In situ measurements of HNO3, NOy,NO, and O3 in the lower stratosphere and upper troposphere

In situ measurements of nitric acid (HNO₃), reactive nitrogen (NO_y), nitric oxide (NO), and ozone (O₃) made in the upper troposphere (UT) and lower stratosphere (LS) between 29° and 33°N latitudes during September 1999 are used to examine NO_y partitioning and correlations between the measured species in these regions. The fast-response (1 s) HNO₃ measurements are acquired with a new autonomous CIMS instrument. In the LS, HNO₃ accounts for the majority of NO_y, and the sum of HNO₃ and NO_x accounts for approximately 90% of NO_y. In the UT, the sum of HNO₃ and NO_x varies between 40% and 100% of NO_y. Both HNO₃ and NO_y are strongly positively correlated with O₃, with larger correlation slopes in the UT than in the LS. In the UT at low values of the quantity (NO_y–NO_x–HNO₃), it is uncorrelated with O₃, while at higher values, a positive correlation with O₃ is found. Of these two air mass types, those with higher (NO_y–NO_x–HNO₃) mixing ratios are likely associated with the presence of peroxyacetyl nitrate (PAN) that is produced by NO_x-hydrocarbon chemistry.     

The effects of the rate for OH + HNO3 and HO2NO2 photolysis on stratospheric chemistry

The effects of the new estimates of the rate of the reaction of OH with HNO₃ and of HO₂NO₂ photolysis on models of stratospheric chemistry are discussed using a one-dimensional model. The new rates could lower the calculated OH concentrations in the altitude range 15–30 km with significant impact on the vertical profiles of ClO, HCl and NO₂ in the stratosphere and on the ozone perturbations due to fluorocarbons.     

Impacts of a strong cold front on concentrations of HONO,HCHO, O3, and NO2 in the heavy traffic urban area of Beijing

Much rain and strong winds caused by a cold front occurred in Beijing during the period of Sep. 27 to Oct. 4, 2004 and led to sharp drops in maximum and mean concentrations of HONO, HCHO, O₃, and NO₂, i.e., the maximum concentrations were reduced by 5.9, 21.3, 45.6, and 44.4 ppb, respectively, and the mean concentrations were decreased by 4.0, 5.5, 30.3, and 32.3 ppb, respectively. For daily HO_x production rates HONO photolysis was the largest contributor and over 90% contributions were from photolysis of HONO and HCHO. Large number and area percentages of soot aggregate from PM10, and high correlations between concentrations of PM10 and chemical formation of HONO suggested that heterogeneous reactions of NO₂ on surfaces of soot aggregate could be a key source of HONO in the heavy traffic areas of Beijing during the night and should be considered in air quality simulations for such areas.     

Sources and Concentrations of Indoor Nitrogen Dioxide in Barcelona,Spain

Abstract

Sources and concentrations of indoor nitrogen dioxide (NO₂) were examined in Barcelona, Spain, during 1996– 1999. A total of 340 dwellings of infants participating in a hospital-based cohort study were selected from different areas of the city. Passive filter badges were used for indoor NO₂ measurement over 7–30 days. Dwelling inhabitants completed a questionnaire on housing characteristics and smoking habits. Data on outdoor NO₂ concentrations were available for the entire period of the study in the areas of the city where indoor concentrations were determined. Bivariate analysis was performed to investigate relationships between indoor NO₂ concentrations on one hand and outdoor NO₂ concentrations, housing, and occupant characteristics on the other. Stepwise multiple linear regression was performed with variables that were 1996 and 27.02 ppb in 1999, with the highest yearly value of 27.82 ppb in 1997. In the same time period, mean outdoor NO₂ concentration ranged between 25.26 and 25.78 ppb with a peak of 30.5 ppb in 1998. Multiple regression analysis showed that principal sources of indoor NO₂ concentrations were the use of a gas cooker, the absence of an extractor fan when cooking, and cigarette smoking. The absence of central heating was also associated with higher NO₂ concentrations. Finally, each ppb increase in outdoor NO₂ was associated with a 1% increase in indoor concentrations.     

