Development of a compound-specific carbon isotope analysis method for 2-methyltetrols, biomarkers for secondary organic aerosols from atmospheric isoprene.

The stable carbon isotope compositions of 2-methyltetrols, biomarker compounds for secondary organic aerosols formed from isoprene in the atmosphere, have been determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In this work, isoprene with various delta(13)C values was used to produce 2-methyltetrols via an oxidation reaction with hydrogen peroxide in sulfuric acid under direct sunlight. The target compounds with different stable carbon isotope compositions were then derivatized by methylboronic acid with a known delta(13)C value and measured by GC/C/IRMS. With delta(13)C values of 2-methyltetrols and methylboronic acid predetermined, isotopic fractionation is evaluated for the derivatization process. Through reduplicate delta(13)C measurements, the carbon isotope analysis achieved excellent reproducibility and high accuracy with an average error of <0.3 per thousand. The differences between the predicted and measured delta(13)C values range from -0.10 to 0.29 per thousand, indicating that the derivatization process does not introduce isotopic fractionation. The delta(13)C values of 2-methyltetrols could be calculated on the basis of the stoichiometric mass balance equation among 2-methyltetrols, methylboronic acid, and methylboronate derivatives. Preliminary tests of 2-methyltetrols in PM(2.5) aerosols at two forested sites were conducted and revealed significant differences in their isotope compositions, implying possible application of the method in helping us understand the primary emission, photochemical reaction, or removal processes of isoprene in the atmosphere.

Determination of the stable carbon isotopic compositions of 2-methyltetrols in ambient aerosols from the Changbai Mountains.

Isoprene is one of the most important non-methane hydrocarbons (NMHCs) in the troposphere: it is a significant precursor of O(3) and it affects the oxidative state of the atmosphere. The diastereoisomeric 2-methyltetrols, 2-methylthreitol and 2-methylerythritol, are marker compounds of the photooxidation products of atmospheric isoprene. In order to obtain valuable information on the delta(13)C value of isoprene in the atmosphere, the stable carbon isotopic compositions of the 2-methyltetrols in ambient aerosols were investigated. The 2-methyltetrols were extracted from filter samples and derivatized with methylboronic acid, and the delta(13)C values of the methylboronate derivatives were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The delta(13)C values of the 2-methyltetrols were then calculated through a simple mass balance equation between the 2-methyltetrols, methylboronic acid and the methylboronates. The delta(13)C values of the 2-methyltetrols in aerosol samples collected at the Changbai Mountain Nature Reserves in eastern China were found to be -24.66 +/- 0.90 per thousand and -24.53 +/- 1.08 per thousand for 2-methylerythritol and 2-methylthreitol, respectively. Based on the measured isotopic composition of the 2-methyltetrols, the average delta(13)C value of atmospheric isoprene is inferred to be close to or slightly heavier than -24.66 per thousand at the collection site during the sampling period.

Composition, source, mass closure of PM2.5 aerosols for four forests in eastern China.

PM2.5 aerosols were collected in forests along north latitude in boreal-temperate, temperate, subtropical and tropical climatic zones in eastern China, i.e., Changbai Mountain Nature Reserve (CB), Dongping National Forest Park in Chongming Island (CM), Dinghu Mountain Nature Reserve (DH), Jianfengling Nature Reserve in Hainan Island (HN). The mass concentrations of PM2.5, organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) as well as concentrations of ten inorganic ions (F-, Cl-, NO3-, SO4(2-), C2O4(2-), NH4+, Na+, K+, Ca2+, Mg2+) were determined. Aerosol chemical mass closures were achieved. The 24-hr average concentrations of PM2.5 were 38.8, 89.2, 30.4, 18 Cig/m3 at CB, CM, DH and HN, respectively. Organic matter and EC accounted for 21%-33% and 1.3%-2.3% of PM2.5 mass, respectively. The sum of three dominant secondary ions (SO4(2-), NO3-, NH4+) accounted for 44%, 50%, 45% and 16% of local PM2.5 mass at CB, CM, DH and HN, respectively. WSOC comprised 35%-65% of OC. The sources of PM2.5 include especially important regional anthropogenic pollutions at Chinese forest areas.

Gas chromatography/combustion/isotope ratio mass spectrometric analysis of the stable carbon composition of tetrols.

The stable carbon isotope compositions of tetrols, erythritol and threitol were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using four tetrols with various delta(13)C values derivatized by methylboronic acid, the carbon isotope analysis method achieved excellent reproducibility and high accuracy. There was no carbon isotopic fractionation during the derivatization processes. The differences in the carbon isotopic compositions of methylboronates between the measured and calculated ranged from -0.20 to 0.12 per thousand, within the specification of the GC/C/IRMS system. It was demonstrated that delta(13)C values of tetrols could be calculated by a simple mass balance equation between tetrols, methylboronic acid, and methylboronates. The analogous 2-methyltetrols, marker compounds of photooxidation products of atmospheric isoprene, should have similar behavior using the same derivatization reagent. This method may provide insight on sources and sinks of atmospheric isoprene.

[Characteristics and influencing factors of carbonaceous aerosols in PM2.5 in Shanghai, China].

Organic carbon (OC) and elemental carbon (EC) in PM2.5 samples collected in urban (Xujiahui) and industrial (Baoshan) areas in Shanghai during 2007-2008 were analyzed with a DRI carbon analyzer using IMPROVE-TOR protocol. The results showed that the seasonal average concentrations of OC and EC were highest in the winter and lowest in the summer. The annual average concentrations of OC and EC were 8.10 and 3.91 microg x m(-3) at the urban sampling site, and 11.91 and 4.69 microg x m(-3) in the industrial area. The annual average OC/EC ratios at the two sites were 2.01 and 2.42, respectively. Strong correlations (R2 0.52-0.87) between OC and EC were found in all seasons, with the highest correlation coefficients in the winter ( R2 0.87 and 0.80) and the lowest in the spring (R2 0.52 and 0.58), indicating that the pollutant sources in spring was more complicated due to the varying wind directions. The annual average concentrations of secondary organic carbon (SOC) were 2.72 and 5.07 microg x m(-3) at the urban and industrial sites, accounting for about 30% of the total OC. The contribution of SOC to OC was the highest (about 40%) in the summer, in accordance with the high temperature and strong solar radiation in the summer. It was also found that precipitation had significant impact on the concentrations of OC and EC, especially in the winter. The average concentrations during periods without precipitation were two times higher than that during periods with precipitation in the winter, whereas no significant difference was found between the concentrations of OC and EC in the periods with and without precipitation in the summer, possibly due to the more stable atmospheric conditions during the periods with precipitation in comparison with those without precipitation. The OC/EC and SOC/OC ratios decreased significantly during precipitation.