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Chemical geology
Elsevier
Chemical geology

Elsevier

0009-2541

Chemical geology/Journal Chemical geologySCIISTPAHCIEI
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    Dissolution of periodic arrays of grains: Upscaling of pore-scale simulations with fast reactions

    Yu, LiangLadd, Anthony J. C.Szymczak, Piotr
    10页
    查看更多>>摘要:Upscaling methods are frequently used to derive transport equations at the macroscopic scale from more fundamental equations formulated at the pore scale. These methods typically give a suitable structure for the macroscopic equations and can also provide explicit expressions for the constitutive parameters, such as permeability and dispersion coefficients. Introducing chemical reactions complicates upscaling in at least two important ways. First, the interplay between chemical reactions and transport processes introduces a new length scale, which can be much smaller than the convective or dispersive length scales. A small reactive length scale breaks one of the key assumptions in upscaling; that there is a significant separation in length between the pore-scale and macro-scale processes. The second complication is that if reactions take place at mineral surfaces (dissolution or precipitation) then the pore space itself is evolving in time. In this paper we suggest ways in which these difficulties can be approached, based on analysis of pore-scale simulation data. First, we noticed that the concentration field in successive unit cells has an almost identical spatial variation, with a single scaling factor for each unit cell that is proportional to the incoming reactant flux. Using pore-scale simulations to determine the mass transfer coefficient in a few unit cells, we can calculate the concentration field in the whole domain, even when dissolution is entirely transport limited. Second, we have noticed a time-dependent mapping of the grain shapes from different unit cells. From these observations, we can deduce constitutive relations where the only time-varying parameter is the porosity. We show that a model based on these ideas can quantitatively account for the pore-scale simulation data.

    Lead isotope geochemistry of plagioclase in the Skaergaard intrusion by LA-ICP-MS: Assessing the effects of crustal contamination and link with East Greenland flood basalts

    Cho, June O.Scoates, James S.Weis, DominiqueAmini, Marghaleray...
    23页
    查看更多>>摘要:The Skaergaard intrusion of East Greenland is one of the best studied layered intrusions on Earth and preserves an exceptional rock record produced during low-pressure, closed-system crystallization of Fe-rich tholeiitic magma. The lead isotope compositions of plagioclase feldspar in cumulates and related igneous rocks of the Skaergaard intrusion were determined directly from single spot analyses in thin section by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) (n = 757). Plagioclase primocrysts, typically with <2 ppm Pb, and feldspar in interstitial pockets from the Layered Series and from most of the Marginal Border , Series have the same Pb isotope compositions within analytical uncertainty (Pb-208/Pb-206 = 2.20 +/- 0.06; Pb-207/Pb-206 = 0.889 +/- 0.028). There are no significant Pb isotope differences between cores and rims of individual plagioclase primocrysts or between different types of interstitial pockets (e.g., interstitial granophyre, symplectites). These Pb isotope compositions are less radiogenic than those from most of the contemporaneous East Greenland flood basalts indicative of crustal contamination at deeper crustal levels prior to emplacement. Plagioclase from three samples of the Marginal Border Series adjacent to host gneisses (<5 m from the contact) Pb-208/Pb-206 have higher (2.30 +/- 0.06, 2.35 +/- 0.02, 2.51 +/- 0.21) compared to the rest of the intrusion. These results confirm that crystallization of the Skaergaard intrusion occurred under essentially closed-system conditions with localized minor incorporation of "amphibolitic" gneiss. Hydrothermal alteration occurred at near-solidus to subsolidus conditions by circulating meteoric fluid that had equilibrated with the overlying flood basalts. This alteration resulted in albitized interstitial granophyre and rare spot analyses from plagioclase primocrysts characterized by Pb isotope compositions comparable to those of the flood basalts. Granophyres of different origins (e.g., transgressive granophyre, granophyric segregation) have variable Pb isotope compositions (Pb-208/Pb-206 = 2.09-2.51; Pb-207/Pb-206 = 0.844-1.013) that are distinct from the Skaergaard cumulates. Based on Pb isotope systematics, combined with published Sr-Nd isotopic compositions and Ar-40/Ar-39 geochronology from East Greenland and Faroe Island basalts, the Skaergaard intrusion is linked to eruption of the earliest of the Plateau Basalts in East Greenland (Milne Land Formation) during continental breakup and opening of the North Atlantic Ocean. This microanalytical study highlights the ability to conduct rapid Pb isotopic measurements in low-Pb concentration materials (e.g., <2 ppm Pb in plagioclase) at high spatial resolution by LA-ICP-MS with precision sufficient to constrain a range of magmatic processes in layered intrusions and other feldspar-bearing rocks preserved in the geological record.

