Urban sprawl and air quality in large US cities

This study presents the results of a paper of urban spatial structure and exceedances of the 8-h national ambient air quality standard for ozone in 45 large US metropolitan regions. Through the integration of a published index of sprawl with metropolitan level data on annual ozone exceedances, precursor emissions, and regional climate over a 13-year period, the association between the extent of urban decentralization and the average number of ozone exceedances per year, while controlling for precursor emissions and temperature, is measured. The results of this analysis support the hypothesis that large metropolitan regions ranking highly on a quantitative index of sprawl experience a greater number of ozone exceedances than more spatially compact metropolitan regions. Importantly, this relationship was found to hold when controlling for population size, average ozone season temperatures, and regional emissions of nitrogen oxides and volatile organic compounds, suggesting that urban spatial structure may have effects on ozone formation that are independent of its effects on precursor emissions from transportation, industry, and power generation facilities.     

Experimental and modeling study of de novo formation of PCDD/PCDF on MSW fly ash

The effect of sulfur dioxide （SO2） on the formation of polychlorinated dibenzo-p-dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） has been studied in an entrained-flow reactor （EFR） under simulated waste combustion conditions. A chlorination model based on conditional probability was employed to evaluate the homologue patterns of PCDDs and PCDFs. Results revealed that the presence of SO2 did not alter the formation pathway although SO2 suppressed PCDD/F formation. The prediction model of PCDF showed good agreement with the experimental data （R--0.95）, whereas the prediction for PCDDs did not correlate well with the experimental data. This may be explained because potential chlorination pathways play a significant role in PCDF formation, whereas PCDDs are mainly formed through condensation reactions. Furthermore, the result indicated that the steric hindrance during formation has more effects on PCDD than on PCDF due to the symmetric molecular structures of PCDDs.     

Preparations of TiO2 film coated on foam nickel substrate by sol-gel processes and its photocatalytic activity for degradation of acetaldehyde

Anatase TiO2 films were successfully prepared on foam nickel substrates by sol-gel technique using tetrabutyl titanate as precursor. The characteristics of the TiO2 films were investigated by XPS, XRD, FE-SEM, TEM and UV-Vis absorption spectra. The photocatalytic activities of TiO2 films were investigated by photocatalytic degradation reactions of gaseous acetaldehyde, an indoor pollutant, under ultraviolet light irradiation. It was found that Ni^2＋ doping into TiO2 films due to the foam nickel substrates resulted in the extension of absorption edges of TiO2 films from UV region to visible light region. The pre-heating for foam nickel substrates resulted in the formation of NiO layer, which prevented effectively the injection of photogenerated electrons from TiO2 films to metal nickel. The TiO2 films displayed high photocatalytic activity for the degradation of acetaldehyde, and were enhanced by calcining the substrates and coating TiO2 films repeatedly. The high activity was mainly attributed to the improvement of the characteristics of substrate surface and the increase of active sites on photocatalyst.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(Ⅲ) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Through the comparison of three model systems consisting of different iron porphyrins, we found that the peroxynitrite/T(p-Cl)PPFeCl system showed the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

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.     

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis(trimethylsily)trifluoroacetamide (BSTFA) and N-methyl-N(trimethylsily) trifluoroacetamide (MSTFA) are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone (E1) and 17(-ethinylestradiol (EE2). In this study, three trimethylsilyl (TMS) steroid derivatives, mono-and di-trimethylsilyl EE2 and mono-trimethylsilyl E1, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz (TMSI) in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.     

江苏盐城地区地下水水化学特征及形成机理

为了查明江苏盐城地区深层地下水咸化的主要影响因素,采集了不同类型水样(河水、浅层地下水、深层地下水和海水),通过对该地区不同水体的水化学特征、离子比值以及氘氧氚同位素组成进行分析,研究了盐城地区深层地下水水化学特征的形成机理。结果表明:浅层微咸水主要是溶解地层盐分和蒸发作用形成,而滨海港镇的部分地区受到一定程度的现代海水入侵影响。深层地下水总体为淡水,水化学演化以正常的水-岩作用为主,而深层微咸水主要分布在两个地区,一是东部滨海地区的灌河口至大丰一带,二是内陆地区的大丰市及其周边一带。滨海地区的深层微咸水主要是淋滤古海相地层盐分形成,黄沙港镇部分地区则受到轻微的现代海水入侵影响,而内陆地区的深层微咸水主要是浅层咸水下渗造成的。因此,盐城东部沿海矿化度增高的区域应大力加强对地下水的保护,特别是随着全球变暖,黄海海平面有上升的趋势,东部的滨海港镇等受海水入侵影响较大的区域更应引起高度重视。     

