Metamorphism of carbonaceous material in the Tono contact aureole, Kitakami Mountains, Japan

Abstract Optical and X-ray studies of carbonaceous material in the Tono contact metamorphic aureole, Kitakami Mountains, northeast Japan, have revealed that metamorphic graphitization proceeded through two discontinuous changes: first, optically anisotropic domains develop within the coaly phytoclast, forming transitional material, and then, ordered graphite crystallizes by the decomposition of pre-existing carbonaceous materials. Coaly material disappears in the uppermost chlorite zone. Transitional material appears in the middle of the lower chlorite zone. Graphite appears in the upper chlorite zone and its modal abundance increases across the andalusite iso-grad to the cordierite isograd where all the carbonaceous materials have converted to graphite. The apparently continuous variation in the crystallographic parameters of the bulk carbonaceous material during graphitization is largely due to variation in the modal proportions of three types of carbonaceous materials. The temperature of graphitization in the present area is at least 100°C higher than the temperature in the Sanbagawa and New Caledonia high-pressure metamorphic terrains, probably due to the slow reaction rate of metamorphic graphitization and to the short duration of contact metamorphism.     

The Palma Volcano-Sedimentary Supersuite,Precambrian Sul-Riograndense Shield,Brazil

Komatiites are generally found in Archean greenstone belts, but have been reported in some Mesozoic volcano-sedimentary sequences. The Palma Volcano-Sedimentary Supersuite (PVSS) is a Neoproterozoic sequence composed of meta-ultramafic volcanic rocks, mafic-to-felsic metavolcanic rocks, and metasedimentary rocks ranging from quartzites to chlorite-mica-quartz schists, marbles, and marls. Original PVSS structures were overprinted by two penetrative deformational surfaces (So//Sn and Sn+1); associated metamorphic assemblages are assigned to the upper greenschist facies. Basalts predominate over andesites and rhyodacites, and their major, minor, trace, and rare-earth elements display compatible geochemical trends characteristic of calc-alkaline magmas. Meta-ultramafic rocks are variable-thickness flows in the metasedimentary sequence. Metamorphism caused the development of a metasomatic tremolite zone around the serpentinite bodies, as well as chlorite and talc schist metasomatic zones. Evaluation of the geochemical mobility of the elements showed that the ratios between major and minor elements have not changed in the serpentinites. It was then possible to investigate the lithogeochemical nature of the serpentinites by studying the minor, trace, and rare-earth elements. The lithogeochemical investigation and the structures of the serpentinite bodies enable them to be regarded as komatiitic flows extruded under shallow water. These komatiite flows and calc-alkaline basalt to rhyodacite flows associated with shallow-water sediments suggest that this volcano-sedimentary sequence was developed in a Neoproterozoic arc-related tectonic setting.     

黄陵断穹核部鳞片石墨矿地球化学特征与成因研究

黄陵断穹核部石墨矿是我国鳞片(晶质)石墨矿的主要产区,对该区石墨矿的研究具有重要理论和实际意义。该区已有石墨矿研究成果多侧重于矿床地质方面,对矿床成因分析缺乏地球化学支撑。为此,本文从地球化学层面查明石墨矿原岩类型,碳质富集岩相、变质作用和晶质石墨的形成,为矿床成因和成矿作用提供地球化学依据。通过系统采集区内主要石墨矿样品,进行主量元素、微量元素、稀土元素和同位素分析,根据矿床地球化学原理和分析方法,阐明石墨矿的物质来源,成矿元素集散行为和矿床形成机制。根据主量元素含量和组合,推断石墨的原岩为碳质粉砂质泥岩。微量元素的双重性指示石墨矿的物质有两个来源:中太古代野马洞岩组和中太古代东冲河片麻杂岩。独特的稀土元素配分型式说明物源转化为原岩时存在着强烈的地球化学反应。石墨矿的碳同位素组成支持碳质来自有机物的观点。     

Occurrence of arsenic (V) in forearc mantle serpentinites based on X-ray absorption spectroscopy study

