大气甲醛稳定碳同位素分析方法研究

利用气相色谱/燃烧/同位素比值质谱(GC/C/IRMS)技术,采用2,4-二硝基苯肼(DNPH)衍生化,初步研究了单体化合物稳定碳同位素方法研究大气甲醛来源问题.根据不同同位素组成的甲醛与DNPH反应,模拟大气采样,具体讨论了甲醛与DNPH衍生化过程的同位素效应及分析方法的重现性与精确度.结果表明,每个甲醛2,4-二硝基苯腙样品分析的最大标准偏差为0.3‰;不同同位素组成的甲醛衍生化产物甲醛2,4-二硝基苯腙与理论值的平均偏差为0.24‰±0.14‰(从0.03‰到0.35‰),小于仪器分析误差0.5‰,该衍生化过程不存在同位素分馏.采用该方法对酒店大厅内外大气甲醛碳同位素组成进行了初步研究,结果表明不同来源的甲醛同位素组成具有显著差异,可以为大气甲醛的来源分析提供非常有效的信息.     

用2,4-二硝基苯肼吸附管涂渍方法测定醛酮类化合物

通过实验确定用2,4-二硝基苯肼吸附管的涂渍方法测定醛酮类化合物;比较了C18柱、佛罗里硅藻土柱及硅胶柱对DNPH的涂渍效率和乙腈对醛酮腙的洗脱效率。结果表明：硅胶柱对DNPH涂渍效率及对醛酮腙的洗脱效率高,是制备2,4-二硝基苯肼吸附柱的最佳填充柱。     

柴油/甲醇组合燃烧尾气中甲醛的检测

利用气相色谱分析技术检测了柴油/甲醇组合燃烧(DMCC)尾气中的非常规排放物--甲醛.通过对不同采样方法和采样条件的比较,设计了采样系统,确定了用吸收液吸收的方法采集尾气中的甲醛.利用尾气中的甲醛与2,4-二硝基苯肼(DNPH)酸性饱和溶液反应生成甲醛腙的特性,通过检测甲醛腙的浓度来检测尾气中的甲醛含量.应用本方法检测一台采用DMCC燃烧模式的发动机尾气,结果表明,该方法可准确测量其尾气中的甲醛浓度.检测数据显示,当发动机运行DMCC燃烧模式时,相同转速下同一负荷时喷醇量越大,尾气中甲醛浓度越多;在相同的甲醇对柴油的替代率条件下,负荷越低尾气中甲醛浓度越高.     

螺旋管-高效液相色谱法在线检测甲醛的研究

研究建立了一种大气环境中气态甲醛在线采样分析系统。该系统通过螺旋管液相吸收和高效液相色谱衍生法,实现了对大气气态甲醛的在线分析。大气中的气态甲醛经过在螺旋管内经液相吸收后,与2,4-二硝基苯肼(DNPH)吸收液在加热条件下充分反应,衍生产物通过高效液相色谱(HPLC)分离后进入紫外检测器(UV)进行检测。采样和分析系统通过DasyLab实现自动运行。该方法可实现在线连续检测,时间分辨率为60min,气态甲醛的检测限可达0.10μg/L。将该方法与乙酰丙酮分光光度法(GB/T15516-1995)进行比对实验,两种方法的检测结果线性相关系数R2=0.9815。采用该方法于2007年10月在北京市进行实际采样分析,得到甲醛浓度平均浓度为4.82μg/L,并呈现明显的日变化,夜间最低,中午及午后较高。     

气相色谱——质谱法测定水发海参中的甲醛

用气相色谱-质谱联机,使用特征离子定量法(GC-MS-SIM)测定水发海参中甲醛。摸索了样品提取方法,考察了样品提取时间及衍生条件等因素的影响,确定最佳提取条件为超声波振荡20min,衍生条件为2g/L的2,4-二硝基苯肼(DNPH)作衍生剂,避光反应6h。采用特征离子m/z63和m/z210进行GC-MS检测。结果表明:本法可消除复杂基体的干扰,简便快速,准确可靠,灵敏度高,回收率在86.4%～97.3%之间,检出限为0.1mg/kg。     

上海市大气PM2.5中羰基化合物的研究

利用2,4-二硝基苯肼(DNPH)作为衍生化试剂,高效液相色谱/紫外检测法(HPLC/UV)定量检测上海市大气PM2.5中单羰基和二羰基化合物,共检测出5种单羰基化合物和2种二羰基化合物(乙二醛和甲基乙二醛).单羰基化合物中浓度最高的是甲醛和乙醛,其年平均浓度分别为(1579.47±672.81)ng/m3和(572.02±470.58)ng/m3;二羰基化合物乙二醛和甲基乙二醛的年平均浓度分别为(63.74±54.27)ng/m3和(97.28±39.62)ng/m3.研究发现上海市大气PM2.5中一些羰基化合物具有明显的日变化和季节变化规律:日变化表现为早晚高峰,而季节性变化单羰基化合物是冬天>夏天,二羰基化合物则是夏季>冬季.此外,PM2.5中羰基化合物的浓度还与温度、湿度、质量浓度具有一定的关系.     

