Contribution of long-term hydrothermal experiments for understanding the smectite-to-chlorite conversion in geological environments

The smectite-to-chlorite conversion is investigated through long-duration experiments (up to 9 years) conducted at 300 °C. The starting products were the Wyoming bentonite MX80 (79 % smectite), metallic iron and magnetite in contact with a Na–Ca chloride solution. The predominant minerals in the run products were an iron-rich chlorite (chamosite like) and interstratified clays interpreted to be chlorite/smectite and/or corrensite/smectite, accompanied by euhedral crystals of quartz, albite and zeolite. The formation of pure corrensite was not observed in the long-duration experiments. The conversion of smectite into chlorite over time appears to take place in several steps and through several successive mechanisms: a solid-state transformation, significant dissolution of the smectite and direct precipitation from the solution, which is over-saturated with respect to chlorite, allowing the formation of a chamosite-like mineral. The reaction mechanisms are confirmed by X-ray patterns and data obtained on the experimental solutions (pH, contents of Si, Mg, Na and Ca). Because of the availability of some nutrients in the solution, total dissolution of the starting smectite does not lead to 100 % crystallization of chlorite but to a mixture of two dominant clays: chamosite and interstratified chlorite/smectite and/or corrensite/smectite poor in smectite. The role of Fe/(Fe + Mg) in the experimental medium is highlighted by chemical data obtained on newly formed clay particles alongside previously published data. The newly formed iron-rich chlorite has the same composition as that predicted by the geothermometer for diagenetic to low-grade metamorphic conditions, and the quartz + Fe-chlorite + albite experimental assemblage in the 9-year experiment is close to that fixed by water–rock equilibrium.     

Comparison of diagenetic and low-grade metamorphic evolution of chlorite in associated metapelites and metabasites: an integrated TEM and XRD study

Chlorite is a common sheet silicate that occurs in various lithologies over a wide grade range involving diagenesis and low‐grade metamorphism. Thus, the reaction progress of chlorite offers a unique opportunity for direct correlation of zonal classification of metasedimentary rocks based on illite crystallinity with metabasite mineral facies. To provide such correlation, chlorite crystallinity indices, apparent mean crystallite sizes and lattice strains, crystallite size distributions and compositions of chlorite from coexisting metapelites and metabasites were determined by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron microprobe (EMP) methods. Samples were from Palaeozoic and Mesozoic formations of the Bükkium (innermost Western Carpathians, Hungary) that underwent Alpine (Cretaceous) orogenic metamorphism. Metapelites range in grade from late diagenesis to epizone, whereas metabasites vary from prehnite–pumpellyite through pumpellyite–actinolite to greenschist facies. Despite significant differences in composition, mineral assemblages and textures, reaction progress, as measured in part by chlorite crystallinity, in metapelites paralleled that in metabasites. Chlorite crystallinity and mean crystallite size increase and the proportion of mixed layers in chlorite decreases, whereas the calculated lattice strain does not change significantly with increasing metamorphic grade. Similar trends, but (especially at higher grades) significant differences, were found in mean crystallite size values using various methods for XRD line profile analyses. The increase in crystallite size with increasing grade was demonstrated also by direct TEM measurements on ion‐milled whole‐rock samples, but with a larger scatter of data at higher grades. In spite of the different kinds of mixed layering in chlorite (Mg‐rich smectitic, mostly random, local corrensite‐like units in metabasites, and Fe‐rich berthierine and dioctahedral smectite in metapelites), XRD‐calculated and TEM‐measured parameters were found to be reliable tools for measuring reaction progress and metamorphic grade of the same degree in both lithotypes.     

Clay Minerals in an Active Hydrothermal Field at Iheya‐North‐Knoll,Okinawa Trough

