Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene

Secondary organic aerosol (SOA) formation from hydroxyl radical (OH.) initiated photooxidation of α-pinene was investigated in a home-made smog chamber. The size distribution of SOA particles was measured using aerodynamic particle sizer spectrometer. The effects of illumination intensity and light application time on SOA formation for α-pinene were evaluated. Experimental results show that the concentration of SOA particles increased significantly with an increasing of illumination intensity, and the light...     

Effect of relative humidity and the presence of aerosol particles on the α-pinene ozonolysis

The α-pinene ozonolysis under the different environmental conditions were observed in a smog chamber. The second-order rate constant(k) was determined to be(7.25 ± 0.06) ×10~(–17)cm~3/(molecule·sec) under 20% of relative humidity(RH) and room temperature. RH showed a marked influence on the α-pinene ozonolysis. The value of k increased with RH increase, which was 1.6 times faster at RH = 80% than that at RH = 20%. Additionally, the value of k apparently changed in the presence of the aerosol particles. The diesel soot increased the k value. The fly ash prohibited the reaction, however, H_2SO_4-treated fly ash promoted the reaction. The information of products gained using FT-IR and SPAMS showed that pinonic acid, 10-hydroxy-pinonic acid and pinic acid could be generated during the α-pinene ozonolysis. Water molecules could take part in the formation of the products, and play a vital role in the degradation of α-pinene. The atmospheric residence time calculation showed that the ozonolysis in the atmosphere is an important way of the α-pinene consumption as compared to that reacted with OH during daytime. The results suggested that the degradation of α-pinene via the ozonization in the atmosphere may be affected greatly by RH, as well as the presence of aerosol particles. The ozonolysis reaction may be an important way of the α-pinene consumption during daytime.     

Atmospheric isoprene and monoterpenes in a typical urban area of Beijing: Pollution characterization, chemical reactivity and source identification

Continuous observation of isoprene, α-pinene and β-pinene was carried out in a typical urban area of Beijing from March 2014 to February 2015, using an AirmoV OC online analyzer. Based on the analysis of the ambient level and variation characteristics of isoprene, α-pinene and β-pinene, the chemical reactivity was studied, and their sources were identified. Results showed that the concentrations of isoprene, α-pinene and β-pinene in the urban area of Beijing were lower than those in richly vegetated areas; the concentrations of isoprene were at a moderate level compared with those of previous studies of Beijing. Concentrations of isoprene, α-pinene and β-pinene showed different seasonal, monthly, daily and diurnal variations, and all of the three species showed higher level at night than those in the daytime as a whole, the variations of isoprene, α-pinene and β-pinene mainly influenced by emission of sources, photochemical reaction, and meteorological parameters. Isoprene was the largest contributor to the total OFP values than α-pinene and β-pinene. α-Pinene was the largest contributor to the total SOAFP values than isoprene and β-pinene in autumn, while isoprene was the largest one in other seasons. Isoprene, α-pinene and β-pinene were derived mainly from biological sources; and α-pinene level were also affected by industrial sources. To reduce the concentrations of isoprene, α-pinene and β-pinene, it is necessary to scientifically select urban green plant species, and more strict control measures should be taken to reduce the emission of α-pinene from industrial sources, such as artificial flavors and resins synthesis processes.     

Removal characteristics and kinetic analysis of an aerobic vapor-phase bioreactor for hydrophobic alpha-pinene

Biofiltration is considered an effective method to control volatile organic compounds (VOCs) pollution. This study was conducted to evaluate the potential use of a bacterial biofilter packed with wood chips and peat for the removal of hydrophobic α-pinene. When inoculated with two pure degraders and adapted activated sludge, a removal efficiency (RE) of more than 95% was achieved after a start-up period of 11 days. The maximum elimination capacity (EC) of 50 g/(m³. hr) with RE of 94% was obtained at empty bed retention time (EBRT) of 102 sec. When higher α-pinene concentrations and shorter EBRTs were applied, the REs and ECs decreased significantly due to mass-transfer and biological reaction limitations. As deduced from the experimental results, approximately 74% of α-pinene were completely mineralized by the consortiums and the biomass yield was 0.60 g biomass/g α-pinene. Sequence analysis of the selected bands excised from denaturing gradient gel electrophoresis revealed that the inoculated pure cultures could be present during the whole operation, and others were closely related to bacteria being able to degrade hydrocarbons. The kinetic results demonstrated that the whole biofiltration for α-pinene was diffusion-limit controlled owing to its hydrophobic characteristics. These findings indicated that this bacterial biofiltration is a promising technology for the remediation of hydrophobic industrial waste gases containing α-pinene.     

