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Chemical geology
Elsevier
Chemical geology

Elsevier

0009-2541

Chemical geology/Journal Chemical geologySCIISTPAHCIEI
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    A bulk annealing and dissolution-based zircon concentration method for mafic rocks

    Hollanda, M. H. B. M.Oliveira, A. L.Schmitz, M. D.Wall, C. J....
    14页
    查看更多>>摘要:Zircon geochronology is applied to a variety of geological problems to precisely and accurately date rocks via U-Pb decay. Zircon is most abundant and easily recovered in intermediate to felsic rocks, including the silicic eruptives of bimodal large igneous provinces, or fractionated granophyres in mafic-ultramafic complexes. However, the concentration of zircon crystals by conventional density and magnetic separation methods is inefficient and/or ineffective for medium- to fine-grained mafic rocks, due to their rarity, small grain size, common association with ferromagnetic minerals, and/or occlusion by paramagnetic modal minerals. To address these shortcomings, we have developed and tested a zircon concentration method that is based on a combination of physical separation and chemical dissolution. The sample is initially ground to sand-size particles and heavy minerals concentrated via density on a water table. The heavy mineral-rich fraction is annealed by heating at 900 degrees C for 60 h, and then put through a series of acid digestions: aqua-regia, hydrofluoric acid, aqua-regia and finally hydrochloric acid. This new method allows the concentration of an almost pure zircon aliquot, since zircon is one of just a few minerals that can survive this bulk rock acid attack. The result is an efficient extraction of analytically viable amounts of zircon for U-Pb geochronology using tens of grams of rock sample, representing an increase up to a hundred times the recovery rates of conventional separation techniques for zircon concentration.

    A comprehensive and internally consistent mineral dissolution rate database: Part I: Primary silicate minerals and glasses

    Hermanska, MatyldaVoigt, Martin J.Marieni, ChiaraDeclercq, Julien...
    32页
    查看更多>>摘要:Mineral dissolution rates control the temporal evolution of many natural processes on the surface and upper crust of the Earth. This is the first of a series of papers describing the development and implementation of a comprehensive and internally consistent database of the dissolution rates of the major rock-forming minerals. In this paper, we describe the retrieval and regression of the dissolution rates of the primary rock-forming silicates, including quartz and other SiO2 polymorphs, feldspars, pyroxenes, amphiboles, micas, volcanic glass, and olivines. Owing to the limited fluid chemistry data available for many of the published experimental studies, BET surface area normalized mineral and most glass dissolution rates (r) were regressed using r = Sigma(i) (A(i)a(H+)(nj) e(Eai/RT)) (1 - exp( - A/sigma RT)) where A(i) stands for pre-exponential factors, a(H+) corresponds to the hydrogen ion activity, n(i) refers to reaction orders, T designates absolute temperature, R denotes the gas constant, E(ai)( )represents activation energies, sigma stands for Temkin's average stoichiometric number, and A denotes the chemical affinity of the dissolution reaction. Where relevant data were lacking, rates were extrapolated assuming that mineral dissolution follows similar trends within the same mineral group. Regression was performed using least-squares algorithms. The average difference between calculated and measured rates ranged from 0.1 to 0.7 log units depending on the mineral. The obtained rate equations were implemented into the carbfix.dat database for direct use in the PHREEQC software but can be extended to other geochemical modeling software, such as TOUGHREACT.

    Highly variable content of fiuorapatite-hosted CO32- in the Upper Cretaceous/Paleogene phosphorites (Morocco) and implications for paleodepositional conditions

