餐馆排放油烟气中羰基化合物浓度及分布特征

通过对餐馆排放的油烟烟气中羰基化合物的研究,发现在20种目标化合物中检测到18种,其中乙醛的浓度最高,其次是甲醛和丙酮。从分布上来看,直链的羰基化合物的浓度远远高于支链和环状的羰基化合物的浓度。因为无论是烹调油或者食物加热时都可以产生大量的羰基化合物。     

生物质锅炉羰基化合物排放特征分析

为了探讨生物质锅炉羰基化合物的排放特征,采用气袋采样-PFPH衍生-GC/MS分析的方法测量了6台生物质锅炉排放烟气中的21种羰基化合物.结果表明,这些生物质锅炉的烟气中羰基化合物排放特征存在明显差异,总体而言,己醛和丙醛浓度在测定的21种目标化合物中比重最高,分别占总量的29%~47%和19%~31%,其次为甲醛和丙酮,乙醛和壬醛.通过羰基化合物排放量与消耗的燃料质量比值估算了排放因子,6台锅炉羰基化合物排放因子介于3.06~18.29mg/kg之间,平均为9.45±6.05mg/kg.采用最大增量反应活性法（MIR）评价了羰基化合物的化学反应活性及臭氧生成潜势（OFP）,平均总的臭氧生成潜势（以O₃计）为5.97gO₃/gVOCs;己醛、丙醛、甲醛对OFP的贡献尤为明显,丙酮虽然占有较高的质量浓度,但对OFP的贡献较低.     

上海市大气羰基化合物水平研究

建立乙腈-水-四氢呋喃三元梯度洗脱方法,利用HPLC-UV分离定量22种羰基化合物,并成功地分离了丙酮和丙烯醛.选取了2个采样点(工业区和商业区)对上海市大气中的羰基化合物进行了研究.结果表明,甲醛、乙醛、丙酮和2-丁酮(C1-C4羰基化合物)是上海市大气浓度较高的化合物,它们分别占羰基化合物总量的78.95%(工业区)和77.63%(商业区).在工业区,甲醛、乙醛、丙酮和2-丁酮的平均浓度分别为10.36、15.32、9.95和4.56μg/m3;在商业区,它们的平均浓度分别为10.00、10.04、7.80和2.81μg/m3.工业区的C1-C4羰基化合物平均水平要高于商业区.羰基化合物总量亦是工业区(53.64μg/m3)高于商业区(41.96μg/m3).羰基化合物的昼夜变化在工业区和商业区也比较一致,均是早高峰和晚上这2个时段的浓度很高,而其它时段较低.     

青岛市大气中醛酮类化合物的分析及浓度变化

自1997年12月～1998年7月,在覆盖整个青岛市区布设了6个采样点,用2,4-二硝基苯肼HPLC法测定了11种醛酮类羰基化合物在不同季节、不同时间的浓度.青岛市大气中甲醛、乙醛、丙酮及醛酮总量的平均浓度冬季分别为3.64,4.18,2.50,13.9mg/m3,夏季分别为9.95, 7.00,5.75,26.9mg/m3,夏季的浓度明显高于冬季,青岛市大气中甲醛占总羰基化合物的26.2%～37%,乙醛、丙酮分别占总羰基化合物的26.0%～30.1%和18.0%～21.4%.甲醛+乙醛+丙酮之和占总羰基化合物的74.3%～84.3%,甲醛和乙醛在冬、夏两季的相关性较差(R2=0.43),而乙醛和丙酮在夏季具有较强的相关性(R2=0.7399).     

不同燃料类型锅炉羰基化合物的排放特征

为探究不同燃料类型锅炉羰基化合物排放特征，选取以煤、生物质、石油焦和天然气为燃料的14台工业锅炉和2台燃煤电站锅炉作为研究对象，采用气袋-PFPH衍生-GC/MS方法采集和分析烟气中的21种羰基化合物.结果表明，不同燃料类型锅炉烟气中羰基化合物呈现明显差异（One-way ANOVA，F=4.458，P=0.028<0.05），其中羰基化合物质量浓度（9%基准氧量）排序是石油焦 > 电站锅炉 > 煤 > 天然气 > 生物质，分别为（6306.25±1335.35），（5745.96±2864.62），（4784.85±1698.20），（3589.51±1534.676），（1341.18±616.46）μg/m³.不同燃料类型的锅炉烟气中羰基化合物组分特征有明显差异性，但甲醛、乙醛、丙酮和丙醛等低分子量的羰基化合物均占比较大，燃石油焦、燃煤电站、燃煤、燃天然气和燃生物质锅炉中低碳羰基化合物总占比分别达到87.56%，91.36%，92.94%，78.70%和45.84%.最后，采用最大增量反应活性（MIR）和OH消耗速率评价烟气中羰基化合物物种的化学反应活性，结果表明，甲醛、丙醛、乙醛等低碳羰基化合物为关键活性物种.     

