我国前寒武纪非金属矿产的分布及其特征

本文总结了我国前寒武纪非金属矿产的分布和特征,指出菱镁矿、硼矿、磷矿、滑石、石墨等非金属矿产赋存于不同的沉积建造、火山堆积以及不同变质岩系之中,是由古陆块的构造部位所决定的。前寒武纪非金属矿床的成矿作用与大陆地壳演化关系密切,古元古代大陆拼合焊接的造山带和新元古代稳定地块的海相沉积是两个十分重要的非金属矿产成矿构造环境,前者在中国北方（如胶辽裂谷、佳木斯地块）形成菱镁矿、硼矿、滑石矿和石墨矿等矿床,后者在南方（如扬子陆块、苏鲁大别带）主要形成磷矿床。前寒武纪产出大型、超大型非金属矿床数十个,成因类型主要有沉积变质型、岩浆热液型和沉积（弱变质）型,文中着重对硼、石墨、菱镁矿、滑石、磷矿等五个主要矿种的资源分布及矿床地质特征作了叙述。     

Strontium isotopes in magnesites from Permian and Triassic strata,Eastern Alps

The Sr isotopic composition of sediment-hosted magnesites in Permian and Scythian series of Upper Austroalpine units (Eastern Alps) has been determined. The results suggest diagenetic-metasomatic magnesite formation by Mg-rich pore solutions. The depositional environment of the magnesite-bearing rocks is reflected by different isotopic compositions with initial ⁸⁷Sr/⁸⁶Sr ratios close to contemporaneous sea water in marine sediments (0.7071–0.7083) and higher ratios being typical for lacustrine and coastal environments influenced from the hinterland (0.7133–0.7139). Coarser grained recrystallized magnesite and magnesite veins show a distinct increase in their Sr isotopic ratios (0.7202–0.7220) which can be attributed to metamorphic fluids of Eoalpine age. The findings of these magnesite occurrences, which have been affected only by very low-grade metamorphism, are compared with similar results from spar magnesites associated with metamorphosed Paleozoic sedimentary rocks. A similar genetic model is proposed for the first magnesite mineralization in those Paleozoic strata, but with variably intense later recrystallisation during metamorphism.     

Formation of weathering-derived magnesite deposits in the New England Orogen, New South Wales, Australia: Implications from mineralogy, geochemistry and genesis of the Attunga magnesite deposit

Nodular, cryptocrystalline, weathering-derived magnesite deposits in the New England Orogen, Australia, provide a significant source of high-purity magnesite. Common textural features and related isotopic fingerprints indicate a close genetic relationship between weathering-derived magnesite deposits hosted by ultramafic rocks at Attunga and by sediments at Kunwarara while silica-carbonate rock alteration and rare hydrothermal magnesite vein deposits reflect contrasting conditions of formation. Localised weathering of carbonates in a soil environment shifts stable isotopic composition towards low δ ¹³C and high δ ¹⁸O typical for weathering-derived magnesites while intrusion-related fluids do not significantly change the isotopic composition of affected carbonates. At Attunga, magnesite consists of irregular, nodular veins and masses filling faults and cracks in the weathered serpentinite host rock as well as soft powdery magnesite in pervasive serpentinite alteration zones. The high-grade magnesite at Attunga can be contaminated by amorphous silica and serpentine relicts but does not contain dolomite or ferroan magnesite as observed for its hydrothermal equivalent, the Piedmont magnesite deposit, or other widespread deposits of silica-carbonate rock in the Great Serpentinite Belt. Heavy δ ¹⁸O values are compatible with a supergene formation from meteoric waters while low δ ¹³C suggests C3-photosynthetic plants as the predominant source of carbon for the Attunga magnesites. We infer that weathering-derived, nodular magnesite deposits hosted in ultramafic rocks like the Attunga magnesite deposit have formed in a two-step process involving the hypogene formation of a pre-cursor magnesite deposit and complete supergene overprinting by meteoric waters that acquired carbon from percolation through soil.     

