氮氧化物检测结果可靠性影响因素研究

针对氮氧化物检测时分析方法及结果可能出现的问题进行了讨论,并对其可靠性进行了验证。以氮氧化物分析仪(化学发光原理)检测氮氧化物(NO_x)为例,分别对是否校准、定值标准的选择及不同工作模式3种情况下氮氧化物浓度测量结果的可靠性及影响因素进行评价,并用另外一种不同工作原理的傅里叶红外变换光谱法进行结果确认。结果表明:氮氧化物分析仪以自动模式进行工作时,不进行校准很可能得到完全错误的分析结果;浓度合适的标准物质的选择有利于提高分析结果的准确度。     

Model Assessment of Air-Pollution in Prague

Results of relatively simple gaussian dispersion model are presented. This model, developed in the beginning of this decade, is suitable mainly for determination of spatial distributions of annual mean concentrations of such kinds of air-pollution as sulphur dioxide (SO₂), mixture of nitrogen oxides (NO_x) or suspended particulate matter (SPM) from all types of emission sources located within the city - point sources, line sources and area sources. Model has been used in years 1994, 1996 and 1998 to assess the air-pollution distributions of the above mentioned kinds in the Prague area and the development of the air quality state. It contributed to the decision making process when possible impact of some changes in traffic system or in system of domestic heating, for example, has been investigated. In this contribution, behaviour of sulphur dioxide (SO₂) and mixture of nitrogen oxides (NO_x) ground concentration distributions are analyzed with respect to changing emission situation in Prague in recent years. Results show that SO₂ ground concentration level decreases mainly due to changes in local heating methods and type of fuel used. Different trend can be seen in NO_x ground concentrations thanks to rapid increase in the traffic density.     

一氧化氮标准气体中二氧化氮杂质FTIR定量方法研究及标气质量分析

一氧化氮标准气体在我国空气质量监测工作中广泛用于氮氧化物分析仪的校准,标准气体的质量对环境空气中氮氧化物的测量结果也有着显著的影响.利用傅里叶变换红外光谱仪建立了一套精确测量低浓度二氧化氮方法,并对一氧化氮标准气体产品中二氧化氮杂质进行了测量.结果显示有少部分样品中存在较高浓度的二氧化氮杂质.进一步讨论了可能导致一氧化...     

Extreme Nitrogen Oxide and Ozone Concentrations in Athens Atmosphere in Relation to Meteorological Conditions

In the present study, we investigate the variation of NO _x (NO + NO₂) and O₃ concentrations and the relation between the extreme events (episodes) of NO _x and O₃ concentrations and the relevant meteorological conditions in the urban atmosphere of the Athens basin. Hourly data of NO, NO₂ and O₃ concentrations from 10 representative monitoring sites located in the Athens basin were used, covering the 10-year time period from 1994 to 2003. The results of our analysis show that the concentrations of air pollutants differ significantly from one monitoring site to another, due to the location and proximity of each station to the emission sources. For each site, there are also significant differences in NO _x and O₃ concentrations from day to day, as well as from month to month and/or from season to season. The annual and seasonal variations show higher NO values in winter and lower in summer. On the contrary, NO₂ and O₃ values are higher in summer (photochemical production of O₃) and lower in winter. These differences are attributed, to a large extent, to the prevailing synoptic and meteorological conditions, the most important between them being the wind direction and speed as well as the atmospheric pressure. Our analysis of the identified 179 extreme NO _x air pollution events shows that most of them took place under anticyclonic conditions, associated with calm or weak winds (speed <2.5 ms⁻¹) of mostly southern to southwestern directions, as well as with low air temperatures and intense stable surface atmospheric conditions. There exists a significant decreasing tendency in NO _x air pollution episodic events over the 10-year study period, resulting in very few to none events in the period from 2000 to 2003. As far as it concerns the extreme O₃ concentrations, 34 air pollution events were identified, occurring under high air temperatures, variable weak winds and intense solar irradiation. The trends of O₃ concentrations are stronger in suburban sites than in urban ones.     

