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A generally accepted method to measure black carbon (BC) or elemental carbon (EC) still does not exist An earlier study in the Vienna area comparing practically all measurement methods in use in Europe gave comparable BC and EC concentrations under summer conditions (Hitzenberger et al., 2006a). Under summer conditions, Diesel traffic is the major source for EC or BC in Vienna. Under winter conditions, space heating (also with biomass as fuel) is another important source (Caseiro et al., 2007). The present study compares the response of thermal methods (a modified Cachier method, Cachier et al., 1989; a thermal-optical method, Schmid et al., 2001; and two thermal-optical (TOT) methods using Sunset instruments, Birch and Cary, 1996 and Schauer et al., 2003) and optical methods (a light transmission method, Hansen et al., 1984; the integrating sphere method, Hitzenberger et al., 1996; and the multiangle absorption photometer MAAP, Petzold and Schönlinner, 2004). Significant differences were found between the TOT methods on the one hand and all other methods on the other. The TOT methods yielded EC concentrations that were lower by 44 and 17% than the average of all measured concentrations (including the TOT data). The largest discrepancy was found when the contribution of brown carbon (measured with the integrating sphere method) was largest. [ABSTRACT FROM AUTHOR]

Biogenic volatile organic compounds (VOCs), such as isoprene and α-/β-pinene, are photo-oxidized in the atmosphere to non-volatile species resulting in secondary organic aerosol (SOA). The goal of this study was to examine time trends and diel variations of oxidation products of isoprene and α-/β-pinene in order to investigate whether they are linked with meteorological parameters or trace gases. Separate day-night aerosol samples (PM1) were collected in a Scots pine dominated forest in southern Finland during 28 July–11 August 2005 and analyzed with gas chromatography/mass spectrometry (GC/MS). In addition, inorganic trace gases (SO2, CO, NOx, and O3), meteorological parameters, and the particle number concentration were monitored. The median total concentration of terpenoic acids (i.e., pinic acid, norpinic acid, and two novel compounds, 3-hydroxyglutaric acid and 2-hydroxy-4-isopropyladipic acid) was 65 ng m−3, while that of isoprene oxidation products (i.e., 2-methyltetrols and C5 alkene triols) was 17.2 ng m−3. The 2-methyltetrols exhibited day/night variations with maxima during day-time, while α-/β-pinene oxidation products did not show any diel variation. The sampling period was marked by a relatively high condensation sink, caused by pre-existing aerosol particles, and no nucleation events. In general, the concentration trends of the SOA compounds reflected those of the inorganic trace gases, meteorological parameters, and condensation sink. Both the isoprene and α-/β-pinene SOA products were strongly influenced by SO2, which is consistent with earlier reports that acidity plays a role in SOA formation. The results support previous proposals that oxygenated VOCs contribute to particle growth processes above boreal forest. [ABSTRACT FROM AUTHOR]

Biomass burning is an important source of smoke aerosol particles, which contain water-soluble inorganic and organic species, and thus have a great potential of affecting cloud formation, precipitation, and climate on global and regional scales. In this study, we have developed a new chromatographic method for the determination of levoglucosan (a specific tracer for biomass burning particles), related polyhydroxy compounds, and 2-methyl- erythritol (recently identified as isoprene oxidation product in fine aerosols in the Amazon) in smoke and in rainwater samples. The new method is based on water extraction and utilizes ion-exclusion high-performance liquid chromatography (IEC-HPLC) separation and spectroscopic detection at 194 nm. The new method allows the analysis of wet samples, such as rainwater samples. In addition, aliquots of the same extracts can be used for further analyses, such as ion chromatography. The overall method uncertainty for sample analysis is 15%. The method was applied to the analysis of high-volume and size-segregated smoke samples and to rainwater samples, all collected during and following the deforestation fires season in flondonia, Brazil. From the analysis of size-segregated samples, itis evidentthatlevoglucosan is a primary vegetation combustion product, emitted mostly in the 0.175-1 1um size bins. Levoglucosan concentrations decrease below the detection limit at the end of the deforestation fires period, implying that it is not present in significant amounts in background Amazon forest aerosols. The ratio of daytime levoglucosan concentration to particulate matter (PM) concentration was about half the nighttime ratio. This observation is rationalized by the prevalence of flaming combustion during day as opposed to smoldering combustion during night This work broadens the speciation possibilities offered by simple HPLC and demonstrates the importance of multianalysis of several kinds of samples for a deeper understanding of biomass burning aerosols. [ABSTRACT FROM AUTHOR]

Sampling of aerosol-nitrate can be problematic because of evaporative loss of the semi-volatile ammonium nitrate or adsorption of nitric acid gas. Such artefacts, which depend on filter type and ambient conditions, are not well documented for the filters in use in Europe and this was the reason to study these in a series of intercomparison trials. The trials were performed within the “INTERCOMP” programme of the AEROSOL subproject of EUROTRAC-2.The major effort was a 2-week field campaign at the rural site of Melpitz, a village near Leipzig in eastern Germany (INTERCOMP2000). Samplers were used containing the most common filter types in use in Europe, i.e. quartz, Teflon, (mixed) cellulose ester and cellulose. The concentration of nitrate in PM2.5, mainly present as ammonium nitrate, was on average 3.3μgm-3. The variability in the concentrations stemming from the samplers appeared to be rather constant: ± 0.5μgm-3 from the average of all samplers. The reason for the constant (but random) variability remains unexplained. Thus, the concentrations stemming from the samplers agreed very well at the average level with relative differences of 15% and less for higher concentrations. This is evidence that the influence of the mentioned artefacts was negligible. The absence is explained by extrapolation of results of tests on the artefacts in a laboratory setting (INTERCOMP99). It was found there that the loss of ammonium nitrate from Teflon and quartz filters is only substantial when temperatures are much higher than those during the field campaign. Cellulose and cellulose-acetate filters quantitatively collected both ammonium nitrate and nitric acid in the laboratory study, but in Melpitz measured nitric acid concentrations were too low to identify its adsorption. Possible artefacts due to adsorption of nitrous acid were negligible. We also used the laboratory information to evaluate the results of a further intercomparison (INTERCOMP98) in the Po-Valley, performed at much higher temperatures than at Melpitz. We found evidence of adsorption of nitric acid by cellulose filters and evaporational loss of aerosol-nitrate from quartz filters. For the conditions encountered during the campaign we parameterised the evaporational loss in a general way as a function of temperature, as follows. There is complete evaporation at temperatures exceeding 25°C and full retention at temperatures less than 20°C. At temperatures between 20 and 25°C the retention is on average 50%, but with high variability.A main conclusion from this study is that under central European conditions quartz is a suitable filter material for sampling nitrate as long as the temperature does not exceed 20°C during sampling. Cellulose-type filters quantitatively collect aerosol nitrate and nitric acid, but negligible amounts of nitrous acid. Teflon filters were more vulnerable for evaporation losses than quartz. Indications for losses from Teflon below 10°C (at Melpitz) were not obtained. [Copyright &y& Elsevier]

Within the EUROTRAC-2 subproject AEROSOL, the intensive field campaign INTERCOMP2000 was conducted to compare aerosol samplers and methods to measure various aerosol properties. Here a comparison of mass concentrations measured with different PM2.5 and PM10 samplers as well as cascade impactors is described. Different filter types were used. In general, the PM2.5 and PM10 mass concentrations obtained on filters agree well. The data agree within 18.1% (PM2.5, all data). If data obtained with the TEOM (18% low) and on Whatman QM-A quartz fibre filters (low face velocity, 38% high) are excluded, PM2.5 data agree within 8.1%. For PM10, the agreement is within 6.6% (again excluding the Whatman QM-A quartz fibre filters, 22% high) or 12.1% (all data). For the impactor samples, the data agreed within 6.3% (excluding the ELPI, which was 92% high) and 8.7% for PM2.5 and PM10. [Copyright &y& Elsevier]

Examines the impact of biomass burning on air quality in the 'Top End' of regional northern Australia. Particulate mass and elemental black carbon analysis; Median levels of fine, coarse and summed particulate matter.

