Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

Characterization of on-road vehicle emission factors and microenvironmental air quality in Beijing,China

In this paper, we report the results and analysis of a recent field campaign in August 2007 investigating the impacts of emissions from transportation on air quality and community concentrations in Beijing, China. We conducted measurements in three different environments, on-road, roadside and ambient. The carbon monoxide, black carbon and ultrafine particle number emission factors for on-road light-duty vehicles are derived to be 95 g kg^?1-fuel, 0.3 g kg^?1-fuel and 1.8 × 10¹⁵ particles kg^?1-fuel, respectively. The emission factors for on-road heavy-duty vehicles are 50 g kg^?1-fuel, 1.3 g kg^?1-fuel and 1.1 × 10¹⁶ particles kg^?1-fuel, respectively. The carbon monoxide emission factors from this study agree with those derived from remote sensing and on-board vehicle emission testing systems in China. The on-road black carbon and particle number emission factors for Chinese vehicles are reported for the first time in the literature. Strong traffic impacts can be observed from the concentrations measured in these different environments. Most clear is a reflection of diesel truck traffic activity in black carbon concentrations. The comparison of the particle size distributions measured at the three environments suggests that the traffic is a major source of ultrafine particles. A four-day traffic control experiment conducted by the Beijing Government as a pilot to test the effectiveness of proposed controls was found to be effective in reducing extreme concentrations that occurred at both on-road and ambient environments.     

Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

Ionic composition of TSP and PM2.5 during dust storms and air pollution episodes at Xi'an,China

TSP and PM_2.5 samples were collected at Xi'an, China during dust storms (DSs) and several types of pollution events, including haze, biomass burning, and firework displays. Aerosol mass concentrations were up to 2 times higher during the particulate matter (PM) events than on normal days (NDs), and all types of PM led to decreased visibility. Water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, F^?, Cl^?, NO₃^?, and SO₄^2?). were major aerosol components during the pollution episodes, but their concentrations were lower during DSs. NH₄⁺, K⁺, F^?, Cl^?, NO₃^?, and SO₄^2? were more abundant in PM_2.5 than TSP but the opposite was true for Mg²⁺ and Ca²⁺. PM collected on hazy days was enriched with secondary species (NH₄⁺, NO₃^?, and SO₄²) while PM from straw combustion showed high K⁺ and Cl^?. Firework displays caused increases in K⁺ and also enrichments of NO₃^? relative to SO₄^2?. During DSs, the concentrations of secondary aerosol components were low, but Ca²⁺ was abundant. Ion balance calculations indicate that PM from haze and straw combustion was acidic while the DSs samples were alkaline and the fireworks' PM was close to neutral. Ion ratios (SO₄^2?/K⁺, NO₃^?/SO₄^2?, and Cl^?/K⁺) proved effective as indicators for different pollution episodes.     

An important pathway for ozonolysis of alpha-pinene and beta-pinene in aqueous phase and its atmospheric implications

The aqueous ozonolysis of α-pinene and β-pinene was conducted under simulated tropospheric conditions at different pHs and temperatures. Three kinds of products, peroxides, carbonyl compounds, and organic acids, were well characterized, and the detection of these products provides effective evidence for understanding the atmospheric aqueous reaction pathway. We have two interesting findings: (1) the unexpected formation of methacrolein (MACR), with a yield of ～40%, in the α-pinene–O₃ aqueous reaction indicates a potentially new SOA formation pathway, because MACR is one of the important precursors of SOA; and (2) the surprisingly high yields of H₂O₂, ～60% for the α-pinene–O₃ reaction and ～100% for the β-pinene–O₃ reaction, indicates that H₂O₂ can be a significant contributor to the origin and transformation of oxidants in the atmosphere, especially in the humid regions. Moreover, we have determined the rate constant for aqueous reaction between MACR and H₂O₂ in pH 2 to 7 and obtained its upper limit as 0.13 M L^?1 s^?1. A mechanism concerning the formation of the species mentioned above is proposed, and it differs from that in the gas-phase reaction. We suggest that water plays a key role in the mechanism, by participating in the reactions as a direct reactant and by removing the excess energy of intermediates formed in the reactions.     

An observational study of the HONO–NO2 coupling at an urban site in Guangzhou City,South China

The temporal behavior of HONO and NO₂ was investigated at an urban site in Guangzhou city, China, by means of a DOAS system during the Pearl River Delta 2006 intensive campaign from 10 to 24 July 2006. Within the whole measurement period, unexpected high HONO mixing ratios up to 2 ppb were observed even during the day. A nocturnal maximum concentration of about 8.43 ± 0.4 ppb was detected on the night of 24 July 2006. Combining the data simultaneously observed by different instruments, the coupling of HONO–NO₂ and the possible formation sources of HONO are discussed. During the measurement period, concentration ratios of HONO to NO₂ ranged from (0.03 ± 0.1) to (0.37 ± 0.09), which is significantly higher than previously reported values (0.01–0.1). Surprisingly, in most cases a strong daytime correlation between HONO and NO₂ was found, contrary to previous observations in China. Aerosol was found to have a minor impact on HONO formation during the whole measurement period. Using a pseudo steady state approach for interpreting the nocturnal conversion of NO₂ to HONO suggests a non-negligible role of the relative humidity for the heterogeneous HONO formation from NO₂.     

