Alteration of crystalline zircon solid solutions: a case study on zircon from an alkaline pegmatite from Zomba–Malosa, Malawi

A natural, altered zircon crystal from an alkaline pegmatite from the Zomba–Malosa Complex of the Chilwa Alkaline Province in Malawi has been studied by a wide range of analytical techniques to understand the alteration process. The investigated zircon shows two texturally and chemically different domains. Whereas the central parts of the grain (zircon I) appear homogeneous in backscattered electron images and are characterised by high concentrations of trace elements, particularly Th, U, and Y, the outer regions (zircon II) contain significantly less trace elements, numerous pores, and inclusions of thorite, ytttrialite, and fergusonite. Zircon II contains very low or undetectable concentrations of non-formula elements such as Ca, Al, and Fe, which are commonly observed in high concentrations in altered radiation-damaged zircon. U–Pb dating of both zircon domains by LA-ICPMS and SHRIMP yielded statistically indistinguishable U–Pb weighted average ages of 119.3 ± 2.1 (2σ) and 118 ± 1.2 (2σ) Ma, respectively, demonstrating that the zircon had not accumulated a significant amount of self-irradiation damage at the time of the alteration event. Electron microprobe dating of thorite inclusions in zircon II yielded a Th–U-total Pb model age of 122 ± 5 (2σ) Ma, supporting the age relationship between both zircon domains. The hydrothermal solution responsible for the alteration of the investigated zircon was alkaline and rich in CO₃ ²⁻, as suggested by the occurrence of REE carbonates and CO₂-bearing fluid inclusions. The alteration of the crystalline, trace element-rich zircon is explained by an interface-coupled dissolution-reprecipitation mechanism. During such a process, the congruent dissolution of the trace element-rich parent zircon I was spatially and temporally coupled to the precipitation of the trace element-poor zircon II at an inward moving dissolution-precipitation front. The driving force for such a process was merely the difference between the solubility of the trace element-rich and -poor zircon in the hydrothermal solution. The replacement process and the occurrence of mineral inclusions and porosity in the product zircon II is explained by the thermodynamics of solid solution-aqueous solution systems.     

Grain-scale variations in trace element composition of fluid-altered zircon,Acasta Gneiss Complex,northwestern Canada

SEM back-scattered electron images of zircon separates from a 2.9 Ga granitic dyke from the Acasta Gneiss Complex, Slave Province, reveal primary igneous oscillatory zoning which is transgressively overprinted by irregular alteration domains. Electron microprobe analyses show that altered zircon domains are depleted in Zr and Si relative to unaltered zircon while retaining a constant Zr/Si ratio. SIMS trace element analyses indicate that LREE are preferentially enriched in the altered domains. Altered zircon contains elevated concentrations of Ba (up to 580 ppm), Ca (up to 2% weight of the element) and common Pb (>50 ppb). The presence of LREE, Ca, Ba and common Pb in the zircons is interpreted to be the result of secondary alteration by an aqueous fluid, and not by primary incorporation during crystallization. We propose that the alteration-related elements are located in amorphous zircon domains.     

Progressive aqueous alteration of CM carbonaceous chondrites

CM chondrites are aqueously altered rocks that contain ∼9 wt% H₂O⁺ (i.e., indigenous water) bound in phyllosilicates; also present are clumps of serpentine-tochilinite intergrowths (previously called “poorly characterized phases” or PCP), pentlandite and Ni-bearing pyrrhotite. We studied 11 CM chondrites that span the known range from least altered to most altered. We used various petrologic properties (many previously identified) that provide information regarding the degree of aqueous alteration. There are no known unaltered or slightly altered CM chondrites (e.g., rocks containing numerous chondrules with primary igneous glass). Some CM properties result from processes associated with early and intermediate stages of the alteration sequence (i.e., hydration of matrix, alteration of chondrule glass, and production of large PCP clumps). Other petrologic properties reflect processes active throughout the alteration sequence; these include oxidation of metallic Fe-Ni, alteration of chondrule phenocrysts, changes in PCP composition (reflecting an increase in the phyllosilicate/sulfide ratio), and changes in carbonate mineralogy (reflecting the development of dolomite and complex carbonates at the expense of Ca carbonate).On the basis of these parameters, we propose a numerical alteration sequence for CM chondrites. Because there are no known CM samples that display only incipient alteration, the least altered sample was arbitrarily assigned to subtype 2.6. The most altered CM chondrites, currently classified CM1, are assigned to subtype 2.0. These highly altered rocks have essentially no mafic silicates; they contain chondrule pseudomorphs composed mainly of phyllosilicate. However, their bulk compositions are CM-like, and they are closer in texture to other C2 chondrites than to CI1 chondrites (which lack chondrule pseudomorphs). Using several diagnostic criteria, we assigned petrologic subtypes (±0.1) to every CM chondrite in our study: QUE 97990, CM2.6; Murchison, CM2.5; Kivesvaara, CM2.5; Murray, CM2.4/2.5; Y 791198, CM2.4; QUE 99355, CM2.3; Nogoya, CM2.2; Cold Bokkeveld, CM2.2; QUE 93005, CM2.1; LAP 02277, CM2.0; MET 01070, CM2.0.The proposed CM numerical alteration sequence improves upon the existing scheme of Browning et al. (1996) in that it does not require a complicated algorithm applied to electron-microprobe data to determine the average matrix phyllosilicate composition. The new sequence is more comprehensive and employs petrologic subtypes that are easier to use and remember than mineralogic alteration index values.New neutron-activation analyses of QUE 97990, QUE 93005, MET 01070, Murchison and Crescent, together with literature data, confirm the compositional uniformity of the CM group; different degrees of alteration among CM chondrites do not lead to resolvable bulk compositional differences. This suggests that the textural differences among individual CM chondrites reflect progressive alteration of similar hypothetical CM3.0 starting materials in different regions of the same parent body, with minimal aqueous transport of materials over appreciable (e.g., meters) distances.     

