GC-MS法测定植物排放的萜烯类化合物

采用流动式采样与气相色谱-质谱联用法研究了意大利撒丁岛Noak’s Ark自然生态区四种主要灌木树种Juniperus phoenicea(腓尼基桧)，Pistacia lentiscus(黄连木)，Phillyrea angustifilia，Chamaerops humilis(欧洲矮棕)的排放速率和排放特征。结果表明，JuniPerus phoenicea(腓尼基桧)，Pistacia lentiscus(黄连本)，Phillyrea angustifilia主要排放萜烯类化合物，其中包括α-蒎烯、β-蒎烯、苎烯、戊花烃、莰烯、β-水芹烯、桧烯、β-香叶烯和3-蒈烯等；Chamaerops humilis(欧洲矮棕)主要排放异戊二烯。在标准条件下(温度30℃，PAR为1000μmo1．m^-2．s^-1)，四种树种的排放速率分别为0.15、2．10、0．20和1．87μg／g(DW)．h。     

长白山温带森林挥发性有机物的排放通量

2010年夏季,在长白山温带森林开展了挥发性有机物(VOC)排放通量以及气象参数、PAR的综合测量.VOC排放通量采用松弛涡度积累(RelaxedEddyAccumulation)技术在森林冠层上进行测量.初步发现长白山阔叶林主要排放α-蒎烯、β-蒎烯、莰烯、香桧烯、月桂烯、蒈烯、柠檬烯、罗勒烯、松油烯、繖花烃、萜品油烯、三环烯等.研究表明,长白山阔叶混交林VOC排放有明显的日变化——早晚较低和中午前后较高.2010年夏季,单萜烯总排放通量的平均值为0.242mg·m·h-2-1,其变化范围为0.005～1.668mg·m·h-2-1;各成分排放通量的平均值(和最大值)分别为α-蒎烯0.072(0.234)、莰烯0.028(0.356)、月桂烯0.027(0.433)、蒈烯0.023(0.173)、柠檬烯0.037(0.197)、罗勒烯0.016(0.168)、萜品油烯0.053(0.320)、繖花烃0.067(0.755)mg·m·h-2-1.研究还发现VOC排放通量与气温之间存在一定的联系.     

珠江三角洲地区天然源碳氢化合物的研究

使用封闭式采样法分析测定了珠江三角洲地区主要优势树种天然碳氢化合物的排放速率,用源调查法推算出该地区天然源碳氢化合物的排放通量,测定树种包括马尾松、湿地松、黎蒴、尾叶桉、南洋楹、大叶相思、荷木.经分析,所测树木排放的碳氢化合物主要有萜烯类和异戊二烯,其中鉴定出的萜烯有a-蒎烯,b-蒎烯,蒈烯,莰烯,桧烯,柠檬烯,罗勒烯等.同时,按9km9km的网格精度估算了珠江三角洲地区森林面积分布数据,根据测定的排放因子以及其他相关资料,首次对该地区天然源碳氢化合物的排放量进行了估算,计算出全年森林向大气中释放碳氢化合物19.610⁴t,占该地区大气中碳氢化合物排放总量的57%.     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.     

珠三角地区林木天然源碳氧化合物的排放及其对臭氧浓度的影响

使用封闭式采术法分析测定了珠江三解洲地区主要优势树种天然碳氢化合物的排放速率，用源调查法推算出该地区天然源碳氢化合物的排放通量，测定树种包括马尾松、湿地松、黎蒴、尾叶桉、南洋楹、大叶相思、荷木。经分析，所测树木排放的碳氢化合物主要有萜烯类和异戊二烯，其中鉴定出的萜烯有α-蒎烯、β-蒎烯、蒈烯、莰烯、桧烯、柠檬烯、罗勒烯等。同时，本报告按9km&;#215;9km的网格精度估算了珠三角地区森林面积分布数据，根据测定的排放因子以及其他地相关资料，首次对该地区天然源碳氢化合物的排放量进行了估算，计算出全年森林向大气中释放碳氢化合物19.6万t，占该地区大气中碳氢化合物排放总量的57%。根据二维格子空气质量模式和CBM-IV机理模拟了天然源排放碳氢化合物对研究地区臭氧产生浓度的影响。     

O3浓度升高对银杏及油松BVOCs排放的影响

以生长在沈阳市区内的银杏及油松为试材,开顶式熏气室模拟升高O3浓度(80 nmol·mol-1)和正常大气O3浓度(≈30nmol·mol-1)条件,采用GC-FID技术对银杏及油松的异戊二烯和7种单萜类物质的排放速率进行测定,探讨高浓度O3对单株银杏及油松挥发性有机物排放规律的影响.结果表明,O3浓度增高可以显著提高银杏和油松的异戊二烯排放速率(p＜0.05),及银杏△3-蒈烯的排放速率(p＜0.05),其分别达到1.96、9.71和0.09 μg·(g·h)-1,而对于其他单萜物质的排放速率,2种树木对高浓度的O3熏蒸均没有表现出显著的变化;树种不同,排放的BVOCs组成也不同,自然条件下银杏排放的BVOCs以异戊二烯为主,而油松以α-蒎烯为主;高浓度O3熏蒸下油松释放的异戊二烯达到其BVOCs组成的64.73%,增加大气O3浓度改变了树木挥发性有机物的组成比例.因此,O3浓度升高对银杏及油松BVOCs排放规律具有显著影响.     

