Approximate analytical model for transient transport and oxygen-limited biodegradation of vapor-phase petroleum hydrocarbon compound in soil.

Volatile organic compounds (VOCs) contamination may occur in subsurface soil due to various reasons and pose great threat to people. Petroleum hydrocarbon compound (PHC) is a typical kind of VOC, which can readily biodegrade in an aerobic environment. The biodegradation of vapor-phase PHC in the vadose zone consumes oxygen in the soil, which leads to the change in aerobic and anaerobic zones but has not been studied by the existing analytical models. In this study, a one-dimensional analytical model is developed to simulate the transient diffusion and oxygen-limited biodegradation of PHC vapor in homogeneous soil. Laplace transformation and Laplace inversion of the Talbot method are adopted to derive the solution. At any given time, the thickness of aerobic zone is determined by the dichotomy method. The analytical model is verified against numerical simulation and experimental results first and parametric study is then conducted. The transient migration of PHC vapor can be divided into three stages including the pure aerobic zone stage (Stage I), aerobic-anaerobic zones co-existence stage (Stage II), and steady-state stage (Stage III). The proposed analytical model should be adopted to accommodate scenarios where the transient effect is significant (Stage II), including high source concentration, deep contaminant source, high biodegradation capacity, and high water saturation. The applicability of this model to determine the breakthrough time for better vapor intrusion assessment is also evaluated. Lower first-order biodegradation rate, higher source concentration, and shallower source depth all lead to smaller breakthrough time.

Two-dimensional analytical solution for subsurface volatile organic compounds vapor diffusion from a point source in layered unsaturated zone.

Although migration of subsurface volatile organic compounds (VOCs) from contaminant sources in unsaturated soil widely exists, the related analytical models are quite limited. A two-dimensional analytical solution is hence developed to simulate vapor diffusion from the subsurface contaminant source in the layered unsaturated zone. The contaminant source is simplified as a point source leaking at a constant rate. The influences of several important factors, including thickness of stagnant air layer, depth of groundwater table, source characteristics and soil layering characteristics, on vapor migration in subsurface soil are comprehensively investigated by the present model. Soil type does not affect the normalized vapor concentration profile for homogeneous soil, which is not valid for layered soil. The width and effective diffusivity of the upward diffusion pathway and downward diffusion pathway are favorable indexes to evaluate the intensity of subsurface vapor horizontal diffusion. The single-layer capillary fringe assumption overestimates the vapor plume, the assumption can give acceptable result for coarse soil while it is recommended to divide the soil into several layers based on the water-filled porosity profile for fine soil.

Analytical model for organic contaminant transport through GMB/CCL composite liner with finite thickness considering adsorption, diffusion and thermodiffusion.

A new analytical model for organic contaminant transport through GMB/CCL (geomembrane and compacted clay liner) composite liner is developed, which can consider adsorption, diffusion and thermodiffusion processes and is applicable for typical bottom boundary conditions. The separation of variables method is adopted to derive the solution. The present model is first verified against experimental results and a numerical model. The influence of thermodiffusion on organic contaminant transport in composite liner is then investigated. Toluene is adopted as the representative organic contaminant. The results reveal that when the Soret coefficient ST is not less than 0.01 K-1, the effect of thermodiffusion should be taken into account on the contaminant transport in GMB/CCL composite liner in wet landfills. When the Soret coefficient ST is 0.03 K-1, the breakthrough time of a GMB + 0.75 m CCL composite liner and a 2 m CCL would be overestimated by 20% to 76% due to omitting of the effect of thermodiffusion. Namely, the barrier performance would be greatly overestimated if the effect of thermodiffusion is neglected in these cases. In other aspects, the thermal conductivity of GMB and CCL has little effect on the contaminants transport in GMB/CCL composite liners, so there is no need to modify the materials for this parameter. The present model is an applicable tool for evaluating the barrier performance of the GMB/CCL composite liner, and can provide valuable advices for improving the liner materials.

Two-dimensional analytical solution for VOC vapor migration through layered soil laterally away from the edge of contaminant source.

A two-dimensional analytical solution is developed to simulate vapor migration in layered soil laterally away from the edge of contaminant source and has advantages in considering the vapor concentration profile in a functional form near the source edge. The analytical solution is validated against existing analytical solution, numerical model and experimental results. It has also proved to be an alternative screening tool to evaluate the vapor intrusion (VI) risk by compared with existing VI assessment tools. The influence of the characteristics of contaminant source and soil layer on the VI risk are investigated. The existence of capillary fringe effectively reduces VI risk. Among all the single-layer-soil cases, the lateral inclusion zone for sand is the widest due to the thinnest capillary fringe and the lowest effective diffusivity ratio between soil and capillary fringe. For layered soil, the lower effective diffusivity layer overlying the higher one enhances the horizontal diffusion and extends the lateral inclusion zone. The width of lateral inclusion zone increases logarithmically with increasing source concentration while it increases linearly with increasing source depth. Based on the calculation results, a simplified formula is proposed to preliminarily estimate the width of lateral inclusion zone for the typical single-layer-soil cases considering the capillary fringe.

Transient analytical solution for one-dimensional transport of organic contaminants through GM/GCL/SL composite liner.

Analytical solution for transport of organic contaminants through composite liner consisting of a geomembrane (GM), a geosynthetic clay liner (GCL), and a soil liner (SL) with finite thickness is presented. The transient diffusion-advection processes in the whole composite liner and adsorption in GCL and SL can be described by the present method. The method is successfully verified against analytical solution to a coupling transient diffusion-advection problem in double-layer porous media. The rationality of the steady-state transport assumption in GM and GCL and the semi-infinite bottom boundary assumption, which are widely adopted in the existing works, is comprehensively investigated. The overestimated zone, underestimated zone and no difference zone caused by the two assumptions under various conditions are identified. With the increase of elapsed time, the overestimated zone disappears, and the underestimated zone becomes smaller and smaller and finally is overwhelmed by the no difference zone. Moreover, the equivalency between GM/GCL/SL and GM/CCL composite liners is also properly assessed by the present method. GM/GCL/SL composite liner performs better than GM/CCL composite liner under high leachate level condition.

[Spiropyran-based fluorescent sensor for Hg2+, Cr3+, Ag+ and their interaction spectra].

A 6',8'-di-tert-butyl-1-hydroxyethyl-3,3-dimethyl-indoline benzospiropyran L1 and its derivative L2 were synthesized and characterized. Chelation-enhanced appearswhen L1 with electron donating groups of 6', 8'-di-tert-butyl touch on benzospiropyran and affect the stability of cyanine structure. L1 exhibited high selectivity to Hg2+, Cr3+, Ag+ over other metal ions. While, there was no obvious interferences of coexist metal ions on Hg2+, Cr3+, Ag+ detection. The Hg2+, Cr+, Ag+ recognition of L1 not only could be achieved by means of fluorescense and absorption "turn-on" spectra but also an obvious color change from colorless to yellowish by naked-eyes. The binding of L1 to Ag+, Cr3+, Hg2+ are in 1 : 1 stoichometry and the detection limits are 7.435 8 x 10(-6), 6.126 8 x 10(-6), 3.452 4 x 10(-6) mol x L(-1). The sensing mechanism was also investigated from L2.