Al-related centers in relation to γ-irradiation

 The charge compensation problem for Si−Al substitution in Brazilian natural quartz is investigated in relation to γ-irradiation darkening response and impurity contents evaluated by atomic absorption spectrometry and infrared absorption spectroscopy. Al⁺³ in as-grown natural quartz is compensated by Li⁺ and H⁺ to form Al−Li and Al−OH centers. The content ratios (Al−Li)/(Al−OH) and Li/(broad OH band) depend on the environmental conditions of crystal growth and influence the formation of Al-hole centers due to γ-irradiation. Al−OH centers are the dominant Al-related centers in quartz from hydrothermal origin while Al−Li centers are dominant for that of pegmatitic origin. The formation of Al-hole centers is little in quartz with a high content of broad OH band which is from low temperature hydrothermal origin. Received May 23, 1995 / Revised, accepted May 8, 1996     

Structure of hydrous aluminosilicate glasses along the diopside-anorthite join: A comprehensive one- and two-dimensional H and Al NMR study

We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (∼2 wt% H₂O) glass samples along the diopside (Di, CaMgSi₂O₆)—anorthite (An, CaAl₂Si₂O₈) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) ¹H and ²⁷Al MAS NMR, and ²⁷Al → ¹H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) ¹H double-quantum (DQ) MAS NMR, ²⁷Al triple-quantum (3Q) MAS NMR, and ²⁷Al → ¹H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas.Aluminum is dominantly present in four coordination (Al^IV), but a small amount of five-coordinate Al (Al^V) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (Al^VI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, Al^VIOH and Al^VOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.     

U-Pb SHRIMP geochronology of Th-poor, hydrothermal monazite: An example from the Llallagua tin-porphyry deposit, Bolivia

In situ U-Pb SHRIMP analysis of hydrothermal monazite virtually free of Th and poor in U (<0.2 ppm Th, 40-103 ppm U) from the world-class Llallagua tin porphyry deposit in Bolivia defines a mineralization age of 23.4 ± 2.2 Ma (MSWD 0.48) confirming earlier K-Ar sericite alteration age data. These ages are, however, in contrast with a weighted mean single crystal ²⁰⁷Pb/²⁰⁶Pb evaporation age of 39.3 ± 6.0 Ma, and a related Pb-Pb inverse isochron age of 42.4 ± 4.0 Ma (MSWD 0.66) on zircon from a post-porphyry dike, as well as with an earlier single crystal Sm-Nd apatite isochron age.Our data points to a significant time gap between emplacement of the ore-hosting porphyry intrusion (magmatism) and its hydrothermal overprint (tin mineralization), suggesting long-lived magmatic-hydrothermal activity in this part of the Andean back-arc crust. The decoupling of porphyry magmatism and hydrothermal activity may explain the unusual occurrence of relatively little fractionated felsic rocks together with extensive tin mineralization.Our study demonstrates the usefulness of the application of the U-Pb SHRIMP method to direct age determination of ore mineralization using Th-poor hydrothermal monazite even when dealing with geological young events. The common assumption of synchronous magmatism and hydrothermal ore formation in porphyry systems may not always be warranted.     

Variation in sericite compositions from fracture zones within the Coso Hot Springs geothermal system

