Rare Earth Element Behaviour in the Wunugetushan Copper – Molybdenum Deposit,Inner Mongolia,and Its Implications1

Abstract Considering porphyry and wall rocks as a whole system, the behaviour of rare earth elements (REE) in hydro thermal alteration and mineralization of the exceedingly large Wunugetushan porphyry Cu-Mo deposit of Inner Mongolia has been studied. It has been found for the first time that there exists complementary REE variation in hydrothermal alteration between porphyry and wall rocks, and Eu depletion has certain significance in indicating mineralization. Based on an analysis of the variation in REE contents of relevant minerals during the hydrothermal alteration, the ore-forming fluids are inferred to be depleted in ∑REE, comparatively enriched in ∑Y and strongly depleted in Eu. In the intermediate-strong alteration zones, porphyry and wall rock took part in hydrothermal metasomatism and alteration almost in equal ratio mass. Furthermore, studies of REE and hydrogen and oxygen isotopes and fluid inclusions confirm the existence of hydrothermal convection and the possibility of supplying part of ore materials by the wall rock and indicate that the application of REE geochemistry in mineral prospecting is promising.     

河北省木吉村铜(钼)矿床蚀变分带过程中元素迁移定量分析

为了研究木吉村斑岩型铜(钼)矿床蚀变过程中元素的迁移规律,拟推流体演化规律,笔者通过对赋矿闪长玢岩体的强硅化带、钾长石化带、石英绢云母化带、青磐岩化带中分别取样测试分析,利用Grant方程定量探讨了各蚀变带围岩中主量元素、稀土元素和微量元素的带入、带出特征,结果表明:岩浆初始热液流体富K而贫Na。相对原岩(蚀变弱的青磐岩化带),在各蚀变带中Fe_2O_3、MgO、P_2O_5和TiO_2从深部强硅化带到浅部石英绢云母化带总体上由带出变为带入,SiO_2、MnO则与上述大体相反,FeO在各蚀变带主体为带出元素。各稀土元素从深部向浅部石英绢云母化带带入特征明显,同时各蚀变带在稀土元素球粒陨石标准化曲线上表现出斜率一致的右倾型特征,说明轻重稀土分馏较明显,轻稀土富集,重稀土亏损。Cu和Mo在石英绢云母化带中富集尤为明显,其次在钾长石化带也明显富集,即海拔400~500 m为主要的Cu、Mo富集区。     

新疆阿尔泰可可托海3号伟晶岩脉研究

新疆阿尔泰可可托海3号伟晶岩脉具有非常完美的结构分带,从边部到核心可以划分出9个共生结构带.本文主要利用前人资料,从该伟晶岩脉的主元素、造岩矿物以及包裹体等角度对各结构带进行了研究,探讨了稀土元素在各带中的分布模式以及演化特征,并对3号岩脉的岩浆~岩浆热液演化阶段和地球化学阶段的划分作了修改.     

The behaviour of trace and rare earth elements (REE) during hydrothermal alteration in the Rangan area (Central Iran)

The rhyolitic dome in the Rangan area has been subjected to hydrothermal alterations by two different systems, (1) A fossil magmatic–hydrothermal system with a powerful thermal engine of a deep monzodioritic magma, (2) An active hydrothermal system dominated by meteoric water. Based on mineralogical and geochemical studies, three different alteration facies have been identified (phyllic, advanced argillic and silicic) with notable differences in REE and other trace elements behaviour. In the phyllic alteration zone with assemblage minerals such as sericite, pyrite, quartz, kaolinite, LREE are relatively depleted whereas HREE are enriched. The advanced argillic zone is identified by the presence of alunite–jarosite and pyrophyllite as well as immobility of LREE and depletion in HREE. In the silicic zone, most of LREE are depleted but HREE patterns are unchanged compared to their fresh rock equivalents. All the REE fractionation ratios (La/Yb)_cn, (La/Sm)_cn, (Tb/Yb)_cn, (Ce/Ce¹)_cn and (Eu/Eu¹)_cn are low in the phyllic altered facies. (Eu/Eu¹)_cn in both advanced and silicic facies is low too. In all alteration zones, high field strength elements (HFSE) (e.g. Ti, Zr, Nb) are depleted whereas transition elements (e.g. V, Cr, Co, Ni, Fe) are enriched. Geochemically speaking, trace and rare earth elements behave highly selective in different facies.     

