Assessment of the Uncertainties in the NO2 and O3 Measurements by Visible Spectrometers

The column amounts of nitrogen dioxide (NO2) and ozone (O3) were measured using a visible spectrometer based on the twilight zenith-sky technique at two observatories located at similar latitudes in the northern part of Japan separated by a distance of 150 km. The measurements began in April 1991 at the Moshiri Observatory (44.4°N, 142.3°E) and in April 1994 at the Rikubetsu Observatory (43.5°N, 143.8°E). Since weather conditions and the possible influence from tropospheric pollution were not always identical at these two observatories, the overall accuracy of the measurements was studied comparing these data sets. The first year data obtained at a solar zenith angle of 90 degrees indicated that the NO2 slant column values at sunrise and sunset agreed within 0.36 and 0.54 × 1016 cm-2, respectively, corresponding to 5 % (June) and to 12 % (December) of the columns. The O3 values agreed within 0.76 × 1019 cm-2, corresponding to 4 % (March) 6 % (August) of the columns, although a part of the difference was systematic. The O3 column amounts were also compared to those obtained by the Dobson spectrometer at Sapporo (43.5°N, 143.8°E), whose latitude is similar to these observatories. When an air mass factor of 17.5 was used, the two-year Moshiri vertical column values agreed with the Dobson direct sun values to within 15 Dobson Units, or 3 6 % of the column. The difference between the two values was found to be due partly to the change in the air mass factor caused by seasonal and day-to-day changes in the shape of the O3 vertical profiles. These results confirm the reliability of the NO2 and O3 measurements by visible spectrometers at these sites for the Network for the Detection of Stratospheric Change (NDSC).     

Parameterization of Ozone Photolysis Frequency in the Lower Troposphere Using Data from Photodiode Array Detector Spectrometers

Spectroradiometers using photodiode array detectors (PDAs) are increasingly applied for airborne and ground-based atmospheric measurements of spectral actinic flux densities due to their high time resolution (less than one second). However they have limited sensitivity of ultraviolet (UV) radiation for wavelengths less than about 305 nm. This results in uncertainties of ozone photolysis frequencies derived from spectral actinic flux density measurements using PDA spectrometers. To overcome this limitation a parameterization method is introduced which extrapolates the data towards the wavelength range of limited sensitivity of the PDA spectrometers (less than about 305 nm). The parameterization is based on radiative transfer simulations and is valid for measurements in the lower troposphere. The components of the suggested parameterization are the lower threshold wavelength of the PDA spectrometer, the slant ozone column (ratio of the total ozone column and the cosine of the solar zenith angle), and the ambient temperature. Tests of the parameterization with simulated actinic flux density spectra have revealed an uncertainty of the derived ozone photolysis frequency of ±5%. Field comparisons of the parameterization results with independent measurements of the ozone photolysis frequency were within ±10% for solar zenith angles less than 70^∘. Finally the parameterization was applied to airborne measurements to emphasize the advantage of high time resolution of PDA spectrometers to study ozone photolysis frequency fields in inhomogeneous cloud condtitions.     

A comparison of photolysis rate parameters estimated from measured and simulated actinic flux for wintertime conditions at Storm Peak Laboratory,Colorado

Photolysis rate parameters depend upon solar actinic flux and chemical species dependent quantum yields and cross sections. Spectrally resolved measurements of actinic flux should be preferred over flux derived from models for the analysis of field observations. Actinic flux can be difficult to derive from the irradiance measurements of flat-plate radiometers. It is also difficult to estimate from models due to uncertainties in the ozone column, aerosol concentrations and distributions, cloud cover, optical depth and surface albedo. A series of actinic flux measurements were performed at Storm Peak Laboratory (3,210 m above sea level), Colorado, United States with spectroradiometers during the wintertime (January 07–10, 2004). The site is relatively remote with a clean atmosphere and during the wintertime the ground is generally covered by fresh snow with a high albedo. The actinic flux measurements were used to estimate the photolysis rate parameters of ozone, nitrogen dioxide and formaldehyde. The measured actinic flux and the photolysis rate parameters derived from the flux were compared to calculations using the Tropospheric Ultraviolet-Visible Model (TUV), version 4.2 (Madronich and Flocke, 1998). The TUV modeled actinic flux, the measured flux and the photolysis rate parameters derived from them had similar temporal patterns. However there were significant differences in their magnitude due to uncertainties in the data available to initialize the TUV model and the calibration of the spectroradiometer.     

