A new method to retrieve the real part of the equivalent refractive index of atmospheric aerosols

This document is the Accepted Manuscript version of the following article: S. Vratolis, et al, ‘A new method to retrieve the real part of the equivalent refractive index of atmospheric aerosols’, Journal of Aerosol Science, Vol. 117: 54-62, March 2018. Under embargo until 29 December 2019. The final, published version is available online at DOI: https://doi.org/10.1016/j.jaerosci.2017.12.013.In the context of the international experimental campaign Hygroscopic Aerosols to Cloud Droplets (HygrA-CD, 15 May to 22 June 2014), dry aerosol size distributions were measured at Demokritos station (DEM) using a Scanning Mobility Particle Sizer (SMPS) in the size range from 10 to 550 nm (electrical mobility diameter), and an Optical Particle Counter (OPC model Grimm 107 operating at the laser wavelength of 660 nm) to acquire the particle size distribution in the size range of 250 nm to 2.5 μm optical diameter. This work describes a method that was developed to align size distributions in the overlapping range of the SMPS and the OPC, thus allowing us to retrieve the real part of the aerosol equivalent refractive index (ERI). The objective is to show that size distribution data acquired at in situ measurement stations can provide an insight to the physical and chemical properties of aerosol particles, leading to better understanding of aerosol impact on human health and earth radiative balance. The resulting ERI could be used in radiative transfer models to assess aerosol forcing direct effect, as well as an index of aerosol chemical composition. To validate the method, a series of calibration experiments were performed using compounds with known refractive index (RI). This led to a corrected version of the ERI values, (ERICOR). The ERICOR values were subsequently compared to model estimates of RI values, based on measured PM2.5 chemical composition, and to aerosol RI retrieved values by inverted lidar measurements on selected days.Peer reviewe

Quantitative assessment of the variability in chemical profiles from source apportionment analysis of PM10 and PM2.5 at different sites within a large metropolitan area

The study aims to assess the differences between the chemical profiles of the major anthropogenic and natural PM sources in two areas with different levels of urbanization and traffic density within the same urban agglomeration. A traffic site and an urban background site in the Athens Metropolitan Area have been selected for this comparison. For both sites, eight sources were identified, with seven of them being common for the two sites (Mineral Dust, non-Exhaust Emissions, Exhaust Emissions, Heavy Oil Combustion, Sulfates & Organics, Sea Salt and Biomass Burning) and one, site-specific (Nitrates for the traffic site and Aged Sea Salt for the urban background site). The similarity between the source profiles was quantified using two statistical analysis tools, Pearson correlation (PC) and Standardized Identity Distance (SID). According to Pearson coefficients five out of the eight source profiles present high (PC > 0.8) correlation (Mineral Dust, Biomass Burning, Sea Salt, Sulfates and Heavy Oil Combustion), one presented moderate (0.8 > PC > 0.6) correlation (Exhaust) and two low/no (PC < 0.6) correlation (non-Exhaust, Nitrates/Aged Sea Salt). The source profiles that appear to be more correlated are those of sources that are not expected to have high spatial variability because there are either natural/secondary and thus have a regional character or are emitted outside the urban agglomeration and are transported to both sites. According to SID four out of the eight sources have high statistical correlation (SID < 1) in the two sites (Mineral Dust, Sea salt, Sulfates, Heavy Oil Combustion). Biomass Burning was found to be the source that yielded different results from the two methodologies. The careful examination of the source profile of that source revealed the reason for this discrepancy. SID takes all the species of the profile equally into account, while PC might be disproportionally affected by a few numbers of species with very high concentrations. It is suggested, based on the findings of this work, that the combined use of both tools can lead the users to a thorough evaluation of the similarity of source profiles. This work is, to the best of our knowledge, the first time a study is focused on the quantitative comparison of the source profiles for sites inside the same urban agglomeration using statistical indicators.The study was supported by “CALIBRA/EYIE” (MIS 5002799) and “PANhellenic infrastructure for Atmospheric Composition and climatE change” (MIS 5021516) implemented under the Action “Reinforcement of the Research and Innovation Infrastructure”, funded by the Operational Programme “Competitiveness, Entrepreneurship and Innovation” (NSRF 2014–2020) and co-financed by Greece and the European Union (European Regional Development Fund). Collection and chemical analysis of samples were supported by LIFE + AIRUSE EU project (ENV/ES/584). Partial support was also received by H2020 ERAPLANET/SMURBS ERANET GA No 689443.Peer reviewe

Combined organic and inorganic source apportionment on yearlong ToF-ACSM dataset at a suburban station in Athens