On the study of aerosol composition at the Great Wall Station, South Pole

The South pole aera offers one of the best locations on the Earth for studying the composition of the background aerosol. For this purpose, aerosol samples were collected in particle size fractions by 8 stages cascade impactors. Aerosol sampling was begun in Jan. and finished in Dec. 1986 at the St. Great Wall, South Pole. The samples were analysed by Proton Induced X-ray Emission (PIXE) method. In order to learn the enrichment factors of various elements all the results were separated into two groups: coarse (> 10μm) and fine (< 10μm) particles. The correlation coefficients of elements of both coarse and fine particles were discussed. The aerosol levels measured at St. Great Wall were compared to those recently measured at some other locations. It can be concluded the South Pole is a good background area on the Earth.     

Organic aerosol molecular composition and gas–particle partitioning coefficients at a Mediterranean site (Corsica)

Molecular speciation of atmospheric organic matter was investigated during a short summer field campaign performed in a citrus fruit field in northern Corsica(June 2011). Aimedat assessing the performance on the field of newly developed analytical protocols, this work focuses on the molecular composition of both gas and particulate phases and provides an insight into partitioning behavior of the semi-volatile oxygenated fraction. Limonene ozonolysis tracers were specifically searched for, according to gas chromatography–mass spectrometry(GC–MS) data previously recorded for smog chamber experiments. A screening of other oxygenated species present in the field atmosphere was also performed. About sixty polar molecules were positively or tentatively identified in gas and/or particle phases. These molecules comprise a wide range of branched and linear, mono and di-carbonyls(C_3–C7),mono and di-carboxylic acids(C_3–C_18), and compounds bearing up to three functionalities.Among these compounds, some can be specifically attributed to limonene oxidation and others can be related to α- or β-pinene oxidation. This provides an original snapshot of the organic matter composition at a Mediterranean site in summer. Furthermore, for compounds identified and quantified in both gaseous and particulate phases, an experimental gas/particle partitioning coefficient was determined. Several volatile products, which are not expected in the particulate phase assuming thermodynamic equilibrium, were nonetheless present in significant concentrations. Hypotheses are proposed to explain these observations, such as the possible aerosol viscosity that could hinder the theoretical equilibrium to be rapidly reached.     

Hygroscopicity of particles generated from photooxidation of α-pinene under diferent oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with diferent sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem diferential mobility analyzer(TDMA) in terms of hygroscopic growth factor(Gf), with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols(SOA) formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor(ACSM) and matrix factorization(PMF) method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.     

Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer （TDMA） in terms of hygroscopic growth factor （Gf）, with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols （SOA） formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor （ACSM） and matrix factorization （PMF） method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.     

Application of sewage sludge and intermittent aeration strategy to the bioremediation of DDT-and HCH-contaminated soil

Adding organic amendments to stimulate the biodegradation of pesticides is a subject of ongoing interest. The effect of sewage sludge on the bioremediation of dichlorodiphenyltrichloroethane（DDT） and hexachlorocyclohexane（HCH） contaminated soil was investigated in bench scale experiments,and intermittent aeration strategy was also used in this study to form an anaerobic–aerobic cycle. Bioremediation of DDT and HCH was enhanced with the addition of sewage sludge and the intermittent aeration. The removal rates of HCH and DDT were raised by 16.8%–80.8% in 10 days. Sewage sludge increased the organic carbon content from 6.2 to218 g/kg,and it could also introduce efficient degradation microbes to soil,including Pseudomonas sp.,Bacillus sp. and Sphingomonas sp. The unaerated phase enhanced the anaerobic dechlorination of DDT and HCH,and anaerobic removal rates of β-HCH,o,p′-DDT and p,p′-DDT accounted for more than 50% of the total removal rates,but the content of α-HCH declined more in the aerobic phase.     

