Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 27Citation - Scopus: 28Fast Formation of Nitro-Pahs in the Marine Atmosphere Constrained in a Regional-Scale Lagrangian Field Experiment(American Chemical Society, 2019) Mulder, Marie D.; Dumanoğlu, Yetkin; Efstathiou, Christos; Kukucka, Petr; Matejovicova, Jana; Maurer, Christian; Pribylova, Petra; Prokes, Roman; Sofuoğlu, Aysun; Sofuoğlu, Sait Cemil; Wilson, Jake; Zetzsch, Cornelius; Wotawa, Gerhard; Lammel, GerhardPolycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 ± 0.2) and (1.5 ± 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NOx conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NOx conditions, are largely underestimated.Article Citation - WoS: 18Citation - Scopus: 21Polybrominated Diphenyl Ethers (pbdes) in Background Air Around the Aegean: Implications for Phase Partitioning and Size Distribution(Springer Verlag, 2017) Besis, Athanasios; Lammel, Gerhard; Kukucka, Petr; Samara, Constantini; Sofuoğlu, Aysun; Dumanoğlu, Yetkin; Eleftheriadis, Kostas; Kouvarakis, Giorgos; Sofuoğlu, Sait Cemil; Vassilatou, Vassiliki; Voutsa, DimitraThe occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m−3, respectively) were found at the remote site Finokalia. Partitioning coefficients, KP, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (PL°) and the octanol-air partition coefficient (KOA), were investigated. The equilibrium adsorption (PL°-based) and absorption (KOA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log KOA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log PL° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.Article Citation - WoS: 108Citation - Scopus: 113Spatial and Seasonal Variations, Sources, Air-Soil Exchange, and Carcinogenic Risk Assessment for Pahs and Pcbs in Air and Soil of Kutahya, Turkey, the Province of Thermal Power Plants(Elsevier Ltd., 2017) Dumanoğlu, Yetkin; Gaga, Eftade O.; Güngörmüş, Elif; Sofuoğlu, Sait Cemil; Odabaşı, MustafaAtmospheric and concurrent soil samples were collected during winter and summer of 2014 at 41 sites in Kutahya, Turkey to investigate spatial and seasonal variations, sources, air-soil exchange, and associated carcinogenic risks of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The highest atmospheric and soil concentrations were observed near power plants and residential areas, and the wintertime concentrations were generally higher than ones measured in summer. Spatial distribution of measured ambient concentrations and results of the factor analysis showed that the major contributing PAH sources in Kutahya region were the coal combustion for power generation and residential heating (48.9%), and diesel and gasoline exhaust emissions (47.3%) while the major PCB sources were the coal (thermal power plants and residential heating) and wood combustion (residential heating) (45.4%), and evaporative emissions from previously used technical PCB mixtures (34.7%). Results of fugacity fraction calculations indicated that the soil and atmosphere were not in equilibrium for most of the PAHs (88.0% in winter, 87.4% in summer) and PCBs (76.8% in winter, 83.8% in summer). For PAHs, deposition to the soil was the dominant mechanism in winter while in summer volatilization was equally important. For PCBs, volatilization dominated in summer while deposition was higher in winter. Cancer risks associated with inhalation and accidental soil ingestion of soil were also estimated. Generally, the estimated carcinogenic risks were below the acceptable risk level of 10− 6. The percentage of the population exceeding the acceptable risk level ranged from < 1% to 16%, except, 32% of the inhalation risk levels due to PAH exposure in winter at urban/industrial sites were > 10− 6.Article Citation - WoS: 49Citation - Scopus: 52Evaluation of a Conceptual Model for Gas-Particle Partitioning of Polycyclic Aromatic Hydrocarbons Using Polyparameter Linear Free Energy Relationships(American Chemical Society, 2016) Shahpoury, Pourya; Lammel, Gerhard; Albinet, Alexandre; Sofuoglu, Aysun; Dumanoğlu, Yetkin; Sofuoğlu, Sait Cemil; Wagner, Zdenek; Zdimal, VladimírA model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35-0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03-1.40 and 0.94-1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected. (Figure Presented).Article Citation - WoS: 45Citation - Scopus: 48Halogenated Volatile Organic Compounds in Chlorine-Bleach Household Products and Implications for Their Use(Elsevier Ltd., 2014) Odabaşı, Mustafa; Elbir, Tolga; Dumanoğlu, Yetkin; Sofuoğlu, Sait CemilIt was recently shown that substantial amounts of halogenated volatile organic compounds (VOCs) are formed in chlorine-bleach-containing household products as a result of reactions of sodium hypochlorite with organic product components. Use of these household products results in elevated indoor air halogenated VOC concentrations. Halogenated VOCs in several chlorine-bleach-containing household products (plain, n=9; fragranced, n=4; and surfactant-added, n=29) from Europe and North America were measured in the present study. Chloroform and carbon tetrachloride were the dominating compounds having average concentrations of 9.5±29.0 (average±SD) and 23.2±44.3 (average±SD) mgL-1, respectively. Halogenated VOC concentrations were the lowest in plain bleach, slightly higher in fragranced products and the highest in the surfactant-added products. Investigation of the relationship between the halogenated VOCs and several product ingredients indicated that chlorinated VOC formation is closely related to product composition. Indoor air concentrations from the household use of bleach products (i.e., bathroom, kitchen, and hallway cleaning) were estimated for the two dominating VOCs (chloroform and carbon tetrachloride). Estimated indoor concentrations ranged between 0.5 and 1030 (34±123, average±SD) μgm-3 and 0.3-1124 (82±194, average±SD) μgm-3 for chloroform and carbon tetrachloride, respectively, indicating substantial increases compared to background. Results indicated that indoor air concentrations from surfactant-added products were significantly higher (p<0.01) than other categories. The highest concentrations were from the use of surfactant-added bleach products for bathroom cleaning (92±228 and 224±334μgm-3, average±SD for chloroform and carbon tetrachloride, respectively). Associated carcinogenic risks from the use of these products were also estimated. The risk levels may reach to considerably high levels for a significant portion of the population especially for those steadily using the surfactant-added bleach products. Based on the results of the present study, it could be recommended that if possible the use of chlorine bleach containing household products should be avoided. If they are to be used, plain products should be preferred since the chlorinated VOC content increase with the number and amount of additives.