Emissions of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs from heavy-duty diesel vehicles with DPF and SCR

In total, 24 polycyclic aromatic hydrocarbons (PAHs) in both gas and particle phases and 35 nitro-PAHs in particle phase were analyzed in the exhaust from heavy-duty diesel vehicles equipped with after-treatment for particulate matter (PM) and NO_X control. The test vehicles were carried out using a chassis dynamometer under highway cruise, transient Urban Dynamometer Driving Schedule (UDDS), and idle operation. The after-treatment efficiently abated more than 90% of the total PAHs. Indeed, the particle-bound PAHs were reduced by >99%, and the gaseous PAHs were removed at various extents depending on the type of after-treatment and the test cycles. The PAHs in gas phase dominated the total PAH (gas + particle phases) emissions for all the test vehicles and for all cycles; that is, 99% of the two-ring and 98% of the three-ring and 97% of the four-ring and 95% of the carcinogenic PAHs were in the gas-phase after a diesel particle filter (DPF) and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must include this volatile fraction and cannot be based on the particle fraction only. The selective catalytic reduction (SCR) did not appear to promote nitration of the PAHs in general, although there might be some selective nitration of phenanthrene. Importantly the after-treatmtent reduced the equivalent B[a]P (B[a]Peq) emissions by >95%, suggesting a substantial health benefit.

Implications: This study demonstrated that after-treatments, including diesel particulate filters (DPF), diesel oxidation catalysts (DOC), and selective catalytic reduction (SCR), significantly reduce the emissions of PAHs from heavy-duty diesel engines. The gas-phase PAHs dominate the total PAH (gas + particle phases) emissions from heavy-duty diesel vehicles retrofitted with various DPFs and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must also include this volatile fraction and cannot be based on the particle fraction only.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

A study of gas/particle partitioning of SVOCs in the tropical atmosphere of Southeast Asia

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were collected at a tropical site in Southeast Asia over 12-h periods during November and December 2006 to determine their gas/particle distributions by analyzing integrated quartz filter and polyurethane foam samples. Gas/particle partitioning coefficients, K_p, were calculated, and their relationship with the subcooled liquid vapor pressure p_L^o for both PAHs and PCBs was investigated. The regressions of log K_p vs. log p_L^o for most of samples gave high correlations for both PAHs and PCBs and the slopes were statistically shallower than ?1, but they were relatively steeper than those obtained in temperate zones of the Northern Hemisphere. By comparison, the particle-bound fraction of low molecular weight (LMW) PAHs was underestimated by both Junge-Pankow adsorption and K_OA (octanol–air partition coefficient) absorption models, while the predicted values agree relatively better with those observed ones for high molecular weight (HMW) PAHs. In addition, the adsorption onto the soot phase (elemental carbon) predicted accurately the gas/particle partitioning of PAHs, especially for LMW compounds. On the other hand, the K_OA absorption model using the measured organic matter fraction (f_OM) value fitted the PCB data much better than the adsorption model did, indicating the sorption of nonpolar compounds to aerosols might be dominated by absorption into organic matters in this area.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

Bioethanol-gasoline fuel blends: exhaust emissions and morphological characterization of particulate from a moped engine

This study was aimed at evaluating the effects of gasoline-ethanol blends on the exhaust emissions in a catalyst-equipped four-stroke moped engine. The ethanol was blended with unleaded gasoline in at percentages (10, 15, and 20% v/v). The regulated pollutants and the particulate matter emissions were evaluated over the European ECE R47 driving cycle on the chassis dynamometer bench. Particulate matter was characterized in terms of total mass collected on filters and total number ofparticles in the range 7 nm-10 microm measured by electrical low-pressure impactor (ELPI). In addition, particle-phase polycyclic aromatic hydrocarbons (PAHs) emissions were evaluated to assess the health impact of the emitted particulate. Finally, an accurate morphological analysis was performed on the particulate by high-resolution transmission electron microscope (TEM) equipped with a digital image-processing/data-acquisition system. In general, CO emission reductions of 60-70% were obtained with 15 and 20% v/v ethanol blends, while the ethanol use did not reduce hydrocarbon (HC) and NOx emissions. No evident effect of ethanol on the particulate mass emissions and associated PAHs emissions was observed. Twenty-one PAHs were quantified in the particulate phase with emissions ranging from 26 to 35 microg/km and benzo[a]pyrene equivalent (BaPeq) emission factors from 2.2 to 4.1 microg/km. Both particulate matter and associated PAHs with higher carcinogenic risk were mainly emitted in the submicrometer size range (<0.1 microm). On the basis of the TEM observations, no relevant effect of the ethanol use on the particulate morphology was evidenced, showing aggregates composed ofprimary particles with mean diameters in the range 17.5-32.5 nm.     

