Boundary-layer ozone depletion as seen in the Norwegian Arctic in spring

Several years of measurements of ozone, hydrocarbons, sulphate and meteorological parameters from Spitsbergen in the Norwegian Arctic are presented. Most of the measurements were taken on the Zeppelin Mountain at an altitude of 474 m a.s.l. The focus is the episodes of ozone depletion in the lower troposphere in spring, which are studied in a climatological way. Episodes of very low ozone concentrations are a common feature on the Zeppelin Mountain in spring. The low ozone episodes were observed from late March to the beginning of June. When the effect of transport direction was subtracted, the frequenty of the low ozone episodes was found to peak in the beginning of May, possibly reflecting the seasonal cycle in the actual depletion process. Analyses based on trajectory calculations show that most of the episodes occurred when the air masses were transported from W-N. Ozone soundings show that the ozone depletion may extend from the surface and up to 3–4 km altitude. The episodes were associated with a cold boundary layer beneath a thermally stable layer, suppressing mixing with the free troposphere. The concentration of several individual hydrocarbons was much lower during episodes of low ozone than for the average conditions. The change in concentration ratio between the hydrocarbons was in qualitative agreement with oxidation of hydrocarbons by Br and Cl atoms rather than by OH radicals.     

Measurement of PAN in the Polluted Boundary Layer and Free Troposphere Using a Luminol-NO2 Detector Combined with a Thermal Converter

Peroxyacetyl nitrate (PAN,CH³C(O)O₂NO₂) has been measured inthe polluted boundary layer and free troposphere by thermal conversion tonitrogen dioxide (NO₂) followed by detection of thedecomposition product with a Scintrex LMA-3 NO₂-luminolinstrument. Following laboratory tests of the efficiency of PAN conversionand investigations of possible interferences, the technique was evaluated atthe West Beckham TOR (Tropospheric Ozone Research) Station near the northNorfolk coast in Eastern England between September 1989 and August 1990. PANmeasured by the new technique was reasonably well correlated with PANrecorded using electron capture gas chromatography (EC/GC). PAN was alsowell correlated with ozone (O³) in the summer months. Springand autumn episodes of simultaneously high concentrations of PAN andO³ were examined in conjunction with air parcelback-trajectories and synoptic- and local-scale meteorology in a study ofthe sources of photooxidants on the east coast of England. Spring-timemeasurements of PAN made in the free troposphere in a light aircraft ataltitudes up to 3.1 km showed the presence of 0.54 and 0.26 ppbv PAN inpolar maritime and mid-latitude oceanic air masses, respectively. Thetechnique is particularly suited to airborne applications because potentialinterferences are minimised and the frequency of measurements is higher thangenerally achieved with EC/GC methods.     

The NO2 absorption spectrum. III: The 200–300 nm region at ambient temperature

Absorption cross-section measurements of NO₂ performed in our laboratory have been extended to the 200–300 nm region at ambient temperature. Low pressures have been used, limiting the effects of the dimer N₂O₄ which has an absorption cross-section from one to two orders of magnitude larger than that of NO₂ in this region. The results have been compared to those of previous authors and are now available for atmospheric purposes at 0.01 nm intervals.Unité de Recherche Associée au CNRS.     

Model analysis of the measured concentration of organic gases in the Norwegian Arctic

A 2-D meridional model for the chemistry and transport in the troposphere is used to study the seasonal variation of the concentration of organic gases like C₂H₂, C₂H₆, C₃H₈, C₆H₆, C₇H₈. CHCl₃ and C₂Cl₄ at high latitudes. The anthropogenic sources for these species were estimated, and the temporal and latitudinal distribution of OH and O₃ was calculated using a complex photochemical reaction system. There is fair agreement between the calculated annual variation and the measured concentrations for C₂H₂, C₂H₆, C₃H₈, C₇H₈ and C₂Cl₄ at Spitsbergen during July 1982 and March/April 1983, with a distinct late winter maximum and summer minimum. For CHCl₃, the direct anthropogenic source is minor compared to indirect anthropogenic or natural sources. For benzene, emission in car exhaust is important, but other anthropogenic sources are required for the calculations to agree with the measurements. Measured C₂H₄ and C₃H₆ concentrations are much higher than the calculated ones based on anthropogenic emissions, and show opposite seasonal trends. This indicates biogenic sources for these compounds.A buildup of PAN (300 pptv) is calculated at high latitudes during winter. This makes it the dominant source for NO_x as the temperature increases in the spring. NO_x is found to be a limiting factor for O₃ production at high latitudes during spring.     