Focuses on the activities undertaken during the dry season campaign in August and September 2000 of the Southern African Regional Science Initiative. Campaign goals and strategy; Experimental design; Airborne platforms and their instrumentation.

A key Earth system science question is the role of atmospheric deposition in supplying vital nutrients to the phytoplankton that form the base of marine food webs. Industrial and vehicular pollution, wildfires, volcanoes, biogenic debris, and desert dust all carry nutrients within their plumes throughout the globe. In remote ocean ecosystems, aerosol deposition represents an essential new source of nutrients for primary production. The large spatiotemporal variability in aerosols from myriad sources combined with the differential responses of marine biota to changing fluxes makes it crucially important to understand where, when, and how much nutrients from the atmosphere enter marine ecosystems. This review brings together existing literature, experimental evidence of impacts, and new atmospheric nutrient observations that can be compared with atmospheric and ocean biogeochemistry modeling. We evaluate the contribution and spatiotemporal variability of nutrient-bearing aerosols from desert dust, wildfire, volcanic, and anthropogenic sources, including the organic component, deposition fluxes, and oceanic impacts.

To control the spread of the novel coronavirus disease 2019 (COVID-19) in China, many anthropogenic activities were reduced and even closed on the national scale. To study the impact of this reduction and closing down, hourly concentrations of PM 2.5 -related elements were measured at a rural site before (12-25 January 2020), during (26 January-9 February 2020) and after (22 March-2 April 2020) the control period when all people remained socially isolated in their homes and could not return to economic zones for work. Nine major sources were identified by the positive matrix factorization model, including fireworks burning, coal combustion, vehicle emissions, dust, Cr industry, oil combustion, Se industry, Zn smelter, and iron and steel industry. Before the control period, K, Fe, Ca, Zn, Ba and Cu were the main elements, and fireworks burning, Zn smelter and vehicle emissions provided the highest contributions to the total element mass with 55%, 12.1% and 10.3%, respectively. During the control period, K, Fe, Ba, Cu and Zn were the dominating elements, and fireworks burning and vehicle emissions contributed 55% and 27% of the total element mass. After the control period, Fe, K, Ca, Zn and Ba were the main elements, and dust and iron and steel industry were responsible for 56% and 21% of the total element mass. The increased contribution from vehicle emissions during the control period could be attributed to our sampling site being near a town hospital and the fact that the vehicle activities were not restricted. The source apportionment results were also related to air mass backward trajectories. The largest reductions of dust, coal combustion, and the industrial sources (Cr industry, Zn smelter, Se industry, iron and steel industry) were distinctly seen for northwest transport (Ulanqab) and were least significant for northeast transport (Tangshan and Tianjin)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Direct infusion analysis using soft ionization techniques coupled to ultra-high-resolution mass spectrometers (UHRMS) allows screening of thousands of organic species in complex samples. Despite the high analytical throughput of direct infusion, this technique is known to be prone to matrix effects caused by changes in the ionization efficiency of an analyte, ion suppression, or enhancement due to the presence of certain compounds and inorganic salts in the sample. In this study we compared two soft ionization sources, that is, heated electrospray ionization (HESI) and nano-ESI for the analysis of atmospheric aerosol samples in the negative ionization mode. In-source fragmentation tests were conducted and experiments involving sample desalting through solid-phase extraction (SPE) with a reversed phase functionalized polymeric sorbent and spiking samples with inorganic salt were performed. Both ionization sources showed specific advantages and disadvantages for the direct infusion analysis of atmospheric aerosol extracts. The mass spectra of aerosol samples analyzed using HESI contained a large number of high molecular weight homologues containing sulfur and nitrogen, suggesting that this source is prone to formation of salt adducts and noncovalent compounds in samples enriched with inorganic salts. Data from the same aerosol sample extracts analyzed using nanoelectrospray ionization (nano-ESI) show less adduct formation; however, a decrease in the number of homologues was observed, as well as loss of molecules at higher mass range, indicating that the nano-ESI source is more prone to ion suppression. Irrespective of ionization source, SPE pretreatment significantly improved ion recoveries for organic species with nonpolar and moderately polar functional groups, but lower recoveries were obtained for highly oxygenated molecules. Therefore, while SPE reduced in-source adduct formation, it also limited the range of compounds identified through a single analysis.

Isoprene (C 5 H 8 ) is the main non-methane hydrocarbon emitted into the global atmosphere. Despite intense research, atmospheric transformations of isoprene leading to secondary organic aerosol (SOA) are still not fully understood, including its multiphase chemical reactions. Herein, we report on the detailed structural characterization of atmospherically relevant isoprene-derived organosulfates (OSs) with a molecular weight (MW) of 212 (C 5 H 8 SO 7 ), which are abundantly present in both ambient fine aerosol (PM 2.5 ) and laboratory-generated isoprene SOA. The results obtained from smog chamber-generated isoprene SOA and aqueous-phase laboratory experiments coupled to the S(IV)-autooxidation chemistry of isoprene, 3-methyl-2(5 H )-furanone, and 4-methyl-2(5 H )-furanone, allowed us for the first time to fully elucidate the isomeric structures of the MW 212 OSs. By applying liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry, we firmly confirmed six positional isomers of the MW 212 OSs in PM 2.5 collected from different sites in Europe and the United States. Our results also show that despite the low solubility of isoprene in water, aqueous-phase or multiphase chemistry can play an important role in the formation of OSs from isoprene. Possible formation mechanisms for the MW 212 OSs are also tentatively proposed.

