Development of a low-density polyethylene-containing passive sampler for measuring dissolved hydrophobic organic compounds in open waters

A passive water sampler with low-density polyethylene (LDPE) as the sorbent phase was built and field-tested for sensing freely dissolved concentrations of hydrophobic organic compounds (HOCs) in fresh and coastal water. Based on the measured LDPE-water partition coefficients (K(pew)) of 12 polycyclic aromatic hydrocarbons (PAHs) and dichlorodiphenyltrichloroethane (DDT) and its seven metabolites, the detection limits with the passive sampler containing 10-g LDPE ranged from 0.04 to 56.9 pg/L in the equilibrium sampling mode. Furthermore, the utility of the passive sampler in measuring dissolved HOC concentrations in open waters was examined through a comparison with solid-phase extraction combined with liquid-liquid extraction (SPE-LLE) and poly(dimethyl)siloxane (PDMS) coated fiber samplers. The total concentrations of PAHs (3.8-16 ng/L) obtained by the passive sampler were lower than those (87.7-115.5 ng/L) obtained through SPE-LLE. This large difference was probably attributable to slower water exchange in and out of the passive sampler as time progressed because of blockage by algae in eutrophia reservoirs and high dissolved organic carbon contents resulting in higher-than-expected PAH concentrations by SPE-LLE. Furthermore, the concentrations and compositional profiles of DDXs (sum of p,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDT, o,p'-DDD, o,p'-DDE, and p,p'-DDMU) at site A obtained by the passive sampler agreed with the results obtained with the PDMS-coated fibers, suggesting that the passive sampler was able to reasonably quantify dissolved HOCs in seawater.     

Validation of a modified flory-huggins concept for description of hydrophobic organic compound sorption on dissolved humic substances

Sorption coefficients (K(DOC)) on dissolved organic matter (DOM) have been determined by means of solid-phase microextraction (SPME) for hydrophobic organic compounds (HOCs) of various classes, for example, polycyclic aromatic hydrocarbons (PAHs), noncondensed arenes, and alkanes. Relating the K(DOC) values obtained to the octanol-water partition coefficients of the solutes results in class-specific correlations. Obviously, PAHs have a higher affinity to DOM than other HOCs with equal K(OW) values. The different K(DOC) to K(OW) correlations can be combined into one general formula based on a modified Flory-Huggins concept. It permits the calculation of sorption coefficients from the solubility parameters (delta) and K(OW) values of the solutes and the solubility parameter of the sorbent. The latter value, which is specific to the DOM under consideration, can be determined from a single measured sorption coefficient. By applying the proposed Flory-Huggins concept, which is based on the presumption of nonspecific interactions between HOCs and DOM, the different affinities of PAHs, noncondensed arenes, and alkanes to DOM can be accurately predicted.     

Effect of dissolved organic matter of various origins and biodegradabilities on the bioaccumulation of polycyclic aromatic hydrocarbons in Daphnia magna

As a preliminary study of the influence of urban organic matter on the bioavailability of polycyclic aromatic hydrocarbons (PAHs), the effect of different types of dissolved organic matter (DOM) on the bioaccumulation of fluoranthene, pyrene, or benzo[a]pyrene in Daphnia magna was studied. Commercial humic substances, DOM from the aeration basin of a wastewater treatment plant, and highly biodegradable DOM (algae or animal extracts) were tested. The bioaccumulation of benzo[a]pyrene was reduced by each DOM (up to 80% reduction with humic substances). Pyrene bioaccumulation was also decreased by each DOM to a lesser extent. Fluoranthene bioaccumulation was affected by the presence of humic acids only. In each experiment, the solution containing humic DOM led to the lowest bioaccumulation. Supposing that only dissolved PAHs were bioavailable, the reduction of bioaccumulation allowed a biological estimate of the partition coefficients of DOM and PAH, K(DOC). The estimated coefficients were positively related to the aromaticity of DOM and negatively related to its biodegradability.     