Hydrothermal alteration of felsic volcanic rocks associated with massive sulphide deposition in the northern Iberian Pyrite Belt (SW Spain)

Massive sulphide deposits of the northern Iberian Pyrite Belt (IPB) are mainly hosted by felsic volcanic rocks of rhyolitic to dacitic composition. Beneath most of the massive ores of this area (e.g., Concepción, San Miguel, Aguas Teñidas Este or San Telmo deposits) there is usually a wide hydrothermal alteration halo associated with stockwork-type mineralization. Within these alteration envelopes there are two principal rock types: (1) chlorite-rich rocks, linked to the inner and more intensely altered zones and dominantly comprising chlorite+pyrite+quartz+sericite (+carbonate+rutile+zircon+chalcopyrite), and (2) sericite-rich rocks, more common in the peripheral zones and showing a dominant paragenesis of sericite+quartz+pyrite+chlorite (+carbonate+rutile+zircon+sphalerite). Mass-balance calculations comparing altered and least-altered felsic volcanic rocks suggest that sericitization was accompanied by moderate enrichment in Mg, Fe and H₂O, with depletion in Si, Na and K, and a slight net mass loss of about 3%. Chloritization shows an overall pattern which is similar to that of the sericitic alteration, but with large gains in Fe, Mg and H₂O (and minor enrichment in Si, S and Mn), and a significant loss of Na and K and a minor loss of Ca and Rb. However, chloritization has involved a much larger net mass change (mass gain of about 28%). Only a few elements such as Nb, Y, Zr, Ti, P and LREE appear to have remained inert during hydrothermal alteration, whilst Ti and Al have undergone very minor mobilization. The results point to the severity of the physico-chemical conditions that prevailed during the waxing stage of the ore-forming hydrothermal systems. Further, mineralogical and geochemical studies of the altered footwall rocks in the studied deposits indicate that hydrothermal ore-bearing fluids reacted with host rocks in a multi-stage process which produced a succession of mineralogical and chemical changes as the temperature increased.     

Zircon alteration,formation and preservation in sandstones

Zircon textures, chemistry and microstructures have been characterized in situ within Carboniferous sandstones from the Midland Valley of Scotland using back‐scattered electron and cathodoluminescence images, electron backscatter diffraction techniques and chemical analyses. The study of polished thin sections reveals a variety of zircon types including unmodified detrital zircon, zircon outgrowths and different forms of modified zircon that formed in low‐temperature conditions within the sedimentary rocks. These rocks have only experienced temperatures of <100 °C during burial; however, altered zircon is abundant and characterized by a low mean atomic number, with relatively high contents of non‐formula elements and a nano‐crystalline or microcrystalline structure. It forms by replacement of detrital zircon that subsequently became metamict. Two types of replacement mechanisms are effective in sedimentary environments and involve either dissolution–reprecipitation or solid‐state reaction, but both require fluid access to the radiation‐damaged areas. The former process appears to become the dominant replacement mechanism as temperature increases and produces highly porous, inclusion‐rich zircon. Metamict zircon is extremely reactive in near‐surface conditions and the production of low‐temperature zircon is sensitive to both parent zircon characteristics and environmental conditions. As such, the alteration of zircon has the potential to yield unique information on the diagenetic history of sedimentary rocks. Low‐temperature zircon would be unlikely to survive sedimentary transport or the rock crushing procedures that characterize many investigations of detrital zircon populations and consequently may generate severe biases in studies of this type.     

