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Long-term field performance of a tunable diode laser absorption spectrometer for analysis of carbon isotopes of CO2 in forest air

Tunable diode laser absorption spectrometry (TDLAS) is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C) of carbon dioxide (CO2) in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site), providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35&permil; for δ13C, but after fixing several problems the isotope precision improved to 0.2&permil; (over the last several months). The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional) seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.
Parameterization of N2O5 reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate

A parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity (RH), particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH4HSO4, (NH4)2SO4, and NH4NO3 were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH4HSO4 and (NH4)2SO4 particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 80% of the laboratory data within a factor of two and 63% within a factor of 1.5. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, RH, sulfate, nitrate, and ammonium. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our equations lay the foundation for future research that will parameterize the suppression of γ when inorganic ammoniated particles are mixed or coated with organic material. Our analyses draw attention to a major uncertainty in the available laboratory data at high RH and highlight a critical need for future laboratory measurements of γ at low temperature and high RH to improve model simulations of N2O5 hydrolysis during wintertime conditions.
Model simulations of stratospheric ozone loss caused by enhanced mesospheric NOx during Arctic Winter 2003/2004

Satellite observations show that the enormous solar proton events (SPEs) in October–November 2003 had significant effects on the composition of the stratosphere and mesosphere in the polar regions. After the October–November 2003 SPEs and in early 2004, significant enhancements of NOx(=NO+NO2) in the upper stratosphere and lower mesosphere in the Northern Hemisphere were observed by several satellite instruments. Here we present global full chemistry calculations performed with the CLaMS model to study the impact of mesospheric NOx intrusions on Arctic polar ozone loss processes in the stratosphere. Several model simulations are preformed with different upper boundary conditions for NOx at 2000 K potential temperature (≈50 km altitude). In our study we focus on the impact of the non-local production of NOx, which means the downward transport of enhanced NOx from the mesosphere to the stratosphere. The local production of NOx in the stratosphere is neglected. Our findings show that intrusions of mesospheric air into the stratosphere, transporting high burdens of NOx, affect the composition of the Arctic polar region down to about 400 K (≈17–18 km). We compare our simulated NOx and O3 mixing ratios with satellite observations by ACE-FTS and MIPAS processed at IMK/IAA and derive an upper limit for the ozone loss caused by enhanced mesospheric NOx. Our findings show that in the Arctic polar vortex (equivalent lat.>70° N) the accumulated column ozone loss between 350–2000 K potential temperature (≈14–50 km altitude) caused by the SPEs in October–November 2003 in the stratosphere is up to 3.3 DU with an upper limit of 5.5 DU until end of November. Further, we found that about 10 DU, but in any case lower than 18 DU, accumulated ozone loss additionally occurred until end of March 2004 caused by the transport of mesospheric NOx-rich air in early 2004. The solar-proton-produced NOx above 55 km due to the SPEs of October–November 2003 had a negligibly small impact on ozone loss processes through the end of November in the lower stratosphere (350–700 K≈14–27 km). The mesospheric NOx intrusions in early 2004 yielded a lower stratospheric ozone loss of about 3.5 DU, and clearly lower than 6.5 DU through the end of March. Overall, the non-local production of NOx is an additional variability in the existing variations of the ozone loss observed in the Arctic.
Increased UV radiation due to polar ozone chemical depletion and vortex occurrences at Southern Sub-polar Latitudes in the period [1997–2005]

The variability of total ozone and UV radiation from Total Ozone Mapping Spectrometer (TOMS) measurements is analyzed as a function of polar vortex occurrences over the southern subpolar regions during the 1997–2005 period. The analysis of vortex occurrences showed high interannual variability in the 40° S–60° S latitude band with a longitudinal asymmetry showing the largest frequencies over the 90° W–90° E region. The impact of vortex occurrences on UV radiation and ozone in clear sky conditions was determined from the comparison between the measurements inside the vortex and a climatology obtained from data outside the vortex over the studied period. Clear sky conditions were determined from TOMS reflectivity data. For measurements outside the vortex, clear sky conditions were selected for reflectivity values lower than 7.5%, while for measurements inside the vortex, a relaxed threshold was determined from statistically similar UV values as a function of reflectivity. UV changes and ozone differences from the climatology were analyzed in the 40° S–50° S and 50° S–60° S latitude bands during the spring period (September to November). The largest UV increases and ozone decreases, reaching ~200% and ~65%, respectively, were found in the 50° S–60° S latitude band in September and October. The heterogeneous ozone loss during vortex occurrences was estimated using a chemical transport model. The largest impact of vortex occurrences was found in October with mean UV increase, total ozone decrease and accumulated ozone loss in the 350–650 K range of, respectively, 47%, 30% and 57%. The region close to South America is the most affected by the Antarctic ozone depletion due to the combined effect of large number of vortex occurrences, lower cloud cover and large ozone decrease. This region would be the most vulnerable in case of cloud cover decrease, due to more frequent occurrence of ozone poor air masses during austral spring.
Mode resolved density of atmospheric aerosol particles

