Oxygen isotopic fractionation in the system quartz-albite-anorthite-water

Oxygen isotopic fractionations have been determined between quartz and water, albite and water, and anorthite and water at temperatures from 300 to 825°C, and pressures from 1.5. to 25 kbar. The equilibrium quartz-feldspar fractionation curves can be approximated by the following equations: 1000ln α_Q?PI = (0.46 + 0.55β)10⁶T^?2 + (0.02 + 0.85β) between 500 and 800°C 1000ln α_Q?PI = (0.79 + 0.90β)10⁶T^?2 — (0.43 ? 0.30β) between 400 and 500°C where β is the mole-fraction of anorthite in plagioclase.Application of these isotopic thermometer calibrations to literature data on quartz and feldspar gives temperatures for some metamorphic rocks which are concordant with quartz-magnetite temperatures. Plutonic igneous rocks typically have quartz-feldspar fractionations which are substantially larger than the equilibrium values at solidus temperatures, indicating substantial retrograde exchange effects.     

Short-chain carboxylates in fluid inclusions in minerals

The carboxylate (formate, acetate, propionate and oxalate) and common inorganic anions (F⁻, Cl⁻ and SO²⁻₄) compositions for aqueous fluid inclusion leachates from 17 mineral samples collected from various deposits have been determined using ion chromatography in conjunction with microthermometric measurements on the fluid inclusions of their host minerals. The minerals, quartz, fluorite, barite, beryl and a few `ore' minerals (wolframite, pyrite and galena), came from hydrothermal vein-type deposits in felsic igneous rocks or Archean metamorphic rocks. The results indicate that short-chain carboxylates are common components in hydrothermal fluids and can be present in considerable amounts. Formic acid (as formate) is the dominant species over other carboxylic acids. The present study raises new questions about the origin and geochemical significance of carboxylates in hydrothermal ore-forming processes.     

Oxygen,hydrogen and carbon isotope studies of the franciscan formation,Coast Ranges,California

Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ¹⁸O of the graywackes (+11 to +14), but that igneous rocks become enriched in ¹⁸O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-¹⁸O type (+16 to +20) associated with chert and a low-¹⁸O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in ¹⁸O than the host rock quartz and in most of the rocks the δ¹⁸O of the clastic quartz is similar to the δ¹⁸O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ¹⁸O values are very uniform (+13 to +16). the δ¹³C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H₂O having δD ≈ +10 to ?20 and δ¹⁸O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in ¹⁸O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ¹⁸O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the $\text{D}\text{H}$ ratios of the OH-bearing minerals in any other Franciscan rock.The δ¹⁸O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in ¹⁸O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H₂O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.     

Hydrogeochemical processes and contaminants enrichment with special emphasis on fluoride in groundwater of Birbhum district,West Bengal,India

The hydrogeochemistry of groundwater in rural parts of Birbhum district, West Bengal, India, has been studied to understand the contaminants and prime processes involved in their enrichment with a focus on F^? concentration. The lithological units consist of Quaternary alluviums with underlying Rajmahal basaltic rocks of Middle Jurassic age. Groundwater occurs in the alluviums, weathered residuum and fracture zone of Rajmahal rocks. Studies show elevated concentration of Cl^?, SiO₂, Fe and F^?; excess Cl^? is attributed to anthropogenic inputs, SiO₂ is ascribed to high degree of weathering of silica rich host rocks, and high Fe is due to the interaction of water with Fe-rich sediments under reducing condition. The F^? concentration is found high (>1.20 mg/L) mainly in water from Rajmahal rocks revealing a lithological control on F^? enrichment. The weathering of silicates and ion exchange are the leading controlling processes for major ions in groundwater. The F^? enrichment is due to the dissolution of F^?-bearing minerals and perhaps also through anion exchange (OH^? for F^?) on clay minerals at high alkaline conditions; precipitation of CaCO₃ favours CaF₂ dissolution leading to elevated F^? concentration. CaHCO₃, the dominant water type, contains low F^? while NaHCO₃ and NaCl types exhibit high F^? concentrations. Among the three spatial associations, Cluster-1 and Cluster-2 are CaHCO₃ type; Cluster-3 shows NaHCO₃ and NaCl waters with low Ca²⁺ and Mg²⁺ and high Na⁺ contents. Cluster-1 and Cluster-2 waters are, in general, drinkable barring the elevated Fe content, while Cluster-3 water is unsafe for drinking due to the high F^? concentration.     

