Contamination of Soil by Obsolete Pesticide Stockpiles: A Case Study of Derince Province, Turkey.

The areal distributions of the soil organochlorine pesticide (OCP) levels were investigated at adjacent and surrounding sites of the obsolete pesticide stockpile warehouse in Kocaeli, Türkiye. OCP levels in soil at neighboring sampling locations (positioned at 0.4 to 3 km from the stockpile) varied from 0.4 to 9 µg/kg and 4.2 to 2226 µg/kg (dry weight) for ΣHCHs and ΣDDXs, respectively. Levels at adjacent locations (positioned within 20 m from the stockpile) were considerably higher, varying from 74 to 39,619 µg/kg and 1592 to 30,419 µg/kg for ΣHCHs and ΣDDXs, respectively. Levels of OCPs dropped abruptly with the horizontal distance from the stockpile and had different transect profiles. The enantiomer fractions (EFs) near the stockpile range from 0.494 to 0.521, 0.454 to 0.515, and 0.483 to 0.533 for α-HCH, o,p'-DDT, and o,p'-DDD, respectively. These near-racemic EFs suggested that observed soil OCP levels were mainly influenced by recent emissions from the stockpile. A comparison of OCP compositions observed in the soil at the present study with the technical HCHs and DDTs revealed that the material in the stockpile primarily contains byproducts that were discarded during DDT and Lindane production at the adjacent plant instead of their technical mixtures.

Air monitoring of organochlorine pesticides (OCPs) in Bursa Türkiye: Levels, temporal trends and risk assessment.

Monitoring concentration levels of persistent organic pollutants (POPs) is required to evaluate the effectiveness of international regulations to minimize the emissions of persistent organic pollutants (POPs) into the environment. In this manner, we evaluated the spatial and temporal variations of 22 organochlorine pesticides (OCPs) using polyurethane foam passive air samplers at ten stations in Bursa in 2017 and 2018. The highest concentration value for Σ22OCPs was detected in Agaköy (775 pg/m3) and Demirtas (678 pg/m3) sampling sites, while the lowest value was observed in Uludag University Campus (UUC, 284 pg/m3) site. HCB, γ-HCH, Endo I, and Mirex were the most frequently detected OCPs, which shows their persistence. Diagnostic ratios of ß-/(α + Î³)-HCH have pointed to historical and possible illegal OCP usage in the study area. The seasonality of air concentrations (with spring and summer concentrations higher than winter and autumn concentrations) was well exhibited by α-HCH, ß-HCH, É£-HCH, HCB, Endo I, and Mirex but not aldrin, dieldrin, and α-chlordane (CC). Levels of OCPs detected in ambient air in the current study were relatively similar to or lower than those reported in previous studies conducted in Türkiye. Back trajectory analysis was applied to identify the possible sources of OCPs detected in the sampling regions. The Clausius-Clapeyron approach was used to investigate the temperature dependence of OCP gas-phase atmospheric concentrations. The data showed that long-range atmospheric transport affects ambient air OCP concentrations in the study area.

Gaseous elemental mercury emissions from informal E-Waste recycling facilities in Pakistan.

Detrimental effects of mercury (Hg) on ecosystems and human health have been well-documented. Whereas emissions of gaseous elemental mercury (GEM) from e-waste recycling have been reported in developed countries, much less is known about the situation in the Global South. Using a total of 132 passive air samplers, seasonally resolved concentrations of GEM in air were measured continuously at 32 informal e-waste recycling facilities and background location in Pakistan for a period of one year between September 2020 and December 2021. Annual average GEM concentrations at the studied locations ranged from 1.8 to 92 ng m-3. Among the studied cities, higher concentrations were measured in Karachi (mean ± s.d: 17 ± 22, range: 4.2-92 ng m-3), Lahore (16 ± 4.2, 8.2-22 ng m-3) and Peshawar (15 ± 17, 4.9-80 ng m-3), while lower levels were measured in Hyderabad (6.9 ± 6.2, 3.1-25 ng m-3), consistent with a higher rate of informal recycling activities in metropolitan areas. Seasonally, higher GEM levels occurred during autumn (15 ± 16: 3.3-92 ng m-3) and summer (13 ± 8.7: 1.8-80 ng m-3) than in winter (12 ± 8.4: 2.5-49 ng m-3) and spring (9.2 ± 7.3: 1.8-80 ng m-3), possibly reflecting enhanced volatilization at higher temperatures and/or varying magnitude of recycling operations in different seasons. Policies and strict regulations related to e-waste management should be developed and implemented urgently in the country.

