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by: Joannie Braun


Marketplace > Texas A&M University > Geoscience > GEOS 489 > SPTP INTRNL POLAR YEAR
Joannie Braun
Texas A&M
GPA 3.85


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Class Notes
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This 34 page Class Notes was uploaded by Joannie Braun on Wednesday October 21, 2015. The Class Notes belongs to GEOS 489 at Texas A&M University taught by Staff in Fall. Since its upload, it has received 24 views. For similar materials see /class/225936/geos-489-texas-a-m-university in Geoscience at Texas A&M University.




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Date Created: 10/21/15
Review Global Water Cycle Largest reservoir Oceans Most other water in Ice Sheets and Ground Water Sea level controlled by amount of continental ice and ocean temperature Humans rely on small amounts of freshwater Water crises draughts political common Atmospheric Water vapor and clouds control climate No obvious trends in atmospheric water vapor or cloudiness in last decade however SST and tropospheric T correlate with water vapor Anthropogenic Aerosols affect climate OXIDATION STATES OF SULFUR S has 6 electrons in valence shell Igt oxidation states from 2 to 6 l Increasing oxidation number oxidation reactions I 2 4 6 FeS2 SO2 HZSO4 Pyrite Sulfur dioxide Sulfuric acid H28 804239 Hydrogen sulfide Sulfate CH3ZS Dimethylsulfide DMS CS2 Carbon disul de COS Carbonyl sulfide Decreasing oxidation number reduction reactions I Inorganic and Organic forms of sulfur sulfate SO42quot sulfite SO32quot thiosulfate 82032quot sulfide 8239 rare forms such as S4062 80 0 amino acidscgtproteins cystine cysteine methionine glutathione sulfate esters 0 others such as penicillin lipoic acid Sulfur SO deposits on Mount Etna in Italy log moles 600 700 800 900 Temperature quotC Figure 8 Multicomponent chemical equilibria in gasisolid liquid systems within Mt St Helens source Symonds and Reed 1993 Pinatubo 10000 ML Si Holens Fernandina Rabuul N yamuragira 1000 Nyamumgira Ny amuragira Cerro Axul Nyamuragim Hekla Sulfur dioxide kt Redoubt 100 Nyamumgim Ye a Figure 9 Volcanic sulfur emissions as established by the TOMS emission group httpskyelgsfcnasagovi Relative Global Sulfur Budget Atmosphere Total 8 1 Biogenic Gases a Combusllon 25 Sea Spray 12 Ram and Dry Biogenlc Gases 13 Deposition 63 Volcanlsm 3 Rivers 36 Ocean Sulfate 390000000 000 yr 39 Sediments Red 3 800000000 OxidS 2000000 000 T Global Sulfur Reservoirs and Turnover Times Reservoir 1012 g S Turnover Time Lithosphere 2000000000 108 y Oceans 300000000 106 y Sediments 30000000 106 y Soils 30000 103 y Lakes 300 3 y Marine Biota 30 1 y Atmosphere 48 825 1 Global Sulfur Cycle WWW Emmamm Willa W 39 wiwmwmgam m 1ampme W m mu m gym lt ltm y mg m Global Sulfur Cycle all values in 1012 g Syr Wet and dry deposition 84 10 20 93 22 Bio genie gases Dust 39 ivers Human mining 149 and extraction 72 Natural weathering and erosion Transport to sea 81 20 Transport to land 258 144 43 10 f x 39 A DCPO Sea Bio enic SitiOH salt lses Pyrite 96 39 Hydrotherma sulfides Important Scontaining trace gases abundance source sink COS 500 ppt ocean land DMS 100 ppt ocean land HZS lt500 ppt anoxic enV oxid CS2 200 ppt oceananthro oxid 802 lt 1 ppb anthropog oxid HZSO4 stratospheric clouds COS precip Scontaining trace gas sources and sinks modified from P Hobbs Introduction to Atmospheric Chemistry Numbers in are abundance in Tg S numbers on arrows are uxes in Tg S per year 24 oxidation and 7 loss to the stratosphere l i 05 T 01 SO 239 V H s 4 80 so CS 0391 gt cos 2 12 2 O f 015 v A 02 39 lt005 03 005 V j V A v Soils and 25 Anoxic Plant and Dry and Wet Anthropogenlc a 363 marshlands Deposition BB FF combust V It A 3011s 8011 Uptake 40 320 7 Biogenic processes Dry Deposition Continents Oceans Continents Sulfur transformations on land D orginosul des SOznndOCS spouuon f F2 Wet Dry Ferzilizcr Manure H25 DMS and i 50 so7 5042 othersul des W and OCS w A11 K on Organic Streams Figure 14 The cycle of sulfur in the soil abbreviations i