Validation of a diffusive sampler for NO2

A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min-1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 micrograms m-3 for a 24 h sample. The capacity is high enough to allow sampling of 150 micrograms m-3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performed well, even at wind speeds higher than 2 m s-1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2-8 h in working environments.     

Effect of Temperature on Absorption Efficiency of NO2 in Arsenite Method

The sodium arsenite method developed by Jacobs andHochheiser is one of the most widely used manualmethods for nitrogen dioxide (NO₂) monitoring inambient air, particularly in developing countries. Asreported, the method gives 82% NO₂ absorptionefficiency (NAE) in the concentration range from 40 to750 g/m³, when only one impinger tube isemployed in the sampling train at a flow rate of 0.2lpm and for 24 h sampling duration. Accordingly,a uniform correction factor (0.82) is used indenominator to calculate the ultimate concentration ofNO₂ in ambient air.In the present investigation, the effect oftemperature on absorption efficiency of NO₂ isstudied employing four impinger tubes in series tocollect the maximum NO₂ generated in the gasstream. The study conducted at 16, 26 and 36 °Ctemperatures shows maximum absorption efficiency(average) of 87.8% at 26°C in 1st impingertube. At lower and higher temperatures, it is foundconsiderably less. A suitable correction factor,therefore, must be applied to estimate actual NO₂concentration in ambient air using arsenite method, intropical countries like India, where atmospherictemperature variations are large (less than 5°Cin winter and more than 45°C in summer).     

湿法脱硫后高湿烟气中SO3酸雾监测方法研究

利用三氧化硫(SO3)发生装置以及模拟烟气湿法脱硫系统,研究了烟气再热温度、恒温水浴温度、采样速率、冷凝管类型规格及吸收瓶个数等不同采样参数对SO3酸雾采集率的影响。结果表明,当烟气再热温度低于烟气酸露点时会导致SO3酸雾收集率下降,采用控制冷凝法采样时应使用大流量(10L/min)采样,冷凝管应选择外套长度为400 mm的蛇形螺旋冷凝管,并将冷凝管置于温度为65℃左右的恒温水浴中;用碱液吸收法采样时应串联3个吸收瓶后,使用小流量(1L/min)采样。烟气温湿度、二氧化硫(SO2)浓度以及烟气中共存组分等对碱性吸收法的采集影响较大,而对控制冷凝法几乎没有影响。因此确立了针对湿法脱硫后高湿烟气环境下SO3酸雾的监测方法为控制冷凝法更为适宜。     

化学吸收法采集固定污染源氨气的影响因素探究

固定污染源氨气的手工监测,干扰因素较多,其中采样环节尤为关键。实验通过催化氧化-化学发光法考察不同采样管线材质对氨气的吸附效果,离子色谱法考察化学吸收法采集氨气的吸收瓶类型、采样流量、吸收液种类、吸收液浓度及体积等采样条件对氨气吸收效率的影响。实验表明,316 L不锈钢与聚四氟乙烯对氨气的吸附较小,氨气的采样流量不宜超过1.0 L/min,棕色气泡式吸收瓶更适用于氨气样品的采集,磷酸溶液作吸收液对氨气的吸收效率较好,对于低浓度的氨气样品,应采用低流量长时间采集。     

Development of a personal monitoring method for nitrogen dioxide and sulfur dioxide with Sep-Pak C18 cartridge sampling and ion chromatographic determination

Personal monitoring methods for the determination of hourly integrated concentrations of NO2 and SO2 in ambient air have been developed. Triethanolamine (TEA)-impregnated C18 Sep-Pak cartridges were used to collect NO2 and SO2 simultaneously. After sampling, NO2 and SO2 as their nitrite, nitrate, sulfite and sulfate analogues were stripped from the cartridges with a solution of 5% methanol in distilled, deionized water (DDW) and then determined by ion chromatography. Laboratory tests were conducted to evaluate the sampling rate, collection and recovery efficiencies, breakthrough volumes, absorption capacity, interference and sample stability on the cartridge during storage. NO2 and SO2 detection limits of 0.3 and 0.4 ppb respectively for 1 h samples were obtained. Recoveries for both NO2 and SO2 exceeded 85%.     

