Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

藏南沙拉岗锑矿流体包裹体红外显微测温研究

沙拉岗锑矿是藏南金锑成矿带内最具有代表性的锑矿床。为了更直接地了解该矿床的流体物理化学特征,本文利用红外显微镜对辉锑矿及紧密共生石英中的流体包裹体进行了显微测温研究。红外显微测温分析结果表明,辉锑矿中包裹体均一温度在134.9～221.9℃,峰值在160～190℃之间,盐度在1.7%～7.3%NaCleqv,峰值在5.0%～6.0%NaCleqv之间,密度在0.879～0.958g/cm3之间,平均值为0.934g/cm3;共生石英中包裹体均一温度在142.5～205.6℃,峰值在160～190℃之间,盐度在2.3%～7.0%NaCleqv,峰值在4.0%～6.0%NaCleqv之间,密度在0.910～0.947g/cm3之间,平均值为0.929g/cm3。通过对比研究认为沙拉岗辉锑矿及共生石英形成于同一物理化学条件,捕获同一成矿流体。结合石英中单个流体包裹体激光拉曼成分分析认为成矿流体为含微量CO2、N2、CH4气体的低温、低盐度和低密度的NaCl-H2O热液体系。成矿流体的沸腾作用是辉锑矿大量沉淀主要原因。     

湖南中西部钨锑砷金矿床中辉锑矿含金性的初步研究

在湖南中西部钨锑砷金矿床中,辉锑矿是金的重要载体矿物之一.除富含Sb的黄铁矿、毒砂可作为金的可靠指示矿物外,辉锑矿中微量元素As和Tc,既是合金辉锑矿的标型元素,又是评价辉锑矿含金性的重要辅助标志性元素.     

Low-temperature crystal structures of stibnite implying orbital overlap of Sb 5s2 inert pair electrons

The crystal structure of stibnite [Sb₂S₃, Pnma, a=11.314(2), b=3.837(2), c=11.234(3) Å, V= 487.7(3) ų at 293 K] was refined in situ at 230, 173, and 128 K. It is a major characteristic of the structure that the Sb–S secondary bonds enclosing Sb 5s² inert lone-pair electrons at 293 K are significantly shorter than the corresponding sum of the Sb and S van der Waals radii. Concerning the temperature dependence, although both the polyhedral volume and the cation eccentricity of the two SbS₇ polyhedra exhibit continuous contractions with decreasing temperature, the sphericity values remain constant, indicating isotropic shrinkage. Consequently, the geometries of Sb 5s² inert lone-pair electrons and ligand atoms remain unchanged at low temperatures. This is because the crystal structure of stibnite at low temperature induces contraction with attractive interactions, which is called the orbital overlap between Sb 5s² inert lone-pair electrons and ligand orbitals to maintain the coordination environment. In this case, Sb 5s² lone-pair electrons are not inert, but active. Such orbital overlaps of inert lone-electron pairs can provide a reasonable explanation for shorter secondary bonds and lower band gap energy of the binary compounds containing heavy elements such as Sb, Te, Pb, and Bi, which are key factors in tracing the origins of color, luster, and semiconductivity of their minerals or compounds.     

贵州晴隆大厂锑矿床辉锑矿中流体包裹体的红外显微测温学研究

应用红外显微镜和流体包裹体显微测温分析技术,对晴隆大厂锑矿床辉锑矿和萤石中的流体包裹体进行了对比研究。研究表明,该矿床辉锑矿与萤石中的流体包裹体类型、均一温度和盐度存在明显差异。辉锑矿中的流体包裹体以含子晶-气-液三相包裹体和气-液两相包裹体为主,具有较高的盐度(0.18%~19.45%Na Cleqv)和均一温度(153~285℃),并具有明显的正相关关系,而萤石则主要发育气-液两相流体包裹体,具有较低的盐度(0.18%~1.91%Na Cleqv)和均一温度(144~176℃),认为形成辉锑矿和萤石的成矿流体来自不同的源区,流体混合导致的温度和盐度降低可能是锑成矿的重要控制因素之一。辉锑矿硫同位素研究进一步揭示其成矿物质主要来自地幔,可能与晴隆地区及其外围的基性-超基性岩浆活动的地质背景有一定的成因联系。     

