Long-path Differential Optical Absorption Spectroscopy Research Articles

Nocturnal downward transport of NO3 radical from the residual layer to a surface site by the mountain breeze in Seoul, South Korea

Using the long-path differential optical absorption spectroscopy (LP-DOAS) technique, the nocturnal mixing ratios of NO3 radicals were measured at an urban site in Seoul, South Korea, from May 13 to June 12, 2022. The primary objectives of the study were to estimate the NO3 radical concentration in the nighttime boundary layer and to examine the variations in their generation and loss over time, including an evaluation of their sources and sinks. The observed mean NO3 mixing ratios and lifetimes were 16 pptv and 73 s, respectively. NO3 concentrations and lifetimes were closely associated with their production, involving O3 and NO2, as well as the loss processes regulated by NO, VOCs, and aerosol surface area. Applying the steady-state assumption for NO3 and N2O5, the mean N2O5 uptake coefficient on the aerosol surface for the entire period was 0.031. When foggy nights were excluded from the analysis, the uptake coefficient decreased to 0.025. These values are within the higher range of the results reported in other studies. High relative humidity, which averaged 75% at night throughout the collection period, favored high N2O5 uptake coefficients. NO3 concentrations generally peaked shortly after sunset and gradually declined until sunrise. However, we frequently observed distinct increases in NO3 throughout the early morning hours, especially during clear nights, when local circulation with the westerly mountain breeze prevailed at the research site. The mountain breeze transported residual air downward, resulting in 110% and 38% higher NO3 and O3 levels at the sampling locations, respectively, compared to normal conditions. This additional source of nocturnal radicals and O3 has consequences for increased secondary aerosols and O3 production, particularly at urban surface levels where they are readily depleted in the early morning hours. To this end, a more thorough examination is required to measure N2O5 and a larger spectrum of VOCs species, as these parameters are crucial for nighttime radical budgets, secondary aerosols, and O3 generation in cities like Seoul.

Investigation of formaldehyde sources and its relative emission intensity in shipping channel environment

Formaldehyde (HCHO) is considered one of the most abundant gas-phase carbonyl compounds in the atmosphere, which can be directly emitted through transportation sources. Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) was used to observe HCHO in the river channel of Wusong Wharf in Shanghai, China for the whole year of 2019. Due to the impact of ship activity, the annual average HCHO level in the channel is about 2.5 times higher than that in the nearby campus environment. To explain the sources of HCHO under different meteorological conditions, the tracer-pair of CO and Ox (NO2+O3) was used on the clustered air masses. The results of the source appointment show that primary, secondary and background account for 24.14% (3.34 ± 1.19 ppbv), 44.78% (6.20 ± 2.04 ppbv) and 31.09% (4.31 ± 2.33 ppbv) of the HCHO in the channel when the air masses were from the mixed direction of the city and channel, respectively. By performing background station subtraction at times of high primary HCHO values and resolving the plume peaks, directly emitted HCHO/NO2 in the channel environment and plume were determined to be mainly distributed between 0.2 and 0.3. General cargo ships with higher sailing speeds or main engine powers tend to have higher HCHO/NO2 levels. With the knowledge of NO2 (or NOx) emission levels from ships, this study may provide data support for the establishment of HCHO emission factors.

Detection of Aircraft Emissions Using Long-Path Differential Optical Absorption Spectroscopy at Hefei Xinqiao International Airport

