Anomalous Trace Elements Contents in the Spetsugli Germanium Deposit (Pavlovka Brown Coal Deposit) Southern Primorye: Communication 1. Antimony

The first data are presented on large-scale Sb accumulation (up to 1175 ppm on a whole coal basis) in the Spetsugli (Special Coals) germanium deposit (Pavlovka brown coal deposit). The distribution of anomalous Sb contents is considered in the coal-bearing molasse section. The close correlation between Ge and Sb abundances in coals together with SEM data indicate an organic mode of Sb occurrence. Such a significant Sb accumulation was caused by the filtration of volcanogenic metalliferous solutions in molasse rocks during early diagenesis of organic matter in the Late Miocene. Extremely high contents and organic mode of Sb occurrence make it possible to consider Ge-bearing coals of the Pavlovka deposit not only as a complex raw material suitable for the extraction of Sb, but also as a potential source of ecological hazard.     

Ge-bearing coals of the Luzanovka Graben, Pavlovka brown coal deposit, southern Primorye

Results of the study of a new Ge-bearing area of the Pavlovka brown coal deposit are presented. Ge is accumulated in bed III₂ lying at the bottom of the Late Paleogene-Early Neogene coal-bearing sequence adjacent to the Middle Paleozoic granite basement. The Ge content in coals and coal-bearing rocks varies in different sections from 10 to 200–250 ppm, reaching up to 500–600 ppm in the highest-grade lower part of the bed. The metalliferous area reveals a geochemical zoning: complex Ge-Mo-W anomalies subsequently grades along the depth and strike into Mo-W and W anomalies. Orebodies, like those at many Ge-bearing coal deposits, are concentric in plan and dome-shaped in cross-section. Coals in their central parts, in addition to Ge, W, and Mo, are enriched in U, As, Be, Ag, and Au. Distribution of Ge and other trace elements in the metalliferous sequence and products of gravity separation of Ge-bearing coals is studied. These data indicate that most elements (W, Mo, U, As, Be) concentrated like Ge in the Ge-bearing bed relative to background values are restricted to the organic matter of coals. The electron microscopic study shows that Ge-bearing coals contain native metals and intermetallic compounds in association with carbonates, sulfides, and halogenides. Coal inclusions in the metalliferous and barren areas of the molasse section strongly differ in contents of Ge and associated trace elements. Ge was accumulated in the coals in the course of the interaction of ascending metalliferous solutions with organic matter of the buried peat bogs in Late Miocene. The solutions were presumably represented by N₂-bearing thermal waters (contaminated by volcanogenic CO₂) that are typical of granite terranes.     

Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.     

Zinc–germanium ores of the Tres Marias Mine,Chihuahua, Mexico

The Tres Marias carbonate-hosted Zn–Ge deposit in Chihuahua, Mexico contains sphalerite with the highest average Ge (960 ppm) and willemite with the highest reported Ge contents of Mississippi-Valley-type (MVT) deposits worldwide. This has prompted current exploration efforts to focus on the deposit as a high-grade source of germanium. The sulfide-rich ore type (>125,000 t at 20% Zn and 250 g/t Ge) contains Fe-rich botryoidal sphalerite (type I) associated with solid hydrocarbons. This type exhibits distinctive intimately intergrown lamellar texture of high-Fe sphalerite (average 9.9 wt.% Fe and 800 ppm Ge) and a somewhat less Fe-rich sphalerite phase (average 5.5 wt.% Fe and 470 ppm Ge). Reddish-brown banded sphalerite (type II, average 5.7 wt.% Fe and 1,320 ppm Ge) is subordinately followed by galena and pyrite. The sulfide-poor “oxidized” zinc ore (up to 50 wt.% Zn; 250 to 300 ppm Ge) is a fine-grained, often friable, alteration product of the sulfide ore and associated limestone and breccia host. While some areas are dominated by carbonates and sulfates, others are enriched in silicates such as hemimorphite and willemite. The gangue assemblage includes goethite, hematite, and amorphous silica or quartz. Minor wulfenite, greenockite, cinnabar, and descloizite also occur. Willemite occurs as interstitial replacement of sphalerite and fracture fillings in the oxidized ore and can be unusually rich in Pb (up to 2.0 wt.%) and Ge (up to 4,000 ppm). Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena by siliceous aqueous fluids. The Tres Marias deposit has hybrid characteristics consisting of a primary low-temperature MVT Ge-rich Zn–Pb sulfide ore body, overprinted by Ge-rich hemimorphite, willemite, and Fe oxide mineralization.     

