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Earth System Science Exploring the Connections

by: Ian Davis

Earth System Science Exploring the Connections MEA 100

Marketplace > North Carolina State University > Marine Science > MEA 100 > Earth System Science Exploring the Connections
Ian Davis
GPA 3.87


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This 204 page Class Notes was uploaded by Ian Davis on Thursday October 15, 2015. The Class Notes belongs to MEA 100 at North Carolina State University taught by Staff in Fall. Since its upload, it has received 5 views. For similar materials see /class/223856/mea-100-north-carolina-state-university in Marine Science at North Carolina State University.

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Date Created: 10/15/15
The role of sulfur in the environment sulfur cycle sulfur resevoirs sulfur in fossil fuels acid rain The Sulfur Cycle The essential steps of the sulfur cycle are Mineralization of organic sulfur to the inorganic form hydrogen sulfide H28 Oxidation of sulfide and elemental sulfur S and related compounds to sulfate 8042 Reduction of sulfate to sulfide Microbial immobilization of the sulfur compounds and subsequent incorporation into the organic form of sulfur The Sulfur Cycle These are often termed as follows Assimilative sulfate reduction sulfur assimilation in which sulfate 8042 is reduced to organic sulfhydryl groups R SH by plants fungi and prokaryotes The oxidation states of sulfur are 6 in sulfate and 2 in R SH Desulfuration and Dissimilative sulfur reduction in which organic molecules containing sulfur can be desulfurated producing H28 Note the similarity to deamination Oxidation of hydrogen sul de produces elemental sulfur SO oxidation state 0 This reaction is done by the photosynthetic green and purple sulfur bacteria and some chemolithotrophs Further oxidation of elemental sulfur produces sulfate The Sulfur Cycle Sullates Jll Jn Eltlmsphere Dry delmltion crf su late and sulfur maxim Sulfur nimble 3an from combustion of furs39sll fuels and sul de metal was J l d PFEGMEIICI39I 39 a ram SHUle l 1 Flacluced sul39 riHES 4 m amadgsalmm Sulfur Reservoirs in Nature Reservoirs of sulfur atoms The largest physical reservoir is the Earth39s crust where sulfur is found in gypsum CaSO4 and pyrite FeS2 The largest reservoir of biologically useful sulfur is found in the ocean as sulfate anions 26 gL dissolved hydrogen sulfide gas and elemental sulfur Other reservoirs include Freshwater contains sulfate hydrogen sulfide and elemental sulfur Land contains sulfate Atmosphere contains sulfur oxide 802 and methane sulfonic acid CH3SO339 volcanic activity releases some hydrogen sulfide into the air Sulfur in Fossil Fuels Human impact on the sulfur cycle is primarily in the production of sulfur dioxide 802 from industry eg burning coal and the internal combustion engine Sulfur dioxide can precipitate onto surfaces where it can be oxidized to sulfate in the soil it is also toxic to some plants reduced to sulfide in the atmosphere or oxidized to sulfate in the atmosphere as sulfuric acid a principal component of acid rain 70 TgS per year in the form of SO2 comes from fossil fuel combustion and industry 28 TgS from wildfires 8 TgS per year from volcanoes Acid Rain Formation of sulfuric acid by radical chemistry In the gas phase sulfur dioxide is oxidized by reaction with the hydroxyl radical via a intermolecular reaction 802 OH gt HOSOZ which is followed by HOSOZ 02 gt H02 SO3 In the presence of water sulfur trioxide 803 is converted rapidly to sulfuric acid 8039 H20l gt HZSO4I httpwwwepagovacidraineffectssurfacewater html Chemistry in Cloud Droplets When clouds are present the loss rate of 802 is faster than can be explained by gas phase chemistry alone This is due to reactions in the liquid water droplets Hydrolysis Sulphur dioxide dissolves in water and then like carbon dioxide hydrolyses in a series of equilibrium reactions SO2 g H2O gt SOzH2O SOzH2O HHSO3 HSO339 9 H803239 Oxidation There are a large number of aqueous reactions that oxidize sulfur from SIV to SVl leading to the formation of sulphuric acid The most important oxidation reactions are with ozone hydrogen peroxide and oxygen reactions with oxygen are catalysed by iron and manganese in the cloud droplets Environmental Effects Water Both the lower pH and higher aluminum concentrations in surface water that occur as a result of acid rain can cause damage to fish and other aquatic animals At pHs lower than 5 most fish eggs will not hatch and lower pHs can kill adult fish As lakes become more acidic biodiversity is reduced Acid rain has eliminated insect life and some fish species including the brook trout in some Appalachian streams and creeks However there has been some debate on the extent to which acid rain contributes to lake acidity ie that many acid lakes may result primarily from characteristics of the surrounding watershed and not the rain itself The EPA39s website states quotOf the lakes and streams surveyed acid rain caused acidity in 75 percent of the acidic lakes and about 50 percent of the acidic streams Environmental Effects Soil Soil biology can be seriously damaged by acid rain Some tropical microbes can quickly consume acids but other microbes are unable to tolerate low pHs and are killed The enzymes of these microbes are denatured changed in shape so they no longer function by the acid The hydronium ions of acid rain also mobilize toxins and leach away essential nutrients and Minerals Acid rain can slow the growth of vulnerable forests and cause leaves and needles to turn brown and fall off High altitude forests are especially vulnerable as they are often surrounded by clouds and fog which are more acidic than rain Other plants can also be damaged by acid rain but the effect on food crops is minimized by the application of fertilizers to replace lost nutrients ln cultivated areas limestone may also be added to increase the ability of the soil to keep the pH stable but this tactic is largely unusable in the case of wilderness lands Effect of acid rain on a forest Jizera Mountains Czech Republic Technical Solutions In the United States many coalburning power plants use Flue gas desulfurization FGD to remove sulphurcontaining gases from their stack gases An example of FGD is the wet scrubber which is commonly used in the US and many other countries A wet scrubber is basically a reaction tower equipped with a fan that extracts hot smoke stack gases from a power plant into the tower Lime or limestone in slurry form is also injected into the tower to mix with the stack gases and combine with the sulphur dioxide present The calcium carbonate of the limestone produces pHneutral calcium sulfate that is physically removed from the scrubber That is the scrubber turns sulfur pollution into industrial sulfates In some areas the sulfates are sold to chemical companies as gypsum when the purity of calcium sulfate is high In others they are placed in landfill