We examined As concentration, mineralogical site, and oxidation state in the serpentinites associated with the Tso Morari eclogitic rocks in the Indus suture zone, northwest Himalaya, to examine how highly fluid-soluble elements like As are transferred from slabs to arc magmas in subduction zones. The serpentinite samples represent hydrated peridotites at the base of the mantle wedge beneath Eurasia, and were exhumed from a depth of ∼100 km during subduction of the Indian continental margin. The bulk serpentinite samples contain total As concentrations ranging from 6 to 275 ppm. Arsenic in the samples is most likely present with magnetite and antigorite, since electron probe analysis yielded up to 90 ppm As in these minerals. X-ray absorption near-edge structure spectra indicate that As in serpentinites is mostly As(V) and that the neighboring atoms of As are O, although there are minute grains of sulfides and arsenides. The ratio of As(V) to total As is greater in samples with higher As contents, suggesting that the major source of As was oxidized As(V), introduced to the mantle wedge. Arsenic(V), originally adsorbed on Fe-oxides in slabs and overlying sediments, was most likely liberated during their subduction and incorporated subsequently in the overlying mantle wedge. Our data constrain the introduction of As into the mantle wedge at relatively shallow levels, much shallower than 25 km. Arsenic incorporated in the serpentinites was transported to deeper levels by mantle flow downward along the subduction zone, to be subsequently exhumed together with eclogitic rocks.     

Geosynthesis of dibenzothiophene and alkyl dibenzothiophenes in crude oils and sediments by carbon catalysis

Sediment extracts and crude oils have been shown to contain methyl substituted biphenyls and dibenzothiophenes, with isomer distributions suggesting a geochemical relationship between the two compound classes. Laboratory simulation experiments have shown that carbon catalyses the reaction between surface adsorbed sulfur and biphenyl to form dibenzothiophene. Similarly, the methyl substituted biphenyls reacted to yield corresponding methyl dibenzothiophenes. We suggest that the widespread distribution of dibenzothiophene and alkylated dibenzothiophenes in sediments and crude oils is the result of a catalytic reaction of biphenyl ring systems and surface-adsorbed sulfur on the surface of carbonaceous material.     

蛇纹石化和俯冲带蛇纹岩变质脱水过程中流体活动性元素的行为

蛇纹石是大洋岩石圈和俯冲带内水和流体活动性元素最重要的载体之一。研究蛇纹石化和蛇纹岩变质脱水过程中流体活动性元素的行为是认识俯冲带元素地球化学循环的关键。蛇纹岩是指主要由蛇纹石类矿物构成的岩石,包括利蛇纹石、纤蛇纹石和叶蛇纹石。蛇纹石化过程中会造成流体活动性元素(B、Li、As、Sb、Pb、Cs、U、Sr和Ba等)的显著富集,并且由于原岩性质、流体成分和氧逸度等条件的不同,大洋岩石圈蛇纹岩和弧前蛇纹岩的特征也略有不同。例如,弧前蛇纹岩具有相对高的As、Sb、B和相对低的U,这反映了俯冲沉积物来源流体的贡献。在俯冲带蛇纹岩的变质脱水过程中,利蛇纹石向叶蛇纹石的转变伴随着矿物内超过50%F和Cl的释放,以及一些流体活动性元素(如B和Li)的迁出;此外,蛇纹石分解形成的变质橄榄石中的流体包裹体指示,蛇纹石脱水分解所产生的流体具有高于原始地幔几个数量级的Cl、Cs、Pb、As、Sb、Ba、Rb、B、Sr、Li和U含量。由于利蛇纹石中的Fe~(3+)含量较叶蛇纹石高,这种矿物相转变过程中也伴随着俯冲通道内的一系列氧化还原过程,从而影响流体性质和新形成的叶蛇纹石的成分。蛇纹岩与岛弧岩浆在流体活动性元素富集规律上的相似性说明蛇纹岩在俯冲带元素循环中扮演着重要的角色。此外,蛇纹石矿物相转变过程中F、Cl、B等元素的释放,可能对于斑岩型金矿、蛇绿岩中的金矿和某些蛇纹岩作为赋矿围岩的硼矿的形成起到重要的作用。     

