大气痕量挥发性有机物碳同位素分析研究进展

对于大气痕量挥发性有机物的研究,浓度测量方法在满足科学研究的要求方面尚有欠缺,相比之下,同位素测量方法具有测量精度高、对源解析准确和测量误差小的特点且发展迅速,该方法在大气痕量挥发性有机物的研究中所起到的作用日益显著;但由于同位素测量技术对大气样品质量的要求很高,故目前该方法在大气环境科学的研究领域中还不能普及,今后随...     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Unregulated emissions from diesel engine with particulate filter using Fe-based fuel borne catalyst

The alteration and formation of toxic compounds and potential changes in the toxicity of emissions when using after-treatment technologies have gained wide attention. Volatile organic compound（VOC）, carbonyl compound and particle-phase polycyclic aromatic hydrocarbon（PAH） emissions were tested at European Steady State Cycle（ESC） to study unregulated emissions from a diesel engine with a fuel-borne catalyst and diesel particulate filter（FBC–DPF）. An Fe-based fuel-borne catalyst was used for this study. According to the results, brake specific emissions of total VOCs without and with DPF were 4.7 and4.9 mg/kWh, respectively, showing a 4.3% increase. Benzene and n-undecane emissions increased and toluene emission decreased, while other individual VOC emissions basically had no change. When retrofitted with the FBC–DPF, total carbonyl compound emission decreased 15.7%, from 25.8 to 21.8 mg/kWh. The two highest carbonyls, formaldehyde and acetaldehyde, were reduced from 20.0 and 3.7 to 16.5 and 3.3 mg/kWh respectively. The specific reactivity（SR） with DPF was reduced from 6.68 to 6.64 mg/kWh. Total particle-phase PAH emissions decreased 66.4% with DPF compared to that without DPF. However, the Benzo[a]pyrene equivalent（BaPeq） with DPF had increased from 0.016 to 0.030 mg/kWh.Fluoranthene and Pyrene had the greatest decrease, 91.1% and 88.4% respectively. The increase of two- and three-ring PAHs with DPF indicates that the fuel-borne catalyst caused some gas-phase PAHs to adsorb on particles. The results of this study expand the knowledge of the effects of using a particulate filter and a Fe-based fuel-borne catalyst on diesel engine unregulated emissions.     

Compositions and sources of organic acids in fine particles (PM2.5) over the Pearl River Delta region, south China

Organic acids as important constituents of organic aerosols not only influence the aerosols' hygroscopic property, but also enhance the formation of new particles and secondary organic aerosols. This study reported organic acids including C14–C32fatty acids, C4–C9dicarboxylic acids and aromatic acids in PM2.5collected during winter 2009 at six typical urban, suburban and rural sites in the Pearl River Delta region. Averaged concentrations of C14–C32fatty acids, aromatic acids and C4– C9 dicarboxylic acids were 157, 72.5 and 50.7 ng/m3, respectively. They totally accounted for 1.7% of measured organic carbon. C20–C32fatty acids mainly deriving from higher plant wax showed the highest concentration at the upwind rural site with more vegetation around, while C14–C18fatty acids were more abundant at urban and suburban sites, and dicarboxylic acids and aromatic acids except 1,4-phthalic acid peaked at the downwind rural site. Succinic and azelaic acid were the most abundant among C4–C9dicarboxylic acids, and 1,2-phthalic and 1,4-phthalic acid were dominant aromatic acids. Dicarboxylic acids and aromatic acids exhibited significant mutual correlations except for 1,4-phthalic acid, which was probably primarily emitted from combustion of solid wastes containing polyethylene terephthalate plastics. Spatial patterns and correlations with typical source tracers suggested that C14–C32fatty acids were mainly primary while dicarboxylic and aromatic acids were largely secondary. Principal component analysis resolved six sources including biomass burning, natural higher plant wax, two mixed anthropogenic and two secondary sources; further multiple linear regression revealed their contributions to individual organic acids. It turned out that more than 70% of C14–C18fatty acids were attributed to anthropogenic sources, about 50%–85% of the C20–C32fatty acids were attributed to natural sources, 80%–95% of dicarboxylic acids and 1,2-phthalic acid were secondary in contrast with that 81% of 1,4-phthalic acid was primary.     

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.     

Effect of a high strength chemical industry wastewater on microbial community dynamics and mesophilic methane generation