Anomalous Concentrations of Rare Metal Elements, Rare-scattered (Dispersed) Elements and Rare Earth Elements in the Coal from Iqe Coalfield, Qinghai Province, China

Total of 23 bench samples were taken from the No. 7 Coal of Iqe Coalfield, Qinghai Province, China, following Chinese Standard Method GB/T 482-2008 (2008). These samples were analyzed by powder X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence (XRF). The results indicate that the No. 7 Coal belongs to a low rank (Ro,ran =0.659%) and high-ash coal (40.54%). Compared to common Chinese and world low-rank coals, the Iqe coal contains anomalous concentrations of rare metal elements, rare-scattered (dispersed) elements and rare earth elements. The highest contents of Rb, Cs, Ga and REY reach to 180, 26, 37, and 397 ppm, respectively. Their average contents of these elements are 10.9, 15, 4.8 and 3.5 times higher than those of world coals, respectively. Minerals in the coal include kaolinite, quartz, muscovite, siderite, and traces of rutile, and brookite. Kaolinite could be main host minerals of Rb, Cs, Ga and REY. The anomalous rare element Rb and Cs accumulation in the Iqe coal is related to both organic and inorganic matter. The REY concentrations may be related to circulation of thermal solutions, contained or sorbed by clayey particles, and organic matter as well.     

Geochemistry of beryllium in Bulgarian coals

The beryllium content of about 3000 samples (coal, coaly shales, partings, coal lithotypes, and isolated coalified woods) from 16 Bulgarian coal deposits was determined by atomic emission spectrography. Mean Be concentrations in coal show great variability: from 0.9 to 35 ppm for the deposits studied. There was no clear-cut relationship between Be content and rank. The following mean and confidence interval Be values were measured: lignites, 2.6 ± 0.8 ppm; sub-bituminous coals, 8.2 ± 3.3 ppm; bituminous coals, 3.0 ± 1.2 ppm; and anthracites, 19 ± 9.0 ppm. The Be contents in coal and coaly shales for all deposits correlated positively suggesting a common source of the element. Many samples of the coal lithotypes vitrain and xylain proved to be richer in Be than the hosting whole coal samples as compared on ash basis. Up to tenfold increase in Be levels was routinely recorded in fusain. The ash of all isolated coalified woods was found to contain 1.1 to 50 times higher Be content relative to its global median value for coal inclusions.Indirect evidence shows that Be occurs in both organic and inorganic forms. Beryllium is predominantly organically bound in deposits with enhanced Be content, whereas the inorganic form prevails in deposits whose Be concentration approximates Clarke values.The enrichment in Be exceeding the coal Clarke value 2.4 to 14.5 times in some of the Bulgarian deposits is attributed to subsynchronous at the time of coal deposition hydrothermal and volcanic activity.     

Geochemistry, mineralogy, and technological properties of the main Stephanian (Carboniferous) coal seams from the Puertollano Basin, Spain

This study is focused on the occurrence and distribution of mineral matter and major and trace elements in the high volatile bituminous coal from Puertollano (south-central Spain). The relationship between ash behaviour and inorganic composition, as well as the possible formation of fouling and slagging deposits in boilers during the conversion process, were investigated. The Puertollano coals do not exhibit plastic properties, despite their rank, probably because of their high ash and inertinite contents.The Puertollano coal has medium to low total S content (0.48% to 1.63% db, with a mean of 1.0% db) and is characterised by relatively high contents of Si, Pb, Sb, and Cs. Some elements such as As, Cd, Co, Cr, Cu, Ge, Li, Mn, Ni, W, and Zn are also present in relatively high contents. The enrichment in a number of heavy metals could be attributed to the common sulphide ores occurring near the Puertollano coal deposit.The following trace elements affinities are deduced: (a) sulphide affinity: As, Co, Cd, Cu, Ni, Sb, Tl, and Zn; (b) aluminum–silicate affinity: K, Ti, B, Co, Cr, Cs, Cu Ga, Hf, Li, Nb, Rb, Sn, Ta, Th, V, Zr, and LREE; (c) Carbonate affinity: Ca, Mg, Mn, and B; (d) organic affinity: B.The very high Si levels and the anomalous enrichment in Cs, Ge, Pb, Sb, and Zn shown by the Puertollano coals account for the high contents of these elements in the Puertollano fly ash when compared with the other Spanish coal fly ashes.The chemical composition of the high temperature ash (HTA) is consistent with the trend shown by the ash fusion temperatures (AFT) and also with the predictive indices related to slagging and fouling propensities. Thus, the ash fusion temperatures increase with high values of Al₂O₃ as well as with the decrease in Fe₂O₃, CaO, and MgO.     

