Levels, distribution, sources and human exposure pathways of alkylphenol and alkylphenol ethoxylates in indoor dust in Turkiye.

Environmental phenolic chemicals, due to their widespread occurrence and potent estrogenic properties, pose a risk to human exposure. The phenolic organic contaminants alkylphenols (APs) and alkylphenol polyethoxylates (APEs) are used in various household applications, and they may enter to the environment during production and use, potentially appearing in indoor dust. However, little is known about the levels of environmental phenolics in indoor environments. In this study, five of these compounds namely octylphenol (OP), 4-Octylphenol Monoethoxylate (4-OPME), 4-tert-octylphenol (4-t-OP), 4-n-nonylphenol (4-n-NP) and nonylphenol diethoxylate (di-NPE) were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in household dust samples (n = 148) collected from Ankara, the capital of Turkiye. OP and 4-OPME was not present in any of the analyzed samples. The median concentrations of the 148 settling dust samples were 35, 520, and 1910 ng g-1 dust for 4-t-OP, 4-n-NP, and di-NPE, respectively. An assessment of the human (children and adults) exposure pathway to APs and APEs, which are recognized as endocrine-disrupting chemicals found in residential dust, revealed that it was approximately 3 times higher for children than for adults at both moderate and heavy exposure levels. The association between chemical exposure, house characteristics, and family lifestyle was investigated using a multivariate logistic regression model. According to the results of this model, while the high concentrations measured for 4-t-OP were not found to be associated with any of the household parameters, high levels of 4-n-NP and di-NPE were associated with the frequency of house cleaning, repairs made during the previous year, residential type, the number of occupants, flooring materials, and the purchase of new household items within the past year. This study provides a basis for prioritizing toxicology and exposure studies for EDCs and mixtures and may offer new tools for exposure assessment in health studies.

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.

Assessment of house dust trace elements and human exposure in Ankara, Turkey.

One of the impacts of the COVID-19 pandemic is leading people remain at homes longer than ever. Considering the elongation of the time people spend indoors, the potential health risks caused by contaminants including heavy metals in indoor environments have become even more critical. The purpose of this study was to evaluate the levels and sources of heavy metals in indoor dust, to assess the exposure to heavy metals via indoor dust, and to estimate the associated health risk. The highest median value was measured for Zn (263 µg g-1), while the lowest median concentration value was observed for Cd (0.348 µg g-1). The levels of elements measured in the current study were found to be within the ranges reported in the other parts of the world, mostly close to the lower end of the range. House characteristics such as proximity to the main street, presence of pets, number of occupants, and age of the building were the house characteristics influencing the observed higher concentrations of certain heavy metals in houses. Enrichment factor values range between 1.79 (Cr) and 20.4 (Zn) with an average EF value of 8.80 ± 6.80 representing that the targeted elements are enriched (EF>2) in indoor dust in Ankara. Positive matrix factorization results showed that the heavy metals in the house dust in the study area are mainly contributed from sources namely outdoor dust, carpets/furniture, solders, wall paint/coal combustion, and cigarette smoke. Carcinogenic and non-carcinogenic risk values from heavy metals did not exceed the safe limits recommended by EPA. The highest carcinogenic risk level was caused by Cr. The risk through ingestion was higher than inhalation, and the risk levels were higher for children than for adults.

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.

Organophosphate esters in house dust: A comparative study between Canada, Turkey and Egypt.

Organophosphate esters (OPEs) are commonly used as flame retardants (FRs) and plasticizers. The usage of OPEs has increased recently due to the ban of several brominated flame retardants, but information on levels in the environment, including the indoor environment is still limited. We investigated the occurrence and distribution of 12 OPEs in urban house dust from Vancouver, Canada; Istanbul, Turkey; and Cairo, Egypt. The median ∑OPE concentration was 41.4 µg/g in the Vancouver samples while median levels in Istanbul and Cairo were significantly lower. The median composition profiles of OPEs in Vancouver and Cairo were dominated by tris (2-butoxyethyl) phosphate (TBOEP), accounting for 56 and 92% of total OPEs respectively while it showed a detection frequency of only 14% in Istanbul. Tris (2-chloropropyl) phosphate (TCPP) was the most abundant chlorinated OPE representing 20 and 36% of the total OPEs in Vancouver and Istanbul respectively, but was below the detection limit in the Cairo dust samples. Consistent with other studies, ΣOPE concentrations were ~1 to 2 orders of magnitude higher than PBDEs and currently used flame retardants in the same dust samples. The mean estimated daily intakes (EDI) of ΣOPE from dust were 115, 38 and 9 ng/kg/bw/day in Vancouver, Cairo and Istanbul respectively for toddlers where adults were ~10 times lower. The total toddler OPE intake ranged from 115 to 2900, 38 to 845 and from 9 to 240 ng/kg bw/day across the three cities. TBOEP had the largest contribution to the EDI in both toddler and adults, where toddler TBOEP exposures via dust represented 4% to 80%, 2% to 44% and 0.1% to 6% of the Reference Doses (RfD) in the mean and high intake scenarios for toddlers in Vancouver, Cairo and Istanbul respectively.

