Mark L. Kram

Complex NAPL Site Characterization Using Fluorescence Part 1: Selection of Excitation Wavelength Based on NAPL Composition

Abstract Fluorescence has been demonstrated to be a viable method for detecting non-aqueous phase liquid (NAPL) contaminants comprised of polycyclic aromatic hydrocarbons (PAHs). Commercially available cone penetrometer (CPT)induced fluorescence based sensor platforms can be used to detect NAPLs such as petroleum oils and lubricants in-situ. In addition, these approaches can be used to detect dense non-aqueous phase liquid (DNAPL) source zones by detecting commingled oils, fuels, and naturally oc curring organic materials entrained by or in solution with DNAPLs and carried to depths below the water table. The currently available CPT-based fluorescence systems are typically restricted to a single wavelength excitation source, each demonstrating specific advantages and disadvantages with respect to detection capabilities for partic ular fluorophores. Several neat NAPLs and mixtures were analyzedfor specificfluores-cence characteristics to determine the optimal excitation source for site characterization efforts. Commercially available cone penetrometer based fluorescence detection systems were ranked according to the potential for likelihood of detection. Our work demon strates that an optimal range of excitation wavelength can be determined for specific fluorophores within NAPL mixtures, and that available systems can be ranked based on the specific contaminant and site characteristics. We have identified optimal excitation sourcesfor a number of common NAPL mixtures, including petroleum-basedfuels and a lubricant mixed with a chlorinated solvent.

Complex NAPL Site Characterization Using Fluorescence Part 2: Analysis of Soil Matrix Effects on the Excitation/Emission Matrix

Abstract Commercially available cone penetrometer (CPT)fluorescence based sensor platforms have been used to detect non-aqueous phase liquids (NAPLs), such as petroleum oils and lubricants, in situf or more than a decade. These approaches have also been used to detect dense non-aqueous phase liquid (DNAPL) source zones by detecting commingled oilsfuels, and naturally occurring organic materials entrained by DNAPLs and carried to depths below the water table. Several neat NAPLs and mixtureswere added to various soil types and analyzedfor specific fluorescence characteristics to determine the optimal excitation source for site characterization efforts. Using excitationlemission matrices (EEMs), we demonstrate that an optimized excitation wavelength can be determinedfor specific fiuowphores within the NAPL mixtures, and that available systems can be ranked based on the specific contaminant and site soil types. An optimal excitation wavelength yields the maximum fluorescence within an EEM spectrum. We ranked commercially available cone penetrometer fluorescence detection systems according to the potential for ease of detection based on maximum fluorescence response. When soils were added tocomplexNAPLmixtures,analytefluorescence emissionwasattenuatedinpreferential portions of the EEM, leading to differences in the optimal excitation source wavelength. Furthermore, impure silica-containing minerals impact the emission signal, potentially leading to incorrect conclusionsf or several commercially available systems. Our find ings suggest that afrequency-agile (e.g., tunable excitation source) probe system would be superior to any other system commercially available, provided the system would be relatively easy to operate and would have rapid in-situ EEM generating capabilitiesfo r optimization in the field.

Complex NAPL Site Characterization Using Fluorescence Part 3: Detection Capabilities for Specific Excitation Sources

Abstract Non-aqueous phase liquid (NAPL) contaminants comprised of polycyclic aromatic hy drocarbons (PAHs) can be detected using fluorescence spectroscopic methods. Dense non-aqueous phase liquid (DNAPL) contaminant source zones can be delineated us ing commercially available cone penetrometer (CPT)devices by detecting commingled oils fuels, and naturally occurring organic materials entrained by DNAPLs and carried to depths below the water table. It has been demonstrated that commercially avail able CPT based fluorescence detection systems can be ranked based on how effectively their excitation source wavelengths induce fluorescence using excitation emission ma trices (EEMs). Several neat NAPLs and dilutions with selected DNAPLs were analyzed for specific fluorescence characteristics to determine the optimal excitation source for site characterization efforts. A comprehensive spectral library and corresponding opti mization matrix were generated for complex petroleum mixtures. Based onfield results documenting successful indirect CPT fluorescence detection of a DNAPL source zone, aviation and dieselfuels were selected from this library, diluted with chlorinated sol vents, and evaluated for fluorescence characteristics. Dilution of these complex NAPL mixtures led to changes in the corresponding EEMs. The optimal excitation source for aviationfuel remained relatively constantf or each dilution. However, sensitivityf or each of the commercially available CPT excitation sources was strongly dependent on diesel concentration, whereby higher energy (lowerwavelength) sources yielded improved sen-sitivityfor lower concentrations. Since field concentrations can be highly variable, these observations support the need for multiple wavelength excitation sources for optimal detection capabilities, particularly when diesel fuel ispresent.

Dynamic Subsurface Explosive Vapor Concentrations: Observations and Implications Republished with permission from Wiley Periodicals, Inc., Remediation , Winter, 2011.

Lorne G. Everett Conventional vapor intrusion characterization efforts can be challenging due to background indoor air constituents, preferential subsurface migration pathways, sampling access, and collection method limitations. While it has been recognized that indoor air concentrations are dynamic, until recently it was assumed by many practitioners that subsurface concentrations did not vary widely over time. Newly developed continuous monitoring platforms have been deployed to monitor subsurface concentrations of methane, carbon dioxide, oxygen, hydrogen sulfide, total volatile organic constituents, and atmospheric pressure. These systems have been integrated with telemetry, geographical information systems, and geostatistical algorithms for automatically generating twoand three-dimensional contour images and time-stamped renderings and playback loops of sensor attributes, and multivariate analyses through a cloud-based project management platform. The objectives at several selected sites included continuous monitoring of vapor concentrations and related physical parameters to understand explosion risks over space and time and to then design a long-term risk reduction strategy. High-frequency data collection, processing, and automated visualization have resulted in greater understanding of natural processes, such as dynamic contaminant vapor intrusion risk conditions potentially influenced by localized barometric pumping. For instance, contemporaneous changes in methane, oxygen, and atmospheric pressure values suggest there is interplay and that vapor intrusion risk may not be constant. As a result, conventional single-event and composite assessment technologies may not be capable of determining worst-case risk scenarios in all cases, possibly leading to misrepresentation of receptor and explosion risks. While dynamic risk levels have been observed in several initial continuous monitoring applications, questions remain regarding whether these situations represent special cases and how best to determine when continuous monitoring should be required. Results from a selected case study are presented and implications derived. Oc 2011 Wiley Periodicals, Inc.