用Y／Ho比值指示俄罗斯乌拉尔南部晶质菱镁矿矿床的成因

乌拉尔省南部赋存有两种类型的晶质菱镁矿:1)白云岩地层中的层状矿体;2)白云质灰岩中的透镜状矿体。晶质菱镁矿矿体位于Riphean系列中下层的白云岩中,而在上层的白云岩单元中缺失。这两种类型的菱镁矿可通过矿体形态、晶体大小、石英和白云石含量不同来进行区分。第一种类型的菱镁矿储量巨大,菱镁矿呈粗粒结构,晶体粒径>10mm(最大达150mm);一般来说,矿体与白云岩围岩界限清楚,这种类型矿床以产在Riphean序列下部为特征。第二种类型的菱镁矿由于菱镁矿矿体穿插进入到白云岩围岩中,矿体很不规则,菱镁矿晶体也相对较小(1-5mm),这种类型的矿体主要产在Riphean中部层位中。这两种矿体都显示了交代成因的特征。但这两种菱镁矿矿石在一些主量元素和稀土元素的分布上具有不同的特征:与第二种类型相比,第一种菱镁矿具有较低的FeO,CaO和SiO2含量,与白云岩围岩(La／Lu>1)相比,具La／Lu<1的轻稀土亏损特征。第二种菱镁矿稀土分馏度较低,在稀土分配方面与白云岩围岩有差别。本文还特别讨论了Y／Ho值的重要性,因为该比值在菱镁矿和围岩中的类似性使得划分菱镁矿形成中的热液和成岩交代过程成为可能。因此我们认为,第一种类型菱镁矿,如具有高Y／Ho比值的Satka和Bakal矿床的形成属于沉积盆地发育过程中的早期成岩阶段;第     

Trace element contents and C-O isotope geochemistry of the different originated magnesite deposits in Lake District (Southwestern Anatolia), Turkey

