A. Hoffer

Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch

In this study the chemical nature of the bulk of water soluble organic compounds in fine atmospheric aerosol collected during summer 1998 at the Jungfraujoch, Switzerland (3580 m asl) is characterised. The mass concentration of water soluble organic substances was similar to those of major inorganic ions, and the water soluble organic matter was found to be composed of two main fractions: (i) highly polyconjugated, acidic compounds with a varying degree of hydrophobicity and (ii) slightly polyconjugated, neutral and very hydrophilic compounds. The contribution of both fractions to the total water soluble organic carbon was about 50%. Separation into individual components was impossible either by HPLC or capillary electrophoresis which indicates the presence of a high number of chemically similar but not identical species. Results obtained by ultrafiltration and HPLC-MS have shown that the molecular weights are of the order of several hundreds. Most of the protonation constants for the acidic compounds determined by capillary electrophoresis were in the range 104–107.

Overview of the inorganic and organic composition of size-segregated aerosol in Rondônia, Brazil, from the biomass-burning period to the onset of the wet season

The aerosol characterization experiment performed within the Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) field experiment carried out in Rondonia, Brazil, in the period from September to November 2002 provides a unique data set of size-resolved chemical composition of boundary layer aerosol over the Amazon Basin from the intense biomass-burning period to the onset of the wet season. Three main periods were clearly distinguished on the basis of the PM10 concentration trend during the experiment: (1) dry period, with average PM10 well above 50 mu g m(-3); (2) transition period, during which the 24-hour-averaged PM10 never exceeded 40 mu g m(-3) and never dropped below 10 mg m(-3); (3) and wet period, characterized by 48-hour-averaged concentrations of PM10 below 12 mu g m(-3) and sometimes as low as 2 mu g m(-3). The trend of PM10 reflects that of CO concentration and can be directly linked to the decreasing intensity of the biomass- burning activities from September through November, because of the progressive onset of the wet season. Two prominent aerosol modes, in the submicron and supermicron size ranges, were detected throughout the experiment. Dry period size distributions are dominated by the fine mode, while the fine and coarse modes show almost the same concentrations during the wet period. The supermicron fraction of the aerosol is composed mainly of primary particles of crustal or biological origin, whereas submicron particles are produced in high concentrations only during the biomass-burning periods and are mainly composed of organic material, mostly water-soluble, and similar to 10% of soluble inorganic salts, with sulphate as the major anion. Size-resolved average aerosol chemical compositions are reported for the dry, transition, and wet periods. However, significant variations in the aerosol composition and concentrations were observed within each period, which can be classified into two categories: (1) diurnal oscillations, caused by the diurnal cycle of the boundary layer and the different combustion phase active during day (flaming) or night (smouldering); and (2) day-to-day variations, due to alternating phases of relatively wet and dry conditions. In a second part of the study, three subperiods representative of the conditions occurring in the dry, transition, and wet periods were isolated to follow the evolution of the aerosol chemical composition as a function of changes in rainfall rate and in the strength of the sources of particulate matter. The chemical data set provided by the SMOCC field experiment will be useful to characterize the aerosol hygroscopic properties and the ability of the particles to act as cloud condensation nuclei.

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

Abstract The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM 2.5 aerosol); (ii) K-puszta, Hungary (rural, PM 1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.

The Red Mud Accident in Ajka (Hungary): Characterization and Potential Health Effects of Fugitive Dust

As a result of a tragic industrial accident, a highly alkaline red mud sludge inundated settlements and agricultural areas near Ajka, Hungary on October 4, 2010. One of the major concerns about the aftermaths of the accident is the potential health effects of vast amounts of fugitive dust from red mud sediment. Thus, we studied the chemical and physical properties of particles of red mud and its respirable fugitive dust, and performed toxicity measurements. Under unfavorable meteorological conditions dry red mud sediment could emit very high amounts of respirable alkaline particles into the air. The number size distribution of fugitive dust peaks above 1 μm aerodynamic diameter; therefore, its inhalation is unlikely to affect the deep regions of the lungs. No significant mineralogical or elemental fractionation was observed between the sediment and dust, with the major minerals being hematite, cancrinite, calcite, and hydrogarnet. Although the high resuspension potential and alkalinity might pose some problems such as the irritation of the upper respiratory tract and eyes, based on its size distribution and composition red mud dust appears to be less hazardous to human health than urban particulate matter.

The NH4+‐NO3−‐Cl−‐SO42−‐H2O aerosol system and its gas phase precursors at a pasture site in the Amazon Basin: How relevant are mineral cations and soluble organic acids?

