Towards characterizing LNAPL remediation endpoints

Remediating sites contaminated with light non-aqueous phase liquids (LNAPLs) is a demanding and often prolonged task. It is vital to determine when it is appropriate to cease engineered remedial efforts based on the long-term effectiveness of remediation technology options. For the first time, the long term effectiveness of a range of LNAPL remediation approaches including skimming and vacuum-enhanced skimming each with and without water table drawdown was simulated through a multi-phase and multi-component approach. LNAPL components of gasoline were simulated to show how component changes affect the LNAPL\u27s multi-phase behaviour and to inform the risk profile of the LNAPL. The four remediation approaches along with five types of soils, two states of the LNAPL specific mass and finite and infinite LNAPL plumes resulted in 80 simulation scenarios. Effective conservative mass removal endpoints for all the simulations were determined. As a key driver of risk, the persistence and mass removal of benzene was investigated across the scenarios. The time to effectively achieve a technology endpoint varied from 2 to 6 years. The recovered LNAPL in the liquid phase varied from 5% to 53% of the initial mass. The recovered LNAPL mass as extracted vapour was also quantified. Additional mass loss through induced biodegradation was not determined. Across numerous field conditions and release incidents, graphical outcomes provide conservative (i.e. more prolonged or greater mass recovery potential) LNAPL remediation endpoints for use in discussing the halting or continuance of engineered remedial efforts

Towards a digital twin for characterising natural source zone depletion: A feasibility study based on the Bemidji site

Natural source zone depletion (NSZD) of light non-aqueous phase liquids (LNAPLs) may be a valid long-term management option at petroleum impacted sites. However, its future long-term reliability needs to be established. NSZD includes partitioning, biotic and abiotic degradation of LNAPL components plus multiphase fluid dynamics in the subsurface. Over time, LNAPL components are depleted and those partitioning to various phases change, as do those available for biodegradation. To accommodate these processes and predict trends and NSZD over decades to centuries, for the first time, we incorporated a multi-phase multi-component multi-microbe non-isothermal approach to representatively simulate NSZD at field scale. To validate the approach we successfully mimic data from the LNAPL release at the Bemidji site. We simulate the entire depth of saturated and unsaturated zones over the 27 years of post-release measurements. The study progresses the idea of creating a generic digital twin of NSZD processes and future trends. Outcomes show the feasibility and affordability of such detailed computational approaches to improve decision-making for site management and restoration strategies. The study provided a basis to progress a computational digital twin for complex subsurface systems

Quantifying the benefits of in-time and in-place responses to remediate acute LNAPL release incidents

Acute large volume spills from storage tanks of petroleum hydrocarbons as light non aqueous phase liquids (LNAPLs) can contaminate soil and groundwater and may have the potential to pose explosive and other risks. In consideration of an acute LNAPL release scenario, we explore the value of a rapid remediation response, and the value of installing remediation infrastructure in close proximity to the spill location, in effecting greater recovery of LNAPL mass from the subsurface. For the first time, a verified three-dimensional multi-phase numerical framework and supercomputing resources was applied to explore the significance of in-time and in-place remediation actions. A sand aquifer, two release volumes and a low viscosity LNAPL were considered in key scenarios. The time of commencement of LNAPL remediation activities and the location of recovery wells were assessed requiring asymmetric computational considerations. The volume of LNAPL released considerably affected the depth of LNAPL penetration below the groundwater table, the radius of the plume over time and the recoverable LNAPL mass. The remediation efficiency was almost linearly correlated with the commencement time, but was a non-linear function of the distance of an extraction well from the spill release point. The ratio of the recovered LNAPL in a well located at the centre of the spill/release compared to a well located 5 m away was more than 3.5, for recovery starting only 7 days after the release. Early commencement of remediation with a recovery well located at the centre of the plume was estimated to recover 190 times more LNAPL mass than a one-month delayed commencement through a well 15 m away from the centre of the LNAPL plume. Optimally, nearly 40% of the initially released LNAPL could be recovered within two months of commencing LNAPL recovery actions

On quantifying global carbon emission from oil contaminated lands over centuries

Petroleum releases into the subsurface contribute to global soil carbon emissions. Quantifying releases and changes in releases of carbon from soils over the lifetime of a spill is complex. Natural source zone depletion (NSZD) of light non-aqueous phase liquids (LNAPLs) embodies all key mechanisms for transformation to carbon gases and their release from soils including partitioning, transport and degradation of petroleum components. Quantification of the interconnected behaviours of the soil microbiome, fluid flow, multi-component transport, partitioning, and biodegradation is crucial for understanding NSZD. Volatilization from LNAPL, aerobic biodegradation, methanogenesis, and heat production all lead to release of greenhouse gases to the atmosphere. To estimate carbon emissions, using a validated computational platform, we modelled the long term NSZD of four petroleum hydrocarbon types; crude oil, diesel, jet fuel and gasoline, to span the major products used globally. For two soil types, we estimated 150 years of carbon emissions from annual minor and 25 mostly major petroleum hydrocarbon land release incidents since 1950 – with an estimated released mass of ~9 million tonnes across the circumstances considered. Up to 2100 the mass of carbon emitted to the atmosphere is estimated to range from 4 to 6 Teragrams, with nearly 60 % currently released. Nomographs generated help predict the fate of LNAPL plumes and carbon emissions due to NSZD, which is crucially important to management of soil and groundwater contamination. The method provides a basis to include additionally identified and future petroleum releases. It is noted that the petroleum mixture composition, degradation rates, volatilization, and subsurface characteristics all can influence carbon emission estimations

Advective and diffusive gas phase transport in vadose zones: Importance for defining vapour risks and natural source zone depletion of petroleum hydrocarbons