Vein-stockwork magnesite in the Madenli area, sedimentary huntite-magnesite in the A?a??t?rtar area, and lacustrine hydromagnesite in the Salda Lake area are located in the Bey?ehir-Hoyran and Lycian nappe rocks around Isparta and Burdur, Southwest Anatolia. The aim of this study is to understand trace element contents and carbon-oxygen isotope ratios in different originated magnesite, magnesite bearing huntite, and hydromagnesite deposits. Also, the element contents and isotope ratios of the magnesite occurrences are to compare with each other and similar magnesite occurrences in Turkey and world. It is found that the Madenli magnesite occurrences in the ?arkikaraa?aç ophiolites, A?a??t?rtar magnesite bearing huntite deposits in the lacustrine rocks of the Miocene-Pliocene, and the Salda hydromagnesite deposits in lacustrine basin on the Ye?ilova ophiolites. The paragenesis contains a common carbonate mineral magnesite, less calcite, serpentine, smectite, dolomite, and talc in the Madenli magnesite occurrences, mostly huntite and locally magnesite, dolomite, calcite, illite, quartz, and smectite in the A?a??t?rtar huntite-magnesite occurrences, and only hydromagnesite mineral in the Salda Lake hydromagnesite occurrences. Vein and stockwork Madenli magnesite deposits were recognized by higher total iron oxide concentrations (mean 1.10 wt%) than sedimentary A?a??t?rtar magnesite bearing huntite (mean 0.13 wt%) and lacustrine Salda hydromagnesite (mean 0.22 wt%) deposits. It is suggested that high Fe content (up to 5%) in the magnesite associated with ultramafic rocks than those from sedimentary environments (≤1% Fe). Based on average Ni, Co, Ba, Sr, As and Zr contents in the magnesite deposits, average Ni (134.63 ppm) and Co (15.19 ppm) contents in the Madenli magnesite and Salda hydromagnesite (36.85 ppm for Ni, 3.15 ppm for Co) have higher values than A?a??t?rtar huntite + magnesite (7.67 ppm for Ni and 0.89 ppm for Co). Average Ni-Co contents of these deposits can have close values depending on ophiolite host rock. Average Ba values of the Madenli (108.09 ppm) and A?a??t?rtar (115.88 ppm) areas are higher than those of Salda hydromagnesite (13.15 ppm). Sediment-hosted A?a??t?rtar magnesite-huntite deposits have the highest Sr contents (mean 505.81 ppm) as reasonably different from ultrabasic rock-related Madenli magnesite (mean 38.76 ppm) and Salda hydromagnesite (mean 36.70 ppm). The highest Sr content of sedimentary A?a??t?rtar deposits reveals that Sr is related to carbonate rocks. As and Zr contents have the highest average values (As 52.76 ppm and Zr 9.67 ppm) in the A?a??t?rtar deposits different from Madenli magnesite (As 0.54 ppm and Zr 1.67 ppm) and Salda hydromagnesite (As 0.5 ppm and Zr 2.58 ppm) deposits. High As and Zr concentrations in the A?a??t?rtar magnesite-huntite deposits may come from volcanic rocks in near country rocks. The δ ¹³C (PDB) isotope values vary between ?10.1 and ?11.4‰ in the Madenli magnesite, 7.8 to 8.8‰ for huntite, 1.7 to 8.3‰ for huntite + magnesite and 4.0‰ for limestone + magnesite in the A?a??t?rtar huntite-magnesite deposits, and 4.4 to 4.9‰ for Salda Lake hydromagnesite. The sources of the CO₂ are hydrothermal solutions, meteoric waters, groundwater dissolved carbon released from fresh water carbonates and marine limestone, soil CO₂, and plant C3 in the Madenli magnesite, and may be deep seated metamorphic reactions in limestone and shales of rich in terms of organic matter. The sources of CO₂ in A?a??t?rtar huntite and Salda hydromagnesite were meteoric water, groundwater dissolved inorganic carbon, fresh water carbonates, and marine limestone. The δ ¹⁸O (SMOW) isotope composition ranges from 26.8 to 28.1‰ in the Madenli magnesite, 30.4 to 32.4‰ for huntite and 29.8 to 35.5‰ for huntite + magnesite and 26.9‰ for limestone + magnesite in the A?a??t?rtar area, and 36.4 to 38.2‰ in the Salda Lake hydromagnesite. The Salda Lake hydromagnesite has heavier oxygen isotopic values than others. The sources of oxygen in the Madenli magnesite deposits are hydrothermal solutions, meteoric water, freshwater carbonates, and marine limestone, but the sources of oxygen of the A?a??t?rtar magnesite-huntite are meteoric water, fresh water carbonates, and marine limestone. The Salda Lake hydromagnesite has very high δ¹⁸O isotope values indicating a strong evaporitic environment. Magnesium (Mg⁺²) and silica are released by disintegration of very weathered-serpentinized ultrabasic rocks of all magnesite deposits and from partly dolomite and dolomitic limestone in the A?a??t?rtar magnesite bearing huntite deposits. In the A?a??t?rtar area, calcium (Ca⁺²) for huntite mineralization is provided by surrounding carbonate rocks. Based on isotopic data, host rocks, petrographic properties of the Madenli magnesite can be described as an ultramafic-associated hydrothermal vein mineralization corresponding to “Kraubath type” deposits, but A?a??t?rtar ve Salda Lake deposits are sedimentary mineralization (lacustrine/evaporitic) corresponding to “Bela Stena type” deposits. The estimated temperature using average δ¹⁸O isotope values is about 33.51 °C for Madenli magnesite, 48.33 °C for A?a??t?rtar huntite-magnesite, and 25 °C for Salda hydromagnesite. Based on isotope data, we can be say that the Madenli magnesite, A?a??t?rtar magnesite-huntite, and Salda hydromagnesite occur at low to moderate-low temperature water and alkaline (pH 8.5–10.5) under surface or near-surface conditions.     