Scrubbing with base solution 802 is an acid gas and thus the typical sorbent slurries or other materials used to remove the 802 from the flue gases are alkaline The reaction taking place in wet scrubbing using a CaCO3 limestone slurry produces CaSO3 calcium sulfite and can be expressed as CaCO3 solid 02 gas gt CaSO3 solid CO2 gas When wet scrubbing with a CaOH2 lime slurry the reaction also produces CaSO3 calcium sulphite CaOH2 solid 02 gas gt CaSO3 solid H20 liquid A similar process is possible with magnesium hydroxide MgOH2 solid 02 gas gt MgSO3 solid H20 liquid Some FGD systems go a step further and oxidize the CaSO3 calcium sulphite to produce marketable CaSO4 2H2O gypsum CaSO3 solid 1202 gas 2H20 liquid gt CaSO4 2H20 solid Power plant in New Mexico before installation of flue gas scrubber Atmospheric Circulation Macroscopic variables P T Pressure is a force per unit area P FA The force arises from the change in momentum as particles hit an object and change direction Temperature derives from molecular motion M is molar mass Greater average velocity results in a higher temperature u IS the veIOCIty Mass and molar mass We can multiply the equation gRT M ltu2gt by the number of moles n to obtain 3 1 2 nRT nM ltu gt 2 2 If m is the mass and M is the molar of a particle then we can also write nM Nm N is the number of particles Mass and molar mass In other words nNA N where NA is Avagadro s number gnRT Nm ltu2gt Key points regarding the microscopic view The kinetic energy of a large number of individual particles is proportional to the temperature of the system As the system heats up we can picture the molecules moving more rapidly Pressure results from the net momentum transfer between the particles and wall of the container Pressure of a dense fluid For a dense fluid or a liquid such as water we can think of the pressure arising from the weight of the column of fluid above the point where the measurement is made The force is due to the mass of water m kg accelerated by gravity g 98 ms2 F m mhmh P amp 9 9 h A A Ah v pg where p is the density p mV The dependence of atomspheric pressure on altitude We can think of the atmosphere is a fluid but it is not dense Moreover unlike water the density of the atmosphere decreases with altitude Thus at high elevations both the pressure and the density are decreased To obtain the dependence of pressure on height h above the earth s surface we use the ideal gas law to define the density of an ideal gas The dependence of atomspheric pressure on altitude The density of an ideal gas is p mV nMV MPRT The dependence of pressure on elevation Is MP9 We need to collect variables of integration on the same side of the equation ELW P RTdh The barometric pressure formula Then we integrate assuming P01 at hO Isotherms We can plot the pressure as a function of the volume as shown below Each of the curves on the plot has a constant temperature Pressure P Volume V Partial pressure For any gas in a mixture of gases the partial pressure is defined as P where xj is the mole fraction of componentj and P is the total pressure The mole fraction is defined as 100 100 l i 90 90 Thermosphere 80 80 39 quotquotquotquotquotquotquotquotquotquotquotquotquotquotquotquotquotquotquotquot quotl A 70 A 70 E E e5 60 5 60 Mesosphere 8 50 a 50 quotg 40 3 40 E g Stratosphere 30 30 20 T 1O 10 Troposphere 0 I l l l l O i i l 10 4 1o 3 10 2 10 1 10 101 102 103 180 200 220 240 260 280 300 Pressure mbar Temperature K a b FIGURE 39 a How pressure varies with altitude in Earth s atmosphere b How temperature varies with altitude in Earth s at mosphere The different regions of the atmosphere determined by temperature regimes are labeled In the troposphere 015 km above the earth the abundance of gas decreases with height which causes a decrease in temperature with increasing altitude In the stratosphere 1550 km above the earth the amount of ozone a strong greenhouse gas increases with height which causes temperatures to rise with altitude Surface area receiving insolation Sun s rays Arrive parallel at Earth Copyright 2004 Pearson Prentice Hall Inc The same amount of radiation reaching the earth is spread over a greater area at higher latitudes than at the equator This differential heating causes temperature gradients on earth Energy South Latitude Absorbed solar energy Emitted infrared energy Copyright 2004 Pearson Prentice Hall Inc Because of the differential heating of the earth there is a net radiation surplus between the tropics and a net radiation deficit at higher latitudes Winds and ocean currents transfer the energy from low latitudes to high latitudes Uplift gt lt c lt I l I II Hadley cell A I Hadley cell l Subsidence Subsidence 12 km I I I I I I I l l I 1 quot4 e u yquot lTCZ Divergence Convergence Divergence l l 45 30 0 30 45 North Latitude a South High Low High pressure pressure pressure Atmospheric Circulation in Low Latitudes The Hadley Cell Air is rising at the equator and descending at the tropics 300 MS 1a39 200 and 80 and 2 quot we ever an 1 99 60775 1004 4S 4W59 4m 5mg 20 39 25 49 1 0 1 9 5aquot Under 25 Under 10 n in non 3000 KiLOMETERS MuDiFIED scours HOWLDGiNE gamma vrmecrioN Worldwide Atmospheric Precipitation Patterns iTCZ Polar front Polar front zone zone Surface High High High Low High High High presswe pressure low pressure pressure pressure low pressure l l l l l l I 90 60 30 0 30 60 90 Northern Hemisphere Southern Hemisphere Latitudels Copyright 2004 Pearson Prentice Hall Inc The NorthSouth Circulation in the Troposphere Stratosphere a m39mu y y nu y circulation circuiaiicn Latitudes where air rises ie the equator have more precipitation than evaporation Latitudes where air descends have more evaporation than precipitation more deserts and higher salinity The pressure gradients on the surface of the earth set up by rising and descending air masses 90 S Copyright 2004 Pearson Prentice Hall Inc a bi Copyright 2004 Pearson Prentice Hall Inc The Coriolis Effect to the right in the northern hemisphere and to the left south of the equator LOW HmH PRESSURE P Pressure Gradient Force C Coriolis Force VG Geostrophic Wind Copyright 2004 Pearson Prentice Hall Inc Geostrophic Winds Balance in Pressure Gradient Force and Coriolis Effect F gt lt olar high A Polar easterlies 600 Subpolar low iv t 1 7 l v aW lntertropical convergence zone gti Qv5 5O Subpolar low Polar easterlies 3O 3 Polar high Copyright 2004 Pearson Prentice Hall Inc Combining the pressure gradient force and the Coriolis effect produces the global wind patterns such as the trade winds and the westerlies FIGURE 49 Pressure a n n 0 an E E E E E E gradient determines wmd N 3 speed N 1 v V g g 9 2 9 g 2 Pressure gradient 21 On a weather radual pressure Steep pressure map 03 the closer spacing of 39 quot 39 gadiem isobars represents a steeper pressure gradient which produces a I strong winds wider spacing of Low isobars denotes a gradual pressure g pressure gradient which leads to light z r m winds LIGHT STRONG WINDS WINDS 39 quot