博斯腾湖流域大气多环芳烃污染特征、干沉降通量及来源

本研究使用大气被动采样器(PAS-PUF)和干沉降被动采样器(PAS-DD),分别于2016年采暖期和2017年非采暖期对新疆博斯腾湖流域及周边地区15种USEPA优控多环芳烃(PAHs)大气浓度和干沉降进行了观测,并对其污染特征和来源进行了研究.结果表明,采暖期和非采暖期博斯腾湖流域PAHs大气浓度范围分别为6. 38～245. 43 ng·m~(-3)和2. 33～74. 76ng·m~(-3);采暖期与非采暖期均呈现出居民区湖泊周边塔中的空间分布.采暖期和非采暖期PAHs大气干沉降通量范围分别为0. 45～18. 10μg·(m~2·d)-1和0. 25～8. 15μg·(m~2·d)-1;采暖期居民区PAHs干沉降通量比湖泊周边和塔中采样点高,但在非采暖期塔中采样点高于其它采样点.整体而言,博斯腾湖流域大气及干沉降中PAHs在采暖期显著高于非采暖期,在采暖期与非采暖期均以菲(Phe)、芴(Flu)、荧蒽(Flua)和芘(Pyr)等3～4环PAHs为主.比值法源解析结果显示,博斯腾湖流域大气和干沉降中PAHs主要来源于煤炭和生物质燃烧; HYSPLIT前向和后向轨迹模拟结果表明,非采暖期居民区较高PAHs排放通过大气传输到达博斯腾湖区,经大气干沉降进入水体,可能会对博斯腾湖水生环境造成影响.     

博斯腾湖流域大气多环芳烃污染特征、干沉降通量及来源

本研究使用大气被动采样器(PAS-PUF)和干沉降被动采样器(Pas-DD),分别于2016年采暖期和2017年非采暖期对新疆博斯腾湖流域及周边地区15种USEPA优控多环芳烃(PAHs)大气浓度和干沉降进行了观测,并对其污染特征和来源进行了研究。结果表明,采暖期和非采暖期博斯腾湖流域PAHs大气浓度范围分别为6.38~245.43 ng·m-3和2.33~74.76 ng·m-3;采暖期与非采暖期均呈现出居民区湖泊周边塔中的空间分布。采暖期和非采暖期PAHs大气干沉降通量范围分别为0.45~18.10μg·(m2·d)-1和0.25~8.15μg·(m2·d)-1;采暖期居民区PAHs干沉降通量比湖泊周边和塔中采样点高,但在非采暖期塔中采样点高于其它采样点。整体而言,博斯腾湖流域大气及干沉降中PAHs在采暖期显著高于非采暖期,在采暖期与非采暖期均以菲(Phe)、芴(Flu)、荧蒽(Flua)和芘(Pyr)等3~4环PAHs为主。比值法源解析结果显示,博斯腾湖流域大气和干沉降中PAHs主要来源于煤炭和生物质燃烧;HYSPLIT前向和后向轨迹模拟结果表明,非采暖期居民区较高PAHs排放通过大气传输到达博斯腾湖区,经大气干沉降进入水体,可能会对博斯腾湖水生环境造成影响。     

阜康大气气溶胶中水溶性无机离子粒径分布特征研究

为了解阜康大气气溶胶中水溶性无机离子的浓度水平、来源以及粒径分布,本研究于2011年2月~2012年2月利用8级惯性撞击式分级采样器采集了阜康大气气溶胶样品,使用离子色谱测定了其中水溶性无机离子含量.分析比较了非采暖期和采暖期主要离子的变化趋势、浓度水平、构成、来源以及粒径分布,在此基础上选取特殊采样日分析了重污染、秸秆燃烧以及春耕期的离子组成以及粒径分布的差异.结果表明,阜康细粒子、粗粒子中总水溶性无机离子(TWSI)在非采暖期和采暖期的浓度分别为11.17、12.68μg·m-3和35.98、22.22μg·m-3;非采暖期的SO2-4主要来自盐碱土扬尘,NO-3和NH+4主要来自农田土壤扬尘,而采暖期的SO2-4、NO-3和NH+4主要来自煤炭等化石燃料燃烧.8种离子在非采暖期和采暖期均呈现双峰分布,相对于非采暖期,采暖期的SO2-4、NO-3和NH+4在细粒径段的峰值发生了粒径增长,SO2-4和NH+4在粗粒径段的峰值出现在3.3~4.7μm处.重污染期间二次污染严重,离子主要分布在1.1~2.1μm处;秸秆燃烧期受生物质燃烧影响大,离子主要分布在<0.65μm粒径段;春耕期土壤扬尘较多,离子主要分布在>3.3μm粒径段.     