Airport emissions have received increased attention because of their impact on atmospheric chemical processes, the microphysical properties of aerosols, and human health. At present, the assessment methods for airport pollution emission mainly involve the use of the aircraft emission database established by the International Civil Aviation Organization, but the emission behavior of an engine installed on an aircraft may differ from that of an engine operated in a testbed. In this study, we describe the development of a long-path differential optical absorption spectroscopy (LP-DOAS) instrument for measuring aircraft emissions at an airport. From 15 October to 23 October 2019, a measurement campaign using the LP-DOAS instrument was conducted at Hefei Xinqiao International Airport to investigate the regional concentrations of various trace gases in the airport’s northern area and the variation characteristics of the gas concentrations during an aircraft’s taxiing and take-off phases. The measured light path of the LP-DOAS passed through the aircraft taxiway and the take-off runway concurrently. The aircraft’s take-off produced the maximum peak in NO2 average concentrations of approximately 25 ppbV and SO2 average concentrations of approximately 8 ppbV in measured area. Owing to the airport’s open space, the pollution concentrations decreased rapidly, the overall levels of NO2 and SO2 concentrations in the airport area were very low, and the maximum hourly average NO2 and SO2 concentrations during the observation period were better than the Class 1 ambient air quality standards in China. Additionally, we discovered that the NO2 and SO2 emissions from the Boeing 737–800 aircraft monitored in this experiment were weakly and positively related to the age of the aircraft. This measurement established the security, feasibility, fast and non-contact of the developed LP-DOAS instrument for monitoring airport regional concentrations as well as NO2 and SO2 aircraft emissions during routine airport operations without interfering with the normal operation of the airport.

Clustering Analysis on Drivers of O3 Diurnal Pattern and Interactions with Nighttime NO3 and HONO

The long-path differential optical absorption spectroscopy (LP-DOAS) technique was deployed in Shanghai to continuously monitor ozone (O3), formaldehyde (HCHO), nitrogen dioxide (NO2), nitrous acid (HONO), and nitrate radical (NO3) mixing ratios from September 2019 to August 2020. Through a clustering method, four typical clusters of the O3 diurnal pattern were identified: high during both the daytime and nighttime (cluster 1), high during the nighttime but low during the daytime (cluster 2), low during both the daytime and nighttime (cluster 3), and low during the nighttime but high during the daytime (cluster 4). The drivers of O3 variation for the four clusters were investigated for the day- and nighttime. Ambient NO caused the O3 gap after midnight between clusters 1 and 2 and clusters 3 and 4. During the daytime, vigorous O3 generation (clusters 1 and 4) was found to accompany higher temperature, lower humidity, lower wind speed, and higher radiation. Moreover, O3 concentration correlated with HCHO for all clusters except for the low O3 cluster 3, while O3 correlated with HCHO/NOx, but anti-correlated with NOx for all clusters. The lower boundary layer height before midnight hindered O3 diffusion and accordingly determined the final O3 accumulation over the daily cycle for clusters 1 and 4. The interactions between the O3 diel profile and other atmospheric reactive components established that higher HONO before sunrise significantly promoted daytime O3 generation, while higher daytime O3 led to a higher nighttime NO3 level. This paper summarizes the interplays between day- and nighttime oxidants and oxidation products, particularly the cause and effect for daytime O3 generation from the perspective of nighttime atmospheric components.

Observation of ambient NO3 radicals by LP-DOAS at a rural site in North China Plain

NO3 radicals can clean the atmospheric primary contaminants during the night. However, it can also effect the formation of secondary organic aerosol (SOA) and nitrate, which may worsen air quality. We report field observations of NO3 radicals with a home-made long path differential optical absorption spectroscopy (LP-DOAS) at a rural site in the polluted North China Plain in the summer of 2014. The detection limit (1σ) of NO3 with 3.4 km optical path was 3.4 ppt. The observed mean NO3 mixing ratios were 21 ppt with the maximum value of 104 ppt. The average calculated production rates and steady state lifetime of NO3 were 952 ppt/h and 103 s, respectively. The increase of both PM2.5 (>60 μg/m3) and RH (>60%) would result in an increase of the loss of NO3. The proportion of indirect losses rise with the increase of RH (>50%). The fitting kNO3 ranged from 0.0018 to 0.012 s−1 while γN2O5 was 0.0012 to 0.072. The ratios of direct loss ranged from 20.95% to 90.36% with an average of 56.81% during the campaign.

