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).     

A physicochemical model of sorption processes in NO2 passive sampling with air humidity effects

Aqueous triethanolamine (TEA) solutions are widely used as sorption medium for passive sampling of ambient NO₂, with NO₂ trapped and accumulated as nitrite ion. The results of test measurements of ambient NO₂ concentrations using passive sampling method showed that the simple approach commonly used to describe passive sampling process might lead to substantial systematic errors. Presented in the article is a new physicochemical model of the process of passive sampling of gaseous NO₂, with aqueous TEA solution used as a trapping medium. The model is based on the available results of experimental studies of interaction of gaseous NO₂ with TEA/water solutions. The key principles underlying the model are: (1) when absorbed by a trapping solution, NO₂ forms nitrite ion only on the condition that TEA is hydrated; (2) coefficient of conversion of NO₂ to NO ₂ ^? is equal to one when reacting with hydrated TEA; and (3) the fraction of hydrated TEA molecules depends on air humidity at the moment of measurement. Validation of the model was made using the data of the field measurements carried out in the Middle Urals in 2007–2009. The new model was used to calculate average NO₂ concentrations. Concentrations calculated agreed well with the results obtained by reference methods. The difference between the datasets was statistically insignificant.     

Evaluation of ogawa passive sampling devices as an alternative measurement method for the nitrogen dioxide annual standard in El Paso, Texas

Nitrogen Dioxide (NO₂) is a common urban air pollutant that results from the combustion of fossil fuels. It causes serious human health effects, is a precursor to the formation of ground level ozone, another serious air pollutant, and is one of the six criteria air pollutants established by the United States (U.S.) Clean Air Act (CAA). Ogawa Passive Sampling Devices (PSDs) for NO₂ were collocated and operated at six NO₂ Federal Reference Method (FRM) monitor locations in the El Paso, Texas area for the 2004 calendar year. Passive samples were taken at 2-week, 3-week, and 4-week intervals and compared against the continuously operating FRM monitors. Results showed that the collective NO₂ annual arithmetic mean for all passive monitors was identical to the NO₂ mean for all FRM monitors. Of the individual locations, three passive annual NO₂ means were identical to their corresponding FRM means, and three passive annual NO₂ means differed from their corresponding FRM means by only one part per billion (ppb). Linear correlation analysis between all readings of the individual NO₂ PSDs and FRM values showed an average absolute difference of 1.2 ppb with an r ² of 0.95. Paired comparison between high and low concentration annual NO₂ sites, seasonal considerations, and interlab quality control comparisons all showed excellent results. The ease of deployment, reliability, and the cost-savings that can be realized with NO₂ PSDs could make them an attractive alternative to FRM monitors for screening purposes, and even possibly an equivalent method for annual NO₂ monitoring. More tests of the Ogawa NO₂ PSD are recommended for different ecosystem and climate regimes.     

川南6市空气中SO2和NO2空间分布特征

利用简单、方便、不用电源的被动采样技术分别对川南地区6市区域范围内空气中SO2和NO2在雨季和旱季的空间分布特征进行研究。按16 km×16 km的均匀网格布设点位162个,并在雨季于6市各选1个空气自动站布设城区点位采集空气中SO2和NO2。获得的样品经0.3%的双氧水浸提后采用离子色谱法进行分析,经换算后获得空气中SO2和NO2的浓度,了解了其含量水平,绘制了SO2和NO2的空间分布图,掌握了其空间分布特征,并对可能的来源进行了浅析。将被动采样监测结果与自动站监测结果进行相关分析,两者高度线性相关,NO2和SO2线性相关系数分别为0.901 3和0.874 5,均大于r0.05(4)=0.811 4。     

Systematic Biases in Measurement of Urban Nitrogen Dioxide using Passive Diffusion Samplers

