Rare earth element study of exhalites within the Willyama supergroup,Broken Hill Block,Australia

A wide variety of unusual rock types, exhalites, are commonly associated with or host to exhalative mineralisation within the Willyama Supergroup. Chondrite normalised REE patterns of feldspar-, gahnite-, calcite-, magnetite-and garnet-rich lithologies in the vicinity of stratiform Broken Hill-type Pb-Zn-Ag mineralisation are LREE and Eu enriched similar to the REE patterns of pure metalliferous sediments and hydrothermal fluids of the East Pacific Rise and the Red Sea. In contrast, tourmaline-, garnet-, amphibole-, feldspar- and gahnite-rich exhalites in strike extension of Broken Hill-type orebodies possess LREE enrichments and negative Eu anomalies and also HREE enrichments and negative Ce anomalies. These REE patterns are the result of decreasing temperatures of the hydrothermal fluids, changing oxidation-reduction conditions and increasing influence of basic volcanism with increasing distance from the sulphide mineralisation.     

Water in garnet of garnetite (metarodingite) and eclogite from the Erzgebirge and the Lepontine Alps

Little is known about water in nominally anhydrous minerals of orogenic garnet peridotite and enclosed metabasic rocks. This study is focused on peridotite-hosted eclogite and garnetite (metarodingite) from the Erzgebirge (EG), Germany, and the Lepontine Alps (LA), Switzerland. Newly discovered, peridotite-hosted eclogite in the Erzgebirge occurs in the same ultra-high pressure (UHP) unit as gneiss-hosted coesite eclogite, from which it is petrologically indistinguishable. Garnet is present in all mafic and ultramafic high pressure (HP) rocks providing for an ideal proxy to compare the H₂O content of the different rock types. Garnet composition is very similar in EG and LA samples and depends on the rock type. Garnet from garnetite, compared to eclogite, contains more CaO (garnetite: 10.5–16.5 wt%; eclogite: 5–11 wt%) and is also characterized by an anomalous REE distribution. In contrast, the infrared (IR) spectra of garnet from both rock types reveal the same OH absorption bands that are also identical to those of previously studied peridotitic garnet from the same locations. Two groups of IR bands, SW I (3,650 ± 10 cm⁻¹) and SW II (3,570–3,630 cm⁻¹) are ascribed to structural hydroxyl (colloquially ‘water’). A third, broad band is present in about half of the analysed garnet domains and related to molecular water (MW) in submicroscopic fluid inclusions. The primary content of structural H₂O, preserved in garnet domains without fluid inclusions (and MW bands), varies systematically—depending on both the location and the rock type. Garnet from EG rocks contains more water compared to LA samples, and garnet from garnetite (EG: 121–241 wt.ppm H₂O; LA: 23–46 wt.ppm) hosts more water than eclogitic garnet (EG: 84 wt.ppm; LA: 4–11 wt.ppm). Higher contents of structural water (SW) are observed in domains with molecular water, in which the SW II band (being not restricted to HP conditions) is simultaneously enhanced. This implies that fluid influx during decompression not only led to fluid inclusions but also favoured the uptake of secondary SW. The results signify that garnet from all EG and LA samples was originally H₂O-undersaturated. Combining the data from eclogite, garnetite and previously studied peridotite, H₂O and CaO are positively correlated, pointing to the same degree of H₂O-undersaturation at peak metamorphism in all rock types. This ubiquitous water-deficiency cannot be reconciled with the derivation of any of these rocks from the lowermost part of the mantle wedge that was in contact with the subducting plate. This agrees with the previously inferred abyssal origin for part of the rocks from the LA (Cima di Gagnone). A similar origin has to be invoked for the Erzgebirge UHP unit. We suggest that all mafic and ultramafic rocks of this unit not only shared the same metamorphic evolution but also a common protolith origin, most probably on the ocean floor. This inference is supported by the presence of peridotite-hosted garnetite, representing metamorphosed rodingite.     