In this study, we investigate the mode resolved density of ultrafine atmospheric particles measured in boreal forest environment. The method used here enables us to find the distinct density information for each mode in atmospheric fine particle population: the density values for nucleation, Aitken, and accumulation mode particles are presented. The experimental data was gained during 2 May 2005–19 May 2005 at the boreal forest measurement station "SMEAR II" in Hyytiälä, Southern Finland. The density values for accumulation mode varied from 1.1 to 2 g/cm3 (average 1.5 g/cm3) and for Aitken mode from 0.4 to 2 g/cm3 (average 0.97 g/cm3). As an overall trend during the two weeks campaign, the density value of Aitken mode was seen to gradually increase. With the present method, the time dependent behaviour of the particle density can be investigated in the time scale of 10 min. This allows us to follow the density evolution of the nucleation mode particles during the particle growth process following the nucleation burst. The density of nucleation mode particles decreased during the growth process. The density values for 15 nm particles were 1.2–1.5 g/cm3 and for grown 30 nm particles 0.5–1 g/cm3. These values are consistent with the present knowledge that the condensing species are semi-volatile organics, emitted from the boreal forest.
A multi-model assessment of pollution transport to the Arctic

We examine the response of Arctic gas and aerosol concentrations to perturbations in pollutant emissions from Europe, East and South Asia, and North America using results from a coordinated model intercomparison. These sensitivities to regional emissions (mixing ratio change per unit emission) vary widely across models and species. Intermodel differences are systematic, however, so that the relative importance of different regions is robust. North America contributes the most to Arctic ozone pollution. For aerosols and CO, European emissions dominate at the Arctic surface but East Asian emissions become progressively more important with altitude, and are dominant in the upper troposphere. Sensitivities show strong seasonality: surface sensitivities typically maximize during boreal winter for European and during spring for East Asian and North American emissions. Mid-tropospheric sensitivities, however, nearly always maximize during spring or summer for all regions. Deposition of black carbon (BC) onto Greenland is most sensitive to North American emissions. North America and Europe each contribute ~40% of total BC deposition to Greenland, with ~20% from East Asia. Elsewhere in the Arctic, both sensitivity and total BC deposition are dominated by European emissions. Model diversity for aerosols is especially large, resulting primarily from differences in aerosol physical and chemical processing (including removal). Comparison of modeled aerosol concentrations with observations indicates problems in the models, and perhaps, interpretation of the measurements. For gas phase pollutants such as CO and O3, which are relatively well-simulated, the processes contributing most to uncertainties depend on the source region and altitude examined. Uncertainties in the Arctic surface CO response to emissions perturbations are dominated by emissions for East Asian sources, while uncertainties in transport, emissions, and oxidation are comparable for European and North American sources. At higher levels, model-to-model variations in transport and oxidation are most important. Differences in photochemistry appear to play the largest role in the intermodel variations in Arctic ozone sensitivity, though transport also contributes substantially in the mid-troposphere.
Dust aerosol optical properties over North China

Aerosol optical properties were obtained from ground-based sunphotometer data at nine observatories over North China during two periods of 1996–1998 and 2002–2003. The seasonal changes of aerosol optical depth (AOD) at five wavelengths were observed, with the highest value of AOD in spring, while the lowest in winter. Four patterns of AOD diurnal variation were obtained, of which the high value occurred in the morning, noon, evening and no remarkable change, respectively. Together with meteorological records, the characteristics of AOD during dust weather were analyzed, and the results show that it was more detailed and accurate to use AOD to depict the strength change of dust weather than to use surface visibility. Based on measurements by aerodynamic instrument for particle size distribution, a positive correlation between dust particle number concentration and Ångström turbidity coefficient β, and a negative correlation between aerosol geometric mean diameter (GMD) and wavelength exponent αwere revealed.
Typical distribution of the solar erythemal UV radiation over Slovakia

