Low molecular weight dicarboxylic acids in PM10 in a city with intensive solid fuel burning

In this work, PM(10) samples were collected in a winter and a summer in Christchurch, a New Zealand city having intensive wood and coal burning and a serious air pollution problem in winter. Oxalic, malonic, succinic, maleic, glutaric and adipic acids in the samples were analysed using ion chromatography. It was suggested that solid fuel burning had large influence on the occurrence of these low molecular weight dicarboxylic acids resulting in significantly higher wintertime concentrations of maleic acid, oxalic acid and glutaric or adipic acid. The most pronounced feature observed was that maleic acid was the second most abundant species of the detected DCAs in the winter (with a mean of 74 ngm(-3) and the highest concentration ever reported of 231 ngm(-3)). In contrast, malonic acid experienced a low abundance in both seasons. The observed seasonal patterns and molecular distribution were inconsistent with those in most other urban areas. On an average, the total detected dicarboxylic acids accounted for about 0.5% of PM(10) mass with a maximum of 1.4% in the winter. The relative importance of different sources to individual dicarboxylic acids varied with seasons and is discussed in detail.     

Size distributions of nano/micron dicarboxylic acids and inorganic ions in suburban PM episode and non-episodic aerosol

The distribution of nano/micron dicarboxylic acids and inorganic ions in size-segregated suburban aerosol of southern Taiwan was studied for a PM episode and a non-episodic pollution period, revealing for the first time the distribution of these nanoscale particles in suburban aerosols. Inorganic species, especially nitrate, were present in higher concentrations during the PM episode. A combination of gas-to-nuclei conversion of nitrate particles and accumulation of secondary photochemical products originating from traffic-related emissions was likely a crucial cause of the PM episode. Sulfate, ammonium, and oxalic acid were the dominant anion, cation, and dicarboxylic acid, respectively, accounting for a minimum of 49% of the total anion, cation or dicarboxylic acid mass. Peak concentrations of these species occurred at 0.54 μm in the droplet mode during both non-episodic and PM episode periods, indicating an association with cloud-processed particles. On average, sulfate concentration was 16–17 times that of oxalic acid. Oxalic acid was nevertheless the most abundant dicarboxylic acid during both periods, followed by succinic, malonic, maleic, malic and tartaric acid. The mass median aerodynamic diameter (MMAD) of oxalic acid was 0.77 μm with a bi-modal presence at 0.54 μm and 18 nm during non-episodic pollution and an MMAD of 0.67 μm with mono-modal presence at 0.54 μm in PM episode aerosol. The concomitant formation of malonic acid and oxalic acid was attributed to in-cloud processes. During the PM episode in the 5–100 nm nanoscale range, an oxalic acid/sulfate mass ratio of 40.2–82.3% suggested a stronger formation potential for oxalic acid than for sulfate in the nuclei mode. For total cations (TC), total inorganic anions (TIA) and total dicarboxylic acids (TDA), major contributing particles were in the droplet mode, with least in the nuclei mode. The ratio of TDA to TIA in the nuclei mode increased greatly from 8.40% during the non-episodic pollution period to 28.08% during the PM episode, favoring dicarboxylic acid formation in the nuclei mode. The evidence suggests stronger formation strength and contribution potential exists for dicarboxylic acids than for inorganic salts in nanoscale particles, especially in PM episode aerosol.     

Origin of low-molecular-weight dicarboxylic acids and their concentration and size distribution variation in suburban aerosol

