The vadose zone acts as a natural buffer that prevents contaminants such as arsenic (As) from contaminating groundwater resources. Despite its capability to retain As, our previous studies revealed that a substantial amount of As could be remobilized from soil under repeated wet-dry conditions. Overlooking this might underestimate the potential risk of groundwater contamination. This study quantified the remobilization of As in the vadose zone and developed a prediction model based on soil properties. 22 unsaturated soil columns were used to simulate vadose zones with varying soil properties. Repeated wet-dry cycles were conducted upon the As-retaining soil columns. Consequently, 13.9-150.6 mg/kg of As was remobilized from the columns, which corresponds to 37.0-74.6 % of initially retained As. From the experimental results, a machine learning model using a random forest algorithm was established to predict the potential for As remobilization based on readily accessible soil properties, including organic matter (OM) content, iron (Fe) content, uniformity coefficient, D30, and bulk density. Shapley additive explanation analyses revealed the interrelated effects of multiple soil prop-erties. D30, which is inter-related with Fe content, exhibited the highest contribution to As remobilization, fol-lowed by OM content, which was partially mediated by bulk density.

The damage caused by petroleum hydrocarbon pollution to soil and groundwater environment is becoming increasingly significant. The vadose zone is the only way for petroleum hydrocarbon pollutants to leak from surface into groundwater. The spatial distribution characteristics of indigenous microorganisms in vadose zone, considering presence of capillary zones, have rarely been reported. To explore the spatial distribution characteristics of indigenous microorganisms in vadose zone contaminated by petroleum hydrocarbons, a onedimensional column migration experiment was conducted using n-hexadecane as characteristic pollutant. Soil samples were collected periodically from different heights during experiment. Corresponding environmental factors were monitored online. The microbial community structure and spatial distribution characteristics of the cumulative relative abundance were systematically analyzed using 16S rRNA sequencing. In addition, the microbial degradation mechanism of n-hexadecane was analyzed using metabolomics. The results showed that presence of capillary zone had a strong retarding effect on n-hexadecane infiltration. Leaked pollutants were mainly concentrated in areas with strong capillary action. Infiltration and displacement of NAPL-phase pollutants were major driving force for change in moisture content ( theta) and electric conductivity (EC) in vadose zone. The degradation by microorganisms results in a downward trend in potential of hydrogen (pH) and oxidation reduction potential (ORP). Five petroleum hydrocarbon -degrading bacterial phyla and 11 degradable straightchain alkane bacterial genera were detected. Microbial degradation was strong in the area near edge of capillary zone and locations of pollutant accumulation. Mainly Sphingomonas and Nocardioides bacteria were involved in microbial degradation of n-hexadecane. Single -end oxidation involved microbial degradation of n-hexadecane (C 16 H 34 ). The oxygen consumed, hexadecanoic acid (C 16 H 32 O 2 ) produced during this process, and release of hydrogen ions (H + ) were the driving factors for reduction of ORP and pH. The vadose zone in this study considered presence of capillary zone, which was more in line with actual contaminated site conditions compared with previous studies. This study systematically elucidated vertical distribution characteristics of petroleum hydrocarbon pollutants and spatiotemporal variation characteristics of indigenous microorganisms in vadose zone considered presence of capillary zone. In addition, the n-hexadecane degradation mechanism was elucidated using metabolomics. This study provides theoretical support for development of natural attenuation remediation measures for petroleum -hydrocarbon -contaminated soil and groundwater.

The hydro-mechanical properties of the vadose zone are strongly influenced by seasonal cycles. The hydraulic behavior of this zone is determined by the coupling of biotic and abiotic factors. The biotic factors are controlled by the physiology and anatomy of the vegetation growing in the area, while the abiotic factors depend on the local soil characteristics, such as water content, void ratio, and matrix structure. In this laboratory-scale investigation, we assess the influence of active biomass, water content, and suction on the particle and pore structure rearrangement. We use x-ray computed tomography and 3D digital image correlation to quantify plant roots at different stages of growth, soil deformation, and water content fluctuations. Our results show that the bulk porosity of vegetated soil is strongly affected by the induced water cycles. The global micro-structure rearrangement due to the double effects of plant water uptake and induced drying-wetting cycles translates into a final bulk porosity increase.

As climate change intensifies, soil water flow, heat transfer, and solute transport in the active, unfrozen zones within permafrost and seasonally frozen ground exhibit progressively more complex interactions that are difficult to elucidate with measurements alone. For example, frozen conditions impede water flow and solute transport in soil, while heat and mass transfer are significantly affected by high thermal inertia generated from water-ice phase change during the freeze-thaw cycle. To assist in understanding these subsurface processes, the current study presents a coupled two-dimensional model, which examines heat conduction-convection with water-ice phase change, soil water (liquid water and vapor) and groundwater flow, advective-dispersive solute transport with sorption, and soil deformation (frost heave and thaw settlement) in variably saturated soils subjected to freeze-thaw actions. This coupled multiphysics problem is numerically solved using the finite element method. The model's performance is first verified by comparison to a well-documented freezing test on unsaturated soil in a laboratory environment obtained from the literature. Then based on the proposed model, we quantify the impacts of freeze-thaw cycles on the distribution of temperature, water content, displacement history, and solute concentration in three distinct soil types, including sand, silt and clay textures. The influence of fluctuations in the air temperature, groundwater level, hydraulic conductivity, and solute transport parameters was also comparatively studied. The results show that (a) there is a significant bidirectional exchange between groundwater in the saturated zone and soil water in the vadose zone during freeze-thaw periods, and its magnitude increases with the combined influence of higher hydraulic conductivity and higher capillarity; (b) the rapid dewatering ahead of the freezing front causes local volume shrinkage within the non-frozen region when the freezing front propagates downward during the freezing stage and this volume shrinkage reduces the impact of frost heave due to ice formation. This gradually recovers when the thawed water replenishes the water loss zone during the thawing stage; and (c) the profiles of soil moisture, temperature, displacement, and solute concentration during freeze-thaw cycles are sensitive to the changes in amplitude and freeze-thaw period of the sinusoidal varying air temperature near the ground surface, hydraulic conductivity of soil texture, and the initial groundwater levels. Our modeling framework and simulation results highlight the need to account for coupled thermal-hydraulic-mechanical-chemical behaviors to better understand soil water and groundwater dynamics during freeze-thaw cycles and further help explain the observed changes in water cycles and landscape evolution in cold regions.