Occurrence, Seasonal Variation, and Size Resolved Distribution of Arsenic Species in Atmospheric Particulate Matter in an Urban Area in Southeastern Austria.

Extensive information is available on total arsenic in particulate matter (PM), but little is known about the relative contribution of each individual species. Recent studies often focus on inorganic arsenic as arsenite and arsenate, neglecting the organoarsenicals, i.e., methylarsine, dimethylarsine, and trimethylarsine or the corresponding oxidized forms methylarsonate, dimethylarsinate, and trimethylarsine oxide, although they were already first detected in PM in the mid-1970s. This work presents results from more than 300 daily PM10 and further size-resolved atmospheric PM samples in the size range from 15 nm to 10 µm collected in an urban environment in Austria during the course of a year. An ion-exchange-HPLC (with anion and cation exchange columns) and an ICPMS/MS system were used to study the seasonal variations of total arsenic and all species known to exist in PM. Inorganic arsenic was present in significant amounts in all samples with highest concentrations during winter, but also all organoarsenicals were detected throughout the year. We show that their contribution cannot be ignored, as particles smaller than <1 µm can contain up to 35% of the water+H2O2 extractable arsenic as methylated species, but only dimethylarsinate showed a clear seasonal trend throughout the year.

Seasonal variation of arsenic in PM10 and PMx in an urban park: The influence of vegetation-related biomethylation on the distribution of its organic species and air quality.

Arsenic (As) levels in particulate matter (PM) are routinely monitored in cities of developed countries. Despite advances in the knowledge of its inorganic species in PM in urban areas, organic species are often overlooked with no information on their behaviour in urban parks - areas with increased potential for As biomethylation. Therefore, the aim of this study was to characterize As distribution, bioaccessibility, seasonal variation and speciation (AsIII, AsV, MMA, DMA and TMAO) in PMx-PM10 of an urban park. Two sites with different distance from the road were selected for winter and summer sampling. From the PM samples, we gravimetrically determined PM10 concentrations in the air and via ICP-MS the total As content there. To assess the portion of bioaccessible As, water extractable As content was analysed. Simultaneously, the As species in PM10 water extracts were analysed via coupling of HPLC with ICP-MS method. There was no seasonal difference in PM10 concentration in the park, probably due to the increased summer PM load related to recreational activities in the park and park design. Spatial distribution of total As in PM10 and As fractional distribution in PMx suggested that As mostly didn't originate from traffic although highest As content was observed in the fine fraction (PM2.5) related to combustion processes. However, significant winter increase of As (determined by AsIII and AsV) despite the unchanged concentration of PM10 indicated a decisive influence of household heating-related combustion and possibly influence of reduced vegetation density. As present in the PM10 was mostly in bioaccessible form. Seasonal influence of As biomethylation was clearly demonstrated on the TMAO specie during the summer campaign. Except the significant summer TMAO increase, the results also indicated the biomethylation influence on DMA. Therefore, an increased risk of exposure to organic As species in urban parks can be expected during summer.

Monitoring of the impact of road salting on spruce forest ecosystem in the vicinity of the highway D1 in the Bohemian-Moravian Highlands, Czech Republic.

Monitoring of pollution in the vicinity of roads connected to winter road maintenance is one of the important tools for optimising winter maintenance technology and reducing its environmental impact. The aim of this study was to determine the relationship between winter road maintenance and the increased concentration of sodium ion to characterise the harm caused by the de-icing agents on selected types of individual components grown in the Norway spruce ecosystem. The model area is located in the immediate vicinity of the D1 motorway connecting Prague and Brno (Czech Republic), at 103 km. The area is thus exposed to long-term contamination from automobile transport, and the monitoring was carried out for 3 consecutive years. A clear effect of the de-icing agents on conifers near the road has been demonstrated by the symptoms of salt damage visually observed in close proximity to the road (at a sampling distance of 5 m). The needles of these spruce trees also showed increased sodium concentrations, regardless of the age of the needles. The study also confirms that sodium accumulates in all selected components of the analysed ecosystem (moos, humus, soil). The sodium concentration has been found to decrease with increasing distance from the road for all of the components.

Assessment of Soil Contamination with Potentially Toxic Elements and Soil Ecotoxicity of Botanical Garden in Brno, Czech Republic: Are Urban Botanical Gardens More Polluted Than Urban Parks?

Though botanical gardens are an important and widely visited component of urban green spaces (UGS) worldwide, their pollution is rarely studied. The aim of this study was to assess botanical garden soil contamination and ecotoxicity and to evaluate whether urban botanical gardens are more contaminated than urban parks. Soil assessments showed serious contamination with Cd, Pb and Zn, emitted predominantly by traffic, agrochemicals and past construction and demolition waste. The discovery of hazardous historical ecological burden in the UGS calls for the necessity of detailed surveys of such areas. Despite prevailing moderate-to-heavy contamination, the soil was only slightly ecotoxic. Maximum immobilisation inhibition of Daphnia magna reached 15%. Growth of Sinapis alba L. was predominantly stimulated (73%), and Desmodesmus subspicatus Chodat was exclusively stimulated, possibly due to soil alkalinity and fertiliser-related nutrients. The hypothesis of a higher contamination of urban botanical gardens compared to urban parks was confirmed. However, urban parks can face a greater risk of soil ecotoxicity, hypothetically due to decreased activity of soil organisms resulting from adverse soil conditions caused by active recreation. The results highlight the need for an increased focus on botanical and ornamental gardens when assessing and managing UGS as areas potentially more burdened with contamination.

Nontuberculous Mycobacteria Prevalence in Aerosol and Spiders' Webs in Karst Caves: Low Risk for Speleotherapy.

