Mixing Ratio Measurements Research Articles

Volcanic CO2 flux measurement at Campi Flegrei by tunable diode laser absorption spectroscopy

Near-infrared room temperature tunable diode lasers (TDL) have recently found increased usage in atmospheric chemistry and air monitoring research, but applications in volcanology are still limited to a few examples. Here, we explored the potential of a commercial infrared laser unit (GasFinder 2.0 from Boreal Laser Ltd) for measurement of volcanic CO2 mixing ratios, and ultimately for estimating the volcanic CO2 flux. Our field tests were conducted at Campi Flegrei near Pozzuoli, Southern Italy, where the GasFinder was used during three campaigns in October 2012, January 2013 and May 2013 to repeatedly measure the path-integrated mixing ratios of CO2 along cross sections of the atmospheric plumes of two major fumarolic fields (Solfatara and Pisciarelli). By using a tomographic post-processing routine, we resolved, for each of the two fields, the contour maps of CO2 mixing ratios in the atmosphere, from the integration of which (and after multiplication by the plumes’ transport speeds) the CO2 fluxes were finally obtained. We evaluate a total CO2 output from the Campi Flegrei fumaroles of ∼490 Mg/day, in line with independent estimates based on in situ (Multi-GAS) observations. We conclude that TDL technique may enable CO2 flux quantification at other volcanoes worldwide.

Measurement of Ambient Ammonia over the National Capital Region of Delhi, India

Mixing ratio of ambient ammonia (NH3) was measured at various locations of the National Capital Region (NCR) of Delhi, India using a NH3-analyzer during January 2010 to June 2012 in campaign mode. The present study has been carried out on campaign based measurement of mixing ratios of NH3 and NOx for short period of time over the NCR of Delhi represent the indicative values over the region. The average mixing ratio of ambient NH3 was 20.9 ± 1.6 ppb during the period. The maximum average mixing ratio of ambient NH3 (28.8 ± 3.0 ppb) was recorded in an industrial area surrounded by intensive vehicular traffic followed by an agricultural farm (27.5 ± 2.1 ppb), whereas the minimum (6.4 ± 1.2 ppb) was recorded in the semi-urban area. The diurnal trend of NH3 depended on the ambient temperature at most of the sites and was affected by wind direction. Ambient NH3 was correlated with the NOx mixing ratio suggesting that the vehicular emission may be one of the sources of ambient NH3 in the NCR of Delhi. However, long-term measurements of ambient NH3 and their precursors will lead to seasonal variation of source apportionment over the NCR, Delhi, India.

Constraining surface carbon fluxes using in situ measurements of carbonyl sulfide and carbon dioxide

AbstractUnderstanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO2 budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO2 but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO2 mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch‐bag gas‐exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow‐through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO2 across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO2 fluxes and (2) a temperature‐dependent normalized uptake ratio of COS to CO2 from soils. Significant nighttime uptake of COS was observed in broad‐leafed species and revealed active stomatal opening prior to sunrise. Continuous high‐resolution joint measurements of COS and CO2 concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.

Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere

Abstract. During the field campaign ZEPTER-2 in autumn 2008 whole air samples were collected on board a Zeppelin NT airship in the planetary boundary layer (PBL) and the lower free troposphere (LFT) over south-west Germany using the ZEppelin Based Isotope Sampler (ZEBIS). These samples were analysed with respect to volatile organic compound (VOC) mixing ratios and stable carbon isotope ratios using a gas chromatograph combustion isotope ratio mass spectrometer (GC-C-IRMS). In this study we present results for toluene, one of the major anthropogenic pollutants, which emphasise the viability of isotope ratio measurements in VOC for atmospheric research, especially to study VOC sources or to track both dynamical and chemical processes. In situ measurements of CO mixing ratios on board the Zeppelin NT were used to allocate the air samples either to the PBL or the LFT. In the PBL we observed rather fresh emissions mixing into the background air. We estimated a toluene source isotope ratio of δ13C = −28.2 ± 0.5‰. Samples from the PBL and the LFT were clearly distinguishable by means of their mixing ratio and isotope ratio signatures. Using the concept of the effective kinetic isotope effect, we were able to separate the effects of dilution processes and photochemical degradation in the free troposphere. We calculated the photochemical age of toluene in the atmosphere in two different ways using isotope ratios and mixing ratios. The results differ strongly in the PBL, probably due to mixing processes, but are compatible with each other in the LFT. Here, they correlate with a slope of 0.90±0.31.

Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I− reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

Characterizing moisture exchange between the Hawaiian convective boundary layer and free troposphere using stable isotopes in water

AbstractThe subtropical convective boundary layer (CBL) plays a critical role in climate by regulating the vertical exchange of moisture, energy, trace gases, and pollutants between the ocean surface and free troposphere. Yet bulk features of this exchange are poorly constrained in climate models. To improve our understanding of moisture transport between the boundary layer and free troposphere, paired measurements of water vapor mixing ratio and the stable isotope ratio 18O/16O are used to evaluate moist convective mixing and entrainment processes near the Big Island of Hawaii. Profile data from the island's east side are consistent with moist adiabatic processes below the trade wind temperature inversion. In contrast, profiles on the west side follow moist adiabatic lapse rates within discrete stable layers, suggesting moist convection sets the humidity structure of even the unsaturated regions around the island. Above the trade wind inversion, the transition from well‐mixed boundary layer to free troposphere is characterized by a simple mixing line analysis, so long as the thermodynamic properties of the air mass at CBL top are known. Deviations from the mixing line identify thermodynamic boundaries in the atmospheric profile, which can persist from one day to the next. These findings indicate residual layers form during strong mixing events and regulate vertical moisture transport for multiple days at a time. Basic assumptions that synoptic‐scale transport controls isotope ratios at CBL top are therefore not sufficient for describing moisture exchange between the boundary layer and free troposphere in the subtropics.

Quasi-16-day period oscillations observed in middle atmospheric ozone and temperature in Antarctica

Abstract. Nightly averaged mesospheric temperature derived from the hydroxyl nightglow at Rothera station (67°34' S, 68°08' W) and nightly midnight measurements of ozone mixing ratio obtained from Troll station (72°01' S, 2°32' E) in Antarctica have been used to investigate the presence and vertical profile of the quasi-16-day planetary wave in the stratosphere and mesosphere during the Antarctic winter of 2009. The variations caused by planetary waves on the ozone mixing ratio and temperature are discussed, and spectral and cross-correlation analyses are performed to extract the wave amplitudes and to examine the vertical structure of the wave from 34 to 80 km. The results show that while planetary-wave signatures with periods 3–12 days are strong below the stratopause, the oscillations associated with the 16-day wave are the strongest and present in both the mesosphere and stratosphere. The period of the wave is found to increase below 42 km due to the Doppler shifting by the strong eastward zonal wind. The 16-day oscillation in the temperature is found to be correlated and phase coherent with the corresponding oscillation observed in O3 volume mixing ratio at all levels, and the wave is found to have vertical phase fronts consistent with a normal mode structure.

Bay breeze climatology at two sites along the Chesapeake bay from 1986-2010: Implications for surface ozone.

Hourly surface meteorological measurements were coupled with surface ozone (O3) mixing ratio measurements at Hampton, Virginia and Baltimore, Maryland, two sites along the Chesapeake Bay in the Mid-Atlantic United States, to examine the behavior of surface O3 during bay breeze events and quantify the impact of the bay breeze on local O3 pollution. Analyses were performed for the months of May through September for the years 1986 to 2010. The years were split into three groups to account for increasingly stringent environmental regulations that reduced regional emissions of nitrogen oxides (NOx): 1986–1994, 1995–2002, and 2003–2010. Each day in the 25-year record was marked either as a bay breeze day, a non-bay breeze day, or a rainy/cloudy day based on the meteorological data. Mean eight hour (8-h) averaged surface O3 values during bay breeze events were 3 to 5 parts per billion by volume (ppbv) higher at Hampton and Baltimore than on non-bay breeze days in all year periods. Anomalies from mean surface O3 were highest in the afternoon at both sites during bay breeze days in the 2003–2010 study period. In conjunction with an overall lowering of baseline O3 after the 1995-2002 period, the percentage of total exceedances of the Environmental Protection Agency (EPA) 75 ppbv 8-h O3 standard that occurred on bay breeze days increased at Hampton for 2003–2010, while remaining steady at Baltimore. These results suggest that bay breeze circulations are becoming more important to causing exceedance events at particular sites in the region, and support the hypothesis of Martins et al. (2012) that highly localized meteorology increasingly drives air quality events at Hampton.