小兴安岭鹿鸣大型钼矿LA-ICP-MS锆石U-Pb和辉钼矿Re-Os年龄及其地质意义

鹿鸣钼矿是小兴安岭地区于近年发现的大型斑岩型钼矿床。为探讨研究区成岩成矿关系及其地质意义,在对矿化特征分析的基础上,采用LA-ICP-MS锆石U-Pb技术对鹿鸣地区含矿二长花岗岩测年,获得成岩年龄为 (187.1±1.2) Ma (n=15, MSWD=0.70) 。通过辉钼矿样品Re-Os同位素分析,获得等值线年龄为(177.4±3.5) Ma (n=11, MSWD=0.71) ,加权平均年龄为(178.08±0.79) Ma (n=11,MSWD=0.46)。两种方法获得的年龄大致相近,表明它们形成于同一成岩成矿系统。鹿鸣钼矿成岩成矿年龄,与乌奴格吐山铜钼矿、兰家沟钼矿和杨家杖子钼矿等矿床辉钼矿Re-Os同位素年龄相近,表明包括小兴安岭地区在内的我国东北地区广泛存在早侏罗世岩浆-成矿作用。微量元素和同位素指纹显示,鹿鸣钼矿形成于地壳挤压向拉伸转换的构造环境,成矿物质为壳幔混合来源。     

四川雪宝顶W-Sn-Be矿床中矿物化学组成及矿床成因

雪宝顶矿床位于四川省的松潘甘孜造山带中,以出产大颗粒含W-Sn-Be-F-P的矿物而闻名,前人对该矿床已经开展了大量的研究,但缺乏对粗粒矿物的主次痕量元素研究.本次研究采用X射线荧光光谱(XRF)、电子探针(EMPA)和电感耦合等离子体质谱(ICP-MS)技术对矿床中各矿物的主次痕量元素进行测试分析.结果显示,雪宝顶矿...     

Uranium-thorium systematics of two Canadian coals

A detailed study of U-Th distribution in two Lower Cretaceous coals in Canada shows that for these coals formed in a continental fluvial and deltaic environment with no marine influence, the U contents are in the range 0.07–7.5 ppm with Th in the range 0.3–11.0 ppm. Average Th/U ratios are near 2 which indicates slight uranium enrichment. The environments of the two coals show different degrees of weathering (montmorillonite-illite and kaolin-gibbsite) and U values are lowest in the more weathered environment In sedimentary profiles associated with the coals, the maximum uranium values are not in the coals but in carbonaceoss clay sediments above and below coal seams. Uranium distribution patterns can be correlated cith Ni, Cu, Rb, Pb, Sr, and Zr, indicating contributions from heavy minerals plus more mobile species (possibly simple organic compounds) which are adsorbed or bonded onto claysor organic matter.     

乌兰图嘎超大型锗矿床含锗煤的矿物学

内蒙古乌兰图嘎锗矿是我国近年来发现的产在煤层中的超大型锗矿床,锗金属储量达1600 t。以乌兰图嘎超大型锗矿床的含锗煤为研究对象,利用X射线衍射(XRD)、带能谱的扫描电镜(SEM-EDX)和电子探针(EPMA)详细研究了乌兰图嘎含锗煤及其同时代的红旗煤矿无矿煤的矿物学特征。分析结果表明,乌兰图嘎含锗煤中的主要矿物包括石英、蒙脱石;次要矿物包括长石、高岭石、伊利石;另含少量三水铝石、角闪石、叶蜡石、石膏、绿泥石、锐钛矿、黄铁矿、方解石、白云石和草酸钙石;微量的锆石、闪锌矿、白钨矿、重晶石、黄铜矿、卤化物、磷酸盐以及含Pb、Bi、Cr、As和Sb矿物。未发现含锗矿物。推测含锗煤中的锗可能主要呈有机结合,而Ba、Zn、Ti、W、Pb、Bi、Cr、Fe、As、Zr、Sb、Cu和REE可能主要与矿物相结合。此外,首次在乌兰图嘎含锗煤及红旗煤矿无矿煤中发现含银颗粒或自然银,推测胜利煤田的褐煤可能有相当规模的Ag矿化。     