Performance of the annular denuder system with different arrangements for HNO3 and HNO2 measurements in Taiwan

Experiments on different annular denuder system (ADS) arrangements for sampling nitrous acid (HNO2) and nitric acid (HNO3) gases were conducted in this study to evaluate their sampling artifacts. The evaluation basis is the one that employed one sodium chloride denuder for sampling HNO3 gas and two sodium carbonate (Na2CO3) denuders for sampling HNO2 gas, which is a commonly employed ADS arrangement in many field applications in the United States. A field study was conducted in Hsinchu, Taiwan, and the results indicated that this ADS arrangement may yield over 80% relative errors for HNO3 gas. It also showed that the relative errors for HNO2 gas can be less than 10% as sampled with only one Na2CO3 denuder. This is attributed to the fact that the ambient HNO3 concentration measured in this study was relatively low while the HNO2 concentration was high, as compared to typical concentrations of these two gases measured in the United States. The sampling error of HNO3 gas may be due to high concentrations of N-containing interfering species present in Taiwan's atmosphere. Because the relative sampling errors of HNO3 and HNO2 gases depend mainly on their concentrations in the atmosphere as well as concentrations caused by interfering species, the risk for high error while measuring low HNO2 concentrations by only one Na2CO3 denuder is also possible. As a result, it is suggested that pretests are necessary to evaluate possible sources and degrees of sampling errors before field sampling of HNO2 and HNO3 gases. The sampling errors of these two gases can, therefore, be minimized with a better arrangement of the ADS.     

Performance of the Annular Denuder System with Different Arrangements for HNO3 and HNO2 Measurements in Taiwan

ABSTRACT

Experiments on different annular denuder system (ADS)arrangements for sampling nitrous acid (HNO₂) and ni-tric acid (HNO₃) gases were conducted in this study toevaluate their sampling artifacts. The evaluation basis isthe one that employed one sodium chloride denuder forsampling HNO₃ gas and two sodium carbonate (Na₂CO₃)denuders for sampling HNO₂ gas, which is a commonlyemployed ADS arrangement in many field applicationsin the United States. A field study was conducted inHsinchu, Taiwan, and the results indicated that this ADSarrangement may yield over 80% relative errors for HNO₃gas. It also showed that the relative errors for HNO₂ gascan be less than 10% as sampled with only one Na₂CO₃denuder. This is attributed to the fact that the ambientHNO₃ concentration measured in this study was relativelylow while the HNO₂ concentration was high, as comparedto typical concentrations of these two gases measured inthe United States.

The sampling error of HNO₃ gas may be due to highconcentrations of N-containing interfering speciespresent in Taiwan’s atmosphere. Because the relative sam-pling errors of HNO₃ and HNO₂ gases depend mainly ontheir concentrations in the atmosphere as well as con-centrations caused by interfering species, the risk for higherror while measuring low HNO₂ concentrations by onlyone Na₂CO₃ denuder is also possible. As a result, it is sug-gested that pretests are necessary to evaluate possiblesources and degrees of sampling errors before fieldsampling of HNO₂ and HNO₃ gases. The sampling errorsof these two gases can, therefore, be minimized with abetter arrangement of the ADS.     

Dry deposition of O3, SO2, and HNO3 to different vegetation in the same exposure environment

Agricultural meteorological modeling techniques are used to investigate the relative and absolute dry deposition fluxes of SO2 (as sulfur), HNO3 (as nitrogen) and O3 to large fields of maize, soybeans, and alfalfa exposed in conditions as measured in northern Illinois, central Pennsylvania, and eastern Tennessee. For HNO3, the differences in seasonal deposition rates among the three types of plant species are small. Within the same environment, the soybean canopy has the potential to receive substantially more gaseous dry deposition of SO2 and O3 than the maize and alfalfa (which are about the same), as a result of lower stomatal resistance and consequently higher deposition velocities. Deposition differences among the sites are small except for the case of SO2, for which deposition rates estimated for northern Illinois are nearly double those at the other locations. The high SO2 deposition at the northern Illinois location is a consequence of the higher air concentrations observed there.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

A new sampling device is described for the simultaneous collection of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min⁻¹ the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH₃, HNO₃, HCL and SO₂ are in the order of 0.1–0.5 μm⁻³. For H₂O₂ the detection limit is 0.01 μm⁻³. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.     

The change in O3, SO2 and NO2 concentrations in Lithuania

Due to the dynamic nature of the atmosphere, substantial amounts of gaseous and particulate pollutants are transported to the areas distant from their sources. In order to determine the regional concentration levels of atmospheric pollutants in Lithuania, concentrations of gaseous O₃, SO₂, NO₂ and other pollutants have been measured at the Preila background station (55°20′ N and 21°00′ E, 5 m a.s.l.) since 1981. The long-term concentration data set enabled us to get temporal trends, both on a seasonal and longer time scale, to identify source areas of pollutants and to relate them to the emission data. Based on the data obtained, the different tendencies in the pollutant concentration changes were revealed. Positive trends for ozone (of 2.9% per year during 1983–2000) and a distinct negative trend for both sulphur dioxide (of 3.8% per year during 1981–2000) and nitrogen dioxide (of 3.8% per year during 1983–2000) were found. The air mass back-trajectory analysis was used to assess the source region of air pollutants transported to Lithuania. The pollutant concentration levels were compared with their emission changes in Europe and Lithuania. The general trends in SO₂ as well as in NO₂ concentrations observed are consistent with changes in SO₂ and NO₂ emissions in Europe and Lithuania.     

