An Illustrated Handbook of LNAPL Transport and Fate in the Subsurface

Executive summary Dense non-aqueous phase liquids (DNAPLs) such as creosote, coal tar, chlorinated solvents and polychlorinated biphenyl oils represent a particular class of soil and groundwater contaminant that exist as a separate liquid phase in the presence of water. DNAPLs come to rest in the subsurface as disconnected blobs and ganglia of liquid referred to as residual DNAPL, and in potentially mobile distributions referred to as pools. The region of the subsurface containing residual and pooled DNAPL is referred to as the source zone. Groundwater flowing through the source zone slowly dissolves the DNAPL, giving rise to aqueous phase plumes of contamination hydraulically down-gradient of the source zone. Some DNAPL compounds are resistant to biodegradation and sorb little; they can therefore give rise to substantial aqueous phase plumes. Other DNAPL compounds are relatively immobile in groundwater and, therefore, are highly retarded relative to the rate of groundwater flow. In unsaturated media, volatile DNAPLs give rise to vapour phase contamination. Because DNAPLs are only slightly soluble in water, DNAPL source zones can persist for many decades and, in some cases, even hundreds of years. Some DNAPLs are highly toxic and even very low concentrations in groundwater or the atmosphere can pose an unacceptable risk to human health or the environment. The fact that DNAPLs are denser than water allows them to migrate to substantial depths below the water table in both unconsolidated deposits and fractured bedrock. Delineating the spatial extent of the DNAPL source zone at a site can be a substantial undertaking, requiring at times several years of investigation and significant financial resources. Remediation strategies are site-specific, with separate approaches often warranted for the DNAPL source zone and its associated aqueous phase plume. There has been limited success in removing all DNAPL from below the water table at sites, particularly in a fractured rock environment. Remediation strategies are therefore often directed towards source zone containment or stabilisation, partial mass removal, plume management or plume interception, within the framework of appropriate risk-management objectives. The purpose of this handbook is to provide a user-friendly overview of the nature of DNAPL contamination in a UK context. It is intended to assist site investigators, site owners and regulators in conducting site investigations, conducting risk assessments and selecting remediation approaches. While this handbook reflects the state-of-the-art at the time of publication, it should be noted that the discipline of groundwater and soil contamination by hazardous organic liquids is evolving continuously and is relatively ‘young’ compared with many other areas of science and engineering. Readers are therefore advised to keep abreast of the new advances in understanding and approaches expected in the foreseeable future.

[1]  Arturo A. Keller,et al.  Effect of spreading coefficient on three‐phase relative permeability of nonaqueous phase liquids , 2003 .

[2]  G. Devaull Indoor vapor intrusion with oxygen-limited biodegradation for a subsurface gasoline source. , 2007, Environmental science & technology.

[3]  T. Gibson,et al.  Limitations of Monitoring Wells for the Detection and Quantification of Petroleum Products in Soils and Aquifers , 1989 .

[4]  David B. McWhorter,et al.  Volume Estimation of Light Nonaqueous Phase Liquids in Porous Media , 1990 .

[5]  Todd H. Wiedemeier,et al.  Technical Protocol for Implementing Intrinsic Remediation with Long-Term Monitoring for Natural Attenuation of Fuel Contamination Dissolved in Groundwater. Volume II. , 1995 .

[6]  H. Mosbaek,et al.  Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark. , 2005, Journal of contaminant hydrology.

[7]  Paul C. Johnson,et al.  Source Zone Natural Attenuation at Petroleum Hydrocarbon Spill Sites—I: Site‐Specific Assessment Approach , 2006 .

[8]  Paul C. Johnson,et al.  Vadose zone natural attenuation of hydrocarbon vapors: An emperical assessment of soil gas vertical profile data , 2001 .

[9]  Jack C. Parker,et al.  Experimental validation of the theory of extending two-phase saturation-pressure relations to three-fluid phase systems for monotonic drainage paths , 1988 .

[10]  T. Sale,et al.  Measurement of LNAPL Flux Using Single‐Well Intermittent Mixing Tracer Dilution Tests , 2012, Ground water.

[11]  David B. McWhorter,et al.  The Behavior of Dense, Nonaqueous Phase Liquids in Fractured Clay and Rock , 1991 .

[12]  S. Thornton,et al.  Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms. , 2009, Journal of contaminant hydrology.

[13]  D. Huntley,et al.  Persistence of LNAPL sources: relationship between risk reduction and LNAPL recovery. , 2002, Journal of contaminant hydrology.

[14]  Michael O. Rivett,et al.  Monitored natural attenuation of organic contaminants in groundwater: principles and application , 2008 .

[15]  Bernard H. Kueper,et al.  A field experiment to study the behavior of tetrachloroethylene in unsaturated porous media , 1992 .

[16]  Kamy Sepehrnoori,et al.  Partitioning Tracer Test for Detection, Estimation, and Remediation Performance Assessment of Subsurface Nonaqueous Phase Liquids , 1995 .

[17]  D. Werner,et al.  The influence of water table fluctuations on the volatilization of contaminants from groundwater , 2002 .

[18]  G. D. Beckett,et al.  Practically impractical - the limits of LNAPL recovery and relationship to risk , 1997 .

[19]  David Redman,et al.  A Field Experiment to Study the Behavior of Tetrachloroethylene Below the Water Table: Spatial Distribution of Residual and Pooled DNAPL , 1993 .

[20]  R. Lenhard,et al.  Measurement and prediction of saturation-pressure relationships in three-phase porous media systems , 1987 .

