Ecological-geological conditions and factors of their formation

Ecological-geological conditions are considered to be an environment created by a set of contemporary morphologically expressed geological factors that influence specific features of the functioning of the biota, including human beings, within the framework of the ecological-geological system. The paper discusses factors (components) of ecological-geological conditions, factors of the formation of ecological-geological conditions, and the role of anthropogenic (technogenic) impacts in the transformation of ecological-geological conditions.     

Geochemical characteristics of some rare element-bearing granites in southeast China and physico-chemical conditions of their formation

The formation of ore-bearing granites in the Yenshanian movement in southeast China and the geochemical characteristics of some RE-bearing granites have been studied through multivariate statistical analysis and physicochemical approach. The main conclusions have Been drawn as follows: (1) The granites are believed to be products of anatexis of the crustal materials. The formation temperature of granitic magma is estimated at about 600°C and the crystallization temperatures range from 600° to 500°C. The temperature of Li-, Fand H₂O-rich residual magma in the latest stage of magmatism is probably below 500°C. (2) A rock series from early lepidomelane-granite through protolithionite-and zinnwalditegranite to lithioniteor lepidolite-granite is considered as a result of actual crystallization. (3) The mineral paragenesis and fades zonation of granite plutons are mainly controlled by Ph₂o, μNa₂O and μK₂O in the magma. (4) During the magmatic evolution the ore-forming elements (REE, Nb, Ta, etc.) are variable in geochemistry. REEs, similar to mafic components, were highly concentrated at the early stage of the magmatic evolution and deposited under favourable conditions in the zinnwaldite-and protolithionite-granites; Nb and Ta have a preference for felsic and volatile components, thus are mainly concentrated at later stages of the magmatic evolution. Nb ore deposits are formed in the lithionite and lepidolite granites, for Ta is intimately associated with Na₂O, Li₂O, F and H₂O.     

Comparison of debris-flow volume and activity under different formation conditions

Debris flows frequently occurred in Wenchuan earthquake region from 2008 to 2010, resulting in great damage to localities and being a prolonged threat to reconstruction. Forty three events' data including debris-flow volume, sediment volume and watershed area are analyzed and compared with other debris-flow events in Eastern Italian Alps, burned areas in USA and in Taiwan. The analysis reveals that there is a strong empirical relationship between debris-flow volume and loose materials volume in the earthquake region. In addition, the relationship between debris-flow volume and watershed area in the earthquake region has a wider variation range than that in other three regions while the debris volume also appears to be larger than that in the other three regions, which implies the volume of debris flows with strong influence of earthquakes is larger than that with no such influence and it is hard to predict the post-quake volume only by the watershed area. The comparison of the maximal debris-flow erosion modulus in the Wenchuan region and in Taiwan indicates that debris flows will be very active in a short time after strong earthquake.     

Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO₄, leading to ferrisicklerite, Li_<1(Fe³⁺,Mn²⁺)PO₄, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li_0.93(3)(Fe²⁺ _0.733(6),Fe³⁺ _0.015(1),Mn²⁺ _0.210(4),Mg_0.063(2))_1.021(8)P_1.00(2)O₄ in addition with ground bulk material were treated with KMnO₄ and 30 % H₂O₂(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and ⁵⁷Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li_0.30(7)(Fe²⁺ _0.049(1)Fe³⁺ _0.65(2)Mn²⁺ _0.218(5)Mg_0.062(2))_0.98(1)P_1.01(3)O₄, with unit cell parameters a?=?4.795(1), b?=?9.992(4), and c?=?5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.     

Dissolution-precipitation reactions controlling fast formation of dolomite under hydrothermal conditions

