Tropospheric Ultraviolet And Visible Research Articles

Analysis of Ozone Photochemistry over Southern Tropical Megacity, Bengaluru, India.

Rapid infrastructure development, increased population, shift in land use practices and higher vehicular emissions have all influenced Ozone (O3 ) production through its precursor gases in southern megacity, Bengaluru, India. We have investigated the photochemistry using hourly measurements of O3 and associated precursor gases conducted in Bengaluru during January to December 2019. The rate of formation of O3 is analyzed for Bengaluru for the first time using a photochemical model involving NOx cycle. On the diurnal scale, O3 showed a midday peak (1200-1500 IST), while its precursors showed a bimodal trend with peaks at 0900 IST and 2100 IST. The photolytic rate constants for and were derived from the tropospheric ultraviolet and visible (TUV) radiation model. Using the photolytic rate constants for and under the triad NO-NO2 -O3 , photostationary state (PSS), Leighton ratio (Ф) and its deviations from unity were estimated over Bengaluru. Positive anomalies (Φ > 1) were obtained, and the computed Φ was utilized to determine the total mixing ratios of the peroxy radical (PO2 ). The seasonal variation in revealed that in the presence of intense solar radiation and NOx, VOCs, CO and NMVOCs in the mixing layer, O3 forms photochemically over the surface.

Impact of Vertical Profiles of Aerosols on the Photolysis Rates in the Lower Troposphere from the Synergy of Photometer and Ceilometer Measurements in Raciborz, Poland, for the Period 2015–2020

The effect of the aerosol vertical distribution on photolysis frequencies of O3 and NO2 is studied. Aerosol measurements in Raciborz (50.08° N, 18.19° E), Poland, made using the CIMEL Sun photometer and collocated CHM-15k “Nimbus” ceilometer are analyzed for the period 2015–2020. Vertical profiles of the aerosol extinction are derived from the Generalized Retrieval of Atmosphere and Surface Properties (GRASP) algorithm combining the ceilometer measurements of the aerosol backscattering coefficient with the collocated CIMEL measurements of the columnar characteristics of aerosols. The photolysis frequencies are calculated at the three levels in the lower troposphere (the surface and 0.5 and 2 km above the surface) using a radiative transfer model, Tropospheric Ultraviolet and Visible (TUV), for various settings of aerosol optical properties in the model input. The importance of the aerosol vertical distribution on photolysis frequencies is inferred by analyzing statistics of the differences between the output of the model, including the extinction profile from the GRASP algorithm, and the default TUV model (based on columnar aerosol characteristics by the CIMEL Sun photometer and Elterman’s extinction profile). For model levels above the surface, standard deviation, 2.5th percentile, 97.5th percentile, and the extremes, calculated from relative differences between these input settings, are comparable with the pertaining statistical values for the input pair providing changes of photolysis frequencies only due to the variability of the columnar aerosol characteristics. This indicates that the vertical properties of aerosols affect the distribution of the photolysis frequencies in the lower troposphere on a similar scale to that due to variations in columnar aerosol characteristics.

Spectrally resolved actinic flux and photolysis frequencies of key species within an indoor environment

Ultraviolet and visible (UV-VIS) radiation is responsible for the photolysis of stable trace gases and production of highly reactive atoms and radicals in the lower boundary layer of the atmosphere. Photolysis frequencies of the key species in the atmosphere depend on the spectrally resolved actinic flux. However, to date direct measurements and modeling of the actinic flux and photolysis frequencies of species relevant for indoor atmospheres are scarce.In this study, we present systematic indoor measurements of actinic fluxes and photolysis frequencies of nitrous acid (HONO), nitrogen dioxide (NO2) and the nitrate radical (NO3) during summer and winter periods. The emerged experimental data of indoor actinic fluxes and the photolysis frequencies were compared to the ambient data obtained by the Tropospheric Ultraviolet and Visible (TUV) model. Finally, an architectural model was run by which integrated spectral irradiance (UV-VIS) values were compared to the measurements performed by the spectroradiometer. The comparison of the measurements with the architectural model yields an equation which can be used in the future to predict the integrated spectral actinic flux values in various indoor environments as a function of the architectural parameters such as orientation of the building, the size and the thickness of the glass windows.