Determination of acrylic acid in air by using diffusion denuder tubes combined with HPLC technique

A procedure for the determination of atmospheric acrylic acid in air at the microgram m-3 to mg m-3 level is described. Diffusion-based sampling, designed to discriminate gaseous analytes from their particulate counterparts, has been used. Acrylic acid is collected with an efficiency of > 98% in tubular denuders coated with sodium hydroxide-barium hydroxide-hydroquinone monomethyl ether, and analyzed by high performance liquid chromatography with UV absorbance detection. The detection limit is 2.9 micrograms m-3 at a flow rate of 0.5 L min-1 and 30 min sampling time. A precision (p = 0.95, n = 10) of 7.5% of the overall procedure was achieved at the 100 micrograms m-3 level. Results of laboratory studies concerning the effect of the coating reagent and the relative humidity on the sampling efficiency as well as possible interferences, in particular by ozone, and the elimination of these interferences are discussed. This method was developed to monitor workplace atmospheres as well as ambient air in industrial environments.     

镀金石英砂吸附-AMA 254测汞仪测定大气中痕量汞的研究

采用镀金石英砂来富集大气中的气态总汞,AMA 254测汞仪测定。结果表明,不同采样时间下的单级吸附管的吸附效率均在90%以上,采样40min时的相对标准偏差为5%左右。与巯基棉吸附和吸收液吸收方法的对比显示,该方法具有吸收效果好、多次采样的精密度高、操作简便并且可以再生重复使用等优点。运用该法,对徐家汇等几个地点的大气总汞进行了测定。     

A multiresidue method for the analysis of phenols and nitrophenols in the atmosphere

A method using GC-MS and derivatization with N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) was developed for the analysis of 20 phenolic compounds in atmospheric samples (gas and particles). Air sampling was carried out using a Hi-Vol sampler with glass fibre filter and XAD-2 resin at a flow rate of 60 m(3) h(-1). The particle and gas phases were collected separately over a period of 4 h. Samples were Soxhlet extracted, evaporated to dryness under nitrogen and refilled with acetonitrile. 100 microl of these extracts were derivatized with 100 microl of MTBSTFA at 80 degrees C for 1 h under strong stirring. Phenolic compounds were injected into a GC-MS in splitless mode and quantified as their TBDMS derivatives in the SIM mode. Mass spectral analysis of the derivatives of the 20 compounds studied indicates that the spectra are highly specific showing an ion at [M - 57]+ which is useful for structure confirmation or analysis at low levels using selected ion monitoring. Quantification limits varied between 5 microg l(-1) and 10 microg l(-1) which correspond to 20 pg m(-3) and 40 pg m(-3) for 250 m(3) of air sampled. This method was successfully applied to atmospheric samples.     

Comparison of Two Manual Methods of Nitrogen Dioxide Determination in Ambient Air

Sodium arsenite (modified Jacobs and Hochheiser method; hereafter referred as SA), the most widely used manual monitoring method for determination of nitrogen dioxide (NO₂) in ambient air, particularly in developing countries has been evaluated and compared with US EPA recommended equivalent method of TGS-ANSA (hereafter referred as ANSA). NO₂ concentrations generated from laboratory test atmosphere were analyzed by these two methods and were compared statistically. Laboratory evaluations showed that SA method has high sensitivity to different sampling conditions, which normally vary during actual field monitoring. Hence, correction factors for absorption efficiency were estimated for SA and ANSA methods. Absorption efficiency of NO₂ in SA method was found to be much lower (64%) as against the reported value of 82% at the method recommended sampling conditions, whereas for ANSA method, it was found 1.0 as against the reported value of 0.93. After applying derived correction factors, both the methods produced almost similar concentration values of NO₂.     

