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1.
To explore environmentally benign solvents for the absorption of NO and NO2, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO2 was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO2 in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO2 decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO2 was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO2.  相似文献   

2.
The CALINE4 roadway dispersion model has been applied to concentrations of NOx and NO2 measured near Gandy Boulevard in Tampa, FL (USA) during May 2002. A NOx emission factor of 0.86 gr mi−1 was estimated by treating NO+NO2 (NOx) as a conserved species and minimizing the differences between measured and calculated NOx concentrations. This emission factor was then used to calculate NO2 concentrations using the NO/NO2 transformation reactions built into CALINE4. A comparison of measured and calculated NO2 concentrations indicates that for ambient O3 concentrations less than 40 ppb the model under-predicts the chemical transformation of NO. The enhanced transformation of NO may be due to reactions of NO with oxidants such as peroxy radicals that are present either in the atmosphere or in vehicle exhaust.  相似文献   

3.
Abstract

The capping of stationary source emissions of NOx in 22 states and the District of Columbia is federally mandated by the NOx SIP Call legislation with the intended purpose of reducing downwind O3 concentrations. Monitors for NO, NO2, and the reactive oxides of nitrogen into which these two compounds are converted will record data to evaluate air quality model (AQM) predictions. Guidelines for testing these models indicate the need for semicontinuous measurements as close to real time as possible but no less frequently than once per hour. The measurement uncertainty required for AQM testing must be less than ±20% (±10% for NO2) at mixing ratios of 1 ppbv and higher for NO, individual NOz component compounds, and NOy. This article is a review and discussion of different monitoring methods, some currently used in research and others used for routine monitoring. The performance of these methods is compared with the monitoring guidelines. Recommendations for advancing speciated and total NOy monitoring technology and a listing of demonstrated monitoring approaches are also presented.  相似文献   

4.
We analyse the air quality data measured at a green area of Buenos Aires City (Argentina) during 38 days in winter. We study the relationships between ambient concentrations of nitric oxide (NO), nitrogen dioxide (NO2), ozone (O3) and nitrogen oxides (NOx=NO+NO2). The variation of the level of oxidant (OX=O3+NO2) with the NOx is obtained. It can be seen that the level of OX at a given location is made up of two contributions: one independent and another dependent on the NOx concentration. The first one can be considered as a regional contribution, equivalent to the background O3 concentration and the second one as a local contribution that depends on the level of primary pollution. Local oxidant sources may include direct NO2 emissions, the reaction of NO with O2 at high-NOx levels, and the emission of species that promote the conversion of NO to NO2. The final category of emissions may include the nitrous acid (HONO) that is emitted directly in vehicle exhaust. Finally, we present a diurnal variation of the local as well as regional contributions and the dependence of the last one on wind direction.  相似文献   

5.
Soils are a significant source for atmospheric NO. However, due to the limited number of measurements and in view of the high temporal and spatial variability of NO emissions, as originating from dependencies from a series of environmental constraints such as soil properties, meteorology or N fertilization, inventories of soil NO emissions are still highly uncertain. In this work, the agricultural DNDC model was modified and applied on site scale in order to evaluate its capability to simulate soil NO emissions. DNDC captured differences in the magnitude of NO emissions between sites, but was less successful when simulating observed day-by-day variations. However, major peak emission events, e.g. due to fertilizer application or following rainfall events, were mostly simulated. DNDC as well as its forest version Forest-DNDC were finally linked to a GIS to calculate NO emissions from agricultural and forest soils across Europe. Using the same databases for agricultural soils, we also compared our estimate with other commonly used methodologies (Skiba-EMEP/CORINAIR, Yienger and Levy, Stehfest and Bouwman). A canopy reduction factor was not applied in this study. Estimates for NO emissions for agricultural soils for EU15 states varied in a range of 48.9–189.8 kt NO-N for the year 2000 depending on the approach used (Yienger and Levy > DNDC > Stehfest and Bouwman > Skiba-EMEP/CORINAIR). For forests, using the model Forest-DNDC as the only approach, we calculated soil NO emissions to be 75.1 kt NO-N yr?1. The results show that soils in EU15 states are significant sources of atmospheric NO, though the share of soil NO emissions on total NOx emissions (incl. NOx emissions by combustion processes) in EU15 was only 4–6%. Given that soil NO emissions are largely driven by the availability of inorganic nitrogen (fertilization) and temperature, emissions are larger during the vegetation period. Especially during early summer when fertilizer-induced NO emissions from agricultural soils are peaking, the contribution of soil emissions to total NOx emissions may most likely be well above 10%.  相似文献   

