Partitioning Of Polychlorinated Biphenyls Research Articles

Target Lipid Model and Empirical Organic Carbon Partition Coefficients Predict Sediment Toxicity of Polychlorinated Biphenyls to Benthic Invertebrates.

Quantifying causal exposure-response relationships for polychlorinated biphenyl (PCB) toxicity to benthic invertebrates can be an important component of contaminated sediment assessments, informing cleanup decisions and natural resource injury determinations. Building on prior analyses, we demonstrate that the target lipid model accurately predicts aquatic toxicity of PCBs to invertebrates, providing a means to account for effects of PCB mixture composition on the toxicity of bioavailable PCBs. We also incorporate updated data on PCB partitioning between particles and interstitial water in field-collected sediments, to better account for effects of PCB mixture composition on PCB bioavailability. To validate the resulting model, we compare its predictions with sediment toxicity data from spiked sediment toxicity tests and a variety of recent case studies from sites where PCBs are the primary sediment contaminant. The updated model should provide a useful tool for both screening-level and in-depth risk analyses for PCBs in sediment, and it should aid in diagnosing potential contributing factors at sites where sediment toxicity and benthic community impairment are observed. Environ Toxicol Chem 2023;42:1134-1151. © 2023 SETAC.

Particle/gas partitioning behavior of polychlorinated biphenyls (PCBs) in global atmosphere: Equilibrium or steady state?

Particle/gas (P/G) partitioning governs the atmospheric transport and fate of semi-volatile compounds (SVOCs). Here, we provide a comprehensive investigation of P/G partitioning of polychlorinated biphenyls (PCBs) by comparing the performance of seven models, (including five equilibrium models: Junge-Pankow model, Harner-Bidleman model, Dachs-Eisenreich model, pp-LFER model, mp-pp-LFER model, one empirical Li-Jia model, and one steady-state Li-Ma-Yang model). For this comparison, 5019 monitoring data points from urban, rural and remote sites for PCBs taken from published papers have been accessed, against which the predictions of these models have been evaluated. Among the 5019 monitoring data points, there are 2791 monitoring data for six selected PCB congeners (CB-28 + 31, −52, −101, −153, −180, −207) and 2228 for dozens of other PCB congeners. We find that in predicting the P/G partition quotient (KP) of the six selected PCB compounds, the Li-Ma-Yang model performs best across the entire logKOA (octanol-air partition coefficient) range (from 7.8 to 15.3), with 86 ± 10% of 2791 monitoring data points lying within a deviation of ±1 log unit of the root mean square error (RMSE) of 0.67 ± 0.18 in urban, rural and remote areas. This model is far superior to the other models in predicting KP, especially in the MP Domain (logKOA ≥ 12.50), with 96% of the data points falling within a deviation of ±1 log unit and a RMSE of 0.48, in comparison to the less than 7% for the five equilibrium models and 20% for the empirical Li-Jia model. These findings suggest that when the particle deposition is not negligible, the P/G partitioning of PCBs in ambient atmosphere is not in equilibrium, but in a steady or quasi-steady state. Similar to PBDEs, the properties of individual PCB congeners, such as KOA, are the primary factors affecting the P/G partitioning of PCBs.

Atropselective Partitioning of Polychlorinated Biphenyls in a HepG2 Cell Culture System: Experimental and Modeling Results.

Cell culture models are used to study the toxicity of polychlorinated biphenyls (PCBs); however, it is typically unknown how much PCB enters the cells and, for chiral PCBs, if the partitioning is atropselective. We investigated the partitioning of racemic PCB 91, PCB 95, PCB 132, and PCB 136 in HepG2 cells following a 72 h incubation. PCBs were present in the cell culture medium (60.7-88.8%), cells (8.0-14.6%), and dishes (2.3-7.8%) and displayed atropisomeric enrichment in the cells (enantiomeric fraction [EF] = 0.55-0.77) and dishes (EF = 0.53-0.68). Polyparameter linear free energy relationships coupled with a composition-based model provided a good estimate of the PCB levels in the cells and cell culture medium. The free concentration was subsequently used to extrapolate from the nominal cell culture concentration to PCB tissue levels and vice versa. This approach can be used for in vitro-in vivo extrapolations for all 209 PCB congeners. However, this model (and modified models based on descriptors incorporating atropselective interactions, i.e., relative retention times on chiral columns) did not predict the atropselective partitioning in the cell culture system. Improved chemical descriptors that account for the atropselective binding of PCBs to biological macromolecules are, therefore, needed to predict the atropselective partitioning of PCBs in biological systems.