Impact of imposed anaerobic conditions and microbial activity on aqueous-phase solubility of polycyclic aromatic hydrocarbons from soil

The influence of anaerobic conditions on aqueous-phase polycyclic aromatic hydrocarbon (PAH) bioavailability was investigated in laboratory microcosms. Highly aged (>70 years), PAH-contaminated soil was incubated under anaerobic conditions by using various anaerobic headspaces, anaerobic headspaces with an oxygen-scavenging complex (titanium(III) citrate) in the aqueous phase, or anaerobic headspaces with electron-acceptor amendments in the aqueous phase. Incubation of soil solely under anaerobic conditions resulted in increased aqueous concentrations of all PAHs tested (fluoranthene, pyrene, benz[a]anthracene, and benzo[a]pyrene). Benz[a]anthracene and benzo[a]pyrene extractable concentrations were above aqueous solubility, by as much as an order of magnitude for the latter. The degree of solubility increase observed was a function of molecular weight of the PAH regardless of initial soil concentration, suggesting formation of stable PAH-soluble organic matter associations. The soil samples incubated aerobically for 90 d before imposition of anaerobic conditions did not release PAHs to the aqueous phase. Methanogenic organisms and sulfate-reducing bacteria were seen to have the most significant effect on increases in aqueous-phase PAHs. Polycyclic aromatic hydrocarbons made more soluble under anaerobic conditions was available to be degraded or transformed under aerobic conditions.     

Dependency of polychlorinated biphenyl and polycyclic aromatic hydrocarbon bioaccumulation in Mya arenaria on both water column and sediment bed chemical activities

The bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by the filter-feeding soft-shell clam Mya arenaria was evaluated at three sites near Boston (MA, USA) by assessing the chemical activities of those hydrophobic organic compounds (HOCs) in the sediment bed, water column, and organisms. Polyethylene samplers were deployed to measure the activities of HOCs in the water column. Sediment activities were assessed by normalizing concentrations with sediment-water sorption coefficient values, including adsorption to black carbon in addition to absorption by organic carbon. Likewise, both lipids and proteins were considered in biota-water partition coefficients used to estimate chemical activities in the animals. Chemical activities of PAHs in M. arenaria were substantially less than those of the corresponding bed sediments in which they lived. In contrast, chemical activities of PCBs in M. arenaria often were greater than or equal to activities in the corresponding bed sediments. Activities of PAHs, such those of pyrene, in the water column were undersaturated relative to the sediment. However, some PCBs, such as congener 52, had higher activities in the water column than in the sediment. Tissue activities of pyrene generally were in between the sediment and water column activities, whereas activity of PCB congener 52 was nearest to water column activities. These results suggest that attempts to estimate bioaccumulation by benthic organisms should include interactions with both the bed sediment and the water column.     

Sorption of 2,4'-dichlorobiphenyl and fluoranthene to a marine sediment amended with different types of black carbon

Recent studies demonstrate that sedimentary black carbon (BC) affects the sorption of some hydrophobic organic contaminants (HOCs) to a greater extent than sedimentary organic carbon (OC). Among HOC, polycyclic aromatic hydrocarbons (PAHs) are known to interact extensively with BC. Currently, data on the sorption of various kinds of HOCs to different types of BC are limited. In this study, we amended a marine sediment with BC from several different sources, humic acid, and inert sand. Equilibration studies with 14C fluoranthene and the polychlorinated biphenyl (PCB) 3H 2,4'-dichlorinated biphenyl were performed to determine the magnitude of sorption as a function of contaminant and BC type. The magnitude of sorption to the BC-amended sediments was greater for the PAH than the PCB as compared to the sediment alone, humic acid, and sand. For example, differences between the log partition coefficient (K(P)) for the PAH and PCB ranged from 0.41 to 0.69 log units for humic acid and sand treatments, while differences ranged from 0.88 to 1.57 log units for the BC-amended sediments. As a result, BC-normalized partition coefficients (log K(BC)) for the PAH averaged 6.41, whereas the PCB log K(BC) values averaged 5.33. These results demonstrate that PAH sorption and most likely bioavailability are influenced strongly by the presence of BC of different types, while sorption of a nonplanar PCB was affected to a lesser degree.     