北京城区可吸入颗粒物分布与呼吸系统疾病相关分析

可吸入颗粒物(PM10)已成为北京市首要空气污染物,严重影响城市环境质量及居民健康.本研究采集了北京市2008～2009年非采暖期与采暖期两个不同时期不同粒径(0.3、0.5、3.0和5.0μm)的大气颗粒物浓度,利用空间分析方法研究其分布规律;同时收集同期患呼吸系统疾病的病人数据,对其进行统计分析;再在回归分析的基础上,运用灰色关联模型探讨可吸入颗粒物与呼吸系统疾病的相关性.结果表明,细颗粒的空间分布情况相异,而粗颗粒物分布规律大致相同.呼吸系统疾病与可吸入颗粒物浓度有一定的关联,采暖期是呼吸系统疾病的高发期,可吸入颗粒物在采暖期对呼吸系统疾病的发病率影响相对较高.无论在采暖期还是非采暖期,细颗粒物的浓度均高于粗颗粒物,且细颗粒物对呼吸系统疾病的影响较大.     

大气颗粒物中多环芳烃的污染特征及来源识别

研究了北京市2000年采暖期和非采暖期2个典型代表月(6月和12月)不同粒径颗粒物的质量浓度特征以及不同粒径颗粒物中ρ(PAHs)分布特征,并同时利用比值法和化学质量平衡(CMB)受体模型对可吸入颗粒物(PM₁₀)中PAHs的来源进行识别和解析.研究结果表明:北京市采暖期ρ(颗粒物)明显高于非采暖期;采暖期和非采暖期不同粒径颗粒物的比例有差别,采暖期、非采暖期ρ(PM₁₀)分别约占ρ(TSP)的0.662和0.734;PAHs具有更明显富集于细颗粒物中的特征;源解析结果表明燃煤污染和机动车污染是PM₁₀中PAHs的最主要来源.      

青岛采暖期不同天气状况下大气颗粒态无机氮分布研究

于2007-10～2008-04采集了青岛近海采暖前及采暖期内大气气溶胶样品,并运用离子色谱法(IC)分析了颗粒物中的无机氮组分.结果表明,采暖期内青岛颗粒物和无机氮的浓度都有明显增加,采暖期颗粒物质量浓度为137.41μg/m3,比采暖前增加了82.2%;NO3--N和NH4+-N浓度分别由采暖前的2.48μg/m3和6.95μg/m3增加到采暖期的4.43μg/m3和10.28μg/m3.天气过程对于青岛颗粒物浓度和无机氮离子浓度均有较大影响.采暖期晴天颗粒物浓度均值为181.34μg/m3,较采暖前增加32.0%,主要源于二次气溶胶的NH4+-N和NO3--N浓度分别为5.56μg/m3和1.86μg/m3,低于采暖前.雾天因为低温高湿和污染物的循环积累,样品中颗粒物、NH4+-N和NO3--N平均浓度比采暖前浓度增加了1～2倍.大风降温天气下颗粒物浓度及无机氮组分浓度均有所降低.采暖期烟尘和飞灰的排放明显影响青岛大气颗粒物和无机氮的粒径分布,特别是细粒子部分.青岛近海颗粒物及NO3--N质量浓度呈现双峰分布,采暖前峰值出现在0.43～0.65μm与3.3～4.7μm的范围内,采暖期积聚模态峰值移至0.65～1.1μm范围内.NH4+-N粒径分布均呈现明显的单峰分布,峰值出现在积聚模态.     

南京夏秋季大气颗粒物和PAHs 组成的粒径分布特征

采集南京市2007 年夏、秋季节灰霾天和非灰霾天不同粒径大气颗粒物,分析了6 月份农村秸秆焚烧对南京市大气中颗粒物和多环芳烃 (PAHs)的浓度、粒径分布和分子组成的影响.结果表明,南京市大气颗粒物在灰霾天呈单模态-积聚模分布,而在其他天气条件下呈积聚模和粗模双模态分布.秸秆焚烧释放出大量细粒子和低分子量PAHs,使低环数(3~4 环) PAHs 的粒径分布由非灰霾天不同粒径上的均匀分布转变为灰霾天的单模态分布,总量增加了约41%,且主要富集在0.4~2.1µm 的细颗粒物上;而高环数(5~6 环)PAHs 的粒径分布和浓度在秸秆焚烧前后均没有显著变化,呈积聚模分布.因秸秆焚烧形成的灰霾期,大气中细颗粒物和低分子量PAHs 的浓度均明显提高.     

