H2O Mixing Ratio Research Articles

Photochemical control of the distribution of Venusian water

We use the JPL/Caltech 1-D photochemical model to solve continuity diffusion equation for atmospheric constituent abundances and total number density as a function of radial distance from the planet Venus. Photochemistry of the Venus atmosphere from 58 to 112km is modeled using an updated and expanded chemical scheme (Zhang et al., 2010, 2012), guided by the results of recent observations and we mainly follow these references in our choice of boundary conditions for 40 species. We model water between 10 and 35ppm at our 58km lower boundary using an SO2 mixing ratio of 25ppm as our nominal reference value. We then vary the SO2 mixing ratio at the lower boundary between 5 and 75ppm holding water mixing ratio of 18ppm at the lower boundary and finding that it can control the water distribution at higher altitudes. SO2 and H2O can regulate each other via formation of H2SO4. In regions of high mixing ratios of SO2 there exists a “runaway effect” such that SO2 gets oxidized to SO3, which quickly soaks up H2O causing a major depletion of water between 70 and 100km. Eddy diffusion sensitivity studies performed characterizing variability due to mixing that show less of an effect than varying the lower boundary mixing ratio value. However, calculations using our nominal eddy diffusion profile multiplied and divided by a factor of four can give an order of magnitude maximum difference in the SO2 mixing ratio and a factor of a few difference in the H2O mixing ratio when compared with the respective nominal mixing ratio for these two species. In addition to explaining some of the observed variability in SO2 and H2O on Venus, our work also sheds light on the observations of dark and bright contrasts at the Venus cloud tops observed in an ultraviolet spectrum. Our calculations produce results in agreement with the SOIR Venus Express results of 1ppm at 70–90km (Bertaux et al., 2007) by using an SO2 mixing ratio of 25ppm SO2 and 18ppm water as our nominal reference values. Timescales for a chemical bifurcation causing a collapse of water concentrations above the cloud tops (>64km) are relatively short and on the order of a less than a few months, decreasing with altitude to less than a few days.

Submillimeter mapping of mesospheric minor species on Venus with ALMA

Millimeter and submillimeter heterodyne spectroscopy offers the possibility of probing the mesosphere of Venus and monitoring minor species and winds. ALMA presents a unique opportunity to map mesospheric species of Venus. During Cycle 0, we have observed Venus on November 14 and 15, 2011, using the compact configuration of ALMA. The diameter of Venus was 11″ and the illumination factor was about 90%. Maps of CO, SO, SO2 and HDO have been built from transitions recorded in the 335–347GHz frequency range. A mean mesospheric thermal profile has been inferred from the analysis of the CO transition at the disk center, to be used in support of minor species retrieval. Maps of SO and SO2 abundance show significant local variations over the disk and contrast variations by as much as a factor 4. In the case of SO2, the spatial distribution appears more “patchy”, i.e. shows short-scale structures apparently disconnected from day-side and latitudinal variations. For both molecules, significant changes occur over a timescale of one day. From the disk averaged spectrum of SO recorded on November 14 at 346.528GHz, we find that the best fit is obtained with a cutoff in the SO vertical distribution at 88±2km and a uniform mixing ratio of 8.0±2.0ppb above this level. The SO2 map of November 14, derived from the weaker transition at 346.652GHz, shows a clear maximum in the morning side at low latitudes, which is less visible in the map of November 15. We find that the best fit for SO2 is obtained for a cutoff in the vertical distribution at 88±3km and a uniform mixing ratio of 12.0±3.5ppb above this level. The HDO maps retrieved from the 335.395GHz show some enhancement in the northern hemisphere, but less contrasted variations than for the sulfur species maps, with little change between November 14 and 15. Assuming a typical D/H ratio of 200 times the terrestrial value in the mesosphere of Venus, we find that the disk averaged HDO spectrum is best fitted with a uniform H2O mixing ratio of 2.5±0.6ppm (corresponding to a HDO mixing ratio of 0.165±0.040ppm). We note that our spectrum is also compatible with a H2O mixing ratio of 1.5ppm in the 80–90km altitude range, and a mixing ratio of 3ppm outside this range, as suggested by the photochemical model of Zhang et al. (2012, Icarus, vol. 217, pp. 714–739). Our results are in good general agreement with previous single dish submillimeter observations of Sandor and Clancy (2005, Icarus, vol. 177, pp. 129–143), Gurwell et al. (2007, Icarus, vol. 188, p. 288), and Sandor et al. (2010, Icarus, vol. 208, pp. 49–60; 2012, Icarus, vol. 217, pp. 839–844 ) and with SPICAV/Venus Express results of Fedorova et al. (2008, J. Geophys. Res., vol. 113, p. E00B25) and Belyaev et al. (2012).