Quantifying the interlinked behaviour of the soil microbiome, fluid flow, multi-component transport and partitioning, and biodegradation is key to characterising vapour risks and natural source zone depletion (NSZD) of light non-aqueous phase liquid (LNAPL) petroleum hydrocarbons. Critical to vapour transport and NSZD is transport of gases through the vadose zone (oxygen from the atmosphere, volatile organic compounds (VOCs), methane and carbon dioxide from the zone of LNAPL biodegradation). Volatilisation of VOCs from LNAPL, aerobic biodegradation, methanogenesis and heat production all generate gas pressure changes that may lead to enhanced gas fluxes apart from diffusion. Despite the importance of the gaseous phase dynamics in the vadose zone processes, the relative pressure changes and consequent scales of advective (buoyancy and pressure driven) / diffusive transport is less studied. We use a validated multi-phase multi-component non-isothermal modelling framework to differentiate gas transport mechanisms. We simulate a multicomponent unweathered gasoline LNAPL with high VOC content to maximise the potential for pressure changes due to volatilisation and to enable the joint effects of methanogenesis and shallower aerobic biodegradation of vapours to be assessed, along with heat production. Considering a uniform fine sand profile with LNAPL resident in the water table capillary zone, results suggest that biodegradation plays the key role in gas phase formation and consequent pressure build-up. Results suggest that advection is the main transport mechanism over a thin zone inside the LNAPL/capillary region, where the effective gaseous diffusion is very low. In the bulk of the vadose zone above the LNAPL region, the pressure change is minimal, and gaseous diffusion is dominant. Even for high biodegradation rate cases, pressure build-up due to heat generation (inducing buoyancy effects) is smaller than the contribution of gas formation due to biodegradation. The findings are critical to support broader assumptions of diffusive transport being dominant in vapour transport and NSZD assessments

Evaluating an analytical model to predict subsurface LNAPL distributions and transmissivity from current and historic fluid levels in groundwater wells: Comparing results to numerical simulations

A recent analytical model predicts free, entrapped, and residual LNAPL saturations and the LNAPL transmissivity in the subsurface from current and historic fluid levels in groundwater wells. As such, the model accounts for effects of fluid level fluctuations in a well. The model was developed to predict LNAPL specific volumes and transmissivities from current fluid level measurements in wells and either recorded historic fluid level fluctuations in wells or estimates. An assumption is made in the model that the predictions are not dependent on whether the historic highest or lowest fluid level elevations in a well occur first. To test the assumption, we conduct two simulations with a modified multiphase flow numerical code TMVOC that incorporates relative permeability-saturation-capillary head relations employed in the model. In one simulation, the initial condition is for fluid levels in a well at the historic highest elevations. In the other simulation, the initial condition is for fluid levels in a well at the historic lowest elevations. We change the boundary conditions so both historical conditions occur followed by generating the current condition. Results from the numerical simulations are compared to model predictions and show the assumption in the analytical model is reasonable. The analytical model can be used to develop/refine conceptual site models and for assessing potential LNAPL recovery endpoints, especially on sites with fluctuating fluid levels in wells

Natural source zone depletion of LNAPL: A critical review supporting modelling approaches

Natural source zone depletion (NSZD) of light non-aqueous phase liquids (LNAPLs) includes partitioning, transport and degradation of LNAPL components. NSZD is being considered as a site closure option during later stages of active remediation of LNAPL contaminated sites, and where LNAPL mass removal is limiting. To ensure NSZD meets compliance criteria and to design enhanced NSZD actions if required, residual risks posed by LNAPL and its long term behaviour require estimation. Prediction of long-term NSZD trends requires linking physicochemical partitioning and transport processes with bioprocesses at multiple scales within a modelling framework. Here we expand and build on the knowledge base of a recent review of NSZD, to establish the key processes and understanding required to model NSZD long term. We describe key challenges to our understanding, inclusive of the dominance of methanogenic or aerobic biodegradation processes, the potentially changeability of rates due to the weathering profile of LNAPL product types and ages, and linkages to underlying bioprocesses. We critically discuss different scales in subsurface simulation and modelling of NSZD. Focusing on processes at Darcy scale, 36 models addressing processes of importance to NSZD are investigated. We investigate the capabilities of models to accommodate more than 20 subsurface transport and transformation phenomena and present comparisons in several tables. We discuss the applicability of each group of models for specific site conditions

The Enigmatic Young Low-Mass Variable TWA 30

TWA 30 is a remarkable young (7+/-3 Myr), low-mass (0.12+/-0.04 Msun), late-type star (M5+/-1) residing 42+/-2 pc away from the sun in the TW Hydrae Association. It shows strong outflow spectral signatures such as [S II], [O I], [O II], [O III], and Mg I], while exhibiting weak Halpha emission (-6.8+/-1.2 Angstroms). Emission lines of [S II] and [O I] are common to T Tauri stars still residing in their natal molecular clouds, while [O III] and Mg I] emission lines are incredibly rare in this same population; in the case of TWA 30, these latter lines may arise from new outflow material colliding into older outflow fronts. The weak Halpha emission and small radial velocity shifts of line emission relative to the stellar frame of rest (generally <=10 km/s) suggest that the disk is viewed close to edge-on and that the stellar axis may be inclined to the disk, similar to the AA Tau system, based on its temporal changes in emission/absorption line strengths/profiles and variable reddening (A_V=1.5-9.0). The strong Li absorption (0.61+/-0.13 Angstroms) and common kinematics with members of the TWA confirm its age and membership to the association. Given the properties of this system such as its proximity, low mass, remarkable outflow signatures, variability, and edge-on configuration, this system is a unique case study at a critical time in disk evolution and planet-building processes.Comment: ApJ in press, 51 pages, 8 tables, 12 figures; converted to preprint style since emulateapj version cut off Tables 4-