Petrology and geochemistry of shoshonitic plutons from the western Kunlun orogenic belt, Xinjiang, northwestern China: implications for granitoid geneses

A series of granitoids from Proterozoic to Cenozoic age occurred in the western Kunlun orogenic belt, Xinjiang, northwestern China. Several intrusions such as the West Datong (Middle Caledonian age), North Kuda (Late Caledonian age) and Kuzigan, Karibasheng, Zankan (Himalayan age) plutons have shoshonitic affinity. Their rock assemblages include (quartz) monzodiorite–(quartz) monzonite–quartz syenite (Middle Caledonian) or monzonitic granite–granite (Late Caledonian) or biotite (monzonitic) granite–diopside granite–diopside syenite (Himalayan). Generally, biotite is iron–phlogopite, with some eastonite and high Mg/(Mg+Fe_T) and Fe³⁺/Fe²⁺ ratio. Amphibole is mainly edenitic hornblende and magnesian hastingsitic hornblende, with some edenite and higher Mg/(Mg+Fe_T) and Fe³⁺/Fe²⁺ ratio. The rocks show SiO₂ contents of 52.77–71.85% and high K₂O+Na₂O (mostly >8%, average 9.14%), K₂O/Na₂O (mostly >1, average 1.50) and Fe₂O₃/FeO (0.85–1.51, average 1.01) and low TiO₂ contents (0.15–1.12%, average 0.57%). Al₂O₃ contents (13.01–19.20%) are high but variable. The granitoids are prominently enriched in LILE, LREE and volatiles such as F. However, the studied shoshonitic granitoids among the three intrusive periods also show differences in isotopic compositions and trace element concentrations, suggesting their different geneses: the origin of the West Datong pluton is probably related to the involvement of subducted oceanic crust sediments into the mantle source; the North Kuda and Himalayan plutons could have been generated by partial melting of subducted oceanic crust sediments or metasediments of thickened continental lower crust in the process of late-orogenic slab break-off or lithospheric thinning.     

Lithium in the interlayer space of synthetic trioctahedral micas

This paper gives several new and strong arguments in favour of the possibility of fixation of anhydrous lithium in the interlayer space of trioctahedral potassium micas. From the chemical viewpoint Li⁺ can replace K⁺, but is located out of the alkaline cation site; it enters pseudo-octahedral cavities limited by the triangular bases of two aluminous tetrahedra of two consecutive sheets. The solubility limit of Li⁺ in the interlayer is a function of the Al^IV content of the mica. It is given by the relation (Li/Li + K)_max = 2[(Al/Si + Al)^IV]². In both micas investigated — phlogopite, KMg₃(Si₃Al)O₁₀(OH)₂, and eastonite, K(Mg_2.5Al_1.5)(Si_2.5Al_1.5)O₁₀(OH)₂ — there is a remarkable agreement between the calculated values of the solubility limits and those measured by exchange reactions with hydrothermal solutions, at 600°C, 2 kbar. In high-Al micas, the interlayer Li content can be very important, with about one-third of K⁺ replaced by Li⁺.

The fixation of Li⁺ according to this model provokes a strong flattening of the interlayer (strong decrease of the reticular distance d₀₀₅) and a slight increase of the reticular distance d₀₆₀. Infra-red (IR) absorption spectrometry shows that vacant K⁺ sites are created when Li⁺ enters the interlayer; one observes low-frequency OH stretching bands attributed to OH dipoles lying towards these empty sites. Fixation of Li⁺ does not provoke any modification of the IR spectra in the region 1200-300 cm⁻¹, indicating that Li⁺ is really out of the sheet. For both cell dimensions and IR spectra, a comparison is made with “ordinary” lepidolites, having Li⁺ in the octahedral sheet; it provides a guide for the distinction between the two species of Li-bearing micas.     

Ferric iron in orthopyroxene: a Mössbauer spectroscopic study

Ferric iron solid solution in synthetic orthopyroxene has been studied along the joins MgSiO₃-Al₂O₃ · Fe₂O₃ and MgSiO₃-Fe₂O₃. The partially reduced synthetic orthopyroxenes showed that major incorporation of ferric iron can only occur together with a concomitant incorporation of Al. Maximum solid solution of ferric iron along the join MgSiO₃-Fe₂O₃ was found to be only 0.63 wt% Fe₂O₃ at 1000°C and 2 kb total pressure. From the observed Mössbauer parameters octahedral ferric iron can be assigned to the MI position in orthopyroxene. Incorporation of Fe³⁺ and/or Al will increase the disorder of Fe²⁺ and Mg between the M1 and M2 sites, which is also observed in a ferric iron-containing aluminous orthopyroxene of metamorphic origin. In the assemblage orthopyroxene + sillimanite + quartz the ferric iron content of orthopyroxene is directly related to oxygen fugacity.     