Ultrahigh-pressure corundum-rich garnetite in garnet peridotite,Sulu terrane,China

Corundum-rich garnetite occurs as an isolated lens in a garnet peridotite body in the Donghai area of the Sulu ultrahigh-pressure (UHP) terrane. This rock consists of garnet and corundum, along with minor crack-related zoisite, pargasite, Mg-staurolite, Mg-chloritoid, sapphirine and chlorite. Pyropic garnet (Prp_54–63Grs_26–36Alm_10–12) exhibits a sinusoidal REE pattern, positive Ta, Pb, and negative Nb, Ti anomalies due to metasomatism. Reddish corundum contains 1.1–1.7 wt% Cr₂O₃, and shows three oriented sets of exsolved rutile needles. Both garnet and corundum contain inclusions of apatite, Mg-allanite (MgO>4 wt%), and Ni-Fe sulfides formed as trapped Ni-Fe-S melt. The protolith of the corundum-rich garnetite could have been spinel websterite formed in the upper mantle. Both the websterite and the host garnet peridotite were subjected to subduction-zone UHP metamorphism at 800 °C and >4 GPa. Crack-related hydrous phases were formed by fluid infiltration during exhumation.Editorial responsibility: T.L. Grove     

Manganoan garnet rocks associated with the Broken Hill Pb–Zn–Ag orebody, Australia

Summary The Palaeoproterozoic Broken Hill Pb–Zn–Ag stratiform orebody is intimately associated with manganoan garnet-bearing rocks. On stratigraphic and chemical grounds it is argued that garnet-rich metasediments below, equivalent to and above massive sulphide were hydrothermal precipitates. Other manganoan garnet rocks formed during pre-metamorphic hydrothermal alteration, syn-metamorphic dehydration and reaction of manganese with prograde pelitic rocks, reaction between cataclastic manganese-bearing sulphide rocks injected along axial planes, shears and faults and pelitic wall rocks and reaction between dolerite dykes and sulphide rocks.     

Ultrahigh pressure metamorphic rocks from the Chinese Continental Scientific Drilling Project: I. Petrology and geochemistry of the main hole (0–2,050 m)

The main hole (MH) of the Chinese Continental Scientific Drilling Project (CCSD) in southern Sulu has penetrated into an ultrahigh-pressure (UHP) metamorphic rock slice which consists of orthogneiss, paragneiss, eclogite, ultramafic rock and minor schist. Recovered eclogites have a UHP metamorphic mineral assemblage of garnet + omphacite + rutile ± phengite ± kyanite ± coesite ± epidote. Ultramafic rocks contain garnet + olivine + clinopyroxene + orthopyroxene ± Ti-clinohumite ± phlogopite. Gneisses and schists contain an amphibolite-facies paragenesis, but their zircons have coesite, garnet, omphacite (or jadeite) and phengite inclusions, indicating that eclogites and gneisses have been subjected to in situ UHP metamorphism. Using available geothermobarometers, P–T estimates of 3.1–4.4 GPa and 678–816°C for eclogites were obtained. If surface outcrops and neighboring shallow drill holes are considered together, we suggest that a huge supracrustal rock slab (> 50 km long × 100 km wide × 5 km deep) was subducted to a depth > 100 km and then exhumed to the surface. The depth interval (0–2,050 m) of the CCSD-MH can be divided into six lithological units. Unit 1 consists of alternating layers of quartz-rich and rutile-rich eclogites, with thin interlayers of gneiss and schist. Eclogites of unit 1 are characterized by Nb, Ta, Sr and Ti depletions, low Mg number and general LREE enrichment. Unit 2 comprises rutile- and ilmenite-rich eclogite and minor “normal” eclogite and is characterized by high TiO₂, total Fe, V, Co and Sr, and very low SiO₂, alkali, Zr, Ba, Nb, Ta and total REE contents, and LREE-depleted REE patterns with slightly positive Eu anomalies. Unit 3 contains ultramafic rock and minor MgO-rich eclogite. Protoliths of UHP rocks from units 1, 2 and 3 represent a layered mafic to ultramafic intrusion at crustal depth. Units 4 and 6 consist of interlayered eclogite and paragneiss; the eclogites are characterized by Th, U, Nb, Ta and Ti depletion and K enrichment and LREE-enriched REE patterns. Paragneisses show Nb, Ta, Sr and Ti depletions and LREE-enriched REE patterns occasionally with slightly negative Eu anomalies, indicating that their protoliths represent metamorphic supracrustal series. Unit 5 consists mainly of orthogneisses, showing distinct Nb, Ta, Sr and Ti depletions, and LREE-enriched REE patterns with pronounced negative Eu anomalies, suggesting granitic protoliths. In conclusion it is proposed that the southern Sulu UHP belt consists of a series of meta-supracrustal rocks, a layered mafic–ultramafic complex and granites.     

Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier,central Australia

Tourmaline rocks of previously unclear genesis and spatially associated with W- (Cu)-bearing calc-silicate rocks occur in Palaeoproterozoic supracrustal and felsic intrusive rocks in the Bonya Hills in the eastern Arunta Inlier, central Australia. Tourmalinisation of metapelitic host rocks postdates the peak of regional low-pressure metamorphism (M₁/D₁, ~500 °C, ~0.2 GPa), and occurred synkinematically between the two main deformation events D₁ and D₂, coeval with emplacement of Late Strangways (~1.73 Ga) tourmaline-bearing leucogranites and pegmatites. Tourmaline is classified as schorl to dravite in tourmaline–quartz rocks and surrounding tourmaline-rich alteration zones, and as Fe-rich schorl to foitite in the leucogranites. Boron metasomatism resulted in systematic depletion of K, Li, Rb, Cs, Mn and enrichment of B, and in some samples of Na and Ca, in the tourmaline rocks compared to unaltered metasedimentary host rocks. Whole-rock REE concentrations and patterns of unaltered schist, tourmalinised schist and tourmaline–quartz veins—the latter were the zones of influx of the boron-rich hydrothermal fluid—are comparable to those of post-Archaean shales. Thus, the whole-rock REE patterns of these rocks are mostly controlled by the metapelitic precursor. In contrast, REE concentrations of leucogranitic rocks are low (10 times chondritic), and their flat REE patterns with pronounced negative Eu anomalies are typical for fractionated granitic melts coexisting with a fluid phase. REE patterns for tourmalines separated from metapelite-hosted tourmaline–quartz veins and tourmaline-bearing granites are very different from one another but each tourmaline pattern mirrors the REE distribution of its immediate host rock. Tourmalines occurring in tourmaline–quartz veins within tourmalinised metasediments have LREE-enriched (La_N/Yb_N=6.3–55), shale-like patterns with higher REE (54–108 ppm). In contrast, those formed in evolved leucogranites exhibit flat REE patterns (La_N/Yb_N=1.0–5.6) with pronounced negative Eu anomalies and are lower in REE (5.6–30 ppm). We therefore conclude that REE concentrations and patterns of tourmaline from the different tourmaline rocks studied are controlled by the host rock and not by the hydrothermal fluid causing boron metasomatism. From the similarity of the REE pattern of separated tourmaline with the host rock, we further conclude that incorporation of REEs in tourmaline is not intrinsically controlled (i.e. by crystal chemical factors). Tourmaline does not preferentially fractionate specific REEs or groups of REEs during crystallisation from evolved boron- and fluid-rich granitic melts or during alteration of clastic metasediments by boron-rich magmatic-hydrothermal fluids.Editorial responsibility: J. Hoefs     

Metamorphic garnet pyroxenite from the 540-600 m main borehole of the Chinese Continental Scientific Drilling (CCSD) project

Compared to other mafic and ultramafic rocks from the CCSD main borehole as well as from the outcrops, rocks from the 540-600 m section is extraordinary in terms of its geophysical as well as geochemical properties. It consists of > 70% hematite-ilmenite garnet pyroxenite (HI-GPX) and < 30% intercalated rutile garnet pyroxenite (R-GPX). Whole-rock geochemical data show that HI-GPXs have: (1) relatively high V with an average of 606 ppm, but lower Nb and Ta; (2) highest TFeO, Fe₂O₃/FeO ratio, and highly variable but strong positive Eu anomalies with Eu/Eu? up to 2.9; (3) anomalously high V/Sc ratios ranging from 8.39 to 43.23, average 15.03; and (4) high amounts of hematite-ilmenite solid solutions with a very fine intergrowth structure down to nanometer scale. V/Sc ratios in the CCSD garnet pyroxenites are correlated negatively with MgO, but positively with Fe₂O₃/FeO ratios. Both suites of pyroxenites have similar rare earth elements and high field strength elements geochemistry. These features demonstrate that these pyroxenites were formed from metamorphism of high-Fe and/or -Ti gabbroic cumulates. This can account not only for low high field strength elements (HFSE) and rare earth elements (REE) but also low Nb/Ta and Zr/Hf ratios in these rocks. Seemingly negative correlation between Nb/Ta and Zr/Hf in the CCSD metabasites, not significantly affected by UHP metamorphism, is also consistent with the silicate differentiation trend in a basaltic magma chamber.     

