Barend L. van Drooge

Polychlorinated biphenyls and hexachlorobenzene in atmosphere, sea-surface microlayer, and water measured with semi-permeable membrane devices (SPMDs)

The time evolution of polychlorinated biphenyl (PCB) levels and hexachlorobenzene (HCB) levels in air, seawater, and at the sea-air boundary layer was examined during autumn and winter at a near-shore location in the Western Wadden Sea (Netherlands), using semi-permeable membrane devices (SPMDs). Performance reference compounds (PRCs) were added to the SPMDs prior to exposure for measuring the in situ exchange kinetics. For PCBs, a fair degree of equilibrium between atmosphere and water was found. HCB concentrations in the atmosphere were about eight times higher than the equilibrium concentration. PCB concentrations in seawater and atmosphere fell by a factor of 2-10, respectively, during the sampling period. HCB concentrations in water increased by a factor of 2. Atmospheric concentrations of HCB showed a decrease by a factor of about 10. Results for the sea-surface microlayer (SSM) deployment showed that the chemical activities at the air-water interface did not differ from those in deeper water layers. This means that the SSM was of no special toxicological significance in this study as far as PCBs and HCB are concerned.

A multidisciplinary approach to characterise exposure risk and toxicological effects of PM 10 and PM 2.5 samples in urban environments

Urban aerosol samples collected in Barcelona between 2008 and 2009 were toxicologically characterised by means of two complementary methodologies allowing evaluation of their Reactive Oxidative Stress (ROS)-generating capacity: the plasmid scission assay (PSA) and the dichlorodihydrofluorescin assay (DCFH). The PSA determined the PM dose able to damage 50% of a plasmid DNA molecule (TD(50) values), an indication of the ability of the sample to exert potential oxidative stress, most likely by formation of ·OH. This toxicity indicator did not show dependency on different air mass origins (African dust, Atlantic advection), indicating that local pollutant sources within or near the city are most likely to be mainly responsible for PM health effect variations. The average TD(50) values show PM(2.5-0.1) samples to be more toxic than the PM(10-2.5) fraction, with doses similar to those reported in previous studies in polluted urban areas. In addition, the samples were also evaluated using the oxidant-sensitive probe DCFH confirming the positive association between the amount of DNA damage and the generation of reactive oxidant species capable of inducing DNA strand break. Results provided by the PSA were compared with those from two other different methodologies to evaluate human health risk: (1) the toxicity of particulate PAHs expressed as the calculated toxicity equivalent of benzo[a]pyrene (BaPteq) after application of the EPA toxicity factors, and (2) the cancer risk assessment of the different PM sources detected in Barcelona with the receptor model Positive Matrix Factorisation (PMF) and the computer programme Multilinear Engine 2 (ME-2) using the organic and inorganic chemical compositions of particles. No positive associations were found between PSA and the toxicity of PAHs, probably due to the inefficiency of water in extracting organic compounds. On the other hand, the sum of cancer risk estimates calculated for each of the selected days for the PSA was found to correlate with TD(50) values in the fine fraction, with fuel oil combustion and industrial emissions therefore being most implicated in negative health effects. Further studies are necessary to determine whether toxicity is related to PM chemical composition and sources, or rather to its size distribution.

Thermal desorption gas chromatography–mass spectrometry as an enhanced method for the quantification of polycyclic aromatic hydrocarbons from ambient air particulate matter

Polycyclic aromatic hydrocarbons (PAHs) from ambient air particulate matter (PM) were analysed by a two-step thermal desorption (TD) injection system integrated to a gas chromatograph-mass spectrometer (GC/MS). The operational variables of the TD method were optimised and the analytical expanded uncertainties were calculated to vary from 8% to 16% over the operative concentration range (40-4000 pg). The performance of the TD method was validated by the analysis of a standard reference material and by comparison of PAH concentrations in PM samples to those obtained by a conventional liquid extraction (LE) method. The TD method reported lower uncertainties than the LE method for the analysis of similar concentrations in air. The TD method also showed advantages for shorter sampling times in comparison to 24 h for source apportionment applications and for reducing losses of more reactive compounds such as benzo[a]pyrene.