Carbonaceous aerosols in high emission areas attract worldwide attention of the scientific community and the public due to their adverse impacts on the environment, human health and climate. However, long-term continuous hourly measurements are scarce on the regional scale. In this study, a one-year hourly measurement (from December 1, 2016 to November 30, 2017) of organic carbon (OC) and elemental carbon (EC) in airborne fine particles was performed using semi-continuous OC/EC analyzers in Beijing, Tianjin, Shijiazhuang and Tangshan in the Beijing-Tianjin-Hebei (BTH) region in China, which is one of high emission areas in China, even in the world. Marked spatiotemporal variations were observed. The highest concentrations of OC (22.8 ± 30.6 μg/m 3 ) and EC (5.4 ± 6.5 μg/m 3 ) occurred in Shijiangzhuang while the lowest concentrations of OC (11.0 ± 10.7 μg/m 3 ) and EC (3.1 ± 3.6 μg/m 3 ) were obtained in Beijing and Tianjin, respectively. Pronounced monthly, seasonal and diurnal variations of OC and EC were recorded. Compared to published data from the past two decades for the BTH region, our OC and EC levels were lower, implying some effect of recent measures for improving the air quality. Significant correlations of OC versus EC (p < 0.001) were found throughout the study period with high slopes and correlation coefficients in winter, but low slopes and correlation coefficients in summer. The estimated secondary OC (SOC), based on the minimum R squared (MRS) method, represented 29%, 47%, 38% and 48% of the OC for Beijing, Tianjin, Shijiazhuang and Tangshan, respectively. These percentages are larger than previous ones obtained for the BTH region in the past decade. There were obvious differences in the potential source regions of OC and EC among the four cities. Obvious prominent potential source areas of OC and EC were observed for Beijing, which were mainly located in the central and western areas of Inner Mongolia and even extended to the Mongolian regions, which is different from the findings in previous studies. For all sites, adjacent areas of the main provinces in northern China were found to be important potential source areas., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The Spring Festival (SF) is the most important holiday in China for family reunion and tourism. During the 2015 SF an intensive observation campaign of air quality was conducted to study the impact of the anthropogenic activities and the dynamic characteristics of the sources. During the study period, pollution episodes frequently occurred with 12days exceeding the Chinese Ambient Air Quality Standards for 24-h average PM 2.5 (75μg/m 3 ), even 8days with exceeding 150μg/m 3 . The daily maximum PM 2.5 concentration reached 350μg/m 3 while the hourly minimum visibility was <0.8km. Three pollution episodes were selected for detailed analysis including chemical characterization and diurnal variation of the PM 2.5 and its chemical composition, and sources were identified using the Positive Matrix Factorization model. The first episode occurring before the SF was characterized by more formation of SO 4 2- and NO 3 - and high crustal enrichment factors for Ag, As, Cd, Cu, Hg, Pb, Se and Zn and seven categories of pollution sources were identified, whereby vehicle emission contributed 38% to the PM 2.5 . The second episode occurring during the SF was affected heavily by large-scale firework emissions, which led to a significant increase in SO 4 2- , Cl - , OC, K and Ba; these emissions were the largest contributor to the PM 2.5 accounting for 36%. During the third episode occurring after the SF, SO 4 2- , NO 3 - , NH 4 + and OC were the major constituents of the PM 2.5 and the secondary source was the dominant source with a contribution of 46%. The results provide a detailed understanding on the variation in occurrence, chemical composition and sources of the PM 2.5 as well as of the gaseous pollutants affected by the change in anthropogenic activities in Beijing throughout the SF. They highlight the need for limiting the firework emissions during China's most important traditional festival., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Stable carbon isotope ratios in marine aerosol collected over the Southern Indian Ocean revealed δ 13 C values ranging from -20.0‰ to -28.2‰. The isotope ratios exhibited a strong correlation with the fractional organic matter (OM) enrichment in sea spray aerosol. The base-level isotope ratio of -20.0‰ is characteristic of an aged Dissolved Organic Matter (DOM) pool contributing a relatively homogeneous background level of DOM to oceanic waters. The range of isotope ratios, extending down to -28.2‰, is characteristic of more variable, stronger, and fresher Particulate Organic Matter (POM) pool driven by trophic level interactions. We present a conceptual dual-pool POM-DOM model which comprises a 'young' and variable POM pool which dominates enrichment in sea-spray and an 'aged' but invariant DOM pool which is, ultimately, an aged end-product of processed 'fresh' POM. This model is harmonious with the preferential enrichment of fresh colloidal and nano-gel lipid-like particulate matter in sea spray particles and the observed depleted δ 13 C ratio resulting from isotope equilibrium fractionation coupled with enhanced plankton photosynthesis in cold water (-2 °C to +8 °C). These results re-assert the hypothesis that OM enrichment in sea-spray is directly linked to primary production and, consequently, can have implications for climate-aerosol-cloud feedback systems.

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

From 30 June 2011 to 2 July 2012 PM10 aerosol samples were simultaneously taken every 4th day at four urban background sites in Flanders, Belgium. The sites were in Antwerpen, Gent, Brugge, and Oostende. The PM10 mass concentration was determined by weighing; organic and elemental carbon (OC and EC) were measured by thermal-optical analysis, the wood burning tracers levoglucosan, mannosan and galactosan were determined by gas chromatography/mass spectrometry, 8 water-soluble ions were measured by ion chromatography, and 15 elements were determined by a combination of inductively coupled plasma atomic emission spectrometry and mass spectrometry. The multi-species dataset was subjected to receptor modeling by PMF. The 10 retained factors (with their overall average percentage contributions to the experimental PM10 mass) were wood burning (9.5%), secondary nitrate (24%), secondary sulfate (12.6%), sea salt (10.0%), aged sea salt (19.2%), crustal matter (9.7%), non-ferrous metals (1.81%), traffic (10.3%), non-exhaust traffic (0.52%), and heavy oil burning (3.0%). The average contributions of wood smoke for the four sites were quite substantial in winter and ranged from 12.5 to 20% for the PM10 mass and from 47 to 64% for PM10 OC. Wood burning appeared to be also a notable source of As, Cd, and Pb. The contribution from wood burning to the PM10 mass and OC was also assessed by making use of levoglucosan as single marker compound and the conversion factors of Schmidl et al. (2008), as done in our previous study on wood burning in Flanders (Maenhaut et al., 2012). However, the apportionments were much lower than those deduced from PMF. It seems that the conversion factors of Schmidl et al. (2008) may not be applicable to wood burning in Flanders. From scatter plots of the PMF-derived wood smoke OC and PM versus levoglucosan, we arrived at conversion factors of 9.7 and 22.6, respectively., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Evidence is provided that the green leaf volatile 3-Z-hexenal serves as a precursor for biogenic secondary organic aerosol through the formation of polar organosulfates (OSs) with molecular weight (MW) 226. The MW 226 C6-OSs were chemically elucidated, along with structurally similar MW 212 C5-OSs, whose biogenic precursor is likely related to 3-Z-hexenal but still remains unknown. The MW 226 and 212 OSs have a substantial abundance in ambient fine aerosol from K-puszta, Hungary, which is comparable to that of the isoprene-related MW 216 OSs, known to be formed through sulfation of C5-epoxydiols, second-generation gas-phase photooxidation products of isoprene. Using detailed interpretation of negative-ion electrospray ionization mass spectral data, the MW 226 compounds are assigned to isomeric sulfate esters of 3,4-dihydroxyhex-5-enoic acid with the sulfate group located at the C-3 or C-4 position. Two MW 212 compounds present in ambient fine aerosol are attributed to isomeric sulfate esters of 2,3-dihydroxypent-4-enoic acid, of which two are sulfated at C-3 and one is sulfated at C-2. The formation of the MW 226 OSs is tentatively explained through photooxidation of 3-Z-hexenal in the gas phase, resulting in an alkoxy radical, followed by a rearrangement and subsequent sulfation of the epoxy group in the particle phase.