Formation Process of Zircon Associated with REE‐Fluorocarbonate and Niobium Minerals in the Nechalacho REE Deposit,Thor Lake,Canada

The two drill holes, which penetrated sub‐horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high‐field‐strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type‐1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type‐2 zircon consists of a porous HREE‐rich core and LREE–Nb–F‐rich rim. Enrichment of F in the rim of type‐2 zircon suggests that F was related to the enrichment of HFSE. The core of type‐2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type‐3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type‐3 zircon has high REE, Nb and F contents. Type‐4 zircon consists of porous‐core and ‐rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type‐5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type‐4 and type‐5 zircon grains have low REE, Nb and F contents. Type‐1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type‐2 and type‐3 zircon grains mainly occur in the shallow units, while those of type‐4 and type‐5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type‐4 and type‐5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO₃, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type‐1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F‐rich hydrothermal zircon formed around HREE‐rich magmatic zircon (type‐2). (iii) type‐3 zircon crystallized through the F and CO₃‐rich hydrothermal alteration of type‐2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO₃‐rich hydrothermal fluid corroded type‐3, forming REE–Nb‐poor zircon (type‐4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb‐leached zircon (type‐4); (v) type‐5 zircon is formed by the more CO₃‐rich hydrothermal alteration of type‐4 zircon, suggested by the fact that type‐4 and type‐5 zircon grains are often included in ankerite. Type‐3 to type‐5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type‐2 zircon in the presence of F‐ and/or CO₃‐rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F‐rich hydrothermal stage caused the crystallization of REE–Nb‐rich zircon (type‐2 rim and type‐3), with abundant formation of phlogopite and fluorite; (ii) F‐ and CO₃‐rich hydrothermal stage led to the replacement of a part of REE–Nb–F‐rich zircon by REE fluorocarbonate; and (iii) CO₃‐rich hydrothermal stage resulted in crystallization of the REE–Nb–F‐poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F‐rich zircon in the hydrothermally altered units.     

Sapphire within zircon-rich gem deposits,Bo Loei,Ratanakiri Province,Cambodia: trace elements,inclusions, U–Pb dating and genesis

Subordinate sapphire accompanies prevalent zircon megacrysts in the Bo Loei basaltic gem field, Ratanakiri Province, Cambodia. These deposits are important for heat-treated gem zircon. Dark blue sapphire, with rare blue-green, orange-brown and yellow stones, up to a few cm in size, include hexagonal-shaped and growth-zoned crystals. Analyses of the sapphires (electron microprobe and laser ablation-inductively coupled plasma-mass spectrometry) showed Fe as the main chromophore (0.6–2.7 wt%), with minor Ti (<0.7 wt%). Sapphire cores show enrichment in Fe relative to rims and some include exotic heavy elements (Nb up to 56, Ta up to 144, Sn up to 5 ppm). The sapphires show high Ga values (271–724 ppm) and Ga/Mg ratios (4.8–77.0) suggesting magmatic associations. Two sapphires with syngenetic inclusions (zircon, Nb-rich rutile) gave U–Pb (Th-disequilibrium corrected) ages at ca 0.93 ± 0.1 Ma. The Bo Loei sapphires show higher Fe and Ga than other magmatic sapphire suites elsewhere in Cambodia (Pailin), Laos (Ban Huai Sai, Ban Sam Sai), South Vietnam (Dak Nong, Dak Lac) and SE Thailand (Chanthaburi-Trat). This suggests potential for geographic typing of sapphire suites between these different fields.     

Radiation damage and alteration of zircon from a 3.3 Ga porphyritic granite from the Jack Hills,Western Australia

Complexly zoned zircons (19 grains, ∼ 3.3 Ga) from a porphyritic granite in the Jack Hills, Western Australia, have been investigated using electron microprobe analysis (EMPA) and transmission electron microscopy (TEM) in order to examine the effects of radiation as a function of dose, as well as the nano-scale microstructure and composition of impurities and secondary alteration phases. In back-scattered electron (BSE) images, zones with bright contrast consist of an almost unaltered zircon with limited amounts of impurity elements. In contrast, the dark zones contain higher concentrations of trace elements: U, Th, Pb, Fe, Y, Ce, Ca and Al. The cumulative doses due to alpha-decay in the dark zones are calculated to be 0.21–1.0 × 10¹⁷ (alpha-decay events/mg), equivalent to 1.0–4.7 dpa (displacements per atom). These doses are much higher than the dose required for radiation-induced amorphization, as determined by ion-beam irradiation of synthetic zircon, 0.3–1.0 dpa (0–600 °C). However, based on high-resolution TEM observations, none of the zircons are fully amorphous, to the result of annealing under ambient conditions. The concentrations of Ca and Al, which was considered to indicate alteration, increase dramatically at a cumulative dose of 1.6 × 10¹⁶ (alpha-decay events/mg). This is the dose at which the first percolation point occurs, as amorphous domains overlap and form an interconnected network. In the altered zones, nanocrystallites of zircon are present with a random orientation, and the amorphous matrix contains the impurity elements. Although the Ce-concentration is extremely high, 1–2 wt.%, the Ce anomaly, Ce/Ce⁎, does not vary significantly as a function of dose or degree of alteration, indicating that the LREE patterns were overprinted by the fluids with a similar Ce-anomaly. The valence of Ce analyzed by EELS (electron energy loss spectroscopy) is tetravalent in the altered zone, suggesting that the altering fluids were oxidizing.     