Fatty liver and impaired hepatic metabolism alter the congener-specific distribution of polychlorinated biphenyls (PCBs) in mice with a liver-specific deletion of cytochrome P450 reductase

Polychlorinated biphenyls (PCBs) are persistent organic pollutants that are linked to adverse health outcomes. PCB tissue levels are determinants of PCB toxicity; however, it is unclear how factors, such as an altered metabolism and/or a fatty liver, affect PCB distribution in vivo. We determined the congener-specific disposition of PCBs in mice with a liver-specific deletion of cytochrome P450 reductase (KO), a model of fatty liver with impaired hepatic metabolism, and wild-type (WT) mice. Eight-week-old male WT (MWT, n = 3), male KO (MKO, n = 5), female WT (FWT, n = 4), and female KO mice (FKO, n = 4) were exposed orally to Aroclor 1254. PCBs were quantified in adipose, blood, brain, and liver tissues by gas chromatography-mass spectrometry. The ΣPCB levels followed the rank order adipose > liver ∼ brain > blood in WT and adipose ∼ liver > brain > blood in KO mice. PCB levels were much higher in the liver of KO than WT mice, irrespective of the sex. A comparison across exposure groups revealed minor genotype and sex-dependent differences in the PCB congener profiles (cos Θ > 0.92). Within each exposure group, tissue profiles showed small differences between tissues (cos Θ = 0.85 to 0.98). These differences were due to a decrease in metabolically more labile PCB congeners and an increase in congeners resistant to metabolism. The tissue-to-blood ratio of PCBs decreased for adipose, increased for the brain, and remained constant for the liver with an increase in chlorination. While these ratios did not follow the trends predicted using a composition-based model, the agreement between experimental and calculated partition coefficients was reasonable. Although the distribution of PCBs differs between KO and WT mice, the magnitude of the partitioning of PCBs from the blood into tissues can be approximated using composition-based models.

Investigation of a decommissioned landfill barrier system containing polychlorinated biphenyl (PCB) waste after 25 years in service

The excavation and analysis of the barrier systems for four engineered containment cells, constructed from 1984 to 1987, is described. Very limited polychlorinated biphenyl (PCB) migration was observed over the 22–25 year period prior to decommissioning. PCBs were predominantly, and preferentially, retarded by the geotextiles (GTXs) and, where present, geomembranes (GMBs). The migration of PCBs in the primary compacted clay liner (CCL) during this period was limited both when used alone and with a GMB. The exhumed GMBs, from both cover and base barriers, had diffusive properties (with respect to volatile organic compounds) comparable to unaged GMBs. For cells with a CCL as the primary base barrier, the inferred PCB diffusion coefficient, De, was 1–2 × 10−10m2/s and distribution coefficient, Kd, was 10–15 mL/g. For cells where a GMB was the primary base barrier, the inferred PCB partitioning coefficient, Sgf, was 150 000 and diffusion coefficient, Dg, was 1 × 10−14m2/s. Modelling beyond the 25 years in service predicts no unacceptable PCB impact of the landfill on groundwater and indicates that the design of the barrier system was adequate for an indefinite period given the low service temperatures to which it was subjected. In this diffusion-governed system, small changes to the diffusive properties were found to have a large impact on migration.

