Measurements of H2O2, aldehydes and organic acids in Los Angeles rainwater: Their sources and deposition rates

Rainwater samples were collected in Los Angeles, during 1985–1991 to determine concentration levels, sources and deposition rates of atmospheric H₂O₂, aldehydes and organic acids, in addition to major cations, anions and pH. Volume-weighted mean concentrations of H₂O₂, aldehydes (formaldehyde + acetaldehyde + glyoxal + methylglyoxal) and organic acids (formic acid + acetic acid) in rain collected at Westwood were 4.4., 3.9 and 16.5 μM, respectively, during the 6-year study period. Monocarboxylic organic acids were estimated to account for 27% (2–80%) of total free acidity (as on overall average) in rain collected at Westwood, whereas sulfuric acid and nitric acid accounted for 39% and 34% of the total acidity, respectively. Concentrations of aldehydes were strongly dependent on precipitation volume and decreased with increasing precipitation volume, whereas H₂O₂ and organic acids were only weakly dependent on precipitation volume. These results indicate that concentrations of aldehydes in rain are mainly controlled by dilution, whereas H₂O₂ and organic acid concentrations are controlled by other factors, such as decomposition of H₂O₂ by reacting with S(IV) and continuous aqueous formation/decomposition of organic acids by reactions involving aldehydes, dissolved OH radicals and H₂O₂. Principal component analyses indicate that aldehydes in rainwater mainly originate from gases and aerosols derived from anthropogenic sources, whereas the sources of H₂O₂ and organic acids in rain do not correlate with anthropogenic sources or marine and continental sources. There is good agreement between reported gas-phase concentrations of H₂O₂, aldehydes and organic acids in Los Angeles and calculated equilibrium concentrations of these chemical species from their rainwater concentrations and Henry's law constants. Temporal variations of concentrations of chemical species indicate that H₂O₂, aldehydes and organic acids were highest in the early afternoon. Summer rains contained the highest concentration of these chemical species, suggesting the photochemical activities during rain storms significantly affect their concentration levels. Estimation of annual rate of wet and dry depositions of H₂O₂, aldehydes and organic acids for the period studied, indicates that 84% of H₂O₂, 97% of aldehydes and 94% of organic acids, respectively, are annually scavenged from the atmosphere, by dry deposition, which is the dominant process for removal of these atmospheric pollutants in Los Angeles.     

Comparison of H2O2 and O3 content in atmospheric samples in the San Bernardino mountains,Southern California

Concentrations of atmospheric H₂O₂ were measured in air, rain, cloud and dew samples in forested areas of the San Bernardino Mountains, southern California, from spring through fall of 1987–1990 O₃ measurements in air were also conducted for comparison. Typical ranges of H₂O₂ concentrations measured were 1–3 ppb in air, 10–90 μM in rain and cloud water, and < μM in dew. The results show that gas-phase H₂O₂ concentrations were slightly higher at nighttime than at daytime or nearly constant throughout a 24-hr period, whereas O₃ concentrations were highest during the afternoon, when polluted air masses from Los Angeles carried by daily sea breezes reached the mountain region. Afternoon concentrations of gaseous H₂O₂ and O₃ in the mountain region were compared with those measured in Los Angeles urban sites to elucidate the regional variation of these oxidants. The results show that ambient concentrations of H₂O₂ and O₃ were about 50–100% higher at the mountains sites than at the Los Angeles sites.     

Large-scale distribution of hydrogen peroxide from aircraft measurements during the TROPOZ II experiment

Aircraft measurements of hydrogen peroxide (H₂O₂) were performed during the TROPOZ II meridional campaign. A specially designed automatic H₂O₂ analyser on board the airplane allowed us to obtain more than 43,000 H₂O₂ measurements. The data set covers a latitude range from 60°N to 60°S and altitudes up to 11 km. Concentration of H₂O₂ ranged from 0.42 ppb (percentile 5) to 6.31 ppb (percentile 95) and exhibited a variability factor of as much as 15. Hydrogen peroxide concentration was typically low (<2 ppb) in the boundary layer of both hemispheres except for the inter-tropical belt, even in America, as well as Africa where the mean mixing ratio reached 5 ppb. In the northern uppermost troposphere a significant increase in H₂O₂ (>3 ppb) could be noticed. Some episodes of high hydrogen peroxide mixing ratio were encountered in the vicinity of cloud systems probably by exchange of H₂O₂ from the liquid phase to the gas phase.     

