中国自然背景地区臭氧浓度时空变化特征分析

为揭示中国自然背景地区臭氧浓度变化特征,并以其为自然背景值指导人为活动导致的臭氧污染控制工作,该研究通过汇总统计中国15个典型自然背景地区与337个地级及以上城市2016—2020年环境空气臭氧自动监测数据,比较分析中国自然背景地区臭氧浓度的年度、季节、日内变化规律与空间分布规律. 结果表明:2016—2020年,中国自然背景地区臭氧年均浓度明显高于城市区域,但臭氧日最大8小时平均浓度的第90百分位数(简称“臭氧年90百分位浓度”)明显低于城市,自然背景地区和城市区域臭氧年均浓度同步快速提升,年均增长分别为1.5和2.0 μg/m3. 中国自然背景地区臭氧浓度季节性变化规律与城市区域存在较大差异,自然背景地区臭氧平均浓度最高值出现在春季,夏、秋、冬三季臭氧平均浓度差异不明显,与东亚环太平洋背景地区臭氧浓度季节性变化规律(春季最高、夏季最低)存在明显差异. 部分自然背景地区受人为活动排放的影响较小,臭氧浓度不存在明显的日内峰谷差,全天臭氧浓度基本保持相同水平;部分自然背景地区可能受邻近城市人为活动排放的臭氧前体物影响,臭氧浓度日内变化规律与邻近城市较为一致,存在明显的日内峰谷差. 研究显示,中国自然背景地区臭氧浓度变化规律与城市区域存在显著差异,臭氧浓度年均值升高迅速,部分自然背景地区臭氧浓度变化规律可能受邻近城市人为活动排放的臭氧前体物传输的影响.      

杭州市夏季臭氧污染特征及一次污染过程分析

文章利用2016-2021年杭州市环境空气质量国控监测站点及杭州光化学网站点监测数据,分析杭州夏季臭氧浓度变化特征,并结合气象资料分析一次臭氧典型污染过程。研究表明,杭州市夏季臭氧污染严重,6月超标天数要高于7月和8月,夏季臭氧浓度日变化呈现“单峰型”,8月平均臭氧日变化的峰值要略高于6月和7月。2021年6月5-9日杭州市出现的一次中度污染的臭氧污染过程,主要是在不利气象条件以及较高浓度前体物影响下的本地生成,而6月7日在本地生成之外,还受到东北方向城市区域的污染传输影响。     

中国城市群臭氧时空分布特征分析

为揭示我国主要城市群近地面臭氧的时空分布规律,使用空气质量监测网站发布的2019年243个城市共计1215个站点的臭氧浓度数据对中国正在稳步建设的19个城市群的臭氧时空分布特征进行分析,结果表明:臭氧污染高发期主要集中在夏季6、7月份,春末秋初次之,冬季基本不发生污染.城市群100μg/m³以上的臭氧浓度占比变化趋势大致表现为不规则的“V”和“W”两大类.2019年我国19个城市群可明显提取出北部和南部两个浓度分布高值中心,分别出现在夏季和秋季,夏季根据污染严重程度又可将高值中心划分为两个层级.城市群臭氧浓度分布具有空间自相关特性,夏季热点区域与北部高值中心重合,秋季则与南部高值中心位置一致,此时冷点区域面积达到最大.由于臭氧污染成因的复杂性,不能简单以现有城市群等级划分结果对其进行分级管理,需要根据实际分布情况对不同城市群制定相应污染防控措施.     

中国臭氧浓度的时空变化特征及分区

采用旋转经验正交函数(REOF)法分析了2016年中国338城市臭氧浓度的时空变化特征,根据2016年污染季节(5月至10月)的REOF分析结果,确定出10个具有明显同比变化的区域,不同区域间臭氧浓度的时间变化趋势彼此独立,受到当地地形因素、气象条件、光化学反应等因素的影响.10个区域中,除华南地区和青藏高原外其他地区2014年至2016年臭氧日最大8小时浓度(O3-8h)均呈上升趋势.臭氧分区受到地形地貌特征的影响较大,显示出地形和地貌对臭氧空间相关性的重要影响.黄淮平原、华北平原、长江中下游地区等3个人口稠密区域臭氧浓度较高,应该作为臭氧污染控制战略的重点区域.     

京津冀区域臭氧时空分布特征及其背景浓度估算

为研究京津冀区域臭氧时空分布特征,并估算区域传输贡献,对2017~2019年京津冀区域68个国控站点资料进行主成分分析,并采用TCEQ法估算京津冀区域及细分的次区域内O₃背景浓度.结果表明,京津冀区域O₃浓度整体上呈现南高北低态势,地理位置的差异及其距离对于各城市臭氧浓度的均匀性分布影响较大.经最大方差法旋转后,主成分分析结果可将京津冀区域划分为河北省中南部、京津冀北部以及渤海西岸地区等3个稳定的次区域.对3个次区域分别采用TCEQ法估算O₃背景浓度,计算得到3个次区域本地生成O₃浓度依次为71,60,59μg/m³,区域背景浓度占O₃日最大8h浓度的比值依次为34.3%,39.4%,42.2%.京津冀区域O₃本地生成占主导,区域传输也不容忽视.     

