Diagenetic crystallization and oxidation of siderite in red bed (Buntsandstein) sediments from the Central Iberian Chain,Spain

Compactional deformation facilitated replacement of dolomite and calcite by siderite and its subsequent oxidation in carbonate cemented red beds of the Triassic Buntsandstein in the Iberian Chain. Locally, the sedimentary clasts were cemented by carbonate that was derived from dissolution of locally exposed dolomite in the basement. Microstructures indicate that during sedimentation of the rocks, oxidizing conditions prevailed in the sediments and the basement was reddened by impregnation of hematite. Reducing conditions prevailed during deformation of the sediments. Ferric iron was reduced to Fe²⁺, that reacted with deformed dolomite and calcite cement to produce fine grained siderite. At a later stage, siderite crystallites were (partly) oxidized to form a secondary phase of brown ferric oxide (goethite). Locally, goethite transformed to fine grained hematite that caused secondary reddening of the sediments. The reactions are associated with a combined volume loss of the solid phases of c. 50% per reaction mol; this was accommodated by the formation of pores. Oxidation of siderite was associated with release of CO₂; localized dissolution took place of feldspar and concurrently growth of kaolinite occurred by acidifying condition during release of CO₂. The relation of redox reactions and deformation is comparable to those in red bed conglomerates in the region. Reductive dissolution occurred at sites of stress concentration, particularly at contact points of pebbles. Late stage precipitation of ferric oxides and pyrolusite took place at oxidizing conditions in association with uplift.     

The mantle,CO2 and the giant Aptian chemogenic lacustrine carbonate factory of the South Atlantic: Some carbonates are made,not born

During the Aptian (Cretaceous), in what is now the South Atlantic, the largest chemogenic (abiotic) carbonate factory so far identified in the Phanerozoic geological record developed as a vast hyper-alkaline lake system. This covered at least 330 000 km², producing carbonates, locally over 500 m thick, in what are now the offshore Santos and Campos basins (Brazil), and Kwanza Basin (Angola). Current evidence supports the view that almost all of this carbonate was chemogenic in origin, precipitated from hyper-alkaline, shallow lake waters, probably by evaporation. This unit, best documented from offshore Brazil and known as the Barra Velha Formation (Santos Basin) and the Macabu Formation (Campos Basin), consists of just two basic carbonate components, millimetre to centimetre sized crystal shrubs and spherulites. These are commonly in situ but can also be reworked into a range of detrital facies. Demonstrable microbialites are generally rare. These carbonates are associated with Mg silicates (as clays) which had a profound influence not only on the textural development of the in situ carbonates, but also on their diagenesis. The dissolution of the clays produced much of the porosity in these limestones, which are the hosts for multi-billion barrel oil fields. The source of the carbonate was most likely from metasomatic alteration of mafic rocks, such as continental flood basalts related to Atlantic opening, with some contribution from much older continental basement. Clear evidence that serpentinization of possible exhumed mantle is lacking but mantle CO₂ is likely to have been a critical factor in determining the composition of the fluids from which the carbonates formed and the high alkalinities of the lake waters.     

Composition and mineralogy of suspended sediment in the fluvio-estuarine zone of the Loire River, France

The fluvio-tidal transition of suspended sediment in terms of mineralogy and composition in the Loire River drainage basin, the largest French river basin, was investigated in the fluvial zone at Montjean and in the tidal zone at Mauves-Thouaré, for a complete seasonal cycle. At Montjean, where the river experiences unidirectional flow, the composition and mineralogy (especially clays and clay minerals) of river suspended material (RSM) are governed by the river discharge, upstream contributions, climatic conditions and microbiological activities. However, due to reversing tidal and river currents at Thouaré, in the zone of tidal dynamics, these relations are changed. In the downstream direction sand and clay content in the RSM decrease while the silt content increases. Among clay minerals, between these two observation stations, montmorillonite remains constant, kaolinite diminishes, and the other minerals increase downstream. Combustible material (organic) and nitrate (NO₃) contents in the RSM increase whereas the phosphate (PO₄^3-) and CaCO₃ contents decline considerably during transport. At the head of the tidal zone, where the river flow encounters the tidal influence, there is a relatively stationary water mass (tidal slack) where sands, clays, phosphate, carbonate and silica are deposited by physical and chemical processes. Physical sedimentation takes place by simple gravitational deposition (sands), and by sorting and complicated differential settling (clays); chemical sedimentation takes place by precipitation (calcite-CaCO₃; apatite-Ca₅ (PO₄)³ (OH,F,Cl); coagulation of dissolved silica-SiO₂) in connection with seasonal algal bloom and eutrophic events.     

