Primary Biogenic Aerosol Particles Research Articles

Source identification of particulate phosphorus in the atmosphere in Beijing

We tracked atmospheric phosphorus (P) in suspended particulate matter (PM) from a site in Beijing, China over a three-year period and found a new relationship between plants and atmospheric P. Concentrations of total phosphorus (TP) in the atmosphere during plant growing seasons were 2.5 times those observed in other months and levels of organic phosphorus (OP) were 3.9 times as high. TP and OP increases during growing seasons were much more significant in PM with diameters of over 2.5 μm (PM>2.5). PM collected during growing seasons included high levels of P but less nitrogen than that in primary biogenic aerosol particles (PBAPs) and differed from other emission sources such as combustion emissions and dust. A time series of OP concentrations in the atmosphere shows a time lag relative to Normalized Difference Vegetation Index (NDVI) data with high levels found during early growing periods and much lower levels found during flourishing periods. Thus, we find that plants contribute to atmospheric P and especially to OP rather than to PBAP levels.

Missed atmospheric organic phosphorus emitted by terrestrial plants, part 2: Experiment of volatile phosphorus

The emission and deposition of global atmospheric phosphorus (P) have long been considered unbalanced, and primary biogenic aerosol particles (PBAP) and phosphine (PH3) are considered to be the only atmospheric P sources from the ecosystem. In this work, we found and quantified volatile organic phosphorus (VOP) emissions from plants unaccounted for in previous studies. In a greenhouse in which lemons were cultivated, the atmospheric total phosphorus (TP) concentration of particulate matter (PM) was 41.8% higher than that in a greenhouse containing only soil, and the proportion of organic phosphorus (OP) in TP was doubled. 31P nuclear magnetic resonance tests (31P-NMR) of PM showed that phosphate monoesters were the main components contributed by plants in both the greenhouse and at an outside observation site. Atmospheric gaseous P was directly measured to be 1–2 orders of magnitude lower than P in PM but appeared to double during plant growing seasons relative to other months. Bag-sampling and gas chromatography mass spectrometry (GCMS) tests showed that the gaseous P emitted by plants in the greenhouse was triethyl phosphate. VOP might be an important component of atmospheric P that has been underestimated in previous studies.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl−, Br−, I−, NO3−, SO42−,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds.The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 μm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 μm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Signatures of Biomass Burning Aerosols in the Plume of a Saltmarsh Wildfire in South Texas.

The most conventional and abundant tracers of biomass combustion in aerosol particles include potassium and biomarkers derived from thermally altered cellulose/hemicellulose (anhydrosugars) and lignin (methoxyphenols). However, little is known of the role biomass combustion plays as a particulate source of major plant polymers to the atmosphere. Here, concentrations of solvent-extractable anhydrosugars and methoxyphenols are compared to the yields of polymeric lignin oxidation products (LOPs) during a smoke plume event in Houston, Texas. Downwind aerosol samples (PM2.5) were collected surrounding a two-day wildfire in the McFaddin National Wildlife Refuge, 125 km southeast of Houston, which was 12-16 h directly downwind during the peak of the burn. Concentrations of all organic markers, potassium, and calcium increased by a factor of 2-13 within 1-2 days of the start of the fire and dropped to prefire levels 3 days after the peak event. Source signatures of anhydrosugars and methoxyphenols during the peak of the plume were identical to those of grass charcoals collected from the site, confirming the use of charcoals as end-members for source input reconstruction during atmospheric transport. An enrichment factor of 20 in the anhydrosugar to methoxyphenol ratio of aerosols versus charcoals can be explained partially by differences in degradation rate constants between the biomarker groups. LOPs comprised 73-91% of all lignin material in the aerosols, pointing to fires as major sources of primary biogenic aerosol particles in which lignin phenols occur predominantly in polymeric form.

