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Atmospheric ambient trace element concentrations of PM10 at urban and sub-urban sites: source apportionment and health risk estimation
(Springer, 2018) Bozkurt, Zehra; Gaga, Eftade O.; Taşpınar, Fatih; Arı, Akif; Pekey, Beyhan; Pekey, Hakan; Döğeroglu, Tuncay
In this study, PM10 concentrations and elemental (Al, Fe, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pb, and Bi) contents of particles were determined in Duzce, Turkey. The particulate matter samplings were carried out in the winter and summer seasons simultaneously in both urban and sub-urban sampling sites. The average PM10 concentration measured in the winter season was 86.4 and 27.3 mu g/m(3), respectively, in the urban and sub-urban sampling sites, while it was measured as 53.2 and 34.7 mu g/m(3) in the summer season. According to the results, it was observed that the PM10 levels and the element concentrations reached higher levels, especially at the urban sampling site, in the winter season. The positive matrix factorization model (PMF) was applied to the data set for source apportionment. Analysis with the PMF model revealed six factors for both the urban (coal combustion, traffic, oil combustion, industry, biomass combustion, and soil) and sub-urban (industry, oil combustion, traffic, road dust, soil resuspension, domestic heating) sampling sites. Loadings of grouped elements on these factors showed that the major sources of the elements in the atmosphere of Duzce were traffic, fossil fuel combustion, and metal industry-related emissions.
Chemical characterization of size-segregated particulate matter (PM) by inductively coupled plasma - Tandem mass spectrometry (ICP-MS/MS)
(Elsevier, 2020) Arı, Akif; Arı, Pelin Ertürk; Gaga, Eftade O.
An analytical method was optimized for quantification of 67 elements including P, S and Si in size-segregated atmospheric particulate matter (PM) samples by Inductively Coupled Plasma-Tandem Mass Spectrometry (ICP-MS/MS). The analytical performance of ICP-MS/MS system using 02 as reaction gas and He as collision gas into the octopole collision/reaction cell (CRC) by mass shift and on mass using single MS modes were evaluated to enhance interference-free analysis. Satisfactory recoveries of elements in the range of 71.5% +/- 3.4% (Ca) and 110.9% +/- 13.1% (Si) were obtained by dissolving and analyzing certified reference material (CRM - NIST 1648a, urban dust). Elemental S in PM samples with high recovery (96.6% +/- 3.9%) was reported for the first time by using an ICP-MS/MS technique. ICY-MS/MS is a very powerful technique and provides interference-free detection of elements in PM samples.
A comprehensive characterization of particulate matter, trace elements, and gaseous emissions of piston-engine aircraft
(Amer Chemical Soc, 2020) Turgut, Enis T.; Açıkel, Gürkan; Gaga, Eftade O.; Çalışır, Duran; Odabaşı, Mustafa; Arı, Akif; Artun, Gülzade
The gaseous and PM10 emissions of a piston-engine aircraft during ground operations at different engine states (six engine speed points and three air/fuel mixtures) representing certain flight phases were concurrently measured from the exhaust duct. PM10 emissions were sampled on a 47 mm-diameter polytetrafluoroethylene (PTFE) filter in order to be analyzed with an inductively coupled plasma mass spectrometry (ICP-MS/MS) to identify the presence and level of forty-eight elements. The most abundant element is found to be Pb (med = 4.6 X 10(6) ng m(-3)), which is 40 times the second most abundant element, Na (med = 1.1 x 10(5) ng m(-3)). The filters used for sampling exhaust gases tend to lighten with an increase in engine speed and leaning of the fuel mixture. The average of measured PM mass concentrations at all engine speeds were calculated to be 27.7 mg m(-3) (full-rich) > 26.7 mg m(-3) (best-power) > 24.7 mg m(-3) (best-economy). The total mass of the trace elements constitutes an average of 24.1 +/- 12.8% of the mass of PM. Electron microscope analyses suggest that the particles enriched by Al tend to agglomerate in a needle-shaped structure.
