Evidence for Instantaneous Oxygen-Limited Biodegradation of Petroleum Hydrocarbon Vapors in the Subsurface

Petroleum hydrocarbon vapors biodegrade aerobically in the subsurface. Depth profiles of petroleum hydrocarbon vapor and oxygen concentrations from seven locations in sandy and clay soils across four states of Australia are summarized. The data are evaluated to support a simple model of biodegradation that can be used to assess hydrocarbon vapors migrating toward built environments. Multilevel samplers and probes that allow near‐continuous monitoring of oxygen and total volatile organic compounds (VOCs) were used to determine concentration depth profiles and changes over time. Collation of all data across all sites showed distinct separation of oxygen from hydrocarbon vapors, and that most oxygen and hydrocarbon concentration profiles were linear or near linear with depth. The low detection limit on the oxygen probe data and because it is an in situ measurement strengthened the case that little or no overlapping of oxygen and hydrocarbon vapor concentration profiles occurred, and that indeed oxygen and hydrocarbon vapors were largely only coincident near the location where they both decreased to zero. First‐order biodegradation rates determined from all depth profiles were generally lower than other published rates. With lower biodegradation rates, the overlapping of depth profiles might be expected, and yet such overlapping was not observed. A model of rapid (instantaneous) reaction of oxygen and hydrocarbon vapors compared to diffusive transport processes is shown to explain the important aspects of the 13 depth profiles. The model is simply based on the ratio of diffusion coefficients of oxygen and hydrocarbon vapors, the ratio of the maximum concentrations of oxygen and hydrocarbon vapors, the depth to the maximum hydrocarbon source concentration, and the stoichiometry coefficient. Whilst simple, the model offers the potential to incorporate aerobic biodegradation into an oxygen‐limited flux‐reduction approach for vapor intrusion assessments of petroleum hydrocarbon compounds.     

Macro- and Micro-Purge Soil-Gas Sampling Methods for the Collection of Contaminant Vapors

Purging influence on soil‐gas concentrations for volatile organic compounds (VOCs), as affected by sampling tube inner diameter and sampling depth (i.e., system volume) for temporary probes in fine‐grained soils, was evaluated at three different field sites. A macro‐purge sampling system consisted of a standard, hollow, 3.2‐cm outer diameter (OD) drive probe with a retractable sampling point attached to an appropriate length of 0.48‐cm inner diameter (ID) Teflon^® tubing. The macro‐purge sampling system had a purge system volume of 24.5 mL at a 1‐m depth. In contrast, the micro‐purge sampling systems were slightly different between the field sites and consisted of a 1.27‐cm OD drive rod with a 0.10‐cm ID stainless steel tube or a 3.2‐cm OD drive rod with a 0.0254‐cm inner diameter stainless steel tubing resulting in purge system volumes of 1.2 and 7.05 mL at 1‐m depths, respectively. At each site and location within the site, with a few exceptions, the same contaminants were identified in the same relative order of abundances indicating the sampling of the same general soil atmosphere. However, marked differences in VOC concentrations were identified between the sampling systems, with micro‐purge samples having up to 27 times greater concentrations than their corresponding macro‐purge samples. The higher concentrations are the result of a minimal disturbance of the ambient soil atmosphere during purging. The minimal soil‐gas atmospheric disturbance of the micro‐purge sampling system allowed for the collection of a sample that is more representative of the soil atmosphere surrounding the sampling point. That is, a sample that does not contain an atmosphere that has migrated from distance through the geologic material or from the surface in response to the vacuum induced during purging soil‐gas concentrations. It is thus recommended that when soil‐gas sampling is conducted using temporary probes in fine‐grained soils, the sampling system use the smallest practical ID soil‐gas tubing and minimize purge volume to obtain the soil‐gas sample with minimal risk of leakage so that proper decisions, based on more representative soil‐gas concentrations, about the site can be made.     