Low-power, open-path mobile sensing platform for high-resolution measurements of greenhouse gases and air pollutants

A low-power mobile sensing platform has been developed with multiple open-path gas sensors to measure the ambient concentrations of greenhouse gases and air pollutants with high temporal and spatial resolutions over extensive spatial domains. The sensing system consists of four trace gas sensors including two custom quantum cascade laser-based open-path sensors and two LICOR open-path sensors to measure CO2, CO, CH4, N2O, NH3, and H2O mixing ratios simultaneously at 10 Hz. In addition, sensors for meteorological and geolocation data are incorporated into the system. The system is powered by car batteries with a low total power consumption (~200 W) and is easily transportable due to its low total mass (35 kg). Multiple measures have been taken to ensure robust performance of the custom, open-path sensors located on top of the vehicle where the optics are exposed to the harsh on-road environment. The mobile sensing system has been integrated and installed on top of common passenger vehicles and participated in extensive field campaigns (>400 h on-road time with >18,000 km total distance) in both the USA and China. The simultaneous detection of multiple trace gas species makes the mobile sensing platform a unique and powerful tool to identify and quantify different emission sources through mobile mapping.

증발장에서 에멀젼연료의 거동특성에 관한 연구

본 논문은 에멀젼연료(Diesel/H₂O₂)에 있어 과산화수소의 혼합비가 혼합연료 액적증발 및 분무거동 특성에 미치는 영향을 연구하였다. 연료혼합을 위한 계면활성제는 span 80, tween 80을 9:1로 혼합하여 에멀젼연료 총 부피의 3%로 고정 혼합하였다. 또한 과산화수소의 혼합비율은 계면활성제의 혼합비를 고려하여 EF (Emulsified Fuel)0, EF2, EF12, EF22, EF32 및 EF42로 설정하였다. 에멀젼연료 액적의 증발특성을 관찰하기 위해 가열판에 액적 방울을 투하시켜 액적이 증발하는 현상을 산란광 및 쉴리렌기법을 통하여 촬영하였다. 또한 혼합비 변화에 따른 혼합연료의 분무거동특성을 해석하기 위하여 혼합연료 EF0~EF22를 선택하여 150℃로 유지된 정적용기에서 증발자유분무 거동해석 실험을 실시하였다. 그 결과 과산화수소의 혼합비율이 EF0보다 높은 EF22 에멀젼연료의 자유분무성장이 연료 속에 혼합된 과산화수소의 증발촉진으로 인하여 보다 신속하였다.

Vertical profiles of H2O, H2SO4, and sulfuric acid concentration at 45–75 km on Venus

A method developed by Krasnopolsky and Pollack (Krasnopolsky, V.A., Pollack, J.B. [1994]. Icarus 109, 58–78) to model vertical profiles of H2O and H2SO4 vapors and sulfuric acid concentration in the Venus cloud layer has been updated with improved thermodynamic parameters for H2O and H2SO4 and reduced photochemical production of sulfuric acid. The model is applied to the global-mean conditions and those at the low latitudes and at 60°. Variations in eddy diffusion near the lower cloud boundary are used to simulate variability in the cloud properties and abundances of H2O and H2SO4. The best version of the model for the global-mean condition results in a lower cloud boundary (LCB) at 47.5km, H2SO4 peak abundance of 7.5ppm at the LCB, and H2O mixing ratios of 7ppm at 62km and 3.5ppm above 67km. The model for low latitudes gives LCB at 48.5km, the H2SO4 peak of 5ppm, H2O of 8.5ppm at 62km and 3ppm above 67km. The model for 60° shows LCB at 46km, the H2SO4 peak of 8.5ppm, H2O of 9ppm at 62km and 4.5ppm above 67km. The calculated variability is induced by the proper changes in the production of sulfuric acid (by factors of 1.2 and 0.7 for the low latitudes and 60°, respectively) and reduction of eddy diffusion near 45km relative to the value at 54km by factors of 1.1, 3, and 4.5 for the low and middle (global-mean) latitudes and 60°, respectively. Concentration of sulfuric acid at the low and middle latitudes varies from ∼98% near 50km to ∼80% at 60km and then is almost constant at 79% at 70km. Concentration at 60° is 98% at 50km, 73% at 63km, and 81% at 70km. There is a reasonable agreement between the model results and observations except for the sulfuric acid concentration in the lower clouds. Variations of eddy diffusion in the lower cloud layer simulate variations in atmospheric dynamics and may induce strong variations in water vapor near the cloud tops. Variations in temperature may affect abundances of the H2O and H2SO4 vapors as well.