The NO2 absorption spectrum. I: Absorption cross-sections at ambient temperature in the 300–500 nm region

New laboratory measurements of NO₂ absorption cross-sections have been performed between 300 and 500 nm at ambient temperature with improved experimental conditions: low gas pressures, long absorption paths, suitable absorbance values, narrow spectral bandwidths. The data, stored at 0.01 nm intervals, have been compared to those of the more recent studies and some reasons of disagreement are discussed.In the photolysis region below 400 nm, our absorption cross-sections are larger than those previously published, suggesting that the photodissociation coefficient calculated from the current data sets is underestimated. In the structured region of the spectrum above 400 nm, improvement of the resolution gives more precise values useful for optical measurements in atmosphere.Unité de Recherche Associée au CNRS.     

Enhancements of Major Aerosol Components Due to Additional HONO Sources in the North China Plain and Implications for Visibility and Haze

The Weather Research and Forecasting/Chemistry model(WRF-Chem) was updated by including photoexcited nitrogen dioxide(NO2) molecules,heterogeneous reactions on aerosol surfaces,and direct emissions of nitrous acid(HONO) in the Carbon-Bond Mechanism Z(CBM-Z).Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components.We calculated percentage changes of major aerosol components and concentration ratios of gas NO y(NOyg) to NO y and particulate nitrates(NO-3) to NO y due to the three additional HONO sources in the North China Plain in August of 2007.Our results indicate that when the three additional HONO sources are included,WRF-Chem can reasonably reproduce the HONO observations.Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO,nitrates(NO 3),ammonium(NH + 4),and PM 2.5(concentration of particulate matter of 2.5 μm in the ambient air) across the North China Plain.The three additional HONO sources produced a～5%-20% increase in monthly mean daytime concentration ratios of NO-3 /NO y,a ～15%-52% increase in maximum hourly mean concentration ratios of NO-3 /NO y,and a ～10%-50% increase in monthly mean concentrations of NO-3 and NH+4 across large areas of the North China Plain.For the Bohai Bay,the largest hourly increases of NO-3 exceeded 90%,of NH+4 exceeded 80%,and of PM 2.5 exceeded 40%,due to the three additional HONO sources.This implies that the three additional HONO sources can aggravate regional air pollution,further impair visibility,and enhance the incidence of haze in some industrialized regions with high emissions of NO x and particulate matter under favorable meteorological conditions.     

The NO2 absorption spectrum. II. Absorption cross-sections at low temperatures in the 400–500 nm region

With improved experimental conditions already used for measurements at ambient temperature (Mérienneet al., 1994), new values have been found for the absorption cross-sections of NO₂ at 240 and 220 K in the 400–500 nm spectral region. Using a better resolution than in previous studies we show that the temperature effect is not negligible and should be taken into account for the optical measurements of atmospheric NO₂ amounts by differential absorption methods.Unité de Recherche Associée au CNRS.     

Measurements of Trace Substances in the Arctic Troposphere as Potential Precursors and Constituents of Arctic Haze

During two measuring campaigns in early spring 1994 and 1995 (March/April) and one campaign in summer 1994, measurements of ozone, PAN, sulfur dioxide, nitric acid, and particulate nitrate, sulfate, and ammonium (only 1995) were recorded in the Arctic. Observations were made by aircraft at various sites in the eastern and western Arctic. Ozone concentrations showed a steady increase with altitude both in spring and summer. During five flights in springtime, low ozone events (LOEs) could be observed near the surface and up to altitudes of 2000 m. SO₂ background concentrations, ranging from detection limit (0.5 nmol/m³) to 5 nmol/m³, were observed during both spring and summer. Distinct maxima up to 55 nmol/m³ in lower altitudes were only obtained in springtime. Concentrations of the organic nitrate PAN were within a similar range as those of the inorganic nitrate HNO₃ during spring campaigns. In contrast, concentrations of particulate nitrate were one half an order of magnitude lower. HNO₃ concentrations increased significantly with altitude. Evidently, HNO₃ was intruded from the stratosphere into the troposphere. Sulfate concentrations ranged between 5 and 30 nmol/m³; ammonium concentrations were obtained within a range from 10 to 50 nmol/m³.     