基于电化学传感器的大气NO2与O3监测研究

利用四电极电化学传感器开展大气NO₂和O₃监测研究.为解决温度和湿度对传感器响应的影响问题,提出了一种具有温湿度补偿与零点校正功能的大气NO₂和O₃测量结果校准模型,通过活性炭吸附特性获得干净的背景气体,实现传感器准确的零点校正,并利用实验系统实测数据结合多元线性回归方法获得校准模型参数.首先对传感器线性响应特性进行了测试,发现O₂和O₃的测量灵敏度分别为3.889 ppbv·mV^-1和4.107 ppbv·mV^-1.同时,在合肥西郊科学岛开展了为期2 d的大气NO₂和O₃连续观测,发现两者的浓度分别为0~30 ppbv和2~100 ppbv.最后将传感器观测结果与NO_x/O₃分析仪测量结果进行了回归分析,发现两者测得的NO₂线性拟合斜率为0.9701±0.0182,R²为0.8378,测得的O₃线性拟合斜率为0.9850±0.0101,R²为0.9431.研究表明,校准后的电化学传感器可用于大气NO₂和O₃的长期监测,可为推动大气环境监测技术发展提供新的思路.     

Lake Michigan Ozone Study (LMOS): Measurements from an instrumented aircraft

As part of the Lake Michigan Ozone Study, the NOAA instrumented King Air research aircraft made a series of flights over Lake Michigan during the summers of 1990 and 1991 to characterize the atmospheric conditions prevailing during times when O₃ concentrations exceeded the air quality standard. Most of the time, O₃ concentrations were within the normal range (40–70 ppbv) for the location and season, but higher concentrations were measured during the afternoon flights at several isolated locations. During three afternoon flights, high O₃ concentrations (> 120 ppbv) were observed along portions of the flight path; the highest 1-min average exceeded 160 ppbv. In two flights the highest O₃ concentrations were observed in the lower boundary layer over the eastern portion of the flight track; in one case the high concentrations were found over the western side of the lake throughout the boundary layer. The increased O₃ was accompanied by moderately increased SO₂ and NO_x (10–20 ppbv); outside the region of elevated O₃, the SO₂ and NO_x were less than 2–3 ppbv. The elevated zone concentrations were related to emissions from the urban region located near the southern and southwestern shores of Lake Michigan.     

纳米Fe/Co合金类Fenton降解盐酸四环素及影响因素

为研究纳米Fe/Co合金对含TCs（盐酸四环素）废水的类Fenton催化性能,以及催化降解体系pH、H₂O₂投加量和活性成分浸出等因素对催化性能的影响.采用液相还原法制备纳米Fe/Co合金,并通过对比试验探究其类Fenton催化性能,Fe、Co的浸出量及其表面积结构变化与活性之间的关系.添加纳米Fe/Co合金的条件下,采用单因素分析方法研究体系pH、H₂O₂投加量和初始TCs浓度分别对TCs去除率的影响.结果表明:①在纳米Fe/Co合金制备过程中,添加PVP（聚乙烯吡咯烷酮）不仅能有效防止纳米Fe/Co合金发生团聚,且促进纳米Fe/Co合金比表面积增大（BET为113.8 m2/g）.②纳米Fe/Co合金具有拓宽催化体系pH使用范围的优势;在pH为3.0~9.0范围内,纳米Fe/Co合金对30 mg/L TCs的去除率（87.2%~91.7%）远大于FeCl₂（0~30.7%）和纳米Fe的去除率（0~28.2%）;H₂O₂投加量超过150 mmol/L后,TCs的去除率达到最佳（86.2%）.③纳米Fe/Co合金催化体系中（pH为3.0~11.0）,活性成分Fe、Co浸出量分别为0.20~0.35和0.20~1.00 mg/L,均满足我国GB 3838—2002《地表水环境质量标准》,长期使用也不会造成浸出成分（Fe、Co）在环境中大量累积,对生态环境等可能造成的潜在风险大大降低.④纳米Fe/Co合金具有再利用性,催化利用4次后,对TCs的去除效果仍达50.0%以上.研究显示,纳米Fe/Co合金对去除TCs具有较高催化性能和再利用性,利于拓宽催化体系pH使用范围,具有稳定活性成分Fe、Co浓度的优势.      