The concentrations and size distributions of low molecular weight dicarboxylic acids in suburban particulate matter collected in early and mid-autumn 2002 and early and mid-summer 2003 in Tainan, Taiwan, were analyzed. PM_2.5 contained, on average, 449.3 ng m⁻³ oxalic acid, 53.0 ng m⁻³ malic acid, 45.5 ng m⁻³ maleic acid, 29.6 ng m⁻³ succinic acid, 20.8 ng m⁻³ malonic acid, and 11.6 ng m⁻³ tartaric acid. Bar tartaric acid, concentrations were higher during the day, indicating that these acids are photochemical products. Furthermore, the malonic acid–succinic acid ratio of 0.79 during daytime and 0.60 during nighttime demonstrates that more succinic acid is converted to malonic acid during daytime, and that aerosol dicarboxylic acids predominantly originate from photochemical oxidation during daytime. The concentration peak of oxalic acid occurred in the condensation and droplet modes (0.32–1.0 μm), as did that of sulfate. In early summer, succinic acid, malonic acid, and oxalic acid major concentration peaks occurred at 0.32–0.54 μm, indicative of the relationship created by photochemical decomposition of succinc acid into malonic acid into oxalic acid. This photochemical decomposition accelerated in mid-summer such that most concentration peaks for succinic and malonic acids also occurred at 0.32–1.0 μm. Mid-summer is also the wettest period of the four in Tainan, with 85% RH. As a result of hygroscopic reactions in mid-summer, malonic acid and oxalic acid major concentration peaks shifted from 0.32–0.54 μm or 0.54–1.0 μm to 1.0–1.8 μm, thus extending the range in which these species were found to larger particle sizes, and this shift was highly correlated with a shift in succinic acid size distribution. This latter observation offers additional evidence that succinic acid is photochemically decomposed into malonic acid and oxalic acid and that the presence of malonic and oxalic acids in the wet mid-summer atmosphere is made more obvious via hygroscopic growth. Close correlation between succinic acid and Na⁺ and succinic acid and NO₃⁻ in the coarse mode is related to sea spray.     

Natural organic compounds as alternative to methyl bromide for nematodes control

Thirty-three organic acids and furfural metabolites were examined for their nematicidal activity against plant-parasitic, free-living and predacious nematodes. Propionic acid, 2-methylhexanoic acid, lactic acid, maleic acid, and furic acid were the most effective nematicides among normal chain organic acids, branched organic acids, hydroxy/keto-acids, dicarboxylic acids and furfural metabolites, respectively. Seven of the tested compounds were found to have more than 90% mortality thus designating them as highly active nematicides. Of the highly active tested compounds, an average octanol/water log P of 0.97 was observed with a range from 0.28 to 2.64, and a Henry's Law constant averaging 2.6 x 10(- 7) atm.m3/mole. Tested chemicals with minor or low nematicidal activity showed an average log P of 1.76 with a range from 0.15 to 3.42 and a Henry's Law constant averaging 16.6 x 10(- 7) atm.m3/mole.     

Organic acids in continental background aerosols

With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m^-3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.     

Identification of dicarboxylic acids and aldehydes of PM10 and PM2.5 aerosols in Nanjing,China

In this study aerosol samples of PM10 and PM2.5 collected from 18 February 2001 to 1 May 2001 in Nanjing, China were analyzed for their water-soluble organic compounds. A series of homologous dicarboxylic acids (C_2–10) and two kinds of aldehydes (methylglyoxal and 2-oxo-malonaldehyde) were detected by GC and GC/MS. Among the identified compounds, the concentration of oxalic acid was the highest at all the five sites, which ranged from 178 to 1423 ng/m³. The second highest concentration of dicarboxylic acids were malonic and succinic acids, which ranged from 26.9 to 243 ng/m³. Higher level of azelaic acid was also observed, of which the maximum was 301 ng/m³. As the highest fraction of dicarboxylic acids, oxalic acid comprised from 28% to 86% of total dicarboxylic acids in PM10 and from 41% to 65% of total dicarboxylic acids in PM2.5. The dicarboxylic acids (C₂, C₃, C₄) together accounted for 38–95% of total dicarboxylic acids in PM10 and 59–87% of dicarboxylic acids in PM2.5. In this study, the total dicarboxylic acids accounted for 2.8–7.9% of total organic carbon (TOC) of water-soluble matters for PM10 and 3.4–11.8% of TOC for PM2.5. All dicarboxylic acids detected in this study together accounted for about 1% of particle mass. The concentration of azelaic acid was higher at one site than others, which may be resulted from higher level of volatile fat used for cooking. The amounts of dicarboxyic acids (C_2,3,4,9) and 2-oxo-malonaldehyde of PM2.5 were higher in winter and lower in spring. Compared with other major metropolitans in the world, the level of oxalic acid concentration of Nanjing is much higher, which may be contributed to higher level of particle loadings, especially for fine particles.     

