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Chemical geology
Elsevier
Chemical geology

Elsevier

0009-2541

Chemical geology/Journal Chemical geologySCIISTPAHCIEI
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    Towards a holistic sulfate-water-O-2 triple oxygen isotope systematics

    Killingsworth, B. A.Cartigny, P.Hayles, J. A.Thomazo, C....
    13页
    查看更多>>摘要:Triple oxygen isotope (Delta O-17 with delta O-18) signals of H2O and O-2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O-2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O-2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O(2 )with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O-2- versus H2O-oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the Delta O-17 and delta O-18 of sulfate's O-2-oxygen source. Within this framework, new Delta O-17 measurements of sulfate constrain similar to 2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

    Coprecipitation of humic acid and phosphate with Fe(III) enhances the sequestration of carbon and phosphorus in sediments

    Luo, ChunYanWen, ShuaiLongLu, YueHanDai, JiaRu...
    9页
    查看更多>>摘要:The coprecipitation of dissolved organic matter (DOM) and phosphate with Fe(III) at the sediment-water interface plays an important role in the biogeochemical cycle of organic carbon (OC) and phosphorus (P) in aquatic ecosystems. However, studies remain limited towards understanding the strength of ternary DOM-phosphate-Fe(III) coprecipitation in sequestering OC and P. Here, we investigated the behaviors of humic acid (HA) and phosphate during their coprecipitation with Fe(III) and compared the coprecipitation behaviors with those during the adsorption process. The results showed that the coprecipitation of HA and phosphate with Fe (III) enhanced as pH decreased or initial Fe(III) concentrations increased. The presence of phosphate had a moderate inhibition effect on HA coprecipitation, leading to 3%-37% of reduction in precipitated HA. Changes in optical properties of DOM (i.e., SUVA(254), E-2/E-3, and fluorescent components) showed that macromolecular, aromatic molecules preferentially coprecipitated, and this selectivity pattern was not influenced by the presence of phosphate. Compared to the adsorption of HA and phosphate to goethite, coprecipitation with Fe(III) displayed stronger binding ability, sequestering more than10 times of HA and phosphate, and was more efficient in sequestering protein-like compounds. The inhibitory effect of phosphate on HA sequestration was weaker during coprecipitation than during adsorption. Moreover, coprecipitation led to a lower degree of compositional fractionation of HA than adsorption, which may be explained by that inclusion, an important pathway for coprecipitation, has low selectivity for chemical compositions. Collectively, our results demonstrate that coprecipitation plays a crucial role in sequestering both OC and P in aquatic systems, arguing that the formation of ternary OC-Fe-P coprecipitates may be an important pathway for sequestering OC and P over a long term and reducing the internal loading of P in eutrophic lakes.

    Clumped isotope thermometry reveals diagenetic origin of the dolomite layer within late Ordovician black shale of the Guanyinqiao Bed (SW China)

    Ziegler, MartinChen, QingHan, LuShi, Zhiqiang...
    14页
    查看更多>>摘要:The origin of widespread dolomite deposits in Paleozoic strata is a longstanding open question. Here we use a suite of geochemical methods to investigate a prominent Paleozoic dolomite occurrence in SW China. The upper Ordovician Wufeng Formation of the upper Yangtze Block (SW China) covers the time interval just before the Ordovician-Silurian Mass Extinction event, consisting of wide-spread black shale with an interlayer of bioclastic limestone, the Guanyinqiao Bed. In the western part of the Yangtze Block, in Shizhu county however, the Guanyinqiao Bed contains a particular organic-rich dolomite interlayer of which the formation mechanism is unclear. To distinguish between potential primary dolomite precipitation and late stage diagenetic/magmatic alteration, we studied this dolomite interlayer with petrological and geochemical techniques including microscopy, REE content and carbonate clumped isotope thermometry. The petrological observations show micritic dolomite with euhedral-subhedral shape and relatively low ordering (0.33 to 0.39). Conventional stable isotope analysis revealed negative carbon (delta(13) C of -3.17 +/- 0.04 parts per thousand to -2.48 +/- 0.03 parts per thousand) and oxygen isotope compositions delta O-18 of -11.28 +/- 0.18 parts per thousand to -10.99 +/- 0.20 parts per thousand), and the organic carbon content ranged from 3.69% to 4.33%. The averaged clumped isotope temperature estimate revealed hot dolomite formation conditions of 87(-10) +11 degrees C, in a presumable fluid source with isotopic composition of delta O-18(w) = -1.8(-1.5)(+1.5) parts per thousand. The elevated formation temperature estimates, the slightly depleted delta O-18 of dolomite (similar to-11.14 parts per thousand) with respect to contemporary deposited limestone (similar to-10 parts per thousand) and the delta O-18(w) which is similar to the assumed late Ordovician seawater points at diagenetic alteration of primary limestone at a burial depth of approximately 3000 m. The analyzed dolomite samples with low contents of Fe, Zn and small Eu anomaly show further evidence for a diagenetic fluid source and exclude magmatic/hydrothermal alteration. We suggest that at this burial depth the temperature pressure conditions triggered significant Mg release from the surrounding clay to the diagenetic fluid, providing ideal conditions to transform the primary limestone into diagenetic dolomite.

