Determination of brominated diphenyl ethers in atmospheric particulate matter using selective pressurized liquid extraction and gas chromatography–mass spectrometry with a negative chemical ionization

This study describes the development and validation of a sensitive and reliable method for determination of polybrominated diphenyl ethers（PBDEs）in atmospheric particulate matter using selective pressurized liquid extraction（SPLE）and gas chromatography–mass spectrometry with a negative chemical ionization（GC-NCI-MS）.Extraction and clean-up were performed using PLE with 2 g florisil and 3 g silica placed in the extraction cells.Under optimal conditions,14 PBDEs were extracted at 70℃ using hexane/dichloromethane（50：50,v/v）as solvent.Validation of SPLE returned excellent recoveries for most analytes,with relative standard deviations mostly below20%.Method detection limits ranged from 0.13 to15.38 ng·mL^-1 for the GC-MS analyses.The method was successfully applied to atmospheric particulate matter of Beijing,where analytes were detected in the range of182.79 to 468.99 pg·m^-3.

Analysis of mass concentration of atmospheric particulate matter in a sandstorm course and its affecting factors in the Taklimakan Desert

During the course of a major sandstorm from April 17 to April 23, 2008 in the Taklimakan Desert, data pertaining to the mass concentrations of different-sized atmospheric particulate matter were observed continuously with Grimm 1.108, Thermo RP 1400a, TSP, and CAWS-600 instruments. The results showed that： （1） during the entire sandstorm process there were some dif- ferences between the daily mean particle concentration peaks and the hourly mean particle concentration peaks because the actual sandstorm lasted for only about 4 hr, whereas more particles were accumulated in the floating dust days before and after the actual sandstorm; （2） the intensity of the sandstorm was enhanced with the increase of wind speed, and this was related to the peak mass concentrations of atmospheric particulate matter; the wind speed directly affected the concentration of atmospheric particulate matter： the higher the wind speed, the higher the mass concentration （〉0.23 μm was 39,496.5 μg/m^3, and 〉20.0 μm was 5,390.7μg/m^3）; （3） the concentration changes of PM10 and TSP were also related to the course and intensity of the sandstorm; and （4） the mass concentration of atmospheric particulate matter had the following sequence during the dust weather： clear day 〈 floating dust 〈 floating and blowing dust 〈 sandstorm. Temperature, relative humidity, and barometric pressure are important factors affecting the strength of storms, which could also indirectly affect the concentration change of atmospheric particulate matter.

Characteristics of air particulate matter and their sources in urban and rural area of Beijing, China

During October 1993 and March 1996, the samples of fine and coarse air particulate matter have been collected at representative urban and rural site of Beijing with the Gent Stacked Filter Unit Sampler. Instrumental neutron activation analysis (INAA) and proton induced X ray emission (PIXE) method were used to determine the elemental composition of the particulate matter. Average elemental concentrations and enrichment factors were calculated for the fine and coarse size fractions. Based on the particulate matter data obtained at urban and rural site together with the chemical constituents of the aerosol from the different sources are discussed. The results show that the relative particulate mass and elemental concentrations of crustal and pollutant elements in the air particulate matter collected over the urban are higher than rural and winter heating period are higher than in ordinary season. Beijing atmosphere is polluted by aerosols from regional and faraway sources. It was noticed that the toxic or harmful elements such as As, Sb, Pb, Cu, Ni, S and Zn were mainly enriched in fine particles with diameter less than 2 μm. A receptor model was used to assess the relative contribution of major air pollution sources at receptor sites in Beijing. Trace elements were used as the markers for the above assessment. Factor analysis method was used to identify possible emission sources of air particles. The major sources of dust soil, coal burning, motor vehicle emission, industry emission and refuse incineration were identified.

Quantification of perfluorinated compounds in atmospheric particulate shows potential connection with environmental event

A method of quantification of perfluorinated compounds(PFCs)from atmospheric particulate matter(APM)is described.A single step pretreatment method,selective pressurized liquid extraction(SPLE),was developed to reduce the high matrix background and avoid contamination from commonly used multiple sample pretreatment steps.An effective sorbent was selected to purify the PFCs during SPLE,followed by liquid chromatography-tandem mass spectrometry(LC–MS/MS),for quantification of PFCs.Conditions affecting the SPLE efficiency,including temperature,static extraction time,and number of extraction cycles used,were studied.The optimum conditions were found to be 120℃,10 min,and 3 cycles,respectively.LC-MS/MS method was developed to obtain the optimal sensitivity specific to PFCs.The method detection limits(MDLs)were 0.006 to 0.48 ng/g for the PFCs studied and the linear response range was from 0.1 to 100 ng/g.To ensure accurate values were obtained,each step of the experiment was evaluated and controlled to prevent contamination.The optimized method was tested by performing spiking experiments in natural particulate matter matrices and good rates of recovery and reproducibility were obtained for all target compounds.Finally,the method was successfully used to measure 16 PFCs in the APM samples collected in Beijing over five years from 2015 to 2019.It is observed that some PFCs follow the trend of total PFC changes,and can be attributed to the environment influencing events and policy enforcement,while others don't seem to change as much with time of the year or from year to year.