辽东海城－大石桥超大型菱镁矿矿床的地质特点及成因

中国海城－大石桥菱镁矿矿床举世闻名，矿床分布于辽东元古宙裂谷海槽北缘的次一级盒地中。含镁建造属元古宙上辽河群大石桥岩组的上部．按含矿建造组成岩石的各种成因标志，确定建造的沉积岩相为闭塞台地相，因此．推测它形成于裂谷边缘的泻湖环境。由于长期潮汐作用，泻湖内有充分的富镁海水周期性地供给，在当时炎热干旱的气候条件下，泻湖中的卤水不断浓缩，并通过化学与生物化学成矿作用，在泻湖盆地内形成了大型－超大型的菱镁矿矿床。元古宙末期矿床遭受了绿片岩－角闪岩相区域动力热流变质作用的改造。     

青海茫崖石棉矿区变质超基性岩的蚀变演化序列：岩石化学及矿物学证据

青海茫崖石棉矿区超基性岩体是由原岩以纯橄岩、辉橄岩和橄辉岩为主体组成的富镁质超基性岩体,经历自变质和后期多期热液的叠加变质蚀变作用,经蛇纹石化后形成蚀变完全的蛇纹岩岩体,其中部分蛇纹岩又进一步发生滑石化及碳酸盐化蚀变为滑石菱镁片岩、菱镁滑石片岩、滑石片岩和菱镁岩等。本文在野外地质调查基础上,在室内通过镜下岩矿综合鉴定、全岩化学成分分析以及电子探针成分分析等手段进行了岩石化学特征、矿物学特征及其蚀变演化过程研究。结果表明,该变质超基性岩体蛇纹岩主要特征组合矿物为蛇纹石(利蛇纹石、叶蛇纹石、纤蛇纹石)、磁铁矿、菱镁矿、滑石、水镁石、铬铁矿,变余矿物有斜方辉石、单斜辉石和铬铁矿,滑石菱镁片岩类主要组成矿物为菱镁矿、滑石、蛇纹石及磁铁矿,局部可见石英脉。该地区变质超基性岩体较完整地记录了橄榄岩水化、滑石化及碳酸盐化作用过程的各个阶段,超基性岩蚀变演化过程主要有两个作用阶段:(Ⅰ)橄榄石、辉石类矿物的蛇纹石化作用及蛇纹石绿泥石化作用;(Ⅱ)富Ca、CO2流体交代蛇纹石、滑石及水镁石的碳酸盐化作用。蛇纹石化等变质蚀变作用促进了Si、Mg及Fe元素化学活动性,使元素发生富集与迁移,对于次生矿物的形成与演化起到了一定的催化作用。多期不同组成流体热液的交代作用过程,清晰地展示了利蛇纹石、纤蛇纹石和叶蛇纹石的演化序列,以及滑石、水镁石、铬铁矿和磁铁矿的形成过程及标形特征。     

Geology,composition, and physicochemical model of sparry magnesite deposits of the Southern Urals

The metasomatic nature of magnesite formation, sequence and timing of geological processes, and solution sources have been established by comprehensive geological and geochemical study of the typical Satka and Ismakaevo deposits of sparry magnesite in the South Ural province. The hydrothermal metasomatic formation of magnesite is related to injection of high-Mg evaporite brine into heated carbonate rocks within permeable rift zones. The numerical physicochemical simulation of solution–rock interaction allowed us to determine the necessary prerequisites for sparry magnesite formation: the occurrence of marine salt solutions with a high Mg/Ca ratio and heating of solutions before or during their interaction with host carbonate rocks. The contribution of compositionally various solution sources, the temperature variation regime, proportions of CO₂ and H₂S concentrations in solution created specific features of particular deposits.     

Genetic and metamorphic conditions constrained by fluid inclusions from Paleoproterozoic (c. 1.8 Ga) magnesite ore deposits, NE Brazil

