臭氧监测仪实验室校准及稳定性测试

以国内监测系统在用的臭氧校准仪为二级传递标准对臭氧监测仪开展了实验室校准,通过计算单次校准所得校准曲线的斜率和截距,符合中国相关标准中关于臭氧监测仪的校准指标:多点校准所得校准曲线的斜率为0.95~1.05,截距为-5~5 nmol/mol。进一步对2台臭氧监测仪进行了稳定性测试,12个月内臭氧监测仪的斜率变化为0.976 05~1.008 42,截距变化为-0.669 00~0.577 93 nmol/mol,臭氧监测仪的斜率、截距均符合臭氧监测仪校准指标的要求。稳定性测试表明,TF 49i型臭氧监测仪和EC 9810型臭氧监测仪经校准后均可用于实验室内臭氧标准传递比对工作。实验中臭氧监测仪更换臭氧涤除器、仪器零件后校准曲线的斜率均有明显变化,建议更换耗材后需采用高浓度臭氧对臭氧监测仪进行饱和并再次校准。     

动态校准仪臭氧间接传递技术

对5台主流动态校准仪开展臭氧间接传递技术研究,对动态校准仪的准确性、可靠性、稳定性及臭氧传递的线性方程等性能参数进行了实验室考察。总体而言,发生型动态校准仪和分析型动态校准仪均可用于臭氧传递工作中。分析型动态校准仪可直接进行臭氧传递,发生型动态校准仪在臭氧传递前必须进行预校准。建议至少每3个月对发生型动态校准仪进行1次臭氧传递,每6个月对分析型动态校准仪进行1次臭氧传递。     

臭氧一级校准数据读取方式对校准的影响研究

臭氧标准参考光度计同时采用串口连接模式、模拟信号连接模式和仪器数据存储-手动输入模式3种数据读取方式对臭氧二级传递标准进行一级校准,比较不同数据读取方式对校准结果的影响。串口连接模式和仪器数据存储-手动输入模式所得到校准曲线的斜率和截距具有很好的一致性,相差较小。经修正转化截距后的模拟信号连接模式所得到的斜率和截距相对于其他2种数据读取方式有一定的差别,但也在校准指标以内。     

环境空气质量自动监测系统中动态校准仪臭氧浓度的复现性研究

通过对含有臭氧发生器的动态校准仪发生的臭氧浓度进行多角度跟踪审查,对其臭氧浓度的复现性进行了评估。总体上,动态校准仪臭氧发生器发生的臭氧浓度存在较大漂移,复现性较差,与臭氧组件的稳定性有很大关系。建议参照美国的臭氧传递分级标准,把动态校准仪作为Level 4级别的传递标准,使用专门用于校准的臭氧分析仪作为Level 3级别的传递标准,在子站现场对动态校准仪和监测用臭氧分析仪进行标准传递,并适当增加传递频次。     

紫外光度法臭氧自动监测仪及其标准传递方法

随着我国经济的快速增长和城市化进程的不断加速,以臭氧为主的光化学污染问题已成为大气环境保护领域关注的重点、热点问题。对臭氧进行自动监测是环境管理和科学研究的需要,文中介绍了臭氧自动监测仪和臭氧量值溯源体系,重点探讨了臭氧监测干扰因素及标准传递方法,并通过实验比较验证了带光度计的臭氧校准仪具有较好的输出稳定性。     

环境监测用5种氯代烯烃混合气体标准样品研制

介绍了1μmol/mol氮气中5种氯代烯气体标准样品的研制方法。这5种氯代烯包括氯乙烯、1,1-二氯乙烯、顺1,2-二氯乙烯、三氯乙烯、四氯乙烯,其中氯乙烯常温下为气态,其他4种为液态,并且沸点低,将这几种氯代烯制备成气体标准样品存在制备精度低、气液转换不完全等困难。经研究,采用2步称量法制备5种氯代烯气体标准样品,重复制备的相对标准偏差小于1.6%。建立了5种氯代烯标准气体瓶内均匀性的实验方法,并通过考察样品量值伴随样品压力的变化来评价样品的均匀性。结果显示,5种氯代烯标准气体是均匀的,最低使用压力为1 MPa。依照ISO 15000.3来考察样品的时间稳定性,样品有效期为12个月。相对扩展不确定度为3%(置信度为95%)。     

用双标准比较法测定氟化物

首先测定待测样品溶液的电位 ,再选择校准曲线几点中最接近未知样品氟浓度高的两点做为标准点 ,测定其电位 ,根据公式即可计算出样品溶液的浓度 :log Cx =log CS1CS2× EX- ES1ES2 - ES1 log CS1　　式中 ES1、ES2 为两标准点的电位 ( - mv) ;EX为未知样品电位 ( - mv) ;CS1、CS2 为所对应的两个标准点溶液的浓度 (μg/ml) ,并且满足 CS2 2 CS1;CX 为未知样品的浓度。本法优点 :1相对标准偏差 <5% ,与标准方法测定结果无显著性差异 ,符合要求。2可以克服电极本身非能斯特性质 ,不受斜率、截距大小制约 ,任何具有一定线性关系…     