内蒙古潮水盆地西部侏罗系煤的岩石学、矿物学及地球化学特征

潮水盆地位于内蒙古西南部和甘肃省东部地区,是我国中新生代含煤断陷盆地.采用粉晶X衍射、ICP-MS、ICP-AES 方法,从煤的岩石学、煤化学及煤地球化学的理论出发,对潮水盆地西部煤样进行了煤化学、显微组分、矿物学及地球化学分析.其研究结果表明潮水盆地西部煤以中等水分、低一中灰分和硫质量分数、高挥发分产率为特征,煤级为烟煤—亚烟煤;煤中有机显微组分以镜质组为主,惰性组次之,煤相类型以潮湿森林沼泽相为主,其次为较浅覆水森林沼泽相;煤中的常量矿物以石英和高岭石为主,部分样品中含有黄铁矿、方解石、菱铁矿和少量的微斜长石;煤中除Sr、B和Cs质量分数相对较高外,其他微量元素质量分数普遍较低.Cr、Ga、Pb、Li、Cu、Ge、V、Sc、Be、W、Th和As,以及Ti和Nb主要与硅铝酸盐矿物有好的亲和性;B和Sr可能主要以碳酸盐矿物的形式存在;S和Mo可能主要以硫化物矿物的形式存在;另外,Ti、Zr、Nb和Ta有好的相关性,可能与重矿物有关.     

赣南草桃背铀矿床中绿泥石地球化学特征及成矿指示意义

赣南草桃背铀矿床位于会昌地区河草坑铀矿田,是一个大型火山岩容矿的铀矿床,成因机制存在较大争议。矿床内发育有大面积的花岗岩和火山岩,矿体主要赋存在火山隐爆角砾岩和震碎花岗岩中。文章以该矿床内花岗岩、火山岩及矿石中广泛发育的蚀变矿物绿泥石为研究对象,采用电子探针及LA-ICP-MS原位微区分析技术对其矿物化学组成进行分析。分析结果表明,花岗岩和矿石中的绿泥石主要为富铁的鲕绿泥石和蠕绿泥石,火山岩中的绿泥石则为相对富镁的密绿泥石。各类绿泥石阳离子置换关系主要以Fe、Mg置换为主,同时存在一定的Tschermak（TK）和二八—三八面体（DT）替换机制。矿石中绿泥石具有相对较高含量的Ti、Li、Be、B、Zn、Ga、Ge、Sn、Cs、U、Rb和Ba等元素,并显示出较低的Th/U比值。矿石中绿泥石的结晶温度区间为201~269℃,平均值为242℃,属于中低温热液作用的产物。矿石中绿泥石的氧逸度（log f O₂）变化于-48.4~-41.2之间,平均值为-44.5,硫逸度（log f S₂）变化于-7.5~+2.8之间,平均值为-1.8,草桃背铀矿床的铀矿化主要形成于低氧逸度、高硫逸度的环境。     

山西平朔安太堡露天矿9号煤层中的微量元素

使用ＩＣＰ－ＡＥＳ方法对安太堡露天矿９号煤层中的微量元素进行了系统测定,检测出５３种微量元素,将研究煤样的平均微量元素质量分数与世界范围微量元素平均质量分数相比较,煤样中Ｌｉ,Ｇａ,Ｓｒ,Ｚｒ,Ｎｂ,Ｓｎ和Ｔａ具有较高的富集,而Ｃｒ,Ｃｏ,Ｎｉ,Ｇｅ,Ｒｂ,Ｙ,Ｃｓ和Ｂａ具有较低的富集,研究资料表明不同微量元素在垂向剖面上其质量分数具有不同的分布特征。经相关分析表明：（１）与镜质组含量相关的元素有     

Geochemical and Sr-Nd-Pb isotopic characteristics of Late Cenozoic leucite lamproites from the East European Alpine belt (Macedonia and Yugoslavia)