A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

CO and NO2 pollution in a long two-way traffic road tunnel: investigation of NO2/NOx ratio and modelling of NO2 concentration

The CO, NO and NO2 concentrations, visibility and air flow velocity were measured using continuous analysers in a long Norwegian road tunnel (7.5 km) with traffic in both directions in April 1994 and 1995. The traffic density was monitored at the same time. The NO2 concentration exceeded Norwegian air quality limits for road tunnels 17% of the time in 1994. The traffic through the tunnel decreased from 1994 to 1995, and the mean NO2 concentration was reduced from 0.73 to 0.22 ppm. The ventilation fan control, based on the CO concentration only, was unsatisfactory and the air flow was sometimes low for hours. Models for NO2 concentration based on CO concentration and absolute air flow velocity were developed and tested. The NO2/NOx ratio showed an increase for NOx levels above 2 ppm; a likely explanation for this phenomenon is NO oxidation by O2. Exposure to high NO2 concentrations may represent a health risk for people with respiratory and cardiac diseases. In long road tunnels with two-way traffic, this study indicates that ventilation fan control based on CO concentration should be adjusted for changes in vehicle CO emission and should be supplemented by air flow monitoring to limit the NO2 concentration.     

Spatial analysis and land use regression of VOCs and NO2 in Dallas, Texas during two seasons

Passive air sampling for nitrogen dioxide (NO(2)) and select volatile organic compounds (VOCs) was conducted at 24 fire stations and a compliance monitoring site in Dallas, Texas, USA during summer 2006 and winter 2008. This ambient air monitoring network was established to assess intra-urban gradients of air pollutants to evaluate the impact of traffic and urban emissions on air quality. Ambient air monitoring and GIS data from spatially representative fire station sites were collected to assess spatial variability. Pairwise comparisons were conducted on the ambient data from the selected sites based on city section. These weeklong samples yielded NO(2) and benzene levels that were generally higher during the winter than the summer. With respect to the location within the city, the central section of Dallas was generally higher for NO(2) and benzene than north and south. Land use regression (LUR) results revealed spatial gradients in NO(2) and selected VOCs in the central and some northern areas. The process used to select spatially representative sites for air sampling and the results of analyses of coarse- and fine-scale spatial variability of air pollutants on a seasonal basis provide insights to guide future ambient air exposure studies in assessing intra-urban gradients and traffic impacts.     

Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.     

液相催化氧化法烟气脱硫热态试验

采用液相催化氧化法和穿流式筛板吸收塔进行了规模为１０００ｍ３／ｈ烟气脱硫热态试验。结果表明，当吸收液为浓度０１Ｍ的Ｆｅ２＋＋Ｍｎ２＋水溶液，烟气风量在８１８～１４１８ｍ３／ｈ，液气比为１Ｌ／ｍ３，ＳＯ２入口浓度在７８７～７８２１ＰＰｍ范围内脱硫率可达４９～６９％。穿流式筛板塔具有处理能力大、阻力小、不易堵塞、结构简单、传质效果好等特点     

固体进样-电热蒸发-原子吸收法测定土壤中的镉

采用固体进样原子吸收法直接测定土壤中的镉,可以避免传统酸消解预处理过程耗时长、试剂消耗大、操作步骤繁琐等缺点,提升镉的检测效率。通过优化测镉仪的仪器参数,确定了固体进样-电热蒸发-原子吸收法的优化仪器条件。采用优化条件测定了不同浓度的土壤样品,研究了该方法的检出限、正确度、精密度。研究结果表明:镉质量范围为0~200 ng时与峰面积的线性相关系数优于0.999 5,空气流下优化的灰化温度和热解温度均为800 ℃,优化的热解气体氢气流量为300 mL/min,当样品进样量为0.1 g时,检出限为0.009 mg/kg,7次连续测定相对标准偏差为1.4%~5.0%,加标回收率为96.2%~102.1%,分析时间小于4 min。该方法操作简便,用时短,无需高压气源,可以用于土壤中镉的高效检测。     