Reduction of nitrobenzene by the catalyzed Fe/Cu process

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams.The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions,and cathodically controlled under the alkaline conditions.Batch experiments were performed to study the effect of solution pH,reaction duration,concentration,type of electrolyte,and dissolved oxygen(DO)on the reduction of nitrobenzene by the ca...     

Computer simulation of the coagulation of suspended solids — The applicability of the Müller–Smoluchowski theory

The results of studies carried out using a computer programme simulating the coagulation of suspensions containing spherical sol particles and spherical coagulant particles are reported.The influence of the degree of dispersion of the system on the coagulation reaction kinetics was investigated. The obtained results of kinetic studies were tested in the light of classical Müller–Smoluchowski equations. The influence of the physical properties of the coagulant,such as size, density and mass, on the coagulation rate was tested. It was found that within the range described in this paper, the rate of the simulated coagulation process fulfils both the kinetic equation of a first-order reaction, and the kinetic equation of a second-order reaction.Within the tested range, a significant influence of the mass and size of the coagulant on the coagulation rate was ascertained. The kinetic Müller–Smoluchowski dependence is fulfilled in a broader range of the degree of dispersion, when the coagulant particle mass and the sol particle mass are equal. When the particle mass increases with an increase in the particle radius, the coagulation rate increases faster that it would result from the Müller's dependence.     

Synthesis, separation and identification of dinitropyrene isomers

Dinitropyrenes (DNP) were prepared by nitration of pyrene, and the product was characterized by MS and elemental analysis. Three isomers of DNP were separated by HPLC and identified by 1H-NMR. The eating sequence on the normal phase column is 1, 3-DNP, 1, 6-DNP and 1, 8-DNP, whereas is 1, 6-DNP, 1. 8-DNP and 1. 3-DNP on the reversed phase column. The separation of three DNP isomers under different chromatographic conditions was also discussed.     

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

The chemical stability of heavy metals in a natural water system

A comprehensive investigation of heavy metal pollutants in Xiangjiang river was accomplished to evaluate their chemical stability through three different ways: (1) Chemical speciation by direct measurements; (2) Chemical equilibrium model simulation; (3) Sediment extraction experiments. All the results demonstrated that the directly bioavailable fraction was in a very limited amount. The metal bound to organic ligands, adsorbed particles and precipitated species presented a buffer for solution species. The majority of metals occured in the residues as solid particulates. It was inferred that the heavy metal pollutants in this aquatic system exhibited a high chemical stability. The critical limits of discharging load and pH values were suggested.     

A study on the interactions among several plant secondary compounds and aphids

The research, focused on the specific interactions among seven plant secondary compounds and aphids, was carried out and the preliminary results showed: (1) "T-typed tube method" was regarded as the best method compared with others designed to observe the interactions. (2) Cabbage aphid was able to be attracted by laurolene while it was not susceptible to α-pinene, β-pinene and diamylene. (3) Gossypol, a major secondary substance in cotton, was able to be implicated as feeding attractant to cotton aphid. (4) Rutin might be implicated repellent to cotton aphid.     

Degradation behavior of 17αup-ethinylestradiol by ozonation in the synthetic secondary effluent

