scholarly journals Changes in Halogen (F, Cl, Br, and I) and S Ratios in Rock-Forming Minerals as Monitors for Magmatic Differentiation, Volatile-Loss, and Hydrothermal Overprint: The Case for Peralkaline Systems

Minerals ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 995 ◽  
Author(s):  
Hans G.M. Eggenkamp ◽  
Michael A.W. Marks ◽  
Petya Atanasova ◽  
Thomas Wenzel ◽  
Gregor Markl
Keyword(s):  
Mineral Chemistry ◽  
Hydrothermal Systems ◽  
Fluid Loss ◽  
Volatile Components ◽  
Compositional Variation ◽  
Magmatic Differentiation ◽  
Charge Balance ◽  
Rock Interaction ◽  
Eudialyte Group ◽  
Volatile Loss

We determined the halogen (F, Cl, Br, and I) and sulfur (S) concentrations in Cl-rich rock-forming minerals from five peralkaline complexes. We investigated sodalite (N = 42), eudialyte-group minerals (N = 84), and tugtupite (N = 8) from representative rock samples derived from Ilímaussaq (South Greenland), Norra Kärr (Sweden), Tamazeght (Morocco), Lovozero, and Khibina (Russian Federation). Taken together, sodalite and eudialyte-group minerals dominate the Cl and Br budget of the investigated rocks. For F, however, several other phases (e.g., amphibole, fluorite, villiaumite, and minerals of the rinkite group and the apatite supergroup) are additional sinks, and parts of the S may be scavenged in generally rare sulfides. The investigated minerals contain Cl at the wt.% level, F and S concentrations are in the hundreds to thousands of µg/g-range, Br is less common (0.2–200 µg/g) and I is rare (mostly well below 1 µg/g). Normalized to Cl, sodalite prefers Br relative to eudialyte-group minerals, while F is always enriched in the latter. Our data show that both F and S may represent important components in eudialyte-group minerals, sometimes at similar levels as Cl, which normally dominates. Sulfur reveals redox-dependent behavior: Under reduced crystallization conditions, S is more compatible in eudialyte-group minerals (EGM) than in sodalite, which flips to the opposite under water-rich and presumably more oxidized conditions. We investigate the applicability of F/Cl, Br/Cl, and S/Cl ratios in these minerals in peralkaline systems to better understand the interplay of magmatic differentiation, fluid loss and hydrothermal overprint. Similar to apatite in metaluminous systems, fractionation of sodalite, and eudialyte-group minerals in peralkaline magmas leads to decreasing Br/Cl ratios. The data presented in this study bear implications for the mineral chemistry and compositional variation of sodalite and especially EGM in general. Volatile components in EGM that are not normally considered, such as F and S, can reach concentrations of thousands of µg/g. Especially in the case of F, with its low atomic weight, the results obtained in this study indicate that it is very significant for formulae calculations, neutral charge-balance, and similar aspects at such concentration levels. This study demonstrates that halogen contents and ratios are sensitive monitors for a variety of processes in magmatic-hydrothermal systems, including magmatic fractionation, volatile loss, and fluid–rock interaction.

scholarly journals Mineralogical and Geochemical Signatures of Metalliferous Sediments in Wocan-1 and Wocan-2 Hydrothermal Sites on the Carlsberg Ridge, Indian Ocean

Minerals ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 26 ◽  
Author(s):  
Samuel Olatunde Popoola ◽  
Xiqiu Han ◽  
Yejian Wang ◽  
Zhongyan Qiu ◽  
Ying Ye ◽  
...  
Keyword(s):  
Indian Ocean ◽  
Volcanic Glass ◽  
Mineral Chemistry ◽  
Hydrothermal Systems ◽  
Bulk Sediment ◽  
Sediment Samples ◽  
Metalliferous Sediments ◽  
Metalliferous Sediment ◽  
Carlsberg Ridge ◽  
Hydrothermal Environments