n g a 1 15 2 2 llt if A iv 39 1 g f I quot 39 39 I vquot I 5 y aGradual 39 39 43w 3 pressure s i gnaw e 39 1 o zoo incomes Ls 39 9 I 07500 400KILOMETERS V I 8 b l The great the pressure gradient force the clos er together the isobars lines of equal pressure the stronger the winds A combination of pressure gradient force and the Coriolis effect cause the winds to blow along lines of equal pressure In the northern hemisphere circulation around a high pressure area is clockwise whereas circulation around a low pressure area is counterclockwise quotI39D u1n5a5xw1nns I 3 Global wind field Winds drive the surface ocean circulation a 1500 anoo Mlles lil P5918273645545372819099 F m U 1500 3000 Kilometers C 3 510152025303540455055600 C Copyright 2004 Pearson Prentice Hall Inc The annual range in global temperatures wintersummer December Solstice December 21 June Solstice June 21 g September Equinox September 22 The tilt of the earth on its rotational axis is responsible for the change in seasons Copyright 2004 Pearson Prentice Hall Inc Differential heating between the land and the ocean sets up a shoreward sea breeze during the day and an offshore land breeze at night an MD I6l1 Emuw 150 5 um my m I20 77 1 w 5 7 wcfiijv i 7 ran a7 m 77 m m 1snEuww1so mu m muMn 160 mow E E The Inter Tropical Convergence Zone ITCZ connects Iow Iatitude low pressure areas It moves seasonally as shown by these maps from January and July 1 4quot High pressure no a ricurn 39 39 o 1000 135 June July D 1000 2000 Miles December January 1 1 a 1 0 1000 2000 Kilometers w quot 2 0 1000 2000 Kilometers 1 60 100 i 50 100 39i39w Monsoon winds in the Indian Ocean n JuneJuly th SW winds from over the ocean bring rains to India whereas the NE winds in DecJan bring dry conditions Precipitation Atmosphere 99 X 1012m3year 3 0001 0013 x 1015m3 Evaporation L L 62 X 1012m3year Y5 Y5 D lt0 I 5 55 Egg Egg Land 82 2 2428 g X lt3 X 336 x 1015m3 UJ g v K N C0 C0 Runoff Oceans 37 x 1012m3year 97571 1350 gtlt 1015m3 b On land there is more rain than evaporation and the difference corresponds to riverine runoff Over the ocean there is more evaporation the precipitation Energy absorbed gt Sublimation Melting Evaporation A Solid Liquid Gas ice liquid water water vapor Freezing Condensation Deposition 4 Energy released Copyright 2004 Pearson Prentice Hall Inc Energy transfer corresponding to phase changes 60 55 50 i 7 45 s 40 7 35 730 a 725 7 720 a i 715 710 s 5 20 0 20 40 Temperature C 40 Copyright 2004 Pearson Prentice Hall Inc SATURATION VAPOR PRESSURE mb The water carrying capacity of the air depends on temperature Warmer air can hold more water at saturation If the air is not saturated with water at a given temperature we can speak of relative humidity For example if the carrying capacity of the air is 4 water at 298 K then the air holds only 2 water at 50 relative humidity ROV OEEEEE h Pressu re Change with COLD WARM 902M saw so39w E Q Height in the a Troposphere Note the differences between the equator and the artic due to temperature Copyright 2004 Pearson Prentice Hall Inc MEA 100 Introduction to Earth Systems This is a stealth course in Environmental Science We will emphasize a quantitative approach based on knowledge of both abiotic and biotic systems coursesncsuedulmea100lecl001l Introduction to Earth System Science MEA100 Lecture Lab Course Term QUIzzes Syllabus Syllabus m Proiect Lecture Dates May13 May14 May15 May16 May17 May18 In Class Lecture Topics Course Intro Systems Origin of Earth and Life Effects of Life on the Atmosphere Greenhouse Systematics The Carbon Cyce Global Warming Exam 1 Readings Ch 1amp2 10 Ch11 Ch3 Ch8 Ch 16 Ch 1210113816 May 22 May 23 May 26 May 27 May 28 Atmospheric Circulation Atmospheric Circulation Ocean Circulation Plate Tectonics LongTerm Climate Regulation Ch4 Ch4 Ch5 Ch7 Ch 12 Ch 45712 May 29 May 30 June 2 June 3 Biodiversity and History Pleistocene Glaciations ShortTerm Climate Variability Exam 2 ShortTerm Climate Variability Ozone Depletion Ch 913 Ch 14 Ch 15 Ch 17 June 4 Human Threats to Biodiversity Ch 18 Questions to Consider for Kyoto June 5 Summit June 6 Class Presentations Kyoto Summit June 9 Excursion I hope Ch 19 June 10 Climate Stability on Earth and Beyond June 11 Review Comprehensive Final Exam Introduction to Earth System Science MEA 100 Summer 2008 Instructor Dr Stefan Franzen Text The Earth System Lee R Kump James F Kasting and Robert G Crane Prentice Hall 2nd Ed 2004 Class Website httpcoursesncsuedumea100lec001 Lab Manual MEA 100L CoursePak Introduction to Earth System Science Spring 2007 MEA 100 Labs Internet Resources A Gateway to Earth System Science Resources Prentice Hall 3 Earth on the Internet A Field Guide for Geoscience Students Why Earth System Science The goal of Earth System Science is to obtain a scientific understanding of the entire Earth system on a global scale by describing how its component parts and their interactions have evolved how they function and how they may be expected to continue to evolve on all timescales The challenge to Earth System Science is to develop the capability to predict those changes that will occur in the next decade to century both naturally and in response to human activity NASA 1986 Course Objectives Develop a basic understanding of the major components and processes of the four primary Earth systems Recognize linkages between the Earth systems Develop an understanding of dynamic equilibrium and feedback loops between and among the Earth systems Deveop an insight for the anthropogenic influences on the Earth systems and Learn to use computer simulations to model behavior of the Earth systems Grading System The course will be graded using a A through F grading system We expect you to read the lab material BEFORE each lab session and to turn in the lab report before you leave each lab session This course will be scored on the basis of accumulated points 100 possible throughout the semester The lab is worth 20 of the course grade contributing 200 points to your total class score The inclass tests are worth 100 points each whereas the Term Project is worth 100 points During the course 5 quizzes valued at 20 points each will be given these should last only 10 minutes and will come from lecture and reading assignments The final comprehensive exam is worth 200 points During the inclass tests and the final exam a 5 x7 note card can be used by students to provide any reference material that they would like Test 1 100 Test 2 100 Test 3 100 Homework 100 Term Project 100 Quizzes 100 Final Exam 200 Lab 200 Total 1000 points Quiz 1 Earth System Science 1 When examining environmental conditions such as temperature and atmospheric gas abundance why is it important to specify the time scale being considered A So you can put the processes in chronological order B Because the conditions and associated processes change over different time scales yielding different results C It really doesn t matter because most conditions and processes are more or less constant