The effect of military conflict zone in the Middle East on atmospheric persistent organic pollutant contamination in its north.

This study aimed to investigate long-range atmospheric transport of selected POPs released due to the effects of military conflicts in regions to the south of Turkey's borders. Ten locations were selected to deploy passive air samplers at varying distances to the border on a southeast-west transect of the country, proximity-grouped as close, middle, and far. Sampling campaign included winter and transition months when desert dust transport events occur. Hypothesis of the study was that a decreasing trend would be observed with increasing distance to the border. Group comparisons based on statistical testing showed that PBDE-183, Σ45PCB, and dieldrin in winter; PBDE-28, PBDE-99, PBDE-154, p,p'-DDE, Σ14PBDE, and Σ25OCP in the transition period; and PBDE-28, PBDE-85, PBDE-99, PBDE-154, PBDE-190, PCB-52, Σ45PCB, p,p'-DDE, and Σ25OCP over the whole campaign had a decreasing trend on the transect. An analysis of concentration ratio to the background showed that long-range atmospheric transport impacted the study sites, especially those of close group in comparison to the local sources. Back-trajectory analyses indicated that there was transport from the conflict areas to sites in the close-proximity group, while farther sampling locations mostly received air masses from Europe, Russia, and former Soviet Union countries, followed by North Africa, rather than the military conflict areas. In consequence, decrease in concentrations with distance and its relation to molecular weight through proportions, diagnostic ratios, analysis of concentration ratio to the background, and back-trajectory analyses support the effect of transport from the military-conflict area to its north.

Selected Persistent Organic Pollutants in Ambient Air in Turkey: Regional Sources and Controlling Factors.

As a result of its unique location, Turkey receives air masses from Europe, Russia, Middle East, and Africa, making it an important place in terms of long-range atmospheric transport (LRT) of contaminants. Atmospheric levels of 22 organochlorine pesticides (OCPs), 45 polychlorinated biphenyls (PCBs), and 14 polybrominated diphenyl ethers (PBDEs) were measured in two metropolitan cities, Istanbul and Izmir, on a weekly basis from May 2014 to May 2015. Dichlorodiphenyltrichloroethane (DDT) and its derivatives were dominant OCP species, followed by isomers of hexachlorocyclohexane (HCH) at both sites. The annual mean concentration of ∑DDX (sum of o,p'-DDT, p,p'-DDT, o,p'-DDD, p,p'-DDD, o,p'-DDE, and p,p'-DDE) was 82 pg/m3 for Istanbul and 89 pg/m3 for Izmir, while these levels were about 46 pg/m3 for ∑HCHs (sum of α-, ß-, γ-, and δ-HCH) at both of the sites. At both stations, tri- and tetra-PCBs and tetra- and penta-PBDEs were dominant congeners. The temperature dependence indicates that both LRT and local contaminated areas contribute to the elevated levels. A Lagrangian particle dispersion model (FLEXPART) showed a few potential source regions in northern Africa and Middle East, southern-southwestern and eastern Europe including Russia, as well as from local domestic metropolitan areas.

First insight into polybrominated diphenyl ethers in car dust in Turkey: concentrations and human exposure implications.