In laboratory experiments, the precipitation of dolomite at ambient temperature is virtually impossible due to strong solvation shells of magnesium ions in aqueous media and probably also due to the existence of a more intrinsic crystallization barrier that prevents the formation of long-range ordered crystallographic structures at ambient surface conditions. Conversely, dolomite can easily form at high temperature (>100 °C), but its precipitation and growth requires several days or weeks depending on experimental conditions. In the present study, experiments were performed to assess how a single heat-ageing step promotes the formation of dolomite under high-carbonate alkaline conditions via dissolution-precipitation reactions. This reaction pathway is relevant for the so-called hydrothermal dolomite frequently observed in carbonate platforms, but still ill-defined and understood. Our precipitation route is summarized by two main sequential reactions: (1) precipitation of Mg-calcite at low temperature (∼20 °C) by aqueous carbonation of synthetic portlandite (Ca(OH)₂) in a highly alkaline medium (1 M of NaOH and 1 M of MgCl₂), leading to precipitation of oriented nanoparticles of low- and high-Mg calcite (∼79 wt%) coexisting with aragonite (∼18 wt%) and brucite (∼3 wt%) after 24 h; (2) fast dolomitization process starting from 1 h of reaction by a single heat-ageing step from ∼20 to 200, 250 and 300 °C. Here, the Mg-calcite acts as a precursor that lowers the overall kinetics barrier for dolomite formation. Moreover, it is an important component in some bio-minerals (e.g. corals and seashells). Quantitative Rietveld refinements of XRD patterns, FESEM observations and FTIR measurements on the sequentially collected samples suggest fast dolomite precipitation coupled with dissolution of transient mineral phases such as low-Mg calcite (Mg < 4 mol%), high-Mg calcite (Mg > 4 mol%), proto-dolomite (or disordered dolomite; Mg > 40 mol%) and Ca-magnesite. In this case, the dolomite formation rate and the time-dependent mineral composition strongly depend on reaction temperature. For example, high-purity dolomitic material (87 wt% of dolomite mixed with 13 wt% of magnesite) was obtained at 300 °C after 48 h of reaction. Conversely, a lower proportion of dolomite (37 wt%), mixed with proto-dolomite (43 wt%), Ca-magnesite (16 wt%) and high-Mg calcite (4 wt%), was obtained at 200 °C after 72 h. The present experiments provide an additional mechanism for the massive dolomite formation in sedimentary environments (ex. deep sea organic-rich carbonate-sediments) if such sediments are subjected to significant temperature variations, for example by hot fluid circulations related to volcanic activity. In such systems, organic degradation increases the carbonate alkalinity (HCO₃⁻) necessary to induce the dolomitization process at low and high temperature.     

Lithogeochemical features of Riphean fine-grained terrigenous rocks in the Kama-Belaya aulacogen and their formation conditions

Lithogeochemical features of Riphean fine-grained terrigenous rocks of the Kama-Belaya aulacogen are discussed. It is shown that aluminosiliciclastic material delivered to the aulacogen during the Riphean was characterized by a low maturity degree. The successively increasing K₂O/Al₂O₃ values in the Riphean summary section correlate negatively with the CIA index values, indicating a gradually strengthening tendency for climate aridization in erosion zones. Data on some indicator ratios of trace elements and REE systematics in Riphean silty mudstones and shales of the Kama-Belaya aulacogen imply the involvement of mafic and ultramafic rocks, in addition to acid igneous and metamorphic varieties, in erosion during accumulation of the Nadezhdino, Tukaevo, Ol’khovka, Usinsk, and Priyutovo formations. Comparison of data on the composition of rocks in provenances based on the mineralogical-petrographic study of sandstones and investigation of geochemical features of silty mudstones and shales revealed their sufficiently high similarity. The geochemical data made it possible to specify the composition of rocks in provenances. Low Ce/Cr values in the fine-grained terrigenous rocks of the Lower Riphean Kyrpy Group suggest their formation with a significant contribution of erosion products of the Archean substrate, which is atypical for higher levels of the section. Thus, the Early-Middle Riphean transition period was likely marked by substantial changes in the mineral composition of material delivered to the Kama-Belaya aulacogen. The lack of exhalative components in the examined specimens of silty mudstones and shales points to a relatively low permeability of the Earth’s crust in the eastern East European Platform through the entire Riphean.     

Present-day formation of pillow lavas under subaerial conditions of Karymskiy Volcano

Gas saturation independent of chemical composition is considered a decisive factor in the formation of pillow and globular lavas. In this case, flourine as the reagent, reduced the viscosity and density of the andesitic-dacitic lava flow. Effervescence or secondary pulsation in the frontal part of the moving flow, due to reduced pressure, caused some of the lava to become detached from the main mass which, traveling ahead of or along the sides of the flow, acquired pillow or globular shapes depending on their mass, velocity and distance traveled. --IGR Staff.     

