珠三角地区大气PM_(2.5)理化特性季节规律与成因

基于珠三角大气超级站2013年8月至2014年3月PM2.5、PM2.5中主要水溶性无机离子组分及其重要气态前体物等参数的逐时在线监测结果,揭示当地大气PM2.5中二次无机组分与其气态前体物的相互作用,以及PM2.5理化特性与成因的季节差异。结果表明,观测期间,PM2.5、PM10的年平均质量浓度分别为64.2、105.1μg/m3,PM2.5在PM10中所占比例(PM2.5/PM10)平均为61.1%。SO2-4、NO-3、NH+4的年平均质量浓度分别为16.6、9.0、10.2μg/m3,3者之和(SNA)占PM2.5的比例(SNA/PM2.5)平均为55.8%,体现了二次转化对珠三角地区PM2.5污染的重要影响;不同季节,SNA/PM2.5为46.0%~64.3%,夏季最低,冬季最高,其中SO2-4、NH+4对PM2.5的贡献相对稳定,NO-3贡献的季节差异较大;秋、冬季各项观测参数浓度的日变化规律相对明显,夏季除HNO3和NH3外,多项观测参数在低浓度水平波动,日变化规律不明显;珠三角大气中具有足量气态NH3以中和硫酸盐和硝酸盐,PM2.5中NH+4、SO2-4、NO-3主要以(NH4)2SO4和NH4NO3形式存在;本研究站点夏季的硫氧化率和氮氧化率均高于广州市,这充分体现了该站点的区域性特征。     

不对称街谷内PM_(2.5)浓度垂直分布特征及成因

当前细颗粒物PM2.5已成为城市环境的主要污染物,研究城市不对称街谷内PM2.5浓度的垂直分布特征,对居民日常生活与健康出行有现实意义。实验选取2013年3个不同阶段对高度在1~35 m范围的街谷进行PM2.5浓度监测,同时引用街谷内流场模型与浓度场模型,对PM2.5浓度垂直分布特征及成因进行探究。结果表明,不对称街谷受大气对流、风速、风向影响,街谷内细颗粒物存在不均匀分布特点,在较高侧随着壁面高度的增加PM2.5浓度大体呈"S"型曲线变化。同时在同一阶段监测的4天中街谷内PM2.5浓度分布特征大体一致,而阶段之间差异明显;街谷内PM2.5浓度垂直分布的最高浓度差出现在阶段1,高达75μg/m3,阶段2与阶段3浓度差相对减弱,仅在20~30μg/m3之间。通过阶段2与阶段3对比可知,北京冬季供暖燃煤对大气细颗粒物的贡献较大,导致颗粒物浓度偏高;而非采暖期气温回升,大气对流作用较强,有助于大气颗粒物扩散,因而街谷内PM2.5污染程度相对较低。     

西安城郊PM_(10)和PM_(2.5)化学组分特征研究——以户县草堂寺为例

为研究西安城郊农村大气PM_(10)和PM_(2.5)中主要化学组分特征,于2014年12月至2015年10月在西安户县草堂寺采集颗粒物样品,分析了每组样品中的16种无机元素、8种水溶性离子、有机碳(OC)和元素碳(EC),对颗粒物和化学组分的浓度水平、时间变化特征进行了讨论。结果表明:(1)PM_(2.5)、PM_(10)年平均值分别为(79.78±59.12)、(118.09±79.27)μg/m~3。(2)PM_(2.5)及PM10中地壳元素浓度总体表现为春季高、秋季低;微量元素浓度表现为冬季高、夏季低。(3)PM_(2.5)和PM_(10)中SO_4~(2-)、NH_4~+、NO_3~-浓度总体表现为冬季秋季春季夏季。(4)冬、春季OC、EC明显高于夏、秋季;由OC/EC的最小值估算得到PM_(2.5)、PM_(10)中二次有机碳(SOC)年平均值分别为(7.90±8.89)、(8.55±8.50)μg/m~3,冬、春季SOC明显高于夏、秋季;秋、冬季OC、EC相关性较强,而春、夏季较弱。     

天津冬季PM2.5与PM10中有机碳、元素碳的污染特征

研究了天津冬季PM2.5和PM10中碳成分的污染特征.结果表明,天津冬季PM2.5和PM10的平均质量浓度分别为(124.4±60.9)、(224.6±131.2)μg/m3;总碳(TC)、有机碳(OC)与元素碳(EC)在PM2.5中的平均质量分数比在PM10中分别高出5.0%、3.6%、1.2%;PM2.5中OC、EC的相关系数较高,为0.95,表明OC、EC的来源相对简单,可能主要反应了燃煤和机动车尾气的贡献.OC/EC的平均值在PM2.5和PM10中分别为3.9、4.9.次生有机碳(SOC)在PM2.55和PM10中的平均质量浓度分别为14.9、23.4/μg/m3,分别占OC的48.5%(质量分数,下同)、49.8%,OC/EC较高可能主要与直接排放源有关;PM2.5中的OC1与OC2的比例明显高于PM10,而聚合碳(OPC)的比例又低于PM10,同时PM2.5与PM10中的EC1含量均较高,表明天津冬季燃煤取暖和机动车尾气是重要的污染源.     