The presence of polybrominated diphenyl ethers (PBDEs) in the car is due to their use as a flame retardant additive in various car components such as dashboard, plastic parts, seat and headliner cushion foams, insulated cables, and electronic circuits. Ingestion of dust inadvertently or dermal contact to dust are significant pathways of human exposure to pollutants including PBDEs. There are no studies documenting presence of car dust associated flame retardants in Turkey. In the current study, a total of 13 PBDEs congeners were investigated in 62 car dust samples collected from Bursa province of Turkey using glass-fiber filters and a vacuum cleaner. Results of the study showed that congener concentrations were within the range of

Links between airborne microbiome, meteorology, and chemical composition in northwestern Turkey.

The composition of atmospheric aerosols is dynamic and influenced by their emission sources, organic and inorganic composition, transport pathways, chemical and physical processes, microorganisms' content and more. Characterization of such factors can improve the ability to evaluate air quality and health risks under different atmospheric scenarios. Here we investigate the microbial composition of the atmospheric particulate matter (<10 µm; PM10), sampled in Bolu, Turkey, and the linkage to the chemical composition changes, and different environmental factors. We show distinct differences between aerosol composition of different sources and air-mass transport patterns, sampled in July-August 2017 and in February 2018. The summer samples had a typical northern component air mass trajectories and higher local wind speed. They were characterized by high PM10 levels, marine and mineral dust tracers and high relative abundance of Ascomycota, suggesting long-range transport of the particles from remote sources. In contrast, samples collected in February were characterized by a dominant contribution of southern air masses, and low wind speed. They had low PM10 values, higher relative abundance of antibiotic resistance genes and anthropogenic ions related to local industries and farming, suggesting a dominance of local sources. With the microbiome analyses reported here for the first time for this region, we show good agreement between airborne microbial composition, aerosol mass load, chemistry, and meteorology. These results allow better air quality evaluation and prediction capabilities.

Brominated flame retardants in a computer technical service: Indoor air gas phase, submicron (PM1) and coarse (PM10) particles, associated inhalation exposure, and settled dust.

Brominated flame retardants (BFRs) are found in multi-media indoors, therefore, may pose serious risks to human health. This study investigated the occurrence of BFRs in particulate matter (PM1 and PM10) and gas phase by active and passive sampling, and settled dust to estimate potential exposure in a computer technical service. Polybrominated diphenyl ethers (PBDEs) and their alternatives (novel BFRs, NBFRs) were studied. PM and gas phase were collected on glass fiber filters and polyurethane foam plugs, respectively, and analyzed with a GC/MS after extraction, clean-up, and concentration. Inhalation exposure of the staff was estimated based on the measured concentrations using Monte Carlo simulation. BDE-209 was the dominating PBDE congener in all media while bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate and 1,2-bis(2,4,6-tribromophenoxy)ethane were those of NBFRs. Submicron particulate matter (PM1) BFR levels constituted about one half of the PM10-associated concentrations, while average PM10 mass concentration (69.9 µg m-3) was nine times that of PM1 (7.73 µg m-3). Calculated log10 dust-gas and PM-gas partitioning coefficients ranged from -5.03 to -2.10, -2.21 to -0.55, and -2.26 to -1.04 for settled dust, PM10, and PM1, respectively. The indoor/outdoor concentration ratios were >1 for all compounds indicating the strength of indoor sources in the service. The estimated potential inhalation exposures, for future chronic-toxic and carcinogenic risk assessments, indicated that the levels of gas-phase and PM1-associated exposures were similar at approximately one half of PM10-associated levels. Results of this study indicate that the occurrence of BFRs in all studied media should be taken into consideration for occupational health mitigation efforts.

Organophosphate ester (OPEs) flame retardants and plasticizers in air and soil from a highly industrialized city in Turkey.

