Trihalomethane formation potential of organic fractions in secondary effluent

Organic matter is known to be the precursor of numerous chlorination by-products. Organic matter in the secondary effluent from the Wenchang Wastewater Treatment Plant （Harbin, China） was physically separated into the following fractions： particulate organic carbon （1.2-0.45 μm）, colloidal organic carbon （0.45-0.1 μm）, fine colloidal organic carbon （0.1-0.025 μm）, and dissolved organic carbon （DOC） （〈 0.025 μm）. Moreover, 〈 0.45 μm fraction was chemically separated into hydrophobic acid （HPO-A）, hydrophobic neutral （HPO-N）, transphilic acid （TPI-A）, transphilic neutral （TPI-N）, and hydrophllic fraction （HPI）. The chlorine reactivity of these organic fractions obtained from both size and XAD fractionations were evaluated. The structural and chemical compositions of the HPO-A, HPO-N, TPI-A, and TPI-N isolates were characterized using elemental analysis （C, H, O, and N）, Fourier transform infrared spectroscopy （FT-IR）, and proton nuclear magnetic resonance spectroscopy （1H-NMR）. Results showed that DOC was dominant in terms of total concentration and trihalomethane formation potential （THMFP）, and there was no statistical difference in both specific THMFP （STHMFP） and specific ultraviolet light absorbance among the 0.45, 0.1, and 0.025 ixm filtrates. HPO-A had the highest STHMFP compared to other chemical fractions. HPO-A, HPO-N, TPI-A, and TPI-N contained 3.02%-3.52% of nitrogen. The molar ratio of H/C increased in the order of HPO-A 〈 HPO-N 〈 TPI-A 〈 TPI-N. The O/C ratio was relatively high for TPI-N as compared to those for the other fractions. ^1H-NMR analysis of the four fractions indicated that the relative content of aromatic protons in HPO-A was significantly higher than those in the others. The ratio of aliphatic to aromatic protons increased in the order of HPO-A 〈 HPO-N 〈 TPI-A 〈 TPI-N. FT-IR analysis of the four fractions showed that HPO-A had greater aromatic C=C content whereas HPO-N, TPI-A, and TPI-N had greater aliphatic C-H content. TPI-N contained more oxygen-containing functional groups than the other fractions.

Removal of disinfection by-products formation potential by biologically intensified process

The removal of disinfection by-products formation potential(DBPFP) in artificially intensified biological activated carbon(IBAC) process which is developed on the basis of traditional ozone granular activated carbon was evaluated. By IBAC removals of 31% and 68% for THMFP and HAAFP were obtained respectively. Under identical conditions, the removals of the same substances were 4% and 32% respectively only by the granular activated carbon(GAC) process. Compared with GAC, the high removal rates of the two formed potential substances were due to the increasing of bioactivity of the media and the synergistic capabilities of biological degradation cooperating with activated carbon adsorption of organic compounds. A clear linear correlation(R 2=0.9562 and R 2=0.9007) between DOC HAAFP removal rate and Empty Bed Contact Time(EBCT) of IBAC process was observed, while that between THMFP removal rate and EBCT of GAC was R 2=0.9782. In addition certain linear correlations between THMFP, HAAFP and UV 254 (R 2=0.855 and R 2=0.7702) were found for the treated water. For IBAC process there are also more advantages such as long backwashing cycle time, low backwashing intensity and prolonging activated carbon lifetime and so on.

Rapid Determination of HAAs Formation Potential of the Reaction of Humic Acid with Chlorine or Chlorine Dioxide

On the basis of gas chromatography（GC） coupled with a short capillary column and an electron capture detector （ ECD）, a simple and rapid method for the determination of five haloaceric acids （ HAAs ） in drinking water was developed by the optimization of derivation conditions and the modification of gas chromatographic program. HAAs formarion potential（HAAFP） of the reaction of humic acid with chlorine was determined via this method. The major advantages of the method are the simplicity of chromatographic temperature program and the short run time of GC. Dichloroaceric acid（DCAA） and Trichloroacetic acid（TCAA）, which were detected in the determination of HAAFP, were rapidly formed in the first 72 h of the reaction of humic acid with chlorine. HAAFP of the reaction of humic acid with chlorine increased with the increase in the concentrations of humic acid and chlorine. The average HAAFP of the reaction of humic acid with chlorine was 39.9μg/mg TOC under the experimental conditions. When the concentration of humic acid was 4 mg/L, the concentration of HAAs, which were produced in the reaction of humic acid with choline, may exceed MCL of 60μg/L HAAs as the water quality standards for urban water supply of China and the first stage of US EPA disinfecrion/disinfection by-products（D/DBP） rule; when the concentration of humic acid was 2 mg/L, the concentration of HAAs may exceed MCL of 30 μg/L HAAs for the second stage of US EPA D/DBP rule. When humic acid was reacted with chlorine dioxide, only DCAA was detected with a maximum concentration of 3.3 μg/L at a humic acid content of 5 mg/L. It was demonstrated that the substitution of chlorine dioxide for chorine may entirely or partly control the formation of HAAs and effectively reduce the health risk associated with disinfected drinking water.