2015年南京市SO2、NO2、CO和O3的污染特征分析

分析了2015年南京市二氧化硫（SO2）、二氧化氮（NO2）、一氧化碳（CO）和臭氧（O3）的污染特征。南京市SO2、NO2、CO和O3的年均浓度分别为19.3 μg·m-3、50.2 μg·m-3、0.972 mg·m-3和114 μg·m-3;SO2和CO污染相对较轻,NO2和O3污染相对严重。SO2、CO和O3的日变化呈"单峰型",而NO2的呈"双峰型";SO2、NO2和CO浓度在冬季最高,夏季最低,而O3相反。秸秆焚烧产物的区域输送在夏收（6月）和秋收（11月）时节对南京市CO的贡献显著。各监测点及全市的气态污染物普遍表现出"反周末效应",指示外来污染源。     

Positive interference of nitrous acid in the determination of gaseous HNO3 by the NOx chemiluminescence-nylon cartridge method: Applications to measurements of ppb levels of HONO in air

Gaseous nitrous acid in air has been simultaneously monitored in environmental chambers by an absolute method, differential optical absorption spectroscopy, and by a nylon cartridge-chemiluminescence NO_x technique originally developed by Spicer and co-workers for gaseous HNO₃. In the absence of HNO₃, the latter technique proved to be a simple and accurate method for measuring ppb levels of HONO in air. However, the positive interference by HONO in the nylon cartridge-chemiluminescence technique may have important ramifications due to possible artifacts in measurements of gaseous HNO₃ by removal on nylon surfaces. Thus, previous observations in night-time atmospheres or environmental chambers attributed entirely to gaseous HNO₃ may have been, at least in part, due to the presence of gaseous HONO.     

Land-surface exchange in a chemically-reactive system; surface fluxes of HNO3, HCl and NH3

Vertical gradients from 0.25 to 2 m of NH₃, HNO₃ and HCl and associated aerosol components have been measured in the field above various surfaces in eastern England. The data have been examined to identify the effect, if any, of chemical reaction processes upon the observed vertical profiles. It is concluded that chemical transformations are too slow to influence concentration gradients and thus the surface exchange process. Assuming chemically conservative behaviour, deposition velocities for HNO₃ and HCl have been calculated; these lie within the range 0.4–7.7 cms⁻¹ and 0.4–6.9 cms⁻¹ for HNO₃ and HCl, respectively. Estimation of resistances to deposition indicates a negligible surface resistance for both species. Fluxes of ammonia were predominantly upward from the ground with a mean value of 0.031 μg m⁻²s⁻¹ which is consistent both with an emission inventory of the U.K. and with the measured atmospheric concentration of NH₃.     

Modeling and monitoring of CO,NO and NO2 in a modern townhouse

Mass-balance models for indoor concentrations of CO, NO and NO₂ were applied to an energy-efficient townhouse. Model parameters included source emission rates, infiltrating airflows, and, for NO₂, loss rate coefficients. Emission factors for CO, NO and NO₂ were estimated for each of the gas-fired appliances in the house. Airflows were estimated using sulfur hexafluoride (SF₆) decay techniques. Loss rates for NO₂ were calculated as the difference between NO₂ removal rates and estimated air exchange rates; CO and NO concentrations decayed at a rate not significantly different than that for SF₆. Comparing model predictions with measured concentrations yielded differences averaging 17% for CO and NO, and 28% for NO₂.     

UV Fourier transform measurements of tropospheric O3, NO2, SO2, benzene, and toluene.

Using the differential optical absorption spectroscopy (DOAS) technique and a Fourier transform spectrometer, NO2, SO2, O3, benzene. and toluene were measured during three measurement campaigns held in Brussels in 1995, 1996, and 1997. The O3 concentrations could be explained as the results of the local photochemistry and the dynamical properties of the mixing layer. NO2 concentrations were anti-correlated to the O3 concentrations, as expected. SO2 also showed a pronounced dependence on car traffic. Average benzene and toluene concentrations were, respectively 1.7 ppb and between 4.4 and 6.6 pbb, but high values of toluene up to 98.8 ppb were observed. SO2 concentrations and to a lesser extent, those of NO2 and 03, were dependent on the wind direction. Ozone in Brussels has been found to be influenced by the meteorological conditions prevailing in central Europe. Comparisons with other measurements have shown that 03 and SO2 data are in general in good agreement, but our NO2 concentrations seem to be generally higher.     

