Publications by authors named "Petr Kukučka"

46 Publications

Open, High-Resolution EI+ Spectral Library of Anthropogenic Compounds.

Front Public Health 2021 9;9:622558. Epub 2021 Mar 9.

RECETOX Centre, Masaryk University, Brno, Czechia.

To address the lack of high-resolution electron ionisation mass spectral libraries (HR-[EI+]-MS) for environmental chemicals, a retention-indexed HR-[EI+]-MS library has been constructed following analysis of authentic compounds via GC-Orbitrap MS. The library is freely provided alongside a compound database of predicted physicochemical properties. Currently, the library contains over 350 compounds from 56 compound classes and includes a range of legacy and emerging contaminants. The RECETOX Exposome HR-[EI+]-MS library expands the number of freely available resources for use in full-scan chemical exposure studies and is available at: https://doi.org/10.5281/zenodo.4471217.
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http://dx.doi.org/10.3389/fpubh.2021.622558DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7985345PMC
May 2021

Trends of Diverse POPs in Air and Water Across the Western Atlantic Ocean: Strong Gradients in the Ocean but Not in the Air.

Environ Sci Technol 2020 Nov 5. Epub 2020 Nov 5.

Harvard John A. Paulson School of Engineering and Applied Science, Harvard University, Cambridge, Massachusetts 02138, United States.

Oceans have remained the least well-researched reservoirs of persistent organic pollutants (POPs) globally, due to their vast scale, difficulty of access, and challenging (trace) analysis. Little data on POPs exists along South America and the effect of different currents and river plumes on aqueous concentrations. Research cruise KN210-04 () offered a unique opportunity to determine POP gradients in air, water, and their air-water exchange along South America, covering both hemispheres. Compounds of interest included polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs). Remote tropical Atlantic Ocean atmospheric concentrations varied little between both hemispheres; for HCB, BDEs 47 and 99, they were ∼5 pg/m, PCBs were ∼1 pg/m, α-HCH was ∼0.2 pg/m, and phenanthrene and other PAHs were in the low 100s pg/m. Aqueous concentrations were dominated by PCB 52 (mean 4.1 pg/L), HCB (1.6 pg/L), and β-HCH (1.9 pg/L), with other compounds <1 pg/L. Target PCBs tended to undergo net volatilization from the surface ocean, while gradients indicated net deposition for -HCH. In contrast to atmospheric concentrations, which were basically unchanged between hemispheres, we detected strong gradients in aqueous POPs, with mostly nondetects in the tropical western South Atlantic. These results highlight the importance of currents and loss processes on ocean scales for the distribution of POPs.
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http://dx.doi.org/10.1021/acs.est.0c04611DOI Listing
November 2020

Three years of atmospheric concentrations of nitrated and oxygenated polycyclic aromatic hydrocarbons and oxygen heterocycles at a central European background site.

Chemosphere 2021 Apr 26;269:128738. Epub 2020 Oct 26.

RECETOX Centre, Masaryk University, Brno, Czech Republic; Multiphase Chemistry Department, Max Planck Institute for Chemistry, Mainz, Germany. Electronic address:

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs, OPAHs) are abundant in the atmosphere and contribute significantly to the health risk associated with inhalation of polluted air. Despite the health hazard they pose, NPAHs and OPAHs were rarely included in monitoring. The aim of this study is to provide the first multi-year temporal trends of the concentrations, composition pattern and fate of NPAHs and OPAHs in air from a site representative of background air quality conditions in central Europe. Samples were collected every second week at a rural background site in the Czech Republic during 2015-2017. Concentrations ranged from 1.3 to 160 pg m for ΣNPAHs, from 32 to 2600 pg m for ΣOPAHs and from 5.1 to 4300 pg m for ΣO-heterocycles. The average particulate mass fraction (θ) ranged from 0.01 ± 0.02 (2-nitronaphthalene) to 0.83 ± 0.22 (1-nitropyrene) for individual NPAHs and from <0.01 ± 0.01 (dibenzofuran) to 0.96 ± 0.08 (6H-benzo (c,d)pyren-6-one) for individual OPAHs and O-heterocycles. The multiyear variations showed downward trends for a number of targeted compounds. This suggests that on-going emission reductions of PAHs are effective also for co-emitted NPAHs and OPAHs.
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http://dx.doi.org/10.1016/j.chemosphere.2020.128738DOI Listing
April 2021

Temporal Trends of Persistent Organic Pollutants across Africa after a Decade of MONET Passive Air Sampling.

Environ Sci Technol 2020 Oct 23. Epub 2020 Oct 23.

RECETOX, Masaryk University, Kamenice 753/5, 625 00 Brno, Czech Republic.

The Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants (POPs) was established to generate long-term data necessary for evaluating the effectiveness of regulatory measures at a global scale. After a decade of passive air monitoring (2008-2019), MONET is the first network to produce sufficient data for the analysis of long-term temporal trends of POPs in the African atmosphere. This study reports concentrations of 20 POPs (aldrin, chlordane, chlordecone, DDT, dieldrin, endrin, endosulfan, HBCDD, HCB, HCHs, heptachlor, hexabromobiphenyl, mirex, PBDEs, PCBs, PCDDs, PCDFs, PeCB, PFOA, and PFOS) monitored in 9 countries (Congo, Ghana, Ethiopia, Kenya, Mali, Mauritius, Morocco, Nigeria, and Sudan). As of January 1, 2019, concentrations were in the following ranges (pg/m): 0.5-37.7 (∑PCB), 0.006-0.724 (∑PCDD/F), 0.05-5.5 (∑PBDE), 0.6-11.3 (BDE 209), 0.1-1.8 (∑HBCDD), 1.8-138 (∑DDT), 0.1-24.3 (∑endosulfan), 0.6-14.6 (∑HCH), 9.1-26.4 (HCB), 13.8-18.2 (PeCB). Temporal trends indicate that concentrations of many POPs (PCBs, DDT, HCHs, endosulfan) have declined significantly over the past 10 years, though the rate was slow at some sites. Concentrations of other POPs such as PCDD/Fs and PBDEs have not changed significantly over the past decade and are in fact increasing at some sites, attributed to the prevalence of open burning of waste (particularly e-waste) across Africa. Modeled airflow back-trajectories suggest that the elevated concentrations at some sites are primarily due to sustained local emissions, while the low concentrations measured at Mt. Kenya represent the continental background level and are primarily influenced by long-range transport.
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http://dx.doi.org/10.1021/acs.est.0c03575DOI Listing
October 2020

Toxic potentials of particulate and gaseous air pollutant mixtures and the role of PAHs and their derivatives.