Efficacy of carbon-based materials for remediating polychlorinated biphenyls (PCBs) in sediment

Polychlorinated biphenyls (PCBs) are persistent hydrophobic compounds that are present widely in the environment. Due to poorly maintained hazardous waste sites, electrical equipment leakage, and illegal disposal, PCBs were deposited in sediments present in bays and estuaries. PCBs continuously partition into the overlying water posing a long-term exposure risk to the environment and human health. This study demonstrates the efficacy of carbon-based materials in reducing the partitioning of PCBs from sediment to the water column. Both existing carbon-based materials [activated carbon (AC), black carbon (BC)] and emerging nanomaterials [graphene (GE), graphene oxide (GO), carbon nanotube (CNT)] were tested to determine their efficacy to bind PCBs in sediment. The comparison between the sorbents was accomplished by examining their distribution coefficient (Ks). The magnitude of Ks provides an idea about the bioavailable fraction of PCBs in the system; the higher the Ks, the greater the strength of sorption by the sorbent and therefore, the lower the PCB bioavailability. Results from the sorption experiment indicated that CNT performed the best overall followed by AC, BC, GO and GE. Results indicated that the Ks value for CNT was 1.16, 1.15, 1.13 and 1.04 log units greater than GE, GO, BC, and AC.

Accounting for water levels and black carbon-inclusive sediment-water partitioning of organochlorines in Lesser Himalaya, Pakistan using two-carbon model.

This study was designed to monitor organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in riverine water of Lesser Himalaya along the altitude. Further, the sediment-water partitioning employing organic carbon and black carbon models were assessed. Results revealed higher water levels of organochlorine pesticides (0.07-41.4ngL-1) and polychlorinated biphenyls (0.671-84.5ngL-1) in Lesser Himalayan Region (LHR) of Pakistan. Spatially, elevated levels were observed in the altitudinal zone (737-975masl) which is influenced by anthropogenic and industrial activities. Sediment-water partitioning of OCPs and PCBs were deduced using field data by employing one-carbon (fOCKOC) and two-carbon Freundlich models (fOCKOC + fBCKBCCWnF-1). Results suggested improved measured vs predicted model concentrations when black carbon was induced in the model and suggested adsorption to be the dominant mechanism in phase partitioning of organochlorines in LHR.

Seasonal soil/snow-air exchange of semivolatile organic pollutants at a coastal arctic site (Tromsø, 69°N)

Soils are a major reservoir of semivolatile organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), and exert a control on their atmospheric occurrence. We present here an assessment of the atmospheric occurrence and seasonality of soil/snow-air partitioning and exchange of PCBs, PAHs, hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs) in the arctic city Tromsø, northern Norway. The fugacities of the organic pollutants in soils and snow were determined using a soil fugacity sampler by equilibrating the air concentrations with those in the surface soil/snow. The concentrations in soils did not show a significant seasonality. Conversely, the ambient air concentrations and the soil (or snow) fugacity showed a clear seasonality for PCBs, HCH, HCB and some PAHs, related to temperature. Fugacities in soil/snow were correlated with those in the ambient gas phase, suggesting a close seasonal air-soil/snow coupling. Generally, there was a net deposition or close to equilibrium conditions during the winter, which contrasts with the net volatilization observed during the warmer periods. The chemicals with lower octanol-air partition coefficients showed a larger tendency for being volatilized and thus remobilized from this coastal arctic environment. Conversely, the more hydrophobic compounds were close to air-soil/snow equilibrium or showed a net deposition.