    Aubineau, JeremieParat, FleuriceAddou, AissamRaji, Otmane...
    17页
    查看更多>>摘要:Phosphorus (P) usually occurs as microcrystalline minerals of carbonate fiuorapatite (CFA) in sediments of upwelling-related areas. The Upper Cretaceous/Paleogene marine sedimentary rocks in Morocco host the world's largest economic reserves in phosphorus, which were deposited on the eastern passive margin of the central Atlantic Ocean. However, a full petrographic, mineralogical and geochemical characterization of the Moroccan phosphate minerals is yet to be determined. Here, we use optical and scanning electron microscopies, X-ray diffraction, and infrared spectroscopy, in combination with a microprobe analyzer to document carbonate (CO32-) substitutions in CFA from two distinct phosphate basins and their possible implications for paleoenvironmental conditions. The Moroccan phosphorus-rich deposits predominantly comprise porous phosphatic peloids and coated grains with a maximum size of 500 um, which in turn consist of high-density nano- to micron-sized rod-shaped and sphere-like crystallites. Bulk and in situ analyses reveal heterogeneous CO32- content in CFA at the regional- and grain-scale. Fourier transform infrared spectra indicate that CO32- accommodates only in the phosphate site within the fiuorapatite structure, as found in other natural phosphate minerals. Bulk CO(3)(2)(- )variationsin CFA between phosphate basins, ranging from 1.97 to 8.24%, are likely related to depositional conditions - and thus of supersaturation with respect to CFA - during mineral formation, transport, and redeposition. Moreover, some phosphatic coated grains have revealed alternations of CO(3)(2)(- )rich and CO(3)(2)(- )poor CFA laminae, pointing out local differences in CO32- concentrations in sediment pore waters. Interestingly, the change in shape and diminution in size of CFA crystallites caused by high content of CFA-hosted CO32- could have possibly increased the intragranular porosity, highlighting an underestimated role of CCO(3)(2)(- )on grain morphology. Considering the higher solubility of CO(3)(2)(- )rich CFA than fiuorapatite, the application of such phosphate rocks from specific Moroccan areas as rock phosphate powders may be of deep interest for long-term soil fertilization. These results further evidence the importance of studying phosphorites for economic, environmental, and scientific interests.

    The origin of nitrogen in Earth's mantle: Constraints from basalts N-15/N-14 and N-2/He-3 ratios

    Labidi, Jabrane
    12页
    查看更多>>摘要:Plate tectonics is thought to be a major driver of volatile redistribution on Earth. The budget of nitrogen in Earth's mantle has been suggested to be almost entirely surface-derived. Recycling would contribute nitrogen with relatively heavy N-15/N-14 isotope ratios to Earth's mantle. This could explain why the Earth's mantle N-15/N-14 isotope ratio is substantially higher than both solar gases and chondritic parent bodies akin to enstatite chondrites. Here, published nitrogen isotope data of mid-ocean ridge and ocean island basalts are compiled and used to evaluate the nitrogen subduction hypothesis. Nitrogen isotope ratios are used in conjunction with published N-2/He-3 and K2O/TiO2 ratios on the same basalts. Assuming that He-3 is not recycled, N-2/He-3 ratios are argued to trace nitrogen addition to mantle sources via subduction. Various mantle source enrichments for basalts are tracked with K2O/TiO2 ratios: elevated K2O/TiO2 ratios are assumed to primarily reflect the contributions of recycled components in the basalts mantle sources. The main result of our data compilation is that for most basalts, delta N-15 and N-2/He-3 remain constant across a vast range of K2O/TiO2 ratios. Mid-ocean ridge basalts have delta N-15 signatures that are lower than air by similar to 4 parts per thousand and an average N-2/He-3 ratio of 3.7 (+/- 1.2) x10(6) (95% confidence, n = 30). Published delta N-15 and N-2/He-3 are invariant across K2O/TiO2 ratios that vary over a factor of similar to 20. Using estimates of slab K2O/TiO2 and [TiO2], the observed invariant delta N-15 and N-2/He-3 may be fit with slabs containing similar to 0.1 ppm N. A mass balance shows that adding similar to 10% recycled slabs to the convective mantle only raises the N-2/He-3 by <5%. Lavas from Iceland, Galapagos and Hawaii have high N-2/He-3 and N-15/N-14 ratios relative to the convective mantle. Only seven samples show nitrogen isotopic signatures that are unaffected by air contamination, although those samples are poorly characterized for N-2/He-3. The seven basalts show delta N-15 between -2 and 0 parts per thousand that do not vary systematically with K2O/TiO2 ratios that vary over a factor of similar to 5. The N-2/He-3 ratios of these seven basalts is unknown, but the high N-2/He-3 mantle may be estimated by combining published N-2/Ar-36 to He-3/Ar-36 ratios. This yields a N-2/He-3 of 2.3 (+/- 1.2) x 10(6) (1 sigma uncertainty). This is indistinguishable from the MORB estimate of 3.7 (+/- 1.2) x 10(6). Invariant delta N-15 across variable degrees of mantle enrichments and MORB-like N-2/He-3 for the high N-2/He-3 mantle are not consistent with nitrogen addition to plume sources with elevated N-2/He-3 ratios. Lavas from the Society plume with low He-3/He-4 ratios show an enriched mantle source, and they have elevated delta N-15 >= +0.5 parts per thousand and N-2/He-3 > 10(7). For those, the addition of slabs with concentrations of similar to 0.1 ppm N to a mantle source can account for the integrated dataset. To summarize, the published data suggest that nitrogen subduction may explain a sub-set of published N isotope data on basalts, but that N recycling has an overall more limited impact on mantle nitrogen than previously thought.