Origin of inorganic and organic components of PM2.5 in subway stations of Barcelona, Spain

The present work assesses indoor air quality in stations of the Barcelona subway system. PM2.5 concentrations on the platforms of 4 subway stations were measured during two different seasons and the chemical composition was determined. A Positive Matrix Factorization analysis was performed to identify and quantify the contributions of major PM2.5 sources in the subway stations. Mean PM2.5 concentrations varied according to the stations design and seasonal periods. PM2.5 was composed of haematite, carbonaceous aerosol, crustal matter, secondary inorganic compounds, trace elements, insoluble sulphate and halite. Organic compounds such as PAHs, nicotine, levoglucosan and aromatic musk compounds were also identified. Subway PM2.5 source comprised emissions from rails, wheels, catenaries, brake pads and pantographs. The subway source showed different chemical profiles for each station, but was always dominated by Fe. Control actions on the source are important for the achievement of better air quality in the subway environment.

Deposition of Semi-Volatile Organochlorine Compounds in the Free Troposphere of the Eastern North Atlantic Ocean

Deposition samples were taken at a height of 2367 m above sea level (m.a.s.l.) on the Island of Tenerife from May 1999 until July 2000 and analysed for 19 polychlorinated biphenyl (PCB) congeners, hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH) and DDTs. This site is located above the inversion layer, so samples represent background concentrations of the free troposphere. The average deposition fluxes of HCB, total HCH, DDTs and PCBs were 86, 400, 110 and 780 ng m(-2) yr(-1), respectively, being lower than those reported at sea level in continental or marine areas. All compounds are generally found in higher abundance in the wet precipitation samples. However, these samples only represent a fraction, e.g. 33%, of the total deposition load. Annual mass balance calculations show that wet precipitation is essentially responsible for the deposition of the low molecular weight OC whereas dry deposition accounts for more than 50% of the higher molecular weight PCBs.

Polycyclic aromatic hydrocarbons in lake sediments from the High Tatras

European alpine lake systems are used as indicators of air quality over the continent. Preliminary data showed high polycyclic aromatic hydrocarbons (PAH) loads in the High Tatras (Eastern Europe) in comparison to other mountain regions. Here, insight on the spatial distribution of PAH is provided from analysis of top-core sediments of 27 alpine lakes distributed along the High Tatras. Top-core sediment concentrations were higher than those in deep-cores, and they were higher than those observed in other European high mountain regions. The PAH profiles were uniform and comparable to those observed in aerosols and snow, indicating that atmospheric deposition was the predominant PAH input pathway to the lakes. Good agreement between estimated atmospheric deposition and sedimentation fluxes was observed. However, in several lakes in the western range higher sediment fluxes may correspond to higher PAH depositions levels. The higher concentrations may also reflect inputs from potential emission source areas.

Developmental effects of aerosols and coal burning particles in zebrafish embryos

Embryo toxicity of particles generated by combustion processes is of special concern for human health. A significant part of these toxic effects is linked to the binding of some pollutants (like polycyclic aromatic hydrocarbons or PAHs) to the Aryl hydrocarbon Receptor (AhR) and the activation of target genes, like the cytochrome P4501A. This activity was analyzed for ambient air and coal-combustion particle extracts in zebrafish embryos (the cyp1aDarT assay) and in two single-cell bioassays: the yeast-based YCM-RYA and the DR-luc (rat cells) assay. Observed AhR ligand activity of samples generally correlated to the predicted toxic effect according to their PAH composition, except for one of the coal combustion samples with an anomalously high activity in the cyp1aDarT assay. This sample induced deformities in zebrafish embryos. We concluded that the combination of morphological and molecular assays may detect embryonic toxic effects that cannot be predicted from chemical analyses or single-cell bioassays.