In this paper, we conduct a comparative study on the mineralogy and geochemistry of metalliferous sediment collected near the active hydrothermal site (Wocan-1) and inactive hydrothermal site (Wocan-2) from Wocan Hydrothermal Field, on the Carlsberg Ridge (CR), northwest Indian Ocean. We aim to understand the spatial variations in the primary and post-depositional conditions and the intensity of hydrothermal circulations in the Wocan hydrothermal systems. Sediment samples were collected from six stations which includes TVG-07, TVG-08 (Wocan-1), TVG-05, TVG-10 (Wocan-2), TVG-12 and TVG-13 (ridge flanks). The mineralogical investigations show that sediment samples from Wocan-1 and Wocan-2 are composed of chalcopyrite, pyrite, sphalerite, barite, gypsum, amorphous silica, altered volcanic glass, Fe-oxides, and hydroxides. The ridge flank sediments are dominated by biogenic calcite and foraminifera assemblages. The bulk sediment samples of Wocan-1 have an elevated Fe/Mn ratio (up to ~1545), with lower U contents (<7.4 ppm) and U/Fe ratio (<~1.8 × 10−5). The sulfide separates (chalcopyrite, pyrite, and sphalerite) are enriched in Se, Co, As, Sb, and Pb. The calculated sphalerite precipitation temperature (Sph.PT) yields ~278 °C. The sulfur isotope (δ34S) analysis returned a light value of 3.0–3.6‰. The bulk sediment samples of Wocan-2 have a lower Fe/Mn ratio (<~523), with high U contents (up to 19.6 ppm) and U/Fe ratio (up to ~6.2 × 10−5). The sulfide separates are enriched in Zn, Cu, Tl, and Sn. The calculated Sph.PT is ~233 °C. The δ34S returned significant values of 4.1–4.3‰ and 6.4–8.7‰ in stations TVG-10 and TVG-05, respectively. The geochemical signatures (e.g., Fe/Mn and U/Fe ratio, mineral chemistry of sulfides separates, and S-isotopes and Sph.PT) suggest that sediment samples from Wocan-1 are located near intermediate–high temperature hydrothermal discharge environments. Additionally, relatively low δ34S values exhibit a lower proportion (less than 20%) of seawater-derived components. The geochemical signatures suggest that sediment samples from Wocan-2 has undergone moderate–extensive oxidation and secondary alterations by seawater in a low–intermediate temperature hydrothermal environments. Additionally, the significant δ34S values of station TVG-05 exhibit a higher estimated proportion (up to 41%) of seawater-derived components. Our results showed pervasive hydrothermal contributions into station TVG-08 relative to TVG-07, it further showed the increased process of seafloor weathering at TVG-05 relative to TVG-10.

scholarly journals Compositional Variation of Eudialyte-Group Minerals from the Lovozero and Ilímaussaq Complexes and on the Origin of Peralkaline Systems

Minerals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 548
Author(s):  
Lia N. Kogarko ◽  
Troels F. D. Nielsen
Keyword(s):  
Linear Trend ◽  
Major And Trace Elements ◽  
High Tech ◽  
Compositional Variation ◽  
Elemental Distribution ◽  
Magma Chambers ◽  
Eudialyte Group ◽  
System A ◽  
Distribution Of Elements ◽  
World Class

The Lovozero complex, Kola peninsula, Russia and the Ilímaussaq complex in Southwest Greenland are the largest known layered peralkaline intrusive complexes. Both host world-class deposits rich in REE and other high-tech elements. Both complexes expose spectacular layering with horizons rich in eudialyte group minerals (EGM). We present a detailed study of the composition and cryptic variations in cumulus EGM from Lovozero and a comparison with EGM from Ilímaussaq to further our understanding of peralkaline magma chambers processes. The geochemical signatures of Lovozero and Ilímaussaq EGM are distinct. In Lovozero EGMs are clearly enriched in Na + K, Mn, Ti, Sr and poorer Fe compared to EGM from Ilímaussaq, whereas the contents of ΣREE + Y and Cl are comparable. Ilímaussaq EGMs are depleted in Sr and Eu, which points to plagioclase fractionation and an olivine basaltic parent. The absence of negative Sr and Eu anomalies suggest a melanephelinitic parent for Lovozero. In Lovozero the cumulus EGMs shows decrease in Fe/Mn, Ti, Nb, Sr, Ba and all HREE up the magmatic layering, while REE + Y and Cl contents increase. In Lovozero EGM spectra show only a weak enrichment in LREE relative to HREE. The data demonstrates a systematic stratigraphic variation in major and trace elements compositions of liquidus EGM in the Eudialyte Complex, the latest and uppermost part of Lovozero. The distribution of elements follows a broadly linear trend. Despite intersample variations, the absence of abrupt changes in the trends suggests continuous crystallization and accumulation in the magma chamber. The crystallization was controlled by elemental distribution between EGM and coexisting melt during gravitational accumulation of crystals and/or mushes in a closed system. A different pattern is noted in the Ilimaussaq Complex. The elemental trends have variable steepness up the magmatic succession especially in the uppermost zones of the Complex. The differences between the two complexes are suggested to be related dynamics of the crystallization and accumulation processes in the magma chambers, such as arrival of new liquidus phases and redistributions by mush melts.

