Aerosol black carbon is a unique primary tracer for combustion emissions. It affects the optical properties of the atmosphere and is recognized as the second most important anthropogenic forcing ...agent for climate change. It is the primary tracer for adverse health effects caused by air pollution. For the accurate determination of mass equivalent black carbon concentrations in the air and for source apportionment of the concentrations, optical measurements by filter-based absorption photometers must take into account the "filter loading effect". We present a new real-time loading effect compensation algorithm based on a two parallel spot measurement of optical absorption. This algorithm has been incorporated into the new Aethalometer model AE33. Intercomparison studies show excellent reproducibility of the AE33 measurements and very good agreement with post-processed data obtained using earlier Aethalometer models and other filter-based absorption photometers. The real-time loading effect compensation algorithm provides the high-quality data necessary for real-time source apportionment and for determination of the temporal variation of the compensation parameter k.
Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. ...The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main parameters controlling their temporal variations (sources, meteorological parameters). Finally, a careful investigation of all the major pollution episodes observed over the region of Paris between 2011 and 2013 was performed and classified in terms of chemical composition and the BC-to-sulfate ratio used here as a proxy of the local/regional/advected contribution of PM. In conclusion, these first 2-year quality-controlled measurements of ACSM clearly demonstrate their great potential to monitor on a long-term basis aerosol sources and their geographical origin and provide strategic information in near real time during pollution episodes. They also support the capacity of the ACSM to be proposed as a robust and credible alternative to filter-based sampling techniques for long-term monitoring strategies.
Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic ...acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21–37 Tg yr−1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2–0.3 Tg, i.e. 0.05–0.1 Tg-C that is about 5–9 % of model-calculated water soluble organic carbon burden.
Aerosol absorption properties are of high importance to assess aerosol impact on regional climate. This study presents an analysis of aerosol absorption products obtained over the Mediterranean basin ...or land stations in the region from multi-year ground-based AERONET observations with a focus on the Absorbing Aerosol Optical Depth (AAOD), Single Scattering Albedo (SSA) and their spectral dependence. The AAOD and Absorption Angström Exponent (AAE) dataset is composed of daily averaged AERONET level 2 data from a total of 22 Mediterranean stations having long time series, mainly under the influence of urban-industrial aerosols and/or soil dust. This dataset covers the 17-yr period 1996–2012 with most data being from 2003–2011 (~89% of level-2 AAOD data). Since AERONET level-2 absorption products require a high aerosol load (AOD at 440 nm > 0.4), which is most often related to the presence of desert dust, we also consider level-1.5 SSA data, despite their higher uncertainty, and filter out data with an Angström exponent < 1.0 in order to study absorption by carbonaceous aerosols. The SSA dataset includes AERONET level-2 products. Sun-photometer observations show that values of AAOD at 440 nm vary between 0.024 ± 0.01 (resp. 0.040 ± 0.01) and 0.050 ± 0.01 (0.055 ± 0.01) for urban (dusty) sites. Analysis shows that the Mediterranean urban-industrial aerosols appear "moderately" absorbing with values of SSA close to ~0.94–0.95 ± 0.04 (at 440 nm) in most cases except over the large cities of Rome and Athens, where aerosol appears more absorbing (SSA ~0.89–0.90 ± 0.04). The aerosol Absorption Angström Exponent (AAE, estimated using 440 and 870 nm) is found to be larger than 1 for most sites over the Mediterranean, a manifestation of mineral dust (iron) and/or brown carbon producing the observed absorption. AERONET level-2 sun-photometer data indicate a possible East-West gradient, with higher values over the eastern basin (AAEEast = 1.39/AAEWest = 1.33). The North-South AAE gradient is more pronounced, especially over the western basin. Our additional analysis of AERONET level-1.5 data also shows that organic absorbing aerosols significantly affect some Mediterranean sites. These results indicate that current climate models treating organics as nonabsorbing over the Mediterranean certainly underestimate the warming effect due to carbonaceous aerosols.