Determination of real-world emission factors of trace metals, EC, OC, BTEX, and semivolatile organic compounds (PAHs, PCBs and PCNs) in a rural tunnel in Bilecik, Turkey
(Elsevier, 2018) Gaga, Eftade O.; Arı, Akif; Akyol, Nesimi; Üzmez, Özlem Özden; Kara, Melik
A field study was performed in a rural tunnel to determine pollutant concentrations, sources and on road vehicle emission factors (EFs) of particulate matter, trace metals, elemental carbon (EC), organic carbon (OC), benzene, toluene, ethyl benzene and xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs). Emission factors (EFs) for polychlorinated naphthalenes (PCNs) and polychlorinated biphenyls (PCBs) were also determined. A 12-day extensive sampling campaign during morning and afternoon periods at inlet and exit stations of the tunnel was conducted. Morphology of the particles was also investigated by Scanning Electron Microcopy (SEM). Correlation analysis, factor analysis and diagnostic PAH ratios were utilized to identify emission sources of trace metals. Identified sources include brake wear (33%), resuspension of road dust (15%), tyre wear (12%), exhaust emissions (10%), and lubricants (9%). Based on the PAH diagnostic ratios, major sources of PAHs were estimated as diesel emissions. EFs were comparable with the literature and varied from 31.5 to 295.4 mg vehicle(-1) km(-1) with an average of 129.2 +/- 80 mg vehicle(-1) km(-1) for PM2.5. PM2.5-10 EFs varied between 15.9 and 236.1 mg vehicle(-1) km(-1) with an average of 96 +/- 30 mg vehicle(-1) km(-1). Average EC EFs were 40.3 +/- 9.8 mg vehicle(-1) km(-1) for PM2.5 samples and 19.5 +/- 0.5 mg vehicle(-1) km(-1) for PM2.5-10 samples while OC EFs were 33.7 +/- 18 and 15.5 +/- 8.4 mg vehicle(-1) km(-1) for fine and coarse particles, respectively. EFs of elements were generally 2 (Al) to 59 (Mg) times higher than those previously reported in the literature. Compared to literature, relatively higher EFs for Sigma(13)PAHs (range: 48.1-168 mu g vehicle(-1) km(-1), average: 84.3 +/- 46.4 mu g vehicle(-1) km(-1)) were obtained. BTEX emission factors were in the range of 4.2 +/- 4.7 mg vehicle(-1) km(-1) (m + p-xylene) and 16.7 +/- 10.5 mg vehicle(-1) km(-1) (toluene). Average EFs for Sigma PCBs and Sigma PCNs were 12.06 +/- 5.3 mu g vehicle(-1) km(-1) and 88.9 +/- 70.4 ng vehicle(-1) km(-1), respectively. (C) 2018 Elsevier B.V. All rights reserved.
Gas-particle partitioning and health risk estimation of polycyclic aromatic hydrocarbons (PAHs) at urban, suburban and tunnel atmospheres: Use of measured EC and OC in model calculations
(Turkish Natl Committee Air Pollution Res & Control-Tuncap, 2019) Gaga, Eftade O.; Arı, Akif
Gas and particle phase ambient concentrations polycyclic aromatic hydrocarbons (Sigma 13PAH) were determined at urban and suburban sites in Eskisehir and in a traffic-tunnel. Organic and elemental carbon (OC and EC) concentrations of total suspended particles (TSP) were also measured. Atmospheric Sigma 13PAH (gas+particle) concentrations measured at suburban sites was found to be lower than that of tunnel and urban site. Concentrations of TSP and OC/EC were highest in the tunnel. Fluorene, Phe, Flt and Pyr were the most dominant PAH compounds in gas phase samples for all three sampling locations, while BaA, Chr, BbF, BkF and BaP were found to be higher in particle phase. Gas-particle partitioning coefficients, (Kp) and particle-phase fractions (Phi) of PAHs were correlated with supercooled vapor pressures (P-L(o)). Non-linear curve fitting of Phi versus log P-L(o) was found to be more robust than linear logarithmic regressions of log Kp versus log P-L(o). Kp of PAHs were estimated by octanol-air and soot-air partitioning models and the results were compared with the experimental Kp values. Measured EC and OC concentrations were used in model calculations. Use of measured carbon concentrations in model calculations resulted much better estimations for tunnel samples. Gas-particle partitioning of PAHs for the majority of the compounds were controlled by adsorption onto soot carbon and adsorption into the organic matter. Cancer risks associated with inhalation and dermal contact were also estimated. Generally, the estimated cancer risks were below 1 x 10(-5) for urban and suburban sampling locations.
Handheld two-stroke engines as an important source of personal VOC exposure for olive farm workers
(SPRINGER HEIDELBERG, 2022) Arı, Akif; Arı, Pelin Ertürk; İlhan, Soner Özenç; Gaga, Eftade O.