A total of 152 aerosol and spider web samples were collected: 96 spider's webs in karst areas in 4 European countries (Czech Republic, France, Italy, and Slovakia), specifically from the surface environment (n = 44), photic zones of caves (n = 26), and inside (aphotic zones) of caves (n = 26), 56 Particulate Matter (PM) samples from the Sloupsko-Sosuvsky Cave System (speleotherapy facility; n = 21) and from aerosol collected from the nearby city of Brno (n = 35) in the Czech Republic. Nontuberculous mycobacteria (NTM) were isolated from 13 (13.5%) spider's webs: 5 isolates of saprophytic NTM (Mycobacterium gordonae, M. kumamotonense, M. terrae, and M. terrae complex) and 6 isolates of potentially pathogenic NTM (M. avium ssp. hominissuis, M. fortuitum, M. intracellulare, M. peregrinum and M. triplex). NTM were not isolated from PM collected from cave with the speleotherapy facility although mycobacterial DNA was detected in 8 (14.3%) samples. Temperature (8.2 °C, range 8.0-8.4 °C) and relative humidity (94.7%, range 93.6-96.6%) of air in this cave were relatively constant. The average PM2.5 and PM10 mass concentration was 5.49 µg m-3 and 11.1 µg m-3. Analysed anions (i.e., F-, Cl-, NO2-, SO42-, PO43- and NO3-) originating largely from the burning of wood and coal for residential heating in nearby villages in the surrounding area. The air in the caves with speleotherapy facilities should be monitored with respect to NTM, PM and anions to ensure a safe environment.

Impact of New Year's Eve fireworks on the size resolved element distributions in airborne particles.

New Year's Eve fireworks represent one of the most unusual atmospheric pollution events in the course of a year. A majority of particles aerosolized by burning of fireworks consist of metals and their compounds used in firework displays. In this study, ambient particulate matter was sampled using a 14 stage cascade impactor in two European cities during turn of the years 2016/17 and 2017/18. Concentrations of 33 elements were determined by inductively coupled plasma mass spectrometry. To assess the impact of New Year's Eve fireworks on ambient air quality, chemically resolved size distributions of particles with diameters between 15 nm and 10 µm collected during fireworks episodes were compared to ones collected in normal winter weeks. For some metals a distinct shift of their concentration maximum related to fireworks could be observed, which is in between the maxima for accumulation and coarse mode particles. Concentrations of these elements (Sr, Ba, Mg, Bi, Al, Cu and K) were also higher during weeks with fireworks episodes than during control weeks. Although New Year's Eve fireworks only take place once a year, these results show that air pollution caused by fireworks can be a potential health risk, especially for people with pre-existing diseases.

Arsenic speciation in aerosols of a respiratory therapeutic cave: A first approach to study arsenicals in ultrafine particles.

Arsenic is ubiquitous in the environment and of special concern due to its varying toxicity depending on the chemical form present. Less is known about arsenic in air, especially about organoarsenicals, their sources and fate. There is also a lack of knowledge regarding arsenic in airborne nanoparticles that are critical for understanding with respect to human health effects due to their size. Here we show results from an arsenic speciation analysis in size-resolved airborne particles with aerodynamic diameters down to 15 nm. Analysis of aerosols from a respiratory therapeutic cave showed temporarily higher concentrations of trimethylarsine oxide than inorganic arsenic and substantial amounts of organoarsenicals, especially in smaller particles. Our method provides guidance for future studies investigating arsenicals in ultrafine particles and their health implications. Furthermore, the method developed can be used to widely monitor particle-bound organoarsenicals to fully understand the importance of As biovolatilization in the environment.

Fast Ecotoxicity Detection Using Biosensors.

The article provides information about a new device, AlgaTox developed in the R&D project sponsored by the Technology Agency (n.TA02030179) and patented in Czech Republic (CZ 305687). Its functionality is based on the use of biosensor, and its main advantage is fast response rate. The toxicity detection is achieved through precise measurement of green algae oxygen production dynamics after their exposure to light of wavelength of 680 nm. Clark sensor with a resolution of 0.05% of the equilibrium oxygen concentrations and stability at a constant pressure and temperature of 0.1% of the equilibrium oxygen concentration at the 24-h measurement is used for the oxygen detection. Laboratory testing of the device has been made using silver nitrate, substance with known inhibitory effect on algae. Real samples of aqueous soil extracts and waste sample from old dried-up industrial tailing pond enriched with insecticide have been also tested. The values of oxygen production inhibition or stimulation determined with the new device in the evaluation of real samples were up to six times higher in comparison with the corresponding values of inhibition (stimulation) of growth rates determined by standard procedure.

Identifying risk sources of air contamination by polycyclic aromatic hydrocarbons.

This article is directed to determining concentrations of polycyclic aromatic hydrocarbons (PAHs), which are sorbed to solid particles in the air. Pollution sources were identified on the basis of the ratio of benzo[ghi]perylene (BghiPe) to benzo[a]pyrene (BaP). Because various important information is lost by determining the simple ratio of concentrations, least squares linear regression (classic ordinary least squares regression), reduced major axis, orthogonal regression, and Kendall-Theil robust diagnostics were utilized for identification. Statistical evaluation using all aforementioned methods demonstrated different ratios of the monitored PAHs in the intervals examined during warmer and colder periods. Analogous outputs were provided by comparing gradients of the emission factors acquired from the measured concentrations of BghiPe and BaP in motor vehicle exhaust gases. Based on these outputs, it was possible plausibly to state that the influence of burning organic fuels in heating stoves is prevalent in colder periods whereas in warmer periods transport was the exclusive source because other sources of PAH emissions were not found in the examined locations.