An oxygenated MW 188 compound is commonly observed in substantial abundance in atmospheric aerosol samples and was proposed in previous studies as an α-pinene-related marker compound that is associated with aging processes. Owing to difficulties in producing this compound in sufficient amounts in laboratory studies and the occurrence of isobaric isomers, a complete assignment for individual MW 188 compounds could not be achieved in these studies. Results from a comprehensive mass spectrometric analysis are presented here to corroborate the proposed structure of the most abundant MW 188 compound as a 2-hydroxyterpenylic acid diastereoisomer with 2R,3R configuration. The application of collision-induced dissociation with liquid chromatography/electrospray ionization-ion trap mass spectrometry in both negative and positive ion modes, as well as chemical derivatization to methyl ester derivatives and analysis by the latter technique and gas chromatography/electron ionization mass spectrometry, enabled a comprehensive characterization of MW 188 isomers, including a detailed study of the fragmentation behavior using both mass spectrometric techniques. Furthermore, a MW 188 positional isomer, 4-hydroxyterpenylic acid, was tentatively identified, which also is of atmospheric relevance as it could be detected in ambient fine aerosol. Quantum chemical calculations were performed to support the diastereoisomeric assignment of the 2-hydroxyterpenylic acid isomers. Results from a time-resolved α-pinene photooxidation experiment show that the 2-hydroxyterpenylic acid 2R,3R diastereoisomer has a time profile distinctly different from that of 3-methyl-1,2,3-butanetricarboxylic acid, a marker for oxygenated (aged) secondary organic aerosol. This study presents a comprehensive chemical data set for a more complete structural characterization of hydroxyterpenylic acids in ambient fine aerosol, which sets the foundation to better understand the atmospheric fate of α-pinene in future studies.

Organic compounds are important constituents of fine particulate matter (PM) in the troposphere. In this study, we applied direct infusion nanoelectrospray (nanoESI) ultrahigh resolution mass spectrometry (UHR-MS) and liquid chromatography LC/ESI-UHR-MS for the analysis of the organic fraction of PM1 aerosol samples collected over a two week period at a boreal forest site (Hyytiälä), southern Finland. Elemental formulas (460-730 in total) were identified with nanoESI-UHR-MS in the negative ionization mode and attributed to organic compounds with a molecular weight below 400. Kendrick Mass Defect and Van Krevelen approaches were used to identify compound classes and mass distributions of the detected species. The molecular composition of the aerosols strongly varied between samples with different air mass histories. An increased number of nitrogen, sulfur, and highly oxygenated organic compounds was observed during the days associated with continental air masses. However, the samples with Atlantic air mass history were marked by a presence of homologous series of unsaturated and saturated C12-C20 fatty acids suggesting their marine origin. To our knowledge, we show for the first time that the highly detailed chemical composition obtained from UHR-MS analyses can be clearly linked to meteorological parameters and trace gases concentrations that are relevant to atmospheric oxidation processes. The additional LC/ESI-UHR-MS analysis revealed 29 species, which were mainly attributed to oxidation products of biogenic volatile compounds BVOCs (i.e., α,β-pinene, Δ3-carene, limonene, and isoprene) supporting the results from the direct infusion analysis.

Rationale: A considerable fraction of atmospheric particulate fine matter consists of organosulfates, with some of the most polar ones originating from the oxidation of isoprene. Their structural characterization provides insights into the nature of gas-phase precursors as well as into formation pathways., Methods: The structures of unknown polar organosulfates present in ambient particulate fine matter were characterized using liquid chromatography/(-)electrospray ionization mass spectrometry (LC/(-)ESI-MS), including ion trap MS(n) and accurate mass measurements, derivatization of the carbonyl group into 2,4-dinitrophenylhydrazones, detailed interpretation of the MS data, and in a selected case comparison of their LC and MS behavior with that of synthesized reference compounds., Results: Polar organosulfates with molecular weights (MWs) of 156, 170, 184 and 200 were attributed to/or confirmed as derivatives of glycolic acid (156), lactic acid (170), 1,2-dihydroxy-3-butanone (184), glycolic acid glycolate (200), 2-methylglyceric acid (200), and 2,3-dihydroxybutanoic acid (200). In the case of the MW 184 compound an unambiguous assignment was obtained through synthesis of reference compounds., Conclusions: A more complete structural characterization of polar organosulfates that originate from isoprene secondary organic aerosol was achieved. An important atmospheric finding is the presence of an organosulfate that is related to methyl vinyl ketone, a major gas-phase oxidation product of isoprene. In addition, minor polar organosulfates related to crotonaldehyde were identified., (Copyright © 2013 John Wiley & Sons, Ltd.)

In the present work, we have evaluated whether isomeric C5-alkene diols (1,2-dihydroxy-2-methyl-3-butene, 1,2-dihydroxy-3-methyl-3-butene, and 1,4-dihydroxy-2-methyl-2-butene (cis + trans)), which have first been detected upon photooxidation of isoprene in the absence of NO and are known to be formed in the ambient atmosphere, can serve as precursors for the 2-methyltetrols, C5-alkene triols, and 2-methylglyceric acid under low-NO(x) conditions. The C5-alkene diols were prepared following published synthesis procedures. It is shown that under the applied chamber conditions the isomeric C5-alkene diols give rise to 2-methyltetrols with different threo/erythro abundance ratios and that certain diols produce 2-methylglyceric acid, but that they do not form C5-alkene triols. Furthermore, it is shown that the photooxidation of isoprene under the applied chamber conditions employing photolysis of H2O2 under dry conditions yields relatively small amounts of C5-alkene triols compared to those of the 2-methyltetrols, unlike under ambient conditions. It is argued that the chamber conditions are not optimal for the formation of C5-epoxydiols, which serve as gas-phase precursors for the C5-alkene triols, and likely as in some previous studies favor the formation of C5-alkene diols as a result of RO2 + RO2 reactions.

Nitrogen-containing organic compounds in the atmosphere have drawn attention owing to their impact on aerosol chemistry and physics and their potential adverse effects on the biosphere. Among them, nitrocatechols and their homologs have recently been associated with biomass burning. In the present study, nitrocatechols, nitrophenols, nitroguaiacols and nitrosalicylic acids (NSAs) were simultaneously quantified for the first time by using a new analytical method based on liquid chromatography/tandem mass spectrometry, which was systematically optimized and validated. Several analyte specific issues regarding the sample preparation and chromatographic analysis were addressed in order to ensure method sensitivity, precision, and accuracy. Sample matrix effects were thoroughly investigated in order to ensure method specificity. The method was found to be sensitive with limits of detection ranging from 0.1 to 1.0 μg L(-1), and with accuracy generally between 90 and 104%. The relative standard deviations for repeatability and intermediate precision were better than 4% and 9%, respectively. The method was applied to the analysis of winter and summer PM(10) samples from the city of Ljubljana, Slovenia. Aerosol concentrations as high as 152 and 134 ng m(-3) were obtained for the major aerosol nitro-aromatics: 4-nitrocatechol (4NC) and methyl-nitrocatechols (MNCs), respectively. Up to 500-times higher concentrations of 4NC and MNCs were found in winter compared to summer aerosols. The correlation analysis for winter samples showed that 4NC, MNCs, and NSAs are strongly inter-correlated (R(2)=0.84-0.96). Significant correlations between these analytes and anhydrosugars support their proposed origin from biomass burning. The studied nitro-aromatics were found to constitute a non-negligible fraction (around 1%) of the organic carbon., (Copyright © 2012 Elsevier B.V. All rights reserved.)