Modeling of NO x Emissions from Oil Refinery Furnaces

The current paper investigates the possibility of establishing an empirically based model for predicting the emission rate of nitrogen oxides (NO _x ) from oil refinery furnaces, in order to continually track emissions with respect to environmental licence limits. Model input data were collected by direct stack monitoring using an electrochemical cell NO _x analyser, as well as a range of telemetry sensors to obtain refinery process parameters. Principal Component Analysis (PCA), in conjunction with Partial Least Squares (PLS) regression was then used to build a series of models able to predict NO _x emissions from the furnaces. The models produced were proven to be robust, with a relatively high accuracy, and are able to predict NO _x levels over the range of operating conditions which were sampled. It was found that due to structural/operational variations a separate model is usually required for each furnace. The models can be integrated with the refinery operating system to predict NO _x emission rates on a continuous basis. Two models representing structurally different furnaces are considered in this paper. This revised version was published online in July 2006 with corrections to the Cover Date.     

Variation in spatial pattern of criteria air pollutants before and during initial rain of monsoon

Spatial patterns of various criteria air pollutants,like SO₂, NO₂, O₃, and TSP were studied atShahdara National Ambient Air Quality Monitoring stationin Delhi (India) in July 1999. The minimum pollutantconcentrations were observed during morning hours,whereas the highest concentrations were found during thelate night hours, which seem to be related with thevehicular emission. Pre-monsoon daily ambient airquality spatial pattern was compared with the spatialpattern during initial and subsequent rain shower ofmonsoon. These spatial patterns were found to beessentially the same before and during rain, however asignificant decrease in SO₂, NO₂ and TSPconcentrations (40-45%) was observed after initial andsubsequent rains of the monsoon, demonstrating theimportance of rainfall in the scavenging of thesecriteria air pollutants.     

A Note on the Emission of Nitrogen Oxides from Silage in Opened Bunker Silos

The evolution of NO_x from grass and maize silages wasmeasured using chemiluminescence in samples kept in airtightcontainers, in the silos and in a 750 kg mass removed to a mixer waggon. Measurements were made on the grass and maizesilos in two consecutive years. The results show that thereis continuous evolution of NO_x after silos have been opened and that high concentrations persist in the mass whichare rapidly released on agitation at the feed-out. The maximumrecorded concentrations of NO and NO₂ were 1985 and 152 ppbv respectively. These values are orders of magnitude greaterthan for rural background levels and exceed the maximum hourlyexposure of 50 ppbv for NO₂ recommended by the UK expertpanel for quality standards.     

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.     

Spatial and temporal variation of surface ozone,NO and NO2 at urban,suburban, rural and industrial sites in the southwest of the Iberian Peninsula

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO_x?=?NO?+?NO₂), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO₂ concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO_x) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO₂ concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00–17:00 UTC) while for NO_x two peaks were observed, at 7:00–10:00 UTC and 20:00–22:00. In the case of rural stations, no hourly peak of ozone or NO_x was registered. The weekend effect was studied by using a statistical contrast tests (Student’s t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO₂, whereas an ozone weekend effect was not detected in any case.     

Fuel characteristics and emissions from biomass burning and land-use change in Nigeria

Nigeria is one of the 13 low-latitude countries that have significant biomass burning activities. Biomass burning occurs in moist savanna, dry forests, and forest plantations. Fires in the forest zone are associated with slash-and-burn agriculture; the areal extent of burning is estimated to be 80% of the natural savanna. In forest plantations, close to 100% of litter is burned. Current estimates of emissions from land-use change are based on a 1976 national study and extrapolations from it. The following non-carbon dioxide (CO₂) trace gas emissions were calculated from savanna burning: methane (CH₄), 145 gigagrams (Gg); carbon monoxide (CO), 3831 Gg; nitrous oxide (N₂O), 2 Gg; and nitrogen oxides (NO_x), 49 Gg. Deforestation rates in forests and woodlands are 300 × 10³ ha (kilohectare, or kha) and 200 × kha per year, respectively. Trace gas emissions from deforestation were estimated to be 300 Gg CH₄, 2.4 Gg N₂O, and 24 Gg NO_x. CO₂ emissions from burning, decay of biomass, and long-term emissions from soil totaled 125 561 Gg. These estimates should be viewed as preliminary, because greenhouse gas emission inventories from burning, deforestation, and land-use change require two components: fuel load and emission factors. Fuel load is dependent on the areal extent of various land uses, and the biomass stocking and some of these data in Nigeria are highly uncertain.     

