Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Henry's law constant, octanol-air partition coefficient and supercooled liquid vapor pressure of carbazole as a function of temperature: application to gas/particle partitioning in the atmosphere

The Henry's law constant for carbazole was experimentally determined between 5 and 35 degrees C using a gas-stripping technique. The following equation was obtained for dimensionless Henry's law constant (H') versus temperature (T, K): ln H' = -3982(T,K)(-1) + 1.01. Temperature-dependent octanol-air partition coefficients (KOA) and supercooled liquid vapor pressures (PL,Pa) of carbazole were also determined using the GC retention time method. The temperature dependence of KOA and PL were explained by the following: log KOA = 4076/(T,K) - 5.65, log PL(Pa) = -3948(T,K)(- 1) + 11.48.The gas and particle-phase carbazole concentrations measured previously in Chicago, IL in 1995 was used for gas/particle partitioning modeling. Octanol based absorptive partitioning model consistently underpredicted the gas/particle partition coefficients (Kp) for all sampling periods. However, overall there was a good agreement between the measured Kp and soot-based model predictions.     

POPs in a major conurbation in Turkey: ambient air concentrations,seasonal variation,inhalation and dermal exposure,and associated carcinogenic risks

Environmental Science and Pollution Research - Semi-volatile organic compounds were monitored over a whole year, by collection of gas and particle phases every sixth day at a suburban site in...     

PCB mass transfer coefficients determined by application of a water surface sampler

A water surface sampler (WSS) was employed in combination with greased surface deposition plates (GSDPs) to measure the particulate dry deposition and gas exchange of polychlorinated biphenyls (PCBs) in Chicago, IL. Vapor phase PCB fluxes were calculated by subtracting the particulate fluxes obtained from GSDPs from total (particulate+gas) fluxes obtained from the WSS. Vapor phase PCB fluxes were divided by ambient air concentrations measured with a high volume sampler to calculate overall gas phase PCB mass transfer coefficients (K(G)). The calculated average PCB MTC was 0.54+/-0.47 cm s(-1). This experimentally determined average gas phase overall mass transfer coefficient, K(G), agreed well with the ones reported from studies using similar techniques and agreed well with modeled values obtained using MTC correlations developed for the WSS.     

Dry deposition and soil-air gas exchange of polychlorinated biphenyls (PCBs) in an industrial area

Ambient air and dry deposition, and soil samples were collected at the Aliaga industrial site in Izmir, Turkey. Atmospheric total (particle + gas) ∑₄₁-PCB concentrations were higher in summer (3370 ± 1617 pg m⁻³, average + SD) than in winter (1164 ± 618 pg m⁻³), probably due to increased volatilization with temperature. Average particulate ∑₄₁-PCBs dry deposition fluxes were 349 ± 183 and 469 ± 328 ng m⁻² day⁻¹ in summer and winter, respectively. Overall average particulate deposition velocity was 5.5 ± 3.5 cm s⁻¹. The spatial distribution of ∑₄₁-PCB soil concentrations (n = 48) showed that the iron-steel plants, ship dismantling facilities, refinery and petrochemicals complex are the major sources in the area. Calculated air-soil exchange fluxes indicated that the contaminated soil is a secondary source to the atmosphere for lighter PCBs and as a sink for heavier ones. Comparable magnitude of gas exchange and dry particle deposition fluxes indicated that both mechanisms are equally important for PCB movement between air and soil in Aliaga.     

Concentrations and gas/particle partitioning of PCBs in Chicago

Thirty seven air samples were collected in Chicago, IL from June to October 1995 and analyzed for gas and particle concentrations of polychlorinated biphenyls (PCBs). Lower molecular weight (MW) PCBs dominated the samples and on average 95% of the Sigma50PCB concentration (gas+particulate) was in the vapor phase. Sigma50PCB concentrations were classified based on prevailing winds (lake and land). The Sigma50PCB concentration varied between 0.42 and 5.21 ng/m3 (1.80+/-1.70 ng/m3) for lake and 0.53 and 8.31 ng/m3 (2.41+/-2.15 ng/m3) for land wind directions. Back trajectory analyses suggested that SW of Chicago can be an important local or regional source sector for PCBs. Partitioning between gas and particulate phases was modeled using the Junge-Pankow model. The measured particle phase concentrations for low MW PCBs were lower than those predicted by the model while the opposite was observed for high MW PCBs. Plots of gas/particle partition coefficient (log Kp) vs. subcooled liquid vapor pressure (log pL(0)) had reasonable correlations for individual samples but the slope varied among the samples. Samples that originated from over the lake had higher slopes than samples that originated from over the land.     

