Air distribution in the Borden aquifer during in situ air sparging

A field experiment was conducted at Canadian Forces Base Borden (CFB Borden) to assess the air distribution from a single in situ air sparging injection point. This aquifer consists of fine to medium sand deposited in horizontal layers. The permeability at the study location varied from 10(-10) to 10(-14) m2 and distinct low permeability horizons were present at approximately 1.2, 2.0, and 2.9 m below the water table. Prior to air injection, a 15x15-m portion of the vadose zone was excavated to the water table (approximately 1 m below ground surface) in order to visually observe air release distribution at the water table. The water table was actively maintained 5 cm above the excavated surface. The sparging system operated for a period of 7 days with an injection flow rate of 200 m3/days (5 scfm). The resulting subsurface air distribution was assessed using a variety of techniques including neutron logging, borehole and surface ground penetrating radar, piezometric head measurements, surface visualization, and hydraulic testing. Through this combination of tests, it was demonstrated that variations in permeability and, hence, capillary pressure at the site were sufficient to cause the injected air to spread laterally, forming stratigraphically trapped air pockets beneath the low permeability horizons. The formation of these air pockets eventually resulted in a buildup of capillary pressure that exceeded the air entry pressure and allowed some air to migrate up through the lower permeability layers. Each of the assessment techniques employed generated information at different spatial scales that prevented a direct comparison of the results from the various techniques; however, the results from all techniques proved to be critical in the interpretation of the experimental data. As a consequence, the different assessment techniques should not be viewed as alternatives, but rather as complimentary techniques.     

Converging hydrostatic and hydromechanic concepts of preferential flow definitions

The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10^− 6 m² s^− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θ^K, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θ^K with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θ^G as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θ^G with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θ^K ≈ θ^G ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths.     

Impact of initial and boundary conditions on preferential flow

Preferential flow in soil is approached by a water-content wave, WCW, that proceeds downward from the ground surface. WCWs were obtained from sprinkler experiments with infiltration rates varying from 5 to 40 mm h^− 1. TDR-probes and tensiometers measured volumetric water contents θ(z,t) at seven depths, and capillary heads, h(z,t) at six depths in a column of an undisturbed soil. The wave is characterized by the velocity of the wetting front, c_W, the amplitude, w_S, and the final water content, θ. We tested with uni-variate and bi-variate linear regressions the impacts of initial volumetric water contents, θ_ini, and input rates, q_S, on c_W, w_S and θ.The test showed that θ_ini influenced θ and w_S and q_S effected c_W. The expected proportionality of w_S ≈ qs^1/3 was weak and c_W ≈ qs^2/3 was strong.     

Simulating the fate and transport of TCE from groundwater to indoor air

This work provides an exploratory analysis on the relative importance of various factors controlling the fate and transport of volatile organic contaminants (in this case, TCE) from a DNAPL source zone located below the water table and into the indoor air. The analysis is conducted using the multi-phase compositional model CompFlow Bio, with the base scenario problem geometry reminiscent of a field experiment conducted by Rivett [Rivett, M.O., (1995), Soil–gas signatures from volatile chlorinated solvents: Borden field experiments. Groundwater, 33(1), 84–98.] at the Borden aquifer where groundwater was observed to transport a contaminant plume a substantial distance without vertical mass transport of the contaminant across the capillary fringe and into the vadose zone. Results for the base scenario model indicate that the structure of the permeability field was largely responsible for deflecting the groundwater plume upward towards the capillary fringe, permitting aqueous phase diffusion to transport the TCE into the vadose zone. Alternative permeability realizations, generated as part of a Monte Carlo simulation process, at times deflected the groundwater plume downwards causing the extended thickness of the saturated zone to insulate the vadose zone from exposure to the TCE by upward diffusive transport. Comparison of attenuation coefficients calculated using the CompFlow Bio and Johnson and Ettinger [Johnson, P.C. and Ettinger, R.A., (1991), Heuristic model for predicting the intrusion rate of contaminant vapors into buildings. Environmental Science and Technology, 25, 1445–1452.] heuristic model exhibited fortuitous agreement for the base scenario problem geometry, with this agreement diverging for the alternative permeability realizations as well as when parameters such as the foundation slab fracture aperture, the indoor air pressure drop, the capillary fringe thickness, and the infiltration rate were varied over typical ranges.     

