Seasonal and spatial variation of organic tracers for biomass burning in PM1 aerosols from highly insolated urban areas

PM₁ aerosol characterization on organic tracers for biomass burning (levoglucosan and its isomers and dehydroabietic acid) was conducted within the AERTRANS project. PM₁ filters (N?=?90) were sampled from 2010 to 2012 in busy streets in the urban centre of Madrid and Barcelona (Spain) at ground-level and at roof sites. In both urban areas, biomass burning was not expected to be an important local emission source, but regional emissions from wildfires, residential heating or biomass removal may influence the air quality in the cities. Although both areas are under influence of high solar radiation, Madrid is situated in the centre of the Iberian Peninsula, while Barcelona is located at the Mediterranean Coast and under influence of marine atmospheres. Two extraction methods were applied, i.e. Soxhlet and ASE, which showed equivalent results after GC-MS analyses. The ambient air concentrations of the organic tracers for biomass burning increased by an order of magnitude at both sites during winter compared to summer. An exception was observed during a PM event in summer 2012, when the atmosphere in Barcelona was directly affected by regional wildfire smoke and levels were four times higher as those observed in winter. Overall, there was little variation between the street and roof sites in both cities, suggesting that regional biomass burning sources influence the urban areas after atmospheric transport. Despite the different atmospheric characteristics in terms of air relative humidity, Madrid and Barcelona exhibit very similar composition and concentrations of biomass burning organic tracers. Nevertheless, levoglucosan and its isomers seem to be more suitable for source apportionment purposes than dehydroabietic acid. In both urban areas, biomass burning contributions to PM were generally low (2 %) in summer, except on the day when wildfire smoke arrive to the urban area. In the colder periods the contribution increase to around 30 %, indicating that regional biomass burning has a substantial influence on the urban air quality.     

High performance liquid chromatographic method for residue determination of sulfosulfuron

A method was developed for sulfosulfuron [(1-(2-ethylsulfonylimidazo [1,2-a] pyridin-3-ylsulfonyl)-3-(4,6-dimethoxy pyrimidin-2yl)] and its three major metabolites by HPLC utilizing photodiode array detector. The method makes use of Lichrosphere RP-8 column and acetonitrile:water:orthophosphoric acid (80:20:0.1 v/v/v) as mobile phase at a flow rate of 1 ml min(-1). Using these condition sulfosulfuron, and compounds II, III and IV were resolved with distinct Rt of 2.088, 2.216, 2.302 and 2.476 minutes, respectively. Sulfosulfuron residues were analysed in soil, wheat grain and straw samples by extracting with a mixture of acetonitrile and 2 M ammonium carbonate (100 ml, 9:1, v/v) using horizontal shaker for soil and Soxhlet apparatus for wheat grain and straw samples. The extracts were cleaned up by partitioning with dichloromethane in case of soil and hexane followed by dichloromethane for plant samples. The percent recovery ranged between 71 to 75.2 for soil and 70.8 to 74.7 for plant samples. The limit of determination of sulfosulfuron was 0.25 microg g(-1).     

Development and validation of a method for determination of trace levels of alkylphenols and bisphenol A in atmospheric samples

A method has been developed and validated in order to assess the occurrence of the alkylphenols tert-octylphenol and the isomers of technical nonylphenol as well as bisphenol A in gasphase and aerosol samples of a remote area. Gasphase samples were adsorbed to XAD2 resin, aerosol samples were taken on glass fiber filters. After ultrasonic extraction, clean-up by column chromatography and silylation of the analytes, ten nonylphenol peaks were quantified separately using a GC-MSD-SIM method. The absolute limits of detection and determination are in the range of a few pg per compound, which is a prerequisite for the quantification of the analytes in relatively unpolluted air. The precision of the whole analytical method is in the range of 1-17% and the recoveries range from 57% to 80%. Problems were encountered during method development due to the tendency of the analytes to sorb to glass surfaces. Silanisation of glassware was crucial to achieve acceptable recoveries. The widespread use of the analytes in plastic resins resulted in sample contamination. For this reason a careful choice of sampling material was necessary. Measured concentrations in gasphase samples (lower nanogram per m3 range) and aerosol samples (upper picogram per m3 range) are one to three orders of magnitude below already published concentrations.     

Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

Development of a green and efficient methodology for the heterocyclic aromatic amine determination in biomass samples generated from cigarette combustion and tobacco

Environmental Science and Pollution Research - A green methodology was developed for the analysis of ten heterocyclic aromatic amines (HAAs) in biomass samples from cigarette combustion such as...     

Gas chromatographic determination of aromatic hydrocarbons in air using a semi-automatic preconcentration method

A practically useful and relatively simple technique for sensitive and selective measurement of aromatic hydrocarbons in air has been developed. It is based on a modification of the method used by Grob and Grob (1971) for concentrating organic compounds, combined with the semi-automatic sampler described by Guicherit et al. (1972) with gas Chromatographic analysis of the extract solutions on a highly polar column. Results of applications of the technique in the Netherlands are described and compared with those of other countries.     

Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: Implications for characterizations of biomass combustion residues

Anhydrosugars, such as levoglucosan and its isomers (mannosan, galactosan), as well as the solvent-extractable lignin phenols (methoxylated phenols) are thermal degradation products of cellulose/hemicellulose and lignin, respectively. These two groups of biomarkers are often used as unique tracers of combusted biomass inputs in diverse environmental media. However, detailed characterization of the relative proportion and signatures of these compounds in highly heterogeneous plant-derived chars are still scarce. Here we conducted a systematic study to investigate the yields of solvent-extractable anhydrosugars and lignin phenols in 25 lab-made chars produced from different plant materials under different combustion conditions. Solvent-extractable anhydrosugars and lignin phenols were only observed in chars formed below 350 °C and yields were variable across different combustion temperatures. The yields of mannosan (M) and galactosan (G) decreased more rapidly than those of levoglucosan (L) under increasing combustion severity (temperature and duration), resulting in variable L/M and L/(M + G) ratios, two diagnostic ratios often used for identification of combustion sources (e.g. hardwoods vs. softwoods vs. grasses). Our observations thus may provide an explanation for the wide ranges of values reported in the literature for these two ratios. On the other hand, the results of this study suggest that the ratios of the major solvent-extractable lignin phenols (vanillyls (V), syringyls (S), cinnamyls (C)) provide additional source reconstruction potential despite observed variations with combustion temperature. We thus propose using a property-property plot (L/M vs. S/V) as an improved means for source characterization of biomass combustion residues. The L/M-S/V plot has shown to be effective in environmental samples (soil organic matter, atmospheric aerosols) receiving substantial inputs of biomass combustion residues.     

Atmospheric polycyclic aromatic hydrocarbons and isomer ratios as tracers of biomass burning emissions in Northern India

Emission from large-scale post-harvest agricultural-waste burning (paddy-residue burning during October–November and wheat-residue burning in April–May) is a conspicuous feature in northern India. The poor and open burning of agricultural residue result in massive emission of carbonaceous aerosols and organic pollutants to the atmosphere. In this context, concentrations of atmospheric polycyclic aromatic hydrocarbons (PAHs) and their isomer ratios have been studied for a 2-year period from a source region (Patiala: 30.2°N; 76.3°E) of two distinct biomass burning emissions. The concentrations of 4—6 ring PAHs are considerably higher compared to 2–3 ring PAHs in the ambient particulate matter (PM_2.5). The crossplots of PAH isomer ratios, fluoranthene?/?(fluoranthene?+?pyrene) and indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene?+?benzo[g,h,i]perylene) for two biomass burning emissions, exhibit distinctly different source characteristics compared to those for fossil-fuel combustion sources in south and south-east Asia. The PAH isomer ratios studied from different geographical locations in northern India also exhibit similar characteristics on the crossplot, suggesting their usefulness as diagnostic tracers of biomass burning emissions.     

A high pressure liquid chromatographic method for the analysis of zearalenone in chicken blood

Abstract

A high pressure liquid chromatographic (HPLC) method is described to determine zearalenone in chicken blood. Samples are extracted with acetonitrile, followed by a hexane cleanup procedure and extracted further with ethyl acetate. The analysis of zearalenone is by HPLC using a reverse phase radial compression separation system, an ultraviolet absorbance detector and a mobile phase of acetonitrile‐water 60:40 (v/v). Recoveries of zearalenone in blood at levels of 50–200 ng/ml are in the range of 66.8–72.6%.     

