Display omitted
•Pronounced seasonal variation in aerosol absorption in Athens over a 4-year period.•Significant BrC contribution (23.7%) to the total aerosol absorption at 370 nm.•Strong winter-time ...correlations between BrC and BB-related organic aerosols.•The BrCsec absorption is related to residential wood burning during winter nights.
This study analyses 4-years of continuous 7-λ Aethalometer (AE-33) measurements in an urban-background environment of Athens, to resolve the spectral absorption coefficients (babs) for black carbon (BC) and brown carbon (BrC). An important BrC contribution (23.7 ± 11.6%) to the total babs at 370 nm is estimated for the period May 2015–April 2019, characterized by a remarkable seasonality with winter maximum (33.5 ± 13.6%) and summer minimum (18.5 ± 8.1%), while at longer wavelengths the BrC contribution is significantly reduced (6.8 ± 3.6% at 660 nm). The wavelength dependence of the total babs gives an annual-mean AAE370-880 of 1.31, with higher values in winter night-time. The BrC absorption and its contribution to babs presents a large increase reaching up to 39.1 ± 13.6% during winter nights (370 nm), suggesting residential wood burning (RWB) emissions as a dominant source for BrC. This is supported by strong correlations of the BrC absorption with OC, EC, the fragment ion m/z 60 derived from ACSM and PMF-analyzed organic fractions related to biomass burning (e.g. BBOA). In contrast, BrC absorption decreases significantly during daytime as well as in the warm period, reaching to a minimum during the early-afternoon hours in all seasons due to photo-chemical degradation. Estimated secondary BrC absorption is practically evident only during winter night-time, implying the fast oxidation of BrC species from RWB emissions. Changes in mixing-layer height do not significantly affect the BrC absorption in winter, while they play a major role in summer.
This study examines the spectral properties and source characteristics of absorbing aerosols (BC: Black Carbon; BrC: Brown Carbon, based on aethalometer measurements) in the urban background of ...Athens during December 2016–February 2017. Using common assumptions regarding the spectral dependence of absorption due to BC (AAEBC = 1) and biomass burning (AAEbb = 2), and calculating an optimal AAEff value for the dataset (1.18), the total spectral absorption was decomposed into five components, corresponding to absorption of BC and BrC from fossil-fuel (ff) combustion and biomass burning (bb), and to secondary BrC estimated using the BC-tracer minimum R-squared (MRS) method. Substantial differences in the contribution of various components to the total absorption were found between day and night, due to differences in emissions and meteorological dynamics, while BrC and biomass burning aerosols presented higher contributions at shorter wavelengths. At 370 nm, the absorption due to BCff contributed 36.3% on average, exhibiting a higher fraction (58.1%) during daytime, while the mean BCbb absorption was estimated at 18.4%. The mean absorption contributions due to BrCff, BrCbb and BrCsec were 6.7%, 32.3% and 4.9%, respectively. The AbsBCff,370 component maximized during the morning traffic hours and was strongly correlated with NOx (R2 = 0.76) and CO (R2 = 0.77), while a similar behavior was seen for the AbsBrCff,370 component. AbsBCbb and AbsBrCbb levels escalated during nighttime and were highly associated with nss-K+ and with the organic aerosol (OA) components related to fresh and fast-oxidized biomass burning (BBOA and SV-OOA) as obtained from ACSM measurements. Multiple linear regression was used to attribute BrC absorption to five OA components and to determine their absorption contributions and efficiencies, revealing maximum contributions of BBOA (33%) and SV-OOA (21%). Sensitivity analysis was performed in view of the methodological uncertainties and supported the reliability of the results, which can have important implications for radiative transfer models.
Display omitted
•New approach to apportion BC - BrC absorption from biomass and fossil fuel burning•Combination of “Brown Carbon” and “Aethalometer” models in winter data in Athens•Biomass burning is the dominant nighttime BrC absorption source at 370–660 nm.•In daytime, traffic controls BC absorption and also affects near-UV BrC absorption.•Regressing BrC on ACSM PMF-resolved OA components provides their MAE and AAE values.
The aerosol chemical composition in air masses affected by wildfires from the Greek islands of Chios, Euboea and Andros, the Dalmatian Coast and Sicily, during late summer of 2012 was characterized ...at the remote background site of Finokalia, Crete. Air masses were transported several hundreds of kilometers, arriving at the measurement station after approximately half a day of transport, mostly during nighttime. The chemical composition of the particulate matter was studied by different high-temporal-resolution instruments, including an aerosol chemical speciation monitor (ACSM) and a seven-wavelength aethalometer. Despite the large distance from emission and long atmospheric processing, a clear biomass-burning organic aerosol (BBOA) profile containing characteristic markers is derived from BC (black carbon) measurements and positive matrix factorization (PMF) analysis of the ACSM organic mass spectra. The ratio of fresh to aged BBOA decreases with increasing atmospheric processing time and BBOA components appear to be converted to oxygenated organic aerosol (OOA). Given that the smoke was mainly transported overnight, it appears that the processing can take place in the dark. These results show that a significant fraction of the BBOA loses its characteristic AMS (aerosol mass spectrometry) signature and is transformed to OOA in less than a day. This implies that biomass burning can contribute almost half of the organic aerosol mass in the area during periods with significant fire influence.