Environ Int 2020 06 20;139:105634. Epub 2020 May 20.

RECETOX, Faculty of Science, Masaryk University, Kamenice 753/5, 625 00 Brno, Czech Republic. Electronic address:

Background: Air pollution, which represents a major environmental risk to human health, comprises a complex mixture of compounds where only little is known about its specific toxicities.

Objectives: This study examined the specific toxicities associated with ambient air pollutant mixtures with respect to gas/particle partitioning, particulate matter (PM) size, pollutant polarity and bioaccessibility from PM, and evaluated the contribution of PAHs and their oxygenated and nitrated derivatives (OPAHs, NPAHs).

Methods: Air samples (gas phase, PM and size-segregated PM), were collected at urban (in winter and summer) and background (winter) sites in the Czech Republic. The total and bioaccessible concentrations were addressed using organic solvent extraction and simulated lung fluid extraction, respectively. Organic extracts were also further fractionated according to polarity. Aryl hydrocarbon receptor (AhR)-mediated activity, anti-/estrogenicity, anti-/androgenicity, thyroid receptor (TR)-mediated activity and cytotoxicity for bronchial cells were determined by human cell-based in vitro bioassays. The contribution of studied compounds to observed effects was assessed by both modelling and reconstructing the mixtures.

Results: Significant effects were detected in the sub-micrometre size fraction of PM (estrogenicity, androgenicity, TR- and AhR-mediated activities) and in the gas phase (TR-mediated activity, antiandrogenicity). Compounds interacting with TR showed high bioaccessibility to simulated lung fluid. Relatively lower bioaccessibility was observed for estrogenicity and AhR-mediated activity. However, the toxicity testing of reconstructed mixtures revealed that the targeted pollutants are not the main contributors, except for urban PM air pollution in winter, where they accounted for 5-88% of several effects detected in the original complex environmental samples.

Discussion: Studied toxicities were mostly driven by polar compounds largely attributed to the easily inhalable PM, which is of high relevance for human health risk assessment. Except of parent PAHs in some cases, the targeted compounds contributed to the detected effects mostly to a relatively low extent implying huge data gaps in terms of endocrine disruptive potencies of targeted substances and the significance of other polar compounds present in ambient air.
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http://dx.doi.org/10.1016/j.envint.2020.105634DOI Listing
June 2020

Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons in Ambient Air-Levels, Phase Partitioning, Mass Size Distributions, and Inhalation Bioaccessibility.

Environ Sci Technol 2020 03 11;54(5):2615-2625. Epub 2020 Feb 11.

Multiphase Chemistry Department, Max Planck Institute for Chemistry, Mainz 55128, Germany.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of ΣOPAHs were 10.0 ± 9.2 ng/m in winter and 3.5 ± 1.6 ng/m in summer. The gradient to the regional background site exceeded 1 order of magnitude. ΣNPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.
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http://dx.doi.org/10.1021/acs.est.9b06820DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7307896PMC
March 2020

Multiyear levels of PCDD/Fs, dl-PCBs and PAHs in background air in central Europe and implications for deposition.

Chemosphere 2020 Feb 14;240:124852. Epub 2019 Sep 14.

Masaryk University, RECETOX, Kamenice 5, 625 00, Brno, Czech Republic.

This study presents four years ambient monitoring data of seventeen 2,3,7,8-chlorine substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), twelve dioxin-like polychlorinated biphenyls (dl-PCBs) and sixteen polycyclic aromatic hydrocarbons (PAHs) designed by the US EPA at a background site in central Europe during 2011-2014. The concentrations expressed as toxic equivalents (TEQs) using the WHO-scheme for PCDD/Fs (0.2 fg m-61.1 fg m) were higher than for dl-PCBs (0.01 fg m-2.9 fg m), while the opposite was found in terms of mass concentrations. ΣPAHs ranged from 0.20 ng m to 134 ng m. The mass concentration profile of PCDD/Fs, dl-PCBs and PAHs was similar throughout the four years. PCDD/Fs and PAHs concentrations were dominated by primary sources peaking in winter, while those of dl-PCBs were controlled by secondary sources characterized by a spring-summer peak. During 2011-2014, no significant decrease in the atmospheric levels of ΣPCDD/Fs was observed. On the other hand, the concentrations of Σdl-PCBs and ΣPAHs were decreasing, with halving times of 5.7 and 2.7 years, respectively. We estimated that 422 pg m year-567 pg m year TEQ PCDD/Fs and 3.48 pg m year-15.8 pg m year TEQ dl-PCBs were transferred from the air to the ground surfaces via dry particulate deposition during 2011-2014.
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http://dx.doi.org/10.1016/j.chemosphere.2019.124852DOI Listing
February 2020

Comparability of long-term temporal trends of POPs from co-located active and passive air monitoring networks in Europe.

Environ Sci Process Impacts 2019 Jul;21(7):1132-1142

RECETOX Centre, Faculty of Science, Masaryk University, Kamenice 753/5, 625 00 Brno, Czech Republic.