Mineralogy,geochemistry, and structural controls of a disseminated gold-bearing alteration halo around the schist-hosted Bullendale orogenic gold deposit,New Zealand

Orogenic gold-bearing quartz veins in the middle Tertiary Bullendale Fault Zone, New Zealand were mined historically for coarse gold in a narrow zone (ca. 5 m thick). However, recent drilling has revealed a broad hydrothermal alteration zone extending into the host schist, in which disseminated sulphide and gold mineralisation has occurred. The evidence of alteration is first seen over 150 m across strike from the fault zone, and the best-developed alteration halo is about 50 m wide. The extent and intensity of alteration is strongly controlled by local structures that developed during regional Tertiary kink folding of the pervasively foliated and fissile metasedimentary schist host. The earliest structures are foliation-parallel microshears (micron to millimeter scale) formed during flexural-slip folding. Later, but related, structures are predominantly normal faults and associated shear zones that have formed extensional sites during the regional folding event. All these structures facilitated hydrothermal fluid penetration and rock alteration, with localised vein formation and brecciation. Where fluid has followed structures, metamorphic chlorite, phengite, and titanite have been altered to hydrothermal ankerite, rutile, and muscovite or kaolinite. Ankerite with Fe/(Fe + Mg) < 0.4 formed in host rocks with Fe/(Fe + Mg) of 0.6, and iron released by ankerite alteration possibly formed pyrite and arsenopyrite that host disseminated gold. Fault zones were extensively silicified and veined with quartz, albite, sulphides, and gold. Host rocks have wide compositional variations because of centimeter-scale metamorphic segregation. However, the alteration halo is characterised by elevated CO₂ and S, as measured by loss-on-ignition (doubled to ca. 6 wt.%), elevated As (100–10,000 ppm), and weakly elevated Sb (up to 14 ppm). Strontium is elevated and Ba depleted in many altered rocks, so Sr/Ba ratio increases from < 1 (host rocks) to > 3 in the most altered and silicified rocks. Many altered and mineralised rocks have low Sr/Ba (< 0.5) as well. The subtle geochemical signature is not useful as a vector to ore because of the strong microstructural control on alteration. Likewise, there is no evidence for spatial mineralogical zonation across the alteration halo, although the most intense alteration is centred on the main fault zone, and intensity of alteration is controlled by microstructures at all scales. As documented in previous studies, hydrothermal alteration haloes enlarge the exploration target for some orogenic gold deposits, and may include disseminated gold, as in this Bullendale example.     

Staurolite-quartzite bands in kyanite quartzite at Big Rock,Rio Arriba County,New Mexico — A discussion

Schreyer and Chinner (1966) described staurolite-quartzite bands of unusual bulk chemical composition associated with the Big Rock kyanite deposit in northern New Mexico. They discussed two possible hypotheses-syngenetic or metasomatic-for the origin of the bands. This paper discusses additional evidence in support of the metasomatic hypothesis.Quartz-muscovite schist and quartz-kyanite rock are believed to be metarhyolite that was altered metasomatically by hydrothermal activity during metamorphism. Experimentally demonstrable reactions that involve ionic exchange equilibria between pore fluid and solid phases best explain the observed alteration. Staurolite-quartzite bands are postulated to be basalts or amphibolites that were hydrothermally altered in a manner analogous to alteration of the enclosing rocks. The process would deplete a basaltic parent rock in alkali and alkaline earth elements and produce a chemical composition similar to the bulk chemical composition of staurolite-quartzite.Schreyer and Chinner used textural evidence to prove that staurolite formed at the expense of chloritoid. Based on the chemical compositions of staurolite and relict chloritoid reported by them, several chemical equations were constructed, using the principle of ionic equilibria between pore fluid and solid phases, in an attempt to realistically portray the reaction. It is suggested that, under open-system metasomatic conditions, the ratio a_Mg+2/a_H+ in the supercritical aqueous fluid is an important parameter that controls the stability of chloritoid vs. staurolite.     