The effect of Lyman α radiation on mini-Neptune atmospheres around M stars: application to GJ 436b

Mini-Neptunes orbiting M stars are a growing population of known exoplanets. Some of them are located very close to their host star, receiving large amounts of UV radiation. Many M stars emit strong chromospheric emission in the H i Lyman α line (Lyα) at 1215.67 Å, the brightest far-UV emission line. We show that the effect of incoming Lyα flux can significantly change the photochemistry of mini-Neptunes’ atmospheres. We use GJ 436b as an example, considering different metallicities for its atmospheric composition. For solar composition, H2O-mixing ratios show the largest change because of Lyα radiation. H2O absorbs most of this radiation, thereby shielding CH4, whose dissociation is driven mainly by radiation at other far-UV wavelengths (∼1300 Å). H2O photolysis also affects other species in the atmosphere, including H, H2, CO2, CO, OH and O. For an atmosphere with high metallicity, H2O- and CO2-mixing ratios show the biggest change, thereby shielding CH4. Direct measurements of the UV flux of the host stars are important for understanding the photochemistry in exoplanets’ atmospheres. This is crucial, especially in the region between 1 and 10−6 bars, which is the part of the atmosphere that generates most of the observable spectral features.

The Taihu Eddy Flux Network: An Observational Program on Energy, Water, and Greenhouse Gas Fluxes of a Large Freshwater Lake

Lakes are an important component of the climate system. They provide moisture for precipitation, buffer temperature variations, and contribute to regional atmospheric carbon budgets. This article describes an eddy covariance (EC) mesonet on Lake Taihu, a large (area 2400 km2) and shallow (depth 2 m) lake situated in the heavily populated Yangtze River Delta, China. The mesonet consists of five lake sites, representing different biological attributes and wind–wave patterns, and a land site near the lake shore. Common to all the sites are standard EC instruments for measurement of the momentum, sensible heat, water vapor, and CO2 flux. One site is also equipped with laser-based analyzers for precise measurement of the CO2, CH4, and H2O mixing ratios and their isotopic compositions. To the authors' best knowledge, this is the first lake eddy flux mesonet. Early results reveal evidence of biological and pollution controls on the surface–air fluxes of energy, momentum, and greenhouse gases across the lake. The...

Observation and modelling of HO<sub>x</sub> radicals in a boreal forest

Abstract. Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

The CO2 continuum absorption in the 1.10- and 1.18-μm windows on Venus from Maxwell Montes transits by SPICAV IR onboard Venus express

One of the difficulties in modeling Venus’ nightside atmospheric windows is the need to apply CO2 continuum opacity due to collision-induced CO2 bands and/or extreme far wings of strong allowed CO2 bands. Characterizing the CO2 continuum absorption at near-IR wavelengths as well as searching for a possible vertical gradient of minor species near the surface require observations over different surface elevations. The largest change in altitude occurs during a passage above Maxwell Montes at high northern latitudes. In 2011, 2012 and 2013 the SPICAV instrument aboard the Venus Express satellite performed three sets of observations over Maxwell Montes with variation of surface altitude from −2 to 9km in the 1.10, 1.18 and 1.28-μm windows. The retrieved CO2 continuum absorption for the 1.10- and 1.18-μm windows varies from 0.29 to 0.66×10−9cm−1amagat−2 and from 0.30 to 0.78×10−9cm−1amagat−2, respectively, depending on the assumed input parameters. The retrieval is sensitive to possible variations of the surface emissivity. Our values fall between the results of Bézard et al., (2009, 2011) based on VIRTIS-M observations and laboratory measurements by Snels et al. (2014). We can also conclude that the continuum absorption at 1.28μm can be constrained below 2.0×10−9cm−1amagat−2. Based on the 1.18μm window the constant H2O mixing ratio varying from 25.7+1.4–1.2ppm to 29.4+1.6–1.4ppm has been retrieved assuming the surface emissivity of 0.95 and 0.6, respectively. No firm conclusion from SPICAV data about the vertical gradient of water vapor content at 10–20km altitude could be drawn because of low signal-to-noise ratio and uncertainties in the surface emissivity.