scholarly journals Geochemistry of Sphalerite from the Permian Volcanic-Hosted Massive Sulphide (VHMS) Deposits in the Tasik Chini Area, Peninsular Malaysia: Constraints for Ore Genesis

Minerals ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 728
Author(s):  
Mohd Basril Iswadi Basori ◽  
Sarah E. Gilbert ◽  
Khin Zaw ◽  
Ross R. Large
Keyword(s):  
Variable Temperature ◽  
Mineral Chemistry ◽  
Peninsular Malaysia ◽  
Massive Sulphide ◽  
Compositional Variation ◽  
Volcanic Origin ◽  
Sedimentary Deposits ◽  
Depositional Processes ◽  
Tasik Chini ◽  
Vhms Deposits

The Bukit Botol and Bukit Ketaya deposits are two examples of volcanic-hosted massive sulphide (VHMS) deposits that occur in the Tasik Chini area, Central Belt of Peninsular Malaysia. The mineralisation is divided into subzones distinguished by spatial, mineralogical, and textural characteristics. The primary sulphide minerals include pyrite, chalcopyrite, sphalerite, and galena, with lesser amounts of Sn- and Ag-bearing minerals, with Au. However, pyrrhotite is absent from both deposits. This study presents the results of sphalerite chemistry analysed by using an electron microprobe. Two types of sphalerite are recognised: sphalerite from the Bukit Botol deposit reveals a range of <DL to 24.0 mole% FeS, whereas sphalerite from the Bukit Ketaya deposit shows a range of <DL to 3 mole% FeS. Significant variations are shown in Zn, Cu, Cd, and Ag levels. Although the sphalerite has a wide variation in composition, a discernible decreasing Fe trend is exhibited from the stringer zone towards massive sulphide. This compositional variation in sphalerites may in part reflect variable temperature and activity of sulphur in the hydrothermal fluids during ore formation. Alternatively, the bimodal composition variations suggest that mineral chemistry relates to contrasting depositional processes. The Zn/Cd ratios for sphalerite from both these deposits are similar to those exhibited by volcano−sedimentary deposits with a volcanic origin. Therefore, the consistently low Cd concentrations and moderate to high Zn/Cd ratios suggest mixing of seawater and minor magmatic fluids controlling the chemistry of sphalerite at both deposits during their formation.

Incorporation of REE into leucophanite: a compositional and structural study

2007 ◽  
Vol 71 (06) ◽  
pp. 625-640 ◽  
Author(s):  
H. Friis ◽  
T. Balić-Žunić ◽  
C. T. Williams ◽  
R. Garcia-Sanchez
Keyword(s):  
Trace Element ◽  
Element Concentration ◽  
Trace Element Concentration ◽  
Compositional Variation ◽  
Chemical Compositions ◽  
Charge Balance ◽  
Element Abundances ◽  
Chemical Factors ◽  
Crystallization Conditions ◽  
Compositional Zonation

Abstract The crystal structures of nine, and the chemical compositions of ten, natural samples of leucophanite, ideally NaCaBeSi2O6F, were investigated. The analysed samples display a large compositional variation with trace-element abundances &gt;50,000 ppm, primarily due to rare earth elements (REE). Fromthese data, we propose a substitution scheme for the incorporation of REE for Ca, with additional Na substituting for Ca and the generation of vacancies to ensure charge balance. Compositional zonation was observed in some samples; this zonation correlates with variations in cathodoluminescence. The crystal structure of the nine analysed samples could all be refined in space group P212121. We found no evidence for a reduction of symmetry with increased trace-element concentration. Various twin combinations were observed and these seem related to crystallization conditions rather than structural or chemical factors.

scholarly journals Tracing fluid transfers in subduction zones: an integrated thermodynamic and <i>δ</i><sup>18</sup>O fractionation modelling approach

Solid Earth ◽  
2020 ◽  
Vol 11 (2) ◽  
pp. 307-328 ◽  
Author(s):  
Alice Vho ◽  
Pierre Lanari ◽  
Daniela Rubatto ◽  
Jörg Hermann
Keyword(s):  
Oxygen Isotope ◽  
Oceanic Crust ◽  
Subduction Zones ◽  
Integrated Modelling ◽  
Fluid Loss ◽  
Rock Composition ◽  
Oxygen Isotope Fractionation ◽  
Rock Interaction ◽  
Dehydration Reactions ◽  
Modelling Approach