Subsurface Venting of Vapors Emanating from Hydrocarbon Product on Ground Water

The results of an API-sponsored pilot-scale subsurface venting system study are presented. The purpose of this study was to evaluate the effectiveness of forced venting techniques in controlling and removing hydrocarbon vapors from a subsurface formation. Both qualitative and quantitative sampling and analytical procedures were developed to measure hydrocarbon vapors extracted from the soil. Vapor recovery and equivalent liquid product recovery rates were measured at each test cell evacuation rate.
Two identical test cells were installed. Each cell contained 16 vapor monitoring probes spaced at distances from 4 to 44 feet from a vapor extraction (vacuum) well. Each cell was also configured with two air inlet wells to allow atmospheric air to enter the subsurface formation. The vapor monitoring probes were installed at three discrete elevations above the capillary zone. In situ vapor samples were obtained periodically from these probes to measure changes in vapor concentration and composition while extracting vapors from the vacuum well at three different flow rates (18.5 scfm, 22.5 scfm and 39.8 scfm). In situ vapor samples were analyzed using a portable gas chromatograph to quantify and speciate the vapors. Vacuum levels were also measured at each vapor sampling probe and at the vacuum well.
The soil venting techniques evaluated during this study offer an alternative approach for controlling and eliminating spilled or leaked hydrocarbons from sand or gravel formations of high porosity and moderate permeability. These techniques may also be used to augment conventional liquid recovery methods. The data collected during this study will be useful in optimizing subsurface venting systems for removing and controlling hydrocarbon vapors in soil. Study results indicate pulsed venting techniques may offer a cost-effective means of controlling or eliminating hydrocarbon vapors in soil.     

Procedures for Sampling Deep Subsurface Microbial Communities in Unconsolidated Sediments

A corehole sampling project utilizing a wireline coring system provided sediment samples for microbiological characterization from deep unconsolidated sediments. Sampling tools were developed or modified to minimize contamination during sample acquisition and to facilitate stringent decontamination requirements. Quality assurance procedures, including the use of tracers, were implemented to minimize and quantify contamination from drilling hardware, drilling fluids and sample processing. Tracers included microspheres, potassium bromide, rhodamine dye, and perfluorocarbons, which enabled the detection and measurement of 1mg of drilling fluid per kg of sediment. In addition, sample processing was performed on-site in an anaerobic chamber to prevent exposure of the subsurface materials to atmospheric oxygen concentrations. Sediment samples were then disbursed to investigators at National Laboratories and universities funded through the Department of Energy Subsurface Science Microbiology Program for microbiological characterization. Results of these efforts demonstrated that representative subsurface samples were collected and disbursed.     

Sampling Method for the Determination of Total Inorganic Carbon (TIC) in Strongly Acidic Waters

Samples from extremely acidic waters should be taken using the introduced syringe technique avoiding atmospheric contact to minimize CO2 evaporation from the samples. The syringe technique inclusive manual injection enables the determination of TIC in acid waters with high precision and accuracy. If a TOC analyser with a small sample volume is used, the vials should be filled directly inside the water sampler without air bubbles, covered with aluminium foil and transported at ambient water temperatures. If an autosampler is used, partial selection of the vials increases the stability of the results. Care should be taken that samples can be analysed within a short time.     

Field Sampling of Residual Aviation Gasoline in Sandy Soil

Two complementary field sampling methods for the determination of residual aviation gasoline content in the contaminated capillary fringe of a fine, uniform, sandy soil were investigated. The first method featured field extrusion of core barrels into pint-size Mason jars, while the second consisted of laboratory partitioning of intact stainless steel core sleeves. The barrel extrusion procedure involved jar headspace sampling in a nitrogen-filled glove box, which delineated the 0.7m thick residually contaminated interval for subsequent core sleeve withdrawal from adjacent boreholes. Soil samples removed from the Mason jars (in the field) and sleeve segments (in the laboratory) were subjected to methylene chloride extraction and gas chromatographic analysis to compare their aviation gasoline content. The barrel extrusion sampling method yielded a vertical profile with 0.10m resolution over an essentially continuous 5.0m interval from the ground surface to the water table. The sleeve segment alternative yielded a more resolved 0.03m vertical profile over a shorter 0.8m interval through the capillary fringe. The two methods delivered precise estimates of the vertically integrated mass of aviation gasoline at a given horizontal location, and a consistent view of the vertical profile as well. In the latter regard, a 0.2m thick lens of maximum contamination was found in the center of the capillary fringe, where moisture filled all voids smaller than the mean pore size. The maximum peak was resolved by the core sleeve data, but was partially obscured by the barrel extrusion observations, so that replicate barrels or a half-pint Mason jar size should be considered for data supporting vertical transport analyses in the absence of sleeve partitions.     

