Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied. We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3-4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic. Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Atmospheric mercury and its deposition during the phasing out of an amalgam electrolysis plant: temporal, seasonal, and spatial patterns.

Large amounts of mercury (Hg) were consumed and emitted into the atmosphere during the process of amalgam electrolysis used to produce chlorine and caustic soda since the nineteenth century. In Europe, amalgam electrolysis has been gradually replaced by advanced Hg-free technologies. In this work, we describe changes in atmospheric Hg and bulk Hg wet deposition during the phasing out of an amalgam electrolytic production line of a chlor-alkali plant in Neratovice, Czech Republic, central Europe. Bulk wet deposition Hg near the chlor-alkali plant was low at 3.6 ± 0.8 µg m-2 year-1 due in part to low annual precipitation amounts (486 ± 97 mm) in the period 2015-2021. Nevertheless, Hg deposition was elevated relative to a nearby reference site both before and after decommissioning of the electrolytic line. Switching off the amalgam electrolytic line did not notably affect bulk wet deposition Hg near the chlor-alkali plant. Levels of gaseous elemental Hg (GEM) and particle-bound Hg (PBM) monitored seasonally four times per year over 24-h time periods indicated rapid declines in four nearby settlements set in cardinal directions from the Hg emission source. Mean atmospheric GEM and PBM concentrations decreased rapidly from 9.0 ± 2.1 ng m-3 and 243 ± 255 pg m-3 in the period 2013-2017 when amalgam electrolysis was operating to 3.3 ± 0.4 ng m-3 and 32 ± 6 pg m-3 in the period 2018-2021 after its decommissioning in November 2017. Seasonal changes of GEM coincided with changes in temperature with the highest concentrations in summer, while PBM air levels were lowest in summer due to the highest seasonal precipitation amount. GEM concentrations at the four monitored settlements at Neratovice remained elevated at 2.8 ng m-3 with respect to regional background, but PBM levels decreased to background levels.

Mass absorption cross-section and absorption enhancement from long term black and elemental carbon measurements: A rural background station in Central Europe.

Black carbon (BC) is a dominant aerosol light absorber, and its brown carbon (BrC) coating can enhance absorption and lead to uncertainties concerning the radiative forcing estimation. This study investigates the mass absorption cross-section of equivalent BC (MACeBC) during a long-term field measurement (2013-2017) at a rural Central European site. The MAC enhancement factor (Eabs) and the contribution of BrC coatings to the absorption coefficient (Babs) were estimated by combining different approaches. The annual mean Babs and MACeBC values decreased slightly over the measurement period associated with change in the submicron aerosol size distribution. Regardless of the wavelength, Babs exhibited clear seasonal and diurnal variations, with higher values in winter when a higher absorption Ångström exponent (1.4) was observed due to the local biomass burning (BB). In contrast, MACeBC did not have a distinct temporal trend at 600 nm (7.84 ± 2.79 m2 g-1), while it showed a seasonal trend at 370 nm with higher values in winter (15.64 ± 4.77 m2 g-1). During this season, Eabs_660 was 1.18 ± 0.27 and did not exhibit any clear wavelength dependence, despite the influence of BB. During the study period, BrC-attributed absorption was observed in 31% of the samples, with a contribution of up to 40% of total Babs. In summer, the Eabs_660 increased to 1.59 ± 0.60, when a larger BC coating could be formed by secondary aerosol fractions. During this season, MACeBC_660 and Eabs_660 showed comparable source profiles that were mainly associated with aged air masses over central Europe, thereby supporting the fact that characteristics of coating materials formed during atmospheric aging are a major factor driving the MACeBC_660 measured at the regional background site. Further field investigations of the composition of BC coatings would help to better understand and estimate uncertainties related to the radiative effect of aerosols.

Characterization of Equivalent Black Carbon at a regional background site in Central Europe: Variability and source apportionment☆.

Characterizing Black Carbon (BC) at regional background areas is important for better understanding its impact on climate forcing and health effects. The variability and sources of Equivalent Black Carbon (EBC) in PM10 (atmospheric particles with aerodynamic diameter smaller than 10 µm) have been investigated during a 5-year measurement period at the National Atmospheric Observatory Kosetice (NAOK), Czech Republic. Ground based measurements were performed from September 2012 to December 2017 with a 7-wavelength aethalometer (AE31, Magee Scientific). The contributions of fossil fuel (EBCff) and biomass burning (EBCbb) were estimated using the aethalometer model. Seasonal, diurnal and weekly variations of EBC were observed that can be related to the sources fluctuations and transport characteristic of pollutants predominantly associated with regional air masses recirculating over the Czech Republic and neighboring countries. The absorption Ångström exponent (α-value) estimated in summer (1.1 ± 0.2) was consistent with reported value for traffic, while the mean highest value (1.5 ± 0.2) was observed in winter due to increased EBCbb accounting for about 50% of the total EBC. This result is in agreement with the strong correlation between EBCbb and biomass burning tracers (levoglucosan and mannosan) in winter. During this season, the concentrations of EBCbb and Delta-C (proxy for biomass burning) reached a maximum in the evening when increasing emissions of wood burning in domestic heating devices (woodstoves/heating system) is expected, especially during the weekend. The diurnal profile of EBCff displays a typical morning peak during the morning traffic rush hour and shows a decreasing concentration during weekends due to lower the traffic emission.