How do certain atmospheric aerosols affect Cu-binding organic ligands in the oligotrophic coastal sea surface microlayer?

It is still unclear how the chemical speciation of Cu in surface seawater is impacted by aerosols from various sources deposited on the sea surface, which is surprising, considering the environmental importance of Cu. Therefore, we used voltammetry to investigate Cu complexing capacity (CuCC) in the sea surface microlayer (SML) and in the underlying water (ULW) of the oligotrophic middle Adriatic Sea during February-July 2019. The focus was on the impacts of specific atmospheric processes such as open-fire biomass burning (BB), pollination season and Saharan dust intrusion. The presence of ligand class L2 (19.9-392.0, average 63.8, median 43.1) nM; log K2 (8.3-10.2, average 9.6, median 9.6) was observed in all samples, while ligand class L1 (40.5-76.1, average 53.6, median 48.9) nM; log K1 (10.3-11.1, average 10.6, median 10.5) was found in only 25% of SML samples. Throughout the period, the SML was enriched with organic ligands by a factor of up to 9.1 compared to the ULW, mainly due to the high sensitivity of the SML to specific atmospheric depositions. In addition, measurements with corresponding specific model aerosols were conducted to analyse their impacts on CuCC. Pollen directly affected CuCC in the SML by increasing the concentration of allochthonous ligands such as proteins. The deposition of BB aerosols rich in nutrients and trace metals stimulated the biological production of organic ligands, showing an indirect effect on CuCC delayed by up to two weeks. Finally, Saharan dust had a negligible impact on CuCC. This study illustrates the susceptibility of oligotrophic coastal area to the effects of pollen and open-fire BB aerosols in altering the Cu-binding organic ligands in the SML.

Ecotoxicity of PM10 emissions generated during controlled burning of waste PET.

Domestic waste is often burned either as fuel for winter heating or in open areas, simply to get rid of waste. Polyethylene terephthalate (PET) represents an important component of plastics usage as well as of plastic waste produced. While most studies attempt to characterize environmental risk of open burning of mixed household waste, present work evaluates chemical and ecotoxicological parameters of particulate matter (PM) produced during controlled burning of PET samples. In the PM10 samples, polycyclic aromatic hydrocarbon and heavy metal concentrations were measured, ecotoxicity was evaluated using the kinetic Vibrio fischeri bioassay. Both chemical composition and ecotoxicity of the 4 samples showed significant correlation, regardless of the colored or colorless nature of the original PET sample. Antimony was found in considerable concentrations, in the range of 6.93-16.9 mg/kg. PAHs profiles of the samples were very similar, showing the dominance of 4-and 5-ring PAHs, including carcinogenic benzo(a)pyrene.

Phytotoxicity of particulate matter from controlled burning of different plastic waste types.

According to careful estimations, open burning of plastic waste affects app. 2 billion people worldwide. While human health risks have become more and more obvious, much less information is available on the phytotoxicity of these emissions. In our study phytotoxicity of particulate matter samples generated during controlled combustion of different plastic waste types such as polyvinyl chloride (PVC), polyurethane (PUR), polypropylene (PP), polystyrene (PS) and polyethylene (PE) was evaluated based on peroxidase levels. While different samples showed different concentration-effect relationship patterns, higher concentration(s) caused decreased peroxidase activities in each sample indicating serious damage.

Ecotoxic emissions generated by illegal burning of household waste.

The practice of burning household waste including different types of plastic is illegal in Hungary, still an existing problem. As environmental consequences are hardly known, this study attempts to give an initial estimation of the ecotoxicity generated during controlled combustion of different waste types. These samples included polystyrene (PS), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyurethane (PU), oriented strand board (OSB) and rag (RAG). Ecotoxicological profiling was completed using the following test battery: Vibrio fischeri bioluminescence inhibition assay, Daphnia magna immobility test and the seedling emergence assay. Also, genotoxicity of plastic waste samples was assessed using the SOS Chromotest. Concerning main pollutants in the samples, the samples could be distinguished as 'PAH-type' and 'heavy metal-type' samples. PVC, PU and PS samples showed the highest toxicity in the Vibrio and Daphnia assays. The PVC sample was characterized by an extremely high cadmium concentration (22.4 µg/L), PS, PP and PU samples on the contrary had high total PAH content. While Vibrio and Daphnia showed comparable sensitivity, the phytotoxicity assay had no response for any of the samples tested. Samples originating from the controlled burning of different plastic types such as PU, PVC, PS and PP were classified as genotoxic, PS sample showed extremely high genotoxicity. Genotoxicity expressed as SOSIF showed strong correlation with most of the PAHs detected.

Biodegradation of two persistent aromatic compounds by using oil shale.

