Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

Observation of atmospheric nitrous acid with DOAS in Beijing, China

Measurements of nitrous acid （HONO） and nitrogen dioxide （NO2） in Beijing City have been performed by means of a developed differential optical absorption spectroscopy （DOAS） system based on photodiode array （PDA）, during the autumn of 2004. HONO and NO2 were simultaneously identified by their characteristic absorption bands in the spectral region between 337 nm and 372 nm with high sensibility and time resolution. The concentrations of HONO exhibit obviously diurnal variation with a nocturnal maximum and a daytime minimum. The highest HONO value up to 11.8 μg/m^3 was observed during the night of 2/3 September. Possible sources of the observed HONO were discussed. Good correlation to NO2 indicates that NO2 is a main source component. The measurement also shows direct emission of HONO is an imnortant source in strongly polluted urban area.     

大气中HONO来源的研究进展

由于亚硝酸(HONO)在大气中所扮演的重要角色如:OH自由基的前体物以及对臭氧和光化学烟雾形成的促进作用而引起科学界的广泛关注,然而对于大气中HONO的来源问题,特别是它的非均相形成过程目前尚未清楚.本文从HONO在大气中的重要意义及目前国际上对HONO来源的研究现状,特别是它的非均相形成机理进行了阐述;由于其在大气化学中的重要意义,提出我国开展大气HONO研究的重要性,并对其来源问题进行了讨论与展望.     

2017年春季常州HONO观测及对大气氧化能力影响的评估

本研究于2017年4月在江苏省常州市环境监测中心使用一套基于湿化学法的仪器对大气中的HONO进行了实时在线观测,HONO浓度范围在0.2～13.9μg·m~(-3)之间,平均值为(2.9±2.3)μg·m~(-3);同时,对O_3、 HCHO、 VOCs、光解频率以及气象参数进行了同步监测.利用MCM箱体模式模拟得到白天·OH浓度最大值范围在1.0×10~6～1.4×10~7个·cm~(-3)之间.同时结合观测结果与模式模拟结果计算了HONO、 O_3、 HCHO和H_2O_2的光解以及烯烃臭氧化反应对·OH的生成速率,定量表征大气氧化性,揭示了这5种来源对大气氧化能力的影响:整体上O_3光解(46.4%)HONO光解(41.1%)烯烃臭氧化反应(10.9%)HCHO光解(1.5%)H_2O_2光解(0.1%);清晨时HONO光解对·OH生成起主要作用,之后随着O_3浓度的增加,O_3光解对·OH的贡献占主导地位;在17:00之后,由于太阳光解频率显著降低,烯烃臭氧化反应对·OH生成有主要贡献;甲醛与过氧化氢的光解对·OH的贡献可忽略.     

Vertical distributions of wintertime atmospheric nitrogenous compounds and the corresponding OH radicals production in Leshan, southwest China

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations were operated from 02 to 21 December 2018 in Leshan, southwest China, to measure HONO, NO₂ and aerosol extinction vertical distributions, and these were the first MAX-DOAS measurement results in Sichuan Basin. During the measurement period, characteristic ranges for surface concentration were found to be 0.26–4.58 km^?1 and averaged at 0.93 km^?1 for aerosol extinction, 0.49 to 35.2 ppb and averaged at 4.57 ppb for NO₂ and 0.03 to 7.38 ppb and averaged at 1.05 ppb for HONO. Moreover, vertical profiles of aerosol, NO₂ and HONO were retrieved from MAX-DOAS measurements using the Heidelberg Profile (HEIPRO) algorithm. By analysing the vertical gradients of pollutants and meteorological information, we found that aerosol and HONO are strongly localised, while NO₂ is mainly transmitted from the north direction (city center direction). Nitrogen oxides such as HONO and NO₂ are important for the production of hydroxyl radical (OH) and oxidative capacity in the troposphere. In this study, the averaged value of OH production rate from HONO is about 0.63 ppb/hr and maximum value of ratio between OH production from HONO and from (HONO+O₃) is > 93% before12:00 in Leshan. In addition, combustion emission contributes to 26% for the source of HONO in Leshan, and we found that more NO₂ being converted to HONO under the conditions with high aerosol extinction coefficient and high relative humidity is also a dominant factor for the secondary produce of HONO.     