趋势分析法评价苯系物标准气体的时间稳定性

根据GB/T 15000.3—2008设计了苯系物标准气体的时间稳定性研究方案,制备了4瓶苯系物标准气体,随着时间的推移进行测定并将结果制图,结果显示量值随时间没有显著的变化趋势。以线性关系为模型,计算线性直线的斜率和斜率的标准偏差,用t检验判断斜率是否显著来评价标准气体的稳定性。计算结果显示,所有斜率均不显著,因此该研究制备的苯系物标准气体能够稳定保存22个月。根据时间稳定性数据计算由不稳定性引起的不确定度,并讨论了这种计算不稳定性引起不确定度的方法对结果有放大的可能性。     

便携式GC-MS测定气体样品中6种典型VOCs的不确定度评定

以便携式GC-MS测定气体样品中6种典型挥发性有机物(VOCs)组分(苯、1,1,2-三氯乙烷、四氯乙烯、乙苯、间二甲苯和1,3,5-三甲基苯)为例,应用不确定度理论,从检测过程和计算方法的角度分析了影响测量不确定度的各种因素:标准气体定值、标准气体稀释、工作曲线的非线性及重复性测定。对各测量不确定度分量进行计算和评定,同时采用稳健统计方法对测定结果进行准确度评价。结果表明:采用便携式GC-MS测定气体样品中VOCs不确定度的主要影响因素是标准气体定值和工作曲线的非线性,其次是重复性测定,标准气体稀释引入的不确定度较小。当VOCs组分含量为200 nmol/mol浓度水平时,测量扩展不确定度为14～17 nmol/mol,测量相对扩展不确定度为7.1%～9.2%(k=2,置信水平为95%),相对误差为1.5%～4.0%。     

臭氧前驱体物监测用氮气中多组分VOCs气体标准物质的研制

介绍了瓶装1μmol/mol臭氧前驱体物监测用氮气中57组分挥发性有机物(VOCs)气体标准物质的研制过程,该气体标准物质严格按照《气体分析 校准用混合气体的制备 第1部分:称量法制备一级混合气体》(GB/T 5274.1-2018)所规定的配制气体标准物质的方法采用称量法制备。建立了GC-MS联用结合选择离子扫描(SIM)的分析方法,研究了目标化合物在气瓶中的均匀性和稳定性。57种目标化合物完全满足美国环保署光化学评估监测站(PAMS)关于臭氧前驱体物VOCs在线监测的技术要求。将气体标准物质分别送至中国环境监测总站和英国国家物理实验室(NPL)进行比对分析,结果良好,表明研制的气体标准物质具有较好的压力均匀性和稳定性,符合使用要求。相对扩展不确定度为5%(k=2),使用有效期为1年,取得国家二级标准物质证书,证书编号为GBW(E)083966。     

美国环境空气臭氧量值传递的经验与启示

新修订的《环境空气质量标准》对环境空气中的臭氧监测提出了明确的要求,一套有效的臭氧量值传递体系已成为保证中国环境空气臭氧监测数据质量的生命线。为加强中国环境空气臭氧量值传递体系的建设,总结了美国环境空气臭氧量值传递体系及其相关的技术规范体系,简要介绍其臭氧量值传递体系各关键环节的质量控制工作要点,并提出了对中国环境空气臭氧量值传递体系建设的建议。     

有机热载体炉大气污染物的适用排放标准

介绍了有机热载体炉的分类和工作原理，并对有机热载体炉与蒸气锅炉的基本特性及其烟尘测试的主要特点进行了比较，提出有机热载体炉大气污染物的适用排放标准应按照GB13271-2001《锅炉大气污染物排放标准》执行。     

Meteorological normalisation and non-parametric smoothing for quality assessment and trend analysis of tropospheric ozone data

Despite extensive efforts to ensure that sampling and installation and maintenance of instruments are as efficient as possible when monitoring air pollution data, there is still an indisputable need for statistical post processing (quality assessment). We examined data on tropospheric ozone and found that meteorological normalisation can reveal (i) errors that have not been eliminated by established procedures for quality assurance and control of collected data, as well as (ii) inaccuracies that may have a detrimental effect on the results of statistical tests for temporal trends. Moreover, we observed that the quality assessment of collected data could be further strengthened by combining meteorological normalisation with non-parametric smoothing techniques for seasonal adjustment and detection of sudden shifts in level. Closer examination of apparent trends in tropospheric ozone records from EMEP (European Monitoring and Evaluation Programme) sites in Finland showed that, even if potential raw data errors were taken into account, there was strong evidence of upward trends during winter and early spring.     

