Characterization of fresh PM deposits on calcareous stone surfaces: Seasonality, source apportionment and soiling potential.

Particulate matter (PM) pollution is one of the major threats to cultural heritage outdoors. It has been recently implied that organic aerosols will prevail over inorganic carbon particulates in the future, changing the main mechanisms of damage caused by poor air quality to calcareous heritage in particular. We studied fresh particulate deposits on marble and limestone surfaces exposed to urban air in sheltered and unsheltered configurations. Due to different air pollution sources in different seasons, the amount and composition of surface deposits varied throughout the year. The main and most constant contributor to PM2.5 (particles smaller than 2.5 µm) were primary traffic emissions (30 %), followed by secondary formation of acidic inorganic aerosols, such as sulphate in summer and nitrate in winter (33 % altogether), and seasonal biomass-burning emissions (14 %). Although biomass burning is the major source of primary organic aerosols including the light-absorbing fraction that prevailed over black carbon (BC) in colder months (up to 60 % carbonaceous aerosol mass), we show that surface darkening causing the soiling effect is still governed by the minor BC fraction of atmospheric aerosols, which remained below 20 % of the carbonaceous aerosol mass throughout the year. This, however, can change in remote environments affected by biomass-burning emissions, such as winter resorts, or by rigorous BC mitigation measures in the future. In the short run, sheltered positions were less affected by different removal processes, but we show that surface deposits are not simply additive when considering longer periods of time. This must be taken into account when extrapolating surface accumulation to longer time scales.

Determination of trace concentrations of simple phenols in ambient PM samples.

Phenols are hazardous, but yet ubiquitous in the environment, including in atmospheric aerosols due to combustion emissions. There, phenols are subjected to secondary transformations, producing even more toxic nitrophenolic air pollutants. However, primary simple phenols, i.e. those containing only hydroxyl, methyl and methoxy substituents are not easy to detect. Trace concentrations, semi-volatile character and poorly ionizable functional groups prevent us from their determination by the most common analytical techniques, such as gas and liquid chromatography with mass spectrometric detection (GC/LC-MS). Here, we present a new derivatization method for MS/MS detection with positive ion electrospray ionization (+ESI-MS/MS) of simple phenols in atmospheric particulate matter (PM) extracts. The method is sensitive, selective, and robust, and requires no sample concentration step, which is critical due to the volatile character of the target analytes. After derivatization with dansyl chloride, phenol, catechol, cresols and guaiacol were detected in urban PM samples from Ljubljana, Slovenia. This method finally enables to study the abundance of primary phenols in atmospheric PM from different sources, which will improve understanding of secondary aerosol (trans)formation pathways and allow for more targeted mitigation strategies in respect to airborne phenolic pollutants.

The first plastic produced, but the latest studied in microplastics research: The assessment of leaching, ecotoxicity and bioadhesion of Bakelite microplastics.

Bakelite, the first synthetic plastic, is a rather unexplored material in the field of ecotoxicology, despite its long production and use. The aim of this study was to investigate the ecotoxicity of Bakelite microplastics (before and after leaching) and its leachates on four aquatic organisms: the crustacean Daphnia magna, the plant Lemna minor, the bacterium Allivibrio fischeri and the alga Pseudokirchneriella subcapitata. Bakelite microplastics before and after leaching and leachates affected all organisms, but to varying degrees. Leachates showed increased ecotoxicity to Daphnia magna, while Pseudokirchneriella subcapitata was more affected by particles. For Lemna minor and Allivibrio fischeri, the effects of particles before leaching and leachate were comparable, while the negative effect of particles after leaching was minimal or not present. All leachates were analysed, and phenol and phenol-like compounds were the predominant organics found. In addition, bioadhesion of Bakelite microplastics to the surface of Daphnia magna and Lemna minor was confirmed, but the particles were mainly weakly adhered. Results of this study suggest that, in addition to the recently studied microplastics from consumer products (e.g. from polyethylene and polystyrene), microplastics from industrial plastics such as Bakelite may be of increasing concern, primarily due to leaching of toxic chemicals.

Pollution levels and deposition processes of airborne organic pollutants over the central Adriatic area: Temporal variabilities and source identification.

First data on polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatic compounds (NACs) in aerosols as well as of PAHs, polychlorinated biphenyls (PCBs) and NACs in bulk and wet atmospheric deposition samples were simultaneously obtained during 6-month-long field campaign at the costal central Adriatic area. Special attention was given to open-fire biomass burning episodes as extreme events common for the overall Mediterranean coastal area in order to gain a better understanding of the atmospheric variabilities and potential sources of trace organic pollutants in coastal environments. Diesel and gasoline combustion related to land and maritime traffic as well as occasional open-fire episodes (forest fires) were found to be the dominant pollution sources of PAHs in PM10 particles. NACs were determined almost exclusively in samples affected by biomass burning episodes. Open-fire episodes had a strong contribution to the overall NACs atmospheric deposition fluxes. Several chlorinated congeners of PCBs were predominantly contributed in deposition samples.

No more waste at the elemental analysis of airborne particulate matter on quartz fibre filters.

Particulate matter (PM) is the major environmental pollutant. Its elemental composition is routinely monitored. Inductively coupled plasma mass spectroscopy (ICPMS) is commonly applied after a PM sample has been digested by an acid during a microwave treatment. In this case, sample preparation procedure is laborious, sometimes incomplete and produces toxic waste. In this paper we show that direct sample introduction to ICPMS by laser ablation (LA-ICPMS) is of huge advantage. Minimal quantity of a sample is required for the analysis (<1 cm2) and no chemical waste is produced. The study focused on the most universal and widely used quartz fibre filter samples and we show that LA-ICPMS can be successfully applied for the determination of the elemental composition of such samples. Some effort is, however, still needed to develop an autosampler for the LA-ICPMS system and to provide commercial matrix-matched standards for this application to be implemented in environment laboratories worldwide.

Injections to pregnant mice produce prenatal stress that affects aggressive behavior in their adult male offspring.

Maternal stress could reprogram the developing fetal nervous system. A common target of maternal glucocorticoids is fetal neuro-endocrine axis. In the present study, pregnant mice were exposed to stress by injection and their male offspring were tested for sexual and aggressive behaviors in adult life. Three groups of pregnant mice were exposed to stress by sham syringe injection. The first group was injected on days 13, 14, and 15 p.c., the second group was injected on days 17 and 18 p.c., and the third group was injected daily from days 13 to 18 p.c. while control mice were not injected. Male offspring that were exposed to stress on days 13-18 p.c. and 17-18 p.c. were less aggressive and had lower blood testosterone levels in comparison to the control group. In male sexual behavior, there were no statistically significant differences between the groups. Body weight differed significantly with groups injected on days 13-18 p.c. and 13-15 p.c. having significantly higher body weight in adult life than the other two groups. After behavioral testing, brains were processed for immunohistochemical staining with antibodies against vasopressin (AVP) and calbindin (CALB). The expression of AVP and CALB in the lateral septum and in the preoptic area, respectively, did not differ between groups, suggesting that these two masculinization markers were not affected by prenatal stress. Present study therefore shows that even presumably mild and short prenatal stress weakens aggressive behavior of adult male mice, possibly due to reduced testosterone levels in blood.