Mechanisms regulating bioavailability of phenanthrene sorbed on a peat soil-origin humic substance

The organic matter-mineral complex plays an important role in regulating the fate of hydrophobic organic compounds (HOCs) in the environment. In the present study, the authors investigated the microbial bioavailability of phenanthrene (PHE) sorbed on the original and demineralized humic acids (HAs) and humin (HM) that were sequentially extracted from a peat soil. Demineralization treatment dramatically decreased the 720-h mineralized percentage of HM-sorbed PHE from 42.5 ± 2.6% to 3.4 ± 1.3%, whereas the influence of this treatment on the biodegradability of HA-associated PHE was much lower. Degradation kinetics of HA- and HM-sorbed PHE showed that its initial degradation rate was negatively correlated with the aromatic carbon content of humic substances (p<0.05). This was attributed to the strong interactions between PHE and the aromatic components of humic substances, which hampered its release and subsequent biodegradation. The 720-h mineralized percentage of PHE was inversely correlated with the estimated thickness of the organic matter layer at the surfaces of HAs and HMs. Therefore, in a relatively long term, diffusion of PHE within the organic matter layer could be an important factor that may limit the bioavailability of PHE to bacteria. Results of the present study highlight the molecular-scaled mechanisms governing bioavailability of PHE sorbed on humic substances.     

Polycyclic aromatic hydrocarbons in air

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds consisting of two or more condense aromatic rings. They are products of incomplete combustion or pyrolysis of organic matter. Because some PAHs such as Benzo[a]pyrene (BaP) are proven carcinogens and mutagens, it is necessary to continuously monitor their concentrations in the air, water, and soil. PAHs with two or three aromatic rings are stable in the gas phase, while most PAHs with five or more aromatic rings bond to particles. Higher concentrations of PAHs are present in the atmosphere of urban areas, mostly in the winter, due to heating. In the summer, these concentrations drop because most PAHs are unstable at high temperatures and break down by oxidation and photooxidation. Measurements of PAHs in the air include sampling on the filter paper or solid adsorbent, extraction, and chromatographic analysis. This review presents the measurements of BaP in some locations in the world and compares them with the findings in Croatia.     

Blood Levels of Polycyclic Aromatic Hydrocarbons in Children of Lucknow,India

Polycyclic aromatic hydrocarbons (PAHs) are compounds with two or more fused benzene rings produced by incomplete combustion of organic substances involved in natural and anthropogenic processes. Children are exposed to these compounds through inhalation, dietary ingestion, and, also, soil at the playground. It has been well established that PAHs have carcinogenic, mutagenic, and teratogenic effects. Considering possible health risks due to PAHs exposure among children, the present study was carried out in collaboration with the Pediatrics Department, King George’s Medical University (KGMU), Lucknow, to determine its exposure in children by estimating blood PAHs levels. Due to the variable composition of PAHs mixtures emitted from different environmental sources, any single compound or metabolite may not be representative of all exposure conditions. For these reasons, the measurement of blood PAHs levels as a possible biomarker, especially of the EPA (Environmental Protection Agency, USA) priority list, has been proposed. Acenaphthylene, anthracene, phenanthrene, fluoranthene, naphthalene, pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene were determined by HPLC-FD/UV. On the basis of the individual compound, the median (50th percentile) of naphthalene (19 ppb) was highest, however, benzo(a)pyrene (4.0 ppb) level was found to be lowest among all detected PAHs. The median level of total noncarcinogenic PAHs (113.55 ppb) was higher than the total carcinogenic PAHs (32.35 ppb) in blood samples of children. A significant correlation was found between period of time spent in the surrounding breathing zone of the cooking place and total noncarcinogenic PAHs (p < 0.05), while the blood carcinogenic PAHs level in children was found to be associated with lower status of their families (p < 0.05). It is speculated that there may be chances of health hazards through exposure to PAHs, those not yet declared hazardous and present at higher concentrations in the Indian environment. Further study with a larger sample size and accompanying environmental data is desired to validate the findings of this pilot study and strengthen the database of PAHs exposure in India.     

A fugacity approach for assessing the bioaccumulation of hydrophobic organic compounds from estuarine sediment

The bioavailability of four sediment-spiked hydrophobic organic contaminants (HOCs; chrysene, benzo[a]pyrene, chlordane, and Aroclor 1254) was investigated by comparing bioaccumulation by the amphipod Corophium colo with uptake into a thin film of ethylene/vinyl acetate (EVA) copolymer. The EVA thin film is a solid-phase extraction medium previously identified as effective at measuring the bioavailable contaminant fraction in sediment. The present study presents the results of 11 separate treatments in which chemical uptake into EVA closely matched uptake into lipid over 10 d. For all compounds, the concentration in EVA was a good approximation for the concentration in lipid, suggesting that this medium would be an appropriate biomimetic medium for assessing the bioaccumulation of HOCs during risk assessment of contaminated sediment. For chrysene and benzo[a]pyrene, limitations on bioaccumulation and toxicity because of low aqueous solubility were observed. The fugacity of the compounds in lipid (flip) and in the EVA thin film (fEVA) also was determined. The ratio of flip to fEVA was greater than one for all chemicals, indicating that all chemicals biomagnified over the duration of the exposure and demonstrating the potential for EVA thin-film extraction to assess trophic transfer of HOCs.     