多尺度PM_(2.5)分布特征的空间插值与遥感反演对比

精确识别污染物浓度的空间分布是进行区域大气污染防治的重要基础。利用MODIS卫星数据,采用基于地面气象和环境空气质量监测站点观测数据为基础的反演模型,反演获取2013年12月珠三角地区典型大气污染过程1 km分辨率的PM_(2.5)浓度数据,对比分析遥感反演及基于环境空气质量监测站点观测数据的空间插值方法对区域、城市和乡镇尺度PM_(2.5)浓度空间分布特征的再现效果差异。结果表明,珠三角地区PM_(2.5)遥感反演结果与地面观测数据的相关性达到0.74,相关性水平较好,遥感反演结果可描述区域、城市和乡镇尺度上PM_(2.5)污染浓度的空间分布特征,识别不同空间位置的污染程度差异;基于站点观测数据的空间插值方法对PM_(2.5)浓度空间分布特征的再现能力有限,在区域尺度PM_(2.5)浓度空间分布特征分析时效果尚可,在站点有限的城市和乡镇尺度分析中效果不佳,容易产生对高浓度污染地区的误判;在需要利用站点观测数据分析区域尺度PM_(2.5)浓度空间分布特征时,析取克里金、反距离权重或径向基函数插值方法的效果相对较好。     

上海市郊春季臭氧及其前体物观测研究

利用上海市郊金山环境监测站沿海站点2007年春季的逐时臭氧浓度及其前体物的观测数据,分析了臭氧浓度的时间变化规律,以及海风和陆风对臭氧和其前体物(NO、NO2和CO)浓度的影响.结果表明,臭氧浓度总体较高,共有10日出现臭氧浓度超标,表现出了比较明显的春季高峰现象;臭氧浓度的日变化表现出了受污染地区的典型特征,而NO和...     

银川市臭氧污染特征及影响因素分析

依据2014年银川市6个自动空气监测子站的监测数据,分析银川市臭氧浓度的污染特征,并对夏季臭氧相关气象因子进行分析。结果表明,从监测点位来看,银湖巷站点臭氧浓度最高,宁安大街次之,宁化生活区臭氧浓度最低。从时间变化规律来看,银川市臭氧浓度呈夏季最高,春季次之,秋季、冬季污染较低,其中臭氧月均浓度最大值出现在5月、6月。臭氧日变化呈单峰变化规律,夜间臭氧浓度较低,白天臭氧浓度较高。夏季臭氧浓度与二氧化氮、相对湿度呈显著的负相关性,与气温、风速呈显著正相关性。     

20世纪90年代以来粤港澳大湾区臭氧污染研究进展

粤港澳大湾区是我国开放程度最高、经济活力最强的区域之一,在国家发展大局中具有重要战略地位.20世纪90年代以来,粤港澳三地政府在空气质量监测、空气污染治理方面做了大量工作,粤港澳大湾区颗粒物浓度持续下降,但臭氧浓度快速增长,臭氧已成为粤港澳大湾区首要污染物.为深化粤港澳大湾区臭氧污染研究及臭氧污染防控,本文综述了粤港澳大湾区20世纪90年代以来臭氧污染观测研究的主要进展,回顾了臭氧监测网络建立、臭氧浓度水平及其时空变化特征、臭氧生成和污染输送的气象过程、区域臭氧来源解释等方面的研究发现,提出新时期粤港澳大湾区臭氧研究的建议.     

珠江三角洲光化学活跃期甲醛及其前体物的源解析研究

选取珠江三角洲大气超级站的三个代表性超级站点（东莞东城城市超级站、深圳莲花山城市超级站和鹤山花果山区域超级站）,同步在线监测和分析了2021年5~10月大气光化学活跃期甲醛（HCHO）及其前体物挥发性有机物（VOCs）组分的时空变化特征,利用多元线性回归法对HCHO来源进行解析,识别出了关键VOCs前体物及其贡献,并对比了三个点位来源及前体物的差异.结果表明：三个站点的HCHO体积浓度存在明显差异,鹤山区域站浓度最高达5.82×10^-9,与历史研究数据相比浓度升高,而城市超级站东城与莲花山浓度水平降低.臭氧浓度与甲醛浓度存在一定相关性,各站点臭氧浓度最高的9月,HCHO的平均浓度水平也高;臭氧超标日的HCHO浓度显著高于臭氧非超标日.利用多元线性回归法,选择甲苯、异戊二烯和O₃作为源示踪剂,结果表明二次源对HCHO来源贡献占比最多,范围为43.5%~54.9%,其中区域站点二次源占比高于其它两个城市站点.基于生成产率法得到各站点二次转化生成HCHO的前体物主要为烯烃,其中贡献最大的是异戊二烯,其次为乙烯和丙烯.综合对比,HCHO的一次人为源的下降导致城市站点HCHO浓度降低,较高的二次转化导致了区域站点HCHO浓度升高,需重点关注甲醛的人为源直接排放和异戊二烯、苯乙烯、乙烯等前体物.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.