Absolute validation of a diode laser hygrometer via intercomparison with the German national primary water vapor standard

Direct tunable diode laser absorption spectroscopy (dTDLAS) is a powerful diagnostic technique for absolute and accurate gas analysis with highest chemical specificity. Due to its first principles approach, dTDLAS is often claimed to be “calibration-free”, but this and the absolute accuracy has not been rigorously validated with respect to a high-accuracy reference. This work describes the first rigorous, side-by-side comparison of a dTDLAS hygrometer—called SEALDH—with a highly accurate, internationally validated, primary reference humidity generator (PHG), which also serves as the German national H2O-standard. This PHG provides a humidified air stream with dew points between −30 °C and +60 °C with an uncertainty of 0.035 K (2σ) (equivalent relative H2O mixing ratio uncertainty: 0.4 %). Without any previous calibration, SEALDH was found to accurately reproduce the PHG reference values over the full range from 600 to 20,000 ppmv investigated in the 1-week lab study. Over this range, the SEALDH–PHG relative deviation was in average −1.45 %, the worst case being −2.5 % at 1,000 ppmv, the best −0.2 % at 600 ppmv. As SEALDH’s relative uncertainty was metrologically determined to be 4.3 % (k = 2), these deviations are for all concentration steps in full compliance with the PHG reference. Systematic contributions to the relative deviation could be correlated with line shape deviations between the measured line profile and the fitted Voigt line shape. Using this information, SEALDHs absolute accuracy can be improved further to down to an average relative deviation to the PHG of +0.21 %.

HO<sub>x</sub> measurements in the summertime upper troposphere over Europe: a comparison of observations to a box model and a 3-D model

Abstract. In situ airborne measurements of OH and HO2 with the HORUS (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy) instrument were performed in the summertime upper troposphere across Europe during the HOOVER 2 (HOx OVer EuRope) campaign in July 2007. Complementary measurements of trace gas species and photolysis frequencies were conducted to obtain a broad data set, which has been used to quantify the significant HOx sources and sinks. In this study we compare the in situ measurement of OH and HO2 with simulated mixing ratios from the constrained box model CAABA/MECCA (Chemistry As A Box Model Application/Module Efficiently Calculating the Chemistry of the Atmosphere), and the global circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry Model). The constrained box model reproduces the observed OH and HO2 mixing ratios with better agreement (obs/mod median 98% OH, 96% HO2) than the global model (median 76% OH, 59% HO2). The observations and the computed HOx sources and sinks are used to identify deviations between the models and their impacts on the calculated HOx budget.

A survey of volatile species in Oort cloud comets C/2001 Q4 (NEAT) and C/2002 T7 (LINEAR) at millimeter wavelengths

The line emission in the coma was measured in the comets C/2001 Q4 (NEAT) and C/2002 T7 (LINEAR), that were observed on five consecutive nights, 7-11 May 2004, at heliocentric distances of 1.0 and 0.7 AU, respectively, by means of high-resolution spectroscopy using the 10-m Submillimeter Telescope (SMT). We present a search for six parent- and product-volatile species (HCN, H2CO, CO, CS, CH3OH, and HNC) in both comets. Multiline observations of the CH3OH J = 5-4 series allow us to estimate the rotational temperature using the rotation diagram technique. We derive rotational temperatures of 54(9) K for C/2001 Q4 (NEAT) and 119(34) K for C/2002 T7 (LINEAR) that are roughly consistent with observations of other comets at similar distances from the Sun. The gas production rates of material are computed using a spherically symmetric molecular excitation code that includes collisions between neutrals and electrons. We find an HCN production rate of 2.96(5)e26 molec.s-1 for comet C/2001 Q4 (NEAT), corresponding to a mixing ratio with respect to H2O of 1.12(2)e-3. The mean HCN production rate during the observing period is 4.54(10)e26 molec.s-1 for comet C/2002 T7 (LINEAR), which gives a Q_HCN/Q_H2O mixing ratio of 1.51(3)e-3. With systematically lower mixing ratios in comet C/2001 Q4 (NEAT), production rate ratios of the observed species with respect to H2O lie within the typical ranges of dynamically new comets in both objects. We find a relative low abundance of CO in C/2001 Q4 (NEAT) compared to the observed range in other comets based on millimeter/submillimeter observations, and a significant upper limit on the CO production in C/2002 T7 (LINEAR) is derived. Depletion of CO suggests partial evaporation from the surface layers during previous visits to the outer Solar System and agrees with previous measurements of dynamically new comets.