Sorption of phenanthrene and atrazine by plant cuticular fractions

Several studies have shown selective preservation of plant cuticular materials in soils. However, very little is known about their function as sorbents for the hydrophobic organic contaminants (HOCs) in the soil. In this study, we investigated the sorption and desorption of phenanthrene and atrazine by cuticular fractions of pepper (bulk, dewaxed, nonsaponifiable, and nonhydrolyzable) to better understand the sorptive activity of cuticular matter in soils. The bulk and dewaxed cuticles exhibited carbon-normalized distribution coefficients (Koc) for phenanthrene and atrazine in the range of that reported for soil humic substances, although both samples were rich in aliphatic structures. No hysteresis was observed in the desorption isotherms of either solute. The nonhydrolyzable residue exhibited a very high Koc value for atrazine, whereas the nonsaponifiable sample be exhibited the lowest Koc value for both sorbates. Based on solubility parameter data, it is suggested that the nonsponifiable sample be considered an intermediate between the physical and chemical mixture of pectin and cutan/lignin-like fractions, whereas the dewaxed cuticle is a chemical blending of cutin and pectin. The n-hexane-normalized sorption data suggest that the pepper cuticle can interact specifically with atrazine. This study leads to the conclusion that the contribution of aliphatic-rich plant biopolymers to the sorption of HOCs can be significant because of their preservation and accumulation in soils.     

Influences of multiwalled carbon nanotubes and plant residue chars on bioaccumulation of polycyclic aromatic hydrocarbons by Chironomus plumosus larvae in sediment

Carbonaceous materials (CMs), including carbon nanotubes (CNTs), and black carbon have been suggested as potential remediation materials for hydrophobic organic contaminants (HOCs) in sediments or soils. However, the concentration-dependent and potential effects of CMs on the decrease in HOC bioavailability are not well understood. In this research, the effects of two types of multiwalled CNTs (MWNT-1 and MWNT-2) and chars (char-stalk produced from stalk and char-wood from wood) on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), including phenanthrene, pyrene, and chrysene, in the benthic organism Chironomus plumosus larvae were studied. When CM content was 1.5% or less in sediments, biota-sediment accumulation factor (BSAF) values for PAHs decreased sharply as CM increased. However, when char and MWNT-1 content was greater than 1.5% in sediments, reduction rates of BSAF were slight. Furthermore, when MWNT-2 content was greater than 1.5%, BSAF values were elevated. This indicated that the MWNT-associated PAHs may have been absorbed by larvae through particle ingestion, and suggested that some CNTs may not be suitable for the remediation of HOC-contaminated sediments because they probably could increase the exposure risk of PAHs to benthic organisms, possibly because of their unique structure.     

UV-B-Induced acute toxicity of pyrene to the waterflea Daphnia magna in natural freshwaters

The effects of various water characteristics in natural freshwaters on the acute toxicity of one polycyclic aromatic hydrocarbon (PAH), pyrene, to a pelagic invertebrate Daphnia magna was studied under ultraviolet B (UV-B) radiation and in the dark. Pyrene was photoactivated and was more toxic to D. magna in the presence of UV-B radiation. Dissolved organic material (DOM), measured as dissolved organic carbon (DOC), significantly reduced the photoenhanced toxicity of pyrene. Under UV-B radiation the EC(50) values were lower and in relation to the amount of DOM, ranging from 3.0 to 30.0 microg/L pyrene, whereas in the dark they were between 29.2 and 54.8 microg/L and not related to the amount of DOM in the waters. Although the condition and mortality of the daphnids in the control groups were not affected by UV-B irradiation, the increased toxicity was considered to be either an additive or a synergistic effect of both the photomodified pyrene and the stressing light conditions of UV-B. The measured binding of pyrene to DOM was low, although it was related to the amount of DOC. Despite the relatively high intensity of UV-B used, humic substances in the waters remained undegraded. It was thus concluded that with their brownish-yellowish color, waters rich in humic substances decreased the photomodification of the freely dissolved parent compound simply by diminishing the light penetration in these waters and, by implication, contact with the intact compound. These results suggest that DOM in surface waters plays an important role in protecting against the photoinduced toxicity of PAHs.     

