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. 2015 May 27;115(10):4497-541.
doi: 10.1021/cr500501m. Epub 2015 Mar 9.

The mesosphere and metals: chemistry and changes

John M C Plane  1 , Wuhu Feng  1 , Erin C M Dawkins  1
Affiliations

The mesosphere and metals: chemistry and changes

John M C Plane et al. Chem Rev. .
No abstract available

PubMed Disclaimer

Figures

Figure 1
Figure 1
Temperature (K) as a function of latitude and height in the MLT for January (left panel) and July (right panel) (averaged from 2004 to 2011). Also plotted are wind vectors (m s–1) which combine the meridional wind v with the vertical wind w (×500). Output from the Whole Atmosphere Community Climate Model.
Figure 2
Figure 2
Energy balance in the MLT: roughly equal inputs of energy from absorption of solar energy by O2 and O3 and breaking gravity waves are balanced by radiative loss principally through 15 μm emission of CO2.
Figure 3
Figure 3
Zonally averaged temperature (K) at 87 km as a function of latitude and month. Output from the Whole Atmosphere Community Climate Model.
Figure 4
Figure 4
Diurnal variation as a function of the height of the (a) O density (1010 atom cm–3), (b) H density (107 atom cm–3), and (c) O3 density (109 molecules cm–3) for October at Kühlungsborn, Germany (54° N, 12° E) (averaged from 2004 to 2011). Output from the Whole Atmosphere Community Climate Model.
Figure 5
Figure 5
Atomic O measurements made by rocket-borne resonance fluorescence instruments during summer in Northern Sweden (67.9° N). Adapted with permission from ref (10). Copyright 2005 Copernicus Publications on behalf of the European Geosciences Union.
Figure 6
Figure 6
Seasonal variation as a function of the height of the zonally averaged (a) NO density (108 molecules cm–3), (b) H2O density (107 molecules cm–3), and (c) H density (107 atom cm–3) at 54° N (averaged from 2004 to 2011). Output from the Whole Atmosphere Community Climate Model.
Figure 7
Figure 7
Structure and trends in the Earth’s atmosphere. The atmospheric layers on the right are defined by the temperature profile (solid line, bottom abscissa). The ionospheric layers on the left are defined by the electron density profile (broken line, top abscissa). Arrows denote the direction of observed changes in the past 3–4 decades: red, warming; blue, cooling; green, no overall temperature change; black, changes in the maximum electron density (horizontal) and the height of ionospheric layers (vertical). Adapted with permission from ref (22). Copyright 2006 American Association for the Advancement of Science.
Figure 8
Figure 8
Annual mean long-term temperature trends (K decade–1) in the mesosphere over the tropical latitudes. The rocketsonde trends of the 1970s and 1980s are compared with the trend obtained during the past two decades using satellite and lidar data (see the text for further details). The horizontal line shading represents roughly the range of trends as revealed during the past two decades. Reprinted with permission from ref (21). Copyright 2011 John Wiley & Sons, Inc.
Figure 9
Figure 9
Comparison of the seasonal PMC frequency of occurrence measured by SBUV radiometers by latitude band and the fit to a linear regression in time and solar activity. The error bars are the confidence limits in the individual seasonal mean values based on counting statistics, which do not reflect other factors such as interannual variability in large-scale dynamics. Reprinted with permission from ref (76). Copyright 2009 John Wiley & Sons, Inc.
Figure 10
Figure 10
Schematic diagrams of the chemistry of Na (left panel) and Fe (right panel) in the mesosphere and lower thermosphere.
Figure 11
Figure 11