Measurement of nitrogen dioxide using passivediffusion tube over 22 months in Cambridge, U.K. areanalysed as a function of sampler exposure time, andcompared with NO₂ concentrations obtained from aco-located chemiluminescence analyser. The averageratios of passive sampler to analyser NO₂ at acity centre site (mean NO₂ concentration 22 ppb)are 1.27 (n = 22), 1.16 (n = 34) and 1.11 (n = 7) forexposures of 1, 2 and 4-weeks, respectively. Modellingthe generation of extra NO₂ arising from chemicalreaction between co-diffusing NO and O₃ in thetube gave a ratio (modelled/measured) of 1.31 for1-week exposures. Such overestimation is greatest whenNO₂ constitutes, on average, about half of totalNO_x (= NO + NO₂) at the monitoring locality.Although 4-week exposures gave concentrations whichwere not significantly different from analyserNO₂, there was no correlation between thedatasets. At both the city-centre site and anothersemi-rural site (mean NO₂ concentration 11 ppb)the average of the aggregate of four consecutive1-week sampler exposures or of two consecutive 2-weeksampler exposures was systematically greater than fora single 4-week exposure.The results indicate two independent and opposingsystematic biases in measurement of NO₂ bypassive diffusion sampler: an exposure-timeindependent chemical overestimation with magnitudedetermined by local relative concentrations of NO andO₃ to NO₂, and an exposure-time dependentreduction in sampling efficiency. The impact of theseand other potential sources of systematic bias on theapplication of passive diffusion tubes for assessingambient concentrations of NO₂ in short (1-week)or long (4-week) exposures are discussed in detail.     

Inter-Laboratory Comparison of No2 and SO2 Generated by Dynamic Dilution System Under Laboratory Conditions: A Technical Discussion

A workshop on analytical quality control (AQC) of ambient air quality measurement methods for nitrogen dioxide (NO₂) and sulphur dioxide (SO₂) was conducted by Central Pollution Control Board (CPCB) for officials involved in National Ambient Air Quality Monitoring (NAAQM) in India. Concentrations of NO₂ and SO₂ were generated by dynamic dilution system under laboratory conditions at low and high levels and measured using static dilution system and wet chemical methods laid down by CPCB under section 16(2)(h) of the air act 1981. CPCB provided the measured values as reference values for comparing the means obtained by the officials participated from thirteen organizations. A tolerance limit of ±15% of the reference values was specified to accept the results. Generated concentrations, which were unknown to the participants, were measured using gaseous sampling assembly (Envirotech APM 411, New Delhi, India), and wet chemical methods laid down by CPCB i.e. the same methodology which is used by the organizations to generate the data of NO₂ and SO₂ in ambient air. Simultaneously, concentrations were checked by CPCB using automatic analyzers as a check on reference concentration. It is observed that results of automatic analyzers for NO₂ and SO₂ were within a tolerance of ±5% with %RSD below 3. On the other hand, results of most of the participants showed variability in the measurements with %RSD ranging between ±0.8 and ±88.6 and exceedences of means from the tolerance limit with bias ranging between 1.4 and −59%. To check the cause of high variability in the measurements obtained under identical conditions, duplicate sampling was performed by one of the participants for SO₂ at low concentration level. In this study, results of wet chemical methods, automatic analyzers and results of duplicate sampling are analysed statistically to assess the cause of high variability in the measurements. Analysis of t-test and analysis of variance (ANOVA) showed highly significant results for NO₂ and SO₂ at high concentration levels (α 0.05) and for SO₂ at both the levels (α 0.01) respectively indicating some bias is existing either in the sampling or in analytical technique. Duplicate sampling performed to check precision in parallel measurements showed high %RSD indicating the presence of systematic error in sampling technique as the same calibration factor (CF) was used to measure the concentration of duplicate samples. Statistical analysis of flow rates of duplicate sampling showed that the sampling assembly could not maintain the constant flow rate within the ±10% with that measured at the start of the sampling. This resulted in high %RSD and deviation from the reference values for the results of most of the participants, even after accepting ±15% tolerance limit. There is a need to improve and evaluate this gaseous sample collection device under laboratory conditions to generate reliable database of NO₂ and SO₂ in ambient air.     