吉林市大气PM_(2.5)污染特征及来源分析

2014年在吉林市设立7个大气PM_(2.5)采样点,分采暖季和非采暖季分别采样分析了吉林市城区大气颗粒物污染特征和可能来源。结果表明:吉林市大气颗粒物以PM_(2.5)为主,PM_(2.5)年均值65μg/m3,超过国家二级标准限值86%,PM_(2.5)/PM10的年平均值为61%;PM_(2.5)中,休闲生活区各个时间段金属元素浓度相对较低,工业混合区浓度较高;非金属离子SO2-4、NH+4、NO-3、Cl-是PM_(2.5)水溶性离子的主要成份,其和占PM_(2.5)质量的13.31%,在采暖期浓度质量全部高于非采暖期;采暖期OC和EC来源基本相同,来源于机动车尾气、燃煤和生物质燃烧等,在非采暖期OC和EC来源差异性较大,主要来源于机动车尾气和工业燃煤等。     

南京北郊大气颗粒物的粒径分布及其影响因素分析

在南京北郊使用FA-3型9级采样器对2014年1~11月颗粒物的粒径分布进行了采样分析.首先将FA-3与中流量分级采样器(KC-120H)和环境保护局在线监测仪器的同期监测结果进行对比,数据相关系数均在0.95以上,对细粒子FA-3分别偏低13.9%和16.6%,而对PM_(10)偏高15.2%和13.3%,但采样偏差在大气采样可接受范围之内,说明其可以对大气颗粒物进行准确分级和采样.南京北郊颗粒物污染严重,PM_(1.1),PM_(2.1)和PM_(10)的年平均浓度分别为(65.6±37.6)、(91.0±54.7)和(168.0±87.0)μg·m-3,污染以细粒子为主,且大部分在1.1μm以下;颗粒物粒径呈双峰分布,峰值位于0.43~0.65μm和9~10μm粒径段;中值粒径为1.83μm,为积聚模态污染.颗粒物粒径分布在冬季细粒径段较高,春季粗粒径段较高,夏季细粒径段降低并不明显,粗粒径段明显低于其他季节;颗粒物浓度的昼夜变化在粗粒径段差异很小,在细粒径段基本表现出夜晚大于白天的特征.除了夏季,降水对各个粒径范围的颗粒物都有清除作用,且在细粒径段表现得更为明显;霾发生时随着霾等级的加重,0.43~2.1μm粒径段颗粒物浓度逐渐增加,该粒径段颗粒物质量浓度与能见度呈显著负相关.以相对湿度70%为界,颗粒物粒径分布发生了明显变化,湿度大于70%后,小于0.43μm粒径段颗粒物质量浓度显著降低,而0.43~2.1μm粒径段明显上升,颗粒物的吸湿增长应是主要原因.南京北郊的气团来源可以分为四类,其中西北方向快速输送的气团最为洁净,细粒径颗粒物浓度明显低于其它方向;本地和周边近距离输送的气团污染最重,粗细粒径颗粒物浓度都较高,其传输距离短,风速小,发生污染的概率最大,达到73.9%,对南京市的空气污染贡献较大.     

鞍山市大气中多环芳烃健康影响评价

通过对鞍山市典型区域（6个污染源、4个居住区、一个对照点）大气颗粒物中PAHs的监测,采用BaP当量致毒系数TEF,研究了鞍山市大气颗粒物中典型PAHs毒性当量分布特征。研究结果表明,鞍山大气中典型PAHs污染主要以4～6环为主,不致癌BaP当量浓度为0．066ng/m3,致癌BaP当量浓度为12．7ng／m3,强致癌BaP当量浓度为8．1ng/m3,很强致癌BaP当量浓度为12．7ng／m3。BaP毒性当量浓度呈现出采暖期要远远高于非采暖期,工业区及工业区周边BaP毒性当量浓度要远远高于居住区和对照点。     

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.     

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.     

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.     

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.