Estimation of ship emission rates at a major shipping lane by long-path DOAS measurements

Abstract. Ships are an important source of SO2 and NOx, which are key parameters of air quality. Monitoring of ship emissions is usually carried out using in situ instruments on land, which depend on favourable wind conditions to transport the emitted substances to the measurement site. Remote sensing techniques such as long-path differential optical absorption spectroscopy (LP-DOAS) measurements can supplement those measurements, especially in unfavourable meteorological conditions. In this study 1 year of LP-DOAS measurements made across the river Elbe close to Hamburg (Germany) have been evaluated. Peaks (i.e. elevated concentrations) in the NO2 and SO2 time series were assigned to passing ships, and a method to derive emission rates of SO2, NO2 and NOx from those measurements using a Gaussian plume model is presented. A total of 7402 individual ship passages have been monitored, and their respective NOx, SO2 and NO2 emission rates have been derived. The emission rates, coupled with the knowledge of the ship type, ship size and ship speed, have been analysed. Emission rates are compared to emission factors from previous studies and show good agreement. In contrast to emission factors (in grams per kilogram fuel), the derived emission rates (in grams per second) do not need further knowledge about the fuel consumption of the ship. To our knowledge this is the first time emission rates of air pollutants from individual ships have been derived from LP-DOAS measurements.

Spatial and temporal representativeness of point measurements for nitrogen dioxide pollution levels in cities

Abstract. In many cities around the world the overall air quality is improving, but at the same time nitrogen dioxide (NO2) trends show stagnating values and in many cases could not be reduced below air quality standards recommended by the World Health Organization (WHO). Many large cities have built monitoring stations to continuously measure different air pollutants. While most stations follow defined rules in terms of measurement height and distance to traffic emissions, the question remains of how representative are those point measurements for the city-wide air quality. The question of the spatial coverage of a point measurement is important because it defines the area of influence and coverage of monitoring networks, determines how to assimilate monitoring data into model simulations or compare to satellite data with a coarser resolution, and is essential to assess the impact of the acquired data on public health. In order to answer this question, we combined different measurement data sets consisting of path-averaging remote sensing data and in situ point measurements in stationary and mobile setups from a measurement campaign that took place in Munich, Germany, in June and July 2016. We developed an algorithm to strip temporal from spatial patterns in order to construct a consistent NO2 pollution map for Munich. Continuous long-path differential optical absorption spectroscopy (LP DOAS) measurements were complemented with mobile cavity-enhanced (CE) DOAS, chemiluminescence (CL) and cavity attenuated phase shift (CAPS) instruments and were compared to monitoring stations and satellite data. In order to generate a consistent composite map, the LP DOAS diurnal cycle has been used to normalize for the time of the day dependency of the source patterns, so that spatial and temporal patterns can be analyzed separately. The resulting concentration map visualizes pollution hot spots at traffic junctions and tunnel exits in Munich, providing insights into the strong spatial variations. On the other hand, this database is beneficial to the urban planning and the design of control measures of environment pollution. Directly comparing on-street mobile measurements in the vicinity of monitoring stations resulted in a difference of 48 %. For the extrapolation of the monitoring station data to street level, we determined the influence of the measuring height and distance to the street. We found that a measuring height of 4 m, at which the Munich monitoring stations measure, results in 16 % lower average concentrations than a measuring height of 1.5 m, which is the height of the inlet of our mobile measurements and a typical pedestrian breathing height. The horizontal distance of most stations to the center of the street of about 6 m also results in an average reduction of 13 % compared to street level concentration. A difference of 21 % in the NO2 concentrations remained, which could be an indication that city-wide measurements are needed for capturing the full range and variability of concentrations for assessing pollutant exposure and air quality in cities.

