珠三角典型城市COVID-19疫情封闭期间臭氧污染的放大效应研究

珠三角地区臭氧(O₃)已经逐步取代颗粒物成为主要大气污染物。对新型冠状病毒肺炎(COVID-19)疫情封闭期间珠三角城市背景污染效应(特别是对O₃的放大效应)进行了量化研究,发现PM_2.5和NO₂质量浓度均为工作日高于节假日,非疫情期高于疫情期。O₃质量浓度节假日高于工作日,其中疫情期节假日浓度最高。减排会增加低温高湿背景下O₃质量浓度,但会降低其极大值,并导致 O₃随温度和相对湿度的变化梯度减弱。疫情封闭期间异地输送对于局地O₃质量浓度的变化贡献突出。叠加疫情封闭影响的春节假期O₃质量浓度比节前工作日增加20.4%~41.7%,与一般年份特征相反,而NO₂降低65.3%~75.6%,降低程度强于一般年份。疫情封闭期春节期间O₃质量浓度比一般年份上升14.0%~25.9%,而NO₂质量浓度降低37.0%~54.5%。低湿晴好的天气为光化学反应提供有利条件,并且疫情封闭扩大了假期人为源减排规模,导致NO_x质量浓度进一步下降,使其对O₃的滴定效应减弱,同时静稳天气有利于O₃浓度的累积,导致局地O₃污染被逐步放大。     

宁波市大气污染概况及影响因素分析

为研究宁波市大气污染状况及其影响因素，利用2013—2018年宁波市国控站点实时监测污染物数据以及气象数据，探讨分析了宁波市大气污染特征以及所受气象因素的影响概况。结果表明：宁波市颗粒物污染和O₃污染呈现典型的季节性特征，颗粒物浓度冬季最高，O₃最大滑动8 h平均质量浓度春、秋季最高。宁波市O₃污染问题越来越突出，且呈现出春、秋季O₃超标天数最多的季节变化特征。O₃小时质量浓度与气温和太阳辐射成正相关关系，NO₂和颗粒物浓度与气温成负相关关系。NO₂与O₃浓度成负相关关系，与颗粒物浓度成正相关关系。     

“Ox增减量”O3人工订正预报方法与应用

为满足环境管理部门"O₃污染过程不漏、AQI类别准确和AQI范围预报准确"的要求,基于大气箱式模型和相似案例分析,引入O_x指标原创性提出"O_x增减量"O₃人工订正预报方法。介绍了该方法的预报思路、预报要点和步骤、历史相似案例库构建与基于大气条件预报的判别分析、方法普适性和局限性等,以期为提高区域、城市O₃业务预报准确率提供技术参考。以东部沿海城市青岛市为研究案例,结果显示,2020年6—9月24 h人工订正AQI类别预报、AQI范围预报准确率分别为91%和68%,比同期业务化运行的WRF-Chem数值模式预报准确率分别提高19%和25%,应用该预报方法可有效提高O₃污染过程预报准确率。     

典型生态功能区臭氧生成敏感性及气象驱动力解析——以千岛湖地区为例

千岛湖地区是我国重要的自然保护区,属于典型生态功能区。当前,臭氧(O₃)正频繁成为影响千岛湖地区空气质量的首要污染物,但对于与此相关的千岛湖地区O₃生成敏感性,研究人员目前仍未了解清楚。利用2019—2021年TROPOMI卫星观测数据,运用O₃生成敏感性指示剂方法,即甲醛对流层垂直柱浓度和二氧化氮对流层垂直柱浓度的比值(FNR),量化解析了千岛湖地区O₃生成敏感区的时空演化特征。结果表明,千岛湖地区FNR呈现逐年升高趋势,且显著高于杭州市主城区。千岛湖地区氮氧化物(NO_x)控制区逐年扩张,自2019年开始,由西南向东北逐步蔓延。截至2021年,NO_x控制区已基本覆盖整个千岛湖地区。千岛湖地区O₃生成敏感区在夏季基本属于NO_x控制区,在其他季节属于NO_x控制区或协同控制区。结合气象再分析数据发现,FNR与温度呈强正相关(r=0.8),与相对湿度呈较弱正相关,与风速和云液态水含量呈较弱负相关。当温度大于7.0 ℃、风速小于6.2 m/s、云液态水含量小于5.5×10^-5 g/m³、相对湿度大于57.5%时,O₃生成趋向于受NO_x控制。此外,与杭州市相比,千岛湖地区O₃生成对气象参数变化更为敏感。研究成果对我国典型生态功能区O₃污染防控具有重要的启示作用。     