Slant Column Measurements of O3 and NO2 During the NDSC Intercomparison of Zenith-Sky UV-Visible Spectrometers in June 1996

In June 1996, 16 UV-visible sensors from 11 institutes measured spectra of the zenith sky for more than 10 days. Spectra were analysed in real-time to determine slant column amounts of O3 and NO2. Spectra of Hg lamps and lasers were measured, and the amount of NO2 in a cell was determined by each spectrometer. Some spectra were re-analysed after obvious errors were found. Slant columns were compared in two ways: by examining regression analyses against comparison instruments over the whole range of solar zenith angles; and by taking fractional differences from a comparison instrument at solar zenith angles between 85° and 91°. Regression identified which pairs of instruments were most consistent, and so which could be used as universal comparison instruments. For O3, regression slopes for the whole campaign agreed within 5% for most instruments despite the use of different cross-sections and wavelength intervals, whereas similar agreement was only achieved for NO2 when the same cross-sections and wavelength intervals were used and only one half-day's data was analysed. Mean fractional differences in NO2 from a comparison instrument fall within ±7% (1-sigma) for most instruments, with standard deviations of the mean differences averaging 4.5%. Mean differences in O3 fall within ±2.5% (1- sigma) for most instruments, with standard deviations of the mean differences averaging 2%. Measurements of NO2 in the cell had similar agreement to measurements of NO2 in the atmosphere, but for some instruments measurements with cell and atmosphere relative to a comparison instrument disagreed by more than the error bars.     

Stratospheric Photolysis Frequencies: Impact of an Improved Numerical Solution of the Radiative Transfer Equation

Numerical schemes for the calculation of photolysis rates are usually employed in simulations of stratospheric chemistry. Here, we present an improvement of the treatment of the diffuse actinic flux in a widely used stratospheric photolysis scheme (Lary and Pyle, 1991). We discuss both the consequences of this improvement and the correction of an error present in earlier applications of this scheme on the calculation of stratospheric photolysis frequencies. The strongest impact of both changes to the scheme is for small solar zenith angles. The effect of the improved treatment of the diffuse flux is most pronounced in the lower stratosphere and in the troposphere. Overall, the change in the calculated photolysis frequencies in the region of interest in the stratosphere is below about 20%, although larger deviations are found for H₂O, O₂, NO, N₂O, and HCl.     

Effect of clouds on the photodissociation of NO2: Observations and modelling

The role of clouds in photodissociation is examined by both modelling and observations. It is emphasized that the photodissociation rate is proportional to the actinic flux rather than to the irradiance. The actinic flux concerns the energy that is incident on a molecule, irrespective of the direction of incidence. The irradiance concerns the energy that is incident on a plane.As far as the modelling aspect is concerned, a multi-layer delta-Eddington model is used to calculate irradiances, actinic fluxes, and photodissociation rates of nitrogen dioxide J(NO₂) as a function of height in inhomogeneous atmospheres. For the considered wavelength interval [290–420 nm], Rayleigh scattering, ozone absorption, and Mie scattering and absorption by cloud drops and aerosols should be taken into account.Further, a three-layer model is used to calculate the actinic flux above and below a cloud, relative to the incident flux, in terms of cloud albedo, zenith angle, and the albedo of the underlying and overlying atmosphere. Cloud albedo is mainly determined by cloud optical thickness. An expression for the incloud actinic flux is given as a function of in-cloud optical thickness. The three-layer model seems to be a useful model for the estimation of photodissociation rates in dispersion models.It is stressed that both models in their present form cannot handle partial cloudiness.It is shown that if no clouds are present, the actinic flux depends primarily on solar zenith angle. Further, the incident flux at the top of the atmosphere diminishes downward into the atmosphere due to the increasing effect of scattering. Therefore, the actinic flux usually increases with height, although above clouds the actinic flux sometimes decreases with height due to a large contribution of the upward scattered light.For cloudy atmospheres, another important parameter with respect to the actinic flux is added: cloud optical thickness. Cloud optical thickness determines cloud albedo. It can be shown that incloud characteristics and cloud height are less important while describing the effect of a cloud on the actinic flux (outside the cloud). The in-cloud values of the actinic flux can exceed the values outside the cloud.Finally, using the photostationary state relationship, a comparison is performed between model results and ground-based measurements as well as in-cloud air craft measurements.     