Synergistic impacts of anthropogenic and biogenic emissions on summer surface O3 in East Asia

A factor separation technique and an improved regional air quality model (RAQM) were applied to calculate synergistic contributions of anthropogenic volatile organic compounds (AVOCs),biogenic volatile organic compounds (BVOCs) and nitrogen oxides (NOx) to daily maximum surface O3(O3DM) concentrations in East Asia in summer (June to August 2000).The summer averaged synergistic impacts of AVOCs and NOx are dominant in most areas of North China,with a maximum of 60 ppbv,while those of BVOCs and NOx are notable only in some limited areas with high BVOC emissions in South China,with a maximum of 25 ppbv.This result implies that BVOCs contribute much less to summer averaged O3DM concentrations than AVOCs in most areas of East Asia at a coarse spatial resolution (1×1) although global emissions of BVOCs are much greater than those of AVOCs.Daily maximum total contributions of BVOCs can approach 20 ppbv in North China,but they can reach 40 ppbv in South China,approaching or exceeding those in some developed countries in Europe and North America.BVOC emissions in such special areas should be considered when O3 control measures are taken.Synergistic contributions among AVOCs,BVOCs and NOx significantly enhance O3 concentrations in the Beijing-Tianjin-Tangshan region and decrease them in some areas in South China.Thus,the total contributions of BVOCs to O3DM vary significantly from day to day and from location to location.This result suggests that O3 control measures obtained from episodic studies could be limited for long-term applications.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

The effect of freezing on the composition of supercooled droplets—I. Retention of HCl,HNO3, NH3 and H2O2

Experiments were done to check on the possibility that cloud droplets might, during freezing, lose acidity by evolution of HCl or HNO₃, lose NH₃ or lose dissolved H₂O₂. A spray of droplets with average diameter 39μm was produced by an ultrasonic transducer. The droplets acquired a temperature between −8 and −12°C and fell onto an ice surface, where they froze. Appropriate analytical techniques were applied to compare the composition of the frozen droplets with that of the sprayed liquid. It was found that the four chemical species studied were totally retained in the ice after freezing.     

The effect of aircraft emissions on tropospheric ozone in the northern hemisphere

The effect of aircraft emissions on tropospheric ozone was studied using a two-dimensional zonal model, of longitude vs altitude, extending between 30°–60°N. An emission inventory for the 1987 civil aircraft fleet was constructed based on fuel usage and civil aviation statistics. The addition of the 1987 civil emissions to a modelled standard atmosphere caused increases in concentrations of O₃ (12%; 10 ppbv), NO_x (40%; 20 pptv) and OH (10%) between 8 and 12 km altitude. A doubling and tripling of the emissions corresponding to a present day inclusion of military aircraft and a future scenario, respectively, caused the increase in O₃ to double (19%) and almost triple (25%). The lightning source of NO_x was found to be an important parameter. When this source was ommitted the change in O₃ at the cruise flight altitude increased to 16%, with respect to a standard atmosphere not containing a lightning source of NO_x.     

Sulfur dioxide reactions on ice surfaces: implications for dry deposition to snow

Controlled exposure of ice to a reactive gas, SO₂, demonstrated the importance of the chemical composition of the ice surface on the accumulation of acidity in snow. In a series of bench-scale continuous-flow column experiments run at four temperatures (−1, −8, −30 and −60°C), SO₂ was shown to dissolve and to react with other species in the ice-air interfacial region at temperatures approaching the melting point of ice. Experiments consisted of passing air containing SO₂ through glass columns packed with 100μm ice spheres of varying bulk composition (0–5μM H₂O₂, and 0–1 mM NaCl), and analysing SO₂ in the air and SO₄²⁻ in the ice. At all temperatures (−60 to −1°C), increased retention volumes were found for increasing ionic strength and oxidant concentration. At the coldest temperatures and with no NaCl, increased retention volumes for −60 vs −30°C are consistent with SO₂ uptake by physical adsorption. At warmer temperatures, −8 and −1°C, the observed tailing in the sorption curves indicated that other processes besides physical adsorption were occurring. The desorption curves showed a rapid decrease for the warmer temperatures, indicating the sorbed SO₂ is irreversibly oxidized to SO₄²⁻. Results indicate that aqueous-phase reactions can occur below −8°C (i.e. −30 and −60°C). Results for different salt concentrations show that increasing ionic strength facilitates SO₂ oxidation at colder temperatures, which is consistent with freezing point depression. One environmental implication is that snowpacks in areas with background SO₂, can accumulate acidity during the winter months. As acidity accumulates, the solubility of SO₂ will decrease causing a concomitant decrease in the air-to-surface flux of SO₂. Modeling dry deposition of gases to snow surfaces should incorporate the changing composition of the ice surface.     