Size distribution and sorption of polychlorinated biphenyls during haze episodes

There is a lack of studies on the size distribution of polychlorinated biphenyls (PCBs) during haze days, and their sorption mechanisms on aerosol particles remain unclear. In this study, PCBs in particle-sized aerosols from urban atmospheres of Beijing, China were investigated during haze and normal days. The concentrations, gas/particle partitioning, size distribution, and associated human daily intake of PCBs via inhalation were compared during haze days and normal days. Compared with normal days, higher particle mass-associated PCB levels were measured during haze days. The concentrations of ∑PCBs in particulate fractions were 11.9–134 pg/m3 and 6.37–14.9 pg/m3 during haze days and normal days, respectively. PCBs increased with decreasing particle size (>10 μm, 10–2.5 μm, 2.5–1.0 μm, and ≤1.0 μm). During haze days, PCBs were overwhelmingly associated with a fine particle fraction of ≤1.0 μm (64.6%), while during normal days the contribution was 33.7%. Tetra-CBs were the largest contributors (51.8%–66.7%) both in the gas and particle fractions during normal days. The profiles in the gas fraction were conspicuously different than those in the PM fractions during haze days, with di-CBs predominating in the gas fraction and higher homologues (tetra-CBs, penta-CBs, and hexa-CBs) concurrently accounting for most of the PM fractions. The mean-normalized size distributions of particulate mass and PCBs exhibited unimodal patterns, and a similar trend was observed for PCBs during both days. They all tended to be in the PM fraction of 1.0–2.5 μm. Adsorption might be the predominating mechanism for the gas-particle partitioning of PCBs during haze days, whereas absorption might be dominative during normal days.

Atmospheric occurrence, transport and gas–particle partitioning of polychlorinated biphenyls over the northwestern Pacific Ocean

Ship-board air samples were collected during March to May 2015 from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) to explore the atmospheric occurrence and gas–particle partitioning of polychlorinated biphenyls (PCBs) when the westerly East Asian Monsoon prevailed. Total PCB concentrations in the atmosphere ranged from 56.8 to 261 pg m−3. Higher PCB levels were observed off the coast and minor temperature-induced changes showed that continuous emissions from East Asia remain as an important source to the regional atmosphere. A significant relationship between Koa (octanol–air partition coefficient) and KP (gas–particle partition coefficient) for PCBs was observed under continental air masses, suggesting that land-derived organic aerosols affected the PCB gas–particle partitioning after long-range transport, while an absence of this correlation was identified in marine air masses. The PCB partitioning cannot be fully explained by the absorptive mechanism as the predicted KP were found to be 2–3 orders of magnitude lower than the measured Kp, while the prediction was closely matched when soot adsorption was considered. The results suggested the importance of soot carbon as a transport medium for PCBs during their long-range transport and considerable impacts of continental outflows on PCBs across the downwind area. The estimated transport mass of particulate PCBs into the ECS and NWP totals 2333 kg during the spring, constituting ca. 17% of annual emission inventories of unintentionally produced PCB in China.

Polychlorinated biphenyls in Nepalese surface soils: Spatial distribution, air-soil exchange, and soil-air partitioning

Regardless of the ban on the polychlorinated biphenyls (PCBs) decade ago, significant measures of PCBs are still transmitted from essential sources in cities and are all inclusive ecological contaminants around the world. In this study, the concentrations of PCBs in soil, the air-soil exchange of PCBs, and the soil-air partitioning coefficient (KSA) of PCBs were investigated in four noteworthy urban areas in Nepal. Overall, the concentrations of ∑30PCBs ranged from 10 to 59.4ng/g dry weight; dw (mean 12.2ng/g ±11.2ng/g dw). The hexa-CBs (22–31%) was most dominant among several PCB-homologues, followed by tetra-CBs (20–29%), hepta-CBs (12–21%), penta-CBs (15–17%) and tri-CBs (9–19%). The sources of elevated level of PCBs discharge in Nepalese soil was identified as emission from transformer oil, lubricants, breaker oil, cutting oil and paints, and cable insulation. Slightly strong correlation of PCBs with TOC than BC demonstrated that amorphous organic matter (AOM) assumes a more critical part in holding of PCBs than BC in Nepalese soil. The fugacity fraction (ff) results indicated the soil being the source of PCB in air through volatilization and net transport from soil to air. The soil-air partitioning coefficient study suggests the absorption by soil organic matter control soil-air partitioning of PCBs. Slightly weak but positive correlation of measured Log KSA with Log KOA (R2 = 0.483) and Log KBC-A (R2 = 0.438) suggests that both Log KOA and Log KBC-A can predict soil-air partitioning to lesser extent for PCBs.

