Geochimica et Cosmochimica Acta最新文献

Autochthonous dissolved organic matter (Auto-DOM) produced by a biological carbon pump using dissolved inorganic carbon (DIC) from carbonate weathering plays an important role in carbon cycling within inland waters. However, little is known regarding how environmental conditions impact the composition and fate of organic matter, especially in surface waters of the semi-arid Loess Plateau, which is enriched in DIC by significant carbonate weathering. To obtain novel insight, we combined hydrochemistry, isotopic composition (δ²H, δ¹⁸O, and δ¹³C_DIC), Rayleigh fractionation model, optical spectroscopy (absorbance and fluorescence), and Fourier transform ion cyclotron resonance mass spectrometry measurements to elucidate how primary production and hydrology impact the composition of DOM and the stability of the resulting Auto-DOM throughout the river–reservoir–wetland aquatic continuum of the Bahe River in the carbonate-mineral-rich semi-arid Loess Plateau where carbonate weathering is significant. The Rayleigh fractionation model results indicated that watershed DIC is primarily consumed through aquatic primary production rather than CO₂ degassing. Further investigation revealed that primary production and evaporation co-occurred in this watershed. With the enrichment of the stable water isotope δ²H, the relative abundances of the allochthonous compounds decreased and the relative abundances of the autochthonous substances increased, suggesting that the terrestrial signal of riverine DOM decreased while autochthonous production increased along the flow pathway. In addition, associations between optical and molecular characteristics among DOM samples from different water bodies revealed that the stability ratio (Fmax(C2/(C2 + C4))) of Auto-DOM to the ratio of carboxylic-rich alicyclic molecules showed a consistent trend, suggesting that phytoplankton-derived and biomineralized C2 compounds are potentially recalcitrant DOM in inland waters. We conclude that hydrology and primary production affect the source, composition, and, potentially, the stability of DOM in DIC-enriched surface waters of the semi-arid Loess Plateau, which may lead to a more humic-like DOM composition in inland water and export this lower bioavailability DOC to the ocean in the long term.

Olivine, typically occurring as a forsterite-fayalite solid solution, is a major rock-forming mineral in mafic and ultramafic igneous rocks, and it is important for understanding the genesis, evolution, and alteration of its host rocks. In this study, both GGA and GGA + U methods were employed to calculate the reduced partition function ratios of Fe, Mg, O, and Si isotopes for the forsterite-fayalite solid solution, aiming to elucidate the impacts of Fe content and Hubbard U correction on the isotope fractionation signatures of Fe, Mg, O, and Si in olivine. On the whole, the β_Fe-factor, β_Mg-factor, β_O-factor, and β_Si-factor decrease with increasing Fe content. The linear correlations between β-factors and bond lengths obtained from GGA + U are better compared to those from GGA. The Hubbard U correction can increase the β_Fe-factor. When Fe/(Fe + Mg) ≤ 1/8, ≤ 1/2, and ≤ 1/2, the effect of Hubbard U correction on β_Mg-factor, β_O-factor, and β_Si-factor can be considered negligible, respectively, suggesting that the β_Mg-factor, β_O-factor, and β_Si-factor of Fe-bearing olivine calculated using GGA + U and those of Fe-free minerals calculated using GGA can be combined to derive 10³lnα and trace geological processes. Furthermore, equilibrium fractionation of Fe, Mg, O, and Si isotopes between olivine and other minerals, including troilite, clinopyroxene, and garnet, were also calculated. Our results are helpful in interpreting the observed data regarding Fe, Mg, O, and Si isotopic compositions of olivine, leading to a comprehensive understanding of relevant geological processes.

Excesses of cosmic-ray produced nuclei in individual components of meteorites indicate “pre-irradiation”, either in the surface region of their parent bodies or as free-floating small particles in the early Solar System. We expand on our earlier work (Beyersdorf-Kuis et al., 2015) and report a study of cosmic-ray produced He and Ne in chondrules and “matrix” (i.e., matrix-dominated) material of several CR2 and CV meteorites as well as the highly primitive, unique, carbonaceous chondrite Acfer 094. In accordance with previous work, no evidence for pre-irradiation was found for CV3 Allende, while for CV3 Vigarano evidence for pre-irradiation is marginal at best. Also, the single chondrule from unique Acfer 094 that we studied has a cosmic ray exposure indistinguishable from the one we found for “matrix” material. Chondrules from Acfer 082 (CV) exhibit both excesses and deficits relative to “matrix”, which points to pre-irradiation of not only chondrules, but also matrix material. A similar case may be Renazzo (CR2), where, however, the identification is complicated by the presence of abundant pre-solar Ne-E. A large number of chondrules (ten) were studied from CR2 El Djouf 001, which yielded slightly variable, small but consistent, excesses relative to “matrix”, corresponding to “nominal” (i.e., irradiation by galactic cosmic rays in 4π geometry) excess ages of 1–2 Ma. Modelling suggests contributions from irradiation in the parent body regolith by solar cosmic rays (SCR) as well as galactic cosmic rays (GCR), where the latter dominates. Reevaluating the large variations previously identified in chondrules from QUE 99177, we suggest either a very different regolith history compared to that of El Djouf 001 or, more likely, pre-irradiation by, primarily, GCR in the early solar system as suggested previously. The case of solar-wind-rich NWA 852 (CR2) shows similarity to El Djouf 001 except for a much larger size of the effects. We suggest that the situation may be common among meteorites with a regolith origin. With independent information on the cosmic ray exposure age, which could be obtained by the study of cosmic-ray produced radionuclides, the individual parent body contributions may be disentangled, providing constraints on regolith dynamics.