Study of temporal variation in ambient air quality during Diwali festival in India

The variation in air quality was assessed from the ambient concentrations of various air pollutants [total suspended particle (TSP), particulate matter ≤10 μm (PM₁₀), SO₂, and NO₂] for pre-Diwali, Diwali festival, post-Diwali, and foggy day (October, November, and December), Delhi (India), from 2002 to 2007. The extensive use of fireworks was found to be related to short-term variation in air quality. During the festival, TSP is almost of the same order as compared to the concentration at an industrial site in Delhi in all the years. However, the concentrations of PM₁₀, SO₂, and NO₂ increased two to six times during the Diwali period when compared to the data reported for an industrial site. Similar trend was observed when the concentrations of pollutants were compared with values obtained for a typical foggy day each year in December. The levels of these pollutants observed during Diwali were found to be higher due to adverse meteorological conditions, i.e., decrease in 24 h average mixing height, temperature, and wind speed. The trend analysis shows that TSP, PM₁₀, NO₂, and SO₂ concentration increased just before Diwali and reached to a maximum concentration on the day of the festival. The values gradually decreased after the festival. On Diwali day, 24-h values for TSP and PM₁₀ in all the years from 2002 to 2007 and for NO₂ in 2004 and 2007 were found to be higher than prescribed limits of National Ambient Air Quality Standards and exceptionally high (3.6 times) for PM₁₀ in 2007. These results indicate that fireworks during the Diwali festival affected the ambient air quality adversely due to emission and accumulation of TSP, PM₁₀, SO₂, and NO_2.     

Laboratory study of the emission of NO and N2O from some Belgian soils

The NO, NO₂ and N₂O emission was measured, upon application of nitrate, ammonium and both, to four Belgian soils with different characteristics. The addition of NH ₄ ⁺ caused higher NO and N₂O emissions than the addition of no nitrogen, or the addition of NO ₃ ^– . In contrast to the two soils with a pH of approximately 8 the two soils with a pH around 6 showed a considerable delay in production of both NO and N₂O upon the application of the ammonium, probably due to the lag-period of nitrification. The soils with a pH of 8 gave higher emissions on the application of NH ₄ ⁺ than the soils with a pH of 6. The emission of NO₂ was found to be considerably lower than the NO emission from the soils. The NO/NO₂ ratio varied between 5–25 at considerable NO emissions (>50 nmol kg^–1). In the controls of soil 1 and soil 2, which showed very low NO emissions ratios of <1 were observed. The N₂O/NO ratios varied between 5–20 when NO emissions were considerable (>50 nmol kg^–1). Soil 3 and 4 gave lower N₂O/NO ratios than soil 1 and 2. In the controls of soil 1 and soil 2, at low NO emissions, N₂O/NO ratios of >300 were observed. Soil 3 and 4 gave higher NO/NO₂ and lower N₂O/NO ratios than soil 1 and 2.     

Estimation of air pollutant emission loads from construction and operational activities of a port and harbour in Mumbai, India

