Solid solutions in the system acanthite (Ag<Subscript>2</Subscript>S)–naumannite (Ag<Subscript>2</Subscript>Se) and the relationships between Ag-sulfoselenides and Se-bearing polybasite from the Kongsberg silver district,Norway, with implications for sulfur–selenium fractionation

Sulfoselenides [Ag₂(S,Se)] and Se-bearing polybasite have been discovered at the Kongsberg silver district. The selenium-bearing minerals occur in two samples from the northern part of the district, forming either single or polyphase inclusions together with chalcopyrite within native silver. The Ag-sulfoselenides show large chemical variations, covering nearly the complete compositional range between acanthite (Ag₂S) and naumannite (Ag₂Se). For the data presented here, there is no local maximum at the composition Ag₄SSe attributed to the distinct phase called aguilarite, suggesting that this composition can be considered as one of many possible along the monoclinic Ag₂S–Ag₂S_0.4Se_0.6 solid solution series rather than a specific mineral phase. We present a model explaining the variations in the Se-content of Ag₂(S,Se) as a result of gradual de-sulfidization of the rock under oxidizing conditions. During this process, sulfur from the Ag₂S-component of Ag₂(S,Se) oxidized and dissolved in the fluid phase as SO₄^2?, resulting in the formation of native silver. The activity ratio \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the system gradually decreased due to the removal of SO₄^2?, which resulted in the stabilization of a sulfoselenide with higher selenium content. As a result of reaction progress, grains of Ag₂(S,Se) became gradually enclosed in newly formed native silver, and therefore isolated from further reactions with the grain-boundary fluid. Grains isolated early during the process show low content of Se reflecting high \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the equilibrium fluid, while grains showing high Se reflect the composition of late low \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) fluids. Analyses of Se-bearing polybasite show that selenium is preferentially partitioned into Ag₂(S,Se) compared to polybasite. The model presented here demonstrates how oxidation of sulfoselenides leads to fractionation of sulfur and selenium.     

Wittite with Se-rich Cosalite and Bismuthinite from Nevskoe Tin Deposit (Magadan District,Russia)

Summary A second confirmed occurrence of wittite, one of the four known Pb-Bi-Se-sulfosalts, has been found in the Nevskoe tin deposit (Eastern Siberia). Microprobe analyses of wittite show pronounced variation of Se content (from 9.5 to 16.5 wt. %), due to S --> Se substitution; Pb and Bi contents vary from 29 and 43%, up to 34 and 46%, respectively. Minor elements are also present: Sb up to 1.5%, Ag up to 1.3 %, and Cu (0 to 0.2%). Comparison of microprobe data of wittite from Nevskoe and Falun, on the one hand, and cannizzarite from different deposits on the other hand, indicate that Ag is incorporated in the wittite/cannizzarite structure through the substitution 2 Pb -> Bi + Ag. Conversely, Ag substraction gives a constant Bi/(Bi + Pb) atomic ratio, independent of the Se/(Se+"S) ratio, and close to 55.1%. Se-rich wittite is compositionally very close to proudite and weibullite. X-ray powder and electron microdiffraction patterns are given; the incommensurate structure agrees with the 7H/12Q match along , like in wittite from Falun. Nevskoe wittite is close to Pb₈Bi₁₀(S, Se)₂₃, but the 7H/12Q match requires the formula Pb_11.61Bi_14.26S₃₃, with about 3% of the Pb atoms in the Q layer replaced by Bi atoms and vacancies (p). Taking into account all microprobe data, the general formula developed is: Pb_{11.61–2x0.13}Ag_x(Bi_14.26+x-ySb_y)(S_1–zSe_z)₃₃ with x and y 0.86 at., and z 0.45. At Nevskoe, associated bismuthinite contains from 5 to 12% Se, with minor Sb, Pb and Cu. Se-rich cosalite contains from 4 to 8% Se, with Sb from 2.7 to 5.3%, and minor Ag and Cu. Wittite in contact with cosalite clearly shows a relative Se-enrichment, that could be due to the pseudo-hexagonal sub-lattice of this incommensurate structure, very similar to the Bi₂(Se, Te, S)3 sheet in the tetradymite series. According to microprobe data, there is a continuous change from Se-free cannizzarite to Se-rich wittite. Therefore, the validity of wittite as a specific mineral species appears questionable, and more accurate crystallographic studies on this incommensurate series are necessary.