Broad spectrum analysis of polar and apolar organic compounds in submicron atmospheric particles

A method for the quantitative analysis of organic compounds on submicron particulate matter (PM1) collected on quartz filters was developed. The compounds analyzed encompassed C22-C35 alkanes, polycyclic aromatic hydrocarbons (PAHs), quinones, levoglucosan, cis-pinonic acid and short chain dicarboxylic acids such as malonic, succinic, glutaric, adipic, suberic, azelaic, malic and phthalic acids. The method included extraction with a pressure liquid extraction system, sample filtration though glass fibre filter, fractionation by high performance liquid chromatography and subsequent analysis by gas chromatography coupled to mass spectrometry. The study of the extraction efficiency of different solvent mixtures showed that DCM:MeOH 1:1 was the one providing the highest recoveries for all compounds. Extraction temperatures of 100°C provided better results than 60°C or 80°C. This method provided comparable extraction efficiency and qualitative and quantitative data to those involving Soxhlet extraction. Method recoveries for alkanes, most PAH, quinones and polar compounds calculated from spiked real samples were 52-72%, 78-101%, 50-62% and 76-104%, respectively, reproducibilities were 2-28%, 7-29%, 10-27% and 5-28%, respectively, limits of quantification were 0.01-0.1ng/m(3), 0.01-0.27ng/m(3), 0.04ng/m(3) and 0.32-2.8ng/m(3), respectively, which affords the quantification of a broad number of primary and secondary organic constituents of submicron aerosols.

Toxicity assessment of atmospheric particulate matter in the Mediterranean and Black Seas open waters.

Atmospheric deposition of particulate matter (PM) is recognized as a relevant input vector for toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs), into the marine environment. In this work we aimed to analyse the biological activity and potential adverse effects of PM constituents to aquatic organisms. Organic extracts of atmospheric PM samples from different sub-basins of the Mediterranean and Black Seas were screened using different toxicological tests. A yeast-based assay (AhR-RYA) revealed that dioxin-like activity correlated with the concentration of total PAHs in the PM samples, as well as with their predicted toxic equivalent values (TEQs). Although the zebrafish embryotoxicity test (the ZET assay) showed no major phenotypical adverse effects, up-regulation of mRNA expression of cyp1a, fos and development-related genes (previously described as related to PM toxicity) was observed in exposed embryos when compared to controls. Results showed that mRNA patterns of the studied genes followed a similar geographic distribution to both PAH content and dioxin-like activity of the corresponding extracts. The analysis also showed a distinct geographical pattern of activation of pancreatic markers previously related to airborne pollution, probably indicating a different subset of uncharacterized particle-bound toxicants. We propose the combination of the bioassays tested in the present study to be applied to future research with autochthonous species to assess exposure and potential toxic effects of ambient PM. The present study emphasizes the need for more in-depth studies into the toxic burden of atmospheric PM on aquatic ecosystems, in order to improve future regulatory guidelines.

Toxicity of atmospheric particle-bound PAHs: an environmental perspective

Atmospheric polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants that represent a risk not only to humans, but to all living organisms. High-molecular weight PAHs are more toxic than lighter relatives, and also have a higher tendency to bind onto air particles (i.e., particle matter, PM). PM is a major constituent of air pollution. Adequate assessment of the biological impact of PM requires the analysis, not only of the effects on human health, but also on the environment. Since the aquatic systems work as a natural sink to these air pollutants, assessing the effects of particle-bound PAHs on aquatic organisms may further characterize its potential aquatic toxicity, also providing simple and low-cost alternative assays to investigate PM biological effects in vivo. We review the current scientific literature, addressing the atmospheric PAHs fate, transformation and deposition, pertinent particle-bound PAHs toxicity data, and the potential aquatic toxic burden. Conceptual and experimental procedures that could improve future investigations and risk assessments are also considered.