The current improvements in aerosol mass spectrometers in resolution and sensitivity, and the analytical tools for mass spectra deconvolution, have enabled the in-depth analysis of ambient organic aerosol (OA) properties. Although OA constitutes a major fraction of ambient aerosol, its properties are determined to a great extent by the mixing characteristics of both organic and inorganic components of ambient aerosol. This work applies a new methodology to a year-long ACSM dataset to assess the sources of organic and total non-refractory species in the Athens background aerosol and provides insights into the interactions between organic and inorganic species. The use of innovative tools for applying positive matrix factorization (PMF, rolling window) enables the study of the temporal variability of the contribution of these sources and seasonal changes in their composition. The mass spectra of both organic and inorganic aerosol were obtained by a time-of-flight aerosol mass spectrometer (ToF-ACSM) for PMF analysis. The results revealed five factors when organic aerosol was analysed separately. Three of them were primary OA factors: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA) and biomass burning organic aerosol (BBOA). The remaining two were secondary, less and more oxidized oxygenated organic aerosol (LO-OOA and MO-OOA respectively). The relative contributions of these factors were HOA 15 %, COA 18 %, BBOA 9 %, MO-OOA 34 % and LO-OOA 24 % (yearly averaged). When a combined organic and inorganic aerosol matrix was analysed, two additional factors were identified that were mainly composed of ammonium sulfate (83.5 %) and ammonium nitrate (73 %). Moreover, two secondary factors were resolved, containing both organics and inorganics and were named more (MOA) and less oxidized aerosol (LOA). The relative contributions on a yearly average of these factors were HOA 7 %, COA 9 %, BBOA 3 %, ammonium nitrate 3 %, ammonium sulfate 28 %, MOA 24 % and LOA 26 %

A new method for the quantification of ambient particulate-matter emission fluxes

An inversion method has been developed in order to quantify the emission fluxes of certain aerosol pollution sources across a wide region in the Northern Hemisphere, mainly in Europe and western Asia. The data employed are the aerosol contribution factors deducted by positive matrix factorization (PMF) on a PM2.5 chemical composition dataset from 16 European and Asian cities for the period 2014 to 2016. The spatial resolution of the method corresponds to the geographic grid cell size of the Lagrangian particle dispersion model (Flexible Particle Dispersion Model, FLEXPART, 1∘ × 1∘) which was utilized for the air mass backward simulations. The area covered is also related to the location of the 16 cities under study. Species with an aerodynamic geometric mean diameter of 400 nm and 3.1 µm and a geometric standard deviation of 1.6 and 2.25, respectively, were used to model the secondary sulfate and dust aerosol transport. Potential source contribution function (PSCF) analysis and generalized Tikhonov regularization were applied so as to acquire potential source areas and quantify their emission fluxes. A significant source area for secondary sulfate on the east of the Caspian Sea is indicated, when data from all stations are used. The maximum emission flux in that area is as high as 10 × 10−12 kg m−2 s−1. When Vilnius, Dushanbe, and Kurchatov data were excluded, the areas with the highest emission fluxes were the western and central Balkans and southern Poland. The results display many similarities to the SO2 emission maps provided by the OMI-HTAP (Ozone Monitoring Instrument-Hemispheric Transport Air Pollution) and ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants) databases. For dust aerosol, measurements from Athens, Belgrade, Debrecen, Lisbon, Tirana, and Zagreb are utilized. The west Sahara region is indicated as the most important source area, and its contribution is quantified, with a maximum of 17.6 × 10−12 kg m−2 s−1. When we apply the emission fluxes from every geographic grid cell (1∘ × 1∘) for secondary sulfate aerosol deducted with the new method to air masses originating from Vilnius, a useful approximation to the measured values is achieved.</p

ECOC comparison exercise with identical thermal protocols after temperature offset correction - Instrument diagnostics by in-depth evaluation of operational parameters

© Author(s) 2015. A comparison exercise on thermal-optical elemental carbon/organic carbon (ECOC) analysers was carried out among 17 European laboratories. Contrary to previous comparison exercises, the 17 participants made use of an identical instrument set-up, after correcting for temperature offsets with the application of a recently developed temperature calibration kit (Sunset Laboratory Inc, OR, US). Temperature offsets reported by participants ranged from -93 to +100 °C per temperature step. Five filter samples and two sucrose solutions were analysed with both the EUSAAR2 and NIOSH870 thermal protocols. z scores were calculated for total carbon (TC); nine outliers and three stragglers were identified. Three outliers and eight stragglers were found for EC. Overall, the participants provided results between the warning levels with the exception of two laboratories that showed poor performance, the causes of which were identified and corrected through the course of the comparison exercise. The TC repeatability and reproducibility (expressed as relative standard deviations) were 11 and 15% for EUSAAR2 and 9.2 and 12% for NIOSH870; the standard deviations for EC were 15 and 20% for EUSAAR2 and 20 and 26% for NIOSH870. TC was in good agreement between the two protocols, TCNIOSH870 =0.98 × TCEUSAAR2 (R2 = 1.00, robust means). Transmittance (TOT) calculated EC for NIOSH870 was found to be 20% lower than for EUSAAR2, ECNIOSH870 = 0.80 × ECEUSAAR2 (R2 = 0.96, robust means). The thermograms and laser signal values were compared and similar peak patterns were observed per sample and protocol for most participants. Notable deviations from the typical patterns indicated either the absence or inaccurate application of the temperature calibration procedure and/or pre-oxidation during the inert phase of the analysis. Low or zero pyrolytic organic carbon (POC), as reported by a few participants, is suggested as an indicator of an instrument-specific pre-oxidation. A sample-specific pre-oxidation effect was observed for filter G, for all participants and both thermal protocols, indicating the presence of oxygen donors on the suspended particulate matter. POC (TOT) levels were lower for NIOSH870 than for EUSAAR2, which is related to the heating profile differences of the two thermal protocols