离子色谱法测废印刷电路板真空热解气相污染物中HBr、NO2和SO2

在淋洗液中加入H2O2和三乙醇胺配制成吸收液,通过离子色谱法同时测定废印刷电路板真空热解气相产物中HBr、NO_2和SO_2的含量,方法简单、快速、准确。当用50 m L吸收液、采样体积为30 L时,3种污染物的检出限分别为0.000 005 7、0.000 003 4、0.000 002 9 mg/L。该方法加标回收率为95.7%~104.8%,完全能满足废印刷电路板真空热解气相污染物中HBr、NO_2和SO_2的同时测定要求。利用该方法和行标方法同时测定环境空气中的HBr、NO_2和SO_2,再利用Excel分析工具对测定数据进行F检验和t检验,检验结果表明2种测定方法无显著差异。     

Assessment of environmental impact on air quality by cement industry and mitigating measures: a case study

In this study, environmental impact on air quality was evaluated for a typical Cement Industry in Nigeria. The air pollutants in the atmosphere around the cement plant and neighbouring settlements were determined using appropriate sampling techniques. Atmospheric dust and CO₂ were prevalent pollutants during the sampling period; their concentrations were recorded to be in the range of 249–3,745 mg/m³ and 2,440–2,600 mg/m³, respectively. Besides atmospheric dust and CO₂, the air pollutants such as NO _x , SO _x and CO were in trace concentrations, below the safe limits approved by FEPA that are 0.0062–0.093 mg/m³ NO _x , 0.026 mg/m³ SO _x and 114.3 mg/m³ CO, respectively. Some cost-effective mitigating measures were recommended that include the utilisation of readily available and low-cost pozzolans material to produce blended cement, not only could energy efficiency be improved, but carbon dioxide emission could also be minimised during clinker production; and the installation of an advance high-pressure grinding rolls (clinker–roller-press process) to maximise energy efficiency to above what is obtainable from the traditional ball mills and to minimise CO₂ emission from the power plant.     

几种空气质量预报方法对冬季预报效果的评估与对比

基于2016年冬季泰州市环境空气质量自动监测数据,定量评估NAQPMS模式、CMAQ模式和人工订正对污染物质量浓度和空气质量等级的预报效果。结果表明,模式预报和人工订正对各污染物预报的相关系数由高到低排列为PM_(2.5)、PM_(10)、NO_2、SO_2、O_3-8h,颗粒物预报效果最好。除O_3-8h外,NAQPMS对各项污染物预报的相关系数R为0.47～0.82,CMAQ为0.75～0.81,人工订正为0.43～0.78,3种预报方式均能准确反映污染物浓度的变化趋势;模式预报、人工订正对O_3-8h预报相关系数均0.4。在发生颗粒物污染过程时,人工订正结果相对更为准确。NAQPMS、CMAQ和人工订正对空气质量等级24 h预报准确率分别为38.9%、41.1%和35.6%,NAQPMS对优类别的预判准确率较高,CMAQ、人工订正对良类别的预判准确率较高。对比不同时效的预报效果,24 h预报时效的准确率高于48和72 h。提出,城市空气质量预报可采用集合预报方式,综合1～2种运行较稳定的主流预报模式预报结果,预报员对模式模拟结果进行人工修订,提高预报准确率。     

Assessment of Temporal and Spatial Variation of Nitrate Removal in Riparian Zones

The aim of this study was to monitor long-term temporal and spatial groundwater NO₃^- removal efficiencies in different riparian zones via a limited number of sampling wells. Groundwater NO₃^- concentrations were measured fortnightly or monthly over a period of two years using transects of ground water sampling wells. Depending on the level of the NO₃^- load (up to 120mgNL^-1 at the input side of the riparian zone a distance of 10 to 30m was needed to remove NO₃^- from the groundwater below 11.3mgNL^-1. Considering all seasons, the mixed vegetation and grass riparian site succeeded to remove groundwater NO₃^- efficiently (92—100% within a distance of 30m. The forested riparian zone removed 72—90% of the total NO₃^- input within a distance of 30m. Evidence emerged that NO₃^- could also be removed actively at depths up to 2m, due to the presence of organically enriched layers of alluvial deposits or roots. Our four dimensional approach (three dimensional space and time), in combination with a limited number of sampling wells, was shown to be a useful monitoring tool to assess the variability of NO₃^- removal in riparian zones.     