Gas/particle partitioning of polycyclic aromatic hydrocarbons in coastal atmosphere of the north Yellow Sea, China

Samples of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) were collected at three sampling stations (Xiaomai Island, Laohutan, and Zhangzi Island) in the north Yellow Sea, China during November 2008 and September 2009 to study their atmospheric transport potential and the gas/particle distributions. The composition of PAHs was dominated by gaseous compounds. The percentages of the particle-phase PAHs to the total concentrations were found to be higher during the heating period than the non-heating period. The ratios of naphthalene and acenaphthene to phenanthrene, chrysene and dibenzo(a,h)anthracene showed an increasing trend from Xiaomai Island to Zhangzi Island, which can be called as the local atmospheric distillation of PAHs. Gas/particle partitioning coefficients (K _p) and their relationship with the sub-cooled liquid vapor pressures (pº_L) of PAHs were investigated. The regressions of logK _p versus logpº_L gave significant correlations for all samples of the three sites with r ² values in the range 0.56–0.66 (p?<?0.01). Both Junge–Pankow adsorption model and octanol–air partition coefficient absorption model tended to underestimate the sorption for most PAHs, but the absorption model appeared to be more suitable for predicting the particle fraction of PAHs than the Junge–Pankow model.     

Emissions of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) in the Shing Mun Tunnel,Hong Kong

Real-world vehicle emission factors for seventeen gas and particulate polycyclic aromatic hydrocarbons (PAHs) were quantified in the Shing Mun Tunnel, Hong Kong during summer and winter 2003. Naphthalene, acenaphthylene, and acenaphthene were the most abundant gas PAHs while fluoranthene and pyrene were the most abundant in the particle phase. Most (98%) of the gas PAHs consisted of two- and three-aromatic rings whereas most of the particle-phase PAHs were in four- (～60%) and five-ring (～17%) for fresh exhaust emissions. Average emission factors for the gas- and particle PAHs were 950–2564 μg veh^?1 km^?1 and 22–354 μg veh^?1 km^?1, respectively. Good correlations were found between diesel markers (fluoranthene and pyrene; 0.85) and gasoline markers (benzo[ghi]perylene and indeno[1,2,3-cd]pyrene; 0.96). Higher PAH emission factors were associated with a higher fraction of diesel-fueled vehicles (DV) passing through the tunnel. Separate emission factors were determined from diesel and non-diesel exhaust by the regression intercept method. The average PAH emission factor (i.e., sum of gas and particle phases) from DV (3085 ± 1058 μg veh^?1 km^?1) was ～5 times higher than that from non-diesel-fueled vehicles (NDV, 566 ± 428 μg veh^?1 km^?1). Ratios of DV to NDV emission factors were high for diesel markers (>24); and low for gasoline markers (<0.4).     

Vapor-phase and fine particulate matter concentrations of polycyclic aromatic hydrocarbons measured during the winter months in a northern Rocky Mountain urban airshed

A fine particulate matter (PM2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM2.5-associated gas/particle partition coefficients (Kp,2.5) ranged from 0 for the lighter phenolics and PAHs to approximately 0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating Kp,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM2.5 are generally at their highest compared with the rest of the year.     

蜂窝煤燃烧烟气中多环芳烃的定量研究及粒径分布特征

通过对蜂窝煤燃烧排放的烟气中多环芳烃的定量分析,研究了17种多环芳烃在烟气颗粒相和气相中的分配以及在不同粒径颗粒物上的分布特征。结果表明：在室温下燃煤排放的多环芳烃总量以在气相中存在为主,但总体毒性则主要存在于颗粒相中;多环芳烃主要分布在亚微米级颗粒上,分子量越大的多环芳烃越趋于富集在细颗粒上,因而对健康的危害就越大。     

Effects of Open Burning of Rice Straw on Concentrations of Atmospheric Polycyclic Aromatic Hydrocarbons in Central Taiwan