Precambrian magnesite occurrences hosted by metadolomites from the Orós belt, Ceará, Brazil, are part of a greenschist–amphibolite, metavolcano-sedimentary terrain, dated at 1.8 Ga, cut by Meso- to Neoproterozoic Brasiliano granites and Neoproterozoic basic sills. These rocks were affected by a shear zone between 580 and 500 Ma. The magnesite-bearing marbles can be grouped as medium-grained (1–9 mm) at the Riacho Fundo ore deposit or sparry magnesite (1–15 cm) at the Cabeça de Negro ore deposit. The sparry magnesite shows textural characteristics related to original sedimentary structures. Both types of magnesite-bearing marbles contain aqueous and aqueous-carbonic fluid inclusions that yield homogenization temperatures between 170 and 370 °C. Applying a pressure correction, these temperatures are compatible with the evolution from greenschist to amphibolite facies metamorphic conditions, as described in previous work on the Orós region. It also agrees with data in specialized literature on the metamorphism of carbonate rocks. Fluid inclusion distribution, composition, and physical-chemical characteristics suggest temperature increase, probably related to metamorphism on these rocks. The medium-grained magnesite records partial contamination of CO₂-rich inclusions by relict carbonaceous material (bitumen, hydrocarbons?) that favors, but does not confirm, a syngenetic sedimentary origin and could have caused the lowering of CO₂ melting point in these inclusions. Therefore, though textural evidence points to a sedimentary-diagenetic model, fluid inclusions record conditions of a metamorphic event.     

大兴安岭北部上古生界极低级变质温度——来自碳质物拉曼光谱的证据

使用Renishaw System-1000型激光拉曼光谱仪, 研究了大兴安岭北部上古生界泥质岩石碳质物的拉曼光谱特征及其对形成温度的表征, 探讨了拉曼光谱参数与镜质体反射率(R_o)的关系。研究表明:研究区上古生界泥质岩石碳质物不具有石墨的拉曼光谱谱带吸收峰, 揭示了地层的变质程度未达到低绿片岩相。利用此次经过完善建立的拉曼光谱地质温度计, 对大兴安岭北部上古生界泥质岩石变质温度的估算结果主要为270~320℃, 表明研究区上古生界遭受了极低级变质作用, 变质程度属近变质带。依据碳质物拉曼光谱参数与镜质体反射率的相互关系, 估算研究区有机质成熟度的R_o值主要分布为3.03%~4.23%, 与实测R_o值吻合, 表明有机质演化处于过成熟阶段, 泥质岩石具有生烃的能力, 部分层位可能具有形成油气资源的潜力。     

High-pressure metamorphism of stratiform sulphide deposits from the Diahot region,New Caledonia

Stratiform Cu-Pb-Zn (-Au-Ag) mineralization associated with black carbonaceous schists and acid metatuffs is restricted to distinct horizons within the Cretaceous sequence of the Diahot region. The sulphides occur in sharply bounded lenses which show varying degrees of compositional banding conformable with the foliation of the country schists. The deposits are sedimentary-exhalative of the Rio Tinto-type and have been modified by mid-Tertiary high-pressure metamorphism (lawsonite-albite and glaucophanitic greenschist facies). The ores are not strongly deformed by the metamorphism and sedimentary structures, pyrite framboids and atoll structures are preserved in some deposits. With increasing metamorphic grade sphalerite becomes more iron-rich, pyrrhotite becomes more abundant, and the sulphides show a general increase in grain-size which parallels that of the silicates in the enclosing rocks. In the more highly metamorphosed deposits the sulphide associations are retrograde assemblages. There is no evidence of large-scale metamorphic remobilization of sulphides. No differences were observed in either the sulphide assemblages or in the composition of the sulphides to indicate that the metamorphism was of the high pressure rather than the low pressure type.     

Mineralogy and Geochemistry of Sedimentary Huntite Deposits in the Egirdir-Hoyran Lake Basin of Southern Turkey

