Athanasios Besis

Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments – A review on occurrence and human exposure

Polybrominated diphenyl ethers (PBDEs) constitute an important group of brominated flame retardants that have been massively produced and extensively used in numerous everyday products, providing longer escape times in case of fire and thus saving lives, as well as reducing the damage of property. In recent years, PBDEs have been recognized as significant pollutants of the indoor environment. This article provides a synthesis and critical evaluation of the state of the knowledge about the occurrence of PBDEs in the indoor environment (air and dust in homes, workplaces and cars) in different countries in Europe, North America, Asia and Australia, as well as about the human exposure via indoor air inhalation and dust ingestion in comparison to outdoor air inhalation and dietary intake.

Air and seawater pollution and air-sea gas exchange of persistent toxic substances in the Aegean Sea: spatial trends of PAHs, PCBs, OCPs and PBDEs

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air–sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-DDT and seawater concentrations of p,p′-DDE and p,p′-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included.

Redox activity and in vitro bioactivity of the water-soluble fraction of urban particulate matter in relation to particle size and chemical composition.

Chemical and toxicological characterization of the water-soluble fraction of size-segregated urban particulate matter (PM) (<0.49, 0.49-0.97, 0.97-1.5, 1.5-3.0, 3.0-7.2 and >7.2 μm) was carried out at two urban sites, traffic and urban background, during the cold and the warm period. Chemical analysis of the water-soluble PM fraction included ionic species (NO3(-), SO4(2-), Cl(-), Na(+), NH4(+), K(+), Mg(2+), Ca(2+)), water-soluble organic carbon (WSOC), and trace elements (Al, As, Ba, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Zn, Pt, Pd, Rh, Ru, Ir, Ca, and Mg). The dithiothreitol (DTT) assay was employed for the abiotic assessment of the oxidative PM activity. Cytotoxic responses were investigated in vitro by applying the mitochondrial dehydrogenase (MTT) and the lactate dehydrogenase (LDH) bioassays on human lung cells (MRC-5), while DNA damage was estimated by the single cell gel electrophoresis assay, known as Comet assay. The correlations between the observed bioactivity responses and the concentrations of water-soluble chemical PM constituents in the various size ranges were investigated. The results of the current study corroborate that short-term bioassays using lung human cells and abiotic assays, such as the DTT assay, could be relevant to complete the routine chemical analysis and to obtain a preliminary screening of the potential effects of PM-associated airborne pollutants on human health.

Source apportionment of the redox activity of urban quasi-ultrafine particles (PM0.49) in Thessaloniki following the increased biomass burning due to the economic crisis in Greece.

Abstract The source apportionment of the redox activity of quasi-ultrafine particles (PM0.49), measured by the cell-free dithiothreitol (DTT) assay, was attempted at two urban sites (urban traffic, UT and urban background, UB) in Thessaloniki, northern Greece, following the increased biomass burning due to the economic crisis. Both, the per-mass and per-volume DTT redox activities of PM0.49 particles were found to be substantially higher at the UB site in the cold season underscoring the increase in PM toxicity with the shift from traditional oil burning to biomass burning for residential heating. Two different approaches were employed to link the measured redox activity of PM0.49 with specific sources: (a) Principal Component Analysis of the chemical components of PM0.49 followed by Multilinear Regression of the measured redox activity on factor tracers (PCA-MLR), and (b) Robotic Chemical Mass Balance receptor modeling of the ambient PM0.49 mass followed by Multilinear Regression of the redox activity on the estimable source contributions (RCMB-MLR). Both approaches indicated that the major contributors to the measured redox activity of PM0.49 were vehicular traffic at the urban traffic site and residential wood burning at the urban background site.

Spatial and seasonal variations of the chemical, mineralogical and morphological features of quasi-ultrafine particles (PM 0.49) at urban sites.

Combining chemical and physical-structural information of particles is a key issue in PM investigations. Chemical, mineralogical, and morphological characterization of quasi-ultrafine particles (PM 0.49) was carried out at two urban sites of varying traffic-influence (roadside and urban background) in Thessaloniki, northern Greece, during the cold and the warm period of 2013. Bulk analyses of chemical species included organic and elemental carbon (OC, EC), water soluble organic carbon (WSOC), ionic species (NO3(-), SO4(2-), Cl(-), Na(+), NH4(+), K(+), Mg(2+), Ca(2+)) and trace elements (As, Ba, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Zn, Pt, Pd, Rh, Ru, and Ir). X-ray diffractometry (XRD) was employed for the mineralogical analysis of PM 0.49 in order to identify and quantify amorphous and crystalline phases. In addition, scanning electron microscopy coupled with energy dispersive spectrometry (SEM-EDS) was employed for morphological characterization and elemental microanalysis of individual particles. Findings of this work could provide the basis for designing epidemiological and toxicity studies to mitigate population exposure to UFPs.

Legacy and emerging organophosphοrus flame retardants in car dust from Greece: Implications for human exposure

Organophosphorus flame retardants (PFRs) and emerging PFRs (ePFRs) are two groups of compounds used as replacements for brominated flame retardants (BFRs). They have already been detected in indoor dust (mainly in homes and offices). To date, few studies investigated the occurrence of FRs in car dust and the information of possible health risks is still limited. The present study reports on the investigation of the levels and profiles of eight target PFRs: tris(2-ethylhexyl) phosphate (TEHP), tris(2-chloroethyl) phosphate (TCEP), tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPHP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri cresyl phosphate (TCP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and four target ePFRs; 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate (V6), isodecyl diphenyl phosphate (iDDPHP), resorcinol bis(diphenylphosphate) (RDP) and bisphenol A-bis(diphenyl phosphate) (BDP) in car dust from Greece. The samples were collected from the interior of 25 private cars in Thessaloniki, Greece, with different years of manufacture (1997-2015) and continents of origin. After ultrasonic extraction and Florisil fractionation, the PFR analysis was carried out by GC-EI/MS, whereas the ePFRs were analyzed by LC-MS/MS. Levels of Σ8PFRs varied from 2000 to 190,000 ng g-1, with mean and median concentrations of 20,000 and 11,500 ng g-1, respectively. The concentrations of Σ4ePFRs ranged from 44 to 8700 ng g-1, with mean and median values at 1100 and 190 ng g-1, respectively. Estimations of human exposure showed that toddlers are more exposed than adults to both PFRs and ePFRs. Yet, the intake via dust ingestion and dermal absorption was several orders of magnitude lower than the corresponding reference doses.