环境空气中醛酮类化合物的测定

样品中的醛酮类化合物与2,4-二硝基苯肼(DNPH)反应生成稳定的腙类衍生物,乙腈洗脱,高效液相色谱分析。丙烯醛和丙酮能较好的分离,精密度、准确度、灵敏度都很高,适合室内、室外及车内空气样品的测定。     

土壤中多环芳烃的稳定碳同位素特征及其对污染源示踪意义

分析了天津市不同功能区土壤中多环芳烃的稳定碳同位素组成特征、土壤中菲、甲基菲、荧葸和芘的δ^13C值范围分别为-29．5‰～-23．2‰、-39．8‰～-23．4‰、-27．2％～-23．6‰和-28．1‰～-22．6‰,不同功能区稳定碳同位素组成的差异反映了PAHs来源的差异．稳定碳同位素组成特征表明,在研究区内,化石燃料燃烧产物的干-湿沉降是土壤PAHs的最主要来源之一,其它可能的来源有污水携带的油污、农作物茎杆及薪柴不完全燃烧产物等．就具体地点而言,土壤PAHs以二元混合输入为主,据此,运用稳定碳同位素组成的二元复合数值模型对不同来源PAHs的相对贡献率进行了估算     

西安周边河流溶解无机碳浓度及同位素组成初探

通过分析西安周边4条主要河流(浐河、灞河、涝河、黑河)的溶解无机碳(DIC)浓度和碳同位素组成,初步探讨了西安周边主要河流溶解无机碳(DIC)的浓度变化及碳源.结果表明西安周边主要河流DIC浓度的变化范围为0.34～5.66mmol.L-1,平均为1.23 mmol.L-1,自源头到下游,DIC浓度呈现升高趋势.4条河流δ13CDIC值的变化范围在-13.3‰～-7.2‰之间,平均值约为-10.1‰,4条河流整体表现为δ13CDIC值在源头偏负(平均值约为-12.6‰),中下游农耕区δ13CDIC值偏正(平均值约为-9.4‰),靠近入渭河河口的城市区δ13CDIC表现为偏负值(平均值为-10.5‰).DIC浓度与河流DIC碳同位素组成的变化规律揭示了河流溶解无机碳来源的变化,土壤CO2的输入可能是源头水体DIC的主要来源;中下游农耕区河水δ13CDIC值偏正是由于农业区农作物存在C4植被(如:玉米),使得农业区土壤CO2和土壤碳酸盐具有偏正的碳同位素组成,进而导致河流水体具有偏正的δ13CDIC值;靠近河口处具有较低δ13C值,污水的大量输入可能导致河水δ13CDIC表现为偏负.结果表明西安周边河流溶解无机碳浓度和同位素组成变化大致指示了河流从源头到下游过程中DIC的可能来源,可为黄土高原小流域河流无机碳来源示踪研究提供参考.     

南京地区大气PM2.5潜在污染源硫碳同位素组成特征

基于南京地区大气PM_(2.5)潜在污染源,采用EA-IRMS技术分别测定了样品中硫碳同位素组成,并分析不同污染源之间的关联性.结果表明,南京地区煤炭烟灰δ~(34)S值范围为1.8‰~3.7‰,δ~(13)C值范围为-25.50‰~-23.57‰;机动车尾气δ~(34)S值范围为4.6‰~9.7‰,δ~(13)C值范围为-26.32‰~-23.57‰;生物质烟灰δ~(34)S值范围为5.2‰~9.9‰,δ~(13)C值范围为-19.30‰~-30.42‰;扬尘δ~(13)C值为-13.45‰.南京地区煤炭烟灰颗粒物的硫同位素较轻,扬尘的碳同位素较重.对比国内外不同污染源δ~(34)S与δ~(13)C值,南京地区大气PM_(2.5)中的潜在污染源的δ~(34)S与δ~(13)C具有明显的区域性.因此,潜在污染源的δ~(34)S、δ~(13)C值可为南京地区大气PM_(2.5)的源解析提供同位素组成源谱支持.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

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.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

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.