PCDD/F and dioxin-like PCB minimization: A 13-year experimental study along the flue gas cleaning system of a secondary aluminium refining plant

A 13-years study shows that a careful design of the flue gas cleaning system of a full scale secondary aluminium refining plant results in a minimized and very stable emission of Polychlorinated Dibenzo–p–Dioxins (PCDD), Polychlorinated Dibenzo Furans (PCDF) and dioxin-like Polychlorinated Biphenyls (PCB). The value of equivalent toxicity of PCDD/F in the emission was definitely of an order of magnitude less than the regulation limit.In the initial flue gas cleaning system, the PCB mean fingerprint after the slow cooling of the flue gas was typical of de novo synthesis. Instead, in the presence of quenching, there was evidence that the fast cooling of flue gas prevented the PCB de novo synthesis. In fact, the PCB profile was similar to that in the air collected from the aspiration hoods for the quenching. The gas-phase and solid-phase partitioning of PCBs, before and after the fabric filters, highlights the predominant role of the vapor phase with respect to the total removal efficiency. The polycyclic aromatic hydrocarbons breakdown could be an additional de novo formation pathway even in industrial plants.

Assessing soil-air partitioning of PAHs and PCBs with a new fugacity passive sampler

Soil-air fluxes of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined using a novel application of passive samplers to measure air and soil air, which is air in close proximity and in equilibrium with soil. Existing methods to measure flux of semi-volatile compounds between soil and air require collecting samples from the top soil layer. Yet, the top soil layer is hard to define and oversampling may misrepresent the exchangeable fraction. Alternatively, modified active samplers can measure soil air in situ, but require electricity while deployed. We present a new method to measure time-weighted averages of soil air concentrations in situ using passive sampling and requiring no electricity: a box is placed over low-density polyethylene passive samplers deployed 1cm above the soil. Passive air samplers were also co-deployed 1.5m above the soil to measure ambient air concentrations in three U.S. locations: near a former PCB manufacturing facility in Anniston, Alabama; on a former creosoting and the current Wyckoff/Eagle Superfund site near Seattle, Washington; and near the site of a recent oil-train derailment and fire in Mosier, Oregon. Following n-hexane extraction, sampler extracts were analyzed for PAHs with gas chromatography-tandem mass spectrometry and PCBs with dual gas chromatography-electron capture detectors. PAHs were generally depositing at Anniston and Mosier sites, but volatilizing from soil in Wyckoff, the site with historically-contaminated soil. PCBs were detected most frequently at the Anniston site, although levels were lower than previous reports. Variability in concentration measurements was greater among soil air samplers than air samplers, likely due to soil heterogeneity. Environmental conditions under the novel soil air box did not substantially change soil-air partitioning behavior. This method of measuring soil air in situ will allow for understanding of source-sink dynamics at sites with recent and historical contamination, and where conventional sampling is challenging.

Particle size distribution and gas-particle partitioning of polychlorinated biphenyls in the atmosphere in Beijing, China.

Size-fractionated samples of urban particulate matter (PM; ≤1.0, 1.0-2.5, 2.5-10, and >10μm) and gaseous samples were simultaneously obtained to study the distribution of polychlorinated biphenyls (PCBs) in the atmosphere in Beijing, China. Most recent investigations focused on the analysis of gaseous PCBs, and much less attention has been paid to the occurrence of PCBs among different PM fractions. In the present study, the gas-particle partitioning and size-specific distribution of PCBs in atmosphere were investigated. The total concentrations (gas + particle phase fractions) of Σ12 dioxin-like PCBs, Σ7 indicator PCBs, and ΣPCBs were 1.68, 42.1, and 345pg/m3, respectively. PCBs were predominantly in the gas phase (86.8-99.0% of the total concentrations). The gas-particle partition coefficients (K p ) of PCBs were found to be a significant linear correlated with the subcooled liquid vapor pressures (P L0) (R 2=0.83, P<0.01). The slope (m r ) implied that the gas-particle partitioning of PCBs was affected both by the mechanisms of adsorption and absorption. In addition, the concentrations of PCBs increased as the particle size decreased (>10, 2.5-10, 1.0-2.5, and ≤1.0μm), with most of the PCBs contained in the fraction of ≤1.0μm (53.4% of the total particulate concentrations). Tetra-CBs were the main homolog in the air samples in the gas phase and PM fractions, followed by tri-CBs. This work will contribute to the knowledge of PCBs among different PM fractions and fill the gap of the size distribution of particle-bound dioxin-like PCBs in the air.

