水中典型内分泌干扰物质的臭氧氧化研究

在静态实验中,考察了臭氧投加量、HCO^-₃浓度和pH值对O₃氧化去除水中典型内分泌干扰物（EDs）E1、E2、EE2、DES和4-n-NP的影响.结果表明,5种EDs的去除率随O₃投加量的增加而增大,O₃浓度达到63.6 μg/L时可去除92.0%以上的EDs,HCO^-₃（0～100 mg/L）的引入抑制了O₃氧化,O₃氧化去除EDs的能力随溶液pH值升高而大幅度提高.在中性（pH≈7.0）和碱性（pH＞10.6）条件下,O₃氧化5种EDs的表观二级反应速率常数(20℃±0.5℃)分别在(1.67～3.89)×10⁶　Ｌ·(mol·s)^-1和(0.93～1.75)×10⁹　Ｌ·(mol·s)^-1范围内,表明这5种物质在水中可被O₃迅速氧化去除.计算得出5种EDs的基元反应速率常数(20℃±0.5℃),发现O₃与离子态的EDs反应活性［1.21×10⁹～3.81×10⁹　Ｌ·(mol·s)^-1］是其与分子态EDs的反应活性［7.62×10⁵～2.55×10⁶　Ｌ·(mol·s)^-1］的10³～10⁴倍.对比不同水质本底下O₃氧化去除EDs的实验发现,滤后水和江水中EDs的去除率较其在超纯水中分别降低了26.5%～50.3%和57.3%～72.0%,表明实际水体中的有机物通过竞争氧化剂,抑制了EDs的O₃氧化去除.     

北京地区边界层大气臭氧浓度变化特征分析

利用2001-03～2006-10的大气臭氧探空资料,分析了近6 a北京边界层（2 km以下）大气臭氧浓度的平均月变化和季节变化规律.结果表明,边界层大气臭氧浓度的月变化很明显,1月臭氧浓度最小,地面臭氧浓度不到10×10^-9(体积分数,下同),上层（即2 km）臭氧浓度也不到50×10^-9.而6月臭氧浓度最大,地面达到85×10^-9,上层大于90×10^-9.臭氧浓度具有明显的季节特征,从臭氧浓度值来看,冬季最小,夏季最大.从地面到上层的臭氧浓度的变化幅度来看,冬季变化最大,夏季变化最小.根据廓线变化方式,臭氧浓度廓线可分为3种类型,冬季型、夏季型、春秋季型.不同高度臭氧月平均浓度也明显不同.分析地面及上层臭氧浓度与气象因子如温度和湿度的相关关系,发现地面臭氧浓度与温度具有较好的线性关系,相关系数在0 .85以上.     

Rapid determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration

A rapid, simple and sensitive method was demonstrated for the determination of phenolic compounds in water samples by alternating-current oscillopolarographic titration. With the presence of sulfuric acid, phenol could be transferred into a nitroso-compound by reacting with NaNO2. The titration end-point was obtained by the formation of a sharp cut in the oscillopolarographic with infinitesimal NaNO2 on double platinum electrodes. The results showed that phenol concentration had an excellent linear relationship over the range of 4.82×10-6-9.65×10-3 mol/L, the RSD of the proposed method was lower than 1.5%, and the spiked recoveries of three real water samples were in the range of 95.6%-106.9%.     

Number concentration and size distributions of submicron particles in Jinan urban area： Characteristics in summer and winter

The aerosol number concentration and size distribution were measured with the newly developed Wide-range Particle Spectrometer in summer and winter of 2006 at the urban site of Jinan City.Here reported the characteristics of fine particles of the different observation seasons.Relative high number concentrations for the particles in the diameter range of 10-500 nm were observed in both seasons.It was found that the dominant number distributed in particle diameter smaller than 100 nm and the percentage over the number concentration of all air particles is much higher than what has been measured in other urban sites over the world.The number mean diameter in summer was much smaller than in winter,strongly suggesting the different origin of ultrafine particles in different seasons.That is, particles in ultrafine mode mainly came from nucleation and new particle formation in summer while from traffic emission in winter. The diurnal variation also supported this point.Number concentration in the diameter range of 10-200 nm got their peak values at noontime,well correlated with the mixing ratio of SO_2 and the intensity of solar radiation in summer.While in winter,those in the same diameter range showed the main peaks during the traffic hours happened in the morning and evening.     

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.     

Laboratory-scale study of the suppression of PCDD/F emission during coal and MSW co-incineration

The experimental test of co-incinerating Chinese raw municipal solid waste （MSW） and coal in a laboratory-scale tubular reactor was first reported in present study, and the emission of normal gas components and the effects of the S/Cl molar ratio or coal mixing percentages on polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDDs/Fs） emission were investigated and discussed. The results indicated that OCDD was the only PCDD homologues since others like TCDD-HpCDD was hardly detected, while as the categories of PCDF homologues were comparatively much more general. The amount of PCDD was much larger than that of PCDF in all operating conditions. Since ZPCDF/∑PCDD〈〈1, the dominant role of the precursor formation was proven in our experimental conductions. With increasing the coal addition to MSW （from 0 to 16%）, PCDD and PCDF were reduced considerably. Coal and MSW may suppress the PCDD/F emissions efficiently （over 95%） during the MSW incineration process. The PCDD/F suppression results of the present study could be helpful guidance to the industrial application of Chinese MSW and auxiliary coal co-incineration processes. The PCDD/F stack emission data of two industrial incinerators using co-incineration technology in China seem to have a great positive reduction of PCDDs/Fs.     