The comparability of data from active (ACT) and passive sampling (PAS) of persistent organic pollutants (POPs) in air is hindered by uncertainties related to the derivation of sampling rates and concentrations, as well as differences in the duration, volume and frequency of sampling. Although data from ACT have been used extensively in short-term PAS calibration studies, no attempts have been made to evaluate the comparability of long-term trends calculated from PAS to established ACT trends. This is crucial, as continuous long-term ACT is unfeasible in most regions of the world. To address these challenges, we calculated and compared trends for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) at the six sites in Europe with at least 5 years of co-located ACT and PAS data (2012-2016): Birkenes, Košetice, Pallas, Råö, Stórhöfði and Zeppelin. Strong agreement of ACT and PAS trends was observed for most OCPs and PCBs. Apart from two PCBs at Stórhöfði, all pairs of ACT and PAS trends followed the same direction. However, differences in the magnitude, significance and confidence intervals of their slopes were observed for some compounds and were primarily attributed to the short duration of the PAS time series. Despite some limitations, our results suggest that the comparability of ACT and PAS POP trends will continue to improve with additional years of data. This study confirms the suitability of PAS for the calculation of long-term POP trends in air, and highlights the importance of continuous sampling at established monitoring sites with consistent analytical methods.
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http://dx.doi.org/10.1039/c9em00136kDOI Listing
July 2019

Fast Formation of Nitro-PAHs in the Marine Atmosphere Constrained in a Regional-Scale Lagrangian Field Experiment.

Environ Sci Technol 2019 Aug 10;53(15):8914-8924. Epub 2019 Jul 10.

Masaryk University , Research Centre for Toxic Compounds in the Environment , Kamenice 5 , 625 00 , Brno , Czech Republic.

Polycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 ± 0.2) and (1.5 ± 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NO conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NO conditions, are largely underestimated.
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http://dx.doi.org/10.1021/acs.est.9b03090DOI Listing
August 2019

Bulk atmospheric deposition of persistent organic pollutants and polycyclic aromatic hydrocarbons in Central Europe.

Environ Sci Pollut Res Int 2019 Aug 14;26(23):23429-23441. Epub 2019 Jun 14.

Research Centre for Toxic Compounds in the Environment, Masaryk University, Brno, Czech Republic.

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for ΣPAHs ranged 23-1100 ng m d, while those for Σ6PCBs and Σ12OCPs ranged 64-4400 and 410-7800 pg m d, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of ΣPAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for ΣOCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase.
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http://dx.doi.org/10.1007/s11356-019-05464-9DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6667414PMC
August 2019

Characterizing Spatial Diversity of Passive Sampling Sites for Measuring Levels and Trends of Semivolatile Organic Chemicals.

Environ Sci Technol 2018 09 29;52(18):10599-10608. Epub 2018 Aug 29.

Research Centre for Toxic Compounds in the Environment, RECETOX , Kamenice 5 , 625 00 Brno , Czech Republic.

Passive air sampling of semivolatile organic compounds (SVOCs) is a relatively inexpensive method that facilitates extensive campaigns with numerous sampling sites. An important question in the design of passive-sampling networks concerns the number and location of samplers. We investigate this question with the example of 17 SVOCs sampled at 14 background sites across the Czech Republic. More than 200 time series (length 5-11 years) were used to characterize SVOC levels and trends in air between 2003 and 2015. Six polychlorinated biphenyls (PCBs), 6 polyaromatic hydrocarbons (PAHs), and 5 organochlorine pesticides (OCPs) at 14 sites were assessed using data from the MONET passive sampling network. Significant decreases were found for most PCBs and OCPs whereas hexachlorobenzene (HCB) and most PAHs showed (mostly insignificant) increases. Spatial variability was rather low for PCBs and OCPs except for dichlorodiphenyltrichloroethane (DDT) and rather high for PAHs. The variability of the SVOC levels and trends depends on characteristics of the sites including their remoteness, landscape, population, and pollution sources. The sites can be grouped in distinct clusters, which helps to identify similar and, thereby, potentially redundant sites. This information is useful when monitoring networks need to be optimized regarding the location and number of sites.
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http://dx.doi.org/10.1021/acs.est.8b03414DOI Listing
September 2018

PCBs and organochlorine pesticides in indoor environments - A comparison of indoor contamination in Canada and Czech Republic.

Chemosphere 2018 Sep 3;206:622-631. Epub 2018 May 3.

RECETOX, Masaryk University, Kamenice 753/5, Pavilion A29, 62500, Brno, Czech Republic.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are restricted compounds that are ubiquitously detected in the environment, including indoor matrices such as air and residential dust. We report concentrations of PCBs and selected OCPs in indoor air and dust from homes in Canada (23 homes) and Czech Republic (20 homes). Indoor air concentrations of PCBs and OCPs were ∼10 times higher than that outdoors. PCB concentrations of ∼450 ng/m were similar in both countries, higher in homes built before the restrictions on PCBs, and had congener profiles consistent with PCB mixtures manufactured or used in each country. All OCP air concentrations were higher in the Czech Republic than in the Canadian samples, suggesting greater indoor use of, for example, DDT and HCH. These data emphasize the persistence of these organochlorine compounds indoors and their presence in homes even decades after new usage was prohibited. Indoor levels of these legacy POPs remain at similar concentrations to compounds of current concern, such as brominated flame retardants and perfluorinated alkyl substances, emphasizing that they deserve ongoing attention in view of knowledge of PCB and OCP toxicity.
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http://dx.doi.org/10.1016/j.chemosphere.2018.05.016DOI Listing
September 2018

A method for analysis of marker persistent organic pollutants in low-volume plasma and serum samples using 96-well plate solid phase extraction.

J Chromatogr A 2018 Apr 27;1546:18-27. Epub 2018 Feb 27.

MTM, School of Science and Technology, Örebro University, 701 82 Örebro, Sweden.