微细浸染状金矿化与脉状金-锑矿化关系:西秦岭阳山金矿带例析

阳山是西秦岭金矿带已探明金储量最大的独立金矿,金矿化主要呈微细浸染状分布于千枚岩和花岗质岩脉中,锑矿化主要分布于花岗质岩脉与千枚岩接触带的石英±方解石脉中,是研究微细浸染状金矿化与脉状金-锑矿化的时间、空间和成因关系的理想选区。成矿主阶段微细浸染状黄铁矿-毒砂矿化已有大量研究,而晚阶段脉状金-锑矿化特征及其与主阶段微细浸染状金矿化关系尚待查明。论文系统研究了成矿晚阶段流体包裹体组合特征、辉锑矿及石英的矿物学、稀土和微量元素特征,并与成矿主阶段进行对比,以期理清阳山金矿带金矿化与锑矿化的关系。流体包裹体组合显微测温结果显示,成矿晚阶段流体均一温度为271.3～288.3℃,具有中低温、低盐度、富Cl和CO_2、还原性的变质流体来源的特征,与成矿主阶段一致。辉锑矿呈轻稀土富集、重稀土亏损的"右倾式"稀土配分模式,并可见中-弱的Eu负异常和强的Ce负异常,与千枚岩和花岗质岩脉的稀土元素配分模式相似。辉锑矿富含Ag、Au、As等微量元素,与赋矿围岩中这些元素的高背景值有关。结合硫化物硫同位素数据,指示阳山金矿带成矿物质来源可能为赋矿的千枚岩和花岗质岩脉:在区域构造抬升引发的退变质过程中,千枚岩和花岗质岩脉发生变质脱挥发分作用,释放出金等成矿物质。金矿化与锑矿化贯穿整个成矿作用,随着成矿温度、压力的变化,以及成矿流体成分的演化,成矿早、主阶段以微细浸染状含金硫化物为主,发育位置较深,成矿晚阶段以自然金-辉锑矿脉为主,发育位置较浅,在矿带尺度上符合造山型金矿地壳连续成矿模式的垂向分布规律。本文查明了阳山金矿带微细浸染状金矿化与脉状金-锑矿化的关系,明确其为造山型金矿浅成金-锑矿化,并在此基础上提出了找矿方向,为西秦岭及其他地区类似金矿床的理论研究与找矿勘探提供了有益参考。     

河南省大河沟锑矿床构造-流体与低温成矿

大河沟锑矿床分布在中元古界秦岭群变质岩内,矿体产出受双槐树深大断裂及其旁侧断裂控制,是一个构造控矿因素明显的低温热液矿床。为了深入探索它的成矿构造与成矿元素富集的有机联系及成矿机理,选择矿床内典型构造岩开展了构造岩特征和矿石的主微量元素、矿石矿物学、同位素地球化学和包裹体测试等分析。研究结果表明:矿床分布受区域韧性剪切带的控制,矿体围岩的糜棱岩化时限198.6"4.74Ma,并具有成矿元素矿源层的性质;辉锑矿可能在单一环境和封闭条件下形成,有独特的辉锑矿晶体特征峰值,含高的As、Au、Ag、Mo、Hg、Pb和Zn元素;方解石矿物的C—O同位素属于岩浆-地幔来源;辉锑矿硫同位素的值域为δ34S介于1.8‰~2.6‰之间,铅同位素显示地层铅的变化与辉锑矿相近;包裹体成分的测定表明流体具有硫酸盐的性质,局部为重碳酸根型水溶液,以热液改造沉积卤水为特征,成矿作用在还原条件下进行,石英包裹体中含有较高的H2暗示成矿流体具有深源性质。综合研究认为,矿床形成作用是深部热流体沿深大断裂活动,萃取了韧性剪切变形构造带中活动的金属元素,然后在还原条件和低温环境中沉淀成矿,成矿类型厘定为构造-流体制约的变质型矿床。     

