Constructing a data-driven receptor model for organic and inorganic aerosol : a synthesis analysis of eight mass spectrometric data sets from a boreal forest site

The interactions between organic and inorganic aerosol chemical components are integral to understanding and modelling climate and health-relevant aerosol physicochemical properties, such as volatility, hygroscopicity, light scattering and toxicity. This study presents a synthesis analysis for eight data sets, of non-refractory aerosol composition, measured at a boreal forest site. The measurements, performed with an aerosol mass spectrometer, cover in total around 9 months over the course of 3 years. In our statistical analysis, we use the complete organic and inorganic unit-resolution mass spectra, as opposed to the more common approach of only including the organic fraction. The analysis is based on iterative, combined use of (1) data reduction, (2) classification and (3) scaling tools, producing a data-driven chemical mass balance type of model capable of describing site-specific aerosol composition. The receptor model we constructed was able to explain 83 +/- 8% of variation in data, which increased to 96 +/- 3% when signals from low signal-to-noise variables were not considered. The resulting interpretation of an extensive set of aerosol mass spectrometric data infers seven distinct aerosol chemical components for a rural boreal forest site: ammonium sulfate (35 +/- 7% of mass), low and semi-volatile oxidised organic aerosols (27 +/- 8% and 12 +/- 7 %), biomass burning organic aerosol (11 +/- 7 %), a nitrate-containing organic aerosol type (7 +/- 2 %), ammonium nitrate (5 +/- 2 %), and hydrocarbon-like organic aerosol (3 +/- 1 %). Some of the additionally observed, rare outlier aerosol types likely emerge due to surface ionisation effects and likely represent amine compounds from an unknown source and alkaline metals from emissions of a nearby district heating plant. Compared to traditional, ionbalance-based inorganics apportionment schemes for aerosol mass spectrometer data, our statistics-based method provides an improved, more robust approach, yielding readily useful information for the modelling of submicron atmospheric aerosols physical and chemical properties. The results also shed light on the division between organic and inorganic aerosol types and dynamics of salt formation in aerosol. Equally importantly, the combined methodology exemplifies an iterative analysis, using consequent analysis steps by a combination of statistical methods. Such an approach offers new ways to home in on physicochemically sensible solutions with minimal need for a priori information or analyst interference. We therefore suggest that similar statisticsbased approaches offer significant potential for un- or semi-supervised machine-learning applications in future analyses of aerosol mass spectrometric data.Peer reviewe

Observations of ozone depletion events in a Finnish boreal forest

We investigated the concentrations and vertical profiles of ozone over a 20-year period (1996–2016) at the SMEAR II station in southern Finland. Our results showed that the typical daily median ozone concentrations were in the range of 20–50 ppb with clear diurnal and annual patterns. In general, the profile of ozone concentrations illustrated an increase as a function of heights. The main aim of our study was to address the frequency and strength of ozone depletion events at this boreal forest site. We observed more than a thousand of 10 min periods at 4.2 m, with ozone concentrations below 10 ppb, and a few tens of cases with ozone concentrations below 2 ppb. Among these observations, a number of ozone depletion events that lasted for more than 3 h were identified, and they occurred mainly in autumn and winter months. The low ozone concentrations were likely related to the formation of a low mixing layer under the conditions of low temperatures, low wind speeds, high relative humidities and limited intensity of solar radiation.Peer reviewe

Non-volatile residuals of newly formed atmospheric particles in the boreal forest

The volatility of sub-micrometer atmospheric aerosol particles was studied in a rural background environment in Finland using a combination of a heating tube and a scanning mobility particle sizer. The analysis focused on nanoparticles formed through nucleation which were subsequently observed during their growth in the diameter range between 5 and 60 nm. During the 6 days of new particle formation shown in detail, the concentrations of newly formed particles increased up to 10 000 cm−3. The number of nucleation mode particles measured after volatilization in the heating tube at 280°C was up to 90% of the total number under ambient conditions. Taking into account the absolute accuracy of the size distribution measurements, all ambient particles found in the rural atmosphere could have a non-volatile core after volatilization at 280°C. As the regional new particle formation events developed over time as a result of further vapor condensation, the newly formed particles grew at an average growth rate of 2.4±0.3 nm h−1. Importantly, the non-volatile cores of nucleation mode particles were also observed to grow over time, however, at a lower average growth rate of 0.6±0.3 nm h−1. One implication of the volatility analysis is that the newly formed particles, which have reached ambient diameters of 15 nm, are unlikely to consist of sulfuric acid, ammonium sulfate, and water alone. A relatively constant ratio between the growth rate of the ambient particles as well as their non-volatile cores indicates that non-volatile matter is formed only gradually in the growing particles. The non-volatile fraction of the particles showed some correlation with the ambient temperature. The composition and formation mechanism of this non-volatile material in nucleation mode particles are, to date, not known