Spatial and temporal analysis of ground level ozone and nitrogen dioxide concentration across the twin cities of Pakistan

The analyses presented in this paper include the concentration levels of NO₂ and O₃ measured during 2 successive years in twin cities (Rawalpindi and Islamabad) of Pakistan from November 2009 to March 2011. NO₂ was determined using the passive sampling method, while ozone was determined by Model 400E ozone analyzer. The average NO₂ and O₃ concentration in twin cities of Pakistan was found to be 44?±?6 and 18.2?±?1.24 ppb, respectively. Results indicate that the concentration of NO₂ and O₃ show seasonal variations. Results also depict that NO₂ and O₃ concentration levels are high in areas of intense traffic flow and congestion. Rawalpindi has more elevated levels of NO₂ and O₃ as compared to the Islamabad due to the narrow roads, enclosing architecture of road network and congestion. Climatic variables also influenced the NO₂ and O₃ concentration, i.e., temperature is positively related with O₃, while negatively related with NO₂, relative humidity is directly related with NO₂ and inversely related with O₃, whereas rainfall show negative association with both NO₂ and O₃ concentration. Comparing the results with WHO standards reveals that NO₂ concentration levels at all the sampling points are above the permissible limit, while ozone concentration is still lower than the WHO standards. Thus, there is a need to take appropriate steps to control these continuously increasing levels of NO₂ and O₃ before they become a serious hazard for the environment and people living in those areas.     

Assessment of Urban Air Quality in South Estonia by Simple Measures

In countries having limited resources, it is difficult to assess urban air quality on contemporaneously, due to the absence of on-line information about air pollution levels and emission rates. An alternative approach is recommended for smaller cities with lower demands of resources. The applied scheme consists of a database of air pollution sources (NO _x and CO from industry, traffic, and domestic heating), the simple Gaussian-plume model AEROPOL and a series of measurements by passive monitors. This method was used in Tartu, a small city situated in the valley of the river Emajõgi, within a landscape with noteworthy topographical variations. Simulations of annual average and maximal concentrations were performed, and a fair agreement obtained with NO₂ monitoring results from passive Palmes monitors. Inventories of pollution sources in 1998 revealed that official statistics of stationary sources covered 64% of SO₂,36% of CO, 37% of NO _x and 32% of total particulate matter emissions. Recommendations for measures for reducing air pollution levels and for further investigations towards improving air quality assessment and management, are given.     

An Analysis of Secondary Pollutants in Buenos Aires City

Air pollutant concentrations from a monitoring campaign in Buenos Aires City, Argentina, are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO _x (=NO + NO₂). This campaign undertaken by the electricity sector was aimed at elucidating the apportionment of thermal power plants to air quality deterioration. Concentrations of carbon monoxide (CO) and sulphur dioxide (SO₂) were also registered. Photo stationary state (PSS) of the NO, NO₂, O₃ and peroxy radicals species has been analysed. The ‘oxidant’ level concept has been introduced, OX (=O₃ + NO₂), which varies with the level of NO _x . It is shown that this level is made up of NO _x -independent and NO _x -dependent contributions. The former is a regional contribution that equates the background O₃ level, whereas the latter is a local contribution that correlates with the level of primary pollution. Furthermore, the anticorrelation between NO₂ and O₃ levels, which is a characteristic of the atmospheric photo stationary cycle has been verified.The analysis of the concentration of the primary pollutants CO and NO strongly suggests that the vehicle traffic is the principal source of them. Levels of continuous measurements of SO₂ for Buenos Aires City are reported in this work as a complement of previously published results.     