Equation of state and crystal structure of Sb<Subscript>2</Subscript>S<Subscript>3</Subscript> between 0 and 10 GPa

High-precision unit-cell volume data of stibnite, collected in the pressure range of 0–10 GPa, was used for fitting a third-order Birch–Murnaghan equation of state. The zero-pressure volume, bulk modulus and its pressure derivative were found to be 487.73(6) ų, 26.91(14) GPa and 7.9(1), respectively. A series of X-ray intensity data was collected in the same pressure range using a CCD-equipped Bruker diffractometer. The high-pressure structures were all refined to R1(|F₀|>4) values of approximately 0.03. Crystal-chemical parameters as polyhedron volume, centroid and eccentricity were calculated for the seven coordinated cation positions using the software IVTON. The cation eccentricity appears to be a very useful tool for quantification of the lone electron pair activity. U₂S₃, Dy₂S₃ and Nd₂Te₃ are all isostructural with stibnite, but the cations in these materials have no lone electron pair. Their eccentricity is much smaller than that of Sb, and close to zero. This confirms that the stibnite structure type alone does not force eccentricity upon the cations involved and it is the lone electron pairs of Sb that generate the eccentricity of cation positions in the structures of stibnite. At increasing pressure the eccentricity of Sb is decreasing. It is therefore reasonable to conclude that the lone electron pair activity is decreasing with increasing pressure.     

Gold and antimony metallogenic relations and ore-forming process of Qinglong Sb(Au) deposit in Youjiang basin,SW China: Sulfide trace elements and sulfur isotopes

In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic.Here we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore sulfides.At Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained stibnite.Three generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur isotopes.The pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic origin.The Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As vs.Au–Sb–Cu–Ag correlations.Early-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for Au.As-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite.The As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ³⁴SH₂S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average + 1.3‰),respectively,indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source.Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits(Shuiyindong,Taipingdong,Nayang,Getang and Lianhuashan)in the NWYB have similar ore-fluidδSH₂S values(-4.5‰to +6.7‰,average-0.6‰)to those of Qinglong.Therefore,we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source(0±5‰)in the NWYB.Moreover,the core of pyrites(Py1)has variable S isotope fractionation(-18.9‰to +18.1‰,mostly +3‰to +12‰),suggesting that the higher-³⁴S H₂S was produced by bacterial sulfate reduction(BSR).The hydrothermal pyrite(Py2 and Py3)δ³⁴S values gradually decrease with increasing As concentrations,and ultimately,within the restricted range(-5‰to +5‰)in As-rich zones.This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites,causing the progressive decreasing δ³⁴S values with As content increase,Hence,the fluid/mineral interaction may have generated the observed variation in δ³⁴S and As contents.Overall,comparing the Au and Sb deposits in the NWYB,we favor a magmatic-related source for the Au–Sb–As-rich fluids,but the Au-and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.     

Stibnite microstructures as imprints of fault movement

The natural deformation of stibnite in relation to the kinematic history of a regional fault is resolved using microstructural analysis of massive stibnite along the Biards Fault in the Massif Central (France). Stibnite underwent intra-crystalline deformation associated with a strong linear and planar anisotropy. Lepidoblastic textures, undulatory extinction of oriented grains, growth of antimony between these grains, and a colour change of stibnite from white to black, result from dynamic recrystallisation. A range of asymmetric microstructures indicate non-coaxial deformation and a left-lateral sense of shear, related to the movement of the fault zone. The computed displacement corresponds to the geological offsets measured along the fault. We conclude that stibnite has microstructurally recorded the bulk kinematics of its host fault zone.Editorial Handling: F. Tornos