Iheya‐North‐Knoll is one of the small knolls covered with thick sediments in the Okinawa Trough back‐arc basin. At the east slope of Iheya‐North‐Knoll, nine hydrothermal vents with sulfide mounds are present. The Integrated Ocean Drilling Program (IODP) Expedition 331 studied Iheya‐North‐Knoll in September 2010. The expedition provided us with the opportunity to study clay minerals in deep sediments in Iheya‐North‐Knoll. To reveal characteristics of clay minerals in the deep sediments, samples from the drilling cores at three sites close to the most active hydrothermal vent were analyzed by X‐ray diffraction, scanning electron microscope and transmission electron microscope. The sediments are classified into Layer 0 (shallow), Layer 1 (deep), Layer 2 (deeper) and Layer 3 (deepest) on the basis of the assemblage of clay minerals. Layer 0 contains no clay minerals. Layer 1 contains smectite, kaolinite and illite/smectite mixed‐layer mineral. Layer 2 contains chlorite, corrensite and chlorite/smectite mixed‐layer mineral. Layer 3 is grouped into three sub‐layers, 3A, 3B and 3C; Sub‐layer 3A contains chlorite and illite/smectite mixed‐layer mineral, sub‐layer 3B contains chlorite/smectite and illite/smectite mixed‐layer minerals, and sub‐layer 3C contains chlorite and illite. Large amounts of di‐octahedral clay minerals such as smectite, kaolinite, illite and illite/smectite mixed‐layer mineral are found in Iheya‐North‐Knoll, which is rarely observed in hydrothermal fields in mid‐ocean ridges. Tri‐octahedral clay minerals such as chlorite, corrensite and chlorite/smectite mixed‐layer mineral in Iheya‐North‐Knoll have low Fe/(Fe + Mg) ratios compared with those in mid‐ocean ridges. In conclusion, the characteristics of clay minerals in Iheya‐North‐Knoll differ from those in mid‐ocean ridges; di‐octahedral clay minerals and Fe‐poor tri‐octahedral clay minerals occur in Iheya‐North‐Knoll but not in mid‐ocean ridges.     

Corrensite and mixed-layer chlorite/corrensite in metabasalt from northern Taiwan: TEM/AEM,EMPA, XRD,and optical studies

Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess Al^VI relative to Al^IV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high Al^VI/Al^IV and low Fe^VI/(Fe+Mg)^VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low Al^IV/Si^IV and low Fe^VI/(Fe+Mg)^VI, while chlorite has high Al^IV/Si^IV and high Fe^VI/(Fe+Mg)^VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower Al^IV/Si^IV and Fe^VI/(Fe+Mg)^VI. The ratios of Fe^VI/(Fe+Mg)^VI and Al^IV/Si^IV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.     

Phyllosilicates in hydrothermally altered basalts from DSDP Hole 504B,Leg 83 — a TEM and AEM study

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or ohvine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from< 100 Å to a few hundred Å. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystal-linity of saponite. by contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of Å thick. The Si/(Si+Al) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe+Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+Al) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite±mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.Contribution No. 488 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan     

Mechanisms of Mg-phyllosilicate formation in a hydrothermal system at a sedimented ridge (Middle Valley,Juan de Fuca)

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24?Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of ≈0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14?Å with Fe/(Fe+Mg) ratios of ≈0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensite/chlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in δ¹⁸O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H₂O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300°?C±30° for chlorite-quartz at 32?m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10–11°/m in the vent region.     

Reaction pathways and reaction progress for the smectite-to-chlorite transformation: evidence from hydrothermally altered metabasites

The transformation from smectite to chlorite has been interpreted as involving either a disequilibrium chlorite/smectite mixed‐layering sequence, or an equilibrated discontinuous sequence involving smectite–corrensite–chlorite. Here, analysis of the smectite to chlorite transition in different geothermal systems leads us to propose that the transformation proceeds via three contrasting reaction pathways involving (i) a continuous mixed‐layer chlorite/smectite series; (ii) a discontinuous smectite–corrensite–chlorite series and (iii) a direct smectite to chlorite transition. Such contrasting pathways are not in accord with an equilibrium mineral reaction series, suggesting that these pathways record kinetically controlled reaction progress. In the geothermal systems reviewed the style of reaction pathway and degree of reaction progress is closely correlated with intensity of recrystallization, and not to differences in thermal gradients or clay grain size. This suggests a kinetic effect linked to variation in fluid/rock ratios and/or a contrast between advective or diffusive fluid transport. The mode of fluid transport provides a means by which the rates of dissolution/nucleation/growth can control the reaction style and the reaction progress of the smectite to chlorite transition. Slow rates of growth are linked to the first reaction pathway involving mixed‐layering, while increasing rates of growth, relative to nucleation, promote the generation of more ordered structures and ultimately lead to the direct smectite to chlorite transition, representative of the third pathway.     