Abstract. Oxygen isotope geochemistry is a powerful tool for investigating rocks that interacted with fluids, to assess fluid sources and quantify the conditions of fluid–rock interaction. We present an integrated modelling approach and the computer program PTLoop that combine thermodynamic and oxygen isotope fractionation modelling for multi-rock open systems. The strategy involves a robust petrological model performing on-the-fly Gibbs energy minimizations coupled to an oxygen fractionation model for a given chemical and isotopic bulk rock composition; both models are based on internally consistent databases. This approach is applied to subduction zone metamorphism to predict the possible range of δ18O values for stable phases and aqueous fluids at various pressure (P) and temperature (T) conditions in the subducting slab. The modelled system is composed of a mafic oceanic crust with a sedimentary cover of known initial chemical composition and bulk δ18O. The evolution of mineral assemblages and δ18O values of each phase is calculated along a defined P–T path for two typical compositions of basalts and sediments. In a closed system, the dehydration reactions, fluid loss and mineral fractionation produce minor to negligible variations (i.e. within 1 ‰) in the bulk δ18O values of the rocks, which are likely to remain representative of the protolith composition. In an open system, fluid–rock interaction may occur (1) in the metasediment, as a consequence of infiltration of the fluid liberated by dehydration reactions occurring in the metamorphosed mafic oceanic crust, and (2) in the metabasalt, as a consequence of infiltration of an external fluid originated by dehydration of underlying serpentinites. In each rock type, the interaction with external fluids may lead to shifts in δ18O up to 1 order of magnitude larger than those calculated for closed systems. Such variations can be detected by analysing in situ oxygen isotopes in key metamorphic minerals such as garnet, white mica and quartz. The simulations show that when the water released by the slab infiltrates the forearc mantle wedge, it can cause extensive serpentinization within fractions of 1 Myr and significant oxygen isotope variation at the interface. The approach presented here opens new perspectives for tracking fluid pathways in subduction zones, to distinguish porous from channelled fluid flows, and to determine the P–T conditions and the extent of fluid–rock interaction.

scholarly journals Tracing fluid transfers in subduction zones: an integrated thermodynamic and δ<sup>18</sup>O fractionation modelling approach

2019 ◽  
Author(s):  
Alice Vho ◽  
Pierre Lanari ◽  
Daniela Rubatto ◽  
Jörg Hermann
Keyword(s):  
Oxygen Isotope ◽  
Subduction Zones ◽  
Integrated Modelling ◽  
Fluid Loss ◽  
Oxygen Isotope Fractionation ◽  
Rock Interaction ◽  
Mafic Rocks ◽  
External Fluid ◽  
Dehydration Reactions ◽  
Modelling Approach

Abstract. Oxygen isotope geochemistry is a powerful tool for investigating rocks that interacted with fluids, to assess fluid sources and quantify the conditions of fluid-rock interaction. We present an integrated modelling approach and the computer program PTLOOP that combine thermodynamic and oxygen isotope fractionation modelling for multi-rock open systems. The strategy involves a robust petrological model performing on-the-fly Gibbs energy minimizations coupled to an oxygen fractionation model both based on internally consistent databases. This approach is applied to subduction zone metamorphism to predict the possible range of δ18O values for stable phases and aqueous fluids at various pressure-temperature (P-T) conditions in the subducting slab. The modelled system is composed by a sequence of oceanic crust (mafic) with sedimentary cover of known initial chemical composition and bulk δ18O. The evolution of mineral assemblage and δ18O values of each phase is calculated along a defined P-T path. Fluid-rock interactions may occur as consequence of (1) infiltration of an external fluid into the mafic rocks or (2) transfer of the fluid liberated by dehydration reactions occurring in the mafic rocks into the sedimentary rocks. The effects of interaction with externally-derived fluids on the mineral and bulk δ18O of each rock are quantified for two typical compositions of metabasalts and metasediments with external fluid influx from serpentinite. The dehydration reactions, fluid loss and mineral fractionation produce minor to negligible variations in bulk δ18O values, i.e. within 1 ‰. By contrast, the interaction with external fluids may lead to shifts in δ18O up to one order of magnitude larger. Such variations can be detected by analysing in-situ oxygen isotope in key metamorphic minerals such as garnet, white mica and quartz. The simulations show that, when the water released by the slab infiltrates the forearc mantle wedge, it can cause extensive serpentinization within fractions of a Myr and significant oxygen isotope variation at the interface. This technique opens new perspectives to track fluid pathways in subduction zones, to distinguish porous from channelized fluid flows, and to determine the P-T conditions and the extent of fluid/rock interaction.