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Wittite avec Cosalite et Bismuthinite Séléniferes du Gisement d'Etain de Hevskoe (District de Magadan, Russie)

Resume Une seconde occurrence de wittite, l'un des quatre sulfosels de Pb-Bi-Se cormus, a été trouvée daps le gisement d'étain de Nevskoe (Sibérie Orientale). Son analyse á la microsonde électronique montre une forte variation de la teneur en sélénium (de 9,5 á 16,5%), qui se substitue au soufre; les teneurs en Pb et Bi varient de 29 à 43 et 34 á 46%, respectivement. On note la présence de Sb (, 1,5%), Ag ( 1,3%) et Cu (< 0,2%). La comparaison des analyses de wittite de Nevskoe et Falun, et de cannizzarite de différents gisements, montre que Bans cette série l'argent est incorporé suivant la substitution 2 Pb Bi + Ag. Après soustraction de Ag, le rapport atornique Bi/(Bi + Pb) corrigé apparaït constant, proche de 55,1%, et indépendant du rapport Se/(S + Se). La wittite la plus riche en Se est chimiquement très proche de la proudite et de la weibullite. Son diagramme de poudre aux rayons X ainsi que son étude en microdiffraction électronique sont présentés; la structure, de type incommensurable, s'accorde aver un ajustement selon le rapport 7H/12Q suivant , comme dans la wittite de Falun. La formule de la wittite de Nevskoe est proche de Pb₈Bi₁₀(S, Se)₂₃, mais l'ajustement 7H/12Q demande la formule Pb_11.61Bi_14.26S₃₃, avec environ 3% des sites à Pb du feuillet Q remplacés par des atomes de Bi et des sites vacants (). La prise en compte de l'ensemble des analyses conduit á la formule développée générale: Pb_11.61-2x0.13Ag_x(Bi_14,26+x–ySb_y)-(S_{1 –z}Se_z)₃₃ avec x et y 0,86 at., et z 0,45. A Nevskoe, la bismuthinite associée contient de 5 à 12% Se, avec Sb, Pb et Cu mineurs. La cosalite contient de 4 a 8% Se, 2,7 á 5,3% Sb, avec Ag et Cu mineurs. Lá où wittite et cosalite sont en contact étroit, la wittite montre clairement un enrichissement relatif en Se, qui pourrait etre du au sousréseau pseudo-hexagonal de cette structure incommensurable, très proche du feuillet Bi₂(Se, Te, S)3 présent dans la série de la tétradymite. Les analyses à la microsonde indiquant une continuité chimique de la cannizzarite sans Se à la wittite 1a plus riche en Se, la validité de la wittite en tant qu'espéce spécifique apparaït discutable. Mais le caractère incommensurable de cette série demande une etude cristallographique plus détaillée.

     

The behavior of noble-metal admixtures during fractional crystallization of As- and Co-containing Cu–Fe–Ni sulfide melts

To study the behavior of macrocomponents and admixtures during the fractional crystallization of sulfide melts and the influence of As on noble metals in this process, we performed a quasi-equilibrium directional crystallization of melt of composition (at.%): Fe—35.5, Ni—4.9, Cu—10.4, and S—48.3, with admixtures of Pt, Pd, Rh, Ru, Ir, Au, Ag, As, and Co (each 0.1 at.%), which imitates the average (by Cu contents) compositions of massive ores at the Noril'sk Cu-Ni deposits. The following sequence of phase formation from melt has been established: mss (zone I) / mss + iss (zone II) / iss (zone III) (mss is (Fe_zNi_1–z)S_1+δ, iss is (Fe_xCu_yNi_1–x–y)_zS_1–z); it corresponds to the distribution of main elements along the sample (primary zoning). Distribution curves for macrocomponents in zones I and II of the sample were constructed, as well as the dependencies of their partition coefficients (k) between solid solutions and sulfide melt on the fraction of crystallized melt. The secondary (mineral) zoning resulted from subsolidus phase transformations has been revealed. Five subzones have been recognized: mss + cp (Ia) / mss + cp + pn (Ib) / mss + pc + pn (IIa) / mss + pc + pn + bn (IIb) / pc + bn + pn + unidentified microphases (III). Admixture species in the sample were studied: (1) admixtures dissolved in primary solid solutions and in main minerals resulted from solid-phase transformations and (2) admixtures forming their own mineral phases. The partition coefficients of Co, Rh, and Ru (mss/L), Ru, Ir, and Rh (mss/cp), and Co, Rh, and Pd (mss/pn) were determined. Minerals of noble metals have been recognized: Pt₃Fe, PtFe, Au, (Ag,Pd), (Au,Pt), Ag, Ag₃Cu, Au₃(Cu,Ag,Pd,Pt), etc., and the regularities of their distribution in the sample have been established. It is shown that some noble-metal admixtures are prone to interact with As. Mineral arsenides and sulfoarsenides of noble metals produced during fractional crystallization have been recognized: PtAs₂, Pd₃As, (RhAsS), (IrAsS), and (Ir,Rh)AsS. The discovered drop-like inclusions of noble-metal arsenides suggest the separation of the initial sulfide-arsenide melt into two immiscible liquids. By indirect features, the micromineral inclusions are divided into primary, crystallized from melt, and secondary, produced in solid-phase reactions. The results of study are compared with literature experimental data obtained by the isothermal-annealing method and with the behavior of noble metals and As during the formation of zonal massive orebodies at the Noril'sk- and Sudbury-type deposits.     