over geologic time D Because the book said so 2 What event does the Big Bang theory explain A Eruption of Mount St Helens B The killing off of dinosaurs as a result of a meteorite impact C The origin of gun powder D The formation of the universe 3 What celestial body keeps the earth at a 23 degree tilt maintaining our seasons but preventing extreme temperature changes on Earth A The moon B The sun C Jupiter D Venus Quiz 1 Earth System Science 1 When examining environmental conditions such as temperature and atmospheric gas abundance why is it important to specify the time scale being considered A So you can put the processes in chronological order B Because the conditions and associated processes change over different time scales yielding different results C It really doesn t matter because most conditions and processes are more or less constant over geologic time D Because the book said so 2 What event does the Big Bang theory explain A Eruption of Mount St Helens B The killing off of dinosaurs as a result of a meteorite impact C The origin of gun powder D The formation of the universe 3 What celestial body keeps the earth at a 23 degree tilt maintaining our seasons but preventing extreme temperature changes on Earth A The moon B The sun C Jupiter D Venus Kvoto Summit Simulation June 6 CountryRegion Responsibilities Each student will be assigned a specific country or region The student is responsible for submitting the country sregion s report via email document should be in Word format about 1 page in length by June 2 US Europe China Russia Africa South America KYOTO SUMMIT DATE Thursday June 6th In Class AGENDA Welcome and Summit Overview 5 min 15 min Identifying Main Issues Who needs what Issues Examined by Economic Level 10 min ie econ Advanced 2nd world 3rd world Solutions to Rising Greenhouse 10 mln Gases 10 min Enforcing the AgreementWorking Capltal 15 min Developing Summit Agreement 5 min Vote on Summit Agreement 5 min Summary Term Project Points Oral Presentation 20 pomts Written Presentation 50 points TOTAL 100 points Oral Presentation 45 minute presentation in class 417 and 419 of executive summary material Web Page In Word format sent via email as Attachment File by June 2nd Executive Summary in Bullet Form One Page Strengths Weaknesses Resources Needs Strategy for Greenhouse Gas Emissions Most Important Document Body Overview of RegionCountry Natural Resources Economy Standard of Living HealthEducation Technology Web Site Material Executive Summary paragraph describing overall strengths weaknesses resources and needs of your country This paragraph should include your overall approach to controlling greenhouse gas emissions Strengths List strengths of countryregion They could be economic military technological people power etc These are the things you can bargain with Weaknesses and Needs What are the main shortcomings of your country What do you need health care technology energy etc These are the things that you want to correct and bargain for Natural Resources What resources do you have primarily in terms of energy Do you have coal oil or gas or do you have to import them Specific Policies for Limitinq Greenhouse Gas Emissions List specific policies that your country plans to implement to reduce green house gas emissions These don t have to be real policies that your country has proposed or enacted but they have to be consistent with the strengthsweaknessesneedsnatura resources of your countryregion Oral Presentations in Class One or more people from the country or group present the Position Statement and Supporting Material essentially the Web Site orally in class 45 minutes max Earth System Science and Global Change Chapters 1 and 2 Systems A Definition an ordered interrelated set of things that function as a whole B Types of Systems 1 Open System Free movement of mass or energy into or out of a system eg Energy balance of the earth 2 Closed System No transfer of mass or energy into or out of a system eg for mass a sealed pressure vessel C Coupling within System components linear relationship 1 Positive coupling a change in one component leads to a change in the same direction in the linked component 2 Negative coupling a change in one component leads to a change in the opposite direction in the linked component D Feedback loops self perpetuating mechanism of change and response 1 Positive feedback the loop amplifies the effects of the disturbance 2 Negative feedback the loop diminishes the effects of the disturbance Geosystems Our quotSphere of Contentsquot olar energ Human activities add more than nine billion tons of carbon to the atmosphere each year News Published online 10 November 2006 doi101038newsO6110618 Carbon tally shows growing global problem World summary of emissions reveals continuing gains Global carbon emissions are now growing by 32 a year according to results presented at an Earth science conference in Beijing on 9 November That39s four times higher than the average annual growth of 08 from 199099 quotWe are not on any of the stabilization pathsquot says Michael Raupach a carboncycle scientist with Australia39s Commonwealth Scientific and Industrial Research Organization CSIRO in Canberra Annan Leaders need courage to ght warming POSTED 717 pm EST November 15 2006 NAIROBI Kenya AP SecretaryGeneral Kofi Annan told the UN conference on climate change Wednesday that those who would deny global warming or delay taking action against it are quotout of stepquot and quotout of time quotLet no one say we cannot afford to actquot Annan declared The United States for one contends that reducing globalwarming gases would be too costly to its economy Hundreds of delegates from some 180 member nations of the 1992 UN climate treaty were entering the final three days of their twoweek annual meeting where they39ve been working on technical issues involving the Kyoto Protocol which obliges 35 industrial nations to reduce emissions of greenhouse gases by 5 percent below 1990 levels by 2012 The United States and Australia are the only major industrialized countries to reject that 1997 treaty annex US President George W Bush says it would harm the US economy and it should have required cutbacks in poorer nations as well Scientists attribute at least some of the past century39s 06degreeCelsius 1 degreeFahrenheit rise in global temperatures to the atmospheric accumulation of carbon dioxide and other heattrapping gases byproducts of power plants automobiles and other fossil fuelburning sources Continued temperature rises could seriously disrupt the climate they say I M NEWS amp OBSERVER Science and Politics mesmmucusymoos Mama acme ae ek Auo momma I 39 V She05 quot7T ii mampogmf MONDAMVJUNEZOQIZbOS ACT o Gk BAL I THE W5 J 39sGEEED 39 WEI39 H L39D Hg gn s E39 I w ms Mtmmam mm my I V m Some global warming evidence Rising land temperatures 08 C Rising ocean temperatures 01 C Melting glaciers tropics and arctic Retreating sea ice 68 loss per decade Rising sealevel 12 cm Changing ocean