Dicarboxylic acids and related compounds in fine particulate matter aerosols in Huangshi,central China

PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) samples were collected in Huangshi, central China, from March 2012 to February 2013 and were analyzed for dicarboxylic acids (diacids) and related compounds (DARCs). Oxalic acid (C₂; 416 ng m^?3) was the most abundant species, followed by phthalic (Ph; 122 ng m^?3), terephthalic (tPh; 116 ng m^?3), succinic (C₄; 70.4 ng m^?3), azelaic (C₉; 67.9 ng m^?3), and adipic (C₆; 57.8 ng m^?3) acids. Relatively high abundances of Ph and tPh differed from the distribution in urban and marine aerosols, indicating contributions from nearby anthropogenic sources. Glyoxylic acid (ωC₂; 41.4 ng m^?3) was the dominant oxoacid, followed by 9-oxononanoic (ωC₉; 40.8 ng m^?3) and pyruvic (Pyr; 24.1 ng m^?3) acids. Glyoxal (Gly; 35.5 ng m^?3) was the dominant α-dicarbonyl. Highest average concentrations were found for C₂, ωC₂, and C₉ in autumn, for C₄, for Pyr and C₆ in spring, for Ph, ωC₉, and Gly in summer, whereas the lowest values were observed in winter. Seasonal variations and correlation coefficients of DARCs demonstrate that both primary emissions and secondary production are important sources. Principal component analysis of selected DARCs species suggests that a mixing of air masses from anthropogenic and biogenic sources contribute to the Huangshi aerosols.

Implications: Both primary emissions and secondary production are important sources of diacids and related compounds in PM_2.5 from Huangshi, central China. Principal component analysis of selected diacids in Huangshi aerosols suggests that mixing of air masses from anthropogenic and biogenic sources contribute to ambient aerosols in central China.     

Source, concentration, and distribution of elemental mercury in the atmosphere in Toronto, Canada

Atmospheric gaseous elemental mercury [GEM] at 1.8, 4, and 59 m above ground, in parking lots, and in indoor and outdoor air was measured in Toronto City, Canada from May 2008-July 2009. The average GEM value at 1.8 m was 1.89 ± 0.62 ng m(-3). The GEM values increased with elevation. The average GEM in underground parking lots ranged from 1.37 to 7.86 ng m(-3) and was higher than those observed from the surface parking lots. The GEM in the indoor air ranged from 1.21 to 28.50 ng m(-3), was higher in the laboratories than in the offices, and was much higher than that in the outdoor air. All these indicate that buildings serve as sources of mercury to the urban atmosphere. More studies are needed to estimate the contribution of urban areas to the atmospheric mercury budget and the impact of indoor air on outdoor air quality and human health.     

Polar organic marker compounds in PM2.5 aerosol from a mixed forest site in western Germany

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.     

Scavenging of SO4− radical anions by mono- and dicarboxylic acids in the Mn(II)-catalyzed S(IV) oxidation in aqueous solution

The rate constants for reactions of the SO₄⁻ radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO₄⁻ reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 10⁵ to 10⁷ M⁻¹ s⁻¹, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO₄⁻ by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO₄⁻ they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).     

Designing green plasticizers: influence of molecular geometry on biodegradation and plasticization properties

The plasticizer di (2-ethylhexyl) phthalate (DEHP) and its metabolites are considered ubiquitous contaminants, which have a range of implications on the environment and human health. This work considered several alternative compounds with structural features similar to DEHP. This added to the understanding of why DEHP is so poorly biodegraded once it enters the environment. These alternative compounds were based on 2-ethylhexyl diesters of maleic acid (cis-isomer), fumaric acid (trans-isomer) and succinic acid (saturated analogue). The rates of biodegradation by the common soil bacterium Rhodococcus rhodocrous were shown to be dependent on the structure of the central unit derived from the diacid used to make the ester. The diacid components of DEHP and the maleate both had a cis orientation and they were the two that were slow to biodegrade. Plasticizing properties were also compared and, because the ester of the saturated succinic acid was degraded quickly and also had good plasticizing properties, it was concluded that the succinic esters of straight chain alcohols would make the best green plasticizers. The maleate ester had excellent plasticizing properties but this is mitigated by a significant resistance to biodegradation.     

