Mineralogy,petrography, and oxygen isotopic compositions of ultrarefractory inclusions from carbonaceous chondrites

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc₄Zr₃O₁₂), and an unnamed ((Ti,Mg,Sc,Al)₃O₅) mineral, davisite (CaScAlSiO₆), eringaite (Ca₃(Sc,Y,Ti)₂Si₃O₁₂), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)₂O₃), lakargiite (CaZrO₃), warkite (Ca₂Sc₆Al₆O₂₀), panguite ((Ti,Al,Sc,Mg,Zr,Ca)_1.8O₃), Y-rich perovskite ((Ca,Y)TiO₃), tazheranite ((Zr,Ti,Ca)O_2−x), thortveitite (Sc₂Si₂O₇), zirconolite (orthorhombic CaZrTi₂O₇), and zirkelite (cubic CaZrTi₂O₇). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰), except for one CH UR CAI, which is uniformly ¹⁶O-depleted (Δ ¹⁷O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ¹⁷O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)₃O₅ (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ¹⁷O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being ¹⁶O-depleted to various degrees relative to uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a ¹⁶O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an ¹⁶O-depleted gaseous reservoir providing an evidence for large variations in Δ¹⁷O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in ¹⁶O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)₃O₅ intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with ¹⁶O-depleted reservoirs occurred.     

Classification of five new ordinary chondrites from North West Africa

We classified five new ordinary chondrites from North West Africa. NWA 3010 is an L6(S5), NWA 3011 is an L5(S5), NWA 3012 is an LL4(S5), NWA 3013 is an L5(S5), and NWA 3014 is an H4(S1). The meteorites experienced a range of terrestrial alteration, with NWA 3010 equal to weathering grade W2, NWA 3011 equal to W3, NWA 3012 equal to W3, NWA 3013 equal to W2, and NWA 3014 equal to W4.     

Compositions of four unusual CM or CM-related Antarctic chondrites

To identify chemical group affinities and infer the occurrence of thermal metamorphism or aqueous alteration in their histories, we quantified 43 trace elements in the CM or CM-related Antarctic carbonaceous chondrites EET 96010, LAP 02277, MET 01070, and WIS 91600. We also analyzed LAP 02206, a CV chondrite, to add to our comparison database. We present whole-rock oxygen isotope data for LAP 02206, LAP 02277, and MET 01070 to complement our trace element results. With these data, we confirm the CV classification of LAP 02206 and CM or CM-like classification for the other four chondrites in this study. On the basis of moderately volatile element content, our results show that EET 96010 experienced open-system heating, while any heating LAP 02277 and MET 01070 may have experienced was in a chemically closed-system. WIS 91600, on a trace element basis, appears to be CM-like material. Our analyses support the idea that CM material has experienced a wide variety of post-accretionary processing.     

Mineralogy and petrology of Al-rich objects and amoeboid olivine aggregates in the CH carbonaceous chondrite North West Africa 739