Solubility of platinum and palladium in silicate melts under high water pressure as a function of redox conditions

The solubility of platinum and palladium in a silicate melt of the composition Di ₅₅ An ₃₅ Ab ₁₀ was determined at 1200°C and 2 kbar pressure in the presence of H₂O-H₂ fluid at an oxygen fugacity ranging from the HM to WI buffer equilibria. The influence of sulfur on the solubility of platinum in fluid-bearing silicate melt was investigated at a sulfur fugacity controlled by the Pt-PtS equilibrium at 1200°C and a pressure defined in such a way that the \(f_{H_2 O} \) and \(f_{O_2 } \) values were identical to those of the experiments without sulfur. The experiments were conducted in a high pressure gas vessel with controlled hydrogen content in the fluid. Oxygen fugacity values above the NNO buffer were controlled by solid-phase buffer mixtures using the two-capsule technique. Under more reducing conditions, the contents of H₂O and H₂ were directly controlled by the argon to hydrogen ratio in a special chamber. The hydrogen fugacity varied from 5.2 × 10^?2 bar (HM buffer) to 1230 bar (\(X_{H_2 } \) = 0.5). Pt and Pd contents were measured in quenched glass samples by neutron activation analysis. The results of these investigations showed that the solubility of Pt and Pd increases significantly in the presence of water compared with experiments in dry systems. The content of Pd within the whole range of redox conditions and that of Pt at an oxygen fugacity between the HM to MW buffer reactions are weakly dependent on \(f_{O_2 } \) and controlled mainly by water fugacity. This suggests that, in addition to oxide Pt and Pd species soluble at the ppb level in haplobasaltic melts, much more soluble (ppm level) hydroxide complexes of these metals are formed under fluid-excess conditions. Despite a decrease in water fugacity under reducing conditions, Pt solubility increases sharply near the MW buffer. It was shown by electron paramagnetic resonance spectrometry that, in contrast to dry melts, fluid-saturated silicate melts do not contain a pure metal phase (micronuggets). Therefore, the increase in Pt solubility under reducing conditions can be explained by the formation of Pt hydride complexes or Pt-fluid-silicate clusters. At a sulfur fugacity controlled by the Pt-PtS equilibrium, the solubility of Pt in iron-free silicate melts as a function of redox conditions is almost identical to that obtained in the experiments without sulfur at the same water and oxygen fugacity values. These observations also support Pt dissolution in iron-free silicate melts as hydroxide species.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

就地应力条件下岩石静动态力学性质的研究

岩石力学性质参数可以通过模拟地层应力条件下的室内岩石力学实验得到,但它只能代表一些离散点,所以,在实际应用中的大多数情况下,石油工程师采用连续的测井曲线计算岩石力学参数,然而由于加载频率的不同,计算值与室内准静态条件下测得的参数值有一定的差异,只有校核后的测井曲线才能用于工程应用中。为了从室内实验结果中得到校核后的连续的测井曲线,对模拟就地应力条件下静动态岩石力学性质进行了初步的研究。     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.     

The role of humic substances in the formation of marble patinas under soil burial conditions

The present work aim to study the effect of burial on the photoluminescnece (PL) spectra of white, crystalline marble surfaces and the physicochemical processes that take place at the marble—soil interface. The PL was studied by an argon ion laser beam, focused through a microscope objective onto the sample, offering a spatial resolution of 3 μm. Long-buried (time scale of 1,000 years) surfaces show a red (at 610 nm) emission due to Mn²⁺, which is also shown on fresh marble spectra and an additional broadband blue-green (380–530 nm) one. Electron paramagnetic resonance (EPR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) indicate that the latter emission originates from humate complexes. The complexes are most probably Ca-humates, the humic substances found in the soil and the divalent calcium cations released by the dissolution of marble calcite. Finally, the examination of recently (time scale of 50 years) buried surfaces shows that the blue-green emission and consequently the presence of humates in marble patinas are not affected by the soil organic matter content. Soil acidity however, is a critical factor, with a total absence of the blue-green emission at pH values lower than 6.     