Microbial population of spruce soil in Tatachia mountain of Taiwan

To investigate the role of microorganisms in the ecology and the nutrient transformation of forest soil, soil property, microbial population, biomass and organic acid content of Spruce soil in Tatachia mountain were determined during January 1997 to November 1999. Soil temperatures were between 5.5 and 15.6 degrees C and soil pH ranged from 3.6 to 5.0. Total organic carbon and nitrogen contents ranged from 5.83% to 34.35% and from 0.90% to 3.19%, respectively. C/N ratio was between 7.07 and 18.24. Each gram of dry soil contained microbial biomass carbon 308-870 microg, microbial biomass nitrogen 107-240 microg, malic acid 74-211 nM and succinic acid 32-175 nM. In addition, each gram of dry organic layer contained microbial biomass carbon 216-653 microg, microbial biomass nitrogen 10.3-33.8 microg, formic acid 256-421 nM, acetic acid 301-435 nM, malic acid 795-1027 nM and succinic acid 204-670 nM. About 45.5-90.9% of topsoil samples had higher microbial population than those of subsoil especially in actinomycetes, cellulolytic and phosphate-solubilizing microorganisms. Although rhizosphere of Spruce had higher total organic carbon and total nitrogen content than non-rhizosphere and dwarf bamboo areas, the microbial population had no significant difference among them.     

鸡粪堆肥水溶性有机物转化特性研究

采用离子色谱和三维荧光光谱,分别对鸡粪堆肥不同阶段水溶性有机物(DOM)中典型小分子有机酸、磷酸和荧光有机物进行了研究。分析显示,所研究的7种酸(乙酸、琥珀酸、苹果酸、草酸、柠檬酸、酒石酸及磷酸)中,苹果酸的含量最高(1 000 mg/L),草酸的浓度最低(3 mg/L),琥珀酸和柠檬酸未检测到。随着堆肥的进行,各种酸的含量先上升而后下降,堆肥结束降至最低;堆肥过程样品所有荧光峰强度之和与COD达到显著相关(R=0.917,P0.05),类蛋白荧光峰强度与总荧光峰强度的比值不断降低,而类富里酸荧光峰强度与总荧光峰强度的比值不断上升。结果表明,堆肥过程小分子有机酸主要出现在堆肥中期;类蛋白荧光强度或类富里酸荧光强度与总荧光强度之比可以有效表征堆肥腐熟过程。     

Implication of organic acids in the long-distance transport and the accumulation of lead in Sesuvium portulacastrum and Brassica juncea

The implication of organic acids in Pb translocation was studied in two species varying in shoot lead accumulation, Sesuvium portulacastrum and Brassica juncea. Citric, fumaric, malic and α-cetoglutaric acids were separated and determined by HPLC technique in shoots, roots and xylem saps of the both species grown in nutrient solutions added with 200 and 400 μM of Pb(II). The lead content of the xylem saps was determined by ICP–MS. Results showed that S. portulacastrum is more tolerant to Pb than B. juncea. Lead concentration in xylem sap of the S. portulacastrum was significantly greater than in that of B. juncea. For both species, a positive correlation was established between lead and citrate concentrations in xylem sap. However minor relationship was observed for fumaric, malic and α-cetoglutaric acids. In the shoots lead treatment also induced a significant increase in citric acid concentration. Both observations suggest the implication of citric acid in lead translocation and shoot accumulation in S. portulacastrum and B. juncea. The relatively high accumulation of citric acid in xylem sap and shoot of S. portulacastrum could explain its high potential to translocate and accumulate this metal in shoot suggesting their possible use to remediate Pb polluted soils.     

Natural organic compounds as alternative to methyl bromide for nematodes control

Thirty-three organic acids and furfural metabolites were examined for their nematicidal activity against plant-parasitic, free-living and predacious nematodes. Propionic acid, 2-methylhexanoic acid, lactic acid, maleic acid, and furic acid were the most effective nematicides among normal chain organic acids, branched organic acids, hydroxy/keto-acids, dicarboxylic acids and furfural metabolites, respectively. Seven of the tested compounds were found to have more than 90% mortality thus designating them as highly active nematicides. Of the highly active tested compounds, an average octanol/water log P of 0.97 was observed with a range from 0.28 to 2.64, and a Henry's Law constant averaging 2.6 × 10^{? 7} atm.m³/mole. Tested chemicals with minor or low nematicidal activity showed an average log P of 1.76 with a range from 0.15 to 3.42 and a Henry's Law constant averaging 16.6 × 10^{? 7} atm.m³/mole.     