Better constraints on sources of carbonaceous aerosols using a combined <sup>14</sup>C – macro tracer analysis in a European rural background site

Abstract. The source contributions to carbonaceous PM2.5 aerosol were investigated at a European background site at the edge of the Po Valley, in Northern Italy, during the period January–December 2007. Carbonaceous aerosol was described as the sum of 8 source components: primary (1) and secondary (2) biomass burning organic carbon, biomass burning elemental carbon (3), primary (4) and secondary (5) fossil organic carbon, fossil fuel burning elemental carbon (6), primary (7) and secondary (8) biogenic organic carbon. The mass concentration of each component was quantified using a set of macro tracers (organic carbon OC, elemental carbon EC, and levoglucosan), micro tracers (arabitol and mannitol), and 14C measurements. This was the first time that 14C measurements covered a full annual cycle with daily resolution. This set of 6 tracers, together with assumed uncertainty ranges of the ratios of OC-to-EC, and the reference fraction of modern carbon in the 8 source categories, provides strong constraints to the source contributions to carbonaceous aerosol. The uncertainty of contributions was assessed with a Quasi-Monte Carlo (QMC) method accounting for the variability of OC and EC emission factors, the uncertainty of reference fractions of modern carbon, and the measurement uncertainty. During winter, biomass burning composed 64 % (±15 %) of the total carbon (TC) concentration, while in summer secondary biogenic OC accounted for 50 % (±16 %) of TC. The contribution of primary biogenic aerosol particles was negligible during the entire year. Moreover, aerosol associated with fossil sources represented 27 % (±16 %) and 41 % (±26 %) of TC in winter and summer, respectively. The contribution of secondary organic aerosol (SOA) to the organic mass (OM) was significant during the entire year. SOA accounted for 30 % (±16 %) and 85 % (±12 %) of OM during winter and summer, respectively. While the summer SOA was dominated by biogenic sources, winter SOA was mainly due to biomass burning and fossil sources. This indicates that the oxidation of semi-volatile and intermediate volatility organic compounds co-emitted with primary organics is a significant source of SOA, as suggested by recent model results and Aerosol Mass Spectrometer measurements. Comparison with previous global model simulations, indicates a strong underestimate of wintertime primary aerosol emissions in this region. The comparison of source apportionment results in different urban and rural areas showed that the sampling site was mainly affected by local aerosol sources during winter and regional air masses from the nearby Po Valley in summer. This observation was further confirmed by back-trajectory analysis applying the Potential Source Contribution Function method to identify potential source regions.

Sources of carbonaceous aerosol in the Amazon basin

Abstract. The quantification of sources of carbonaceous aerosol is important to understand their atmospheric concentrations and regulating processes and to study possible effects on climate and air quality, in addition to develop mitigation strategies. In the framework of the European Integrated Project on Aerosol Cloud Climate Interactions (EUCAARI) fine (Dp < 2.5 μm) and coarse (2.5 μm < Dp <10 μm) aerosol particles were sampled from February to June (wet season) and from August to September (dry season) 2008 in the central Amazon basin. The mass of fine particles averaged 2.4 μg m−3 during the wet season and 4.2 μg m−3 during the dry season. The average coarse aerosol mass concentration during wet and dry periods was 7.9 and 7.6 μg m−3, respectively. The overall chemical composition of fine and coarse mass did not show any seasonality with the largest fraction of fine and coarse aerosol mass explained by organic carbon (OC); the average OC to mass ratio was 0.4 and 0.6 in fine and coarse aerosol modes, respectively. The mass absorbing cross section of soot was determined by comparison of elemental carbon and light absorption coefficient measurements and it was equal to 4.7 m2 g−1 at 637 nm. Carbon aerosol sources were identified by Positive Matrix Factorization (PMF) analysis of thermograms: 44% of fine total carbon mass was assigned to biomass burning, 43% to secondary organic aerosol (SOA), and 13% to volatile species that are difficult to apportion. In the coarse mode, primary biogenic aerosol particles (PBAP) dominated the carbonaceous aerosol mass. The results confirmed the importance of PBAP in forested areas. The source apportionment results were employed to evaluate the ability of global chemistry transport models to simulate carbonaceous aerosol sources in a regional tropical background site. The comparison showed an overestimation of elemental carbon (EC) by the TM5 model during the dry season and OC both during the dry and wet periods. The overestimation was likely due to the overestimation of biomass burning emission inventories and SOA production over tropical areas.