Epithermal Gold-Silver Mineralization of the Asachinskoe Deposit in South Kamchatka, Russia

The Asachinskoe epithermal Au‐Ag deposit is a representative low‐sulfidation type of deposit in Kamchatka, Russia. In the Asachinskoe deposit there are approximately 40 mineralized veins mainly hosted by dacite–andesite stock intrusions of Miocene–Pliocene age. The veins are emplaced in tensional cracks with a north orientation. Wall‐rock alteration at the bonanza level (170–200 m a.s.l.) consists of the mineral assemblage of quartz, pyrite, albite, illite and trace amounts of smectite. Mineralized veins are well banded with quartz, adularia and minor illite. Mineralization stages in the main zone are divided into stages I–IV. Stage I is relatively barren quartz–adularia association formed at 4.7 ± 0.2 Ma (K‐Ar age). Stage II consists of abundant illite, Cu‐bearing cryptomelane and other manganese oxides and hydroxides, electrum, argentite, quartz, adularia and minor rhodochrosite and calcite. Stage III, the main stage of gold mineralization (4.5–4.4 ± 0.1–3.1 ± 0.1 Ma, K‐Ar age), consists of a large amount of electrum, naumannite and Se‐bearing polybasite with quartz–adularia association. Stage IV is characterized by hydrothermal breccia, where electrum, tetrahedrite and secondary covellite occur with quartz, adularia and illite. The concentration of Au+Ag in ores has a positive correlation with the content of K₂O + Al₂O₃, which is controlled by the presence of adularia and minor illite, and both Hg and Au also have positive correlations with the light rare‐earth elements. Fluid inclusion studies indicate a salinity of 1.0–2.6 wt% NaCl equivalent for the whole deposit, and ore‐forming temperatures are estimated as approximately 160–190°C in stage III of the present 218 m a.s.l. and 170–180°C in stage IV of 200 m a.s.l. The depth of ore formation is estimated to be 90–400 m from the paleo‐water table for stage IV of 200 m a.s.l., if a hydrostatic condition is assumed. An increase of salinity (>C_NaCl≈ 0.2 wt%) and decrease of temperature (>T ≈ 30°C) within a 115‐m vertical interval for the ascending hydrothermal solution is calculated, which is interpreted as due to steam loss during fluid boiling. Ranges of selenium and sulfur fugacities are estimated to be logfSe2 = ?17 to ?14.5 and logfS2 = ?15 to ?12 for the ore‐forming solution that was responsible for Au‐Ag‐Se precipitation in stage III of 200 m a.s.l. Separation of Se from S‐Se complex in the solution and its partition into selenides could be due to a relatively oxidizing condition. The precipitation of Au‐Ag‐Se was caused by boiling in stage III, and the precipitation of Au‐Ag‐Cu was caused by sudden decompression and boiling in stage IV.     

Typomorphic Characteristics of Molybdenite from the Bystrinsky Cu–Au Porphyry–Skarn Deposit,Eastern Transbaikal Region,Russia

The paper presents pioneering data on the composition, texture, and crystal structure of molybdenite from various types of molybdenum mineralization at the Bystrinsky Cu–Au–Fe porphyry–skarn deposit in the eastern Transbaikal region, Russia. The data were obtained using electron microprobe analysis (EMPA), laser ablation–inductively coupled plasma mass spectrometry (LA-ICP-MS), and high-resolution transmission electron microscopy (HRTEM). Molybdenite found at the deposit in skarn, sulfide-poor quartz veins, and quartz–feldspar alteration markedly differs in the concentrations of trace elements determined by their species in the mineral, as well as in its structural features. Molybdenite-2H from skarn associated with phyllosilicates occurs as ultrafine crystals with uniform shape and texture; no dislocations or inclusions were found but amorphous silica was. The molybdenite composition is highly contrasting in the content and distribution of both structure-related (Re, W, and Se) and other (Mn, Co, Ni, Cu, Zn, As, Ag, Cd, Sb, Te, Ag, Pd, Au, Hg, Pb, and Bi) metals. In the sulfide-poor quartz veins, highly structurally heterogeneous (2H + 3R) molybdenite microcrystals with abundant defects (dislocations and volumetrically distributed inclusions) are associated with illite, goethite, and barite. Some single crystals are unique three-phase (2H + 3R polytypes + amorphous MoS₂). The mineral has a low concentration of all trace elements, which are uniformly distributed. However, individual domains with uniquely high Pd, Te, Ni, Hg, and W concentrations caused by mineral inclusions are found in some grains. Molybdenite from quartz–feldspar alteration is characterized by low concentrations of all trace elements except for Re and Se, which enrich some domains of the grains. Our data indicate that the compositional and structural heterogeneity of molybdenite from the Bystrinsky deposit are its crucial features, which obviously correlate with the types of Mo mineralization.     

