Do bromine and surface-active substances influence the coastal atmospheric particle growth?

New particle formation (NPF) is considered a major source of aerosol particles and cloud condensation nuclei (CCN); however, our understanding of NPF and the subsequent particle growth mechanisms in coastal areas remains limited. This study provides evidence of frequent NPF events followed by particle growth in the middle Adriatic Sea during the summer months at the coastal station of Rogoznica in Croatia. To our knowledge, this is the first study to report such events in this region. Our research aims to improve the understanding of NPF by investigating particle growth through detailed physicochemical characterization and event classification. We used a combination of online measurements and offline particle collection, followed by a thorough chemical analysis. Our results suggest the role of bromine in the particle growth process and provide evidence for its involvement in combination with organic compounds. In addition, we demonstrated the significant influence of surface-active substances (SAS) on particle growth. NPF and particle growth events have been observed in air masses originating from the Adriatic Sea, which can serve as an important source of volatile organic compounds (VOC). Our study shows an intricate interplay between bromine, organic carbon (OC), and SAS in atmospheric particle growth, contributing to a better understanding of coastal NPF processes. In this context, we also introduced a new approach using the semi-empirical 1st derivative method to determine the growth rate for each time point that is not sensitive to the nonlinear behavior of the particle growth over time. We observed that during NPF and particle growth event days, the OC concentration measured in the ultrafine mode particle fraction was higher compared to non-event days. Moreover, in contrast to non-event days, bromine compounds were detected in the ultrafine mode atmospheric particle fraction on nearly all NPF and particle growth event days. Regarding sulfuric acid, the measured sulfate concentration in the ultrafine mode atmospheric particle fraction on both NPF event and non-event days showed no significant differences. This suggests that sulfuric acid may not be the primary factor influencing the appearance of NPF and the particle growth process in the coastal region of Rogoznica.

Direct quantification of PAHs and nitro-PAHs in atmospheric PM by thermal desorption gas chromatography with electron ionization mass spectroscopic detection.

In this work, we developed and optimized a method for the analysis of PAHs and nitro-PAHs in atmospheric particulate matter (PM) samples by using thermal desorption gas chromatography coupled with electron ionization single quadrupole mass spectrometry (TD-GC-(EI)-MS). The method uses thermal desorption from a PM on a filter sample as means of sample introduction to a column and obviates the need for complex extraction procedures, which are time-consuming and require environmentally unfriendly solvents. Moreover, the possibility of systematic errors is minimized and a significantly smaller amount of sample is required compared to traditional techniques requiring a pre-extraction step (approx. 10-times). Thirteen PAHs and three nitro-PAHs were used during method development. Although Tenax cartridges are typically used to capture volatile pollutants from the air, we found that glass-wool liner is the most suitable trap for the examined analytes after desorption from a quartz filter. Among the various instrument parameters which were tested and optimized, TD desorption flow and hold time, and temperature of the cooled injection system (CIS) proved to be most critical. We also found out that the matrix effect is especially pronounced in the case of high PM loadings, which should be kept in mind when planning the analysis. After the optimization, standard reference materials (ERM-CZ100 and NIST 1648a) were used for partial method validation and finally, real PM10 and PM2.5 samples from two Slovenian cities were successfully analyzed.

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.

Impact of air pollution on outdoor cultural heritage objects and decoding the role of particulate matter: a critical review.

Atmospheric gases and particulate matter (PM) in contact with the material's surface lead to chemical and physical changes, which in most cases cause degradation of the cultural heritage material. Atmospheric damage and soiling are recognized as two pivotal forms of deterioration of cultural heritage materials caused by air pollution. However, the atmospheric damage effect of PM is rather complicated; its variable composition accelerates the deterioration process. Considering this, one of the important contributions of this work is to review the existing knowledge on PM influence on atmospheric damage, further recognize, and critically evaluate the main gaps in current understanding. The second phenomenon related to cultural heritage material and PM pollution is soiling. Even if soiling was recognized long ago, its definition and knowledge have not changed much for several decades. In the past, it was believed that black carbon (BC) was the primary soiling agent and that the change of the lightness could effectively measure the soiling. With the change of pollution situation, the lightness measurements do not represent the degree of soiling correctly. The additional contribution of this work is thus, the critical evaluation of soiling measurements, and accordingly, due to the change of pollution situation, redefinition of soiling is proposed. Even though numerous studies have treated soiling and atmospheric damage separately, there is an overlap between these two processes. No systematic studies exist on the synergy between soiling and atmospheric damage caused by atmospheric PM.