Measurement of low-ppm mixing ratios of water vapor in the upper troposphere and lower stratosphere using chemical ionization mass spectrometry

Abstract. A chemical ionization mass spectrometer (CIMS) instrument has been developed for the fast, precise, and accurate measurement of water vapor (H2O) at low mixing ratios in the upper troposphere and lower stratosphere (UT/LS). A low-pressure flow of sample air passes through an ionization volume containing an α-particle radiation source, resulting in a cascade of ion-molecule reactions that produce hydronium ions (H3O+) from ambient H2O. The production of H3O+ ions from ambient H2O depends on pressure and flow through the ion source, which were tightly controlled in order to maintain the measurement sensitivity independent of changes in the airborne sampling environment. The instrument was calibrated every 45 min in flight by introducing a series of H2O mixing ratios between 0.5 and 153 parts per million (ppm, 10−6 mol mol−1) generated by Pt-catalyzed oxidation of H2 standards while overflowing the inlet with dry synthetic air. The CIMS H2O instrument was deployed in an unpressurized payload area aboard the NASA WB-57F high-altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX) mission in March and April 2011. The instrument performed successfully during seven flights, measuring H2O mixing ratios below 5 ppm in the lower stratosphere at altitudes up to 17.7 km, and as low as 3.5 ppm near the tropopause. Data were acquired at 10 Hz and reported as 1 s averages. In-flight calibrations demonstrated a typical sensitivity of 2000 Hz ppm−1 at 3 ppm with a signal to noise ratio (2 σ, 1 s) greater than 32. The total measurement uncertainty was 9 to 11%, derived from the uncertainty in the in situ calibrations.

An experimental set-up for carbon isotopic analysis of atmospheric CO 2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the δ 13C measurement is established based on repeat analyses of CO2±0.03‰. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, ‘OASIS AIRMIX’ is prepared mixing CO2 from a high purity cylinder with O2 and N2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are ±7 (n = 169) $\upmu $ mol·mol − 1 and ±0.05 (n = 169) ‰ based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009–December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2‰ correction in the δ 13C value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.

Cross-band relative absorption technique for the measurement of molecular mixing ratios

We describe a new method for the measurement of molecular mixing ratios called Cross-Band Relative Absorption (CoBRA). The proposed method is based on relative measurements in different molecular bands referenced to a band of O2 with properly selected wavelength combinations providing high level of cancelation in temperature sensitivities. The CoBRA approach is particularly promising for satellite based remote sensing of molecular mixing ratios of the atmospheric trace gases. Very low temperature sensitivities and the potential of achieving close weighting function matching for the measurement and reference wavelengths are the main advantages of the method. The effectiveness of CoBRA approach is demonstrated for the retrieval of CO2 mixing ratios (XCO2) with application to the ASCENDS mission.

High-resolution measurements of atmospheric molecular hydrogen and its isotopic composition at the West African coast of Mauritania

Abstract. Oceans are a net source of molecular hydrogen (H2) to the atmosphere, where nitrogen (N2) fixation is assumed to be the main biological production pathway followed by photochemical production from organic material. The sources can be distinguished using isotope measurements because of clearly differing isotopic signatures of the produced hydrogen. Here we present the first ship-borne measurements of atmospheric molecular H2 mixing ratio and isotopic composition at the West African coast of Mauritania (16–25° W, 17–24° N). This area is one of the biologically most active regions of the world's oceans with seasonal upwelling events and characterized by strongly differing hydrographical/biological properties and phytoplankton community structures. The aim of this study was to identify areas of H2 production and distinguish H2 sources by isotopic signatures of atmospheric H2. For this more than 100 air samples were taken during two cruises in February 2007 and 2008. During both cruises a transect from the Cape Verde Islands towards the Mauritanian Coast was sampled to cover differing oceanic regions such as upwelling and oligotrophic regimes. In 2007, additionally, four days were sampled at high resolution of one sample per hour to investigate a possible diurnal cycle of atmospheric H2. Our results indicate the influence of local sources and suggest the Banc d'Arguin as a pool for precursors for photochemical H2 production, whereas oceanic N2 fixation could not be identified as a source for atmospheric H2 during these two cruises. The variability in diurnal cycles is probably influenced by released precursors for photochemical H2 production and also affected by a varying origin of air masses. This means for future investigations that only measuring the mixing ratio of H2 is insufficient to explain the variability of an atmospheric diurnal cycle and support is needed, e.g. by isotopic measurements. Nevertheless, measurements of atmospheric H2 mixing ratios, which are easy to conduct online during ship cruises, could be a useful indicator of production areas of biological precursors such as volatile organic compounds (VOCs) for further investigations.

