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‘rvionmenal Potton, Vol 98, No. 2, pp. 239-252, 1997 101998 Elsevier Science Lid’ All igh reserved Printed i Great Brin PUt: $0269-7491(97)00126-7 0268°709/97 1700+ 0.00 cisevien MULTI-PHASE PARTITIONING AND CO-SOLVENT EFFECTS FOR POLYNUCLEAR AROMATIC HYDROCARBONS (PAH) IN AUTHENTIC PETROLEUM- AND CREOSOTE-CONTAMINATED SOILS Michael G. Zemanek," Simon J. T. Pollard,’ Sandra L. Kenefick® and Steve E. Hrudey™ “Contaminated Sites Decommissioning Branch, Chemicals Assessment and Management Division, Alberta Environmental Protection, 9820 - 106 Street, Edmonton, Alberta, Canada, TSK 26 ‘Environmental Strategy Directorate, Scoutish Environment Protection Agency, Head Office, Erskine Court The Castle Business Park, Stirling FK9 4TR, Scotland, UK “Beo-Research Chair in Environmental Risk Management, Environmental Health Program, Department of Public Health Sciences, Faculty of Medicine, University of Alberta, Edmonton, Alberta, Canada, T6G 263 (Received 20 July 1997; accepted | September 1997) Abstract because these compounds are persistent in the environ- The residual oil phase, present at substantial levels in ment, they exhibit documented carcinogenic, mutagenic hydrocarbon-contaminated soils, was found to be the and toxic effects, and because stringent assessment cri- principal medium for retention of polynuclear aromatic teria have been developed for their control (Hrudey and ‘hydrocarbons (PAH). Using authentic petroleum and Pollard, 1993), PAH are well-recognised as constituents creosote-contaminated soils containing 2-6% w/w solvent of hydrocarbon oils. Because they are non-polar and extractable matter, individual PAH were shown to exist hydrophobic, they reside primarily in the residual oil in the oil phase at values between 84 and 95% w|w of the phase at these sites, although they may partition to total mass of each compound in the system, with the other organic phases such as soil organic matter (SOM). exception of naphthalene (70% w/w). Evaluation of the An understanding of the behaviour and distribution of hase partitioning of PAH in creosote-contaminated soil hazardous components within the oil-soil-water matrix confirmed that PAH were predominantly in the creosote at oil-contaminated sites is fundamental to evaluating oil phase, with substantially lower proportions associated human, animal and plant exposures and risks, for pre- with soil organic matter and soil water. In the aqueous dicting air, soil and groundwater conditions and ulti Phase, solubility enhancement was observed for PAH with mately for selecting remediation strategies (Sims, 1990; the degree of enhancement more evident for the hydro- Pollard et al., 1992). phobic PAH. A normalised solubility enhancement factor The distribution of individual PAH between oil, soil ESF’) was derived to illustrate the combined effect of and water can be predicted by extending the isotherm increased PAH solubility in the aqueous phase. Values of models developed for two-phase systems to the three log ESF’ varied from ~4.97 (naphthalene) 10 0.09 (ben- phase ‘oil-soil-water system’ encountered at oil-con- z0/zhiJperylene). The findings suggest limitations exist taminated sites. The relative concentrations of PAH {for successful remediation of PAH contamination in the between each of the three distinet phases provides an soils evaluated and indicate that the focus of remedia- explicit measure of the propensity for PAH to exist in tion must be on the residual oil phase if total PAH are each phase and yields information for predicting treat- 10 be removed. © 1998 Elsevier Science Lid. All rights ment potential, contaminant migration, biological reserved uptake and human exposure. In this paper, we examine the chemical partitioning of PAH in a multiphase soil environment using authentic contaminated _ soils INTRODUCTION obtained from petroleum and ereosote sites in Alberta, Canada The presence of polynuclear aromatic hydrocarbons The ratio of equilibrium concentrations of a solute (PAH) at hydrocarbon-contaminated waste sites often partitioned between two immiscible solvents under Grives the processes of risk assessment and remediation steady-state conditions is constant, and independent of relative volumes. The Nemst Distribution Law, for two liguid phases, and Henry's Law, for a gas and a liquid To whom correspondence should be addressed. Present address: Department of Chemistry, Okanagan Unie Phase describe this linear relationship for the partition- versity College, 3333 College Way, Kelowna, BC, Canada, ing of small amounts of solutes between two immiscible viviv7, phases. In general, for a system at equilibrium: 239 240 M. G. Zemanek et al a nics a where K is the partition coefficient and C; and C; are equilibrium solute concentrations in their respective phases. For the oil-contaminated soil environment, both oil and SOM can act as organic phases in a water) immiscible ‘solvent’ partition model (Hamaker ef al., 1972; Chiou er al, 1979; Karickhoff et al. 1979; Means et al. 1979), Soil/water partitioning for hydrophobic compounds, including