Genesis of the hydrothermal gold deposits in the Canan area,Lepaguare District,Honduras

The Canan area (Honduras) is characterized by a gold-bearing ore deposit that is associated with quartz-veined shear zones. Gold mineralization occurs in low-to medium-grade metamorphic host-rocks (graphitic and sericitic schists). Hydrothermal fluids, which are associated with the emplacement of Cretaceous-Tertiary granodioritic intrusions, are responsible for the formation of quartz veins and the hydrothermal alteration of wall-rocks. Three main altered zones have been detected in the wall-rocks as far as 150 cm from the quartz veins. The distal zone (up to 50-cm thick) contains quartz, chlorite and illite. The intermediate zone is the thickest (up to 80 cm) and is marked by quartz, muscovite, sulphides, kaolinite and native elements such as Au and Ag. The proximal zone, which is close to the quartz veins, is rather thin (up to 25 cm) and contains clay minerals, Al-oxides-hydroxides and sulphides. The transition from the distal to the proximal zone is accompanied by the enrichment of SiO₂ and the depletion of all other major elements, except for Fe₂O_3(tot). Precious metals occur in the highest concentrations in the intermediate zone (Au up to 7.6 ppm and Ag up to 11 ppm). We suggest that gold was transported as a reduced sulphur complex and was precipitated from the hydrothermal solution by the reaction of the sulphur complexes with Fe²⁺ from the alteration of the mafic minerals of the host-rock. Fluid–wall-rock interactions seem to be the main cause of gold mineralization. Genetic relationships with a strike-slip fault system, hydrothermal alteration zones within the metamorphic wall-rocks, and an entire set of geochemical anomalies are consistent with orogenic-type gold deposits of the epizonal class.     

Geochemical behavior of rare earth elements in hydrothermally altered rocks of the Kuroko mining area,Japan

In this study we analyzed the chemical composition of hydrothermally altered dacite and basalt from the Kuroko mining area, northeastern Honshu, Japan, by REE (rare earth element). Features of rare earth element analyses include: (1) altered footwall dacite exhibits a negative Eu anomaly compared with fresh dacite, suggesting preferential removal of Eu²⁺ from the altered dacite via hydrothermal solutions, (2) altered hangingwall dacite and basalt and dacite and basalt adjacent to ore deposits exhibit positive Eu anomalies compared with fresh dacite and basalt, suggesting addition of Eu²⁺ from hydrothermal solutions, (3) LREE ratio (∑LREE/∑REE) from altered dacite of chlorite–sericite zone and K-feldspar zone show a negative relationship with δ¹⁸O, and La/Sm ratios show a positive correlation with the K₂O index. These trends indicate the addition of light rare earth elements such as La to the altered dacite from hydrothermal solution and/or leaching of heavy rare earth elements such as Sm and Yb, (4) Principal component analysis (PCA) indicates that light rare earth elements enrichment is related to the formation of sericite zone near the Kuroko deposits but not to the formations of chlorite and K-feldspar zones, and (5) The correlations among REE features (LREE ratio, MREE ratio, HREE ratio, Eu/Eu?), δ¹⁸O and K₂O index are not found for montmorillonite zone, mixed layer clay mineral zone and mordenite zone. Therefore, it is inferred that sericite, chlorite and K-feldspar alterations are related to the Kuroko and vein-type mineralization, but montmorillonite and mordenite alterations are not related to the mineralizations, and probably they formed at the post-mineralization stage.     

The Late Neoproterozoic rift-related metarhyolite–basalt association of the Glushikha trough (Yenisei Ridge): petrogeochemical composition,age, and formation conditions