Particle-Dissolved Phase Partition of Polychlorinated Biphenyls in High Altitude Alpine Lakes.

We investigated whether polychlorinated biphenyls (PCBs) partitioning between the dissolved and particulate phases in two high altitude alpine lakes was determined by the quantity, size structure, or composition of suspended particles. Within- and between-lakes differences in water-particulate phase partition coefficient (Kp) were not related to total suspended matter, phytoplankton biomass, or taxonomic composition. Yet, a seasonal relationship between Kp and Kow was detected for both lakes, revealing equilibrium of PCBs partition when lakes were ice covered. On the contrary, PCBs partitioning between particles and water appeared kinetically limited during the open water season. Partition is therefore mainly governed by thermodynamic laws during the ice-covered period, while none of the tested physical or biological parameters seemed to explain the distribution of these particle-reactive contaminants in the open water period. PCBs were always mainly associated with particulate matter, but partitioning within different particulate size-fractions varied between seasons and between years during open water periods. When ice cover is absent, PCBs were mainly adsorbed on microplankton, the largest phytoplanktonic size fraction, which is the least likely to get grazed by pelagic microconsumers.

Influential role of black carbon in the soil–air partitioning of polychlorinated biphenyls (PCBs) in the Indus River Basin, Pakistan

Levels of polychlorinated biphenyls (PCBs) were assessed in surface soils and passive air samples from the Indus River Basin, and the influential role of black carbon (BC) in the soil–air partitioning process was examined. ∑26–PCBs ranged between 0.002–3.03pgm−3 and 0.26–1.89ngg−1 for passive air and soil samples, respectively. Lower chlorinated (tri- and tetra-) PCBs were abundant in both air (83.9%) and soil (92.1%) samples. Soil–air partitioning of PCBs was investigated through octanol–air partition coefficients (KOA) and black carbon–air partition coefficients (KBC–A). The results of the paired-t test revealed that both models showed statistically significant agreement between measured and predicted model values for the PCB congeners. Ratios of fBCKBC–AδOCT/fOMKOA>5 explicitly suggested the influential role of black carbon in the retention and soil–air partitioning of PCBs. Lower chlorinated PCBs were strongly adsorbed and retained by black carbon during soil–air partitioning because of their dominance at the sampling sites and planarity effect.

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon

Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls.

Atmospheric concentration characteristics and gas/particle partitioning of PCBs from the North Pacific to the Arctic Ocean

Polychlorinated biphenyls (PCBs) were measured in atmospheric samples collected from the North Pacific to the Arctic Ocean between July and September 2012 to study the atmospheric concentration characteristics of PCBs and their gas/particle partitioning. The mean concentration of 26 PCBs (vapor plus particulate phase) (ΣPCBs) was 19.116 pg/m3 with a standard deviation of 13.833 pg/m3. Three most abundant congeners were CB-28, −52 and −77, accounting for 43.0% to ΣPCBs. The predominance of vapor PCBs (79.0% to ΣPCBs) in the atmosphere was observed. ΣPCBs were negative correlated with the latitudes and inverse of the absolute temperature (1/T). The significant correlation for most congeners was also observed between the logarithm of gas/particle partition coefficient (logKP) and 1/T. Shallower slopes (from −0.15 to −0.46, average −0.27) were measured from the regression of the logarithm of sub-cooled liquid vapor pressures (logpL○) and logKP for all samples. The difference of the slopes and intercepts among samples was insignificant (p>0.1), implying adsorption and/or absorption processes and the aerosol composition did not differ significantly among different samples. By comparing three models, the J-P adsorption model, the octanol/air partition coefficient (KOA) based model and the soot-air model, the gas/particle partitioning of PCBs in the Arctic atmosphere was simulated more precisely by the soot-air model, and the adsorption onto elemental carbon is more sensitive than the absorption into organic matters of aerosols, especially for low-chlorinated PCB congeners.