The aluminum-rich (>10 wt% Al₂O₃) objects in the CH carbonaceous chondrite North West Africa (NWA) 739 include Ca,Al-rich inclusions (CAIs), Al-rich chondrules, and isolated mineral grains (spinel, plagioclase, glass). Based on the major mineralogy, 54 refractory inclusions found in about 1 cm² polished section of NWA 739 can be divided into hibonite-rich (16%), grossite-rich (26%), melilite-rich (28%), spinel-pyroxene-rich (16%) CAIs, and amoeboid olivine aggregates, (AOA's, 17%). Most CAIs are rounded, 25–185 μm (average=70 μm) in apparent diameter, contain abundant, tiny perovskite grains, and typically surrounded by a single- or double-layered rim composed of melilite and/or Al-diopside; occasionally, layers of spinel+hibonite and forsterite are observed. The AOAs are irregularly shaped, 100–250 μm (average=175 μm) in size, and consist of forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, and minor spinel. One AOA contains compact, rounded melilite-spinel-perovskite CAIs and low-Ca pyroxene replacing forsterite. The Al-rich (>10 wt% bulk Al₂O₃) chondrules are divided into Al-diopside-rich and plagioclase-rich. The Al-diopside-rich chondrules, 50–310 μm (average=165 μm) in apparent diameter, consist of Al-diopside, skeletal forsterite, spinel, ±Al-rich low-Ca pyroxene, and ±mesostasis. The plagioclase-rich chondrules, 120–455 μm (average=285 μm) in apparent diameter, are composed of low-Ca and high-Ca pyroxenes, forsterite, anorthitic plagioclase, Fe,Ni-metal nodules, and mesostasis. The isolated spinel occurs as coarse, 50–125 μm in size, subhedral grains, which are probably the fragments of Al-diopside chondrules. The isolated plagioclase grains are too coarse (60–120 μm) to have been produced by disintegration of chondrules or CAIs; they range in composition from nearly pure anorthite to nearly pure albite; their origin is unclear. The Al-rich objects show no evidence for Fe-alkali metasomatic or aqueous alteration; the only exception is an Al-rich chondrule fragment with anorthite replaced by nepheline. They are texturally and mineralogically similar to those in other CH chondrites studied (Acfer 182, ALH85085, PAT91467, NWA 770), but are distinct from the Al-rich objects in other chondrite groups (CM, CO, CR, CV). The CH CAIs are dominated by very refractory minerals, such as hibonite, grossite, perovskite and gehlenitic melilite, and appear to have experienced very low degrees of high-temperature alteration reactions. These include replacement of grossite by melilite, of melilite by anorthite, diopside, and spinel, and of forsterite by low-Ca pyroxene. Only a few CAIs show evidence for melting and multilayered Wark-Lovering rims. These observations may suggest that CH CAIs experienced rather simple formation history and escaped extensive recycling. In order to preserve the high-temperature mineral assemblages, they must have been efficiently isolated from the hot nebular region, like some chondrules and the zoned Fe,Ni-metal grains in CH chondrites.     

Mineralogy,petrography, and oxygen and aluminum-magnesium isotope systematics of grossite-bearing refractory inclusions

Grossite (CaAl₄O₇) is one of the one of the first minerals predicted to condense from a gas of solar composition, and therefore could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Grossite-bearing Ca,Al-rich inclusions (CAIs) are a relatively rare type of refractory inclusions in most carbonaceous chondrite groups, except CHs, where they are dominant. We report new and summarize the existing data on the mineralogy, petrography, oxygen and aluminum-magnesium isotope systematics of grossite-bearing CAIs from the CR, CH, CB, CM, CO, and CV carbonaceous chondrites. Grossite-bearing CAIs from unmetamorphosed (petrologic type 2―3.0) carbonaceous chondrites preserved evidence for heterogeneous distribution of ²⁶Al in the protoplanetary disk. The inferred initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] in grossite-bearing CAIs is generally bimodal, ˜0 and ˜5×10⁻⁵; the intermediate values are rare. CH and CB chondrites are the only groups where vast majority of grossite-bearing CAIs lacks resolvable excess of radiogenic ²⁶Mg. Grossite-bearing CAIs with approximately the canonical (²⁶Al/²⁷Al)₀ of ˜5×10⁻⁵ are dominant in other chondrite groups. Most grossite-bearing CAIs in type 2–3.0 carbonaceous chondrites have uniform solar-like O-isotope compositions (Δ¹⁷O ˜ ‒24±2‰). Grossite-bearing CAIs surrounded by Wark-Lovering rims in CH chondrites are also isotopically uniform, but show a large range of Δ¹⁷O, from ˜ ‒40‰ to ˜ ‒5‰, suggesting an early generation of gaseous reservoirs with different oxygen-isotope compositions in the protoplanetary disk. Igneous grossite-bearing CAIs surrounded by igneous rims of ±melilite, Al-diopside, and Ca-rich forsterite, found only in CB and CH chondrites, have uniform ¹⁶O-depleted compositions (Δ¹⁷O ˜ ‒14‰ to ‒5‰). These CAIs appear to have experienced complete melting and incomplete O-isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2‰) gas in the CB impact plume generated about 5 Ma after CV CAIs. Grossite-bearing CAIs in metamorphosed (petrologic type >3.0) CO and CV chondrites have heterogeneous Δ¹⁷O resulted from mineralogically-controlled isotope exchange with a ¹⁶O-poor (Δ¹⁷O ˜ ‒2 to 0‰) aqueous fluid on the CO and CV parent asteroids 3–5 Ma after CV CAIs. This exchange affected grossite, krotite, melilite, and perovskite; corundum, hibonite, spinel, diopside, forsterite, and enstatite preserved their initial O-isotope compositions. The internal ²⁶Al-²⁶Mg isochrons in grossite-bearing CAIs from weakly-metamorphosed CO and CV chondrites were not disturbed during this oxygen-isotope exchange.HCCJr is grateful to Klaus Keil for all his sound profession counsel and collegial friendship over the years. He has always been willing to talk and has the generous nature of listening and sharing his thoughts freely and constructively. Professor Klaus Keil has been a mentor to and played a key role in the careers of three of the authors of this paper (ANK, KN, and GRH). He has also influenced the careers of the other authors and most of the people who have worked on meteorites over the past 50+ years. We therefore dedicate this paper to Professor Keil and present it in this Special Issue of Geochemistry.     