Two types of white micas are found in drillhole samples within the geothermal system at Coso Hot Springs. Low-permeability zones of the crystalline basement contain coarse-grained relict muscovite, whereas rock alteration near fracture zones at temperatures > 150°C is characterized by abundant finegrained sericite in association with secondary calcite and quartz and unaltered relict microcline. In this hydrothermal sericite there is an increase in interlayer K, octahedral Mg + Fe_total and tetrahedral Al with increasing temperature between ~215° to >250°C.Thermodynamic activity of the Al₂Si₄O₁₀(OH)₂ component of serielles, calculated using site-mixing approximations of Helgeson and Aagaard (1985), decreases with increasing temperature between ~215° and >250°C. As a consequence of the observed variations in the interlayer, octahedral and tetrahedral site occupancies, the activity of KAl₂(AlSi₃O₁₀(OH)₂ is essentially constant in the Coso seriates over this temperature range. The calculated equilibrium distribution of aqueous species in the hydrothermal solutions produced from well 16−8, together with cation-activity phase diagrams that account for variations in sericite composition, requires a pH of ~6.7–6.8 at temperatures between 236° and 250°C. Comparison of predicted and observed phase relations with fluid compositions indicate that seriates are in local equilibrium with the geothermal reservoir fluid, whereas relict metamorphic muscovites are metastable.Although the compositions of hydrothermal sericites are a complex function of temperature, pressure and geothermal fluid composition, compositional relations observed at Coso together with published compositions of hydrothermal dioctahedral layer-silicates from the Salton Sea geothermal system demonstrates that elemental compositions of interlayer K and tetrahedral Al increase systematically with increasing temperature despite the dramatic differences in fluid compositions between these two geothermal systems. This suggests that the observed variations in interlayer and tetrahedral site occupancy is largely dependent on the enthalpy of hydrolysis reactions representing equilibrium between sericite solid solutions and the geothermal reservoir fluids.     

Characterization of hydrothermally generated oil from the Uzon caldera,Kamchatka

This paper reports the analyses of unusual oils that accumulate in the Uzon Caldera, situated in the central volcanic region of Kamchatka, Russia. Gas chromatography–mass spectrometry (GC–MS) was used to determine the primary constituents, and the ¹³C and ¹⁴C compositions provided information about the potential source and age of the oils. The ¹⁴C ages determined are 1030 ± 40 a BP (measured) or 940 ± 40 a BP (conventional). The δ¹³C value is −30.6‰ versus the PDB standard, a value consistent with a biological origin. The nearly contemporary age of the C content indicates a geologically recent origin from biogenic detritus and not by synthesis from mantle C. The biogenic origin is supported by the presence of sterane and hopane biomarkers and the δ¹³C value of the bulk oil. The overall compositions of the oils indicate that they are derived from rapid hydrothermal alteration of algal/bacterial mat detritus buried by volcanic ashfall deposits of the Uzon Caldera. The oils represent the youngest hydrothermal petroleum reported to date.     

Characterization of the hydrothermal systems associated with Archean VMS-mineralization at Panorama,Western Australia,using hyperspectral,geochemical and geothermometric data

Airborne hyperspectral imagery was used to study the distribution of white mica minerals in Archean (3.2 Ga) submarine hydrothermal systems associated with volcanogenic massive sulfide mineralization in a well-exposed volcanic sequence of the Soansville greenstone belt in the Pilbara, Western Australia. White mica mineral abundance and distribution maps were compared with published hydrothermal alteration maps and differences were interpreted using whole-rock geochemistry and temperature estimates from oxygen isotope geothermometric studies of hydrothermally altered rocks. Three different zones were identified from the hyperspectral imagery: 1) Al-rich white mica zones in the upper parts of the volcanic sequence which are related to recharge of unevolved seawater, 2) Al-poor white mica zones at middle and upper levels of the volcanic sequence predominantly related to K alteration by more-evolved hydrothermal fluids, and 3) high to intermediate Al-content white mica zones in lower levels of the sequence and in cross-cutting zones related to intense alteration by laterally flowing and upwelling evolved fluids. The integrated study of the spatial distribution of hyperspectrally detected white mica minerals together with published maps and rock analyses allowed characterization of the hydrothermal systems and reconstruction of paleo fluid pathways.     

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

On the mechanisms for H and Al incorporation in stishovite

The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al₂O₃ content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm⁻¹. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm⁻¹. All H is present on one site, with interstitial H both coupled to Al³⁺ substitutional defects on adjacent octahedral (Si⁴⁺) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al³⁺ substitution for Si⁴⁺ charge-balanced by oxygen vacancies at low bulk Al₂O₃ contents, and coupled substitution of Al³⁺ onto octahedral (Si⁴⁺) and interstitial sites at high bulk Al₂O₃ contents. Trends in OH stretching frequencies as a function of Al₂O₃ content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).     