川西龙门山地区元古代VMS铜矿床:硫化物微量元素和硫同位素证据

川西龙门山地区元古宙变质火山碎屑岩系中发育一系列块状黄铁矿型铜矿床,含矿围岩形成于岛弧构造环境.矿石中黄铁矿占金属矿物总质量分数的90%左右,黄铜矿质量分数为0.8%~3.0%,闪锌矿为1%~4%.矿石主要元素为Fe、S、Zn、Cu、Mn等,其次为Ag、Au、Pb、Se、Cd、Ga、Ti、V、Co等元素,全区各矿层矿石中δ(34S)分布范围为 -1.5‰~+15.9‰,平均为 +7.6‰,N(32S)/N(34S)值为22,据此推断成矿物质应来自地壳深部,与洋壳俯冲作用有关.主要金属硫化物及其微量元素和硫同位素组成特征表明矿床类型为火山成因块状硫化物矿床,即VMS矿床.     

滇西金宝山铂钯矿床元素地球化学

金宝山铂钯矿床位于扬子板块西缘红河断裂东侧,宁蒗-弥渡镁铁-超镁铁岩带内,矿体呈似层状、透镜状产于辉石橄榄岩中。辉石橄榄岩和铂钯矿石均富集LREE,具有弱的Eu负异常和较强的Sr、Ba负异常;与N-MORB相比,辉石橄榄岩具有较低的(Nb/Th)PM比值和较高的(Th/Yb)PM比值,表明金宝山岩体受到了地壳物质混染;通过(Th/Yb)PM-(Nb/Yb)PM图解估算得到地壳混染程度在55%~70%之间,强烈地壳混染表明岩浆中的S达到饱和并使得硫化物发生大规模熔离。而利用硅酸盐岩浆/硫化物的质量比值(R因子)方程进行模拟计算,得到金宝山矿床R因子集中于5000~1000之间,明显大于金川、图拉尔根、白马寨等典型岩浆硫化物矿床,说明金宝山岩体形成时岩浆中的硫化物熔离程度较低。辉石橄榄岩和铂钯矿石的S/Se和Cu/Pd比值也同样反映了硫化物低程度熔离的特征。与Nb、Th等元素含量相对稳定的高场强元素相比,S、Se、Pd等元素在硫化物部分熔解以及热液作用过程中更容易发生迁移。类似于River Valley和Platreef矿床等大型层状PGE矿床,金宝山铂钯矿床的形成是一个两阶段的过程,早阶段在岩浆通道或深部岩浆房中,地壳混染使得硫化物发生强烈熔离并在有限的空间内大量聚集,产生富PGE岩浆;后由于硫化物的部分熔解,岩浆中硫化物熔体富集Se、Pd,亏损S、Fe,岩浆中的S由饱和变为不饱和。晚阶段在浅部岩浆房,少量地壳S的加入并未使得S饱和从而发生硫化物大规模熔离。金宝山岩体具有较低的Cu/Pd、Cu/Pt比值,即出现Cu/Pd比值较低的岩体也可能有较大的成矿潜力,这与传统意义上所认为的具有较高Cu/Pd、Cu/Pt比值的矿体不同。     

Fe-Zn exchange reaction between tetrahedrite and sphalerite in natural environments

Microprobe and fluid inclusion analyses of hydrothermal ore deposits containing the subassemblage sphalerite+ tetrahedrite-tennantite [(Cu, Ag)₁₀(Fe, Zn)₂(As,Sb)₄S₁₃] reveal that the Gibbs energies of the reciprocal reaction Cu₁₀Zn₂Sb₄S₁₃ + Cu₁₀Fe₂As₄S₁₃ = Cu₁₀Fe₂Sb₄S₁₃ + Cu₁₀Zn₂As₄S₁₃ and the Fe-Zn exchange reaction 1/2Cu₁₀Fe₂Sb₄S₁₃ + ZnS = 1/2Cu₁₀Zn₂Sb₄S₁₃ + FeS are within the uncertainties of the values established by Sack and Loucks (1985) and Raabe and Sack (1984), 2.59±0.14 and 2.07±0.07 kcal/gfw. However, this study suggests that the Fe-Zn exchange reaction between sphalerite and Sb and Ag-rich tetrahedrites does not obey the simple systematics suggested by Sack and Loucks (1985) wherein tetrahedrite is assumed to behave as an ideal reciprocal solution. Instead these studies show that the configurational Gibbs energy of this exchange reaction,RTln[(X _Fe/X _Zn)^TET(X _ZnS/X _FeS)^SPH], corrected for sphalerite nonideality exhibits both a local maximum and minimum as a function of Ag/(Cu+Ag) ratio at a givenX _FeS ^SPH and temperature. The local maximum forX _FeS ^SPH 0.10 corresponds to the position of the cell edge maximum established for natural tetrahedrites by Riley (1974), Ag/(Ag+Cu)0.4. These studies and the results of structural refinements of Ag-bearing tetrahedrites suggest that in low silver tetrahedrites Ag is preferentially incorporated in trigonal-planar sites but that in tetrahedrites with intermediate and greater Ag/(Ag+Cu) ratio, Ag is preferentially incorporated in tetrahedral sites. A nonconvergent site ordering model for tetrahedrite is developed to quantify and extrapolate these predictions.     