salinity patterns Rainfall patterns Extreme weather events d Some smaller glaciers are melting Mt Kilimanjaro Tanz V ll disappear in 10 yrs Ice sheet was 12000 years old Mpenmnmml uh c M mummwm v n a Anmmnu gsmc mm 5an wnn ma 20m 39 yaw 547 mu unlum my ln39c HIhush Anlhlvpogu slcming 25 9 Grey mode Pew am W W as as E MamaAu W 1 law I550 2 Global Temperature in 2050 90 W 0 1 0 1 2 3 4 Annual mean temperature change C l WASHINGTON President Bush will announce today a planto combat global warming that relies on voluntary ac tions by companies but doesn39t set yearly goals for reducing the amount I gases put mtoft Earthwarming Eiti speech iNation 6 96 39wOul mental ogress 39 ee mouse 5 New pollefdoesnt Thlia admignasisftr tionltlso prorniises lng at ornpaniESt at vorntariy re uce SEt targets or cu emis ions now won39t l penalized if greenhouse gases cuts eCome mandatory in the future v T t is the pmsident s long ByTraci Watson aw e 39 ative totl e Kyoto Protox 39 USATODAY y developed by 180 nations V greenhouse gases The presi int he would rates from par edquot in ty because ham 1 economy an burdzen on industri s 2 approachjis based on the sense idea that sustainable c growthis39th key to environ 53339 president 395 to deliver today a draft of the Many scientists say greenhouse gas USA TODAY THURSDAY FEBRUARY 1420023A es are partly to blame for global warm ing The Bush lan re ects the admini stration s belie that the science of the phenomenon 15 too uncertain to take major steps that could hurt the econo mgiVSo rather than trying to cut the U 39 output of greenhouse gases the d reduce the annual growth lions generally grow as the 39 grows because for example u u e using more energy to pro 7a Theepresident39s plan calls glmv moreslowly as S ilQWIyCl 51 says reen a 0 Pew nteroncmm warming it is ambitious tar alittle trepidation says Quin Changega theselimits by buying credits group ithat ram against globalquot Bush globalWarming plan voluntary get and our emissions would continue 39 to growquot she says Other industry groups say however that Bush s goal an 18 reduction in growth of emissions wouldn39t 39 to meet i suspect most of o bers will look at an 18 reducti the Edison Electric Institute a that represents electric corn WEDN Power plants produce subs amounts of greenhouse gases The plan also calls for power p12 cut their output of nongreen es such as sulfur dioxide eads to acid rain nitrogen oxi ingredient in smog and mercu plan would allow companies to e other rms that reduce pollution nal required levels mac it as evide V TnNrwsicOBSERVEB 539m MARCH 28 2001 on Kyoto SCRIPPS HOWARD NEWS SERVICE ce that it is w C02 mmn Pmmw inSm I BORENerm 39 kaHT RIDDER NEWSPAPERS WASHINGTON Carbon di0xid the 2ch cause of global Warm ingicannotberegulated as aPOIi lutan t the EnvironmentalProrv AgenCY 39 Thequot ion which a I 39dioxide emiss39ions from cars z 399 the Bu39shajadminiStration a decid d that dioside 1s a pollutant and It could shav reqtiiredexpensive new poke quot lu on centrgls on cars a perhaps on whnch administrative I sition thg Bush adminis V CleanAirAato reducecarbom EPAtG39enerel OounSel Robert E Fabr icanttmk thevoppositeposi gi39f tion39 in his 12page detision 4 ursda y Because the ICIeanh 39 Act does not authorize reg i u lation to address climate change Fab cant wrote it fol iwbon dioxide and iEPAV of cials said they relied US Supreme 2 ruling Food andDrugAdmin istration v Brown 39ampWillihmson r 39 that said when it tried rvi39Jonathan Cannon general counsel who wrote the nowreversed 1998 decision said They re trying to put a stake in the heart for a11ypos sibleex 39 39 isting avenue for dealing with in administration to 39reg iilate tobacco asa drug the gi39obal cliniate change Either b this administration or any 39 Auto industry slauided Fabric ant s position Why would youireg ulateapoi 39 lutant thatis an inert gas39that39is 39 vital to plant photosynthesis and 39 thatpeople exhale when they breathe said Eton 110ku a spokesman for the39Alliahce of Au39 tomobile I hat not a pollutant 39 While carbOn dioxide39does no i sayiit39causes globai warmingre increa39sesintheat 39 39 I hygasesf39that sunlight damages eeosystemsui Carbon dioxide istheleading ulprit rds expert say BY m J HANLEY THE ASSOCIATED PRESS MAUNA LOA 0355mm Hawaii Carbon dioxide the gas largely blamed for global wanning has reached record high levels in the atmosphere scientists say The researchers at this station atop a volcano say the gas s prevalence has been growing at an acceler ated pace in the past year The reason for the faster build up of the most important green house gas will require further analysis the us government ex perts say But the big picture is that C02 is continuing to go up said Rus sell Schnje ll deputy director of the National Oceanic and At mospheric Administration s clis mate monitoring laboratory in Boulder Colo which operates the Mauna 39Loa Observatory on a e island of Hawaii foss fuels traps heat that other wise would radiate into space 39 Global temperatures increased by about 1 degree Fahrenheit 06 degrees CelSius during the 20th century and international panels of scientists sponsoredby world governments have concluded that most of the warming probably was due to greenhouse gases I con tinnedquot quot temperature will disrupt the climate cause seas to rise and lead to other unprea dictable consequences unpre 39 dictabl einzpart because of tainties in Computer modeling oi future 39 a 739 The Debate Goes On Clinton Bush 39flat wrong39 on climate CNN Friday December 9 2005 Posted 356 pm EST 2056 GMT MONTREAL Quebec AP Former US President Bill Clinton told a global audience of diplomats environmentalists and others on Friday that the Bush administration is quotflat wrongquot in claiming that reducing greenhouse gas emissions to fight global warming would damage the US economy With a quotserious disciplined effortquot to develop energysaving technology he said quotwe could meet and surpass the Kyoto targets in a way that would strengthen and not weaken our economiesquot Clinton a champion of the Kyoto Protocol the existing emissionscontrols agreement opposed by the Bush administration spoke in the final hours of a two week UN climate conference at which Washington has come under heavy criticism for its stand Most delegations appeared ready Friday to leave an unwilling United States behind and open a new round of negotiations on future cutbacks in the emissions blamed for global warming quotThere39s no longer any serious doubt that climate change is real accelerating and caused by human activitiesquot said Clinton whose address was interrupted repeatedly by enthusiastic applause 1005 CF Six countries form anti pOllution pactv A BY H Josef HEBERT THE ASSOCIATED PRESS V WASHINGTQNbTheIInitedStates and ve and Paci c nations including China and India agreed on a partnership to use cleaner energy techangmg to try tocurtail whim the UnitedSta esf veaemhracedv White House of cials see the partiership