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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

Organochlorine pesticides (OCPs) were analyzed in three different ages (half-, 1.5-, 2.5-year-old) for needles and semi permeable membrane devices (SPMDs) at three deployment periods from sea level to 1881 meter above sea level. Individual HCHs concentrations ranged between 1.4 and 129 pg/g fw depending on the age and sampling season while 2.5-year-old needles showed higher HCHs levels compared to half and 1.5- year-old. Correlation between elevation and HCH concentration in SPMDs was found but not in needle samples. Concentrations of HCHs in SPMDs indicated clearly cold condensation effect on accumulation in winter period and increased with altitude. Concentrations of DDTs in half and 1.5-year-old needles were lower than 2.5-year-old needles. The highest total concentration of DDTs was detected in 1-year-period SPMD. Higher concentrations were found in 2.5-year-old needles for other OCPs. Seasonal and altitude-dependent changes were not observed for other OCPs in SMPDs. Total accumulation of OCPs in SPMDs were found higher than in needles. On the contrary, an increased accumulation rate was observed for HCHs in SPMD. In general, Total concentrations of DDTs and HCHs were similar to total of other OCPs in all altitudes when dominating endosulfan wasnot taken into account in the computation of total concentration of other OCPs.

Levels, seasonal variation, and air-soil exchange of 22 organochlorine pesticides (OCPs) and 15 polychlorinated biphenyls (PCBs) were determined in addition to the first insight into the enantiomeric signatures of chiral OCPs in an agricultural region of Turkey. A total of 47 polyurethane foam disk passive air samples and 34 surface/indepth soil samples were analyzed. Sigma OCP and Sigma PCB levels in air samples were 32.6-741 pg/m(3) and nd-2764 pg/m(3), while they were nd-28.1 ng/g dw and nd-0.302 ng/g dw in soil samples, respectively. Dichlorodiphenyl-trichloroethane (DDT) and its metabolites and endosulfan isomers were the most prevalent chemicals along with the light-weighted PCB congeners. During this study, lower or similar contamination levels were observed compared to global studies conducted in agricultural regions. The enantiomer fractions of o,p'-DDT in air samples might be due to re-volatilization of equally depleted enantiomers or fresh input of racemic o,p'-DDT to the air. The fugacity fractions showed that net deposition is the dominant mechanism.

Polyurethane foam (PUF) disks passive air samplers were deployed in an agricultural region with hot climate to determine atmospheric concentrations of 22 organochlorine pesticides (OCPs) and 15 polychlorinated biphenyls (PCBs). Sampling rates (2.39–15.9 m3.day−1) increased with rising ambient air temperatures. Total OCP and PCB concentrations were 0.884–97.0 pg.m−3 and nd-213 pg.m−3, respectively. The most prominent OCPs in the samples were hexachlorocyclohexane (HCH) isomers, chlordane compounds, dichlorodiphenyltrichloroethane (DDT) derivatives, and endosulfan isomers. The isomer ratios of DDT and Chlordane in the samples indicated older usage while endosulfan ratios showed recent input of technical endosulfan in the region. Total PCB levels were dominated by low chlorinated congeners. The contaminant levels in air samples were mainly lower or similar by comparison to other studies conducted at agricultural regions worldwide. Although the production and use of these chemicals have been banned, results of this study show that some of the chemicals could still be found in agricultural areas. Presence of these chemicals in environmental samples may be result of the degradation of formerly used chemicals, atmospheric transport or illegal use of banned chemicals.

The trophic magnification of polybrominated diphenyl ethers (PBDEs) and selected nonlegacy halogenated organic compounds (HOCs) was determined in the food web of Lake Ontario (ON, Canada). In all, 28 Br3 -Br8 -PBDEs and 24 HOCs (10 of which had not been targeted previously) were analyzed. Average concentrations of Σ28 PBDEs in fish ranged between 79.7 ± 54.2 ng/g lipid weight in alewife (Alosa pseudoharengus) and 815 ± 695 ng/g lipid weight in lake trout (Salvelinus namaycush). For invertebrates, concentrations were between 13.4 ng/g lipid weight (net plankton; >110 μm) and 41.9 ng/g lipid weight in Diaporeia (Diaporeia hoyi). Detection frequency (DF) for HOCs was highest for anti-Dechlorane Plus (anti-DDC-CO), 1,3-diiodobenzene (1,3-DiiB), tribromo-methoxy-methylbenzene (ME-TBP), allyl 2,4,6-tribromophenyl ether (TBP-AE), pentabromocyclododecene (PBCYD), α+β-tetrabromocylcooctane (TBCO), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), and pentabromotoluene (PBT; DF for all = 100% in lake trout). Tetrabromoxylene (TBX), dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), and syn-DDC-CO were also frequently detected in trout (DF = 70-78%), whereas 2,3,4,5,6-pentabromoethyl benzene (PBEB) was detected only in plankton. Several HOCs were reported in aquatic biota in the Great Lakes (USA/Canada) for the first time in the present study, including PBCYD, 1,3DiiB, BATE, TBP-DBPE, PBT, α + β-TBCO, and ME-TBP. The Br4-6 -BDEs (-47, -85, -99, -100, -153, and -154) all had prey-weighted biomagnification factors (BMFPW ) values >6, whereas BMFPW values for Br7-8 -BDEs were

