Iason Verginelli

Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.

Pilot-scale ISCO treatment of a MtBE contaminated site using a Fenton-like process

This paper reports about a pilot-scale feasibility study of In-Situ Chemical Oxidation (ISCO) application based on the use of stabilized hydrogen peroxide catalyzed by naturally occurring iron minerals (Fenton-like process) to a site formerly used for fuel storage and contaminated by MtBE. The stratigraphy of the site consists of a 2-3 meter backfill layer followed by a 3-4 meter low permeability layer, that confines the main aquifer, affected by a widespread MtBE groundwater contamination with concentrations up to 4000 μg/L, also with the presence of petroleum hydrocarbons. The design of the pilot-scale treatment was based on the integration of the results obtained from experimental and numerical modeling accounting for the technological and regulatory constraints existing in the site to be remediated. In particular, lab-scale batch tests allowed the selection of the most suitable operating conditions. Then, this information was implemented in a numerical software that allowed to define the injection and monitoring layout and to predict the propagation of hydrogen peroxide in groundwater. The pilot-scale field results confirmed the effective propagation of hydrogen peroxide in nearly all the target area (around 75 m(2) using 3 injection wells). As far as the MtBE removal is concerned, the ISCO application allowed us to meet the clean-up goals in an area of 60 m(2). Besides, the concentration of TBA, i.e. a potential by-product of MtBE oxidation, was actually reduced after the ISCO treatment. The results of the pilot-scale test suggest that ISCO may be a suitable option for the remediation of the groundwater plume contaminated by MtBE, providing the background data for the design and cost-estimate of the full-scale treatment.

Vapor Intrusion Screening Model for the Evaluation of Risk-Based Vertical Exclusion Distances at Petroleum Contaminated Sites

The key role of biodegradation in attenuating the migration of petroleum hydrocarbon vapors into the indoor environments has been deeply investigated in the last decades. Very recently, empirical screening levels for the separation distance from the source, above which the potential for vapor intrusion can be considered negligible, were defined. In this paper, an analytical solution that allows one to predict risk-based vertical screening distances for hydrocarbons compounds is presented. The proposed solution relies on a 1-D vapor intrusion model that incorporates a piecewise first-order aerobic biodegradation limited by oxygen availability and accounts also for the effect of the building footprint. The model predictions are shown to be consistent with the results obtained using a 3-D numerical model and with the empirical screening criteria defined by U.S.EPA and CRC care. However, the different simulations carried out show that in some specific cases (e.g., large building footprint, high methane concentration, and low attenuation in the capillary fringe), the respect of these empirical screening criteria could be insufficient to guarantee soil-gas concentrations below acceptable risk-based levels.

A two‐dimensional analytical model of petroleum vapor intrusion

In this study we present an analytical solution of a two-dimensional petroleum vapor intrusion model, which incorporates a steady-state diffusion-dominated vapor transport in a homogeneous soil and piecewise first-order aerobic biodegradation limited by oxygen availability. This new model can help practitioners to easily generate two-dimensional soil gas concentration profiles for both hydrocarbons and oxygen and estimate hydrocarbon indoor air concentrations as a function of site-specific conditions such as source strength and depth, reaction rate constant, soil characteristics and building features. The soil gas concentration profiles generated by this new model are shown in good agreement with three-dimensional numerical simulations and two-dimensional measured soil gas data from a field study. This implies that for cases involving diffusion dominated soil gas transport, steady state conditions and homogenous source and soil, this analytical model can be used as a fast and easy-to-use risk screening tool by replicating the results of 3-D numerical simulations but with much less computational effort.

A Petroleum Vapor Intrusion Model Involving Upward Advective Soil Gas Flow Due to Methane Generation

At petroleum vapor intrusion (PVI) sites at which there is significant methane generation, upward advective soil gas transport may be observed. To evaluate the health and explosion risks that may exist under such scenarios, a one-dimensional analytical model describing these processes is introduced in this study. This new model accounts for both advective and diffusive transport in soil gas and couples this with a piecewise first-order aerobic biodegradation model, limited by oxygen availability. The predicted results from the new model are shown to be in good agreement with the simulation results obtained from a three-dimensional numerical model. These results suggest that this analytical model is suitable for describing cases involving open ground surface beyond the foundation edge, serving as the primary oxygen source. This new analytical model indicates that the major contribution of upward advection to indoor air concentration could be limited to the increase of soil gas entry rate, since the oxygen in soil might already be depleted owing to the associated high methane source vapor concentration.