New data are presented on the petrogeochemical composition, age, and formation conditions of the Late Neoproterozoic metarhyolite–basalt association of the Glushikha trough (Yenisei Ridge). The association is localized within the subaerial and shallow-water terrigenous-carbonate sediments of the Orlovka Group, which overlies Proterozoic rocks with unconformity. The felsic volcanics are essentially potassic and enriched in Rb, U, Th, and Fe. They show a weakly fractionated REE pattern with a prominent negative Eu anomaly. The basalts and picrite basalts have higher contents of Ti, Fe, P, HFSE, REE, U, Th, Ba, and Sr, and their spidergrams show no Nb or Ta depletion with respect to Th and LREE. These rocks have the petrochemical parameters of intraplate magmatic associations in continental rift zones. New geochronological data (SHRIMP II) on single zircon grains from the felsite porphyry of the metarhyolite–basalt association (717 ± 15 Ma) indicate Late Neoproterozoic volcanism in the Yenisei part of the Central block of the Trans-Angara region. According to Sm–Nd isotopic data, the rhyolites originate from Paleoproterozoic crust (T_Nd(DM) = 1757 Ma; T_Nd(DM-2st) = 1651 Ma; ∑ _Nd(T) = ? 2.7). The Orlovka volcanosedimentary rocks are rift-related, as evidenced by the following facts: (1) localization of the volcanosedimentary rocks in a narrow fault-line trough; (2) bimodal rhyolite-basaltic composition of the volcanics; and (3) petrology and geochemistry of the picrite basalts and basalts, typical of intraplate environments. The studies show that Late Neoproterozoic rifting and intraplate plume magmatism took place not only in the Tatarka–Ishimba fault zone but also in the Yenisei fault zone of the Yenisei Ridge.     

Variation of the chemical composition of sediments under middle- and low-temperature hydrothermal conditions in the southern trough of Guaymas Basin,Gulf of California: Communication 2. Results of the study of grain size fractions of sediments

The chemical composition of grain size fractions of the Upper Pleistocene sediments in the southern trough of Guaymas Basin (Gulf of California) is studied based on materials from DSDP Hole 477 (191 m). The sediments are located in the upper part of the main long-lived hydrothermal system. Therefore, they were subjected to long-term reworking by the middle- and low-temperature solutions (100?300°C) and short-term hydrothermal impact during the intrusion of basalt sills. The upper part of the main hydrothermal system is divided into three middle- to low-temperature hydrothermal alteration zones: lower (III), middle (II), and upper (I). In zone III (250?300°C), hydrothermal alterations of sediments are most significant. The coarsegrained fractions are enriched in Fe, S, Ni, Cu, Zn, Mo, Co, Se, Cd, Bi, Pb, and Ag due to the formation of sulfides and precipitation of native metals. The silt fractions are enriched in Be, Sc, Nb, Ta, W, Th, U, Y, and REE. In contrast, the pelite fractions are depleted in most of these elements. The fine-dispersed (<0.001 mm) pelite fractions are appreciably enriched in Mg (due to the formation of the authigenic Mg-chlorite), as well as MnO, Cr, V, Ga, Pb, and Zr. Virtually all grain size fractions are depleted in K₂O, Li, Rb, Cs, and Tl due to the dissolution of the K-bearing terrigenous minerals. In zones II (146?170 m) and I (110?146 m), where the temperature of hydrothermal solutions dropped successively from 250 to 180?195 and 100°C, the sedimentary environment was unfavorable for the concentration of Fe, S, and a large group of ore elements that are typical for sediments in zone III. Intrusion of basalt sills and a short-term hydrothermal impact changed concentrations of several components in the sediments overlying the sill complex: CaO, K₂O, Li, Rb, Cs, and Tl acquired a trend typical of the high-temperature lower zone III, whereas Fe, MgO, P₂O₅, TiO₂, V, Sc, and Y distribution pattern became typical of the low-temperature upper zone I. Significant compositional variations in the grain size fractions of sediments are lacking beneath the sill base.     