Titanian clinohumite–garnet–pyroxene rock from the Su-Lu UHP metamorphic terrane, China: chemical evolution and tectonic implications

A garnet–pyroxene rock containing abundant Ti-clinohumite (ca. 40 vol.%) occurs along with eclogites as small blocks in quartzo-feldsparthic gneiss in the southern end of the Chinese Su-Lu ultrahigh-pressure (UHP) metamorphic terrane. It consists of three aggregates: (1) Ti-clinohumite-dominated aggregate with interstitial garnet and pyroxene, (2) garnet+pyroxene aggregate with Ti-clinohumite inclusions, and (3) Ti-clinohumite-free aggregate dominated by garnet. Apatite, phlogopite, zircon, hematite, pentlandite, and an unknown Ni-Fe-volatile-Si (NFVS) mineral, which is replaced by Ni-greenalite, occur as accessories. Serpentine is the major secondary mineral. Garnet (Prp_63.9–64.6Alm_25.8–26.9Grs_1.4–7.9Uva_0.5–7.6Sps_1.0) in all three aggregates is pyrope-rich with very low grossular component, with that in the aggregate (2) most enriched in Cr (Cr₂O₃=2.55 wt.%). Orthopyroxene is depleted in Al (Al₂O₃=0.16 wt.% in the cores) and Ca (CaO=0.06–0.09 wt.% in the cores), with X_Mg (Mg/(Mg+Fe)) values at ca. 0.900. Clinopyroxene is chromian diopside with Fe³⁺≥Fe²⁺. Matrix clinopyroxene has a lower X_Mg (0.862) than that (0.887) included in Ti-clinohumite. The rock contains modest amount of heavy rare earth elements (HREE) (10 to 12×C1 chondrite), with significant enrichment in Cr, Co, Ni, V, Sr, and light rare earth elements (LREE) (22 to 33×C1 chondrite). The clinopyroxene is very enriched in Cr (Cr₂O₃ is up to 2.09 wt.% in the cores) and Sr (ca. 350 ppm) and LREE (Ce_N/Yb_N=157.7). Ti-clinohumite is enriched in Ni (1981 ppm), Co (123 ppm), and Nb (85 ppm).

While it is possible to enrich ultramafites in incompatible elements in a subducted slab, the high Al, Fe, Ti, and low Si, Ca, and Na contents in the Ti-clinohumite rock are difficult to account for by crustal metasomatism of an ultramafite. On the other hand, the similarity in major and trace element compositions and their systematic variations between the Ti-clinohumite-garnet-pyroxene rock of this study and those of Mg-metasomatised Fe–Ti gabbros reported in the literature suggest that crustal metasomatism occurred in a gabbroic protolith, which resulted in addition of Cr, Co, Ni, and Mg and removal of Si, Ca, Na, Al, and Fe. This implies that the rock was in contact with an ultramafite at low pressure. During subsequent subduction, the metagabbro was thrust into the country gneiss, where gneiss-derived hydrous fluids caused enrichment of Sr and LREE in recrystallised clinopyroxene. P–T estimates for the high-pressure assemblage are ca. 4.2 GPa and ca. 760 °C, compatible with those for the eclogites and gneisses in this terrane. It is possible that the Ti-clinohumite-garnet-pyroxene rock and associated eclogites represent remnants of former oceanic crust that was subducted to a great depth.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Phase relations of pumpellyite-actinolite facies metabasites in the Sanbagawa metamorphic belt in central Shikoku, Japan

Sanbagawa metabasites metamorphosed at conditions near the upper limit of the pumpellytic-actinolite facies were examined in terms of phase equilibria in the five component system Al₂O₃---Fe₂O₃---CaO---MgO---FeO. The Fe³⁺ content of epidote measured as X^Ep_Fe (=Fe/(Fe + Al) of epidote) in the assemblage epidote-chlorite-actinolite-pumpellyite decreases gradually towards the higher-grade, pumpellyite-free areas. The progressive change in X_Fe^Ep can be detected within one metabasite bed 200 meters thick near the upper limit of the pumpellyite-actinolite facies. The Mg---Fe²⁺ substitution, as expressed by variation of Fe/(Fe + Mg) in chlorite (0.40–0.55) has little effect on the Fe³⁺ + Al) ratios of epidote and pumpellyite in the above-mentioned assemblage. The lowet X_Fe^Ep in the pumpellite-bearing assemblage is 0.15 and hence the upper limit of the pumpellyite-actinolite facies is defined by the appearance of an epidote-chlorite-actinolite assemblage with X^Ep_Fc = C.15     