Mineral Chemistry of Albite-Enriched Granitoids at Um Ara,Southeastern Desert,Egypt

Mineral chemistry and typomorphic characteristics are used to monitor the physicochemical evolution of late-magmatic to postmagmatic alteration processes that resulted in the development of a radioactive and albite-enriched microgranite stock. The mineral paragenesis indicates that postmagmatic fluids were enriched in Nb, Zn, Mn, U., Th, Zr, and Y, in addition to Rb, Li, and F Manganocolumbite with extremely high Nb/(Nb+Ta) (0.99), Mn/(Mn+Fe) (0.82), and zircon with high Zr/(Zr+Hf) (0.97) indicate crystallization under alkaline, relatively high-temperature conditions (>425° C). The close association of manganocolumbite, Nb-Mn-Zn- rich ilmenite (with 1.2 to 14.5 wt% ZnO), spessartine garnet (with 68.2-89.4 mol% spessartine), zircon, xenotime, zinnwaldite mica (up to 5.98 wt% F), and fluorite indicates the strong affinity of the elements of Nb, Y., Zr, Mn, and Zn for stable complexing by K⁺, Na⁺, Li⁺, and F^? rich supercritical fluids during the course of extraction and transportation.

The enrichment of the interacting fluid in U and Th is depicted by the presence of up to 1.6% UO₂ in manganocolumbite and Hf-bearing zircon, and up to 10.5% ThO₂ in monazite, in addition to locally abundant thorite and uranophane. It is suggested that the uranium mineralization, mainly as fracture fillings, formed during the waning stage of hydrothermal activity.     

Mineral chemistry of a zircon-bearing, composite, veined and metasomatised upper-mantle peridotite xenolith from kimberlite

Zircon-bearing veins in a harzburgite xenolith from kimberlite have imposed Ca-metasomatism on the harzburgite wall rock, in addition to adding K, Fe, Ti and OH. The zircon, previously dated to have an age similar to that of the xenolith-hosting kimberlite, shows higher Y, Nb, Ba, REE, Th and U contents than other mantle-derived zircons. Peripheral alteration of the zircon to baddeleyite and zirconolite, and alteration of vein ilmenite to perovskite suggest reaction with an evolving carbonatitic kimberlite melt. The high Cr₂O₃ content (0.77 wt%) of the zirconolite extends the compositional range of terrestrial zirconolite.     

Acid-sulphate Type Alteration and Mineralization in the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea

Abstract: The Onsen acid‐sulphate type of mineralization is located in the Desmos caldera, Manus back‐arc basin. Hydrothermal precipitates, fresh and altered basaltic andesite collected from the Desmos caldera were studied to determine mineralization and mobility of elements under seawater dominated condition of hydrothermal alteration. The mineralization is characterized by three stages of advanced argillic alteration. Alteration stage I is characterized by coarse subhedral pyrophyllite with disseminated anhedral pyrite and enargite which were formed in the temperature range of 260–340°C. Alteration stage II which overprinted alteration stage I was formed in the temperature range of 270–310°C and is characterized by euhedral pyrite, quartz, natroalunite, cristobalite and mixed layer minerals of smectite and mica with 14–15 Å XRD peak. Alteration stage III is characterized by amorphous silica, native sulphur, covellite, marcasite and euhedral pyrite, which has overprinted alteration stages I and II. Relative to the fresh basaltic andesite samples, the rims and cores of the partly altered basaltic andesite samples have very low major, minor and rare earth elements content except for SiO₂ which is much higher (58–78 wt%) than SiO₂ content of the fresh basaltic andesite (55 wt%). REE patterns of the partly altered basaltic andesite specimens are variably depleted in LREE and have pronounced negative Eu anomalies. Normalization of major, minor and REE content of the partly altered basaltic andesites to the fresh basaltic andesite indicates that all the elements except for SiO2 in the partly altered basaltic andesite are strongly lost (e.g. Al₂O₃ = ‐8.3 to ‐10.9 g/100cm³, Ba = ‐2.2 to ‐5.6 mg/100cm³, La = ‐130 to ‐200 μg/100cm³) during the alteration process. Abnormal depletion of MgO, total Fe as Fe₂O₃, LREE especially Eu and enrichment of SiO₂ in the altered basaltic andesites from the Desmos caldera seafloor is caused by interaction of hot acidic hydrothermal fluid, which originates from a mixing of magmatic fluid and seawater.     

Zircon textures and composition: refractory recorders of magmatic volatile evolution?