相山铀矿田云际矿床碱交代型铀矿化蚀变作用及组分迁移规律研究

云际矿床是江西相山火山岩型铀矿田内最典型的碱交代型铀矿床,其矿体主要赋存于碎斑熔岩中。本文以两个典型矿化剖面为研究对象,系统研究了碱交代型铀矿化的蚀变分带特征、蚀变和矿石矿物组合以及热液蚀变过程中元素迁移变化规律。详细的岩相学观察表明,碱交代型铀矿化发育明显的侧向水平分带,由内到外可细分为矿化中心带、近矿强蚀变带、远矿蚀变带和新鲜围岩,各蚀变带之间并无明显的界线;发育的主要蚀变类型为钠长石化、赤铁矿化、碳酸盐化、绿泥石化和磷灰石化;铀赋存状态主要以独立铀矿物(钛铀矿和铀石为主)、类质同象和吸附状态3种形式存在。Isocon标准化图解法表明,从远矿弱蚀变带到矿化中心带,CaO、Na₂O、P₂O₅、MgO、TiO₂、Fe₂O₃、U、HREE、Sr、Cr、Co、Ni、Zr、Hf的迁入量呈逐渐升高的趋势,其中CaO、P₂O₅、MgO、U、Sr在矿化中心带表现为强烈的富集,而SiO₂、K₂O、LREE、Ba、Rb、Cs则呈明显的迁出趋势;各蚀变带均呈现Na₂O的大量富集和K₂O的极度贫化,且均不伴有钍富集和钼富集。矿石中显著升高的Y/Ho值、δEu值以及Fe₂O₃/(Fe₂O₃+FeO)值暗示碱交代铀成矿流体具有较高的氧逸度,可能为多来源流体混合形成的复杂成因流体;矿石中强烈的“去硅”作用、Zr的富集以及极高的Na⁺/K⁺值和Zf/Hf值表明碱交代成矿流体具有较高的碱度。综合岩相学、蚀变带元素迁移特征及前人研究成果,本文认为碱交代铀成矿流体在演化过程中呈现氧逸度、pH值和温度逐渐降低的趋势,流体中的铀可能主要以碳酸铀酰络合物的形式迁移,CO₂挥发分的大规模逸散可导致铀矿物和大量磷灰石、碳酸盐的共同沉淀富集并形成富大矿体;此外,铀磷络合物可能也是本矿床成矿流体中铀的赋存、迁移形式之一。

     

Subseafloor hydrothermal alteration during the Early Proterozoic at Garpenberg,Central Sweden

The Early Proterozoic sulfide deposit at Garpenberg is located in the metallogenetic province of central Sweden. It is a strata-bound massive sulfide deposit contained in a supracrustal sequence of mainly acid metavolcanic rocks. Stratiform Zn-Pb-Cu mineralization is underlain by Cu-bearing stockwork ore and an extensive alteration zone. The sulfide ores and their altered wall rocks were formed by subseafloor hydrothermal activity. The alteration pattern observed in the wall rocks of this deposit is consistent with a hydrothermal system where the fluid consists mainly of seawater and a high water/rock mass ratio predominates. The hydrothermal activity caused the destruction of the primary mineralogy, mainly feldspars, and a general redistribution of the chemical elements in the altered wall rocks which were principally depleted in Ca, Na and Eu and enriched in Mg. Eu was redeposited with the ore metals near or at the seafloor and Ca was deposited as limestone. Most of the major and trace elements show large mobility during the alteration; only Ti, Zr, Y and REE (excluding Eu) behaved as relatively immobile elements.     

Geochemistry of Trace Elements during Ore-Forming Processes in Yinshan Deposit

ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅＹｉｎｓｈａｎｄｅｐｏｓｉｔｉｎｔｈｅｎｏｒｔｈｅａｓｔｅｒｎＪｉａｎｇｘｉＰｒｏｖｉｎｃｅｏｆＣｈｉｎａｉｓａｌａｒｇｅ ｓｕｐｅｒｌａｒｇｅｐｏｌｙｍｅｔａｌｌｉｃＣｕ Ｚｎ Ｐｂ Ａｇ Ａｕｄｅ ｐｏｓｉｔ.Ｔｈｏｕｇｈｔｈｅｒｅａｒｅｍａｎｙｄｉｆｆｅｒｅｎｔａｒｇｕｍｅｎｔｓａｂｏｕｔｔｈｅｇｅｎｅｓｅｓｏｆｔｈｅｄｅｐｏｓｉｔ(Ｈａｏ ,1998;Ｚｈａｎｇ ,1997;ＪｉａｎｇｘｉＧｅｏ ｌｏｇｉｃＥｘｐｌｏｒａｔｉｏｎＢｕｒｅａｕ ,1996 ;Ｚｈａｎｇ ,1996 ;Ｈｕａ ,1987;Ｙ…     

