A Review of Research Progress in the Genesis of Colloform Pyrite and Its Environmental Indications

Colloform pyrite is a special form of nano-micro polycrystalline aggregation growth, for which a suitable term is ＂aggregates of nano-micro crystals＂. This kind of colloform texture is observed in various geological bodies, such as ancient sedimentary rocks, modern marine and lake sediments, various types of ore deposits, and modern seafloor hydrothermal vents. This paper summarizes the latest developments and research into the definition, formation mechanisms, and environmental indications of colloform pyrite. There appears to be three main formation mechanisms of colloform pyrite： pseudomorphic replacement; biogenic precipitation; and inorganic precipitation. The morphology, particle size, trace element content and preferential growth orientations of coUoform pyrite microcrystals can be important indicators for sedimentary environments, hydrothermal activity, and ore-forming processes. We suggest that the microscopic features of nano-micro crystals in colloform pyrite and their aggregation growth patterns need further investigation. The relationships between formation mechanisms of colioform pyrite, organic activity and depositional environments require further exploration. To reveal the nature of nano-micro grain aggregation growth in colloform pyrite and analyse its growth environment and evolutionary history, it is supposed to apply nanoscientific and nanotechnological methods, further integrate consideration of macroscopic geological backgrounds and microscopic mineral growth phenomena, combine high-resolution imaging systems and in situ quantitative microanalysis methods and constitute a mergence of earth science, thermodynamics and kinetics, life science, material science, and chemistry in the study.

Genesis of Strata-bound Sulfide Orebodies in the Tongling Polymetallic Mineralization Cluster, SE China: Evidence from Colloform Pyrite

Colloform pyrite(CPy)is widely distributed in the Tongling mineralization cluster of the Middle-Lower Yangtze River Mineralization Belt(MLYRMB),China.There have many debates as to whether such CPy is associated with Late Mesozoic igneous or Carboniferous sedimentation.CPy from the Xinqiao deposit,a representative of the stratabound sulfide deposits in the MLYRMB,was studied by powder X-ray diffraction(XRD),field-emission scanning electron microscopy(SEM),and high-resolution transmission electron microscopy(TEM).The results show that CPy mainly comprises pyrite,pyrrhotite,quartz,and illite.Pyrite in CPy shows cubic,globule,and xenomorphic morphologies.No octahedral or pyritohedron was observed.Most of the quartz crystals display xenomorphic morphology,where pyrite mold are popular on the surface.Organic matter(OM),which is usually bound to illite,is an important component in CPy.Morphological investigations which exhibit detrital features of quartz and clay minerals indicate that they were derived from continental weathering.Specially,some hexagonal pyrrhotite nanoparticles which show mackinawite morphology are coexisted with OM.The results indicate that the transformation process of sulfides possibly is mackinawite(the precursor)—hexagonal pyrrhotite-pyrite.Thus,compositional and micro-textural characteristics of CPy in Xinqiao deposit suggest it to be a sedimentary origin rather than a hydrothermal origin which is associated with Yanshanian magmatism.Moreover,the coexistence of CPy and stratabound sulfide orebodies in the MLYRMB suggests a causal link between the two.It is considered that CPy might have served as a Cu mineralization geochemical barrier for the Cu-bearing ore-forming fluids,which originated from the Mesozoic magma in the MLYRMB.

安徽铜陵矿集区铜官山矿田胶状黄铁矿矿物学特征及其对成矿作用的制约

铜官山矿田是铜陵矿集区内五大矿田之一,矿田内顺层产出的层状硫化物矿体是铜金矿床的主矿体,矿体内含有较多的胶状黄铁矿,其成因的争议制约了对铜金矿床成矿作用的解析。本文主要利用场发射扫描电镜(FE-SEM)等纳米矿物学手段,并结合光学显微镜、粉晶X射线衍射(XRD)、微区激光拉曼光谱分析等方法,对矿田内铜官山矿床及天马山矿床内层状硫化物矿体中胶状黄铁矿矿石的矿物组成、微形貌、微结构等特征进行系统研究,结果表明胶状黄铁矿矿石多呈胶状、鲕状结构,具有同心环状构造,同心环被赤铁矿、菱铁矿与黄铜矿脉穿切。同心环主要由白铁矿+有机质与胶状黄铁矿交替组成。胶状黄铁矿的黄铁矿颗粒粒径从纳米至亚微米均有分布,以自形-半自形立方体为主,少数呈他形,脉体边部胶状黄铁矿颗粒较大,自形程度较高,重结晶显著。矿石中含有少量白云石、伊利石微晶体,与胶状黄铁矿紧密共存,显示典型沉积特征。共存石英磨圆度较高,存在次生加大现象,表面存在胶状黄铁矿印模,显示为碎屑成因。这些综合信息表明胶状黄铁矿非岩浆热液成因,而是与石炭系地层同沉积成岩成因,并可能有微生物作用参与。高孔隙率、高化学活性及较高有机质含量的胶状黄铁矿可能为燕山期岩浆热液演化的含铜成矿流体提供了沉淀剂,对矿田内铜金硫化物矿体的层控性发挥了重要的控制作用。

