1-6-anhydro-beta-glucopyranose and galactosan

This is a brief review key to the literature on the determination of organic tracers from biomass burning which are detectable even after long-range global transport in total extracts of atmospheric particles. The major tracers are thermal degradation products from the biopolymer cellulose, namely the didehydromonosaccharide derivatives levoglucosan, galactosan and mannosan and the resin acid derivative dehydroabietic acid, with minor beta-sitosterol. Dehydroabietic acid is emitted primarily from burning of conifer fuel and these tracers are found in most aerosol samples from the North American continent. Particulate matter from the atmosphere over oceanic areas contains organic tracers from both natural and biomass burning emissions. The major biomarker compounds characterized are natural products from continental vegetation consisting primarily of epicuticular wax components and trace components from biomass burning emissions. The presence of these tracers in atmospheric particulate matter over the ocean confirms the long-range transport of smoke from biomass burning off the continents.

Topics: Abietanes; Air Pollutants; Atmosphere; Biomass; Cellulose; Diterpenes; Environmental Monitoring; Fires; Galactose; Gas Chromatography-Mass Spectrometry; Glucose; Mannose; Organic Chemicals; Smoke; Sterols

Biomass burning (BB) emissions are a significant source of particles to the atmosphere, especially in the Southern Hemisphere, where the occurrence of anthropogenic and natural wild fires is common. These emissions can threaten human health through increased exposure, whilst simultaneously representing a significant source of trace metals and nutrients to the ocean. One well known method to track BB emissions is through monitoring the atmospheric concentration of specific monosaccharide anhydrides (MAs), specifically levoglucosan and its isomers, mannosan and galactosan. Herein, a new method for the determination of levoglucosan and its isomers in marine and terrestrial aerosol samples is presented, which delivers both high selectivity and sensitivity, through the coupling of ion chromatography and triple quadrupole tandem mass spectrometry. Optimal chromatographic conditions, providing baseline separation for target anhydrosugars in under 8 min, were obtained using a Dionex CarboPac

Topics: Anhydrides; Atmosphere; Australia; Cations; Chromatography; Environmental Monitoring; Galactose; Glucose; Isomerism; Limit of Detection; Lithium; Mannose; Monosaccharides; Reference Standards; Tandem Mass Spectrometry

Cryoconite is a dark, dusty aggregate of mineral particles, organic matter, and microorganisms transported by wind and deposited on glacier surfaces. It can accelerate glacier melting and alter glacier mass balances by reducing the surface albedo of glaciers. Biomass burning in the Tibetan Plateau, especially in the glacier cryoconites, is poorly understood. Retene, levoglucosan, mannosan and galactosan can be generated by the local fires or transported from the biomass burning regions over long distances. In the present study, we analyzed these four molecular markers in cryoconites of seven glaciers from the northern to southern Tibetan Plateau. The highest levels of levoglucosan and retene were found in cryoconites of the Yulong Snow Mountain and Tienshan glaciers with 171.4 ± 159.4 ng g

Topics: Biomarkers; Biomass; Dust; Environmental Monitoring; Fires; Galactose; Glucose; Ice Cover; Mannose; Phenanthrenes; Tibet; Wind

An interlaboratory comparison was performed to evaluate the analytical methods for quantification of anhydrosugars - levoglucosan, mannosan, galactosan - and biosugars - arabitol, glucose and mannitol - in atmospheric aerosol. The performance of 10 laboratories in Italy currently involved in such analyses was investigated on twenty-six PM (particulate matter) ambient filters, three synthetic PM filters and three aqueous standard solutions. An acceptable interlaboratory variability was found, determined as the mean relative standard deviation (RSD%) of the results from the participating laboratories, with the mean RSD% values ranging from 25% to 46% and decreasing with increasing sugar concentration. The investigated methods show good accuracy, evaluated as the percentage error (ε%) related to mean values, since method biases ranged within ±20% for most of the analytes measured in the different laboratories. The detailed investigation (ANOVA analysis at p < 0.05) of the contribution of each laboratory to the total variability and the measurement accuracy shows that comparable results are generated by the different methods, despite the great diversity in terms of extraction conditions, chromatographic separation - more recent LC (liquid chromatography) and EC (exchange chromatography) methods compared to more widespread GC (gas chromatography) - and detection systems, namely PAD (pulsed amperometric detection) or mass spectrometry.

Topics: Aerosols; Air Pollutants; Carbohydrates; Chromatography, Liquid; Environmental Monitoring; Galactose; Gas Chromatography-Mass Spectrometry; Glucose; Italy; Mannose; Mass Spectrometry; Observer Variation; Particulate Matter; Sugar Alcohols

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.