From February 2010 to February 2011 PM10 aerosol samples were simultaneously taken every 4th day at 7 monitoring sites in Flanders, Belgium. Two of the sites (i.e., Borgerhout and Gent) were urban background sites; one (i.e., Mechelen) a suburban background site, and the other four (i.e., Hamme, Lier, Retie, and Houtem) rural background sites, whereby Hamme and Lier were expected to be particularly impacted by biomass burning. The samplings were done for 24h and 47-mm diameter Pallflex® Tissuquartz™ 2500 QAT-UP filters were used. After sampling the PM10 mass concentration was determined by weighing; organic and elemental carbon (OC and EC) were measured by thermal-optical transmission analysis and the wood burning tracers levoglucosan, mannosan, and galactosan were determined by means of gas chromatography/mass spectrometry. The atmospheric concentrations of levoglucosan and the other two monosaccharide anhydrides showed a very clear seasonal variation at each site, with highest levels in winter, followed by autumn, spring, and summer. The levoglucosan levels for 5 of our 7 sites (i.e., Retie, Lier, Mechelen, Borgerhout, and Gent) were very highly correlated with each other (all between site correlation coefficients r>0.9, except for one value of 0.86) and the levels in the parallel samples of these 5 sites were similar, indicating that wood burning at these 5 sites was a regional phenomenon and that it was taking place in many individual houses on similar occasions (e.g., on cold days, weekends or holidays). The levoglucosan levels at Houtem and the correlation coefficients of the 5 sites with Houtem were lower, which is explained by the fact that the latter site is at less than 20 km from the North Sea so that the air there is often diluted by rather clean westerly maritime air. A peculiar behavior was seen for Hamme, with on many occasions very high levoglucosan levels, which was attributed to the fact that there is wood burning going on in several houses nearby this site. From our levoglucosan/mannosan ratios we derived the relative contributions of softwood and hardwood burning, thereby following the same approach as used by Schmidl et al. (Atmos Environ 2008;38:126-41). It was found that softwood burning accounted, on average, for about 70%, and there was little variation in this percentage with site or with season. The levoglucosan data were used to assess the contribution of wood burning to the OC and to the PM10 mass, again following the approach of Schmidl et al. (2008). The annual average contributions of wood burning OC to the PM10 OC were in the range of 20-25% for 6 of our 7 sites and 36% for Hamme; the averages for summer were 2.0-3.9% for the 6 sites and 14.5% for Hamme; the corresponding data for winter were 36-43% and 60%. As to the contribution from wood burning to the PM10 mass, the annual averages were in the range of 4.8-6.3% for 6 of our 7 sites and 13.3% at Hamme; the averages for summer were 0.51-1.14% for the 6 sites and 5.0% for Hamme; the corresponding data for winter were 8.6-11.3% and 22%. Our finding that wood burning is an important contributor to the OC and the PM10 mass, especially in winter, is in line with published data from various other sites in other European countries., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A specially designed annular diffusion denuder for simultaneous removal of organic gaseous compounds and atmospheric oxidants in carbonaceous aerosol sampling is presented. Various kinds of denuder coatings were compared with respect to the collection efficiency of both organic gaseous compounds and NO(2) and ozone. The optimum sorbent is a mixture of activated charcoal and sulfite on molecular sieve. To ensure high collection efficiency over long-term field operation, two annular diffusion denuders are combined in series. The first half of the first denuder is filled with Na(2)SO(3) on molecular sieve (23 cm long layer) while the second half of the first denuder and the whole second denuder are filled with activated charcoal (the total length of the charcoal section is 67 cm). At a flow rate of 16.6 L min(-1), the collection efficiency of organic gaseous compounds and atmospheric oxidants in the annular diffusion denuder is better than 95%. Only small losses of aerosol particles (<3.6% in number concentration) were observed in the size range 0.12-2.26 μm. The annular diffusion denuder is compatible with the collection of aerosols on 47-mm diameter quartz fiber filters at a flow rate of 16.6 L min(-1). The use of this denuder enables one to sample carbonaceous aerosols on filters without positive sampling artefacts from volatile organic compounds and interferences from atmospheric oxidants. The annular diffusion denuder has been applied successfully for the sampling of carbonaceous aerosols during field campaigns of typically 1 month each at urban and forested sites in Europe., (Copyright © 2011 Elsevier B.V. All rights reserved.)

In this study, we present liquid chromatographic and mass spectral data for predominant terpenoic acids formed through oxidation of α-pinene, β-pinene, d-limonene, and Δ(3)-carene that occur in fine forest aerosol from K-puszta, Hungary, a rural site with coniferous vegetation. Characterization of these secondary organic aerosol tracers in fine ambient aerosol is important because it allows one to gain information on monoterpene precursors and source processes such as oxidation and aging processes. The mass spectral data were obtained using electrospray ionization in the negative ion mode, accurate mass measurements, and linear ion trap tandem mass spectrometric experiments. Emphasis is given to the mass spectrometric differentiation of isobaric terpenoic acids, such as, e.g. the molecular weight (MW) 186 terpenoic acids, cis-pinic, cis-caric, homoterpenylic, ketolimononic, and limonic acids. Other targeted isobaric terpenoic acids are the MW 184 terpenoic acids, cis-pinonic and cis-caronic acids, and the MW 204 tricarboxylic acids, 3-methyl-1,2,3-butanetricarboxylic and 3-carboxyheptanedioic acids. Fragmentation pathways are proposed to provide a rational explanation for the observed isomeric differences and/or to support the suggested tentative structures. For the completeness of the data set, data obtained for recently reported lactone-containing terpenoic acids (i.e. terpenylic and terebic acids), related or isobaric compounds (i.e. norpinic acid, diaterpenylic acid acetate, and unknown MW 188 compounds) are also included, the rationale being that other groups working on this topic could use this data compilation as a reference., (Copyright © 2011 John Wiley & Sons, Ltd.)