Lithium distribution and isotopic fractionation during chemical weathering and soil formation in a loess profile

Lithium (Li) is a fluid-mobile element and δ⁷Li in secondary deposits represents an excellent proxy for silicate weathering and authigenic mineral formation. The soil samples from 1205 to 1295 cm in the Weinan profile, one of the best developed loess-paleosol sequences covering the last glacial–interglacial climatic cycle, were collected and chemically separated into detritus and carbonate fractions for subsequent analyses of Li, δ⁷Li, major and trace elements. Other desert specimens (i.e., Qaidam Desert, Tengger Desert, Badain Juran Desert and Taklimakan Desert) near the Chinese Loess Plateau (CLP) and various standard clays were analyzed for assisting provenance determination. The Li and δ⁷Li distributions in the detritus are rather homogeneous, 1.4–2.0 μg/g and +2.5‰ to +4.7‰, respectively, compared with the carbonate fraction. The detrital δ⁷Li varies systematically with magnetic susceptibility and grain size changes, reflecting significant Li isotopic variation associated with sources and mineralogy of detrital material. On the other hand, Li and δ⁷Li in carbonates show large changes, 781–963 ng/g and −4.1‰ to +10.2‰, respectively. These carbonate δ⁷Li correlated well with the estimated index of chemical weathering, as a result of Li mobilization and soil formation during chemical weathering.     

Reconstruction of nearshore chemical conditions in the Mesoproterozoic: evidence from red and grey beds of the Yangzhuang formation,North China Craton

ABSTRACT

Mesoproterozoic red beds near ancient coasts have not aroused extensive interest. A new geochemical study of the alternating red and grey dolostones from the Yangzhuang Formation provides a better understanding of the redox conditions of nearshore sedimentary environments. In this contribution, whole-rock samples are characterized by positive correlations of rare earth elements (REE) vs. Th and Fe_T vs. Th and flat-type REE distribution patterns, indicating massive terrigenous input, which is considered to be inherited from felsic rocks. Relatively high (Fe_mag+Fe_ox)/Fe_T and Fe³⁺/Fe²⁺ ratios in red beds indicate more oxidized conditions in supratidal environments compared with the lower oxygen contents in intertidal environments. Under these two distinct chemical sedimentary conditions, acetic acid-leached red and grey samples both have HREE-depleted distributions, suggesting significant freshwater invasion. Moreover, limited terrigenous redox-sensitive elements (RSEs) can reach the coast where the red beds are deposited, whereas relatively high RSE enrichment factors originating from shallow oceans are recorded in grey beds. In the Mesoproterozoic, limited oxidative weathering, shallow seawater desalination, and low organic production occurred near the coast. Meanwhile, a prolonged period of low Mo and U availability preserved in carbonate minerals confirmed that marine oxygen levels failed to satisfy the deposition of offshore red beds. During the regression, potentially exposed sediments connected to atmospheric oxygen guaranteed the oxidation of iron and the formation of red beds, and these events were coupled with negative δ¹³C_carb shifts in the Yanliao rift zone.     

Effects of sulphate reduction and geogenic CO2 incorporation on the determination of 14C groundwater ages – a case study of the Palaeogene groundwater system in north-eastern Syria

Groundwater from the Palaeogene aquifer system in north-eastern Syria has been studied using chemical and isotopic methods to determine the effects of carbonate dissolution, sulphate reduction and geogenic CO₂ incorporation in the dilution of ¹⁴C activity, and later to correct the conventional ¹⁴C water ages. The reason for this non-classical approach of correction is because the groundwater in this karstified and Nummulitic carbonate aquifer occurs under confined and partly confined conditions, and is located in an area very close to deep faults and fractures. Furthermore, the interconnection with the Upper Cretaceous formations, which commonly contain gypsum and hydrocarbons, can facilitate the processes of sulphate reduction and geogenic CO₂ incorporation, which should not be excluded. The dilution factor related to carbonate dissolution was estimated to be about 0.60–0.75. The dilution factor associated with sulphate reduction, which only depends on H₂S content, was rather low (about 0.95). However, as a result of the local tectonic setting in this area, the influence of geogenic CO₂ incorporation was clearly high. The dilution factor associated with this effect ranges between 0.24–0.64. Consequently, the corrected ¹⁴C ages are considerably reduced compared with those determined by classical models. Accordingly, the groundwater in the study area can be divided into three main groups: (1) fresh, shallow and cold water of less than 1 ka age; (2) brackish, deep and thermal water of rather old age (10.9–12.3 ka B.P.); and (3) an admixed groundwater of intermediate quality and age (1.9–6.7 ka B.P.). Electronic Publication     