Amoeboid olivine aggregates and related objects in carbonaceous chondrites: records of nebular and asteroid processes

Amoeboid olivine aggregates (AOAs) are the most common type of refractory inclusions in CM, CR, CH, CV, CO, and ungrouped carbonaceous chondrites Acfer 094 and Adelaide; only one AOA was found in the CB_b chondrite Hammadah al Hamra 237 and none were observed in the CB_a chondrites Bencubbin, Gujba, and Weatherford. In primitive (unaltered and unmetamorphosed) carbonaceous chondrites, AOAs consist of forsterite (Fa_<2), Fe, Ni-metal (5-12 wt% Ni), and Ca, Al-rich inclusions (CAIs) composed of Al-diopside, spinel, anorthite, and very rare melilite. Melilite is typically replaced by a fine-grained mixture of spinel, Al-diopside, and ±anorthite; spinel is replaced by anorthite. About 10% of AOAs contain low-Ca pyroxene replacing forsterite. Forsterite and spinel are always ¹⁶O-rich (δ^17,18O∼−40‰ to −50‰), whereas melilite, anorthite, and diopside could be either similarly ¹⁶O-rich or ¹⁶O-depleted to varying degrees; the latter is common in AOAs from altered and metamorphosed carbonaceous chondrites such as some CVs and COs. Low-Ca pyroxene is either ¹⁶O-rich (δ^17,18O∼−40‰) or ¹⁶O-poor (δ^17,18O∼0‰). Most AOAs in CV chondrites have unfractionated (∼2-10×CI) rare-earth element patterns. AOAs have similar textures, mineralogy and oxygen isotopic compositions to those of forsterite-rich accretionary rims surrounding different types of CAIs (compact and fluffy Type A, Type B, and fine-grained, spinel-rich) in CV and CR chondrites. AOAs in primitive carbonaceous chondrites show no evidence for alteration and thermal metamorphism. Secondary minerals in AOAs from CR, CM, and CO, and CV chondrites are similar to those in chondrules, CAIs, and matrices of their host meteorites and include phyllosilicates, magnetite, carbonates, nepheline, sodalite, grossular, wollastonite, hedenbergite, andradite, and ferrous olivine.Our observations and a thermodynamic analysis suggest that AOAs and forsterite-rich accretionary rims formed in ¹⁶O-rich gaseous reservoirs, probably in the CAI-forming region(s), as aggregates of solar nebular condensates originally composed of forsterite, Fe, Ni-metal, and CAIs. Some of the CAIs were melted prior to aggregation into AOAs and experienced formation of Wark-Lovering rims. Before and possibly after the aggregation, melilite and spinel in CAIs reacted with SiO and Mg of the solar nebula gas enriched in ¹⁶O to form Al-diopside and anorthite. Forsterite in some AOAs reacted with ¹⁶O-enriched SiO gas to form low-Ca pyroxene. Some other AOAs were either reheated in ¹⁶O-poor gaseous reservoirs or coated by ¹⁶O-depleted pyroxene-rich dust and melted to varying degrees, possibly during chondrule formation. The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into magnesian (Type I) chondrules. Secondary mineralization and at least some of the oxygen isotope exchange in AOAs from altered and metamorphosed chondrites must have resulted from alteration in the presence of aqueous solutions after aggregation and lithification of the chondrite parent asteroids.     

