Average daily contributions (90% CI black bar) to PM10 in relative (%, left pie charts), OPAA and OPDTT per source’s mass in absolute (OPm in nmol/min m−3, middle bar plot) and OPAA and OPDTT per ...volume in relative (OPv in %, right bar plot) values grouped according to sources common activities. Arrows indicate (additional) associations between the sources.
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•Concentrations of PM10 at the site are comparable to other Alpine valleys, however, OP levels are higher compared to European sites.•Extensive tests with PMF were performed including organic tracers.•The most important sources of PM10, OP per µg of source as well as OP per m3 at the site are biomass burning and activities related to cement production.•Sources with important contributions to PM10 do not necessarily have high OP.•An unusual chloride-rich source was identified with high OP per µg of source.
Toxicity of particulate matter (PM) depends on its sources, size and composition. We identified PM10 sources and determined their contribution to oxidative potential (OP) as a health proxy for PM exposure in an Alpine valley influenced by cement industry. PM10 filter sample chemical analysis and equivalent black carbon (eBC) were measured at an urban background site from November 2020 to November 2021. Using an optimized Positive Matrix Factorization (PMF) model, the source chemical fingerprints and contributions to PM10 were determined. The OP assessed through two assays, ascorbic acid (AA) and dithiothreitol (DTT), was attributed to the PM sources from the PMF model with a multiple linear regression (MLR) model. Ten factors were found at the site, including biomass burning (34, 40 and 38% contribution to annual PM10, OPAA and OPDDT, respectively), traffic (14, 19 and 7%), nitrate- and sulphate-rich (together: 16, 5 and 8%), aged sea salt (2, 2 and 0%) and mineral dust (10, 12 and 17%). The introduction of innovative organic tracers allowed the quantification of the PM primary and secondary biogenic fractions (together: 13, 8 and 21%). In addition, two unusual factors due to local features, a chloride-rich factor and a second mineral dust-rich factor (named the cement dust factor) were found, contributing together 10, 14 and 8%. We associate these two factors to different processes in the cement plant. Despite their rather low contribution to PM10 mass, these sources have one of the highest OPs per µg of source. The results of the study provide vital information about the influence of particular sources on PM10 and OP in complex environments and are thus useful for PM control strategies and actions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NO
= NO + NO
). ...PAN enables the transport and release of NO
to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30 %), acetone (7 %), and a suite of other isoprene and terpene oxidation products (19 %). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37 %) and alkanes (14 %). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NO
is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.
Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics ...of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225 m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of the samples were influenced by North American wildfire emissions transported in the free troposphere and one by North American outflow mainly transported within the marine boundary layer. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used to determine the detailed molecular composition of the samples. Thousands of molecular formulas were assigned to each of the individual samples. On average ∼60 % of the molecular formulas contained only carbon, hydrogen, and oxygen atoms (CHO), ∼30 % contained nitrogen (CHNO), and ∼10 % contained sulfur (CHOS). The molecular formula compositions of the two wildfire-influenced aerosol samples transported mainly in the free troposphere had relatively low average O∕C ratios (0.48±0.13 and 0.45±0.11) despite the 7–10 days of transport time according to FLEXPART. In contrast, the molecular composition of the North American outflow transported mainly in the boundary layer had a higher average O∕C ratio (0.57±0.17) with 3 days of transport time. To better understand the difference between free tropospheric transport and boundary layer transport, the meteorological conditions along the FLEXPART simulated transport pathways were extracted from the Global Forecast System analysis for the model grids. We used the extracted meteorological conditions and the observed molecular chemistry to predict the relative-humidity-dependent glass transition temperatures (Tg) of the aerosol components. Comparisons of the Tg to the ambient temperature indicated that a majority of the organic aerosol components transported in the free troposphere were more viscous and therefore less susceptible to oxidation than the organic aerosol components transported in the boundary layer. Although the number of observations is limited, the results suggest that biomass burning organic aerosol injected into the free troposphere is more persistent than organic aerosol in the boundary layer having broader implications for aerosol aging.
Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon‐like OA (HOA) and several types of oxygenated OA (OOA) components. ...HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Recent field studies have found large discrepancies in the measured vs. modeled SOA mass loadings in both urban and regional polluted atmospheres. The reasons for these large differences are unclear. ...Here we revisit a case study of SOA formation in Mexico City described by Volkamer et al. (2006), during a photochemically active period when the impact of regional biomass burning is minor or negligible, and show that the observed increase in OA/ΔCO is consistent with results from several groups during MILAGRO 2006. Then we use the case study to evaluate three new SOA models: 1) the update of aromatic SOA yields from recent chamber experiments (Ng et al., 2007); 2) the formation of SOA from glyoxal (Volkamer et al., 2007a); and 3) the formation of SOA from primary semivolatile and intermediate volatility species (P-S/IVOC) (Robinson et al., 2007). We also evaluate the effect of reduced partitioning of SOA into POA (Song et al., 2007). Traditional SOA precursors (mainly aromatics) by themselves still fail to produce enough SOA to match the observations by a factor of ~7. The new low-NOx aromatic pathways with very high SOA yields make a very small contribution in this high-NOx urban environment as the RO2·+NO reaction dominates the fate of the RO2· radicals. Glyoxal contributes several μg m−3 to SOA formation, with similar timing as the measurements. P-S/IVOC are estimated from equilibrium with emitted POA, and introduce a large amount of gas-phase oxidizable carbon that was not in models before. With the formulation in Robinson et al. (2007) these species have a high SOA yield, and this mechanism can close the gap in SOA mass between measurements and models in our case study. However the volatility of SOA produced in the model is too high and the O/C ratio is somewhat lower than observations. Glyoxal SOA helps to bring the O/C ratio of predicted and observed SOA into better agreement. The sensitivities of the model to some key uncertain parameters are evaluated.
Samples of lichens, mosses and soil were used to compare lichen
Hypogymnia physodes
and moss
Hypnum Cupressiforme
as air pollution bioindicators by heavy metals and for air and soil pollution ...estimation. The content of heavy metals Bi, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was determined by flame atomic absorption spectrometry, and Hg was determined by cold vapour atomic absorption spectrometry. Mean concentrations of Bi, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn in lichens were 17.77, 0.49, 1.20, 7.73, 9.61, 4179, 0.014, 35.05, 7.30, 12.18 and 41.32 mg/kg, in mosses 19.34, 0.62, 3.01, 11.34, 10.48, 1696, 0.043, 135, 13.68, 54.52 and 54.79 mg/kg, and finally in soil 96.50, 2.23, 15.77, 46.79, 30.35, 24,343, 0.338, 833, 55.71, 42.86 and 86.19, respectively. Comparison of metal content in lichens and mosses sampled at the same locations showed a very strong to strong correlation for Bi, Ni, Cd, Fe, Pb, Co and Cr. Metal content in biological materials ranged from very high naturality to very high alteration. Very strong correlations of Bi with Cd and Pb and strong correlations for the pairs of Bi–Co, Cu, Fe, Ni, Ni–Co, Cr–Cu, Cd–Co, Co–Cr and Co–Hg were obtained in lichens. In the case of mosses, very strong correlations were obtained for Bi–Cd and Bi–Pb and strong correlations of Cd with Co, Ni, and Pb, Cr with Hg and Co were determined. In addition, the results were interpreted through enrichment factors reflecting the atmospheric availability of anthropogenic pollutant heavy metals.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is ...located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 plus or minus 0.7 mu g m-3. On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 plus or minus 51%), followed by sulfate (23 plus or minus 28%), nitrate (13 plus or minus 10%), chloride (2 plus or minus 3%), and elemental carbon (2 plus or minus 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100-1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests that the aerosol collected at the Pico Mountain Observatory had undergone cloud processing before reaching the site. Finally, the air masses of 9/25 were more aged and influenced by marine emissions, as indicated by the presence of organosulfates and other species characteristic of marine aerosol. The change in the air masses for the two samples was corroborated by the changes in ethane, propane, and ozone, morphology of particles, as well as by the FLEXPART retroplume simulations. This paper presents the first detailed molecular characterization of free tropospheric aged aerosol intercepted at a lower free troposphere remote location and provides evidence of low oxygenation after long-range transport. We hypothesize this is a result of the selective removal of highly aged and polar species during long-range transport, because the aerosol underwent a combination of atmospheric processes during transport facilitating aqueous-phase removal (e.g., clouds processing) and fragmentation (e.g., photolysis) of components.