The objective of this study was to develop and validate a 96-well plate solid phase extraction method for analysis of 23 lipophilic persistent organic pollutants (POPs) in low-volume plasma and serum samples which is applicable for biomonitoring and epidemiological studies. The analysis of selected markers for internal exposure: 16 polychlorinated biphenyls (PCBs), 5 organochlorine pesticides (OCPs), octachlorinated dibenzo-p-dioxin (OCDD), and polybrominated diphenylether 47 (BDE 47) was evaluated by comparing two SPE sorbents and GC-HRMS or GC-MS/MS detection. The final method extracted 23 POPs from 150 μL of serum and plasma using a 96-well extraction plate containing 60 mg Oasis HLB sorbent per well prior to GC-HRMS magnetic sector analysis. The extraction method was applied to 40 plasma samples collected for an epidemiological study. The recovery of selected POPs ranged from 31% to 63% (n = 48), and detection limits ranged from 2.2 to 45 pg/mL for PCBs, 4.2 to 167 pg/mL for OCPs, 7.8 pg/mL for OCDD and 6.1 pg/mL for BDE 47. This method showed good precision with relative standard deviations of selected POP concentrations in quality control samples (n = 48) ranging from 11% to 25%. The trueness was determined with standard reference material serum (n = 48) and the deviation from certified values ranged from 1 to 27%. Of the 23 POPs analyzed, 18 were detected in 43% to 100% of plasma samples collected for the epidemiological study. The method showed good robustness with low inter-well plate variation (11-31%) determined by twelve 96-well plate extractions, and can extract 96 samples, including quality controls and procedural blanks in 2-3 days. Comparison with GC-MS/MS analysis showed that similar concentrations (within 0.5% to 30%) of most POPs could be obtained with GC-APCI-MS/MS. Larger deviations were observed for PCB 194 (60%) and trans-nonachlor (43%). The developed method produces accurate concentrations of low-level marker POPs in plasma and serum, providing a suitable high-throughput sample preparation procedure for biomonitoring and epidemiological studies involving large sample size and limited sample volume. GC-HRMS was chosen over GC-MS/MS, however the latter showed promising results, and could be used as an alternative to GC-HRMS analysis for most POPs.
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http://dx.doi.org/10.1016/j.chroma.2018.02.057DOI Listing
April 2018

A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan.

Environ Sci Pollut Res Int 2018 Nov 7;25(32):31863-31873. Epub 2017 Nov 7.

Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ, UK.

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑PBDE concentrations in air and soil were 7.13 ± 1.66 pg m and 168 ± 57 pg g, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g), comprising ~ 96% of ∑PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.
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http://dx.doi.org/10.1007/s11356-017-0573-2DOI Listing
November 2018

Polybrominated diphenyl ethers (PBDEs) in background air around the Aegean: implications for phase partitioning and size distribution.

Environ Sci Pollut Res Int 2017 Dec 9;24(36):28102-28120. Epub 2017 Oct 9.

Department of Chemistry, Environmental Pollution Control Laboratory, Aristotle University of Thessaloniki, Thessaloniki, Greece.

The occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m, respectively) were found at the remote site Finokalia. Partitioning coefficients, K , were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (P °) and the octanol-air partition coefficient (K ), were investigated. The equilibrium adsorption (P °-based) and absorption (K -based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log K , were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95-1.5, 1.5-3.0, 3.0-7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log P ° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.
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http://dx.doi.org/10.1007/s11356-017-0285-7DOI Listing
December 2017

Legacy and alternative halogenated flame retardants in human milk in Europe: Implications for children's health.

Environ Int 2017 11 24;108:137-145. Epub 2017 Aug 24.

Research Centre for Toxic Compounds in the Environment, Faculty of Science, Masaryk University, Kamenice 753/5, 625 00 Brno, Czech Republic; Institute for Chemical and Bioengineering, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093 Zürich, Switzerland. Electronic address:

In this study, 10 polybrominated diphenyl ethers (PBDEs) and 19 alternative halogenated flame retardants (AFRs) were determined in >450 human milk samples across three European countries, representing northern, western and eastern Europe. This study provides first insights into the occurrence of selected AFRs in mother milk samples and compares them among three European countries. Sums of median concentrations of the most frequently detected PBDEs were 2.16, 0.88 and 0.45ngg lipid weight (lw) in Norway, the Netherlands and Slovakia, respectively. The sum of the concentrations of AFRs ranged from 0.14 to 0.25ngglw in all countries, which was 2 to 15 times less compared to ΣPBDEs. The Penta-BDE replacement, bis(2-ethylhexyl) tetrabromophthalate, BEH-TEBP, was present at the greatest concentrations of any of the AFRs and in some samples exceeded concentrations of BDE 47 and BDE 153. Four AFRs including bromobenzenes (hexabromobenzene, pentabromobenzene, pentabromotoluene) and another Penta-BDE replacement (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB) were detected in >42% of all human milk samples. Because of the potential developmental neurotoxicity of the halogenated flame retardants, infant dietary intakes via breastfeeding were estimated; in four cases the intakes of BDE 47 exceeded the reference dose indicating that the present concentrations may pose a risk for children.
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http://dx.doi.org/10.1016/j.envint.2017.08.008DOI Listing
November 2017

Passive Air Samplers As a Tool for Assessing Long-Term Trends in Atmospheric Concentrations of Semivolatile Organic Compounds.

Environ Sci Technol 2017 Jun 12;51(12):7047-7054. Epub 2017 Jun 12.

Research Centre for Toxic Compounds in the Environment RECETOX, Kamenice 5, 625 00 Brno, Czech Republic.

Many attempts have been made to quantify the relationship between the amount of persistent organic pollutants sequestered by passive air sampling devices and their actual concentrations in ambient air. However, this information may not be necessary for some applications. In this study, two sets of 30 ten-year-long time series of simultaneous passive and high-volume active air sampling carried out at the Košetice observatory in the Czech Republic were used for a comparison of temporal trends. Fifteen polyaromatic hydrocarbons, seven polychlorinated biphenyls and eight organochlorine pesticides were investigated. In most cases, a good agreement was observed between the trends derived from passive and active monitoring with the exception of several compounds obviously affected by sampling artifacts. Two sampling artifacts were observed: breakthrough of high-volume sampler filters for penta- and hexachlorobenzene and semiquantitative values for PAHs with a high molecular weight. It has been suggested before that annually aggregated results of passive air monitoring may be used directly for the assessment of the long-term behavior of these compounds. The extensive set of long-term data used in this study allowed us to confirm this finding and to demonstrate that it is also possible to derive temporal trends and the compounds' half-lives in air from the passive-sampling time series.
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http://dx.doi.org/10.1021/acs.est.7b02319DOI Listing
June 2017

Bioindication of PBDEs and PCBs by native and transplanted moss Pleurozium schreberi.

