Characterization of organic matter in total suspended particles by thermodesorption and pyrolysis-gas chromatography-mass spectrometry

The organic matter in tropospheric aerosol plays an important role in atmospheric physical and chemical processes. The bulk of organic matter, representing a significant proportion of the total suspended particulate （TSP） mass, is bound to polymeric material whose structure and properties are largely unknown. Here we used thermodesorption gas chromatography/mass spectrometry （Td-GC/MS） to study organic compounds of low molecular mass and pyrolysis gas chromatography/mass spectrometry （Py-GC/MS） to characterize the chemical structure of macromolecules in TSP samples collected in different seasons from different sites in Guangzhou. n-Alkanes, fatty acids and nitriles were the predominant compounds in the thermodesorption products, whereas aromatics, fatty acids, nitriles and n-alkanes/alkenes were the major compounds in the pyrolysates. The results indicated that aromatics were main units in macromolecules. The fatty acids and nltriles formed from carboxylic ammonium salts were detected in both thermodesorption products and pyrolysates at a certain concentration, indicating the importance of these compounds in TSP formation. The TSP source mainly determined the occurrence of compounds in samples from urban, suburban and forest sites, whereas the TSP source and formation process maybe controlled the seasonal variation in compounds detected. High levels of nitriles in summer samples from suburban and forest sites coincide with the release of ammonium from the land and of fatty acids from vegetation at these sites.

Dry deposition velocity of total suspended particles and meteorological influence in four locations in Guangzhou,China

Dry deposition velocity of total suspended particles （TSP） is an effective parameter that describes the speed of atmospheric particulate matter deposit to the natural surface. It is also an important indicator to the capacity of atmosphere self-depuration. However, the spatial and temporal variations in dry deposition velocity of TSP at different urban landscapes and the relationship between dry deposition velocity and the meteorological parameters are subject to large uncertainties. We concurrently investigated this relationship at four different landscapes of Guangzhou, from October to December of 2009. The result of the average dry deposition velocity is （1.49 ± 0.77）, （1.44 ± 0.77）, （1.13 ±0.53） and （1.82± 0.82） cm/sec for urban commercial landscape, urban forest landscape, urban residential landscape and country landscape, respectively. This spatial variation can be explained by the difference of both particle size composition of TSP and meteorological parameters of sampling sites. Dry deposition velocity of TSP has a positive correlation with wind speed, and a negative correlation with temperature and relative humidity. Wind speed is the strongest factor that affects the magnitude of TSP dry deposition velocity, and the temperature is another considerable strong meteorological factor. We also find out that the relative humidity brings less impact, especially during the dry season. It is thus implied that the current global warming and urban heat island effect may lead to correlative changes in TSP dry deposition velocity, especially in the urban areas.

Polychlorinated biphenyls in the atmosphere of Taizhou,a major e-waste dismantling area in China

PM2.5, total suspended particles （TSP） and gas phase samples were collected at two sites of Talzhou, a major e-waste dismantling area in China. Concentrations, seasonal variations, congener profiles, gas-particle partitioning and size distribution of the atmospheric polychlorinated biphenyls （PCBs） were studied to assess the current state of atmospheric PCBs after the phase out of massive historical dismantling of PCBs containing e-wastes. The average ∑38PCBs concentration in the ambient air （TSP plus gas phase） near the e-waste dismantling area was （12,407 ± 9592） pg/m^3 in winter, which was substantially lower than that found one decade ago. However, the atmospheric PCBs level near the e-waste dismantling area was 54 times of the reference urban site, indicating that the impact of the historical dismantling of PCBs containing e-wastes was still significant. Tri-Penta-CBs were dominant homologues, consisting with their dominant global production. Size distribution of particle-bound PCBs showed that higher chlorinated CBs tended to partition more to the fine particles, facilitating its long range air transportation.

Characteristics of air pollution by polychlorinated dibenzo-p-dioxins and dibenzofurans in the typical industrial areas of Tangshan City,China

The ambient air in vicinity of different industrial sources for PCDD/PCDFs was sampled by TSP/PM10 active samplers and passive PUF disk samplers in Tangshan City, a metropolis containing clusters of various industrial plants. The TEQ concentrations of PCDD/PCDFs ranged from 44.2 to 394.1 fg I-TEQ/m^3 with an average of 169.9 fg I-TEQ]m^3. 2,3,4,7,8-PeCDF was the dominant contributor to ∑TEQ, contributing 41% （12% to 55%）, while 1,2,3,4,6,7,8-HpCDE OCDD and OCDF were the major congeners for the total concentrations. The ratios of ∑PCDF/∑PCDD reached 2.54 on average, suggesting that de novo synthesis in thermal processes played an important role to the airborne pollution of PCDD/PCDFs. The similarities congener profiles indicated that TSP and PM10 active sampling methods are comparable for the determination of the PCDD/PCDFs in ambient air, and the ratios of concentrations determined by the two methods suggested that the PCDD/PCDFs tended to stay in fine particles. It was found that 2,3,7,8-TCDF and OCDD were the dominating congeners in the passive PUF disks samples. Through principal components analysis, the coke industry was suggested to be a relatively high potential emission source for PCDD/PCDFs in the ambient air of Tangshan, which was possibly formed by de novo synthesis mechanism. In this study, the atmospheric impacts to the environment from different industrial sources could be ranked as follows （from high to low）： coking, iron sintering, steel making, power generation and chlorinate alkali chemical production industries.