Atmospheric CO2 column measurements with an airborne intensity-modulated continuous wave 157 μm fiber laser lidar

The 2007 National Research Council (NRC) Decadal Survey on Earth Science and Applications from Space recommended Active Sensing of CO(2) Emissions over Nights, Days, and Seasons (ASCENDS) as a midterm, Tier II, NASA space mission. ITT Exelis, formerly ITT Corp., and NASA Langley Research Center have been working together since 2004 to develop and demonstrate a prototype laser absorption spectrometer for making high-precision, column CO(2) mixing ratio measurements needed for the ASCENDS mission. This instrument, called the multifunctional fiber laser lidar (MFLL), operates in an intensity-modulated, continuous wave mode in the 1.57 μm CO(2) absorption band. Flight experiments have been conducted with the MFLL on a Lear-25, UC-12, and DC-8 aircraft over a variety of different surfaces and under a wide range of atmospheric conditions. Very high-precision CO(2) column measurements resulting from high signal-to-noise ratio (>1300) column optical depth (OD) measurements for a 10 s (~1 km) averaging interval have been achieved. In situ measurements of atmospheric CO(2) profiles were used to derive the expected CO(2) column values, and when compared to the MFLL measurements over desert and vegetated surfaces, the MFLL measurements were found to agree with the in situ-derived CO(2) columns to within an average of 0.17% or ~0.65 ppmv with a standard deviation of 0.44% or ~1.7 ppmv. Initial results demonstrating ranging capability using a swept modulation technique are also presented.

An airborne amplitude-modulated 1.57 μm differential laser absorption spectrometer: simultaneous measurement of partial column-averaged dry air mixing ratio of CO<sub>2</sub> and target range

Abstract. Simultaneous measurements of the partial column-averaged dry air mixing ratio of CO2 (XCO2) and target range were demonstrated using airborne amplitude-modulated 1.57 μm differential laser absorption spectrometer (LAS). The LAS system is useful for discriminating between ground and cloud return signals and has a demonstrated ability to suppress the impact of integrated aerosol signals on atmospheric CO2 measurements. A high correlation coefficient (R) of 0.987 between XCO2 observed by LAS and XCO2 calculated from in situ measurements was obtained. The averaged difference in XCO2 obtained from LAS and validation data was within 1.5 ppm for all spiral measurements. An interesting vertical profile was observed for both XCO2LAS and XCO2val, in which lower altitude CO2 decreases compared to higher altitude CO2 attributed to the photosynthesis over grassland in the summer. In the case of an urban area where there are boundary-layer enhanced CO2 and aerosol in the winter, the difference of XCO2LAS to XCO2val is a negative bias of 1.5 ppm, and XCO2LAS is in agreement with XCO2val within the measurement precision of 2.4 ppm (1 SD).

Economic crisis detected from space: Air quality observations over Athens/Greece

Using both satellite observations of tropospheric NO2 columns and a number of economic metrics, we investigate the impact of the economic crisis (from 2008 onward) on air quality over Greece, and Athens in particular. The multiannual analysis shows that NO2 columns over Athens have been significantly reduced in the range 30–40%. This decline is further supported by surface measurements of atmospheric NO2 mixing ratios. Additionally, the declining local concentrations of NO, CO, and SO2 are associated with an increase in ozone due to reduced titration by NO. In particular, regression analysis revealed that the reduction of NO2 (0.3 ± 0.2 ppbv y−1) and SO2 (0.2 ± 0.1 ppbv y−1) during the period 2000–2007, significantly accelerated during the economic crisis period (from 2008 onward), reaching 2.3 ± 0.2 ppbv y−1 and 0.7 ± 0.1 ppbv y−1, respectively. The strong correlations between pollutant concentrations and economic indicators show that the economic recession has resulted in proportionally lower levels of pollutants in large parts of Greece.

Extreme <sup>13</sup>C depletion of CCl<sub>2</sub>F<sub>2</sub> in firn air samples from NEEM, Greenland

Abstract. A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than δ13C = −80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near −40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to −120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change is likely to have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological advances in the CFC production process over the last 80 yr, though direct evidence is lacking.