Verification of the Contribution of Vehicular Traffic to the Total NMVOC Emissions in Germany and the Importance of the NO3 Chemistry in the City Air

In 1997 and 1998 several field campaigns for monitoring non-methane volatile organic compounds (NMVOCs) and nitrogen oxides (NO_x) were carried out in a road traffic tunnel and in the city center of Wuppertal, Germany. C₂–C₁₀ aliphatic and aromatic hydrocarbons were monitored using a compact GC instrument. DOAS White and long path systems were used to measure aromatic hydrocarbons and oxygenated aromatic compounds. A formaldehyde monitor was used to measure formaldehyde. Chemiluminescence NO analysers with NO₂ converter were used for measuring NO and NO₂. The high mixing ratios of the NMVOCs observed in the road traffic tunnel, especially 2.9 ppbv phenol, 1.5ppbv para-cresol and 4.4 ppbv benzaldehyde, in comparison with themeasured background concentration clearly indicate that these compounds were directly emitted from road traffic. Para-Cresol was for the first timeselectively detected as primary pollutant from traffic. From the measured data a NMVOC profile of the tunnel air and the city air, normalised to benzene (ppbC/ppbC), was derived. For most compounds the observed city air NMVOC profile is almost identical with that obtained in the traffic tunnel. Since benzene originates mainly from road traffic emission, the comparison of the normalised emission ratios indicate that the road traffic emissions in Wuppertal have still the largest impact on the city air composition, which is in contrast to the German emission inventory. In both NMVOC profiles, aromatic compounds have remarkably large contributions of more than 40 ppbC%. In addtion, total NMVOC/NO_x ratios from 0.6 up to 3.0ppbC/ppb in the traffic tunnel air and 3.4± 0.5 in the city air of Wuppertal were obtained. From the observed para-cresol/toluene and ortho-cresol/toluene ratios in the city air, evidence was found thatalso during daytime NO₃ radical reactions play an important role in urban air.     

闪电产生氮氧化物对青藏高原臭氧低谷形成的影响

为了进一步了解青藏高原闪电的产生氮氧化物（LNO_x）经由光化学反应对O₃浓度变化及夏季O₃低谷形成的可能影响,本文利用2005~2013年由OMI卫星得到的对流层NO₂垂直浓度柱（NO₂ VCD）、O₃总浓度柱（TOC）和O₃廓线以及星载光学瞬变探测器OTD和闪电成像仪LIS获取的总闪电数资料,对青藏高原和同纬度长江中下游地区的TOC和NO₂ VCD月均值时空分布特征、闪电与NO₂ VCD的相关性和O₃的垂直分布特征及其与LNO_x的关系进行了对比分析。结果表明,青藏高原的O₃低谷主要出现在夏季和秋季,其TOC值比同纬度长江中下游地区低约10~15 DU（Dobson unit）。青藏高原NO₂VCD总体较小,表现为夏高冬低的分布特征。青藏高原夏季O₃浓度受南亚高压的影响总体呈减小趋势,但因强雷暴天气导致对流层中上部LNO_x浓度升高,并随强上升气流向对流层顶输送,同时通过光化学反应使O₃浓度增加,缩小了青藏高原和同纬度地区的O₃浓度差,减缓了O₃总浓度的下降,抑制了夏季O₃低谷的进一步深化。     

The partitioning of nitrogen oxides in the lower Arctic troposphere during spring 1988

