深圳市商业厨房排放非甲烷碳氢化合物污染特征研究

随着我国餐饮业的快速发展,餐饮源逐渐成为城市大气非甲烷碳氢（NMHCs）的主要来源之一.因此,深入研究餐饮源NMHCs的排放特征是餐饮业科学减排的重要基础.本研究采集了深圳市6类典型餐馆（西式快餐、茶餐厅、职工食堂、湘菜馆、浙菜馆和家常菜馆）排放的NMHCs,并分析了其相应的排放特征、排放因子（EF）、臭氧生成潜势（OFP）和二次有机气溶胶生成潜势（SOAp）.结果显示,6类餐馆排放NMHCs中,茶餐厅、家常菜馆和浙菜馆排放的烷烃浓度最高,而西式快餐和职工食堂排放的烯烃浓度最高,湘菜馆油烟中烷烃和烯烃浓度相近.采用灶台数及用油量作为EF的核算基准,结果显示西式快餐和职工食堂的EF较高.餐饮排放的NMCHs中乙烯、丙烯、1,3-丁二烯、间/对二甲苯、甲苯及癸烷的OFP最高,而环己烷、正庚烷、正辛烷和正癸烷则具有较高的SOA生成潜势.此外,甲苯和苯不仅具有高的O₃生成潜势,还对SOA的生成有明显贡献,是油烟中值得重点关注的污染物.     

北京市冬季灰霾期NMHCs空间分布特征研究

2005年冬季一个典型灰霾期,在北京市城区和郊区选择了6个代表性采样点(北四环、天安门、苹果园、垡头、首都机场和密云)同时采集并分析了非甲烷烃(NMHCs)和NO x样品.采样期间NMHCs污染水平从高到低依次是:北四环(1 101.29μg·m-3)>垡头(692.40μg·m-3)>天安门(653.28μg·m-3)>苹果园(370.27μg·m-3)>首都机场(350.36μg·m-3)>密云(199.97μg·m-3),采样期北京大气苯污染较严重.北京市城区采样点NMHCs/NO x(2.1~6.3)指示采样期北京市大气臭氧峰值浓度受挥发性有机污染物(VOCs)控制;丙烯等效浓度和臭氧生成潜势均显示,NMHCs的反应性从高到低的次序为:北四环>垡头>天安门>苹果园>首都机场>密云.苯/甲苯比值(0.52~0.76)表明北京冬季除机动车污染外,还存在煤燃烧等其它排放源的影响;异戊烯的区域变化特征表明,北京市冬季异戊烯的人为源有所增加而植物排放减少;丙烷和丁烷浓度的区域变化表明,北京存在城区液化石油气排放.     

北京市典型餐饮企业VOCs排放特征研究

选取北京市餐饮业中的烧烤、中式快餐、西式快餐、川菜和浙菜这5种典型菜系,借鉴EPA相关方法,对典型餐饮企业排放油烟气中的挥发性有机物(volatile organic compounds,VOCs)进行了采样分析,研究了各菜系排放VOCs的浓度水平和组分构成.结果表明按基准风量折算后,烧烤的VOCs排放浓度水平最高,达到12.22 mg·m-3,中、西式快餐、川菜和浙菜为4mg·m-3左右.5种典型菜系中,烧烤的VOCs排放组分构成与非烧烤类菜系具有明显区别,主要组分有丙烯、1-丁烯和正丁烷等.非烧烤菜系的主要组分是乙醇,其中西式快餐排放的醛酮类有机物比重较高.通过分析各菜系的单个灶头基准风量浓度可知,同等规模的烧烤类餐饮企业对大气环境质量的影响高于非烧烤类餐饮企业,应是重点管控对象.     

沧州市春季NMHCs空间分布特征

2015年春季在沧州市城区、郊区和潜在污染源附近选择了15个采样点进行同期采样.研究表明沧州市NMHCs总体上市区高于近郊及远郊区县;市区以高新区NMHCs浓度最高;郊县采样点除河间市略高外,其它采样点的浓度均明显低于市区浓度;机动车的道路排放是沧州市NMHCs的重要来源之一;沧州大化和沧州炼油在停产期间未对市区NMHCs产生明显影响;大港油田采油三厂采取了较完善的油气回收措施,未对市区NMHCs产生明显影响;平均来看,沧州市NMHCs中烷烃占65%,烯烃占16%,芳烃占19%;臭氧生成潜势(ozone formation potential,OFPs)主要来源于二甲苯(19%)、乙烯(14%)、甲苯(11%)、丙烯(5%)、异戊烷(5%)和异戊烯(5%)等;气溶胶生成潜势(formation potential of secondary organic aerosol,SOAFPs)主要来源于甲苯(28%)、蒎烯(28%)、二甲苯(16%)、乙苯(9%)和苯(9%)等.     