长沙地区O3污染潜势广义可加模型的季节分异性

基于长沙市2016—2019年臭氧（O₃）浓度的逐时监测资料以及该时段同时次的气象观测数据，首先利用相关性分析和方差膨胀因子相结合的方法排除了相对湿度、太阳辐射、气温、风速、气压之间存在多重共线性问题，进而构建了春、夏、秋、冬四季O₃日最大8 h滑动平均质量浓度（O₃-8 h）与上述气象因子的广义可加模型（GAMs），分析了O₃污染潜势GAMs模型的季节分异特征。结果表明：①春、夏、秋、冬四季O₃与相对湿度、太阳辐射、气温、风速、气压各变量之间多呈现出非线性关系（自由度大于1）。②春、夏、秋、冬四季多变量GAMs模型方差解释率（IRV）分别为80.7%、60.2%、83.0%、81.4%，调整判定系数R²分别为0.795、0.564、0.819、0.795，即不同季节气象因子在GAMs模型中对O₃的解释能力存在显著差异，秋季最好，冬春季次之，夏季最差。③相对湿度、太阳辐射、气温是决定春、夏、秋、冬四季O₃浓度变化最重要的气象要素，但其重要性排序随季节有所变化，对应的太阳辐射的F统计值分别为140.841、36.606、14.16、46.377，相对湿度的F统计值分别为3.291、4.158、15.82、8.105，气温的F统计值分别为7.030、2.113、15.79、3.340。该结论揭示了气象因子对O₃演化影响的复杂性，并为后续O₃污染潜势的预报奠定了基础。     

嘉善前体物与气象因子对臭氧生成的影响及臭氧潜在源区分析

利用2017年嘉善善西超级站臭氧（O₃）及其前体物（NO_x和VOCs）以及气象因子（温度、湿度、风速）逐小时数据，分析了2017年全年NO_x和O₃的变化特征以及春季（4—5月）、夏季（7—8月）NO_x和气象因子对O₃生成的影响，利用O₃生成潜势（OFP）评估了VOCs大气化学反应活性，并通过潜在源区贡献（PSCF）和浓度权重轨迹（CWT）方法分析了嘉善春、夏季O₃潜在源区贡献特征。研究发现：O₃日变化特征为单峰结构，NO_x为弱双峰结构。O₃浓度在3—9月较高，春、夏季O₃浓度峰值分别出现在15：00和14：00，春、夏季的NO_x、O₃日变化与2017年全年日变化趋势基本一致。NO_x对O₃存在滴定作用，且低湿高温有利于O₃浓度的升高。春、夏季O₃生成潜势贡献均表现为烯烃 > 芳香烃 > 烷烃，由于烯烃光化学活性较高，夏季烯烃浓度升高导致其贡献较春季增长约18.1个百分点，且夏季VOCs平均最大O₃增量反应活性高于春季。PSCF和CWT分析结果表明，嘉善春季的潜在源区主要为本地、西南方向和东南方向，夏季的潜在源区主要为本地、西北方向、西南方向以及东南方向。     