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.

Inventory development for perfluorooctane sulfonic acid (PFOS) in Turkey: challenges to control chemicals in articles and products.

Perfluorooctane sulfonic acid (PFOS) and related substances have been listed as persistent organic pollutants (POPs) in the Stockholm Convention. Countries which have ratified the Convention need to take appropriate actions to control PFOS use and release. This study compiles and enhances the findings of the first inventory of PFOS and related substances use in Turkey conducted within the frame of the Stockholm Convention National Implementation Plan (NIP) update. The specific Harmonized Commodity Description and Coding System (Harmonized System (HS)) codes of imported and exported goods that possibly contain PFOS and 165 of Chemical Abstracts Service (CAS) numbers of PFOS-related substances were assessed for acquiring information from customs and other authorities. However, with the current approaches available, no useful information could be compiled since HS codes are not specific enough and CAS numbers are not used by customs. Furthermore, the cut-off volume in chemical databases in Turkey and the reporting limit in the HS system (0.1 %) are too high for controlling PFOS. The attempt of modeling imported volumes by a Monte Carlo simulation did not also result in a satisfactory estimate, giving an upper-bound estimate above the global production volumes. The replies to questionnaires were not satisfactory, highlighting that an elaborated approach is needed in the communication with potentially PFOS-using stakeholders. The experience of the challenges of gathering information on PFOS in articles and products revealed the gaps of controlling highly hazardous substances in products and articles and the need of improvements.

Determination of heavy metals in indoor dust from Istanbul, Turkey: estimation of the health risk.

Levels of eight potentially toxic heavy metals in indoor dust from homes and offices in Istanbul were investigated. The concentrations of heavy metals in indoor dust from homes+office ranged from 62 to 1800 µgg(-1) for Cu, 3-200 µgg(-1) for Pb, 0.4-20 µgg(-1) for Cd, 210-2800 µgg(-1) for Zn, 2.8-460µgg(-1) for Cr, 8-1300µgg(-1) for Mn, 2.4-25µgg(-1) for Co, 120-2600µgg(-1) for Ni. Results of the study were comparable to other studies conducted on indoor dust and street dust from a variety of cities globally. Considering only ingestion + inhalation, the carcinogenic risk level of Cr for adults and children (3.7×10(-5) and 2.7×10(-5)) in Istanbul was in the range of EPA's safe limits (1×10(-6) and 1×10(-4)), indicating that cancer risk of Cr due to exposure to indoor dust in Istanbul can be acceptable. According to calculated Hazard Quotient (HQ), for non-cancer effects, the ingestion of indoor dust appears to be the major route of exposure to the indoor dust that results in a higher risk for heavy metals, followed by dermal contact and inhalation pathways. However, compared to ingestion and dermal contact exposure, exposure through inhalation is almost negligible. Hazard Index (HI) values for all studied elements were lower than safe limit of 1 and this result suggested that none of the population groups would likely to experience potential health risk due to exposure to heavy metals from indoor dust in the study area.

Current-use pesticides in inland lake waters, precipitation, and air from Ontario, Canada.

Concentrations of current-use pesticides (CUPs) in water, zooplankton, precipitation, and air samples as well as stereoisomer fractions (SF; herbicidally active/total stereoisomers) of metolachlor were determined in water samples collected from 10 remote inland lakes in Ontario, Canada, between 2003 and 2005. The most frequently detected chemicals in lake water, precipitation, and air were α-endosulfan, atrazine, metolachlor, chlorpyrifos, chlorothalonil, and trifluralin, and α-endosulfan and chlorpyrifos were the chemicals detected frequently in zooplankton. Air concentrations of these CUPs were within the range of previously reported values for background sites in the Great Lakes basin. High detection frequency of CUPs in lake water and precipitation was attributed to high usage amounts, but some CUPs such as ametryn and disulfoton that were not used in Ontario were also detected. Mean bioaccumulation factors (wet wt) in zooplankton for endosulfan ranged from 160 to 590 and from 20 to 60 for chlorpyrifos. The overall median SF of metolachlor in precipitation samples (0.846) was similar to that of the commercial S-metolachlor (0.882). However, the median SF of metolachlor in water from all sampled inland lakes (0.806) was significantly lower compared with Ontario rivers (0.873) but higher compared with previous measurements in the Great Lakes (0.710). Lakes with smaller watershed areas showed higher SFs, supporting the hypothesis of stereoselective processing of deposited metolachlor within the watersheds, followed by transport to the lakes.

Comparison of concentrations and stereoisomer ratios of mecoprop, dichlorprop and metolachlor in Ontario streams, 2006-2007 vs. 2003-2004.

Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.

Chiral current-use herbicides in Ontario streams.