PAH, is linear over a broad range of centrations. The behaviour is described by the partition coefficient: Q where Ky is the soil-water partition coefficient; X, the ‘equilibrium concentration of sorbate bound to the sedi- ment; and C, the equilibrium concentration in the water phase, Departure from isotherm linearity occurs when aqueous concentrations typically approach 60 to 70% of a compound's saturated water solubility. Kp values can be related to the organic carbon content of the soil organic matter and standardized for a given soil fraction. using the relationship: K, ms 2 where Ko. is the organic carbon-water partition coeffi- cient; and foe, the fraction of organic carbon in the soil K.. is considered to be a unique property of the com- pound being sorbed, implying that sorption of PAH is relatively independent of other sorbent related proper- ties of the soil, such as ion exchange capacity, pH and clay mineralogy. A considerable research effort has been based on this premise and sorption models developed around the concept of SOM as a homogenous ‘solvent’ for hydrophobic compounds in soils (Gauthier et al, 1987; Rutherford 7 al., 1992). However, the chemical nature of SOM itself appears to have some degree of control over the binding of PAH. Organic matter asso- Giated with larger particle size soil fractions is sig~ nificantly less effective as a sorbent than that associated with finer particle sizes, suggesting a stronger affinity of the organic compound for organic matter in later stages of decomposition (Karickhotf ef al., 1979; Evans et al., 1990) With respect to oil phase partitioning, an analogous situation exists. Free oil and ‘residual saturation’ in the unsaturated zone can both be treated as a homogenous partition medium or as a mixture of co-soivents. The complexity, varying solubility and degree of weathering for the oil phase will influence the distribution of PAH in the aqueous phase. At, or near waste disposal or spill sites, soil pore water is most likely to be a mixture or emulsion of water and several organic co-solvents (Rao et al, 1985; Rao, 1990). Fu and Luthy (19864,b) demonstrated that an increase in the volume of miscible solvent in an aqueous phase produces a semi-logarith- mic increase in solubility of PAH and attending decrease in soil sorption, The level of enhanced solubi- lity caused by co-solvents for individual non-polar solutes appears in proportion to the solute hydro- Phobicity. It follows that co-solvents may enhance the solution of “low solubility’ (i.e. more hydrophobic) PAH in the water phase to a greater extent than PAH of “higher solubility’ Movement of oil in soil and subsequent entrapment in the soil matrix creates a residual organic phase from which PAH can potentially distribute into fixed SOM or into aqueous solution, SOM has been shown to be a significant medium for the uptake of PAH but, by its very hydrophobic nature and as the source of PAH in the soil, the residual oif phase itself acts as the primary sink for PAH. Sun and Boyd (1991) have suggested that a threshold exists at which the oil content in soil reaches a critical levet and forms a discrete sorptive phase highly effective in removing hydrophobic compounds from aqueous solution, These workers determined that 0.1% w/w oil (1000mg kg~!) in soil is sufficient for the oil phase to function as a distinct partitioning phase, sepa rate from SOM. In its simplest form, a relationship based on partition theory may exist whereby the con- centrations in the oil and SOM phases can be expressed as: 4) where fis the concentration of the PAH in the liquid organic phase (ug mi-!), Mp the concentration of the PAH in the solid soil phase (ug g~!); Myo the mass of PAH existing in the liquid organic phase (1g); Vy the volume of liquid organic phase (ml); M,,. the mass of PAH adsorbed by the soil (1g); M,, the mass of soil (g); and K, the liquid organic phase/soil partition coefficient (g mi), Rearranging (4): () For the purposes of the experimental rationale explained below, itis useful to express this equation and view the mass fraction of PAH in the oil phase as a relationship between the volume of oil and the mass fraction of PAH sorbed on soil: Mpo Mr Mos, Yo Mr My © where Mr is the total mass of PAH in the system (1g). Evaluation of these relationships and parameters for authentic contaminated site soils yields important Multi-phase partitioning and co-solvent effects for polynuclear aromatic hydrocarbons 241 information as to the direction of partitioning in multi- ‘media systems, hence valuable data with respect to exposure assessment. We discuss our rationale for the experimental design and our approach below. METHODS Experimental rationale PAH-contaminated soil contains PAH dissolved in the oil and pore water phases, and sorbed on SOM. These PAH are at indeterminate levels because neither the oil nor soil can be independently extracted for quantitative analysis. However, using an approach analogous to that for “standard additions’ in analytical chemistry, the volume of the oil phase (V.) can be artificially increased by