immobilization m mineralization 3 plant uptake L root exudation and turnover so oxidation l leaching sr139cduction after Havlin er 1 l999 Sulfur budget for the oceans all values in 1012 g Syr DMS Other reduced 40 gases lt 6 Precipitation 502 amp dry fall 11 247 Sea salt 144 Rivers 1 3 1 Hyd rother al Pyrite 96 39 From Schlesinger WH 1997 Salt Brackish quotI Mieregram sulfur 111 h Figure 12 The relative emuuute of reduced sulfur species released frum various water bodies with the tetal emissien rate shuwn as histugrame source DeLeuue e mi 2002 Potential Climate Feedbacks of Oceanic DMS Emissions aka CLAW hypothesis Reference Charlson Lovelock Andreae Warren 1987 Oceanic phytoplankton atmospheric sulfur cloud albedo and climate Nature 326 655661 Radiation Mtge Clau albedo l Cloud condensation Glmm39 minimum nunleu l i Sulfam unrng l i I 1 4 Climate luadbucks so LJ J ansphgra DMS quot Ocean Marine mallow Phytoplunk ran 1 4 Dr abundance and 39 specialism Development of Anthropogenic Sulfur Emissions 19 Syeuv s cm and HWSCNIerHBBO a Km V956 a x Robinson and Rama new V850 70 80 9019000 20 5o 40 53 n 70 RC Vent Note that these numbers exceed 100 Tg S The current estimate slide 11 is 75 Tg S a major improvement due to smoke stack emissions reductions Pemem Global Su lfur Emissions 90 5a 23 o Lamune lAmhropogenlc I Marine I Terrestrial a Volranlv I Biomass Burning GLOBAL SULFUR EMISSION TO THE ATMOSPHERE 1990 annual mean Natyra Emi ssio n 1990 Anthmp oge nic Emission 1990 w GON SUN 0 305 seam 505 905 903 180 WZOW 60W 60E 120E 180 130 120W 50W 0 605 120E 150 0 20 100 5110 2003 25297 Chin et al 2000 Review Atmospheric oasphase chemistry Radical Chain Chemistry Oxidation Initiation via photolysis such as 03 Most important cleansing agent 39OH Radical Most important OH radical reaction partners methane CH4 and carbon monoxide CO OH lifetime 1 s l Other cleansing mechanisms Reactions with other oxidants such as ozone Wet and dry deposition Ultimate Products 002 and solubles Figure 5 Ranges ofequivalenc diameters for some types ofaerosol and hydrosol particles For perspec tive the diameters of molecules are also shown L nm 0 A Particle Radius pm J 00L L 01 00L T 3 Molecules VIIIIIIIIIIIIIIIIIIIIIIIA Metallurgical fume Colloids VIIIIIIIIIlIIIIIIIIIlIl Viruses VIIIIIIIA Combustion nuclei Accum mode particles Bacteria Windblown dust Sea salt VIII Algae Pollen VIIIIIIIA Ta Global 30111103 of Atmospheric Aerosols in megatonnes per year Adapted by L Barrie Animal SOHI39H S Total Emissions Emissions D lt 25 nu D lt 1 11m Munnmde Pl39inlillj ludns1 rial lust 40 130 2065 Snot 10730 1030 Binmuss burning 507190 50190 Vimllilowu 11th 8 20 140 leis Particle Conversion of 022 Smelterspower plants 120480 1207180 NOR Am uspmver plants 20 50 510 Anthropogenic V0 3 525 525 Total Mamuado Sources 10654325 565640 Natural Primary Vimllllowu lust 10003000 265 Forest res 3 150 2775 Sl il Salt 1000710000 20100 Volcanoes 410000 047100 Orgauivs 2650 gt GasParrirle Conversion of DMS 1128 60110 607110 Vulcanjc 502 1030 1030 Biogonic NOx 1040 10 40 Bingenic VOCS 40200 40 200 to NHr salts 811270 807270 Total Natural Sources 13633550 39771390 Aerosol mixing ratio particles mg alrquot 1nnn I I I I I I I I I I I I I I I I 1 00 3939 Q 3939 39 393 a 39 39 I 10 39 393 quot o 39 I39m 039 o quot n 39 I o u v N c 3 5 a S a E g g g 3 39U 8 8 8 93 i E L a a 11 x lt gt 3 z 91 w a 1 LL I l Lquot l l I I 3 0 I I z 1972 1974 1976 1973 1980 1982 1984 1986 Maximum stratospheric aerosol mixing ratios for particles gt03 mm from balloon data collected until 1986 Laramie Wyoming USA Included are the dates of major volcanic eruptions Hofmann et al Geophysical Research Letters 13 614617 1987 H t Chemical Conversion of Gases to Low vapor Volatility Vapors Condensation Coagulation Chain Aggregates Homogeneous Nucleation Wind Blown Dusl Emissions Sea Spray Coagulation Volcanos Cuagulatmn Plant Panicles Coagulation 0002 001 2 10 100 01 l PARTICLE DIAMETER urn H Jlf 39 12l l 2 Fine Panicles Accumulaxion Mechanically General3d ange Aerosol Flange Coarse Parllcles Figure 54 Motions ofwind driven soil particles at