Chemical composition of the primary aqueous phase of the earth and origin of life

Prokaryotes and cytoplasm of eukaryotes are dominated by K⁺, whereas the extracellular fluid of most species of multicellular organisms is dominated by Na⁺. It was substantiated that the K⁺/Na⁺ ratio in the salt constituent of the cells of modern organisms qualitatively reflects the proportions between these elements in the aqueous phase, in which the first forms of life and the protocell originated. The same conclusion is done by Armen Y. Mulkidjanian et al. (PNAS 13, 2012, E821-830). The chemical composition of primary aqueous phase of the Earth was reconstructed using thermodynamic numerical simulation of the equilibrium composition of the ??carbonaceous chondrite material-water??, ??primitive mantle material-water??, ??ultramafic rock-water??, ??mafic rocks-water?? systems that are open with respect to CO₂ and CH₄. It was shown that at 25°C, total pressure of 1 bar, and partial pressures of CO₂ and CH₄ 10^?5?C10^?8 and 10^?2?C10^?8 bar, respectively, the aqueous phase of the systems with carbonaceous chondrite and primitive mantle has K⁺/Na⁺ > 1, which corresponds to the proportions of these elements in the intracellular solution. The aqueous phase is characterized by pH = 8?C9, Eh = ?450 ± 50 mV, the presence of ammonium nitrogen, and concentrations of K, Na, and Mg close to those in the inferred intracellular fluid. The interaction of water with ultramafic and mafic rocks provides K⁺/Na⁺ < 1 in aqueous solution, which corresponds to the chemical composition of the modern natural waters of the Earth??s crust. Simulation results show that the protocell could arise in the primary aqueous phase of the Earth during differentiation of chondritic material into the Earth??s core and mantle, after the formation of the nitrogen atmosphere containing CH₄, CO₂, NH₃, H₂, H₂S, CO and other gases, but prior to the formation of the modern rocks of the Earth??s crust (first billion years of the planet??s lifetime).     

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

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

A study on the high fluoride concentration in the magnesium-rich waters of hard rock aquifer in Krishnagiri district, Tamilnadu, India

Excess fluoride in groundwater affects the human health and results in dental and skeletal fluorosis. Higher concentration of fluoride was noted in hard rock terrain of the south India, in the Krishnagiri district of Tamilnadu. The region has a complex geology ranging from ultra basic to acid igneous rocks, charnockite and gneissic rocks. Thirty-four groundwater samples were collected from this study area and analysed for major cations and anions along with fluoride. The order of dominance of cations is Na⁺?>?Mg²⁺?>?Ca²⁺?>?K⁺ and the anions in the following order HCO₃ ^??>?Cl^??>?NO₃ ^??>?SO₄ ^2?. It is found that nearly 58 % of the samples have more fluoride ranging from 1 to 3 mg/L. It is also noted that high fluoride waters correspond to magnesium water types. This is due to the release of fluoride from the magnesium-bearing minerals like, biotite, hornblende, etc., or weathering of apatite/hydroxyapatites found in charnockites.     

Experimental study of the physico-chemical conditions of skarn formation

Experimental results show that skarns can—800°C and 500–1,000 bars. Starting materials include intermediate-acidic igneous rocks, volcanic rocks, metamorphic rocks, carbonates of various purities and chemical reagents of analytical purity-grade. Experimental media are: NaCl, NaCl+CaCl₂, NaCl+CaCl₂+MgCl₂, Na₂CO₃ and Na₂SiO₃ solutions. Experimental results show that skarns can be formed under wide physico-chemical conditions:T=400°–800°C,P=500–1,000 bars,pH=4–11, and \(f_{O_2 } = 10^{ - 23} - 10^{ - 11} \) bar. The mineralogy of skarns and the chemical compositions of skarn minerals are generally controlled by the combined factors: the chemical composition of the original rocks, pH values, redox conditions, temperatures and pressures. Isomorphous substitution may have agreat effect on the temperature of formation andfo ₂ of some major skarn minerals. It is found that skarnization occurs preferentially in NaCl and NaCl+CaCl₂ solutions and subortinately in MaCO₃ and Na₂SiO₃ soiutions.     