Hepatitis A Virus Disinfection in Water by Solar Photo–Fenton Systems

This study evaluates and compares the effectiveness of solar photo–Fenton systems for the inactivation of hepatitis A virus (HAV) in water. The effect of solar irradiance, dark- Fenton reaction and three different reactant concentrations (2.5/5, 5/10 and 10/20 mg/L of Fe²⁺/H₂O₂) on the photo–Fenton process were tested in glass bottle reactors (200 mL) during 6 h under natural sunlight. Disinfection kinetics were determined both by RT-qPCR and infectivity assays. Mean water temperatures ranged from 25 to 27.3 °C, with a maximum local noon UV irradiances of 22.36 W/m². Photo–Fenton systems yielded increased viral reduction rates in comparison with the isolated effect under the Fenton reaction in darkness (negligible viral reduction) or the solar radiation (0.25 Log of RNA reduction). With the highest concentration employed (10–20 mg/L Fe²⁺–H₂O₂), an average RNA reduction rate of ~ 1.8 Log (initial concentration of 10⁵ pfu/mL) and a reduction of 80% in the infectivity capacity were reached. Results showed a strong synergistic effect between Fe²⁺/H₂O₂ and sunlight, demonstrating that significant disinfection rates of HAV under photo–Fenton systems may occur with relatively higher efficiency at middle environmental temperatures and without the need for an energy-intensive light source.     

Fe/Zn-TMS体系吸收去除催化裂化干气中H2S的性能

本研究采用FeCl3·6H2O、ZnCl2和环丁砜(TMS)复配形成的Fe/Zn-TMS体系脱除催化裂化(FCC)干气中的H2S,并用30%H2O2氧化再生Fe/Zn-TMS体系.同时,研究了各活性成分比例、吸收液体积浓度、吸收液pH值等对脱硫效率的影响,以及H2O2用量、吸收富液pH值对Fe2+氧化率的影响.结果表明,n(FeCl3·6H2O)∶n(ZnCl2)∶n(TMS)为0.45∶0.55∶1,吸收液pH为0.75,体积浓度(W)为50%的条件下能长时间高效脱硫,最高脱硫率达99.9%;在n(Fe2+)∶n(H2O2)为2∶1,吸收富液pH为0.65的条件下,Fe2+氧化率达96.7%.体系可循环使用3次,且能耗低、操作简单.     

Intercomparison of tunable diode laser and gas filter correlation measurements of ambient carbon monoxide

An intercomparison that involved a standards intercomparison, interferant spiking tests and simultaneous ambient measurements was carried out between two CO measurement systems: a tunable diode laser absorption spectrometer (TDLAS) and a gas filter correlation, non-dispersive infrared absorption instrument (GFC). Both the TDLAS and the GFC techniques responded to CO. No major interferences were found for the TDLAS system; tested species included H₂O, O₃ and OCS. The GFC instrument exhibited no interference from H₂O or O₃, but only a relatively high upper limit could be placed on the O₃ interference. For CO measurements in ambient air at levels from 100 to 1500 ppbv, the results from the two instruments agreed within their combined uncertainties. On average the GFC technique was 6% higher than the TDLAS system, and there was no systematic, constant offset. The precision of the GFC instrument was about 10%, and the precision of the TDLAS system was better than 4%.     

A laboratory study on the scavenging of SO2 by snow crystals

A laboratory experiment is described where the uptake of SO₂ by dendritic snow crystals was studied. In a first experimental series the uptake of SO₂ was investigated during the growth of the snow crystals from water vapor with and without the presence of H₂O₂ in the air. In a second series of experiments we studied the uptake of SO₂ by snow crystals which had completed their growth. The results of our experiments showed that under both conditions SO₂ became scavenged by snow crystals. The uptake of SO₂ was particularly pronounced during the growth of the snow crystals, and at temperatures close to 0°C where a quasi-liquid layer exists at the surface of ice. As expected, the SO₂ uptake becomes enhanced in the presence of H₂O₂. The present results are in qualitative agreement with previous studies involving bulk ice.     

