[Fe + Ni + Co] ratios (0.02–0.36) and elemental Re–Os ratios between 0.5 and 46 (12 of 14 inclusions) typical of eclogitic to more pyroxenitic mantle sources. Re–Os isotope systematics indicate two generations of diamonds: (1) those on a 1.7 Ga age array with initial ¹⁸⁷Os/¹⁸⁸Os (¹⁸⁷Os/¹⁸⁸Os_i) of 0.46 ± 0.07 and (2) those on a 1.1 Ga array with ¹⁸⁷Os/¹⁸⁸Os_i of 0.30 ± 0.11. The radiogenic initial Os isotopic composition for both generations of diamond suggests that components with high time-integrated Re–Os are involved, potentially by remobilization of ancient subducted oceanic crust and hybridization of peridotite. A single sulfide with higher Os and Ni content but significantly lower ¹⁸⁷Os/¹⁸⁸Os hosted in a diamond with less aggregated N may represent part of a late generation of peridotitic diamonds. The paucity of peridotitic sulfide inclusions in diamonds from Jagersfontein and other kimberlites from the Kaapvaal craton contrasts with an overall high relative abundance of diamonds with peridotitic silicate inclusions. This may relate to extreme depletion and sulfur exhaustion during formation of the Kaapvaal cratonic root, with the consequence that in peridotites, sulfide-included diamonds could only form during later re-introduction of sulfur.     

含有普通锇的辉钼矿Re-Os同位素定年研究

通过大量数据统计,表明较高比例的辉钼矿中存在普通锇。普通锇可能以类质同像形式存在于辉钼矿样品中,理论上辉钼矿中可能含有较高含量普通锇。辉钼矿样品含有较高含量普通锇可能对Re-Os定年结果产生很大影响,从原理上并结合实例证实了普通锇含量对辉钼矿Re-Os年龄影响程度。对于一般辉钼矿样品来讲,如果187Os总量(放射成因187Os与非放射成因187Os之和)与普通锇比值小于20,需要考虑普通锇对Re-Os模式年龄的影响,并提出了对于含有普通锇辉钼矿模式年龄的计算方法。先做出187Os/188Os-187Re/188Os等时线,求得初始187Os/188Os值,再根据初始187Os/188Os值和单个样品的普Os含量求得非放射成因的普Os中187Os的量。最后根据Re含量以及放射成因187Os含量得到模式年龄。     

Origin of the inconsistent apparent Re–Os ages of the Jinchuan Ni–Cu sulfide ore deposit,China: Post-segregation diffusion of Os

Apparent Re–Os ages of some magmatic sulfide ore deposits are older than the zircon and baddeleyite U–Pb ages which are interpreted as the formation age of the host intrusions. The Jinchuan Ni–Cu–PGE deposit of China, the world's third largest, is such a case. We report apparent Re–Os isochron ages of 1117 ± 67 Ma, 1074 ± 120 Ma and 867 ± 75 Ma with initial ¹⁸⁷Os/¹⁸⁸Os ratios of 0.120 ± 0.012, 0.162 ±0.017 and 0.235 ± 0.027 for disseminated ores, sulfides from the disseminated ores and massive ores from Jinchuan, respectively. Using these data and Re–Os ages from the literature, we find that the oldest apparent Re–Os age and lowest initial Os isotope ratio are from disseminated ores which contain small amounts of sulfide minerals, the highest initial Os isotope ratios and youngest apparent Re–Os ages, consistent with the zircon and baddeleyite U–Pb ages, are from massive ores containing 90–100 modal% sulfide, and net-textured ores with about 25 modal% sulfides yield apparent Re–Os ages and initial Os ratios intermediate between those of the disseminated and massive ores.Because Os diffusion between sulfides is inhibited by the intervening silicates even at high temperatures, re-equilibration did not occur in the disseminated ore and the samples retained the Os ratios of the contaminated magma, leading to geologically meaningless ages that are older than the formation age of the rocks. While Os-bearing sulfide minerals and magnetite show low closure temperatures of Os diffusion and the sulfide minerals in the massive ore are closely connected with each other, facilitating fast diffusion of Os, re-equilibration of Os was achieved during cooling of the ore from about 850 °C after the segregation to about 400 °C. Thus, an age corresponding to the formation time and an elevated initial Os ratio were yielded by the massive ore. Os isotopes in the net-textured ore behave in the way intermediate between the disseminated and massive ores. Pb isotope data support the Os results. Disseminated ores have heterogeneous Pb isotope ratios whereas Pb in the massive ores is more uniform, consistent with Pb isotopic equilibration in the massive ores, but not in the disseminated ores.     