Ambient daytime and nighttime PM(10) and PM(2.5) samples were collected in parallel at a kerbside in Dar es Salaam in August and September 2005 (dry season) and in April and May 2006 (wet season). All samples were analyzed for the particulate matter mass, for organic, elemental, and total carbon (OC, EC, and TC), and for water-soluble OC (WSOC). The average PM(10) and PM(2.5) mass concentrations and associated standard deviations were 76+/-32microg/m(3) and 26+/-7microg/m(3) for the 2005 dry season and 52+/-27microg/m(3) and 19+/-10microg/m(3) for the 2006 wet season campaign. On average, TC accounted for 29% of the PM(10) mass and 49% of the PM(2.5) mass for the 2005 dry season campaign and the corresponding values for the 2006 wet season campaign were 35% and 59%. There was little difference between the two campaigns for the WSOC/OC ratios with the PM(2.5) fraction having higher ratios than the PM(10) fraction during each campaign. Also for EC/TC higher ratios were noted in PM(2.5) than in PM(10), but the ratios were substantially larger in the 2006 wet season than in the 2005 dry season. The large EC/TC ratios (means 0.22-0.38) reflect the substantial impact from traffic at Dar es Salaam, as was also apparent from the clear diurnal variation in OC levels, with higher values during the day. A simple source apportionment approach was used to apportion the OC to traffic and charcoal burning. On average, 70% of the PM(10) OC was attributed to traffic and 30% to charcoal burning in both campaigns. A definite explanation for the substantially larger EC/TC ratios in the 2006 campaign as compared to the 2005 campaign is not available.

Novel secondary organic aerosol (SOA) products from the monoterpene alpha-pinene with unique dimer-forming properties have been identified as lactone-containing terpenoic acids, i.e., terpenylic and 2-hydroxyterpenylic acid, and diaterpenylic acid acetate. The structural characterizations were based on the synthesis of reference compounds and detailed interpretation of mass spectral data. Terpenylic acid and diaterpenylic acid acetate are early oxidation products generated upon both photooxidation and ozonolysis, while 2-hydroxyterpenylic acid is an abundant SOA tracer in ambient fine aerosol that can be explained by further oxidation of terpenylic acid. Quantum chemical calculations support that noncovalent dimer formation involving double hydrogen bonding interactions between carboxyl groups of the monomers is energetically favorable. The molecular properties allow us to explain initial particle formation in laboratory chamber experiments and are suggested to play a role in new particle formation and growth above forests, a natural phenomenon that has fascinated scientists for more than a century.

Mass concentrations, mass size distributions, time series, and diel variations for organic tracers and major inorganic ions in aerosols from K-puszta, Hungary, during a 2003 summer period are reported. Emphasis was placed on alpha-beta-pinene secondary organic aerosol (SOA) tracers comprising cis-pinic acid, 3-hydroxyglutaric acid, and 3-methyl-1,2,3-butanetricarboxylic acid. Only cis-pinic acid and the d-limonene SOA tracer 3-carboxyheptanedioic acid exhibited diel variations with highest concentrations at night Malic acid was fairly well correlated with succinic and oxalic acid, pointing to a similar SOA formation process. No day-night variations were observed for the latter acids, suggesting that they are formed over relatively longtime scales. Of the ionic species sulfate, ammonium, and nitrate, only nitrate showed clear diel variations with highest concentrations at night. As to the size-segregated samples, the 2-methyltetrols were present in both the fine and coarse modes, while the C5-alkene triols and the alpha-/beta-pinene SOA tracers were only associated with the fine mode. The ionic species sulfate, ammonium, and nitrate made up for, on average, 24, 10, and 26% of the PM2.5 mass, while organic matter was responsible for 47% of that mass. Isoprene and alpha-pinene secondary organic carbon (SOC) accounted, on average, for, respectively, 6.8 and at least 4.8% of the PM2.5 organic carbon, but the contribution of isoprene SOC was more pronounced during daytime (9.6%), whereas that of alpha-pinene SOC was largest at night (at least 6.0%).

Atmospheric inputs of iron to the open ocean are hypothesized to modulate ocean biogeochemistry. This review presents an integration of available observations of atmospheric iron and iron deposition, and also covers bioavailable iron distributions. Methods for estimating temporal variability in ocean deposition over the recent past are reviewed. Desert dust iron is estimated to represent 95% of the global atmospheric iron cycle, and combustion sources of iron are responsible for the remaining 5%. Humans may be significantly perturbing desert dust (up to 50%). The sources of bioavailable iron are less well understood than those of iron, partly because we do not know what speciation of the iron is bioavailable. Bioavailable iron can derive from atmospheric processing of relatively insoluble desert dust iron or from direct emissions of soluble iron from combustion sources. These results imply that humans could be substantially impacting iron and bioavailable iron deposition to ocean regions, but there are large uncertainties in our understanding.

The molecular composition of PM2.5 (particulate matter with an aerodynamic diameter <2.5 microm) aerosol samples collected during a very warm and dry 2003 summer period at a mixed forest site in Jülich, Germany, was determined by gas chromatography/mass spectrometry in an effort to evaluate photooxidation products of biogenic volatile organic compounds (BVOCs) and other markers for aerosol source characterization. Six major classes of compounds represented by twenty-four individual organic species were identified and measured, comprising tracers for biomass combustion, short-chain acids, fatty acids, sugars/sugar alcohols, and tracers for the photooxidation of isoprene and alpha-/beta-pinene. The tracers for the photooxidation of alpha-/beta-pinene include two compounds, 3-hydroxyglutaric acid and 3-methyl-1,2,3-butanetricarboxylic acid, which have only recently been elucidated. The characteristic molecular distribution of the fatty acids with a strong even/odd number carbon preference indicates a biological origin, while the presence of isoprene and terpene secondary organic aerosol products suggests that the photooxidation of BVOCs contributes to aerosol formation at this site. The sum of the median concentrations of the isoprene oxidation products was 21.2 ng m(-3), while that of the terpene oxidation products was 19.8 ng m(-3). On the other hand, the high median concentration of malic acid (37 ng m(-3)) implies that photooxidation of unsaturated fatty acids should also be considered as an important aerosol source process. In addition, the occurrence of levoglucosan and pyrogallol indicates that the site is affected by biomass combustion. Their median concentrations were 30 and 8.9 ng m(-3), respectively.

Organosulfates of isoprene, alpha-pinene, and beta-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%.

In the present study, we have characterized in detail the MS(2) and MS(3) fragmentation behaviors, using electrospray ionization (ESI) in the negative ion mode, of previously identified sulfated isoprene secondary organic aerosol compounds, including 2-methyltetrols, 2-methylglyceric acid, 2-methyltetrol mononitrate derivatives, glyoxal and methylglyoxal. A major fragmentation pathway for the deprotonated molecules of the sulfate esters of 2-methyltetrols and 2-methylglyceric acid and of the sulfate derivatives of glyoxal and methylglyoxal is the formation of the bisulfate [HSO(4)](-) anion, while the deprotonated sulfate esters of 2-methyltetrol mononitrate derivatives preferentially fragment through loss of nitric acid. Rational interpretation of MS(2), MS(3) and accurate mass data led to the structural characterization of unknown polar compounds in K-puszta fine aerosol as organosulfate derivatives of photooxidation products of unsaturated fatty acids, i.e. 2-hydroxy-1,4-butanedialdehyde, 4,5- and 2,3-dihydroxypentanoic acids, and 2-hydroxyglutaric acid, and of alpha-pinene, i.e. 3-hydroxyglutaric acid. The deprotonated molecules of the sulfated hydroxyacids, 2-methylglyceric acid, 4,5- and 2,3-dihydroxypentanoic acid, and 2- and 3-hydroxyglutaric acids, showed in addition to the [HSO(4)](-) ion (m/z 97) neutral losses of water, CO(2) and/or SO(3), features that are characteristic of humic-like substances. The polar organosulfates characterized in the present work are of climatic relevance because they may contribute to the hydrophilic properties of fine ambient aerosol. In addition, these compounds probably serve as ambient tracer compounds for the occurrence of secondary organic aerosol formation under acidic conditions., (Copyright (c) 2008 John Wiley & Sons, Ltd.)

