Noble metal mineralization in carbonaceous rocks: A synthesis of data on the Russian Far East

The relationship between noble metal mineralization and carbonaceous rocks (black shales and brown coals) is considered. We have confirmed the previous conclusions of multistage syn- and epimetamorphic formation of gold-bearing deposits in black shales and syn- and epigenetic accumulation of noble metals in brown coals. The gold and PGE in the brown coals of the Verkhnii Amur region and Primorye were presumably derived by disintegration of adjacent ore sources in the Cenozoic. Addition studies and sampling are required at the coal and graphite objects of the Russian Far East to solve this problem.     

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.     

A new approach to precious metals recovery from brown coals: Correlation of recovery efficacy with the mechanism of metal-humic interactions

The presence of gold and platinum group elements (PGE) in low-rank brown coals around the world has promoted interest in the industrial exploitation of this alternative source of precious metals. However, due to low efficacy of the methods traditionally used for the processing of mineral ores, there exists a high demand for new strategies of precious metal recovery from refractory carbonaceous materials that could significantly increase the economic potential of gold- and PGE-bearing organic resources. Here we discuss the possibility of gold and PGE recovery from alkaline extracts of brown coals using the difference in colloidal stability of bulk organic matter and its fractions enriched with precious metals. This approach enables one to avoid complete oxidation or combustion of brown coals prior to gold recovery, to minimize organic content in gold concentrate, and to obtain a valuable by-product - humic extracts. Using gold-bearing brown coals from several deposits located in the South Far East of Russia, we show that up to 95% of gold can be transferred to alkaline extracts of humic acids (HA) and up to 85% of this gold can be recovered by centrifugation at pH 4.0-6.0, when only 5-15% of HA precipitated simultaneously. We have shown that the high efficacy of gold recovery can be attributed to the occurrence of fine-dispersed elemental gold particles stabilized by HA, which differ significantly in colloidal stability from the bulk organic matter and, thus, can be separated by centrifugation.     

Metal sources for the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation,South China

Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.     

Multi-Element Reference Samples of Black Shale

This paper describes the creation of two new reference samples of black shale, SCHS-1 and SLg-1, collected in the Bodaibo Region of Irkutsk District (Siberia, Russia). These samples have been developed as State Standard Samples to meet the requirements of Russia's Normative Documents, so that they can be recognised by the Russian State Certification Agency and included on the State Register of certified reference materials. SCHS-1 was produced from shale of the Khomolkho suite; SLg-1 represents the average composition of the Sukhoy Log gold deposit (within Au mineralisation). The homogeneity was assessed by applying the concept of potential inhomogeneity, and the inhomogeneity uncertainties (σ_inhom) for the indicator elements that were estimated experimentally by silicate XRF analysis. It was found that a majority of the indicator elements was characterised by σ_inhom/Δ_p < 1/8 (Δ_p is the permissible certification uncertainty), and so σ_inhom was neglected for the indicator elements and all other elements that were included in their respective group. The value of σ_inhom calculated for Fe (σ_inhom,Fe/Δ_p > 1 /8) was taken into consideration for the noble metals and their associated elements (e.g., Ag, As, Au, etc.). More than fifty laboratories (thirty-seven from Russia) were involved in the interlaboratory experiment (ILE) to analyse these reference samples. The data obtained from the ILE allowed SCHS-1 and SLg-1 to be certified for, fifty-one and forty-three elements, respectively, as State Standard Samples.     

四川攀枝花云鹿矿区特殊类型铂族元素成矿作用的发现

四川攀枝花云鹿铜铂金矿区是一个新发现的比较罕见的新类型含铂族元素矿床,其特殊性至少表现为:矿化体赋存在炭质岩系中、炭质岩系中富含镁电气石(MgO含量7.68%～8.64%,平均8.15%)、表生过程中低温条件下铂族元素发生了活化转移(含铜钟乳石中含PGE0.14×10-6)。铂族元素的最初富集可能与元古宙的海底喷气活动有关。此类铂族元素的矿化在国内外罕见,有可能是第一次发现,但类似的成矿地质条件在中国西南地区普遍存在,应该在今后的地质研究与找矿过程中加以注意。     