铜陵包村金(铜)矿床中胶状黄铁矿矿物学及成因解析

黄铁矿是安徽铜陵包村金(铜)矿床中主要硫化物,对热液成因的显晶质黄铁矿已有大量研究,而胶状黄铁矿研究较少且成因存在争议。本文以粉晶X射线衍射、扫描电镜(SEM)、透射电镜(TEM)以及拉曼光谱(RS)为主要研究方法和手段,对包村金(铜)矿床中胶状黄铁矿的矿物组成和微结构进行研究。包村胶状黄铁矿主要由黄铁矿组成,含有白铁矿、菱铁矿、石英、含铁白云石、高岭石和有机质。黄铁矿主要以纳米-亚微米粒径的自形、半自形的立方体为主,少量微米级他形颗粒,显著不同于胶体或非晶态的无定型黄铁矿。由黄铁矿、白铁矿和有机质组成的胶状结构中,白铁矿和有机质富集在暗色环带,黄铁矿相对富集在浅色环带,浅色和暗色交替变化主要由三者含量变化所致,与矿物粒径无关。结合铜陵地区胶状黄铁矿研究成果,我们认为铜陵地区乃至长江中下游成矿带内铜-金-铁多金属硫化物矿床相关研究文献中记载的胶状黄铁矿为铁硫化物、碳酸盐矿物、黏土矿物、石英和有机质组成的矿物集合体,是在陆源物质输入受限的半封闭海盆环境下经生物化学作用直接沉淀的纳米-亚微米黄铁矿为主的矿物集合体。虽然胶状黄铁矿经历沉积成岩作用和中生代岩浆热液叠加改造作用,但是沉积微结构、矿物成因信息仍然被有效保存。

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ^34 S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ^34 S values(>0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the 34 S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ^34 S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H^32/2S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.

沥青路面的再生机理与再生剂研究

沥青路面再生的关键技术是对老化沥青的再生。从沥青的微观化学结构入手,分析了胶体结构理论中各组成成分对沥青性能的影响,并剖析了沥青的老化机理,从而提出了再生剂性能的技术要求,在分析了再生剂应有的组成成分的基础上试配了RT-A型再生剂并对其性能进行了试验研究,发现其再生效果显著。

胶状黄铁矿成因类型与鉴别特征

胶状黄铁矿广泛分布在多种地质体中,对其成分标型进行深入研究可以获得大量成因信息。通过分析胶状黄铁矿的矿物形态、晶体结构,并利用Fe-S、Co-Ni、S-Se、Se-Te和δ^(34)S图解,对胶状黄铁矿的组成特征进行对比研究,可以有效区分其成因类型。沉积成因的胶状黄铁矿多呈球形、椭球状和团块状的聚合形态,Co/Ni<l,S/Se>2.5×10^(4),Se/Te<0.45,δ^(34)S值变化范围较宽(-13‰~+13‰),显微镜下常具有鲕粒替代的假象结构。热液成因的胶状黄铁矿多呈不规则的脉状,微观结构常具有一定的定向性,1<Co/Ni<5,S/Se<2.5×10^(4),Se/Te>0.45,其中岩浆热液成因的胶状黄铁矿Co/Ni、S/Se和Se/Te均高于变质热液成因,δ^(34)S值范围较窄,通常集中于0~5‰。沉积成因的胶状黄铁矿成核和晚期环带生长的过程主要发生在厌氧的早期成岩阶段,在硫酸盐还原菌的作用下结晶出纳米粒级的微晶黄铁矿,H 2 S存在的厌氧环境中,Cu、Zn、Mo等金属元素以硫化物固溶体的形式进入结晶的纳米级黄铁矿颗粒而富集。而热液成因的胶状黄铁矿可作为一种载体矿物,Au、As等元素按层状-岛状生长模型赋存在胶状黄铁矿的生长环带中;中低温条件下可相变为磁黄铁矿等矿物,进一步促进Cu等元素沉淀。

铜陵矿集区层状硫化物矿床成因--来自胶状黄铁矿-菱铁矿型矿石矿物学制约

新桥硫铁矿床是铜陵矿集区重要的硫(铁、铜、金)多金属矿床,长期以来对其成矿作用存在争议。采用光学显微镜、粉晶X射线衍射(XRD)、场发射扫描电镜(FE-SEM)和高分辨透射电镜(HR-TEM)等矿物学研究手段,对新桥硫铁矿床层状矿体中胶状黄铁矿—菱铁矿型矿石矿物学进行了研究,结果表明该矿石主要由黄铁矿和菱铁矿组成(含量分别为74.3%和24.4%),含少量石英和伊利石;黄铁矿主要呈现纳米—亚微米粒径的自形、半自形立方体形态,菱铁矿以20~50μm的半自形菱面体产出,石英和伊利石呈现碎屑颗粒形态;偏光显微镜下胶状黄铁矿和菱铁矿呈现共生关系,FE-SEM下观察到微米粗粒菱铁矿与纳米—亚微米黄铁矿之间呈现镶嵌关系,可观察到菱铁矿表面存在黄铁矿的印模。FE-SEM和HR-TEM观察和能谱分析确证胶状黄铁矿—菱铁矿型矿石中仍然保存有少量的微生物残体和有机质。这些综合信息反映新桥胶状黄铁矿非岩浆热液成因,而是生物化学沉积成因。该层状铁硫化物—碳酸盐建造由于具有较高的地球化学活性,对燕山期岩浆活动驱动热液形成层状矿体发挥了重要的控制作用。