贡嘎山本底站大气中VOCs的研究

为研究中国西南地区大气中挥发性有机物（VOCs）区域性本底浓度和变化特征,利用不锈钢钢瓶采样、三步冷冻浓缩进样-气相色谱/质谱联用技术（GC/MS）,测定了贡嘎山大气本底站大气中的VOCs组成、浓度及季节变化,并利用PCA（principal component analysis）受体模型对大气中VOCs来源进行了初步分析.结果表明,贡嘎山地区TVOCs和NMHCs的年平均浓度（体积分数）分别为9.40×10-9±4.55×10-9和7.73×10-9±4.43×10-9,且两者的最高和最低浓度都出现在同一次采样.在TVOCs中,芳香烃所占比例最大,为37.3%,烷烃（30.0%）和卤代烃（19.8%）次之,烯烃的比例最低,为12.9%.通过PCA受体模型分析发现,贡嘎山地区大气中VOCs的主要来源可以归结为交通源、生物源和燃烧源.贡嘎山地区大气中TVOCs呈现明显的季节变化,变化特征为秋季〉冬季〉春季〉夏季,秋季和冬季大气中的TVOCs浓度分别极显著（P〈0.01）和显著地高于夏季（P〈0.05）,由于光化学性质的差异,4种类型的VOCs季节变化也呈现出不同的特征.异戊二烯是生物源的重要排放物,其排放速率与大气温度呈指数相关,在20℃以上随着温度的升高排放速率明显增强,其最高和最低值分别出现在夏季的下午和冬季的上午.与其他地区的研究结果相比,贡嘎山地区TVOCs的排放处于中等水平,有着明显的本底站排放特征.     

某沿海城市典型行业NMHCs排放特征及对二次污染物生成潜势研究

采用SUMMA罐采样、GC-FID技术分析了威海市渔具、造船和橡胶等6种典型行业代表企业废气中59种非甲烷碳氢化合物（NMHCs）组分及占比,并计算了各行业NMHCs的臭氧（O₃）和二次有机气溶胶（SOA）生成潜势,提出了NMHCs治理建议.结果表明,涉及溶剂使用的渔具、造船、汽车制造业喷涂工序的NMHCs组分以芳香烃为主,橡胶和化工行业以芳香烃和烷烃为主,光纤制造业以烷烃为主.不同行业喷涂废气特征成分存在差异,渔具喷涂废气主要组分为甲苯和邻二甲苯,造船喷涂废气主要组分为邻二甲苯、乙苯和间/对二甲苯,汽车制造喷漆废气主要组分为二乙苯、1,2,4-三甲苯和1,2,3-三甲苯,甲基环己烷和甲苯分别是橡胶和化工行业的主要组分,异丁烷和异戊烷是光纤行业的主要组分.研究结果可为构建当地典型行业NMHCs成分谱、精准制定控制O₃和PM_2.5污染的NMHCs优先减排行业提供基础和参考依据.     

佛山市冬夏季非甲烷烃污染特征研究

2014年冬季和2015年夏季在佛山市采集了30个非甲烷烃(NMHCs)的样品,定量分析了多种化合物.结果表明,采样期间佛山市冬季和夏季NMHCS的浓度分别为122.30μg·m~(-3)和56.22μg·m~(-3).其中冬季和夏季NMHCs中浓度最高的5个物种由大到小依次为:甲苯(25.12μg·m~(-3))、间/对-二甲苯(13.76μg·m~(-3))、丙烷(9.17μg·m~(-3))、乙苯(7.25μg·m~(-3))、乙烯(6.77μg·m~(-3))和甲苯(6.18μg·m~(-3))、间/对-二甲苯(5.21μg·m~(-3))、邻-二甲苯(4.15μg·m~(-3))、β-蒎烯(3.75μg·m~(-3))、丙烷(3.29μg·m~(-3)).相比2008年,NMHCs有大幅度下降.冬季芳烃、烷烃、烯烃和炔烃所占比例分别为51.20%、34.70%、10.04%和4.05%;夏季芳烃、烷烃、烯烃和炔烃所占比例分别为43.93%、33.99%、19.20%和2.88%.因为NMHCs/NOx的冬、夏季值分别为0.90和1.88,表明采样期间佛山市大气臭氧峰值浓度都是受NMHCs控制,还应继续加强NMHCs的控制.佛山市NMHCs冬季和夏季的丙烯等效浓度和臭氧生成潜势分别为45.09μg·m~(-3)和40.64μg·m~(-3)、392.77μg·m~(-3)和207.77μg·m~(-3).间/对-二甲苯、甲苯和间/对-二甲苯、异戊二烯分别对冬季和夏季的臭氧生成潜势起到很重要的贡献.采样期间佛山市冬季和夏季的苯/甲苯的值为0.15和0.20,表明佛山市冬夏季NMHCs的主要来源是工业过程.相对2008年,本研究中异戊烷不属于佛山市NMHCs中浓度最高的5种污染物,说明佛山市在防止汽油挥发对环境造成影响方面的措施取得了明显成效.     