Map showing the locations (red stars) of ground-based lidar observations published since 2004. The box attached to each location indicates the metals that have been measured and a footnote which lists the location and a recent reference: a, South Pole; b, Syowa, Antarctica; c, Davis, Antarctica; d, McMurdo, Antarctica; e, Rothera, Antarctica; f, Cerra Pachon, Chile; g, São José dos Campos, Brazil; h, Kototabang, Indonesia; i, Gadanki, India; j, Arecibo, Puerto Rico; k, Maui, HI; l, Hefei, China; m, Wuhan, China; n, Uji, Japan; o, Albuquerque, NM; p, Beijing; q, Boulder, CO; r, Ft. Collins, CO; s, Vancouver, Canada; t, Kühlungsborn, Germany; u, Poker Flat, AK; v, Sondrestrom, Greenland; w, Andøya, Norway; x, Tromsø, Norway; y, Spitsbergen, Norway.
Figure 12
Figure 12
Seasonal variation of the monthly mean Fe concentration (103 cm–3) at Wuhan, China (30° N) (a, lidar measurements; b, WACCM-Fe simulation) and at the South Pole (c, lidar measurements; d, WACCM-Fe simulation). Adapted with permission from ref (130). Copyright 2013 John Wiley & Sons, Inc.
Figure 13
Figure 13
Removal of metal atoms in the presence of NLC ice particles. (a) Simultaneous observations of the atomic Fe density and NLC backscatter signal at the South Pole on Jan 19, 2000, made with an Fe Boltzmann lidar operating at 372 and 374 nm, respectively. The PMC backscatter signal is expressed as equivalent Fe atoms per cubic centimeter for comparison with the atomic Fe resonance fluorescence signal. Adapted with permission from ref (134). Copyright 2004 American Association for the Advancement of Science. (b) Comparison of K profiles measured by lidar at Spitsbergen, Norway (79° N), with a 1-D model for early May (pre-NLC seasons, gray lines) and July (peak of the NLC season, black lines). The monthly data are averaged over 3 years (2001–2003). Adapted with permission from ref (138). Copyright 2007 John Wiley & Sons, Inc.
Figure 14
Figure 14
Fe Boltzmann lidar measurements at McMurdo, Antarctica (78° S), on May 28, 2011: (a) contour of thermospheric Fe densities from 110 to 155 km, showing fast gravity waves in the thermosphere; (b) contour of Fe temperatures from 75 to 115 km, showing waves in the MLT region; (c) vertical profile of temperatures for 1 h of integration around 15 UT (universal time). The temperature errors plotted as horizontal bars are less than 5 K below 110 km. Rayleigh lidar temperatures are plotted below 70 km. The MSIS00 model is a standard semiempirical atmospheric model. Reprinted with permission from ref (114). Copyright 2011 John Wiley & Sons, Inc.
Figure 15
Figure 15
Na and Fe density profiles measured by lidar on May 18–19, 2006, at Wuhan, China (30° N). The black curves show the point at which the high-altitude Nas peak density reached its maximum value. The blue dashed curves are the mean layer profiles during that night. Note that the Fes layer had a peak density much larger than that of the main Fe layer, while the Nas layer was slightly smaller in peak density than the main Na layer. Reprinted with permission from ref (145). Copyright 2010 Elsevier.
Figure 16
Figure 16
Annual mean profiles of the dynamical (blue), chemical (green), and eddy (red) transport coefficients for atomic Na measured at the Starfire Optical Range (35° N). Reprinted with permission from ref (170). Copyright 2010 John Wiley & Sons, Inc.
Figure 17
Figure 17
Fe lidar measurements between 70 and 120 km, recorded over a period of 30 h at the ALOMAR observatory, Norway (69° N). Note the appearance of Fe between 70 and 78 km when the mesosphere is sunlit (solar elevation angle >−9°). Provided courtesy of J. Höffner (Leibniz-Institute of Atmospheric Physics (IAP), Kühlungsborn, Germany).
Figure 18
Figure 18
Na column abundance (109 atoms cm–2) as a function of latitude and month: (a) a Na reference atmosphere derived mostly from observations using the Na d line at 590 nm in the dayglow; (b) WACCM-Na model results averaged from 2004 to 2011.
Figure 19
Figure 19
K column abundance (107 atoms cm–2) as a function of latitude and month: (a) observations using the K d1 line at 769.9 nm in the dayglow; (b) WACCM-K model results, averaged from 2004 to 2011.
Figure 20
Figure 20
Mg+ column abundance (109 atoms cm–2) as a function of latitude and month: (a) observations using the Mg+ line at 279 nm in the dayglow; (b) WACCM-Mg model results, averaged from 2004 to 2011.