Atmospheric concentrations and phase partitioning of polybrominated diphenyl ethers (PBDEs) in Izmir, Turkey

Atmospheric concentrations of 7 PBDE congeners (BDE-28, -47, -99, -100, -153, -154 and -209) were determined at four sites (i.e. Suburban, Urban 1, Urban 2, Industrial) in Izmir, Turkey and their gas/particle partitioning was investigated. Total PBDE ( summation operator(7)PBDE) concentrations ranged between 11 (Urban 1) and 149pgm(-3) (Industrial) in summer, while in winter, they ranged from 6 (Suburban) to 81pgm(-3) (Industrial). BDE-209 was the dominant congener at all sites, followed by BDE-99 and -47. Investigation of source profiles indicated that the air samples were dominated by congeners of the penta and deca-technical BDE mixtures. The measured PBDE particle fractions were compared to the predictions of the K(OA) (octanol-air partition coefficient)-based equilibrium partitioning model and to the dynamic uptake model developed by others for passive samplers, which was adapted to model gas-particle partitioning in this study. For BDE-28, good agreement was observed between the experimental particle fractions and those predicted by the equilibrium partitioning model. However, this model overestimated the particle fractions of other congeners. The predictions of the dynamic uptake model supported the hypothesis that the unexpectedly high partitioning of BDEs (except BDE-28) to the gas-phase is due to their departure from equilibrium partitioning. When congeners with very large octanol-air partition coefficients (i.e. BDE-100, -99, -154, -153, and -209) are emitted from their sources in the gas-phase, they may remain in that phase for several months before reaching equilibrium with atmospheric particles. This may also have important implications for the transport of atmospheric PBDEs. For example, in addition to particle-bound transport, the gas-phase transport of highly brominated congeners (i.e. BDE-209) may also be important.     

Ambient concentrations and source apportionment of PCBs and trace elements around an industrial area in Izmir, Turkey

Atmospheric concentrations of polychlorinated biphenyls (PCBs) and trace elements were measured at two sites (Industrial and Urban) located around the Aliaga industrial region, Izmir, Turkey. Average sigma 36PCB concentrations were 3136+/-824 and 1371+/-642 pg m(-3) for summer and winter periods, respectively in the Industrial site and they were 314+/-129 and 847+/-610 pg m(-3) in the Urban site. The elemental content showed that the PM(10) measured at the Industrial site was dominated by terrestrial elements and trace elements emitted by the iron-steel plants (Fe, Zn and Pb). The elemental profile at the Urban site was typical for Aegean Region that was dominated by terrestrial elements (Ca, Al, Mg) and sea salt (Na). Sources of particle-phase PCBs and trace elements were identified using factor analysis (FA) and were apportioned by chemical mass balance (CMB) model. FA suggested that the steel industry, fuel oil combustion, or the nearby vinyl chloride process in the petrochemical plant, and soil were significant PCB sources. CMB results showed that at the Industrial site, the contribution of steel industry and soil to particle-phase PCBs were 71% and 22%, respectively, while at the Urban site, the contributions were 33% and 49%, respectively. Steel industry was also the dominant contributor for trace elements around the site. Fugacity calculations in air and soil showed that the soil acts as a secondary source to the atmosphere for low molecular weight PCBs especially in summer and as a sink for the higher molecular weight ones.     

Characterization of Volatile Organic Compounds (VOCs) and Their Sources in the Air of Izmir, Turkey

Air samples were collected in Izmir, Turkey at two (suburban and urban) sites during three sampling programs in 2002 and 2004 to determine the ambient concentrations of several monoaromatic, chlorinated and oxygenated volatile organic compounds (VOCs). Samples were analyzed for 60 VOCs using gas chromatography/mass spectrometry and 28 compounds were detected in most samples. On the average, urban air VOC concentrations were about four times higher than those measured at the suburban site. Toluene (40.6%) was the most abundant compound in suburban site and was followed by benzene (7.4%), o,m-xylene (6.5%), and 1,2-dichloroethane (5.1%). In urban site, toluene (30.5%), p-xylene (14.9%), o,m-xylene (11.4%), and ethyl benzene (7.2%) were the dominating compounds in summer. In winter, toluene (31.1%), benzene (23.9%), 1,2-dichloroethane (9.5%), and o,m-xylene (8.2%) were the most abundant compounds. Receptor modeling (positive matrix factorization) has been performed to estimate the contribution of specific source types to ambient concentrations. Six source factors (gasoline vehicle exhaust, diesel vehicle exhaust+residential heating, paint production/application, degreasing, dry cleaning, and an undefined source) were extracted from the samples collected in the urban site. Three source factors (gasoline vehicle exhaust, diesel vehicle exhaust, and paint production/application) were identified for the suburban site.     

Determination of Henry’s Law Constant of Formaldehyde as a Function of Temperature: Application to Air–Water Exchange in Tahtali Lake in Izmir, Turkey

The Henry's law constant (H) is an important parameter in predicting the transport, behavior and fate of organic compounds in environment. H is also required to model the air-water exchange of chemicals. Henry's law constant of formaldehyde (HCHO) was determined at six temperatures (50, 40, 30, 20, 10, and 5 degrees C) using a bubble-column technique. The apparent Henrys law constant (H*) values were strongly correlated to inverse of temperature (1/T, K) and the following relationship was obtained: In H* = (-1,641.3/T)-3.089. Seven concurrent ambient air and aqueous samples were also collected between October 11-17, 2005 at a sampling site located on the shoreline of Tahtali dam Lake in Izmir, Turkey to determine the magnitude and direction (deposition or gas-out) of HCHO flux. In all cases, the modeled gas-phase flux was positive (average +/- SD, 3,181 +/- 408 microg m(-2) day(-1)) indicating that atmospheric HCHO deposited to the Tahtali Lake.