Interference from HONO in the measurement of ambient air NO2 via photolytic conversion and quantification of NO

The reference method to quantify mixing ratios of the criteria air pollutant nitrogen dioxide (NO₂) is NO-O₃ chemiluminescence (CL), in which mixing ratios of nitric oxide (NO) are measured by sampling ambient air directly, and mixing ratios of NO_x (= sum of NO and NO₂) are measured by converting NO₂ to NO using, for example, heated molybdenum catalyst or, more selectively, photolytic conversion (P-CL). In this work, the nitrous acid (HONO) interference in the measurement of NO₂ by P-CL was investigated. Results with two photolytic NO₂ converters are presented. The first used radiation centered at 395 nm, a wavelength region commonly utilized in P-CL. The second used light at 415 nm, where the overlap with the HONO absorption spectrum and hence its photolysis rate are less. Mixing ratios of NO₂, NO_x and HONO entering and exiting the converters were quantified by Thermal Dissociation Cavity Ring-down Spectroscopy (TD-CRDS). Both converters exhibited high NO₂ conversion efficiency (CF_NO2; > 90%) and partial conversion of HONO. Plots of CF against flow rate were consistent with photolysis frequencies of 4.2 s^-1 and 2.9 s^-1 for NO₂ and 0.25 s^-1 and 0.10 s^?1 for HONO at 395 nm and 415 nm, respectively. CF_HONO was larger than predicted from the overlap of the emission and HONO absorption spectra. The results imply that measurements of NO₂ by P-CL marginally but systematically overestimate true NO₂ concentrations, and that this interference should be considered in environments with high HONO:NO₂ ratios such as the marine boundary layer or in biomass burning plumes.     

施肥后土壤HONO排放特征及排放因子研究

近年发现土壤可以排放亚硝酸（HONO）,对大气氧化性具有潜在的重要影响.施肥能增加土壤含氮气体的排放,通常用排放因子表征气体排放量对化肥的响应关系.但HONO的相关研究尚为空白,制约了对这一新的地气交换机制的环境效应的评估.为此,在珠三角对一块菜地施用3种化肥（复合肥、碳酸氢铵和尿素）,利用动态箱测量施肥前后的HONO排放通量.结果表明,土壤施用3种氮肥后的最大HONO排放通量分别为23.1、19.5和57.4 ng·m^-2·s^-1,分别是施肥前最大值的3.5、3.2和9.4倍;3种氮肥的HONO排放因子分别为8.60×10^-5、1.44×10^-4和2.48×10^-4;施肥后HONO排放通量呈现白天高夜间低的特征,且与土壤温度、土壤孔隙含水量（WFPS,在低含水量区间）呈正相关关系.证实了施肥对HONO排放具有显著促进作用,通过外场实测获得的3种化肥HONO排放因子,将为编制HONO排放清单等后续研究提供依据.     

北京夏季大气HONO的监测研究

在2007-08-14～2007-08-24期间,利用差分光学吸收光谱（DOAS）技术,对北京市大气中HONO、NO₂和O₃等污染物进行了连续监测,分析了HONO和NO₂的日变化特征,讨论了夜间直接排放对HONO来源的贡献,进行了24 h和夜间13 h HONO非均相反应形成与黑碳气溶胶（BC）和相对湿度（RH）等要素的相关分析.结果表明,HONO和NO₂均在01:00左右达到峰值,HONO的另一峰值浓度出现在06:00,比NO₂第2个峰值出现时间07:00早1 h;夜间（19:00～次日07:00）直接排放对HONO的贡献最大达到31.3％,出现在20:00,平均贡献为15％;夜间HONO_corr/NO₂比率与BC和RH具有非常明显的相关性,说明HONO的非均相生成速率与NO₂的浓度以及反应介质BC表面的吸附水的浓度即RH成正比,得到夜间HONO平均转化率(HONO/NO₂)为0.8%·h^-1;而且RH的增加对HONO的非均相形成有利,但是当RH>80%对反应也将产生抑制作用,通过对监测期间的个例分析也证实了这一假设.     

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO₂ on different surfaces play an important role in atmospheric NO_x removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO₂ uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime. However, the uptake behavior of NO₂ varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO₂ uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO₂ uptake coefficients (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions, with the measured γ varied from <10^?8 to 3.2 × 10^?7 under different humidity. A photo-enhanced uptake of NO₂ on urban grime was observed, with the obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9 × 10^?6 at 5% relative humidity (RH) and 5.8 × 10^?6 at 70% RH on urban grime, showing a positive RH dependence for both NO₂ uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO₂-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.     

Effect of potential HONO sources on peroxyacetyl nitrate (PAN) formation in eastern China in winter

As an important secondary photochemical pollutant, peroxyacetyl nitrate (PAN) has been studied over decades, yet its simulations usually underestimate the corresponding observations, especially in polluted areas. Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events, but the current model still cannot reproduce the observations, and researchers speculated that nitrous acid (HONO) played a key role in PAN formation. For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry (WRF-Chem) model in February of 2017. The results showed that the potential HONO sources significantly improved the PAN simulations, remarkably accelerated the RO_x (sum of hydroxyl, hydroperoxyl, and organic peroxy radicals) cycles, and resulted in 80%–150% enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50% enhancements in the areas around 35–40°N within 3 km during a heavy haze period. The direct precursors of PAN were aldehyde and methylglyoxal, and the primary precursors of PAN were alkenes with C > 3, xylenes, propene and toluene. The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.