Temporal variations in black carbon concentrations with different time scales in Helsinki during 1996?2005

International audienceVariations in black carbon (BC) concentrations over different timescales, including annual, weekly and diurnal changes, were studied during ten years in Helsinki, Finland. Measurements were made in three campaigns between 1996 and 2005 at an urban area locating two kilometres of the centre of Helsinki. The first campaign took place from November 1996 to June 1997, the second from September 2000 to May 2001 and the third from March 2004 to October 2005. A detailed comparison between the campaigns was only made for winter and spring months when data from all campaigns existed. The effect of traffic and meteorological variables on the measured BC concentrations was studied by means of a multiple regression analysis, where the meteorological data was obtained from a meteorological pre-processing model (MPP-FMI). The BC concentrations showed annual pattern with maxima in fall and late winter due to the weakened mixing and enhanced emissions. Between 1996 and 2005, the campaign median BC concentrations decreased slightly from 1.11 to 1.00 ?g m?3. The lowest campaign median concentration (0.93 ?g m?3) was measured during the second campaign in 2000?2001, when also the lowest traffic rates were measured. The strongest decrease between Campaigns 1 and 3 was observed on weekday daytimes, when also the traffic rates are highest. The variables affecting the measured BC concentrations most were traffic, wind speed and mixing height. On weekdays, traffic had clearly the most important influence before the wind speed and on weekends the effect of wind speed diluted the effect of traffic. The affecting variables and their influence on the BC concentrations were similar in winter and spring. The separate examination of the three campaigns showed that the effect of traffic on the BC concentrations had decreased during the studied years. This reduction was caused by lower emitting vehicles, since between years 1996 and 2005 the traffic rates had increased

Black carbon concentration trends in Helsinki during 1996?2005

International audienceThe black carbon (BC) concentration trends were studied during ten years in Helsinki, Finland. Measurements were made in three campaigns between 1996 and 2005 at an urban area locating two kilometres from the centre of Helsinki. The first campaign was from November 1996 to June 1997, the second from September 2000 to May 2001 and the third from March 2004 to October 2005. In this study, only data from winter and spring months was analysed. The effect of traffic and meteorological variables on the measured BC concentrations was studied by means of a multiple regression analysis, where the meteorological data was obtained from a meteorological pre-processing model (MPP-FMI). During the ten years, the campaign median BC concentrations were found to decrease slightly from 1.11 to 1.00 ?g m?3. The lowest campaign median concentration (0.93 ?g m?3) was measured during the second campaign in 2000?2001, when also the lowest traffic rates were measured. The strongest decrease between campaigns 1 and 3 was observed during weekday daytimes, when the traffic rates are highest. The variables affecting the measured BC concentrations most were traffic, wind speed and mixing height. On weekdays, traffic had clearly the most important influence and on weekends the effect of wind speed diluted the effect of traffic. The affecting variables and their influence on the BC concentration were similar in winter and spring. The separate examination of the three campaigns showed that the effect of traffic on the BC concentrations had decreased during the studied years. This reduction was caused by cleaner emissions from vehicles, since between years 1996 and 2005 the traffic rates had increased. A rough estimate gave that vehicle number-scaled BC mass concentrations have decreased from 0.0028 to 0.0020 ?g m?3 between campaigns 1 and 3

Comprehensive analysis of particle growth rates from nucleation mode to cloud condensation nuclei in boreal forest

