Indoor Air Inhalation Risk Assessment for Volatiles Emanating from Light Nonaqueous Phase Liquids

The indoor air inhalation pathway for volatile contaminants in soil and groundwater has received much attention recently. The risk of exposure may be higher when volatile organic compounds (VOCs) reside as constituents of a free product plume below residential or commercial structures than when dissolved in groundwater or adsorbed on soil. A methodology was developed for assessing the potential for vapor phase migration—and associated risk of indoor air inhalation—of volatile constituents from a light nonaqueous phase liquid (LNAPL) plume on top of the water table. The potential risk from inhalation of VOCs in indoor air emanating from a subsurface Jet Fuel 4 (JP-4) plume by hypothetical residential receptors was assessed at a site. Chemicals of concern (COCs) were identified and evaluated using data from the composition of JP-4 mixtures and published chemical, physical, and toxicological data. The method estimates the equilibrium vapor concentrations of JP-4 constituents using Raoult's Law for partial vapor pressure of mixtures based on assumptions about the mixture composition of JP-4. The maximum allowable vapor concentration at the source (immediately above the LNAPL) corresponding to an indoor air target concentration based on acceptable risk levels are calculated using the Johnson and Ettinger model. The model calculates the attenuation factor caused by the migration of the vapor phase VOCs through the soil column above the JP-4 plume and through subsurface foundation slabs. Finally, the maximum allowable soil gas concentrations above the LNAPL for individual constituents were calculated using this methodology and compared to the calculated equilibrium vapor concentrations of each COC to assess the likelihood of potential risk from the indoor air inhalation pathway.     

Importance of Different Volatile Petroleum Hydrocarbon Fractions in Human Health Risk Assessment

Soil vapor data for benzene and four aliphatic and aromatic hydrocarbon fractions from five volatile petroleum hydrocarbon (VPH)-contaminated sites in western Canada were used together with the Canadian Council of Ministers of the Environment (CCME) Canada-Wide Standard for petroleum hydrocarbons to investigate the relative importance of benzene and the different fractions in human health risk assessment. VPH concentrations in soil vapor samples ranged from 4.0 to 4200?mg/m³, of which 0 to 4.6% was BTEX and 90 to 95% was hydrocarbons of the C_5–8 aliphatic fraction. VPH inhalation exposure by an adult receptor in a hypothetical, commercial building was modelled deterministically assuming 16- and 70 year occupational tenures. The magnitude of hazard quotients varied widely between sites, but their hydrocarbon fraction signatures were consistent, and characterized by higher hazard quotients in the C_5–8 and C_9–10 aliphatic and C_9–10 aromatic fractions relative to benzene and the TEX aromatic fraction. This work has shown that the C_5– and C_9–10 aliphatic fractions yield greater relative risk than the commonlyregulated TEX compounds, and that benzene becomes the primary chemical of potential concern only when an occupational tenure approaching 70 years is assumed.     

Prediction of leachate concentrations in petroleum‐contaminated soils

The efficacy of cleanup methods in reducing gasoline contamination at spill sites is typically determined by measuring benzene, toluene, xylene (BTX), and total petroleum hydrocarbon (TPH) concentrations in soil samples. Although these values may provide a direct measurement of soil contamination, they may not be indicative of what is transferred to percolating water. This study addresses this issue by measuring TPH, toluene, m‐ and p‐xylene, and naphthalene levels in gasoline‐contaminated soil columns before and after forced‐air venting and relating these values to the aqueous‐phase concentrations measured when water is percolated through the same columns.

Sandy soils with and without organic matter were packed into glass columns. The soils were brought to residual water and residual gasoline saturations by applying a vacuum to a ceramic pressure plate at the column bottom. Venting was performed by passing clean, moist air through the columns. The columns were subsequently leached under unsaturated conditions.

Soil samples were taken from the bottom of the columns upon completion of the venting or leaching phases of the experiments. Toluene, m‐ and p‐xylene, naphthalene, and TPH values were measured in soil samples extracted with either freon or methanol. Aqueous phase concentrations of these compounds were predicted using measured soil concentrations and either Raoult's law or organic matter‐water and fuel‐water partitioning theory (Boyd and Sun, 1990). The predicted results were compared with measured leachate concentrations from the same columns.