Abstract

The sizes and concentrations of 21 atmospheric polycyclic aromatic hydrocarbons (PAHs) were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan in October and December 2005. Air samples were collected using semi-volatile sampling trains (PS-1 sampler) over 16 days for rice-straw burning and nonburning periods. These samples were then analyzed using a gas chromatograph with a flame-ionization detector (GC/FID). Particle-size distributions in the particulate phase show a bimode, peaking at 0.32–0.56 μm and 3.2–5.6 μm at the two sites during the nonburning period. During the burning period, peaks also appeared at 0.32–0.56 μm and 3.2–5.6 μm at Jhu-Shan, with the accumulation mode (particle size between 0.1 and 3.2 μm) accounting for approximately 74.1% of total particle mass. The peaks at 0.18–0.32 μm and 1.8–3.2 μm at Shin-Gang had an accumulation mode accounting for approximately 70.1% of total particle mass. The mass median diameter (MMD) of 3.99–4.35 μm in the particulate phase suggested that rice-straw burning generated increased numbers of coarse particles. The concentrations of total PAHs (sum of 21 gases + particles) at the Jhu-Shan site (Sin-Gang site) were 522.9 ± 111.4 ng/m? (572.0 ± 91.0 ng/m?) and 330.1 ± 17.0 ng/m? (or 427.5 ± 108.0 ng/m?) during burning and nonburning periods, respectively, accounting for a roughly 58% (or 34%) increase in the concentrations of total PAHs due to rice-straw burning. On average, low-weight PAHs (about 87.0%) represent the largest proportion of total PAHs, followed by medium-weight PAHs (7.1%), and high-weight PAHs (5.9%). Combustion-related PAHs during burning periods were 1.54–2.57 times higher than those during nonburning periods. The results of principal component analysis (PCA)/absolute principal component scores (APCS) suggest that the primary pollution sources at the two sites are similar and include vehicle exhaust, coal/wood combustion, incense burning, and incineration emissions. Open burning of rice straw was estimated to contribute approximately 5.0–33.5% to the total atmospheric PAHs at the two sites.     

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: Part I. PAHs,PCBs and OCPs and the matrix chemical composition

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1–30 ng m^?3 (corresponding to 15–35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2–11 pg m^?3 (4–26 % of the total) and of DDT compounds were 2–12 pg m^?3 (4–23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM_0.95) were 73–90 %, 34–71 % and 36–81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3–29.7)_×10^?6 cm^?1 (44–70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.     

Fast and quantitative measurement of benzene,toluene and C2-benzenes in automotive exhaust during transient engine operation with and without catalytic exhaust gas treatment

Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C₂-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.     

Vapor-Phase and Fine Particulate Matter Concentrations of Polycyclic Aromatic Hydrocarbons Measured during the Winter Months in a Northern Rocky Mountain Urban Airshed

Abstract

A fine particulate matter (PM_2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM_2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM_2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM_2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM_2.5-associated gas/particle partition coefficients (K_p,2.5) ranged from 0 for the lighter phenolics and PAHs to ~0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating K_p,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM_2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM_2.5 are generally at their highest compared with the rest of the year.     

Gas-particle concentration and distribution of n-alkanes and polycyclic aromatic hydrocarbons in the atmosphere of Prato (Italy)

Air samples were collected in an urban and industrialised area of Prato (Italy) during 2002, as part of a study to identify and measure aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs). Total concentrations of aliphatic hydrocarbons ranged between 170 and 282ngm(-3) in the gas phase and from 48.9 to 276ngm(-3) in the particulate phase. The average total PAH concentrations (gas+particulate) were 59.4+/-26.5ngm(-3), and both gas and particulate phase PAH concentrations decreased with increasing temperature. Source identification using diagnostic ratios and principal component analysis identified automobile traffic, in particular, the strong influence of diesel fuel burning, as the major PAH source. Gas-particle partition coefficients (K(p)'s) of n-alkane and PAHs were well correlated with the sub-cooled liquid vapour pressure (P(L)(0)) and indicate stronger sorption of PAHs to aerosol particles compared with n-alkanes.     

Effects of diesel/biodiesel blends on regulated and unregulated pollutants from a passenger vehicle operated over the European and the Athens driving cycles

This paper presents the regulated and unregulated exhaust emissions of a diesel passenger vehicle, operated with low sulphur automotive diesel and soy methyl ester blends. Emission and fuel consumption measurements were conducted under real driving conditions (Athens Driving Cycle, ADC) and compared with those of a modified New European Driving Cycle (NEDC) using a chassis dynamometer. A Euro II compliant diesel vehicle was used in this study, equipped with an indirect injection diesel engine, fuelled with diesel fuel and biodiesel blends at proportions of 5, 10, and 20% respectively. Unregulated emissions of 11 polycyclic aromatic hydrocarbons (PAHs), 5 nitro-PAHs, 13 carbonyl compounds (CBCs) and the soluble organic fraction (SOF) of the particulate matter were measured. Qualitative hydrocarbon analysis was also performed on the SOF. Regulated emissions of NO_x, CO, HC, CO₂, and PM were also measured over the two test cycles. It was established that some of the emissions measured over the (hot-start) NEDC differed from the real-world cycle. Significant differences were also observed in the vehicle's fuel consumption between the two test cycles. The addition of biodiesel reduced the regulated emissions of CO, HC and PM, while an increase in NO_x was observed over the ADC. Carbonyl emissions, PAHs and nitro-PAHs were reduced with the addition of biodiesel over both driving cycles.     