上甸子区域背景站VOCs污染特征及其对臭氧生成贡献

大气中的挥发性有机物(volatile organic compounds,VOCs)作为对流层臭氧和二次有机气溶胶的前体物,在光化学反应和细颗粒物污染中发挥着重要的作用.本研究于2017年9月1～27日在上甸子区域背景站开展VOCs的连续在线观测,对VOCs的浓度水平,时空变化特征,化学反应活性及其对臭氧生成的贡献进行了研究,并运用特征物种比值法对初始VOCs的来源进行了分析.结果表明, 2017年9月上甸子站总VOCs平均体积分数为12.53×10~(-9),其中,烷烃是体积分数最大的组分,占到了总VOCs的65.3%,其次是烯烃和芳香烃,分别占到了总VOCs的26.7%和6.5%.从大气化学活性来看,上甸子站总的L~(·OH)(·OH损耗率)为5.2 s~(-1),其中C4～C5烯烃占到了61%,其次是C2～C3烯烃,占到了12.8%.VOCs的臭氧生成潜势平均值为36.5×10~(-9),烯烃是贡献最大的组分,占到了71.2%.烯烃中又以C4～C5烯烃的贡献最为突出,而体积分数较大的烷烃对臭氧生成的贡献却不大.对特征物种的比值研究发现,上甸子站VOCs受生物质燃烧和燃煤排放的影响较大,除此之外,交通排放源也有一定的影响,完全不受工业排放源的影响.     

北京2011年10月连续灰霾过程的特征与成因初探

选择2011年北京地区灰霾典型发生月——10月,利用在中国环境科学研究院监测的φ(SO₂)、φ(O₃)、φ(NO₂)、φ(CO)、ρ(PM₁₀)、ρ(PM_2.5)、ρ(BC)等数据,对该地区秋季典型灰霾过程特征及成因进行了研究. 在观测期间51.5%的时间内出现了灰霾,其中13.6%属于重度灰霾. 对灰霾期间污染物时间分布特征的分析表明:在灰霾过程中ρ(PM₁)、ρ(PM_2.5)、ρ(PM₁₀)及ρ(BC)较各自月均值的升幅均大于20%,ρ(PM₁)/ρ(PM_2.5)(78.7%)也明显增大.大气能见度的降低与细颗粒物及亚微米颗粒物有直接关系. 对观测期间的气象因素、气体污染物时间序列和颗粒物浓度累积特征的研究表明,10月连续灰霾过程的成因可能是该月频繁出现的鞍型场静稳天气及北京周边地区存在的基数较大的细颗粒物排放源所致.      

铸造行业挥发性有机物排放成分谱及影响

采用气袋-吸附管采样方法对京津冀地区9家铸造企业重点工序有组织和无组织排放气体进行采集,运用气相色谱-质谱联用技术（GC-MS）测定了56种VOCs组分,首次建立了铸造行业基于生产工序的VOCs源成分谱,并且结合臭氧生成潜势分析了VOCs对臭氧生成的贡献.结果表明,铸造行业VOCs特征组分主要为芳烃、卤代烃和含氧VOCs,平均占比分别为：50.9%、20.8%和12.6%.总体而言,甲苯、苯、间/对-二甲苯等芳烃,二氯甲烷、三氯乙烯等卤代烃,丙酮、乙酸乙酯、环戊酮等含氧VOCs和部分高碳烷烃是铸造行业的特征物种.铸造企业不同生产工序的VOCs特征物种与所使用溶剂、表面处理剂的成分相关.喷漆工序是铸造行业中排放浓度最高的环节,其次为造型、硅溶胶和浇注工序.不同生产工序排放VOCs的OFP在0.29~96.09 mg·m^-3之间.喷漆工序是铸造行业OFP最高的环节,其次是造型、熔炼和浇注工序;芳烃和含氧VOCs是各生产工序OFP贡献较高的组分.1,3,5-三甲苯、1,2,4-三甲苯、甲苯和间/对-二甲苯等芳烃是铸造行业OFP贡献较高的物种,总贡献比例超过60%.建议重点对喷漆工序排放VOCs采取有效治理措施;对造型、熔炼和浇注等工序排放VOCs应采取有效收集和治理措施.