Mole fractions estimated from soil concentrations and TPH values used in Raoult's law gave good predictions of aqueous phase concentrations for compounds that had a high mole fraction in the residual nonaqueous phase liquid (NAPL). For compounds at low concentrations in the residual NAPL, an approach using a distribution coefficient that accounted for both the organic matter and residual NAPL in the soil provided better estimates than those based on Raoult's law.     

A Method for Assessing Leaching Potential for Petroleum Hydrocarbons Release Sites: Multiphase and Multisubstance Equilibrium Partitioning

This article presents the rationale for the mathematical fate and transport model, which has been provided in the accompanying spreadsheet (GWProt). This spreadsheet model may be used as a simple and scientifically defensible regulatory tool for determining the risk-based soil clean up level of petroleum release sites to protect groundwater quality. The model incorporates either a three- or four-phase partitioning equilibrium mechanism, depending on the detection of Non-Aqueous Phase Liquid phase presence mathematically, as well as Raoult's Law convention and default dilution and attenuation factors. A database of contaminant-specific parameters, including solubility and organic-carbon partition-coefficient, molecular weight, and Henry's Law constant, is assembled for benzene, toluene, ethylbenzene, xylenes, and 12 other TPH equivalent carbon fractions. In addition to distributing organic chemicals among aqueous, sorbed solid, air, and NAPL phases, according to traditional partitioning equations, the algorithm incorporates equations for the conservation of mass and volume. A unique solution is obtained by solving a series of mass balance equations simultaneously using the iterative spreadsheet routine built in MICROSOFT EXCEL^TM Solver — with the restrictions that the volume is conserved and the sum of the mole fractions is equal to one. Sample calculations are presented for a range of parameter values to illustrate the use of the model and the relative leach-ability of a wide range of representative fuels. Sensitivity analysis was also performed to quantify the effects of uncertainty in the estimates of the key model parameters on model results. Model predictions were compared with the results from a water-fuel experiment. The noncar-cinogenic Hazard Index (HI) for groundwater through direct ingestion was calculated using predetermined oral reference dose (R_fd) values. Applications and limitations of the model are also discussed.     

Viscosity properties of mineral paraffinic base oils as a key factor in their primary biodegradability

The primary biodegradability of two types of paraffinic base oils (solvent and catalytically dewaxed oils) and their blends was evaluated using the CEC L-33-A-93 test. The biodegradability values varied between 10% and 75%. Base oil mixtures displayed varying contents in aromatic and polar compounds and a wide range of kinematic viscosity (KV) values, from roughly 10 to 600 cSt (at 40°C), while their viscosity indices were almost constant (90-100). The biodegradability of oils was closely related to their content in polycyclic aromatic hydrocarbons and was also decreasing with kinematic viscosity. For the two types of base oils, a linear relationship could be set between the biodegradation percentages and the logarithms of KV values. These results show that, beside overall chemical features such as the contents in aromatic compounds, KV may be a prominent parameter for assessing the primary biodegradability of mineral base oils.     

Emulsifier of Arthrobacter RAG-1: specificity of hydrocarbon substrate.

The purified extracellular emulsifying factor produced by Arthrobacter RAG-1 (EF-RAG) emulsified light petroleum oil, diesel oil, and a variety of crude oils and gas oils. Although kerosine and gasoline were emulsified poorly by EF-RAG, they were converted into good substrates for emulsification by addition of aromatic compounds, such as 2-methylnaphthalene. Neither aromatic nor aliphatic fractions of crude oil were emulsified by EF-RAG; however, mixtures containing both fractions were emulsified. Pure aliphatic or aromatic hydrocarbons were emulsified poorly by EF-RAG. Binary mixtures containing an aliphatic and an aromatic hydrocarbon, however, were excellent substrates for EF-RAG-induced emulsification. Of a variety of alkylcyclohexane and alkylbenzene derivatives tested, only hexyl- or heptylbenzene and octyl- or decylcyclohexane were effectively emulsified by EF-RAG. These data indicate that for EF-RAG to induce emulsification of hydrocarbons in water, the hydrocarbon substrate must contain both aliphatic and cyclic components. With binary mixtures of methylnaphthalene and hexadecane, maximum emulsion was obtained with 25% hexadecane.     

Emulsifier of Arthrobacter RAG-1: specificity of hydrocarbon substrate.