Application of simple soil-water flow models to the transfer of surface-applied solutes to streams

In the context of leaching of surface-applied nitrate fertilizer to runoff, this paper evaluates the performance of five simple predictive models, based upon: (1) field capacity; (2) uniform displacement; (3) wetting front; (4) by-passing (preferential) flow; and (5) soil-water domains. Predicted behaviour and observed on an 85-cm depth soil are compared for leaching depth and outflow response. Predictive success of outflow by the models for 40 monitored rainfall events were: (1) 60%; (2) 52%; and (3) 76%. For the by-passing flow model (4), simple prediction of pedal excess flow (4a) gave a success of 80%; where calculations of the operational volume in preferential flow were involved (4b), variations from 20 to 100% success occurred for a range of operational volumes, the lowest volumes giving the greatest success (4c). The soil-water domain model (5) is a simple, predictive scheme involving the classification of outflow events according to antecedent soil moisture (θ_a); the method uses the mobile: retained water content (θ_r) at 2 bars and field capacity (θ_fc). Using soil-water domains alone was of limited success but when the domains were combined with rainfall intensity, the scheme specified outflow exactly. Thus, for θ_a < θ_r, no soil-water outflow occurred, even at high rainfall intensity; for θ_a >θ_fc outflow always occurred, even at low rainfall intensity and for θ_a >θ_r < θ_fc the simple by-passing model (4a) achieved 100% predictive success. The implications for fertilizer application are discussed.     

Comparison of physical technologies for biomass control in biofilters treating gaseous toluene

Excessive accumulation of biomass within gas-phase biofilters often results in the deterioration of removal performance. Compared with chemical and biological technologies, physical technologies are more effective in removing biomass and inducing less inhibition of the biofilter performance. This study applied different physical technologies, namely, air sparging, mechanical mixing, and washing with water at various temperatures, to remove excess biomass in biofilters treating toluene. Filter pressure drop, removed dry biomass, biofilter performance, and microbial metabolic characteristics were analyzed to evaluate the effectiveness of the methods. Results showed that air sparging was inefficient for biomass removal (1 kg dry biomass/m³ filter), whereas mechanical mixing significantly inhibited removal efficiencies (<30%). Washing of the packing with fluids was feasible, and hot fluids can remove a large amount of biomass. However, hot fluids reduce microbial activity and inhibit removal performance. Washing of the packing with either 20°C or 50°C water showed efficiency as >3 kg dry biomass/m³ filter can be removed at both temperatures with removal efficiencies at approximately 40% after treatment. Finally, different technologies were compared and summarized to propose an optimized strategy of biomass control for industrial biofilters.

Implications: This study is to apply different physical technologies, namely, air sparging, mechanical mixing, and washing with water of different temperatures, to remove the excess biomass in biofilters treating toluene. The filter pressure drop, removed dry biomass, biofilter performance, and microbial metabolic characteristics were all analyzed to evaluate the effectiveness of the methods. The results of this study provide useful information regarding biomass control of industrial biofilters.     

Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Global environmental cycling of γ-HCH and DDT in the 1980s – A study using a coupled atmosphere and ocean general circulation model

A coupled atmosphere–ocean general circulation model, ECHAM5-MPIOM, was used to study the multicompartmental cycling and long-range transport of persistent and semivolatile organics. Multiphase systems in air and ocean are covered by submodels for atmospheric aerosols, HAM, and marine biogeochemistry, HAMOCC5, respectively. The model, furthermore, encompasses 2D surface compartments, i.e. top soil, vegetation surfaces and sea-ice. The total environmental fate of γ-hexachlorocyclohexane (γ-HCH, lindane) and dichlorophenyltrichloroethane (DDT) in agriculture were studied.DDT is mostly present in the soils, the water-soluble γ-HCH in soils and ocean. DDT has the longest residence time in almost all compartments. Quasi-steady state with regard to substance accumulation is reached within a few years in air and vegetation surfaces. In seawater the partitioning to suspended and sinking particles contributes to the vertical transport of substances. On the global scale deep water formation is, however, found to be more efficient. Up to 30% of DDT but only less than 0.2% of γ-HCH in seawater are stored in particulate matter.On the time scale studied (1 decade) and on global scale substance transport in the environment is determined by the fast atmospheric circulation. The meridional transport mechanism, for both compounds, is significantly enhanced by multi-hopping. Net meridional transport in the ocean is effective only regionally, mostly by currents along the western boundaries of Africa and the Americas. The total environmental burdens of the substances experience a net northward migration from their source regions, which is more pronounced for DDT than for γ-HCH. Due to the application distribution, however, after 10 years of simulation 21% of the global environmental burden of γ-HCH and 12% of DDT have accumulated in the Arctic.     