Removal characteristics of disinfection by-products formation potential by bioaugmentation activated carbon process

The high-active bacteria were screened from 8 dominant bacteria obtained from the natural water body,and then the bioaugmentation activated carbon was formed by hydraulic immobilization of the high-active bacteria. Plant-scale studies on removal characteristics of disinfection by-products formation potentials (DBPFP) by bioaugmentation activated carbon process were conducted for micro-polluted raw water treatment. The results show that the bioaugmentation activated carbon process has adopted better purification efficiency to THMFP and HAAFP than traditional biological activated carbon process,and that average removal efficiencies of THMFP and HAAFP can reach 35% and 39.7% during the test period,increasing by more than 10% compared with traditional biological activated carbon process. The removal efficiencies of THMFP and HAAFP are stable because of the biodegradation of the high-active bacteria and the adsorption of active carbon. The biodegradability of CHCl3 formation potential is better as compared with that of CHCl2Br and CHClBr2 formation potentials among THMFP,and high removal efficiency of CHCl3formation potential is obtained by bioaugmentation degradation of the high-active bacteria. The biodegradability of HAAFP is better in comparison with that of THMFP,and the chemical properties of HAAFP are propitious to adsorption of activated carbon. Thus,HAAFP is on predominance during the competitive removal process with THMFP.

Characterization of disinfection byproduct formation potential in 13 source waters in China

The formation potential of four trihalomethanes （THMFP） and seven haloacetic acids （HAA7FP） in 13 source waters taken from four major water basin areas in China was evaluated using the simulated distribution system （SDS） chlorination method. The specific ultraviolet absorbance （SUVA254： the ratio of UV254 to dissolved organic carbon （DOC））, which ranged between 0.9 and 5.0 L/（mg.m）, showed that the organic compounds in different source waters exhibited different reactivities with chlorine. The HAA7FP of source waters ranged from 20 to 448 μg/L and the THMFP ranged from 29 to 259 μg/L. The HAA7FP concentrations were higher than the THMFP concentrations in all but one of the samples. Therefore, the risks of haloacetic acids （HAAs） should be of concern in some source waters. TCM （chloroform） and BDCM （bromodichloromethane） were the major THM constituents, while TCAA （trichloroacetic acid） and DCAA （dichloroacetic acid） were the major HAA species. Br-THM （brominated THM species） were much higher than Br- HAA （brominated HAA species）, and the formation of Br-DBP （Br-THM and Br-HAA） should be of concern when the bromide concentration is over 100 μg/L.

Comparative investigation of coal-and oil-fired boilers based on emission factors,ozone and secondary organic aerosol formation potentials of VOCs

Volatile organic compounds(VOCs)are the important precursors of the tropospheric ozone(O3)and secondary organic aerosols(SOA),both of which are known to harm human health and disrupt the earth’s climate system.In this study,VOC emission factors,O3 and SOA formation potentials were estimated for two types of industrial boilers:coal-fired boilers(n=3)and oil-fired boilers(n=3).Results showed that EVOCs concentrations were more than nine times higher for oil-fire d boilers compared to those for coal-fired boilers.Emission factors ofΣVOCs were found to be higher for oil-fired boilers(9.26-32.83 mg-VOC/kg)than for coal-fired boilers(1.57-4.13 mg-VOC/kg).Alkanes and aromatics were obtained as the most abundant groups in coal-fired boilers,while oxygenated organics and aromatics were the most contributing groups in oil-fired boilers.Benzene,n-hexane and o-ethyl toluene were the abundant VOC species in coal-fired boiler emissions,whereas toluene was the most abundant VOC species emitted from oil-fired boilers.O3 and SOA formation potentials were found 12 and 18 times,respectively,higher for oil-fired than for coal-fired boilers.Total OFP ranged from 3.99 to 11.39 mg-O3/kg for coal-fired boilers.For oil-fired boilers,total OFP ranged from 36.16 to 131.93 mg-O3/kg.Moreover,total secondary organic aerosol potential(SOAP)ranged from 65.4 to 122.5 mg-SOA/kg and 779.9 to 2252.5 mg-SOA/kg for the coal-fired and oil-fired boilers,respectively.

Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential

Fifteen heavy-duty diesel vehicles were tested on chassis dynamometer by using typical heavy duty driving cycle and fuel economy cycle. The air from the exhaust was sampled by 2,4- dinitrophenyhydrazine cartridge and 23 carbonyl compounds were analyzed by high performance liquid chromatography. The average emission factor of carbonyls was 97.2 mg/km, higher than that of light-duty diesel vehicles and gasoline-powered vehicles. Formaldehyde, acetaldehyde, acetone and propionaidehyde were the species with the highest emission factors. Main influencing factors for carbonyl emissions were vehicle type, average speed and regulated emission standard, and the impact of vehicle loading was not evident in this study. National emission of carbonyls from diesel vehicles exhaust was calculated for China, 2011, based on both vehicle miles traveled and fuel consumption. Carbonyl emission of diesel vehicle was estimated to be 45.8 Gg, and was comparable to gasolinepowered vehicles （58.4 Gg）. The emissions of formaldehyde, acetaldehyde and acetone were 12.6, 6.9, 3.8 Gg, respectively. The ozone formation potential of carbonyls from diesel vehicles exhaust was 537 mg O3/km, higher than 497 mg O3/km of none-methane hydrocarbons emitted from diesel vehicles.

Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes： Formation potential and integrated toxicity

The comprehensive control efficiency for the formation potentials（FPs） of a range of regulated and unregulated halogenated disinfection by-products（DBPs）（including carbonaceous DBPs（C-DBPs）, nitrogenous DBPs（N-DBPs）, and iodinated DBPs（I-DBPs）） with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment（coagulation–sedimentation, pre-sand filtration）, ozone-biological activated carbon（O_3-BAC） advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated.The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide,and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O_3-BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON.After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles（HANs）》haloacetamides（HAMs） 〉haloacetic acids（HAAs） 〉 trihalomethanes（THMs） 〉 halonitromethanes（HNMs） 》I-DBPs（I-HAMs and I-THMs）. I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored.

Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process

Benzophenones （BPs） are a class of widely used UV filters, which have been frequently detected within multiple environmental matrices. Disinfection is a necessary process in water treatment processes. The transformation behaviors and toxicity changes of 14 BP-type UV filters during chlorination disinfection treatment were investigated in this study. A new index, the acute toxicity formation potential, was proposed to evaluate the toxicity changes and potential risks of BP-type UV filters during chlorination treatment. It was found that 13 of 14 BP-type UV filters exhibited toxicity decreases in the chlorination disinfection process, more or less, while one showed a toxicity increase. The toxicity changes were dependent on substitution effects, such that 2,4-di-hydroxylated or 3-hydroxylated BPs exhibited significant toxicity decreases after chlorination treatment due to the ready cleavage of the aromatic ring. Importantly, the acute toxicity changes could be duplicated in an ambient water matrix.

Formation potential and analysis of 32 regulated and unregulated disinfection by-products: Two new simplified methods

Water disinfection is an essential process that provides safe water by inactivating pathogens that cause waterborne diseases. However, disinfectants react with organic matter naturally present in water, leading to the formation of disinfection by-products(DBPs). Multi-analyte methods based on mass spectrometry(MS) are preferred to quantify multiple DBP classes at once however, most require extensive sample pre-treatment and significant resources. In this study, two analytical methods were developed for the quantification of 32 regulated and unregulated DBPs. A purge and trap(P&T) coupled with gas chromatography mass spectrometry(GC-MS) method was optimized that automated sample pre-treatment and analyzed volatile and semi-volatile compounds, including trihalomethanes(THMs), iodinated trihalomethanes(I-THMs), haloacetonitriles(HANs), haloketones(HKTs) and halonitromethanes(HNMs). LOQs were between 0.02-0.4 μg/L for most DBPs except for 8 analytes that were in the low μg/L range. A second method with liquid chromatography(LC) tandem mass spectrometry(MS/MS) was developed for the quantification of 10 haloacetic acids(HAAs) with a simple clean-up and direct injection. The LC-MS/MS direct injection method has the lowest detection limits reported(0.2-0.5 μg/L). Both methods have a simple sample pre-treatment, which make it possible for routine analysis. Hyperchlorination and uniform formation conditions(UFC) formation potential tests with chlorine were evaluated with water samples containing high and low TOC. Hyperchlorination formation potential test maximized THMs and HAAs while UFC maximized HANs. Ascorbic acid was found to be an appropriate quencher for both analytical methods. Disinfected drinking water from four water utilities in Alberta, Canada were also evaluated.