Endocrine disrupting chemicals (EDCs) in the secondary effluent discharged from wastewater treatment plants (WWTPs) are of great concern in the process of water reuse. Ozonation has been reported as a powerful oxidation technology to eliminate micropollutants in water treatment. Due to the complexity of the wastewater matrix, orthogonal experiments and single factor experiments were conducted to study the influence of operational parameters on the degradation of 17αup-ethinylestradiol (EE2) in the synthetic secondary effluent. The results of the orthogonal experiments indicated that the initial ozone and natural organic matter (NOM) concentration significantly affected EE2 degradation efficiency, which was further validated by the single factor confirmation experiments. EE2 was shown to be effectively degraded by ozonation in the conditions of low pH (6), NOM (10 mg/L), carbonate (50 mg/L), but high suspended solid (20 mg/L) and initial ozone concentration (9 mg/L). The study firstly revealed that the lower pH resulted in higher degradation of EE2 in the synthetic secondary effluent, which differed from EDCs ozonation behavior in pure water. EE2 degradation by ozone molecule instead of hydroxyl radical was proposed to play a key role in the degradation of EDCs by ozonation in the secondary effluent. The ratio between O₃ and TOC was identified as an appropriate index to assess the degradation of EE2 by ozonation in the synthetic secondary effluent.     

A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m³ fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO₂, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

Pollution characteristics, sources and lung cancer risk of atmospheric polycyclic aromatic hydrocarbons in a new urban district of Nanjing, China

This paper focused on the pollution characteristics,sources and lung cancer risk of atmospheric polycyclic aromatic hydrocarbons(PAHs) in a new urban district of Nanjing,China.Gaseous and aerosol PM_(2.5)(particulate matter with aerodynamic diameter smaller than2.5 urn) samples were collected in spring of 2015.Sixteen PAHs were extracted and analyzed after sampling.Firstly,arithmetic mean concentrations of PAHs and BaP_(eq)(benzo[a]pyrene equivalent) were calculated.The mean concentrations of PAHs were 29.26±14.13,18.14±5.37 and 48.47±16.03 ng/m~3 in gas phase,particle phase and both phases,respectively.The mean concentrations of BaP_(eq) were 0.87±0.51,2.71±2.17 and 4.06±2.31 ng/m~3 in gas phase,particle phase and both phases,respectively.Secondly,diagnostic ratios and principal component analysis were adopted to identify the sources of PAHs and the outcomes were the same:traffic exhaust was the predominant source followed by fuel combustion and industrial process.Finally,incremental lung cancer risk(ILCR) induced by whole year inhalation exposure to PAHs for population groups of different age and gender were estimated based on a Monte Carlo simulation.ILCR values caused by particle phase PAHs were greater than those caused by gas phase PAHs.ILCR values for adults were greater than those for other age groups.ILCR values caused by total(gas + particle) PAHs for diverse groups were all greater than the significant level(10~6),indicating high potential lung cancer risk.Sensitivity analysis results showed that cancer slope factor for BaP inhalation exposure and BaP_(eq) concentration had greater impact than body weight and inhalation rate on the ILCR.     

Experimental continuous sludge microwave system to enhance dehydration ability and hydrogen production from anaerobic digestion of sludge

Dehydrating large amounts of sludge produced by sewage treatment plants is difficult.Microwave pretreatment can effectively and significantly improve the dewaterability and hydrogen production of sludge subjected to anaerobic digestion. The aim of this study was to investigate the effects of different microwave conditions on hydrogen production from anaerobic digestion and dewaterability of sludge. Based on an analysis of the electric field distribution, a spiral reactor was designed and a continuous microwave system was built to conduct intermittent and continuous experiments under different conditions. Settling Volume, Capillary Suction Time, particle size, and moisture content of the sludge were measured. The results show that sludge pretreatment in continuous experiments has equally remarkable dehydration performance as in intermittent experiments; the minimum moisture content was 77.29% in the intermittent experiment under a microwave power of 300 W and an exposure time of 60 sec, and that in the continuous experiment was 77.56% under a microwave power of 400 W and an exposure time of 60 sec.The peak measured by Differential Scanning Calorimeter appeared earliest under a microwave power of 600 W and an exposure time of 180 sec. The heat flux at the peak was 4.343 W/g, which is relatively small. This indicates that microwave pretreatment induced desirable effects. The maximum yield of hydrogen production was 7.967% under the conditions of microwave power of 500 W, exposure time of 120 sec, and water bath at 55°C. This research provides a theoretical and experimental basis for the development of a continuous microwave sludge-conditioning system.