Hydro-chemical analysis and ionic flux of meltwater runoff from Khangri Glacier,West Kameng,Arunachal Himalaya,India

The detailed hydro-chemical study of meltwater draining from Khangri glacier Arunachal Pradesh has been carried out to evaluate the major ion chemistry and weathering processes in the drainage basin. The investigative results shows that the meltwater is almost neutral to slightly acidic in nature with Mg–HCO₃-dominated hydro-chemical facies. In glacial meltwater, Ca^+?2 is the most dominated cation followed by Mg⁺², Na⁺, and K⁺, while HCO₃^? is the most dominant anion followed by SO₄^2?, NO₃^?, and Cl^?. The dominant cations such as Ca⁺² and Mg⁺² show a good relation with the minerals abundance of the rocks. Calcite (CaCO₃) and biotite [K(Mg,Fe)₃AlSi₃O₁₀(F,OH)₂] are the most abundant minerals in the deformed carbonate-rich metasedimentary rocks near to the snout with some K feldspar (KAlSi₃O₈) and quartz (SiO₂). This suggests Ca⁺² have definitely entered into the water due to the dissolution of calcite and Ca feldspar (CaAl₂Si₂O₈), while one of the source of Mg⁺² is biotite. Na feldspar (NaAlSi₃O₈) has contributed towards the availability of sodium ion, while potassium ion is derived from the chemical weathering of K feldspar and biotite. The chemical weathering is the foremost mechanism controlling the hydro-chemistry of the Khangri glacier because of the least anthropogenic interferences. The mineralogy of surrounding rocks is studied to understand better, the rock–water interaction processes, and their contribution towards ionic concentration of meltwater. The meltwater discharge and individual ion flux of the catchment area have also been calculated, to determine the ionic denudation rate for the ablation season. The high elemental ratio of (Ca?+?Mg)/(Na?+?K) (7.91?±?0.39 mg/l) and low elemental ratio of (Na?+?K)/total cations (0.11?±?0.004) indicate that the chemical composition of meltwater is mainly controlled by carbonate weathering and moderately by silicate weathering. The scatter plot result between (Ca?+?Mg) and total cations confirms that carbonate weathering is a major source of dissolved ions in Khangri glacier meltwater. In addition, the statistical analysis was also used to determine the correlation between physical parameters of glacier meltwater which controlled the solute dynamics.     

Fluid composition and origin in the hydrothermal system of the Nezhdaninsky gold deposit,Sakha (Yakutia), Russia

Petrochemical characteristics of igneous, sedimentary, and metasomatic rocks; chemical and isotopic compositions of minerals and fluids; and PT parameters of mineral formation at the Nezhdaninsky deposit are reported. A model of hydrothermal system formation is developed on this basis. In addition to decreasing Ba/Rb and Li/Mg ratios in the course of the hydrothermal process, resulting in the formation of ore-bearing metasomatic rocks, increasing K/Ba and diminishing K/Cs ratios indicate the probable participation of magmatic fluid in the ore deposition. The agreement of the K/Rb and K/Ba ratios with the values typical of the main trend of igneous rocks (MT) implies that the K, Rb, and Ba contents were distributed in the ore-forming hydrothermal fluid according to the ratios in the source magmatic chamber. The K/Rb ratios in metasomatic rocks correspond to the MT and approach the pegmatitic-hydrothermal trend and the composition of orthomagmatic fluid of Mo-W greisen. Similar REE patterns of igneous and terrigenous rocks do not allow the REE source to be constrained unequivocally. The lithological control of lithophile element distribution testifies to the supply of host rock components to the hydrothermal system. All studied rocks and minerals are enriched in LREE. The REE total and the contribution of HREE decrease from preore to synore metasomatic rocks, from preore to regenerated carbonates, and from older to younger scheelite. A similar tendency is noted in granitoids of the Kurum pluton. The δ¹⁸O values of quartz range from +10.3 to +12.6‰ in Au-Mo-W zones, from +15.9 to +16.4‰ in metasomatic rocks, from +14.8 to +16.6‰ in gold-ore veins, and from +13.5 to +16.9‰ in silver-base-metal ore mineralization. The estimates of \(\delta ^{18} O_{H_2 O} \) suggest that water was supplied from a magmatic source (δ¹⁸O = +(5.5?9.0‰)) and as a product of sedimentary rock dehydration. High-temperature (up to 390°C) and highly concentrated (up to 31 wt % NaCl equiv) fluids participated in the mineral formation. The phase separation of the fluid into H₂O-CO₂ liquid and predominantly carbon dioxide gas was combined with mixing of a high-temperature and relatively highly concentrated chloride solution with a low-temperature and poorly mineralized fluid. The redox conditions varied from equilibrium with CH₄-bearing fluid at the gold-molybdenum-tungsten stage to equilibrium with CO₂-bearing fluid during the gold-ore stage.     