asanimportantstepin set ngupasystemtohdp meri ing industrial produce 39 pecianyearbons fom fossil fuels Pfesl ent Bush called it a f re Memento ershipquot 1mm d6 cleahenh nd moreef cient to meet hational pollutionredue tion e d 39 change cosmos said of a S 1 Rice andE39nergy j Bodman 39 quot7 e l rmel sl 11939 the agreement will complement Kyoto said39JaniesChnuni ightonh chairmen39 39of SCOHIF theatnlosPher En Si0nS are Vgrowingattherateo wpercent j ialyear cu quot E vir hme moaany 1111 Kyoto pact iifhieh the for a other pollution f UnitedStatesbasrejectedrequires39 that industrial countriesreduoe their greenho 39 use gas emissions The Bush administration prefers to address climate change through voluntary actions and by empha the need to develop techV nolog ies that cut emissions and I Capture Connaughton mentionedtech V nology masters and exehanges 39 Rumearetheothersgto of ideas as ways the partnership couldworkonclilnatemand The six countries pledged to V I enhance cooperation to addrew Xthe growthofelimate hanging Tpoliution while still meeting their growing energyneeds and to work for nonbinding commit ments to develop cleaneoal nu v do and hydroelectrich 39 sites that are less carbo The United States has been ea getfto nd ways toget China In dia and othemt dly industnahz 39 39 ingnations to deal with climate mousse o tials say that One problem with the Kyotopact is that it does not require erg andilndia whose growingen r iquot also mean 81mins i z r enhouse to commit to F 39 ion reductions w UnitedStatesacoounts fer bnequartef the Worlds green house gases that are SQinE into ri39 The role of phosphorous in the environment phosphorous cycle sources of phosphorous applications of phosphorous eutrophication The Phosphorus Cycle The Phosphorus Cycle Hmnw 39pnmam m ngamr phus mus 39 mmeri s mama WWW V39 Mmura L 1 um mm mm The Phosphorus Cycle The phosphorus cycle is the biogeochemical cycle that describes the movement of phosphorus through the lithosphere hydrosphere and biosphere Unlike many other biogeochemical cycles the atmosphere does not play a significant role in the movements of phosphorus because phosphorus and phosphorusbased compounds are usually solids at the typical ranges of temperature and pressure found on Earth Phosphorus moves slowly from deposits on land and in sediments to living organisms and than much more slowly back into the soil and water sediment The phosphorus cycle is the slowest of the matter cycles Naturally Occurring Phosphorus Phosphorus normally occurs in nature as PO43 which is called orthophosphate Most phosphates are found as salts in ocean sediments or in rocks Over time geologic processes can bring ocean sediments 0 0 O to land and weathering Will II II P HO P OH HO P O P OH 0 0 carry terrestrial ions to the I I I I I 0H 0H 0H H P P Ocean Plants absorb urthuphusphuncaud pyruphusphuncaud phosphates from the soil and 0 0 0 they proceed up the food chain II II II HO P O P O P OH After death the animal or plant I I I 0H 0H 0H decays and the phosphates are returned to the soil Runoff tlvl fl 3 may carry them back to the HOYOTOTOTOH ocean or they may be 0H 0H reincorporated into rock Biological Phosphorus The primary biological importance of phosphates is as a component of nucleotides which serve as energy storage within cells ATP or when linked together form the nucleic acids DNA and RNA Phosphorus is also found in bones whose strength is derived from calcium phosphate and in phospholipids found in all biological membranes Phosphates move quickly through plants and animals however the processes that move them through ml the soil or ocean are very N r339h39 slow making the phosphorus 39 39339 I jam cycle overall one ofthe Lquot F39 539 p G T U I slowest biogeochemical cycles U U U Fertilizer Human influences on the phosphate cycle come mainly from the introduction and use of commercial synthetic fertilizers The phosphate is obtained through mining of certain deposits of calcium phosphate called apatite Huge quantities of sulfuric acid are used in the conversion of the phosphate rock into a fertilizer product called quotsuper phosphatequot Plants may not be able to utilize all of the phosphate fertilizer applied as a consequence much of it is lost form the land through the water runoff The phosphate in the water is eventually precipitated as sediments at the bottom of the body of water In certain lakes and ponds this may be redissolved and recyled as a problem nutrient Calcnu m apatite Apatite is a group of phosphate mineralsI usually referring to 39 39 d 39 amed I I an I n high concentrations of OH39I F39I or Cl39 ionsI respectivelyI in the crystalI written as Ca5P043OHI FI Cl Apatite is one of few minerals that are produced and used by biological microenvironmental systems Hydroxylapatite is the major component of tooth enamel Bone material is Ca5PO432C03 Fluoroapatite is more resistant to acid attack than hydroxyapatite For this reason toothpaste typically contains a source off luoride anions eg sodium fluoride or sodium monofluorophosphate Fluoridated water allows exchange in the teeth of fluoride ions for hydroxyl groups in apatite Phosphate Rock as a Resource Phosphate rock is the only economical source of phosphorus for manufacturing phosphatic fertilizers and chemicals Deposits are widely distributed throughout the world and are generally mined by using surface mining methods The United States is the world39s largest producer of phosphate rock with annual production of about 45 Mt of marketable rock accounting for more than 30 percent of total world production Florida and North Carolina produce the largest amounts with a combined 85 percent of the US output followed by Idaho and Utah Phosphate rock when used in an untreated form is not very soluble and provides little available phosphorus to plants except in some moist acidic soils Treating phosphate rock with sulfuric acid makes phosphoric acid the basic material for producing most phosphatic fertilizers Phosphate Rock as a Resource Phosphatic fertilizers include diammonium phosphate DAP and monoammonium phosphate MAP which are produced by reacting phosphoric acid with ammonia and triple super phosphate produced by treating phosphate rock with phosphoric acid More than 90 percent of the phosphate rock mined in the United States is used to produce about 12 Mtyr of phosphoric acid Domestic consumption of phosphate in fertilizers has averaged 45 Mtyr since 1994 The United States supplies most of the phosphate fertilizers in the world Overall more than 50 percent of the phosphoric acid produced in the United States is exported as finished fertilizers or commercial acid The United States accounts for more than 50 percent of global interregional trade in phosphates 90 percent in MAP and 75 percent in DAP The United States also imports some phosphate rock for processing about 18 Mtyr Human Influences on the Phosphate Cycle Mining Phosphate Ruck Phosphates in fertilizers Run ff Elf39Id erosion Animal WEEtES