Comparison of synthetic surfactants and biosurfactants in enhancing biodegradation of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbon (PAH) contamination of the environment represents a serious threat to the health of humans and ecosystems. Given the human health effects of PAHs, effective and cost-competitive remediation technologies are required. Bioremediation has shown promise as a potentially effective and low-cost treatment option, but concerns about the slow process rate and bioavailability limitations have hampered more widespread use of this technology. An option to enhance the bioavailability of PAHs is to add surfactants directly to soil in situ or ex situ in bioreactors. Surfactants increase the apparent solubility and desorption rate of the PAH to the aqueous phase. However, the results with some synthetic surfactants have shown that surfactant addition can actually inhibit PAH biodegradation via toxic interactions, stimulation of surfactant degraders, or sequestration of PAHs into surfactant micelles. Biosurfactants have been shown to have many of the positive effects of synthetic surfactants but without the drawbacks. They are biodegradable and nontoxic, and many biosurfactants do not produce true micelles, thus facilitating direct transfer of the surfactant-associated PAH to bacteria. The results with biosurfactants to date are promising, but further research to elucidate surfactant-PAH interactions in aqueous environments is needed to lead to predictive, mechanistic models of biosurfactant-enhanced PAH bioavailability and thus better bioremediation design.     

Molecular simulation of a model of dissolved organic matter

A series of atomistic simulations was performed to assess the ability of the Schulten dissolved organic matter (DOM) molecule, a well-established model humic molecule, to reproduce the physical and chemical behavior of natural humic substances. The unhydrated DOM molecule had a bulk density value appropriate to humic matter, but its Hildebrand solubility parameter was lower than the range of current experimental estimates. Under hydrated conditions, the DOM molecule went through conformational adjustments that resulted in disruption of intramolecular hydrogen bonds (H-bonds), although few water molecules penetrated the organic interior. The radius of gyration of the hydrated DOM molecule was similar to those measured for aquatic humic substances. To simulate humic materials under aqueous conditions with varying pH levels, carboxyl groups were deprotonated, and hydrated Na+ or Ca2+ were added to balance the resulting negative charge. Because of intrusion of the cation hydrates, the model metal-humic structures were more porous, had greater solvent-accessible surface areas, and formed more H-bonds with water than the protonated, hydrated DOM molecule. Relative to Na+, Ca2+ was both more strongly bound to carboxylate groups and more fully hydrated. This difference was attributed to the higher charge of the divalent cation. The Ca-DOM hydrate, however, featured fewer H-bonds than the Na-DOM hydrate, perhaps because of the reduced orientational freedom of organic moieties and water molecules imposed by Ca2+. The present work is, to our knowledge, the first rigorous computational exploration regarding the behavior of a model humic molecule under a range of physical conditions typical of soil and water systems.     

Joint toxicity of linear alkylbenzene sulfonates and pyrene on Folsomia fimetaria

Surfactants may enhance the biodegradation of hydrophobic substances in soils. This has partly been attributed to an increase in the bioavailability, brought about by the presence of surfactants. The aim of this study was to examine the ecotoxicological effects of the detergent linear alkylbenzene sulfonate (LAS) and the polycyclic aromatic hydrocarbon pyrene, alone and in combination, using the survival and reproduction of the collembolan Folsomia fimetaria as endpoints. The EC(50) and EC(10) were 803 and 161 mg kg(-1) for LAS, and 23 and 15 mg kg(-1) for pyrene. If LAS was able to increase the bioavailability of pyrene to springtails, it was expected that the combined effect of the two substances would exceed the effect found for each of the compounds tested separately. However, the results showed no effect of LAS on the toxicity of pyrene in the concentration range tested (1-750 mg LAS kg(-1) dry weight). Both the toxic unit concept and the isobologram method indicated that an additive approach would be the most useful when assessing the risk of these two compounds.     