俄罗斯远东地区铂族金属矿床勘查进展及找矿启示

近年来,俄罗斯远东地区铂族金属矿床勘查取得了长足进展,发现铂族金属矿化与金矿化密切相关,铂族金属矿床与中心型环带状基性-超基性侵入杂岩体在空间和成因上有密切联系,在黑色岩系及褐煤矿床中也发现了铂族金属矿化.上述成果指明了该区铂族金属矿床的找矿方向,发现并探明了一批铂族金属矿床.这些勘查进展对我国的铂族金属矿床勘查具有借鉴意义.     

Observations on New Approaches for the Determination of Platinum-Group Elements, Gold and Silver in Different Geochemical Samples from Siberia and the Far East

Some recent experiments on the determination of Au and the platinum-group elements (PGE) in geochemical samples are reviewed. Emphasis is given to the determination of ultra-low levels of PGE concentrations in resistant matrices, including chromites, molybdenites and ultrabasic ores. The problems and features of PGE determination in samples of various chemical composition are considered. For each sample type studied, a series of sample preparation techniques are proposed. These techniques included acid digestion, fusion with sodium peroxide, cold sintering with an oxidizing mixture of Na₂O₂+ Na₂CO₃ and also oxidizing fluorination with bromine trifluoride. A new approach for preparing geochemical material prior to digestion, based on mechano-chemical activation with simultaneous hyperfine grinding, is proposed and studied. The instrumental determination of PGE contents was carried out directly by AAS from extracted organic phases. It was found that a combination of digestion processes was required to achieve geochemical background levels of Au and PGE concentrations with the following detection limits: Pd, Rh - 1 ng g⁻¹, Pt, Ru - 10 ng g⁻¹, Au - 0.2 ng g⁻¹, Ag - 0.1 ng g^−1. The uncertainty in PGE and Au determination in geochemical samples is dependent on metal concentration, and also on their distribution in samples. The total analytical uncertainty of the proposed method is between 15-30%.     

贵州寻找铂族元素矿床的思考

贵州省具有形成铂族元素矿床的地质条件，也存在铂族元素矿化的地质与地球化学信息，可能存在的矿床类型包括热液型、煤岩型、黑色页岩型等多种，可能发现矿床的地区除了在西部峨眉山玄武岩分布区之外，峨眉山玄武岩分布区外围的卡林型金矿和Hg、As、Sb等浅成低温热液型矿床分布区也值得重视。在找矿过程中，要充分研究哪些异常是由玄武岩引起的，哪些可能是由矿引起的。在采样时，由于铂族元素分布的极端不均性，天然重砂和人工重砂的配合是必要的。     

青海省铂族矿找矿方向探讨

根据铂族元素的成矿特征和青海省构造运动的多期性、继承性，复合叠加改造成矿作用明显及各种含铂岩石建造的分布特征，研究认为：在青海省内铂族元素矿产的找矿工作，不仅要重视寻找与基性一超基性岩有关铂矿，而且也要注意在黑色页岩型、热液型、红色造山建造中寻找含铜砂岩型等矿床的研究与评价。     

湖南省寒武系黑色岩系页岩型钒矿概论

湖南省寒武系黑色岩系蕴藏着丰富的钒矿资源,钒矿床产于寒武系底部富含有机质的碳、磷、硅质黑色岩系中;矿体呈层状、似层状,形态简单,产状稳定。多项测试结果表明,钒的载体岩石为黑色页岩(碳质页岩、硅质碳质页岩);钒主要呈类质同象形式赋存于伊利石晶格中;矿石类型主要为钒矿石,少数矿床中石煤钒矿石也是重要的矿石类型;钒的价态以V3+为主。钒的富集主要发生在沉积阶段,与黑色岩系的沉积过程一致;矿床形成于缺氧环境中,大部分钒被黏土质吸附,随有机质、黏土质和硅质呈胶态腐泥沉入海底;在成岩过程中,云母类黏土矿物结构发生再结晶,将原有表面吸附的钒(V3+)转化为类质同象形式进入云母晶格中取代部分铝(Al3+),形成含钒伊利石并聚集成为钒矿床。研究表明,本区黑色岩系及其有关的钒矿在沉积成岩成矿过程中都离不开生物地球化学作用,矿床成因属于在热水作用参与下沉积形成的海相化学和生物地球化学沉积矿床,矿床类型为黑色页岩型钒矿。     