Emission and dry deposition of accumulation mode particles in the Amazon Basin

Abstract. Size-resolved vertical aerosol number fluxes of particles in the diameter range 0.25–2.5 μm were measured with the eddy covariance method from a 53 m high tower over the Amazon rain forest, 60 km NNW of Manaus, Brazil. This study focuses on data measured during the relatively clean wet season, but a shorter measurement period from the more polluted dry season is used as a comparison. Size-resolved net particle fluxes of the five lowest size bins, representing 0.25–0.45 μm in diameter, were in general dominated by deposition in more or less all wind sectors in the wet season. This is an indication that the source of primary biogenic aerosol particles may be small in this particle size range. Transfer velocities within this particle size range were observed to increase linearly with increasing friction velocity and increasing particle diameter. In the diameter range 0.5–2.5 μm, vertical particle fluxes were highly dependent on wind direction. In wind sectors where anthropogenic influence was low, net upward fluxes were observed. However, in wind sectors associated with higher anthropogenic influence, deposition fluxes dominated. The net upward fluxes were interpreted as a result of primary biogenic aerosol emission, but deposition of anthropogenic particles seems to have masked this emission in wind sectors with higher anthropogenic influence. The net emission fluxes were at maximum in the afternoon when the mixed layer is well developed, and were best correlated with horizontal wind speed according to the equation log10 F=0.48 · U+2.21 where F is the net emission number flux of 0.5–2.5 μm particles [m−2 s−1] and U is the horizontal wind speed [ms−1] at the top of the tower.

Aerosol number fluxes over the Amazon rain forest during the wet season

Abstract. Number fluxes of particles with diameter larger than 10 nm were measured with the eddy covariance method over the Amazon rain forest during the wet season as part of the LBA (The Large Scale Biosphere Atmosphere Experiment in Amazonia) campaign 2008. The primary goal was to investigate whether sources or sinks dominate the aerosol number flux in the tropical rain forest-atmosphere system. During the measurement campaign, from 12 March to 18 May, 60% of the particle fluxes pointed downward, which is a similar fraction to what has been observed over boreal forests. The net deposition flux prevailed even in the absolute cleanest atmospheric conditions during the campaign and therefore cannot be explained only by deposition of anthropogenic particles. The particle transfer velocity vt increased with increasing friction velocity and the relation is described by the equation vt = 2.4×10−3×u* where u* is the friction velocity. Upward particle fluxes often appeared in the morning hours and seem to a large extent to be an effect of entrainment fluxes into a growing mixed layer rather than primary aerosol emission. In general, the number source of primary aerosol particles within the footprint area of the measurements was small, possibly because the measured particle number fluxes reflect mostly particles less than approximately 200 nm. This is an indication that the contribution of primary biogenic aerosol particles to the aerosol population in the Amazon boundary layer may be low in terms of number concentrations. However, the possibility of horizontal variations in primary aerosol emission over the Amazon rain forest cannot be ruled out.

Characterization of primary biogenic aerosol particles in urban, rural, and high-alpine air by DNA sequence and restriction fragment analysis of ribosomal RNA genes