Size-segregated chemistry of particulate dicarboxylic acids in the Arctic atmosphere

Gas–particle interactions of low-molecular-weight dicarboxylic acids were studied at a coastal Arctic site during the summer. Size segregated measurements with a Berner low-pressure impactor displayed up to four modes for ionic compounds: an Aitken mode, an accumulation mode, and two supermicron modes. The lower supermicron mode was ascribed to sea-salt, whereas the upper mode consisted mostly of species associated with continental particles. All four modes could be identified for oxalic acid, with the lower supermicron mode being the dominant. Malonic acid displayed a supermicron mode but was not found in the submicron size range. Succinic acid had an accumulation mode and, in a few samples, a supermicron mode. Glutaric acid displayed sometimes and accumulation mode, sometimes a supermicron mode, and occasionally both. The most probable formation pathway for submicron oxalic and glutaric acid was condensation from the gas phase, even though production in cloud droplets cannot be ruled out either. A slightly different formation pathway may have been important for submicron succinic acid production. Supermicron oxalic acid was probably formed by condensation from the gas-phase, by heterogeneous reactions occurring on the surface of pre-existing sea-salt and continental particles, or in cloud droplets. A larger mass median diameter for supermicron malonic and glutaric acid might be indicative of liquid-phase production in aqueous sea-salt particles. Evidence on possibly substantial sampling artifacts related to measuring dicarboxylic acids using filters were also obtained.     

Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley,RSA)

In this study aerosol samples from the South African savanna were analyzed for their polar organic constituents. Samples were collected with a front/back-up filter tandem system of quartz fiber filters (dual filter strategy). In all samples (n=15) dicarboxylic acids and a variety of phthalates, aldehydes and monocarboxylic acids were observed. Oxalic acid was the dominating compound with an average amount of 79.2 ng m⁻³ on the front filter and 11.3 ng m⁻³ on the back-up filter. The presence of significant concentrations of dicarboxylic acids on the back-up filter was rather unexpected. There are two possible sources to explain the presence of individual compounds on the back-up filter – particle penetration through the front filter or adsorption of compound parts from the gas phase. Interpretation of the data indicates that the dicarboxylic acid concentrations on the back-up filters appear to be caused by the adsorption of gaseous organic species. Dicarboxylic acids semivolatilic behavior is evident with this results. This conclusion refutes the commonly held view that dicarboxylic acids in the atmosphere were associated with the aerosol phase only. Additionally, it was found that the distribution of dicarboxylic acids between the gas and particle phase in the atmosphere is not only dependent on their vapor pressures. The actual gas phase concentration appears to be more determined by the chemical properties of the particles than by pure physical influences. Surprisingly, malonic acid exhibits an anomaly, as it does not show a semivolatile tendency.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

Gas chromatography/mass spectrometry of paraquat UV-ozonation products

The chromatographic and mass spectral properties of 13 compounds isolated from the reaction of UV and ozone on paraquat are described. The products were extracted from the acidified reaction mixture and converted to TMS derivatives. The identified products were the diTMS ester of oxalic acid (m/z 234), the TMS ester of 4-picolinic acid (m/z 195), the diTMS ester of succinic acid (m/z 262), the diTMS derivative of N-formylglycine, 4,4'-bipyridyl (m/z 156), the triTMS derivative of malic acid (m/z 350), and the diTMS derivative of a hydroxy-4-picolinic acid. Structural features and tentative identification of some of the remaining compounds are discussed. The most prominent peak on the chromatogram has a probable molecular ion at m/z 219, isomeric to the diTMS derivative of glycine. The structures presented suggest that demethylation, ring oxidation and fragmentation of one or both rings of the bipyridinium di-cation occur during UV-ozonation of paraquat.