Phosphates in municipal sewage h Excess Pheshate disselved in water C Ophardt 6199 Phosphorus Run Off Eutrophication Phosphorus is recognized as one of the major nutrients contributing to the increased eutrophication of lakes and other natural waters This has led to many water quality problems including increased purification costs interference with the recreational and conservation value of impoundments loss of livestock and the possible sublethal effects of algal toxins on humans using eutrophic water supplies for drinking The International Conference on the Protection of the North Sea has recommended a 50 reduction in the input of phosphoruscontaining compounds while the EU Urban Wastewater Treatment Directive will require an effluent standard of no more than 1mgl phosphate for large treatment works Eutrophication Algal blooms can be destructive germe but they are not unnatural In fact quot quotI a natural cycle where populations rise and crash such as in the Baltic Sea can be a part of a healthy marine ecosystem In this case regulation is desirable but reversal measures if excessive can be counterproductive Thus the aim of restoration efforts must then be not to eliminate the blooms but return them to their original frequency Biological Effects of Eutrophication 1 Phosphorus ferilizes small Sunlight Fish die because of lack of 02 Phosphorous Removal Phosphate removal is currently achieved largely by chemical precipitation which is both expensive and increases sludge volumes by up to 40 An alternative biotechnological approach is that of 39Enhanced Biological Phosphate Removal39 39EBPR39 which utilises the ability of some microorganisms to accumulate phosphate as polyphosphate in excess of their normal metabolic requirements EBPR systems although economicallyattractive require anaerobic pretreatment zones and display inconsistencies in performance requiring either periodic organic matter supplementation andor chemical 39polishing39 to meet compliance limits Pleistocene Glaciations Pliocene Sea level During the past 65 million years global temperatures have gradually cooled and sea level has fallen as polar glaciers have grown During the past 2 million years the Pleistocene northern polar glaciers have advanced and retreated causing sea level to rise and fall by 120 meters Relative Sigmlicanne of Piazzsses mar Allen Climale my Imowno uuo v omnm m lawman u i mom l sumomy u om lawman WI am am LaNi ane mm swam MI Valunml smmm was wwnwg mammam Rnngmlu aimquot lnlnwnnnuri m w sm man mom lerl 5 law lzt um lE39FlE an 25 in 2a 5 ma 39Cl m m am There are several factors controlling climate on the earth 1 Sunlight reaching the earth and greenhouse gases 2 Global distribution of the continents ocean 3 Orbital and solar variability 4 Others They have different characteristic time scales for affecting global climate Maximum Extent of Pleistocene Ice Sheets Copyright 2004 Pernrentice Hall Inc Changes in seale ve in the past 18000 yrs scam in mm W In Sana Ina AI nhh Insmod During the Pleistocene when northern glaciers are abundant sea level is lower by 120 meters making what is today our continental shelf dry land When the northern glaciers melt over a period of 1015 ky sea level rises to their current high level sea stands O 0 O O 39 g g E v o O 0 22 a w 2 5 Ice sheet per mil 0 H20 containing 1 30 0 H20 containing 180 Copyright 2004 Pearson Prentice Hall Inc Processes Affecting the Distribution of 180160 Evaporation concentrates 160 in the vapor and precipitation concentrates 180 in the rain leaving the vapor even more depleted in 180 which is what makes the glaciers so low in 18O lnterglacial 25 warm I 35 tr l l 9 I ll l V l asylylrl V Glacial cold 55Illrrllrlr 00 05 10 15 20 25 30 Age my ago Copyright 2004 Pearson Prentice Hall Inc Deepsea record of 18O of seawater during the Pleistocene Epoch based on benthic forms Myr ago temperatu re 0 05 20 25 More ice lt gt Less ice Colder 5180 o 5 4 3 i lt SEE E 5 3 EF 1 Slow drift in trend 3 53 Warm er 41 000 years 30220 5 100000 years gt 2 temperature 100000year cycles dominant Transition interval 41 OOOyear cycles dominant smaller 23000year cycles First ice rafting 275 Myr ago Power Power Power 0 Long Summer insulation 6539 N Till 23000 41 000 Ice volume 275 09 Myr ago 41000 23000 Precession 19000 AA Ice volume 09 0 Myr ago 100000 41000 23000 Orbitalcycle period years 1 Short Ptr v31 39CII39JJTlEIZII mm Firm 39 I EIIIIIIII wars g39vt39 39 3iIiIquotIll wars Copyright 2004 Pearson Prentice Hall Inc Eccentricity 100ky Tilt 41 ky Precession 26 ky Changes in the earth s movements that have climatic implications 9 Solar irradiance 10 Wm 2 200 100 100 200 300 400 500 600 Tim e thousands of years The combination of eccentricity tilt and precession contribute to a variable amount of sunlight reaching the earth s surface which causes the northern variability in glaciation during the Pleistocene Orbital forcing of Ice Ages Why glaciations occur at 100 ky frequency and end abruptly remains an enigma 6100 rec r 39 summujnsgrg ianssm i 4 L L 5 as i I Musicquot 39 r aquot 39 I E 2 0 g 5 2 r y E 2 I 4 I 0 5 25 o 39 A 2 1 Icevu nnle275m9Myr Igo amp a 7 3 4106039 amp r 23000 r g 35 an r 3 o quot J 4 lczvolumgaLB 0 Myrna r 4 glacial Cycles recorded in the v ostok me can s I r I I I I l l a i39 l f r ll r l r Li E II W II vr l 391 if in 1 a r s r Y r l f t I E l P l Figure 1 Changes In razmnspharm carbon dlrriiirde empirically infrared rampart ture and methane 1mm 3 420000 year record from me Warm ice care For a dealer repoh of rhcae measurements see Petit er al II 1999 Image Enrnplrmrerrra le li39iEirPle39P Aiii During glacial times carbon dioxide levels are low 200 ppm whereas du ng interglacial times warm periods the carbon dioxide levels are higher 280 ppm Interglacial Glacial Global average temperature gt Copyright 2004 Pearson Prentice Hall lnc Climate rocks back and forth between Glacial and Interglaciatial modes because of solar forcing Q 65 N June 565 C 9 g E E g 5 W I 400 41 5 I O 1 00 200 300 Eccentricity Band 0 CD k Obliquity Band k Precession Band about 23 ky 19 ky about y ab ut 1 y 75 75 75 E 775 775 775 i1 i1 i1 1 1 1 1 WW 3150 I I 1 U 1 00 200 300 400 mm m Inso at 5 30 Copyright 2004 Pearson Prentice Hall Inc Northern Hemisphere insolation solar energy during June and its relation to oxygen isotopes Intensity of summer 0 Global mean temperature insolation at high northern latitudes Growth of continental ice sheets A Planetary albedo Copyright 2004 Pearson Prentice Hall Inc Positive feedback mechanism between glacial growth and global temperature but it still takes longer to form the northern glaciers than to melt them Riverine delivery A A A A A A A The Marine Organic matter A export Low nutrient B1010glcal concentrations Surface ocean Pump uh High nutrient Upwelling concentrations Deep ocean I I I I I I I l I I I I l l I II II II II II 39 Q Burial in sediments Copyright 2004 Pearson Prentice Hall inc lnterglacial sea level Phosphorusrich sedimentsquot quot 39V 