Passive air samples were collected at eight sites in Bursa, Turkey during five sampling periods between February-December 2014. Locations encompassed urban, suburban, industrial, rural and background environments. Soil samples (n=8) were collected at each site during February 2014. Six OPEs were detected in samples: tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP), triphenyl phosphate (TPHP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-ethylhexyl) phosphate (TEHP), and tris(2-isopropylphenyl) phosphate (T2iPPP). Frequency of detection in air samples was TCPP and TPHP (100%)>TBOEP (88%)>TCEP (85%)>TEHP (78%)>T2iPPP (20%). Total OPEs in air per site by sampling period (excluding non-detects) ranged from 529 to 19,139pg/m3. In soil, total OPEs ranged from 38 to 468ng/g dw. In air, alkylated OPEs dominated followed by halogenated and aryl OPEs. In air, annual mean concentrations were TBOEP>TCPP>TPHP>T2iPPP>TEHP>TCEP. In soils, alkylated OPEs were dominant at six sites and chlorinated OPEs at two sites. A comparison of OPE profiles between air and soil suggests that soils may be partly a source of OPEs to air. Mean concentrations in air were not directly proportional to temperature, and there were differences between alkylated compared to halogenated and aryl OPEs. In air, total and alkylated OPEs levels were fairly uniform, whereas more variability was found for the halogenated and aryl compounds. The relative contribution to total OPEs decreases for alkylated OPEs and increases for halogenated OPEs in samples going from background to suburban to urban and industrial sites. Levels of individual OPEs were all positively correlated between air and soils. In air, correlations between individual compounds were weak to moderate and were only statistically significant for TBOEP and TPHP. In soils, correlations were generally stronger and statistically significant only for TPHP and T2iPPP.

Polyurethane foam (PUF) disk passive samplers derived polychlorinated biphenyls (PCBs) concentrations in the ambient air of Bursa-Turkey: Spatial and temporal variations and health risk assessment.

Polyurethane foam (PUF) passive samplers were employed to assess air concentrations of polychlorinated biphenyls (PCBs) in background, agricultural, semi-urban, urban and industrial sites in Bursa, Turkey. Samplers were deployed for approximately 2-month periods from February to December 2014 in five sampling campaign. Results showed a clear rural-agricultural-semi-urban-urban-industrial PCBs concentration gradient. Considering all sampling periods, ambient air concentrations of Σ43PCBs ranged from 9.6 to 1240 pg/m3 at all sites with an average of 24.1 ± 8.2, 43.8 ± 24.4, 140 ± 190, 42.8 ± 24.6, 160 ± 280, 84.1 ± 105, 170 ± 150 and 280 ± 540 pg/m3 for Mount Uludag, Uludag University Campus, Camlica, Bursa Technical University Osmangazi Campus, Hamitler, Agakoy, Kestel Organised Industrial District and Demirtas Organised Industrial District sampling sites, respectively. The ambient air PCB concentrations increased along a gradient from background to industrial areas by a factor of 1.7-11.4. 4-Cl PCBs (31.50-81.60%) was the most dominant homologue group at all sampling sites followed by 3-Cl, 7-Cl, 6-Cl and 5-Cl homologue groups. Sampling locations and potential sources grouped in principal component analysis. Results of PCA plots highlighted a large variability of the PCB mixture in air, hence possible related sources, in Bursa area. Calculated inhalation risk levels in this study indicated no serious adverse health effects. This study is one of few efforts to characterize PCB composition in ambient air seasonally and spatially for urban and industrial areas of Turkey by using passive samplers as an alternative sampling method for concurrent monitoring at multiple sites.

Historical sediment record and levels of PCBs in sediments and mangroves of Jobos Bay, Puerto Rico.

Polychlorinated biphenyls (PCBs) were quantified in 18 surface sediment samples, 1 sediment core, and several mangrove tissue samples collected in Jobos Bay, Puerto Rico in September 2013. Total PCBs in surface sediments ranged from 0.42 to 1232ngg-1 dw. Generally, higher levels were observed near-shore close to urban and industrial areas. The levels suggest significant pollution in Jobos Bay with respect to PCBs. Two-thirds of the sites were dominated by lighter PCB congeners (tri- to penta-chlorinated PCBs) while one-third had heavy PCB congeners (hexa- to octa-chlorinated PCBs) dominant. Total PCBs in a sediment core indicated levels fluctuating according to historical usage patterns. Total PCBs were measured in mangal leaves (14-747ngg-1 dw), roots (0.26-120ngg-1 dw), and seeds (16-93ngg-1 dw), suggesting bioaccumulation from sediments. This is the first report of a historical profile of PCBs in the study area and of PCB bioaccumulation in mangroves. This article provides new and useful information on PCBs in the Caribbean area of the GRULAC region.

