利用热活化过硫酸盐技术去除阿特拉津

利用热活化过硫酸盐(S2O2-8)技术去除水中的阿特拉津(ATZ).结果表明,增加溶液中S2O2-8浓度或提高溶液反应温度,可加速ATZ的降解.ATZ的降解是一个二级反应,其速率和溶液中ATZ和S2O2-8的浓度都成正比.初始pH为3.0~10.0时,S2O2-8对ATZ都有很好的降解效果,在酸性和中性时,降解效率高于碱性条件.利用自由基探针发现,在酸性和中性条件下,起降解作用的主要是SO·-4,而碱性条件下OH·占主导.ATZ的降解受到Cl-、CO2-3和腐殖质(HA)的影响.其中,Cl-对反应的影响比较复杂,低浓度时Cl-会生成具有高氧化还原电位的Cl·促进ATZ的降解,而高浓度时Cl·会继续反应生成氧化能力相对较弱的Cl2·-,从而抑制反应的进行.HA和CO2-3都对反应有明显的抑制作用.     

李氏禾湿地系统净化Cr（Ⅵ）污染水体的机理研究

利用湿生铬超富集植物李氏禾构建了三段式波形潜流式人工湿地,并以相同设计的无植物湿地系统作为对照,比较研究了李氏禾湿地系统对Cr(Ⅵ)的净化效果.同时,综合运用电子顺磁共振(EPR)、X光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)等手段,并结合有机质含量、pH、Eh和Cr质量平衡分析,探讨了李氏禾湿地系统对Cr(Ⅵ)的去除机理.结果显示,李氏禾湿地系统对Cr(Ⅵ)的去除率显著高于对照湿地,且李氏禾湿地基质中的有机质含量是对照湿地的3倍.这表明李氏禾增加了湿地基质中的有机质含量,从而提高了湿地系统对Cr(Ⅵ)的净化能力.李氏禾组织中的Cr主要以Cr(Ⅲ)形式存在,其中,茎部和叶部未检测到Cr(Ⅵ),而仅有1.95%的Cr以Cr(Ⅵ)形式存在于根部中.EPR分析结果显示,李氏禾叶部中的Cr(Ⅲ)以有机酸结合态的形式存在,根部中的Cr(Ⅲ)以氢氧化物的形式存在,这表明李氏禾能有效地将Cr(Ⅵ)还原成Cr(Ⅲ).基质表面吸附的Cr大部分为Cr(Ⅲ),而Cr(Ⅵ)仅占4.99%.XPS分析进一步证明,基质表面同时吸附了Cr(Ⅲ)和Cr(Ⅵ),但主要以Cr(Ⅲ)为主,且Cr(Ⅲ)可能以氢氧化物的形式存在.由此判断,进入湿地的Cr(Ⅵ)在基质中被还原成Cr(Ⅲ).FTIR分析结果显示,基质表面的羟基、氨基、羧基、CO、C—O、C—H等基团与Cr的吸附有关,这表明湿地基质中的有机质作为电子供体参与了Cr(Ⅵ)的还原.李氏禾湿地系统能将水体中可溶性的Cr(Ⅵ)有效地还原成难溶的Cr(Ⅲ)化合物,并将其转化成湿地生态系统物质循环的惰性部分.     

Expression of sulfur uptake assimilation-related genes in response to cadmium, bensulfuron-methyl and their co-contamination in rice roots

The responses of sulfur （S） uptake assimilation-related genes＇ expression in roots of two rice cultivars to cadmium （Cd）, bensulfuron-methyl （BSM） and their co-contamination （Cd＋BSM） were investigated by gene-chip microarray analysis and quantitative real-time PCR （QRT-PCR） technology. Treatments of Cd and Cd＋BSM induced expression of sulfate transporter and permease genes, and promoted sulfate uptake in rice roots. Cd＋BSM could alleviate Cd toxicity to cv. Fengmeizhan seedlings, probably due to Cd＋BSM promoting greater S absorption by seedlings. Cd and Cd＋BSM induced expression of sulfate assimilation-related genes, and thus activated the sulfur assimilation pathway. Cd and Cd＋BSM induced expression of phytochelatin synthase and metallothionein genes, and induced expression of glutathione S-transferases （GSTs）, glutathione synthase （GS） and S- containing antioxidation enzyme genes, which detoxified Cd2＋. It is suggested that （to cope with the toxicity of Cd, BSM and their co-contamination） the S uptake and assimilation pathway was activated in rice roots by increased expression of related genes, thus enhancing the supply of organic S for synthesis of Cd or BSM resistance-related substances.     

Arsenic removal from groundwater by acclimated sludge under autohydrogenotrophic conditions

Arsenic in the environment is attracting increasing attention due to its chronic health effects. Although arsenite(As(III)) is generally more mobile and more toxic than arsenate(As(V)), reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation with sulfide or by adsorption or complexation with other metal sulfides. The performance of As(V) bio-reduction under autohydrogenotrophic conditions was investigated with batch experiments. The results showed that As(V) reduction was a biochemical process while both acclimated sludge and hydrogen were essential. Most of the reduced arsenic remained in a soluble form, although 20% was removed with no addition of sulfate, while 82% was removed when sulfate was reduced to sulfide. The results demonstrated that the reduced arsenic was re-sequestered in the precipitates, probably as arsenic sulfides. Kinetic analysis showed that pseudo first-order kinetics described the bio-reduction process better than pseudo second-order. In particular, the influences of pH and temperature on As(V) reduction by acclimated sludge under autohydrogenotrophic conditions and total soluble As removal were examined. The reduction process was highly sensitive to both pH and temperature, with the optimum ranges of pH 6.5–7.0 and 30–40°C respectively. Furthermore, Arrhenius modeling results for the temperature effect indicated that the As(V) reduction trend was systematic. Total soluble As removal was consistent with the trend of As(V) reduction.     

Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles

Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium （Pd） nanoparticles was studied for the first time. The effects of Pd loading, dye concentration and reuse repetitions of membranes were investigated. In reduction, the dye concentration decreased whereas the pH rose gradually. An optimal Pd loading was found. The catalytic membranes were able to be reused more than 3 times.     

催化还原法净化处理氮氧化物的工程实例

针对不锈钢产品酸洗处理过程中产生的氮氧化物浓度高、对大气污染的影响大、且难于净化治理等特性,在上海某不锈钢项目中设计了一套酸雾净化系统。该设计解决了酸洗中产生的氮氧化物难以净化的问题,提升了氮氧化物处理技术,它将成为不锈钢酸洗行业中氮氧化物净化处理技术的发展方向。     

Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006-2011

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.     

FBC-DPF在柴油机颗粒物控制中的应用研究

目前针对加装FBC-DPF(燃油添加剂-柴油机颗粒捕集器)后的柴油机放特性研究较少,并且缺乏FBC-DPF对颗粒物中PAHs排放量的影响效果研究.为全面评估加装FBC-DPF后柴油机颗粒物排放特性和FBC-DPF对柴油机尾气中的颗粒物排放污染控制效果,在发动机台架上对装有FBC-DPF的重型柴油机进行了颗粒物排放特性试验.利用电子低压撞击仪(ELPI)测量加装FBC-DPF前、后柴油机颗粒物的数浓度与粒径分布,用玻璃纤维滤膜采集加装FBC-DPF前、后尾气中的固相PAHs,利用色谱质谱联用仪对加装FBC-DPF前、后尾气中的固相PAHs进行定量分析.结果表明:①加装FBC-DPF后柴油机排放的颗粒物数浓度大幅降低,FBC-DPF对尾气中颗粒物的捕集效率平均值在95%左右;②加装FBC-DPF后柴油机固相PAHs总比排放量有所降低,在大负荷区域降幅在25.0%～88.0%之间;③加装FBC-DPF前的颗粒物中位直径为30～89 nm,而加装FBC-DPF后的颗粒物中位直径为41～98 nm,平均增幅为38.2%.对于国Ⅳ及未来国Ⅴ柴油机排放法规,FBC-DPF是解决柴油机颗粒物排放的有效手段;此外,FBC-DPF可以大幅降低柴油机尾气中的有毒成分,并且能够适应高含硫量的燃油环境.     

有机蒙脱石负载纳米铁去除溶液中四溴双酚A的研究

研究了改性蒙脱石负载纳米铁材料(NZVI-CMT)在甲醇-水体系中对四溴双酚A(TBBPA)的去除作用,并确定了反应温度、TBBPA初始浓度以及材料投加量等因素对去除效果的影响.结果表明,在25℃条件下,0.02 g NZVI-CMT对初始浓度为10 mg·L-1TBBPA溶液的去除率可达97.5%,而且NZVI-CMT对TBBPA的去除率明显高于两种单一材料即纳米零价铁(NZVI)及有机蒙脱石(CMT)的去除率(18.3%、67.3%),同时也大于两者之和(85.6%).利用NZVI-CMT对TBBPA进行重复去除实验时,前3次的去除率均可达到90%以上.通过检测降解产物并分析材料对TBBPA去除过程的特性,发现NZVI-CMT对TBBPA的去除以吸附为主,并伴有少量还原脱溴反应发生,而且较高的反应温度对降解反应有利.     

直接大红4BE的磷钨酸均相光催化还原脱色

以磷钨酸(H3PW12O40,PW12)为光催化剂,异丙醇(Isopropanol)作为电子给体的条件下对偶氮染料直接大红4BE进行均相光催化还原脱色研究,考察PW12用量、IS浓度、直接大红4BE和盐浓度等因素的影响,结果表明杂多蓝(PW1-2)对直接大红4BE具有明显的还原脱色作用.pH=2.0,直接大红4BE初始浓度50 mg·L-1,PW12浓度为600 mg·L-1,IS浓度为0.13mol·L-1,50 min直接大红4BE的脱色率可达到90.39%.4BE的光催化还原脱色速率随PW12和IS浓度的增加而增加,最后趋于恒定;直接大红4BE初始浓度增加,其光反应一级速率常数降低;PW12、IS和4BE浓度之间存在交互影响.离子强度增加,4BE脱色速率减小,表现为负的盐效应,推测4BE与光反应生成的杂多蓝(PW1-2)进行复合,然后发生电子转移引起偶氮染料还原脱色和杂多蓝氧化复原.本研究结果表明PW12/IS/UV能够有效用于偶氮染料直接大红4BE的还原脱色处理.