佛山市冬夏季羰基化合物污染特征

2014年冬季和2015年夏季在佛山市采集了36个羰基化合物的样品,检测出了其中14种化合物并进行了定量分析.结果表明,佛山市冬夏季羰基化合物污染严重,采样期间冬季和夏季平均浓度分别为36.15μg/m~3±3.45μg/m~3和33.25μg/m~3±4.25μg/m~3.冬季三种主要污染物为:甲醛(8.54μg/m~3,23.65%)丙酮(8.20μg/m~3,22.69%)乙醛(5.79μg/m~3,16.03%);夏季主要污染物为:甲醛(14.63μg/m~3,44.01%)乙醛(6.22μg/m~3,18.70%)丙酮(5.23μg/m~3,15.73%);冬季羰基化合物日变化不大,上午与晚上浓度相近,下午浓度略高于上午和晚上;夏季羰基化合物日变化较大,上午与晚上浓度相近,下午浓度明显高于上午和晚上;佛山市冬季C1/C2和C2/C3的浓度比分别为1.56和14.35,夏季C1/C2和C2/C3的浓度比分别为2.63和15.56.佛山大气羰基化合物主要来源于人类活动.冬夏季采样期间甲醛、乙醛、丙酮和丙醛之间具有较好的相关性,可以表明这些羰基化合物可能有相似的来源.     

基于PMF和源示踪物比例法的大气羰基化合物来源解析:以南京市观测为例

大气羰基化合物在对流层大气化学中发挥着重要作用,其受到直接排放和二次生成的共同影响,来源研究面临挑战.本研究基于2017年3月在南京市开展的羰基化合物观测,分别利用源示踪物比例法（STR）和正交矩阵因子模型（PMF）对羰基化合物进行来源解析,并将二者结果进行比较,以探讨导致来源解析不确定性的因素.本研究共检测出11种羰基化合物,总体积分数范围为2.57×10^-9~22.83×10^-9,其中甲醛、乙醛和丙酮是主要组分,分别占羰基化合物总平均体积分数的36.8%、21.6%和18.5%.通过比较乙炔和甲苯作为示踪物时,以及第5和第10百分数作为背景体积分数时解析结果的差异,探讨了示踪物选取和背景体积分数对STR解析结果的影响.PMF解析出了交通排放源、石化化工源、涂料与溶剂使用源、二次生成及背景源和化工源这5类源.二次生成及背景源是羰基化合物最主要的来源,对甲醛、乙醛和丙酮的贡献分别为56.4%、48.2%和58.3%.STR和PMF解析结果的比较发现,STR法依赖于示踪物的选取,在VOCs来源复杂地区应用时需要进行严格评估.     

广州医院低分子量羰基化合物研究

2004年1月2日-3月20日对广州市区4家医院室内外的低分子量羰基化合物进行了检测.实验方法是应用羰基化合物和2,4-二硝基苯肼(DNPH)迅速反应生成衍生物,产物在高效液相色谱上进行检测;每家医院连续采样5 d.结果表明:广州医院丙酮的质量浓度最高,其次是乙醛和甲醛,除甲醛外,室内羰基化合物的质量浓度稍高于室外;羰基化合物之间的相关性不好,可能是它们的来源比较复杂,如车辆排放、建筑装饰材料、医用试剂等,其中广泛使用酒精消毒可能是医院乙醛质量浓度偏高的原因.对医院甲醛、乙醛在人体内的暴露水平做了讨论,与其他类似场所相比,医院的暴露风险相对较小.      

北京及周边地区大气羰基化合物的时空分布特征初探

利用2,4-二硝基苯肼（DNPH）/HPLC方法,于2010年6月24日、7月22日、8月24日、9月14日（夏季）和2011年1月13日（冬季）,在北京及周边地区38个采样点组织5次同步观测,测定了大气中23种羰基化合物的浓度水平.观测结果表明,北京市各类站点夏季和冬季的总羰基化合物体积分数分别为（16.38±6.03）×10-9,（8.50±5.27）×10-9;周边城市夏季和冬季的体积分数分别为（13.19±5.71）×10-9,（13.05±2.44）×10-9.区域大气中最主要的羰基化合物是甲醛、乙醛和丙酮,三者约占总羰基化合物浓度的78%～91%.夏季羰基化合物的浓度水平明显高于冬季,并且上午09：00～12：00时段的浓度高于下午13：00～16：00时段的浓度.在空间分布上,北京市夏季羰基化合物的高值区主要集中在交通密集的主城区,而冬季受西北风影响呈现由西北向东南递增的趋势.夏季,机动车尾气对大气羰基化合物有显著的一次和二次贡献,同时在不利的气象条件影响下,造成城市地区羰基化合物的污染现象.冬季,大气羰基化合物以一次排放为主,燃煤和机动车可能是主要的污染源.     

北京市城区大气羰基化合物的季节变化

2006年8月19～22日（夏季）、 10月24～30日（秋季）和2007年1月20～23日（冬季）,利用被动式扩散采样器(DSD-DNPH)对北京市城区5个地点C₁～C₁₀羰基化合物进行了采样.通过高效液相色谱(high performance liquid chromatography, HPLC)分析, 20种羰基化合物被检测出,在夏季、秋季和冬季其总浓度分别为(89.1±23.6)、(85.2±17.5)和(40.0±9.8) μg/m³.其中,甲醛、乙醛和丙酮是浓度最高的3种羰基化合物,它们的浓度从冬季的(7.1±2.1)、(10.3±3.1)、(9.5±1.8) μg/m³增长到夏季的(15.3±9.2)、(12.9±4.9)、(13.3±3.5) μg/m³和秋季的(13.2±4.0)、(13±4.4)、(15.3±4.0) μg/m³.定性分析表明,羰基化合物的污染来源,冬季主要是机动车污染,而夏季和秋季则是来自光化学反应、机动车和餐馆油烟的综合污染.此外,在风速较大、扩散条件较好的条件下,甲醛、乙醛和丙酮等主要污染物浓度明显降低,表明扩散条件对羰基化合物浓度的影响较明显.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

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.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.