螺、蚌对污水处理厂再生水环境的改善稳定作用

通过选用昆明市第五污水处理厂的一级A标出水和水处理厂外排污泥作为静态实验环境,研究不同混养密度下铜锈环棱螺、椭圆背角无齿蚌对污水处理厂再生水环境的净化性能,筛选出净化效果较好的放养密度。结果表明:放养30 d,铜锈环棱螺、椭圆背角无齿蚌对污水处理厂再生水环境的水质、底质均有一定的净化作用,扣减空白对照影响,水中COD、TP、NH3-N及底泥有机质平均去除率分别为22.26%、26.10%、25.60%和25.69%,底泥厚度平均减少3.8 cm;与对照相比,放养螺蚌45 d内水均能清澈见底,透明度均>70 cm,能明显稳定水体透明度,改善水环境。综合螺蚌生长适应性和净化效果考虑:污水处理厂再生水静态环境中,螺蚌混养密度应≤3 000 g/m3,在2 000～2 500 g/m3为宜,其中铜锈环棱螺的最适放养密度在400 g/m3,椭圆背角无齿蚌为1 600～2 100 g/m3。     

混凝-生物接触氧化处理合成橡胶碱洗废水

对化学合成橡胶碱洗废水进行了有机组分和可生化性分析,废水主要含有氯甲烷、六甲苯、异丁醇、甲醇等污染物质,生化降解实验中废水TOC可在6 d内从60.9 mg/L下降至0.0 mg/L,可生化降解性好,适于生化处理。选择混凝-生物接触氧化组合工艺对废水进行处理,采用优化条件(pH=8、PAC=40 mg/L、PAM=8 mg/L)进行混凝,碱洗废水COD去除率为9.95%~72.94%(平均31.51%);混凝后的碱洗废水与冲洗废水1∶5混合进行接触氧化处理,在HRT为36 h的情况下,COD去除率为65.6%~72.6%(平均70.4%),出水COD为134~331 mg/L,满足企业废水排放市政管网的要求;同时,实验发现COD去除率与COD容积负荷存在指数函数变化关系。     

反渗透膜处理维生素C凝结水的最优工艺条件

针对维生素C生产工艺中产生的凝结水产量大、处理成本高、存储运输困难和营养物质含量偏低等问题,采用反渗透技术对VC凝结水进行处理。实验建立小试规模反渗透膜处理装置,采用无量纲化多元回归分析方法,分析了操作条件指标与渗透水评价指标两套指标体系之间的关系,定量评价了各个操作条件指标对渗透水评价指标的整体影响程度,并在此基础上研究了最佳操作条件的工艺参数。结果表明：建立的无量纲化多元回归分析方法切实有效,在正交实验设计水平范围内,压力、pH和回流比均是多目标系统的影响因子,操作条件指标对渗透水评价指标的整体影响程度大小顺序为：压力〉pH〉回流比〉温度,且各自影响程度所占比例分别为43．02％、29．01％、25．07％和2．89％。各个操作因子对多指标系统的影响是独立的。在只考虑系统收益而不考虑膜污染的情况下,最佳操作条件分别为：温度r=30．65,压力P=1．5MPa,回流比r=0．78,pH=7．475。     

陶瓷印花废水处理的混凝剂及工艺条件

采用混凝剂聚合氯化铝（PAC）、聚丙烯酰胺（PAM）、聚合硫酸铁（PFS）对陶瓷印花废水进行混凝沉降处理,监测水样的吸光度、浊度、悬浮物,以脱色率、浊度去除率、悬浮物去除率评价混凝处理的效果。结果表明：PAC是陶瓷印花废水沉降处理的理想混凝剂;水样的吸光度、浊度、悬浮物随混凝剂用量增大和沉降时间延长而呈降低趋势,而脱色率、浊度去除率、悬浮物去除率随混凝剂和沉降时间的增大呈增大的趋势;PAC投加量为20mg／L,沉降时间约为24h,水样脱色率达到90．0％,而当PAC投加量达到100mg／L,沉降时间约为4h,陶瓷印花水的脱色率可达到96．0％。证明了药剂用量的增加与沉降时间的延长对混凝过程具有增效作用。