The sediment-hosted huntite-magnesite deposits are located in the Egirdir-Hoyran lake basin in the Isparta Angle (southern Turkey). The deposits occur at two different localities in the region: (1) Kemersirti huntite deposit, (2) Köytepe huntite-magnesite deposit. The huntite-magnesite occurrences are found in shallow lacustrine rocks of the Miocene-Pliocene Kizilcik Formation and formed as a result of Neogene tectonic activity. Based on X-ray diffraction and scanning electron microscopic studies, the mineral assemblage of huntite deposits contains mostly huntite, less magnesite, dolomite, very little calcite, illite, simectite, brucite, and quartz in the Kemersirti area but contain huntite, magnesite, dolomite, and calcite in the Köytepe area.In the huntite and magnesite-bearing huntite samples, MgO varies from 32.70 to 37.95 wt. %, CaO from 7.83 to 15.10 w.t. %, and SiO₂ from 0.99 to 10.60 w.t. %. Ba and Sr are dominant minor elements in the deposits. Ba and Sr for huntite and magnesite bearing huntite in the study area vary from 11 to 233 ppm and from 325 to 765 ppm, respectively. As, U, Zr, V and Ce contents ranged from 11.5-146 ppm, 0.5-3.7 ppm, 1.4-13.2 ppm, 7-34 ppm, and 0.9-2.7 ppm respectively. The huntite-magnesite is characterized by relatively lower Ni (0.5-2.4 ppm) and Co (0.5-1.1 ppm) contents. The huntite and magnesite-bearing huntite occurrences have higher Ba, Sr, As, Zr, V, and U contents than those of the other elements. The d13C isotope values vary between 7.8‰ to 8.8‰ PDB for huntite+magnesite, 8.2‰ PDB for huntite, 1.4‰ PDB for magnesite+dolomite, and 4.0‰ PDB for limestone from deposits in the study area. The δ¹⁸O isotope values of the huntite deposits ranged from 30.4 to 35.5‰ SMOW for huntite+magnesite, 32.4‰ SMOW for huntite, 29.8‰ SMOW for magnesite+ dolomite, and 26.9‰ SMOW for limestone.The presence of nodular huntite and the abundance of gastropod, ostracoda and Chura shells in the carbonate units indicate that the huntite occurrences are precipitated at shallow, alkaline (8.5-9.5 pH) and lower temperature (approximately 25°C) lake conditions. The Mg⁺⁺, Ca⁺⁺ and Si⁺⁺ ions for the huntite formation were derived from the surrounding rocks such as ultrabasic rocks, dolomite, dolomitic limestone, and limestone in the Egirdir-Hoyran lake basin. Also, the C isotope ratios indicate that the CO₂ source for the huntite formations results to sedimentary basin from metamorphic CO₂, carbonate rocks, fresh water carbonates, and ground water. The source of oxygen for the huntite formation may come from marine limestone, fresh water carbonates and meteoric water.     

Magnesite-bearing stratificated levels and their lithological nature in the Riphean dolomite sequences of the southern Urals

Three stratificated levels of magnesite-bearing dolomites—Lower Riphean (Bakal-Satka-Suran), Middle Riphean (Avzyan), and Upper Riphean (Min’yar)—are recognized in the Riphean section of the Bashkir Anticlinorium of the southern Urals. Dolomites contain submicroscopic (～1 μm) magnesite dissemination (MgO/CaO > 0.714). The Lower and Middle Riphean magnesite-bearing dolomites host metasomatic magnesite stocks, lenses, pockets, and large stratiform lodes formed as products of hydrothermal activity. No metasomatic magnesite bodies are known in areas without indications of the hydrothermal reworking of magnesite-bearing dolomites. Magnesite deposits of the southern Urals are typical elisional-hydrothermal products related to sedimentation and lithogenesis of carbonate rocks in isochemical system of sedimentary basin. Juvenile components did not participate in the formation of magnesite deposits in the southern Urals.     