Reduction of DOM fractions and their trihalomethane formation potential in surface river water by in-line coagulation with ceramic membrane filtration

This research was aimed at investigating the reduction of DOM fractions and their trihalomethane formation potential （THMFP） by in-line coagulation with 0.1 μm ceramic membrane filtration. The combination of ceramic membrane filtration with a coagulation process is an alternative technology which can be applied to enhance conventional coagulation processes in the field of water treatment and drinking water production. The Ping River water （high turbidity water） was selected as the raw surface water because it is currently the main raw water source for water supply production in the urban and rural areas of Chiang Mai Province. From the investigation, the results showed that the highest percent reductions of DOC, UV-254, and THMFP （47.6%, 71.0%, and 67.4%, respectively） were achieved from in-line coagulation with ceramic membrane filtration at polyaluminum chloride dosage 40 mg/L. Resin adsorption techniques were employed to characterize the DOM in raw surface water and filtered water. The results showed that the use of a ceramic membrane with in-line coagulation was able to most efficiently reduce the hydrophobic fraction （HPOA） （68.5%）, which was then followed by the hydrophilic fraction （HPIA） （49.3%）. The greater mass DOC reduction of these two fractions provided the highest THMFP reductions （55.1% and 37.2%, respectively）. Furthermore, the in-line coagulation with ceramic membrane filtration was able to reduce the hydrophobic （HPOB） fraction which is characterized by high reactivity toward THM formation. The percent reduction of mass DOC and THMFP of HPOB by in-line coagulation with ceramic membrane filtration was 45.9% and 48.0%, respectively.

ICRF Experiments and Potential Formation on the GAMMA 10 Tandem Mirror

Target plasmas, on which the formation of the electrostatic potentials and the improvement of the confinement are studied, are produced with ICRF in the GAMMA 10 tandem mirror. The ion temperature of more than 10 keV has been achieved in relatively low density plasmas. When the strong ICRF heating is applied, it is observed that the high frequency and the low frequency fluctuations are excited and suppress the increase of the plasma parameters. Recently, a new high power gyrotron system has been constructed and the ECRH power in plug extends up to 370 kW. The improvement of the confinement due to the formation of the potential in the axial direction and the strong radial electric field shear has been observed.

Transformations of particles, metal elements and natural organic matter in different water treatment processes

Characterizing natural organic matter （NOM）, particles and elements in different water treatment processes can give a useful information to optimize water treatment operations. In this article, transformations of particles, metal elements and NOM in a pilot-scale water treatment plant were investigated by laser light granularity system, particle counter, glass-fiber membrane filtration, inductively coupled plasma-optical emission spectroscopy, ultra filtration and resin absorbents fractionation. The results showed that particles, NOM and trihalomethane formation precursors were removed synergistically by sequential treatment of different processes. Preozonation markedly changed the polarity and molecular weight of NOM, and it could be conducive to the following coagulation process through destabilizing particles and colloids; mid-ozonation enhanced the subsequent granular activated carbon （GAC） filtration process by decreasing molecular weight of organic matters. Coagulation-flotation and GAC were more efficient in removing fixed suspended solids and larger particles; while sand-filtration was more efficient in removing volatile suspended solids and smaller particles. Flotation performed better than sedimentation in terms of particle and NOM removal. The type of coagulant could greatly affect the performance of coagulation-flotation. Pre-hydrolyzed composite coagulant （HPAC） was superior to FeCl3 concerning the removals of hydrophobic dissolved organic carbon and volatile suspended solids. The leakages of flocs from sand-filtration and microorganisms from GAC should be mitigated to ensure the reliability of the whole treatment system.