    Revised astronomically calibrated Ar-40/Ar-39 ages for the Fish Canyon Tuff sanidine - Closing the interlaboratory gap

    Phillips, D.Matchan, E. L.Dalton, H.Kuiper, K. F....
    8页
    查看更多>>摘要:The Ar-40/Ar-39 geochronology method is capable of high precision (<0.05%), but remains limited by relatively large uncertainties in K-40 decay constants and the ages of natural reference mineral standards. The most widely used Ar-40/Ar-39 reference mineral is the well-known ca. 28 Ma Fish Canyon Tuff sanidine (FCTs). Several studies have attempted to calibrate FCTs against astronomically tuned tephra in Crete (Faneromeni A1 tephra) and Morocco (Messadit Mes4 tuff) as well as deep-sea sedimentary sequences. Previously reported astronomically tuned ages range from 28.126 +/- 0.019 to 28.21 +/- 0.18 Ma (2 sigma), a range of similar to 0.3%, compared to precision levels of <0.05% achievable by new generation, multi-collector mass spectrometer systems. In this study, we revisit the astronomical calibration of FCTs. Relative to ages of 6.943 +/- 0.005 Ma for A1 tuff sanidine (A1Ts) and 6.791 +/- 0.010 Ma (2 sigma) for Mes4 tuff sanidine (Mes4Ts), we calculate revised astronomically tuned ages for Fish Canyon Tuff sanidine of 28.175 +/- 0.012 Ma (+/- 0.023 Ma, including the uncertainty in the age of A1Ts) and 28.176 +/- 0.010 Ma (+/- 0.042 Ma, including the uncertainty in the age of Mes4Ts), respectively (assuming negligible differential Ar-39 recoil loss). This age is within uncertainty of most recent astronomical intercalibrations, permitting calculation of inter-laboratory mean ages of 28.176 +/- 0.010 (+/- 0.023) Ma and 28.179 +/- 0.009 (+0.042) Ma, respectively. As the astronomical age of the A1 tuff is more precise than that of the Mes4 tuff, we recommend that the former value is adopted as the astronomical age for FCTs. This age is consistent with available U-Pb zircon age data, but remains distinctly older than recent astronomical ages of 28.10 and 28.150 Ma inferred from deepsea Ocean Drilling Program sediments, indicating that further work is required to align the astronomical tuning of terrestrial versus deep-sea sediments. Based on previous R-values for the Alder Creek Rhyolite sanidine (ACRs) and Mount Dromedary biotite (MD-2b) reference minerals, co-irradiated with FCTs, we calculate revised astronomically calibrated ages of 1.18342 +/- 0.00069 (+/- 0.009) Ma for ACRs and 99.323 +/- 0.077 (+/- 0.33) Ma for MD-2b, the latter amended to 99.20 +/- 0.01 (+/- 0.38) Ma to account for relative recoil loss of Ar-39 K. To further enhance the accuracy of Ar-40/Ar-39 ages, our study also highlights the need to carefully control neutron fluence gradients and consider recoil effects.