In the East European Alpine belt, leucite-sanidine-phlogopite-olivine-bearing volcanic rocks of Late Cenozoic age occur at eight localities within the Vardar suture zone and at one locality in the Southern Carpathian fold-and-thrust belt. Most of these volcanics are characterized by high Mg# (66.6–78.6), high abundances of Ni (117–373 ppm) and Cr (144–445 ppm) as well as high primary K₂O contents (5.63–7.01 %) and K₂O/Na₂O values (1.93–4.91). Rocks with more differentiated compositions are rare. A lamproite affinity of these rocks is apparent from their relatively low contents of Al₂O₃ (9.9–14.3 wt%) and CaO (6.2–8.3 wt%) in combination with high abundances of Rb (85–967 ppm), Ba (1,027–4,189 ppm), Th (18.9–76.5 ppm), Pb (19–54 ppm), Sr (774–1,712 ppm) and F (0.16–0.52 wt%), and the general lack of plagioclase. Although eruption of the magmas took place in post-collisional extensional settings, significant depletions of Nb and Ta relative to Th and La, low TiO₂ contents (0.92–2.17 %), low ratios of Rb/Cs, K/Rb and Ce/Pb as well as high ratios of Ba/La and Ba/Th suggest close genetic relationships to subduction zone processes. Whereas Sr and Nd isotope ratios show relatively large variations (⁸⁷Sr/⁸⁶Sr = 0.7078–0.7105, ¹⁴³Nd/¹⁴⁴Nd = 0.51242–0.51215), Pb isotope ratios display a very restricted range with ²⁰⁶Pb/²⁰⁴Pb = 18.68–18.88 and variable but generally high 7/4 (11–18) and 8/4 (65–95) values. The observed petrographic, geochemical and isotopic characteristics are best explained by a genetic model involving preferential melting of phlogopite-rich veins in an originally depleted lithospheric mantle source, whereby the metasomatic enrichment of the mantle source is tentatively related to the addition of components from subducted sediments during consumption of Tethyan oceanic lithosphere.Editorial responsibility: J. Hoefs     

Petrological,geochemical, and mineralogical compositions of the low-Ge coals from the Shengli Coalfield,China: A comparative study with Ge-rich coals and a formation model for coal-hosted Ge ore deposit

To better understand the formation mechanism of coal-hosted Ge ore deposits, this paper reports on the petrological, mineralogical, and geochemical compositions of the low-Ge coals in the Shengli Coalfield (Inner Mongolia, China), using optical microscopy, field emission-scanning electron microscopy, X-ray fluorescence, X-ray diffraction, and inductively coupled plasma mass spectrometry. The samples in the present study closely neighbor the previously-reported Wulantuga coal-hosted Ge ore deposit (both No. 6 Coal). In comparison with the Wulantuga Ge-rich coals, the low-Ge coals of the Shengli field display higher moisture (27.59% on average) and lower pyritic sulfur contents (0.53%). Both the low-Ge and Ge-rich coals are generally high in inertinite, and have varying but relatively low huminite contents. Preservation of fecal pellets as macrinite is notable in both the low-Ge and Ge-rich coals, and the position of the fecal pellets appears to be within tunnels or chambers within the wood. Quartz, kaolinite, pyrite, and gypsum are the major crystalline phases identified in most of the Ge-rich and low-Ge coals, but the low-Ge coals contain significantly less pyrite and are more abundant in non-mineral Ca and Mg. Ca-oxalate of authigenic origin is observed, generally occurring as cell-fillings in the low-Ge coals. Otherwise mineral-free organic matter in the low-Ge coals would be expected to have an inherent ash yield of around 6%, derived from the inorganic elements (mainly non-mineral Ca and Mg) that occur either in the organic matter or as dissolved ions in the pore water and form the sulfate species in low-temperature (oxygen-plasma) ash residues. The highly-elevated trace elements, including Be, Ge, As, Sb, W, Hg, and Tl, that occur in the Ge-rich coals of the Wulantuga deposit, are significantly depleted in the low-Ge coals. Lateral migration of Ge–W- and As–Hg–Sb–Tl-rich solutions through the original peat swamp for the Wulantuga Ge ore deposit has led to significant enrichment of Ge on the margin of the coal basin but decreasing Ge concentrations toward to the inner part of the basin. Such a migration direction is different to those in the previously-reported for the hydrothermal solutions in the Lincang (Yunnan of China) and Spetzugli (Russian Far East) Ge ore deposits, where the solutions migrated vertically from granite to peat along faults and led to a dome-shaped Ge distribution in the relevant coal seam.     