Observations of key gaseous trace pollutants, namely NO, NOy, CO, SO2 and O3, performed at several curb, residential, industrial, background and free-troposphere sites were analyzed to assess the ...temporal and spatial variability of pollution in Cyprus. Notably, the analysis utilized one of the longest datasets of 17 years of measurements (2003–2019) in the East Mediterranean and the Middle East (EMME). This region is considered a regional hotspot of ozone and aerosol pollution.
A trend analysis revealed that at several stations, a statistically significant decrease in primary pollutant concentration is recorded, most likely due to pollution control strategies. In contrast, at four stations, a statistically significant increase in ozone levels, ranging between 0.36 ppbv y−1 and 0.82 ppbv y−1, has been observed, attributed to the above strategies targeting the reduction of nitrogen oxides (NOx) but not that of Volatile Organic Compounds (VOCs).
The NO and NOy, and CO levels at the Agia Marina regional background station were two orders of magnitude and four times lower, respectively, than the ones of the urban centers. The latter denotes that local emissions are not negligible and control a large fraction of the observed interannual and diurnal variability. Speciation analysis showed that traffic and other local emissions are the sources of urban NO and NOy. At the same time, 46 % of SO2 and 40 % of CO, on average, originate from long-range regional transport.
Lastly, a one-year analysis of tropospheric NO2 vertical columns from the TROPOMI satellite instrument revealed a west-east low-to-high gradient over the island, with all major hotspots, including cities and powerplants, being visible from space. With the help of an unsupervised machine learning approach, it was found that these specific hotspots contribute overall around 10 % to the total NO2 tropospheric columns.
Local vs. Regional pollution at the urban centers in Cyprus: Decreasing trends of trace pollutants NO, NOz, CO and SO2 are observed for the years considered in this study (2003–2019) at the major urban centers of Cyprus, possibly associated with pollution mitigation strategies. In contrast, ozone has either remained constant or increased in those VOC-limited urban regimes. The largest fraction of NO and NOz in these cities emanates from local traffic and/or background urban sources (top panel, grey bars) while, at the same time, a large fraction of the observed SO2 and CO of around 40 % and 45 %, respectively, is regional (blue bars). Notably, the rural background station Agia Marina located at the center of the island encounters elevated ozone levels in summer despite the low measured abundance in precursor species suggesting that, over the island, and in the broader Eastern Mediterranean region, ozone is regionally produced and transported.
Cyprus, a view from space: Analysis of NO2 vertical columns from the TROPOMI S5P instrument revealed a west-east low-to-high gradient over the island (bottom panel), with all major hotspots, including cities and powerplants, being visible from space. It was found that these local hotspots contribute overall only around 10 % to the total NO2 tropospheric columns in Cyprus, highlighting the importance of the role of other local sources and regional pollution in the area. Display omitted
•A decreasing trend for all gas pollutants, except ozone, is revealed.•A statistically significant increase in ozone levels is observed in urban stations.•A large fraction of the ambient SO2 and CO in urban centers is of regional origin.•NO2 pollution from powerplants is not proportional to their operating capacity.•Cities and powerplants contribute 10 % to the total tropospheric NO2 VCDs in Cyprus.
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.
Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget ...and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.
An Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed to investigate the size-resolved chemical composition of single particles at an urban background site in Paris, France, as part of ...the MEGAPOLI winter campaign in January/February 2010. ATOFMS particle counts were scaled to match coincident Twin Differential Mobility Particle Sizer (TDMPS) data in order to generate hourly size-resolved mass concentrations for the single particle classes observed. The total scaled ATOFMS particle mass concentration in the size range 150–1067 nm was found to agree very well with the sum of concurrent High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and Multi-Angle Absorption Photometer (MAAP) mass concentration measurements of organic carbon (OC), inorganic ions and black carbon (BC) (R2 = 0.91). Clustering analysis of the ATOFMS single particle mass spectra allowed the separation of elemental carbon (EC) particles into four classes: (i) EC attributed to biomass burning (ECbiomass), (ii) EC attributed to traffic (ECtraffic), (iii) EC internally mixed with OC and ammonium sulfate (ECOCSOx), and (iv) EC internally mixed with OC and ammonium nitrate (ECOCNOx). Average hourly mass concentrations for EC-containing particles detected by the ATOFMS were found to agree reasonably well with semi-continuous quantitative thermal/optical EC and optical BC measurements (r2 = 0.61 and 0.65–0.68 respectively, n = 552). The EC particle mass assigned to fossil fuel and biomass burning sources also agreed reasonably well with BC mass fractions assigned to the same sources using seven-wavelength aethalometer data (r2 = 0.60 and 0.48, respectively, n = 568). Agreement between the ATOFMS and other instrumentation improved noticeably when a period influenced by significantly aged, internally mixed EC particles was removed from the intercomparison. 88% and 12% of EC particle mass was apportioned to fossil fuel and biomass burning respectively using the ATOFMS data compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNOx particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM) "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies.
Online non-refractory submicron aerosol mass spectrometer (AMS) measurements in urban areas have successfully allowed the apportionment of specific sources and/or physical and chemical properties of ...the organic fraction. However, in order to be fully representative of PM pollution, a comprehensive source apportionment analysis is needed by taking into account all major components of submicron aerosols, creating strengthened bonds between the organic components and pollution sources. We present here a novel two-step methodology to perform such an analysis, by taking advantage of high time resolution of monitoring instruments: the aerosol chemical speciation monitor (ACSM) and the multi-wavelength absorption measurements (Aethalometer AE31) in Paris, France. As a first step, organic aerosols (OA) were deconvolved to hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and oxygenated OA (OOA) with positive matrix factorization (PMF), and black carbon was deconvolved into its wood burning and fossil fuel combustion fractions. A second PMF analysis was then carried out with organic factors, BC fractions and inorganic species (nitrate, sulfate, ammonium, chloride), leading to a four-factor solution allowing highly time-resolved characterization of the major sources of PM1. Outputs of this PMF2 include two dominant combustion sources (wood burning and traffic) as well as semi-volatile and low-volatile secondary aerosols. While HOA is found to be emitted by both wood burning and traffic, the latter sources occurred to significantly contribute also to OOA.
Gaining knowledge on the process of particle resuspension from urban paved roads is of particular importance considering the increasing relevance of this source in urban air quality management and ...the lack of basic information on emission factors and source contributions. In this study we performed extensive field measurements for the quantification of the emission factors from different types of road in the city of Paris, and investigated the causes of their variability and the contributions to the ambient air PM10 observed across one year at one traffic monitoring site in the ring road of Paris. Results show agreement between lower road dust loadings (RD10: 0.7–2.2 mg m−2) and emission factors (5.4–9.0 mg vehicle−1 km−1) at inner-roads of Paris, compared to the ring road (2.4 mg m−2 and 17 mg vehicle−1 km−1, respectively), where the two parameters are estimated independently. The higher values in the ring road were likely caused by the poor state of pavement and higher share of heavy duty vehicles. Road wear, brake wear and a carbonaceous source, were almost equally responsible for 96% of RD10. At the traffic monitoring site located at the ring road (220,000 vehicle/day), the contributions of road dust emissions were estimated by receptor modeling to be 13% of PM10 on an annual mean (6.3 μg m−3), while the sum of vehicle exhaust and wear accounted for 47% resulting in a total traffic contribution of 60% of PM10. Road salting resulted to be a minor contributor (1% of annual mean) also in winter time (2%).
•Road dust loadings in Paris varied within 0.7–2.4 mg m−2, sources were investigated.•Emission factors for road dust were estimated at 5.4–17.0 mg vehicle−1 km−1.•Higher emission factors were found at the ring road, rather than inner roads.•At the ring road monitoring site, road dust contributed 13% of PM10 on an annual basis.•Road salt is a minor contributor to kerbside PM10.
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