固定源可凝结颗粒物稀释采样器的设计

固定污染源烟气排放进入大气环境后稀释降温,气相中部分饱和蒸气压较低的组分转化为可凝结颗粒物,这部分颗粒物在固定源烟气颗粒物监测中通常被忽略.为评价固定源可凝结颗粒物的排放情况,本文设计开发并评测了一套稀释采样器.稀释采样器稀释比在10：1~40：1范围内,混合停留时间为5~10 s.实验室评测结果表明,稀释气颗粒物背景值低（（~0.1±0.08） 个·cm^-3）,稀释采样器气密性良好,烟气和稀释气能够均匀混合,颗粒物损失较少,细颗粒物 （PM_2.5）损失在5%以下.本稀释采样器能模拟烟气与环境空气混合降温过程,可用于固定源可凝结颗粒物的测量.     

民用固体燃料燃烧大气污染物排放稀释采样器的研制与应用

为研究民用固体燃料燃烧大气污染物的排放特征,研制开发了一套紧凑型稀释采样器,主要由烟气进气部分、稀释空气部分、稀释混合部分及采样部分四部分组成.结果表明,该采样器可测量排放的一次PM_(2.5)、CO_2、CO、SO_2、NO_x等气态污染物排放浓度,并可根据碳平衡法获得各污染物的排放因子.稀释采样器的稀释比在20∶1～30∶1范围内,样气在稀释器内的停留时间为10 s.性能评价表明,稀释器气密性良好,稀释空气中颗粒物浓度低于3μg·m~(-3),气流混合均匀,理论稀释比与实际稀释比的偏差均小于2%,细颗粒在采样器内的损失小.利用稀释器测试了两种典型民用炉具和煤种组合的大气污染物的排放,发现高效反烧炉与无烟煤球组合的PM_(2.5)的排放因子要显著低于传统正烧炉与烟煤组合,且前者CO和NO_x的排放因子也要低于后者,两种CO_2排放因子相当.     

应用受体模型(CMB)对北京市大气PM_(2.5)来源的解析研究

为研究影响北京市大气环境PM2.5污染水平的主要来源,于2012年8月—2013年7月,依托北京市大气地面观测网络在10个监测点采集的491 d(次)大气PM2.5有效样本,对其化学组分进行了测试分析;从城市大气污染源组成出发,建立和完善了5类固定点源、2类流动源、4类无组织面源的PM2.5排放成分谱.应用受体模型(CMB)开展了来源解析研究.结果显示:1观测期间大气环境PM2.5的来源主要包括:一次来源机动车(16%)、燃煤(15%)、土壤尘(6%)、二次硫酸铵和硝酸铵(36%),以及有机物(20%)和其他未识别来源(7%);与历史解析结果相比,燃煤源分担率有所下降,二次无机盐与有机物分担率上升,且二次硝酸盐有赶超二次硫酸盐之势;2从主要组分的来源看,观测期间环境大气PM2.5中近25%的硫酸盐来自于燃煤锅炉和电厂排放,17%的有机物来自机动车排放;3北京市PM2.5来源类型大致相同,但各点位PM2.5来源种类和分担率具有一定差异,对一些排放量较大的局地排放源有比较明确的响应.研究表明,开展区域性PM2.5治理、大力削减前体物、严格控制本地机动车、燃煤等PM2.5排放都是改善北京市空气质量的重要途径.     

基于虚拟撞击原理的固定源PM10/PM2.5采样器的研制

目前我国尚无固定源PM2.5采样标准方法,现有商业化的固定源PM2.5采样器在使用中存在明显不足,因此本研究开发了一种固定源PM10/PM2.5双级虚拟撞击采样器.经实验室标定,该采样器切割效率曲线优于国际标准ISO 7708:1995对采样器的规定,采样器横截面直径为74 mm,满足我国固定源采样口尺寸要求.采样器既可以安装滤膜,也可以安装滤筒,适用于不同浓度的烟尘采样.虚拟撞击器的切割点与次流所占比值呈负相关,比值减小时,切割点增大.为降低颗粒物损失,虚拟撞击器喷嘴距收口的距离至少应为喷嘴直径的1.5~2倍.     