滁州市臭氧污染特征及一次连续臭氧污染过程分析

利用滁州市环境空气质量监测数据和气象观测数据,分析了滁州市O₃污染基本特征,并着重分析了一次连续O₃污染过程中气象因素、VOCs以及其他污染物对于O₃浓度的影响。结果表明:滁州市环境空气污染类型正由"PM_2.5型"向"PM_2.5和O₃混合型"转变,O₃污染程度呈现加重趋势,污染持续时间有所拉长。9月4—9日一次连续O₃污染过程中O₃呈单峰状;受到光化学生成和区域传输共同影响,峰值时气温大多在30℃以上,相对湿度较小,风速大多处于小风区(WS≤1 m/s),也有部分处于风速较大区域(WS>3 m/s);VOCs/NO_x比值法和O₃/NO_x比值法均反映此次连续O₃污染为VOCs控制;体积分数较大的VOCs物种主要为烷烃,其中单个体积分数最大的物种是乙烷;烯烃是对O₃生成贡献最大的关键活性组分,对O₃生成潜势的贡献为53.5%,控制1-戊烯、反2-戊烯、异戊二烯、间/对二甲苯等物种可以有效控制光化学生成对此次O₃污染过程的影响。     

2022年春季南京臭氧污染特征及成因分析

2022年春季,受新一轮新冠疫情影响,长三角各城市采取了一系列管控措施,使得大气污染物排放水平降低。对2022年春季(3—5月)南京及长三角地区的六项污染物尤其是臭氧(O₃)的变化特征进行了分析,从气象因素和O₃前体物方面,同时利用基于观测的模型(OBM)对南京O₃污染变化原因进行了研究,并分析了南京挥发性有机物(VOCs)的关键活性组分和来源。结果表明:2022年春季,南京PM_2.5、PM₁₀、NO₂和CO均值浓度均同比下降,但O₃日最大8 h滑动平均质量浓度(O₃-8 h)同比上升19.8%,O₃-8 h超标时间同比增加9 d;长三角区域O₃-8 h同比上升17.9%,O₃-8 h超标天数为2021年同期的2.5倍。南京O₃浓度上升的原因:一方面是由于不利的气象条件,另一方面是由于南京O₃生成处于VOCs控制区,但氮氧化物(NO_x)降幅大于VOCs降幅,同时结合O₃前体物削减方案的分析结果发现,VOCs和NO_x不当的削减比例会导致O₃浓度不降反升。南京O₃生成的关键VOC活性物种依次为乙醛、丙烯、间/对二甲苯、丙烯醛和乙烯;正定矩阵因子分解(PMF)解析结果显示,机动车尾气是南京城区VOCs的主要来源,其次为液化石油气/天然气使用和石油化工。     

两种消解法测定沉积物总磷的对比

通过过硫酸钾消解法与HClO₄-H₂SO₄消解法对土壤和水系沉积物的标准物质,以及三峡水库沉积物未知样品中的总磷含量进行测定,并对检测结果进行对比,分析过硫酸钾消解法测定沉积物总磷的可行性。结果表明,在标准样品中,HClO₄-H₂SO₄消解法的检测结果是标准值的83%~100%,并且所有结果均在其不确定度范围之内;过硫酸钾消解法的检测结果仅达到标准值的19%~42%,超出其不确定度范围,不能作为有效数据。在未知样品中,过硫酸钾消解法检测结果也远低于HClO₄-H₂SO₄消解法检测结果,只达到后者的32%~52%。由此可见,过硫酸钾消解法测定沉积物或土壤中总磷,仍需要进一步的研究,以达到符合实际的检测结果。     

2019年江苏省PM2.5和O3多模式集合预报算法效果评估

基于江苏省重污染天气监测预报预警系统多模式预报结果,分析了不同数值模式对江苏省13个城市细颗粒物(PM_2.5)和臭氧(O₃)的预报偏差特征,发展了多模式集合预报算法,并对其进行了评估。结果表明,相较于单一数值模式,集合预报算法显著改善了PM_2.5和O₃预报的准确率,其对江苏省PM_2.5和O₃空气质量分指数等级的预报准确率超过了80%。就江苏省整体而言,PM_2.5集合预报的准确率相比最优单一数值模式提升了6%。O₃浓度较低时,集合预报能有效改善各模式存在的高估现象。但受限于目前的校正策略,出现高浓度O₃污染时,集合预报对预报效果的提升相对有限。     