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air

The performances and applicability of a diffusion tubesampler for the simultaneous measurements of NO₂ andSO₂ in ambient air were evaluated. SO₂ andNO₂are collected by the passive sampler using triethanolamine astrapping agent and are determined as sulphate and nitrite withion chromatography. The detection limit (2.3 g m^-3 ofNO₂ and 4.2 g m^-3 of SO₂ for two weekssampling) is adequate for the determination of concentrationsin urban and industrial areas. Precision of the method as RSDis in mean 5% for NO₂ and 12% for SO₂ at theconcentration levels in urban areas. Calibration of the methodwas performed in the field conditions by comparison between theresponses of sampler and the concentrations measured by thecontinuous monitors. High degree of linearity (correlationcoefficients > 0.8) is found between the passive sampler tubeand the continuous monitor data for both NO₂ and SO₂.To reduce the wind velocity influence on passive sampling ofdiffusion tubes, a protective shelter was tested in this study.The overall uncertainty of one measure for the optimised methodis estimated at 5 g m^-3 for NO₂ and 6g m^-3 for SO₂. Suitability of this passivesampling method for air pollution monitoring in urban areas wasdemonstrated by the results shown in this paper on a campaigncarried out in the French agglomeration.     

Analysis and evaluation of nitrate levels in groundwater at Al-Hashimiya area, Jordan

Water with high nitrate concentration (NO₃ ⁻) is unfit for human consumption, especially when its concentration exceeded the threshold limit (50 mg/l) recommended by the health authorities such as the World Health Organization (WHO). In Jordan, there is a great concern for determination and monitoring organic and inorganic pollutants that may reach groundwater. Nitrate is highly mobile and present in domestic, agricultural and industrial waste in Jordan, and thus this study focused initially on nitrate as both a contaminant of concern and as an indicator of potential groundwater contamination. The present study determined the extent of nitrate contamination in groundwater in the study area and examined the likely sources of NO₃ ⁻. A total of 248 groundwater samples were collected from 16 wells in different sites of Al-Hashimiya area, Zerqa Governorate, Jordan, and investigated for NO₃ ⁻ concentrations. Moreover, measurements of temperature, electrical conductivity and pH were carried out in the field. Analysis was carried out according to the methods described by the American Public Health Association (APHA). Results showed that there was a dramatic increasing in NO₃ ⁻ concentrations from the year 2001 to 2006 for some selected wells in the present study. NO₃ ⁻ concentration in 2006 was ranged from 10 to 330 mg/l with an average of 77 mg/l. Overall, groundwater had elevated nitrate concentration with 92% of the samples containing more than 20 mg/l NO₃ ⁻, indicating the influence of human activities. This study has shown that there is a strong correlation between the nitrate concentration and the wastewater effluents as a source of pollution.     

A necessary distinction between spatial representativeness of an air quality monitoring station and the delimitation of exceedance areas

The European legislation on ambient air quality introduces the concepts of spatial representativeness of a monitoring station and spatial extent of an exceedance zone. Spatial representativeness is an essential macro-scale siting criterion which should be evaluated before the setting-up and during the life of a monitoring point. As for the exceedance area, it has to be defined each time an environmental objective is exceeded in an assessment zone. No specific approach is prescribed to delimit such areas. A probabilistic methodology is presented, based on a preliminary kriging estimation of atmospheric concentrations at each point of the domain. It is applied to NO₂ pollution on the urban scale. In the proposed approach, a point belongs to the area of representativeness of a station if its concentration differs from the station measurement by less than a given threshold. To take the estimation uncertainty into account, the standard deviation of the kriging error is used in a probabilistic framework. The choice of the criteria used to deal with overlapping areas is first tested on NO₂ annual mean concentration maps of France, built by combining surface monitoring observations and outputs from the CHIMERE chemistry transport model. At the local scale, data from passive sampling surveys and high -resolution auxiliary variables are used to provide a more precise estimation of the background pollution in different French cities. The traffic-related pollution can also be accounted for in the map by additional predictors such as distance to the road, and traffic-related NO_x emissions. Similarly, the proposed approach is implemented to identify the points, at a given statistical risk, where the NO₂ concentration is above the annual limit value.     