Apply appropriate models in the study of dry deposition fluxes of particulate matter and polycyclic aromatic hydrocarbons (PAHs) in Tsukuba, Japan

In this study, plates for downward flux and upward flux were used to measure atmospheric dry deposition fluxes for particulate mass and polycyclic aromatic hydrocarbons (PAHs) in TERC (Tsukuba), Japan. Ambient particles concentrations were also collected using a high-volume air sampler, and ambient particle size distributions between 0.01 μm and 13.1 μm were measured using a low-pressure cascade impactor to characterise the PAHs levels and dry deposition. The results indicated that the average cumulative fraction of dry deposition flux for particles and PAHs which attached with them was caused by the particle size of greater than 1.2-6.3 μm (97%).     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

Modelling fuel consumption and pollutant emissions based on real-world driving patterns: the HBEFA approach

Emissions of passenger cars and light-duty vehicles with complex exhaust gas after-treatment are difficult to predict, especially if the prediction is only based on kinematic parameters without vehicle-specific data. A new method for modelling fleet emission factors based on testbench data is presented. It has been used for modern passenger cars and light-duty vehicles (EURO-2 and -3) in the new version 2.1 of the German-Austrian-Swiss Handbook Emission Factors for Road Transport (HBEFA). The new method, not relying on vehicle-specific data, avoids decomposing the measured real-world driving behaviour and all associated uncertainties. Emission factors can be predicted for any given driving pattern which is characterised through kinematic parameters or representative time series of vehicle speed. The methodology determines the linear combination of measured driving patterns that is most representative for the driving pattern whose emissions are to be predicted. The approach is illustrated using testbench real-world measurements of 44 passenger cars of technology stages EURO-2 and -3.     

Particulate organic compounds emitted from motor vehicle exhaust and in the urban atmosphere

The emission rate of particle-phase petroleum biomarkers in vehicular exhaust compared to the concentrations of these biomarkers in ambient air is used to determine the particulate organic compound concentration due to primary particle emissions from motor vehicles in the southern California atmosphere. A material balance on the organic particulate matter emitted from motor vehicle traffic in a Los Angeles highway tunnel first is constructed to show the proportion which is solvent-extractable and which will elute from a GC column, the ratio of resolved to unresolved compound mass, the portion of the resolved material that can be identified as single organic compounds, and the contribution of different classes of organic compounds to the overall identified fraction. It is shown that the outdoor ambient concentrations of the petroleum biomarkers track primary emissions measured in the highway tunnel, confirming that direct emissions of these compounds from vehicles govern the observed ambient petroleum biomarker concentrations. Using organic chemical tracer techniques, the portion of fine organic particulate matter in the Los Angeles atmosphere which is attributable to direct particle emissions from vehicle exhaust is calculated to vary from 7.5 to 18.3% at different sites throughout the air basin during a summertime severe photochemical smog episode. A similar level of variation in the contribution of primary motor vehicle exhaust to fine particulate organic matter concentrations during different times of day is seen. While peak atmospheric concentrations of fine particulate organic carbon are observed during the 1200–1600 PDT afternoon sampling period, only 6.3% of that material is apportioned to the directly emitted particles from vehicle exhaust. During the morning traffic peak between 0600–1000 PDT, 19.1% of the fine particulate organic material is traced to primary emissions from motor vehicles.     

Equilibrium partitioning of PCB congeners in the water column: Field measurements from the Hudson River

The environmental behavior of hydrophobic organic compounds in water is driven by partitioning between dissolved and sorbed phases. Partitioning behavior of a compound is often based on empirical relationships to other properties of the chemical, such as water solubility and octanol-water partition coefficients, but actual partitioning in the environment may differ significantly from such predictions. We conducted intensive studies of the distribution of PCBs in the fresh water portion of the Hudson River, using sensitive capillary-column gas chromatography methods to calibrate and resolve quantitations for 90 PCB congeners in 48 samples at 10 locations. A linear equilibrium model of PCB congener partitioning, when corrected for temperature and suspended-matter organic carbon content, provides a good representation of phase distribution. When particulate-phase concentrations are predicted from dissolved concentrations with a two-phase model, the predictions are unbiased for the majority of samples and the average percent difference between observed and predicted particulate concentrations is ±43 percent. Estimated in situ partition coefficients show systematic differences from partition coefficients predicted from octanol-water partitioning. Partitioning to colloids appears to be a significant component of total concentration for mono- and dichlorobiphenyls, but not for more highly chlorinated congeners.The colloidal fraction may still cause significant overestimation of the bioavailable fraction for more hydrophobic congeners when a two-component model is used.