城市垃圾填埋场渗滤液中污染物检测与分析

垃圾渗滤液水质复杂,危害性大,对其无害化处理尚未得到很好解决。溶解性有机物(DOM)是导致渗滤液处理难以达标的主导性污染物。采用GC-MS技术可将渗滤液中DOM标识划分为亲水性和疏水性两类物质,为DOM的针对性处理提供了新的思路。采用ICP-AES从渗滤液中检测出美国环境保护局颁布的13种优先污染重金属中的11种,其含量大幅超标。废弃的电子材料、颜料涂料、电池以及药物等物质的不分类收集是导致渗滤液中重金属浓度超标、毒性增强的主要原因。在垃圾渗滤液处理领域,认为BOD5/COD小于0.3就不可以采用生物法处理的传统观点已经不符合实验与工程现实。通过检测与分析,掌握了垃圾渗滤液的水质特性与污染源头,能够为制定切实可行的处理方案提供借鉴。     

Characterization of the Leachate in an Urban Landfill by Physicochemical Analysis and Solid Phase Microextraction-GC/MS

The aim of this study is to evaluate extensively the characterization and identification of major pollutant parameters by paying attention to the organic chemical pollution for unregulated dumping site leachate in Eskişehir/Turkey. The study that is first and only one research has been very important data related with before new sanitary landfill site in Eskişehir city. For this purpose, in this study leachate samples were collected in-situ at monthly interval for a period of 8 months. Firstly, thirty three physicochemical parameters were monitored. Secondly, SPME technique was used for identification of organic pollutants. Meteorological data were also recorded for the same sampling period to correlate meteorological data and physicochemical parameters. Mean values are used in the correlation analysis. Correlation is shown only for the relationship between air temperature and NO₃ ⁻. No correlation has been found between rain and leachate quality parameters since the amount of rain was very low during the sampling period. However, analysis results were generally decreased in winter season when each parameter and each sampling point are examined separately. According to correlation between every parameter, especially solid content and dissolved oxygen concentration of leachate is affecting to other parameters. Also, sodium and potassium are changing proportionally with same parameters (suspended solids, fixed solids, dissolved oxygen) and high correlation between chloride and heavy metal concentration is showing. The results were statistically evaluated by use of SPSS 10.0 program. Second part of the study, the leachate was extracted by Solid Phase Microextraction (SPME) technique and then analyzed. Of the methodologies tested in this study, the best one selected was based on 100 μ m polydimethylsiloxane coated fiber (PDMS), headspace with heating (Δ HS) sampling mode and an extraction time of 15 min. at a temperature of 50 ^o C. Thirty three organic compounds in leachate were identified by GC/MS.     

Toxicity Testing of Leachate from Waste Landfills Using Medaka (Oryzias Latipes) for Monitoring Environmental Safety

To investigate the environmental safety of waste disposal landfill sites and of land reclaimed from such sites, we evaluated the toxicity of leachate from these sites by a combination of bioassays in the Japanese killifish medaka Oryzias latipes. We tested for lethal toxicity in adult and larval medaka and for hatching inhibition of embryos from eggs. As biochemical evidence of the effects of leachate exposure, CYP1A (EROD activity) and vitellogenin (Vtg) were induced. We also bioassayed water-treated leachate and downstream river water. Leachate solution was lethal to larval and adult medaka. Embryo hatchability was inhibited, and abnormal hatching, spinal deformity and anisophthalmia occurred in embryos exposed to leachate solution. CYP1A was induced by exposure to leachate solution diluted to 1.0%, and EROD activity was significantly higher than in control. Vtg and unknown proteins were induced in the sera of male medaka exposed to the diluted leachate solution. Conventional water treatments worked effectively to remove toxic compounds but did not work well to remove element ions, including heavy metals. Treated leachate produced neither lethal toxicity nor hatching abnormalities during the exposure period. Fish toxicity tests for leachate would be useful for monitoring the environmental safety of landfill sites.     