Surface observations of several nitrogen oxides in the Canadian high Arctic during the period March-April 1988 are reported. These include data on NO₂, the inorganic nitrates HNO₃ and particulate nitrate, and the organic nitrates PAN and C₃–C₇ alkyl-nitrates. It is found that the organic nitrates make up 70–80% of the sum of the measured nitrogen oxides. Based on concurrently measured sulphur oxides, the period of observation was divided into two halves with the first half representing less polluted, more aged air than the second. The preponderance of the organic nitrates was less in the first period than the second. In contrast, there was little difference in the inorganic nitrates and NO₂ concentrations. The dominant inorganic nitrate shifted from particulate nitrate in the first period towards gaseous HNO₃ in the second. No correlation between the nitrates (inorganic or organic) and O₃ was observed; although some indication of a positive correlation between NO₂ and O₃ has been reported earlier (Bottenheimet al., 1990). Possible explanations for these observations are proposed. A survey of other potential nitrogen oxides that may be present in the Arctic air but not measured in these experiments suggests that the nitrogen oxides not measured here constitute a minor fraction of the total reactive nitrogen (NO _y ).Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

New laboratory measurements of NO₂ absorption cross-section were performed using a Fourier transform spectrometer at 2 and 16 cm^-1 (0.03 and 0.26 nm at 400 nm) in the visible range (380–830 nm) and at room temperature. The use of a Fourier transform spectrometer leads to a very accurate wavenumber scale (0.005 cm^-1, 8×10^-5 nm at 400 nm). The uncertainty on the new measurements is better than 4%. Absolute and differential cross-sections are compared with published data, giving an agreement ranging from 2 to 5% for the absolute values. The discrepancies in the differential cross-sections can however reach 18%. The influence of the cross-sections on the ground-based measurement of the stratospheric NO₂ total amount is also investigated.     

Measurements of Photolyzable Halogen Compounds and Bromine Radicals During the Polar Sunrise Experiment 1997

As part of the Polar Sunrise Experiment (PSE) 1997, concentrations of halogen species thought to be involved in ground level Arctic ozone depletion were made at Alert, NWT, Canada (82.5°N, 62.3°W) during the months of March and April, 1997. Measurements were made of photolyzable chlorine (Cl₂ and HOCl) and bromine (Br₂ and HOBr) using the Photoactive Halogen Detector (PHD), and bromine radicals (BrO_x) using a modified radical amplifier. During the sampling period between Julian Day 86 (March 27) and Day 102 (April 12), two ozone depletion episodes occurred, the most notable being on days 96-99, when ozone levels were below detectable limits (1 ppbv). Concentrations of BrO_x above the 4 pptv detection limit were found for a significant part of the study, both during and outside of depletion events. The highest BrO_x concentrations were observed at the end of the depletion event, when the concentration reached 15 pptv. We found substantial amounts of Br₂ in the absence of O₃, indicating that O₃ is not a necessary requirement for production of Br₂. There is also Br₂ present when winds are from the south, implying local scale (e.g. from the snowpack) production. During the principal O₃ depletion event, the HOBr concentration rose to 260 pptv, coincident with the BrO_x maximum. This implies a steady state HO₂ concentration of 6 pptv. During a partial O₃ depletion event, we estimate that the flux of Br₂ from the surface is about 10 times greater than that for Cl₂.     

The NO2 Absorption Spectrum. IV: The 200–400 nm Region at 220 K

Previous experiments in the 400–500 nm region (Coquart et al., 1995) have been extended to the 200–400 nm region to determine the absorption cross-sections of NO₂ at 220 K. The NO₂ and N₂O₄ cross-sections are obtained simultaneously from a calculation applied to the data resulting from measurements at low pressures. A comparison between the NO₂ cross-sections at 220 K and at ambient temperature shows that the low temperature cross-sections are generally lower, except in the region of the absorption peaks. Comparisons are also made with previous data at temperature close to 220 K.     

Investigating the Halogen Chemistry From High-Latitude Nighttime Stratospheric Measurements of OClO and NO2

Two cases of simultaneous nighttime measurements of NO₂ and OClO in the winter polar stratosphere are analyzed in order to test our present knowledge of halogen chemistry in the presence of high amount of NO₂ at low temperature. Comparisons with Lagrangian model calculations using several hypotheses are performed. First simulations, using the admitted constant rates of chemical reaction, strongly underestimate the measured OClO while the NO₂ profiles are correctly reproduced. If uncertainties in actinic fluxes calculations are taken into account, simulation results do not show a significant reduction of the underestimation. A better agreement can be achieved if the formation of unstable isomers of ClONO₂ and of BrONO₂ occurs in the cold conditions of the polar stratosphere. An approximate value of the branching ratios of the channels leading to ClONO₂ and ClOONO, and to BrONO₂ and BrOONO, necessary to reproduce both OClO and NO₂ is given and discussed.     