Conditions of the formation of gold-enriched horizons of ore-hosting black shale sequences (illustrated by Permian and recent marine sediments of Northeastern Asia)

The problems of the origin of Au-rich horizons, which host all significant gold-ore deposits of the region, including valuable objects on a global level (Natalka and Nezhdaninskoe deposits), are considered, exemplified by Permian black shale deposits of the Ayan-Yuryakh anticlinorium of the Yana-Kolyma foldbelt and recent bottom sediments of the Chukchi Sea continental shelf.     

湘黔下寒武统黑色岩系不同矿物组合中的铂族元素特征

贵州遵义和湖南张家界黑色岩系中的矿物组合非常复杂,用X射线衍射仪分析并结合前人的研究成果,显示其中的硫化物矿物、粘土矿物和有机质含量较高;经破碎和分选流程对样品进行处理后,用ICP-MS方法测定了黑色页岩和分选后样品中的铂族元素含量,对贵州遵义和湖南张家界黑色岩系中的铂族元素赋存特征进行研究,结果表明:贵州遵义和湖南张家界的黑色页岩系中赋存高含量的铂族元素,且含量表现较高的稳定性;低温氧化条件下,铂族元素的化学活动性足以使之以相当规模活化、迁移并在还原条件下沉淀富集;经强风化淋滤作用,富含碳硫钼矿黑色页岩中铂族各元素含量都有不同程度的降低;绝大部分的铂族元素富集于黑色页岩的有机质和黄铁矿中;铂族元素的分布模式具规律性,铂族元素的明显分异说明此黑色页岩的分布模式不具有地外物质的特征。     

黔北黑色岩系的铂族元素地球化学特征及成因探讨

采用中子活化分析方法,系统测定了黔北黑色岩系的铂族元素含量。结果表明:金属富集层是铂族元素富集的首选层位。根据铂族元素丰度、元素相关性、特征参数值和元素配分模式,认为铂族元素并非来源于地外物质,而是海底含矿热卤水沿深大断裂而来。铂族元素的异常富集是海底热卤水与正常海水共同作用的结果。     

南秦岭山阳—柞水矿集区夏家店金矿床微量-铂族元素地球化学特征及其对矿床成因的指示

夏家店金矿床位于南秦岭造山带内,是一个受构造和地层控制的大型金矿床,矿石类型为角砾岩型、碎裂岩型和石英脉型3种类型,赋矿围岩主要为寒武系水沟口组的炭泥质板岩、炭硅质板岩、硅质岩及白云岩,次为泥盆系西岔河组的角砾岩。本文对夏家店金矿床中矿石（角砾状炭硅质板岩、碎裂硅化白云岩、碎裂炭泥质板岩和石英脉状矿化的硅质岩）和围岩（硅质岩、硅化白云岩和硅质板岩）的微量元素、铂族元素（PGE）质量分数进行测试,进而探讨成矿物质来源以及矿床成因。结果表明：不同类型的矿石与其各自的围岩具有高度的相似性,均富集Sr、Ga、Zr等元素;不同类型的矿石稀土总量均高于各类围岩,但是两者具有相似的稀土配分模式,轻稀土富集,重稀土亏损,均表现出负Eu异常（δEu值为0.51~0.63）;不同类型的矿石PGE总量（7.71×10^-9~38.30×10^-9,平均值23.00×10^-9）均明显大于各类围岩PGE总量（1.28×10^-9~2.44×10^-9,平均值1.86×10^-9）,相比上地壳,不同类型的矿石均明显富集Os、Ir、Pt和Pd,亏损Ru、Rh,而各类围岩均富集Os,亏损Pt、Ru、Rh、Pd,但两者的铂族元素配分曲线具有高度相似性,呈Ru亏损的V型,为地壳的（Os）-Pt-Pd型配分模式。以上特征表明不同类型的矿石和围岩具有明显的微量、稀土元素和PGE地球化学继承性,暗示夏家店下寒武统有可能是重要的矿源层之一。同时,所有矿石和围岩的Au/Ir值（分别为4 821~299 666）和406~8 050）及Pd/Ir值（分别为16.9~588.0和15.2~47.5）变化范围均较大,两者Au/Ir值远高于炭质球粒陨石和原始地幔值、Pd/Ir值远高于岩浆成因矿石值,且夏家店金矿床矿石和围岩的PGE配分曲线与典型热液成因矿床一致。这些特征显示夏家店金矿床具有明显的热液成因,是构造-热液流体成矿作用的产物。     