Low-cost oil shale was investigated as a biodegradation promoter material, in order to exploit its potential for more widespread and efficient usage in the elimination of pollution. Degradation of two model pollutants, 4-nitrophenol and phenol, was examined in the presence of oil shale in a batch system. In order to investigate the role of the natural microflora of the oil shale in degradation, sodium azide was added to inhibit microbial growth. The effect of metal ions was also investigated. In the sodium azide-free solutions the model pollutants were completely degraded up to 2000 µmol/L concentration in a dose-dependent way, while the addition of sodium azide delayed greatly but did not stop the degradation. Manganese(II) ions increased the rate of the degradation of 4-nitrophenol, and given quantities of iron(II), manganese(II) or zinc(II) ions were also effective in degradation of phenol. Our results suggest that oil shale is not only an adsorbent but has an active role in the degradation of pollutants by its natural microflora. Utilizing these features of oil shale, it is a suitable candidate as an ameliorating agent, which can also be used in industrial size.

Ecotoxicity testing of airborne particulate matter-comparison of sample preparation techniques for the Vibrio fischeri assay.

The bioassay based on the bioluminescence inhibition of the marine bacterium Vibrio fischeri has been the most widely used test for the assessment of airborne particulate matter ecotoxicity. Most studies available use an extract of the solid sample, either made with water or organic solvents. As an alternative, a whole-aerosol test is also available where test bacteria are in actual contact with contaminated particles. In our study, different extraction procedures were compared to this direct contact test based on the V. fischeri assay and analytical measurements. The lowest PAH content and the highest EC50 were determined in water extract, while the highest PAH amount and lowest EC50 were measured in dichloromethane, hexane, and dimethyl-sulphoxide extracts. EC50 of the direct contact test was comparable to that of the methanol extract. Our results suggest that the sensitivity of the direct contact test equals to that of extraction procedures using organic solvents, moreover, it is mimicking an environmentally realistic exposure route.

Diurnal variation of aethalometer correction factors and optical absorption assessment of nucleation events using multi-wavelength photoacoustic spectroscopy.

A field measurement campaign was carried out during the late winter and early spring of 2015 in Budapest, the capital of Hungary. The size distribution (SD) and optical absorption of carbonaceous particulate matter (CPM) was measured online using a Scanning Mobility Particle Sizer (SMPS), a 7λ-aethalometer and an inhouse developed 4λ-Photoacoustic Spectrometer. Based on the SD data, the measurement period could be classified into days with and without new particle formation events (normal days and nucleation days), although particular nucleation-like events were observed on normal days as well. Three characteristic size modes were observed with CMDs of circa 15, 25 and 110 nm that corresponded to the nucleation, traffic and heating modes. Based on the temporal behavior of these modes both types of days were divided into distinctive daily periods (heating hours, traffic hours and nucleation hours). The optical absorption spectra (OAC and AAE) also displayed the same part of day behavior to that of SD. That way this paper is among the first to assess the optical response of urban nucleation events. Due to the simultaneous measurement of OAC by the 7λ-aethalometer and a 4λ-Photoacoustic Spectrometer, OAC was measured overall at 11 wavelengths. That way aethalometer correction factors (f and C) were determined at all aethalometer wavelengths using in situ reference photoacoustic measurements. Correction factors were found to have both wavelength and time of the day variation. In the case of f, no clear trend could be observed, however, Cref values increased both as a function of wavelength.

Adapting the Vegetative Vigour Terrestrial Plant Test for assessing ecotoxicity of aerosol samples.

Plants, being recognized to show high sensitivity to air pollution, have been long used to assess the ecological effects of airborne contaminants. However, many changes in vegetation are now generally attributed to atmospheric deposition of aerosol particles; the dose-effect relationships of this process are usually poorly known. In contrast to bioindication studies, ecotoxicological tests (or bioassays) are controlled and reproducible where ecological responses are determined quantitatively. In our study, the No. 227 OECD Guideline for the Testing of Chemicals: Terrestrial Plant Test: Vegetative Vigour Test (hereinafter referred to as 'Guideline') was adapted and its applicability for assessing the ecotoxicity of water-soluble aerosol compounds of aerosol samples was evaluated. In the aqueous extract of the sample, concentration of metals, benzenes, aliphatic hydrocarbons and PAHs was determined analytically. Cucumis sativus L. plants were sprayed with the aqueous extract of urban aerosol samples collected in a winter sampling campaign in Budapest. After the termination of the test, on day 22, the following endpoints were measured: fresh weight, shoot length and visible symptoms. The higher concentrations applied caused leaf necrosis due to toxic compounds found in the extract. On the other hand, the extract elucidated stimulatory effect at low concentration on both fresh weight and shoot length. The test protocol, based on the Guideline, seems sensitive enough to assess the phytotoxicity of aqueous extract of aerosol and to establish clear cause-effect relationship.

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.

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.

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.