Composition of barian mica in multiphase solid inclusions from orogenic garnet peridotites as evidence of mantle metasomatism in a subduction zone setting

Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg₃(Si₃Al)O₁₀(OH)₂, kinoshitalite BaMg₃(Al₂Si₂)O₁₀(OH)₂ and ferrokinoshitalite BaFe₃(Al₂Si₂)O₁₀(OH)₂. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (X_Mg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFe^IVAlClK_?1Mg_?1Si_?1(OH)_?1. A minor amount of Cr and ^VIAl enters octahedral sites following a substitution vector ^VI(Cr,Al)₂□^VI(Mg,Fe)_?3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.     

Empirical prediction of the Pitzer’s interaction parameters for cationic Al species with both SiO2(aq) and CO2(aq): Implications for the geochemical modelling of very saline solutions

The Pitzer’s interaction parameters, λ_N–M, involving the Mth cationic Al species Al³⁺ or AlOH²⁺ or AlO⁺ and the Nth neutral species SiO_2(aq) (at temperatures of 25–300 °C) or CO_2(aq) (at temperatures of 25–150 °C), have been evaluated through empirical linear relationships between λ_N–M and the surface electrostatic field of the ionic species of interest. These relationships have been obtained starting from the known λ_N–M for both SiO_2(aq) and CO_2(aq) with the main dissolved cations. The Pitzer’s interaction parameter thus estimated for the pair CO_2(aq)–Al³⁺ at 25 °C, 0.327, is 20–40% higher than the corresponding values obtained from CO₂ solubilities in concentrated solutions of AlCl₃, 0.272 ± 0.010 (2σ), and Al₂(SO₄)₃, 0.232 ± 0.002 (2σ), partly corroborating the empirical approach adopted in this study. To test the Pitzer’s interaction coefficients for cationic Al species with aqueous SiO₂, the log K values of the kaolinite dissolution reaction have been computed starting from available experimental data at 23–25 °C and ionic strengths of 0.0001–0.12 mol/kg adopting, alternatively, the Pitzer’s equations and the Debye–Hückel equation. A satisfactory agreement has been found between the log K values obtained through these two approaches, with maximum deviations of 0.11–0.12 log units. This good convergence of results is encouraging as it represents a necessary condition to prove the reliability of the Pitzer’s interaction coefficients estimated in this work. These results are a first step to take into account specific interactions among solutes in concentrated electrolyte solutions, such as those hosted in sedimentary basins or geothermal waters, for instance through the Pitzer’s equations. However, experimental or field data at higher ionic strengths are absolutely necessary to validate the reliability of the Pitzer’s interaction coefficients determined in this study.     

Dissolution of illite in saline-acidic solutions at 25 °C

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.     

Use of micro-XRF chemical analysis for mapping volcanogenic massive sulfide related hydrothermal alteration: Application to the subaqueous felsic dome-flow complex of the Cap d'Ours section,Glenwood rhyolite,Rouyn-Noranda,Québec,Canada

A new analytical method using micro-X-ray fluorescence (XRF) is presented for the in situ analysis of major elements in rock samples. This approach has allowed for a separate study of hydrothermal alteration of matrix versus fragments in volcaniclastic material (i.e. flow breccia). This is particularly important for volcanogenic massive sulfide (VMS) exploration in subaqueous felsic dome-flow complexes, where brecciated facies are omnipresent and the imprint of hydrothermal alteration is typically heterogeneous. In this study, eleven elements are measured with a 1.7 by 1.3 mm window considered to be representative of each sample, based on replicate analyses. An average is calculated for the analyzed window and yields a nearly complete analysis with the exception of loss of ignition (LOI). Micro-XRF data were validated using whole rock XRF analyses performed on the same sample block. The application of this chemical method has been tested successfully on thin sections from the Cap d'Ours section of the Glenwood rhyolite in the Rouyn-Noranda region of Québec, Canada. With 58 samples spaced at approximately 50 m intervals, two styles of alteration zoning were recognized: (1) a lateral and concordant zoning expressed by vent-proximal silicification in the west grading toward vent-distal chlorite–sericite alteration to the east, and (2) vertical and discordant zoning expressed by stronger sericitization in the upper part of later volcanic quartz- and feldspar-phyric endogenous lobes. The former is typical of cooling induced by seawater interaction at the lava–water interface at temperatures greater than 400 °C, whereas the latter is related to lower temperature (< 300 °C) hydrothermal mineralization associated with endogenous lobe emplacement within the volcanic pile. The presented results clearly demonstrate the potential use of the micro-XRF data for characterizing weak to intense hydrothermal alteration in highly fragmented volcanic rocks.     