Zircon textures and composition have been used to infer magmatic processes including closed-system fractional crystallization, magma mixing or replenishment, and country-rock assimilation. Here, we propose that zircon textures and composition may also be refractory recorders of magmatic volatile evolution. We present field, whole-rock chemical, textural, mineral chemical, and U–Pb age data from evolved, fine-to-coarse-grained granite intrusions on Melville Peninsula, Nunavut, Canada. Zircon forms two main populations in these granites, Type-1 and Type-2 zircon. Type-1 zircon is present in all samples, but predominant in fine-grained granite. Crystals are euhedral and inclusion-rich and show periodic, fine-scale oscillatory zoning, comparatively low concentrations of U (<2,200 ppm) and Hf (<1.6 wt%), high Zr/Hf (~40–62), and pervasive alteration. Type-2 zircon is predominant in coarse-grained granite. Crystals form overgrowths on Type-1 zircon and individual crystals. They are subhedral and inclusion-poor and show weak, irregular, large-scale oscillatory zoning, high U (up to ~7,250 ppm) and Hf (1.5–2.0 wt%), low Zr/Hf (~37–44), and only local alteration. Compatible trace-element concentrations and Zr/Hf change sharply across the boundary of Type-1 to Type-2 zircon; ²⁰⁷Pb/²⁰⁶Pb ages preclude a significant hiatus between crystallization of the two types. We argue against magmatic versus hydrothermal crystallization, country-rock assimilation, or magma mixing as causes for the crystallization of Type-1 and Type-2 zircon. We propose instead that Type-1 zircon formed from volatile-undersaturated magmas and that Type-2 zircon formed from volatile-saturated magmas. Magmas fractionated by volatile-driven filter pressing into crystal-rich mush and crystal-poor magma. Crystal-rich mush with abundant Type-1 zircon crystallized to fine-grained granite. Volatile-rich magma crystallized to Type-2 zircon and coarse-grained granite. While Type-1 zircon was pervasively altered by exsolving magmatic volatiles, Type-2 zircon was only locally affected by subsolidus hydrothermal alteration.     

Impact of iron on nuclear glass alteration in geological repository conditions: A multiscale approach

Interactions between nuclear glass and Fe were investigated in a clayey environment to better understand the mechanisms and driving forces controlling the long-term behavior of high-level waste glass in a geological repository. An integrated experiment involving a Glass–Iron–Clay (GIC) stack was run at a laboratory scale in anoxic conditions for 2 years and the interfaces were characterized by a multiscale approach using scanning electron microscopy coupled with energy dispersive spectroscopy, transmission electron microscopy, Raman microspectroscopy and scanning transmission X-ray microscopy at the SLS Synchrotron. The characterization of glass alteration patterns on cross sections revealed an increase in glass alteration with the Fe content and the proximity between the glass and Fe. The alteration layers are polyphase and stratified with an inner porous gel layer incorporating Fe and an outer layer composed of nanocrystalline Fe-silicates. Several mechanisms which could affect the glass alteration kinetics and the transport properties of the alteration layer are proposed to explain this pattern: (i) consumption of hydrolyzed silica by precipitation of Fe-silicates; (ii) penetration of Fe within the gel porosity probably as precipitates such as Fe oxyhydroxide or Fe-silicates. These new data may imply some consequences when considering the long-term behavior of glass in geological disposal conditions.     

Magnetic properties related to hydrothermal alteration processes at the Escondida porphyry copper deposit,northern Chile

Fluid–rock interaction related to the circulation of hydrothermal fluids can strongly modify the physicochemical properties of wall rocks in porphyry Cu deposits. These processes can also produce compositional and textural changes in ferromagnetic minerals, which can be quantified using magnetic methods. In the Escondida porphyry Cu deposit of northern Chile, each hydrothermally altered lithology is characterized by a discrete assemblage of Fe–Ti oxide minerals. These minerals have distinctive bulk magnetic susceptibility (K _bulk), temperature-dependent magnetic susceptibility, and magnetic hysteresis parameters. Selectively altered rocks (i.e., potassic and chloritic alteration types) exhibit the highest K _bulk values (>3.93?×?10^?3 SI units), and their hysteresis parameters indicate multidomain magnetic mineral behavior. This suggests that these rocks are composed of the coarsest magnetic grain sizes within the deposit. Optical analyses and susceptibility–temperature curves confirm that the magnetic signals in selectively altered rocks are mainly carried by secondary magnetite. In contrast, pervasively altered rocks (i.e., quartz-sericite and argillic alteration types) exhibit low K _bulk values (<1.93?×?10^?4 SI units) and contain smaller pseudo-single domain magnetic grain assemblages. This is consistent with the destruction and/or reduction in size of magnetite under acidic conditions. The results therefore demonstrate a genetic relationship between the hydrothermal alteration processes, Fe–Ti oxide minerals, and magnetic properties of the wall rock in the Escondida deposit. These magnetic methods can be considered a sensitive and efficient petrophysical tool for the identification and semi-quantification of alteration assemblages, and facilitating the recognition and mapping of discrete hydrothermal zones during exploration and operation of porphyry Cu deposits.     