Boron isotopic fractionation between minerals and fluids: New insights from in situ high pressure-high temperature vibrational spectroscopic data

Equilibrium boron isotopic fractionations between trigonal B(OH)₃ and tetragonal B(OH)₄⁻ aqueous species have been calculated at high P-T conditions using measured vibrational spectra (Raman and IR) and force-field modeling to compute reduced partition function ratios for B-isotopic exchange following Urey’s theory. The calculated isotopic fractionation factor at 300 K, α_3/4 = 1.0176(2), is slightly lower than the formerly calculated value of α_3/4 = 1.0193 (Kakihana and Kotaka, 1977), due to differences in the determined vibrational frequencies. The effect of pressure on α_3/4 up to 10 GPa and 723 K is shown to be negligible relative to temperature or speciation (pH) effects. Implications for the interpretation of boron fractionation in experimental and natural systems are discussed. We also show that the relationship between seawater-mineral B isotope fractionation and pH can be expressed using two variables, α_3/4 on one hand, and the pK_a of the boric acid-borate equilibrium on the other hand. This latter value is given by the equilibrium of boron species in water for the carbonate-water exchange, but could be governed by mineral surface properties in the case of clays. This may allow defining intrinsic paleo-pHmeters from B isotope fractionation between carbonate and authigenic minerals. Finally, it is shown that fractionation of boron isotopes can be rationalized in terms of the changes in 1) coordination of B from trigonal to tetrahedral in both fluids and minerals; and 2) the ligand nature around B from OH⁻ in the fluid and some hydrous minerals to non-hydrogenated O in many minerals. Relationships are established that allow predicting the isotopic fractionation factor of B between minerals and fluid.     

Metal accumulation rates in northwest Atlantic pelagic sediments

Measurements of ²³⁰Th, ${}^{87}\text{Sr}{}^{86}\text{Sr}$ and twenty-four metals were made on cores from the Nares Abyssal Plain. The sediment is characterized by slowly-accumulating (0.3–0.7 g/cm² 10³ yr) pelagic red clays and rapidly deposited grey clays transported by turbidity currents. Despite their colour differences and the enrichment of Mn, Fe, Cu, Co, Ni, Zn, V and, to a lesser degree, the rare earths in the red clays, Sr isotope evidence demonstrates that the clays have the same terrigenous origin. The excesses of metals in the red clays have been attributed to metal removal from the water column and a comparison with the grey clays has enabled the authigenic fluxes of metals to be estimated. The fluxes obtained are in the ranges 20–50 μmol/cm² 10³ yr for Mn and Fe, 0.1–0.4 μmol/cm² 10³ yr for Cu, Co, Ni, Zn, V, Sr and Ce, 10–20 nmol/cm² 10³ yr for La and Nd, and 0.5-3 nmol/cm² 10³ yr for Sm, Eu, Gd, Dy, Er and Yb. Authigenic fluxes of Y, Nb, Cr, Zr, Rb, U and Th were not resolvable. Fluxes appear to be near constant on the Plain but comparison with other areas shows that they are quite variable both between and within ocean basins. The chief factor controlling authigenic fluxes is the geochemical abundances of the elements but fractionation within both the transition element and rare earth series can be recognized from inter-element comparisons and from differences in fluxes between Atlantic and Pacific red clays corresponding to the oceanic reactivities of the elements.     

Geochemistry of carbonated mineral waters from the Fadeevskoe deposit of the Primorye region

The geochemical study of bed rocks, underground and surface waters, and associated gases in the Fadeevskoe deposit of carbonated waters (Sikhote Alin, Primorye region) revealed that the chemical composition of these waters is formed in the zone of active water exchange in the limited area of the discharge zone, where hydro carbonate calcic waters with mineralization of up to 1 g/1 are formed in largely potassic-sodic rocks. Calculations of the saturation indices show that the mineral waters are characterized by the early stage of Ca saturation, being undersaturated with carbonates and aluminosilicates. The main factors that influence the water mineralization are the excess carbon dioxide in water and the circulation time. The oxygen and carbon isotope ratios indicate the atmospheric genesis of the aqueous component (δ²H = —117; δ¹⁸O = —15.4%o) and the carbon isotope content in the CO₂ implies the mantle nature of the carbon dioxide (δ¹³C = -9.9%o).     