High-resolution methane profiles across anoxic brine–seawater boundaries in the Atlantis-II, Discovery, and Kebrit Deeps (Red Sea)

A decrease in temperature (ΔT up to 45.5 °C) and chloride concentration (ΔCl up to 4.65 mol/l) characterises the brine–seawater boundary in the Atlantis-II, Discovery, and Kebrit Deeps of the Red Sea, where redox conditions change from anoxic to oxic over a boundary layer several meters thick. High-resolution (100 cm) profiles of the methane concentration, stable carbon isotope ratio of methane, and redox-sensitive tracers (O₂, Mn⁴⁺/Mn²⁺, Fe³⁺/Fe²⁺, and SO₄²⁻) were measured across the brine–seawater boundary layer to investigate methane fluxes and secondary methane oxidation processes.

Substantial amounts of thermogenic hydrocarbons are found in the deep brines (mostly methane, with a maximum concentration up to 4.8×10⁵ nmol/l), and steep methane concentration gradients mainly controlled by diffusive flow characterize the brine–seawater boundary (maximum of 2×10⁵ nmol/l/m in Kebrit Deep). However, locally the actual methane concentration profiles deviate from theoretical diffusion-controlled concentration profiles and extremely positive δ¹³C–CH₄ values can be found (up to +49‰ PDB in the Discovery Deep). Both, the actual CH₄ concentration profiles and the carbon-13 enrichment in the residual CH₄ of the Atlantis-II and Discovery Deeps indicate consumption (oxidation) of ¹²C-rich CH₄ under suboxic conditions (probably utilizing readily available—up to 2000 μmol/l—Mn(IV)-oxihydroxides as electron acceptor). Thus, a combined diffusion–oxidation model was used to calculate methane fluxes of 0.3–393 kg/year across the brine–seawater boundary layer. Assuming steady-state conditions, this slow loss of methane from the brines into the Red Sea bottom water reflects a low thermogenic hydrocarbon input into the deep brines.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

稀有金属矿物溶解度对花岗伟晶岩成矿作用的制约

花岗伟晶岩型矿床是稀有金属矿床重要的类型之一。在花岗伟晶岩中,稀有金属元素Li、Be、Nb和Ta主要以独立矿物的形式存在,前人对稀有金属独立矿物在硅酸盐熔体中的溶解度及其影响因素展开了系统研究。本文综合分析了已有的实验数据,其结果表明,影响稀有金属独立矿物溶解度最为重要的2个参数是温度(T)和铝饱和指数(ASI)。因此本文建立了稀有金属独立矿物,尤其是铌锰矿和钽锰矿溶解度,与温度(T)和铝饱和指数(ASI)之间的定量关系: lg [w(Li)/10^-6]=-0.37×[1 000/(T/K)]+4.56,R²=0.44 lg [w(BeO)/10^-6]=-4.21×[1 000/(T/K)]+6.86,R²=0.91 lg [K_sp(Nb)/(mg²·kg^-2)]=-(2.86±0.14)×ASI_(Mn+Li)-(4.95±0.31)×[1 000/(T/K)]+(4.20+0.28),R²=0.86 lg [K_sp(Ta)/(mg²·kg^-2)]=-(2.46±0.11)×ASI_(Mn+Li)-(4.86±0.30)×[1 000/(T/K)]+(4.00+0.30),R²=0.80 式中,温度T为热力学温度,ASI_(Mn+Li)(ASI=Al₂O₃/(CaO+Na₂O+K₂O+Li₂O+MnO),摩尔分数比)和T的适用范围分别为0.6~1.2和1 073~1 373 K的范围内。上述公式为估算硅酸盐熔体中稀有金属含量提供了便利,为量化花岗伟晶岩成矿模型提供了基础。 稀有金属独立矿物溶解度随温度降低和铝饱和指数的增加而急剧降低,因此,在岩浆演化过程中,由岩浆侵位、分离结晶以及流体作用等因素引起的岩浆温度降低和铝饱和指数的增加,是导致稀有金属独立矿物结晶的主要机制。     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.     