Heating duration of igneous rim formation on a chondrule in the Northwest Africa 3118 CV3oxA carbonaceous chondrite inferred from micro-scale migration of the oxygen isotopes

Due to their common occurrence in various types of chondrites, igneous rims formed on pre-existing chondrules throughout chondrule-forming regions of the solar nebula. Although the peak temperatures are thought to reach similar values to those achieved during chondrule formation events, the heating duration in chondrule rim formation has not been well defined. We determined the two-dimensional chemical and oxygen isotopic distributions in an igneous rim of a chondrule within the Northwest Africa 3118 CV3_oxA chondrite with sub-micrometer resolution using secondary ion mass spectrometry and scanning electron microscopy. The igneous rim experienced aqueous alteration on the CV parent body. The aqueous alteration resulted in precipitation of the secondary FeO-rich olivine (Fa_40–49) and slightly disturbed the Fe-Mg distribution in the MgO-rich olivine phenocrysts (Fa_11–22) at about a 1 μm scale. However, no oxygen isotopic disturbances were observed at a scale greater than 100 nm. The MgO-rich olivine, a primary phase of igneous rim formation, has δ¹⁷O = −6 ± 3‰ and δ¹⁸O = −1 ± 4‰, and some grains contain extreme ¹⁶O-rich areas (δ¹⁷O, δ¹⁸O = ∼−30‰) nearly 10 μm across. We detected oxygen isotopic migration of approximately 1 μm at the boundaries of the extreme ¹⁶O-rich areas. Using oxygen self-diffusivity in olivine, the heating time of the igneous rim formation could have continued from several hours to several days at near liquidus temperatures (∼2000 K) in the solar nebula suggesting that the rim formed by a similar flash heating event that formed the chondrules.     

焦家式金矿水-岩交换作用——成矿流体氢氧同位素组成研究

焦家式金矿位于胶东半岛西北部，矿体赋存于花岗片麻岩－花岗闪长岩类岩石断裂带内，呈破碎黄铁绢英岩化浸染状矿石。矿体中均伴有富含金的成矿前、后中基性脉岩。成矿作用包括乳白色块状黄铁矿石英和（或）伟晶石英脉阶段、含金硫化物石英阶段和方解石石英阶段。三个阶段石英δ＾１８Ｏ值平均为１２．４‰、１３．２‰、和１４．４‰。计算的石英δ＾１８ＯＨ２ｏ值平均分别为４．７‰、３．５‰和３．５‰。三个阶段石英流体包裹体     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999     

Remnants of premetamorphic fluid and oxygen isotopic signatures in eclogites and garnet clinopyroxenite from the Dabie-Sulu terranes, eastern China

A combined oxygen‐isotope and fluid‐inclusion study has been carried out on high‐ and ultrahigh‐pressure metamorphic (HP/UHPM) eclogites and garnet clinopyroxenite from the Dabie‐Sulu terranes in eastern China. Coesite‐bearing eclogites/garnet clinopyroxenite and quartz eclogites have a wide range in whole‐rock δ¹⁸O_VSMOW, from 0 to 11‰. The high‐T oxygen‐isotope fractionations preserved between quartz and garnet preclude significant retrograde isotope exchange during exhumation, and the wide range in whole‐rock oxygen‐isotope composition is thought to be a presubduction signature of the precursors. Aqueous fluids with variable salinities and gas species (N₂‐, CO₂‐, or CH₄‐rich), are trapped as primary inclusions in garnet, omphacite and epidote, and in quartz blebs enclosed within eclogitic minerals. In high‐δ¹⁸O HP/UHPM rocks from Hujialin and Shima, high‐salinity brine and/or N₂ inclusions occur in garnet porphyroblasts, which also contain inclusions of coesite, Cl‐rich blue amphibole and dolomite. In contrast, in low‐δ¹⁸O eclogites from Qinglongshan and Huangzhen, the Cl concentrations in amphibole are very low, < 0.2 wt.%, and low‐salinity aqueous inclusions occur in quartz inclusions in epidote porphyroblasts and in epidote cores. These low‐salinity fluid inclusions are believed to be remnants of meteoric water, although the fluid composition was modified during pre‐ and syn‐peak HP/UHPM. Eclogites at Houshuichegou and Hetang contain CH₄‐rich fluid inclusions, coexisting with high‐salinity brine inclusions. Methane was probably formed under the influence of CO₂‐rich aqueous fluids during serpentinisation of mantle‐derived peridotites prior to or during plate subduction. Remnants of premetamorphic low‐ to high‐salinity aqueous fluid with minor N₂ and/or other gas species preserved in the Dabie‐Sulu HP/UHPM eclogites and garnet clinopyroxenite indicate a great diversity of initial fluid composition in the precursors, implying very limited fluid–rock interaction during syn‐ and post‐peak HP/UHPM.     