Indexing method for assessment of pollution potential of leachate from non-engineered landfill sites and its effect on ground water quality

Dumping of solid waste in a non-engineered landfill site often leads to contamination of ground water due to leachate percolation into ground water. The present paper assesses the pollution potential of leachate generated from three non-engineered landfill sites located in the Tricity region (one each in cities of Chandigarh, Mohali and Panchkula) of Northern India and its possible effects of contamination of groundwater. Analysis of physico-chemical properties of leachate from all the three landfill sites and the surrounding groundwater samples from five different downwind distances from each of the landfill sites were collected and tested to determine the leachate pollution index (LPI) and the water quality index (WQI). The Leachate Pollution Index values of 26.1, 27 and 27.8 respectively for landfill sites of Chandigarh (CHD), Mohali (MOH) and Panchkula (PKL) cities showed that the leachate generated are contaminated. The average pH values of the leachate samples over the sampling period (9.2 for CHD, 8.97 for MOH and 8.9 for PKL) show an alkaline nature indicating that all the three landfill sites could be classified as mature to old stage. The WQI calculated over the different downwind distances from the contamination sites showed that the quality of the groundwater improved with an increase in the downwind distance. Principal component analysis (PCA) carried out established major components mainly from natural and anthropogenic sources with cumulative variance of 88% for Chandigarh, 87.1% for Mohali and 87.8% for Panchkula. Hierarchical cluster analysis (HCA) identifies three distinct cluster types for the groundwater samples. These clusters corresponds to a relatively low pollution, moderate pollution and high pollution regions. It is suggested that all the three non-engineered landfill sites be converted to engineered landfill sites to prevent groundwater contamination and also new sites be considered for construction of these engineered landfill sites as the present dumpsites are nearing the end of their lifespan capacity.     

北京市废弃物处理温室气体排放特征

基于《2006年IPCC国家温室气体清单指南》推荐的方法，结合《省级温室气体清单编制指南（试行）》和《城市温室气体核算工具指南》的部分数据与核算范围，针对固体废弃物填埋、焚烧和废水处理等过程，核算了北京市2005-2014年废弃物处理过程中温室气体总排放量。结果表明：2005-2014年北京市废弃物处理过程温室气体总排放量呈逐渐上升趋势，2014年温室气体总排放量比2005年增长98%。10年间，固体废弃物填埋过程一直是最主要的温室气体排放源，到2014年排放量达到最大，为416.3×10⁴t二氧化碳当量（CO₂e）。废弃物填埋、废水处理和废弃物焚烧过程占总排放量的比例分别为78.5%（CO₂e质量分数，下同）、13.5%和8%。结合已有研究，系统优化国内7个典型城市废弃物处理温室气体排放因子，核算7个城市排放情况，并对比分析了北京市排放情况。     

多波长法用于减小浊度对水源水中甲醛测定结果的影响

比较了减小水样浊度对样品结果影响的各种方法,包括过滤法、双波长法、三波长法,3种方法均基于乙酰丙酮分光光度法,测定波长均为414 nm。结果表明,以480 nm为参比波长的双波长法所得方法检出限为0.027 mg/L,采用470 nm与360 nm、460 nm与370 nm、450 nm与380 nm 3对参比波长的三波长法测得方法检出限为0.025~0.028 mg/L,这些方法用于检测0.100 mg/L标准点样品时,检测结果 RSD介于8.0%~8.6%。双波长法适合低浊度样品的直接分析,而浊度较高或双波长法测得结果大于方法检出限时,应采用三波长法进行定量分析,他们的使用有助于提高方法的准确度及减少工作量。用于地表水样品分析时,0.200、0.400 mg/L加标样品的回收率介于90.3%~101%,对应RSD介于0.0%~4.2%。     

多元线性回归pH滴定同时测定垃圾渗滤液中重金属浓度

垃圾渗滤液中的高浓度重金属离子严重抑止了废水生化处理过程中微生物的生长与代谢。通过建立多元线性回归模型,结合pH络合滴定方法,实现了同时测定垃圾渗滤液中络合稳定常数极为接近的多种重金属离子浓度。该方法操作简便,准确可靠,适用于大批量相同组成试样的分析。     