C2-C7 Hydrocarbon Concentrations in Arctic Snowpack Interstitial Air: Potential Presence of Active Br within the Snowpack

Samples of interstitial air from within the snow pack on an ice floe on the Arctic Ocean were collected during the April 1994 Polar Sunrise Experiment. The concentrations of C₂-C₇ hydrocarbons are reported for the first time in the snow pack interstitial air. Alkane concentrations tended to be higher than concentrations in free air samples above the snow but very similar to winter measurements at various locations in the Arctic archipelago. However, ethyne concentrations in both interstitial and free air were highly correlated with ozone mixing ratios, consistent with previous demonstrations of the effects of Br atom chemistry. The analysis of total bromine within the snow pack indicate an enrichment in total Br at the interface layer between snow and free troposphere. The mixing ratios of some brominated compounds, such as CHBr₃ and CHBr₂Cl, are found to be higher in this top layer of snow relative to the boundary layer. Results were inconclusive due to the limited number of samples, but suggest the possible presence of active bromine in the snow pack and also that some differences exist between chemical reactions occurring in interstitial air compared to air in the boundary layer.     

Kinetics of the reaction of nitrogen dioxide with ozone

The kinetics of the reaction of NO₂ with O₃ have been investigated at 296 K, using UV absorption spectroscopy to monitor decay of NO₂ or O₃ and infrared laser absorption spectroscopy to monitor formation of the reaction product N₂O₅. The results both for the rate coefficient at 296 K (k ₁=3.5×10^-17 cm³ molecule^-1 s^-1) and the reaction stoichiometry (NO₂/O₃=1.85±0.09) are in good agreement with previous studies, confirming that the two step mechanism involving formation of symmetrical NO₃ as an intermediate is predominant.% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaaeOmaaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaa% bodaaeqaaOWaa4ajaSqaaaqabOGaayPKHaGaaeOtaiaab+eadaWgaa% WcbaGaae4maaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaabkdaaeqa% aaaa!41D7!\[{\text{NO}}_{\text{2}} + {\text{O}}_{\text{3}} \xrightarrow{{}}{\text{NO}}_{\text{3}} + {\text{O}}_{\text{2}} \]% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaae4maaqabaGccqGHRaWkcaqGobGaae4tamaaBaaa% leaacaqGYaaabeaakiabgUcaRiaab2eadaGdKaWcbaaabeGccaGLsg% cacaqGobWaaSbaaSqaaiaabkdaaeqaaOGaae4tamaaBaaaleaacaqG% 1aaabeaakiabgUcaRiaab2eaaaa!4464!\[{\text{NO}}_{\text{3}} + {\text{NO}}_{\text{2}} + {\text{M}}\xrightarrow{{}}{\text{N}}_{\text{2}} {\text{O}}_{\text{5}} + {\text{M}}\]A possible minor role for the unsymmetrical ONOO species is suggested to account for the lower-than-expected stoichiometry factor. The importance of this reaction in the oxidation of atmospheric NO₂ is discussed.     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

Tropospheric Ozone at High Latitudes in Clean and Polluted Air Masses, a Climatological Study

Several years of continuous measurements of surfaceozone at Norwegian monitoring sites are studied in aclimatological way. The monitoring sites are at rurallocations extending from 58°N, a few hundredkilometers from the European continent and into theArctic at 79°N. The ozone observations are sorted intoclasses of integrated NO_x emissions along 96 h backtrajectories. The average seasonal cycles of ozone areestimated for each class separately. The differencesindicate the change from the background air due toanthropogenic emissions. The average seasonal cycle ofozone in the cleanest air masses showed a maximum inspring and a minimum during summer and autumn at allsites, but the spring maximum was more pronounced atthe southernmost locations. Polluted air masses showedan ozone deficit during winter and a surplus duringsummer. The deviation from the background was clearlylinked to the integrated NO_x emission along thetrajectories. In summer the calculations indicate thatthe number of ozone molecules formed per NO_x moleculedrops with increasing emissions. The average seasonalcycle of ozone at Birkenes for different transportsectors indicate that the most pronounced ozoneformation takes place in air masses from E-Europe/Russia.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.