Use of triolein-semipermeable membrane devices to assess the bioconcentration and sediment sorption of hydrophobic organic contaminants in the Huaihe River,China

Triolein-containing semipermeable membrane devices (triolein-SPMD) were deployed I m above the sediments at two sampling sites in the Huaihe River, China, for a period of 28 d. Sediment and fish samples were simultaneously collected from the same sampling sites. Concentrations of substituted benzenes, selected pesticides, polycyclic aromatic hydrocarbon (PAH), and polychlorinated biphenyls (PCBs) were measured in triolein-SPMDs, sediments, and fishes. The concentrations of these hydrophobic organic contaminants (HOCs) in fish and in sediment organic carbon were correlated with HOCs accumulation in triolein-SPMDs. Our results showed reasonably good correlations between the log concentrations of contaminants in fish lipid and in triolein-SPMDs. Good correlations were also found between the log concentrations of contaminants in sediment organic carbon and in triolein-SPMDs (except for PAHs). The results were discussed in terms of the partitioning of hydrophobic organic contaminants among different compartments in the aquatic environment and the suitability of using triolein-SPMDs to predict bioconcentration factor (BCF) and sediment-water partitioning coefficient (K(oc)).     

Predicting single and mixture toxicity of petrogenic polycyclic aromatic hydrocarbons to the copepod Oithona davisae

In the present study, the acute toxicity of 10 polycyclic aromatic hydrocarbons (PAHs) associated with the Prestige fuel oil spill (Spain, 2002) were evaluated, either as single substances or in mixtures, in adults of the copepod Oithona davisae. All but dimethylphenanthrene had negative effects on O. davisae survival at concentrations below their water solubility, with 48-h median lethal concentrations for naphthalene and pyrene of 56.1 and 0.8 micromol/L, respectively, making these the least and most toxic compounds. Polycyclic aromatic hydrocarbons had narcotic effects on copepods, as evidenced by the lack of motility at lower concentrations than those causing death. Naphthalene showed the greatest narcotic effects, and phenanthrene showed minor effects. Acute toxicity of the tested PAHs was inversely related (r2 = 0.9) with their octanol-water partition coefficient, thereby confirming the validity of the baseline quantitative structure-activity regression models for predicting the toxicity of PAH compounds in copepod species. When supplied in mixtures, the toxic effect of PAHs was additive. These results indicate that the many PAHs in an oil spill can be considered unambiguous baseline toxicants (class 1) acting additively as nonpolar narcotics in copepods; hence, their individual and combined toxicity can be predicted using their octanol-water partition coefficient.     

Anaerobic Degradation of Phenanthrene and Pyrene in Mangrove Sediment

This study investigated the anaerobic degradation of the polycyclic aromatic hydrocarbons (PAHs) phenanthrene and pyrene in mangrove sediment from Taiwan. The anaerobic degradation of PAH was enhanced by the addition of acetate, lactate, pyruvate, sodium chloride, cellulose, or zero-valent iron. However, it was inhibited by the addition of humic acid, di-(2-ethylhexyl) phthalate (DEHP), nonylphenol, or heavy metals. Of the microorganism strains isolated from the sediment samples, we found that strain MSA3 (Clostridium pascui), expressed the best ability to biodegrade PAH. The inoculation of sediment with the strain MSA3 could enhance PAH degradation.     

An experimental study of the penetration of polycyclic aromatic hydrocarbons through a model of the bronchial lining layer

The penetration of benzo[a]pyrene (BaP) through a nonbiological experimental model of the bronchial lining layer (BLL) was studied. The purpose was to investigate how the lipid-aqueous structure of the BLL might influence the rate of penetration of polycyclic aromatic hydrocarbons (PAHs) from the ambient air to the bronchial epithelium. The experimental model was built up in a petri dish by (A) a thin layer of paraffin at the bottom, simulating the lipophilic membranes of the epithelial cells; (B) an aqueous starch gel on top of the paraffin, simulating the viscous aqueous region of the BLL; and (C) a thin layer of phosphatidylcholine, simulating the surfactant lipid layer at the air interface. BaP was administered on top of the barrier either diffusely or from a point source, and the penetration was studied by measuring the concentration of BaP as a function of time both in the liquid phase and in the paraffin. Comparisons were made with a purely aqueous barrier without the thin phospholipid layer. The results show that the rate of penetration of BaP through the purely aqueous barrier is orders of magnitude higher than that of the lipid-aqueous barrier. A thin layer of phospholipids at the air interface thus has a tremendous influence on the rate of penetration of lipophilic substances and probably this, rather than the release rate of PAHs from their carrier particles, is the rate-determining step in the overall transport of PAHs from such particles to the bronchial epithelium.