内蒙古贺根山蛇纹岩化流体来源的H-O-B同位素地球化学制约

对内蒙古贺根山蛇绿岩带内3个采样点的蛇纹岩样品开展了主量、微量元素和H-O-B同位素分析,以揭示其构造属性、蛇纹石化温度和流体来源。贺根山蛇纹岩具有低Al_2O_3含量(0.2%~1.3%)、高Mg~#(89~92)特征,为难熔地幔残余。蛇纹岩的U型稀土元素配分模式、相对富集LILE和亏损HFSE的微量元素地球化学特点,反映其原岩为化学成分高度亏损的俯冲带型(SSZ)超基性岩。样品的dD值相对均一(dD=-120‰~-133‰);理论计算显示,这些蛇纹岩的H同位素组成可能是蛇绿岩剥露地表后与区域大气降水发生再平衡作用的结果。贺根山蛇纹岩的d~(18)O变化在4.3‰~9.8‰之间,反映不同地点蛇纹石化的温度存在差别:其中贺根山东样品具有相对较高的d~(18)O值(d~(18)O=7.7‰~9.8‰),蛇纹石化温度为90~130℃,同时部分样品中出现碳酸盐矿物,表明蛇纹石化作用发生在近海底环境;小坝梁样品具有最低的d~(18)O值(d~(18)O=4.3‰~5.0‰),其蛇纹石化温度在205~235℃之间;贺根山南样品的d~(18)O值变化范围较大(d~(18)O=6.0‰~9.7‰),其蛇纹石化温度在90~170℃之间。3个采样点蛇纹岩的d~(11)B值也显示出一定的变化(d~(11)B=9.1‰~14.7‰),指示蛇纹石化流体来源于脱水的蚀变洋壳和海底沉积物;理论模拟和计算结果显示,这些板片流体的d~(11)B值变化在15‰~25‰之间。     

The Early Cretaceous Anoxic Basin of the Russian Plate: Sedimentology and Geochemistry

The profile comprising a series of lower Aptian sections from Ul'yanovsk to Saratov in the Russian Plate has been studied. It is shown that the unit of organic-rich rocks is characterized by the lack of bioturbation and elevated concentration of many chemical elements. The petrography and geochemistry of organic matter (OM) indicate the prevalence of basinal OM in carbonaceous sediments, while continental OM dominates in host rocks. Sedimentological, biotic, and geochemical data testify to the deposition of organic-rich sediments under anoxic conditions. The anoxic environment in the Aptian basin of the Russian Plate correlates with the global OASE-1a anoxic event. The mechanism of Aptian carbonaceous sedimentation is discussed.     

A nephrite deposit in the great serpentine belt of New South Wales

A nephrite jade deposit within the Great Serpentine Belt of N.S.W., near Tamworth, occurs as several tabular bodies up to 3.5 m thick on the serpentinite country‐rock contact. The occurrence is interpreted as a low‐temperature reaction zone, similar to those observed around Alpine serpentinites elsewhere. The nephrite probably formed as a result of dynamothermal metasomatism associated with the emplacement of serpentinites along the Peel Fault.     

Sedimentation History of Neogene Lacustrine Sediments of Sueoka Bela Stena Based on Geochemical Parameters(Valjevo-Mionica Basin,Serbia)

Sediments of the western part of the Valjevo-Mionica basin(Serbia)were examined both geochemically and mineralogically to explain,on the basis of their sedimentologicai characteristics,the causes of changes in their qualitative and quantitative composition.A total of 62 samples obtained from the drilihole at depths up to 400 m was investigated.Using correlation of the obtained data,six geochemical zones were defined,two of which being specially distinguished by their mineralogical, geochemical and sedimentological characteristics.The first one,upper zone A,consists of banded marlstones interbedded with clay and oil shales and is characterized by presence of analcite and searlesite.These minerals and very high contents of Na_2O indicate sedimentation in alkaline conditions with increased salinity in arid climate.That provided pronounced water stratification,as well as higher bioproductivity in the basin and sedimentary organic matter preservation.Therefore,the zone A sediments are characterized by high organic matter contents of the type which provides good potential for production of liquid hydrocarbons.Another specific zone,zone F,contains sediments with very high MgO,K_2O and Li concentrations.Their geochemical correlation,as well as almost complete absence of illite in this zone,indicates the presence of interstratified clay mineral type illite-saponite (lithium-bearing Mg-smectite).     