Intracavity widely-tunable quantum cascade laser spectrometer

A grating-tuned extended-cavity quantum cascade laser (EC-QCL) operating around 7.6 µm was assembled to provide a tuning range of ~80 cm⁻¹ with output power of up to 30 mW. The EC-QCL output power was shown to be sensitive to the presence of a broadband absorbing gas mixture contained in a 2-cm cell introduced inside the extended laser cavity. In this arrangement, enhanced absorption relative to single path linear absorption was observed. To describe observations, in the QCL rate-equation model was included the effect of intracavity absorption. The model qualitatively reproduced the absorption behavior observed. In addition, it allowed quantitative measurements of mixing ratio of dimethyl carbonate, which was used as a test broadband absorber. A number of alternative data acquisition and reduction methods were identified. As the intracavity absorber modifies the laser threshold current, phase-sensitive detection of the laser threshold current was found to be the most attractive way to determine the mixing ratio of the absorber. The dimethyl carbonate detection limit was estimated to be 1.4 ppmv for 10 second integration. Limitations and possible ways of improvements were also identified.

Tropospheric ozone over Siberia in spring 2010: remote influences and stratospheric intrusion

We have identified and characterised different factors influencing the tropospheric ozone over Siberia during spring 2010. This was done by analysing in-situ measurements of ozone, carbon dioxide, carbon monoxide, and methane mixing ratios measured by continuous analysers during an intensive airborne measurement campaign of the YAK-AEROSIB project, carried out between 15 and 18 April 2010. The analysis and interpretation of the observations, spanning 3000 km and stretching from 800 to 6700 m above ground level, were enhanced using the Lagrangian model FLEXPART to simulate backward air mass transport. The analysis of trace gas variability and simulated origin of air masses showed that plumes coming from east and west of the west Siberian plain and from north-eastern China related to biomass burning and anthropogenic activity had enhanced ozone mixing ratios during transport. In one case, low ozone mixing ratios were observed over a large region in the upper troposphere above 5500 m. The air mass was transported from the marine boundary layer over the Norwegian Sea where O3 background concentrations are low in the spring. The transport was coherent over thousands of kilometres, with no significant mixing with mid–upper troposphere air masses rich in O3. Finally, the stratospheric source of ozone to the troposphere was observed directly in a well-defined stratospheric intrusion. Analysis of this event suggests an input of 2.56±0.29×107 kg of ozone associated with a regional downward flux of 9.75±2.9×1010 molecules cm−2 s−1, smaller than hemispheric climatology.

Airborne observations of formic acid using a chemical ionization mass spectrometer

Abstract. The first airborne measurements of formic acid mixing ratios over the United Kingdom were measured on the FAAM BAe-146 research aircraft on 16 March 2010 with a chemical ionization mass spectrometer using I− reagent ions. The I− ionization scheme was able to measure formic acid mixing ratios at 1 Hz in the boundary layer. In-flight standard addition calibrations from a formic acid source were used to determine the instrument sensitivity of 35 ± 6 ion counts pptv−1 s−1 and a limit of detection of 25 pptv. Routine measurements were made through a scrubbed inlet to determine the instrumental background. Three plumes of formic acid were observed over the UK, originating from London, Humberside and Tyneside. The London plume had the highest formic acid mixing ratio throughout the flight, peaking at 358 pptv. No significant correlations of formic acid with NOx and ozone were found, but a positive correlation was observed between CO and HCOOH within the two plumes where coincident data were recorded. A trajectory model was employed to determine the sources of the plumes and compare modelled mixing ratios with measured values. The model underestimated formic acid concentrations by up to a factor of 2. This is explained by missing sources in the model, which were considered to be both primary emissions of formic acid of mainly anthropogenic origin and a lack of precursor emissions, such as isoprene, from biogenic sources, whose oxidation in situ would lead to formic acid formation.

Measurements of NO2 mixing ratios with topographic target light scattering-differential optical absorption spectroscopy system and comparisons to point monitoring technique

A topographic target light scattering-differential optical absorption spectroscopy (ToTaL-DOAS) system is developed for measuring average concentrations along a known optical path and studying surface-near distributions of atmospheric trace gases. The telescope of the ToTaL-DOAS system points to targets which are located at known distances from the measurement device and illuminated by sunlight. Average concentrations with high spatial resolution can be retrieved by receiving sunlight reflected from the targets. A filed measurement of NO2 concentration is performed with the ToTaL-DOAS system in Shijiazhuang in the autumn of 2011. The measurement data are compared with concentrations measured by the point monitoring technique at the same site. The results show that the ToTaL-DOAS system is sensitive to the variation of NO2 concentrations along the optical path.