Concentrations, gas-particle partitioning, and seasonal variations of polycyclic aromatic hydrocarbons at four sites in Turkey.

Ambient air polycyclic aromatic hydrocarbon (PAH) samples were collected at traffic, residential, coastal, and semiurban sites in Bursa, Turkey, between June 2008 and June 2009. For the traffic, residential, coastal, and semiurban sites, the average gas phase total PAH (∑12PAH) concentrations were 113 ± 131, 142 ± 204, 53 ± 73, and 19 ± 34 ng/m(3), respectively, whereas the average particle phase total PAH concentrations were 28 ± 36, 56 ± 85, 24 ± 40, and 11 ± 23 ng/m(3), respectively. Phenanthrene and fluoranthene had the highest concentrations of all of the sampling sites in the gas phase. The PAH concentrations in the heating period were 5-7 times greater than the nonheating period concentrations. Principal component analysis (PCA) was used to investigate the relationship between the levels of PAHs determined in ambient samples and their possible sources. The PCA model shows that coal combustion and vehicle emissions affected PAH emissions. Moreover, the molecular diagnostic ratios indicated that coal-burning and traffic emissions were the dominant PAH sources. The multiple linear regression analysis indicated that the meteorological parameters also affected the ambient PAH concentrations. The sampling site characteristics, meteorological conditions, dispersion, and local sources all affected the concentration levels.

Can car air filters be useful as a sampling medium for air pollution monitoring purposes?

Urban air quality and real human exposure to chemical environmental stressors is an issue of high scientific and political interest. In an effort to find innovative and inexpensive means for air quality monitoring, the ability of car engine air filters (CAFs) to act as efficient samplers collecting street level air, to which people are exposed to, was tested. In particular, in the case of taxis, air filters are replaced after regular distances, the itineraries are almost exclusively urban, cruising mode is similar and, thus, knowledge of the air flow can provide with an integrated city air sample. The present pilot study focused on polycyclic aromatic hydrocarbons (PAHs), the most important category of organic pollutants associated with traffic emissions. Concentrations of ΣPAHs in CAFs ranged between 650 and 2900 µg CAF(-1), with benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[123-cd]pyrene being the most abundant PAHs. Benzo[a]pyrene (BaP) ranged between 110 and 250 µg CAF(-1), accounting regularly for 5-15% of the total carcinogenic PAHs. The CAF PAH loads were used to derive road-level atmospheric PAH concentrations from a standard formula relating to the CAF air flow. Important parameters/assumptions for these estimates are the cruising speed and the exposure duration of each CAF. Based on information obtained from the garage experts, an average 'sampled air volume' of 48,750 m(3) per CAF was estimated, with uncertainty in this calculation estimated to be about a factor of 4 between the two extreme scenarios. Based on this air volume, ΣPAHs ranged between 13 and 56 ng m(-3) and BaP between 2.1 and 5.0 ng m(-3), suggesting that in-traffic BaP concentrations can be many times higher than the limit values set by the UK (0.25 ng m(-3)) and the European Union (1.0 ng m(-3)), or from active sampling stations normally cited on building roof tops or far from city centres. Notwithstanding the limitations of this approach, the very low cost, the continuous availability of very high amounts of "sample", and the "retroactivity" render it very useful and complementary to existing passive sampling techniques. This approach yields estimated air concentrations that reflect the pollutant concentrations to which taxi drivers, pedestrians, cyclists and road-related professionals are exposed.

Air-soil exchange of PCBs: seasonal variations in levels and fluxes with influence of equilibrium conditions.