6.
ABSTRACT

This article presents the results of an industrial-scale study (on 400 MWe lignite fired unit) of simultaneous NOx, SO2, and HgT removal in FGD absorber with oxidant injection (NaClO2) into flue gas. It was confirmed that the injection of sodium chlorite upstream the FGD (Flue Gas Desulfurization) absorber oxidize NO to NO2, Hg0 to Hg2+, and enhancing NOx and HgT removal efficiency from exhaust gas in FGD absorber. Mercury removal efficiency grows with the rise of degree of oxidation NO to NO2 and was limited by the phenomenon of re-emission. For NOx removal the most critical parameters is slurry pH and temperature. There was no negative effect on sulfur dioxide removal efficiency caused by oxidant injection in tested FGD absorber. Based on the data provided, NOx and HgT emissions can be reduced by adjusting the FGD absorber operating parameters combined with oxidant injection.  相似文献   

7.
Recent research has demonstrated that nitrogen oxides are transformed to nitrogen acids in indoor environments, and that significant concentrations of nitrous acid are present in indoor air. The purpose of the study reported in this paper has been to investigate the sources, chemical transformations and lifetimes of nitrogen oxides and nitrogen acids under the conditions existing in buildings. An unoccupied single family residence was instrumented for monitoring of NO, NO2, NOy, MONO, HNO3, CO, temperature, relative humidity, and air exchange rate. For some experiments, NO2 and HONO were injected into the house to determine their removal rates and lifetimes. Other experiments investigated the emissions and transformations of nitrogen species from unvented natural gas appliances. We determined that HONO is formed by both direct emissions from combustion processes and reaction of NO2 with surfaces present indoors. Equilibrium considerations influence the relative contributions of these two sources to the indoor burden of HONO. We determined that the lifetimes of trace nitrogen species varied in the order NO ~ HONO > NO2 >HNO3. The lifetimes with respect to reactive processes are on the order of hours for NO and HONO, about an hour for NO2, and 30 minutes or less for HNO3. The rapid removal of NO2 and long lifetime of HONO suggest that HONO may represent a significant fraction of the oxidized nitrogen burden in indoor air.  相似文献   

8.
The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO2?+?O3), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO x -independent ‘regional’ contribution (i.e. the O3 background), and a linearly NO x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO2 increases with the increase in NO x concentration during the day. The higher proportion of NO2 observed at night must be due to the conversion of NO to NO2 by the NO?+?O3 reaction. With regards to the source of the local NO x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O2?=?2NO2, at high-NO x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO2, J NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.  相似文献   

9.
The annual air quality standard of NO2 is often exceeded in urban areas near heavy traffic locations. Despite significant decrease of NOx emissions in 1986–2005 in the industrial and harbour area near Rotterdam, NO2 concentrations at the urban background remain at the same level since the end of the nineties. Trend analysis of monitoring data revealed that the ozone/NOx equilibrium is a more important factor than increasing direct NO2 emissions by traffic. The latter has recently been identified as an additional NO2 source due to the introduction of oxy-catalytic converters in diesel vehicles and the growing number of diesel vehicles. However, in Rotterdam over the period 1986–2005 direct NO2 emissions by road traffic only increased 3–4%. Due to the importance of the ozone/NOx equilibrium, it is concluded that local NOx emissions in Rotterdam need substantial reduction to achieve lower NO2 urban background levels. This is a relatively costly abatement strategy and, therefore, a “hotspot” approach aiming at reducing NOx emissions by local traffic measures is more effective to meet European air quality standards.  相似文献   

10.
Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O3), nitric oxide (NO) and nitrogen dioxide (NO2) as a function of NOx, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O3 and NO2) varies with the level of NOx, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NOx-independent and NOx-dependent contributions. The former is effectively a regional contribution which equates to the regional background O3 level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO2 emissions, (ii) the thermal reaction of NO with O2 at high NOx, and (iii) common-source emission of species which promote NO to NO2 conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HOx radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NOx, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO2 and O3, are used to define expressions which describe the likely variation of annual mean NO2 as a function of NOx at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O3.  相似文献   

11.
The Environmental Protection Agency is reviewing the need for a short-term NO2 standard based on an averaging time of three hours or less. State Implementation plans and New Source Reviews will require air quality simulation techniques capable of estimating ambient NO2 concentrations. There is a need for multi-source (urban) models and for point source models.