PubMed ID: 33475343 2-s2.0-85100240278 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 ?-, ?-, ?-, and ?-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. © 2021 American Chemical Society. 112Y315 Consejo Nacional para Investigaciones Científicas y Tecnológicas, CONICIT We acknowledge funding from Turkish Scientific and Technological Research Council (TUBITAK) for the financial support under the grant scheme of The Scientific and Technological Research Projects Funding Program (Grant No. 112Y315).

Levels of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NFRs) were measured in ambient outdoor air, indoor air and indoor dust collected in homes and offices at urban, semi-urban and rural locations in Istanbul, Turkey. Indoor air levels of Sigma 12PBDEs in homes and offices ranged from 36 to 730 pg/m(3) and 160 to 10 100 pg/m(3), respectively, while levels of Sigma(12)NFRs ranged from 180 to 7600 pg/m(3) and 180 to 42 400 pg/m(3), respectively. Outdoor air levels ranged from 110 to 620 pg/m(3) for Sigma 12PBDEs and 750 to 2800 pg/m(3) for Sigma(12)NFRs. I/O ratios that are greater than 1 suggest that air concentrations detected in indoor environments are mainly from indoor sources. Indoor dust levels in homes and offices of Sigma 12PBDEs ranged from 400 to 12 500 ng/g and 330 to 32 200 ng/g respectively and levels of Sigma(12)NFRs ranged from 320 to 31 400 ng/g and 910 to 97 900 ng/g, respectively. The I/O ratios >1 for PBDEs and NFRs may indicate that emissions of these chemicals detected in homes and offices are mainly from indoor sources. Due to childrens' frequent hand-to-mouth behaviour, lower body weight and increased dust ingestion rate compared to adults, exposure rates to target chemicals for children were greater than those of adults. Based on median concentrations of chemicals of interest in dust and air samples from Istanbul, we estimate that exposure rates of children to PBDEs and NFRs are up to 160 times higher compared to adults but none of the estimated exposure rates results for children or adults were than the recommended daily oral reference dose values of certain analytes. (C) 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.

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/m3at 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/m3for 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., Scientific and Technological Research Council of Turkey (21514107-221.01-8290); TUBITAK (112Y315)

Symposium on Legacy and Emerging Flame Retardants - Occurrence, Human Exposure and Toxicokinetics (DIOXIN) -- 2018 -- Krakow, POLAND WOS:000472694200025 PubMed ID: 31129402 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 mu g m(-3)) was nine times that of PM1 (7.73 mu g m(-3)). Calculated log(10) 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. (C) 2019 Elsevier Ltd. All rights reserved.

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.

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 (

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 medianSOPE concentration was 41.4 mu g/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, SOPE concentrations were similar to 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 SOPE from dust were 115, 38 and 9 ng/kg/bw/day in Vancouver, Cairo and Istanbul respectively for toddlers where adults were similar to 10 times lower. The total toddler OPE intake ranged from 115 to 2900, 38 to 845 and from9 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. Crown Copyright (C) 2018 Published by Elsevier B.V. All rights reserved.

Atmospheric levels of 43 PCBs, 22 OCPs, and 14 PBDEs were determined in 16 cities at urban and rural sites by passive sampling to generate the first large-scale nationwide dataset of POP residues in Turkey's atmosphere. Sampling campaign was performed from May 2014 to April 2015 with three-month sampling periods at locations on east-west and north-south transects through the country to investigate seasonal and spatial variations, including long range atmospheric transport (LRAT). Factor analysis was conducted to infer on the potential sources. Overall average Σ43PCBs concentration was 108 ± 132 pg/m3. PCB-118 (26.3 ± 44.6 pg/m3) was the top congener, and penta-CBs had the highest contribution with 54.3%. ΣDDTs had the highest annual mean concentration with 134 ± 296 pg/m3 among the OCP groups among which the highest concentration compound was p'p-DDE (97.6 ± 236 pg/m3). Overall average concentration of Σ14PBDEs was 191 ± 329 pg/m3 with the highest contribution from BDE-190 (42%). Comparison of OCPs and PCBs concentrations detected at temperatures which were above and below annual average temperature indicated higher concentrations in the warmer periods, hence significance of secondary emissions for several OCPs and Σ43PCBs, as well as inference as LRAT from secondary emissions. The first nationwide POPs database constructed in this study, point to current use, local secondary emissions, and LRAT for different individual compounds, and indicate the need for regular monitoring. The first country-wide passive sampling of selected POPs showed no unequivocal trends reflecting transitional location of Turkey., TUBITAK (112Y314)