Actinic fluxes: The role of clouds in photodissociation

The role of clouds in photodissociation is examined by both modeling and observations. It is emphasized that the photodissociation rate is proportional to the actinic flux rather than to the irradiance. (The actinic flux concerns the energy that is incident on a molecule, irrespective of the direction of incidence. The irradiance concerns the energy that is incident on a plane.) A 3-layer model is used to calculate the actinic flux above and below a cloud, relative to the incident flux, in terms of cloud albedo, zenith angle and the albedo of the underlying and overlying atmosphere. Cloud albedo is mainly determined by cloud optical thickness. An expression for the in-cloud actinic flux is given as a function of in-cloud optical thickness. The 3-layer model seems to be an useful model for estimation of photodissociation rates in dispersion models. Further, a multi-layer delta-Eddington model is used to calculate irradiances, actinic fluxes and photodissociation rates of nitrogen dioxide J(NO₂) as a function of height in inhomogeneous atmospheres. For the considered wavelength interval [290–420 nm], Rayleigh scattering, ozone absorption and Mie scattering and absorption by cloud drops and aerosols should be taken into account. It is stressed that both models are one-dimensional and as such are unable to deal with partial cloudiness. It is shown that if no clouds are present, the actinic flux depends primarily on the solar zenith angle. The actinic flux usually increases with height. For cloudy atmospheres, another important parameter with respect to the actinic flux is added: cloud optical thickness, which determines cloud albedo. It can be shown that in-cloud characteristics and cloud height are less important in describing the effect of a cloud on the actinic flux (outside the cloud). The in-cloud values of the actinic flux can exceed the values outside the cloud. Finally, using the photostationary state relationship, good agreement is found between model results and aircraft measurements.     

Transformation of Irradiance Measurements into Spectral Actinic Flux for Photolysis Rates Determination

The actinic flux is the only radiometric quantity suitable for photolysisfrequency determination. It is derived from solar spectral irradiancemeasurements performed by a portable spectroradiometer in the 300–850nm wavelength range. The spectral irradiance is first divided into a directpart and a diffuse part, according to the atmospheric conditions, and thenconverted into the corresponding actinic flux quantity. As an intermediary,the ratio of diffuse actinic flux to diffuseirradiance is calculated by the spherical harmonics radiative code withrespect to wavelength, solar zenith angle, surface albedo, and aerosolproperties.The results of extensive sensitivity studies of asa function of the main atmospheric parameters are discussed and lead to theconclusion that aerosol optical depth is the major critical value for aprecise determination. The global algorithm totransform spectral irradiance into actinic flux is finally applied forphotodissociation rate calculations by convolution of the obtained actinicflux spectra with the absorption cross-sections and quantum yields of themolecule studied. Photolysis rates of different atmospheric photooxidants havebeen measured with this spectroradiometric method during the summers of 1993and 1994 in Brittany and in Portugal. The ozone and nitrogen dioxidephotodissociation rates obtained present a good agreement with thej(O₃) and j(NO₂) actinometerresults, for the same experimental conditions in Brittany.     

A reliable and efficient two-stream algorithm for spherical radiative transfer: Documentation of accuracy in realistic layered media