A bench-scale rock-plant filter investigation

Three bench-scale rock filters containing 0.6 m of gravel were used in this investigation. Two of the filters were planted withSagittaria Iancifolia andScirpus validus, while the third filter was an unvegetated control filter. The wastewater directed through these systems was a synthetic mixture containing nutrient broth as the carbon source. An 80-day experiment was run on the filters using eight combinations of two flow rates and four influent biochemical oxygen demand (BOD₅) concentrations, each combination remaining constant for ten days. These combinations resulted in BOD₅ surface loadings from 4.63–30.96 g/day/m². From other studies of batch and continuous flow rock-plant filter systems, the first-order BOD₅ reaction rate constant was found to decrease exponentially with detention time. In this study, however, little correlation was found between BOD₅ loading rate and removal percentages, which averaged 69%, 57%, and 47% for theScirpus, Sagittaria, and control systems, respectively. This is probably due to the relatively small change in detention times studied and the short time period of each loading rate. Oxidation/reduction potential (ORP) and dissolved oxygen (DO) measurements within these systems indicated that no free oxygen was available at any depth. Total Kjeldahl nitrogen (TKN) removal was higher in the plant systems relative to the control, with theScirpus system achieving a higher overall removal than theSagittaria system.     

高效液相色谱-串联质谱法测定废水中5种喹诺酮类抗生素

建立高浓度有机废水中5种喹诺酮类抗生素的高效液相色谱-串联质谱测定方法。水样经HLB固相萃取小柱富集净化,12 ml甲醇洗脱、浓缩并加入内标溶液后,定容至1 mL待测。以C18柱为分离柱,含0.01%甲酸的甲醇-含0.01%甲酸的水溶液为流动相,目标物质在10 min内分离。在0.25~1 250 ng/mL范围内,目标物质线性关系良好(R20.99)。基质加标试验结果表明,纯水中的回收率为61.40%~91.92%,废水中的回收率为54.92%~101.87%,检出限为0.25~2.5 ng/L,方法定量限为0.36~3.99 ng/L。应用该方法对21家猪场的64份废水样品进行分析,5种喹诺酮类抗生素的检出频率为47%~95%,平均检出浓度为980~5 734 ng/L。该方法快速、准确,适用于高浓度有机废水中喹诺酮类抗生素的同时测定。     

The use of isotopes to identify landfill gas effects on groundwater

An evaluation of the source of volatile organic compounds in groundwater samples was performed at a landfill in southern California. The 3H (tritium) content of the water in leachate and water from the gas-collection system (condensed water and entrained water droplets) and the delta 13C and 14C content of the inorganic carbon in landfill gas CO2, leachate, and gas-collection system water were used to characterize the dissolved inorganic carbon (DIC) inside the landfill, while the same parameters were monitored in groundwater samples from affected monitoring wells and an unaffected well. Tritium levels from leachate and gas-collection system condensate ranged from approximately 2000 TU to over 4000 TU, orders of magnitude higher than unaffected groundwater. The average 14C content of DIC in the landfill pore-water samples was 121 pMC and the 14C content of unaffected groundwater DIC was 93 pMC, while the 14C content of the dissolved inorganic carbon in groundwater with VOC detections ranged from 105 to 119 pMC. The delta 13C of DIC in pore water was consistently above 0 per thousand and the delta 13C of unaffected groundwater DIC was -20.3 per thousand, while the delta 13C of DIC in affected groundwater samples was increased from -17.3 to -13.2 per thousand. The increases in both delta 13C and 14C in landfill gas-impacted groundwater DIC generally correlated with the number of volatile organic compounds detected and their concentrations. Based on the tritium and DIC 14C levels in leachate and water from the gas-collection system compared to those of unaffected water, significant increases in the tritium content of the water would be expected to accompany VOC detections and increases in delta 13C and 14C caused by landfill water. The results rule out landfill water as the VOC source, leaving landfill gas as the source. The identities and concentrations of the specific VOCs in affected groundwater samples varied among wells as well as between two leachate samples, ruling out the use of a VOC "fingerprint" for leachate or landfill gas to be compared to groundwater VOC concentrations.