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.

Design and performance of a Nafion dryer for continuous operation at CO<sub>2</sub> and CH<sub>4</sub> air monitoring sites

Abstract. In preparation for routine deployment in a network of greenhouse gas monitoring stations, we have designed and tested a simple method for drying ambient air to near or below 0.2% (2000 ppm) mole fraction H2O using a Nafion dryer. The inlet system was designed for use with cavity ring-down spectrometer (CRDS) analyzers such as the Picarro model G2301 that measure H2O in addition to their principal analytes, in this case CO2 and CH4. These analyzers report dry-gas mixing ratios without drying the sample by measuring H2O mixing ratio at the same frequency as the main analytes, and then correcting for the dilution and peak broadening effects of H2O on the mixing ratios of the other analytes measured in moist air. However, it is difficult to accurately validate the water vapor correction in the field. By substantially lowering the amount of H2O in the sample, uncertainties in the applied water vapor corrections can be reduced by an order of magnitude or more, thus eliminating the need to determine instrument-specific water vapor correction coefficients and to verify the stability over time. Our Nafion drying inlet system takes advantage of the extra capacity of the analyzer pump to redirect 30% of the dry gas exiting the Nafion to the outer shell side of the dryer and has no consumables. We tested the Nafion dryer against a cryotrap (−97 °C) method for removing H2O and found that in wet-air tests, the Nafion reduces the CO2 dry-gas mixing ratios of the sample gas by as much as 0.1 ± 0.01 ppm due to leakage across the membrane. The effect on CH4 was smaller and varied within ± 0.2 ppb, with an approximate uncertainty of 0.1 ppb. The Nafion-induced CO2 bias is partially offset by sending the dry reference gases through the Nafion dryer as well. The residual bias due to the impact of moisture differences between sample and reference gas on the permeation through the Nafion was approximately −0.05 ppm for CO2 and varied within ± 0.2 ppb for CH4. The uncertainty of this partial drying method is within the WMO compatibility guidelines for the Northern Hemisphere, 0.1 ppm for CO2 and 2 ppb for CH4, and is comparable to experimentally determining water vapor corrections for each instrument but less subject to concerns of possible drift in these corrections.

Observations of D/H ratios in H2O, HCl, and HF on Venus and new DCl and DF line strengths