We present a fast and well documented two-stream algorithm for radiative transfer and particle transport in vertically inhomogeneous, layered media. The physical processes considered are internal production (emission), scattering, absorption, and Lambertian reflection at the lower boundary. The medium may be forced by internal sources as well as by parallel or uniform incidence at the top boundary. This two-stream algorithm is based on a general purpose multi-stream discrete ordinate algorithm released previously. It incorporates all the advanced features of this well-tested and unconditionally stable algorithm, and includes two new features: (i) corrections for spherical geometry, and (ii) an efficient treatment of internal sources that vary rapidly with depth. It may be used to compute fluxes, flux divergences and mean intensities (actinic fluxes) at any depth in the medium. We have used the numerical code to investigate the accuracy of the two-stream approximation in vertically inhomogeneous media. In particular, computations of photodissociation and warming/cooling rates and surface fluxes of ultraviolet and visible radiation for clear, cloudy and aerosol-loaded atmospheres are presented and compared with results from multi-stream computations. The O₃ +hv O(¹D) + O₂ and O₃ +hv O(³P) + O₂ photodissociation rates were considered for solar zenith angles between 0.0–70.0° and surface albedos in the range 0.0–1.0. For small and moderate values of the solar zenith angle and the surface albedo the error made by the two-stream approximation is generally smaller, <10%, than the combined uncertainty in cross sections and quantum yields. Surface ultraviolet and visible fluxes were calculated for the same range of solar zenith angles and surface albedos as the photodissociation rates. It was found that surface ultraviolet and visible fluxes may be calculated by the two-stream approximation with 10% error or less for solar zenith angles less than 60.0° and surface albedos less than 0.5. For large solar zenith angles and/or large surface albedos, conditions typical at high latitudes, the error made by the two-stream approximation may become appreciable, i.e. 20% or more for the photodissociation rates in the lower stratosphere and for ultraviolet and visible surface fluxes for large surface albedos. The two-stream approximation agrees well with multi-stream results for computation of warming/cooling rates except for layers containing cloud and aerosol particles where errors up to 10% may occur. The numerical code provides a fast, well-tested and robust two-stream radiative transfer program that can be used as a software tool by aeronomers, atmospheric physicists and chemists, climate modellers, meteorologists, photobiologists and others concerned with radiation or particle transport problems. Copies of the FORTRAN77 program are available to interested users.     

A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

Three-Dimensional Calculation of Photolysis Frequencies in the Presence of Clouds and Impact on Photochemistry

For atmospheric photochemistry, clouds can significantly affect actinic flux distributions. In this paper, we examine the effects of convective clouds on the three-dimensional distribution of the spectral actinic flux and on photolysis frequencies for various chemical species. Three-dimensional solutions of the UV-VIS radiative transfer equation are produced using the Spherical Harmonic Discrete Ordinary Method solution technique. This solver uses as input the 3-D cloud characteristics simulated by a dynamical cloud model. The ultraviolet and visible spectra are divided into 5 intervals in order to explore the wavelength dependency of the cloud effect on the actinic flux. Results show that the distribution of the actinic flux over the cloud domain is far from homogeneous and depends primarily on the cloud extinction associated with the hydrometeors. Maximum actinic flux is found at the top edge of the cloud and is related to scattering by ice crystals. The actinic flux is enhanced by a factor of 2 to 5, compared to clear air values, above, at the top edge, and around the cloud. The 3-D actinic flux is used to calculate the photolysis rates for some chemical species (e.g. NO₂, O₃, and HCHO). Forcomputing photolysis rates, a discretized spectral representation of the absorption wavelengths is used in the model. The calculated photolysis rates are distributed inhomogeneously throughout the cloud, and maxima are found in regions where the actinic flux is enhancement is large. Temperature effects on absorption are found in the photolysis frequencies of some species. Finally, the potential importance of this photolysis enhancement on photochemistry is studied using box model simulations. Results show that enhanced OH concentrations are found in the upper troposphere (120–200%) overthe clouds and changes in ozone production rates (+15%) are obtained in quasi-steady state conditions.     

High-Latitude Springtime Photochemistry. Part I: NOx, PAN and Ozone Relationships

Springtime measurements of NO_x, ozone, PAN,J(NO₂), and other compounds were made near Ny-Ålesund,Svalbard (78°54N, 11°53E), in 1994 and Poker Flat,Alaska (65°08N, 147°29W), in 1995. At Svalbard medianmixing ratios for PAN and NO_x of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NO_x were 79.5 and 85.9 pptv, respectively. These data areused to estimate thermal PAN decomposition using several differentapproaches. At Svalbard PAN decomposition was very small, while at PokerFlat up to 30 pptv/h PAN decomposed. At both sites the NO_x/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NO_x source. In-situozone production was calculated from the measured NO, NO₂,O₃, J(NO₂), and temperature data, using thesteady state assumption Median ozone production was 605 pptv/h at PokerFlat, and one order of magnitude smaller at Svalbard during the daytime.Only at Poker Flat could a direct influence on the diurnal ozone cycle beobserved from in-situ production. These results imply that PAN decompositionis a major source of NO_x in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.     