Port causes environmental and health concerns in coastal cities if its operation and development are not made environmentally compatible and sustainable. An emission inventory is necessary to assess the impact of port projects or growth in marine activity as well as to plan mitigation strategies. In this study, a detailed emission inventory of total suspended particulate (TSP) matter, respirable particulate matter (PM₁₀), sulphur dioxide (SO₂) and oxides of nitrogen (NO_x) for a port having operation and construction activities in parallel is compiled. The study has been done for 1 year. Results show that the maximum contribution of emission of air pollutants in the port area was from TSP (68.5%) and the minimum was from SO₂ (5.3%) to the total pollutants considered in this study. Total TSP emission from all activities of the port was 4,452 tyr^???1 and PM₁₀ emission was 903 tyr^???1 in the year 2006. Re-suspension of dust from paved roads was the major contributor of TSP and PM₁₀ in the road transport sector. Construction activities of the port had contributed 3.9% of TSP and 7.4% of PM₁₀ to total emission of particulate matter. Of the total particulate emissions from various port activities approximately 20% of TSP could be attributed to PM₁₀. The sectoral composition indicates that major contribution of SO₂ emission in the port was from maritime sector and major contribution of NO_x was from road transport sector.     

Photoacoustic measurements of black carbon light absorption coefficients in Irbid city, Jordan

The goal of this work is the analysis of air quality levels in the area of Volos, a city of average size on the eastern seaboard of Central Greece. For this purpose, concentration measurements of sulfur dioxide, nitrogen oxide, and nitrogen dioxide, for a 4-year period (2001–2004) are analyzed. Air pollution data were obtained by a monitoring station, fully automated, which was established by the Hellenic Ministry of the Environment, Physical Planning, and Public Works, in order to measure air pollution levels in Volos, a medium-sized city, which faces the effects of industrialization. The main conclusions from the statistical analysis of the 4-year measurements of hourly SO₂, NO₂, and NO concentrations in the city of Volos, showed that the mean seasonal variation of the examined air pollutant concentration presents a minimum during the warm period of the year and a maximum during the cold period. Although the local geomorphology and meteorology encourage particularly the accumulation of air pollutants, the analysis shows that the SO₂ and NO₂ concentration levels remain lower than corresponding thresholds for human health protection set by the European Union, in this urban measuring site, during the examined period. The application of harmonic analysis revealed the difference between the annual variation of the SO₂ and NO _x concentrations. Regarding NO _x , the variation is mainly due to the first harmonic term (anthropogenic factor), while the SO₂ variation is interpreted by the two harmonic terms, which represent the anthropogenic and meteorological factors, respectively.     

Assessment of Ambient Air Quality in Urban Centres of Haryana (India) in Relation to Different Anthropogenic Activities and Health Risks

Considering the mounting evidences of the effects of air pollution on health, the present study was undertaken to assess the ambient air quality status in the fast growing urban centres of Haryana state, India. The samples were collected for total suspended particulate matter (TSPM), respirable suspended particulate matter (PM₁₀), sulfur dioxide (SO₂), and oxides of nitrogen (NO₂) during different seasons from 8 districts of Haryana during January, 1999 to September, 2000. The four types of sampling sites with different anthropogenic activities i.e. residential, sensitive, commercial and industrial were identified in each city. The ambient air concentration of TSPM and PM₁₀ observed was well above the prescribed standards at almost all the sites. The average ambient air concentrations of SO₂ and NO₂ were found below the permissible limits at all the centres. Comparatively higher concentration of SO₂ was observed during winter seasons, which seems to be related with the enhanced combustion of fuel for space heating and relatively stable atmospheric conditions. Air Quality Index (AQI) prepared for these cities shows that residential, sensitive and commercial areas were moderately to severely polluted which is a cause of concern for the residents of these cities. The high levels of TSPM and SO₂ especially in winter are of major health concern because of their synergistic action. The data from Hisar city reveals a significant increase in the total number of hospital visits/admissions of the patients with acute respiratory diseases during winter season when the level of air pollutants was high.     