北京餐饮源排放细粒子理化特征及其对有机颗粒物的贡献

调研了北京餐饮业发展现状,通过在线监测、采样分析等手段研究北京4家不同烹调方式的餐馆所排放颗粒物的质量浓度、粒径分布、形貌特征、化学组分,并初步估算餐饮源排放细粒子对北京细粒子中颗粒有机物的贡献.结果表明,餐馆的原料、烹饪过程、油烟去除装置以及客流量都会影响餐馆所排放颗粒物的物理、化学性质.样本餐馆营业期间排放颗粒物PM_{2 .5}质量浓度是当日环境大气PM_{2 .5}质量浓度的8～35倍,PM_{1 .0}在PM_{2 .5}的质量浓度中约占50%～85%.餐饮源排放颗粒物多以固态和液态颗粒物形貌存在,化学组分质量百分数由多到少依次是有机物、无机离子和元素碳,分别占到PM_{2 .5}质量浓度的70%左右、5%～11%和小于2%.初步估计结果表明,北京餐饮源排放细粒子对有机颗粒物的贡献和交通源的排放相当,成为北京细粒子有机颗粒物的主要来源之一.认识餐饮源排放颗粒物的理化性质,可以为改善北京空气质量和保证居民身体健康提供数据支持.     

北京市春季交通干道移动源非甲烷总烃的在线跟踪观测与特征分析

机动车排放(Vehicular Emission,VE)是地面非甲烷烃(Non-methane hydrocarbon,NMHCs)的重要人为源之一.为获得北京市交通主干道NMHCs的实际排放情况,本研究以自主研发的吸附/热解吸前处理-单光子/化学复合软电离源飞行时间质谱(SPI/CI-TOFMS)为检测手段,于2018年3月14日在北京四环、五环主干道,对C_2～C_(10)挥发性有机物进行了车载在线跟踪观测.结果表明,C_2、C_3高挥发性物质浓度较高,其次是苯系物和丁烷;从空间分布来看,NMHCs浓度在离市中心较近的四环主干道相对较高,且车流量较大的南五环公路和西四环处NMHCs污染也较为严重;从NMHCs的结构组成来看,烷烃(63%、52%)占比最多,芳香烃(23%、32%)次之,烯烃(14%、16%)最少;对NMHCs特征物质之间的线性关系和比值关系进行分析,确定机动车排放对此次观测中NMHCs的生成贡献较大;通过计算各物种臭氧生成潜势(OFP),评估出C_3、C_4烯烃类物质和苯系物为北京四、五环地区优先控制物种.     

京津地区大气中非甲烷烃(NMHCs)质量浓度水平和反应活性研究

2006年8月15日—9月15日同时在北京和天津对大气中的非甲烷烃（NMHCs）进行了同步观测,利用最大增量反应活性（MIR）计算了两地NMHCs的臭氧生成潜势以估计其对臭氧生成的影响. 结果表明,北京大气中ρ（NMHCs）平均值比天津高78.0 　μg/m3.用上午的ρ（NMHCs）计算了京津地区臭氧生成潜势,分别为1 470 和814 　μg/m3,其中苯系物对臭氧生成的影响最大,分别占总臭氧生成潜势的75%和73%,其次是烯烃（占13%和11%）和烷烃（占12%和16%）. 比较两地ρ（NMHCs）和NMHCs的反应活性可知,北京地区大气中NMHCs的组成比天津的稳定,且其反应活性强于天津. 结合臭氧浓度发现,北京地区大气的氧化能力比天津强.      

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.