A review of currently available techniques for the estimation of NO2 concentrations resulting from NOx point sources is presented. The available methods include simple screening techniques and refined reactive plume models. The screening techniques first use a standard gaussian dispersion model to estimate the maximum 1 hr NOx concentration caused by the source. The second step involves estimating the fraction of this NO* concentration occurring as NO2.

Reactive plume models numerically simulate the simultaneous effects of dispersion and chemistry on NO2 concentrations. Organic as well as inorganic reactions are incorporated. Reactive plume models should be used, where screening techniques indicate the potential for violation of the NO2 standard.

Current generation reactive plume models neglect the effect of turbulent concentration fluctuation on NO2 formation and use inappropriately large dispersion coefficients to estimate plume concentrations. Approaches being developed to resolve these problems are discussed.  相似文献   

12.
The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX?=?O3?+?NO2), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO2 and OX cycles. The variation of OX concentrations with NO x is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO x -independent ‘regional’ contribution (i.e. the O3 background), and a linearly NO x -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO x was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO2]/[OX] and [NO2]/[NO x ] vs. [NO x ] were analysed to find the fraction of OX in the form of NO2, and the possible source of the local NO x -dependent contribution, respectively. The progressive increase of the ratio [NO2]/[OX] with [NO x ] observed shows a greater proportion of OX in the form of NO2 as the level of NO x increases. The higher measured values in the ratio [NO2]/[NO x ] should not be attributed to NO x emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO2 photolysis, J NO2?=?0.18–0.64 min?1, a key atmospheric reaction that influence O3 production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.  相似文献   

13.
Abstract

A remote sensing device was used to obtain on-road and in-use gaseous emission measurements from three fleets of schools buses at two locations in Washington State. This paper reports each fleet’s carbon monoxide (CO), hydrocarbon (HC), nitric oxide (NO), and nitrogen dioxide (NO2) mean data. The fleets represent current emission retrofit technologies, such as diesel particulate filters and diesel oxidation catalysts, and a control fleet. This study shows that CO and HC emissions decrease with the use of either retrofit technology when compared with control buses of the same initial emission standards. The CO and HC emission reductions are consistent with published U.S. Environmental Protection Agency verified values. The total oxides of nitrogen (NOx), NO, and the NO2/NOx ratio all increase with each retrofit technology when compared with control buses. As was expected, the diesel particulate filters emitted significantly higher levels of NO2 than the control fleet because of the intentional conversion of NO to NO2 by these systems. Most prior research suggests that NOx emissions are unaffected by the retrofits; however, these previous studies have not included measurements from retrofit devices on-road and after nearly 5 yr of use. Two 2006 model-year buses were also measured. These vehicles did not have retrofit devices but were built to more stringent new engine standards. Reductions in HCs and NOx were observed for these 2006 vehicles in comparison to other non-retrofit earlier model-year vehicles.  相似文献   

14.
The present study reviews the sampling environments and chemical transformations of nitrogen oxides that may occur within probes and sample lines while sampling combustion products. Experimental data are presented for NOx transformations in silica and 316 stainless steel tubing when sampling simulated combustion products in the presence of oxygen, carbon monoxide, and hydrogen. A temperature range of 25° to 400°C is explored. In the absence of CO and H2, 316 stainless steel is observed to promote the reduction of nitrogen dioxide to nitric oxide at temperatures in excess of 300°C, and silica is found to be passive to chemical transformation. In the presence of CO, reduction of N02 to NO is observed in 316 stainless steel at temperatures in excess of 100°C, and reduction of NO2 to NO in silica is observed at 400°C. In the presence of H2, NO2 is reduced to NO in 316 stainless steel at 200°C and NOx is removed at temperatures exceeding 200°C. In silica, the presence of H2 promotes the reduction of NO2 to NO at 300°C and the removal of NOx above 300°C.  相似文献   

15.
ABSTRACT

A previous paper1 discusses the methodology for a new method for deriving the nitrogen dioxide/nitrogen oxide (NO2/NOx) ratio in plumes that originally are composed mainly of (NOx). It is called the Plume Volume Molar Ratio Method (PVMRM). This paper documents its performance against six different data sets. These performance evaluations show that the PVMRM can realistically predict the NO2 fraction at close-in receptors yet still provide conservative estimates so that the air quality standards can be protected.  相似文献   

16.
ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO2) and sulfur dioxide (SO2) in a packed-bed reactor. A prior study found that NO2 reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO2 present in the gas stream, NO2 also reacted with S(IV), a product of SO2 removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO2. Subsequent acidification of the sorbent by the removal of NO2 and SO2 facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO2 removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO2 removal, NO2 removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO2 and NOx by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO2. These x 2 results are relevant to dry scrubbing technology for combined SO2 and NOx removal that first oxidizes NO to NO2 by the addition of methanol into the flue duct.  相似文献   