西安市冬、夏两季PM2.5中碳气溶胶的污染特征分析

为研究西安市冬、夏两季大气颗粒物PM2.5中碳组分的污染变化规律,利用TEOM系列RP1400a采样仪于2010年冬季和夏季进行采样,测定了样品中的有机碳(OC)、无机碳(EC)和水溶性有机碳(WSOA)的含量。结果显示,PM2.5中OC和EC的季节平均浓度值冬季较高,分别是夏季的2.62,1.75倍,这表明西安市冬季碳气溶胶污染严重。OC和EC日变化在不同季节均呈现双峰分布特征,这主要是由交通源的排放和不利的气象条件造成的。OC和EC在冬、夏两季都有较强的相关性(R2分别为0.823和0.543),且OC/EC平均值分别为5.36和3.58,均大于2,表明采样各时段有二次有机碳(SOC)生成。     

西安市PM2.5污染特征及其估测模型

为了研究大气中PM25污染特征以及其随时间变化规律,基于西安市2013年1月-2014年4月间SO2、NO2、CO、03、日最高温度(Tmax)、日最低温度(Tmin)、PM2.5、PM10等因素的监测数据.运用统计学原理和多元回归分析方法,分析了PM25的污染特征及相关因素对其产生的贡献度,进一步建立了四季的最优多元回归模型.研究结果表明,西安市年平均质量浓度124.9 μg/m3,四季的平均污染浓度从大到小依次为冬、春、秋、夏;春夏两季贡献较大的为SO2、CO;秋冬两季贡献较大的为NO2、CO;最终建立的模型的相关系数较高,模型很好地拟合了冬春两季PM2.5变化趋势,能较准确地反映了西安市PM2.5的污染特征,具有一定的理论和实用价值.     

宝鸡市大气PM_(10)中水溶性物质的组成及特征研究

2008年冬、春季在宝鸡市4个不同功能区采集PM10样品,探讨了PM10中水溶性物质的化学组成、时空分布特征以及来源。结果表明,冬、春季PM10的平均质量浓度分别为(402±100)、(410±160)μg/m3,无明显季节差异,冬季以交通干道区的PM10浓度为最高,而春季则以商贸区的PM10浓度为最高;冬、春季PM10中水溶性有机碳(WSOC)浓度最高值均出现在商贸区,最低值则分别出现在背景点和交通干道区,水溶性无机碳(WSIC)浓度最高值分别出现在交通干道区和商贸区,最低值均出现在背景点;冬、春季PM10中所含大多数无机离子浓度不存在显著空间差异,但不同功能区PM10中无机离子所占质量分数差异较明显;冬、春季PM10中的水溶性物质质量浓度分别为207、151μg/m3,在PM10中所占质量分数分别为51%和40%,其中,冬、春季水溶性物质浓度最高的分别为居民区和商贸区;冬季PM10中WSOC浓度与SO24-、NO3-浓度有较好的相关性,说明冬季PM10中WSOC的主要组分为二次有机气溶胶,而春季PM10中WSOC浓度与SO42-、NO3-浓度的相关性相对较差,这是由于一次有机气溶胶对WSOC的贡献率较冬季显著增大;宝鸡市与北京市大气PM10浓度、PM10中的SO42-、NO3-、NH4+浓度最为接近;广州市大气PM10中的SO42-所占质量分数(14%)要高于北方城市(宝鸡市和北京市均为9%)。     

冬季关中城市及农村颗粒物的污染特征

为比较冬季城市和农村大气颗粒物浓度及化学组分等特征,本文分别采集分析了西安市区、安康农村冬季大气PM2.5颗粒物与PM0.1颗粒物。分析结果表明:两地大气中PM2.5日均浓度均超过国家二级标准(75μg·m~(-3)),空气质量不容乐观;其中农村样品中PM0.1颗粒物约占PM2.5颗粒物浓度的36.8%左右;所有颗粒物中有机碳远高于无机碳组分,而市区大气颗粒物中多环芳烃浓度显著高于农村浓度,说明城市空气中来源于机动车尾气的污染较为严重;从颗粒物粒径分布特征来看,粒径为0.300~0.374μm颗粒物具有最高数浓度和比表面积浓度,粒径为0.374~0.465μm的颗粒物具有最高质量浓度;由于农村污染源较为单一,安康样品颗粒物浓度受燃煤和油烟的影响较大。此外,由于受燃煤机动车排放影响,西安大气中PM0.1颗粒物中水溶性离子主要为NO_3~-与SO24,而安康大气PM0.1颗粒物中水溶性离子主要以SO_4~(2-)与Ca2+为主,PM2.5颗粒物中水溶性离子以NO_3~-、SO_4~(2-)和NH_4~+为主,这与农村环境中使用燃煤、农田灌溉、家畜喂养以及有机质降解等有关。     