Analysis and modeling of metals release from MBT wastes through batch and up-flow column tests.

The leaching behavior of wastes coming out from Mechanical Biological Treatment (MBT) plants is still poorly investigated in literature. This work presents an attempt to provide a deeper insight about the contaminants release from this type of waste. To this end, results of several batch and up-flow percolation tests, carried out on different biologically treated waste samples collected from an Italian MBT plant, are reported. The obtained results showed that, despite MBT wastes are characterized by relatively high heavy metals content, only a limited amount was actually soluble and thus bioavailable. Namely, the release percentage was generally lower than 5% of the total content with the only exception of dissolved organic carbon (DOC), Zn, Ni and Co with release percentages up to 20%. The information provided by the different tests also allowed to highlight some key factors governing the kinetics release of DOC and metals from this type of material. In particular, results of up-flow column percolation tests showed that metals such as Cr, Mg, Ni and Zn followed essentially the leaching trend of DOC suggesting that these elements were mainly released as organo-compounds. Actually, a strong linear correlation (R(2) > 0.8) between DOC and metals concentration in eluates was observed, especially for Cr, Ni and Zn (R(2)>0.94). Thus, combining the results of batch and up-flow column percolation tests, partition coefficients between DOC and metals concentration were derived. These data, coupled with a simplified screening model for DOC release, allowed to get a very good prediction of metal release during the different column tests. Finally, combining the experimental data with a simplified model provided some useful indications for the evaluation of long-term emissions from this type of waste in landfill disposal scenarios.

Analysis and interpretation of the leaching behaviour of waste thermal treatment bottom ash by batch and column tests

This paper investigates the leaching behaviour of specific types of waste thermal treatment bottom ash (BA) as a function of both pH and the liquid-to-solid ratio (L/S). Specifically, column percolation tests and different types of batch tests (including pH-dependence) were applied to BA produced by hospital waste incineration (HW-I), Refuse Derived Fuel (RDF) gasification (RDF-G) and RDF incineration (RDF-I). The results of these tests were interpreted applying an integrated graphical and modelling approach aimed at identifying the main mechanisms (solubility, availability or time-controlled dissolution and diffusion) governing the release of specific constituents from each type of BA. The final aim of this work was in fact to gain insight on the information that can be provided by the leaching tests applied, and hence on which ones may be more suitable to apply for assessing the leaching concentrations expected in the field. The results of the leaching tests showed that the three samples of analysed BA presented differences of orders of magnitude in their leaching behaviour, especially as a function of pH, but also in terms of the L/S. These were mainly related to the differences in mineralogy of the samples. In addition, for the same type of bottom ash, the comparison between the results of batch and percolation column tests, expressed in terms of cumulative release, showed that for some constituents (e.g. Mg for HW-I BA and Cu for RDF-G BA) differences of over one order of magnitude were obtained due to variations in pH and DOC release. Similarly, the eluate concentrations observed in the percolation tests, for most of the investigated elements, were not directly comparable with the results of the pH-dependence tests. In particular, in some cases the percolation test results showed eluate concentrations of some constituents (e.g. K and Ca in HW-I BA) of up to one order of magnitude higher than the values obtained from the pH-dependence experiments at the same pH value. This was attributed to a rapid washout from the column of the soluble phases present in the BA. In contrast, for other constituents (e.g. Mg and Ba for the RDF-G BA), especially at high L/S ratios, the concentrations in the column tests were of up to one order of magnitude lower than the solubility value, indicating release under non-equilibrium conditions. In these cases, batch pH-dependence tests should be preferred, since column tests results could underestimate the concentrations expected in the field.