Intensities of the spectral lines in the fundamental bands of D35Cl and DF were calculated using the semi-empirical dipole moment functions derived from the most accurate and precise measurements of intensities of the ro-vibrational lines of H35Cl and HF. Values obtained in this way for the deuterated species are superior to any available measured or calculated data to date.Our study of the D/H ratios in H2O, HCl, and HF on Venus is based on spatially-resolved high-resolution spectroscopy using the CSHELL spectrograph at NASA IRTF. Search for DF on Venus using its R5 (1-0) line at 3024.054cm−1 results in a DF mixing ratio of 0.23±0.11ppb that corresponds to (D/H)HF=420±200 times that in the Standard Mean Ocean Water (SMOW). H2O abundances on Venus were retrieved using lines at 3022.366 and 3025.761cm−1 that were observed at an exceptionally low overhead telluric water abundance of 0.3pr.mm. The measured H2O mixing ratios at 74km vary insignificantly between 55°S and 55°N with a mean value of 3.2ppm. When compared with simultaneous observations of HDO near 2722cm−1, this results in (D/H)H2O=95±15 times SMOW. Reanalysis of the observation of the D35Cl R4 (1-0) line at 2141.540cm−1 (Krasnopolsky, V.A. [2012b]. Icarus 219, 244–249) using the improved line strength and more thorough averaging of the spectra gives (D/H)HCl=190±50 times SMOW.The similarity of the measured (D/H)H2O=95±15 at 74km with 120±40 observed by De Bergh et al. (De Bergh, C., Bezard, B., Owen, T., Crisp, D., Maillard, J.P., Lutz, B.L. [1991]. Science 251, 547–549) below the clouds favors the constant (D/H)H2O from the surface to the mesosphere, in accord with the prediction by theory. D/H≈100 removes a difference of a factor of 2 between H2O abundances in the observations by Krasnopolsky (Krasnopolsky, V.A. [2010b]. Icarus 209, 314–322) and the Venus Express nadir observations (Cottini, V., Ignatiev, N.I., Piccioni, G., Drossart, P., Grassi, D., Markiewicz, W.J. [2012]. Icarus 217, 561–569). Equivalent widths of the HDO and H2O lines are similar in our observations; therefore some errors cancel out in their ratios. Photochemistry of HCl in the mesosphere tends to enrich D in HCl and deplete it in H2O. This may be an explanation of the twofold difference between the observed D/H in HCl and H2O.An alternative explanation is based on (D/H)H2O≈200 observed in the mesosphere by Bjoraker et al. (Bjoraker, G.L., Larson, H.P., Mumma, M.J., Timmermann, R., Montani, J.L. [1992]. Bull. Am. Astron. Soc. 24, 995) and Fedorova et al. (Fedorova, A. et al. J. Geophys. Res. 113, E00B22). This means an effective exchange of D between H2O and HCl and almost equal D/H in both species. However, this requires a twofold increase in D/H from the lower atmosphere to the mesosphere. This increase is not supported by theory; furthermore, condensation processes usually deplete D/H above the clouds.Photochemistry of HF has not been studied; it proceeds mostly in the lower thermosphere, and D/H in HF may be very different from that in H2O. Overall, the observational data on D/H in all hydrogen-bearing species on Venus are helpful to solve the problem of deuterium fractionation on Venus.

Determining water sources in the boundary layer from tall tower profiles of water vapor and surface water isotope ratios after a snowstorm in Colorado

Abstract. The D/H isotope ratio is used to attribute boundary layer humidity changes to the set of contributing fluxes for a case following a snowstorm in which a snow pack of about 10 cm vanished. Profiles of H2O and CO2 mixing ratio, D/H isotope ratio, and several thermodynamic properties were measured from the surface to 300 m every 15 min during four winter days near Boulder, Colorado. Coeval analysis of the D/H ratios and CO2 concentrations find these two variables to be complementary with the former being sensitive to daytime surface fluxes and the latter particularly indicative of nocturnal surface sources. Together they capture evidence for strong vertical mixing during the day, weaker mixing by turbulent bursts and low level jets within the nocturnal stable boundary layer during the night, and frost formation in the morning. The profiles are generally not well described with a gradient mixing line analysis because D/H ratios of the end members (i.e., surface fluxes and the free troposphere) evolve throughout the day which leads to large uncertainties in the estimate of the D/H ratio of surface water flux. A mass balance model is constructed for the snow pack, and constrained with observations to provide an optimal estimate of the partitioning of the surface water flux into contributions from sublimation, evaporation of melt water in the snow and evaporation from ponds. Results show that while vapor measurements are important in constraining surface fluxes, measurements of the source reservoirs (soil water, snow pack and standing liquid) offer stronger constraint on the surface water balance. Measurements of surface water are therefore essential in developing observational programs that seek to use isotopic data for flux attribution.

Annual survey of water vapor vertical distribution and water–aerosol coupling in the martian atmosphere observed by SPICAM/MEx solar occultations