燃煤污染源排放颗粒物采样方法实验室比对研究

为研究适用于我国燃煤污染源排放颗粒物的分级采样标准测试方法,采用民用小煤炉排放装置结合烟气采集系统,对比研究了直接采样法(双级虚拟撞击PM₁₀/PM_2.5采样器、旋风采样器、总烟尘采样器)和稀释采样法(低压荷电撞击器ELPI配备稀释系统)对烟气中不同粒径颗粒物测试结果的稳定性、相关性、仪器可操作性等特点,并分析了煤质对颗粒物分级测试结果的影响. 结果表明:①从决定系数和残差平方和角度分析,稀释采样法测试结果自身拟合性相对直接采样法差,实测数据点相对分散,95%置信带较宽. 直接采样法中,基于本文确定的清洗和收集方式,旋风采样器测试得到的PM₁₀和PM_2.5浓度拟合度高达0.999;双级虚拟撞击PM₁₀/PM_2.5采样器测试结果稳定性也较高,其测试得到的PM₁₀和PM_2.5浓度拟合度也为0.999. ②不同颗粒物采样器对烟气中PM_2.5、PM₁₀、TSP的浓度测试结果均表明,稀释采样法与直接采样法测试结果相关性较低;而各直接采样法之间呈高度相关,Pearson相关系数在0.993~0.999之间. ③稀释采样法分级测试结果显示,当颗粒物排放浓度较低时,各级滤膜称量误差叠加可导致PM₁₀、PM_2.5浓度测试结果误差较大. 因此,针对常温且颗粒物浓度较低的烟气,建议采用直接采样法;针对高温烟气,稀释采样法可捕集稀释降温过程中形成的可凝结颗粒物. ④各采样方法测试结果表明,相对于燃用无烟煤(如蜂窝煤),燃用烟煤产生的烟气中颗粒物浓度相对较高,且PM_2.5占比较高. 研究显示:稀释采样法能模拟燃煤污染源高温烟气排入大气环境中可凝结颗粒物的形成过程,测试结果更接近真实排放情况;对于常温颗粒物浓度较低的烟气,更适宜采用直接采样法.      

固定污染源排气中PM2.5采样方法综述

我国新的环境空气质量标准已于2012年颁布并将自2016年起全面实施.为使新标准规定的细颗粒物(PM2.5)达标,各地需对固定污染源排气中PM2.5进行监测和控制,但目前国内尚无固定源PM2.5采样标准方法.本文系统地介绍了国内外固定源PM2.5采样方法及相应的国际标准,包括直接采样法和稀释采样法,并分析了这些方法的优缺点及用于我国固定源PM2.5测量的可行性.为了便于环境管理和监测,建议确立基于虚拟惯性撞击原理的烟道内直接采样方法为标准方法,用于测定固定源排气中的可捕集PM2.5;为了评估固定源PM2.5排放对大气环境质量和健康的影响,建议同时确立以烟道外稀释采样为基础的标准方法,用于测定固定源排气中包括可捕集和可凝结的PM2.5.     

海口市PM_(2.5)和PM_(10)来源解析

以海口市为例,研究了我国典型热带沿海城市——海口市环境空气颗粒物的污染特征和主要来源.2012年春季和冬季在海口市区4个采样点同步采集了环境空气中PM10和PM2.5样品,同时采集了多种颗粒物源样品,并使用多种仪器分析方法分析了源与受体样品的化学组成,建立了源化学成分谱.使用CMB(化学质量平衡)模型对海口市大气颗粒物进行源解析.结果表明:污染源贡献具有明显的季节特点,并存在一定的空间变化.冬季城市扬尘、机动车尾气尘、二次硫酸盐和煤烟尘是海口市PM10和PM2.5中贡献较大的源,在PM10和PM2.5中贡献率分别为23.6%、16.7%,17.5%、29.8%,13.3%、15.7%和13.0%、15.3%;春季机动车尾气尘、城市扬尘、建筑水泥尘和二次硫酸盐是海口市PM10和PM2.5中贡献较大的源,在PM10和PM2.5中贡献率分别为27.5%、35.0%,20.2%、14.9%,12.8%、6.0%和9.5%、10.5%.冬季较重的颗粒物污染可能来自于华南内陆地区的区域输送,特别是,本地排放极少的煤烟尘和二次硫酸盐受区域输送的影响更为显著.     

