9-year trends of PM₁₀sources and oxidative potential in a rural background site in France

Long-term monitoring at sites with relatively low particulate pollution could provide an opportunity to identify changes in pollutant concentration and potential effects of current air quality policies. In this study, a 9-year sampling of PM10 (particles with an aerodynamic diameter below 10 µm) was performed in a rural background site in France from February 28, 2012 to December 22, 2020. The Positive Matrix Factorization (PMF) method was used to apportion sources of PM10 based on quantified chemical constituents and specific chemical tracers from collected filters. Oxidative potential (OP), an emerging health-metric that measures PM capability to potentially cause anti-oxidant imbalance in the lung, was also measured using two acellular assays: dithiothreitol (DTT) and ascorbic acid (AA). The contribution of PMF-resolved sources to OP were also estimated using multiple linear regression (MLR) analysis. In terms of mass contribution, the dominant sources are secondary aerosols (nitrate- and sulphate-rich), associated with long-range transport (LRT). However, in terms of OP contributions, the main drivers are traffic, mineral dust, and biomass burning factors. There is also some OP contribution apportioned to the sulphate- and nitrate-rich sources influenced by processes and aging during LRT that could have encouraged mixing with other anthropogenic sources. The study indicates much lower OP values than in urban areas. A substantial decrease (58 % reduction from year 2012 to 2020) in the mass contributions from the traffic factor was found, however, this is not clearly reflected in its OP contribution. Nevertheless, the findings in this long-term study in the OPE site could signal effectiveness of implemented emission control policies, as also seen in other long-term studies conducted in Europe, mainly for urban areas.

Nitro- and oxy-PAHs in grassland soils from decade-long sampling in central Europe

Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Košetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g−1 and 4.03 ± 3.03 ng g−1, respectively, in Košetice, while slightly higher concentrations of 0.54 ± 0.45 ng g−1 and 5.91 ± 0.45 ng g−1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Košetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.

Chemically speciated mass size distribution, particle effective density and origin of non-refractory PM₁measured at a rural background site in Central Europe

The seasonal variability of non-refractory PM1 (NR-PM1) was studied at a rural background site (National Atmospheric Observatory Košetice – NAOK) in the Czech Republic to examine the impact of atmospheric regional and long-range transport in Central Europe. NR-PM1 measurements were performed by compact time-of-flight aerosol mass spectrometry (C-ToF-AMS), and the chemically speciated mass size distributions, effective density, and origin were discussed. The average PM1 concentrations, calculated as the sum of the NR-PM1 (after collection efficiency corrections – CE corrections of 0.4 and 0.33 in summer and winter, respectively) and the equivalent black carbon (eBC) concentrations measured by an aethalometer (AE), were 8.58 ± 3.70 μg m−3 in summer and 10.08 ± 8.04 μg m−3 in winter. Organics dominated during both campaigns (summer/winter: 4.97 ± 2.92/4.55 ± 4.40 μg m−3), followed by sulphate in summer (1.68 ± 0.81/1.36± 1.38 μg m−3) and nitrate in winter (0.67 ± 0.38/2.03 ± 1.71 μg m−3). The accumulation mode dominated the average mass size distribution during both seasons, with larger particles of all species measured in winter (mode diameters: Org: 334/413 nm, NO3−: 377/501 nm, SO42−: 400/547 nm, and NH4+: 489/515 nm) pointing to regional and long-range transport. However, since the winter aerosols were less oxidized than the summer aerosols (comparing fragments f44 and f43), the importance of local sources in the cold part of the year was not negligible. The average PM1 particle effective density, defined as the ratio of the mass to the volume of a particle, corresponded to higher inorganic contents during both seasons (summer: ∼ 1.30 g cm−3 and winter: ∼ 1.40 g cm−3). However, the effective densities during episodes of higher mass concentrations calculated based on the particle number (mobility diameter) and mass size distribution (vacuum aerodynamic diameter) were even higher, ranging from 1.40–1.60 g cm−3 in summer and from 1.40–1.75 g cm−3 in winter. Although aged continental air masses from the SE were rare in summer (7 %), they were connected with the highest concentrations of all NR-PM1 species, especially sulphate and ammonium. In winter, slow continental air masses from the SW (44 %) were linked to inversion conditions over Central Europe and were associated with the highest concentrations among all NR-PM1 measurements.