The vertical distribution of water vapor is a very important diagnostic to determine the physical and chemical processes that drive the martian water cycle. Yet, very few direct measurements have been performed so far, and our knowledge of the H2O vertical distribution on Mars relies on General Circulation Models (GCMs). The study presented here follows for the first time the evolution of water vapor profile during a martian year. 120 profiles, obtained by the SPICAM spectrometer onboard Mars Express with the solar occultations technique, are retrieved. They cover the northern spring-summer season and the southern spring of Mars Year (MY) 29. The seasonal evolution of H2O mixing ratio vertical distribution reveals its strong dynamism, especially during southern spring. There are significant discrepancies with the predictions of the General Circulation Model developed at the Laboratoire de Météorologie Dynamique (LMD-GCM). The LMD-GCM underestimates the water vapor content in the middle atmosphere. The measured profiles also exhibit often abrupt temporal variations and a greater variety of shapes, with the frequent presence of detached layers. We believe that the model underestimates the strength of the coupling between water vapor and aerosols, whose slant optical depth profile is obtained by SPICAM simultaneously with H2O. The SPICAM measurements can be grouped according to the mutual behavior of the two profiles. Individual features are often related too. The presence of water supersaturation and of correlated aerosol–water detached layers highlights the role of water ice clouds as a favorable location for the dust–water coupling. The water vapor vertical distribution is more reactive than expected to regional perturbations, which can propagate rapidly through the atmosphere, create abrupt water vapor and aerosol upsurges and influence the large-scale vertical evolution of these two constituents. This phenomenon has been observed thrice during MY29. The martian annual water cycle revealed by the SPICAM profiles exhibits a different behavior with respect to nadir observations. This result suggests a generally weak connection between the upper atmosphere and the lower atmospheric layers, to whom the nadir measurements are most sensitive and that are not resolved by SPICAM occultations, and hints at a significant influence of surface-atmosphere interactions on the water cycle.

Dosage de la 25OH D : enquête descriptive et rétrospective de 627 dosages pendant l’hiver 2010–2011 dans un centre hospitalier du Nord de la France

Intensities of the spectral lines in the fundamental bands of D35Cl and DF were calculated using the semi-empirical dipole moment functions derived from the most accurate and precise measurements of intensities of the ro-vibrational lines of H35Cl and HF. Values obtained in this way for the deuterated species are superior to any available measured or calculated data to date.Our study of the D/H ratios in H2O, HCl, and HF on Venus is based on spatially-resolved high-resolution spectroscopy using the CSHELL spectrograph at NASA IRTF. Search for DF on Venus using its R5 (1-0) line at 3024.054 cm−1 results in a DF mixing ratio of 0.23 ± 0.11 ppb that corresponds to (D/H)HF = 420 ± 200 times that in the Standard Mean Ocean Water (SMOW). H2O abundances on Venus were retrieved using lines at 3022.366 and 3025.761 cm−1 that were observed at an exceptionally low overhead telluric water abundance of 0.3 pr. mm. The measured H2O mixing ratios at 74 km vary insignificantly between 55°S and 55°N with a mean value of 3.2 ppm. When compared with simultaneous observations of HDO near 2722 cm−1, this results in (D/H)H2O = 95 ± 15 times SMOW. Reanalysis of the observation of the D35Cl R4 (1-0) line at 2141.540 cm−1 (Krasnopolsky, V.A. [2012b]. Icarus 219, 244–249) using the improved line strength and more thorough averaging of the spectra gives (D/H)HCl = 190 ± 50 times SMOW.The similarity of the measured (D/H)H2O = 95 ± 15 at 74 km with 120 ± 40 observed by De Bergh et al. (De Bergh, C., Bezard, B., Owen, T., Crisp, D., Maillard, J.P., Lutz, B.L. [1991]. Science 251, 547–549) below the clouds favors the constant (D/H)H2O from the surface to the mesosphere, in accord with the prediction by theory. D/H ≈ 100 removes a difference of a factor of 2 between H2O abundances in the observations by Krasnopolsky (Krasnopolsky, V.A. [2010b]. Icarus 209, 314–322) and the Venus Express nadir observations (Cottini, V., Ignatiev, N.I., Piccioni, G., Drossart, P., Grassi, D., Markiewicz, W.J. [2012]. Icarus 217, 561–569). Equivalent widths of the HDO and H2O lines are similar in our observations; therefore some errors cancel out in their ratios. Photochemistry of HCl in the mesosphere tends to enrich D in HCl and deplete it in H2O. This may be an explanation of the twofold difference between the observed D/H in HCl and H2O.An alternative explanation is based on (D/H)H2O ≈ 200 observed in the mesosphere by Bjoraker et al. (Bjoraker, G.L., Larson, H.P., Mumma, M.J., Timmermann, R., Montani, J.L. [1992]. Bull. Am. Astron. Soc. 24, 995) and Fedorova et al. (Fedorova, A. et al. J. Geophys. Res. 113, E00B22). This means an effective exchange of D between H2O and HCl and almost equal D/H in both species. However, this requires a twofold increase in D/H from the lower atmosphere to the mesosphere. This increase is not supported by theory; furthermore, condensation processes usually deplete D/H above the clouds.Photochemistry of HF has not been studied; it proceeds mostly in the lower thermosphere, and D/H in HF may be very different from that in H2O. Overall, the observational data on D/H in all hydrogen-bearing species on Venus are helpful to solve the problem of deuterium fractionation on Venus.