Complementary Textural, Trace Element, and Isotopic Analyses of Sulfides Constrain Ore-Forming Processes for the Slate-Hosted Yuhengtang Au Deposit, South China

2021 ◽  
Vol 116 (8) ◽  
pp. 1825-1848
Author(s):  
Wei Li ◽  
Nigel J. Cook ◽  
Gui-Qing Xie ◽  
Jing-Wen Mao ◽  
Cristiana L. Ciobanu ◽  
...  
Keyword(s):  
Trace Element ◽  
South China ◽  
Sulfur Isotope ◽  
Gold Mineralization ◽  
Oscillatory Zoning ◽  
Compositional Variation ◽  
Rock Interaction ◽  
Icp Ms ◽  
Isotopic Analyses ◽  
Stage 1

Abstract Yuhengtang is a representative slate-hosted Au deposit in the Jiangnan orogenic belt, South China, with a reserve of ~55 t Au and an average grade of ~3.9 g/t. Gold mineralization is characterized by veinlet and disseminated ores comprising native gold, auriferous pyrite, and arsenopyrite. Paragenesis of the Yuhengtang deposit can be divided into three stages. Pre-ore stage 1 is composed of bedding-parallel layers of pyrite in slate of the Neoproterozoic Banxi Group. Main ore stage 2 represents the Au mineralization stage, and two distinct types of mineralization can be distinguished: visible Au-arsenopyrite-pyrite in quartz veinlets and auriferous arsenopyrite-pyrite disseminated within altered slate. Post-ore stage 3 consists of quartz-pyrite-calcite-ankerite veins. In this study, we integrate electron microprobe, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and high-resolution ion microprobe (SHRIMP) analyses to document textural, isotopic, and compositional variation among texturally complex pyrite and arsenopyrite assemblages in veinlet and disseminated ores. Additionally, LA-ICP-MS sulfur isotope mapping of pyrite highlights the covariation behavior between trace elements and sulfur isotopes at the grain scale, thus allowing the factors controlling sulfur isotope fractionation in hydrothermal Au deposits to be constrained. Pyrite, of sedimentary origin (stage 1), hosts negligible Au (&lt;1.6 ppm) but is enriched in δ34S (15.6–25.8‰). Pyrite and arsenopyrite from stage 2 veinlet mineralization both display porous and dissolution-reprecipitation textures, have low Au concentrations (&lt;4 and &lt;78 ppm, respectively), and show a large variation in δ34S (–2.7 to 14.7‰ and –10.3 to 12.1‰, respectively). Pyrite and arsenopyrite from disseminated mineralization are, in contrast, characterized by oscillatory zoning textures and homogeneous appearance in backscattered electron (BSE) images, respectively, and are obvious by their relatively high contents of invisible Au (up to 90 and 263 ppm, respectively) and restricted range of δ34S values (0–5.3‰). These data suggest that magmatic-hydrothermal fluids contribute most of the Au and S budget in the Yuhengtang Au deposit. The major differences between veinlet and disseminated mineralization in terms of texture, trace element concentrations, and δ34S signatures of pyrite and arsenopyrite reflect contrasting mechanisms of Au precipitation and an evolution of physicochemical parameters of the ore-forming processes, particularly fO2 and the intensity of fluid-rock interaction. Pyrite from stage 3 appears homogeneous in BSE images yet displays a wide variation in δ34S values (1.2–31.4‰), further highlighting the controlling role played by physicochemical condition (i.e., pressure) on the δ34S signature of sulfides. Results of the coupled LA-ICP-MS sulfur and trace element mapping reveal that some zoned pyrite grains from stage 2 formed via overgrowth of Au-rich, light δ34S (2.4‰) hydrothermal rims onto Au-poor, heavy δ34S (18.1–18.5‰) sedimentary cores. All results support that multiple depositional mechanisms within a dynamic mineral system were responsible for Au concentration and define the specific textural, compositional, and sulfur isotope signatures of sulfides in coexisting vein/veinlet and disseminated mineralization. The new data highlight the ore-forming processes-based interpretation for ore genesis and underpin the importance of performing complementary in situ mineralogical analyses to elucidate the source and evolution of ore-forming fluids and enable correct interpretation of the architecture of the hydrothermal Au system.

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