The possible role of the surface active substances (SAS) in the airborne transmission of SARS-CoV-2.

Surface active substances (SAS) have the potential to form films at different interfaces, consequently influencing the interfacial properties of atmospheric particulate matter (PM). They can be derived from both human activities and natural processes and can be found in an indoor and outdoor environment. This paper's fundamental question is the possible role of the SAS in stabilizing respiratory aerosols in the closed space. In that context, we discuss results of preliminary measurements of the SAS and dissolved organic carbon (DOC) concentrations in the water-soluble fractions of PM2.5 and PM10 that were sampled simultaneously in primary school inside and outside of the building. The concentrations of SAS were determined using highly sensitive electrochemical measurements. It was observed that SAS and DOC concentrations have been enhanced indoor in both PM fractions. Consistent with these results, a discussion arises on the possibility that SAS could play a crucial role in respiratory droplet dispersion as stabilizers, especially in a closed space. At the same time, we assume that they could prolong the lifetime of respiratory aerosols and as well viability of some (possible SARS-CoV-2) virus inside of the droplets.

Electrochemistry as a Tool for Studies of Complex Reaction Mechanisms: The Case of the Atmospheric Aqueous-Phase Aging of Catechols.

The ultimate goal in the understanding of complex chemical processes is a complete description of the underlying reaction mechanism. In the present study and for this purpose, a novel experimental platform is introduced that builds upon electrochemistry capable of generating reactive intermediate species at the electrode surface. The atmospherically relevant nitration of catechols is taken as a case example. First, we confirm the recently proposed nitration mechanism, advancing the understanding of atmospheric brown carbon formation in the dark. We are able to selectively quantify aromatic isomers, which is beyond the limits of conventional electroanalysis. Second, we identify a new pathway of nitrocatechol hydroxylation, which proceeds simply by oxidation and the addition of water. This pathway can be environmentally significant in the dark aqueous-phase formation of secondary organic aerosols. Third, the developed methodology is capable of selectively detecting a wide range of nitroaromatics; a possible application in environmental monitoring is proposed.

Nighttime Aqueous-Phase Formation of Nitrocatechols in the Atmospheric Condensed Phase.

Yellow-colored methylnitrocatechols (MNC) contribute to the total organic aerosol mass and significantly alter absorption properties of the atmosphere. To date, their formation mechanisms are still not understood. In this work, the intriguing role of HNO2 (catalytic and oxidative) in the dark transformation of 3-methylcatechol (3MC) under atmospherically relevant aqueous-phase conditions is emphasized. Three possible pathways of dark 3-methyl-5-nitrocatechol and 3-methyl-4-nitrocatechol formation, markedly dependent on reaction conditions, were considered. In the dominant pathway, HNO2 is directly involved in the transformation of 3MC via consecutive oxidation and conjugated addition reactions (nonradical reaction mechanism). The two-step nitration dominates at a pH around the p Ka of HNO2, which is typical for atmospheric aerosols, and is moderately dependent on temperature. Under very acidic conditions, the other two nitration pathways, oxidative aromatic nitration (electrophilic) and recombination of radical species, gain in importance. The predicted atmospheric lifetime of 3MC according to the dominant mechanism at these conditions (2.4 days at pH 4.5 and 25 °C) is more than 3-times shorter than that via the other two competitive pathways. Our results highlight the significance of a catechol oxidation-conjugated addition reaction in a nighttime secondary nitroaromatic chromophore formation in the atmosphere, especially in polluted environments with high NO x concentrations and relatively acidic particles (pH around 3).