The purified extracellular emulsifying factor produced by Arthrobacter RAG-1 (EF-RAG) emulsified light petroleum oil, diesel oil, and a variety of crude oils and gas oils. Although kerosine and gasoline were emulsified poorly by EF-RAG, they were converted into good substrates for emulsification by addition of aromatic compounds, such as 2-methylnaphthalene. Neither aromatic nor aliphatic fractions of crude oil were emulsified by EF-RAG; however, mixtures containing both fractions were emulsified. Pure aliphatic or aromatic hydrocarbons were emulsified poorly by EF-RAG. Binary mixtures containing an aliphatic and an aromatic hydrocarbon, however, were excellent substrates for EF-RAG-induced emulsification. Of a variety of alkylcyclohexane and alkylbenzene derivatives tested, only hexyl- or heptylbenzene and octyl- or decylcyclohexane were effectively emulsified by EF-RAG. These data indicate that for EF-RAG to induce emulsification of hydrocarbons in water, the hydrocarbon substrate must contain both aliphatic and cyclic components. With binary mixtures of methylnaphthalene and hexadecane, maximum emulsion was obtained with 25% hexadecane.     

Gasoline Vapor Biofiltration

While gasoline vapor emissions are common sources of air pollution, very few results have been published on the biofilter biodegradation of gasoline vapors in flowing waste gases. This investigation reports on a bench‐scale biofilter of an ID of 50 mm and a bed height of 850 mm with an inexpensive fire clay chip medium as a packing material. The biofilter was inoculated with a concentrate of a mixed culture of the common microflora. After an acclimatization period of three weeks, loading tests were carried out at increasing gasoline inlet concentrations at a constant Empty Bed Retention Time (EBRT) of 16 min. Evaluating the removal rate and efficiency of aliphatic and aromatic fractions of the gasoline vapor, it was found that in a range of overall organic loading (OL_TPH) up to 33.6 g/m³ h the removal efficiency of aromatic hydrocarbons decreased from 90 to 70 %, while that of the aliphatic components decreased much more significantly from 60 to 10 % after six months of operation. The removal rate and efficiency achieved for total petroleum hydrocarbons were 13 g/m³ h and 45 %, respectively. The microbial strains and genera of culturable cells in the inoculum and in the biofilm after six months of gasoline degradation were evaluated.     

Aliphatics vs. aromatics hydration thermodynamics

By comparing the hydration thermodynamics of benzene with that of a hypothetical aliphatic hydrocarbon having the same accessible surface area (ASA) of benzene, Makhatadze and Privalov concluded that the whole difference is due to the weak H-bonds that water forms with the aromatic ring. The formation of such H-bonds would be characterized by a negative Gibbs energy change, slightly increasing in magnitude with temperature, and a positive entropy change over a large temperature range. The latter thermodynamic feature is not physically reliable for the formation of H-bonds. In the present article, by using a statistical mechanical dissection scheme of hydration, a microscopic interpretation for the numbers obtained by Makhatadze and Privalov is proposed. The difference in hydration Gibbs energy should be attributed to the different strength of van der Waals interactions that benzene can do with water, owing to the larger polarizability of the aromatic ring with respect to an aliphatic hydrocarbon of equal size. In addition, the difference in hydration entropy should account for the different extent of H-bond reorganization upon the insertion of benzene and the corresponding aliphatic hydrocarbon in water.     

Calculation of phase diagrams for non-ideal mixtures of lipids,and a possible non-random distribution of lipids in lipid mixtures in the liquid crystalline phase

An approach is presented which can simulate phase diagrams for binary mixtures of lipid molecules showing close agreement with experimental data and using a single parameter to describe the non-ideality of mixing in each phase. It is suggested that lipid mixtures form non-ideal mixtures in the liquid crystalline phase. Application of the theory of athermal solutions allows an estimate to be made of the relative distribution of like and unlike lipid molecules about a central lipid molecule.     

Characterization of a Polycyclic Aromatic Hydrocarbon-Degrading Microbial Consortium from a Petrochemical Sludge Landfarming Site