Real-time measurements of ammonia, nitric acid, hydrochloric acid, sulfur dioxide and the water-soluble inorganic aerosol species, ammonium, nitrate, chloride, and sulfate were performed at a pasture site in the Amazon Basin (Rondonia, Brazil). The measurements were made during the late dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions) using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC). Measurements were conducted from 12 September to 14 November 2002 within the framework of LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate). Real-time data were combined with measurements of sodium, potassium, calcium, magnesium, and low-molecular weight (LMW) polar organic acids determined on 12-, 24-, and 48-hours integrated filter samples. The contribution of inorganic species to the fine particulate mass (Dp = 2.5 µm) was frequently below 20% by mass, indicating the preponderance of organic matter. The measured concentration products of NH3 × HNO3 and NH3 × HCl persistently remained below the theoretical equilibrium dissociation constants of the NH3/HNO3/NH4NO3 and NH3/HCl/NH4Cl systems during daytime (RH 90%) fine-mode NH4NO3 and NH4Cl are predicted to be formed in the aqueous aerosol phase. Probably, Cl- was driven out of the aerosol phase largely by reaction of pyrogenic KCl with HNO3 and H2SO4. As shown by an updated version of the equilibrium simplified aerosol model (EQSAM2), which incorporates mineral aerosol species and lumped LMW polar organic acids, daytime aerosol NH4 + was mainly balanced by organic compounds.

Photocatalytic degradation of 1,5-naphthalenedisulfonate on colloidal titanium dioxide.

Photocatalytic degradation of 1,5-naphthalenedisulfonate (NDS) was investigated by monitoring the absorption and emission spectral changes, chemical oxygen demand, total organic carbon (TOC) content as well as pH and sulfate concentration. Intermediates formed during the irradiation were also detected by liquid chromatographic-mass spectrometric analysis. The results obtained by the applied analytical techniques clearly indicate that the initial step of degradation is oxygenation (hydroxylation) of the starting surfactant resulting in the formation of an 8-hydroxy derivative, although desulfonation and some mineralization, that is, decrease of TOC indicating carbon dioxide generation, also take place at this stage. Further oxygenation and desulfonation lead to the destruction of the diaromatic naphthalene system, then to ring fission, producing diols, aldehydes, and carboxylic acids on the side-chains. A tentative scheme involving possible pathways of degradation is proposed, taking the intermediates detected by mass spectrometry into consideration. On the basis of the results of quantum chemical calculations, the most possible points of attack by HO radical were identified, supplementing the MS results, and elucidating the initial oxidation step in the degradation of NDS and the benzenesulfonate (BS) intermediate. Thus, in the case of NDS para position is favored for hydroxylation, while for BS, formation of the ortho-hydroxy derivative is preferred.

Surface-active substances in atmospheric aerosol: an electrochemical approach

ABSTRACT We characterised surface-active substances (SASs) in aqueous extract of atmospheric aerosols by using phase sensitive alternating current voltammetry. The electrochemical method has mainly been used for the quantification of surfactants in sea water but has not been applied to atmospheric aerosols yet. The advantage of the method is its simplicity and sensitivity that enables direct analysis of aerosol extracts without the need for sample concentration. Aerosol samples were collected at Middle Adriatic Martinska station influenced by different air masses as well as from urban (Zagreb, Croatia) and rural (K-puszta, Hungary) areas from late spring to early autumn in 2010. The highest SAS concentrations, expressed in equivalents of T-X-100, ranging from 0.34 to 0.91 µg m−3 were detected in urban samples. The SAS concentrations obtained for marine, regional and continental samples ranged from 0.14 to 0.31, 0.18 to 0.42 and 0.07 to 0.28 µg m−3, respectively. The SAS concentrations in K-puszta aerosols ranged from 0.13 to 0.46 µg m−3. Investigation of humic-like substances isolated from K-puszta samples (2008) confirmed their significant surfactant nature. Different SAS chemistry was noticed for urban and non-urban samples. Investigations at different pH revealed anionic character of SASs in aerosol samples.

Microbiological characterization of stable resuspended dust

OBJECTIVES Air quality in the stables is characterized by elevated level of dust and aeroallergens which are supposed to directly cause or exacerbate several respiratory disorders. The most often recognized problem is recurrent airway obstruction (RAO), previously known as chronic obstructive pulmonary disease (COPD). There is some indication that aeroallergens (among them endotoxins) may also cause inflammation in human airways and may exceed safe levels in stables. Monitoring studies have covered mainly the determination of the concentration of respirable particles and of culturable fungi and their toxins. However, these particles do not only directly affect the respiratory system, but might act as a carrier conveying toxic contaminants and biological agents such as bacteria. In a typical, 20-horse Hungarian stable, microbial community of respirable fraction of resuspended dust has been characterized to reveal if these particles convey hazardous pathogenic bacteria, posing risk to either horses or staff. MATERIAL AND METHODS Resuspended dust was sampled using a mobile instrument. The instrument contains a PARTISOL-FRM model 2000 sampler that was operated at a flow rate of 16.7 l/min and a cyclone separator which collected the particulate matter with an aerodynamic size between 1 μm and 10 μm (PM1-10) fraction. Microbial taxa were identified by culture-independent next generation sequencing (NGS) of variable 16S ribosomal ribonucleic acid (rRNA) gene regions. RESULTS In total, 1491 different taxa were identified, of them 384 were identified to species level, 961 to genus level. The sample was dominated by common ubiquitous soil and organic material-dwelling taxa. CONCLUSIONS Pathogens occurred at low abundance, and were represented by mostly facultative human pathogens, with the prevalence of Staphylococcus species.