Chloritoid-bearing rocks associated with blueschists and eclogites, northern New Caledonia

Abstract Chloritoid-bearing metasedimentary rocks occur in close proximity to blueschists and eclogites in the Tertiary high-pressure metamorphic belt of northern New Caledonia. The typical assemblage of chloritoid-bearing rocks in the epidote zone is quartzchlorite-muscovite-garnet-chloritoid. In the omphacite zone, epidote is an additional member of the chloritoid-bearing assemblage. Paragonite is rare, plagioclase was not detected, and rutile and ilmenite are the Fe-Ti oxide phases. Chloritoid-glaucophane is not a common assemblage. Chloritoid-bearing rocks have relatively low (Ca+K+Na)/Al ratios and the chloritoids are relatively Mg-rich with Mg/ (Mg+Fe) up to about 0.4. A comparison of the mineral assemblages and mineral chemistry with experimental and computed phase equilibria suggest an upper temperature limit near 560° C in the omphacite zone and a minimum temperature limit near 450° C at 10 kbar. An empirical garnet-chlorite Fe-Mg exchange thermometer does not yield consistent results for the higher-grade rocks, suggesting T s ranging from 390 to 535° C in the omphacite zone and 420–465° C in the epidote zone. The distribution coefficient K _D = (Fe/Mg)_ctd/(Fe/Mg)_chl for chloritoid and chlorite ranges from 3.9 to 6.4, values which are lower than those (=10) from lower greenschist facies rocks, but are near those of upper greenschist facies and albite-epidote amphibolite facies.     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

The effect of whole-rock MnO content on the stability of garnet in pelitic schists during metamorphism

Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H₂O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with X_Mn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (X_Mn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.     

Chlorite crystallinity: an empirical approach and correlation with illite crystallinity, coal rank and mineral facies as exemplified by Palaeozoic and Mesozoic rocks of northeast Hungary

Abstract Fairly strong (r= 0.75–0.85) positive linear correlations were found between crystallinity indices (peak widths) measured on the first two basal reflections of chlorite and those of illite–muscovite in <2-μm fractions of a representative shale–slate–phyllite series from Palaeozoic and Mesozoic formations of northeast Hungary. The metamorphic grade ranges from late or deep diagenesis through anchizone to epizone conditions. Chlorite crystallinity values measured on air-dried and ethylene-glycol-solvated samples suggest that the effects of expandable interlayers are negligable, especially in the higher grade (～temperature) part of the series. However, the greater scattering of crystallinity values for the chlorite 001 reflection compared to those of the 002 reflection may be related to the effects of minor amounts of interlayered and/or discrete smectite and/or vermiculite. With increasing metamorphic grade and advancing equilibrium recrystallization, the chlorite compositions in different samples become more homogenous. No correlation exists between crystallinity and changes in chlorite composition as estimated from the intensity ratios of basal reflections. Hence an increase of domain size and a decrease of lattice distortion with increasing grade (～temperature) may be decisive factors affecting chlorite crystallinity. Chlorite crystallinity can be applied as a reliable regional, statistical technique complementary with, or instead of, the illite crystallinity method. The illite and chlorite crystallinity scales used here are related to Kübler's epi-, anchi- and diagenetic zones and correlated with coal rank, conodont colour alteration and mineral facies data. As the effects of the detrital white mica can be observed even in the <2-μm fractions of anchizonal metapelites, the anchizone boundaries determined solely on the base of ‘fixed’illite crystallinity values may vary with amounts of detrital and newly formed muscovite–illite. Hence a complex approach utilizing more than one method for determination of grade is preferred for petrogenetic purposes, even if relationships between crystallinity scales, coal rank and mineral facies also vary strongly in different tectonic settings and lithologies.     

Integrated TEM, XRD and electron microprobe investigation of mixed-layer chlorite–smectite from the Point Sal ophiolite, California

Abstract Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite–smectite identified for each specimen: (i) L2036 ± 50%, (ii) L2035 ± 70 and 20%, (iii) 1A-13 ± 70%, (iv) 1B-42 ± 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that 'chlorite'analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate.
Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-Å layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-Å periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (<0.5)–smectite exists. Images of lower lava sample 1B-55 show predominantly 14-Å layers. Units of 24 Å tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.     

The smectite–chlorite transition in drillhole NJ-15, Nesjavellir geothermal field, Iceland: XRD, BSE and electron microprobe investigations

Abstract In well NJ-15 of the Nesjavellir geothermal field, Iceland, the transition of discrete smectite into discrete chlorite has been studied from drill cuttings recovered at depths of less than 1714 m and over a continuous range of temperatures between 60 and 300° C. At temperatures below 180° C, the clay fractions contain mixtures of di- and trioctahedral smectites, whose layer charge increases with depth. Between 200 and 240° C, discrete smectites have transformed into smectite-rich, randomly interstratified chlorite and smecite ( R 0 C/S). Because the abundance of chlorite interlayers in this C/S is generally <20%, its presence can be detected only by electron microprobe techniques and not by X-ray diffraction. Between 245 and 265° C, both regularly ( R 1) and randomly interstratified C/S are the predominant layer silicates. Discrete chlorite first appears at approximately 270° C and coexists with minor amounts of R 0 C/S at higher temperatures.
R 0 and R 1 C/S form a nearly complete compositional series between trioctahedral saponite and discrete chlorite end-members. The interlayer cation and Si content of smectites and C/S decrease with increasing temperature. The Mg/(Mg + Fe) content of smectite, C/S, and chlorite is unrelated to temperature. The percentage of chlorite in C/S, as determined by electron microprobe analyses, increases continuously with increasing temperature, except for occurrences of smectite-rich C/S in fresh basaltic dykes which have not thermally equilibrated with the higher grade country rocks.     