Anthracene, phenanthrene, and pyrene are polycyclic aromatic hydrocarbon (PAHs) that display both mutagenic and carcinogenic properties. They are recalcitrant to microbial degradation in soil and water due to their complex molecular structure and low solubility in water. This study presents the characterization of an efficient PAH (anthracene, phenanthrene, and pyrene)-degrading microbial consortium, isolated from a petrochemical sludge landfarming site. Soil samples collected at the landfarming area were used as inoculum in Warburg flasks containing soil spiked with 250 mg kg^-1 of anthracene. The soil sample with the highest production of CO₂-C in 176 days was used in liquid mineral medium for further enrichment of anthracene degraders. The microbial consortium degraded 48%, 67%, and 22% of the anthracene, phenanthrene, and pyrene in the mineral medium, respectively, after 30 days of incubation. Six bacteria, identified by 16S rRNA sequencing as Mycobacterium fortuitum, Bacillus cereus, Microbacterium sp., Gordonia polyisoprenivorans, two Microbacteriaceae bacteria, and a fungus identified as Fusarium oxysporum were isolated from the enrichment culture. The consortium and its monoculture isolates utilized a variety of hydrocarbons including PAHs (pyrene, anthracene, phenanthrene, and naftalene), monoaromatics hydrocarbons (benzene, ethylbenzene, toluene, and xylene), aliphatic hydrocarbons (1-decene, 1-octene, and hexane), hydrocarbon mixtures (gasoline and diesel oil), intermediary metabolites of PAHs degradation (catechol, gentisic acid, salicylic acid, and dihydroxybenzoic acid) and ethanol for growth. Biosurfactant production by the isolates was assessed by an emulsification index and reduction of the surface tension in the mineral medium. Significant emulsification was observed with the isolates, indicating production of high-molecular-weigh surfactants. The high PAH degradation rates, the wide spectrum of hydrocarbons utilization, and emulsification capacities of the microbial consortium and its member microbes indicate that they can be used for biotreatment and bioaugumentation of soils contaminated with PAHs.     

Energetics of interactions of aromatic hydrocarbons with water

The thermodynamics of transfer of aromatic (benzene, toluene) and aliphatic (ethane, propane, butane) hydrocarbons from the gas phase into water in the temperature range 5–125°C have been analyzed in order to determine the net hydration effect of these compounds. In the case of the aromatic hydrocarbons the enthalpic contribution predominates over the entropic contribution to the Gibbs energy of hydration. This results in a negative value of the hydration Gibbs energy of aromatic hydrocarbons, in contrast to the positive Gibbs energy of hydration of aliphatic hydrocarbons. The different sign of the hydration Gibbs energies indicates that the mechanism causing hydrophobicity of aromatic hydrocarbons has different nature than that causing the hydrophobicity of aliphatic hydrocarbons. The comparison of hydration of aliphatic and aromatic hydrocarbons leads to the following thermodynamic parameters for these additional interactions between the benzene ring and water at 25°C: enthalpy −5.4 kJ/mol, entropy 26.8 J/K mol and Gibbs energy −13.4 kJ/mol. The large enthalpic contribution to the Gibbs energy of hydration of aromatic hydrocarbons probably comes from the ability of the aromatic ring to accept hydrogens from water, forming hydrogen bonds.     

Effect of ewe's milk versus milk-replacer rearing on mineral composition of suckling lamb meat and liver

The effect of ewe's milk versus artificial rearing on the mineral content of suckling lambs muscle and liver was investigated, using a practically non-destructive sampling of carcasses. Mineral content was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES).Significant differences in mineral composition of muscle and liver were observed between the two groups belonging to each type of weaning. In muscle, these differences were mostly detected for Na, Zn and particularly Mn contents. As for the liver's mineral content, significant higher concentrations of K, P and Cu and lower amounts of Zn and Mn were observed in samples from ewe's milk reared lambs, when compared to those from hand reared ones.Results obtained lead to the conclusion that mineral composition of suckling lamb's muscle and liver differed significantly according to the mineral intake of the ingested milk or formula. However, determination of the mineral content of either lambs’ muscle or liver does not seem to provide an accurate and sensible method for discriminating between carcasses from either type of rearing.     

Removal of BTEX compounds by industrial sludge microbes in batch systems: statistical analysis of main and interaction effects

Biodegradation is an effective technique to remediate polluted soil and groundwater. In the present experimental study, a mixed microbial culture obtained from the wastewater treatment sludge of a chemical industry was used to degrade liquid phase benzene, toluene, ethyl benzene, and xylene (BTEX), at individual initial concentrations varying between 15 and 75 mg/l. Experiments were conducted according to 2 ^k−1 fractional factorial design at the low (15 mg/l) and high (75 mg/l) levels of BTEX concentrations, to identify the main and interaction effects of parameters and their influence on biodegradation of individual BTEX compounds in mixtures. The individual removals varied between 16% and 75% when the concentrations of B, T, E, and X were sufficiently low in the mixture. However, both synergistic (removal of ethyl benzene) and antagonistic (removal of benzene) behavior were noticed when the concentrations of toluene and xylene was increased to higher levels. The individual removals were greater than 67% at their center point levels. The total BTEX removal values were later statistically analyzed and based on the Fischer’s variance ratio (F) and Probability values (P) it was observed that the main effects for total BTEX removal were significant than the squared and interaction effects.     

