成都市大气环境VOCs污染特征及其健康风险评价

于2012年9月,在成都市分别选取代表城市大气环境和路边大气环境的两个采样点对大气中挥发性有机物(VOCs)进行采样,对不同大气环境中VOCs的浓度水平与变化特征、组成和反应活性进行分析,并对其中的芳香烃化合物进行健康风险评价.结果表明,成都市城市大气环境和路边大气环境中TVOCs的平均质量浓度分别为(108.57±52.43)μg·m~(-3)和(132.61±49.31)μg·m~(-3),不同大气环境中各烃类物质浓度均呈现出烷烃芳香烃烯烃炔烃的趋势;城市和路边大气环境中芳香烃和烯烃对臭氧生成潜势(OFP)贡献较大,关键物种均为间/对二甲苯、甲苯、乙烯、邻二甲苯和丙烯;不同大气环境中的苯、甲苯、乙苯和二甲苯(BTEX)对人体的非致癌风险和危害指数均小于1,对暴露人群不存在非致癌风险;致癌物质苯对人体的致癌风险高于安全阈值1.00E-06,对暴露人群可能存在致癌风险.     

上海某石化园区周边区域VOCs污染特征及健康风险

为了解石化周边区域大气VOCs污染特征,使用在线GC-FID监测仪于2017年10月对上海市某近石化周边居民区大气VOCs进行了为期1个月的连续观测;通过最大增量反应活性(MIR)法估算了VOCs对臭氧(O_3)生成的贡献,并进行了健康风险研究.结果表明,观测期间VOCs总质量浓度的范围16. 4～1 947. 8μg·m~(-3),平均浓度为40. 7μg·m~(-3);烷烃、烯/炔烃和芳香烃的平均占比分别为66. 2%、25. 9%和7. 9%. VOCs总浓度日变化特征呈现单峰型变化,峰值浓度为127. 9μg·m~(-3)(07:00). VOCs总浓度的平均臭氧生成潜势(OFP)为249. 7μg·m~(-3),烯、炔烃对OFP的贡献最高,达到153. 4μg·m~(-3);丙烯、反-2-丁烯、乙烯是关键的活性组分.己烷、苯、甲苯、乙苯、邻-二甲苯和间/对-二甲苯的健康风险较小.     

合肥市典型交通干道大气苯系物的特征分析

为研究合肥市交通干道大气苯系物污染状况,采用自主研制的差分吸收光谱(DOAS)系统,于2016年3月期间对合肥市交通主干道大气苯系物(苯、甲苯、间二甲苯和邻二甲苯)以及常规污染物NO_2、SO_2等进行了连续观测.观测结果显示,观测期间苯、甲苯、间二甲苯和邻二甲苯的平均浓度分别为:21.7、63.6、33.9和98.7μg·m~(-3).与国内外其它城市比较显示,合肥市交通干道大气苯和甲苯的污染处于中等水平,二甲苯的污染较为严重.结合观测期的间风速风向、T/B特征比值以及与CO等污染物的相关性,对上述苯系物来源进行了分析,结果显示观测期间T/B值为0.8~4.5,苯、甲苯与CO的相关性系数R分别为0.55和0.34.表明机动车尾气排放是观测区域苯和甲苯的主要排放源之一,同时也受到周边工业园区排放的影响,二甲苯的主要排放源为观测地点北偏东方向的涂料行业工业园区.苯和甲苯的夜间高浓度峰值分析结果表明,夜间的高浓度苯和甲苯可能主要来源于观测地点周边工业园区的排放.观测区域苯系物的臭氧生成潜势(OFP)表现为邻二甲苯间二甲苯甲苯苯,其中二甲苯的OFP占总OFP的85%,表明周边工业园区的排放对该地区臭氧生成的贡献较大.     

上海市文教区大气中苯系物冬季污染特征

2004年冬天对上海市文教区大气中的苯系物(BTEX-苯,甲苯,乙苯和二甲苯)浓度进行了监测.结果表明,上海市文教区冬季苯、甲苯、乙苯、对问二甲苯、邻二甲苯的平均浓度分别为13.23 μg/m3,43.66 μ g/m3,13.50μg/m3,16.49 μ g/m3,5.52μg/m3,高于国内外相似功能区的苯系物浓度,与国外大城市交通干道附近的浓度相近.所测苯系物中,甲苯的含量最高,达47.3%.白天苯系物浓度高于夜间.甲苯、乙苯、二甲苯相互间具有较好的相关性,但与苯的相关性不显著,说明苯的来源不同与其他苯系物.     

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.     

合肥市典型区域夏季苯系物的浓度变化研究

通过对长江西路苯系物浓度数据的分析,得到了合肥市交通干道苯系物浓度的时间变化规律。结果表明,长江西路苯系物中苯、甲苯、乙苯和二甲苯、甲基乙苯和三甲苯的月均浓度分别是3. 31μg/m~3、9. 93μg/m~3、11. 56μg/m~3和5. 75μg/m~3。工作日苯系物浓度比周末要高,但苯系物的浓度整体较低,其污染情况与国内外其他城市相比,处于相对良好的水平。CO与苯系物都具有显著的相关性,并且苯系物间各物质也具有显著的相关性,说明苯系物都主要来自交通源。B/T的值为0. 33,说明除了受交通源的影响外还有可能受乙醇汽油、涂料的使用和溶剂的挥发等的影响。     