Topics: Aerosols; Air Pollutants; Belgium; Environmental Monitoring; Galactose; Glucose; Mannose; Particulate Matter; Smoke; Wood

Based on the newly established high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD), the saccharides in PM2.5 and PM10 in Beijing from 2011 - 2012 were quantified. Fourteen saccharides were synchronously detected in the aerosols samples in Beijing, which can be divided into three categories, i. e. anhydrosugar, sugar and sugar alcohol. Anhydrosugar, coming from biomass burning, include levoglucosan, mannosan and galactosan. Sugar and sugar alcohol, emitted by the primary biogenic emission, include glucose, fructose, trehalose, arabitol, mannitol, glycerol, threitol, 2-meythltrtols (2-methylthreitol and 2-methylerythrito), xylitol and inositol. The concentrations of monosaccharide anhydrides in summer and autumn were obviously higher than those in spring and winter, while the concentrations of sugar and sugar alcohol in winter were significantly lower than those in other seasons. The results of positive matrix factorization analysis suggested that saccharides compounds in atmospheric PM in Beijing can be derived from biomass burning, suspended soil or dust, isoprene SOA, as well as direct release of airborne fungal spores and pollen.

Topics: Aerosols; Air Pollutants; Beijing; Carbohydrates; Dust; Environmental Monitoring; Galactose; Glucose; Mannose; Particulate Matter; Seasons; Sugar Alcohols

Biomass burning is becoming an increasing contributor to atmospheric particulate matter, and concern is increasing over the detrimental health effects of inhaling such particles. Levoglucosan and related monosaccharide anhydrides (MAs) can be used as tracers of the contribution of wood burning to total particulate matter. An improved gas chromatography-mass spectrometry method to quantify atmospheric levels of MAs has been developed and, for the first-time, fully validated. The method uses an optimised, low-volume methanol extraction, derivitisation by trimethylsilylation and analysis with high-throughput gas chromatography-mass spectrometry (GC-MS). Recovery of approximately 90 % for levoglucosan, and 70 % for the isomers galactosan and mannosan, was achieved using spiked blank filters estimates. The method was extensively validated to ensure that the precision of the method over five experimental replicates on five repeat experimental occasions was within 15 % for low, mid and high concentrations and accuracy between 85 and 115 %. The lower limit of quantification (LLOQ) was 0.21 and 1.05 ng m(-3) for levoglucosan and galactosan/mannosan, respectively, where the assay satisfied precisions of ≤20 % and accuracies 80-120 %. The limit of detection (LOD) for all analytes was 0.105 ng m(-3). The stability of the MAs, once deposited on aerosol filters, was high over the short term (4 weeks) at room temperature and over longer periods (3 months) when stored at -20 °C. The method was applied to determine atmospheric levels of MAs at an urban background site in Leicester (UK) for a month. Mean concentrations of levoglucosan over the month of May were 21.4 ± 18.3 ng m(-3), 7.5 ± 6.1 ng m(-3) mannosan and 1.8 ± 1.3 ng m(-3) galactosan.

Topics: Aerosols; Air Filters; Air Pollutants; Anhydrides; Biomass; Carbon; Environmental Monitoring; Filtration; Galactose; Gas Chromatography-Mass Spectrometry; Glucose; Mannose; Monosaccharides; Particulate Matter; Reproducibility of Results; Smoke; Temperature; United Kingdom; Wood

The recent economic crisis in Greece resulted in a serious wintertime air pollution episode in Thessaloniki. This air quality deterioration was mostly due to the increased price of fuel oil, conventionally used as a source of energy for domestic heating, which encouraged the residents to burn the less expensive wood/biomass during the cold season. A wintertime sampling campaign for fine particles (PM2.5) was conducted in Thessaloniki during the winters of 2012 and 2013 in an effort to quantify the extent to which the ambient air was impacted by the increased wood smoke emissions. The results indicated a 30% increase in the PM2.5 mass concentration as well as a 2-5-fold increase in the concentration of wood smoke tracers, including potassium, levoglucosan, mannosan, and galactosan. The concentrations of fuel oil tracers (e.g., Ni and V), on the other hand, declined by 20-30% during 2013 compared with 2012. Moreover, a distinct diurnal variation was observed for wood smoke tracers, with significantly higher concentrations in the evening period compared with the morning. Correlation analysis indicated a strong association between reactive oxygen species (ROS) activity and the concentrations of levoglucosan, galactosan, and potassium, underscoring the potential impact of wood smoke on PM-induced toxicity during the winter months in Thessaloniki.

Topics: Air Pollutants; Air Pollution; Economic Recession; Environmental Monitoring; Fires; Galactose; Glucose; Greece; Heating; History, 21st Century; Mannose; Particulate Matter; Seasons; Smoke; Wood