Effects of non-stoichiometry on the spinel structure at high pressure: Implications for Earth’s mantle mineralogy

A non-stoichiometric sample of spinel with composition ^T(Mg_0.4Al_0.6)^M(Al_1.8□_0.2)O₄ was investigated by single-crystal X-ray diffraction in situ up to about 8.7 GPa using a diamond anvil cell. The P(V) data were fitted using a third-order Birch-Murnaghan equation of state and the unit-cell volume V₀, the bulk modulus K_T0 and its first pressure derivative K′ were refined simultaneously providing the following coefficients: V₀ = 510.34(6) Å³, K_T0 = 171(2) GPa, K′ = 7.3(6). This K_T0 value represents the lowest ever found for spinel crystal structures. Comparing our data with a stoichiometric and natural MgAl₂O₄ (pure composition) we observe a decrease in K_T0 by about 11.5% and a strong increase in K′ by about 33%. These results demonstrate how an excess of Al accompanied by the formation of significant cation vacancies at octahedral site strongly affects the thermodynamic properties of spinel structure. If we consider that the estimated mantle composition is characterized by 3-5% of Al₂O₃ this could imply an Mg/Al substitution with possible formation of cation vacancies. The results of our study indicate that geodynamic models should take into account the potential effect of Mg/Al substitution on the incompressibility of the main mantle-forming minerals (olivine, wadsleyite, ringwoodite, Mg-perovskite).     

Groundwater chemistry of Al under Dutch sandy soils: Effects of land use and depth

Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)₃ and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L⁻¹ at pH > 7 to 1941 μmol L⁻¹ at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al³⁺ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)₃ minerals (e.g. gibbsite or amorphous Al(OH)₃), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.     

Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

西南天山中新生代盆地成矿流体运移规律

乌拉根铅锌矿床和萨热克铜矿床是西南天山中新生代盆地最有代表性的两个层控砂砾岩型矿床,乌拉根铅锌矿床产于下白垩统克孜勒苏群第五岩性段(K₁kz5)的粗砂质细砾岩中,后期经历了弱的构造改造作用;萨热克铜矿床产于上侏罗统库孜贡苏组上段(J₃k2)杂砾岩中,其北矿段后期经历了强烈的构造改造作用,南矿段可见岩浆热液蚀变作用后的褪色化及叠加成矿作用。为了研究成矿流体和岩浆热液在岩石中的运移规律,分别对上述两个矿区以沉积作用、构造改造作用和岩浆作用为主的代表性岩石测定了孔隙度和渗透率。测试结果表明乌拉根矿区岩(矿)石的孔隙度和渗透率总体比萨热克矿区岩石的孔隙度和渗透率要小;乌拉根铅锌矿区和萨热克铜矿区北矿段矿石的孔隙度和渗透率均小于下盘围岩的孔隙度和渗透率;萨热克铜矿区南矿段经历了岩浆热液蚀变,岩石的孔隙度和渗透率明显小于未受岩浆作用的岩石孔隙度和渗透率,且辉绿岩脉下盘岩石的孔隙度和渗透率明显小于上盘。同时通过岩(矿)石组构分析,上述岩(矿)石在成岩和成矿后孔隙度和渗透率的变化均与成矿流体或岩浆热液的作用密切相关。在西南天山中新生代层控型矿床中,当成矿流体沿切层断裂上升后会优先选择孔隙度和渗透率高的岩层进行渗滤、扩散、充填和交代作用。岩石中的砾石砾径越大,砾石间隙越大;岩石的硬度越大,其在后期构造变形中越容易形成构造裂隙,对成矿越有利,这也是造成萨热克铜矿北矿带中的金属硫化物颗粒明显大于乌拉根铅锌矿中金属硫化物的重要原因。上述结果表明沉积盆地中成矿流体或岩浆热液的成矿作用越强,岩石受其影响在成岩成矿后的孔隙度和渗透率越会变小,从岩石的孔隙度和渗透率可间接反映成矿过程中成矿作用的强弱,为寻找富矿体提供理论依据。      