Chemical fractionation of transition elements in Pacific pelagic sediments

Partitioning of transition elements in Pacific pelagic sediments (35 samples) was performed by sequential chemical leaching with barium chloride/triethanolamine (easily extractable fraction), acidic cation exchange resin (carbonate phases), and hydroxylamine hydrochloride and dilute hydrochloric acid solutions (hydrous oxides). Residual metal percentages are highest in red-brown clays and siliceous ooze, intermediate in calcareous materials and low in micronodules (2 samples, > 125 μm): residual metal contents seem to be controlled predominantly by the rate of admixture of volcanoclastic materials. At higher bulk metal concentrations, the non-residual fractions of Mn, Cu, Ni and Zn generally increase both in red-brown pelagic clays and in siliceous ooze. Mn, Ni, and Co concentrations are mainly associated with the easily reducible fraction (0.1 M NH₂OH·HCl), whereas Fe, Cu, and Zn exhibit higher percentages in the hydrochloric acid soluble fractions (0.3 M HCl); Zn and Cu are associated to some extent with the carbonate phase, copper with the easily extractable fraction.     

Fixed-ammonium in clays associated with crude oils

The association of ammonium (NH₄⁺) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH₄ in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH₄-substitution occurs near mature hydrocarbons. Results show higher fixed-NH₄ concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH₄ concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH₄ in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.T_max = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH₄ averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH₄-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.T_max = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH₃ during crude oil generation or migration is recorded byNH₄⁺ substitution in clays.Fixed-NH₄ and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH₄⁺ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH₄⁺ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.     

The Mid-Cenomanian Event in shallow marine environments: Influence on carbonate producers and depositional sequences (northern Aquitaine Basin,France)

The Mid-Cenomanian Event was a positive carbon-isotope (δ¹³C) excursion recorded in hemipelagic basins of the western Tethyan Sea, North to Tropical Atlantic Ocean, and Japan. It is thought of as a prelude to the Oceanic Anoxic Event 2. However, the Mid-Cenomanian Event has never been studied in detail in shallow marine platform deposits and it is not known how it relates to carbonate production and stratigraphic geometry. To better understand how this carbon cycle disruption influenced the neritic biological communities in shallow carbonates during the Cenomanian, a facies, geochemical, diagenetic, and sequence stratigraphic study of the northern Aquitaine platform has been conducted. Seventy-six δ¹³C and δ¹⁸O measurements have been made on micrite, rudists, and diagenetic cements. Fifteen sedimentary facies have been arranged into four depositional environments. Three third-order sequences (C_B, C_C, C_D) are defined from late early Cenomanian to early late Cenomanian and are well correlated with eustatic cycles in European basins. Two peaks of the Mid-Cenomanian Event (MCE1a, +1.2‰, and MCE1b, +1.7‰) have been identified for the first time in shallow marine carbonates. Analysis of diagenetic blocky calcite cements suggests that diagenesis did not affect the δ¹³C of micrite, which can be discussed in terms of the initial signal. The Mid-Cenomanian Event was synchronous with a turnover in neritic carbonate producers marking a transition from photozoan to heterozoan facies. This facies change resulted from the establishment of mesotrophic to eutrophic conditions at the early/mid-Cenomanian transition, reflecting a clear connection between the Mid-Cenomanian Event and neritic biological communities. Depositional geometry and carbonate production varied with δ¹³C during the Mid-Cenomanian Event on the Aquitaine platform. When δ¹³C values were between 2.5‰ and 3‰, the geometry was a flat platform with a high carbonate sedimentation rate leading to the formation of sandbars and rudist bioherms (Accommodation/Sedimentation ratio less than 1, A/S < 1). When the δ¹³C value exceeded 3‰, a carbonate demise occurred and clays and marls were deposited in the lower offshore environment (A/S >> 1). The general carbonate demise affecting the northern Aquitaine platform during the mid-Cenomanian can be explained by both a eustatic sea-level rise and the establishment of eutrophic conditions. The coincidence of the Mid-Cenomanian Event with both (1) the occurrence of mesotrophic to eutrophic conditions marked by carbonate producer turnover from photozoan to heterozoan facies and (2) the transgressive cycles, suggests that eustatic sea-level rise leading to high trophic conditions could explain this positive δ¹³C excursion in the Atlantic and western Tethyan domain. During the mid-Cenomanian, carbon cycle perturbations largely controlled the neritic biological communities on shallow carbonate platforms in a part of the western Tethyan domain.     