Air quality at a snowmobile staging area and snow chemistry on and off trail in a Rocky Mountain subalpine forest, Snowy Range, Wyoming

A study was begun in the winter of 2000–2001 and continued through the winter of 2001–2002 to examine air quality at the Green Rock snowmobile staging area at 2,985 m elevation in the Snowy Range of Wyoming. The study was designed to evaluate the effects of winter recreation snowmobile activity on air quality at this high elevation site by measuring levels of nitrogen oxides (NO _x , NO), carbon monoxide (CO), ozone (O₃) and particulate matter (PM₁₀ mass). Snowmobile numbers were higher weekends than weekdays, but numbers were difficult to quantify with an infrared sensor. Nitrogen oxides and carbon monoxide were significantly higher weekends than weekdays. Ozone and particulate matter were not significantly different during the weekend compared to weekdays. Air quality data during the summer was also compared to the winter data. Carbon monoxide levels at the site were significantly higher during the winter than during the summer. Nitrogen oxides and particulates were significantly higher during the summer compared to winter. Nevertheless, air pollutants were well dispersed and diluted by strong winds common at the site, and it appears that snowmobile emissions did not have a significant impact on air quality at this high elevation ecosystem. Pollutant concentrations were generally low both winter and summer. In a separate study, water chemistry and snow density were measured from snow samples collected on and adjacent to a snowmobile trail. Snow on the trail was significantly denser and significantly more acidic with significantly higher concentrations of sodium, ammonium, calcium, magnesium, fluoride, and sulfate than in snow off the trail. Snowmobile activity had no effect on nitrate levels in snow.     

大气硝酸测量方法研究进展

大气中硝酸(HNO3)的生成是排放到空气中氮氧化物(NOx)的主要沉降途径,对降水酸化、二次细颗粒物中硝酸盐的形成以及在研究光化学污染和霾形成等大气复合污染过程之间的联系中具有重要作用.获得高时间分辨率、准确的大气HNO3测量数据对研究和认识大气中NOx的循环机理是十分必要和迫切的.大气中的HNO3浓度低且具有很强的吸...     

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。     

能源结构变化对兰州市大气质量的影响

将2001—2010年的主要能源材料消耗、主要污染物变化及主要行业分布进行了相关性分析,结果表明:兰州市大气4种主要污染物中除烟尘呈下降趋势外,废气总量、SO2、NOx仍呈上升趋势;主要污染源为燃煤,主要污染行业为电力、蒸汽热水产供业;废气和SO2排放总量与燃煤和燃气呈强正相关,而NOx排放只与燃气呈强正相关。建议发挥兰州地域优势,加大以水电供应为主的能源结构调整,对改善当地空气质量有重要价值。     

Three-year monitoring results of nitrate and ammonium wet deposition in Thailand

Wet deposition is one of the important sources of nitrogen input into the ecosystem. It also contributes to rain acidity in some environments. In this study we reported the annual as well as seasonal trends of nitrogen wet deposition at three locations in Thailand: Bangkok, Chiang Mai and Nan. Comparison of nitrogen wet deposition between in rural and in the urban areas was also made. Daily rainfall was measured and monthly rainwater was collected for nitrogen analysis during 1999–2002. The average NO₃ ^– concentration in rainwater collected from the rural sites (60 km from urban area) was around 0.2–0.3 mg L^–1, while that from the urban areas of Chiang Mai and Nan cities it was 0.4–0.5 mg L^–1. NH₄ ⁺ concentration in rainwater showed the similar ranges to that of NO₃ ^– , except at Nan where concentration was not significantly different between the urban and rural sites. On the other hand, the average concentrations of NO₃ ^– were higher at Bangkok site than other sites, while concentration of NH₄ ⁺ was almost the same between Chiang Mai and Bangkok. Wet deposition of NO₃ ^– at the rural sites of Chiang Mai and Nan ranged from 2.1 to 3.2 kg N ha^–1 yr^–1, while at the urban sites this ranged from about 6 kg N ha^–1 yr^–1 in Chiang Mai and Nan Cities to 8.6 kg N ha^–1 yr^–1 in Bangkok. Wet deposition of NH₄ ⁺ at the rural sites of Chiang Mai and Nan was about 2.4 to 3.6 kg N ha^–1 yr^–1 and at the urban sites of Chiang Mai, Nan and Bangkok this was 7.7, 4.9 and 8.1 kg N ha^–1 yr^–1, respectively. Thus, it was concluded that wet deposition of both nitrogen species was significantly higher at the urban sites than at the rural sites.