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

Stratospheric volume mixing ratio profiles of N₂O₅, CH₄, and N₂O have been retrieved from a set of 0.052 cm^–1 resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44° N latitude) on 12 October 1990. The N₂O₅ results have been derived from measurements of the integrated absorption by the 1246 cm^–1 band. Assuming a total intensity of 4.32×10^–17 cm^–1/molecule cm^–2 independent of temperature, the retrieved N₂O₅ volume mixing ratios in ppbv (parts per billion by volume, 10^–9), interpolated to 2 km height spacings, are 1.64±0.49 at 37.5 km, 1.92±0.56 at 35.5 km, 2.06±0.47 at 33.5 km, 1.95±0.42 at 31.5 km, 1.60±0.33 at 29.5 km, 1.26±0.28 at 27.5 km, and 0.85±0.20 at 25.5 km. Error bars indicate the estimated 1- uncertainty including the error in the total band intensity (±20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.Laboratoire associé aux Universités Pierre et Marie Curie et Paris Sud.     

地基曙暮光光谱观测反演平流层O3和NO2柱含量

用差分光学吸收光谱(DOAS)方法,从曙暮光天顶散射可见光光谱资料反演了北京上空的O3和NO2柱含量,并对反演结果进行了验证和误差分析.斜柱含量的反演采用了线性和非线性最小二乘拟合方法,拟合时考虑了O3、NO2和H2O的吸收、Ring效应和散射的影响;斜柱含量除以空气质量因子转换成垂直柱含量.空气质量因子的计算使用伪球面DISORT辐射传输模式.O3和NO2总量的检验分别用北京的Dobson O3资料和卫星SAGE Ⅱ的NO2廓线资料.反演的O3总量与Dobson O3总量相比偏差小于10%;NO2总量与SAGE Ⅱ的偏差约20%.     

Observation of the Stratospheric NO2 Latitudinal Distribution in the Northern Winter Hemisphere

During a series of flights in the winters 1991/92 to 1994/95 total stratospheric NO2 was measured by means of the DOAS (Differential Optical Absorption Spectroscopy) technique on board a C160 (Transall) aircraft. In an area covering 60°W to 60°E, and 16°N to 86°N, the total stratospheric NO2 was observed to vary markedly with latitude and season (winter and spring). In the mid-winter Arctic vortex extremely low total stratospheric NO2 (< 3.1014/cm2) was always found, generally larger amounts of NO2 occurred outside the vortex in winter and towards the spring both inside and outside the vortex. This behaviour of stratospheric NO2 can be explained by the denoxification of the wintertime polar stratosphere. Ambient to the vortex in mid-winter however, sudden increases of total stratospheric NO2 by about a factor of 3 were observed. These sudden increases in stratospheric NO2 coincide with a change in the wavenumber 2 of the geopotential height at 60°N, which indicates that most likely the events are caused by planetary waves efficiently transporting air masses rich in NOx from lower to higher latitudes. The monitoring of stratospheric NO2, during latitudinal traverses ranging from the Arctic (80°N) to the Subtropics (18°N) in spring also unexpectedly showed a large variability in total stratospheric NO2 at mid-latitudes. Since photochemistry almost certainly can be excluded, it is proposed that the observed variability may be due to the planetary wave activity of the stratospheric surf zone, known to dynamically connect the tropical and the polar stratosphere.     

An open path,fast response infrared absorption gas analyzer for H2O and CO2

An open path infrared absorption based instrument for fast response measurements of H₂O and CO₂ fluctuations is described. This instrument performed reliably in several field experiments in both terrestrial and marine environments, on both fixed (tower) and mobile (boat, plane) flux platforms. Noise levels for H₂O and CO₂ concentrations were less than 10 mg/m³ and 300 g/m³, respectively for frequencies between 0.005 and 10 Hz. Drifts in instrument output, associated with changes in instrument temperature, are compensated for electronically.     

In situ Measurement of H2O and CH4 with Telecommunication Laser Diodes in the Lower Stratosphere: Dehydration and Indication of a Tropical Air Intrusion at Mid-Latitudes

Telecommunication laser diodes emitting near 1.39 m and 1.65 m in combination with direct-differential absorption spectroscopy are efficient tools to monitor in situ stratospheric H₂O andCH₄ with a good precision error (a few percents), a high temporal resolution (ranging from 10 ms to 1 s), a large dynamic range in the concentration measurements (four orders of magnitude) and a high selectivity in the analyte species. To illustrate the capability of laser probing technique, we report balloonborne H₂Oand CH₄ simultaneous measurements obtained on October 2001 atmidlatitudes (43° N). The H₂O vertical profile achieved with the lasersensor in the lower stratosphere is compared with the H₂O data yielded by a balloonborne frost-point hygrometer. The total hydrogen mixing ratio in the lower stratosphere, 2[CH₄] + [H₂O], appears to beconstant at 7.5 ± 0.1 ppmv. Nevertheless, an unexpected largedehydration of 0.5 ppmv was detected by both the laser sensor and thehygrometer between 16 km and 23 km. We suspect the occurrence of a tropicalair intrusion into mid-latitudes. We support this interpretation using a high-resolution advection model for potential vorticity.     