Polychlorinated biphenyl (PCB), metal, and chlorine contents of samplesincluding waste mineral oil, engine oil, edible oil, oily waste (industrial/domestic), and number 10 lube (NTL)were investigated to evaluate possible hazards to the environment. Analyses were conducted using Turkish and United States Environmental Protection Agency standards. The results showed an uneven distribution of pollutants among all type of samples or samples that were collected from the same area at different time intervals. Although PCB usage was banned in Turkey many years ago, indicator PCB congeners were observed in NTL samples that were predominantly used as alternative fuel in heavy duty diesel engines. Waste oil and oily waste samples should be recycled as raw materials and/or recovered as an energy source, but the findings of this study yields disposal as a hazardous material due to high metal (Cr) content. The overall results of the study show that uncontrolled combustion of waste oil and oily wastes may cause environmental problems, and use of these wastes and products should be controlled and managed by strict precautions.

Kurt-Karakus, Perihan Binnur/0000-0001-6737-3475; Alegria, Henry/0000-0003-1685-2008, WOS: 000426356600056, PubMed: 29291570, 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 (T2-iPPP). 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 19,139 pg/m(3). In soil, total OPEs ranged from 38 to 468 ng/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. (C) 2017 Elsevier B.V. All rights reserved.

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.

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 μg g−1 for Cu, 3–200 μg g−1 for Pb, 0.4–20 μg g−1 for Cd, 210–2800 μg g−1 for Zn, 2.8–460 μg g−1 for Cr, 8–1300 μg g−1 for Mn, 2.4–25 μg g−1 for Co, 120–2600 μg g−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. Keywords: Indoor dust, Heavy metals, Exposure, Health risk assessment, Istanbul

Concentrations of atrazine and metolachlor and stereoisomer fractions (SF = herbicidally active/total stereoisomers) of metolachlor were determined in 101 surface water samples collected from the five Laurentian Great Lakes in 2005-2006. Geometric mean (GM) concentrations of atrazine ranged from 5.5 to 61 ng L(-1), decreasing from lakes Ontario approximately Michigan approximately ErieHuronSuperior, while metolachlor concentrations ranged from 0.28 to 14 ng L(-1) and showed similar trends among the lakes. Median SFs ranged from 0.527 (Superior) to 0.844 (Erie) with an overall value of 0.708, and were significantly different among the Great Lakes (p0.05), except for Michigan vs Huron and Michigan vs Ontario. The SF in Erie was closest to that of the dominant product in use, S-metolachlor (SF = 0.880), while Superior showed an SF similar to that of racemic metolachlor (SF = 0.500). The median SFs in lakes Ontario, Huron and Erie were significantly lower than the median SF in Ontario stream samples collected in 2006-2007. The lower SFs in lakes suggest in-lake stereoselective processing of metolachlor or hold-up of older racemic metolachlor residues.

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 andor = 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.

Chiral pesticides frequently undergo enantioselective degradation in soils. Prior studies to characterize chiral signatures have focused on treated agricultural soils, rather than background (untreated) soils, and tracking signatures in the atmosphere for source apportionment purposes. In this study, we investigated the chiral signatures in 65 background soils collected from different locations across the world. The soils were taken from different ecosystems (e.g., grasslands, forests), and the enantiomeric fractions (EFs) of chiral chlordanes, alpha-hexachlorocyclohexane (alpha-HCH), and o,p'-DDT were determined. Chlordanes in most of the soils showed the usual pattern of enantioselective degradation seen in agricultural soils, depletion of (+)-trans-chlordane (TC) and (-)-cis-chlordane (CC). However, some samples showed opposite enantiomer degradation patterns for TC, CC, and chlordane compound MC5. Correlations were tested between the deviation of EFs from racemic (DEVrac = absolute value of 0.500 - EF), the percent soil organic matter (% SOM), annual mean temperature, and the ratio of TC to the more stable compound trans-nonachlor (TN). Significant positive correlations were found between DEVrac and % SOM for TC and CC (p = 0.0022 and 0.0031), but not for the other OCPs. No significant correlations were found between DEVrac and annual mean temperature for any of the OCPs. DEVrac for TC was negatively correlated with the TC/TN ratio, but the regression was driven by two points with high ratios of TC/CC. Removing these two points resulted in a nonsignificant regression. The range of EFs for TC, CC, and alpha-HCH in soils was greater than in ambient air, providing evidence of in situ degradation after atmospheric deposition in some cases. Variable EFs in soil suggest that caution is needed when considering the enantiomer signatures in air as a marker of volatilization of weathered soil-derived organochlorines.