Metamorphic and Thermal History of a Fore-Arc Basin: the Fossil Bluff Group, Alexander Island, Antarctica

The Himalia Ridge Formation (Fossil Bluff Group), AlexanderIsland is a 2·2-km-thick sequence of Upper Jurassic–LowerCretaceous conglomerates, sandstones and mudstones, derivedfrom an andesitic volcanic arc and deposited in a fore-arc basin.The metamorphic and thermal history of the formation has beendetermined using authigenic mineral assemblages and vitrinitereflectance measurements. Metamorphic effects include compaction,pore-space reduction, cementation and dissolution and replacementof detrital grains by clay minerals (smectite, illite/smectite,corrensite and kaolinite), calcite, chlorite, laumontite, prehnite,pumpellyite, albite and mica, with less common quartz, haematite,pyrite and epidote. The authigenic mineral assemblages exhibita depth-dependence, and laumontite and calcite exhibit a strongantipathetic relationship. Detrital organic matter in the argillaceouslayers has vitrinite reflectance values (R_o) ranging from 2·3to 3·7%. This indicates considerable thermal maturation,with a systematic increase in reflectivity with increasing depth.There is good correlation of metamorphic mineral assemblageswith chlorite crystallinity and vitrinite reflectance values—allindicating temperatures in the range of 140 ± 20°Cat the top of the sequence to 250 ± 10°C at the baseof the sequence. The temperatures suggest a geothermal gradientof 36–64°C/km and a most likely gradient of 50°C/km.It is suggested that this higher-than-average gradient for afore-arc basin resulted either from rifting during basin formationor from a late-stage arc migration event. KEY WORDS: Antarctica; diagenesis; fore-arc basin; low-temperature metamorphism; vitrinite reflectance     

Very low-grade metamorphism of the Taveyanne greywacke, Glarus Alps, Switzerland

Detailed textural and chemical data for mineral assemblages on a regional scale are presented for the metaandesitic Eocene-Oligocene Taveyanne greywacke of the Glarus Alps, Eastern Switzerland. Presented data indicate an increase of metamorphic grade from zeolite facies to prehnite-pumpellyite and pumpellyite-actinolite facies. Low-grade outcrops contain laumontite, minor corrensite and pumpellyite (assemblage type 1), whereas outcrops of higher metamorphic grade contain prehnite and two populations of pumpellyite (type 2), prehnite—pumpellyite-(Al)—white mica (type 3), a single outcrop shows pumpellyite-actinolite facies (type 4). From the zeolite to prehnite-pumpellyite/pumpellyite-actinolite facies there are indications for an increase of the chemical equilibrium domain size for the critical paragenesis from a single detrital grain ≤1 mm) in type 1, to a few millimetres in type 2, and to a whole thin section in type 3. Metamorphic P - T conditions were determined by a combination of chlorite thermometry, fluid inclusion and vitrinite reflectance data. Peak temperatures range from 170-190 C for zeolite facies to 270-310 C for prehnite-pumpellyite and pumpellyite-actinolite facies. For the higher temperature range, pressures of 2-3 kbar are derived indicating a geothermal gradient of 24-32 C km^-1. The well-constrained temperature estimations derived for the assemblages provide a useful test of the different empirical calibrations of chlorite thermometers recently proposed. The best correspondence to the temperatures determined here is for the Cathelineau calibration. In addition, in the lower grade samples differences in textures and calculated temperatures provide a mean to distinguish between detrital and newly formed chlorites.     

