Controls of Mineral Solubility on Adsorption-Induced Molecular Fractionation of Dissolved Organic Matter Revealed by 21 T FT-ICR MS.

Mineral adsorption-induced molecular fractionation of dissolved organic matter (DOM) affects the composition of both DOM and OM adsorbed and thus stabilized by minerals. However, it remains unclear what mineral properties control the magnitude of DOM fractionation. Using a combined technique approach that leverages the molecular composition identified by ultrahigh resolution 21 T Fourier transform ion cyclotron resonance mass spectrometry and adsorption isotherms, we catalogue the compositional differences that occur at the molecular level that results in fractionation due to adsorption of Suwannee River fulvic acid on aluminum (Al) and iron (Fe) oxides and a phyllosilicate (allophane) species of contrasting properties. The minerals of high solubility (i.e., amorphous Al oxide, boehmite, and allophane) exhibited much stronger DOM fractionation capabilities than the minerals of low solubility (i.e., gibbsite and Fe oxides). Specifically, the former released Al3+ to solution (0.05-0.35 mM) that formed complexes with OM and likely reduced the surface hydrophobicity of the mineral-OM assemblage, thus increasing the preference for adsorbing polar DOM molecules. The impacts of mineral solubility are exacerbated by the fact that interactions with DOM also enhance metal release from minerals. For sparsely soluble minerals, the mineral surface hydrophobicity, instead of solubility, appeared to be the primary control of their DOM fractionation power. Other chemical properties seemed less directly relevant than surface hydrophobicity and solubility in fractionating DOM.

Sulfur dynamics in forest soil profiles developed on granite under contrasting climate conditions.

Sulfur (S) dynamics in soils formed from granite remain poorly understood despite its importance as an essential plant macronutrient and component of soil organic matter. We used stable S isotope ratios to trace the sources and biogeochemical processes of S in four forest soil profiles developed on granite under contrasting climate conditions. The soil S is derived mainly from decomposing litter; no significant geogenic contribution to its content is noted as a result of the low S concentration of the granite (~ 5 µg/g). Colder/drier climate results in high organic S retention at the surface due to weak mineralization of organic S. Although warmer/wetter climate increases the S mineralization and leaching loss, SO42- adsorption is an important S retention process in the subsurface. The vertical distribution of S isotope compositions in the soil profiles across the four sites indicates (i) a downward increase in δ34S values in the upper profiles due to continuous mineralization of organic S with an occasional decrease in δ34S values in the subsurface due to dissimilatory sulfate reduction (DSR), (ii) constantly high δ34S values in the middle profiles due to the low water permeability, and (iii) a downward decrease in δ34S values in the low profiles due to increased contribution of bedrock with depth. Regardless of the variation in soil depth and climate, the total S concentration is proportional to the pedogenic Fe/Al minerals, suggesting the important role of secondary Fe/Al minerals in retaining S in soils. This study provides an integration and synthesis of controls of climatic and edaphic variables on S dynamics in forest soil profiles developed on granite.

[Biogeochemical processes of the major ions and dissolved inorganic carbon in the Guijiang River].

Within the drainage basin, information about natural processes and human activities can be recorded in the chemical composition of riverine water. The analysis of the Guijiang River, the first level tributary of the Xijiang River, demonstrated that the chemical composition of water in the Guijiang River was mainly influenced by the chemical weathering of carbonate rocks within the drainage basin, in which CO2 was the main erosion medium, and that the weathering of carbonate rock by H2SO4 had a remarkable impact on the water chemical composition in the Guijiang River. Precipitation, human activities, the weathering of carbonate rocks and silicate rocks accounted for 2.7%, 6.3%, 72.8% and 18.2% of the total dissolved load, respectively. The stable isotopic compositions of dissolved inorganic carbon (delta13C(DIC)) indicated that DIC in the Guijiang River had been assimilated by the phytoplankton in photosynthesis. The primary production of phytoplankton contributed to 22.3%-30.9% of particulate organic carbon (POC) in the Guijiang River, which implies that phytoplankton can transform DIC into POC by photosynthesis, and parts of POC will sink into the bottom of the river in transit, which leads into the formation of burial organic carbon.