Hydrogen isotope evidence for the origin and evolution of the carbonaceous chondrites

We present new hydrogen isotope data for separated matrix, hydrated chondrules, and other hydrated coarse silicate fragments from nine carbonaceous chondrites. These data were generated using a micro-analytical method involving stepped combustion of tens to hundreds of micrograms of hydrous solids. We also re-evaluate hydrogen isotope data from previous conventional stepped combustion experiments on these and other carbonaceous chondrites.Hydrogen isotope compositions of matrix and whole-rock samples of CM chondrites are correlated with oxygen isotope indices, major and minor-element abundances, and abundance and isotope ratios of other highly volatile elements. These correlations include a monotonic decrease in δD with increasing extent of aqueous alteration and decreasing abundances of highly volatile elements (including C, N and Ar), between extremes of ∼0‰ (least altered, most volatile rich) and −200‰ (most altered, least volatile rich). In plots involving only abundances and/or isotope ratios of highly volatile elements, CI chondrites fall on the high-δD, volatile rich end of the trends defined by CM chondrites; i.e., CI chondrites resemble the least altered CM chondrites in these respects. These trends suggest the protoliths of the CM chondrites (i.e., before aqueous alteration) contained an assemblage of volatiles having many things in common with those in the CI chondrites. If so, then the volatile-element inventory of the CI chondrites was a more widespread component of early solar system objects than suggested by the scarcity of recognized CI meteorites. Differences in volatile-element chemistry between the CI and average CM chondrites can be attributed to aqueous alteration of the latter.Previous models of carbonaceous chondrite aqueous alteration have suggested: (1) the protoliths of the CM chondrites are volatile poor objects like the CO or CV chondrites; and (2) the CI chondrites are more altered products of the same process producing the CM chondrites. Both suggestions appear to be inconsistent with hydrogen isotope data and other aspects of the volatile-element geochemistry of these rocks. We present a model for aqueous alteration of the CM chondrites that reconciles these inconsistencies and suggests revised relationships among the major subtypes of carbonaceous chondrites. Our model requires, among other things, that the water infiltrating CM chondrites had a δD value of ∼−158‰, consistent with initial accretion of CM parent bodies at ∼4 AU.     

胶东新立构造蚀变岩型金矿床元素地球化学行为

新立金矿位于华北克拉通东部胶东金矿省内,是一个典型的蚀变岩型(焦家型)金矿床,矿床受区域三山岛-仓上断裂带控制,产出于蚀变的玲珑花岗岩中。在主断裂带下盘蚀变矿化发育,可以划分为五个阶段:钾长石化阶段、绢英岩化阶段、黄铁绢英岩矿化阶段、多金属硫化物矿化阶段和碳酸盐化阶段。不同的蚀变矿化过程导致各阶段样品具有不同的矿物组合和地球化学特征。钾长石化花岗岩以高钾钠含量为特征,因为样品中含有新生成的二次钾长石及残留的钠长石;绢英岩的钙钠含量明显低于钾长石化花岗岩,是绢英岩化阶段斜长石蚀变分解所致;黄铁绢英岩FeT2O3含量普遍较高且SiO 2含量波动明显,与该阶段样品中大量黄铁矿的产出及部分样品中包含石英团块或石英脉相一致;多金属硫化物矿化样品的元素含量与黄铁绢英岩基本类似;碳酸盐化蚀变样品以高CaO含量为特征,与该阶段大量沉淀析出的方解石相符。在原始地幔标准化微量元素配分图上,不同阶段矿化蚀变样品,大离子亲石元素Rb、Ba、K、Sr差异性明显,而高场强元素Zr、Hf、Nb、Ta、P差异性较小,表明热液蚀变过程中大离子亲石元素活动性较强,高场强元素相对稳定。在稀土元素球粒陨石标准化图中,不同阶段样品均呈明显的右倾性,蚀变早期(钾长石化阶段)样品铕异常不明显,蚀变矿化主期(绢英岩化阶段至多金属硫化物矿化阶段)样品普遍具有负铕异常,而蚀变晚期(碳酸盐化阶段)样品普遍具有正铕异常。元素相关性分析表明,金与银、砷、铋和硫具明显正相关,与铜、铅具有一定的相关性。成矿元素因子分析也显示出金与砷、硫、铁、钴在矿化过程中具有类似的地球化学行为。实测剖面上不同位置样品元素地球化学特征的差异性主要受构造及蚀变矿化类型、强度控制,成矿元素在主断裂附近达到峰值,在远离主断裂方向上,其含量整体呈下降趋势,但在次级矿化断裂发育地段,含量又明显回升;另外在断裂附近由于微裂隙及节理相对发育,有利于热液的渗透,蚀变较强,对成矿元素的空间分布亦具有控制作用。     

