Seasonal study of stable carbon and nitrogen isotopic composition in fine aerosols at a Central European rural background station

A study of the stable carbon isotope ratios (δ13C) of total carbon (TC) and the nitrogen isotope ratios (δ15N) of total nitrogen (TN) was carried out for fine aerosol particles (PM1) and was undertaken every 2 days with a 24&thinsp;h sampling period at a rural background site in Košetice (Central Europe) from 27 September 2013 to 9 August 2014 (n=146). We found a seasonal pattern for both δ13C and δ15N. The seasonal variation in δ15N was characterized by lower values (average of 13.1±4.5&thinsp;‰) in winter and higher values (25.0±1.6&thinsp;‰) in summer. Autumn and spring were transition periods when the isotopic composition gradually changed due to the changing sources and ambient temperature. The seasonal variation in δ13C was less pronounced but more depleted in 13C in summer (-27.8±0.4&thinsp;‰) as compared to winter (-26.7±0.5&thinsp;‰). A comparative analysis with water-soluble ions, organic carbon, elemental carbon, trace gases and meteorological parameters (mainly ambient temperature) has shown major associations with the isotopic compositions, which has provided greater knowledge and understanding of the corresponding processes. A comparison of δ15N with NO3-, NH4+ and organic nitrogen (OrgN) revealed that although a higher content of NO3- was associated with a decrease in the δ15N of TN, NH4+ and OrgN caused increases. The highest concentrations of nitrate, mainly represented by NH4NO3 related to the emissions from biomass burning leading to an average δ15N of TN (13.3&thinsp;‰) in winter. During spring, the percentage of NO3- in PM1 decreased. An enrichment of 15N was probably driven by the equilibrium exchange between the gas and aerosol phases (NH3(g)&thinsp;↔&thinsp;NH4+(p)), which is supported by the increased ambient temperature. This equilibrium was suppressed in early summer when the molar ratios of NH4+/SO42- reached 2, and the nitrate partitioning in aerosol was negligible due to the increased ambient temperature. Summertime δ15N values were among the highest, suggesting the aging of ammonium sulfate and OrgN aerosols. Such aged aerosols can be coated by organics in which 13C enrichment takes place by the photooxidation process. This result was supported by a positive correlation of δ13C with ambient temperature and ozone, as observed in the summer season. During winter, we observed an event with the lowest δ15N and highest δ13C values. The winter event occurred in prevailing southeast air masses. Although the higher δ13C values probably originated from biomass-burning particles, the lowest δ15N values were probably associated with agriculture emissions of NH3 under low-temperature conditions (&lt;&thinsp;0&thinsp;∘C).</p

Recommendations for reporting equivalent black carbon (eBC) mass concentrations based on long-term pan-European in-situ observations

A reliable determination of equivalent black carbon (eBC) mass concentrations derived from filter absorption photometers (FAPs) measurements depends on the appropriate quantification of the mass absorption cross-section (MAC) for converting the absorption coefficient (babs) to eBC. This study investigates the spatial–temporal variability of the MAC obtained from simultaneous elemental carbon (EC) and babs measurements performed at 22 sites. We compared different methodologies for retrieving eBC integrating different options for calculating MAC including: locally derived, median value calculated from 22 sites, and site-specific rolling MAC. The eBC concentrations that underwent correction using these methods were identified as LeBC (local MAC), MeBC (median MAC), and ReBC (Rolling MAC) respectively. Pronounced differences (up to more than 50 %) were observed between eBC as directly provided by FAPs (NeBC; Nominal instrumental MAC) and ReBC due to the differences observed between the experimental and nominal MAC values. The median MAC was 7.8 ± 3.4 m2 g-1 from 12 aethalometers at 880 nm, and 10.6 ± 4.7 m2 g-1 from 10 MAAPs at 637 nm. The experimental MAC showed significant site and seasonal dependencies, with heterogeneous patterns between summer and winter in different regions. In addition, long-term trend analysis revealed statistically significant (s.s.) decreasing trends in EC. Interestingly, we showed that the corresponding corrected eBC trends are not independent of the way eBC is calculated due to the variability of MAC. NeBC and EC decreasing trends were consistent at sites with no significant trend in experimental MAC. Conversely, where MAC showed s.s. trend, the NeBC and EC trends were not consistent while ReBC concentration followed the same pattern as EC. These results underscore the importance of accounting for MAC variations when deriving eBC measurements from FAPs and emphasize the necessity of incorporating EC observations to constrain the uncertainty associated with eBC.</p

A European aerosol phenomenology - 7: High-time resolution chemical characteristics of submicron particulate matter across Europe

Similarities and differences in the submicron atmospheric aerosol chemical composition are analyzed from a unique set of measurements performed at 21 sites across Europe for at least one year. These sites are located between 35 and 62°N and 10° W – 26°E, and represent various types of settings (remote, coastal, rural, industrial, urban). Measurements were all carried out on-line with a 30-min time resolution using mass spectroscopy based instruments known as Aerosol Chemical Speciation Monitors (ACSM) and Aerosol Mass Spectrometers (AMS) and following common measurement guidelines. Data regarding organics, sulfate, nitrate and ammonium concentrations, as well as the sum of them called non-refractory submicron aerosol mass concentration ([NR-PM1]) are discussed. NR-PM1 concentrations generally increase from remote to urban sites. They are mostly larger in the mid-latitude band than in southern and northern Europe. On average, organics account for the major part (36–64%) of NR-PM1 followed by sulfate (12–44%) and nitrate (6–35%). The annual mean chemical composition of NR-PM1 at rural (or regional background) sites and urban background sites are very similar. Considering rural and regional background sites only, nitrate contribution is higher and sulfate contribution is lower in mid-latitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (μg/m³) of one or more components of NR-PM1 can be observed at all sites, as well as in the chemical composition of NR-PM1 (%) at most sites. Significant diel cycles in the contribution to [NR-PM1] of organics, sulfate, and nitrate can be observed at a majority of sites both in winter and summer. Early morning minima in organics in concomitance with maxima in nitrate are common features at regional and urban background sites. Daily variations are much smaller at a number of coastal and rural sites. Looking at NR-PM1 chemical composition as a function of NR-PM1 mass concentration reveals that although organics account for the major fraction of NR-PM1 at all concentration levels at most sites, nitrate contribution generally increases with NR-PM1 mass concentration and predominates when NR-PM1 mass concentrations exceed 40 μg/m³ at half of the sites. © 2021 The Author