Concentrations of mecoprop, dichlorprop, and metolachlor were investigated in 393 samples from Ontario streams in 2003-2004. Maximum concentrations of mecoprop, dichlorprop, and metolachlor were 1900, 6.62, and 1560 ng L(-1), respectively in 2003, and 103,000, 110, and 5290 ng L(-1), respectively, in 2004. Concentrations of metolachlor in agricultural watersheds were significantly (p < 0.0001) higher than those in urban watersheds, whereas concentrations of mecoprop did not differ (p > 0.1) between the two watershed types. Enantiomer fractions (EFs) of the acid herbicide mecoprop ranged from 0.236 to 0.928 and for dichlorprop EFs ranged from 0.152 to 0.549. EFs of mecoprop did not differ significantly (p > 0.1) between agricultural and urban land usage. Mecoprop EFs > or = 0.5 were found in 54% of samples, a situation expected during the transition years when racemic mecoprop was replaced by mecoprop-P, consisting of only the R(+) enantiomer. However, EFs < 0.5 were found in 46% of samples, which suggests preferential degradation of R(+) or conversion of R(+) to S(-). The four stereopluisomers of metolachlor were separated by HPLC and are reported as the ratio of the two herbicidally active stereoisomers (aS,1'S and aR,1'S) to the two inactive stereoisomers (aS,1'R and aR,1'R). The average S/R of metolachlor in streams was 6.73 +/- 2.28 and ranged from 1.08 to 12.7. Samples with higher concentrations of metolachlor had S/R ratios similar to the S/R of S-metolachlor (enriched in aS,1'S and aR,1'S stereoisomers) whereas samples with lower concentrations display lower S/R ratios with greater variability, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation. S/R values were significantly higher (p < 0.001) in agricultural than urban watersheds. Streamwater from row crop areas showed higher S/R ratios than streamwater from fruit growing areas (p = 0.036).

Enantioselective degradation of organochlorine pesticides in background soils: variability in field and laboratory studies.

Variability in the enantioselective degradation of chiral organochlorine pesticides (alpha-HCH, cis- and trans-chlordane (CC and TC), and o,p'-DDT) in the field and laboratory was investigated. Background soils presumably receive the same EF signature of a compound via atmospheric deposition and then degrade that compound in a way that can vary over small spatial areas. Background soils from woodland and grassland areas were sampled to compare chiral signatures and determine the spatial variability within a few square meters. The enantiomer fractions, EF = areas of the (+)/[(+)+(-)]-enantiomers, showed variability between and within ecosystems. For example, the EF of CC varied between 0.272 -and 0.558 in nine samples taken over a few square meters, and a range of 0.431-0.506 was found within depths of a few centimeters. Woodland and grassland soils were spiked with alpha-HCH, TC, CC, and o,p'-DDT, and one portion was placed in the field to monitor changes in EF under in situ conditions and the other taken to the laboratory. In general, the enantiomer degradation preferences in the laboratory paralleled those in the field, with some differences. Soil organic matter content and pH exerted a minor influence on this variability. The results of this study have implications for the use of chiral compounds to make inferences about air-soil exchange and for the mechanisms of biodegradation/ biotransformation of anthropogenic compounds in soils.

Measurement of DDT fluxes from a historically treated agricultural soil in Canada.

Organocohlorine pesticide (OCP) residues in agricultural soils are of concern due to the uptake of these compounds by crops, accumulation in the foodchain, and reemission from soils to the atmosphere. Although it has been about three decades since DDT was banned for agricultural uses in Canada, residues persist in soils of some agricultural areas. Emission of DDT compounds to the atmosphere from a historically treated field in southern Ontario was determined in fall 2004 and spring 2005. The sigmaDDTs concentration in the high organic matter (71%) soil was 19 +/- 4 microg g(-1) dry weight. Concentration gradients in the air were measured at 5, 20, 72, and 200 cm above soil using glass fiber filter-polyurethane foam cartridges. Air concentrations of sigmaDDTs averaged 5.7 +/- 5.1 ng m(-3) at 5 cm and decreased to 1.3 +/- 0.8 ng m(-3) at 200 cm and were 60-300 times higher than levels measured at a background site 30 km away. Soil-air fugacity fractions, fs/(fs + fa), of p,p'-DDE, p,p'-DDD, and p,p'-DDT ranged from 0.42 to 0.91 using air concentrations measured above the soil and > or = 0.99 using background air concentrations, indicating that the soil was a net source to the background air. Fractionation of DDT compounds during volatilization was predicted using either liquid-phase vapor pressures (PL) or octanol-air partition coefficients (KOA). Relative emissions of p,p'-DDE and p,p'-DDT were better described by PL than KOA, whereas either PL or KOA successfully accounted for the fractionation of p,p'-DDT and o,p'-DDT. Soil-to-air fluxes were calculated from air concentration gradients and turbulent exchange coefficients determined from micrometeorological measurements. Average fluxes of sigmaDDTs were 90 +/- 24 ng m(-2) h(-1) in fall and 660 +/- 370 ng m(-2) h(-1) in spring. Higher soil temperatures in spring accounted for the higher fluxes. A volatilization half-life of approximately 200 y was estimated for sigmaDDT in the upper 5 cm of the soil column, assuming the average flux rate for 12 h d-(1) over 8 months of the year. Thus, in the absence of other dissipation processes, the soil will continue to be a source of atmospheric contamination for a very long time.