The effect of organic matter on chemical weathering: study of a small tropical watershed: nsimi-zoétélé site,cameroon

The effect of organic matter during soil/water interaction is still a debated issue on the controls of chemical weathering in a tropical environment. In order to study this effect in detail, we focused on the weathering processes occurring in a small tropical watershed (Nsimi-Zoetélé, South Cameroon). This site offers an unique opportunity to study weathering mechanisms in a lateritic system within a small basin by coupling soil and water chemistry.The lateritic cover in this site can reach up to 40 m in depth and show two pedological distinct zones: unsaturated slope soils on the hills and/or elevated areas; and water-saturated soils in the swamp zone which represent 20% of the basin surface. The study present chemical analysis performed on water samples collected monthly from different localities between 1994–1997 and on soil samples taken during a well drilling in December 1997. The results suggest the existence of chemical and spatial heterogeneities of waters in the basin: colored waters flooding the swamp zone have much higher concentrations of both organic matter (i.e., DOC) and inorganic ions (e.g., Ca, Mg, Al, Fe, Th, Zr) than those from springs and groundwater from the hills. Nevertheless, these organic-rich waters present cation concentrations (Na, Ca, Mg, K) which are among the lowest compared to that of most world rivers. The main minerals in the soils are secondary kaolinite, iron oxi-hydroxides, quartz, and accessory minerals (e.g., zircon, rutile). We mainly focused on the mineralogical and geochemical study of the swamp zone soils and showed through SEM observations the textural characterization of weathered minerals such as kaolinite, zircon, rutile, and the secondary recrystallization of kaolinite microcrystals within the soil profile. Water chemistry and mineralogical observations suggest that hydromorphic soils of the swamp zone are responsible for almost all chemical weathering in the basin. Thus, in order to explain the increase of element concentration in the organic-rich waters, we suggest that organic acids enhance dissolution of minerals such as kaolinite, goethite, and zircon and also favors the transport of insoluble elements such as Al, Fe, Ti, Zr, and REE by chemical complexation. SiO₂(aq) concentrations in these waters are above saturation with respect to quartz. Dissolution of phytholithes (amorphous silica) may be responsible for this relatively high SiO₂(aq.) concentration. Al/Mg ratios obtained for the soil and the Mengong river waters show that a significant amount of Al does not leave the system due to kaolinite recrystallisation in the swamp zone soils. Geochemical data obtained for this watershed show the important contribution of vegetation and organic matter on chemical weathering in the swamp zone. Quantitatively we propose that the increasing amount in total dissolved solid (TDS) due to organic matter and vegetation effect is about 35%. In summary, this interaction between soils and waters occurs mostly in soils that are very depleted in soluble elements. Thus, the low concentration of major elements in these water is a direct consequence of the depleted nature of the soils.     

Importance of volcanic glass alteration to sediment stabilization: offshore Japan

A minor amount (ca 1 wt%) of amorphous silica cement sourced from volcanic glass inhibits consolidation of hemipelagic sediment approaching the Nankai Trough subduction zone throughout the Shikoku Basin. The distribution and nature of the cement were examined via secondary and backscattered electron imaging. The amorphous silica occurs as altered material in contact with volcanic glass, coating grains (including grain contacts) and filling pores. Based on chemical and petrographic evidence, the cement is probably sourced from volcanic glass; this is in contrast to a previous suggestion that this silica cement is sourced dominantly from biogenic silica. Amorphous silica sourced from disseminated volcanic glass shards has the ability to form a thin coating on clay‐dominated sediment throughout the Shikoku Basin. Measured amorphous silica content in hemipelagic sediments suggests that the cementing process is active throughout the Shikoku Basin (at sites separated by >500 km). The cementation process may occur in other locations where sediment containing hydrated disseminated volcanic glass is buried sufficiently for heat to facilitate alteration (i.e. Central America, Cascadia and the Gulf of Alaska).     

Fate of trace elements during alteration of uraninite in a hydrothermal vein-type U-deposit from Marshall Pass, Colorado, USA