Soot reference materials for instrument calibration and intercomparisons: A workshop summary with recommendations

Soot, which is produced from biomass burning and the incomplete combustion of fossil and biomass fuels, has been linked to regional and global climate change and to negative health problems. Scientists measure the properties of soot using a variety of methods in order to quantify source emissions and understand its atmospheric chemistry, reactivity under emission conditions, interaction with solar radiation, influence on clouds, and health impacts. A major obstacle currently limiting progress is the absence of established standards or reference materials for calibrating the many instruments used to measure the various properties of soot. The current state of availability and practicability of soot standard reference materials (SRMs) was reviewed by a group of 50 international experts during a workshop in June of 2011. The workshop was convened to summarize the current knowledge on soot measurement techniques, identify the measurement uncertainties and limitations related to the lack of soot SRMs, and identify attributes of SRMs that, if developed, would reduce measurement uncertainties. The workshop established that suitable SRMs are available for calibrating some, but not all, measurement methods. The community of users of the single-particle soot-photometer (SP2), an instrument using laser-induced incandescence, identified a suitable SRM, fullerene soot, but users of instruments that measure light absorption by soot collected on filters did not. Similarly, those who use thermal optical analysis (TOA) to analyze the organic and elemental carbon components of soot were not satisfied with current SRMs. The workshop, and subsequent, interactive discussions, produced a number of recommendations for the development of new SRMs, and their implementation, that would be suitable for the different soot measurement methods

A new methodology to assess the performance and uncertainty of source apportionment models II: The results of two European intercomparison exercises

The performance and the uncertainty of receptor models (RMs) were assessed in intercomparison exercises employing real-world and synthetic input datasets. To that end, the results obtained by different practitioners using ten different RMs were compared with a reference. In order to explain the differences in the performances and uncertainties of the different approaches, the apportioned mass, the number of sources, the chemical profiles, the contribution-to-species and the time trends of the sources were all evaluated using the methodology described in Belis et al. (2015). In this study, 87% of the 344 source contribution estimates (SCEs) reported by participants in 47 different source apportionment model results met the 50% standard uncertainty quality objective established for the performance test. In addition, 68% of the SCE uncertainties reported in the results were coherent with the analytical uncertainties in the input data. The most used models, EPA-PMF v.3, PMF2 and EPA-CMB 8.2, presented quite satisfactory performances in the estimation of SCEs while unconstrained models, that do not account for the uncertainty in the input data (e.g. APCS and FA-MLRA), showed below average performance. Sources with well-defined chemical profiles and seasonal time trends, that make appreciable contributions (>10%), were those better quantified by the models while those with contributions to the PM mass close to 1% represented a challenge. The results of the assessment indicate that RMs are capable of estimating the contribution of the major pollution source categories over a given time window with a level of accuracy that is in line with the needs of air quality management

A new methodology to assess the performance and uncertainty of source apportionment models II : The results of two European intercomparison exercises

The performance and the uncertainty of receptor models (RMs) were assessed in intercomparison exercises employing real-world and synthetic input datasets. To that end, the results obtained by different practitioners using ten different RMs were compared with a reference. In order to explain the differences in the performances and uncertainties of the different approaches, the apportioned mass, the number of sources, the chemical profiles, the contribution-to-species and the time trends of the sources were all evaluated using the methodology described in Bells et al. (2015). In this study, 87% of the 344 source contribution estimates (SCEs) reported by participants in 47 different source apportionment model results met the 50% standard uncertainty quality objective established for the performance test. In addition, 68% of the SCE uncertainties reported in the results were coherent with the analytical uncertainties in the input data. The most used models, EPA-PMF v.3, PMF2 and EPA-CMB 8.2, presented quite satisfactory performances in the estimation of SCEs while unconstrained models, that do not account for the uncertainty in the input data (e.g. APCS and FA-MLRA), showed below average performance. Sources with well-defined chemical profiles and seasonal time trends, that make appreciable contributions (>10%), were those better quantified by the models while those with contributions to the PM mass close to 1% represented a challenge. The results of the assessment indicate that RMs are capable of estimating the contribution of the major pollution source categories over a given time window with a level of accuracy that is in line with the needs of air quality management. (C) 2015 The Authors. Published by Elsevier Ltd.Peer reviewe