    Geochemistry of Late Permian basalts from boreholes in the Sichuan Basin, SW China: Implications for an extension of the Emeishan large igneous province

    Liu, XiaoyuQiu, NanshengSoager, NinaFu, Xiaodong...
    17页
    查看更多>>摘要:The emplacement of the Late Permian Emeishan large igneous province (ELIP) in the Upper Yangtze craton, SW China, is considered to be a crucial factor that triggered the end-Guadalupian biodiversity crisis. However, the contribution of ELIP remains debated because of its relatively modest known size. The restricted assessment of its areal extent is, in part, due to the lack of study of the potential volcanic rocks concealed beneath younger strata. Here we present the first geochemical and isotopic variations and detailed spatial distribution of Late Permian basaltic rocks penetrated by deep exploratory boreholes in the Sichuan Basin. The Late Permian basaltic rocks are mainly distributed in the western and northeastern parts of the Sichuan Basin and are positioned at the same stratigraphic level as the Emeishan flood basalts. Petrography, whole-rock trace elements and Sr-Nd-Pb isotopic compositions demonstrate that these rocks are alkaline basalts and have oceanic island basalt - like characteristics, indicating a similar origin as the Emeishan flood basalts. The trace element and isotope ratios suggest that the basaltic magmas in the western Sichuan Basin were derived by low degrees of partial melting of a garnetbearing source. In contrast, the basalts in the northeastern part of the basin were generated by higher degrees of melting of a shallower mantle source in the spinel-garnet transition zone. Varying amounts of contamination by lower continental crustal melts are suggested by rough correlations between isotope and immobile trace element ratios. The spatial changes in composition and origin of the basaltic rocks in the Sichuan Basin can be interpreted as the result of varying extents of Emeishan mantle plume-lithosphere interaction under different lithospheric stress backgrounds, such that the reactivation of pre-existing basement faults controlled the emplacement of basaltic magma in the periphery of the ELIP. Our work reveals a substantially broader extent of the ELIP in buried sedimentary strata, which might have contributed to the abrupt end-Guadalupian climatic change.

    Clumped isotope acid fractionation factors for dolomite and calcite revisited: Should we care?

    Koeshidayatullah, ArdiansyahSwart, Peter K.Lu, ChaojinMurray, Sean...
    12页
    查看更多>>摘要:During the analysis of the Delta(47) values of CO2 derived from carbonates, the acid fractionation factor not only allows Delta(47) values produced from carbonates and reacted at different temperatures (usually 25 and 90 degrees C) to be compared to one another, but also provides an effective tool to better understand the mechanism and rate of isotopic exchange of oxygen with water during the phosphoric acid digestion of carbonate minerals. In this study, experiments have been conducted in which calcite (1 sample) and dolomite (4 samples), with varying Delta(47) values, have been digested in phosphoric acid (H3PO4) at five different temperatures between 25 and 90 degrees C using both the common acid bath and sealed vessel methods. From these experiments, we show that calcite has an acid fractionation factor which is independent of the reaction method. In contrast, all four dolomites show significant differences between the two methods with the sealed vessel reactions showing much smaller acid fractionation factors than the common acid bath. The magnitude of the acid fractionation factor in the dolomites is also dependent upon the absolute Delta(47) value of the sample, with samples possessing lower Delta(47) values producing lower acid fractionation factors than those with higher Delta(47) values. The explanation for the difference in the behavior of acid fractionation factors between calcite and dolomite, in regard to the technique used, is believed to be related to the rate of reaction of the two minerals and thus the time in which the CO2 is in contact with the acid and allowed to exchange with the H2O in the acid and produced during the reaction.