HDO and SO2thermal mapping on Venus: evidence for strong SO2 variability

We have been using the TEXES high-resolution imaging spectrometer at the NASA Infrared Telescope Facility to map sulfur dioxide and deuterated water over the disk of Venus. Observations took place on January 10–12, 2012. The diameter of Venus was 13 arcsec, with an illumination factor of 80%. Data were recorded in the 1344–1370 cm −1 range (around 7.35 μm) with a spectral resolving power of 80 000 and a spatial resolution of about 1.5 arcsec. In this spectral range, the emission of Venus comes from above the cloud top (z = 60–80 km). Four HDO lines and tens of SO2 lines have been identified in our spectra. Mixing ratios have been estimated from HDO/CO2 and SO2/CO2 line depth ratios, using weak neighboring transitions of comparable depths. The HDO maps, recorded on Jan. 10 and Jan. 12, are globally uniform with no significant variation between the two dates. A slight enhancement of the HDO mixing ratio toward the limb might be interpreted as a possible increase of the D/H ratio with height above the cloud level. The mean H2O mixing ratio is found to be 1.5 +/−0.75 ppm, assuming a D/H ratio of 0.0312 (i.e. 200 times the terrestrial value) over the cloud deck. The SO2 maps, recorded each night from Jan. 10 to Jan. 12, show strong variations over the disk of Venus, by a factor as high as 5 to 10. In addition, the position of the maximum SO2 mixing ratio strongly varies on a timescale of 24 h. The maximum SO2 mixing ratio ranges between 75 +/−25 ppb and 125 +/−50 ppb between Jan. 10 and Jan. 12. The high variability of sulfur dioxide is probably a consequence of its very short photochemical lifetime.

Gravity wave events from mesoscale simulations, compared to polar stratospheric clouds observed from spaceborne lidar over the Antarctic Peninsula

We compare Gravity Waves (GW) and Polar Stratospheric Clouds (PSC) above the Antarctic Peninsula for winters (June to September) between 2006 and 2010. GW activity is inferred from stratospheric temperature and vertical winds from the Weather and Research Forecast mesoscale model (WRF), and documented as a function of time and geography for the studied period. Significant GW activity affects 36% of days and follows the Peninsula orography closely. Volumes of PSC, composed of ice and Nitric Acid Trihydrate (NAT), are retrieved using observations from the spaceborne lidar CALIOP (Cloud‐Aerosol Lidar with Orthogonal Polarization). They are documented against GW activity as a function of time and longitude. Sixty‐three percent of ice PSC are observed during GW events, when the average volume of PSC per profile doubles. Maximum ice PSC volumes are seen directly over the Peninsula (65°W), while maximum NAT PSC volumes appear downstream further East (∼35°W). Effects of GW events on NAT PSC are felt as far East as 40°E. Our results support the importance of gravity waves as a major mechanism driving the evolution of ice PSC in the area, but the effects on NAT PSC are harder to detect. After a GW event ends, volumes of ice PSC get back to their usual levels in less than 24 h, while this process takes more than 48 h for NAT PSC. Daily profiles of H2O and HNO3 mixing ratios, retrieved from MLS observations, are used to derive ice and NAT frost points with altitude and time. Combining these frost points with modeled stratospheric temperatures, the volumes of air able to support ice and NAT crystals are quantified and compared with PSC volumes. Correlation is high for ice crystals, but not for NAT, consistent with their much slower nucleation mechanisms. Observations of ice PSC over the domain are followed by a strong increase (+50–100%) in NAT PSC formation efficiency 2 to 6 h later. This increase is followed by a steep drop (6–10 h later) and a longer period of slow decline (10–24 h later), at the end of which the NAT PSC formation efficiency is less than half its initial value. The fact that these effects tend to cancel each other out, coupled to the important lag in NAT PSC reaction to GW activity, suggest why it is especially difficult to quantify how GW activity impacts NAT PSC cover.