Effect Of Reagent (Dye) Addition In Wet Chemical Method Of Sulfur Dioxide Determination In Ambient Air

For measurement of sulfur dioxide (SO₂) in ambient air, the United States Environment Protection Agency (US EPA) had recommended the PRA dye-based colorimetric method as a reference technique. The method has been developed and applied in many countries for a longtime; however information regarding the sensitivity of the method with respect to sampling and analysis conditions is not available. Collaborative studies conducted in some of the South East Asian countries indicated substantial variations (of the order of 50%) in the measured concentrations against the true values. It was observed that dye used for color development plays an important role and even a slight variation in the way the dye solution is prepared can cause substantial variation in the measured SO₂ concentration. Because a major objective of air quality measurements is to relate air pollution concentration to the effects of air pollution, it is important that the method used should yield accurate levels of the pollutant, so that appropriate management plans can be devised and implemented effectively. In the present investigation, therefore, the role of dye used in SO₂ monitoring method has been highlighted. Different makes of dyes prepared in different modes were used to study the variation in the measured SO₂ concentration levels. Specifications of all the dyes were also tested. Need for use of certified reference material (CRM) for SO₂ has also been emphasized.     

多泥沙水体中六六六(HCH)残留SPE提取方法的优化

多泥沙河流中六六六(HCH)的提取一直是分析化学领域的难点之一。选定固相萃取法(SPE)作为样品的提取方法,并以α-HCH、β-HCH、γ-HCH、δ-HCH为标准溶液,对提取方法进行了优化,确定了适应于多泥沙水体中六六六农药残留的SPE提取流程。该流程适用于地表水和地下水、工业废水等含泥沙或不含泥沙的水体中六六六农药残留的提取,且有很强的适应性和可重复性。     

郑州市对流层NO2柱浓度时空变化及其影响因素

基于郑州市2005—2015年的OMI遥感反演资料以及地面相关监测数据,研究了郑州市对流层NO_2的时空分布特征,并利用灰色关联法对郑州市NO_2柱浓度变化的主要影响因素进行分析。与地面观测数据对比检验显示,对流层NO_2柱浓度年均值数据与近地面监测站NO_2浓度的实测年均值数据呈显著的正相关,相关系数分别为0.884 6和0.940 2,表明OMI数据资料可以较好地反映地面NO_2浓度的变化。郑州市的对流层NO_2柱浓度在2005—2013年间呈现波动变化且2013—2015年NO_2柱浓度显著减小的特征。季节变化上NO_2柱浓度主要表现为冬季秋季春季夏季的特点。郑州市对流层NO_2柱浓度的空间变化分布主要表现为由北部向南部逐渐递减的趋势,年际变化上高值区与低值区变化不够显著,中值区近年来不断扩大。灰色关联度分析结果显示,汽车保有量与对流层NO_2柱浓度的灰色关联度最低为0.571,而标准煤消耗量、工业用电量以及采暖供热量与对流层NO_2柱浓度的灰色关联度比较高,分别为0.956、0.828、0.862,即大气中工业过程及采暖期煤炭燃烧排放的NO_2占较大比例,汽车尾气排放所占的比例相对较小。     

A Comparison of Biomonitoring Methods for the Estimation of Atmospheric Pollutants in an Industrial Town in Austria

In the period between 1999 and 2000 epiphytic bryophytes were taken as bioindicators for air pollution by use of the IAP method (Index of Atmospheric Purity) and the VDI method within the Association of Engineers standards list (adapted from guideline 3799, 1995) in the heavy industrialized town of Linz, Austria. 52 study sites (265 trees) were analysed regarding species richness, coverage, and vitality. Q-values (sensitivity factors), calculated for each species showed significant differences for the various host tree species. The results gained by the IAP and the VDI methods were diverse, regarding the various sites where only 25% were classified identical. These differences can mainly be attributed to the differing host tree species and the size of the recording area on the various trees. Clusters of similar pollution levels were calculated and drawn as maps for both methods tested. Comparing the results of the IAP and the VDI methods with data derived from technical measurements (SO₂, NO, NO₂, and dust) a correlation between IAP-indices and SO₂ concentrations could be observed. No correlation was detected between the results derived from VDI recording and for NO, NO₂, and dust.