Hygroscopic and chemical characterisation of Po Valley aerosol

Continental summer-time aerosol in the Italian Po Valley was characterised in terms of hygroscopic properties and the influence of chemical composition therein. Additionally, the ethanol affinity of particles was analysed. The campaign-average minima in hygroscopic growth factors (HGFs, at 90% relative humidity) occurred just before and during sunrise from 03:00 to 06:00 LT (all data are reported in the local time), but, more generally, the hygroscopicity during the whole night is very low, particularly in the smaller particle sizes. The average HGFs recorded during the low HGF period were in a range from 1.18 (for the smallest, 35nm particles) to 1.38 (for the largest, 165 nm particles). During the day, the HGF gradually increased to achieve maximum values in the early afternoon hours 12:00–15:00, reaching 1.32 for 35 nm particles and 1.46 for 165 nm particles. Two contrasting case scenarios were encountered during the measurement period: Case 1 was associated with westerly air flow moving at a moderate pace and Case 2 was associated with more stagnant, slower moving air from the north-easterly sector. Case 1 exhibited weak diurnal temporal patterns, with no distinct maximum or minimum in HGF or chemical composition, and was associated with moderate non-refractory aerosol mass concentrations (for 50% size cut at 1 μ) of the order of 4.5 μg m⁻³. For Case 1, organics contributed typically 50% of the mass. Case 2 was characterised by >9.5 μg m⁻³ total non-refractory mass (<1 μ) in the early morning hours (04:00), decreasing to ~3 μg m⁻³ by late morning (10:00) and exhibited strong diurnal changes in chemical composition, particularly in nitrate mass but also in total organic mass concentrations. Specifically, the concentrations of nitrate peaked at night-time, along with the concentrations of hydrocarbon-like organic aerosol (HOA) and of semi-volatile oxygenated organic aerosol (SV-OOA). In general, organic growth factors (OGFs) followed a trend which was opposed to HGF and also to the total organic mass as measured by the aerosol mass spectrometer. The analysis of the HGF probability distribution function (PDF) reveals an existence of a predominant "more hygroscopic" (MH) mode with HGF of 1.5 around noon, and two additional modes: one with a "less hygroscopic" (LH) HGF of 1.26, and another with a "barely hygroscopic" (BH) mode of 1.05. Particles sized 165 nm exhibited moderate diurnal variability in HGF, ranging from 80% at night to 95% of "more hygroscopic" growth factors (i.e. HGFs 1.35–1.9) around noon. The diurnal changes in HGF progressively became enhanced with decreasing particle size, decreasing from 95% "more hygroscopic" growth factor fraction at noon to 10% fraction at midnight, while the "less hygroscopic" growth factor fraction (1.13–1.34) increased from 5% at noon to > 60% and the "barely hygroscopic" growth factor fraction (1.1–1.2) increased from less than 2% at noon to 30% at midnight. Surprisingly, the lowest HGFs occurred for the period when nitrate mass reached peak concentrations (Case 2). We hypothesised that the low HGFs of nitrate-containing particles can be explained by a) an organic coating suppressing the water-uptake, and/or by b) the existence of nitrates in a less hygroscopic state, e.g. as organic nitrates. The latter hypothesis allows us to explain also the reduced OGFs observed during the early morning hours (before dawn) when nitrate concentrations peaked, based on the evidence that organic nitrates have significant lower ethanol affinity than other SV-OOA compounds

Model evaluation of marine primary organic aerosol emission schemes

In this study, several marine primary organic aerosol (POA) emission schemes have been evaluated using the GEOS-Chem chemical transport model in order to provide guidance for their implementation in air quality and climate models. These emission schemes, based on varying dependencies of chlorophyll &lt;i&gt;a&lt;/i&gt; concentration ([chl &lt;i&gt;a&lt;/i&gt;]) and 10 m wind speed (&lt;i&gt;U&lt;/i&gt;&lt;sub&gt;10&lt;/sub&gt;), have large differences in their magnitude, spatial distribution, and seasonality. Model comparison with weekly and monthly mean values of the organic aerosol mass concentration at two coastal sites shows that the source function exclusively related to [chl &lt;i&gt;a&lt;/i&gt;] does a better job replicating surface observations. Sensitivity simulations in which the negative &lt;i&gt;U&lt;/i&gt;&lt;sub&gt;10&lt;/sub&gt; and positive [chl &lt;i&gt;a&lt;/i&gt;] dependence of the organic mass fraction of sea spray aerosol are enhanced show improved prediction of the seasonality of the marine POA concentrations. A top-down estimate of submicron marine POA emissions based on the parameterization that compares best to the observed weekly and monthly mean values of marine organic aerosol surface concentrations has a global average emission rate of 6.3 Tg yr&lt;sup&gt;−1&lt;/sup&gt;. Evaluation of existing marine POA source functions against a case study during which marine POA contributed the major fraction of submicron aerosol mass shows that none of the existing parameterizations are able to reproduce the hourly-averaged observations. Our calculations suggest that in order to capture episodic events and short-term variability in submicron marine POA concentration over the ocean, new source functions need to be developed that are grounded in the physical processes unique to the organic fraction of sea spray aerosol

Top-down and bottom-up aerosol–cloud closure: towards understanding sources of uncertainty in deriving cloud shortwave radiative flux