batch equilibration of the soil with a small amount of non-polar organic solvent, such as dichloromethane (DCM). which is completely miscible with the oil and easily separated by centrifugation. Miscibility between oil and DCM implies that the two liquids have a similar non-polar nature. Addition of DCM causes a shift in the soil’s equilibrium countered by a change in PAH concentration in SOM. At equilibrium, the organic DCM dissolves all organic compounds from the resi- dual free oil phase plus some organics partitioned from the fixed SOM, because the hydrophobic solutes have a greater affinity for the additional, non-polar solvent (Sun and Boyd, 1991). Consequently, the total mass of PAH in the combined organic liquid phase (M,o) would increase from the original soil condition. A plot, based on Equation (6), of the mass fraction of PAH in the liquid organic phase against the volume of added organic liquid, standardized to the weight of soil, can then be constructed from a series of soil batch equilibria with known and varied volumes of added solvent fol- lowed by mass quantitation of PAH in the solvent phase. The PAH existing in the original oil phase can then be estimated by back extrapolation, as in a ‘stan- dard additions’ method, to the original condition of the soil where no organic solvent is added Site descriptions Soil samples from five priority hydrocarbon waste sites in Alberta were used for investigation (Pollard et al., 1992), An abandoned oilfield battery site in east central Alberta was selected as representative of similar plants operating in the 1940s-1950s. At these sites, crude oil was dewatered and desalted, lighter fractions removed for further processing off-site and the residual heavy oil process wastes disposed of on-site, typically in unlined pits. Wastes identified at this site include spilled crude oil, flowing heavy oil seepage and consolidated asphaltic material. Creosote-contaminated soils were obtained from the process area of a former wood-treatment facility in central Alberta which, over a period of 60 years, used pentachlorophenol, coal-tar creosote and chromated copper arsenate treatment solutions for wood preservation. Surficial soils comprising the “drip pad! of the process area were highly contaminated with creosote solutions, most visibly in front of the creosote pressure treatment retorts. ‘Sampling and analysis On-site sampling and sample preparation of soil sub- samples has been reported previously (Pollard et al, 1992), Approximatcly 10 to 20g of soil was Soxhlet extracted with 150ml of double distilled DCM solvent (16h), Extracts were dried through a Na;S03 column and concentrated to <50ml on a rotary evaporator at 30°C. Extracts were washed into SOml_ volumetric flasks, brought up to volume, then stored in Teflon lined sereweap vials at 4°C until required. Ten millilitre ali- quots of concentrate were placed in shallow, preweighed aluminum dishes and allowed to dry in a fumehood for approximately 1h for complete evaporation of the DCM. Recovery of solvent-extractable organic maker was calculated from: % solvent extractable matter = MoE RFE) (7, where Mpr is the mass of dried extract (g); RFE, the reciprocal of the fraction of the whole extract used in analysis (50ml 10ml~!= 5); and Ms, the mass of soil used in Soxhlet extraction (g). A Florisi! solid-phase extraction (SPE) cartridge was conditioned with two column volumes of DCM and dried. A I-ml aliquot of extract was applied and the cartridge eluted with three column volumes of DCM. The eluate was reduced by Nz blow- down and exchanged into Iml hexane to precipitate interfering asphaltenes, Extracts stil contained interfering aliphatic and polar compounds requiring removal by further alumina column cleanup. A 10x254mm cham- pagne column was packed with approximately 10g of 80-200 mesh alumina activated at 225°C for 16h. The packing was topped with I cm of Na;S0¢ and conditioned with 50 ml hexane. Extracts from the preceding Florisil cleanup, were deposited on top of the packing, followed by three 2ml hexane rinsings of the vial containing the extract. The column was then washed with a final 10 ml volume of hexane. All cluate from the hexane application was discarded. PAH were then desorbed with 100m! DCM. These eluates collected were reduced to approxi mately 5 ml by rotary evaporation and Nz blowdown, Concentrations of PAH in Iml of cleaned extracts were determined on a Hewlett Packard $890 gas chro- matograph (70°C to 280°C; 10°Cmin=') fitted with a 30mx0.25 mm id. DB-1301 (J&W Scientific) column of 0.25 am film thickness connected to a $970 mass selec tive detector (GC/MS). Major ions and two minor ions of each PAH were monitored using selected ion mon- itoring (SIM) and analyte quantitation was based on the signal response of the major selected ions for each PAH compound compared to a S-component deuterated internal standard (Supelco cat. #4-8902) which was added prior to extraction. Compound recoveries were determined in triplicate on 20-g sub-samples of two standard sediments (HS-3

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