Sedimentation History of Neogene Lacustrine Sediments of Suseocka Bela Stena Based on Geochemical Parameters (Valjevo-Mionica Basin, Serbia)

Sediments of the western part of the Valjevo-Mionica basin (Serbia) were examined both geochemically and mineralogically to explain, on the basis of their sedimentological characteristics, the causes of changes in their qualitative and quantitative composition. A total of 62 samples obtained from the drillhole at depths up to 400 m was investigated. Using correlation of the obtained data, six geochemical zones were defined, two of which being specially distinguished by their mineralogical, geochemical and sedimentological characteristics. The first one, upper zone A, consists of banded marlstones interbedded with clay and oil shales and is characterized by presence of analcite and searlesite. These minerals and very high contents of Na2O indicate sedimentation in alkaline conditions with increased salinity in arid climate. That provided pronounced water stratification, as well as higher bioproductivity in the basin and sedimentary organic matter preservation. Therefore, the zone A sediments are characterized by high organic matter contents of the type which provides good potential for production of liquid hydrocarbons. Another specific zone, zone F, contains sediments with very high MgO, K2O and Li concentrations. Their geochemical correlation, as well as almost complete absence of illite in this zone, indicates the presence of interstratified clay mineral type illite-saponite (lithium-bearing Mg-smectite).     

The Moon

Recent geochemical and geophysical data from the Moon enable a revision of earlier interpretations regarding lunar origin, structure and bulk composition. Earth and Moon show many similarities among their isotopic compositions, but they have evolved in totally dissimilar ways, probably related to the deficiency of water and volatile elements in the Moon as well as the vast differences in size and internal pressure. Some global geochemical differences from the Earth such as volatile depletion based on K/U ratios have been established. However, all current lunar samples come from differentiated regions, making the establishment of a bulk composition more reliant on bulk geophysical properties or isotopic similarities; it remains unclear how the latter arose or relate to whole Moon composition. The lack of fractionation effects among the refractory and super-refractory elements indicates that the proto-lunar material seems unlikely to have been vaporized while the presence of volatile elements may place lower limits on proto-lunar temperatures. The apparent lack of geochemical evidence of an impacting body enables other possible impactors, such as comets, to be considered. Although the origin of the Moon remains currently unknown, it is generally believed that the Moon originated as the result of a giant impact on the Earth.     

Oxygen and nitrogen isotopes as tracers of fluid activities in serpentinites and metasediments during subduction

Summary N and O isotope systematics of a suite of high-pressure (HP) and ultrahigh-pressure (UHP) metasediments of the Schistes Lustrés nappe and metaperidotites of the Erro Tobbio Massif from the Alpine-Appennine system are compared with their unmetamorphosed or hydrothermally-altered equivalent from the same localities and from the South West Indian Ridge (SWIR). The HP and UHP rocks studied represent a sequence of pelagic sediments and altered ultramafic rocks subducted to different depths of down to 90 km along a cold geothermal gradient (8 °C/km). Unmetamorphosed and HP metasediments show the same range in δ¹⁵N values irrespective of their metamorphic grade and bulk nitrogen concentrations. Together with several other geochemical features (K, Rb and Cs contents, δD), this indicates that δ¹⁵N values were unaffected by metamorphism and N was not released during subduction. N isotope analysis of serpentinites coupled with δ¹⁸O systematics suggests the involvement of a mafic (crustal) component during partial deserpentinization of the subducted oceanic mantle at the depth locus of island arc magmatism. This does not imply large-scale fluxes as the metagabbros are spatially associated with the analyzed serpentinites. It rather indicates preservation of presubduction chemical and isotopic heterogeneities on a local scale as documented for the metasediments.     