浙江火山岩区金矿床黄铁矿的找矿矿物学研究

论文给出了中国浙江火山岩区金矿床中黄铁矿的微量元素、形态和物理性质找矿标型特征.例如.(在许多)浙江火山岩区重要金-银矿床中黄铁矿相对富含铅、锌、钼、锡、砷、锑、铋而贫钴,镍、硒、碲:并且S/Se、Ag/Au、Pb/Ni、Se/Te、(As+sb+Bi)/(Se+Te)比值较高,Co/Nj、Ag/Pb、Ag/Zn、Cu/Zn和(Co+Ni)/(Pb+Zn)比值较低,再如含金黄铁矿比不含金黄铁矿的反射率低.总之,黄铁矿的标型性研究对于寻找金矿具有重大的理论意义和实际意义.     

山西高凡银金矿床黄铁矿的微量元素标型特征及其应用

高凡银金矿床黄铁矿的微量元素研究发现富Au、Ag、Pb、Zn、As、Sb,贫Co、Ni、Se,且S/Se较大,S/As和Fe/(Pb+Zn)较小,As/(Co+Ni)、(Pb+Zn)/(Co+Ni)>10。同时高凡矿田中的滩上铜钼矿化点的黄铁矿则显示相反的特征。总结出一套区分两类矿化黄铁矿微量元素的标型特征,对高凡矿田和五台地区各矿化点的判别和评价中显示了一定的适用性,可作为本区寻找同类金银矿床的找矿标型特征。     

黝铜矿-砷黝铜矿矿物学研究进展

黝铜矿-砷黝铜矿系列矿物(Tetrahedrite -Tennantite Series Mineral,TTSM)作为含Cu、Ag、S、Sb、As、Hg及少量Au、Fe、Zn、Cd、Bi、Te、Se的硫盐矿物广泛存在于世界各地的Cu、Ag、Au、Pb、Zn多金属矿床中.为了能够更好的认识该系列矿物,提高矿物中有用元素的回收率,扩大黝铜矿型铜矿床的经济效益,本文对TTSM的化学组成和类质同象置换规律,晶胞参数和晶体结构的形变,矿物人工合成和有用元素的浸出试验等研究进展进行了综述.天然TTSM矿物一般化学式为:(Cu,Ag)6 Cu4 (Fe,Zn,Cu,Hg,Ag,Cd)2 (Sb,As,Bi,Te)4 (S,Se)13,其中S-Se、Sb-As-Bi-Te、Ag-Cu、Cu-Hg-Fe-Pb-Zn-Cd的类质同象置换相当普遍;TTSM晶体结构中不同结构位置离子置换规律更多的受限于离子价键,而同一结构位置不同离子的置换除受限于离子价键还受限于该位置空间大小,晶胞参数与离子置换类型和数量密切相关;人工合成实验证实形成TTSM矿物的温度范围为350～540℃,浸出试验证明随反应温度增高、浸出浓度增大、矿物颗粒减小时,TTSM中有用元素的浸出速率增大.     

Ag2(S,Se) solid solutions in the ores of the Rogovik gold-silver deposit (northeastern Russia)

The relationships and chemical compositions of silver sulfoselenides in the ores of the Rogovik gold-silver deposit (northeastern Russia) were studied to refine the low-temperature region of the Ag₂S-Ag₂Se phase diagram and identify contradictions between natural and experimental data. Two types of relationships between the phases of the system Ag₂S-Ag₂Se have been recognized using optical and scanning electron microscopy: (1) Se-acanthite and S-naumannite occur as monomineral microinclusions or fill cracks in the grains or the interstices of other minerals, and acanthite (free of impurities) forms rims on Fe-sphalerite; (2) Se-acanthite forms rims on S-naumannite. Electron probe microanalysis of silver sulfoselenides from the Rogovik ores revealed 0–7.9 wt.% Se in acanthite and 0–3.2 wt.% S in naumannite, which corresponds to the acanthite series Ag₂S-Ag₂S₀.₇₄Se₀.₂₆ and naumannite series Ag₂S₀.₂₈Se₀.₇₂-Ag₂Se. The composition ranges of the studied acanthite and naumannite series are wider than those of natural silver sulfoselenides from the Guanajuato (Mexico), Silver City (USA), Salida (Indonesia), and other deposits (Ag₂S-Ag₂S0.85Se0.₁5 and Ag₂S0.₁₂Se0.88-Ag₂Se, respectively) but are significantly narrower than the composition ranges of synthetic samples: Ag₂S-Ag₂S0.₄Se0.6 and Ag₂S0.3Se0.₇-Ag₂Se. The presence of intergrowths of two phases of the Ag₂S-Ag₂Se series in the form of Se-acanthite rims on S-naumannite in the Rogovik ores and the absence of three-phase intergrowths of silver sulfoselenides Ag₂S_1 -xSe_x from this and other deposits do not confirm the assumption on the existence of the third solid solution. The results of earlier studies of natural Ag₂(S,Se) solid solutions show the existence of two solid solutions (of the acanthite and naumannite series) in the Ag₂S-Ag₂Se system and confirm the experimental data. It is necessary to carry out a detailed examination of natural silver sulfoselenides falling in the interval from Ag2S0.4Se0.6 to Ag2S0.3Se0.7 in order to identify the limits of two-phase immiscibility.     