Ozone Indicators Determined at Rural Sites in the Eastern United States by two Monitoring Networks

Ozone levels at Clean Air Status andTrends Network (CASTNet) and nearby rurally-designatedState and Local Air Monitoring Stations (SLAMS) siteslocated in the eastern United States (U.S.) arecompared using daily indicators (i.e., maximum, range,and SUM06) based on hourly O₃ measurements. Comparisons are also made using monthly and summertimethree-month SUM06 determinations aggregated from dailydata. Comparison of O₃ indicators at the pairedCASTNet-SLAMS sites generally shows better agreementfor O₃ maximum than for range or SUM06. Thehighest correlation of daily O₃ indicators occursfor paired sites that are separated by less than 100miles, and the correlation diminishes with increasingseparation distance. Correlation coefficients exceed0.70 in 49% of the comparisons of maximum, in23% of range comparisons and in 5% ofSUM06 comparisons, suggesting that substitution ofSLAMS for CASTNet O₃ measurements would fail tocapture a substantial amount of the variability inO₃ indicators present at the CASTNet sites. Correlations of O₃ indicators at CASTNet andpaired nearby SLAMS sites are 0.80 in a relativelysmall number of cases. Despite the high correlationin even these cases, O₃ behavior at paired sitesis not identical and shows systematic differences thatare reflected in the O₃ minimum, hourly averageconcentrations, and the monthly and three-month SUM06. Ozone measurements at nearby rurally-designated SLAMSsites may not capture the `rural' nature of the airquality being monitored at CASTNet sites and, in mostcases, may not be sufficiently representative of theconcentration at CASTNet sites to permit O₃measurements at SLAMS sites to be used in lieu ofmeasurements at CASTNet sites. As a result, if ruralO₃ concentration data are needed, then O₃monitoring at carefully chosen, rurally representativesites is recommended.     

平流层臭氧深度侵入对典型城区的影响过程分析

中纬度平流层臭氧深度侵入是造成对流层至近地面臭氧浓度突增的原因之一。筛选春夏季臭氧浓度升高时段的高分辨率大气再分析数据ERA5,以位涡值的下沉趋势分析了对流层顶折叠位置及变化过程;以AIRS数据反演了臭氧浓度、一氧化碳浓度和相对湿度的垂直廓线,并估计了其分布及相关性;以近地表污染物浓度变化、HYSPLIT模型后向轨迹分析结果证实了臭氧侵入气团的运移轨迹和局地效应;通过激光雷达监测结果观测臭氧垂直浓度分布,确定了臭氧浓度最大值所处高度,判定了受影响近地点的浓度升高时刻;以边界层高度变化、气象条件分析结果及当地与周边城市地面监测数据的逐小时变化情况等综合信息,进行了区域确认和近地面影响判定。通过以上数值综合分析,对城市地区受平流层臭氧深度侵入影响的过程和具体时间进行了详细再现,可为排除非人为排放因素导致的近地表臭氧浓度增加提供回溯分析,为臭氧污染防控决策提供依据。     

The Characteristics of Tropospheric Ozone Seasonality Observed from Ozone Soundings at Pohang, Korea

This paper presents the first analysis of vertical ozone sounding measurements over Pohang, Korea. The main focus is to analyze the seasonal variation of vertical ozone profiles and determine the mechanisms controlling ozone seasonality. The maxima ozone at the surface and in the free troposphere are observed in May and June, respectively. In comparison with the ozone seasonality at Oki (near sea level) and Happo (altitude of 1840 m) in Japan, which are located at the same latitude as of Pohang, we have found that the time of the ozone maximum at the Japanese sites is always a month earlier than at Pohang. Analysis of the wind flow at the surface shows that the wind shifts from westerly to southerly in May over Japan, but in June over Pohang. However, this wind shift above boundary layer occurs a month later. This wind shift results in significantly smaller amounts of ozone because the southerly wind brings clean wet tropical air. It has been suggested that the spring ozone maximum in the lower troposphere is due to polluted air transported from China. However, an enhanced ozone amount over the free troposphere in June appears to have a different origin. A tongue-like structure in the time-height cross-section of ozone concentrations, which starts from the stratosphere and extends to the middle troposphere, suggests that the ozone enhancement occurs due to a gradual migration of ozone from the stratosphere. The high frequency of dry air with elevated ozone concentrations in the upper troposphere in June suggests that the air is transported from the stratosphere. HYSPLIT trajectory analysis supports the hypothesis that enhanced ozone in the free troposphere is not likely due to transport from sources of anthropogenic activity.