DOAS Zenith Sky Observations: 1. BrO Measurements over Bremen (53°N) 1993–1994

Observations of stratospheric BrO over Bremen (53°N) are reported for winter and early spring periods of 1993 and 1993/94. The BrO was observed by ground-based near-UV absorption spectroscopy of sunlight scattered in the zenith. Differential slant column densities for solar zenith angles 90°/80° in the range of9× 10¹³ (detection limit) to 4.5×10¹⁴ molecules/cm² having a high day-to-day variability were found. For the majority of the measurements no significant difference was observed between the morning and evening behaviour of BrO. Exceptions are the morning measurements from the winter of 1992/93 where an accelerated production of BrO was observed. We believe the latter best to be explained by the early morning rapid photolysis of elevated amounts of photo-labile Br-reservoirs formed during the night. The largest differential slant column densities of BrO were measured in December 1993 when the temperatures at 30 hPa dropped below 205 K. This might be an indication of heterogeneous conversion of bromine compounds on sulfate and other aerosols.     

Modelling radiation quantities and photolysis frequencies in the troposphere

STAR (System for Transfer of Atmospheric Radiation) was developed to calculate accurately and efficiently the irradiance, the actinic flux, and the radiance in the troposphere. Additionally a very efficient calculation scheme to computer photolysis frequencies for 21 different gases was evolved. STAR includes representative data bases for atmospheric constituents, especially aerosol particles. With this model package a sensitivity study of the influence of different parameter on photolysis frequencies in particular of O₃ to Singlet D oxygen atoms, of NO₂, and of HCHO was performed. The results show the quantitative effects of the influence of the solar zenith angle, the ozone concentration and vertical profile, the aerosol particles, the surface albedo, the temperature, the pressure, the concentration of NO₂, and different types of clouds on the photolysis frequencies.Notation I _A(, ) actinic flux - I _H(, ) irradiance - L(, , , ) radiance - wavelength - azimuth angle - cosine of zenith angle - _s cosine of solar zenith angle - optical depth - _s scattering coefficient - _c extinction coefficient - _o single scattering albedo - p _mix mixed phase function - g _mix mixed asymmetry factor - J _gas photolysis frequency     

ROx Budgets and O3 Formation during Summertime at Xianghe Suburban Site in the North China Plain

Photochemical smog characterized by high concentrations of ozone (O3) is a serious air pollution issue in the North China Plain (NCP) region, especially in summer and autumn. For this study, measurements of O3, nitrogen oxides (NOx), volatile organic compounds (VOCs), carbon monoxide (CO), nitrous acid (HONO), and a number of key physical parameters were taken at a suburban site, Xianghe, in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O3 formation and find an optimal way to control O3 pollution. Here, the radical chemistry and O3 photochemical budget based on measurement data from 1-23 July using a chemical box model is investigated. The daytime (0600-1800 LST) average production rate of the primary radicals referred to as ROx (OH + HO2+ RO2) is 3.9 ppbv h-1. HONO photolysis is the largest primary ROx source (41％). Reaction of NO2 + OH is the largest contributor to radical termination (41％), followed by reactions of RO2 + NO2 (26％). The average diurnal maximum O3 production and loss rates are 32.9 ppbv h-1 and 4.3 ppbv h-1, respectively. Sensitivity tests without the HONO constraint lead to decreases in daytime average primary ROx production by 55％ and O3 photochemical production by 42％, highlighting the importance of accurate HONO measurements when quantifying the ROx budget and O3 photochemical production. Considering heterogeneous reactions of trace gases and radicals on aerosols, aerosol uptake of HO2 contributes 11％ to ROx sink, and the daytime average O3 photochemical production decreases by 14％. The O3-NOx-VOCs sensitivity shows that the O3 production at Xianghe during the investigation period is mainly controlled by VOCs.