工程机械不同工况下PM_(2.5)排放及其碳质组分特征

我国工程机械排放控制起步较晚.为研究实际工况下工程机械的PM2.5排放特性及其碳质组分构成,采用便携式颗粒物稀释采样系统,对3台工程机械(2台挖掘机和1台装载机)在不同典型工况(行驶、作业和怠速)下的PM2.5及其碳质组分〔OC(有机碳)和EC(元素碳)〕的现场排放特征进行了测试.结果表明:沃尔沃挖掘机、山河智能挖掘机的PM2.5排放因子(基于燃油)分别为1.85~3.26和1.56~2.62 g/kg,厦工装载机的PM2.5排放因子为0.98~1.48 g/kg.不同工况对PM2.5排放因子影响较大,怠速工况下PM2.5排放因子是行驶工况下的1.49~1.76倍.工程机械排放的PM2.5中,碳质组分是最主要的成分,其质量分数高达71.0%~84.5%.其中,w(OC)为44.6%~72.0%,在怠速工况下最高;w(EC)则为8.6%~30.9%,在行驶工况下较高.测试工程机械的PM2.5排放水平较高,因此应尽快加强工程机械排放的污染防治.     

基于曲面响应建模的PM2.5可控人为源贡献解析

以东莞市PM_(2.5)重污染月份为例,使用强力法(Brute Force)和RSM/CMAQ曲面响应模型法分别解析了珠三角地区人为源排放对东莞PM_(2.5)的贡献,以及区域传输的可控人为源SO_2、NO_x和一次颗粒物(PM)在不同控制比例下(25%、50%、75%和100%)对东莞PM_(2.5)的累积浓度贡献.强力法研究结果表明,2014年1月珠三角地区人为源二次转化对东莞市PM_(2.5)的贡献(约58.10%)大于一次PM排放贡献(约41.90%),其中,人为源NH_3排放贡献最大,约占总量的21.66%.RSM/CMAQ动态源贡献结果显示,东莞市PM_(2.5)的人为可控源排放贡献(SO_2、NO_x和一次PM)占比为82.17%,受本地排放影响较大,且叠加区域排放的影响;一次PM减排对PM_(2.5)环境浓度的贡献高于仅减排SO_2和NO_x.在减排比例较低时,一次PM减排可有效削减东莞市PM_(2.5)浓度;随控制比例加大,二次前体物(SO_2和NO_x)减排对东莞市PM_(2.5)浓度削减率的影响加大.进一步使用HYSPLIT模式和轨迹聚类分析方法研究了2014年1月东莞市PM_(2.5)污染传输过程.结果显示,该时段共有6条长、短距离污染传输路径,污染物主要来自东莞市东、东北及东南方向,途经其上风向区域(惠州、深圳和广州等)传输至东莞;惠州是各主导上风向出现频率最高的城市,因而其区域传输对东莞PM_(2.5)的贡献也较大,深圳次之.     

我国钢铁工业一次颗粒物排放量估算

针对我国钢铁工业生产工艺以及颗粒物控制技术的分类,建立了一个细化到排放节点的自下而上的颗粒物排放模型.结合我国钢铁工业各地区活动水平以及颗粒物控制技术分布的历史变化趋势分析,利用此模型计算了2006—2012年我国钢铁工业一次颗粒物的排放系数和排放量.模型计算结果显示,2006年以来,我国钢铁工业颗粒物控制水平不断提高,PM_(2.5)、PM_(2.5)~10和PM10的排放系数分别降低了21.2%、19.3%和19.0%.钢铁工业一次颗粒物排放量在2006—2011年间持续增长,2011年TSP排放量为602×104t,PM10排放量为200×104t,PM_(2.5)排放量为124×104t;2012年排放量出现下降,TSP排放量为561×104t,PM10排放量为187×104t,PM_(2.5)排放量为116×104t.2012年我国钢铁工业一次PM_(2.5)排放量中的有组织排放占39.5%,无组织排放占60.5%;除加严有组织源管控之外,减少颗粒物无组织排放,对于钢铁工业颗粒物排放控制也非常重要.我国钢铁工业颗粒物排放量分布不均衡,河北、山东、江苏、辽宁、山西5个省的排放超过全国总排放的50%.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.