Garnet-bearing tonalitic porphyry from East Kunlun,Northeast Tibetan Plateau: implications for adakite and magmas from the MASH Zone

A garnet-bearing tonalitic porphyry from the Achiq Kol area, northeast Tibetan Plateau has been dated by SHRIMP U-Pb zircon techniques and gives a Late Triassic age of 213 ± 3 Ma. The porphyry contains phenocrysts of Ca-rich, Mn-poor garnet (CaO > 5 wt%; MnO < 3 wt%), Al-rich hornblende (Al₂O₃ ~ 15.9 wt%), plagioclase and quartz, and pressure estimates for hornblende enclosing the garnet phenocrysts yield values of 8–10 kbar, indicating a minimum pressure for the garnet. The rock has SiO₂ of 60–63 wt%, low MgO (<2.0 wt%), K₂O (<1.3 wt%), but high Al₂O₃ (>17 wt%) contents, and is metaluminous to slightly peraluminous (ACNK = 0.89–1.05). The rock samples are enriched in LILE and LREE but depleted in Nb and Ti, showing typical features of subduction-related magmas. The relatively high Sr/Y (~38) ratios and low HREE (Yb < 0.8 ppm) contents suggest that garnet is a residual phase, while suppressed crystallization of plagioclase and lack of negative Eu anomalies indicate a high water fugacity in the magma. Nd–Sr isotope compositions of the rock (εNd_T = −1.38 to −2.33; ⁸⁷Sr/⁸⁶Sr_i = 0.7065–0.7067) suggest that both mantle- and crust-derived materials were involved in the petrogenesis, which is consistent with the reverse compositional zoning of plagioclase, interpreted to indicate magma mixing. Both garnet phenocrysts and their ilmenite inclusions contain low MgO contents which, in combination with the oxygen isotope composition of garnet separates (+6.23‰), suggests that these minerals formed in a lower crust-derived felsic melt probably in the MASH zone. Although the rock samples are similar to adakitic rocks in many aspects, their moderate Sr contents (<260 ppm) and La/Yb ratios (mostly 16–21) are significantly lower than those of adakitic rocks. Because of high partition coefficients for Sr and LREE, fractionation of apatite at an early stage in the evolution of the magma may have effectively decreased both Sr and LREE in the residual melt. It is suggested that extensive crystallization of apatite as an early phase may prevent some arc magmas from evolving into adakitic rocks even under high water fugacity.     

Metavolcanic host rocks,mineralization, and gossans of the Shaib al Tair and Rabathan volcanogenic massive sulphide deposits of the Wadi Bidah Mineral District,Saudi Arabia

The Wadi Bidah Mineral District of Saudi Arabia contains more than 16 small outcropping stratabound volcanogenic Cu–Zn–(Pb) ± Au-bearing massive sulphide deposits and associated zones of hydrothermal alteration. Here, we use major and trace element analyses of massive sulphides, gossans, and hydrothermally altered and least altered metamorphosed host rock (schist) from two of the deposits (Shaib al Tair and Rabathan) to interpret the geochemical and petrological evolution of the host rocks and gossanization of the mineralization. Tectonic interpretations utilize high-field-strength elements, including the rare earth elements (REE), because they are relatively immobile during hydrothermal alteration, low-grade metamorphism, and supergene weathering and therefore are useful in constraining the source, composition, and physicochemical parameters of the primary igneous rocks, the mineralizing hydrothermal fluid and subsequent supergene weathering processes. Positive Eu anomalies in some of the massive sulphide samples are consistent with a high temperature (>250°C) hydrothermal origin, consistent with the Cu contents (up to 2 wt.%) of the massive sulphides. The REE profiles of the gossans are topologically similar to nearby hydrothermally altered felsic schists (light REE (LREE)-enriched to concave-up REE profiles, with or without positive Eu anomalies) suggesting that the REE experienced little fractionation during metamorphism or supergene weathering. Hydrothermally altered rocks (now schists) close to the massive sulphide deposits have high base metals and Ba contents and have concave-up REE patterns, in contrast to the least altered host rocks, consistent with greater mobility of the middle REE compared to the light and heavy REE during hydrothermal alteration. The gossans are interpreted to represent relict massive sulphides that have undergone supergene weathering; ‘chert’ beds within these massive sulphide deposits may be leached wall-rock gossans that experienced silicification and Pb–Ba–Fe enrichment from acidic groundwaters generated during gossan formation.     