Evaluation of Subsurface Oxygen Sensors for Remediation Monitoring

Continuous remediation monitoring using sensors is potentially a more effective and inexpensive alternative to current methods of sample collection and analysis. Gaseous components of a system are the most mobile and easiest to monitor. Continuous monitoring of soil gases such as oxygen, carbon dioxide, and contaminant vapors can provide important quantitative information regarding the progress of bioremediation efforts and the area of influence of air sparging or soil venting. Laboratory and field tests of a commercially available oxygen sensor show that the subsurface oxygen sensor provides rapid and accurate data on vapor phase oxygen concentrations. The sensor is well suited for monitoring gas flow and oxygen consumption in the vadose zone during air sparging and bioventing. The sensor performs well in permeable, unsaturated soil environments and recovers completely after being submerged during temporary saturated conditions. Calibrations of the in situ oxygen sensors were found to be stable after one year of continuous subsurface operation. However, application of the sensor in saturated soil conditions is limited. The three major advantages of this sensor for in situ monitoring arc as follows: (1) it allows data acquisition at any specified time interval; (2) it provides potentially more accurate data by minimizing disturbance of subsurface conditions; and (3) it minimizes the cost of field and laboratory procedures involved in sample retrieval and analysis.     

Measurement of Carbon Dioxide in Soil Gases for Indication of Subsurface Hydrocarbon Contamination

A preliminary field evaluation of a new application of soil-gas measurement for delineation of subsurface organic contamination is described. The method measures carbon dioxide concentrations in soil gases and is based on the hypothesis that carbon dioxide concentrations from subsurface oxidation of organic compounds will be porportional to the extent of organic contamination. A correlation coefficient (r) of 0.81 (n=6) was observed between ground water dissolved organic carbon ground water concentrations and carbon dioxide concentrations in the overlying soil gases at one site. Soil-gas carbon dioxide concentrations measured ranged from 0.09 percent to 0.45 percent.     

Evaluation of Subsurface Structure at Soultz Hot Dry Rock Site by the AE Reflection Method in Time-frequency Domain

—?Because the Soultz Hot Dry Rock (HDR) site, France, is to be expanded to a scientific pilot plant of greater depth, measurement of the deep area below the predeveloped artificial reservoir is gaining importance. In this paper, we present estimates of deep subsurface structure at the Soultz HDR site, obtained by a reflection method using acoustic emission (AE) signals, that is, induced seismicity, as the wave source. First, we briefly describe the AE reflection method in the time-frequency domain with wavelet transform. Then we show estimates of the subsurface structure by using 101 high-energy AE events observed in 1993. We compare and discuss the results obtained, using the AE reflection method in two wells with other independent borehole observations. Furthermore, we present the results of an investigation of the frequency dependence of reflectors identified by hodogram linearity as a possible means of further characterizing detected structures.     

地下流体化学动态频谱分析及应用初探

地震观测数据受各种周期性因素影响,其动态曲线表现为周期性变化特征,是大小不同的周期和非周期因素相互作用的结果。利用MATLAB工具包编程幅频分析和滤波程序,以福州乌鸦咀泉水氧的模拟观测数据为例。对其幅频谱特征和震例进行初步探讨。     

Soil-Gas Surveying for Subsurface Gasoline Contamination Using Total Organic Vapor Detection Instruments Part I. Theory and Laboratory Experimentation

Factors influencing the response of total organic vapor detection instruments used in soil-gas surveying for subsurface gasoline leakage were investigated through performing theoretical assessments and laboratory experiments. Theoretical assessments indicate that total organic vapor measurements will depend on response conditions and the relative concentration of constituents in soil gas, in addition to absolute constituent levels. Laboratory tests conducted using flame ionization, photoionization and explosimeter devices indicated that conditions influencing their responses included instrument flow rate and soil-air permeability when performing direct-probe sampling; the linear range of the instrument; the multicomponent nature of gasoline vapors; and levels of oxygen, nitrogen, carbon dioxide and relative humidity in soil air. If an instrument's response to these conditions is not taken into account, survey results may be misleading. To circumvent adverse instrument responses, a serial dilution technique is presented.     