    Examining the effects of chemical cleaning, leaching, and partial dissolution on zinc and cadmium isotope fractionation in marine carbonates

    Druce, MatthewStirling, Claudine H.Rolison, John M.Bostock, Helen C....
    13页
    查看更多>>摘要:The application of zinc (Zn) and cadmium (Cd) isotopes as palaeo-proxies in carbonate sediment is rapidly expanding due to their potential for tracing changes in biological productivity in the modern and past oceans. However, there are limited investigations into the chemical cleaning methods required to produce the most consistent and accurate data for these novel isotope systems. This could impact their use as palaeo-proxies to reconstruct ocean-atmosphere-climate interactions throughout Earth's history. To address this concern and expand the utility of the Zn and Cd stable isotope systems as palaeo-productivity tracers, the performance of two standard chemical cleaning protocols for acquiring robust and reliable Zn and Cd isotope datasets were assessed. These include (i) the Cd-cleaning method that uses a reductive step to selectively leach contaminating secondary iron (Fe)-manganese (Mn) (oxyhydr)oxide coatings from the carbonate surface, and an oxidative step that is used to remove post-depositional organic matter and sulphide precipitates; and (ii) the magnesium/calcium cleaning protocol that includes an oxidative step only, leaving secondary Fe-Mn (oxyhydr)oxide coatings largely intact. Well-preserved Holocene-, and Mesozoic-aged carbonate sediments were used to test the reliability of these two chemical cleaning methods. The Holocene samples comprised not only aliquots of bulk sediment, but also individual species of planktic and benthic foraminifera. Our results show that the best practice chemical cleaning method for retrieving consistent and accurate Zn and Cd isotope, and Zn/Ca and Cd/Ca datasets for carbonate sediments, requires both reductive and oxidative cleaning following the Cd-cleaning method. This differs from most methodological approaches applied to date that remove the reductive step from the chemical cleaning protocol and apply an oxidative step only, or no chemical cleaning at all. Inclusion of the reductive step in the chemical cleaning method typically shifts delta Zn-66 by similar to 0.1 parts per thousand lower and delta Cd-114 by 0.3 parts per thousand higher in the solid phase, while Zn/Ca and Cd/Ca typically decrease 2-fold. The benthic foraminifera, C. wuellerstorfi, that live in ocean bottom waters where the seawater Zn and Cd isotope composition is homogeneous display evidence of Zn and Cd isotope fractionation between seawater and carbonate on the order of 0.08 +/- 0.08 parts per thousand (25E, n = 4) and - 0.25 +/- 0.13 parts per thousand (2SE, n = 4), respectively, in agreement with experimental constraints. Furthermore, evidence of Zn isotope fractionation effects are recorded in a naturally-dissolved carbonate sediment, together with laboratory-controlled carbonate dissolution experiments. Based on these results, we recommend the Cd-cleaning method and the application of Zn and Cd isotope fractionation factors to accurately reconstruct past seawater Zn and Cd isotope compositions from carbonate sediments.

    Isotopes of carbon and oxygen of siderite and their genetic indications for the Late Permian critical-metal tuffaceous deposits (Nb-Zr-REY-Ga) from Yunnan, southwestern China

    Wang, NingDai, ShifengNechaev, Victor P.French, David...
    18页
    查看更多>>摘要:This paper describes numerous siderite occurrences from Nb-Zr-REY-Ga-enriched beds of tuffaceous mudstone from the Yujingshan borehole, eastern Yunnan, southwestern China. The mineral phases in the samples were identified and characterized through macroscopic observation, XRD (X-ray diffraction) analysis, optical microscopy, and FE-SEM (field emission-scanning electron microscopy). The results show that the siderite occurs in the drill core from depths of 664.07 to 729.21 m, where its content varies from 15.1 to 65.7%, 31.3% on average. Modes of occurrence of authigenic siderite include irregular banded or massive aggregates, discrete fine particles, oolitic aggregates, and double or multi-ring ellipsoid-shaped or rhombohedral aggregates. The mineralogical association with quartz, anatase, ilmenite, chromite, and zircon with sharp-edged outlines, high-temperature cracks and/or corroded embayments, and REE-bearing minerals and geochemical characteristics such as Al2O3/TiO2 between 3 and 8, less commonly 8-23.77, indicate that abundant siderite was produced by hydrothermal alteration of airborne volcaniclastic materials. The delta C-13(PDB), delta O-18(PDB), and delta O-18(SMOW) values of siderite in the argillized tuff range from -12.56 to -1.32 parts per thousand, -8.98 to -5.88 parts per thousand, and 21.60 to 24.80 parts per thousand, respectively. In the delta C-13(PDB)-delta O-18(SMOW) diagram, plots of the studied siderite are distributed between the fields of marine carbonate rocks, sedimentary organic matter, and carbonates of hydrothermal ores. Some siderite from the upper part of the studied borehole is isotopically close to REY carbonates from the Abramovka lignite deposit, Far Eastern Russia, which precipitated from evolved basinal waters mixed with CO2 from a mantle source. In summary, this indicates a hybrid origin for the studied siderite including carbonate dissolution, dehydroxylation of sedimentary organic matter, and hydrothermal activity. Furthermore, the paleosalinity (Z) and paleotemperature (T) of the ore-forming fluids were calculated based on the age-corrected stable carbon and oxygen isotopic data in the samples. The Z values range from 96.65 to 121.5 parts per thousand, suggesting the formation of siderite under brackish-water conditions. The T values vary from 19.47 to 47.12 degrees C, with some sharp fluctuations that may be due to ash falls and/or hydrothermal injections. Overall, our data support the model for critical-metal Nb(Ta)-Zr(Hf)-REY-Ga enrichment in tuffaceous deposits of southwest China including a combination of volcanic activity and terrestrial organic-rich sedimentation under warm and humid conditions, followed by low-temperature alteration evolved from acidic leaching, which is responsible for the Nb-Zr-REY-Ga enrichment, and, subsequently, formation of authigenic siderite with associated quartz, sulfide minerals, and phosphate minerals under reducing neutral/weakly alkaline conditions.