Partitioning of polychlorinated biphenyls into human cells and adipose tissues: evaluation of octanol, triolein, and liposomes as surrogates.

Whereas octanol, triacylglycerides, and liposomes have all been proposed as surrogates for measuring the affinity of hydrophobic organic contaminants to human lipids, no comparative evaluation of their suitability exists. Here we conducted batch sorption experiments with polyoxymethylene passive samplers to determine the partition coefficients at 37 °C of 18 polychlorinated biphenyls (PCBs) from water into (i) triolein (Ktriolein/water), (ii) eight types of liposomes (Kliposome/water), (iii) human abdominal fat tissues (KAFT/water) from seven individuals, and (iv) human MCF-7 cells cultured in vitro (Kcell/water). Differences between KAFT/water among individuals and between Kliposome/water among liposome types were very small and not correlated to structural attributes of the PCBs. Similarly, the length and degree of saturation of the phospholipid carbon chains, the headgroup, and the composition of the liposome did not affect the partitioning of PCBs into the studied liposomes. Whereas Kliposome/water values were similar to literature values of Koctanol/water adjusted to 37 °C, they both were lower than KAFT/water and Kcell/water by a factor of 3 on average. Partitioning of PCBs into triolein on the other hand closely mimicked that into human lipids, for which triolein is thus a better surrogate than either octanol or liposomes. Previously published polyparameter linear free energy relationships for partitioning from water into storage lipids and liposomes predicted the measured partition coefficients with a root-mean-square error of less than 0.15 log units, if the chosen equations and solute descriptors do not allow chlorine substitution in the ortho-position to influence the prediction. By guiding the selection of (i) a surrogate for the experimental determination and (ii) a method for the prediction of partitioning into human lipids, this study contributes to a better assessment of hydrophobic organic contaminant bioaccumulation in humans.

Partitioning and bioaccumulation of PCBs and PBDEs in marine plankton from the Strait of Georgia, British Columbia, Canada

The Strait of Georgia is a large, deep, fjord-like estuary on the southern coast of British Columbia which is subject to local and atmospheric inputs of persistent environmental contaminants. We measured 204 polychlorinated biphenyls (PCBs) and 61 polybrominated diphenyl ethers (PBDEs) seasonally in water (two depths; dissolved and particle-bound) and plankton (vertical tow) samples collected at two stations. Principal components analysis clearly distinguished the dissolved and particulate water fractions and plankton samples, with the latter two compartments associated more with heavier congeners. Bioaccumulation factors (logBAFs) for PCBs and PBDEs in plankton were best described by parabolic relationships against octanol–water partitioning coefficients (logKow), peaking at a logKow of 5–7, underscoring the important role of physico-chemical properties in driving the uptake of these persistent contaminants by plankton from water. The estimated total quantity of PCBs (annual average of 0.61±SEM 0.12kg) and PBDEs (annual average of 0.64±0.19kg) in Strait of Georgia plankton biomass were remarkably similar, highlighting the emergence of currently-used PBDEs as a priority concern. The estimated total of 52.1±8.41kg of PCBs in water (dissolved+particle-bound) was higher than the estimated 26.8±5.20kg of PBDEs (dissolved+particle-bound), reflecting the dichotomous use histories for these two contaminant classes. Results provide insight into the biological availability of PCBs and PBDEs to the Strait of Georgia food web, and describe an important initial partitioning process by which the region’s endangered killer whales have become highly contaminated.