Mineral resources and development in the Russian Arctic

The paper concerns issues of geology and metallogeny of the Russian Arctic, namely, (i) limits of the Russian oceanic Arctic in the context of the continental origin of territories under jurisdictional dispute; (ii) geology and tectonic history of the region; (iii) distribution of mineral deposits; (iv) outlook for diamond, PGE, Ni, rare metals, gold, and bauxite resources development.Advanced diamond exploration and development can be expected proceeding from geology of new potentially diamondiferous areas, the Phanerozoic history and composition of lithospheric mantle beneath the Siberian craton which were controlled by the Siberian superplume at the Permian–Triassic boundary, and from new exploration approaches adapted to the prospecting conditions of Arctic Siberia.According to the available knowledge of Ni and PGE mineralization in the Noril’sk region, it is reasonable to develop depleted ores and tailings (mining dumps at the Noril’sk and Talnakh deposits). However, the key solution consists in new large discoveries within the Dzheltula and Kharaelakh volcanic and plutonic complexes.Gold production enhancement may be associated with black shale-hosted Au-As mineralization in the northeastern Russian Arctic, but the problem is in the lack of efficient and environmentally safe dressing technologies for these ores.Most of rare metals in the area (Nb, Sc, Y, and other elements) are stored in the giant Tomtor field, which has a complex structure and history. A special technology designed for the Tomtor ores ensures more than 60% extraction of ore components.Good prospects for the bauxite potential are expected from the Timan district where bauxite may occur in Vendian and Early Carboniferous formations.It is suggested to include the development of the Russian Arctic as a priority target in the national economic strategy.     

宁夏固原炭山地区中侏罗统延安组油页岩特征及其沉积环境

宁夏固原炭山地区存在大量与煤伴生的油页岩资源,油页岩主要赋存于中侏罗统延安组中下部各含煤层系中。本文采集钻孔所获延安组油页岩岩心样品,通过低温干馏、主量元素测定以及钻井录井等方法对炭山地区油页岩特征进行了研究,明确了油页岩测井识别依据,恢复了油页岩沉积环境。研究表明：炭山地区油页岩主要以黑色、灰黑色、深灰色为主,质地较轻,密度小,硬度小,断口参差状、贝壳状,具油脂光泽、沥青光泽,块状层理发育;油页岩含油率为3.60%~9.00%,灰分质量分数为42.50%~79.05%,全硫质量分数为0.07%~1.37%,发热量为11.01 kJ/g（平均值）,属中品质、硅质灰分、低硫且与煤伴生的油页岩;油页岩中w（SiO₂）变化较大,为53.89%~65.55%,w（Al₂O₃）为17.45%~23.29%,w（K₂O）明显高于w（Na₂O）,w（Fe₂O₃+MgO）为12.75%~21.98%,表明油页岩中含有较多的含钾矿物和镁铁成分;另外,Al₂O₃/（CaO+Na₂O）值为3.09~21.12,揭示油页岩稳定组分含量较高。炭山地区油页岩测井曲线特征明显区别于煤层和泥岩,油页岩长距伽马、声波时差和密度介于煤层与泥岩之间,而电阻率明显低于煤层和泥岩。炭山地区油页岩化学蚀变指数为74.87~84.35,Sr/Ba值为0.33~0.83,平均为0.61,Th/U值为1.00~3.50,表明本地区油页岩沉积环境为温暖、温润的缺氧、贫氧的陆相淡水湖泊环境和沼泽环境。     