A two‐dimensional analytical model of vapor intrusion involving vertical heterogeneity

In this work, we present an analytical chlorinated vapor intrusion (CVI) model that can estimate source-to-indoor air concentration attenuation by simulating two-dimensional (2-D) vapor concentration profile in vertically heterogeneous soils overlying a homogenous vapor source. The analytical solution describing the 2-D soil gas transport was obtained by applying a modified Schwarz-Christoffel mapping method. A partial field validation showed that the developed model provides results (especially in terms of indoor emission rates) in line with the measured data from a case involving a building overlying a layered soil. In further testing, it was found that the new analytical model can very closely replicate the results of three-dimensional (3-D) numerical models at steady state in scenarios involving layered soils overlying homogenous groundwater sources. By contrast, by adopting a two-layer approach (capillary fringe and vadose zone) as employed in the EPA implementation of the Johnson and Ettinger model, the spatially and temporally averaged indoor concentrations in the case of groundwater sources can be higher than the ones estimated by the numerical model up to two orders of magnitude. In short, the model proposed in this work can represent an easy-to-use tool that can simulate the subsurface soil gas concentration in layered soils overlying a homogenous vapor source while keeping the simplicity of an analytical approach that requires much less computational effort.

Role of the source to building lateral separation distance in petroleum vapor intrusion

The adoption of source to building separation distances to screen sites that need further field investigation is becoming a common practice for the evaluation of the vapor intrusion pathway at sites contaminated by petroleum hydrocarbons. Namely, for the source to building vertical distance, the screening criteria for petroleum vapor intrusion have been deeply investigated in the recent literature and fully addressed in the recent guidelines issued by ITRC and U.S.EPA. Conversely, due to the lack of field and modeling studies, the source to building lateral distance received relatively low attention. To address this issue, in this work we present a steady-state vapor intrusion analytical model incorporating a piecewise first-order aerobic biodegradation limited by oxygen availability that accounts for lateral source to building separation. The developed model can be used to evaluate the role and relevance of lateral vapor attenuation as well as to provide a site-specific assessment of the lateral screening distances needed to attenuate vapor concentrations to risk-based values. The simulation outcomes showed to be consistent with field data and 3-D numerical modeling results reported in previous studies and, for shallow sources, with the screening criteria recommended by U.S.EPA for the vertical separation distance. Indeed, although petroleum vapors can cover maximum lateral distances up to 25-30m, as highlighted by the comparison of model outputs with field evidences of vapor migration in the subsurface, simulation results by this new model indicated that, regardless of the source concentration and depth, 6m and 7m lateral distances are sufficient to attenuate petroleum vapors below risk-based values for groundwater and soil sources, respectively. However, for deep sources (>5m) and for low to moderate source concentrations (benzene concentrations lower than 5mg/L in groundwater and 0.5mg/kg in soil) the above criteria were found extremely conservative as the model results indicated that for such scenarios the lateral screening distance may be set equal to zero.

Assessment of biogas production from MBT waste under different operating conditions

In this work, the influence of different operating conditions on the biogas production from mechanically-biologically treated (MBT) wastes is investigated. Specifically, different lab-scale anaerobic tests varying the water content (26-43% w/w up to 75% w/w), the temperature (from 20 to 25°C up to 55°C) and the amount of inoculum have been performed on waste samples collected from a full-scale Italian MBT plant. For each test, the gas generation yield and, where applicable, the first-order gas generation rates were determined. Nearly all tests were characterised by a quite long lag-phase. This result was mainly ascribed to the inhibition effects resulting from the high concentrations of volatile fatty acids (VFAs) and ammonia detected in the different stages of the experiments. Furthermore, water content was found as one of the key factor limiting the anaerobic biological process. Indeed, the experimental results showed that when the moisture was lower than 32% w/w, the methanogenic microbial activity was completely inhibited. For the higher water content tested (75% w/w), high values of accumulated gas volume (up to 150Nl/kgTS) and a relatively short time period to deplete the MBT waste gas generation capacity were observed. At these test conditions, the effect of temperature became evident, leading to gas generation rates of 0.007d(-1) at room temperature that increased to 0.03-0.05d(-1) at 37°C and to 0.04-0.11d(-1) at 55°C. Overall, the obtained results highlighted that the operative conditions can drastically affect the gas production from MBT wastes. This suggests that particular caution should be paid when using the results of lab-scale tests for the evaluation of long-term behaviour expected in the field where the boundary conditions change continuously and vary significantly depending on the climate, the landfill operative management strategies in place (e.g. leachate recirculation, waste disposal methods), the hydraulic characteristics of disposed waste, the presence and type of temporary and final cover systems.