江西九瑞坳下地区矽卡岩的矿物化学、氧同位素特征及成矿潜力探讨

江西九瑞矿集区是长江中下游成矿带上重要的铜金资源产地,近年来地勘单位在该区西南部的坳下远景区发现物化探异常,并布置钻探工作,在奥陶系白云岩与隐伏黑云母花岗斑岩侵入体的接触带上,揭露了矽卡岩和矿化。本文以这些矽卡岩为研究对象,运用电子探针及同位素质谱仪测定矿物的化学成分和氧同位素组成,在此基础上探讨了热液的物理化学条件,流体来源及演化过程。结果表明,形成坳下矽卡岩的热液流体,进蚀变阶段温度为516~663℃,平均597℃,氧同位素值(δ~(18)O_(Fluid))为9.3‰,偏还原性;退蚀变阶段温度为263~317℃,平均290℃,氧同位素值(δ~(18)O_(Fluid))为-4.9‰,偏氧化性。与九瑞的武山、东雷湾、邓家山等矽卡岩矿床相比,坳下镁矽卡岩组分更高,发现了以往九瑞地区的矽卡岩矿床中未见的橄榄石、金云母。经综合分析,认为高盐度的、较热的、氧化性弱的岩浆热液,与稀释的、较冷的、氧化性强的大气降水的流体混合过程,是坳下矽卡岩及其矿化的形成机制。这一过程,对形成有价值的矽卡岩型矿床非常有利,在九瑞矿集区后续的勘查工作中,应关注侵入体与奥陶系白云岩接触带形成的镁矽卡岩相关矿床,以及志留系和奥陶系地层硅钙界面处受到岩浆热液叠加形成的层状矿体。     

Stable carbon and oxygen isotopic evidence for late Pleistocene to middle Holocene climatic fluctuations in the interior of southern Africa

Stable carbon and oxygen isotope analyses of ungulate grazers from four archaeological sites located in different environs within the Caledon River Valley have provided a relatively well‐dated proxy palaeoenvironmental and palaeoclimatic sequence for the period between 16 000 and 6000 calendar (cal.) yr BP. Within the overall trend towards hot mid‐Holocene temperatures and a summer rainfall pattern, stable carbon isotope results show that there were three periods when growth season temperatures were cool enough for C₃ grasses to be present: 16 000–14 000; 10 200–9600, and 8400–8000 cal. yr BP. Similar trends were recorded in stable oxygen isotope values, reflecting shifts in either temperature or available moisture. Although having a similar pattern to that of the lower altitude site, sites situated in foothills and montane portions of the valley consistently maintained lower temperatures until the mid‐Holocene altithermal. At this time growth season temperatures warmed sufficiently for a 100% C₄ grassland to expand in altitude from the warmer low lying localities. In relation to present understanding of synoptic and global climatic patterning, these findings suggest that the early to middle Holocene transition was not a gradual warming trend, but rather it was marked by a series of climatic fluctuations. Of particular note is the possible global, rather than regional, occurrence of the 8200 cal. yr BP ‘event’. Copyright © 2002 John Wiley & Sons, Ltd.     

Mineralogy, geochemistry, and Nd isotope composition of the Rainbow hydrothermal field, Mid-Atlantic Ridge