罗河铁矿的硫同位素分馏机制和矿床形成的物理化学条件的研究

罗河铁矿(又称庐枞铁矿)是我国长江中下游火山岩地区大型铁矿床之一,是一种重要的矿床类型。十多年来,各研究单位和生产部门对该矿床进行了多方面、较系统的研究,取得可喜成果(张荣华等,1974;张荣华,1981;陈锦石等,1982)。然而,要进一步阐明这类矿床的成矿机理,还需要对该矿床的蚀变和成矿条件进行深入研究。本文着重讨论罗河铁矿的硫同位素分馏机制,并在此基础上结合地质和矿物包裹体的资料,近似定量地推算该矿床形成各阶段的物理化学条件范围及变化规律。     

Geochemical behavior during mineralization and alteration events in the Baiyinchang volcanic-hosted massive sulfide deposits,Gansu Province,China

The Zheyaoshan deposit is the largest within the Baiyinchang (BYC) volcanic-hosted massive sulfide (VHMS) district, located in the northern Qilian orogenic belt of North China. The deposit is hosted by quartz keratophyre tuffs, with wall-rock alteration mainly comprising chlorite, sericite, quartz, pyrite and epidote. Mineral assemblages within the altered host rocks can be divided into a sericite-quartz-dominant assemblage (sericite-silicified zone), a chlorite-dominant assemblage (chlorite-dominant zone) and a pyrite-dominant assemblage (mineralized zone) based on geochemical analysis and alteration characteristics. We have conducted detailed processing and critical analysis of the geochemical data of both the altered and least-altered host rocks in order to investigate the problem of closure in the geochemical dataset to eliminate the influence that each component has on the other in terms of mass change, and have applied the standardized method of the mass change calculation to analyze this data. The results show that: (1) the sericite-silicified zone formed along fissures due to the ingress of hydrothermal fluids, with MnO₂, Na₂O and CaO being mobilized into the hydrothermal fluids leached and MgO, Fe₂O₃, SiO₂, K₂O, BaO deposited. Additionally, Ag, Cu and chalcophile elements (Ag, As and Bi) were enriched while Pb, Zn and large ion lithophile elements (LILEs) (Cs, Sr, Eu, Be) were mobilized into hydrothermal fluids; (2) the physiochemical conditions and pH levels of the hydrothermal fluids changed during sericitization, with MgO, Fe₂O₃, BaO being further enriched and MnO, Na₂O, CaO further depleted, leading to formation of chlorite and the initial precipitation of metallogenic the (Cu, Zn, Pb) and chalcophile elements (Ag, As, Bi); (3) the negative Eu anomaly was mainly due to its strong activity when Eu is mobilized into the hydrothermal fluids during since plagioclase break-down during the sericite-silicification process; (4) AI and CCPI values gradually increase towards the orebody. The chlorite-dominant assemblage and sericite-quartz-dominant assemblage on the periphery of the chlorite-dominant zone can all be used as vectors towards the volcanic massive sulfide orebody and for regional-scale mineral exploration. Either leached elements or enriched elements can be considered as significant indicator elements and as prospective indicators for geochemical exploration within the BYC district. The Eu anomaly may be especially useful as an indicator for distinguishing the least-altered rocks which has great significance for exploration on the regional scale.     

GEOCHEMICAL KINETIC SIMULATION ON WALL—ROCK ALTERATION ZONING IN THE BAOBAN GOLD FIELD，SOUTH CHINA

The Baoban gold field,located in the area of Hainan Island ,South China ,bears three gold de-posits :Tuwaishan ,Baoban ,and Erjia ,which belong to the wall-rock alteration type.In terms of the petrography data,four alteration zones can be recognized from the ore-vein outwards(1)the silicification zone;(2)the sericitization zone;(3)the chloritization zone;and (4)the calcitization zone.The geochemical kinetic simulation was carried out on sericitization and chloritization .Results of the study showed that the formation of the alteration zones is connected with the properties of hydrothermal fluids:the initial concentration of Al (O H)3,the diffusion coefficient and the velocity of fluid flow.The alteration zones in this field are the result of multiple interaction between hydrothermal fluids and wall rocks.     