Creeping motion of a particle moving as a consequence of a wind speed slightly greater than threshold b A coarse particle liftedinto the air by turbulent air fluctuations c A particle collision with the surface followed by breaking off of smaller particles that were encrus ted on the colliding particle39s surface cl A particle collision fol lowed by splashing of the soil Adapted with permission from D Gillette Major contributions of natural primary continental aero sols Source mechanism Annar if the New York Amdemy Stiemer 338 548 358 Copyright 1980 by New York Academy of Sciences Deposition velocity cm 5 1 Particle Deposition SlimModel 10 39 39 396 I 1 I 01 gure 57 The deposition velocity of particles to grass Field data for a number of experiments o by different research groups are shown some by data points and I I tted lines some by hatched areas 03901 Courtesy of A Garland Atomic 01 1 10 Energy Research Establishment Aerodynamic diameter pm LENGTH MEASURE pm 104 103 102 101 o 102 1o3 lllllllIlllllI Visible light uy quotlite i l N a Fa infrared infrared Comparisons lt Gas gtl 4gtHlt7 k Solar kaerrestriaI pl molecules Mean lree radiation radiation 02 66 002 pathlength STP N2 8 382 Visibility to naked eye in darklield gtlt in brightlield 2 Nomenclature Production and removal Colloid chemistry mggeeig Colloidal disperse gtllti Coarse disperse 7 Cloud k Clouds Fog pk yH Ea CIOUd Physlcs39 k condensation nuclei HI MiSl Drizzle Sell science r e riclay H t Air chemistry Condensation nuclei Large Aerosol Aitken particles 5395quot pa 39des O S particles physics Nucleation Accumulation I mo e me e llt gt Rayleigh r r Mie particles Small ions 14 Large ions gtUItralarge ions tmospheric optics Air elec ricity Gastoparticie conversion Wet removal Dry removal Coagulation gtllt gtlt Integral properties w 239 mi 22 227 quot395 9 physical properties in genera bulk properties Total numberakslg laac39gk Total mass Electrical conductivity k gtI Turbidity Vis llity Ilt gtl Dry deposited mess ouection possible for anisokinetic conditions isokinetic conditions kiNuclei counter gtl lt Sedimentation H lmpacior Impinger Thermal preciplta ion gt lt Electrical precipitation gtI lt Centrifuge gt lt Dlll usion 44 l llters Amine nar hla munlar Review of atmospheric transport Timescales Ground to top of Boundary Layer 1 hour Ground to Tropopause 1 month Across the ITCZ 1 year Across the Tropopause 2 years Around the globe 2 weeks Processes Hadley Circulation Tropics Trade winds Baroclinic Disturbances midlatitudes Convection large scale and small scale LocalRegional Flows eg sea breeze 2229ng 3755 6lpeb Figure 225 Schematic of air ow with respect to midlatimde barocljuic disturbance from Palm n and Newton 1969 pressure hPa methanol ppb acetone ppb 855 860 865 870 0 2 4 6 8 10 1200 06 12 18 24 30 iiiiiiiiiiiiiiiiiiiiiiiiiiii 290 7 gt1 2 4 day of year 2000 00 10 20 30 40 10 5 0 5 105 0 5 1015 20 precipitation mm dewpoint deg C air temperature deg C Fundamentals of Atmospheric Chemistry EnergyInput via UVVis radiation eg photolysis Mass input from surface emissions andor insiz u eg CO both emitted and formed in atmosphere Centered on ozone O3 cycling O3 chemistry at the heart of almost all reactions Radical chemistry unpaired electrons seeking for a match Thermodynamic opportunity but Kinetic Stability chain reactions lead to net reactions 20 HI 100 ALTITUDE km D o 0y 0 I r I I I I 10 quot 104 1039s 10395 10 7 10396 10 5 10quot 10393 10 2 IO391 1 MlXING RATIO 7 Figure 17 Typical vertical distribution of the concentration 0139 chemical constituents In the atmosphere Some lines are shown as dashes for clarity F11 CF01 and F12 CF 3913 Goody 1995 The ozone house budget I loss I production Chemical and Physical Sinks in the Atmosphere Chemical Reaction Oxidation Daytime OH most gases 03 some gases photolysis some gases Nighttime 03 or NO3 some gases Both dissolution in liquid phase and reaction few Physical Wet deposition Washoutrainout dissolution Dry deposition AdsorptionAbsorption gravitational settling impaction


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