Growth of aerosol particles to sizes at which they can act as cloud condensation nuclei (CCN) is a crucial factor in estimating the current and future impacts of aerosol–cloud–climate interactions. Growth rates (GRs) are typically determined for particles with diameters (dP) smaller than 40&thinsp;nm immediately after a regional new particle formation (NPF) event. These growth rates are often taken as representatives for the particle growth to CCN sizes (dP&thinsp;&gt;&thinsp;50–100&thinsp;nm). In modelling frameworks, the concentration of the condensable vapours causing the growth is typically calculated with steady state assumptions, where the condensation sink (CS) is the only loss term for the vapours. Additionally, the growth to CCN sizes is represented with the condensation of extremely low-volatility vapours and gas–particle partitioning of semi-volatile vapours. Here, we use a novel automatic method to determine growth rates from below 10&thinsp;nm to hundreds of nanometres from a 20-year-long particle size distribution (PSD) data set in boreal forest. With this method, we are able to detect growth rates also at times other than immediately after a NPF event. We show that the GR increases with an increasing oxidation rate of monoterpenes, which is closely coupled with the ambient temperature. Based on our analysis, the oxidation reactions of monoterpenes with ozone, hydroxyl radical and nitrate radical all are capable of producing vapours that contribute to the particle growth in the studied size ranges. We find that GR increases with particle diameter, resulting in up to 3-fold increases in GRs for particles with dP&thinsp; ∼ &thinsp;100&thinsp;nm in comparison to those with dP&thinsp; ∼ &thinsp;10&thinsp;nm. We use a single particle model to show that this increase in GR can be explained with aerosol-phase reactions, in which semi-volatile vapours form non-volatile dimers. Finally, our analysis reveals that the GR of particles with dP&thinsp;&lt;&thinsp;100&thinsp;nm is not limited by the condensation sink, even though the GR of larger particles is. Our findings suggest that in the boreal continental environment, the formation of CCN from NPF or sub-100&thinsp;nm emissions is more effective than previously thought and that the formation of CCN is not as strongly self-limiting a process as the previous estimates have suggested.</p

The role of highly oxygenated molecules (HOMs) in determining the composition of ambient ions in the boreal forest

In order to investigate the negative ions in the boreal forest we have performed measurements to chemically characterise the composition of negatively charged clusters containing highly oxygenated molecules (HOMs). Additionally, we compared this information with the chemical composition of the neutral gas-phase molecules detected in the ambient atmosphere during the same period. The chemical composition of the ions was retrieved using an atmospheric pressure interface time-of-flight mass spectrometer (APiTOF-MS) while the gas-phase neutral molecules (mainly sulfuric acid and HOMs) were characterised using the same mass spectrometer coupled to a nitrate-based chemical ionisation unit (CI-APi-TOF). Overall, we divided the identified HOMs in two classes: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). During the day, among the ions, in addition to the well-known pure sulfuric acid clusters, we found a large number of HOMs clustered with nitrate (NO3-) or bisulfate (HSO4-), with the first one being more abundant. During the night, the distribution of ions, mainly composed of HOM clustered with NO3-, was very similar to the neutral compounds that are detected in the CI-APi-TOF as adducts with the artificially introduced primary ion (NO3-). For the first time, we identified several clusters containing up to 40 carbon atoms. These ions are formed by up to four oxidised alpha-pinene units clustered with NO3-. While we know that dimers (16-20 carbon atoms) are probably formed by a covalent bond between two alpha-pinene oxidised units, it is still unclear what bonding formed larger clusters. Finally, diurnal profiles of the negative ions were consistent with the neutral compounds revealing that ONs peak during the day while HOMs are more abundant at night-time. However, during the day, a large fraction of the negative charge is taken up by the pure sulfuric acid clusters causing differences between ambient ions and neutral compounds (i.e. less available charge for HOM and ON).Peer reviewe

Mode resolved density of atmospheric aerosol particles

In this study, we investigate the mode resolved density of ultrafine atmospheric particles measured in boreal forest environment. The method used here enables us to find the distinct density information for each mode in atmospheric fine particle population: the density values for nucleation, Aitken, and accumulation mode particles are presented. The experimental data was gained during 2 May 2005–19 May 2005 at the boreal forest measurement station &quot;SMEAR II&quot; in Hyytiälä, Southern Finland. The density values for accumulation mode varied from 1.1 to 2 g/cm&lt;sup&gt;3&lt;/sup&gt; (average 1.5 g/cm&lt;sup&gt;3&lt;/sup&gt;) and for Aitken mode from 0.4 to 2 g/cm&lt;sup&gt;3&lt;/sup&gt; (average 0.97 g/cm&lt;sup&gt;3&lt;/sup&gt;). As an overall trend during the two weeks campaign, the density value of Aitken mode was seen to gradually increase. With the present method, the time dependent behaviour of the particle density can be investigated in the time scale of 10 min. This allows us to follow the density evolution of the nucleation mode particles during the particle growth process following the nucleation burst. The density of nucleation mode particles decreased during the growth process. The density values for 15 nm particles were 1.2–1.5 g/cm&lt;sup&gt;3&lt;/sup&gt; and for grown 30 nm particles 0.5–1 g/cm&lt;sup&gt;3&lt;/sup&gt;. These values are consistent with the present knowledge that the condensing species are semi-volatile organics, emitted from the boreal forest