我国夏季不同类型植被BVOCs排放观测与模拟研究

植物排放的挥发性有机物（天然源VOCs,BVOCs）对大气二次污染的形成有重要作用,为了解我国不同植被类型BVOCs排放特征,应用动态封闭式采样法和热脱附-气相色谱质谱联用（TD-GC-MS）技术对不同植被类型植物的单萜烯排放进行定量观测,应用MEGAN 2.1排放模式建立2018年夏季我国高时空分辨率BVOCs排放清单.结果表明：针叶树具有较高的单萜烯排放速率,其中以排放异松油烯、顺式-β-罗勒烯、柠檬烯、香桧烯为主;阔叶树种排放的单萜烯以α-蒎烯为主;农作物、草地、灌木中排放速率最高的化合物分别为异松油烯、反式-β-罗勒烯和柠檬烯. 2018年夏季我国BVOCs排放总量为33.6×10¹² g,异戊二烯、单萜烯、倍半萜烯和其他VOCs分别占64.13%、9.63%、2.11%和24.31%,其中阔叶树排放贡献率最高,为56.01%,灌木排放贡献率为14.16%.我国夏季BVOCs排放主要分布在东北、华东和华中地区,6种植被类型的排放受植被分布的影响呈现出不同的空间分布特征.研究显示：各类型植被单萜烯排放速率大小呈针叶树>阔叶树>草地>农作物&...     

我国夏季不同类型植被BVOCs排放观测与模拟研究

植物排放的挥发性有机物（天然源VOCs,BVOCs）对大气二次污染的形成有重要作用,为了解我国不同植被类型BVOCs排放特征,应用动态封闭式采样法和热脱附-气相色谱质谱联用（TD-GC-MS）技术对不同植被类型植物的单萜烯排放进行定量观测,应用MEGAN 2.1排放模式建立2018年夏季我国高时空分辨率BVOCs排放清单.结果表明：针叶树具有较高的单萜烯排放速率,其中以排放异松油烯、顺式-β-罗勒烯、柠檬烯、香桧烯为主;阔叶树种排放的单萜烯以α-蒎烯为主;农作物、草地、灌木中排放速率最高的化合物分别为异松油烯、反式-β-罗勒烯和柠檬烯. 2018年夏季我国BVOCs排放总量为33.6×10¹² g,异戊二烯、单萜烯、倍半萜烯和其他VOCs分别占64.13%、9.63%、2.11%和24.31%,其中阔叶树排放贡献率最高,为56.01%,灌木排放贡献率为14.16%.我国夏季BVOCs排放主要分布在东北、华东和华中地区,6种植被类型的排放受植被分布的影响呈现出不同的空间分布特征.研究显示：各类型植被单萜烯排放速率大小呈针叶树>阔叶树>草地>农作物&...     

O3浓度升高对银杏及油松BVOCs排放的影响

以生长在沈阳市区内的银杏及油松为试材,开顶式熏气室模拟升高O₃浓度（80 nmol·mol^-1）和正常大气O₃浓度（≈30 nmol·mol^-1）条件,采用GC-FID技术对银杏及油松的异戊二烯和7种单萜类物质的排放速率进行测定,探讨高浓度O₃对单株银杏及油松挥发性有机物排放规律的影响.结果表明,O₃浓度增高可以显著提高银杏和油松的异戊二烯排放速率（p＜0.05）,及银杏Δ3-蒈烯的排放速率（p＜0.05）,其分别达到1.96、 9.71和0.09 μg·(g·h)^-1,而对于其他单萜物质的排放速率,2种树木对高浓度的O₃熏蒸均没有表现出显著的变化;树种不同,排放的BVOCs组成也不同,自然条件下银杏排放的BVOCs以异戊二烯为主,而油松以α-蒎烯为主;高浓度O₃熏蒸下油松释放的异戊二烯达到其BVOCs组成的64.73%,增加大气O₃浓度改变了树木挥发性有机物的组成比例.因此,O₃浓度升高对银杏及油松BVOCs排放规律具有显著影响.     

典型树种挥发性有机物(VOCs)排放成分谱及排放特征

为研究典型树种的挥发性有机物（VOCs）排放特征,并获得基础排放速率,应用动态封闭式采样系统对毛果杨、北美枫香和马尾松的排放进行了实验室测量.利用热脱附-气相色谱-飞行质谱仪对排放样品进行定性和定量分析,包括异戊二烯、单萜烯、倍半萜烯、烷烃和烯烃,计算获得各树种VOCs排放速率及其排放谱特征.研究表明：毛果杨、北美枫香和马尾松的总VOCs排放速率分别为19.51、17.19和0.67μg/（g·h）.毛果杨的异戊二烯排放最高（18.51μg/（g·h））,占其总排放的94.86%;马尾松排放的异戊二烯仅占4.03%,单萜烯贡献最高,为49.09%;北美枫香的单萜烯排放速率最高,为0.84μg/（g·h）;3个树种排放的倍半萜烯占各自VOCs总排放的比重均较小（<1.5%）;各树种的烷烃排放强度高于倍半萜烯,部分化合物甚至高于异戊二烯和单萜烯的排放强度.反式-β-罗勒烯是毛果杨排放最多的单萜烯化合物,占其单萜烯总排放的99.84%;北美枫香排放的单萜烯主要以香桧烯和β-蒎烯为主;马尾松以α-蒎烯、香桧烯和β-蒎烯为主.石竹烯、葎草烯、δ-杜松烯和β-愈创木烯是主要的倍半萜烯物种.烷烃排放主要为C4和C5的化合物,特别是异丁烷和正丁烷;各树种排放的烯烃中,1-丁烯排放占比最高.     

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.