Petrological, geochemical, and Nd isotopic analyses have been carried out on rock samples from the Rainbow vent field to assess the evolution of the hydrothermal system. The Rainbow vent field is an ultramafic-hosted hydrothermal system located on the Mid-Atlantic Ridge characterized by vigorous high-temperature venting (∼365°C) and unique chemical composition of fluids: high chlorinity, low pH and very high Fe, and rare earth element (REE) contents (Douville et al., Chemical Geology 184:37–48, 2002). Serpentinization has occurred under a low-temperature (<270°C) retrograde regime, later overprinted by a higher temperature sulfide mineralization event. Retrograde serpentinization reactions alone cannot reproduce the reported heat and specific chemical features of Rainbow hydrothermal fluids. The following units were identified within the deposit: (1) nonmineralized serpentinite, (2) mineralized serpentinite—stockwork, (3) steatite, (4) semimassive sulfides, and (5) massive sulfides, which include Cu-rich massive sulfides (up to 28wt% Cu) and Zn-rich massive sulfide chimneys (up to 5wt% Zn). Sulfide mineralization has produced significant changes in the sulfide-bearing rocks including enrichment in transition metals (Cu, Zn, Fe, and Co) and light REE, increase in the Co/Ni ratios comparable to those of mafic Cu-rich volcanic-hosted massive sulfide deposits and different ¹⁴³Nd/¹⁴⁴Nd isotope ratios. Vent fluid chemistry data are indicative of acidic, reducing, and high temperature conditions at the subseafloor reaction zone where fluids undergo phase separation most likely under subcritical conditions (boiling). An explanation for the high chlorinity is not straightforward unless mixing with high salinity brine or direct contribution from a magmatic Cl-rich aqueous fluid is considered. This study adds new data, which, combined with the current knowledge of the Rainbow vent field, brings compelling evidence for the presence, at depth, of a magmatic body, most likely gabbroic, which provides heat and metals to the system. Co/Ni ratios proved to be good tools used to discriminate between rock units, degree of sulfide mineralization, and positioning within the hydrothermal system. Deeper units have Co/Ni <1 and subsurface and surface units have Co/Ni >1.     

西天山智博铁矿床磁铁矿地球化学及氧同位素特征

智博铁矿是阿吾拉勒铁铜成矿带成矿作用演化的典型代表。本文在详细的野外地质调查和室内研究的基础上,将该矿床的成矿阶段划为岩浆成矿期和热液成矿期两个期次,并将其矿石产状类型划分为块状矿石、浸染状矿石、角砾状矿石、网脉状矿石等。本文选取智博铁矿两期磁铁矿单矿物作为研究对象,通过其稀土微量元素及氧同位素等特征的研究来查明该矿床成矿物质特征及其来源。研究表明,智博铁矿的两期磁铁矿微量元素特征具有一定差异性,岩浆型磁铁矿相对富V、Ni、Ga等元素,而热液型矿石中相对富Co,贫V、Ni。两期磁铁矿单矿物稀土配分模式与矿区火山岩接近,暗示成矿物质与火山岩同源;Y/Ho比值接近球粒陨石,在Y/Ho-La/Ho图中和(La/Sm)_N-(La/Yb)_N图中,两期磁铁矿表现出同源性,暗示矿区内多数矿石的形成与火山岩浆作用有关。岩浆期的磁铁矿δ~(18)O值平均为3.4‰,与基鲁纳型铁矿和拉科铁矿的磁铁矿δ~(18)O非常接近;而热液期的磁铁矿δ~(18)O值平均为4.1‰,比岩浆期磁铁矿的δ~(18)O值范围更大些,可能与热液流体参入及矿物重结晶等因素有关。磁铁矿的地球化学特征及氧同位素均暗示智博铁矿矿石的形成主要与火山-岩浆活动密切相关,但也受到后期热液活动的影响。     

川东南地区洗象池组碳氧同位素特征、古海洋环境及其与储集层的关系

本文在野外剖面调查的基础上,结合薄片观察,对川东南地区三汇剖面寒武系洗象池组237块碳酸盐岩样品进行了系统的碳氧同位素组成研究,结果表明,δ~(18)O值主要分布在-8‰～-6‰,平均为-7.63‰;δ~(13)C值介于-5.53‰～3.44‰之间。利用碳氧同位素数值计算古盐度及古温度结果表明,绝大多数Z值高于120‰,且δ~(13)C值大于-2‰,古海水温度主要集中在19～25℃,说明整体为海水-咸化海水沉积环境与温暖或炎热的亚热带气候。认为洗象池组沉积期海平面变化有五个阶段:早期缓慢上升与下降,中期快速海侵,中后期缓慢海退,后期动荡,末期海退。三汇剖面洗象池组储集层岩性主要为颗粒云岩及晶粒云岩,储集空间以溶蚀孔洞、粒间孔与晶间孔为主。多期的海平面的下降,对应碳同位素多旋回负漂,从而发育向上变浅的多旋回韵律性地层,形成纵向上的多套储集层,洗象池组储集层的形成与演化受海平面变化控制,主要发育在古地貌较高处与滩体向上变浅旋回的上部。另外,依据δ~(13)C值显著的正漂移,明确了芙蓉统地层的底界,为四川盆地寒武系地层的划分提供了证据。     