地表水自动与常规监测评价结果一致性对比分析

选择分布在不同流域的15个与自动监测站位置一致性较好的断面,对其进行为期1年的“同时同点位”对比监测。分析数据发现:由于采样时间和位置的偏差,自动监测月均值与常规手工监测数据的可比性并不理想。采用以下4种方法评价水质:自动5项、手动5项、手动21项、自动5项+手动16项。比较第1和第2种方法,水质评价类别相同与变化一类(发生一个水质类别变化)的占比之和在85%左右;比较第1和第3种方法,类别相同与变化一类的占比之和在80%左右;比较第3和第4种方法,类别相同与变化一类的占比之和接近90%,因此该组合是更合理的地表水水质评价方法。     

Colorimetric determination of formaldehyde in air using a hanging drop of chromotropic acid

A simple and sensitive method to determine parts per billion (ppb) of atmospheric formaldehyde in situ, using chromotropic acid, is described. A colorimetric sensor, coupled to a droplet of 15.5 microL chromotropic acid, was constructed and used to sample and quantify formaldehyde. The sensor was set up with two optical fibers, a light emitting diode (LED) and two photodiodes. The reference and transmitted light were measured by a photodetection arrangement that converts the signals into units of absorbance. Air was sampled around the chromotropic acid droplet. A purple product was formed and measured after the sampling terminated (typically 7 min). The response is proportional to the sampling period, analyte concentration and sample flow rate. The detection limit is approximately 2 ppb and can be improved by using longer sampling times and/or a sampling flow rate higher than that used in this work, 200 mL min-1. The present technique affords a simple, inexpensive near real-time measurement with very little reagent consumption. The method is selective and highly sensitive. This sensor could be used either for outdoor or indoor atmospheres.     

污染源废气中二噁英监测采样应注意的几个问题

解析废气中二噁英监测采样的现状及不足,针对生活垃圾焚烧炉(炉排炉)、蓄热式焚烧炉(RTO)和危险废物焚烧炉(回转窑)3种不同类型焚烧炉,考察了采样过程中烟道类型、采样时间和采样时间间隔不同对二噁英监测的影响。结果表明,在水平烟道和垂直烟道采样测得二噁英排放浓度水平相当,有垂直烟道时,优先在垂直烟道采样;间隔采样和连续采样二噁英测定结果基本一致,为了便于操作,建议均采用连续采样方式;采样时间上,生活垃圾焚烧炉应保证超过1 h,蓄热式焚烧炉以2 h左右为宜;间歇投料危险废物焚烧炉应尽量满足2 h以上,条件不许可时,可通过增加采样流量缩短采样时间保证采样量,并在危险废物完全燃烧前结束采样工作。     

主动采样法采集博物馆空气中微量污染气体

根据博物馆污染气体的种类,对气体主动采样法进行了采样器种类、吸收液种类和浓度、吸收液体积的选择。验证了气体采样流量、采样时间与气体采样浓度的线性关系,确定了酸性和碱性污染气体的主动采样方法,为监测文物保存环境污染气体提供了可行方法。     

On-site simultaneous determination of anions and cations in drainage water using a flow injection-capillary electrophoresis system with contactless conductivity detection

Drainage water diverted from a farm pasture, which was heavily loaded with manure, was monitored during a rain event. Concurrent anion and cation determinations at intervals of 10 min could be achieved with a new capillary electrophoresis system employing dual injection at opposite ends of the separation capillary. The flow injection approach enabled automation of the sampling process. Interruption of the separation voltage was not necessary. Contactless conductivity detection with an electrolyte solution optimized for the purpose allowed the facile simultaneous detection of the inorganic ions Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), NO(2)(-), NH(4)(+), K(+), Ca(2+), Na(+) and Mg(2+) and the acquisition of temporal concentration profiles of these species. The detection limits achieved were between 20 and 200 [micro sign]g l(-1) for all ions and the repeatability of peak areas and peak heights was better than 1%. The quantitative results were verified by analysing individual samples later in the laboratory with photometry and ion chromatography and the average deviations were found to be between 4 and 12%. This contribution presents a further step in the development of capillary electrophoresis towards a fully automated, low maintenance field method.