Silicate oxygen isotope geochemistry: History,principles, techniques,and application to petrological problems

The importance of oxygen isotope geochemistry in studies of terrestrial and extra-terrestrial silicate rocks was recognized nearly sixtyeight years ago soon after the discovery of O¹⁸ and O¹⁷. As early as 1934, the significance of oxygen isotope variations in rocks and minerals was stressed by Russian geochemists who also pioneered the discipline of silicate oxygen isotope geochemistry. It is now known that processes involving isotopic interaction between rock and water, magmatic differentiation, and metamorphic recrystallization fractionate oxygen isotopes in the lithosphere. δO¹⁸ (the conventional notation for reporting O¹⁸/O¹⁶ ratios in rocks and minerals) is highest in sedimentary rocks (17 to 35 ‰) and lowest in igneous rocks (4 to 12‰). Metamorphic rocks have intermediate values. δO¹⁸ in mafic minerals (1 to 8‰) is lower than in felsic minerals (8 to 16‰). In igneous and metamorphic rocks, quartz is most enriched in O¹⁸ (10 to 16‰) and magnetite the least (1 to 2‰). An important application of O¹⁸/O¹⁶ techniques is in geothermometry, where these are capable of elucidating several petrological processes.     

Fe–Mg interdiffusion rates in clinopyroxene: experimental data and implications for Fe–Mg exchange geothermometers

Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X _Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10^?11 to 10^?17 bar. Diffusion couples were prepared by ablating an olivine (X _Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D ^Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di₉₃–Di₆₅) or oxygen fugacity could be detected within the resolution of the study. The lack of fO₂-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D ^Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D ^Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D ^Ca–Mg) while it is slower than D ^Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks).     

Chemical reactions and porosity changes during sedimentary diagenesis

It is of interest to simulate the porosity changes associated with fluid flow and water–rock reactions in sedimentary systems. The chemical species taken into account are: {H₂O, H⁺, Ca⁺⁺, HCO₃⁻, Mg⁺⁺, Al(OH)₄⁻, H₄SiO₄, K⁺, Na⁺, Cl⁻}. The solution is assumed to be locally at equilibrium with different mineral assemblages including at least calcite, dolomite and one Mg–Al-silicate. These assemblages buffer the partial pressure of CO₂ (Pco₂ ) which increases with temperature (T) as is commonly observed in natural systems. The nature of the Mg–Al-silicate and the presence or absence of other at-equilibrium minerals (i.e. the feldspars) do not modify the Pco₂–T relationship. Considering complete transfer between the solution and the solid phases, computed relative porosity increases with increasing temperature for all the systems that were investigated. However, the direction and the amount of the clay transfer depend on the presence of feldspars. Furthermore, it is shown that computing mass transfer using a prescribed Pco₂, as is commonly done, leads to very different values of mineral transfers. Hence, it must be concluded that prescribing a Pco₂ value, even if the proper Pco₂–T relationship is used, leads to erroneous results.     

Laboratory actinide partitioning: Whitlockite/liquid and influence of actinide concentration levels

Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting “haplobasaltic” silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10^?8.5 and 10^?0.7 bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO₂ = 10^?8.5), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu⁺³, Pu⁺⁴, Th⁺⁴, U⁺⁴, and U⁺⁶ are, for whitlockite 3.6/<?0.6/1.2/0.5/?0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO₂ indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ? Ca + 2P being the most likely mechanism. D_u is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.     