Formation and emission characteristics of VOCs from a coal-fired power plant

On-site measurements of volatile organic compounds(VOCs)in different streams of flue gas were carried out on a real coal-fired power plant using sampling bags and SUMMA canisters to collect gas samples,filters to collect particle samples.Gas chromatography-flame ionization detector/mass spectrometry and gas chromatography-mass spectrometry was the offline analysis method.We found that the total mass concentration of the tested 102 VOC species at the outlet of wet flue gas desulfuration device was(13456±47)μg·m^(-3),which contained aliphatic hydrocarbons(57.9%),aromatic hydrocarbons(26.8%),halogen-containing species(14.5%),and a small amount of oxygen-containing and nitrogencontaining species.The most abundant species were 1-hexene,n-hexane and 2-methylpentane.The top ten species in terms of mass fraction(with a total mass fraction of 75.3%)were mainly hydrocarbons with a carbon number of 6 or higher and halogenated hydrocarbons with a lower carbon number.The mass concentration of VOC species in the particle phase was significantly lower than that in the gas phase.The change of VOC mass concentrations along the air pollution control devices indicates that conventional pollutant control equipment had a limited effect on VOC reduction.Ozone formation potential calculations showed that aromatic hydrocarbons contributed the highest ozone formation(46.4%)due to their relatively high mass concentrations and MIR(maximum increment reactivity)values.

上海某居民区恶臭污染溯源、臭氧生成潜势及健康风险评估

针对上海某居民区恶臭投诉问题,对恶臭物质来源、特征及其风险评估展开相关研究。利用正定矩阵因子分解(positive matrix factorization,PMF)模型对居民区恶臭点连续监测数据进行来源解析,共识别出3个排放源,分别为餐厨垃圾源(41.24%)、农业源(32.85%)、二次生成和尾气排放混合源(25.91%),确定餐厨垃圾源为居民区恶臭的主要来源。通过分析监测点位间主要致臭物质异味活度值(odor active value,OAV)的相关性,可知居民区受到餐厨垃圾预处理车间和生化车间的恶臭污染为主,全天受影响程度具有间歇式变化特征。通过计算预处理、生化处理和深加工3个车间排气筒的恶臭物质的臭氧生成潜势(ozone formation potential,OFP),可知各物质种类对OFP的贡献率从大到小依次为羰基类(37.46%)、醇类(21.38%)、烯烃类(15.52%)、挥发性脂肪酸类(13.70%)、芳香烃类(4.02%)、含氮化合物(3.90%)、烷烃类(1.77%)、酯类(1.29%)、硫化物(0.95%)、含氯有机物(0.01%),羰基类、醇类、烯烃类、挥发性脂肪酸类为该厂区OFP贡献的代表物质种类。各车间的OFP从高到低依次为预处理车间(27051.82μg/m^(3))、生化车间(7547.51μg/m^(3))、深加工车间(1647.14μg/m^(3)),乙醛、丙烯酸、1-丁烯、甲醛、乙醇、丙烯和苯酚对OFP的贡献率在3个排气筒中均较高,是该餐厨垃圾处理厂区生成臭氧的主要污染物质,并且乙醛对OFP的贡献率最高。敏感点恶臭物质的健康风险评估结果表明,监测期间累计非致癌风险指数与致癌风险指数均超过美国国家环境保护局(U.S.Environmental Protection Agency,U.S.EPA)推荐的安全阈值,主要贡献物质分别为丙烯醛和甲醛。因此,乙醛、丙烯醛和甲醛应作为餐厨垃圾处理厂中恶臭物质的优先监控指标。

The underappreciated role of fugitive VOCs in ozone formation and health risk assessment emitted from seven typical industries in China

Fugitive emission from industrial sources may result in ozone formation and health risk,while the exact contribution of this source remains incompletely understood.In this study,emission characteristics,ozone formation potential(OFP)and health risk of fugitive VOCs in7 representative industries were investigated.Chemical material industry was the dominant contributor to VOCs of fugitive emission in comparison with other industries.The OFP of VOCs from fugitive emission was in the range of 1.45×10^(3)-3.98×10^(5)μg/m^(3),with a higher value than that of organized emission in seven industries except for the coking industry and the chemical material industry,suggesting that fugitive VOCs should be taken into account while developing control strategies.Acetaldehyde,m,p-xylene,n-nonane,ethylene,vinyl chloridethe and other high OFP-contributing species were the major reactive species that should be targeted.Health risk assessment investigated non-cancer and cancer risks of fugitive VOCs in 7 industries were all above safe level(HR>1 and LCR>1×10^(-4)),posing remarkable health threats to human health.OVOCs were the main contributor to non-cancer risk,while halohydrocarbons and aromatics contributed most to cancer risks,posing remarkable health threat on human health.Our findings highlighted the contribution of fugitive VOCs on ozone formation and health risk was underestimated,indicating which should be considered in emission control strategies of industrial sources.