Global baseline pollution studies XI: Congener specific determination of polychlorinated biphenyls (PCB) and occurrence of alpha- and gamma-hexachlorocyclohexane (HCH), 4,4′-DDE and 4,4′-DDT in continental air

The hexachlorocyclohexane-isomers (HCH), hexachlorobenzene (HCB), the polychlorinated biphenyls (PCB), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (4,4′-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (4,4′-DDE) have been measured in urban and rural air around the city of Ulm (F. R. G., 48.4° N, 10.0° E). The sampling stations are typical for continental air in the westerlies of the northern hemisphere including local and regional influences. The analytical method consists of adsorptive sampling of large volumes (1000 m³) of air on silica gel, solvent desorption with CH₂Cl₂, preseparation of the collected chlorinated C₆/C₁₄ hydrocarbons by liquid adsorption chromatography on silica gel, and high resolution capillary gas chromatography with electron capture-(HRGC/ECD) or mass-selective detection (HRGC/MSD). The concentrations found in the lower troposphere under different meteorological conditions reflect regional input and long range transport. The levels found range from 1 pg/m³ for 4,4′-DDT to 10 ng/m³ for gamma HCH.     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

A field trial to assess the performance of CO2-supersaturated water injection for residual volatile LNAPL recovery

A pilot scale field trial was conducted to evaluate the recovery of volatile, light non-aqueous phase liquids (LNAPLs) using a novel remediation method termed supersaturated water injection (SWI). SWI uses a patented technology to efficiently dissolve high concentrations of CO₂ into water at elevated pressures. This water is injected into the subsurface resulting in the nucleation of CO₂ bubbles at and away from the injection point. The nucleating bubbles coalesce, rise and volatilize residual LNAPL ganglia. In this study, an LNAPL composed of 103 kg of volatile pentane and hexane, and 30 kg of non-volatile Soltrol was emplaced below the water table at residual saturation. The SWI technology removed 78% of the pentane and 50% of the less volatile hexane. Contaminant mass was still being removed when the system was shut down for practical reasons. The mass removed is comparable to that expected for air sparging but a much smaller volume of gas was injected using the SWI system.     

Carbonyl products of the gas-phase reaction of ozone with 1-alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas-phase reaction of ozone with the 1-alkenes (RCH = CH 2) 3-methyl-l-butene (R = i-propyl), 4-methyl-l-pentene (R = i-butyl), 3-methyl-l-pentene (R= s-butyl), 3,3-dimethyl-l-butene (R = t-butyl) and styrene (R = C₆H₅) at ambient T and p = 1 atm of air. Sufficient cyclohexane was added to scavenge OH in order to minimize reactions of OH with the alkenes and with their carbonyl products. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃ + RCH = CH₂ → α(HCHO + RCHOO) + (1 - α) (H₂COO + RCHO), where formaldehyde and RCHO are the primary carbonyls and H₂COO and RCHOO are the biradicals. Measured sums of the primary carbonyl formation yields were 1.006 ± 0.053 (1 S.D.) for formaldehyde + methylpropanal from3-methyl-l-butene(α = 0.494 ± 0.049), 1.025 ± 0.017 for formaldehyde + 2-methylbutanal from 3-methyl-l-pentene (α = 0.384 ± 0.013),1.147 ± 0.050 for formaldehyde + 3-methylbutanal from 4-methyl-l-pentene (α = 0.384 ± 0.020), 0.986 ± 0.014 for formaldehyde + 2,2-dimethylpropanal from 3,3-dimethyl-l-butene (α = 0.320 ± 0.012) and 0.980 ± 0.086 for formaldehyde + benzaldehyde from styrene (α = 0.347 ± 0.059). Carbonyls other than the primary carbonyls were identified; formation pathways are proposed that involve subsequent reactions of the monosubstituted biradicals RCHOO. Similarities and differences between branched-chain 1-alkenes and n-alkyl-substituted 1-alkenes are discussed.     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Particle size distribution of airborne Aspergillus fumigatus spores emitted from compost using membrane filtration

Information on the particle size distribution of bioaerosols emitted from open air composting operations is valuable in evaluating potential health impacts and is a requirement for improved dispersion simulation modelling. The membrane filter method was used to study the particle size distribution of Aspergillus fumigatus spores in air 50 m downwind of a green waste compost screening operation at a commercial facility. The highest concentrations (approximately 8 × 10⁴ CFU m⁻³) of culturable spores were found on filters with pore diameters in the range 1–2 μm which suggests that the majority of spores are emitted as single cells. The findings were compared to published data collected using an Andersen sampler. Results were significantly correlated (p < 0.01) indicating that the two methods are directly comparable across all particles sizes for Aspergillus spores.     