[21]  W. Shiu,et al.  Illustrated handbook of physical-chemical properties and environmental fate for organic chemicals. Volume 5: pesticide chemicals. , 1992 .

[22]  R. Efroymson,et al.  Role of partitioning in biodegradation of phenanthrene dissolved in nonaqueous-phase liquids. , 1994, Environmental science & technology.

[23]  Paul C. Johnson,et al.  Heuristic model for predicting the intrusion rate of contaminant vapors into buildings , 1991 .

[24]  Thomas E. McHugh,et al.  Remediation Progress at California LUFT Sites: Insights from the GeoTracker Database , 2012 .

[25]  M. Rivett,et al.  Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones. , 2011, Journal of contaminant hydrology.

[26]  Subsurface Book Natural Attenuation Of Fuels And Chlorinated Solvents In The Subsurface , 2016 .

[27]  George G. Vadas,et al.  Aqueous solubility of liquid hydrocarbon mixtures containing dissolved solid components , 1991 .

[28]  B. Kueper,et al.  Numerical Examination of the Factors Controlling DNAPL Migration Through a Single Fracture , 2002, Ground water.

[29]  R. Efroymson,et al.  Biodegradation in soil of hydrophobic pollutants in nonaqueous‐phase liquids (NAPLs) , 1994 .

[30]  J. Cherry,et al.  A Method for Assessing Residual NAPL Based on Organic Chemical Concentrations in Soil Samples , 1991 .

[31]  S F Thornton,et al.  Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer. , 2001, Journal of contaminant hydrology.

[32]  T. Sale,et al.  Use of Single‐Well Tracer Dilution Tests to Evaluate LNAPL Flux at Seven Field Sites , 2012, Ground water.

[33]  D. Durnford,et al.  LNAPL Thickness in Monitoring Wells Considering Hysteresis and Entrapment , 1996 .

[34]  John A. Cherry,et al.  Dense Chlorinated Solvents and other DNAPLs in Groundwater , 1996 .

[35]  K. U. Mayer,et al.  Vadose zone attenuation of organic compounds at a crude oil spill site - interactions between biogeochemical reactions and multicomponent gas transport. , 2010, Journal of contaminant hydrology.

[36]  H. Richnow,et al.  Assessment of MTBE biodegradation in contaminated groundwater using 13C and 14C analysis: Field and laboratory microcosm studies , 2011 .

[37]  J. C. Parker,et al.  Estimation of Free Hydrocarbon Volume from Fluid Levels in Monitoring Wells , 1990 .

[38]  B. Patterson,et al.  Measurement and Modeling of Temporal Variations in Hydrocarbon Vapor Behavior in a Layered Soil Profile , 2005 .

[39]  Paul C. Johnson,et al.  Source Zone Natural Attenuation at Petroleum Hydrocarbon Spill Sites—II: Application to a Former Oil Field , 2006 .

[40]  E. Agency An illustrated handbook of DNAPL transport and fate in the subsurface , 2003 .

[41]  Paul C. Johnson,et al.  Effect of vapor source-building separation and building construction on soil vapor intrusion as studied with a three-dimensional numerical model. , 2005, Environmental science & technology.

[42]  D. Lerner,et al.  Assessing the transport and fate of MTBE-amended petroleum hydrocarbons in the Chalk aquifer, UK. , 2002 .

[43]  D. Lerner,et al.  Sediment filled fractures in the Permo-Triassic sandstones of the Cheshire basin: observations and implications for pollutant transport. , 2001, Journal of contaminant hydrology.

[44]  Andrew J. Kirkman,et al.  Identification and Assessment of Confined and Perched LNAPL Conditions , 2013 .

[45]  J. W. Wallace,et al.  Nonaqueous Phase Hydrocarbon in a Fine‐Grained Sandstone: 2. Effect of Local Sediment Variability on the Estimation of Hydrocarbon Volumes , 1994 .

[46]  Christopher Hook,et al.  Framework for integrating sustainability into remediation projects , 2011 .

[47]  James W. Mercer,et al.  A review of immiscible fluids in the subsurface: properties, models, characterization and remediation , 1990 .

[48]  G. Davis,et al.  A conservative vapour intrusion screening model of oxygen-limited hydrocarbon vapour biodegradation accounting for building footprint size. , 2013, Journal of contaminant hydrology.

[49]  Thomas W. Wietsma,et al.  Behavior of a Viscous LNAPL Under Variable Water Table Conditions , 2006 .

[50]  George DeVaull,et al.  Vapor Intrusion Screening at Petroleum UST Sites , 2013 .

[51]  Larry W. Lake,et al.  Free‐Product Recovery of Petroleum Hydrocarbon Liquids , 2000 .

[52]  Ludger Evers,et al.  A software tool for the spatiotemporal analysis and reporting of groundwater monitoring data , 2014, Environ. Model. Softw..

[53]  R. Baciocchi,et al.  Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation. , 2011, Journal of contaminant hydrology.

[54]  K Hunt,et al.  Environmental Protection Act 1990--Part I. , 1991, Health estate journal : journal of the Institute of Hospital Engineering.

[55]  M. Kemblowski,et al.  Hydrocarbon Thickness Fluctuations in Monitoring Wells , 1990 .

[56]  A. Corey Mechanics of Immiscible Fluids in Porous Media , 1986 .

[57]  D. Huntley,et al.  Nonaqueous Phase Hydrocarbon in a Fine‐Grained Sandstone: 1. Comparison Between Measured and Predicted Saturations and Mobility , 1994 .

[58]  S. Thornton,et al.  Challenges in Monitoring the Natural Attenuation of Spatially Variable Plumes , 2004, Biodegradation.