    Incorporation of Na and S in bamboo coral skeletons

    Floeter, SebastianFietzke, JanGutjahr, MarcusNehrke, Gernot...
    11页
    查看更多>>摘要:Ocean environmental conditions can be inferred from the chemical composition of bamboo coral skeletons. The high magnesium calcite internodes of these long-living octocorals may therefore represent a potential archive for seawater properties such as salinity or temperature where instrumental time series are absent. To extend these time series into the past using a natural archive the principles of temperature and salinity signal incorporation into cold-water coral skeletal material need to be investigated. Since skeletal Na and S concentrations have been proposed as environmental proxies, we mapped the spatial distribution and concentration of these elements in two Atlantic specimens of Keratoisis grayi (family Isididae). These measurements were conducted with an electron microprobe applying a spatial resolution of 4 um. The mean apparent distribution coefficient of Na/Ca for the two samples was within 2.5 and 2.8*10(-4), while that of S shows a similar depletion relative to seawater with 3.8 and 3.6*10(-3). The two elements show an inverse correlation in bamboo coral skeletons. The mean apparent distribution coefficient of Na is similar to that of abiotic calcites. This similarity can be interpreted as the absence of significant vital effects for skeletal Na/Ca. Hence it corroborates the idea that the average skeletal composition of bamboo corals holds the potential to record past seawater conditions. In contrast, it appears unlikely that the spatial variations of the element distribution of seemingly simultaneously precipitated material along growth rings are exclusively controlled by environmental factors. We further exclude Rayleigh fractionation, ion-specific pumping, and Ca/proton exchange as the driver of Na and S distribution in bamboo corals. Instead, we adapt a calcification model originally proposed for scleractinians to bamboo corals. This model can explain the observed distribution of Na and S in the skeleton by a combination of Ca/proton pumping, bicarbonate active transport, and the formation of an organic skeletal matrix. The adapted model can further be used to predict the theoretical behaviour of other elements and disentangle vital effects from external factors influencing compositional features. It is therefore a useful tool for future studies on the potential of bamboo corals as environmental archives.

    Biogeochemistry of three different shallow gas systems in continental shelf sediments of the South-Eastern Baltic Sea (Gulf of Gdansk): Carbon cycling, origin of methane and microbial community composition

    Borkowski, AndrzejIdczak, JakubBolalek, JerzyBrodecka-Goluch, Aleksandra...
    21页
    查看更多>>摘要:The objective of the study was to describe the biogeochemistry of three different shallow gas systems, with particular emphasis on the content of carbon forms, origin of gas and microbial community composition of sediments. Surface sediments (1-1.2 m) in the areas above geophysically different shallow gas structures located in south-eastern Baltic Sea (Gulf of Gdansk) were investigated: MET1-MP - an active deepwater pockmark with gas seepage and upward infiltration of freshwater, MET2 - shallow gas regular accumulation with lower availability of sulphates and high input of terrestrial organic matter, and MET3 - shallow gas elongated sub-bottom furrow with sulphate presence in the whole sediment profile. For comparison purposes, a reference site (ZGG) without any gas structures in sediments was included in the study. At each station, the following parameters were examined: CH4, C-ORG and C-INORG in sediments; DIC, DOC, H2S, SO42-, NH4+, Cl- in pore and near-bottom waters; stable isotopes in DIC (delta C-13-DIC), in gases (delta C-13-CH4, (delta C-13-CO2, (delta H-2-CH4), and microbial communities in sediments (16S rRNA). In addition, general physico-chemical conditions in bottom waters (dO(2), T, S, pH and Eh) as well as molecular composition of gas emitted from MET1-MP pockmark were determined. In order to be able to better compare the geological background of these shallow gas systems, the sediments were investigated by non-invasive acoustic methods: multi-beam echosounder and sub-bottom profiler. Moreover, relative AOM rates were estimated. The first system (MET1-MP) was characterised by a dramatic decrease in the availability of sulphate down the sediment, acetoclastic methanogenesis taking place in surface sediments, the AOM limited to a very thin topmost sediment layer, average stable isotope values of (delta C-13-CH4 = -58.9 parts per thousand, (delta H-2-CH4 = -310 parts per thousand, (delta C-13-CO2 = -6.9 parts per thousand, carbonate precipitation and both methanogenic as well as methanotrophic Archaea present in the whole sediment profile without clear zonation. In the shallow gas regular accumulation, in a close proximity to the coast (MET2), methane was virtually trapped in subsurface sediment layers, even despite not-high sulphate concentrations resulting from lower salinity (similar to 7.5 PSU). In that area, the bacterial community was, unlike typical marine sediments, dominated by Firmicutes, and average stable isotope values were: (delta C-13-CH4 = -67.0 parts per thousand, (delta H-2-CH4 = -243 parts per thousand, (delta H-2-CH4 = -7.9 parts per thousand. The third shallow gas system (MET3) was characterised by most efficient AOM, mostly due to sulphate presence in a relatively thick sediment layer, even several dozen cm below the SMT. The average stable isotope ratios for gases were as follows: (delta C-13-CH4 = -75.8 parts per thousand, delta H-2-CH4 = -241 parts per thousand and (delta H-2-CH4 = -11.9 parts per thousand. Despite high concentrations of methane, the methanogenic Archaea were virtually absent in the sediment profile, while the methanotrophic ones showed clear zonation, with ANME-2a-2b present in shallower sediments and ANME-1 in deeper layers. From the environmental point of view, active pockmark shallow-gas systems can be considered as the least efficient in preventing methane from migration to surface sediment layers and the water column, especially when freshwater infiltration occurs, which additionally dilutes the pool of sulphates available for AOM. In our study, the MET1-MP active pockmark was the most "leaky" in terms of methane release to the water column. In contrast, the shallow gas systems being under influence of additional sources of oxidants (in our case - MET2; influence of riverine discharge introducing Fe(III), together with high concentrations of oxygen in bottom waters) or having sulphate present in a relatively thick sediment layer (e.g. due to sulphide reoxidation below