Oxide and sulphide isograds along a Late Archean, deep-crustal profile in Tamil Nadu, south India

Oxide–sulphide–Fe–Mg–silicate and titanite–ilmenite textures as well as their mineral compositions have been studied in felsic and intermediate orthogneisses across an amphibolite (north) to granulite facies (south) traverse of lower Archean crust, Tamil Nadu, south India. Titanite is limited to the amphibolite facies terrane where it rims ilmenite or occurs as independent grains. Pyrite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade. Pyrrhotite is confined to the high‐grade granulites. Ilmenite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade and occurring primarily as hemo‐ilmenite in the high‐grade granulite facies rocks. Magnetite is widespread throughout the traverse and is commonly associated with ilmenite. It decreases in abundance with increasing metamorphic grade. In the granulite facies zone, reaction rims of magnetite + quartz occur along Fe–Mg silicate grain boundaries. Magnetite also commonly rims or is associated with pyrite. Both types of reaction rims represent an oxidation effect resulting from the partial subsolidus reduction of the hematite component in ilmenite to magnetite. This is confirmed by the presence of composite three oxide grains consisting of hematite, magnetite and ilmenite. Magnetite and magnetite–pyrite micro‐veins along silicate grain boundaries formed over a wide range of post‐peak metamorphic temperatures and pressures ranging from high‐grade SO₂ to low‐grade H₂S‐dominated conditions. Oxygen fugacities estimated from the orthopyroxene–magnetite–quartz, orthopyroxene–hematite–quartz, and magnetite–hematite buffers average 2.5 log units above QFM. It is proposed that the trends in mineral assemblages, textures and composition are the result of an external, infiltrating concentrated brine containing an oxidizing component such as CaSO₄ during high‐grade metamorphism later acted upon by prograde and retrograde mineral reactions that do not involve an externally derived fluid phase.     

矿物成因族的演化及其地质找矿信息

基于对胶东、晋北寒武纪变质岩系、超基性岩、基性岩、花岗岩类、火山岩类、硅铁建造铁矿、金矿蚀变带内 1 1个不同地质产状的 34个角闪石、 2 51个绿泥石、 60个黑云母单矿物的提纯 ,矿物的共生组合、物理性质、化学成分、X光衍射分析、热分析、红外吸收光谱分析、双矿物地质温度计、矿物压力计的测定 ,提出了角闪石、绿泥石、黑云母矿物成因族的地壳物质演化、成岩成矿作用、变质岩原岩恢复、地层对比、变质相、蚀变带的演化规律和地质找矿信息。     

Compositional homogeneity in low-temperature chlorites

Electron microprobe analyses of small chlorite grains (10–20 μm width) in diagenetically altered rocks from three deep wells and a series of outcrop samples ranging in maximum age from 4 to 1300 Ma show an increasingly smaller range in grain-to-grain composition as a function of the average age of the specimens in a series. The scatter of composition in a sample in each series changes little with depth despite present day, or estimated maximum temperature differences of 70° C to 100° C from top to bottom. Comparison of these chlorite compositions with those published for geothermal and metamorphic rocks formed under conditions of 300–450° C indicates that the homogeneity of chlorite composition is a function of both the temperature of equilibration and its duration. Apparently total homogenization of Fe/(Fe+Mg), Al/(Al+Mg+Fe) content will occur after 10¹⁰ years at low temperatures. Simple calculations indicate that a slow process such as solid state diffusion could be responsible for the eventual homogenization of mineral grain composition to reach chemical equilibrium after phase equilibrium has been reached.     

Analcimic zones in the tertiary of anatolia and their geological positions

The Anatolian Tertiary and especially the Neogene have some geological series with analcime as the principal rock-forming mineral. Sedimentation basins receiving material in suspension and in solution permit the authigenesis of analcime dolomite, calcite and opal(C-T). Analcimes formed by hydrothermal alteration on the ocean floor, after the pillow lava and diabasic dyke complexes of ophiolites, can form a source of detrital analcime when they are on the continental medium. Continental alteration of the pillow lavas and diabasic dykes permits the formation of solutions suitable in composition for analcime authigenesis. Analcimes formed in these environments are particularly related to the silica content of these media.Principal clay minerals formed with analcimic formations are smectites and (14_s—14_c) mixed layers. Illite, chlorite and corrensite are also present in smaller quantities.     

酸性岩的变质相

在沸石相变质条件下,花岗岩里浊沸石交代了斜长石和石英,在酸性火山岩里产生明矾石、埃洛石或高岭石。经受绿纤石-葡萄石相变质的花岗岩,其中黑云母变为钙铝榴石、帘石、绿纤石和葡萄石集合体,同时斜长石发生绢云母化。绿片岩相内酸性岩的浅色矿物有石英、微斜长石、钠长石和绿帘石,暗色矿物有绿泥石和黑云母。在角闪岩相变质的酸性岩中,开始出现中、基性斜长石,其中暗色矿物黑云母的镁铁比值要大于角闪石的镁铁比值。经受麻粒岩相变质后,紫苏花岗岩的矿物组成没有变化,但有铀、钍和钾的迁出。