Platinum-group elements distribution and spinel composition in podiform chromitites and associated rocks from the upper mantle section of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco

The distribution of platinum-group elements (PGEs), together with spinel composition, of podiform chromitites and serpentinized peridotites were examined to elucidate the nature of the upper mantle of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco. The mantle section is dominated by harzburgite with less abundant dunite. Chromitite pods are also found as small lenses not exceeding a few meters in size. Almost all primary silicates have been altered, and chromian spinel is the only primary mineral that survived alteration. Chromian spinel of chromitites is less affected by hydrothermal alteration than that of mantle peridotites. All chromitite samples of the Bou Azzer ophiolite display a steep negative slope of PGE spidergrams, being enriched in Os, Ir and Ru, and extremely depleted in Pt and Pd. Harzburgites and dunites usually have intermediate to low PGE contents showing more or less unfractionated PGE patterns with conspicuous positive anomalies of Ru and Rh. Two types of magnetite veins in serpentinized peridotite, type I (fibrous) and type II (octahedral), have relatively low PGE contents, displaying a generally positive slope from Os to Pd in the former type, and positive slope from Os to Rh then negative from Rh to Pd in the latter type. These magnetite patterns demonstrate their early and late hydrothermal origin, respectively. Chromian spinel composition of chromitites, dunites and harzburgites reflects their highly depleted nature with little variations; the Cr# is, on average, 0.71, 0.68 and 0.71, respectively. The TiO₂ content is extremely low in chromian spinels, <0.10, of all rock types. The strong PGE fractionation of podiform chromitites and the high-Cr, low-Ti character of spinel of all rock types imply that the chromitites of the Bou Azzer ophiolite were formed either from a high-degree partial melting of primitive mantle, or from melting of already depleted mantle peridotites. This kind of melting is most easily accomplished in the supra-subduction zone environment, indicating a genetic link with supra-subduction zone magma, such as high-Mg andesite or arc tholeiite. This is a general feature in the Neoproterozoic upper mantle.     

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer,Greece

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ¹¹B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH₄ concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.     

Changes in geochemistry and mineralogy of thermally altered coal, Upper Hunter Valley, Australia

Igneous intrusions thermally and geochemically alter coal, commonly causing economic and safety problems for many coal mines. The effects of two dykes on the inorganic content of the Late Permian bituminous Upper Wynn seam were determined from analyses of 44 samples that were collected along transects approaching the intrusions. Petrographic and XRD data were used to determine sample mineralogy, and INAA and XRF spectrometry were utilised to determine the contents of 57 elements. The mineralogy of the unaltered coal, altered coal and dyke is dominated by carbonates, particularly dawsonite, which formed by epigenetic precipitation at a late stage, after thermal alteration. Ankerite and siderite are the products of thermal alteration and are restricted to the altered coal and dykes.Principal component analysis, correlations and compositional trends approaching the intrusions were used to subdivide the elements into groups and to identify the mineralogical affinity of each group. Geochemical data are more sensitive than mineralogy for defining the size of the alteration halo, and three zones ranging from unaltered coal, through altered coal to highly coked coal are recognised as each intrusion is approached.The alteration halos differ in extent (9.5 and 56 m wide), but their size is not a multiple of the size of the causative intrusion. At the contact between coal and intrusion, concentrations of elements with affinities to some aluminosilicates, oxides, carbonates, sulphides and organic components are enriched, while other aluminosilicate-related elements are depleted. In the altered coal towards the edge of the alteration halo, some aluminosilicate elements are enriched and oxide elements are depleted.     

Proterozoic seawater — felsic volcanics interaction W. Bergslagen,Sweden. Evidence for high REE mobility and implications for 1.8 Ga seawater compositions

Mg enrichment in diffusely bounded, schistose alteration zones occurring in Proterozoic submarine felsic volcanics NE of Hjulsjö, W. Bergslagen is shown to result from felsic rock-seawater interaction in a sub-seafloor hydrothermal system. The alteration is apparently in two stages, feldspar being altered first to a kaolinite-type clay which is then replaced by Mg-chlorite. Major and trace element data are presented for the schist and sheridanite (chlorite). Relative to the least altered felsic volcanics, and for negligible volume change, the schist shows strong addition of Mg and to a lesser extent Si; K, Al and Rb are apparently conserved, while most other elements are strongly depleted, including the REEs which are removed for ～75%, indicating a high degree of mobility. The chlorite, with its HREE enriched pattern, is considered to have equilibrated with the hydrothermal fluid, which consisted predominantly of seawater. Comparison with modern seawater leads to the tentative conclusion that the Proterozoic seawater HREE composition was not drastically different from that of modern seawater.