膜生物反应器处理甲苯性能及机制

采用膜生物反应器处理甲苯有机废气,研究了进气浓度、停留时间、循环液喷淋密度和pH值对甲苯去除率的影响.膜生物反应器能高效净化挥发性有机废气,甲苯去除率可达99%.适宜运行条件为:pH值为7.2、停留时间为6.4 s、循环液喷淋密度为2.5 m3.(m2.h)-1.采用GC-MS分析出口气样,研究结果表明乙醛酸(C2H2O3)和乙烯基甲酸(C3H4O2)为甲苯生物降解的中间产物.膜生物反应器处理甲苯机制为甲苯气体通过中空纤维膜传质到生物膜,被生物降解为乙醛酸和乙烯基甲酸,然后继续好氧降解为最终产物二氧化碳和水.     

Effect of Al2O3 doping on the structure and performance of an Al2O3/Fe2O3 catalyst for mercury oxidation

In this study,the thermal stability of a Fe_2 O_3 catalyst for mercury oxidation was significantly improved by doping with Al_2 O_3.After 1 hr,the catalyst doped with 10 wt.% Al_2 O_3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al_2 O_3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe_2 O_3 was 23.4 nm;however,the corresponding values for 1%Al_2 O_3/Fe_2 O_3,3%Al_2 O_3/Fe_2 O_3,and 10%Al_2 O_3/Fe_2 O_3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al_2 O_3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.     

Influence of drying and calcination temperatures for Ce-Cu-Al trimetallic composite catalyst on simultaneous removal H2S and PH3: Experimental and DFT studies

This work explored the influences of the drying and calcination temperatures on a Ce-Cu-Al trimetallic composite catalyst for the simultaneous removal of H₂S and PH₃. The effects of both temperatures on the structural features and activity were examined. The density functional theory method was used to calculate adsorption energies and further analyze their adsorption behavior on different slabs. Experiments revealed suitable drying and calcination temperatures to be 60 and 500°C, respectively. The capacity reached 323.8 and 288.1 mg/g. Adjusting drying temperature to 60°C is more inclined to form larger and structured grains of CuO. Rising calcinating temperature to 500°C could increase the grain size and redox capacity of CuO to promote performance. Higher temperatures would destroy the surface structure and lead to a crystal phase transformation, which was that the CuO and Al₂O₃ were gradually recombined into CuAl₂O₄ with a spinel structure. The exposed crystal planes of surficial CuO and CuAl₂O₄ were determined according to characterization results. Calculation results showed that, compared with CuO (111), H₂S and PH₃ have weaker adsorption strength on CuAl₂O₄ (100) which is not conducive to their adsorption and removal.     

Studies on the formation of H2O2 in the ozonolysis of alkenes

The formation of H₂O₂ in the reactions of ozone with alkenes, isoprene and some terpenes has been studied with tunable diode laser absorption spectroscopy. The measured yields of H₂O₂ were found to be considerably enhanced in the presence of water vapour. H₂O₂ is thought to be formed in the ozonolysis of the alkene with O₃ by direct reaction of an intermediate with water vapour. The yield of H₂O₂ relative to the reacted alkene in the ozonolysis of trans-2-butene in the presence of water vapour was also studied with long path FTIR spectroscopy. Irrespective of the analytical methods and reaction conditions applied, the H₂O₂ yields in the reaction of O₃ with the different alkenes in the presence of water vapour were found to be in the range of a few per cent or less. Under the assumption that the reactive species forming H₂O₂ in the ozonolysis is the Criegee biradical, the overall rate constants for the reactions of some biradicals with water vapour were measured relative to the rate constant of the biradical with SO₂. For the H₂COO biradical a rate constant of (5.8 ± 2.5) × 10⁻¹⁷ cm³ s⁻¹ was determined and for the (CH₃)₂COO biradical (2.9 ± 1.5) × 10⁻¹⁷ cm³ s⁻¹; in the latter case with the assumption that (CH₃)₂COO reacts with SO₂ as fast as CH₂COO.