Browsing by Author "Jin, Yan"
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Item Organo-mineral associations and size-fractionated colloidal organic carbon dynamics in a redox-controlled wetland(Geoderma, 2023-10-02) Afsar, Mohammad Zafar Afsar; Vasilas, Bruce; Jin, YanThe formation of organo-mineral associations serves as a crucial mechanism for stabilizing soil organic matter, particularly for determining the fate of soil organic carbon (OC) in redox dynamic wetlands characterized by high C content. Despite its importance, few studies have assessed the retention, transformation, and transport of colloids (1–1000 nm) and colloidal OC (COC) in those environments. This leaves a crucial knowledge gap concerning the quantities of colloids and COC and their molecular compositions, especially considering the significant role of metabolically active depressional wetlands that may play as biogeochemical hotspots for C cycling. To address this gap, we conducted a study in a Delmarva Bay depressional wetland located in Blackbird State Forest, Delaware, USA. We established a transect encompassing upland (U), transition (T), and wetland (W) zones based on seasonal hydrologic conditions. We installed piezometers at 50 cm, 100 cm, and 200 cm depths within each zone and collected pore-water samples from 11/2017 to 05/2019. We then fractionated these samples into dissolved (<2.3 nm), natural nanoparticle (NNP, 2.3–100 nm), fine colloid (100–450 nm), and particulate (450–1000 nm) fractions via sequential centrifugation and ultrafiltration, and quantified their concentration and molecular composition. We observed variations in the concentration and molecular composition of soil COC both vertically at different soil depths and horizontally along a redox gradient from the U-T-W transect. The sum of the NNP and fine colloid fractions accounted for 47±20% of the operationally defined “dissolved” (<450 nm) fraction. Isotope ratio mass spectrometry and X-ray photoelectron spectroscopy analyses further revealed that the NNP fraction is more enriched in heavier δ13C isotope and oxidized carbonyl/carboxyl C functional groups (C=O, p<0.05) with significantly higher surficial atomic percentages of C (p<0.01), N (p<0.01), and Mg:Al ratios (p<0.05), and lower atomic percentages of Al (p<0.01) and Si (p<0.01) compared to the larger particles. The formation of cation bridges and/or hydrogen bonds between carboxylic OC and phyllosilicate minerals likely dominated the mineral-OC association in the NNP fraction. The higher surface C enrichment in the particulate fraction compared to the NNP fraction suggests a patchy distribution of more plant-derived OC through organo-organic interactions in the larger fractions. Along the transect, Zone U exhibited significant enrichment of heavier δ13C isotope and lower SUVA values than the Zones T and W indicating inefficient decomposition and dissociation of SOM from minerals due to the reductive dissolution of Fe and Al oxides under anoxic conditions. Furthermore, an increase in low molecular weight microbial metabolites with reduced aromatic OC content was observed at deeper depths in Zones U and T. Our study provides new insights into the concentration and molecular composition of size-fractionated COC, highlighting the need to separately consider the NNP and fine colloid fractions from the operationally defined “dissolved” phase. This is crucial for assessing the biogeochemical cycling of OC in redox-active wetlands, a pressing need amidst the growing concerns about the impacts of climate change. Highlights • Molecular composition of COC impacts SOM stability, mobility, and C storage in wetlands. • Anoxic conditions promote the release of plant-derived C, which is δ13C depleted and highly aromatic. • NNP fraction comprises a significant portion of the traditionally defined dissolved phase. • NNP fraction shows significant δ13C enrichment and oxidized C compared to the larger fractions.Item Spontaneous Detachment of Colloids from Primary Energy Minima by Brownian Diffusion(Public Library of Science (PLOS), 2016-01-19) Wang, Zhan; Jin, Yan; Shen, Chongyang; Li, Tiantian; Huang, Yuanfang; Li, Baoguo; Zhan Wang, Yan Jin, Chongyang Shen, Tiantian Li, Yuanfang Huang, Baoguo Li; Jin, YanThe Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energy profile has been frequently used to interpret the mechanisms controlling colloid attachment/detachment and aggregation/disaggregation behavior. This study highlighted a type of energy profile that is characterized by a shallow primary energy well (i.e., comparable to the average kinetic energy of a colloid) at a small separation distance and a monotonic decrease of interaction energy with separation distance beyond the primary energy well. This energy profile is present due to variations of height, curvature, and density of discrete physical heterogeneities on collector surfaces. The energy profile indicates that colloids can be spontaneously detached from the shallow primary energy well by Brownian diffusion. The spontaneous detachment from primary minima was unambiguously confirmed by conducting laboratory column transport experiments involving flow interruptions for two model colloids (polystyrene latex microspheres) and engineered nanoparticles (fullerene C60 aggregates). Whereas the spontaneous detachment has been frequently attributed to attachment in secondary minima in the literature, our study indicates that the detached colloids could be initially attached at primary minima. Our study further suggests that the spontaneous disaggregation from primary minima is more significant than spontaneous detachment because the primary minimum depth between colloid themselves is lower than that between a colloid and a collector surface.Item The unexplored role of preferential flow in soil carbon dynamics(Soil Biology and Biochemistry, 2021-08-28) Franklin, Shane M.; Kravchenko, Alexandra N.; Vargas, Rodrigo; Vasilas, Bruce; Fuhrmann, Jeffry J.; Jin, YanWater is a crucial factor controlling the fate and processing of soil organics. Water commonly flows through the vadose zone via preferential flow pathways, resulting in nonuniform and rapid infiltration. Hence, a large portion of the soil matrix is bypassed. Preferential flow paths, often associated with well-connected macropore networks (>300 μm Ø), offer a unique balance between water availability, nutrient delivery, and re-oxygenation upon drainage. The heightened concentrations of moisture, nutrients, and oxygen make these locations optimal for high rates of microbial activity. Flow paths often display temporal stability. This stability results in repeated wetting and biogeochemical reactivation through time creating a lasting impact on micro-environmental conditions relevant to microbial functioning and carbon cycling in soil. Despite decades of research on preferential flow, there is still a need to link flow paths and the resultant heterogeneous moisture distributions to soil function. In this review, we discuss how preferential flow can serve as a framework of reference for the spatially and temporally heterogeneous biogeochemical cycling of soil carbon. We highlight the importance of combining current knowledge of pore-scale carbon dynamics with an appreciation of connected networks of hydraulically active pores/paths within the soil profile. Such combination opens new possibilities for upscaling pore-scale processes with the inclusion of resource heterogeneity at the macroscale. Working within this hydraulically connected framework can provide insight for the mechanistic representation of hot moments, which are temporally isolated large pulses of CO2 after rewetting or thawing events. We conclude with suggestions on knowledge gaps and stress the critical need of linking soil physics with biology to mechanistically understand soil functions. Highlights • Preferential flow paths play a key role in soil carbon dynamics. • Pore-scale carbon dynamics could be upscaled using hydraulic connectivity. • A conceptual model is presented that considers how soil pores function from hydrological and microbial perspectives.