Detection of O<sub>4</sub> absorption around 328 and 419 nm in measured atmospheric absorption spectra

Abstract. Retrieving the column of an absorbing trace gas from spectral data requires that all absorbers in the corresponding wavelength range are sufficiently well known. This is especially important for the retrieval of weak absorbers, whose absorptions are often in the 10−4 range. Previous publications on the absorptions of the oxygen dimer O2–O2 (or short: O4) list absorption peaks at 328 and 419 nm, for which no spectrally resolved literature cross sections are available. As these absorptions potentially influence the spectral retrieval of various trace gases, such as HCHO, BrO, OClO and IO, their shape and magnitude need to be quantified. We assume that the shape of the absorption peaks at 328 and 419 nm can be approximated by their respective neighbouring absorption peaks. Using this approach we obtain estimates for the wavelength of the absorption and its magnitude. Using long-path differential optical absorption spectroscopy (LP-DOAS) observations and multi-axis DOAS (MAX-DOAS) observations, we estimate the peak absorption cross sections of O4 to be (1.96 ± 0.20) × 10−47 cm5 molec−2 and determine the wavelength of its maximum at 328.59 ± 0.15 nm. For the absorption at 419.13 ± 0.42 nm a peak O4 cross-section value is determined to be (5.0 ± 3.5) × 10−48 cm5 molec−2.

Observations of atmospheric trace gases in China using a compact LED long path DOAS system

In this paper, we present the development and evaluation of a new designed light emitting diodes (LEDs) based optical fiber coupling long-path differential optical absorption spectroscopy (LP-DOAS) instrument for atmospheric SO2, O3 and NO2 detections. The strongest absorption structures of these trace gases scattered along a wide spectral range which could not be covered by a single LED. Therefore, a new fiber optic coupling telescope was developed to combine multiple LEDs with different spectral emission ranges as broad band light source for atmospheric trace gas detections. Details of the experimental setup, measurement and retrieval procedure, error analysis and the atmospheric measurement results are presented. The new LED LP-DOAS measurement results show perfect agreements with a co-located Xenon Lamp coaxial LP-DOAS observations with Pearson correlation coefficient (R) larger than 0.9 for SO2, O3 and NO2 observations. The estimated background light contributes about 3–10% of the total measurement error during daytime, which is improved by a factor of 3–10 compared to previous study. Diurnal analysis of the measurement results shows a similar diurnal pattern of NO2 and SO2 which implies that they are probably originated from similar emission sources. Satellite observation and backward trajectories analysis indicated local and regional transports of pollutants have significant impacts on the air quality in Hefei. Analysis of the wind speed and wind direction show that elevated NO2 and SO2 levels were related to the emissions of the power plant and factories located at the east and northeast of the measurement site.

Study on the daytime OH radical and implication for its relationship with fine particles over megacity of Shanghai, China

To investigate on the daytime OH and its implication to fine particle, the long-path differential optical absorption spectroscopy (LP-DOAS) system was employed to observe the main OH precursors of O3, HCHO and HONO, as well as NO2 and NO3 radical from April to August 2013 over Shanghai, China. The main OH production paths from HONO, HCHO and O3 were estimated to be occupied around 57.6%, 30.5% and 11.9% during daytime. The daytime OH radical concentration under steady-state was averaged at 1.02 × 107 molec cm−3, which was significantly impacted by the photolytic processes. The relationship between photolysis frequency j(O1D) and OH radical suggests that heavy fine particle loads can make the photolytic reactions less efficiently and decrease the OH production and concentration. Utilizing CO as the indicator, the part of PM2.5 mass related to primary emitted sources was found less impacted by the OH levels. The contribution of secondary organic aerosol with metrics of O3 was enhanced with the increases of the OH levels, while secondary inorganic part of PM2.5 was favor of the condition that smaller OH concentrations that 5 × 105–5 × 106 molec cm−3. Meantime, a simplified multivariate model was employed to evaluate the influences of OH levels on different parts of fine particles related to different emission and sources. Normalized by solar radiation, this part of OH unrelated to radiation was found to be inversely related to the PM2.5, which indicates the self-cleansing capability of the atmosphere.