An Aerodyne Aerosol Mass Spectrometer (AMS) was deployed at the CENICA Supersite, during the Mexico City Metropolitan Area field study (MCMA-2003) from 31 March-4 May 2003 to investigate particle ...concentrations, sources, and processes. The AMS provides real time information on mass concentration and composition of the non-refractory species in particulate matter less than 1 µm (NR-PM1) with high time and size-resolution. In order to account for the refractory material in the aerosol, we also present estimates of Black Carbon (BC) using an aethalometer and an estimate of the aerosol soil component obtained from Proton-Induced X-ray Emission Spectrometry (PIXE) analysis of impactor substrates. Comparisons of AMS + BC + soil mass concentration with other collocated particle instruments (a LASAIR Optical Particle Counter, a PM2.5 Tapered Element Oscillating Microbalance (TEOM), and a PM2.5 DustTrak Aerosol Monitor) show that the AMS + BC + soil mass concentration is consistent with the total PM2.5 mass concentration during MCMA-2003 within the combined uncertainties. In Mexico City, the organic fraction of the estimated PM2.5 at CENICA represents, on average, 54.6% (standard deviation σ=10%) of the mass, with the rest consisting of inorganic compounds (mainly ammonium nitrate and sulfate/ammonium salts), BC, and soil. Inorganic compounds represent 27.5% of PM2.5 (σ=10%); BC mass concentration is about 11% (σ=4%); while soil represents about 6.9% (σ=4%). Size distributions are presented for the AMS species; they show an accumulation mode that contains mainly oxygenated organic and secondary inorganic compounds. The organic size distributions also contain a small organic particle mode that is likely indicative of fresh traffic emissions; small particle modes exist for the inorganic species as well. Evidence suggests that the organic and inorganic species are not always internally mixed, especially in the small modes. The aerosol seems to be neutralized most of the time; however, there were some periods when there was not enough ammonium to completely neutralize the nitrate, chloride and sulfate present. The diurnal cycle and size distributions of nitrate suggest local photochemical production. On the other hand, sulfate appears to be produced on a regional scale. There are indications of new particle formation and growth events when concentrations of SO2 were high. Although the sources of chloride are not clear, this species seems to condense as ammonium chloride early in the morning and to evaporate as the temperature increases and RH decreases. The total and speciated mass concentrations and diurnal cycles measured during MCMA-2003 are similar to measurements during a previous field campaign at a nearby location.
Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The ...measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.
Two Aerodyne Aerosol Mass Spectrometers (Q-AMS) were deployed in Mexico City, during the Mexico City Metropolitan Area field study (MCMA-2003) from 29 March–4 May 2003 to investigate particle ...concentrations, sources, and processes. We report the use of a particle beam width probe (BWP) in the field to quantify potential losses of particles due to beam broadening inside the AMS caused by particle shape (nonsphericity) and particle size. Data from this probe show that no significant mass of particles was lost due to excessive beam broadening; i.e. the shape- and size-related collection efficiency (Es) of the AMS during this campaign was approximately one. Comparison of the BWP data from MCMA-2003 with other campaigns shows that the same conclusion holds for several other urban, rural and remotes sites. This means that the aerodynamic lens in the AMS is capable of efficiently focusing ambient particles into a well defined beam and onto the AMS vaporizer for particles sampled in a wide variety of environments. All the species measured by the AMS during MCMA-2003 have similar attenuation profiles which suggests that the particles that dominate the mass concentration were internally mixed most of the time. Only for the smaller particles (especially below 300 nm), organic and inorganic species show different attenuation versus particle size which is likely due to partial external mixing of these components. Changes observed in the focusing of the particle beam in time can be attributed, in part, to changes in particle shape (i.e. due to relative humidity) and size of the particles sampled. However, the relationships between composition, atmospheric conditions, and particle shape and size appear to be very complex and are not yet completely understood.
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