Biomass burning is a major source of Brown Carbon (BrC), strongly contributing to radiative forcing. In urban areas of the climate-sensitive Southeastern European region, where strong emissions from ...residential wood burning (RWB) are reported, radiative impacts of carbonaceous aerosols remain largely unknown. This study examines the absorption properties of water- and methanol-soluble organic carbon (WSOC, MeS_OC) in a city (Ioannina, Greece) heavily impacted by RWB. Measurements were performed during winter (December 2019 – February 2020) and summer (July – August 2019) periods, characterized by RWB and photochemical processing of organic aerosol (OA), respectively. PM2.5 filter extracts were analyzed spectrophotometrically for water- and methanol-soluble BrC (WS_BrC, MeS_BrC) absorption. WSOC concentrations were quantified using TOC analysis, while those of MeS_OC were determined using a newly developed direct quantification protocol, applied for the first time to an extended series of ambient samples. The direct method led to a mean MeS_OC/OC of 0.68 and a more accurate subsequent estimation of absorption efficiencies. The mean winter WS_BrC and MeS_BrC absorptions at 365 nm were 13.9 Mm−1 and 21.9 Mm−1, respectively, suggesting an important fraction of water-insoluble OA. Mean winter WS_BrC and MeS_BrC absorptions were over 10 times those observed in summer. MeS_OC was more absorptive than WSOC in winter (mean mass absorption efficiencies – MAE365: 1.81 vs 1.15 m2 gC−1) and especially in summer (MAE: 1.12 vs 0.27 m2 gC−1) due to photo-dissociation and volatilization of BrC chromophores. The winter radiative forcing (RF) of WS_BrC and MeS_BrC relative to elemental carbon (EC) was estimated at 8.7 % and 16.7 %, respectively, in the 300–2500 nm band. However, those values increased to 48.5 % and 60.2 % at 300–400 nm, indicating that, under intense RWB, BrC forcing becomes comparable to that of soot. The results highlight the consideration of urban BrC emissions in radiative transfer models, as a considerable climate forcing factor.
Display omitted
•Water/methanol-soluble BrC absorptions under intense residential wood burning conditions•New protocol for measurement of methanol-soluble organic carbon provides reliable MAE.•Methanol-soluble BrC absorption 1.6 times higher than water-soluble BrC in winter•Wood burning linked to higher MAE and lower AAE for MeS_BrC compared to WS_BrC•Near-UV radiative forcing by BrC relative to EC of 48.5 % (WS_BrC) and 60.2 % (MeS_BrC)
During the last years the atmosphere of the Great Athens Area (GAA) and other Greek cities is burdened from extended residential biomass burning for heating purposes. In this work, a series of near ...real-time and off-line biomass burning tracers are analyzed during intense wood burning events in Athens. The measurements were conducted at an urban background site located in the center of Athens, and in the heart of wood burning activities (winter 2013–2014). The measured tracers include high resolution measurements of non-sea salt potassium (nss-K+), wood burning black carbon (BCwb), the m/z 60 fragment associated with levoglucosan and monosaccharide anhydrides (levoglucosan, mannosan and galactosan) determined on selected filter samples. The suitability of these tracers was evaluated when the prevailing meteorological conditions with low dispersion and deposition mechanisms (low wind speed, absence of precipitation) were associated with high biomass burning emissions at nighttime. During the severe smog periods, the levels of K+, BCwb, m/z 60 and levoglucosan were up to 2.2 μg m−3, 12.5 μg m−3, 3.4 μg m−3 and 8.6 μg m−3, respectively, higher by a factor of at least two, relatively to the non smog periods due to biomass burning. Correlations between biomass burning tracers as well as between monosaccharide anhydrides provided information about the type of material and wood being burned.
•High temporal resolution measurements were deployed during wintertime in Athens to track and identify a number of different biomass burning tracers.•Biomass burning tracers such as non sea salt potassium (nss-K+), black carbon (BCwb), the organic fraction m/z 60 and levoglucosan were monitored.•The enhanced levels of chloride (Cl−) could provide evidence of combustion of inappropriate materials being used as fuel.•Sodium (Na+) was also shown to be an alternative combustion tracer.•The significant correlation between PM2.5 and levoglucosan, indicated that wood burning could be responsible for PM2.5 higher than 45 μg m−3.