Implementation of state-of-the-art ternary new-particle formation scheme to the regional chemical transport model PMCAMx-UF in Europe

Abstract. The particle formation scheme within PMCAMx-UF, a three-dimensional chemical transport model, was updated with particle formation rates for the ternary H2SO4–NH3–H2O pathway simulated by the Atmospheric Cluster Dynamics Code (ACDC) using quantum chemical input data. The model was applied over Europe for May 2008, during which the EUCAARI-LONGREX (European Aerosol Cloud Climate and Air Quality Interactions–Long-Range Experiment) campaign was carried out, providing aircraft vertical profiles of aerosol number concentrations. The updated model reproduces the observed number concentrations of particles larger than 4 nm within 1 order of magnitude throughout the atmospheric column. This agreement is encouraging considering the fact that no semi-empirical fitting was needed to obtain realistic particle formation rates. The cloud adjustment scheme for modifying the photolysis rate profiles within PMCAMx-UF was also updated with the TUV (Tropospheric Ultraviolet and Visible) radiative-transfer model. Results show that, although the effect of the new cloud adjustment scheme on total number concentrations is small, enhanced new-particle formation is predicted near cloudy regions. This is due to the enhanced radiation above and in the vicinity of the clouds, which in turn leads to higher production of sulfuric acid. The sensitivity of the results to including emissions from natural sources is also discussed.

Correction of UVS-AB-T UV Radiometers Using a Radiative Transfer Model

AbstractObservation of UV radiation is of major importance to human health and to the calculation of photochemical reaction rates. However, the sensitivity of UV radiometers decays because of equipment aging. A correction method is therefore proposed by using a decrement formula that is approximately a quadratic function of time and is obtained by fitting the clear-sky observation data from an aged UVS-AB-T UV radiometer with the data simulated by the Tropospheric Ultraviolet and Visible (TUV) radiative transfer model. The corrected data from the older radiometer are verified by the data from another newer radiometer on selected clear-sky days. The results show a high correlation and a low bias between the radiometers, and the mean of the corrected data from the older radiometer is 94.5% of that from the newer radiometer. After a long time of use, the decrement of the observation data would increase dramatically and errors of the data after correction would still be significant. In Dongguan, China, a recommendation is made that a UV radiometer should not be used for more than 5 years when the decrement rate reaches 50%.

Modelling VOC source impacts on high ozone episode days observed at a mountain summit in Hong Kong under the influence of mountain-valley breezes

A top-down approach to evaluate high ozone (O3) formation, attributed to different emission sources, is developed for anti-cyclonic conditions in a region of Hong Kong influenced by meso-scale circulations. A near-explicit photochemical model coupled with the Master Chemical Mechanism (MCMv3.2) is used to investigate the chemical characteristics in the region. Important features have been enhanced in this model including the photolysis rates, simulated by the National Center for Atmospheric Research (NCAR) Tropospheric Ultraviolet and Visible (TUV) Radiation Model, as well as hourly variation of Volatile Organic Compound (VOC) concentration input from on-site sampling. In general, the combined model gives a reasonably good representation of high O3 levels in the region. The model successfully captured a multi-day O3 event in the autumn of 2010. Source apportionment via Positive Matrix Factorization (PMF) was carried out on the sampled VOC data, to determine the major sources in the region. Based on the outcomes of the PMF source apportionment, a sensitivity analysis using the developed photochemical model was conducted and used to estimate O3 reduction under different source removal regimes. Results indicate that vehicular emissions are the dominant VOC source contributing to O3 formation. This study has demonstrated a potentially efficient secondary pollutants control methodology, using a combined field measurements and modelling approach.

Ambient formaldehyde and its contributing factor to ozone and OH radical in a rural area