17.
Abstract

The ozone (O3) sensitivity to nitrogen oxides (NOx, or nitric oxide [NO] + nitrogen dioxide [NO2]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O3/NOy (where NOy represents the sum of NO + NO2 + nitric acid [HNO3] + peroxyacetyl nitrate [PAN] + others), NOy, and the semiempirically derived O3/NOz surrogate (where NOz surrogate is the derived surrogate NOz, and NOz represents NOx reaction products, or NOy – NOx) with results of numerical predictions reproducing the transition regimes between NOx and VOC sensitivities. Ambient air concentrations of O3, NOx, and NOy were measured from April 14 to 25, 2004 in one downwind receptor site of photo-chemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O3/NOy, O3/NOz surrogate, and NOy in MCMA suggest that O3 in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NOx ratios, have concluded that O3 in Mexico City is NOx-sensitive. Simulated MCMA-derived sensitive transition values for O3/NOy, hydrogen peroxide (H2O2)/HNO3, and NOy were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O3/NOz and O3/HNO3 was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O3 concentrations and 6:00- to 9:00-a.m. NOx and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NOx emissions in MCMA might cause an increase in presently high O3 levels.  相似文献   

18.
Measurement of NO2 and NO has been carried out in Piedmont, N. C. and in the southern Appalachian Mountains. Average values for the Piedmont were: continuous NO2 measured 30 ft above surface, 0.76 pphm (14.3 μg/m3), 1 20 ft, 0.61 pphm (11.5 μg/m3); simultaneous values (also Piedmont) (2-hr discrete samples) taken at an earlier time at 4 ft, NO2, 0.56 pphm (10.6 μg/m3), NO, 0.19 pphm (2.34 μg/m3). The mountain top values (5120 ft, 1573 m) were: NO2, 0.46 pphm (6.4 μg/m3), NO, 0.26 pphm (2.72 μg/m3). The results of this study furnish further proof that tropospheric NO and NO2 are produced at the surface of the earth. Data obtained are consistent with the belief that a major sink for NOx is reaction with O3 and ultimate conversion to nitrate.

Ozone values frequently increased and NOx values decreased ahead of cold fronts, probably as a result of deep vertical mixing. Also, in small scale turbulence the changes in NOx values and in the O3 values tended to be “out of phase,” i.e., as O3 concentration increased, NOx concentration decreased and vice versa. Values of NOx from Green Knob, N. C. (mountain top) also tended to be higher at times when O3 values were lowest.

The NO2 hourly average values in Piedmont, N. C, demonstrated a diurnal cycle reminiscent of diurnal urban changes. An early morning peak was followed by a minimum in mid-afternoon. Next, the values rose to a broad evening peak and then decreased slowly during the night. Reported urban concentrations are usually about ten times those found in Piedmont, N. C.  相似文献   

19.
Abstract

In this paper, we examine the changes in ambient ozone concentrations simulated by the Community Multiscale Air Quality (CMAQ) model for summer 2002 under three different nitrogen oxides (NOx) emission scenarios. Two emission scenarios represent best estimates of 2002 and 2004 emissions; they allow assessment of the impact of the NOx emissions reductions imposed on the utility sector by the NOx State Implementation Plan (SIP) Call. The third scenario represents a hypothetical rendering of what NOx emissions would have been in 2002 if no emission controls had been imposed on the utility sector. Examination of the modeled median and 95th percentile daily maximum 8-hr average ozone concentrations reveals that median ozone levels estimated for the 2004 emission scenario were less than those modeled for 2002 in the region most affected by the NOx SIP Call. Comparison of the “no-control” with the “2002” scenario revealed that ozone concentrations would have been much higher in much of the eastern United States if the utility sector had not implemented NOx emission controls; exceptions occurred in the immediate vicinity of major point sources where increased NO titration tends to lower ozone levels.  相似文献   

20.
基于2008年及2009年分4个季节对北京市3种类型道路(开阔型、交叉路口型和峡谷型)空气中的NOx的现场监测结果,分析了3种类型道路空气中NOx的污染现状和时空变化规律及影响因素。实验结果表明,昼间北京市各类型街道空气中NOx浓度呈早晚浓度高、中午浓度低的变化规律,NOx浓度随季节和车流量变化较明显。交通道路空气中NO占NOx的分担率高,且有较好的相关性,而NO2分担率较低,与NOx相关性较差。  相似文献   

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