Personal exposure to volatile organic compounds (VOCs) is mainly associated with indoor exposures; however, elevated short-term exposures may also occur during ambient activities. Handheld two-stroke gasoline-powered engines have widespread use in agriculture, but so far, no studies have been conducted on the potential health risks due to the inhalation of emitted VOCs. A one-week passive sampling has been conducted on olive farm workers during the harvesting season to monitor personal exposure levels to VOCs. The first group of workers was selected to represent the contribution of gasolinepowered shaker to daily personal VOC exposures, and one another group of workers was selected as the control, whose have not been using the device. Higher concentrations of 1-pentene, n-hexane, isopentane, n-pentene, and toluene were observed in personal samples collected from machine operators. Personal exposure concentrations of a total of 45 monitored VOCs varied between 29.2 +/- 10.7 and 3733.4 +3300.1 mu g m(-3) among 20 volunteer workers. Estimated carcinogenic risks were between the acceptable levels of 10(-4) and 10(-6) for all workers. All individual chronic HQs and HIs (as the sum of individual HQs) were below the benchmark value of 1 for regular workers in 3 different sampling sites, whereas HI values in both acute (short term) and chronic exposure scenarios were exceeded 1 for shaker machine operators. This represented potential noncarcinogenic health hazards for exposed shaker operators, along with elevated VOCs.
Lung deposition of PM-bound trace elements and corresponding human health risk assessment in commercial kitchens serving Mediterranean cuisine
(Turkish Natl Committee Air Pollution Res & Control-Tuncap, 2024) Varli, Semra Navruz; Bilici, Saniye; Ari, Pelin Erturk; Gaga, Eftade O.; Lhan, Mustafa Necmi; Ari, Akif
The service offered by commercial kitchens and the catering industry is becoming more and more popular all around the world. However, the health risks of sector workers are often overlooked. In this study, size-segregated Particulate Matter (PM) samples were collected from the indoor environments of five commercial kitchens, and elemental concentrations were quantified to estimate the corresponding health risks. Lung-deposited fractions of trace elements in three different regions of the respiratory tract were estimated and used to assess carcinogenic and non-carcinogenic health risks. Besides, the deterioration in lung capacity of the cooks was also evaluated by spirometry tests to correlate indoor pollutants. Exposure to trace elements was dominated by Na, S, Al, Fe, and Mg. Estimated carcinogenic risk through inhalation exposure to Cr was between the moderate risk level of 10-6 to 10-4, while the Hazard Index (HI) values were lower than the acceptable level of 1. This, along with elevated indoor PM levels, represented a significant potential for carcinogenic health hazards for the kitchen staff. According to the results of the lung function tests, a significant decrease was determined in the respiratory functions of the cooks, and it was associated with elevated exposure to fine PM, Pb, Cr, Cu, K, Ni, and Mn. Workplace health and safety measures to better protect the health of kitchen staff are urgently needed and should attract more public attention.
Organic chemical characterization of size segregated particulate matter samples collected from a thermal power plant area
(Elsevier Sci Ltd, 2020) Arı, Pelin Ertürk; Arı, Akif; Dumanoğlu, Yetkin; Odabaşı, Mustafa; Gaga, Eftade O.
Kutahya city, a thermal power plant (TPPs) affected region of Turkey, has serious air quality problems like similar industrial regions of the world due to the emissions from three closely-located coal-fired TPPs, residential coal combustion along with the contribution of several industrial stacks. The organic chemical speciation of ambient size-segregated particulate matter (PM) was investigated during two seasons at two sites with different pollution characteristics (urban and rural). The ambient PM was collected using a high volume cascade impactor, with 6 stages: PM>10.2, PM10.2-4.2, PM4.2-2.1, PM2.1-1.3, PM1.3-0.69 and PM<0.69. Collected PM samples were extracted with organic solvents and the organic composition (Polycyclic aromatic hydrocarbons (PAHs), n-alkanes and carboxylic acids) was determined by GC-MS. Sources of the organic species were assessed using molecular PAH diagnostic ratios, carbon preference index and wax percentages. More than 70% of the PM-bound PAHs were quantified in submicron particles. Similarly, 34-42% of n-alkanes and approximately 30% of the carboxylic acids were found on the smallest particles. The main sources of the PM-bound organic species were considered as the anthropogenic emissions such as coal and biomass combustion and also vehicular emissions rather than the biogenic sources. Considerably high cancer risk levels were obtained through inhalation of PAHs. Seasonal variations and size distributions of the carboxylic acids and levoglucosan were also evaluated. Polar organic compound concentrations were higher in the summer period at both locations probably due to the higher sunlight intensity and temperature favoring their photochemical formation. (C) 2020 Elsevier Ltd. All rights reserved.
Seasonal variation, sources, and gas/particle concentrations of PCBs and OCPs at high altitude suburban site in Western Black Sea Region of Turkey
(Royal Soc Chemistry, 2012) Karakaş, Serpil Yenisoy; Öz, Muhammed; Gaga, Eftade O.