Re-Os systematics of komatiites and komatiitic basalts at Dundonald Beach, Ontario, Canada: Evidence for a complex alteration history and implications of a late-Archean chondritic mantle source

Osmium isotopic compositions, and Re and Os concentrations have been examined in one komatiite unit and two komatiitic basalt units at Dundonald Beach, part of the 2.7 Ga Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Ontario, Canada. The komatiitic rocks in this locality record at least three episodes of alteration of Re-Os elemental and isotope systematics. First, an average of 40% and as much as 75% Re may have been lost due to shallow degassing during eruption and/or hydrothermal leaching during or immediately after emplacement. Second, the Re-Os isotope systematics of whole rock samples with ¹⁸⁷Re/¹⁸⁸Os ratios >1 were reset at ∼2.5 Ga, possibly due to a regional metamorphic event. Third, there is evidence for relatively recent gain and loss of Re in some rocks.Despite the open-system behavior, some aspects of the Re-Os systematics of these rocks can be deciphered. The bulk distribution coefficient for Os (D_Os^solid/liquid) for the Dundonald rocks is ∼3 ± 1 and is well within the estimated D values obtained for komatiites from the nearby Alexo area and stratigraphically-equivalent komatiites from Munro Township. This suggests that Os was moderately compatible during crystal-liquid fractionation of the magmas parental to the Kidd-Munro komatiitic rocks. Whole-rock samples and chromite separates with low ¹⁸⁷Re/¹⁸⁸Os ratios (<1) yield a precise chondritic average initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.1083 ± 0.0006 (γ_Os = 0.0 ± 0.6) for their well-constrained ∼2715 Ma crystallization age. The chondritic initial Os isotopic composition of the mantle source for the Dundonald rocks is consistent with that determined for komatiites in the Alexo area and in Munro Township, suggesting that the mantle source region for the Kidd-Munro volcanic assemblage had evolved with a long-term chondritic Re/Os before eruption. The chondritic initial Os isotopic composition of the Kidd-Munro komatiites is indistinguishable from that of the projected contemporaneous convective upper mantle. The uniform chondritic Os isotopic composition of the Kidd-Munro komatiites contrasts with the typical large-scale Os isotopic heterogeneity in the mantle sources for ca. 89 Ma komatiites from the Gorgona Island, arc-related rocks and present-day ocean island basalts. This suggests that the Kidd-Munro komatiites sampled a late-Archean mantle source region that was significantly more homogeneous with respect to Re/Os relative to most modern mantle-derived rocks.     

Subgrain-scale decoupling of Re and Os and assessment of laser ablation ICP-MS spot dating in molybdenite

Reproducibility of Re-Os molybdenite ages depends on sample size and homogeneity, suggesting that Re and Os are decoupled within individual molybdenite crystals and do not remain spatially linked over time. In order to investigate the Re-Os systematics of molybdenite at the subgrain (micron) scale, we report LA-ICP-MS Re-Os ages for an Archean molybdenite crystal from Aittojärvi, Finland, analyzed in situ in a white aplite matrix. A related Aittojärvi molybdenite (A996D), in the form of a very fine-grained mineral separate, is used as one of our in-house NTIMS standards, and thus its age of 2760 ± 9 Ma is well established. Measurements of (¹⁸⁷Re + ¹⁸⁷Os)/¹⁸⁵Re on micron scale spots along 200 μm traverses across the crystal yield a wide range of ages demonstrating that, in this case, microsampling of molybdenite does not produce geologically meaningful ages. Experimentation with mineral separations and sample size over a 7-yr period predicted that this would be the outcome. We suggest that ¹⁸⁷Os is more likely to be the mobile species, based on its charge and ionic radius, and that ¹⁸⁷Os becomes decoupled from parent ¹⁸⁷Re with time on the micron and larger scale. Incompatible charge and ionic radius for Os ions formed during reduction of molybdenite-forming fluids may explain the widely observed absence of common (initial) Os in molybdenite. Geologically accurate ages for molybdenite can only be obtained for fully homogenized crystals (or crystal aggregates) so that any post-crystallization ¹⁸⁷Re-¹⁸⁷Os decoupling is overcome.A growing number of geologically accurate ID-NTIMS ¹⁸⁷Re-¹⁸⁷Os ages for homogenized molybdenite suggest that postcrystallization mobility of radiogenic ¹⁸⁷Os must be limited to within the molybdenite mineral phase. We suggest that radiogenic ¹⁸⁷Os may be stored in micron scale dislocations, kink bands, and delamination cracks produced by deformation, and that the unusual structure and deformation response of molybdenite results in an increased chemical stability in this mineral. Migration of ¹⁸⁷Os into adjacent silicate phases is highly unlikely, but other contacting sulfides may take in Os. In an example from a Proterozoic skarn deposit at Pitkäranta (western Russia), we demonstrate minor loss of radiogenic ¹⁸⁷Os from molybdenite and a corresponding gain in adjacent chalcopyrite such that the molybdenite age is not perceptibly disturbed, whereas the resulting chalcopyrite ages are impossibly old. Therefore, it is unadvisable to perform Re-Os analytical work on any sulfide in contact or intimate association with molybdenite. In addition to large errors in the age, if the isochron method is employed, initial ¹⁸⁷Os/¹⁸⁸Os ratios could be erroneously high, leading to seriously errant genetic interpretations.