A novel dual-LED based long-path DOAS instrument for the measurement of aromatic hydrocarbons

Aromatic hydrocarbons are well known air toxics which are regulated by the US EPA and other air quality agencies. Accurate, long-term monitoring of these compounds at low part-per-billion levels, as well as identifying emission point sources is therefore crucial to protect human health in neighborhoods near large emission sources. Here we present a new long-path differential optical absorption spectroscopy (LP-DOAS) instrument specifically designed to monitor aromatic hydrocarbons. The system is based on a novel dual - light emitting diode (LED) light source, which eliminates the requirement to suppress spectrometer stray light. This light source, together with a high stability fiber-based sending/receiving telescope, allows the measurement of aromatic hydrocarbons on once-folded absorptions paths of 200–1200 m length. The new instrument shows very good agreement with simultaneous in-situ measurements if inhomogeneities of the trace gas spatial distributions are considered. The new instrument performed well during a three-month field test as an automated fence-line monitor at a refinery, successfully distinguishing upwind background levels of ∼1 ppb from emissions reflected in elevated mixing ratios of 3–4 ppb. A two-dimensional measurement network based on two identical LP-DOAS instruments operating on seven crossed light paths was operated successfully in Houston, TX. Qualitative and quantitative analysis of two events with toluene and xylene plumes demonstrate how this setup can be used to derive the spatial distribution of aromatic hydrocarbons, and identify point sources.

Development of a portable active long-path differential optical absorption spectroscopy system for volcanic gas measurements

Abstract. Active long-path differential optical absorption spectroscopy (LP-DOAS) has been an effective tool for measuring atmospheric trace gases for several decades. However, instruments were large, heavy and power-inefficient, making their application to remote environments extremely challenging. Recent developments in fibre-coupling telescope technology and the availability of ultraviolet light emitting diodes (UV-LEDS) have now allowed us to design and construct a lightweight, portable, low-power LP-DOAS instrument for use at remote locations and specifically for measuring degassing from active volcanic systems. The LP-DOAS was used to measure sulfur dioxide (SO2) emissions from La Fossa crater, Vulcano, Italy, where column densities of up to 1.2 × 1018 molec cm−2 (~ 500 ppmm) were detected along open paths of up to 400 m in total length. The instrument's SO2 detection limit was determined to be 2 × 1016 molec cm−2 (~ 8 ppmm), thereby making quantitative detection of even trace amounts of SO2 possible. The instrument is capable of measuring other volcanic volatile species as well. Though the spectral evaluation of the recorded data showed that chlorine monoxide (ClO) and carbon disulfide (CS2) were both below the instrument's detection limits during the experiment, the upper limits for the X / SO2 ratio (X = ClO, CS2) could be derived, and yielded 2 × 10−3 and 0.1, respectively. The robust design and versatility of the instrument make it a promising tool for monitoring of volcanic degassing and understanding processes in a range of volcanic systems.

Intercomparison of NO<sub>3</sub> radical detection instruments in the atmosphere simulation chamber SAPHIR