The variations in the occurrences of PCB congeners both in soil and air were investigated in conjunction with each other, and the changes in the fugacity fractions and flux levels were examined on a seasonal basis. Air and soil samples were collected concurrently two or three times in a month during a one-year monitoring at two different locations in Bursa, located in the northwestern Turkey. Fugacity fractions and net flux levels of PCB congeners were calculated. Air and soil PCB levels increased together as the soil temperature increased, suggesting the influence of instantaneous air-soil exchange towards the equilibrium conditions. The flux levels and fugacity fractions also showed a positive significant correlation with soil temperature. Flux levels were positive for the dates with fugacity fractions above 0.5, indicating volatilization from soil to air.

Atmospheric polybrominated diphenyl ethers (PBDEs) in the United Kingdom.

The occurrence of PBDEs has been studied in the atmosphere of four sites in the United Kingdom over a period of ten years. The concentrations have exhibited a sharp decrease after 2001-2003. This is evident in the urban sites of Manchester and London and at the semi-rural site of Hazelrigg. The average ΣPBDE half-lives for these three sites were 3.4, 2.0 and 3.5 years respectively. ΣPBDEs concentrations in the UK (in 2010 ΣPBDEs < 10 pg m(-3)) are among the lowest reported in literature. Comparison of concentrations to estimated emissions and employment of PBDE profiles suggest that PBDEs in the UK atmosphere originate from primary emissions from products that contain mainly the penta-BDE technical mixture. The detection of BDE-183 in the majority of samples hints that octa-bromodiphenylether has also been used extensively in the UK, however to a smaller extent than the penta- product.

Determination of the sampler type and rainfall effect on the deposition fluxes of the polychlorinated biphenyls.

Atmospheric concentration and deposition samples were collected between June 2008 and June 2009 in an urban sampling site Yavuzselim, Turkey. Eighty-three polychlorinated biphenyl (PCB) congeners were targeted in the collected samples. It was found that 90% of the total PCB concentration was in the gas phase. Deposition samples were collected by a wet-dry deposition sampler (WDDS) and a bulk deposition sampler (BDS). Average total deposition fluxes measured with the BDS in dry periods was 5500 ± 2400 pg/(m(2)day); average dry deposition fluxes measured by the WDDS in the same period were 6400 ± 3300 pg/(m(2)day). The results indicated that the sampler type affected the measured flux values. Bulk deposition samples were also collected in rainy periods by using the BDS and the average flux value was 8700 ± 3100 pg/(m(2)day). The measured flux values were lower than the values reported for the urban and industrial areas. Dry deposition velocities for the WDDS and BDS samples were calculated 0.48 ± 0.35 cm/s and 0.13 ± 0.15 cm/s, respectively.

Seasonal atmospheric deposition variations of polychlorinated biphenyls (PCBs) and comparison of some deposition sampling techniques.

INTRODUCTION: Ambient air and bulk deposition samples were collected between June 2008 and June 2009. Eighty-three polychlorinated biphenyl (PCB) congeners were targeted in the samples. DISCUSSION: The average gas and particle PCB concentrations were found as 393 ± 278 and 70 ± 102 pg/m(3), respectively, and 85% of the atmospheric PCBs were in the gas phase. Bulk deposition samples were collected by using a sampler made of stainless steel. The average PCB bulk deposition flux value was determined as 6,020 ± 4,350 pg/m(2) day. The seasonal bulk deposition fluxes were not statistically different from each other, but the summer flux had higher values. Flux values differed depending on the precipitation levels. The average flux value in the rainy periods was 7,480 ± 4,080 pg/m(2) day while the average flux value in dry periods was 5,550 ± 4,420 pg/m(2) day. The obtained deposition values were lower than the reported values given for the urban and industrialized areas, yet close to the ones for the rural sites. The reported deposition values were also influenced by the type of the instruments used. The average dry deposition and total deposition velocity values calculated based on deposition and concentration values were found as 0.23 ± 0.21 and 0.13 ± 0.13 cm/s, respectively.