Reactivity of ambient volatile organic compounds(VOCs) in summer of 2004 in Beijing

Ambient volatile organic compounds （VOCs） were sampled at six sites in Beijing in the summer of 2004 and analyzed by GCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates （LOH） and ozone formation potentials （OFPs）. Top 15 reactive species, mainly alkenes and aromatics, were identified by these two methods, and accounted for more than 70% of total reactivity of VOCs. In urban areas, isoprene was the most reactive species in term of OH loss rate, contributing 11.4% to the LOH of VOCs. While toluene, accounting for 9.4% of OFPs, appeared to have a long-time role in the photochemical processes. Tongzhou site is obviously influenced by local chemical industry, but the other five sites showed typical urban features influenced mainly by vehicular emissions.

Preozonation of bromide-bearing source water in south China

The effectiveness of preozonation was evaluated on treating a bromide-bearing dam source water in south China through batch-scale experiments. Preozonation at ozone doses of 0.5-1.0 mg/L （at ozone consumption base） enhanced total organic carbon （TOC） removal through coagulation, and resulted in an almost linear reduction of ultraviolet absorbance at 254 nm （LW2s4）. The removals of TOC （after coagulation） and UV254 at the ozone dose of 1.0 mg/L were 36% and 70%, respectively. Preozonation at an ozone dose between 0.5 and 1.0 mg/L resulted in the removal of disinfection byproducts formation potential （DBFP） including trihalomethane formation potential （THMFP） and haloacetic acid formation potential （HAAFP） for about 50%. The removals of THMFP and HAAFP decreased with the further increase of ozone dose. Ozonation of bromide-bearing water （bromide concentration, 34 μg/L） produced a bromate concentration under the detection limit（2μg/L） at ozone doses 〈1.5 mg/L. However, bromate 〉10μg/L could be produced when the bromide concentration was increased to 96 μg/L.

Semiconducting behavior of the anodically passive films formed on AZ31B alloy

This work includes determination of the semiconductor character and estimation of the dopant levels in the passive film formed on AZ31B alloy in 0.01 M NaOH,as well as the estimation of the passive film thickness as a function of the film formation potential.Mott-Schottky analysis revealed that the passive films displayed n-type semiconductive characteristics,where the oxygen vacancies and interstitials preponderated.Based on the Mott-Schottky analysis,it was shown that the calculated donor density increases linearly with increasing the formation potential.Also,the electrochemical impedance spectroscopy(EIS)results indicated that the thickness of the passive film was decreased linearly with increasing the formation potential.The results showed that decreasing the formation potential offer better conditions for forming the passive films with higher protection behavior,due to the growth of a much thicker and less defective films.

Characteristics and source apportionment of ambient volatile organic compounds and ozone generation sensitivity in urban Jiaozuo,China

In recent years,many cities have taken measures to reduce volatile organic compounds(VOCs),an important precursor of ozone(O_(3)),to alleviate O_(3) pollution in China.116 VOC species were measured by online and offline methods in the urban area of Jiaozuo from May to October in 2021 to analyze the compositional characteristics.VOC sources were analyzed by a positive matrix factorization(PMF)model,and the sensitivity of ozone generation was determined by ozone isopleth plotting research(OZIPR)simulation.The results showed that the average volume concentration of total VOCs was 30.54 ppbv and showed a bimodal feature due to the rush-hour traffic in the morning and at nightfall.The most dominant VOC groups were oxygenated VOCs(OVOCs,29.3%)and alkanes(26.7%),and the most abundant VOC species were acetone and acetylene.However,based on the maximum incremental reactivity(MIR)method,the major VOC groups in terms of ozone formation potential(OFP)contribution were OVOCs(68.09μg/m^(3),31.5%),aromatics(62.90μg/m^(3),29.1%)and alkene/alkynes(54.90μg/m^(3),25.4%).This indicates that the control of OVOCs,aromatics and alkene/alkynes should take priority.Five sources of VOCs were quantified by PMF,including fixed sources of fossil fuel combustion(27.8%),industrial processes(25.9%),vehicle exhaust(19.7%),natural and secondary formation(13.9%)and solvent usage(12.7%).The empirical kinetic modeling approach(EKMA)curve obtained by OZIPR on O_(3) exceedance days indicated that the O_(3) sensitivity varied in different months.The results provide theoretical support for O_(3) pollution prevention and control in Jiaozuo.