Seasonal variation and chemical composition of particulate matter： A study by XPS, ICP-AES and sequential microanalysis using Raman with SEM/EDS

During the winter period（January–March 2016）, the total suspended particles（TSP） and particulate matter smaller than 2.5 μm（PM2.5） were characterized by the application of various analytical techniques in four zones of the Metropolitan Area of Monterrey in Mexico. To evaluate the seasonal variation of some elements in the particulate matter, the results of this study were compared with those obtained during the summer season（July–September 2015）. The speciation of the C_（1s） signal by X-ray photoelectron spectroscopy revealed the contribution of aromatic and aliphatic hydrocarbons as the main components in both seasons. Conversely, carboxylic groups associated with biogenic emissions were detected only in winter. The percentages of SO_4^（2-） ions were lower in winter, possibly caused by the decrease in the solar radiation, and relative humidity recorded. The results of the ICP analysis revealed that Fe, Zn and Cu were the most abundant metals in both TSP and PM2.5 in the two seasons. There were significant seasonal variations for concentrations of As, Ni and Zn in the urban area and for Fe, As, Cd, Ni and Zn in the industrial zone. This was attributed to the greater burning of fuels as well as to an increase in vehicular traffic, the effect of thermal inversion and changes in some meteorological parameters. The results of the sequential microanalysis by Raman spectroscopy and SEM/EDS allowed observation of deposits of carbonaceous material on the particles and to perform the speciation of particles rich in Fe and Pb, which helped infer their possible emission sources.

Atmospheric particle-bound polycyclic aromatic compounds over two distinct sites in Pakistan:Characteristics,sources and health risk assessment

Much attention is drawn to polycyclic aromatic hydrocarbons(PAHs)as an air pollutant due to their toxic,mutagenic and carcinogenic properties.Therefore,to understand the levels,seasonality,sources and potential health risk of PAHs in two distinct geographical locations at Karachi and Mardan in Pakistan,total suspended particle(TSP)samples were collected for over one year period.The average total PAH concentrations were 31.5±24.4 and 199±229 ng/m^(3) in Karachi and Mardan,respectively.The significantly lower concentration in Karachi was attributed to diffusion and dilution of the PAHs by the influence of clean air mass from the Arabian sea and high temperature,enhancing the volatilization of the particle phase PAHs to the gas phase.Conversely,the higher concentration(^(-)6 times)in Mardan was due to large influence from local and regional emission sources.A clear seasonality was observed at both the sites,with the higher values in winter and post-monsoon due to higher emissions and less scavenging,and lower values during monsoon season due to the dilution effect.Diagnostic ratios and principal component analysis indicated that PAHs in both sites originated from traffic and mixed combustion sources(fossil fuels and biomass).The average total Ba P equivalent concentrations(Ba P eq)in Karachi and Mardan were 3.26 and 34 ng/m^(3),respectively,which were much higher than the WHO guideline of 1 ng/m^(3).The average estimates of incremental lifetime cancer risk from exposure to airborne Ba P eq via inhalation indicated a risk to human health from atmospheric PAHs at both sites.

Polybrominated diphenyl ethers(PBDEs)in ambient air samples at the electronic waste(e-waste)reclamation site

Polybrominated diphenyl ethers(PBDEs)have been used as flame retardants in various building materials,plastic and other polymers,airplanes,electronics,etc.All or some of their congeners have been already banned in many countries,due to their persistency and adverse health effects.In this study,we are focusing on e-wastes as a source of emission of PBDEs in ambient air during reclamation processes.The ambient air particulate matter(PM)samples were collected at and near an e-waste reclamation site in Bangkok,Thailand.Results showed the presence of various homologues,viz:tri-,tetra-,penta-,hexa-,and hepta-PBDEs in both PM2.5 and total suspended particle(TSP)samples.The comparison of samples as a function of distance from the reclamation site indicated elevated levels of PBDEs in close proximity to the e-waste site.Interestingly,a shift in the congener pattern was observed with lower brominated PBDEs being more prevalent in nearby off-site samples as compared to the PM collected at the e-waste site.The total penta-PBDEs concentration is almost double in the e-waste site PM2.5 compared to the control site samples.For TSP,tetra,penta,and hepta-PBDEs congeners are at higher concentrations at the e-waste sites and its vicinity compared to reference sites.Overall,a clear trend can be observed indicating a debromination of PBDEs to more toxic tri and tetra congeners during the reclamation process and PBDEs are being translocated from treated materials to ambient air PM.BDE 30 is uniquely detected in our studies as a dominant final debromination product,that can be used as a marker of thermal e-waste activity.This work indicates potential hazards related to the reclamation of e-wastes and remediation of sites containing PBDEs.In particular,thermal treatment methods can lead to congener transformation and increased emissions of more toxic lower brominated congeners.