中国辽东地区超大型菱镁矿矿床的地球化学特征和成因模式

我国辽东地区早元古代大石桥组镁质碳酸盐-泥质岩建造中赋存有多个超大型菱镁矿矿床。在这些矿床中,菱铁矿矿体均只限定在大石桥组三段岩层中。该层岩石主要由白云质大理岩、菱镁质大理岩、菱镁矿和少量泥质板岩薄层组成。赋矿层位之下地层为大石桥组二段的云母片岩;其下为大石桥组一段的白云质大理岩与云母片岩夹层。在大石桥组一段中未见菱铁矿体产出。研究表明,菱铁矿的δ18O值为5.2‰~13.8‰,低于围岩大理岩的δ18O值(11.2‰~22.8‰)。但两音的δ13C值大多接近零值,其中菱镁矿δ13C值变化为-1.4‰~1.2‰,大理岩δ13C值变化为-4.5‰~4 4‰。在菱镁矿层位中发现有石膏成层和脉状产出,其δ34S值为23.9‰~26.5‰,显示海相蒸发沉积特征。菱镁矿的稀土元素分析表明存在三种不同页岩标准化配分模式。类型Ⅰ显示中稀土富集特征,类型Ⅲ显示重稀土富集和正铕异常特征,它们可能反映了不同时期成矿热液的特征。而类型Ⅱ显示与围岩大理岩相同的平坦型,反映继承了原岩沉积碳酸盐岩的特征。本文认为,辽东地区的镁质碳酸盐岩(镁方解石和白云石)可能是从蒸发的泻湖盆地中沉积的,而菱镁矿石则主要是沉积后富镁卤水下渗交代原岩碳酸盐岩形成的。由于大石桥组二段云母片岩渗透率低隔水性强,因此菱铁矿的矿化交代作用只发     

Graphitization of carbonaceous matter during metamorphism with references to carbonate and pelitic rocks of contact and regional metamorphisms,Japan

This study is an attempt to correlate the graphitization process of carbonaceous matter during metamorphism with metamorphic grade. Graphitization can be parameterized using crystal structure and chemical and isotopic compositions. The extent of graphitization could be characterized mainly by temperature, duration of metamorphism and rock composition. We compared the graphitization trends for two metamorphic terrains, a contact aureole of the Kasuga area and a regional metamorphic terrain of high-temperature/low pressure type of the Ryoke metamorphic terrain in Northern Kiso area, Central Japan, and for two different lithologies (carbonate and pelite), using X-ray diffractogram, DTA-TG analysis, and chemical and stable isotope analyses. During contact metamorphism, graphitization and carbon isotopic exchange reactions proceeded simultaneously in pelitic and carbonate rocks. The decreases in basal spacing d(002) of the carbonaceous matter in carbonate rocks is greatly accelerated at temperatures higher than about 400° C. Furthermore, carbon isotopic ratios of graphite in carbonate rocks also change to ¹³C-enriched values implying exchange with carbonates. The beginning of this enrichment of ¹³C in the carbonaceous matter coincides with an abrupt increase of the graphitization processes. Carbon isotopic shifting up to 5 in pelites could be observed as metamorphic temperature increased probably by about 400° C. Carbonaceous matter in pelitic rocks is sometimes a mixture of poorly crystallized organic matter and well-crystallized graphite detritus. DTA-TG analysis is an effective tool for the distinction of detrital graphitic material. Two sources for the original carbon isotopic composition of carbonaceous matter in pelites in the Kasuga contact aureole can be distinguished, about-28 and-24 regardless of the presence of detrital graphite, and were mainly controlled by depositional environment of the sediments. Graphitization in limestones and pelitic rocks in regional metamorphism proceeds further than in a contact aureole. In the low-temperature range, the differences in extent of graphitization between the two metamorphic regions is large. However, at temperatures higher than 600° C, the extent of graphitization in both regions is indistinguishable. The degree of graphitization is different in limestones and pelitic rocks from the Ryoke metamorphic terrain. We demonstrate that the graphitization involves a progressive re-construction process of the crystal structure. The sequence of the first appearance of crystal inter planar spacing correlates with the metamorphic grade and indicates the crystal growth of three-dimensional structured graphite.     