A Method for Installing Miniature Multilevel Sampling Wells

Abstract. A method has been developed to install miniature multilevel ground-water sampling wells in shallow, unconsoli-dated aquifers at sites without truck access. An advantage of these wells over the traditional bundle-type multilevel is that this type of installation causes minimal aquifer disturbance. Thus, miniature multilevels can be installed while a tracer test is in progress. Furthermore, only hand tools are needed in the field, and equipment and materials are easily obtained and inexpensive. The time required for installation is comparable to other methods.     

Eine mathematische Methode zur Durchführung von Adsorptionsanalysen A Mathematical Method for Evaluation of Adsorption Analysis

Adsorption analysis is a method for describing an overall isotherm of a mixture of unknown composition such as natural organic substances or chemical industries wastewater by dividing into fictive components of different adsorbability. The adsorption behaviour of the fictive components is characterized by using the Freundlich isotherm. The competitive adsorption between these components is described by the Ideal Adsorbed Solution Theory (IAST). Usually, at given Freundlich parameters K and n, the initial concentrations of the fictive components must be adjusted in order to obtain a good fit between calculated and measured isotherm data points. The results of this adjustment depend to some extent on the minimization criteria. Previously, the modeling was done with empirical or numerical methods which required a lot of computation time and sometimes caused numerical problems which made the interpretation of the results difficult. This paper describes a mathematical method for the evaluation of isotherms by adsorption analysis.     

Field Evaluation of Arid Soils Wetting Pattern in Subsurface Drip Irrigation Scheme

A field study evaluating wetted radius (Wr), downward depth (Dd), and upward movement (Um) under different emitter discharges and lateral depths was conducted. Four emitter discharges (2, 4, 8, and 16 L/h) and four lateral depths (0, 10, 20, and 30 cm) were tested in a clay loam soil. Relationships were found between the emitter discharge and lateral depth versus Wr, Dd, and Um. Wetting area at the surface occurs under different emitter discharges and lateral depths except at 30 cm lateral depth. At lateral depth of 0 and 10 cm, Wr and emitter discharge were positively correlated. The Dd was not affected by emitter discharge except for laterals installed at 20 cm depth. At 30 cm lateral depth, the correlations between each of Wr, Um, and Dd with emitter discharge were poor. The ratios of Wr/Dd and Um/Dd, with respect to emitter position, were less than unity over different emitter discharges and lateral depths. These results shed some light on the design of subsurface drip irrigation scheme so that the spacing between emitters should be determined based on the lateral depths and discharge of emitters. Evaporation losses were negligible for the 30‐cm‐lateral depth since the upward moisture movement has not reached the soil surface area at all discharge rates tested in the study.     

A Novel Concept for the Removal of Solvent Vapors from Exhaust Air

The emission of large amounts of solvent vapors with exhaust air from industrial production into the environment is a serious problem. In Germany, industry‐sector‐specific threshold values are applied and technical measures for pollution reduction are required. Different techniques for exhaust air cleaning are in use but still posing problems concerning costs and reliability. For these reasons, the development of processes for exhaust air treatment is the subject of the current research. A new concept for exhaust air cleaning is introduced that combines absorption of a solvent vapor by an organic fluid and a subsequent adsorption by a molecular sieve placed in the absorber. It was managed to close the loops of solvent recovery and sorbents regeneration. In laboratory‐scale experiments it was possible to reduce an initial ethylacetate pollution of 800 mg/m³ or 349 mg C/m³ below the limit value of 75 mg C/m³ over 60 h duration. Thermogravimetric measurements assisted to define optimum conditions for solvent recovery at 180°C from the molecular sieve. One unexpected positive finding was the considerable increase in the solvent release in the presence of the absorption fluid while adsorption isotherms revealed first insight into this process.     

Adsorption Behaviour of Low-Biodegradable Organics on Activated Carbon Surfaces

Adsorption isotherms of various low-biodegradable aromatic compounds on two different activated carbons were determined experimentally and described by FREUNDLICH-type isotherm equations. The equilibrium solid loadings derived from the measurements correlate reasonably well with the adsorbent surface areas and show decreasing values in the order 3-nitro-aniline ～ 4-chloroaniline > 3.5-dinitrobenzoic acid < phenylurea. Kinetic experiments in a differential column batch reactor were conducted in order to evaluate liquid-phase mass transfer and intraparticle diffusion parameters. The homogeneous surface diffusion model could be successfully applied for calculating surface diffusivities and predicting experimental concentration/time profiles.