Figure 21
Figure 21
Nightglow spectrum (light gray line) between 500 and 700 nm recorded on the ESI spectrometer on the Keck II telescope in Mauna Kea, HI. The spectrometer has a resolution (λ/Δ) of 7000 and a wavelength accuracy of 0.005 Å. The red line is a laboratory spectrum of the FeO “orange arc” emission bands, red-shifted by 5 nm, which may indicate different vibrational development of the excited state(s) of FeO involved in the emission.
Figure 22
Figure 22
(a) Histogram of the occurrence frequency of Na d line ratio measurements. A total of 706 measurements were made between Oct 7 and Nov 19, 2007. The solid line is a fitted three-parameter Gaussian. (b) Correlation diagram for the electronic potential energy surfaces connecting the reactants NaO(A) + O and NaO(X) + O with the products Na + O2, through the NaO2 intermediate. Quartet surfaces have been omitted for clarity; these are highly repulsive states which do not influence the electronic nature of the products. (c) Laboratory study of the dependence of RD on the ratio [O]/[O2]. The experimental data (solid points) are from Slanger et al. The solid line is a fit using the reaction scheme R38–R41. Adapted with permission from ref (198). Copyright 2012 Elsevier.
Figure 23
Figure 23
Rocket-borne study of the Na layer and charged MSPs. (a) Comparison of the atomic O profile measured by the NEMI instrument on the HotPay 2 rocket payload, with the Na density measured by the ground-based ALOMAR Na lidar 5 min before the rocket launch. The payload passed within 2.58 km of the lidar at an altitude of 90 km. (b) Comparison of the profiles of positive ions and electrons measured by an ion probe and Faraday rotation technique on HotPay 2, compared with the predictions of the plasma model (including a profile of negative ions). The removal of electrons between 80 and 90 km is due to the charging of MSPs. (c) Vertical profile of negatively charged aerosols measured by a dust detector on HotPay 2, compared with the prediction from the dusty plasma model. The difference between the measured positive ions and electrons in (b) is also shown. Adapted with permission from ref (125). Copyright 2014 Elsevier.
Figure 24
Figure 24
MSP work function. (a) Photoelectron currents measured during the flight of rocket payload ECOMA08. Black, green, and red symbols indicate the currents produced by the three different flashlamps (see the legend), where FX1162, FX1161, and FX1160 have cutoff wavelengths at 110, 190, and 225 nm, respectively. The dotted horizontal line marks the 2σ noise level of the unsmoothed measurements. (b) Optimized geometries of possible embryonic meteoric smoke particles: (FeOH)4, (MgOH)4, (FeSiO3)3, and (Mg2SiO4)4. The vertical ionization potentials are shown alongside each cluster. Note that these are 2 eV larger when the cluster contains a silicon atom. Adapted with permission from ref (215). Copyright 2012 Copernicus Publications on behalf of the European Geosciences Union.
Figure 25
Figure 25
Comparison of measured MSP extinction (labeled SOFIE/AIM) with values calculated using MSP number concentrations from the UMSLIMCAT model and Rayleigh theory for an assumed olivine (MgFeSiO4) composition and for the same pyroxene (Mg0.4Fe0.6SiO4) species used to fit the SOFIE data by Hervig et al. Also shown are the predicted MSP extinction profiles from the WACCM and CHEM2D models. Reprinted with permission from ref (279). Copyright 2012 Copernicus Publications on behalf of the European Geosciences Union.
Figure 26
Figure 26
(a) Schematic diagram of the pulsed laser photolysis/laser-induced fluorescence detection apparatus used to study the reactions of Mg+ ions. The metal precursor (magnesium acetyl acetonate) is placed in a tantalum boat in the side arm of the reactor. PMT = photomultiplier tube, MC = monochromator, PD = photodiode, and BE = beam expander. (b) Time-resolved profile of the LIF signal obtained by pumping the Mg+(32P1)–Mg+(31S0) transition at 279.6 nm and monitoring emission at the same wavelength, following the pulsed photolysis at 193.3 nm of magnesium acetyl acetonate. The solid line is a fit to the form A exp(−k′t).