Abstract. The detection of atmospheric NO3 radicals is still challenging owing to its low mixing ratios (≈ 1 to 300 pptv) in the troposphere. While long-path differential optical absorption spectroscopy (DOAS) has been a well-established NO3 detection approach for over 25 yr, newly sensitive techniques have been developed in the past decade. This publication outlines the results of the first comprehensive intercomparison of seven instruments developed for the spectroscopic detection of tropospheric NO3. Four instruments were based on cavity ring-down spectroscopy (CRDS), two utilised open-path cavity-enhanced absorption spectroscopy (CEAS), and one applied "classical" long-path DOAS. The intercomparison campaign "NO3Comp" was held at the atmosphere simulation chamber SAPHIR in Jülich (Germany) in June 2007. Twelve experiments were performed in the well-mixed chamber for variable concentrations of NO3, N2O5, NO2, hydrocarbons, and water vapour, in the absence and in the presence of inorganic or organic aerosol. The overall precision of the cavity instruments varied between 0.5 and 5 pptv for integration times of 1 s to 5 min; that of the DOAS instrument was 9 pptv for an acquisition time of 1 min. The NO3 data of all instruments correlated excellently with the NOAA-CRDS instrument, which was selected as the common reference because of its superb sensitivity, high time resolution, and most comprehensive data coverage. The median of the coefficient of determination (r2) over all experiments of the campaign (60 correlations) is r2 = 0.981 (quartile 1 (Q1): 0.949; quartile 3 (Q3): 0.994; min/max: 0.540/0.999). The linear regression analysis of the campaign data set yielded very small intercepts (median: 1.1 pptv; Q1/Q3: −1.1/2.6 pptv; min/max: −14.1/28.0 pptv), and the slopes of the regression lines were close to unity (median: 1.01; Q1/Q3: 0.92/1.10; min/max: 0.72/1.36). The deviation of individual regression slopes from unity was always within the combined accuracies of each instrument pair. The very good correspondence between the NO3 measurements by all instruments for aerosol-free experiments indicates that the losses of NO3 in the inlet of the instruments were determined reliably by the participants for the corresponding conditions. In the presence of inorganic or organic aerosol, however, differences in the measured NO3 mixing ratios were detectable among the instruments. In individual experiments the discrepancies increased with time, pointing to additional NO3 radical losses by aerosol deposited onto the filters or on the inlet walls of the instruments. Instruments using DOAS analyses showed no significant effect of aerosol on the detection of NO3. No hint of a cross interference of NO2 was found. The effect of non-Lambert–Beer behaviour of water vapour absorption lines on the accuracy of the NO3 detection by broadband techniques was small and well controlled. The NO3Comp campaign demonstrated the high quality, reliability and robustness of performance of current state-of-the-art instrumentation for NO3 detection.

Iodine chemistry in the eastern Pacific marine boundary layer

Observations of gas‐phase iodine species were made during a field campaign in the eastern Pacific marine boundary layer (MBL). The Climate and Halogen Reactivity Tropical Experiment (CHARLEX) in the Galápagos Islands, running from September 2010 to present, is the first long‐term ground‐based study of trace gases in this region. Observations of gas‐phase iodine species were made using long‐path differential optical absorption spectroscopy (LP‐DOAS), multi‐axis DOAS (MAX‐DOAS), and resonance and off‐resonance fluorescence by lamp excitation (ROFLEX). These measurements were supported by ancillary measurements of ozone, nitrogen oxides, and meteorological variables. Selective halocarbon and ultrafine aerosol concentration measurements were also made. MAX‐DOAS observations of iodine monoxide (IO) display a weak seasonal variation. The maximum differential slant column density was 3.8 × 1013 molecule cm−2 (detection limit ~7 × 1012 molecule cm−2). The seasonal variation of reactive iodine IOx (= I + IO) is stronger, peaking at 1.6 pptv during the warm season (February–April). This suggests a dependence of the iodine sources on the annual cycle in sea surface temperature, although perturbations by changes in ocean surface iodide concentration and solar radiation are also possible. An observed negative correlation of IOx with chlorophyll‐a indicates a predominance of abiotic sources. The low IO mixing ratios measured (below the LP‐DOAS detection limit of 0.9 pptv) are not consistent with satellite observations if IO is confined to the MBL. The IOx loading is consistent with the observed absence of strong ozone depletion and nucleation events, indicating a small impact of iodine chemistry on these climatically relevant factors in the eastern Pacific MBL.