北京大气中NO、NO2和O3浓度变化的相关性分析

臭氧（O₃）是城市污染大气中的首要光化学污染物,其变化规律与氮氧化物(NO_x=NO+NO₂)关系密切.采用49C臭氧分析仪和42CTL氮氧化物分析仪对北京城区O₃和NO_x浓度进行了连续观测,时间为2004-08～2005-07.结果显示,O₃和OX（O₃+NO₂）浓度在午后15:00左右出现峰值,NO_x呈双峰态日变化,在07:00和23:00左右出现峰值.不同季节污染物的浓度变化存在差异,O₃和NO_x浓度分别在夏季和冬季达到最大.NO_x浓度存在100×10^-9(体积分数)的“分界点”,NO_x低浓度时以NO₂为主,NO_x高浓度时NO占大部分.OX区域贡献和局地贡献存在明显的季节变化,前者主要受区域背景O₃的影响,在春季最大,后者主要受局地NO_x光化学反应的制约,在夏季最强,同时OX组分呈现显著的昼夜差异.     

生物活性炭内吸附与生物降解协同去除有机污染物

本研究建立了一个确定BAC内2种机理去除有机物分配比例的试验方法.该方法以BAC进出水中溶解性有机碳（DOC）与可生物降解有机碳（BDOC）浓度变化作为评价参数,并利用此方法确定了臭氧投加量对2种去除机理的影响.臭氧化可以使BDOC浓度增加,臭氧投量为2～8mg/L时,BDOC增加0.12～0.54mg/L;BAC过滤使出水BDOC浓度降低为0.23～0.31mg/L.随着臭氧投量增加（2～8mg/L）,在BAC内生物降解作用去除有机物比例从46%增加到89%.     

城市降雨径流水文模拟的参数局部灵敏度及其稳定性分析

基于Morris筛选法,在厦门城市小流域采用8场实测降雨数据对城市降雨径流模型SWMM的水文水力模块进行局部灵敏度及其稳定性分析.结果表明,Area、%Imperv和Dstore-Imperv是影响降雨总径流量和流量峰值最灵敏的参数.对于总径流量,Area、%Imperv和Dstore-Imperv的灵敏度分别为0.46～1.0、0.61～1.0和-0.050～-5.9;而对于流量峰值,它们的灵敏度分别为0.48～0.89、0.59～0.83和0～-9.6.其中降雨强度最小的场次降雨的各个参数降雨总径流量和流量峰值的灵敏度都最大,而降雨强度较大的场次降雨的总径流量和流量峰值的灵敏度都较小.不同场次降雨模型参数的灵敏度分析具有很大的差异性,但%Zero-Imperv对总径流量和流量峰值模拟输出影响的稳定性最小,表现在变异度最大,高达221.24%和228.10%,而Conductivity参数稳定性最大,变异系数都为0.     

Effect of elevated tropospheric ozone on methane and nitrous oxide emission from rice soil in north India

Physiological changes in crop plants in response to the elevated tropospheric ozone (O₃) may alter N and C cycles in soil. This may also affect the atmosphere-biosphere exchange of radiatively important greenhouse gases (GHGs), e.g. methane (CH₄) and nitrous oxide (N₂O) from soil. A study was carried out during July to November of 2007 and 2008 in the experimental farm of Indian Agricultural Research Institute, New Delhi to assess the effects of elevated tropospheric ozone on methane and nitrous oxide emissions from rice (Oryza sativa L.) soil. Rice crop was grown in open top chambers (OTC) under elevated ozone (EO), non-filtered air (NF), charcoal filtered air (CF) and ambient air (AA). Seasonal mean concentrations of O₃ were 4.3 ± 0.9, 26.2 ± 1.9, 59.1 ± 4.2 and 27.5 ± 2.3 ppb during year 2007 and 5.9 ± 1.1, 37.2 ± 2.5, 69.7 ± 3.9 and 39.2 ± 1.8 ppb during year 2008 for treatments CF, NF, EO and AA, respectively. Cumulative seasonal CH₄ emission reduced by 29.7% and 40.4% under the elevated ozone (EO) compared to the non-filtered air (NF), whereas the emission increased by 21.5% and 16.7% in the charcoal filtered air (CF) in 2007 and 2008, respectively. Cumulative seasonal emission of N₂O ranged from 47.8 mg m⁻² in elevated ozone to 54.6 mg m⁻² in charcoal filtered air in 2007 and from 46.4 to 62.1 mg m⁻² in 2008. Elevated ozone reduced grain yield by 11.3% and 12.4% in 2007 and 2008, respectively. Global warming potential (GWP) per unit of rice yield was the least under elevated ozone levels. Dissolved organic C content of soil was lowest under the elevated ozone treatment. Decrease in availability of substrate i.e., dissolved organic C under elevated ozone resulted in a decline in GHG emissions. Filtration of ozone from ambient air increased grain yield and growth parameters of rice and emission of GHGs.