    Re-assessment of the effect of fractional crystallization on Mo isotopes: Constraints from I-type granitoids and their enclosed mafic magmatic enclaves

    Chen, ShuoNiu, YaolingGong, HongmeiWang, Xiaohong...
    12页
    查看更多>>摘要:In recent years, considerable progress has been made on the study of Mo isotopes in high-temperature geological processes. However, it is still controversial whether Mo isotope fractionation occurs during magmatic differentiation. Here we reassess the effect of magma differentiation on Mo isotope fractionation using published data in conjunction with our new analysis of Mo isotopes in well-characterized I-type granitoids and their enclosed mafic magmatic enclaves (MMEs) from two plutons in the North Qilian Orogen. The MMEs in each pluton, representing earlier cumulates with greater modal proportions of amphibole and biotite, show similar Mo elemental and isotopic compositions to their host granitoids. The absence of covariation of Mo isotopes with Dy/Dy*, Fe2O3 and K/Rb in both plutons further indicates that fractional crystallization of amphibole, biotite and Fe3+-rich minerals does not fractionate Mo isotopes in these granitoids. On the basis of re-assessment of published and our newly obtained Mo isotope data, we find that there is no clear evidence for Mo isotope fractionation during fractional crystallization in igneous rock. Instead, Mo isotopes of our samples correlate positively with Sr isotopes and Rb/La ratios, and negatively with Nd isotopes and Ce/Pb ratios, indicating clearly that magma source compositional variation controls the variation of Mo isotope compositions of these granitoids.

    Micro-Raman water calibration in ultrapotassic silicate glasses: Application to phono-tephrites and K-foidites of Colli Albani Volcanic District (Central Italy)

    Bonechi, BarbaraGaeta, MarioPerinelli, CristinaMoschini, Piergiorgio...
    13页
    查看更多>>摘要:This study investigates the potential use of micro-Raman spectroscopy for the quantification of water in ultra-potassic silicate glasses. A calibration was developed using experimental phono-tephritic glasses with water content ranging from similar to 1 to similar to 3 wt%. The calibration curve showed a typical direct proportionality between water content and the ratio of high- (3100-3750 cm(-1)) and low-wavenumber (100-1500 cm(-1)) spectral regions, with a linear fit coefficient m = 1.74. The comparison with the m coefficients available in literature for other silicate compositions showed a deviation of our composition as a function of some major oxides such as FeO, TiO2 and K2O, highlighting the possible influence of the polymerization degree (NBO/T: non-bridging oxygens per tetrahedron) on m coefficient. In this respect, we observed a linear relationship between m coefficient and NBO/T and a positive correlation between the area underneath the silicate region (100-1500 cm(-1)) and NBO/T for the phono-tephrite of this study and for other compositions spanning from basalts to phonolite and rhyolites available in literature. For ultrapotassic natural and experimental glasses characterized by the presence of CO2, documented by the carbonate peak at 1062-1092 cm(-1), it has been possible to extrapolate the CO2 content by using the model of Morizet et al. (2013) obtaining values of similar to 1.1 +/- 0.3 and similar to 1.7 +/- 0.2 wt%, respectively. The obtained m coefficient was applied to estimate water content of natural phono-tephritic glasses belonging to the Colli Albani Volcanic District. Moreover, we estimated water content also for some natural K-foiditic glasses from the same volcanic district. Since the m coefficient results to be strongly dependent on the chemical composition of the sample of interest, the coefficient estimated for the phono-tephrites of this study could result in significant overestimation or underestimation of the water content of the Colli Albani Volcanic District K-foiditic natural samples. Thus, we extrapolated the m coefficient for the K-foiditic samples by means of an equation obtained in this study as function of the polymerization degree (NBO/T).