The association of organic matter (OM) with minerals is recognized as the most important stabilization mechanism for soil organic matter. This study compared the properties of Fe-OM complexes formed from adsorption (reaction of OM to postsynthesis ferrihydrite) versus coprecipitation (formation of Fe solids in the presence of OM). Coprecipitates and adsorption complexes were synthesized using dissolved organic matter (DOM) extracts from a forest little layer at varying molar C/Fe ratios of 0.3-25.0. Sample properties were studied by N2 gas adsorption, XRD, FTIR, Fe EXAFS, and STXM-NEXAFS techniques. Coprecipitation resulted in much higher maximum C contents (∼130 mg g(-1) C difference) in the solid products than adsorption, which may be related to the formation of precipitated insoluble Fe(III)-organic complexes at high C/Fe ratios in the coprecipitates as revealed by Fe EXAFS analysis. Coprecipitation led to a complete blockage of mineral surface sites and pores with ≥177 mg g(-1) C and molar C/Fe ratios ≥2.8 in the solid products. FTIR and STXM-NEXAFS showed that the coprecipitated OM was similar in composition to the adsorbed OM. An enrichment of aromatic C was observed at low C/Fe ratios. Association of carboxyl functional groups with Fe was shown with FTIR and STXM-NEXAFS analysis. STXM-NEXAFS analysis showed a continuous C distribution on minerals. Desorption of the coprecipitated OM was less than that of the adsorbed OM at comparable C/Fe ratios. These results are helpful to understand C and Fe cycling in the natural environments with periodically fluctuating redox conditions, where coprecipitation can occur.

Aqueous Fe(II) is known to catalyze the abiotic transformation of ferrihydrite to more stable Fe minerals. However, little is known about the impacts of coprecipitated OM on Fe(II)-catalyzed ferrihydrite transformation and its consequences for C dynamics. Accordingly, we investigated the extent and pathway of Fe(II)-induced transformation of OM-ferrihydrite coprecipitates as a function of C/Fe ratios and aqueous Fe(II) concentrations, and its implications for subsequent C dynamics. The coprecipitated OM resulted in a linear decrease in ferrihydrite transformation with increasing C/Fe ratios. The secondary mineral profiles upon Fe(II) reaction with OM-ferrihydrite coprecipitates depend on Fe(II) concentrations At 0.2 mM Fe(II), OM completely inhibited goethite formation and stimulated lepidocrocite formation. At 2 mM Fe(II), whereas goethite was formed in the presence of OM, OM reduced the amount of goethite and magnetite formation and increased the formation of lepidocrocite. The solid-phase C content remained unchanged after reaction, suggesting that OM remains associated with Fe minerals following ferrihydrite transformation to more stable Fe minerals. However, C desorbability by H2PO4(-) from the resulting Fe minerals following reaction was enhanced. The study indicates a "lepidocrocite favoring effect" by OM and suggests that Fe(II)-catalyzed transformation of ferrihydrite may decrease OM stability in natural environments under moderately reducing conditions.

The estimation of the size and changes of soil organic carbon (SOC) stocks is of great importance for decision makers to adopt proper measures to protect soils and to develop strategies for mitigation of greenhouse gases. In this paper, soil data from the Second State Soil Survey of China (SSSSC) conducted in the early 1980s and data published in the last 5 years were used to estimate the size of SOC stocks over the whole profile and their changes in China in last 20 years. Soils were identified as paddy, upland, forest, grassland or waste-land soils and an improved soil bulk density estimation method was used to estimate missing bulk density data. In the early 1980s, total SOC stocks were estimated at 89.61 Pg (1 Pg 5 10 3 Tg 5 10 15 g) in China's 870.94 Mha terrestrial areas covered by 2473 soil series. In the paddy, upland, forest and grassland soils the respective total SOC stocks were 2.91 Pg on 29.87 Mha, 10.07 Pg on 125.89 Mha, 34.23 Pg on 249.32 Mha and 37.71 Pg on 278.51 Mha, respectively. The SOC density of the surface layer ranged from 3.5 Mg ha À1 in Gray Desery grassland soils to 252.6 Mg ha À1 in Mountain Meadow forest soils. The average area-weighted total SOC density in paddy soils (97.6 Mg ha À1 ) was higher than that in upland soils (80 Mg ha À1 ). Soils under forest (137.3 Mg ha À1 ) had a similar average area-weighted total SOC density as those under grassland (135.4 Mg ha À1 ). The annual estimated SOC accumulation rates in farmland and forest soils in the last 20 years were 23.61 and 11.72 Tg, respectively, leading to increases of 0.472 and 0.234 Pg SOC in farmland and forest areas, respectively. In contrast, SOC under grassland declined by 3.56 Pg due to the grassland degradation over this period. The resulting estimated net SOC loss in China's soils over the last 20 years was 2.86 Pg. The documented SOC accumulation in farmland and forest soils could thus not compensate for the loss of SOC in grassland soils in the last 20 years. There were, however, large regional differences: Soils in China's South and Eastern parts acted mainly as C sinks, increasing their average topsoil SOC by 132 and 145 Tg, respectively. In contrast, in the Northwest, Northeast, Inner Mongolia and Tibet significant losses of 1.38, 0.21, 0.49 and 1.01 Pg of SOC, respectively, were estimated over the last 20 years. These results highlight the importance to take measures to protect grassland and to improve management practices to increase C sequestration in farmland and forest soils.