    Geochemical modelling of CO2 interactions with shale: Kinetics of mineral dissolution and precipitation on geological time scales

    Fatah, AhmedBen Mahmud, HishamBennour, ZiadGholami, Raoof...
    11页
    查看更多>>摘要:The research on Carbon Capture and Storage (CCS) has become fruitful as energy-intensive industries are working towards transitioning to low carbon energy industry. Shale gas reservoirs have been recently considered as suitable geological targets for carbon dioxide (CO2) storage. However, due to the high reactivity of shales to CO2, the mineralogical changes after CO2/brine/shale interactions play a decisive role in defining the sealing properties of shales at geological time scales. Up to date, this issue is rarely investigated; therefore, in this study, a simplified 1-D reactive transport model was constructed based on the properties obtained from Eagle Ford and Mancos shales. PHREEQC software was utilized to simulate equilibrium and kinetic behavior and evaluate the alterations in minerals at 177 atm and 70 degrees C. The equilibrium model indicated that calcite and clay minerals dissolved in CO2-saturated brine, while quartz grains precipitated, due to the formation of carbonic acid. This behavior confirmed the high reactivity of shales to the injection of CO2-saturated brines. The kinetic model indicated that the geological time scale for CO2/brine/shale interaction can be divided into three phases. Primary minerals alterations occurred during the first 10 years, however, the main alteration in mineralogy occurred between 10 and 100 years, whereas the reactants continued to dissolve in low portions until the equilibrium state was reached beyond 100 years. The model showed that carbonate and clay minerals dissolved during the CO2/brine/shale interaction, which could provide the potential for mineral trapping as an effective sealing mechanism in the middle phases of the storage lifetime in shales, confirming the high potential of shales for CO2 containment. The main observations and conclusions obtained from this work can be easily extrapolated to other shale formations with similar mineral compositions.

    Cenozoic reorganization of fluvial systems in eastern China: Sedimentary provenance of detrital K-feldspar in Taiwan

    Zhang, ZengjieDaly, J. StephenYan, YiBadenszki, Eszter...
    11页
    查看更多>>摘要:Cenozoic passive margin sediments in Taiwan provide an important natural archive to reconstruct drainage reorganization in eastern China. In this study, we used Pb isotope compositions of detrital K-feldspar to investigate the sedimentary provenance of Cenozoic strata in Taiwan and to constrain fluvial system evolution in eastern China. Eocene to lower Oligocene sandstones in Taiwan are characterized by radiogenic K-feldspar grains (Pb-206/Pb-2(04)>18.4), indicating that the eastern Cathaysia Block served as the dominant sediment contributor. In contrast, a late Oligocene sample has a Pb isotopic character indistinguishable from that of the Gan River, a major tributary of the Yangtze River. This provenance change is interpreted as the result of headward (westward) migration of the paleo-Min River to the Wuyishan (Wuyi Mountains) during the late Oligocene. Miocene deposits are enriched in relatively unradiogenic K-feldspar (Pb-206/Pb-2(04)<17.0) which can be reliably traced back to the Dabie and Sulu orogenic belts. Since the early Miocene, the paleo-Yangtze River, mainly draining the Yangtze Craton and the Dabie orogenic belt, delivered a large volume of detritus to the East China Sea Shelf Basin and also to the proto-Taiwan region.