Top-down and bottom-up aerosol–cloud shortwave radiative flux closures were conducted at the Mace Head Atmospheric Research Station in Galway, Ireland, in August 2015. This study is part of the BACCHUS (Impact of Biogenic versus Anthropogenic emissions on Clouds and Climate: towards a Holistic UnderStanding) European collaborative project, with the goal of understanding key processes affecting aerosol–cloud shortwave radiative flux closures to improve future climate predictions and develop sustainable policies for Europe. Instrument platforms include ground-based unmanned aerial vehicles (UAVs)1 and satellite measurements of aerosols, clouds and meteorological variables. The ground-based and airborne measurements of aerosol size distributions and cloud condensation nuclei (CCN) concentration were used to initiate a 1-D microphysical aerosol–cloud parcel model (ACPM). UAVs were equipped for a specific science mission, with an optical particle counter for aerosol distribution profiles, a cloud sensor to measure cloud extinction or a five-hole probe for 3-D wind vectors. UAV cloud measurements are rare and have only become possible in recent years through the miniaturization of instrumentation. These are the first UAV measurements at Mace Head. ACPM simulations are compared to in situ cloud extinction measurements from UAVs to quantify closure in terms of cloud shortwave radiative flux. Two out of seven cases exhibit sub-adiabatic vertical temperature profiles within the cloud, which suggests that entrainment processes affect cloud microphysical properties and lead to an overestimate of simulated cloud shortwave radiative flux. Including an entrainment parameterization and explicitly calculating the entrainment fraction in the ACPM simulations both improved cloud-top radiative closure. Entrainment reduced the difference between simulated and observation-derived cloud-top shortwave radiative flux (δRF) by between 25 and 60 W m−2. After accounting for entrainment, satellite-derived cloud droplet number concentrations (CDNCs) were within 30 % of simulated CDNC. In cases with a well-mixed boundary layer, δRF is no greater than 20 W m−2 after accounting for cloud-top entrainment and up to 50 W m−2 when entrainment is not taken into account. In cases with a decoupled boundary layer, cloud microphysical properties are inconsistent with ground-based aerosol measurements, as expected, and δRF is as high as 88 W m−2, even high (> 30 W m−2) after accounting for cloud-top entrainment. This work demonstrates the need to take in situ measurements of aerosol properties for cases where the boundary layer is decoupled as well as consider cloud-top entrainment to accurately model stratocumulus cloud radiative flux

Effects of two different biogenic emission models on modelled ozone and aerosol concentrations in Europe

Biogenic volatile organic compound (BVOC) emissions are one of the essential inputs for chemical transport models (CTMs), but their estimates are associated with large uncertainties, leading to significant influence on air quality modelling. This study aims to investigate the effects of using different BVOC emission models on the performance of a CTM in simulating secondary pollutants, i.e. ozone, organic, and inorganic aerosols. European air quality was simulated for the year 2011 by the regional air quality model Comprehensive Air Quality Model with Extensions (CAMx) version 6.3, using BVOC emissions calculated by two emission models: the Paul Scherrer Institute (PSI) model and the Model of Emissions of Gases and Aerosol from Nature (MEGAN) version 2.1. Comparison of isoprene and monoterpene emissions from both models showed large differences in their general amounts, as well as their spatial distribution in both summer and winter. MEGAN produced more isoprene emissions by a factor of 3 while the PSI model generated 3 times the monoterpene emissions in summer, while there was negligible difference (∼4&thinsp;%) in sesquiterpene emissions associated with the two models. Despite the large differences in isoprene emissions (i.e. 3-fold), the resulting impact in predicted summertime ozone proved to be minor (&lt;10&thinsp;%; MEGAN O3 was higher than PSI O3 by ∼7&thinsp;ppb). Comparisons with measurements from the European air quality database (AirBase) indicated that PSI emissions might improve the model performance at low ozone concentrations but worsen performance at high ozone levels (&gt;60&thinsp;ppb). A much larger effect of the different BVOC emissions was found for the secondary organic aerosol (SOA) concentrations. The higher monoterpene emissions (a factor of ∼3) by the PSI model led to higher SOA by ∼110&thinsp;% on average in summer, compared to MEGAN, and lead to better agreement between modelled and measured organic aerosol (OA): the mean bias between modelled and measured OA at nine measurement stations using Aerodyne aerosol chemical speciation monitors (ACSMs) or Aerodyne aerosol mass spectrometers (AMSs) was reduced by 21&thinsp;%–83&thinsp;% at rural or remote stations. Effects on inorganic aerosols (particulate nitrate, sulfate, and ammonia) were relatively small (&lt;15&thinsp;%).</p

ACTRIS ACSM intercomparison – Part 2: Intercomparison of ME-2 organic source apportionment results from 15 individual, co-located aerosol mass spectrometers

Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2 %, COA: 15.0 ± 3.4 %, OOA: 41.5 ± 5.7 %, BBOA: 29.3 ± 5.0 %). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2 %.JRC.H.2-Air and Climat

Progress in the Analysis of Complex Atmospheric Particles

This article presents an overview of recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surface interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multimodal chemical characterization of particles with both molecular and lateral specificity. When combined, these approaches provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore the environmental effects of air-surface interactions

ACTRIS ACSM intercomparison – Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall – early-winter period (November–December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.JRC.H.2-Air and Climat

ACTRIS ACSM intercomparison - Part 2: Intercomparison of ME-2 organic source apportionment results from 15 individual, co-located aerosol mass spectrometers

Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2 %, COA: 15.0 ± 3.4 %, OOA: 41.5 ± 5.7 %, BBOA: 29.3 ± 5.0 %). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2 %

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