华北克拉通新太古代板块俯冲作用:来自山西云中山地区变质高镁火成岩组合的证据

在华北克拉通中部的山西云中山地区,新太古代花岗闪长质片麻岩中存在一些超镁铁质岩-镁铁质岩块及由斜长角闪岩、角闪变粒岩、石英岩和石榴夕线黑云片岩等岩石类型构成的变质表壳岩残片,其中的超镁铁质-镁铁质岩、斜长角闪岩和角闪变粒岩构成一套高镁火成岩组合。超镁铁质岩已变质为橄榄绿泥阳起片岩等岩石类型,呈变余斑状结构,橄榄石斑晶仍有保存;岩石SiO_2含量为39.22%～44.99%,Al_2O_3为8.82%～13.47%,Mg O为19.24%～22.13%,Na_2O+K_2O=0.71%～1.11%,CaO为5.75%～8.42%;Al_2O_3/TiO_2=14.8～17.4,CaO/Al_2O_3=0.60～0.84;化学成分上与科马提岩有一定的相似性。与之紧密伴生的斜长角闪岩也具有高镁特征,Mg O含量为11.28%～15.09%,铝、硅和碱质均偏低,具正铕异常,显示堆晶辉长岩的特征。非高镁斜长角闪岩有相对高的铝、硅和碱质,其原岩应为钙碱性玄武岩。角闪变粒岩样品的SiO_2含量为54.21%～55.71%,Al_2O_3为14.24%～15.49%,Mg O为6.26%～8.28%,Fe OT/Mg O=1.11～1.58,高钠低钾,Na_2O+K_2O=3.7%～4.78%,Na_2O/K_2O=5.15%～13.13,Mg#=53.0～61.5,属于高镁安山岩。由超镁铁质质岩-斜长角闪岩-角闪变粒岩构成的变质高镁火山岩组合具有钙碱性系列趋势。超镁铁质岩稀土元素含量总量较低,具有轻稀土富集和重稀土亏损的稀土型式;斜长角闪岩与超镁铁质岩比较,除富集大离子亲石元素和Cr、Ni明显较低外,具有相似的微量元素图谱形态。三种岩石类型在微量元素蛛网图上均显示出Ta、Nb、Ti负异常和Pb正异常。野外产状和岩石地球化学特征表明超镁铁质岩和高镁斜长角闪岩属于阿拉斯加型杂岩体,角闪变粒岩属于赞岐岩质高镁安山岩。在Zr/Nb-Nb/Th和Nb/Y-Zr/Y构造环境判别图解上显示出与俯冲相关的演化趋势,在Hf-Th-Ta、Nb/La-(La/Sm)N和Th/Yb-Nb/Yb图解上也落在岛弧钙碱性岩石区域。以上特征表明高镁火成岩组合形成于与板块俯冲相关的岛弧构造背景。野外地质关系和锆石U-Pb年龄限定高镁火成岩组合形成时代在～2.5Ga。云中山地区阿拉斯加型镁铁质-超镁铁质杂岩与赞岐岩质高镁安山岩共生,表明该地区存在新太古代的板块俯冲作用,为太古宙存在板块构造机制提供了新证据。     

A comparative study of aquifer systems occurring at the Paraná sedimentary basin, Brazil: U-isotopes contribution

The radioactivity due to ²³⁸U and ²³⁴U in three aquifer systems occurring within the Paraná sedimentary basin, South America, has been investigated. Uranium is much less dissolved from fractured igneous rocks than from the porous sedimentary rocks as indicated by the U-mobility coefficients between 7.6 × 10^?6 and 1.2 × 10^?3 g cm^?3. These values are also compatible with the U preference ratios relative to Na, K, Ca, Mg and SiO₂, which showed that U is never preferentially mobilized in the liquid phase during the flow occurring in cracks, fissures, fractures and faults of the igneous basaltic rocks. Experimental dissolution of diabase grains on a time-scale laboratory has demonstrated that the U dissolution appeared to be a two-stage process characterized by linear and second-order kinetics. The U dissolution rate was 8 × 10^?16 mol m^?2 s^?1 that is within the range of 4 × 10^?16–3 × 10^?14 mol m^?2 s^?1 estimated for other rock types. The ²³⁴U/²³⁸U activity ratio of dissolved U in solutions was higher than unity, a typical result expected during the water–rock interactions when preferential ²³⁴U-leach from the rock surfaces takes place. Some U-isotopes data allowed estimating 320 ka for the groundwater residence time in a sector of a transect in São Paulo State. A modeling has been also realized considering all U-isotopes data obtained in Bauru (35 samples), Serra Geral (16 samples) and Guarani (29 samples) aquifers. The results indicated that the Bauru aquifer waters may result from the admixture of waters from Guarani (1.5 %) and Serra Geral (98.5 %) aquifers.     