苏鲁超高压变质带中蛇纹岩的地球化学特征及岩石成因

青岛的仰口和日照的梭罗树是苏鲁超高压变质带中重要的蛇纹岩出露区。系统的岩石地球化学分析表明,仰口和梭罗树地区的蛇纹岩具有高Mg、低Al_2O_3/Si O_2、贫高场强元素(Nb、Th、Zr和Hf)和重稀土元素(HREE)的特征,其原岩是经历了不同程度部分熔融后的地幔残余,符合弧前地幔橄榄岩的特征。经模拟估算,仰口蛇纹岩的原岩熔融程度15%,梭罗树蛇纹岩的原岩熔融程度在20%~25%之间。蛇纹岩富流体迁移元素(U、Pb和LREE),且LREE和HFSE无明显相关性的地球化学特征表明,研究区蛇纹岩原岩在弧前地幔楔环境下,受到俯冲板片释放的含H_2O流体作用发生蛇纹石化,形成了流体迁移元素富集的蛇纹岩。     

湘江下游河床沉积物元素地球化学背景值估算

本研究对湘江下游河床沉积物进行了元素地球化学分析,在认识沉积物元素地球化学特征、甄别人为源与自然源重金属的基础上,估算了沉积物的元素地球化学背景值。结果表明:SiO2、TiO2、Al2O3、Fe2O3、K2O等主量元素及V、Co、Cr、Ba、Sc、U、Sr、Ga、Ge、Rb、Nb、Y、REE等微量元素在沉积物中含量变化相对稳定(Cv<0.2),分布相对均匀,且富集不明显(EF<2.0,Sr明显亏损)。而MnO、MgO、CaO、Na2O、P2O5等主量元素,及Cd、Mn、Cu、Pb、Zn等重金属在沉积物中含量变化大(Cv>0.25),分布极不均匀,且沉积物中重金属明显富集(EF>2.0)。主成分及Pearson线性相关性分析显示,沉积物中不明显富集的微量元素主要赋存于难溶硅酸盐矿物相中,为自然源元素。而沉积物中显著富集的重金属主要赋存于铁—锰氧化物等矿物相中,为有人为源叠加的元素。故针对不同来源特征的元素用不同的方法进行了背景值计算,求得沉积物中47个元素的背景值。再利用元素比值等方法对所得背景值进行检验。结果表明,本文得到的湘江沉积物元素背景值合理,可用作流域沉积物重金属污染评价参考。     

Lithological and Geochemical Characteristics of the Paleocene/Eocene Sediments corresponding to the PETM Biospheric Event in the Eastern Crimea (Nasypnoe Section)

The paper reports lithological and geochemical data on the stratigraphic interval corresponding to the Paleocene/Eocene Thermal Maximum (PETM) event in the Paleogene section of Eastern Crimea (Nasypnoe section). The section is located on the western continuation of the sublatitudinal profile consisting of 15 PETM sections spanning the area from Crimea to Tajikistan (over 2500 km). It is shown that PETM sediments have the negative δ¹³C and δ¹⁸O isotope excursions and are enriched in kaolinite, which is typical of most sections of this interval around the world. At the same time, the extremely low content of organic matter (OM) in sediments of the Nasypnoe section makes them sharply different from the highly carbonaceous rocks of the PETM interval in Central and Eastern Caucasus, and Central Asian regions. This is correlated with the low contents of many chemical elements in the studied rocks, and their extremely high contents in the highly carbonaceous rocks of the easterly sections. Thus, Eastern Crimea in the end of the Paleocene?beginning of the Eocene was occupied by the low-bioproductive marine paleobasin, whereas the coeval paleobasin in Central Asia was characterized by extremely high bioproductivity owing to the presence of significant amount of phosphorus.     

Sedimentology,geochemistry, and biota of Volgian carbonaceous sequences in the northern part of the central Russian Sea (Kostroma region)

Lithological, geochemical, stratigraphic, and paleoecological features of carbonaceous sediments in the Late Jurassic Volgian Basin of the East European Platform (Kostroma region) are considered. The shalebearing sequence studied is characterized by greater sedimentological completeness as compared with its stratotype sections in the Middle Volga region (Gorodishche, Kashpir). Stratigraphic position and stratigraphy of the shale-bearing sequence, as well as the distribution of biota in different sedimentation settings, are specified. It is shown that Volgian sediments show a distinct cyclic structure. The lower and upper elements of cyclites consist of high-carbonaceous shales and clayey-calcareous sediments, respectively, separated by transitional varieties. Bioturbation structures in different rocks are discussed. Microcomponent composition and pyrolytic parameters of organic matter, as well as distribution of chemical elements in the lithologically variable sediments are analyzed. Possible reasons responsible for the appearance of cyclicity and accumulation of organicrich sediments are discussed.     

