RESUMEN
Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are semi-volatile organic compounds (SVOCs) existing in the atmosphere in the gas and particulate phase, remain persistent for a long time and pose a high risk to the environment and human health. In this study, PCDD/F measurements were made in an urban area between June 2022 and April 2023. In order to understand the fate of PCDD/Fs, the gas/particle (G/P) partitioning was studied. Although various models have been developed to determine the G/P partitioning of SVOCs, only logKp-logPL0, Junge-Pankow and Harner-Bidleman models are generally used for PCDD/Fs. In this study, nine different models (Junge-Pankow, Harner-Bidleman, Dachs-Eisenreich, Li-Ma-Yang, pp-LFER, mp-pp-LFER, QSPR, logKp-logPL0, logKp-logKOA) were employed to determine the G/P partitioning. To the best of our knowledge, pp-LFER, mp-pp-LFER and QSPR models were evaluated for PCDD/Fs for the first time in this study. In addition, the performance of the models within the equilibrium (EQ), non-equilibrium (NE) and maximum partitioning (MP) domain was investigated for PCDD/Fs for the first time in this study. Accordingly, models based on absorption in the EQ domain, adsorption in the NE domain and adsorption and absorption mechanisms in the MP domain were found to be effective in explaining the G/P transitions. It was determined that there is no equilibrium situation in the G/P partitioning. The Junge-Pankow, pp-LFER, Li-Ma-Yang and QSPR models under-predicted the particle fraction values while the other models showed a high prediction profile. The Li-Ma-Yang model showed the closest results to the measured particle fraction values, and it determined that deposition mechanisms are of non-negligible importance in the G/P partitioning of PCDD/Fs. One of the new models, the pp-LFER model, has shown remarkable success at high logKOA values. The mp-pp-LFER model, which overestimated the contribution of the adsorption mechanism, showed a very high prediction profile compared to the measured values.
RESUMEN
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) cause significant environmental concerns. Atmospheric PCDD/Fs permeate water bodies and other ecosystems through wet and dry deposition. In an urban site, dry deposition flux samples of gaseous phase PCDD/Fs were collected by a water surface sampler (WSS) operated between June 2022 and June 2023. There is a conspicuous absence of literature on the direct measurement of dry deposition flux levels in the gaseous phase of PCDD/Fs. In the study, PCDD/Fs in the gas phase reaching the WSS dissolved in the water according to Henry's Law. The PCDD/Fs in the water were transferred to an XAD-2 resin column, sorbing the dissolved PCDD/Fs. The average monthly gas phase dry deposition flux was 34.07 ± 9.35 pg/m2-day (7.35 ± 2.16 pg I-TEQ/m2-day). The highest flux was measured in March (49.53 pg/m2-day), and the lowest was in August (18.64 pg/m2-day). These values indicated the direct flux from air to water. The atmospheric concentration of the gas-phase ranged from 68.38 to 126.88 fg/m3 (13.22-25.01 fg I-TEQ/m3). Dry deposition fluxes and concentrations of atmospheric PCDD/Fs were bigger in the colder months than in the warmer months. This was probably due to a significant increase in residential heating during the colder months, decreased photochemical reactions, and lower mixing heights. Regarding congeners in the dry deposition flux and concentration values in I-TEQ units, 2,3,7,8-TCDD compound predominated with the proportions of 31.61 ± 7.76% and 29.09 ± 12.34%, respectively. Concurrently measured dry deposition flux (Fg) and ambient air concentration (Cg) of PCDD/Fs were considered in the determination of mass transfer coefficient (MTC = Fg/Cg) calculation for each PCDD/F congener. The average MTC for targeted 17 PCDD/Fs was 0.45 ± 0.15 cm/s, and it fluctuated between 0.89 ± 0.30 cm/s for 2,3,7,8-TCDF and 0.2 ± 0.16 cm/s for OCDD.
Asunto(s)
Contaminantes Atmosféricos , Dibenzofuranos Policlorados , Monitoreo del Ambiente , Dibenzodioxinas Policloradas , Dibenzodioxinas Policloradas/análisis , Dibenzofuranos Policlorados/análisis , Monitoreo del Ambiente/métodos , Contaminantes Atmosféricos/análisis , Agua/química , CiudadesRESUMEN
Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are pollutants of concern due to their toxic effects. No active sampling study on PCDD/Fs has been conducted in Bursa. This study aimed to fill this gap by measuring PCDD/F levels in the region. Accordingly, the samples were collected from an urban area in Bursa, covering four seasons between June 2022 and April 2023. The total (gas+particulate) ambient air concentrations were between 312.23 and 829.80 fg/m3 (mean: 555.05 ± 173.62 fg/m3). In terms of toxic equivalents (TEQ), the average concentration was 43.29 ± 9.18 fg WHOTEQ/m3. Based on the concentration values obtained, cancer and non-carcinogenic risk values of PCDD/Fs were calculated for three different age groups. The results indicated negligible health risks for all age groups. In addition, a seasonal assessment was also made and it was observed that PCDD/F concentration values varied with the ambient air temperatures. In general, higher values were measured in colder months compared to warmer months. This was probably due to the additional sources and adverse meteorological conditions. Moreover, the gas/particle partitioning of PCDD/Fs was investigated in detail. The average gas and particulate phase concentrations for PCDD/Fs were 101.81 ± 20.77 and 453.24 ± 172.50, respectively. It was found that an equilibrium state was not reached in the gas/particle partitioning. Two different gas/particle partition models based on adsorption and absorption mechanisms were compared, and the absorption model gave more consistent predictions. The Principal Component Analysis (PCA) was employed to identify the possible PCDD/F sources. The results indicated that the region was influenced by vehicle emissions, residential heating, organized industrial zones and metal recycling facilities. In addition, 72-hour backward air mass trajectory analyses were performed to understand the long-range transported air masses. However, it was found that the transported air masses did not significantly affect the concentration values measured in the sampling site.