Elimination of persistent organic pollutants (POPs) under national and international regulations reduces “primary” emissions, but “secondary” emissions continue from residues deposited in soil, water, ice and vegetation during former years of usage. In a future, secondary source controlled world, POPs will follow the carbon cycle and biogeochemical processes will determine their transport, accumulation and fate. Climate change is likely to affect mobilisation of POPs through e.g., increased temperature, altered precipitation and wind patterns, flooding, loss of ice cover in polar regions, melting glaciers, and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially degraded) sources. This paper discusses the rationale for this approach and suggests applications where chiral POPs could aid investigation of climate-mediated exchange and degradation processes. Multiyear measurements of two chiral POPs, trans-chlordane and α-HCH, at a Canadian Arctic air monitoring station show enantiomer compositions which cycle seasonally, suggesting varying source contributions which may be under climatic control. Large-scale shifts in the enantioselective metabolism of chiral POPs in soil and water might influence the enantiomer composition of atmospheric residues, and it would be advantageous to include enantiospecific analysis in POPs monitoring programs.

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.

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

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 (p0.0001) higher than those in urban watersheds, whereas concentrations of mecoprop did not differ (p0.1) 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 (p0.1) between agricultural and urban land usage. Mecoprop EFsor = 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, EFs0.5 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 (p0.001) in agricultural than urban watersheds. Streamwater from row crop areas showed higher S/R ratios than streamwater from fruit growing areas (p = 0.036).

Background soils (a230 samples) were analyzed for DDT and its an average p,pc-DDT/p,pc-DDE ratio of 1.5. Soil-to-air fluxes of DDT

Variability in the enantioselective degradation of chiral organo- chlorine pesticides (OCPs: D -HCH, cis- and trans-chlordane (CC and TC), chlordane MC5 and o,pc-DDT) in background soils was investigated on a global scale and in small-scale transect studies. Background soils collected from 32 countries displayed a wide range of enantiomer profiles for a particular compound, showing varying degradation preferences. In some locations, grassland and woodland soils which were collected only a few hundred meters apart showed differences in the enantiomer profiles and even reversals in degradation preferences. Further studies at small plots in Scotland indicated that such differences could be found within a few meters horizontally and a few centimeters in depth. Soil organic matter content and pH exerted a minor influence on the variability. For chlordanes, the enantiomer profiles in background soils were much more variable than those in ambient air, suggesting that degradation occurred following atmospheric deposition. Thus, background soils play a role in sequestering and degrading OCPs, although enantiomer profiles are not a quantitative measure of overall degradation. The results of this study show that caution is needed when considering the enantiomer signatures in air as a marker of volatilization of weathered soil-derived OCPs.

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p0.001), co-PCBs (p0.01) and PCBs, HCB, PCDD/F (p0.05); TOC and BC were correlated with each other (p0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.

Soils have an important role to play in supplying and receiving contaminants from the atmosphere, and in the global cycling of certain persistent organic pollutants (POPs). A microcosm study was conducted, in which some aspects of air–soil exchange likely to be important for the global cycling of POPs were simulated. HCB and PCBs were introduced into a sealed chamber, which contained soils of varying organic matter content, and in which soil mixing was a variable. Uptake of these compounds on to the soils was monitored over time. Subsequently, the primary chemical source was removed and further changes in the residues retained on the soils were monitored. The rates of uptake onto the different soil treatments are compared and the influence of the soil organic matter content and mixing evaluated. The implications for the global cycling of POPs are discussed.

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.

Elimination of persistent organic pollutants (POPs) under national and international controls reduces “primary” emissions, but “secondary” emissions continue from residues deposited in soil, water, ice and vegetation during former years of high usage. Secondary sources are expected to dominate in the future, when POPs transport and accumulation will be controlled by air–surface exchange and the biogeochemical cycle of organic carbon. Climate change is likely to affect mobilization of POPs through, e.g., increased temperature, loss of ice cover in polar regions, melting glaciers and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially altered) sources. Here we explain the rationale for this approach and suggest applications where chiral POPs could aid investigation of climate–mediated exchange and degradation processes. Examples include distinguishing agricultural vs. non–agricultural and recently used vs. residual pesticides, degradation and sequestration processes in soil, historical vs. recent atmospheric deposition, sources in arctic air and influence of ice cover on volatilization.