Maps of solar erythemal ultraviolet (EUV) irradiance daily doses were created for every month with a horizontal resolution of 500 m at the geographical domain 47.15 N–49.86 N×16.94 E–22.81 E covering the territory of Slovakia. The cloud modification factor for the EUV radiation (cmfUV) was modeled utilizing the relation between the cloud modification factor of global and EUV radiation. The maps of the cmfUV factor were created by utilizing measurements of global irradiance performed at nine observatories during the period 1995–2004 and modeling of the cmfUV dependence on altitude. Maps of the EUV irradiance daily dose corresponded to clear-sky conditions and EUV irradiance daily dose affected by average cloudiness were constructed for mean monthly total ozone, its upper and lower monthly limits, for two probability levels of snow cover occurrence as criteria for the snow effect incorporation in the model and for one day representing typical values for every month. The map-set can be regarded as an atlas of solar EUV radiation over Slovakia.
Inhibition of ice crystallisation in highly viscous aqueous organic acid droplets

Homogeneous nucleation of ice within aqueous solution droplets and their subsequent crystallisation is thought to play a significant role in upper tropospheric ice cloud formation. It is normally assumed that homogeneous nucleation will take place at a threshold supersaturation, irrespective of the identity of the solute, and that rapid growth of ice particles will follow immediately after nucleation. However, it is shown here through laboratory experiments that droplets may not readily freeze in the very cold tropical tropopause layer (TTL, typical temperatures of 186–200 K). In these experiments ice crystal growth in citric acid solution droplets did not occur when ice nucleated below 197±6 K. Citric acid, 2-hydroxypropane-1,2,3-tricarboxyllic acid, is a molecule with similar functionality to oxygenated organic compounds which are ubiquitous in atmospheric aerosol. It is therefore thought to be a sensible proxy for atmospheric organic material. Evidence is presented that suggests citric acid solution droplets become ultra-viscous and form glassy solids under atmospherically relevant conditions. Diffusion of liquid water molecules to ice nuclei is expected to be very slow in ultra-viscous solution droplets and nucleation is negligible in glassy droplets; this most likely provides an explanation for the experimentally observed inhibition of ice crystallisation. The implications of ultra-viscous and glassy solution droplets for ice cloud formation and supersaturations in the TTL are discussed.
Technical Note: A new global database of trace gases and aerosols from multiple sources of high vertical resolution measurements

A new database of trace gases and aerosols with global coverage, derived from high vertical resolution profile measurements, has been assembled as a collection of binary data files; hereafter referred to as the "Binary DataBase of Profiles" (BDBP). Version 1.0 of the BDBP, described here, includes measurements from different satellite- (HALOE, POAM II and III, SAGE I and II) and ground-based measurement systems (ozonesondes). In addition to the primary product of ozone, secondary measurements of other trace gases, aerosol extinction, and temperature are included. All data are subjected to very strict quality control and for every measurement a percentage error on the measurement is included. To facilitate analyses, each measurement is added to 3 different instances (3 different grids) of the database where measurements are indexed by: (1) geographic latitude, longitude, altitude (in 1 km steps) and time, (2) geographic latitude, longitude, pressure (at levels ~1 km apart) and time, (3) equivalent latitude, potential temperature (8 levels from 300 K to 650 K) and time. In contrast to existing zonal mean databases, by including a wider range of measurement sources (both satellite and ozonesondes), the BDBP is sufficiently dense to permit calculation of changes in ozone by latitude, longitude and altitude. In addition, by including other trace gases such as water vapour, this database can be used for comprehensive radiative transfer calculations. By providing the original measurements rather than derived monthly means, the BDBP is applicable to a wider range of applications than databases containing only monthly mean data. Monthly mean zonal mean ozone concentrations calculated from the BDBP are compared with the database of Randel and Wu, which has been used in many earlier analyses. As opposed to that database which is generated from regression model fits, the BDBP uses the original (quality controlled) measurements with no smoothing applied in any way and as a result displays higher natural variability.