Figure 27
Figure 27
Schematic diagram of a fast flow tube apparatus used to study the reactions of neutral Ca (probed by LIF at 422.7 nm) and CaO (probed by LIF at 385.9 nm). P = photomultiplier tube. I1, I2, and I3 are reagent inlets.
Figure 28
Figure 28
Photoionization cross-section of Na atoms adsorbed on ice (black points and line), compared with gas-phase Na atoms (red line). The blue line is the solar photon flux (right-hand ordinate).
Figure 29
Figure 29
(a) Experimental system used for the photochemical generation, detection, capture and optical extinction measurements of MSP mimics. (b) Transmission electron microscopy images and an electron diffraction image taken from the indicated area within a smoke aggregate formed following the irradiation of a mixture of Fe(CO)5, O3/O2, and tetraethyl orthosilicate. Adapted with permission from ref (201). Copyright 2006 Elsevier.
Figure 30
Figure 30
Ablation/sputtering profiles of individual elements from a 5 μg meteoroid entering the atmosphere at 20 km s–1 and at 37° to the zenith. The particle temperature is shown with the solid black line, referenced to the top abscissa. Adapted with permission from ref (96). Copyright 2008 Copernicus Publications on behalf of the European Geosciences Union.
Figure 31
Figure 31
An observed meteor with the following best fit parameters: initial velocity 36 km s–1; entry angle 1° (to zenith); mass 10–8 kg; density 3500 kg m–3. (a) Meteor range-time intensity, measured with the 430 MHz Arecibo radar. (b) Modeled (line) and observed (tilted squares) meteor altitude–velocity profile. (c) Modeled (black) and observed (red) meteor signal-to-noise ratio. (d) Modeled meteor radar cross-section. (e) Ablation profiles of the main elements (bottom axis) and total amount of electrons produced (upper axis), predicted by CABMOD. The horizontal line across the plots shows that the observed enhancement in SNR is due to the rapid ablation of the alkali metals Na and K. Reprinted with permission from ref (261). Copyright 2009 John Wiley & Sons, Inc.
Figure 32
Figure 32
(a) Meteoric ablation flux of Fe (cm–2 s–1) as a function of latitude and season. (b) Global annual mean Fe injection rate (cm–3 s–1) as a function of height. Adapted with permission from ref (130). Copyright 2013 John Wiley & Sons, Inc.
Figure 33
Figure 33
Three days of WACCM-Fe model output sampled every 30 min for Urbana from July 1, 2005: (a) temperature (K); (b) Fe mixing ratio (pptv); (c) perturbation in temperature (difference from the 3-day average); (d) perturbation in Fe mixing ratio. The time in the plot is universal time (UT). Local time = UT – 6 h. Adapted with permission from ref (130). Copyright 2013 John Wiley & Sons, Inc.
Figure 34
Figure 34
WACCM total column Na (cm–2) at 0000 UT on Jan 22 and Feb 6, 2009. A major sudden stratospheric warming event occurred on Jan 24. Reprinted with permission from ref (188). Copyright 2013 John Wiley & Sons, Inc.
Figure 35
Figure 35
Zonal average plots for January (top) and July (bottom) of the MSP concentration, mass density, and effective radius for the control simulation. The data are an average of the last 7 years of a 10 year simulation using WACCM coupled to the CARMA aerosol microphysics model. The effective radius is calculated as the ratio of the third and second moments of the dust size distribution. Reprinted with permission from ref (278). Copyright 2008 John Wiley & Sons, Inc.
Figure 36
Figure 36
Map of the annual mean Fe deposition rate (μmol of Fe m–2 year–1) of mesospheric Fe from MSPs. Reprinted with permission from ref (232). Copyright 2013 John Wiley & Sons, Inc.
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References

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