Ecotoxicol Environ Saf 2017 Sep 18;143:136-142. Epub 2017 May 18.

Radboud University Nijmegen, Institute for Water and Wetland Research, Department of Environmental Science, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands. Electronic address:

PBDEs and PCBs are toxic, persistent organic pollutants (POPs), and the use of PCBs is forbidden, but they are still present in many environments and biota. 90-day assays were conducted with the moss Pleurozium schreberi transplanted from an uncontaminated control site to ten sites (rural and urban) selected in one of the most polluted regions of Upper Silesia in Poland. Native P. schreberi mosses were collected from the same ten polluted sites. Concentrations of PBDEs (28, 47, 66, 85, 99, 100, 153, 154, 183 and 209) and PCBs (28, 52, 101, 118, 138, 153, 180) were determined in all native and transplanted P. schreberi from all sites. Native P. schreberi contained the highest ΣPBDE and ΣPCB levels (63.6ngg and 4.47pgg, respectively) when collected in the vicinity of a steel smelter. After 90 days of the experiment native and transplanted P. schreberi contained the highest concentrations of the same BDE 209 congener (88-91% of total PBDEs in the native mosses and 85-90% of the total PBDE burden in the transplants). The native and transplanted mosses from the industrial sites after 90 days of exposure contained significantly higher concentrations of all the examined PBDE and PCB congeners (except for 153 and 180) than mosses from rural sites. PBDE and PCB values were higher in native than in transplanted mosses after 90 days of exposure in both rural and industrial sites.
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http://dx.doi.org/10.1016/j.ecoenv.2017.05.025DOI Listing
September 2017

Persistent organic pollutants (POPs) in the atmosphere of coastal areas of the Ross Sea, Antarctica: Indications for long-term downward trends.

Chemosphere 2017 Jul 27;178:458-465. Epub 2017 Feb 27.

Department of Chemistry "Ugo Schiff", University of Florence, Sesto Fiorentino, Florence, Italy; Institute for the Dynamics of Environmental Processes, Italian National Research Council (IDPA-CNR), Dorsoduro, Venice, Italy. Electronic address:

Passive air samplers were used to evaluate long-term trends and spatial distribution of trace organic compounds in Antarctica. Duplicate PUF disk samplers were deployed at six automatic weather stations in the coastal area of the Ross sea (East Antarctica), between December 2010 and January 2011, during the XXVI Italian Scientific Research Expedition. Among the investigated persistent organic compounds, Hexachlorobenzene was the most abundant, with air concentrations ranging from 0.8 to 50 pg m. In general, the following decreasing concentration order was found for the air samples analyzed: HCB > PeCB > PCBs > DDTs > HCHs. While HCB concentrations were in the same range as those reported in the atmosphere of other Antarctic sampling areas and did not show a decline, HCHs and DDTs levels were lower or similar to those determined one or two decades ago. In general, the very low concentrations reflected the pristine state of the East Antarctica air. Backward trajectories indicated the prevalence of air masses coming from the Antarctic continent. Local contamination and volatilization from ice were suggested as potential sources for the presence of persistent organic pollutants in the atmosphere.
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http://dx.doi.org/10.1016/j.chemosphere.2017.02.118DOI Listing
July 2017

Mixture-specific gene expression in zebrafish (Danio rerio) embryos exposed to perfluorooctane sulfonic acid (PFOS), perfluorohexanoic acid (PFHxA) and 3,3',4,4',5-pentachlorobiphenyl (PCB126).

Sci Total Environ 2017 Jul 7;590-591:249-257. Epub 2017 Mar 7.

Man-Technology-Environment Research Centre (MTM), School of Science and Technology, Örebro University, Fakultetsgatan 1, S-701 82 Örebro, Sweden.

Perfluorooctane sulfonic acid (PFOS) and 3,3',4,4',5-pentachlorobiphenyl (PCB126) are persistent organic pollutants of high concern because of their environmental persistence, bioaccumulation and toxic properties. Besides, the amphiphilic properties of fluorinated compounds such as PFOS and perfluorohexanoic acid (PFHxA) suggest a role in increasing cell membrane permeability and solubilizing chemicals. The present study aimed at investigating whether PFOS and PFHxA are capable of modifying the activation of PCB126 toxicity-related pathways. For this purpose, zebrafish embryos were exposed in semi-static conditions to 7.5μg/L of PCB126 alone, in the presence of 25mg/L of PFOS, 15.7mg/L of PFHxA or in the presence of both PFOS and PFHxA. Quantitative PCR was performed on embryos aged from 24h post fertilization (hpf) to 96 hpf to investigate expression changes of genes involved in metabolism of xenobiotics (ahr2, cyp1a), oxidative stress (gpx1a, tp53), lipids metabolism (acaa2, osbpl1a), and epigenetic mechanisms (dnmt1, dnmt3ba). Cyp1a and ahr2 expression were significantly induced by the presence of PCB126. However, after 72 and 78h of exposure, induction of cyp1a expression was significantly lower when embryos were co-exposed to PCB126+PFOS+PFHxA when compared to PCB126-exposed embryos. Significant upregulation of gpx1a occurred after exposure to PCB126+PFHxA and to PCB126+PFOS+PFHxA at 30 and 48 hpf. Besides, embryos appeared more sensitive to PCB126+PFOS+PFHxA at 78 hpf: acaa2 and osbpl1a were significantly downregulated; dnmt1 was significantly upregulated. While presented as environmentally safe, PFHxA demonstrated that it could affect gene expression patterns in zebrafish embryos when combined to PFOS and PCB126, suggesting that such mixture may increase PCB126 toxicity. This is of particular relevance since PFHxA is persistent and still being ejected into the environment. Moreover, it provides additional information as to the importance to integrate mixture effects of chemicals in risk assessment and biomonitoring frameworks.
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http://dx.doi.org/10.1016/j.scitotenv.2017.02.232DOI Listing
July 2017

Persistent Organic Pollutants (POPs) in the atmosphere of three Chilean cities using passive air samplers.