胶-辽-吉造山带辽河群石墨矿碳同位素特征及成因分析

作为华北克拉通周缘三条石墨成矿带之一的东部带,胶-辽-吉古元古代石墨成矿带是研究早前寒武纪石墨成矿机制及地球早期气候特征的天然实验室。本文对胶-辽-吉造山带辽河群石墨矿(甜水乡马沟石墨矿)进行了详细的岩相学、地球化学、拉曼光谱学以及碳同位素等方面的研究。研究结果表明辽河群含石墨矿岩石主要为含石墨变质杂砂岩、含石墨黑云母长英质片麻岩和含石墨透闪大理岩,在log(Fe₂O₃/K₂O)-log(SiO₂/Al₂O₃)判别图解中,这些含石墨岩石位于砂岩和页岩区域内,它们具有和太古宙后澳大利亚平均页岩(PAAS)相似的稀土元素特征;地球化学特征表明它们具有低的成熟度,未经历长途搬运,是快速堆积的产物,主要沉积于活动大陆边缘弧后盆地环境。碳同位素研究表明辽河群石墨矿碳同位素值具有很宽的变化范围(δ¹³C_PDB=-16.49‰~-25.93‰),是有机物在变质过程中脱CH_4造成的。结合拉曼光谱学特征,我们认为辽河群石墨矿是由有机物经过变质作用形成的,其变质程度可以达到高角闪岩相(551~627℃)。综合分析前人年代学数据,我们认为辽河群石墨矿的沉积时代为2.13~2.17Ga,在后期的弧-陆碰撞造山以及后碰撞作用过程中(2000~1895Ma;1875~1850Ma),有机物逐渐发生变质形成石墨并聚集形成石墨矿床。华北克拉通周缘大量石墨矿的沉积时代(2.3~2.05Ga)和大氧化事件发生的时间一致,可能是地球早期大氧化事件的沉积响应。     

Vein graphite deposits: geological settings,origin, and economic significance

Graphite deposits result from the metamorphism of sedimentary rocks rich in carbonaceous matter or from precipitation from carbon-bearing fluids (or melts). The latter process forms vein deposits which are structurally controlled and usually occur in granulites or igneous rocks. The origin of carbon, the mechanisms of transport, and the factors controlling graphite deposition are discussed in relation to their geological settings. Carbon in granulite-hosted graphite veins derives from sublithospheric sources or from decarbonation reactions of carbonate-bearing lithologies, and it is transported mainly in CO₂-rich fluids from which it can precipitate. Graphite precipitation can occur by cooling, water removal by retrograde hydration reactions, or reduction when the CO₂-rich fluid passes through relatively low-fO₂ rocks. In igneous settings, carbon is derived from assimilation of crustal materials rich in organic matter, which causes immiscibility and the formation of carbon-rich fluids or melts. Carbon in these igneous-hosted deposits is transported as CO₂ and/or CH₄ and eventually precipitates as graphite by cooling and/or by hydration reactions affecting the host rock. Independently of the geological setting, vein graphite is characterized by its high purity and crystallinity, which are required for applications in advanced technologies. In addition, recent discovery of highly crystalline graphite precipitation from carbon-bearing fluids at moderate temperatures in vein deposits might provide an alternative method for the manufacture of synthetic graphite suitable for these new applications.     

The Features of the Transformation of Organic Matter of Precambrian Carboniferous Rocks of the Ukrainian Crystalline Shield

The main features of the transformation of organic matter (OM) in the greenschist, amphibolite, and granulite facies of metamorphism are considered based on the example of the Ukrainian crystal shield. The occurrence area and OM content in highly carbonaceous ancient rocks are characterized. The composition of primary sedimentary rocks and the processes of accumulation of biophile elements under the OM transformation are reconstructed.     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Geochemical peculiarities of ores from the largest Natalka gold deposit in Northeastern Russia

This study of the behavior of trace and rare earth elements in ores from the Natalka gold deposit allows us to draw several conclusions. It is suggested that ore formation is related to the regional metamorphism of the host terrigenous carbonaceous rocks, which could be the major source for trace and rare earth elements. Minor enrichment of the Natalka ores in W is evidence of the contribution of magmatic fluid, which could be superimposed on early quartz veins, in ore formation. Our results support the metamorphic–magmatic model of formation of economic gold–quartz deposits of the Yana–Kolyma Belt. The similarity of metasomatites of the Natalka deposit with disseminated gold–sulfide refractory ores from the Nezhdaninskoe and Bakyrchik deposits points to the possible presence of such ores in the Natalka deposit. Our data are important for forecasting regional metallogenic reconstructions, search, and evaluation of gold deposits.