Daily gas and particle phase samples were collected during winter and summer seasons in Bolu, which is located in the high altitude Western Black Sea Region of Turkey. Samples were analyzed to determine the concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Concentrations of endosulfan sulfate and methoxychlor were found to be highest in the summer and winter periods, respectively. The measured average concentration of endrin was considerably higher (10-50 fold) than the values reported in the literature for similar sites. The agricultural areas located to the south, south-east and south-west of the sampling point were identified as source regions. PCBs were found predominantly in the gas phase in both seasons and 3-chlorinated biphenyls were found to be abundant in the winter period, due to pollutants transported from the city centre and a waste incineration plant by southerly and easterly winds. The concentrations of PCB-180 and PCB-194 were found to be higher than values reported in the literature. The correlation between atmospheric concentrations and temperature was obtained by using Clausius-Clapeyron (CC) plots. The CC plots for most of the OCPs showed shallow negative slopes with low r(2) values, which might be due to the presence of local sources, i.e., agricultural areas around the sampling site and the dominance of evaporation. The CC plots showed steep positive slopes for most of the PCB compounds. Most of the PCB compounds were carried from the ongoing local sources.
Source characterization and risk assessment of occupational exposure to volatile organic compounds (VOCs) in a barbecue restaurant
(Pergamon-Elsevier Science Ltd, 2020) Arı, Akif; Arı, Pelin Ertürk; Karakaş, Serpil Yenisoy; Gaga, Eftade O.
Food cooking is a significant source of indoor volatile organic compounds (VOCs) that can pose serious adverse health effects. The use of liquefied petroleum gas (LPG), charcoal and wood as the cooking fuels for grilled or fried products can be a major source of the emitted pollutants inside industrial and commercial restaurants. This paper attempts to determine the inhalation exposure of VOCs generated by the food cooking process of barbecued and fried products in the kitchen area of a commercial barbecue restaurant. A broad range of VOCs was sampled and analyzed in a commercial barbecue restaurants' kitchen atmosphere for 30 days to investigate the exposure levels of the employee. The median concentration of carcinogenic VOCs were 6.11 mu g/m(3) for benzene, 3.51 mu g/m(3) for chloroform, 1.58 mu g/m(3) for styrene, 1.12 mu g/m(3) for ethylbenzene, 0.11 mu g/m(3) for tetrachlommethane and 0.06 mu g/m(3) for 1,2-dichloroethane. Sources of the quantified VOCs were mainly attributed to cooking styles and fuels, cleaning products and building materials. The carcinogenic potential of the indoor VOC exposure was between 3.4X10(-8) and 1.1X10(-5) that indicating a possible risk of lung cancer.
Uncertainty of high resolution inductively coupled plasma mass spectrometry based aerosol measurements
(Elsevier Science Bv, 2009) Karakaş, Serpil Yenisoy; Gaga, Eftade O.; Cankur, Oktay; Karakaş, Duran
Simultaneous and multi-elemental method was optimized to determine 35 elements in 274 coarse and fine aerosol samples by using HR-ICP-MS. The procedures were validated. Measurement uncertainties of all elements including sampling uncertainties were calculated by applying bottom-up approach. The average recoveries obtained for each element ranged between 79% and 129% using NIST SRM 1648, urban dust. The calculated uncertainties of the analytical methods were between 2.9% and 18% for both sample types. The major contributions to the uncertainty budget come from the calibration curves, repeatability and volume of air. (C) 2009 Elsevier B.V. All rights reserved.
Validation of one-step cleanup and separation method of polychlorinated biphenyls, organochlorine pesticides, and polycyclic aromatic hydrocarbons from atmospheric gas- and particle-phase samples
(Elsevier Science Bv, 2013) Karakaş, Serpil Yenisoy; Gaga, Eftade O.
A one-step cleanup method is described for the determination of PAHs, PCBs and OCPs in air (gas and particulate phase) samples. Analytes were extracted from ambient air samples using soxhlet extraction with a solvent mixture of dichloromethane and petroleum ether (1:4) for 24 h. They were concentrated, separated and fractionated on a florisil and alumina column. The amounts of florisil (1 g or 2 g) with/ without alumina were tested in the cleanup column. The study systematically investigated the effects of solvent types, and the amounts of florisil and alumina, on the performance of the cleanup process. The first fraction was eluted with 25 mL hexane, and analyzed for PCBs. The second fraction was collected via 40 mL hexane ethyl acetate (1:1) solvent mixture, and analyzed for OCPs and PAHs. The optimized method yielded average recoveries between 88% and 99% for PCBs; 56% and 118% for PAHs; and 51% and 128% for OCPs. Other validation parameters were also investigated, such as MDL, LOQ linear range, sensitivity (r(2)). An oven-program optimization and adjustment of GC-MS were performed. For internal quality control, surrogate recoveries and field blanks values were calculated. External calibration curves were prepared for PAHs, and internal calibration curves were preferred for OCP and PCBs. (c) 2013 Elsevier B.V. All rights reserved.

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