The Role of Partial Melting and Fractional Crystallization in Determining Discordant Migmatite Leucosome Compositions

Anatectic migmatite leucosomes in the Quetico MetasedimentaryBelt (Superior Province) are discordant to the host rock layering.Two morphological varieties within the anatectic leucosome suiteare distinguished. The first type show little compositionalor textural variation either across, or along, the leucosomes.In contrast, the second variety exhibits both compositionaland textural variations in a single leucosome, typically withinternal cross-cutting relationships. Major-oxide contents varycomparatively little in the Quetico anatectic leucosome suite,but there is a considerable range in the incompatible element(REE, Hf, Zr, Y and Th) concentrations. In particular La contentsrange from 1.8 to 78.1 p.p.m. and the La/Yb ratios from 9.1to 101.9. Samples with high REE contents have negative Eu anomalies,whereas those with low total REE abundances have positive Euanomalies, which indicate that feldspar fractionation was importantin their petrogenesis. Three samples which have no Eu anomalies,and which are taken not to have experienced significant feldsparfractionation, are regarded as the closest approximation toa primary melt composition. Petrographic evidence indicates that only the most aluminousbulk compositions in the host rocks have melted, with cordieriteand biotite as the principal residual phases. Batch partialmelting models indicate that the three leucosomes without Euanomalies could have been derived from 40–80 per centpartial melting of the aluminous metasediments, but garnet musthave been a residual phase. Since the residuum from 40 per centpartial melting is more mafic than any of the rocks currentlyexposed in the area, it is concluded that the melting whichgave rise to the leucosomes occurred at greater depth. Crystallization models indicate that the observed range of leucosomecompositions can be derived by crystal fractionation of meltcompositions similar to the three leucosomes lacking Eu anomalies(i.e. the assumed primary melts). Samples with high abundancesof incompatible elements and negative Eu anomalies representfractionated melts, whereas those with low levels of REE andpositive Eu anomalies represent cumulates. Leucosome composition,morphology and texture can be related to crystallization history,notably the timing of crystallization with respect to leucosomeintrusion. In particular, those leucosomes that exhibit compositionaland textural zoning are interpreted to have undergone crystalfractionation during intrusion. Although a suite of migmatite leucosomes may be derived by partialmelting, it is concluded that the trace-element compositionof any particular leucosome depends, to a great extent, uponits segregation and crystallization history. Indeed, the primarymelt composition may not be preserved.     

Garnet and Zircon U-Pb Geochronology and Geochemistry Reveal Genesis of the Dafang Au-Pb-Zn-Ag Deposit, Southern Hunan

Garnet is a primary mineral in skarn deposits and plays a significant role in recording copious mineralization and metallogenic information. This study systematically investigates the geochemistry and geochronology of garnet and zircon in the Dafang Au-Pb-Zn-Ag deposit, which represents prominent gold mineralization in southern Hunan, China. Garnet samples with distinct zoning patterns and compositional variations were identified using various analytical techniques, including Backscattered Electron (BSE) imaging, Cathodoluminescence (CL) response, textural characterization, and analysis of rare-earth elements (REE), major contents, and trace element compositions. The garnet was dated U-Pb dating, which yielded a lower intercept age of 161.06 ± 1.93 Ma. This age is older than the underlying granodiorite porphyry, which has a concordia age of 155.13 ± 0.95 Ma determined by zircon U-Pb dating. These results suggest that the gold mineralization may be related to the concealed granite. Two groups of garnet changed from depleted Al garnet to enriched Al garnet, and the rare earth element (REE) patterns of these groups were converted from light REE (LREE)-enriched and heavy REE (HREE)-depleted with positive europium (Eu) anomalies to medium REE (MREE)-enriched from core to rim zoning. The different REE patterns of garnet in various zones may be attributed to changes in the fluid environment and late superposition alteration. The development of distal skarn in the southern Hunan could be a significant indicator for identifying gold mineralization.     