Petrochemical characteristics of carbonaceous shales in the eastern Bureya massif and their precious-metal mineralization

Some geological, petrochemical, and geochemical characteristics of carbonaceous shales as a new unconventional natural source of gold and PGE are considered by the example of the Kimkan and Sutyr’ units of the Bureya massif (southern Far East, Russia). It is shown that shales of the units belong to the terrigenous-carbonaceous and siliceous-carbonaceous formations. They accumulated in deep-water trenches, and the active continental margin was probably their main provenance. The carbonaceous terrigenous-sedimentary units and precious-metalores in them show specific petrochemical characteristics different for complexes with predominantly PGE and gold mineralization. According to these characteristics, carbonaceous complexes with high Fe contents, low total contents of alkalies, and high K/Na ratios are promising for PGE-rich ores. Gold ores are usually localized in black-shale strata with high total contents of alkalies and low K/Na. In this respect, the shales and Fe-ores of the Kimkan unit obviously contain high-PGE mineralization, while the rocks of the Sutyr’ unit can bear gold deposits. We assume that the PGE mineralization is genetically related to the formation and transformation of carbonaceous rocks. At the same time, most of gold in the carbonaceous shales is native and is not related to carbon; it is present in mineral assemblages resulted from superimposed sulfidization and silicification.     

鄂尔多斯盆地南部长7暗色泥岩与黑色页岩生烃动力学特征对比分析

以往对鄂尔多斯盆地南部地区长7油层组(简称长7)中烃源岩生烃潜力的研究主要是采用静态地球化学指标进行的,目前尚无对生烃动态特征的系统评价,因而制约了对长7烃源岩生烃潜力和页岩油资源分布有利岩性的客观认识。为此,选取长7不同类型的烃源岩样品,通过开放和封闭热模拟实验,对比分析了不同类型烃源岩的动力学参数、生烃产物、产率特征及生烃演化规律。结果表明:(1)黑色页岩活化能分布范围比暗色泥岩更为集中,且主频活化能和频率因子均低于暗色泥岩,体现了快速生烃的特性;(2)在外推到地质条件下,黑色页岩主要生烃期对应的R_o值(0.70%~0.87%)低于暗色泥岩(1.06%~1.72%),且以生油为主;(3)R_o在0.9%~1.3%范围内,黑色页岩的总烃产率高于暗色泥岩,生油量高于暗色泥岩。结合研究区两类烃源岩的地球化学资料综合分析表明,黑色页岩是研究区页岩油资源形成与分布的有利烃源岩。     

鄂尔多斯盆地北部山西组页岩沉积相及其对页岩储层的控制作用

鄂尔多斯盆地北部山西组页岩气储层与煤层共生,页岩有机质含量较高,具有较大的资源勘探潜力。为精细表征控制山西组页岩储层分布的沉积微相,根据测井数据、录井数据、岩芯观察描述、薄片分析、粒度分析、X射线衍射全岩分析以及总有机碳含量(TOC),研究了山西组页岩储层岩相与沉积微相类型,在山西组识别出(灰)黑色碳质页岩、(灰)黑色含碳质页岩、(灰)黑色含碳质(粉)砂质页岩、(深)灰色含碳质页岩、(深)灰色页岩、(深)灰色(粉)砂质页岩和含钙质页岩7种岩相。这些岩相沉积在富植沼泽、贫植沼泽、三角洲平原分流间洼地、曲流河河间洼地、天然堤与决口扇远端微相环境,其中富植沼泽、贫植沼泽与成煤的泥炭沼泽、泥炭坪环境比邻共生,且在山二段时期更发育。富植沼泽和贫植沼泽微相控制了具有较高TOC的(灰)黑色碳质页岩、(灰)黑色含碳质页岩、(灰)黑色含碳质(粉)砂质页岩和(深)灰色含碳质页岩的分布,是控制山西组页岩储层分布的有利微相。