Intense pyrite formation under low-sulfate conditions in the Achterwasser lagoon, SW Baltic Sea

In comparison to similar low-sulfate coastal environments with anoxic-sulfidic sediments, the Achterwasser lagoon, which is part of the Oder estuary in the SW Baltic Sea, reveals unexpectedly high pyrite concentrations of up to 7.5 wt%. Pyrite occurs mainly as framboidal grains variable in size with diameters between 1 and 20 μm. Pyritization is not uniform down to the investigated sediment depth of 50 cm. The consumption of reactive-Fe is most efficient in the upper 20 cm of the sediment column, leading to degrees of pyritization (DOP) as high as 80 to 95%.Sediment accumulation in the Achterwasser takes place in high productivity waters. The content of organic carbon reaches values of up to 10 wt%, indicating that pyrite formation is not limited by the availability of organic matter. Although dissolved sulfate concentration is relatively low (<2 mmol/L) in the Achterwasser, the presence of H₂S in the pore water suggests that sulfate is unlikely to limit pyrite authigenesis. The lack of free Fe(II) in the pore waters combined with the possibility of a very efficient transformation of Fe-monosulfides to pyrite near the sediment/water interface suggests that pyrite formation is rather controlled by (i) the availability of reactive-Fe, which limits the FeS formation, and by (ii) the availability of an oxidant, which limits the transformation of FeS into pyrite. The ultimate source for reactive-Fe is the river Oder, which provides a high portion of reactive-Fe (∼65% of the total-Fe) in the form of suspended particulate matter. The surficial sediments of the Achterwasser are reduced, but are subject to oxidation from the overlying water by resuspension. Oxidation of the sediments produces sulfur species with oxidation states intermediate between sulfide and sulfate (e.g., thiosulfate and polysulfides), which transform FeS to FeS₂ at a significant rate. This process of FeS-recycling is suggested to be responsible for the formation of pyrite in high concentrations near the sediment surface, with DOP values between 80 and 95% even under low sulfate conditions.A postdepositional sulfidization takes place in the deeper part of the sediment column, at ∼22 cm depth, where the downward diffusion of H₂S is balanced by the upward migration of Fe(II). The vertical fluctuation of the diffusion front intensifies the pyritization of sediments. We suggest that the processes described may occur preferentially in shallow water lagoons with average net-sedimentation rates close to zero. Such environments are prone to surficial sediment resuspension, initiating oxidation of Fe-sulfides near the sediment/water interface. Subsequent FeS₂ formation as well as postdepositional sulfidization leads to a major pyrite spike at depth within the sediment profile.     

Trace element partitioning between vapor, brine and halite under extreme phase separation conditions

Experiments were conducted to investigate the partitioning of Li, Br, Rb, Cs and B between vapor, brine and halite during subcritical and supercritical phase separation in the NaCl-H₂O system (388-550 °C, 250-350 bars). Results indicate that Li and Br partition preferentially into the low-salinity vapor fluids, while Rb and Cs become more enriched in the coexisting brines. Under more extreme conditions of pressure and temperature in the two-phase region, especially near the vapor-brine-halite boundary, strong salting-out effects imposed on neutral aqueous species enhance significantly partitioning of all trace elements into the low-salinity fluid. Dissolved boron is strongly affected by this and a particularly strong enrichment into vapors is observed, a trend that can be effectively correlated with changes in reduced density. Exclusion of Li, Br, Rb, Cs and B from halite, when precipitated, further increases the solubility of these species in the coexisting Cl-poor fluid. In general, the lack of distortion in the partitioning behavior of trace elements between vapor, brine and/or halite with the transition from subcritical to supercritical conditions in the NaCl-H₂O system precludes the need for special reference to the critical point of seawater when interpreting phase relations in submarine hydrothermal systems. The combination of experimentally determined trace element partitioning data with constraints imposed by mineral solubility provides a means to better understand the origin and evolution of hot spring vent fluids. For example, in Brandon hydrothermal system (21°S EPR) supercritical phase separation and subseafloor mixing appear to be the main heat and mass transport mechanisms fueled by a shallow magmatic intrusion, with boron systematics ruling out major contributions from magmatic degassing processes accompanying the near-seafloor volcanism.     

Relationships among Gibbs free energies and enthalpies of formation of phosphates,oxides and aqueous ions

Two parameters _GO^2– and _HO^2– are defined as the differences between respectively the Gibbs free energies and the enthalpies of formation of an oxide and its corresponding aqueous cation. The Gibbs free energies and enthalpies of formation of phosphates from their consituent oxides are shown to be linear functions of respectively _GO^2– and _HO^2– of their constituent cations.