滇东南丘北县大铁铝土矿稀土元素特征研究

本文以丘北大铁铝土矿含铝岩系为研究对象, 通过ICP-MS分析测试, 研究了含铝岩系与下伏灰岩、玄武岩的稀土元素特征。研究结果表明, 丘北大铁铝土矿含铝岩系稀土配分模式曲线为向右倾斜的曲线, 与下伏马平组、黄龙组灰岩的稀土配分曲线相似, 而与峨眉山组玄武岩的稀土配分曲线相差较大; 灰岩具有较明显的Ce负异常和Eu负异常, 部分铝土矿和铁铝质岩具明显的Ce正异常和较明显的Eu负异常, 而多数铝土矿、铁铝质岩和铝质粘土岩则无明显的Ce、Eu异常。含铝岩系的稀土元素特征, 反映出其成矿物质来源于下伏灰岩而非玄武岩, 同时也反映出铝土矿的成矿物质来源于风化壳, 成矿物质搬运距离较近, 与海水的水合作用不甚明显。     

新疆蒙库铁矿床稀土元素地球化学及对铁成矿作用的指示

新疆富蕴县蒙库大型铁矿呈层状、似层状、透镜状赋存于下泥盆统康布铁堡组变质火山-沉积岩系中.矿体中发育矽卡岩,但矽卡岩并不产在侵入岩接触带上.绿帘石、石榴石和矿石的稀土配分模式具有相似性,均为轻稀土富集,正铕异常,基本上无铈异常,暗示它们之间存在成因联系.石榴石稀土配分模式呈折线型,具有明显的正铕异常,石榴石流体包裹体中熔融包裹体、熔流包裹体和气液包裹体共存,表明石榴石矽卡岩具有岩浆成因和热液成因的特征,形成于晶体 熔体 流体三相共存的岩浆-热液过渡阶段.矿床地质特征、矽卡岩矿物和矿石稀土特征表明蒙库铁矿为矽卡岩型矿床.     

General relations in the trace-element composition of zircons from eclogites with implications for the age of eclogites in the belomorian mobile belt

Analysis of currently available data (877 individual high-precision zircon analyses) on the composition of zircons from eclogite complexes worldwide reveals general relations in the zircon composition: an anomalous decrease in the Th concentration (no higher than 3 ppm on average) and the Th/U ratio (0.33 on average), a significant decrease in the concentrations of all REE (to 22 ppm) and particularly LREE (<2 ppm), and relatively low concentrations of Y (34 ppm), U (100 ppm), and P (41 ppm) at an elevated Hf concentration (11 400 ppm on average). The REE patterns of eclogitic zircons are noted for pronounced flat HREE patterns, poorly pronounced (if any) negative Eu anomalies, strongly reduced positive Ce anomalies (Ce/Ce* = 11 on average), and U-shaped configurations of LREE patterns up to the development of negative Nd anomalies. The relations detected in the distribution of trace elements and REE in eclogitic zircons are of universal nature and occur irrespective of the rock type (metabasites, metaultrabasites, or gneisses) and the metamorphic pressure (eclogites of high and ultrahigh pressure). The application of the aforementioned criteria makes it possible to reliable distinguish eclogitic zircons from those of magmatic or metamorphic genesis (not related to high-pressure metamorphism). Eclogites in the Belomorian Mobile Belt (in the Salma and Gridino areas) were determined to contain zircons in metagabbro eclogites; the cores of these zircons have an age of 2.8?C2.9 Ga and are of magmatic genesis, whereas their outer metamorphic zones have an age of 1.9 Ga and a trace-element composition typical of eclogitic zircons. Hence, the Belomorian Mobile Belt was affected only by single (Svecofennian, at ??1.9 Ga) episode of eclogite metamorphism of Archean rocks.     