紫外LED光纤耦合长程DOAS系统监测大气SO2和O3的研究

紫外LED光纤耦合长程DOAS系统监测大气SO2和O3的研究

Comparing different light-emitting diodes as light sources for long path differential optical absorption spectroscopy NO2 and SO2 measurements

In this paper, we present a comparison of different light-emitting diodes (LEDs) as the light source for long path differential optical absorption spectroscopy (LP-DOAS) atmospheric trace gas measurements. In our study, we use a fiberoptic design, where high power LEDs used as the light source are coupled into the telescope using a Y shape fiber bundle. Two blue and one ultraviolet (UV) LEDs with different emission wavelength ranges are tested for NO2 and SO2 measurements. The detailed description of the instrumental setup, the NO2 and SO2 retrieval procedure, the error analysis, and the preliminary results from the measurements carried out in Science Island, Hefei, Anhui, China are presented. Our first measurement results show that atmospheric NO2 and SO2 have strong temporal variations in that area and that the measurement accuracy is strongly dependent on the visibility conditions. The measured NO2 and SO2 data are compared to the Ozone Monitoring Instrument (OMI) satellite observations. The results show that the OMI NO2 product underestimates the ground level NO2 by 45%, while the OMI SO2 data are highly influenced by clouds and aerosols, which can lead to large biases in the ground level concentrations. During the experiment, the mixing ratios of the atmospheric NO2 and SO2 vary from 8 ppbv to 36 ppbv and from 3 ppbv to 18 ppbv, respectively.

NO<sub>2</sub> measurements in Hong Kong using LED based long path differential optical absorption spectroscopy

Abstract. In this study we present the first long term measurements of atmospheric nitrogen dioxide (NO2) using a LED based Long Path Differential Optical Absorption Spectroscopy (LP-DOAS) instrument. This instrument is measuring continuously in Hong Kong since December 2009, first in a setup with a 550 m absorption path and then with a 3820 m path at about 30 m to 50 m above street level. The instrument is using a high power blue light LED with peak intensity at 450 nm coupled into the telescope using a Y-fibre bundle. The LP-DOAS instrument measures NO2 levels in the Kowloon Tong and Mongkok district of Hong Kong and we compare the measurement results to mixing ratios reported by monitoring stations operated by the Hong Kong Environmental Protection Department in that area. Hourly averages of coinciding measurements are in reasonable agreement (R = 0.74). Furthermore, we used the long-term data set to validate the Ozone Monitoring Instrument (OMI) NO2 data product. Monthly averaged LP-DOAS and OMI measurements correlate well (R = 0.84) when comparing the data for the OMI overpass time. We analyzed weekly patterns in both data sets and found that the LP-DOAS detects a clear weekly cycle with a reduction on weekends during rush hour peaks, whereas OMI is not able to observe this weekly cycle due to its fix overpass time (13:30–14:30 LT – local time).

Monitoring of atmospheric nitrogen dioxide by long-path pulsed differential optical absorption spectroscopy using two different light paths

Measurements of the local distribution of atmospheric nitrogen dioxide (NO(2)) by long-path pulsed differential optical absorption spectroscopy (LP-PDOAS) in Tokyo during August 2008 are presented. Two LP-PDOAS systems simultaneously measured average NO(2) temporal mixing ratios along two different paths from a single observation point. Two flashing aviation obstruction lights, located 7.0 km north and 6.3 km east from the observation point, were used as light sources, allowing spatiotemporal variations of NO(2) in Tokyo to be inferred. The LP-PDOAS data were compared with ground-based data measured using chemiluminescence. Surface wind data indicated that large inhomogeneities were present in the spatial NO(2) distributions under southerly wind conditions, while northerly wind conditions displayed greater homogeneity between the two systems. The higher correlation in the NO(2) mixing ratio between the two LP-PDOAS systems was observed under northerly wind conditions with a correlation factor R(2) = 0.88. We demonstrated that the combined deployment of two LP-PDOAS systems oriented in different directions provides detailed information on the spatial distribution of NO(2).

Vertical profiles of nitrous acid in the nocturnal urban atmosphere of Houston, TX

Abstract. Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three nighttime periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NOx emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced by the model for 1–2 and 7–8 September in the nocturnal boundary layer (NBL). The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be due to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed an increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger NOx emission. Vertical transport was found to be the dominant source of HONO aloft.

Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics

We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.