Air quality degradation events in the urban environment are often attributed to anthropogenic aerosol sources related to combustion of liquid or solid fuels in various activities. The effects of ...massive cooking emissions during Greek nationwide traditional festivities were investigated by a combined characterization of particulate matter (PM) levels and organic aerosol (OA) sources. Focus was centered on periods around two major festivities, namely “Fat Thursday” and Easter Sunday along six different years. OA sources were apportioned through Positive Matrix Factorization (PMF) on Aerosol Chemical Speciation Monitor (ACSM) mass spectra, while the spatial characteristics of the episodes were assessed through a low-cost, sensor-based PM2.5 monitoring network operating in Athens and other Greek cities. Contrasts were examined by considering a 15-day period around each event, while the effect of the 2020–2021 mobility restrictions, related to COVID-19, was also assessed. An episode-specific cooking organic aerosol (COA) spectral profile was delineated, and can be considered as a reference for ambient COA from meat grilling. Severe pollution episodes that affected the entire Athens basin were recorded, with PM2.5 concentrations exceeding 300 μg m−3 on occasions. COA contributions dominated primary organic aerosol (POA) and made up almost half of OA concentrations. During “Fat Thursday” COA concentrations and contributions peaked during night-time (23.2 μg m−3 and 46 %, respectively) while for Easter Sunday COA maxima were recorded in the early afternoon (27.4 μg m−3 and 39 %). Analyzing a full-year OA source dataset, revealed a pronounced recreational cooking pattern in central Athens, with COA concentrations rising towards the weekend, reflecting the impact of the food service sector. In view of the upcoming review of the EU air quality directive, foreseeing stricter annual PM2.5 limits as well as 24-h limit values and related alerts, the mitigation of cooking emissions appears as a potent instrument for achieving tangible air quality benefits.
Display omitted
•Severe air quality degradation documented during festivities involving meat grilling•During meat grilling events COA contributions to organic aerosol mass nearly doubled•Urban extent of cooking aerosols spatially expands during meat grilling events.•COA temporal variability under normal conditions follows a recreational pattern.•Meat charbroiling ambient COA spectrum extracted from extended “Fat Thursday” measurements
While cloud condensation nuclei (CCN) production associated with atmospheric new particle formation (NPF) is thought to be frequent throughout the continental boundary layers, few studies on this ...phenomenon in marine air exist. Here, based on simultaneous measurement of particle number size distributions, CCN properties and aerosol chemical composition, we present the first direct evidence on CCN production resulting from NPF in the eastern Mediterranean atmosphere. We show that condensation of both gaseous sulfuric acid and organic compounds from multiple sources leads to the rapid growth of nucleated particles to CCN sizes in this environment during the summertime. Sub-100 nm particles were found to be substantially less hygroscopic than larger particles during the period with active NPF and growth (the value of κ was lower by 0.2–0.4 for 60 nm particles compared with 120 nm particles), probably due to enrichment of organic material in the sub-100 nm size range. The aerosol hygroscopicity tended to be at minimum just before the noon and at maximum in the afternoon, which was very likely due to the higher sulfate-to-organic ratios and higher degree of oxidation of the organic material during the afternoon. Simultaneous with the formation of new particles during daytime, particles formed during the previous day or even earlier were growing into the size range relevant to cloud droplet activation, and the particles formed in the atmosphere were possibly mixed with long-range-transported particles.
Measurements of atmospheric ions in the size range 0.8-42 nm were conducted at the environmental research station of the University of Crete at Finokalia from April 2008 to April 2009 in the frame of ...the EUCAARI project. Both positive and negative atmospheric ions were found to have a clear annual cycle, with minimum concentrations in summer. Their concentrations were found to vary with the prevailing meteorology and the abundance of aerosol particles in the atmosphere. High concentrations of ions were observed during new particle formation events. There were 53 nucleation events recorded. It was found that under certain atmospheric conditions enhanced ion concentrations can be observed during night. Overall, 39 night-time events were observed, all of them observed for the negatively charged particles while only 21 were observed for the positively charged particles. Night-time enhanced ion concentrations were more frequent during spring and autumn and no such events were recorded from July to September. A strong anti-correlation was found between air ion concentrations, especially at cluster sizes (1.25-1.66 nm), and condensation and coagulation sinks. Enhanced ion concentrations at night were found to be more frequent when air masses had traveled over the island of Crete, indicating possible association with local biogenic sources.
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.
•Long term on line submicron aerosol chemical speciation measurements performed at 21 European sites were analysed.•Seasonal and diel variations in the aerosol chemical composition can generally be observed.•Most submicron aerosol mass consists of organics.•Nitrate contribution increases with the aerosol mass concentration at most sites.
Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact ...cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10–15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m−3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 µg m−3; thus, organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening, and nighttime hours.The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air mass origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.
PDF