Strain accumulation and fluid–rock interaction in a naturally deformed diamictite,Willard thrust system,Utah (USA): Implications for crustal rheology and strain softening

Structural and geochemical patterns of heterogeneously deformed diamictite in northern Utah (USA) record interrelations between strain accumulation, fluid–rock interaction, and softening processes across a major fault (Willard thrust). Different clast types in the diamictite have varying shape fabrics related to competence contrasts with estimated effective viscosity ratios relative to micaceous matrix of: ∼6 and 8 for large quartzite clasts respectively in the Willard hanging wall and footwall; ∼5 and 2 for less altered and more altered granitic clasts respectively in the hanging wall and footwall; and ∼1 for micaceous clasts that approximate matrix strain. Within the footwall, matrix X–Z strain ratios increase from ∼2 to 8 westward along a distinct deformation gradient. Microstructures record widespread mass transfer, alteration of feldspar to mica, and dislocation creep of quartz within matrix and clasts. Fluid influx along microcracks and mesoscopic vein networks increased westward and led to reaction softening and hydrolytic weakening, in conjunction with textural softening from alignment of muscovite aggregates. Consistent Si, Al, and Ti concentrations between matrix, granitic clasts, and protoliths indicate limited volume change. Mg gain and Na loss reflect alteration of feldspar to phengitic muscovite. Within the hanging wall, strain is overall lower with matrix X–Z strain ratios of ∼2 to 4. Microstructures record mass transfer and dislocation creep concentrated in the matrix. Greater Al and Ti concentrations and lower Si concentrations in matrix indicate volume loss by quartz dissolution. Na gain in granitic clasts reflects albitization. Large granitic clasts have less mica alteration and greater competence compared to smaller clasts. Differences in strain and alteration patterns across the Willard thrust fault suggest overall downward (up-temperature) fluid flow in the hanging wall and upward (down-temperature) fluid flow in the footwall.     

福建政和东际金-银矿床的热液蚀变特征及其勘探指示意义

福建东际金-银矿床产于中生代东坑火山岩盆地西缘的流纹质凝灰岩中,矿区及周边火山-沉积岩系遭受了广泛且强度不等的热液蚀变。本文工作采用红外反射光谱技术在东际矿区三个勘探剖面上对钻孔岩心进行系统性高密度采样分析,结果显示蚀变矿物组合及分带的大框架样式主要受原岩成分控制,具体表现为绢云母化趋向于发育于流纹质火山岩中,而绿泥石化则富集在安山质和英安质火山岩中。在更小的矿区局部空间范围内或单一岩性中,热液作用的物化条件作为次级控制因素决定着特定蚀变矿物的成分变化和蚀变类型的强度差异。从层状硅酸盐组合考虑,东际矿区热液蚀变以绢云母化和绿泥石化为最主要类型,而缺失发育良好的蒙脱石带,金-银矿化赋存在以伊利石为主的绢云母化带中,表明成矿环境属于低硫到中硫之间的浅成热液系统。含矿火山岩的热液蚀变组合和强度变化,以及金-银矿化的似层状特点,均指示成矿时流体是沿着南园组凝灰岩层内侧向流动,而蚀变分带细节显示在凝灰岩层中存在着二至三条流体主通道,金-银矿化则赋存在主通道中。流体主通道的热液蚀变标志是富铝绢云母,其与主通道之外的相对贫铝绢云母在红外光谱特征上反差明显。因此,采用红外光谱技术圈定整体热液蚀变系统的空间构型、解译成矿环境的物化条件及变化、并确定绢云母的铝含量变化用以判断成矿流体主通道位置,可以有效地缩小勘探目标和提高找矿工作的预测性。     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.