Minerals of the beudantite–segnitite series from the oxidation zone of the Berezovskoe gold deposit,middle Urals: Chemical variations,behavior of admixtures,and antimonian varieties

In the oxidation zone of the Berezovskoe gold deposit in the middle Urals, Russia, minerals of the beudantite–segnitite series (idealized formulas PbFe₃ ³⁺ AsO₄)(SO₄)(OH)₆ and PbFe₃ ³⁺ AsO₄)(AsO₃OH)(OH)₆, respectively) form a multicomponent solid solution system with wide variations in the As, S, Fe, Cu, and Sb contents and less variable P, Cr, Zn, Pb, and contents K. The found minerals of this system correspond to series from beudantite with 1.25 S apfu to S-free segnitite, with segnitite lacking between 1.57 and 1.79 As apfu. Segnitite at the Berezovskoe deposit contains presumably pentavalent Sb (up to 15.2 wt % Sb₂O₅ = 0.76 Sb apfu, the highest Sb content in the alunite supergroup minerals), which replaces Fe³⁺. The Sb content increases with increasing As/S value. On the contrary, beudantite is free of or very poor in Sb (0.00–0.03 Sb apfu). Many samples of segnitite are enriched in Cu (up to 8.2 wt% CuO = 0.83 Cu apfu, uncommonly high Cu content for this mineral) and/or in Zn (up to 2.0 wt% ZnO = 0.19 Zn apfu). Both Cu and Zn replace Fe. The generalized formula of a hypothetic end member of the segnitite series with 1 Sb apfu is Pb(Fe³⁺ M ²⁺Sb⁵⁺)(AsO₄)₂(OH)₆, where M = Cu, Zn, Fe²⁺. The chemical evolution of beudantite–segnitite series minerals at the Berezovskoe deposit is characterized by an increase in the S/As value with a decrease in the Sb content from early to late generations.     

A review of sulfur to selenium ratios in magmatic nickel–copper and platinum-group element deposits

Deviations in the sulfur to selenium ratios (S/Se) from mantle values in magmatic Ni–Cu–Platinum Group Elements (PGE) sulfide deposits have been widely used to constrain the ore forming processes. Basically, S/Se ratios greater than mantle values are interpreted to be the result of contamination of the mantle derived magma by S-rich sedimentary rocks, whereas S/Se ratios lower than mantle values are thought to be the result of S loss during post-crystallization. However, there are many other processes involved in producing a deposit and it is possible that these may be also important in controlling S/Se ratios. In order to investigate the relative importance of these processes, we have compiled a data base of S, Se, δ³⁴S and metal values from Ni–Cu–PGE sulfide deposits. This compilation shows that processes affecting S/Se ratios can be divided into two main classes: the magmatic processes and the late- to post-magmatic processes.

• 1)Magmatic processes include the well-known addition of S from sedimentary rocks, variations in the sulfide to silicate liquid ratio (R-factor), depletion of the silicate magma in Se by early segregation of the sulfide liquid, and the moderate incompatibility of Se into the first sulfide minerals to crystallize from a sulfide liquid, the monosulfide-solid-solution (MSS). This incompatibility results in a change in S/Se ratio between the Fe-rich and Cu-rich zones of magmatic sulfide ores. The fractionation of Se during crystallization of sulfide liquids has not previously been appreciated.
• 2)Late- to post-magmatic processes include: hydrothermal alteration, high-grade metamorphism, serpentinization and supergene weathering. Some metamorphosed Cu-deposits have low S/Se ratios suggesting S-loss by breakdown of sulfide minerals during a high-grade metamorphic event. However, the effectiveness of this process remains unclear and alternative models exist. The preferential remobilization of S relative to Se during hydrothermal alteration, serpentinization and supergene weathering leads to a moderate decrease of S/Se ratios values and can mask the initial S/Se ratio.