Formaldehyde (HCHO), as well as correlative pollutants was measured from 1 to 31 July in 2007 at Mazhuang, a rural site located in the east of China. Gaseous HCHO was scrubbed from the air with an acidic 2,4-dinitrophenylhydrazine (DNPH) solution, which leaded to the reaction of HCHO with DNPH and produced a stable product, 2,4-dinitrophenylhydrazone, followed by online analysis by high-performance liquid chromatography (HPLC) coupled with Ultraviolet detector. During the observation period, mixing ratios of HCHO ranged from 0.2 ppbv to 6.2 ppbv, with an average of 1.5 ± 0.67 ppbv. HCHO shows an evident diurnal variation, the maximum appeared during 12:00–14:00. The average concentration diurnal variations of measured HCHO, ozone (O 3), Methylhydroperoxides (MHP, CH 3OOH), hydrogen peroxide (H 2O 2), nitrogen oxides (NO x) and meteorological parameters were compared. The similar variations of HCHO, O 3 and radiation imply that photo-oxidation of hydrocarbons might be the major source for HCHO. Based on the maximum incremental reactivity (MIR) coefficient of HCHO, the calculation shows that HCHO contributes about 20% to total observed O 3 during the study period. In order to compare the contributions of O 3, HCHO and HONO to OH radical, photolysis rate parameters ( J-values) of the three compounds were calculated by the Tropospheric Ultraviolet and Visible (TUV) Radiation Model (4.4 version). Based on the comparison, this study reaches the conclusion that O 3 is the dominant source of OH radical at Mazhuang. This study also uses P(HCHO)/P(O 3) which represents the ratio of contrbutions of HCHO and O 3 to OH radical, to discuss the action of HCHO in OH radical soucers. The result shows that P(HCHO)/P(O 3) is 12.5% on average, with the maximum of 21.0% at 13:00 P.M. and minimum of 7.5% before 9:00 A.M. and after 17:00 P.M..Therefore HCHO is also an important source of OH radical and cannot be ignored.

Using the optical properties of aerosols from the AERONET database to calculate surface solar UV-B irradiance in Córdoba, Argentina: Comparison with measurements

The main purpose of this study was to perform an evaluation of the particles’ optical parameters’ influence on surface solar UV-B (280–315 nm) irradiance in Córdoba, Argentina. To achieve this objective UV-B irradiance dataset, AERONET (AErosol RObotic NETwork) database, and TUV (Tropospheric Ultraviolet and Visible) model were used to analyze the effects of aerosols on surface irradiance on cloudless days during specific days of winter and spring of the period 1999–2006. Together with a direct observer, total irradiance (300–3000 nm) measurements were used as an ancillary tool to verify the cloudless condition. Every year, during this period, important reductions in surface irradiance are observed due to the aerosol load. Aerosols were incorporated in the model through the aerosol optical depth at 340 nm, the asymmetry parameter at 440 nm, and the single scattering albedo at 440 nm, all of them provided by AERONET Córdoba-CETT site. These factors vary from near to zero up to 1.4, from 0.56 up to 0.83 and from 0.43 up to 0.99, respectively. The behaviors of these factors along the year are analyzed considering the meteorology of Córdoba. When AERONET data are included in the TUV model they allow an accurate simulation of the UV-B irradiance, making the agreement with the experimental measurements substantially better. Only a small differences (±2%) remains, which can be attributed to diverse factors. As the AERONET site is 20 km away from the irradiance measurement site, these results show the regional character of the aerosols in Córdoba, although small contributions of urban aerosols are not discarded. An episode of high aerosol and pollutants laden due to fires in the surrounding hills is briefly analyzed. A set of additional studies are needed to describe comprehensively the characteristics and behavior of the Córdoba aerosols. Some of them are being already carried out.

Comparison of UV-RSS spectral measurements and TUV model runs for clear skies for the May 2003 ARM aerosol intensive observation period

Abstract. The first successful deployment of the fully-operational ultraviolet rotating shadow-band spectroradiometer occurred during the May 2003 US Department of Energy's Atmospheric Radiation Measurement program's Aerosol Intensive Observation Period. The aerosol properties in the visible range were characterized using redundant measurements with several instruments to determine the column aerosol optical depth, the single scattering albedo, and the asymmetry parameter needed as input for radiative transfer calculations of the downwelling direct normal and diffuse horizontal solar irradiance in clear-sky conditions. The Tropospheric Ultraviolet and Visible (TUV) radiative transfer model developed by Madronich and his colleagues at the US National Center for Atmospheric Research was used for the calculations of the spectral irradiance between 300–360 nm. Since there are few ultraviolet measurements of aerosol properties, most of the input aerosol data for the radiative transfer model are based on the assumption that UV input parameters can be extrapolated from the visible portion of the spectrum. Disagreements among available extraterrestrial spectra, which are discussed briefly, suggested that instead of comparing irradiances, measured and modeled spectral transmittances between 300–360 nm should be compared for the seven cases studied. Transmittance was calculated by taking the ratios of the measured irradiances to the Langley-derived, top-of-the-atmosphere irradiances. The cases studied included low to moderate aerosol loads and low to high solar-zenith angles. A procedure for retrieving single scattering albedo in the ultraviolet based on the comparisons of direct and diffuse transmittance is outlined.