Determination of malic acid and other C4 dicarboxylic acids in atmospheric aerosol samples

An ion chromatographic method was developed which is able to separate five unsubstituted and hydroxy C4 dicarboxylic acids, succinic, malic, tartaric, maleic and fumaric acid, besides the other unsubstituted C2-C5 dicarboxylic acids, oxalic, malonic and glutaric acids, as well as inorganic ions in samples extracted from atmospheric particulate matter. By the application of this method it was found for both rural and urban sites and for various types of air masses that in the summer-time malic acid is the most prominent C4 diacid (64 ng m(-3) by average), exceeding succinic acid concentration (28 ng m(-3) by average) considerably. In winter-time considerably less, a factor of 4-15, C4 acids occurred and succinic acid was more concentrated than malic acid. Tartaric, fumaric and maleic acids were less concentrated (5.1, 5.0 and 4.5 ng m(-3) by average, respectively). Tartaric acid was observed for the first time in ambient air. The results indicate that in particular anthropogenic sources are important for the precursors of succinic, maleic and fumaric acids. Biogenic sources seem to influence the occurrence of malic acid significantly.     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

A highly resolved temporal and spatial air pollutant emission inventory for the Pearl River Delta region, China and its uncertainty assessment

A highly resolved temporal and spatial Pearl River Delta (PRD) regional emission inventory for the year 2006 was developed with the use of best available domestic emission factors and activity data. The inventory covers major emission sources in the region and a bottom–up approach was adopted to compile the inventory for those sources where possible. The results show that the estimates for SO₂, NO_x, CO, PM₁₀, PM_2.5 and VOC emissions in the PRD region for the year 2006 are 711.4 kt, 891.9 kt, 3840.6 kt, 418.4 kt, 204.6 kt, and 1180.1 kt, respectively. About 91.4% of SO₂ emissions were from power plant and industrial sources, and 87.2% of NO_x emissions were from power plant and mobile sources. The industrial, mobile and power plant sources are major contributors to PM₁₀ and PM_2.5 emissions, accounting for 97.7% of the total PM₁₀ and 97.2% of PM_2.5 emissions, respectively. Mobile, biogenic and VOC product-related sources are responsible for 90.5% of the total VOC emissions. The emissions are spatially allocated onto grid cells with a resolution of 3 km × 3 km, showing that anthropogenic air pollutant emissions are mainly distributed over PRD central-southern city cluster areas. The preliminary temporal profiles were established for the power plant, industrial and on-road mobile sources. There is relatively low uncertainty in SO₂ emission estimates with a range of −16% to +21% from power plant sources, medium to high uncertainty for the NO_x emissions, and high uncertainties in the VOC, PM_2.5, PM₁₀ and CO emissions.     

Temporal and spatial distribution of atmospheric antimony emission inventories from coal combustion in China

A multiple-year inventory of atmospheric antimony (Sb) emissions from coal combustion in China for the period of 1980-2007 has been calculated for the first time. Specifically, the emission inventories of Sb from 30 provinces and 4 economic sectors (thermal power, industry, residential use, and others) are evaluated and analyzed in detail. It shows that the total Sb emissions released from coal combustion in China have increased from 133.19 t in 1980 to 546.67 t in 2007, at an annually average growth rate of 5.4%. The antimony emissions are largely emitted by industrial sector and thermal power generation sector, contributing 53.6% and 26.9% of the totals, respectively. At provincial level, the distribution of Sb emissions shows significant variation. Between 2005 and 2007, provinces always rank at the top five largest Sb emissions are: Guizhou, Hunan, Hebei, Shandong, and Anhui.     

A rapid method for determination of Aroclor 1260 in cattle adipose tissue

Abstract

A simple analytical procedure for the determination of Aroclor 1260 in cattle adipose tissue is described. The polychlorinated biphenyls residues are extracted from the tissue using a soxhlet extractor and the extracts are cleaned up using a florisil SEP‐PAK cartridge. The residues are detected using a gas chromatograph equipped with an electron capture detector. The effect of extraction time of the Aroclor 1260 residues from the tissue has been investigated and a period of four hours is found to give satisfactory percent recoveries. Greater than 85 percent recoveries were obtained from adipose tissue spiked with Aroclor 1260. The method can be used to detect Aroclor 1260 residue levels as low as 0.10 parts per million.