Detailed organic analysis of fine (PM2.5) rural aerosol collected during summer at K-puszta, Hungary from a mixed deciduous/coniferous forest site shows the presence of polar oxygenated compounds that are also formed in laboratory irradiated alpha-pinene/NOx/air mixtures. In the present work, two major photooxidation products of alpha-pinene were characterized as the hydroxydicarboxylic acids, 3-hydroxyglutaric acid, and 2-hydroxy-4-isopropyladipic acid, based on chemical, chromatographic, and mass spectral data. Different types of volatile derivatives, including trimethylsilyl ester/ether, methyl ester trimethylsilyl ether, and ethyl ester trimethylsilyl ether derivatives were measured by gas chromatography/mass spectrometry (GC/MS), and their electron ionization (El) spectra were interpreted in detail. The proposed structures of the hydroxydicarboxylic acids were confirmed or supported with reference compounds. 2-Hydroxy-4-isopropyladipic acid formally corresponds to a further reaction product of pinic acid involving addition of a molecule of water and opening of the dimethylcyclobutane ring; this proposal is supported by a laboratory irradiation experiment with alpha-pinene/NOJ0 air. In addition, we report the presence of a structurally related minor alpha-pinene photooxidation product, which was tentatively identified as the C7 homolog of 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid. The detection of 2-hydroxy-4-isopropyladipic acid in ambient aerosol provides an explanation for the relatively low atmospheric concentrations of pinic acid found during daytime in forest environments.

Median atmospheric concentrations of Pb, Br, S, As, Se, and particulate matter (PM) decreased, and median concentrations of Sb, Cu, Zn, Fe, Ca, Cr and Ba increased in urban aerosol in downtown Budapest between 1996 and 2002. The changes in Pb and Br concentrations were unambiguously attributed to the phasing out of leaded gasoline. The increments were mainly related to and explained by non-exhaust vehicular emissions. The mechanical wear of asbestos-free brake linings of road vehicles contributed to the concentration of Cu and Sb on average by 69% and 66%, respectively in the PM10 size fraction. Tire rubber abrasion was a major source for atmospheric Zn; on average, non-crustal sources accounted for 67% of Zn in the PM10 size fraction. Contribution of the tire wear component to the PM10 mass was estimated to be 6% at most, while its contribution to organic aerosol was of the order of 15%.

Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C(5)H(8)) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO(x) conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO(x) level, with acidic products formed under high-NO(x) conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO(x) conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise approximately 22-34% of the high-NO(x) SOA mass. Under low-NO(x) conditions, organic peroxides contribute significantly to the low-NO(x) SOA mass (approximately 61% when SOA forms by nucleation and approximately 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C(5) alkene triols and 2-methyltetrols under low-NO(x) conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO(x) chamber experiments.

Water-soluble inorganic ions in aerosol samples have been studied. The sample collection took place during summer in 2003 at a European background site which is operating within the framework of the European Monitoring and Evaluation Program. Gent type PM10 stacked filter unit (SFU) samplers were operated in parallel on a day and night basis to collect particles in separate coarse (2.0-10 microm) and fine (<2.0 microm) size fractions. Particulate masses were measured gravimetrically; the filters from one of the SFU samplers were analyzed by particle-induced X-ray emission spectrometry (PIXE) and instrumental neutron activation analysis (INAA). Filters from the other SFU sampler were analyzed by ion chromatography (IC) for major inorganic anions (MSA-, NO2(-), NO3(-), Cl-, Br-, SO4(2-), oxalate) and cations (Na+, K+, NH4(+), Mg2+, Ca2+). The water-soluble inorganic ions measured were responsible for 44% and 16% of the total fine and coarse particulate mass, respectively. In the fine size fraction, the main ionic components were SO4(2-) and NH4(+) accounting for about 90% of fine ionic mass. In the coarse fraction the main ionic components were Ca2+ and NO3(-), followed by SO4(2-). Significant day and night difference in the mass concentrations was observed only for fine NO3(-). The molar ratios of fine NH4(+) to SO4(2-) indicated their complete neutralization to (NH4)2SO4. According to the cation-to-anion ratios the coarse particles were alkaline, while the fine particles were slightly acidic or neutral. By comparing the corresponding concentrations obtained from PIXE/INAA and IC, we determined the water-extractable part of the individual species. We also investigated the effect of long-range transported air masses on the local air concentrations, and we found that the air quality of this background monitoring station was affected by regional pollution sources.

In the present study, we have tentatively identified the structures of three oxygenated derivatives of isoprene in Amazonian rain forest aerosols as the C(5) alkene triols, 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene. The formation of these oxygenated derivatives of isoprene can be explained by acid-catalyzed ring opening of epoxydiol derivatives of isoprene, namely, 1,2-epoxy-2-methyl-3,4-dihydroxybutane and 1,2-dihydroxy-2-methyl-3,4-epoxybutane. The structural proposals of the C(5) alkene triols were based on chemical derivatization reactions and detailed interpretation of electron and chemical ionization mass spectral data, including data obtained from first-order mass spectra, deuterium labeling of the trimethylsilyl methyl groups, and MS(2) ion trap experiments. The characterization of 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene in forest aerosols is important from an atmospheric chemistry viewpoint in that these compounds hint at the formation of intermediate isomeric epoxydiol derivatives of isoprene and as such provide mechanistic insights into the formation of the previously reported 2-methyltetrols through photooxidation of isoprene., (Copyright 2005 John Wiley & Sons, Ltd.)

Detailed organic analysis of natural aerosols from the Amazonian rain forest showed considerable quantities of previously unobserved polar organic compounds, which were identified as a mixture of two diastereoisomeric 2-methyltetrols: 2-methylthreitol and 2-methylerythritol. These polyols, which have the isoprene skeleton, can be explained by OH radical-initiated photooxidation of isoprene. They have low vapor pressure, allowing them to condense onto preexisting particles. It is estimated that photooxidation of isoprene results in an annual global production of about 2 teragrams of the polyols, a substantial fraction of the Intergovernmental Panel on Climate Change estimate of between 8 and 40 teragrams per year of secondary organic aerosol from biogenic sources.