豫西宜阳地区三叠纪早期孙家沟组上段湖相碳酸盐岩碳氧同位素和古环境分析

孙家沟组是华北板块二叠纪和三叠纪转折时期的沉积记录,选择记载气候变化的材料,揭示气候的连续性变化,对于分析华北板块在这一转折时期古环境的重大变革具有重要意义。本项研究选择地层出露良好的华北板块南部豫西宜阳地区,以孙家沟组上段呈韵律型发育的薄层碳酸盐岩为研究对象,分析这些碳酸盐岩层中碳酸盐矿物的碳氧同位素组成及其变化,结合宏观沉积环境的分析,揭示这些碳酸盐岩层的成因,以及它们所蕴含的古环境信息。研究表明,孙家沟组上段碳酸盐岩的碳酸盐矿物主要为自生碳酸盐,且没有发生显著的后期变化,碳氧同位素组成及其变化可以用于古环境的重建。根据孙家沟组上段碳酸盐岩碳氧同位素的组成和受控因素,结合宏观沉积环境分析,认为孙家沟组上段的盐酸盐岩形成于湖盆环境。δ~(18)O-7.97‰时,δ~(13)C和δ~(18)O呈明显的正相关关系,湖泊处于封闭环境,碳酸盐矿物富含白云石,且结晶程度较差;δ~(18)O-7.97‰时,δ~(13)C和δ~(18)O呈明显的负相关关系,湖泊处于开放环境,碳酸盐矿物富含镁方解石,且结晶程度较好。根据孙家沟组上段由下部到上部碳酸盐岩碳氧同位素的变化,揭示出当时的湖泊环境经历了由相对开放到相对封闭,再到相对开放的演化,并显示出温度变低,湿度变小,植被变差的演化趋势。孙家沟组上段湖泊环境的形成可能与南部北秦岭造山带的隆升有关,薄层碳酸盐岩层与上覆紫色泥岩层组成的韵律层主要与气候变化引起的降雨量有关。孙家沟组上段所记录的古环境及其变化与全球二叠纪末期生物大灭绝以后陆地环境的变化规律相吻合。     

Sulphur and carbon isotopic composition of power supply coals in the Pannonian Basin, Hungary

The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in ³⁴S isotopes (δ³⁴S_organic = + 12.74‰, δ³⁴S_pyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes.     

Carbon and oxygen isotopic variations in peritidal stromatolite cycles, Paleoproterozoic Kajrahat Limestone, Vindhyan basin of central India

Variations of carbon and oxygen isotopic ratios in response to cyclical sea level fluctuations have been documented from a Paleoproterozoic peritidal stromatolite succession. The upper division of the Kajrahat Limestone, Vindhyan Supergroup of central India consists of several shallowing upward stromatolite cycles identified by regular and systematic changes in stromatolite size. Normally, larger stromatolites are followed upward in the succession by smaller stromatolites and microbial laminites that occupy the top of the cycle. Desiccation cracks are found in all the facies indicating subaerial exposure. We investigated the stable isotope compositional variations across nine complete stromatolite cycles showing frequent subaerial emergence. Carbon and oxygen isotopic values of the limestones, in general, are comparable to contemporary marine values available from earlier studies but show regular depletion in response to shallowing of the water level. The δ¹³C and δ¹⁸O values of the limestones vary within an individual stromatolite cycle; depleted values characterize the topmost part of the cycles. The isotope pattern is explained by micritic carbonate deposition in different sub environments of the shallow marine domain having different salinity and variable duration of exposure. These variations also probably caused the observed scatter in δ¹³C and δ¹⁸O values of supratidal microbial laminites.     

40Ar/39Ar and oxygen isotope studies of polymetamorphism from Tinos Island, Cycladic blueschist belt, Greece

Abstract Petrological, oxygen isotope and ⁴⁰Ar/³⁹Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some ⁴⁰Ar/³⁹Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ¹⁸O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ¹⁸O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.