Alteration of uraninite from a hydrothermal vein-type U-deposit in Marshall Pass, Colorado, has been examined by electron microprobe analysis in order to investigate the release and migration of trace elements W, As, Mo, Zr, Pb, Ba, Ce, Y, Ca, Ti, P, Th, Fe, Si, Al, during alteration, under both reducing and oxidizing conditions. The release of trace elements from uraninite is used to establish constraints on the release of fission product elements from the UO₂ in spent nuclear fuels. Uraninite occurs with two different textures: (1) colloform uraninite and (2) fine-grained uraninite. The colloform uraninite contains 1.04-1.75 wt% of WO₃, 0.16-1.70 wt% of As₂O₃, 0.06-0.88 wt% of MoO₃; whereas, the fine-grained uraninite retains 2.25-4.93 wt% of WO₃, up to 5.76 wt% of MoO₃, and 0.26-0.60 wt% of As₂O₃. The near constant concentration of incompatible W in the colloform uraninite suggests W-incorporation into the uraninite structure or homogeneous distribution of W-rich nano-domains. Incorporation of W and Mo into the uraninite and subsequent precipitation of uranyl phases bearing these elements are critically important to understanding the release and migration of Cs during the corrosion of spent nuclear fuel, as there is a strong affinity of Cs with W and Mo. Zoning in the colloform texture is attributed to variation in the amount of impurities in uraninite. For unaltered zones, the calculated amount of oxygen ranges from 2.08 to 2.32 [apfu, (atom per formula unit)] and defines the stoichiometry as UO_2+x and U₄O₉; whereas, for the altered zones of the colloform texture, the oxygen content is 2.37-2.48 [apfu], which is probably due to the inclusion of secondary uranyl phases, mainly schoepite. The supergene alteration resulted in precipitation of secondary uranyl minerals at the expense of uraninite. Four stages of colloform uraninite alteration are proposed: (i) formation of an oxidized layer at the rim, (ii) corrosion of the oxidized layer, (iii) precipitation of U⁶⁺-phases with well-defined cleavage, and (iv) fracture of the uraninite surface along the cleavage planes of the U⁶⁺-phases.     

Implication of Apatite and Anhydrite for Formation of an Iron‐Oxide‐Apatite (IOA) Rare Earth Element Prospect,Benjamin River,Canada

The Benjamin River apatite prospect in northern New Brunswick, Canada, is hosted by the Late Silurian Dickie Brook plutonic complex, which is made up of intrusive units represented by monzogranite, diorite and gabbro. The IOA ores, composed mainly of apatite, augite, and magnetite at Benjamin River form pegmatitic pods and lenses in the host igneous rocks, the largest of which is 100 m long and 10–20 m wide in the diorite and gabbro units. In this study, 28 IOA ore and rock samples were collected from the diorite and gabbro units. Mineralogical observations show that the apatite–augite–magnetite ores are variable in the amounts of apatite, augite, and magnetite and are associated with minor amounts of epidote‐group minerals (allanite, REE‐rich epidote and epidte) and trace amounts of albite, titanite, ilmenite, titanomagnetite, pyrite, chlorite, calcite, and quartz. Apatite and augite grains contain small anhydrite inclusions. This suggests that the magma that crystallized apatite and augite had high oxygen fugacity. In back scattered electron (BSE) images, apatite grains in the ores have two zones of different appearance: (i) primary REE‐rich zone; and (ii) porous REE‐poor zone. The porous REE‐poor zones mainly appear in rims and/or inside of the apatite grains, in addition to the presence of apatite grains which totally consist of a porous REE‐poor apatite. This porous REE‐poor apatite is characterized by low REE (<0.84 wt%), Si (<0.28 wt%), and Cl (<0.17 wt%) contents. Epidote‐group minerals mainly occur in grain boundary between the porous REE‐poor apatite and augite. These indicate that REE leached from primary REE‐rich apatite crystallized as allanite and REE‐rich epidote. Magnetite in the ores often occurs as veinlets that cut apatite grains or as anhedral grains that replace a part of augite. These textures suggest that magnetite crystallized in the late stage. Pyrite veins occur in the ores, including a large amount of quartz and calcite veins. Pyrite veins mainly occur with quartz veins in augite. These textures indicate pyrite veins are the latest phase. Apatite–augite–magnetite ore, gabbro–quartz diorite and feldspar dike collected from the Benjamin River prospect contain dirty pure albite (Ab₉₈Or₂–Ab₁₀₀) under the microscope. The feldspar dikes mainly consist of dirty pure albite. Occurrences of the dirty pure albite suggest remarkable albitization (sodic alteration) of original plagioclase (An_25.3–An₆₀ in Pilote et al., 2012) associating with intrusion of monzogranite into gabbro and diorite. SO₄^2? bearing magma crystallized primary REE‐rich apatite, augite and anhydrite reacted with Fe in the sodic fluids, which result in oxidation of Fe²⁺ and release of S^2? into the sodic fluids. REE, Ca and Fe from primary REE‐rich apatite, augite and plagioclase altered by the sodic fluids were released into the fluids. Then Fe³⁺ in the sodic fluids precipitated as Fe oxides and epidote‐group minerals in apatite–augite–magnetite ores. Finally, residual S^2? in sodic fluids crystallized as latest pyrite veins. In conclusion, mineralization in Benjamin River IOA prospect are divided into four stages: (1) oxidized magmatic stage that crystallized apatite, augite and anhydrite; (2) sodic metasomatic stage accompanying alteration of magmatic minerals; (3) oxidized fluid stage (magnetite–epidote group minerals mineralization); and (4) reduced fluid stage (pyrite mineralization).