The method was used to analyze thirty‐one cattle adipose tissue samples out of which twenty‐six samples were taken from cattle suspected of exposure to a pasture containing electrical transformers and capacitors containing Aroclor 1260. Five control samples were collected from cattle with no known exposure. All twenty‐six samples were found to contain non‐detectable Aroclor 1260 residues.     

A passive sampling method for radiocarbon analysis of atmospheric CO2 using molecular sieve

Radiocarbon (¹⁴C) analysis of atmospheric CO₂ can provide information on CO₂ sources and is potentially valuable for validating inventories of fossil fuel-derived CO₂ emissions to the atmosphere. We tested zeolite molecular sieve cartridges, in both field and laboratory experiments, for passively collecting atmospheric CO₂. Cartridges were exposed to the free atmosphere in two configurations which controlled CO₂ trapping rate, allowing collection of sufficient CO₂ in between 1.5 and 10 months at current levels. ¹⁴C results for passive samples were within measurement uncertainty of samples collected using a pump-based system, showing that the method collected samples with ¹⁴C contents representative of the atmosphere. δ¹³C analysis confirmed that the cartridges collected representative CO₂ samples, however, fractionation during passive trapping means that δ¹³C values need to be adjusted by an amount which we have quantified. Trapping rate was proportional to atmospheric CO₂ concentration, and was not affected by exposure time unless this exceeded a threshold. Passive sampling using molecular sieve cartridges provides an easy and reliable method to collect atmospheric CO₂ for ¹⁴C analysis.     

Historical estimation of carbonaceous aerosol emissions from biomass open burning in China for the period 1990-2005

Multi-year inventories of carbonaceous aerosol emissions from biomass open burning at a high spatial resolution of 0.5° × 0.5° have been constructed in China using GIS methodology for the period 1990-2005. Black carbon (BC) emissions have increased by 383.03% at an annual average rate of 25.54% from 14.05 Gg in 1990 to 67.87 Gg in 2005; while organic carbon (OC) emissions have increased by 365.43% from 57.37 Gg in 1990 to 267.00 Gg in 2005. Through the estimation period, OC/BC ratio for biomass burning was averagely 4.09, suggesting that it was not the preferred control source from a climatic perspective. Spatial distribution of BC and OC emissions were similar, mainly concentrated in three northeastern provinces, central provinces of Shandong, Jiangsu, Anhui and Henan, and southern provinces of Guangxi, Guangdong, Hunan and Sichuan basin, covering 24.89% of China’s territory, but were responsible for 63.38% and 67.55% of national BC and OC emissions, respectively.     

Characterization of organic compounds and molecular tracers from biomass burning smoke in South China I: Broad-leaf trees and shrubs

Biomass burning smoke constituents are worthy of concern due to its influence on climate and human health. The organic constituents and distributions of molecular tracers emitted from burning smoke of six natural vegetations including monsoon evergreen broad-leaf trees and shrubs in South China were determined in this study. The gas and particle samples were collected and analyzed by gas chromatography–mass spectrometry. The major organic components in these smoke samples are methoxyphenols from lignin and saccharides from cellulose. Polycyclic aromatic hydrocarbons (PAHs) are also present as minor constituents. Furanose, pyranose and their dianhydrides are the first reported in the biomass burning smoke. Some unique biomarkers were detected in this study which may be useful as specific tracers. The corresponding tracer/OC ratios are used as indicators for the two types of biomass burning. U/R (1.06–1.72) in the smoke samples may be used as parameters to distinguish broad-leaf trees and shrubs from fossil fuel. Other useful diagnostic ratios such as methylphenanthrene to phenanthrene (MPhe/Phe), phenanthrene to phenanthrene plus anthracene (Phe/(Phe + Ant)) and fluoranthene to fluoranthene plus pyrene (Flu/(Flu + Pyr)) and octadecenoic acid/OC are also identified in this study. These results are useful in efforts to better understand the emission characterization of biomass burning in South China and the contribution of regional biomass burning to global climate change.