Methods,fluxes and sources of gas phase alkyl nitrates in the coastal air

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3–C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO₂ levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Component-specific toxic concerns of the inhalable fraction of urban road dust

Continuous global urbanisation causes an ever-growing ecological footprint of pollution. Road dust (RD), one of these pollutants, poses a health concern due to carcinogenic and toxic components potentially present in the micron-sized fractions. The literature reports on the concentrations of trace, toxic metals and metalloids present in RD (Hooker and Nathanail in Chem Geol 226:340–351, 2006), but the literature on its molecular composition is limited. Recent reports on the bioaccessibility of platinum group metals are also reported (Colombo et al. in Chem Geol 226:340–351, 2008). In vitro and animal toxicological studies confirmed that the chemical composition of inhaled particles plays a major role in its toxic, genotoxic and carcinogenic mechanisms, but the component-specific toxic effects are still not understood. Particle-bound airborne transition metals can also lead to the production of reactive oxygen species in lung tissue; a special concern amongst particularly susceptible cohorts (children and elderly). The characterisation of the molecular composition of the fine fraction is evidently of importance for public health. During a pilot study, partially characterised size-fractioned RD samples (Barrett et al. in Eviron Sci Technol 44:2940–2946, 2010) were analysed for their elemental concentration using X-ray fluorescence spectrometry and inductively coupled plasma mass spectrometry. In addition, separately dispersed particles (200 particles per size fraction) were analysed individually by means of computer-controlled electron probe X-ray micro-analysis (CC-EPXMA) and their molecular structure probed by studying elemental associations. These were correlated with micro-Raman spectroscopy (MRS) results. It was found that the fine fraction (<38?μm) had the highest Pb (238?ppm) and Cr (171?ppm) concentrations. The CC-EPXMA data showed >50?% association of Cr-rich particles with Pb, and the MRS data showed that the Cr was mostly present as lead chromate and therefore in the Cr(VI) oxidation state. Concentrations of both Pb and Cr decreased substantially (279 (<38?μm)–13?ppm (<1?mm); 171 (<38?μm)–91?ppm (<?1?mm), respectively) in the larger fractions. Apart from rather alarmingly high concentrations of oxidative stressors (Cu, Fe, Mn), the carcinogenic and toxic potential of the inhalable fraction is evident. Preliminary bioaccessibility data indicated that both Cr and Pb are readily mobilised in artificial lysosomal liquid and up to 19?% of Cr and 47?% of Pb were released.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

Comparative overview of indoor air quality in Antwerp, Belgium

This comprehensive study, a first in Belgium, aimed at characterizing the residential and school indoor air quality of subgroups that took part in the European Community Respiratory Health Survey and the International Study of Asthma and Allergy in Childhood [Masoli M, Fabian D, Holt S, Beasley R. Global Burden of Asthma, Medical Research Institute of New Zealand, University of Southampton; 2004.] questionnaire-based asthma and related illnesses studies. The principal aim was to perform a base-line study to assess the indoor air quality in Antwerp in terms of various gaseous and particulate pollutants. Secondly, it aimed to establish correlations between these pollutants investigated, the pollutant levels in the indoor and outdoor micro-environments, findings of the previous questionnaire-based studies and an epidemiological study which ran in conjunction with this study. Lastly, these results were compared and evaluated with current indoor and ambient guidelines in various countries This paper presents selected results on PM1, PM2.5 and PM10 mass concentrations and elemental C estimates as black smoke, as well as gaseous NO(2), SO(2), O(3) and BTEX concentrations of 18 residences and 27 schools. These are related to current guidelines of Flanders, Germany, Norway, China and Canada and evaluated with reference to selected similar studies. It was found that indoor sources such as tobacco smoking and carpets, the latter causing re-suspension of dust, are responsible for elevated indoor respirable particulate matter and place school children and residents at risk. Both PM2.5 and PM10 equalled or exceeded the current guidelines adopted by Flanders, noting that 12-h and 24-h PM2.5 were compared with an annual limit value. Indoor and ambient NO(2) concentrations in the school campaign were higher than the annual EU ambient norm. The other studied pollutant levels were below the current guidelines.     

Elemental composition of bottom-sediments from Pangani river basin,Tanzania: lithogenic and anthropogenic sources

River-bed sediments from the Pangani basin, Tanzania, were characterized for elemental compositions, following contamination risks from rapid expansions of human activities in the area. Samples were collected during two individual seasons and analyzed by high-polarizing beam energy dispersive X-ray fluorescence (EDXRF) for eight major and 14 trace elements. Evaluation of enrichment factors (EFs) was used to investigate the elemental flux and assess the contributions of natural and anthropogenic influences. The abundances of the major elements followed the order Si?>?Al?>?Fe?>?Ca?>?K?>?Ti?>?Mn?>?P, similar to that of the upper earth's crust, and were generally from the weathering of the bed-rock. The high concentrations of typical anthropogenic trace-elements (Cr??1, V??1, Ni??1, Cu??1, La??1) coupled with high EFs (>2) in some locations indicated contamination associated with agricultural and industrial activities. Factor analysis extracted five principal components that contributed to 96.0% of the total observed variance. The results indicated that river-bed sediments of the Pangani basin were influenced to a larger extent by lithogenic sources than anthropogenic impacts.