Magnetic Properties of Tree Leaves and Their Significance in Atmospheric Particle Pollution in Linfen City,China

Fifty-one tree leaves were sampled in the industrial area,residential area,and Fenhe River ecological zone,for the purpose of a magnetic study on atmospheric pollution in Linfen City,Shanxi Province,China.Measurements of mass-specific magnetic susceptibility(χ) show a significant variation range(from 11.6 × 10-8 m3/kg to 129.7 × 10-8 m3/kg).Overall values of magnetic susceptibility decline in the following sequence:industrial area > residential area > Fenhe River ecological zone.The relatively elevated concentration-related magnetic parameters(saturation isothermal remanent magnetization,anhysteretic remanent magnetization and magnetic susceptibility) appear in the industrial area,with their highest values in the vicinity of Linfen Steel Mill.Magnetic particles are dominated by multidomain,magnetite-like minerals.Magnetic particle concentration and grain size both decrease with the increasing distance from industrial area,indicating the industrial area,especially Linfen Steel Mill,is the main source of atmospheric particle pollution.Residential area and Fenhe River ecological zone are also affected by industrial emission to a certain extent.The results of this study indicate that magnetic measurements of tree leaves are practicable for monitoring and determination of atmospheric pollution in Linfen City.

Concentrations,sources,and influential factors of water-soluble ions of atmospheric particles in Dunhuang Mogao Grottoes,a world heritage site in China

Atmospheric particle pollution is one of the major factors leading to degradation of ancient wall paintings,particularly heritage sites in arid and semi-arid regions.However,current systematic research on the changes,sources,and influential factors of atmospheric particulate matter and its water-soluble ion concentrations is not sufficient.Thus,the major water-soluble ion concentrations,sources,and influential factors of atmospheric particles PM_(2.5) and PM_(10)(particulate matter with an aerodynamic equivalent diameter≤2.5 and 10.0μm,respectively,in ambient air)were collected from Cave 16 and its ambient exterior environment in the Dunhuang Mogao Grottoes,China,between April 2015 and March 2016.Results showed that the concentrations of PM_(2.5) and PM_(10) inside and outside the cave were the highest in March 2016 and the lowest in December 2015.The higher particle concentration from March to May was related to the frequent occurrence of sand and dust events,and the lower particle concentration from June to September was associated with good diffusion conditions,increased precipitation,and an established cave shelterbelt.The concentration of particulate matter inside the cave was affected by the concentration of particles in the air outside the cave.Ca2+,NH+4,Na+,Cl-,and SO2-4were the main components of the total ions of PM_(2.5) and PM_(10) both inside and outside the cave.The total ions inside the cave were frequently affected by the disturbance of tourists'activities during the peak tourist season from May to August.Under the influence of dust,the total concentrations of Cl-,SO2-4,Na+,NH+4,and Ca2+in particles of different sizes inside and outside the cave increased,and the concentrations of Cl-,SO2-4,Na+,and Ca2+decreased during precipitation period.Backward air mass trajectory analysis suggested that the pollutants were mainly from Xinjiang,China.The pollutant sources of air particulates are straw burning,secondary pollution sources,soil dust,dry spring rivers,and tourist activities.

Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area

In order to understand the size distribution and the main kind of heavy metals in particulate matter on the lead and zinc smelting affected area, particulate matter （PM） and the source samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and the results were discussed and interpreted. Atmospheric particles were collected with different sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of different sizes, collected from the air and from factories, were measured using an inductively coupled plasma mass spectrometry （ICP-MS）. The results indicated that the average concentration of PM, chromium （Cr）, arsenic （As）, cadmium （Cd） and lead （Pb） in PM was 177.3 ± 33.2 μg/m^3, 37.3 ± 8.8 ng/m^3, 17.3 ± 8.1 ng/m^3, 4.8 ± 3.1 ng/m^3 and 141.6 ± 49.1 ng/m^3, respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM size distribution was at 1.1-2.1 μm, followed by 9-10 μm. The size distribution of As, cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of 1.1-2.1 μm and 9-10 μm ranges while for Cr, only a single-mode at 4.7-5.8 μm was observed. PM （64.7%, As （72.5%）, cd （72.2%） and Pb （75.8%） were associated with the fine mode below 2.1 μm, respectively, while Cr （46.6%） was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting sources.

Surface property and in vitro toxicity effect of insoluble particles given by protein corona:Implication for PM cytotoxicity assessment

In vitro toxicological assessment helps explore key fractions of particulate matter(PM)in association with the toxic mechanism.Previous studies mainly discussed the toxicity effects of the water-soluble and organic-soluble fractions of PM.However,the toxicity of insoluble fractions is relatively poorly understood,and the adsorption of proteins is rarely considered.In this work,the formation of protein corona on the surface of insoluble particles during incubation in a culture medium was investigated.It was found that highly abundant proteins in fetal bovine serum were the main components of the protein corona.The adsorbed proteins increased the dispersion stability of insoluble particles.Meanwhile,the leaching concentrations of some metal elements(e.g.,Cu,Zn,and Pb)from PM increased in the presence of proteins.The toxicity effects and potential mechanisms of the PM insoluble particle–protein corona complex on macrophage cells RAW264.7 were discussed.The results revealed that the PM insoluble particle–protein corona complex could influence the phagosome pathway in RAW264.7 cells.Thus,it promoted the intracellular reactive oxygen species generation and induced a greater degree of cell differentiation,significantly altering cell morphology.Consequently,this work sheds new light on the combination of insoluble particles and protein corona in terms of PM cytotoxicity assessment.

Review of heterogeneous photochemical reactions of NOy on aerosol-A possible daytime source of nitrous acid (HONO) in the atmosphere

As an important precursor of hydroxyl radical, nitrous acid （HONO） plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3 , by photocatalytic reaction of NO2 on TiO2 or TiO2 -containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.