Composition and temporal behavior of ambient ions in the boreal forest

A recently developed atmospheric pressure interface mass spectrometer (APi-TOF) measured the negative and positive ambient ion composition at a boreal forest site. As observed in previous studies, the negative ions were dominated by strong organic and inorganic acids (e.g. malonic, nitric and sulfuric acid), whereas the positive ions consisted of strong bases (e.g. alkyl pyridines and quinolines). Several new ions and clusters of ions were identified based on their exact masses, made possible by the high resolution, mass accuracy and sensitivity of the APi-TOF. Time series correlograms aided in peak identification and assigning the atomic compositions to molecules. Quantum chemical calculations of proton affinities and cluster stabilities were also used to confirm the plausibility of the assignments. Acids in the gas phase are predominantly formed by oxidation in the gas phase, and thus the concentrations are expected to vary strongly between day and night. This was also the case in this study, where the negative ions showed strong diurnal behavior, whereas the daily changes in the positive ions were considerably smaller. A special focus in this work was the changes in the ion distributions occurring during new particle formation events. We found that sulfuric acid, together with its clusters, dominated the negative ion spectrum during these events. The monomer (HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt;) was the largest peak, together with the dimer (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; &amp;middot; HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt;) and trimer ((H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; &amp;middot; HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt;). SO&lt;sub&gt;5&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; also tracked HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; at around 20% of the HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; concentration at all times. During the strongest events, the tetramer and a cluster with the tetramer and ammonia were also detected. Quantum chemical calculations predict that sulfuric acid clusters containing ammonia are much more stable when neutral, thus the detection of a single ion cluster implies that ammonia can be an important compound in the nucleation process. We also believe to have made the first observations of an organosulfate (glycolic acid sulfate) in the gas phase. This ion, and its cluster with sulfuric acid, correlates with the HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt;, but peaks in the early afternoon, some hours later than HSO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; itself. A list of all identified ions is presented in the supplementary material, and also a list of all detected masses not yet identified

Resolving anthropogenic aerosol pollution types - deconvolution and exploratory classification of pollution events

Mass spectrometric measurements commonly yield data on hundreds of variables over thousands of points in time. Refining and synthesizing this raw data into chemical information necessitates the use of advanced, statisticsbased data analytical techniques. In the field of analytical aerosol chemistry, statistical, dimensionality reductive methods have become widespread in the last decade, yet comparable advanced chemometric techniques for data classification and identification remain marginal. Here we present an example of combining data dimensionality reduction (factorization) with exploratory classification (clustering), and show that the results cannot only reproduce and corroborate earlier findings, but also complement and broaden our current perspectives on aerosol chemical classification. We find that applying positive matrix factorization to extract spectral characteristics of the organic component of air pollution plumes, together with an unsupervised clustering algorithm, k -means C C, for classification, reproduces classical organic aerosol speciation schemes. Applying appropriately chosen metrics for spectral dissimilarity along with optimized data weighting, the source-specific pollution characteristics can be statistically resolved even for spectrally very similar aerosol types, such as different combustion-related anthropogenic aerosol species and atmospheric aerosols with similar degree of oxidation. In addition to the typical oxidation level and source-driven aerosol classification, we were also able to classify and characterize outlier groups that would likely be disregarded in a more conventional analysis. Evaluating solution quality for the classification also provides means to assess the performance of mass spectral simi-larity metrics and optimize weighting for mass spectral variables. This facilitates algorithm-based evaluation of aerosol spectra, which may prove invaluable for future development of automatic methods for spectra identification and classification. Robust, statistics-based results and data visualizations also provide important clues to a human analyst on the existence and chemical interpretation of data structures. Applying these methods to a test set of data, aerosol mass spectrometric data of organic aerosol from a boreal forest site, yielded five to seven different recurring pollution types from various sources, including traffic, cooking, biomass burning and nearby sawmills. Additionally, three distinct, minor pollution types were discovered and identified as amine-dominated aerosols.Peer reviewe