贵州戈塘金矿萤石微量元素特征及钐—钕测年

对与戈塘金矿共生的萤石微量元素特征研究表明:萤石中Mo,W,As,Cd,Bi等高温元素含量均高于地壳值,V,Cr,Cu,Cs,Th,Mo,Ga和Ge等元素变异系数大,活化能力强。萤石的稀土总量很低,仅为10.299×10-6～17.455×10-6,明显富集重稀土(LREE/HREE为0.48～0.69),并具有Eu和Ce的负异常(δEu为0.71～0.91,δCe为0.62～0.78),Tb/Ca-Tb/La图解显示萤石为热液成因且为热液的晚期阶段。萤石的Rb/Sr比值和初始87Sr/86Sr比值均与地幔值较为接近,反映出其成矿流体主要来源于上地幔或(岩浆)深部。萤石的形成经历了长期演化的热液活动,成矿温度较低(<200°～250°),成矿年龄为(35.83±0.37)Ma(Sm-Nd等时线年龄)。     

Extreme variations in strontium initial ratios in ore-related fluids

Magmato-hydrothermal cassiterite-topaz ore at the Carboniferous East Kemptville (EK) greisenhosted tin deposit (Nova Scotia, Canada) is cross-cut by veins containing apatite, triplite, vivianite and fluorite. Initial ⁸⁷Sr/⁸⁶Sr ratios of these minerals have an extreme range (0.7135 to 0.8284). The initial ratios of the host rocks, EK quartz-topaz rock and Davis Lake biotite monzogranite (0.729±0.001, 0.727±0.004), are also high. The adjacent Meguma Group metasedimentary rocks are more typical of crustal material (0.712–0.719 at 330 Ma). Rb and Sr contents of EK fluorite (max.: 13.0, 1420 ppm) and apatite (max.: 88.1, 6660 ppm) are unusually high and variable. Unexpectedly, high Sr contents correlate positively with the high initial ⁸⁷Sr/⁸⁶Sr ratios. Fluorite and phosphate minerals from the first set of post-greisen veins at East Kemptville reflect the unusual chemistry of a high ⁸⁷Sr/⁸⁶Sr fluid present in the deposit after ore formation. The most extreme composition of this fluid was characterized by ⁸⁷Sr/⁸⁶Sr>0.8284, high Rb/Sr, high P, Rb, Cu, Zn and Fe contents, but low abundances of Ca, Pb and Sn with respect to the Davis Lake monzogranite. Such a fluid could have been derived from the greisen fluid and modified by reaction with the overlying Meguma metawacke. A second alternative, which cannot be well constrained at present, is that an extremely radiogenic fluid entered the deposit after ore formation and mixed with the postore fluid. In either case, the modified fluid subsequently mixed with meteoric water and precipitated the minerals with much lower ⁸⁷Sr/⁸⁶Sr ratios and Rb and Sr contents.     

White mica trace element and boron isotope evidence for distinctive infiltration events during exhumation of deeply subducted continental crust

ABSTRACT

Previous study of subducted continental crust within the Luliang Shan terrane in Northwest China has documented metasomatic formation of thick, hydrated phengite + garnet-rich selvages at the interface between mafic eclogite blocks and quartzofeldspathic host gneiss. Whole rock concentrations of Cs and Ba within the selvage are enriched by two orders of magnitude relative to the eclogite blocks and host gneiss. We performed in situ ion microprobe analyses of Li, Be, B, Rb, Sr, Cs and Ba and δ¹¹B of phengite within the Luliang Shane terrane to better constrain the source(s) of the infiltrating fluid. The phengite within the selvage are enriched in Li, Cs and Ba and yield δ¹¹B values between ?30‰ and ?9‰, values that are lower than mantle values. High Ba/Rb, Cs/Rb coupled with low B/Be, B/Li and highly negative δ¹¹B values indicate that the high-pressure fluid that formed the selvage was derived from highly devolatilized rocks within the subduction channel. In contrast, muscovite, which crystallized in the adjacent host gneiss during a subsequent lower pressure phase of fluid infiltration at approximately 0.9 GPa depths, has much lower Li, Cs and Ba relative to the high-pressure phengite. These retrograde muscovite have very high concentrations of B (up to 5500 ppm) and Be (up to 50 ppm) and high (?2 to +8‰) δ¹¹B values that are consistent with crystallization from a fluid derived from shallower and less devolatilized regions of the subduction zone. Additional host gneiss samples, regionally distributed and kilometres away from the studied area lack the B-rich signature and indicate that the late stage fluids were likely localized to the region near the studied traverse.