深圳市秋季VOCs空间分布特征与关键减排物种

于2019年11月6~9日开展了深圳全市11点位105种VOCs组分的离线观测,评估了深圳市不同区域的臭氧生成潜势（OFP）和二次有机气溶胶生成潜势（SOAFP）的空间分布特征.结果表明：观测期间深圳市总VOCs,总OFP和总SOAFP分别为44.3×10^-9,272.6和1.1μg/m³.从空间分布来看,VOCs,OFP与SOAFP具有相似特征,均呈现西高东低,北高南低的趋势,西北部工业区存在较多工业排放源,是削减VOCs的关键区域.从物种组成来看,体积浓度较高的物种有丙酮、二氯甲烷、乙烷;OFP较高的物种有1,3-丁二烯、甲苯、乙醛;SOAFP较高的物种有甲苯和二甲苯;且甲苯/苯比值表明溶剂排放等工业源对VOCs影响显著.从空间分布差异来看,正丁烷、甲苯和2,3-二甲基丁烷区域差异性较大.综合以上分析得出,正丁烷、异丁烷、甲苯、二甲苯和1,3-丁二烯作为化学活性较高且本地排放特征最显著的物种,是深圳市区域性O₃和PM_2.5协同防治的关键VOCs组分.     

煤化工产业园区挥发性有机物污染特征及其对大气复合污染的贡献

为研究煤化工产业园区挥发性有机物(VOCs)污染特征及其对大气细颗粒物(PM_2.5)和臭氧(O₃)的贡献,本研究于2021年夏季利用气相色谱/质谱联用仪在某大型煤化工产业园区开展了环境空气115种VOCs的在线监测研究,分析了VOCs的浓度水平、组成特征、日变化特征、潜在来源及其对O₃和PM_2.5中二次有机气溶胶(SOA)的生成贡献. 结果表明:①观测期间,园区站点VOCs的平均体积分数为89.32×10?9±50.57×10?9,显著高于该园区所在城市的城区站点VOCs浓度水平. ②含氧VOCs (OVOCs)是该园区VOCs的主要特征污染物,占总VOCs体积分数的48.2%,乙醇、丙醛和甲醛是体积分数排名前三的物种. ③VOCs的臭氧生成潜势(OFP)为595.64 μg/m3,各组分对O₃贡献潜势的大小表现为OVOCs>烯烃>芳香烃>烷烃>卤代烃>含硫VOC>炔烃. OFP排名前十的物种均为OVOCs、烯烃和芳香烃,其中丙醛对OFP的贡献占比最高,占总OFP的22.2%. ④间/对-二甲苯、邻二甲苯和乙苯等苯系物对二次有机气溶胶生成潜势(SOAFP)的贡献突出,其中间/对-二甲苯的SOAFP最大,占总SOAFP的29.6%,主导了SOA生成. 研究显示,煤化工产业园区中丙醛和甲醛等OVOCs、顺-2-丁烯等烯烃以及间/对-二甲苯与邻二甲苯等芳香烃对大气复合污染贡献较大,是开展PM_2.5和O₃污染协同控制重点关注的物种.      

轿车内苯系物的健康风险评价

为分析车内苯系物污染对不同性别驾乘人员的致癌风险和非致癌风险,对65辆轿车内空气中ρ(苯)、ρ(甲苯)、ρ(乙苯)和ρ(二甲苯)进行评价;提出车内苯的基本致癌风险浓度与危险致癌风险浓度概念及其计算公式,并与国内外相关标准中苯系物浓度标准限值进行对比分析. 结果表明:65辆轿车内空气中苯系物H_fz(综合非致癌指数)的最大值为0.44,低于US EPA(美国国家环境保护局)规定的非致癌风险基本值(1),对乘客与司机均不存在非致癌风险;但苯对司机H_za(致癌指数)的平均值为129.3×10-6,致癌风险较高;苯对男性乘客、女性乘客、男性司机与女性司机的C_wx(危险致癌风险浓度)分别为450.0、470.0、67.5和70.4 μg/m3. GB/T 27630—2011《乘用车内空气质量评价指南》中苯浓度标准限值对司机H_za的平均值为1.59×10-4,大于US EPA规定的苯致癌风险危险值(1×10-4),构成致癌危害;苯系物浓度标准限值对司机H_fz的平均值为1.15,构成非致癌危害. 轿车内空气中ρ(苯)、ρ(甲苯)、ρ(乙苯)和ρ(二甲苯)的合理限值分别为0.068、1.000、1.350和1.350 mg/m3.      

天津大气中BTEX的变化特征与健康风险评估

采用AMA GC5000BTX在线色谱仪监测天津城区2012年10月~2013年2月大气中苯、甲苯、乙苯、邻二甲苯和间-对二甲苯(苯系物,BTEX)的浓度,采用气溶胶生成系数(FAC)计算各组分的SOA生成潜势,采用US EPA的健康风险评价模型对BTEX的人体健康风险进行评估.结果表明,观测期间BTEX浓度均值为40.02±23.66μg/m~3,其中甲苯浓度最高,苯和间-对二甲苯次之,邻二甲苯最低,雾-霾日BTEX平均值为49.78±25.03μg/m~3,远高于非雾-霾日(28.57±15.18μg/m~3).BTEX浓度日变化差异明显,非雾-霾日B/T均值为0.70,雾-霾日增至0.77,表明观测期间以机动车排放污染为主,雾-霾污染期间BTEX来源复杂,生物质燃烧和燃煤等的贡献增大.甲苯对SOA的贡献最大,间、对-二甲苯次之,雾-霾日BTEX对SOA的贡献值高于非雾-霾日.观测期间BTEX的HI为0.455,其中雾-霾日HI为0.578,非雾-霾日HI为0.309,均低于EPA认定安全范围,表明苯系物非致癌风险在安全阈值范围内,但苯的致癌风险值为7.64×10-5,高于EPA规定的安全阈值,需要引起高度关注.     

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.