    Hydrothermal and magmatic contributions to surface waters in the Aso caldera, southern Japan: Implications for weathering processes in volcanic areas

    Okamura, KokiDelmelle, PierreAmann, ThorbenBoettcher, Michael E....
    16页
    查看更多>>摘要:The role of hydrothermal fluids in the dissolution of primary minerals in volcanic areas, hotspots of silicate weathering at the global scale, is not well quantified. This study aims to determine the hydrothermal contribution to the lateral export of solutes from the Aso caldera, southern Japan. A set of indicators for the hydrothermally related contribution is systematically discussed. Spring, groundwater and river water samples were collected along the two main rivers of the caldera, and their major and trace element concentrations, as well as the stable isotopic compositions of water (delta H-2 and delta O-18), dissolved inorganic carbon (delta C-13), and sulphate (delta S-34 and delta O-18) were analysed. Hydrothermal springs in the study area are associated with a substantial sulphate contribution of magmatic origin. In contrast, the hydrochemistry of non-hydrothermal springs reflects surface water-soil interactions. In particular, non-hydrothermal waters have significantly higher selenium to sulphate ratios than hydrothermal waters. The selenium to sulphate ratios allow to distinguish two different sulphur sources in the Aso catchment: hydrothermal waters impacted by the oxidation of sulphides or controlled by disproportionation reactions of SO2, and non-hydrothermal sulphate. Overall, the results show that hydrothermal waters strongly influence the sulphur budget, accounting for 67 to 91% of the total sulphate flux at the caldera outlet. The dissolution of magmatic CO2 and SO2 contribute to >60% of the observed weathering fluxes in this volcanic area. This suggests that magmatic gases and hydrothermal fluids should be considered for the estimation of biogeochemical budgets at the regional and global scales. However, the temporal variation of the magmatic activity and its effect on the chemistry of waters have to be investigated in future work.

    Authigenic uranium isotopes of late Proterozoic black shale

    Dang, D. H.Wang, W.Gibson, T. M.Kunzmann, M....
    11页
    查看更多>>摘要:The evolution of early life is intimately related to environmental changes on Earth, and in particular, the accumulation of oxygen in the atmosphere and oceans. However, the record of environmental O-2 abundance in the middle to late Proterozoic Eon, during which many new eukaryotic lineages emerged, is sparse and controversial. Here we present a uranium (U) isotope record from late Proterozoic shales from northwestern Canada, Arctic Canada (Baffin Island), Svalbard, and Greenland, coupled with a novel approach for inferring authigenic U isotope values (delta U-238(authigenic)). A compilation comprising our new data and available literature data (854 delta U-238 auth i gerde values) through geologic time indicates a consistent rise in delta U-238 auth i geff i c values following the Great Oxidation Event. This gradual increase in delta U-238 can be interpreted as an increase in the frequency of transient oxygenation events and also as a variation of U isotope fractionation factors between authigenic uptake and seawater (Delta U-2(38)) associated with different redox conditions occurring over the Earth's history. In conjunction with the U isotopic signature, we used previously published Fe speciation data from our samples to infer local controls on U incorporation and isotopic fractionation. The results suggest that late Proterozoic oceans were dominantly ferruginous, punctuated by periods of transient oxygenation. During these transient oxic conditions, high U isotope fractionation resulted in delta U-238 values as high as similar to 1.2 parts per thousand relative to the delta U-238(crust). However, under ferruginous conditions, smaller isotopic fractionation led to Delta U-238 values <0.6 parts per thousand. Integrating conclusions from our study with other geochemical studies suggests the occurrence of several spatially localized oxygenation events across the globe during the late Proterozoic. These conclusions help to better integrate geochemical and fossil records in the context of early evolution of complex life.

    REE enrichment of phosphorites: An example of the Cambrian Georgina Basin of Australia

    Valetich, MatthewZivak, DianaSpandler, CarlDegeling, Helen...
    15页
    查看更多>>摘要:Phosphate-rich sedimentary rocks (phosphorites) host significant concentrations of rare earth elements (REE, including Y) that are critical for development of 'green' technologies and renewable energy supply. Cambrian (ca. 505 Ma) phosphorites from the epicontinental Georgina Basin can contain up to 0.5 wt% REE, marking them as among the most REE-enriched phosphorites globally. This contrasts with previous work that proposed generally poor REE endowment of Cambrian phosphorites across the world. Here, we report orders of magnitude variation in REE concentration across the northern, central and southern parts of the Georgina Basin. We use principal component analysis (PCA) on centred-log ratio (CLR) transformed whole rock geochemical data to show that the southern phosphate prospects of the basin (Ardmore, Duchess, Phosphate Hill) have higher concentrations of elements that substitute into the major primary phosphate mineral carbonate fluorapatite (CFA) (P2O5, CaO, Na2O, REE, Sr and possibly Ba), while those of the central and northern prospects (Lily and Sherrin Creek, Barr Creek, DTREE, Paradise South and Paradise North) show a greater contribution of terrigenous material characterised by a higher concentrations of elements typically excluded from the CFA lattice (SiO2, TiO2, Al2O3, K2O, MgO, Zr, Nb, Cs, Ga and Rb). REE concentrations are up to two orders of magnitude higher in the southern prospects than in the central and northern prospects, while phosphorites from all prospects display modern seawater-like REE patterns. It is unlikely that global secular changes of seawater chemistry through time are the dominant control on the REE content of the Georgina Basin phosphorites, given the relative short time span of phosphogenesis (ca. <5 m. y.), the restricted interaction of the epicontinental and open sea waters, and the order of magnitude variations in REE concentration on a localised basin scale. Instead, variations in REE concentrations across the Basin are likely due to: 1) textural differences, with apatitic non-pelletal mudstones dominating the northern and central prospects, and largely pelletal (granular) phosphorites in the south; 2) local seawater composition that reflected the proximal basement rocks and riverine/groundwater input. Higher concentrations of REE in the southern prospects may be explained by surface and groundwater interaction with A-type granite and schistose metasedimentary basement rocks. We suggest, therefore that REE prospectivity of phosphatic sedimentary rocks is not primarily controlled by temporal variations in global seawater chemistry, but rather by local sedimentological and source region factors.