Sci Total Environ 2017 May 4;586:107-114. Epub 2017 Jan 4.

Universitá degli Studi di Siena, Dipartimento Scienze fisiche, della Terra e dell'ambiente, Siena, Italy.

In this study passive air samplers containing polyurethane foam (PUF) disks were deployed in three cities across Chile; Santiago (STG) (n=5, sampling sites), Concepciόn (CON) (n=6) and Temuco (TEM) (n=6) from 2008 to 2009. Polychlorinated biphenyls (PCBs) (7 indicator congeners), chlorinated pesticides hexachlorocyclohexanes (HCHs), dichlorodiphenyl trichloroethanes (DDTs) and flame retardants such as polybrominated diphenyl ethers (PBDEs) were determined by gas chromatography coupled mass spectrometry (GC/MS). A sampling rate (R) typical of urban sites (4m/day) was used to estimate the atmospheric concentrations of individual compounds. PCB concentrations in the air (pg/m) ranged from ~1-10 (TEM), ~1-40 (STG) and 4-30 (CON). Higher molecular weight PCBs (PCB-153, -180) were detected at industrial sites (in Concepción). The HCHs showed a prevalence of γ-HCH across all sites, indicative of inputs from the use of lindane but a limited use of technical HCHs in Chile. DDTs were detected with a prevalence of p,p'-DDE accounting for ~50% of the total DDTs. PBDE concentrations in air (pg/m) ranged from 1 to 55 (STG), 0.5 to 20 (CON) and from 0.4 to 10 (TEM), and were generally similar to those reported for many other urban areas globally. The pattern of PBDEs was different among the three cities; however, PBDE-209 was dominant at most of the sites. These results represent one of the few assessments of air concentrations of POPs across different urban areas within the same country. These data will support Chilean commitments as a signatory to the Stockholm Convention on POPs and for reporting as a member country of the Group of Latin America and Caribbean Countries (GRULAC) region.
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http://dx.doi.org/10.1016/j.scitotenv.2016.11.054DOI Listing
May 2017

Passive air sampling of persistent organic pollutants (POPs) and emerging compounds in Kolkata megacity and rural mangrove wetland Sundarban in India: An approach to regional monitoring.

Chemosphere 2017 Feb 29;168:1430-1438. Epub 2016 Nov 29.

Universitá degli Studi di Siena, Dipartimento Scienze fisiche, della Terra e dell'Ambiente, Via Mattioli 4, 53100, Siena, Italy.

Polyurethane foam (PUF) disk passive air samplers were deployed concurrently at five sites across Kolkata megacity and the rural mangrove wetland of Sundarban (UNESCO World Heritage Site) between January-March in 2014. Samples were analyzed for hexachlorocyclohexanes (HCHs), dichlorodiphenyltricholoroethanes (DDTs), polychlorinated biphenyls (PCBs) and, polybrominated diphenyl ethers (PBDEs) using gas chromatography and mass spectrometry (GC-MS). Derived air concentrations (pg/m) for Kolkata ranged: for ∑α- and γ-HCH between 70 and 207 (114 ± 62), ∑DDTs: 127-216 (161 ± 36), ∑PCBs: 53-213 (141 ± 64), and ∑PBDEs: 0.30-23 (11 ± 9). Low values for all the studied POPs were recorded in the remote area of the Sundarban site (with the exception of DDTs: o,p'-DDT and p,p'-DDT), where ∑DDTs was 161 ± 36. In particular, the site of Ballygunge, located in the southern part of Kolkata, showed the highest level of all the metabolites/congeners of POPs, suggesting a potential hot spot of usage and emissions. From HCHs, α-/γ-HCH isomers ratio was low (0.67-1.96) indicating a possible sporadic source of lindane. γ-HCH dominated the HCH signal (at 3 sites) reflecting wide spread use of lindane both in Kolkata and the Sundarban region; however, isomeric composition in Kolkata also suggests potential technical HCHs use. Among DDT metabolites, both o,p'-DDT and p,p'-DDT shared the dominant percentages accounting for ∼26-46% of total DDTs followed by p,p'-DDE (∼12-19%). The PCB congener profile was dominated by tri- and tetra-Cl at the southern and eastern part of Kolkata. These results are one of the few contributions that reports air concentrations of POPs, concurrently, at urban and remote villages in India. These data are useful to assess atmospheric pollution levels and to motivate local and regional authorities to better understand the potential human exposure risk associated to urban areas in India.
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http://dx.doi.org/10.1016/j.chemosphere.2016.09.055DOI Listing
February 2017

Screening for halogenated flame retardants in European consumer products, building materials and wastes.

Chemosphere 2017 Feb 14;168:457-466. Epub 2016 Nov 14.

Research Centre for Toxic Compounds in the Environment (RECETOX), Masaryk University, Kamenice 753/5, 625 00, Brno, Czechia.

To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of ΣHBCDDs of 300 mg kg in polystyrenes. The highest median concentration of ΣPBDEs was found in recycled plastic materials, reaching 4 mg kg. The lowest concentrations were observed for NFRs, where the median of ΣNFRs reached 0.4 mg kg in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.
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http://dx.doi.org/10.1016/j.chemosphere.2016.11.032DOI Listing
February 2017

Analysis of brominated flame retardants and their derivatives by atmospheric pressure chemical ionization using gas chromatography coupled to tandem quadrupole mass spectrometry.

Talanta 2017 Jan 15;162:618-624. Epub 2016 Oct 15.

MTM Research Centre, School of Science and Technology, Örebro University, 701 82 Örebro, Sweden.