Characterization of Indoor Particle Sources Using Continuous Mass and Size Monitors

ABSTRACT

A comprehensive indoor particle characterization study was conducted in nine Boston-area homes in 1998 in order to characterize sources of PM in indoor environments. State-of-the-art sampling methodologies were used to obtain continuous PM_2.5 concentration and size distribution particulate data for both indoor and outdoor air. Study homes, five of which were sampled during two seasons, were monitored over week-long periods. Among other data collected during the extensive monitoring efforts were 24hr elemental/organic carbon (EC/OC) particulate data as well as semi-continuous air exchange rates and time-activity information.

This rich data set shows that indoor particle events tend to be brief, intermittent, and highly variable, thus requiring the use of continuous instrumentation for their characterization. In addition to dramatically increasing indoor PM₂₅ concentrations, these data demonstrate that indoor particle events can significantly alter the size distribution and composition of indoor particles. Source event data demonstrate that the impacts of indoor activities are especially pronounced in the ultrafine (d_a < 0.1 um) and coarse (2.5 < d_a < 10 |um) modes. Among the sources of ultrafine particles characterized in this study are indoor ozone/terpene reactions. Furthermore, EC/OC data suggest that organic carbon is a major constituent of particles emitted during indoor source events. Whether exposures to indoor-generated particles, particularly from large short-term peak events, may be associated with adverse health effects will become clearer when biological mechanisms are better known.     

Forensic Applications of Nitrogen and Oxygen Isotopes in Tracing Nitrate Sources in Urban Environments

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing i 15 N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urba areas.     

Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston,TX

Nitrous acid is an important component of nighttime N-oxide chemistry, and provides a significant source of both OH and NO in polluted urban air masses shortly after sunrise. Several recent studies have called for new sources of HONO to account for daytime levels much higher than are consistent with current understanding. However, measurement of HONO is problematic, with most in-situ techniques reporting higher values than simultaneous optical measurements by long-path DOAS, especially during daytime. The discrepancy has been attributed to positive interference in the in-situ techniques, negative interference in DOAS retrievals, the difficulty of comparing the different air masses sampled by the methods, or combinations of these.During August and September 2006, HONO mixing ratios from collocated long-path DOAS and automated mist-chamber/ion chromatograph (MC/IC) systems ranged from several ppbv during morning rush hour to daytime minima near 100 pptv. Agreement between the two techniques was excellent across this entire range during many days, showing that both instruments accurately measured HONO during this campaign. A small bias towards higher LP-DOAS observations at night can be attributed to slow vertical mixing leading to pronounced HONO profiles. A positive daytime bias of the MC/IC instrument during several days in late August/early September was correlated with photochemically produced compounds such as ozone, HNO₃ and HCHO, but not with NO₂, NO_x, HO₂NO₂, or the NO₂ photolysis rate. While an interferant could not be identified organic nitrites appear a possible explanation for our observations.     

Rain and snow scavenging of HNO3 vapor in the atmosphere

The coefficients for the wet removal of HNO₃ vapor from the atmosphere by rain (in-cloud and below-cloud) and snow have been derived under a number of approximations. The wet removal coefficients are parametrized in terms of precipitation rate. These coefficients are intended to represent the average scavenging from large precipitation bands or frontal systems where there is widespread weakly ascending air motion. Consequently, the derived coefficients would be appropriate, on an interim basis, for inclusion into regional or mesoscale models which include the wet removal of HNO₃ vapor. These coefficients, when combined with altitude-dependent precipitation rates and vertical profiles of HNO₃ concentrations, are also useful to estimate the flux of HNO₃ to the earth's surface. The derived snow scavenging coefficients are consistent with those of recent measurements by Huebert et al. Both rain and snow scavenging coefficients are also consistent with recent observations of ionic composition in winter precipitation samples which indicated that snow removes HNO₃ vapor more efficiently than rain.     

A theoretical evaluation on the HNO3 artifact of the annular denuder system due to evaporation and diffusional deposition of NH4NO3-containing aerosols

A mathematical model was developed to evaluate HNO₃ artifact of the annular denuder system due to evaporation and diffusional deposition of nitrate-containing aerosols. The model performance was validated by comparing its numerical solutions with laboratory and numerical data available in the literature for evaporation and diffusional deposition of monodisperse and polydisperse NH₄NO₃ aerosols. Measurement artifacts were evaluated by varying typical sampling ranges of ambient temperature, HNO₃ gas concentration, aerosol number concentration, aerosol mass median diameter, and nitrate mass fraction of <2.5 μm aerosols to see their respective effects. Potential application of the present model on estimating HNO₃ artifacts was demonstrated using literature data sampled in USA, Taiwan, Netherlands, Korea and Japan. Significant measurement artifact could be found in Taiwan and Netherlands due either to low HNO₃ gas concentration and high nitrate concentration in <2.5 μm aerosols or to high ambient temperature.