Declining levels of PCB, HCB and p,p′-DDE in adipose tissue from food producing bovines and swine in Sweden 1991–2004

The official control programme for organochlorine (OC) contaminants in food producing animals in Sweden was used to study temporal and spatial trends of the polychlorinated biphenyl CB 153, hexachlorobenzene (HCB) and p,p′-DDE in adipose tissue from bovines and swine 1991–2004. Our results show that efforts to decrease OC contamination of animal feed and the environment have had a positive impact on the contamination of the animal production. OC concentrations declined significantly in almost all studied regions of Sweden. OC temporal trends were slower in bovines (6–8% per year) than in swine (10–12%). Power analyses showed that data from more than 10 years of sampling were needed for a detection of an annual OC level change of 5% in both species in the control programme, due to large within- and between-year variation in OC levels. CB 153 and p,p′-DDE levels were higher in southern than in northern Sweden. Levels decreased with age in milk cows, but not in young nulliparous cows (heifers) and bulls. Moreover, milk cows and bulls had significantly lower OC levels than heifers. Levels were not age-dependent among swine, but castrated male swine (barrows) had significantly lower OC levels than young female swine (gilts). Levels of the studied OCs are now in many cases below the LOQ of the analytical method used. Future time trend studies of these OCs thus depend on lowered LOQs in the control programme.     

Regional differences of column-related aerosol parameters in Germany

With the development of satellite experiments supplementary and validating ground-based measurements are gaining growing importance for the inference and evaluation of radiation-related aerosol parameters. Both kinds of measurements have been conducted and interpreted mainly under globally or locally restricted aspects for a limited time period only. Results are presented from four rural regions (coastal zone, lowlands, highlands, high mountain); they are column-related aerosol parameters, deduced from monitoring programs of spectral aerosol optical depth (AOD) as well as almucantar sky irradiance measurements. After 13 years of continuous measurements of trends and variations in aerosol optical depths, these results are based on 5 years of data collection (1994–1998). There are significant differences among the parameters of the four regions when related to the inversion method of the AOD spectra. A clear interdependence was found between all column-related parameters and the real part of the refractive index, which in turn depends on the chosen retrieval method. The differences among the four regions are characterized mainly by their different altitudes, with relative humidity being responsible for their internal variation. An increase in the relative humidity from 35 to 55–60% influences the most interesting parameters such as refractive index (real part), hemispheric backscattered fraction b, and direct radiative forcing ΔF as follows: The real part of the refractive index decreases from 1.6±0.05 to 1.42±0.04, b decreases by 8–10%, and, due to the increase in AOD, ΔF increases by about 20% in the spectral region 0.4–1.0 μm. The quantities of the parameters depend on the retrieval methods too.     

Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

Modeling of air sparging of VOC-contaminated soil columns

Air sparging is a remediation technology currently being applied for the restoration of sites contaminated with volatile organic compounds (VOCs). Attempts have been made by various researchers to model the fate of VOCs in the gas and liquid phase during air sparging. In this study, a radial diffusion model with an air–water mass transfer boundary condition was developed and applied for the prediction of VOC volatilization from air sparging of contaminated soil columns. The approach taken was to use various parameters such as mass transfer coefficients and tortuosity factors determined previously in separate experiments using a single air channel apparatus and applying these parameters to a complex system with many air channels. Incorporated in the model, is the concept of mass transfer zone (MTZ) where diffusion of VOCs in this zone was impacted by the volatilization of VOCs at the air–water interface but with negligible impact outside the zone. The model predicted fairly well the change in the VOC concentrations in the exhaust air, the final average aqueous VOC concentration, and the total mass removed. The predicted mass removal was within 1% to 20% of the actual experimental mass removed. The results of the model seemed to suggest that air-sparged soil columns may be modeled as a composite of individual air channels surrounded by a MTZ. For a given air flow rate and air saturation, the VOC removal was found to be inversely proportional to the radius of the air channel. The approach taken provided conceptual insights on mass transfer processes during air sparging operations.