A validated method using an atmospheric pressure chemical ionization source for coupling gas chromatography (GC-APCI) to tandem quadrupole mass spectrometry (MS/MS) for the determination of brominated flame retardants (BFRs) is presented. Polybrominated diphenyl ethers (PBDEs), their methoxylated derivatives (MeO-PBDEs) and other emerging BFRs were included in this study. The method showed good linearity and repeatability. The relative standard deviation (RSD) of the relative response factors (RRFs) of all compounds was below 16%. Repeatability for BFRs was tested on one or two concentration levels of calibration standards with RSDs for RRFs below 16%. The lowest calibration standards (0.075-0.1pg/µL for emerging BFRs, BDE 209 and MeO-PBDEs mixtures, 0.625-6.25pg/µL for Br PBDEs mixtures) were used as instrument detection limits (IDL). The method was applied on biotic samples, including fish, osprey, and seal. In general, BDE 209 and decabromodiphenyl ethane (DBDPE) were detected in 50% of the seal samples. A 100% detection rate was achieved for 6-MeO-BDE 47 in all the samples (72-580pg/g ww in osprey samples, 24,000-96,000pg/g ww in seal samples and 78-99pg/g ww in fish samples). All Br PBDEs (BDE 28, 47, 99, 100, 153, 154) were detected in all the samples (ranging from 12 to 20,000pg/g ww), while BDE 183 was detected in 60% of the osprey eggs, 20% of the seal samples and below MDL in all fish samples. The results presented indicate the capability of the GC-APCI-MS/MS system for the detection and quantification of BFRs.
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http://dx.doi.org/10.1016/j.talanta.2016.10.060DOI Listing
January 2017

An effective clean-up technique for GC/EI-HRMS determination of developmental neurotoxicants in human breast milk.

Anal Bioanal Chem 2017 Feb 9;409(5):1311-1322. Epub 2016 Nov 9.

Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 753/5, 625 00, Brno, Czech Republic.

The increasing number of children suffering from developmental disorders has raised questions regarding their association with the presence of environmental contaminants in mothers and children. We therefore developed a new method for the determination of 78 proven and potential developmental neurotoxicants, including polychlorinated biphenyls, legacy pesticides, pyrethroids, and old and new halogenated flame retardants in breast milk. The essential part of sample preparation was dialysis as a non-destructive clean-up step which was newly used at 10 °C and showed more efficient lipid removal (up to 96%) than the conventional methods such as gel permeation chromatography or freezing-lipid filtration and thus ensured low limits of detection (LOD) by reducing the sample volume prior to injection. Next advantages were significant solvent reduction and no risk of sample cross-contamination. Gas chromatography coupled with high resolution mass spectrometry (GC-HRMS) was subsequently used for the separation and compound quantification. The method was validated using breast milk samples fortified with the analyzed compounds. Recoveries for most of the compounds ranged from 63 to 121% with a relative standard deviation of 2-25%, and LODs ranged between 0.001 and 0.87 ng g lipid weight. The method was applied to breast milk samples from a Dutch birth cohort where 35 out of the 78 compounds were quantified in more than 60% of the samples. For novel flame retardants, the method provides unique results regarding their occurrence in human matrices in Europe. Overall, the analysis of a complex mixture of developmental neurotoxicants could be useful for the assessment of the influence of the studied compounds to child health and development. Graphical abstract Flow diagram of the method and levels of the developmental neurotoxicants in Dutch human milk samples.
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http://dx.doi.org/10.1007/s00216-016-0059-yDOI Listing
February 2017

Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of Buenos Aires Province, Argentina (South eastern part of the GRULAC region).

Sci Total Environ 2017 Jan 22;575:1470-1476. Epub 2016 Oct 22.

Masaryk University, Faculty of Science, Research Center for Toxic Compounds in the Environment (RECETOX), Kamenice 753/5, 625 00 Brno, Czech Republic.

PCBs and PBDEs (7 and 10 congeners, respectively) were analyzed in four coastal surface sediments collected from the northern shore of Bahía Blanca estuary and in nine soils from different locations of Bahía Blanca city and the surrounding region (Southwest of Buenos Aires Province, Argentina). Sediment samples showed PCBs concentrations ranged from 0.61 to 17.6ngg (dry weight=dw) and PBDEs from 0.16 to 2.02ngg dw, whereas in soil samples ranged from 0.04 to 1.67ngg dw for PCBs and 0.04 to 10.7ngg dw for PBDEs. The highest concentrations of both chemicals were detected in the urban and industrial/port areas showing a dominance of the higher chlorinated PCB congeners: in sediments for PCB-180 (56±33%) and PCB-153 (11±6%); and in soils for PCB-138 (23±3%), PCB-153 (22±2%) and PCB-180 (18±7%). In contrast, lower chlorinated PCB congeners were predominant at more distant sites; in sediments for congeners PCB-28 (33±4%) and PCB-52 (14.5±0.2%); and in soils PCB-28 (56±14%) and PCB-52 (33±19%). PBDE-209 (high brominated PBDE) showed the highest relative abundance in both sample types i.e., sediment (94±7%) and soil (80±12%). These findings can be considered lower or similar when compared with other sites of the world, and are likely associated with anthropogenic activities in their surrounding area, which has experienced a fast industrial growth in the last decade. This is the first investigation of PBDEs levels in the whole study area and of PCBs in soils from the Bahía Blanca city and surrounding region. This article provides new and useful information on POP levels in the South eastern part of the GRULAC region.
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http://dx.doi.org/10.1016/j.scitotenv.2016.10.013DOI Listing
January 2017

Organochlorine pesticides and polychlorinated biphenyls along an east-to-west gradient in subtropical North Atlantic surface water.

Environ Sci Pollut Res Int 2017 Apr 18;24(12):11045-11052. Epub 2016 Aug 18.

Max Planck Institute for Meteorology, Hamburg, Germany.