    Investigating the influence of temperature and seawater delta O-18 on Donax obesulus (Reeve, 1854) shell delta O-18

    Warner, Jacob P.DeLong, Kristine L.Chicoine, DavidThirumalai, Kaustubh...
    14页
    查看更多>>摘要:The coastline of Peru lacks long-lived marine organisms useful for paleoclimatic reconstructions generating a need for novel archives. Short-lived (<5 years) bivalves are commonly found in geological and archaeological deposits and thus can provide "snapshots" of past climatic variability (i.e., seasonal range), similar to data obtained by individual foraminifera analysis, rather than continuous, cross-dated time series (e.g., trees and corals). Previous studies have found success using the short-lived intertidal clam Mesodesma donacium. However, M. donacium are vulnerable to die-offs from the warmer sea surface temperatures (SST) associated with El Nino events and are functionally extinct in northern Peru thus limiting the possibility of modern analog studies for that region. Here we investigate the short-lived (1-3 years) surf clam, Donax obesulus, commonly found in northern Peru, as a paleoclimate archive. Donax obesulus populations are able to survive the warmer SSTs present during El Nino years although they are vulnerable to colder SSTs associated with La Ninas. We assessed the environmental drivers underlying subannual delta O-18 variability in D. obesulus from live collected shells from fish markets and coastal beaches near the Nepena Valley, Peru in 2012 (La Nina), 2014 (ENSO-neutral), and 2016 (El Nino). Forward modeling of pseudo-shell delta O-18 reveals that SST variations are a dominant driver with secondary contributions from seasonally-varying seawater delta O-18( delta O-18(sw)). By accounting for varying delta O-18(sw), we isolated the temperature dependent variable resulting in a paleotemperature equation for D. obesulus delta O-18. We verified our results with the delta O-18 record of a D. obesulus shell collected in 2006. Our results suggest that the paleotemperature equation we developed is useful for reconstructing El Nino-Southern Oscillation (ENSO)-related climatic variations in this region and the pseudo-shell approach may be useful for understanding shell delta O-18 in other locations.

    Apatite low-temperature chronometry and microstructures across a hydrothermally active fault zone

    Berger, AlfonsEgli, DanielGlotzbach, ChristophValla, Pierre G....
    12页
    查看更多>>摘要:Low-temperature chronometers offer potential to gain insights into the temporal evolution of hydrothermal systems. The long-lived fault-bound Grimsel pass hydrothermal system (including a fossil and an active part) in the Central European Alps serves here as a key site to test such an application. Zircon and apatite grains were separated from samples collected along a fault transect. The resulting zircon (U-Th)/He ages are homogenous along the profile at 8-9 Ma and thus record the regional cooling evolution, remaining unaffected by the younger hydrothermal activity. In contrast, the apatite (U-Th)/He ages show three age groups: One Group (1) of ca. 5 Ma inside and outside the hydrothermal zone matches the low-temperature part of the regional cooling trend, while group (2) with ages as young as 1-2 Ma occurs in a central narrow zone associated with hydrothermal activity. One sample (group 3) displays older apparent ages compared to the regional cooling trend. Group (2) apatite samples reveal a different cathodoluminescence texture and trace-element chemistry, which we interpret together with the young age as apatite growth or re-crystallization within the hydrothermal system. Forward 1D modelling of He diffusion indicates that apatite (U-Th)/He ages should always be reset when exposed to hot thermal waters (up to similar to 140 degrees C) present over ka timescales or to intermediate temperature waters (similar to 90 degrees C) over Ma timescales. Combining our measured apatite (U-Th)/He ages with forward modelling results highlight that, besides regional cooling trends, local heat anomalies within hydrothermal zones are very variable in space and time. Combined trace-element geochemistry and (U-Th)/He dating shows local occurrence of newly-formed apatites crystals, which are best described as geochronometers rather than thermochronometers. Such information is important to explore the longevity of hydrothermal systems and associated spatial distributions of heat anomalies.