Biomass burning has a strong influence on the atmospheric aerosol composition through particulate organic, inorganic, and soot emissions. When biomass burns, cellulose and hemicelluloses degrade, producing monosaccharide anhydrides (MAs) such as levoglucosan, mannosan, and galactosan. Therefore, these compounds have been commonly used as tracers for biomass burning. In this study, a fast water-based method was developed for the routine analysis of MAs, based on high-performance anion-exchange chromatography with electrospray ionization mass spectrometry detection. This method combines simple sample preparation, fast separation, and the advantages of the selective detection with MS. Analysis run was optimized to the maximum separation of levoglucosan, mannosan, and galactosan with 15-min analysis. The validation results indicated that the method showed good applicability for determination of MA isomer concentrations in ambient samples. The limit of detection was 100 pg for levoglucosan and 50 pg for mannosan and galactosan. Wide determination ranges enabled the analysis of samples of different concentration levels. The method showed good precision, both for standard solutions (3.9-5.9% RSD) and for fine particle samples (4.3-8.5% RSD). Co-elution of internal standard (carbon-13-labeled levoglucosan) and sugar alcohols with levoglucosan decreased the sensitivity of levoglucosan determination. The method was used to determine the MA concentrations in ambient fine particle samples from urban background (Helsinki) and rural background (Hyytiälä) in Finland. The average levoglucosan, mannosan, and galactosan concentrations were 77, 8.8, and 4.2 ng m(-3) in Helsinki (winter 2008-2009) and 17, 2.3, and 1.4 ng m(-3) in Hyytiälä (spring 2007), respectively. The interrelation of the three MA isomers was fairly constant in the ambient fine particle samples.

Topics: Chromatography; Chromatography, High Pressure Liquid; Environmental Monitoring; Galactose; Glucose; Mannose; Mass Spectrometry; Particulate Matter

Twelve positional isomers of diamino pseudodisaccharide derivatives with gluco-gluco configuration have been prepared using aziridine-ring cleavage of epimino derivatives of 1,6-anhydro-beta-D-hexopyranoses of the D-allo, D-manno, and D-galacto configuration by 2-, 3-, and 4-amino derivatives of 1,6-anhydro-beta-D-glucopyranose. The N-substitution of the aziridine ring by a 2-nitrobenzenesulfonyl group and ionic-liquid solvent (N-methylpyridinium tosylate) was used to obtain cleavage products in high yield (64-93%). The cleavage reactions proceeded according to the Fürst-Plattner rule and only trans-diaxial stereoisomers were formed.

Topics: Amino Sugars; Aziridines; Carbohydrate Conformation; Carbohydrate Sequence; Galactose; Glucose; Hexoses; Magnetic Resonance Spectroscopy; Mannose; Molecular Structure; Stereoisomerism

Levels of the monosaccharide anhydride (MA) levoglucosan and its isomeric compounds galactosan and mannosan were quantified in the PM10 fraction (particulate matter < or = 10 microm in aerodynamic diameter) of ambient aerosols from an urban (Oslo) and a suburban (Elverum) site in Norway, both influenced by small-scale wood burning. MAs are degradation products of cellulose and hemicellulose, and levoglucosan is especially emitted in high concentrations during pyrolysis and combustion of wood, making it a potential tracer of primary particles emitted from biomass burning. MAs were quantified using a novel high-performance liquid chromatography/ high-resolution mass spectrometry-time of flight method. This approach distinguishes between the isomeric compounds of MAs and benefits from the limited sample preparation required before analysis, and no extensive derivatization step is needed. The highest concentrations of levogucosan, galactosan, and mannosan (sigmaMA) were recorded in winter because of wood burning for residential heating (sigmaMA(MAX) = 1,240 ng m(-3)). This finding was substantiated by a relatively high correlation (R2 = 0.64) between the levoglucosan concentration and decreasing ambient temperature. At the suburban site, sigmaMA accounted for 3.1% of PM10, whereas the corresponding level at the urban site was 0.6%. The mass size distribution of MAs associated with atmospheric aerosols was measured using a Berner cascade impactor. The size distribution was characterized with a single mode at 561 nm. Ninety-five percent of the mass concentration of the MAs was found to be associated with particles < 2 micro.m. A preliminary attempt to estimate the contribution of wood burning to the mass concentration of PM10 in Oslo using levoglucosan as a tracer indicates that 24% comes from wood burning. This is approximately a factor of 2 lower than estimated by the AirQUIS dispersion model.

Topics: Aerosols; Air Pollutants; Chromatography, High Pressure Liquid; Cities; Environmental Monitoring; Galactose; Glucose; Heating; Mannose; Mass Spectrometry; Models, Theoretical; Norway; Particle Size; Seasons; Temperature; Uncertainty; Wood

A conspicuous fraction of the water soluble organic compounds (WSOC) in fog and fine aerosol samples is composed by monosaccharide anhydrides, such as levoglucosan and its stereoisomers, galactosan and mannosan. Levoglucosan is produced exclusively during wood combustion processes, making it a very useful tracer for plant combustion emissions in the atmosphere. This paper describes a new experimental approach, based on electrospray-tandem mass spectrometry (ESI-MS/MS), for the identification of levoglucosan in fog water samples. The analytical method proposed allows to identify the specific sugar anhydrides directly in the liquid phase without the need of any derivatization process.

Topics: Aerosols; Air Pollutants; Biomass; Galactose; Gas Chromatography-Mass Spectrometry; Glucose; Incineration; Mannose; Spectrometry, Mass, Electrospray Ionization; Stereoisomerism; Water

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.

Topics: Aerosols; Air Pollutants; Cities; Environmental Monitoring; Galactose; Gas Chromatography-Mass Spectrometry; Glucose; Mannose; Monosaccharides; Sensitivity and Specificity

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%.

Topics: Aerosols; Air Pollutants; Cities; Environmental Monitoring; Galactose; Glucose; Mannose; Tropical Climate