滇西银厂坪花岗斑岩岩体的地球化学及年代学特征

银厂坪花岗斑岩岩体位于扬子陆块的西南缘,处于鲜水河-小江碱性岩带和金沙江-哀牢山富碱斑岩带之间。其主量元素具有高碱,高Na₂O/K₂O值,低TiO₂特征,属于高钾钙碱性系列岩石。微量元素富集LILE,LREE和过渡金属元素(Cu、Ni、Co),具有明显的“Ta-Nb-Ti"负异常,Eu负异常不明显。锆石LA-ICP-MS U-Pb年龄表明该区岩石的结晶年龄为(37.39±0.33) Ma。εHf(t)值为-1.8~+1.8,两阶段模式年龄为996~1 226 Ma。该区岩石具有较低的εNd(t)值（-7.4~-3.6）,较高的(87Sr/86Sr)i比值（0.706 077~0.706 231）,以及具有造山带铅特征的207Pb/204Pb值（15.567~15.574）和208Pb/204Pb值（38.321~38.335）。对银厂坪岩体的元素地球化学以及Sr-Nd-Pb-Hf同位素组成特征分析研究认为,研究区的花岗斑岩形成于近似大陆弧环境,同位素地球化学属于EMI-EMII过渡型源区,岩体形成于壳幔混合层。银厂坪岩体的地球化学属性更靠近安宁河碱性岩带,是该带分异末端的酸性端员组分。     

Trace elements in primitive meteorites—V. Abundance patterns of thirteen trace elements and interelement relationships in enstatite chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 11 samples representing 9 chondrites of grades E4–6. These chondrites exhibit systematic intra- and inter-grade differences particularly for highly-variable elements, the differences being E4 ? E3 > E6 ? E5. The abundance pattern for these 13 and an additional 16 elements in E3-6 chondrites differs from those of other primitive meteorites—the carbonaceous and unequilibrated ordinary chondrites. A search for statistically-significant interelement relationships among the 13 elements (for grades E4–6) reveal that 40 elementpairs are linearly and/or exponentially correlated. Similar consideration of data for 37 elements in 12 chondrites (grades E3–6) reveals that 191 element-pairs exhibit such relationships, 170 involving linear and/or exponential correlations, the remainder involving anti-correlations. The patterns depicting these relationships—i.e. the correlation profiles—and elemental abundance patterns, factor analysis and two-element correlation diagrams are consistent with all enstatite chondrites representing a single evolutionary sequence. The primary process responsible for the chemical trends of these chondrites involved thermal fractionation accompanied by geochemical fractionation of sulfide-plus-metal from silicate, probably during condensation and accretion of solid material from the solar nebula. Chalcophile elements may have been fractionated during condensation or, after accretion, during thermal metamorphism in the parent body. No genetic model proposed thus far accounts for the detailed chemical trends, although the constrained equilibrium theory and two-component condensation theories qualitatively seem most satisfactory. The correlation profiles of enstatite, carbonaceous and unequilibrated ordinary chondrites are distinctly different, pointing to major differences in the formation conditions of these different sorts of primitive meteorites.     

Conditions of the accumulation of organic matter and metals in the bottom sediments of the Chukchi Sea

The chemical composition of bottom sediments in the Chukchi and, partly, East Siberian Seas was studied. In the south and west of the Chukchi Sea, a zone has been detected with the accumulation of sediments rich in organic carbon, an increased background content and anomalies of sulfophile metals (Mo, Zn, Hg, Ag, Au), iron-group metals (V, Ni, Co), and some PGE (Ru, Pt). This zone is confined to the neotectonic active system of rift troughs extending from the Bering Strait and eastern Chukchi Peninsula to the continental slope, where it is bounded by the Cenozoic Charlie rift basin of the Canadian hollow. The geochemical features of the carbon-enriched sediments evidence that they formed under oxygen-deficient conditions and, sometimes, in suboxic and anoxic environments near endogenic water and gas sources. The high carbon and metal contents suggest that the very fine-grained sediments in the rift troughs of the Chukchi Sea are a possible analog of some types of ancient highly carbonaceous sediments belonging to black shales.