成都市大气颗粒物污染特征及与气象因子的关联性分析

利用成都市2013年6月至2014年5月的PM10和PM2.5浓度监测数据,分析大气颗粒物污染特征,并探讨其与气温、相对湿度、降雨、风向、风速等气象因子的关联性。结果表明:成都市大气PM2.5污染较严重;PM10和PM2.5浓度及超标率均表现为冬季秋季春季夏季,秋季和冬季为大气颗粒物污染高发期;PM2.5对PM10贡献显著;气温超过10℃时,PM10和PM2.5最高浓度大体随气温升高而降低;相对湿度为40%~80%时,PM10和PM2.5浓度随相对湿度增加而升高;相对湿度超过80%时,易发生降雨,PM10和PM2.5浓度降低;降雨对PM10的清除量高于PM2.5,但降雨后PM10和PM2.5浓度较快回升;PM10和PM2.5浓度在偏西风下高于其他风向;PM10主要受局地源影响,而PM2.5主要受西北方向上的外来源影响。     

广州市夏、冬季室内外PM2.5质量浓度的特征

2004年7月2日至8月13日和2004年11月29日至2005年1月6日分别在广州市3种类型区域(一般城市区域、道路旁、工业源附近)9个居民住宅的室内和室外同步采集了PM2.5颗粒.采用标准称重法测定PM2.5质量浓度,得到广州市夏季住宅室内外PM2.5平均质量浓度分别为67.7、74.5 μg/m3,冬季室内外PM2.5平均质量浓度分别为109.9、123.7 μg/m3.广州市PM2.5平均质量浓度,与美国PM2.5标准相比,与国内PM10标准基础上假设的PM2.5限值相比,与其他一些国内、亚洲和欧美城市的文献记录相比,结果均显示广州市PM2.5处于相当严重污染状态.广州市PM2.5质量浓度呈现明显的空间分布特征和季节变化特征;PM2.5室内质量浓度并不总是低于室外质量浓度,反映了室内空气污染的存在.     

Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death,age, and season

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 microg/m3 particulate matter (PM) of median diameter < or = 10 microm (PM10); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO2; 1.6% (1.1-2.0%) per 31.2 ppb O3; and 0.9% (0.7-1.2%) per 9.4 ppb SO2 (daily maximum concentration for O3, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM10 and SO2. Larger effect sizes were observed for respiratory mortality for all pollutants except O3. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Meta-Analysis of Time-Series Studies of Air Pollution and Mortality: Effects of Gases and Particles and the Influence of Cause of Death,Age, and Season

Abstract

A comprehensive, systematic synthesis was conducted of daily time-series studies of air pollution and mortality from around the world. Estimates of effect sizes were extracted from 109 studies, from single- and multipollutant models, and by cause of death, age, and season. Random effects pooled estimates of excess all-cause mortality (single-pollutant models) associated with a change in pollutant concentration equal to the mean value among a representative group of cities were 2.0% (95% CI 1.5-2.4%) per 31.3 μg/m³ particulate matter (PM) of median diameter <10 μm (PM₁₀); 1.7% (1.2-2.2%) per 1.1 ppm CO; 2.8% (2.1-3.5%) per 24.0 ppb NO₂; 1.6% (1.1-2.0%) per 31.2 ppb O₃; and 0.9% (0.7-1.2%) per 9.4 ppb SO₂ (daily maximum concentration for O₃, daily average for others). Effect sizes were generally reduced in multipollutant models, but remained significantly different from zero for PM₁₀ and SO₂. Larger effect sizes were observed for respiratory mortality for all pollutants except O₃. Heterogeneity among studies was partially accounted for by differences in variability of pollutant concentrations, and results were robust to alternative approaches to selecting estimates from the pool of available candidates. This synthesis leaves little doubt that acute air pollution exposure is a significant contributor to mortality.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

骆马湖富营养化和生态状况调查与评价

为了了解骆马湖水质状况，在2005年对骆马湖富营养化状态和生态特性进行了调查，并结合“十五”期间的监测资料进行了分析。2005年骆马湖水体中总氮和总磷的平均值超《地表水环境质量标准》（GB3838-2002）中Ⅲ类，超标情况分别为0．78倍和0．54倍，达到湖库特定项目Ⅳ类水标准，骆马湖处于轻度富营养化状态。对骆马湖生态特征分析表明，由于该湖泊的形态以及“藻型浊水状态”和“泥沙型浊水状态”交替出现，遏制了湖水从高营养盐含量向全面富营养化状态演变，保障了底栖动物的良好生长环境，从而形成了骆马湖独特的环境生态平衡。     

剩余污泥浓缩脱水投药量优化和模型建立

应用高分子阳离子絮凝剂（CPF-100）和聚丙烯酰胺（PAM）对污水厂剩余污泥进行浓缩脱水实验，研究表明：CPF-100的浓缩脱水效果优于PAM；当CPF-00投加量为1．16‰时，污泥沉降性能改善程度为37．51％；且在CPF-100投加量逐渐增大的初始阶段，污泥沉降性能改善程度随投加量的增加而增大，但CPF-100投加量也不宜过大，当CPF-100投加量超过1．16‰后，反而会使浓缩脱水效果变差。同时，建立了污泥沉降性能改善程度与絮凝剂CPF-100投加量、沉降时间之间的数学模型，其能较好地反映污水厂剩余污泥的浓缩脱水效果。     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.