     

Thermodynamics of Arsenates,Selenites, and Sulfates in the Oxidation Zone of Sulfide Ores. XIV. Selenium Minerals in the Oxidation Zone of the Yubileynoe Massive Sulfide Deposit,the South Urals

Selenium is one of the most important minor elements in massive sulfide ores. This study focuses on selenium minerals present in the oxidation zone of the Yubeleinoe massive sulfide deposit, the South Urals, Russia: clausthalite (PbSe), tiemannite (HgSe), and naumannite (Ag₂Se). These minerals are associated with goethite and siderite. Thermodynamic modeling was used to estimate the physicochemical parameters of selenide stability and the possible formation of Pb, Hg, and Ag selenites as a result of sulfide ore oxidation. The Eh–pH diagrams for the Fe–S–CO₂–H₂O and Fe–Se–CO₂–H₂O systems were calculated to estimate the physicochemical formation conditions of the Yubileinoe oxidation zone, as well as for the M–Se–Н₂О and M–S–H₂O (M = Hg, Pb, Ag) systems. The physicochemical parameters of clausthalite, naumannite, and tiemannite stability are consistent with these conditions. Only the formation of PbSeO3 is theoretically possible among Pb, Ag, and Hg selenites.

     

Comparative Determination of Mass Fractions of Elements with Variable Chalcophile Affinities in Geological Reference Materials with and without HF‐desilicification

Desilicification elevates extraction of Re and platinum‐group elements (PGEs) from many geological reference materials (RMs), but the extent to which it affects less chalcophile elements has been investigated rarely. To further evaluate the effect of desilicification, mass fractions of elements with variable chalcophile affinities (In, Cd, Cu, Ag, S, Se, Te, Re and PGEs) in different RMs were obtained by isotope dilution and digestion procedures involving HF‐HNO₃ in bombs versus HNO₃‐HCl in Carius tubes. The results show that the extraction efficiencies of HF‐desilicification vary in different RMs and for different elements. HF‐desilicification led to a significant increase (30–70%) for In and Cd mass fractions in all analysed RMs, but it played a negligible role in other strongly chalcophile elements in many samples (e.g., UB‐N and WGB‐1). Noticeably, desilicification led to a 10–30% increase in the mass fractions of Cu, Ag, S, Se and Te in BHVO‐2 and BIR‐1a, but less so in BCR‐2. These results could be attributed mainly to the variable chalcophile affinities of elements and their relative budget in sulfides, alloys and silicates. Desilicification should thus be preferred to determine chalcophile elements for most samples, except in cases where they are negligibly hosted in silicates.     

Use of multivariate statistical analysis to determine the relationship between the magnetic properties of urban topsoil and its metal, S, and Br content

Multivariate statistical analysis has been used for detailed examination of the relationship between the magnetic properties of Xuzhou urban topsoil, for example concentration-dependent properties (mass magnetic susceptibility (χ), susceptibility of anhysteretic remanent magnetization (χ _ARM), saturation isothermal remanent magnetization (SIRM), soft remanent magnetization (SOFT), and frequency-dependent magnetic susceptibility (χ _FD)) and feature-dependent properties (S _{−100 mT} ratio, SIRM/χ ratio and F _{300 mT} ratio), and the concentrations of metals (Ti, Fe, Cr, Al, Ga, Pb, Sc, Ba, Li, Cd, Be, Co, Cu, Mn, Ni, V, Zn, Mo, Pt, Pd, Au, As, Sb, Se, Hg, Bi, Ag, and Sn), S, and Br in the soil. The results show that SIRM/χ ratios correlate best with the heavy metals (Hg, Cr, Sb, As, and Bi) which are mainly derived from coal-combustion emissions whereas χ _FD correlates best with the metals (Al, Ti, V, Be, Co, Ga, Mn, and Li) which principally originate from soil parents. Concentration-dependent magnetic properties (χ _ARM, χ, SIRM, and SOFT) correlate well with elements (Se, Pb, Cu, Zn, Fe, Ag, Sc, Ba, Mo, Br, S, Cd, Ni, etc.) which are mainly derived from road-traffic emissions. For the same chemical element, χ _ARM, SIRM, and SOFT values are frequently better correlated than χ values, and χ _ARM values are the best indicators of the concentrations of these elements associated with traffic emissions in this study area. In addition, S _{−100 mT} ratios significantly correlate positively with Se, Sc, Pb, Cu, Zn, Mo, and S whereas F _{300 mT} ratios only correlate positively with Pt and negatively with Fe. These results confirm the suitability of different magnetic properties for characterizing the concentrations of heavy metals, S, and Br in Xuzhou urban topsoil.     

Mineralogy, geochemistry and stratigraphy of the Maslovsky Pt–Cu–Ni sulfide deposit, Noril’sk Region, Russia