Evidences of felsic volcanism and hydrothermal activities from clays associated with the Palaeoproterozoic Porcellanite Formation of the Vindhyan Supergroup,Central India

Chemico-mineralogical attributes of authigenic clays associated with the altered volcanic tuffs that occur in the Palaeoproterozoic Porcellanite Formation contain evidences of hydrothermal alteration and diagenetic processes in a marine environment. Previous sedimentological and geochemical studies on Porcellanite Formation were restricted to the Chopan area, but, the details related to provenance, nature and source of volcanism archived in these clays have not been ascertained. In order to understand these aspects, present study on these authigenic clays were carried out. Clay minerals represent dominance of illite with subordinate amount of montmorillonite. Moreover, low abundance of kaolinite is also noticed. The illite fibers and plates associated with the kaolinite indicate illitization. The kaolinite to illite transformation is favoured by incorporation of K⁺ ions, derived from the K-feldspar dissolution and its overgrowth. Major oxide contents of these clays and their ratios when plotted over diagrams marked with standard illite, kaolinite, smectite and chlorite compositional fields show clustering within or close to the illite field. Thermodynamic components calculated for these clays when plotted over AR₂³⁺AlSi₃O₁₀(OH)₂ − R₂³⁺Si₄O₁₀(OH)₂ − AR²⁺R³⁺Si₄O₁₀(OH)₂ ternary diagram, data plots lie within the illite, mixed layer I/S and smectite fields. Binary major oxide data plots between bulk rock and authigenic clay compositions showed felsic affinity. Montmorillonite and illite predominated in the eastern and western marginal areas of the Vindhyan Basin, respectively. However, former resulted from the hydrothermal alteration of volcanic glass associated with the ferruginous breccia and altered tuffs and remnants of the volcanic vents, whereas, later is associated with the tuffaceous beds. Owing to the adsorption, Ba, Rb and Sr is enriched in clays comparing to the bulk rock composition. Low (< 15 ppm) Sc values suggested major contribution from the felsic component. Also, low Rb/Sr and Th/U values revealed moderate insitu weathering. The dominance of K-feldspar alteration and insitu weathering is also evident from clustering of clay data plots in the A-CN-K ternary diagram. Pronounced negative Eu anomaly together with higher LREE/HREE values associated with these clay minerals implied proximity to source and their possible derivation from the silicified felsic tuffs available in the provenance.     

Microscale carbon isotope variability in ALH84001 carbonates and a discussion of possible formation environments

The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ¹³C values ranging from +27 to +64‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively ¹³C depleted and the Mg-rich, later forming carbonates, are ¹³C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO₂-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.     

江西41 4含钽、铌钠长石化花岗岩风化壳中三水铝石的发现及其成因研究

The Wucheng trona deposit, one of the rare ancient trona deposits in the world, is genetically of typical terrestrial facies carbonate sediments of brine lake. Contained in an Eogene block basin composed of terrigenous clastic-evaporite rocks some 2400 m in thickness, it occurs 650 to over 900 m beneath the earth's surface in the form of multilayers, the lower part being pure trona beds while the upper part consisting of trona beds interbedded with halite streaks. Saline minerals are trona and to a much less amount, halite and nahcalite, associated with such minerals as shortite and northupite. Mirabilite, a rather common mineral in the carbonate salt lake, has not yet been found here. The unusually developed sedimentary cyclothem of the host rock, predo-minantly argillaceous dolomite- kuchersite- (halite-bearing) trona, makes up a most striking feature of this deposit, and the trona bed lies invariably on the kuchersite-dolomite facies. Although belonging to one of the minerogenetic series of saline deposit, the trona deposit, instead of being simply a product of the evaporation of brine, has its specific mineral-forming conditions and sedimentation mechanism. Trona is a typical product of the terrestrial facies carbonate lake. lts formation, therefore, requires the persistent supply of large quantities of Na-rich carbonate type water which, being actually surface water or ground water circulating through the metamorphic and igneous rocks at the periphery of the basin, constitutes an indispensable factor in the sedimentation of trona by its concentration and evaporation. Besides, the coicentration of CO_{8<.sub>^-2 and HCO8^- in the solution is related to the partial pressure of CO2. Only when sufficient CO2 is unceasingly supplied can nahcalite and trona be precipitated. CO2, in turn, depends on the presence of large amounts of organism for its formation. These factors are prerequisites for the precipitation of the trona deposit, making it distinctly different from other saline deposits. Other formation conditions of the Wucheng trona deposit, such as the existence of a closed basin controlled by tectonics, the alternate arid and semiarid climates, are quite analogous to those of other saline deposits. Some controversial problems concerning this kind of deposit are also put for ward in this paper for further investigation, including the feasibility of taking the abundance of sulfate minerals as a criterion of distinguishing ancient tronas from recent ones, the influence of material resources and climate conditions upon the variation of ore types, and the origin of the highly-concentrated sodium brine in areas adjacent to the Wucheng deposit.}     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