Exploration rock geochemistry for Pinnacles-type mineralization at Broken Hill, N.S.W., Australia

Geochemical responses in weathered and oxidized surface metasedimentary rocks associated with stratiform lead-zinc mineralization at Stirling Hill (6 km west of Broken Hill) are compared with the geochemical responses in fresh drill core from an equivalent lithostratigraphic section with stratiform lead-zinc mineralization at the Pinnacles Mine (8 km south of Stirling Hill). Mineralization is interpreted as being volcanic exhalative and it lies within highly metamorphosed (sillimanite grade) rocks of the Willyama Supergroup.Surface rocks were classified into groups by discriminant analysis using drill core data from the Pinnacles Mine as the initial training set. The behaviour of elements in surface rocks varies with the rock group but Zn, Pb, Mn, Fe, and Co are leached from all surface rocks relative to fresh drill core.Nothwithstanding the leaching effects of weathering, common geochemical responses to mineralization have been identified in drill core and surface rocks. Coincident positive anomalies for Zn/Ba and Fe/(Na × Ba) ratios and negative anomalies for Na/(Mn × Ca) ratios uniquely define mineralization in both weathered surface rocks and in fresh drill core.The results demonstrate that the pattern of geochemical responses to Pinnacles-type stratiform volcanic-exhalative mineralization in surface rocks has survived the intensive weathering regime in the Broken Hill region.     

Petrogenetic significance of rare-earth element behavior in the basement rocks of southern Obudu Plateau, Bamenda Massif, southeastern Nigeria

Rock samples representing various igneous and metamorphic rocks of southern Obudu Plateau were analyzed for rare-earth element ( REE ) behavior by ICP-MS. Results of the analyses indicate a range of REE abundances and distinctive patterns from highly fraetionated patterns with negative Eu anomalies in granitic rocks to relatively low abundances and less REE fractionated flat patterns with little Eu anomaly in some paragneisses, schists, enderbites and dolerites to unfractionated patterns with positive Eu anomalies in some paragneisses and charnockites. Over all, there are low to high ∑ REE contents with negative to positive Eu anomalies. The ratios of different parameters, especially La/Yb and Ce/Yb, show behaviors consistent with crustal to mantle derivation. The heterogeneity of REE abundances and REE patterns reflects mantle to crustal petrogenetic variations of different rock suites on the Plateau. The LREE content is higher than the HREE content in the highly differentiated rocks, as evidenced by their La/Yb,Ce/Yb and La/Sm ratios, which are normally higher in residual products than in primary melts. The dominantly intermediate nature of the source rock of the orthogneisses is suggested by the generally low ∑ REE. The granites enriched in LREE and depleted in HREE and some of the charnockites with negative Eu anomalies were probably formed by partial melting and crystallization.     

The trace element composition of silicate inclusions in diamonds: a review

On a global scale, peridotitic garnet inclusions in diamonds from the subcratonic lithosphere indicate an evolution from strongly sinusoidal REE_N, typical for harzburgitic garnets, to mildly sinusoidal or “normal” patterns (positive slope from LREE_N to MREE_N, fairly flat MREE_N–HREE_N), typical for lherzolitic garnets. Using the Cr-number of garnet as a proxy for the bulk rock major element composition it becomes apparent that strong LREE enrichment in garnet is restricted to highly depleted lithologies, whereas flat or positive LREE–MREE slopes are limited to less depleted rocks. For lherzolitic garnet inclusions, there is a positive relation between equilibration temperature, enrichment in MREE, HREE and other HFSE (Ti, Zr, Y), and decreasing depletion in major elements. For harzburgitic garnets, relations are not linear, but it appears that lherzolite style enrichment in MREE–HREE only occurs at temperatures above 1150–1200 °C, whereas strong enrichment in Sr is absent at these high temperatures. These observations suggest a transition from melt metasomatism (typical for the lherzolitic sources) characterized by fairly unfractionated trace and major element compositions to metasomatism by CHO fluids carrying primarily incompatible trace elements. Melt and fluid metasomatism are viewed as a compositional continuum, with residual CHO fluids resulting from primary silicate or carbonate melts in the course of fractional crystallization and equilibration with lithospheric host rocks.

Eclogitic garnet inclusions show “normal” REE_N patterns, with LREE at about 1× and HREE at about 30× chondritic abundance. Clinopyroxenes approximately mirror the garnet patterns, being enriched in LREE and having chondritic HREE abundances. Positive and negative Eu anomalies are observed for both garnet and clinopyroxene inclusions. Such anomalies are strong evidence for crustal precursors for the eclogitic diamond sources. The trace element composition of an “average eclogitic diamond source” based on garnet and clinopyroxene inclusions is consistent with derivation from former oceanic crust that lost about 10% of a partial melt in the garnet stability field and that subsequently experienced only minor reenrichment in the most incompatible trace elements. Based on individual diamonds, this simplistic picture becomes more complex, with evidence for both strong enrichment and depletion in LREE.

