Search

Acidity profoundly affects almost every aspect that shapes the composition of ambient particles and their environmental impact. Thermodynamic analysis of gas-particle composition datasets offers robust estimates of acidity, but they are not available for long periods of time. Fog composition datasets, however, are available for many decades; we develop a thermodynamic analysis to estimate the ammonia in equilibrium with fog water and to infer the pre-fog aerosol pH starting from fog chemical composition and pH. The acidity values from the new method agree with the results of thermodynamic analysis of the available gas-particle composition data. Applying the new method to historical (25 years) fog water composition at the rural station of San Pietro Capofiume (SPC) in the Po Valley (Italy) suggests that the aerosol has been mildly acidic, with its pH decreasing by 0.5–1.5 pH units over the last decades. The observed pH of the fog water also increased 1 unit over the same period. Analysis of the simulated aerosol pH reveals that the aerosol acidity trend is driven by a decrease in aerosol precursor concentrations, and changes in temperature and relative humidity. Currently, NOx controls would be most effective for PM2.5 reduction in the Po valley both during summer and winter. In the future, however, seasonal transitions to the NH3-sensitive region may occur, meaning that the NH3 reduction policy may become increasingly necessary., Paglione, M., Decesari, S., Rinaldi, M., Tarozzi, L., Manarini, F., Gilardoni, S., Facchini, M. C., Fuzzi, S., Bacco, D., Trentini, A., Pandis S. N., and Nenes A. : Historical Changes in Seasonal Aerosol Acidity in the Po Valley (Italy) as Inferred from Fog Water and Aerosol Measurements, Environ. Sci. Technol., May 17, 2021, https://doi.org/10.1021/acs.est.1c00651

not available

Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O/C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50-57%, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73-100% modern

EDITORIAL

The light-absorbing properties of water-soluble brown carbon (WS-BrC) and methanol-soluble brown carbon (MeS-BrC) were studied in PM10 aerosols collected at the "Nepal Climate Observatory-Pyramid" (NCO-P) station (5079m above sea level) during the period 2013-2014. The light absorption coefficients of WS-BrC and MeS-BrC were the highest during the premonsoon season and the lowest during monsoon. MeS-BrC absorbs about 2 times higher at 365nm and about 3 times more at 550nm compared to WS-BrC. The mass absorption cross section (MAC) of WS-BrC measured at 365nm is similar to that observed previously at South Asian low-altitude sites. Fractional solar radiation absorption by BrC compared to BC considering the full solar spectrum showed that WS-BrC absorbs 4 +/- 1% and MeS-BrC absorbs 9 +/- 2% compared to BC at NCO-P. Such ratios become 8 +/- 1% (for WS-BrC respect to BC) and 17 +/- 5% (for MeS-BrC respect to BC) when accounting for correction factors proposed by previous studies to convert absorption coefficients in bulk solutions into light absorption by accumulation mode aerosol particles. These results confirm the importance of BrC in contributing to light-absorbing aerosols in this region of the world. However, the BrC absorption at 550nm appears small compared to that of BC (1-5%, or 3-9% with conversion factors), and it is lower compared to global model estimates constrained by Aerosol Robotic Network observations. Finally, our study provides no clear evidence of a change in the fractional contribution of BrC with respect to BC to light absorption in the middle troposphere respect to the Indo-Gangetic plain boundary layer.

Mt. Cimone (44.18N, 10.70E, 2165 m a.s.l.) is the highest peak of the Italian northern Apennines and is characterised by a 360° free horizon. As being located South of the Alps and of the polluted Po basin, the observations of atmospheric composition conducted at this GAW-WMO station, provide useful information for evaluating the role of regional and long-range transport processes in modifying the tropospheric background conditions in the Mediterranean basin/Southern Europe. Moreover, this long-term monitoring activity helps in quantifying the existing trend of climate-altering substances and atmospheric pollutants (e.g. Maione et al., 2010).

Initial efforts toward developing a combined organic-inorganic sea spray source function parameterization for large-scale models made use of chlorophyll-a (Chl-a) and wind speed as input parameters to combine oceanic biology and atmospheric dynamics. These studies reported a modest correlation coefficient (0.55) between chlorophyll-a and organic matter (OM) enrichment in sea spray, suggesting that chlorophyll-a is only partially suitable for predicting organic enrichment. A reconstructed chlorophyll-a field of the North Atlantic Ocean from GlobColour reveals an improved correlation of 0.72 between the fractional mass contribution of organics in sea spray and chlorophyll-a concentration. A similar analysis, using colored dissolved and detrital organic material absorption and particulate organic carbon concentration, revealed slightly lower correlation coefficients (0.65 and 0.68). These results indicate that to date, chlorophyll-a is the best biological surrogate for predicting sea spray organic enrichment. In fact, considering the minimal difference between the correlation coefficients obtained with the three ocean color products, there is no reason to substitute chlorophyll-a, which is the most accurate parameter obtained from ocean color data, with other biological surrogates being generally affected by larger and less known errors. The observed time lag between chlorophyll-a concentration and organic matter enrichment in aerosol suggests that biological processes in oceanic surface waters and their timescales should be considered when modeling the production of primary marine organic aerosol.