We developed and validated a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and the related monosaccharide anhydrides, mannosan, galactosan and 1,6-anhydro-beta-D-glucofuranose in urban atmospheric aerosols collected on quartz fiber filters. The method is based on extraction with dichloromethane-methanol (80 : 20, v/v), trimethylsilylation, multiple reaction monitoring in the tandem mass spectrometric mode using the ion at m/z 217, and the use of an internal standard calibration procedure with the structurally related compound methyl beta-L-arabinopyranoside. In addition, the method allows the quantification of other saccharidic compounds, arabitol, mannitol, glucose, fructose, inositol and sucrose, which were found to be important in summer aerosols. The recovery of levoglucosan was estimated by spiking blank filters and was better than 90%. The precision evaluated by analyzing parts of the same filters was about 2% for the monosaccharide anhydrides and 7% for the other saccharidic compounds in the case of a winter aerosol sample, and the corresponding values for a summer aerosol sample were 5% and 8%. The method was applied to urban PM(10) (particulate matter of <10 microm aerodynamic diameter) aerosols collected at Ghent, Belgium, during a 2000-2001 winter and a 2001 summer episode and revealed interesting seasonal variations. While monosaccharide anhydrides were relatively more important during the winter season owing to wood burning, the other saccharidic compounds were more prevalent during the summer season, with some of them, if not all, originating from the vegetation., (Copyright 2002 John Wiley & Sons, Ltd.)

An improved analytical method was developed and validated for the determination of the monosaccharide anhydrides levoglucosan, mannosan, and galactosan in atmospheric aerosol samples. The method uses an external recovery standard, extraction in dichloromethane, trimethylsilylation, addition of an internal standard (1-phenyl dodecane), and analysis by gas chromatography with flame ionization detection (GC-FID) and gas chromatography/mass spectrometry (GC/MS). As external recovery standard, we selected 1,2,3-trihydroxyhexane, which has a similar polarity as the monosaccharide anhydrides; furthermore, it was ensured that the trimethylsilylation step leads to complete derivatization into trimethylsilyl ethers. The reproducibility of the combined trimethylsilylation and analysis of levoglucosan was about 2% for standard solutions, whereas the precision of the entire method for the sum of all three monosaccharide anhydrides (MAs) in real aerosol filter samples was about 5%. The method was applied to aerosol samples from urban and tropical locations. The atmospheric concentration of the MAs in fine (<2.5 microm) aerosols at a primary forest site in Rondĵnia, Brazil, was on average 2.15 microg m(-3) during the dry season when intensive biomass burning occurs, which was almost 400 times higher than during the wet (nonburning) season. Urban total aerosols collected in Gent, Belgium, showed an average atmospheric concentration of MAs of 0.56 microg m(-3) for the winter season, which was a factor of 20 higher than for the summer season. The carbon in the MAs accounted on average for about 5.1% and 1.8% of the organic carbon in the Brazilian dry season and Gent winter aerosols, respectively. Levoglucosan was the major MA, with a relative abundance in the range of 76-93%.

Three unknown di- and tricarboxylic acids were characterized in the fine size fraction of aerosols which were collected during the wet season in the Amazon basin (Rondonia, Brazil). For the structural characterization of the methyl esters of these unknown compounds, mass spectrometry with electron ionization (EI) and tandem mass spectral techniques combined with gas chromatographic (GC) separation were employed. Fragment and parent ion spectra were recorded during elution of the GC peaks by linked scanning of the B and E sectors in combination with high-energy collision-induced dissociation. The fragmentation patterns of significant ions in the first-order EI spectra were also obtained for nonanedioic acid, which was examined as a model compound. The compounds were tentatively identified as 4-acetyloxyheptanedioic acid and cis and trans isomers of 5-hexene-1,1,6-tricarboxylic acid. Since there were indications of biomass burning during the aerosol sampling the di- and tricarboxylic acids characterized in the present work could be markers for biomass burning. Furthermore, the characterization of di- and tricarboxylic acids in the fine size fraction of atmospheric aerosols may be important for assessing the effects of organic aerosols in cloud formation., (Copyright 2001 John Wiley & Sons, Ltd.)

Determination of Rb, Br, Se, Zn, Cu, Fe, and Br/Rb ratio in tissues of mice inoculated with colon and melanoma cancer cells is described. A group of 19 Balb/c mice inoculated with C26 colon carcinoma, 4 C57B1/6 mice inoculated with B16 melanoma, and 13 control mice of both kinds were under investigation. The study was conducted on samples of blood, liver, kidneys, colon, and skin, and the trace element levels in normal and inoculated mice were compared. The inoculation was by subcutaneous injection either at the back or intrafootpad. The blood samples were taken 1, 2, and 3 wk after inoculation, and after 4 wk all the animals were sacrificed. Two nondestructive, complementary analytical methods were used: a modified X-ray fluorescence (XRF) for solid tissue and particle-induced X-ray emission (PIXE) for blood samples. The detection limit (DL) in the PIXE method was 0.35 microg/g dry wt in 600 s counting time and in XRF, 1 microg/g dry sample for Rb, Br, Se and Zn and 2 microg/g for Cu and Fe in 200 s counting time. In all the cases studied, cancerous tissue developed at the site of the injection, and a significant difference in the trace element levels was observed between tissue samples obtained from normal and inoculated mice. The most pronounced effect was an increase in Rb level in the tumor by a factor ranging between 4 and 10 relative to normal tissue, with a corresponding decrease in the Br/Rb ratio (p < 0.05). Smaller changes were found in the Br, Se, Zn, and K levels. The changes in trace element levels in the inner organs were much smaller and seem to be influenced by the site of injection.

An acute or chronic intoxication by i.p. injection of CCl4 was used to induce liver injuries (liver necrosis, steatosis and cirrhosis) in rats. Liver, kidneys and blood serum were collected from the experimental animals and from controls. The tissues were analyzed by particle-induced X-ray emission analysis (PIXE) for up to 12 elements (i.e., K, Ca, Mn, Fe, Cu, Zn, As, Se, Br, Rb, Sr and Mo). The acute intoxication (leading to necrosis and steatosis) caused definite alterations of many trace element levels. The alterations were most pronounced in the liver, as expected. In this organ, Ca exhibited a strongly increased concentration. Important alterations for the elements K, Zn and Se were also observed.

An analytical particle-induced X-ray emission (PIXE) procedure for the multielement analysis of biological materials consists of various stages. These include sample and specimen preparation, specimen bombardment, spectral data processing, quantification and correction for matrix effects. Critical aspects of the procedure are contamination and/or losses during sample and specimen preparation and the danger of radiation or heat-induced losses during specimen bombardment. With optimized PIXE procedures precisions of 1-2% and an accuracy of better than 5% are obtainable, whereas the detection limits are down to 0.1 microgram/g. Because of its inherent characteristics, PIXE offers great potential for trace element analysis in the biological and medical fields, and this is demonstrated through selected examples of applications.

Individual aerosol particles from the remote marine atmosphere were investigated by scanning electron microscopy and electron microprobe analysis. A large fraction of the silicate mineral component of the aerosol was found to be internally mixed with sea-salt aerosol particles. This observation explains the unexpected similarity in the size distributions of silicates and sea salt that has been observed in remote marine aerosols. Reentrainment of dust particles previously deposited onto the sea surface and collision between aerosol particles can be excluded as possible source mechanisms for these internally mixed aerosols. The internal mixing could be produced by processes within clouds, including droplet coalescence. Cloud processes may also be responsible for the observed enrichment of excess (nonsea-salt) sulfate on sea-salt particles.