Trace element data for sublithospheric inclusions in diamonds are less abundant. REE in majoritic garnets indicate source compositions that range from being similar to lithospheric eclogitic sources to strongly LREE enriched. Lower mantle sources, assessed based on CaSi–perovskite as the principal host for REE, are not primitive in composition but show moderate to strong LREE enrichment. The bulk rock LREE_N–HREE_N slope cannot be determined from CaSi–perovskites alone, as garnet may be present in these shallow lower mantle sources and then would act as an important host for HREE. Positive and negative Eu anomalies are widespread in CaSi–perovskites and negative anomalies have also been observed for a majoritic garnet and a coexisting clinopyroxene inclusion. This suggests that sublithospheric diamond sources may be linked to old oceanic slabs, possibly because only former crustal rocks can provide the redox gradients necessary for diamond precipitation in an otherwise reduced sublithospheric mantle.     

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(–Fe) Deposits in Japan

Abstract: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(-Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits are of meteoric water origin whereas those for the Yoshiwara-Sannotake Cu(-Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively-coupled plasma mass spectrometry (ICP-MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase-clinopyroxene rock, called Inishi rock) from the Kamioka Zn-Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara-Sannotake Cu(-Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite-normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn-Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara-Sannotake Cu(-Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.     

Rare earth element geochemistry of Archean metasedimentary rocks from Kambalda,Western Australia

Archean sedimentary rocks of very limited lateral extent from horizons within basaltic and ultramafic volcanic sequences at Kambalda, Western Australia, are extremely variable in major elements, LIL and ferromagnesian trace element compositions. The REE patterns are uniform and do not have negative Eu anomalies. Two samples have very low total REE abundances and positive Eu anomalies attributed to a very much greater proportion of chemically deposited siliceous material. Apart from these two samples, the Kambalda data are similar to REE abundances and patterns from Archean sedimentary rocks from Kalgoorlie, Western Australia and to average Archean sedimentary rock REE patterns. These show a fundamental distinction from post-Archean sedimentary rock REE patterns which have higher $\text{La}\text{Yb}$ ratios and a distinct negative Eu anomaly.     

High-Pressure Dehydration Melting of Metapelites: Evidence from the Migmatites of Yaounde (Cameroon)

The migmatites of Yaound? consist essentially of anatectic metapelitickyanite-garnet gneisses characterized by granulite-facies mineralassemblages. Several types of migmatitic rocks have been recognized:(1) leucosomes associated with garnet-rich melanosomes, conformablewith the regional metamorphic layering; some leucosomes aregranitic in composition whereas some others are granodioriticand characterized by low K and Rb and by the lack of HREE fractionation;(2) quartzo-feldspathic differentiations without the relatedmelanosomes, occurring as veins conformable with or cross-cuttingthe regional metamorphic layering or along shear-zones, andcorresponding mineralogi-cally to granitic or quartz-rich v?ins;(3) garnet-rocks mainly composed of garnet with abundant accessories,occurring as intrusive bodies within the migmatitic series. Structural and petrographic data suggest that the migmatitesare not derived from the surrounding granulite-facies gneissesbut that both types of rock result from a single dehydrationmelting event. The formation of migmatites or gneisses, interpretedin terms either of absence of melt extraction or of shear-inducedmelt segregation, is ascribed to variations in strain distributionwithin the metamorphic pile. The chemical characteristics of the rocks and petrogenetic modellingsuggest that the migmatites of Yaounde arose from the superimpositionof the following events: (1) subsolidus differentiation of biotite-gneisses;(2) dehydration melting of biotite-gneisses at temperaturesaround 800?C (P=10–12 kbX leading to low amounts of melt(F<0?2), which was either tectonically segregated (migmatites)or not (granulite-facies gneisses); (3) injection of anatecticmaterial comprising both partial melts and garnet-rich residues,corresponding to high melt fractions (F>0?5) and probablyformed at higher temperatures (850?C) and at deeper structurallevels. The REE signature of equilibrium partial melts (9?3<Ce_N/Yb_N78;l?2<Yb_N<5?4) indicates that granitic magmas cannot bederived from dehydration melting of biotite-bearing metapelitesonly. Several other possibilities are discussed.