We report new data on the stratigraphy, mineralogy and geochemistry of the rocks and ores of the Maslovsky Pt–Cu–Ni sulfide deposit which is thought to be the southwestern extension of the Noril’sk 1 intrusion. Variations in the Ta/Nb ratio of the gabbro-dolerites hosting the sulfide mineralization and the compositions of their pyroxene and olivine indicate that these rocks were produced by two discrete magmatic pulses, which gave rise to the Northern and Southern Maslovsky intrusions that together host the Maslovsky deposit. The Northern intrusion is located inside the Tungusska sandstones and basalt of the Ivakinsky Formation. The Southern intrusion cuts through all of the lower units of the Siberian Trap tuff-lavas, including the Lower Nadezhdinsky Formation; demonstrating that the ore-bearing intrusions of the Noril’sk Complex post-date that unit. Rocks in both intrusions have low TiO₂ and elevated MgO contents (average mean TiO₂ <1 and MgO?=?12?wt.%) that are more primitive than the lavas of the Upper Formations of the Siberian Traps which suggests that the ore-bearing intrusions result from a separate magmatic event. Unusually high concentrations of both HREE (Dy+Yb+Er+Lu) and Y (up to 1.2 and 2.1?ppm, respectively) occur in olivines (Fo_79.5 and 0.25% NiO) from picritic and taxitic gabbro-dolerites with disseminated sulfide mineralization. Thus accumulation of HREE, Y and Ni in the melts is correlated with the mineral potential of the intrusions. The TiO₂ concentration in pyroxene has a strong negative correlation with the Mg# of both host mineral and Mg# of host rock. Sulfides from the Northern Maslovsky intrusion are predominantly chalcopyrite–pyrrhotite–pentlandite with subordinate and minor amounts of cubanite, bornite and millerite and a diverse assemblage of rare precious metal minerals including native metals (Au, Ag and Pd), Sn–Pd–Pt–Bi–Pb compounds and Fe–Pt alloys. Sulfides from the Southern Maslovsky intrusion have δ ³⁴S?=?5–6‰ up to 10.8‰ in two samples whereas the country rock basalt have δ ³⁴S?=?3–4‰, implying there was no in situ assimilation of surrounding rocks by magmas.     

Genetic Environment of the Intrusion-related Yuryang Au-Te Deposit in the Cheonan Metallogenic Province, Korea

Abstract. The Yuryang gold deposit, comprising a Te‐bearing Au‐Ag vein mineralization, is located in the Cheonan area of the Republic of Korea. The deposit is hosted in Precambrian gneiss and closely related to pegmatite. The mineralized veins display massive quartz textures, with weak alteration adjacent to the veins. The ore mineralization is simple, with a low Ag/Au ratio of 1.5:1, due to the paucity of Ag‐phases. Ore mineralization took place in two different mineral assemblages with paragenetic time; early Fe‐sulfide mineralization and late Fe‐sulfide and Au‐Te mineralization. The early Fe‐sulfide mineralization (pyrite + sphalerite) occurred typically along the vein margins, and the subsequent Au‐Te mineralization is characterized by fracture fillings of galena, sphalerite, pyrrhotite, Te‐bearing minerals (petzite, altaite, hessite and Bi‐Te mineral) and electrum. Fluid inclusions characteristically contain CO₂ and can be classified into four types (Ia, Ib, IIa and IIb) according to the phase behavior. The pressure corrected temperatures (≥500d?C) indicate that the deposit was formed at a distinctively high temperature from fluids with moderate to low salinity (<12 wt% equiv. NaCl) and CH₄ (1?22 mole %). The sphalerite geo‐barometry yield an estimated pressure about 3.5 ?2.1 kbar. The dominant ore‐deposition mechanisms were CO₂ effervescence and concomitant H₂S volatilization, which triggered sulfidation and gold mineralization. The measured and calculated isotopic compositions of fluids (δ¹⁸O_H2^O = 10.3 to 12.4 %o; δD_H2^O = ‐52 to ‐77 %o) may indicate that the gold deposition originated from S‐type magmatic waters. The physicochemical conditions observed in the Yuryang gold deposit indicate that the Jurassic gold deposits in the Cheonan area, including the Yuryang gold deposit are compatible with deposition of the intrusion‐related Au‐Te veins from deeply sourced fluids generated by the late Jurassic Daebo magmatism.     

Stromeyerite and mckinstryite from the Godejord polymetallic sulphide deposit,central Norweigan Caledonides

The Cu-Ag-S minerals, stromeyerite and mckinstryite, have been found for the first time in a stratabound polymetallic pyritic deposit in the Caledonides of central Norway. The surface specimens examined contained approximately 0.5% Ag, 1.8% Cu, 15.0% Zn and over 10 g/t Au and showed the mineral association pyrite, sphalerite, chalcopyrite, galena, tennantite, bornite, Cu-Ag sulphides, covelline, native Au, a Cu-Sn sulphide, and a new mineral of composition Ag₅CuTeS₂. The Cu-Ag sulphides appear to be replacing preexisting sulphides, with the exception of pyrite and sphalerite. The nature of this replacement is discussed. Analyses, by microprobe, of the Cu-Ag-S phases are reported and compared with published data. The stromeyerite shows an average composition Cu_1.01Ag S, the mckinstryite Cu_0.77Ag_1.19S. Values are reported of the reflectance at 542 nm for both minerals. The data indicate that stromeyerite is optically positive with Rg: 30.7%, Rm: 27.3%, Rp: 25.8% while mckinstryite is negative with Rg: 32.5%, Rm: 31.9%, Rp: 27.6%.