Despite the fact that most persistent toxic substances have hardly been primarily emitted for several decades, their concentrations are only slowly decreasing in the global oceans. Surface seawater samples were collected along a 38°-24° N/28°-67° W transect in the subtropical North Atlantic Ocean. While the concentration levels of hexachlorobenzene (2.1-6.1 pg L), dichlorodiphenyltrichloroethane (DDT, up to 2.1 pg L) and polychlorinated biphenyls (PCB, 10.8-24.9 pg L) were in the same range as observed earlier in the North Atlantic, hexachlorocyclohexane (HCH, 90-627 pg L) was found elevated, partly also relative to previous measurements in the same sea region. Hereby, the ratio α-HCH/γ-HCH was very low, 0.09-0.13. Chlordane and endosulfan were found in the range <3.0-11.1 and <5.8-8.8 pg L respectively. DDT metabolites, endrin and related pesticides were found below quantification limits. Spatial pollution patterns in surface seawaters seem to be determined by atmospheric and oceanic transport patterns, rather than by mixing and air-sea equilibrium. The comparison with global multicompartment chemistry-transport model predictions of surface seawater levels indicate underestimated degradation of PCBs and overestimated emissions of endosulfan.
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http://dx.doi.org/10.1007/s11356-016-7429-zDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5393290PMC
April 2017

Seasonality and indoor/outdoor relationships of flame retardants and PCBs in residential air.

Environ Pollut 2016 Nov 16;218:392-401. Epub 2016 Jul 16.

Research Centre for Toxic Compounds in the Environment (RECETOX), Kamenice 753/5, 62500, Brno, Czech Republic.

This study is a systematic assessment of different houses and apartments, their ages and renovation status, indoors and outdoors, and in summer vs. winter, with a goal of bringing some insight into the major sources of semivolatile organic compounds (SVOCs) and their variability. Indoor and outdoor air concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and novel flame retardants (NFRs) were determined at 17-20 homes in Czech Republic in winter and summer. Indoor concentrations were consistently higher than outdoor concentrations for all compounds; indoor/outdoor ratios ranged from 2-20, with larger differences for the current use NFRs than for legacy PCBs. Seasonal trends differed according to the use status of the compounds: the PCBs had higher summer concentrations both indoors and outdoors, suggesting volatilization as a source of PCBs to air. PBDEs had no seasonal trends indoors, but higher summer concentrations outdoors. Several NFRs (TBX, PBT, PBEB) had higher indoor concentrations in winter relative to summer. The seasonal trends in the flame retardants suggest differences in air exchange rates due to lower building ventilation in winter could be driving the concentration differences. Weak relationships were found with building age for PCBs, with higher concentrations indoors in buildings built before 1984, and with the number of electronics for PBDEs, with higher concentrations in rooms with three or more electronic items. Indoor environments are the primary contributor to human inhalation exposure to these SVOCs, due to the high percentage of time spent indoors (>90%) combined with the higher indoors levels for all the studied compounds. Exposure via the indoor environment contributed ∼96% of the total chronic daily intake via inhalation in summer and ∼98% in winter.
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http://dx.doi.org/10.1016/j.envpol.2016.07.018DOI Listing
November 2016

Brominated flame retardants in the indoor environment - Comparative study of indoor contamination from three countries.

Environ Int 2016 Sep 29;94:150-160. Epub 2016 May 29.

School of Public and Environmental Affairs, Indiana University, 702 Walnut Grove Avenue, Bloomington, IN 47405, United States.

Concentrations of more than 20 brominated flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs) and emerging FRs, were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013. Among the PBDEs, the highest concentrations were generally BDE-209 in all three matrices, followed by Penta-BDEs. Among alternative FRs, EHTBB and BEHTBP were detected at the highest concentrations. DBDPE was also a major alternative FR detected in dust and air. Bromobenzenes were detected at lower levels than PBDEs and other alternative FRs; among the bromobenzenes, HBB and PBEB were the most abundant compounds. In general, FR levels were highest in the US and lowest in the Czech Republic - a geographic trend that reflects the flame retardants' market. No statistically significant differences were detected between bedroom and living room FR concentrations in the same house (n=10), suggesting that sources of FRs are widespread indoors and mixing between rooms. The concentrations of FRs in air, dust, and window film were significantly correlated, especially for PBDEs. We found a significant relationship between the concentrations in dust and window film and in the gas phase for FRs with log KOA values <14, suggesting that equilibrium was reached for these but not compounds with log KOA values >14. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for FRs with log KOA values >14.
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http://dx.doi.org/10.1016/j.envint.2016.04.029DOI Listing
September 2016

Distribution of legacy and emerging semivolatile organic compounds in five indoor matrices in a residential environment.

Chemosphere 2016 Jun 24;153:179-86. Epub 2016 Mar 24.

Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 753/5, Pavilion A29, 625 00 Brno, Czech Republic.

Seven types of indoor samples, covering five indoor matrices, were collected in a residential room, and analyzed for five classes of semivolatile organic compounds (SVOCs). The goal was to improve the understanding of the relationship between indoor air, surface films and dust, based on differences in sources, physicochemical properties, and indoor environmental characteristics. Comparisons of the five matrices (gas- and particle-phase air, floor dust, surface dust/films and window films) demonstrated that within our test room a semi-quantitative measurement of the SVOC distributions and concentrations could be obtained by air, and composite dust or furniture surface wipes. Dust concentrations varied within the room, and spot samples were not necessarily representative of the average room conditions. Polyurethane foam passive air samplers (PUF-PAS) successfully quantified the total air concentrations of the studied SVOC compound groups, as indoor air concentrations were dominated by gas-phase compounds, however air concentrations of individual particle-bound compounds had higher uncertainty. Measured concentrations of dust/surfaces could be used to estimate air concentrations of legacy SVOCs, demonstrating equilibrium in the room. However, air concentrations of current-use compounds (flame retardants, polycyclic aromatic hydrocarbons (PAHs)) could not be estimated from dust/surface concentrations, demonstrating the influence of ongoing primary emissions and non-equilibrium status in the room.
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http://dx.doi.org/10.1016/j.chemosphere.2016.03.012DOI Listing
June 2016