Abstract. This study explores the applicability of DNA analyses for the characterization of primary biogenic aerosol (PBA) particles in the atmosphere. Samples of fine particulate matter (PM2.5) and total suspended particulates (TSP) have been collected on different types of filter materials at urban, rural, and high-alpine locations along an altitude transect in the south of Germany (Munich, Hohenpeissenberg, Mt. Zugspitze). From filter segments loaded with about one milligram of air particulate matter, DNA could be extracted and DNA sequences could be determined for bacteria, fungi, plants and animals. Sequence analyses were used to determine the identity of biological organisms, and terminal restriction fragment length polymorphism analyses (T-RFLP) were applied to estimate diversities and relative abundances of bacteria. Investigations of blank and background samples showed that filter materials have to be decontaminated prior to use, and that the sampling and handling procedures have to be carefully controlled to avoid artifacts in the analyses. Mass fractions of DNA in PM2.5 were found to be around 0.05% in urban, rural, and high-alpine aerosols. The average concentration of DNA determined for urban air was on the order of ~7 ng m−3, indicating that human adults may inhale about one microgram of DNA per day (corresponding to ~108 haploid bacterial genomes or ~105 haploid human genomes, respectively). Most of the bacterial sequences found in PM2.5 were from Proteobacteria (42) and some from Actinobacteria (10) and Firmicutes (1). The fungal sequences were characteristic for Ascomycota (3) and Basidiomycota (1), which are known to actively discharge spores into the atmosphere. The plant sequences could be attributed to green plants (2) and moss spores (2), while animal DNA was found only for one unicellular eukaryote (protist). Over 80% of the 53 bacterial sequences could be matched to one of the 19 T-RF peaks found in the PM2.5 samples, but only 40% of the T-RF peaks did correspond to one of the detected bacterial sequences. The results demonstrate that the T-RFLP analysis covered more of the bacterial diversity than the sequence analysis. Shannon-Weaver indices calculated from both sequence and T-RFLP data indicate that the bacterial diversity in the rural samples was higher than in the urban and alpine samples. Two of the bacterial sequences (Gammaproteobacteria) and five of the T-RF peaks were found at all sampling locations.

Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

Abstract. Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores. Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7–2.3 μg m−3). For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10–68 ng m−3), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7–49 ng m−3), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17–43 ng m−3), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m−3), we have also calculated a value of ~17 Tg yr−1 as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³–104 m−3; ~0.1–1 μg m−3). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 μg m−3 and ~50 Tg yr−1. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr−1 of anthropogenic primary organic aerosol; 12–70 Tg yr−1 of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Fine mode aerosol composition at three long‐term atmospheric monitoring sites in the Amazon Basin

The Amazon Basin tropical rain forest is a key region to study processes that are changing the composition of the global atmosphere, including the large amount of fine mode aerosol particles emitted during biomass burning that might influence the global atmosphere. Three background monitoring stations, Alta Floresta, Cuiabá, and Serra do Navio, are operating continuously measuring aerosol composition. Fine (dp < 2.0 μm) and coarse (2.0 < dp < 10 μm) mode aerosol particles were collected using stacked filter units. Particle‐induced X‐ray emission was used to measure concentrations of up to 20 elements in the fine mode: Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, and Pb. Soot carbon and gravimetric mass analysis were also performed. Absolute Principal Factor Analysis (APFA) has derived absolute elemental source profiles. APFA showed four aerosol particle components: soil dust (Al, Ca, Ti, Mn, Fe), biomass burning (soot, fine mode mass concentration, K, Cl), natural primary biogenic particles with gas‐to‐particle component (K, S, Ca, Mn, Zn), and marine aerosol (Cl). Biogenic and biomass burning aerosol particles dominate the fine mode mass concentration, with the presence of K, P, S, Cl, Zn, Br, and fine mode mass concentration (FPM). At the Alta Floresta and Cuiabá sites, during the dry season, a strong component of biomass burning is observed. Inhalable particulate matter (dp < 10 μm) mass concentration up to 700 μg/m3 was measured. Fine particle mass concentration alone can go as high as 400 μg/m3 for large regions. The fine mode biogenic and biomass burning components show remarkable similarities in the elemental composition, even though the sampling sites are more than 3000 km apart. Fine mode sulfur concentration is entirely associated with the primary biogenic aerosol particles, with gas‐to‐particle conversion and the biomass burning component. Large amounts of essential plant nutrients like P are mobilized into the atmosphere and possibly lost from the Amazon Basin ecosystem by long‐range transport.