A high strength chemical industry wastewater was assessed for its impact on anaerobic microbial com- munity dynamics and consequently mesophilic methane generation. Cumulative methane production was 251 mL/g total chemical oxygen demand removed at standard temperature and pressure at the end of 30 days experimental period with a highest recorded methane percentage of 80.6% of total biogas volume. Volatile fatty acids （VFAs） analysis revealed that acetic acid was the major intermediate VFAs produced with propionic acid accumulating over the experimental period. Quantitative analysis of microbial communities in the test and control groups with quantitative real time polymerase chain reaction highlighted that in the test group, Eubacteria （96.3%） was dominant in comparison with methanogens （3.7%）. The latter were dominated by Methanomicrobiales and Methanobacteriales while in test groups increased over the experimental period, reaching a maximum on day 30. Denaturing gradient gel electrophoresis profile was performed, targeting the 16S rRNA gene of Eubacteria and Archaea, with the DNA samples extracted at 3 different time points from the test groups. A phylogenetic tree was constructed for the sequences using the neighborhood joining method. The analysis revealed that the presence of organisms resembling Syntrophomonadaceae could have contributed to increased production of acetic and propionic acid intermediates while decrease of organisms resembling Pelotomaculum sp. could have most likely contributed to accumulation of propionic acid. This study suggested that the degradation of organic components within the high strength industrial wastewater is closely linked with the activity of certain niche microbial communities within eubacteria and methanogens.     

江苏省人为源挥发性有机物排放清单

掌握VOCs排放特征是研究区域大气复合污染特征和控制策略的前提.对江苏省VOCs人为源进行系统分类,收集活动水平数据,应用国内外排放因子研究成果及江苏省行业调研结果,采用排放因子法建立了江苏省2010年分行业、分城市的人为源VOCs排放清单.结果表明:江苏省人为源VOCs排放总量约为179.20×104t,其中化石燃料燃烧源、生物质燃烧源、工业过程源、溶剂使用源、移动源、油品储运源的排放量分别占排放总量的24.1%、3.3%、22.3%、25.3%、18.4%和6.6%,工业过程源中石油炼制、有机化工、医药制造是重点行业,溶剂使用源中机械装备制造、电子设备制造是重点行业.南京、苏州、无锡、常州、南通5个苏南城市VOCs排放量明显高于苏北和苏中地区,占全省总排放量的60.0%,苏州、南京、无锡排放量居前3位.各城市化石燃料燃烧源和移动源排放所占比例均超过10.0%,其他重点行业差异显著,其中南京市为石油炼制、有机化工,苏州市为有机化工、机械涂装,无锡市为有机化工、电子设备制造.     

武汉市大气PM_(2.5)中有机酸的季节变化及其来源解析

经过预处理的样品用BSTFA/TMCS衍生化试剂衍生后,采用GC-MS技术对武汉市一年四季3个不同类型采样点中大气气溶胶中有机酸进行定量分析。共测定武汉市大气PM2.5中22种饱和脂肪酸(C11~C32)、油酸(C18∶1)、亚油酸(C18∶2)和8种二元羧酸(di-C2~di-C9)。3个采样点四季脂肪酸均呈现出明显的碳偶数优势,其中最丰富的物种均为棕榈酸(年均值ID:85.86 ng/m3,DT:56.43 ng/m3,BG:52.39 ng/m3)和硬脂酸(年均值ID:57.05 ng/m3,DT:32.68 ng/m3,BG:37.37 ng/m3)。同时通过C18∶1与C18∶0的比值用来判断武汉市不同季节、不同类型污染源气溶胶的老化程度。二元羧酸中最丰富的物种为草酸(年均值ID:254.62 ng/m3,DT:367.38 ng/m3,BG:235.19 ng/m3),其次为丁二酸(年均值ID:214.70 ng/m3,DT:312.44 ng/m3,BG:168.46 ng/m3)、丙二酸(年均值ID:103.45 ng/m3,DT:70.56 ng/m3,BG:44.48 ng/m3),二元羧酸总浓度呈现出明显的季节变化,表现为夏季>春季>秋季>冬季。通过di-C2与di-C3之比之来判断二次源对不同类型采样点气溶胶的贡献程度。主成分分析法结果显示化石燃料燃烧、机动车排放及光化学氧化、生物质燃烧、肉类烹饪是武汉市大气气溶胶中有机酸的主要来源。     

新型IC反应器在山梨醇废水处理中的工程应用

将布水装置优化后的新型内循环(IC)反应器应用于某山梨醇生产企业实际废水的二级厌氧生化处理,获得了较好的处理效果。调试阶段的结果表明:经过IC反应器的处理后,废水COD浓度由处理前的2 374~4 967 mg/L降至301~823 mg/L,COD去除率达81.4%~91.2%,COD容积负荷达8.1~13.7 kg/(m3·d);总体来说,当水力负荷增大时,COD容积负荷也相应增大;IC反应器的出水挥发性脂肪酸(VFA)基本控制在200 mg/L以下;厌氧出水再依次经过接触氧化池和絮凝沉淀池等配套工艺的处理后,COD降至80 mg/L以下,实现达标排放。     

气相色谱法测定废水中6种挥发性脂肪酸含量

挥发性脂肪酸(VFA)是厌氧消化过程的重要中间产物,在反应器运行中,出水VFA用作重要的控制指标。通过色谱条件探索将各种脂肪酸分离,同时研究了水样酸碱度,吸附等对测定的影响,进一步优化了废水中挥发性脂肪酸的测定。方法的检出限在0.99~1.77 mg/L,回收率在90.9%~102.7%之间,相对标准差(n=5)在1.3%~3.8%之间。