Crude Oil Biodegradation by a Soil Indigenous Bacillus sp. Isolated from Lavan Island

The application of microorganisms for removing crude oil pollution from contaminated sites as a type of bioremediation has long been a matter of study in scientific communities. In this study, 35 morphologically different spore-forming Bacilli were isolated from an oil-contaminated soil in Lavan Island. The objective of this study was to investigate the oil-biodegrading ability of these indigenous bacilli. Therefore, their biosurfactant production, using Du Neuy ring, and the crude oil aliphatic and aromatic content alteration after bacterial treatment, respectively, using gas chromatography and high-performance liquid chromatography, were studied. An isolate with high endurance of a wide range of temperature and pH and optimized growth at 30°C and pH 6.8 that could reduce the surface tension from 60 to 40 mN/m and cause the most alteration in aliphatic and aromatic content of crude oil was selected. Using biochemical and molecular analyses of 16SrRNA, this suitable bacterium for oil biodegradation was characterized as Bacillus cereus sp. 4.     

Evaluation of health risks from a buried mass of diesel fuel before and after bioremediation

Plans are being formulated for in situ bioremediation of a subsurface plume of diesel fuel No. 2 that resulted from an accidental fuel release. Raoult's law and the aqueous solubilities of the toxic components were used to estimate organic contaminant concentrations in leachate from the untreated fuel mass. Carcinogenic risks and noncarcinogenic hazard indices were calculated for undiluted leachate. An 80% decrease in hydrocarbon mass and increases in the average molecular weights of the component fractions were assumed to result from the treatment. Sample calculations are provided to show how to evaluate results of analyses for petroleum hydrocarbons after bioremediation.     

Influence of aromatic hydrocarbons on growth,plant growth promoting activities and survival in soil of Azotobacter chroococcum strain JL104

This study was undertaken to determine the effect of aromatic hydrocarbons on growth and plant growth promoting activities of Azotobacter chroococcum strain JL104. The organism was grown on Jensen’s media without sucrose, supplemented with different concentrations of aromatic hydrocarbons. Azotobacter chroococcum strain JL104 was able to grow in the presence of benzene, toluene, aniline and benzoic acid and was able to utilize these as sole carbon source as well. The culture showed the highest growth in presence of 0.5% concentrations of aniline and benzoic acid and 0.01% concentrations of benzene and toluene. Maximum indole acetic acid (IAA) production and acetylene reduction activity (ARA) were recorded with benzene and benzoic acid, respectively. Among other substituted benzene derivatives such as xylene, p-hydroxybenzoic acid, di-nitrophenol and di-chlorophenol, xylene was observed to be the least toxic and di-nitrophenol the most toxic hydrocarbon. The highest soil survival was found in soil amended with 1% sucrose however, the population of A. chroococccum strain JL104 declined continuously in unamended soil. Amongst various hydrocarbons, 0.1% toluene amended soil supported the maximum survival, indicating it to be least toxic aromatic hydrocarbon carbon in soil.     

Distribution and Volatilization of Organic Compounds Following Uptake by Hybrid Poplar Trees

Hybrid poplar trees were exposed to eleven organic compounds in hydroponic systems. The eleven contaminants were common pollutants with a wide range of physio-chemical properties such as the octanol-water partition coefficient, Henry's constant, vapor pressure, and molecular weight. Contaminants, ¹⁴C-labeled, were introduced into the root zone, and contaminant transport and fate were examined. Aqueous concentrations were monitored throughout each experiment as was vapor phase concentrations in the air stream passing over the leaves. At experiment conclusion, plant tissues were oxidized to determine ¹⁴C concentrations. The uptake, distribution, and volatilization of these contaminants varied greatly among the 11 contaminants in the study. Uptake and translocation of the contaminants ranged from < 0.3% (of the applied ¹⁴C-labeled compound) for 1,2,4-trichlorobenzene to 20% for benzene. Volatile compounds were volatilized from the leaves. Volatilization in the transpiration stream was related to the vapor pressure of the compound. The fate and transport mechanisms investigated in this study provide valuable insight into the potential fate of contaminants in full-scale phytoremediation.