Inter-diffusion coefficients parallel to the C-Axis in iron-rich clinopyroxenes calculated from microstructures

Subsolidus marginal zoning in calcium-poor clinopyroxenes and intermediate zoning in discontinuously zoned subcalcic- to calcium-rich clinopyroxenes from ironrich igneous rocks is used to calculate the interdiffusion coefficient, D_Ca?(Fe,Mg), parallel to the crystallographic caxis. Wagner's mathematical models describing the displacement of interfaces in solids as the result of isothermal diffusion are adopted. The steady-state heat flow equation is used to approximate the diffusion times. The calculated interdiffusion coefficients are of a reasonable order of magnitude, viz. 6.0×10^?20?2.0×10^?17cm²· sec^?1 at about 900° C.     

Arsenic-bearing carbonate waters: Geochemical and thermodynamic analysis of their genesis,transformation of arsenic migration species,and models for the genesis of hydrogenic as sulfide mineralization

Analysis of hydrogeochemical materials on As distribution in CO₂-bearing (carbonate) waters in various regions and the thermodynamic simulation of geochemical processes in rock-CO₂-bearing water systems made it possible to constrain the optimal conditions for As transfer from rocks into carbonate waters and the accumulation of this element in the waters. The problem was solved with regard for the various rates of As transitions from rocks to water: (a) high rates of As transitions from rocks in compliance with the ion exchange mechanism and (b) low rates of As transitions from rocks in compliance with the mechanism involving the decomposition of As-bearing minerals. Various mechanisms of As extraction from rocks result in the compositional diversity of the aqueous phase and various As migration species in CO₂-bearing waters, which, in turn, control the equilibrium concentration levels of this element. The principally important boundary conditions of As enrichment in CO₂-bearing waters are high \(P_{CO_2 } \) and R/W ratios in the geochemical systems, a preliminary increase in the Cl concentration in the CO₂-bearing waters, and the origin of these waters at high-density heat fluxes. As migration species were simulated for the model solutions and real carbonate waters of various geochemical types, and it is demonstrated that the predominant As species are oxygen-bearing HAsO ₂ ⁰ , and AsO ₂ ^? at a subordinate role of the sulfide HAs₂S ₄ ^2? , and As₂S ₄ ^2? — species even at high Σ S^2? in the system. Two models of the genesis of solid As sulfides in CO₂-bearing waters are analyzed: (1) with oxygen-bearing species (HAsO ₂ ⁰ , and AsO ₂ ^? ), which occur most widely, and (2) with sulfide species (As₂S ₄ ^2? , HAs₂S ₄ ^? , and As₄S ₇ ^2? ), which occur not as widely.     

Steady-state kinetics and equilibrium between ground water and granitic rock

A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D_25°C = 3 × 10^?22 and 1.5 × 10^?20 cm²sec^?1 at P_CO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10^?8 to n × 10^?5 cm according to the temperature and P_CO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)₃](_1?x)[SiO₂]_x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al³⁺] + xlog [H₄SiO₄] ? (3 ? 3x) log [H⁺] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.     

Hydrogen isotope fractionation between OH-bearing minerals and water

Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, α_e.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 10³ In α_{e(mineral-water)} = ? 22.4 (10⁶T^?2) + 28.2 + (2X_Al ? 4X_Mg ? 68X_Fe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of α_e with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of X_Al, X_Mg, and X_Fe for these minerals, the relationship between α_e and T is 10³ In α_e = αT^?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.