河南吴城天然碱矿床地质特征及戍因探讨

吴城碱矿是世界罕见的古代天然碱矿床之一,属于典型的陆相碳酸盐型盐湖沉积。矿床赋存于一个早第三纪断陷盆地中,该盆地发育了厚约2400余米的陆相碎屑—蒸发岩。天然碱距地表650—900余米,呈多层状产出,下部为天然碱矿层,上部则为含岩盐天然碱层。矿床盐类矿物组合以天然碱为主,次为石盐、重碳酸钠盐。共生矿物有磷钠钙石、氯碳钠镁石,未见通常在碳酸盐湖中出现的硫酸盐矿物——芒硝。     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Stable carbon and oxygen isotopic study of carbonate along a loess/paleosol section in Lantian County, Shaanxi Province, on the southeastern edge of the Chinese Loess Plateau

Studies of carbonate carbon isotope of loess/paleosol (δ¹³C_carb) in the Chinese Loess Plateau (CLP) have shown δ¹³C_carb less negative in loess and more negative in paleosol, which is opposite to that of bulk organic matter. Although some mechanisms have been proposed to explain this inconsistency, few studies have been conducted to investigate how carbonate migration could affect the reliability of utilizing δ¹³C_carb as an effective indicator. Here, a loess/paleosol profile with a nodule horizon intercalated in the loess layer, located on the southeastern edge of the CLP, was investigated to understand the influence of carbonate eluviation and reprecipitation on δ¹³C_carb along the section. The mean grain size and magnetic susceptibility generally conform to the field observed loess/paleosol stratigraphy. However, carbonate content shows distinct differences in the two sides of the nodule horizon, clearly indicating eluviation along the section. The variation of carbon and oxygen isotopic compositions of soil carbonate (δ¹³C_SC and δ¹⁸O_SC) and nodule carbonate (δ¹³C_NC and δ¹⁸O_NC) along the profile does not present a clearly meaningful picture. Generally, δ¹³C_SC and δ¹⁸O_SC have a similar change trend along the profile and are positively correlated, but there is no apparent relationship between δ¹³C_NC and δ¹⁸O_NC. More importantly, δ¹⁸O_NC values fall in the range of δ¹⁸O_SC, whereas δ¹³C_NC values are much more positive than δ¹³C_SC. Detailed analyses of the data indicate migration of carbonate along the profile, which is an important factor that determines that loess/paleosol δ¹³C_carb could not be employed as a high-resolution paleovegetational and paleoenvironmental indicator in the CLP, at least on or below the glacial/interglacial scales.     

毕节市北部岩溶地下水水化学特征及影响因素的多元统计分析

本文利用层次聚类分析和因子分析两种多元统计方法探讨了贵州省毕节市岩溶地下水水化学组分特征及影响因素。结果表明:研究区地下水组分浓度变化范围较大,具有明显的空间变异性,其受到地理因素、水岩作用过程、土壤等自然因素、人类活动的影响。这四个影响因素能够解释地下水水化学组分82%的特征,其中,水岩作用过程和人类活动是主要影响因素。地下水中HCO3-、SO42-、Ca2+和Mg2+主要来源于碳酸盐岩矿物的溶解,同时也受到人类采煤活动的影响;Cl-、K+、Na+和NO3-则主要受到人类活动,特别是农业化肥、粪肥、农药施用和生活污水排放等因素的影响。本研究有助于深化对西南岩溶地下水水化学特征的理解,有助于有效预测岩溶地下水污染物来源,且对岩溶区水资源的合理开发利用具有积极的指导意义。