A European aerosol phenomenology - 7 : High-time resolution chemical characteristics of submicron particulate matter across Europe

Similarities and differences in the submicron atmospheric aerosol chemical composition are analyzed from a unique set of measurements performed at 21 sites across Europe for at least one year. These sites are located between 35 and 62 degrees N and 10 degrees W - 26 degrees E, and represent various types of settings (remote, coastal, rural, industrial, urban). Measurements were all carried out on-line with a 30-min time resolution using mass spectroscopy based instruments known as Aerosol Chemical Speciation Monitors (ACSM) and Aerosol Mass Spectrometers (AMS) and following common measurement guidelines. Data regarding organics, sulfate, nitrate and ammonium concentrations, as well as the sum of them called non-refractory submicron aerosol mass concentration ([NR-PM1]) are discussed. NR-PM1 concentrations generally increase from remote to urban sites. They are mostly larger in the mid-latitude band than in southern and northern Europe. On average, organics account for the major part (36-64%) of NR-PM1 followed by sulfate (12-44%) and nitrate (6-35%). The annual mean chemical composition of NR-PM1 at rural (or regional background) sites and urban background sites are very similar. Considering rural and regional background sites only, nitrate contribution is higher and sulfate contribution is lower in midlatitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (mu g/m(3)) of one or more components of NR-PM1 can be observed at all sites, as well as in the chemical composition of NR-PM1 (%) at most sites. Significant diel cycles in the contribution to [NR-PM1] of organics, sulfate, and nitrate can be observed at a majority of sites both in winter and summer. Early morning minima in organics in concomitance with maxima in nitrate are common features at regional and urban background sites. Daily variations are much smaller at a number of coastal and rural sites. Looking at NR-PM1 chemical composition as a function of NR-PM1 mass concentration reveals that although organics account for the major fraction of NR-PM1 at all concentration levels at most sites, nitrate contribution generally increases with NR-PM1 mass concentration and predominates when NR-PM1 mass concentrations exceed 40 mu g/m(3) at half of the sites.Peer reviewe

A European aerosol phenomenology - 7: High-time resolution chemical characteristics of submicron particulate matter across Europe

Similarities and differences in the submicron atmospheric aerosol chemical composition are analyzed from a unique set of measurements performed at 21 sites across Europe for at least one year. These sites are located between 35 and 62°N and 10° W – 26°E, and represent various types of settings (remote, coastal, rural, industrial, urban). Measurements were all carried out on-line with a 30-min time resolution using mass spectroscopy based instruments known as Aerosol Chemical Speciation Monitors (ACSM) and Aerosol Mass Spectrometers (AMS) and following common measurement guidelines. Data regarding organics, sulfate, nitrate and ammonium concentrations, as well as the sum of them called non-refractory submicron aerosol mass concentration ([NR-PM1]) are discussed. NR-PM1 concentrations generally increase from remote to urban sites. They are mostly larger in the mid-latitude band than in southern and northern Europe. On average, organics account for the major part (36–64%) of NR-PM1 followed by sulfate (12–44%) and nitrate (6–35%). The annual mean chemical composition of NR-PM1 at rural (or regional background) sites and urban background sites are very similar. Considering rural and regional background sites only, nitrate contribution is higher and sulfate contribution is lower in mid-latitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (μg/m³) of one or more components of NR-PM1 can be observed at all sites, as well as in the chemical composition of NR-PM1 (%) at most sites. Significant diel cycles in the contribution to [NR-PM1] of organics, sulfate, and nitrate can be observed at a majority of sites both in winter and summer. Early morning minima in organics in concomitance with maxima in nitrate are common features at regional and urban background sites. Daily variations are much smaller at a number of coastal and rural sites. Looking at NR-PM1 chemical composition as a function of NR-PM1 mass concentration reveals that although organics account for the major fraction of NR-PM1 at all concentration levels at most sites, nitrate contribution generally increases with NR-PM1 mass concentration and predominates when NR-PM1 mass concentrations exceed 40 μg/m³ at half of the sites

Comparing the conventional displacement BIE and the BIE formulations of the first andconceptual interaction in indirect directive second kind in frictionless contact problems

There are several formulations of boundary integral equations (BIEs) used in the general numerical procedure known as boundary element method (BEM). There are also several approaches to deal with contact problems using BEM. In this paper, a comparison between the following procedures: the conventional discretization of the displacement BIE by collocations, the Galerkin discretizations of the symmetric BIE formulation of the first kind and the non-symmetric BIE formulation of the second kind, is performed. Although several aspects of these procedures are discussed, the emphasis is put on the accuracy of the results obtained with identical meshes. The comparison is carried out including problems with analytical solutions or in the presence of singularities, covering conforming, advancing and receding contact problems. Linear elements, conforming discretizations of surfaces in contact and absence of friction define the frame where the study is performed. © 2002 Elsevier Science Ltd. All rights reserved