柴达木黑北凹地早更新世新型砂砾层卤水水化学特征与成因

柴达木黑北凹地深部砂砾石层内的承压水是近期在柴达木西部新发现的规模巨大的孔隙卤水,水位埋深8~24 m,接近地表;富水性中等偏强;矿化度较高,KCl含量达到可开发利用的要求,井采时不易结盐,可作为后续开发钾盐的备选区域.离子统计分析结果显示,TDS、Cl-、Na+、Cs+、B₂O₃、Ca2+、Mg2+、Sr+、NO₃-、Rb+在卤水中的浓度变化幅度小,分布较均匀;SO₄2-的变化幅度大,分布极不均匀;Br-、I-、Li+、K+变化幅度和均匀程度介于二者之间;Na+、Cl-、Ca2+、Sr2+、TDS呈正态负偏高峰态,K+、SO₄2-、Li+呈非正态正偏高峰态.成分聚类分析图中,K+、SO₄2-、Li+首先聚为一亚类,Cl-、TDS、Na+聚为一亚类.从离子含量变化曲线图中可以看到,该孔隙卤水从东至西,Na+、Cl-含量和变化趋势相同,且它们与TDS、B₂O₃的变化趋势相同.K+、SO₄2-、Mg2+三种组分含量较一致,变化趋势相同,且同时与Li+的变化趋势相同.孔隙卤水钠氯系数C_Na/C_Cl值为0.85~0.96,溴氯系数为0.01~0.34,与盐岩溶滤卤水接近.在Na+、K+、Mg2+//Cl--H₂O四元体系和Na+、K+、Mg2+//Cl-、SO₄2--H₂O五元体系25 ℃介稳相图中反映出2种析盐规律,一种为硫酸镁亚型,另一种是氯化物型.其形成可能与化学沉积层中高矿化度晶间卤水与砂砾石层中原始孔隙(淡)水相互作用有关.      

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Influence of volcanic activity on spring water chemistry at Popocatepetl Volcano, Mexico

The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO₄²⁻, Cl⁻, F⁻, HCO₃⁻, B, and SO₄²⁻/Cl⁻ variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na⁺, Ca²⁺, SiO₂ and Mg²⁺ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO₂ in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO₂. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F⁻ in one spring.     

基于实测光谱指数法的ASTER遥感数据岩性信息提取

目前,光谱波段比值法可以用于岩性信息提取与识别。以新疆北山坡北造山带辉长岩、橄榄岩、橄榄辉长岩以及闪长岩为研究对象,深入分析这四种岩性在VNIR（可见光-近红外）-SWIR（短波红外）谱域的光谱差异。基于辉长岩、橄榄辉长岩、橄榄岩以及闪长岩在2 300 nm附近存在-OH的吸收特征,建立了第8波段的相对吸收深度RBD₈;基于橄榄辉长岩、橄榄岩以及闪长岩在400~700 nm出现的弱吸收特征,建立比值指数RI₂₁来反映四种岩性含Fe³⁺矿物的丰度;基于四种岩性在1 100 nm附近都存在由Fe²⁺引起的宽而强的吸收谱带,建立了比值指数RI₅₄来估计Fe²⁺含量。利用RBD₈、RI₂₁以及RI₅₄三个比值指数分别对影像进行增强处理,并对增强后的影像进行RGB彩色合成,不仅识别和提取出辉长岩、橄榄岩、橄榄辉长岩和闪长岩,还有效区分出片岩以及碳酸盐岩等岩性信息。     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Fe---Mg partitioning between coexisting garnet and phengite at high pressure, and comments on a garnet-phengite geothermometer

The Fe---Mg exchange reaction between coexisting garnet and phengite has been studied by reacting a natural phengite (mg = 67) in the presence of quartz and water at pressures of 20–35 kb and temperatures of 800–1000°C. Compositions of coexisting garnet and mica indicate a linear relation between both the InK_D((Fe/Mg) garnet/(Fe/Mg) phengite) and temperature, and InK_D and pressure in the above P.T range. This Fe---Mg exchange reaction between garnet and phengite is shown to be dependent on the Ca-content of the garnet, and on the mg number of the bulk composition. These two composition effects have been studied by usin phengitic mica mixes with mg numbers of 23 and 46, and by using a synthetic basaltic composition. The overall results allow broad empirical calibration of separate geothermometers for pelitic and basaltic systems, respectively. However, because of non-ideality in the exchange reaction, this geothermometer should not be used in any practical application outside the composition ranges studied. Also, careful consideration of the presence of Fe³⁺ in phengite must be made. If the Fe³⁺ content of the natural phengite is unknown, then the temperatures obtained will be maximum temperatures only.     

An experimental study of calcite dissolution rates at acidic conditions and 25 °C in the presence of NaPO3 and MgCl2

Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO₃ and MgCl₂. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl₂ at pH 1 and 3. The presence of trace quantities of NaPO₃, which dissociates in solution to Na⁺ and H₂PO₄⁻, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg²⁺ may not adsorb, whereas aqueous phosphate, present as either the anion H₂PO₄⁻ or the neutral species H₃PO₄⁰, readily adsorbs on calcite surfaces leading to significant dissolution inhibition.     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.