39 of the continental shelf Glacial sea level Copyright 2004 Pearson Prentice Hall lnc The shelfnutrient hypothesis During low sea level periods sediments on the shelf are eroded releasing their nutrients to the ocean causing more primary production and lower global temperatures Global surface temperature Glacralrce volume I Atmgsgrenc Sea level f g Intensity of biological pump Shelf exposure Oceanic concentration Riverine flux of of phosphate phosphate Copyright 2004 Pearson Prentice Hall Inc The Shelf Nutrient Hypothesis for the reduction of atmospheric 002 during glacial times Atmospheric carbon Global average Equatortopole dioxide content 39 surface temperature 0 temperature gradient ll Intensity of oceanic 1 Delivery of iron to I EastWest biological pump ocean via aerosols wind speeds Copyright 2004 Pearson Prentice Hall lnc The iron fertilization hypothesis for increasing the marine biological pump and decreasing atmospheric carbon dioxide levels during glacial periods Glacial icevolume 0 Sea level 0 Shelfexposure T Global surface temperature Atmospheric 02 Reef growth Copyright 2004 Pearson Prentice Hall lnc Coral Reef Hypothesis As sea level rises following a glacial period coral growth expands which releases carbon dioxide to the atmosphere causing warmer temperatures 1 Duo Miles Forest I Grassland Grassland Savannah Savannah u quot f 40 30quot Am a Reconstructed vegetation cover 1 8 ky ago D Present day quotpotentialquot vegetation cover Copyright 2004 Pearson Prentice Hall Inc The Negative Feedback loop During glacial times the terrestrial biomass was lower which would tend to raise 002 levels and temperatures 7 Age ky ago 1 3 133 558 86 I I Warm Relatwelemperature l I 1 Cold 5C W Hquot quotV f S C I I I I 40 Q Q 30 e e C gt Ct 20 E 1 1 g 1 o quotxx O l l I I I I I I I I I I I I l I I O 500 1 000 I 500 2000 Depth m Copyright 2004 Pearson Prentice Hall Inc Al 9 a I p rod u cti o n a n d Bmogemc aerosol Cbud abedo production cloud condensation A nuclei affect cloud albedo on glacial i I m e I Marine algal C Global surface productivity temperature Copyright 2004 Pearson Prenllce Hall Incl The Origin of Earth and Life The origin of the Universe The origin of the solar system The planets and their properties The earth The origin of organic matter MillerUrey experiment Living organisms and evolution The Big Bang About 137 billion years ago the universe bursts in existence with all of the matter and energy it will ever hold In the first fraction of a second the universe undergoes a period of inflation growing from the size of an atom to the size of a grapefruit The first elements H He form 100000 s of years after the Big Bang The first stars form 200 million years after the BB The Universe is made of 4 atoms ordinary matter 23 unknown type of dark matter and 73 mysterious dark energy like antigravity 15 mausand million years 300 thousand years 3 minues 1r seconds 4w seconds e 1 0 second R 6000 degrees 13 degrees 3 degrees K electron Consteliation in which 93 axy Virgo Corona Eorealis Hydra Velocity kms mis 1200 745 21500 13351 6190061881 Distance from sun lightyears 43000000 728000000 1950000000 Shit of absolption lines Violet i observation implies that the universe is expanding I The HUBBLE Telescope fincz 01 2 a Star Formation in the Eagle Nebula Supernova Explosion 10000 Years Ago Jets of Si Come Out near Surface Fe Located in The core of the Neutron star Xray picture From the Chandra telescope in space shuttle 10000 Luminosity solar units 001 0001 30000 o 100 h R0 Main Sequence 10R 39SiriusB I j39s 1 Re Whlle Dwarf Region o Procyon roiima Centauri 10000 6000 3000 Surface temperature K AF0M Spectral classi cation Luminosity solar units 01000 0 yquot SII IUSA 39l Altairx 00i 000i l i i 10000 6000 3000 Surface temperature K AFGM Spectral classification 30000 0 i Copyright 2004 Pearson Prentice Hall Inc Solar System Evolution a A slowly rotating portion of a large nebula becomes a distinct globule as a mostly gaseous cloud collapses by gravitational attraction b Rotation of the cloud prevents collapse of the equatorial disk while a dense central mass forms c A protostar ignites and warms the inner part of the nebula possibly vaporizating preexisting dust As the nebula cools condensation produces solid grains that settle to the central plane of the nebula d The dusty nebula clears by dust aggregation into planetesimals or by ejection during a T Tauri stage of the star s evolution A star and a system of cold bodies remains Gravitational accretion of these small bodies leads to the development of a small number of major planets Copyright 2004 Pearson Prentice Hall inc Dust Surrounding the Star Beta Pictoris Em nl Plum395 flr51 Warped D514 Beta Fictmis Hubhla Spam Teleswpe Wide Field Filanetary Eamera E mama IE and LN radium 39 rhulm zmma nn Mona mm J39E Hallo amlaalm 35 Hank139 as Cumni39lumg Radio Imi uim 39 f Em min nniulu p zirlgh apnla and shunHm mmnliu mgiunl 33 md quotHajl The Effects of Greenhouse Gases on Planetary Temperatures Venus Earth Mars Energy Reaching 2643 1370 593 Planet Surface Wattsm2 Albedo re ectivity 80 30 22 220 255 212 Temperature 53 C 18 C 61 C Degrees K Actual Surface m 288 218 Temperature 437 C 15 C 55 C in Degrees K degrees C A Tm Cmed 510 33 6 by We Want Jupiter Neptune Uranus are lmbrium Sea of Raips A B C D E A marsesized body 01 to 02 Earth as es approaches the proto Earth at an oblique arig e The two bodies collide The ejeota from the impact fly off at an angle and he protoEarlh starts spinning rapidly The ejecta from the impact form a disk around the proterarth The again Wit 1 e protoe art becomes part of its core The Moon is initially only a few Earth radii 20000 km away rorn the now nearly fully formed Ea a spins rapidly as a result of the collision The daylength is ours Because they are so close together the Moon and the Earth generate huge tides in each other that dissipate energ and transfer angular momentum from the Earth to the Moon Over time Earth s rotation slows while the Moon retreats to its present orbital distance of 60 Eart radii 384400 km The Moon39s current rate 0 recession is 1 cm yr Copyright 2004 Pearson Prentice Hall Inc Proto Earth The Formation Of the Moon Determination of the age of the earth 1oorf 90 80 slope of line age 455 x 109y 70l Sol 50 207Pb204pb 4o 30 20 Primordial lead 0 l I I I 41 L I I I l I I L I 50 100 150 206Pb204Pb gt FIGURE 82 An isochron diagram showing lead isotope ratios from a collection of chondritic meteorites The fact that all the data fall on a straight line shows that all the meteorites have the same age The age of the mete orites 455 by is determined from the slope of the line The age of the earth is about 46 billion years as determined from radiometric dating techniques lso Isotope lso lsooe39t T lso lsooexptlt T is the time constant Halflife 12 9XP39T12IT 112 Ih2 t 06931 Radiometric Dating Principles Dating rocks by radioactive timekeepers is simple in theory It relies on these basic assumptions Beginning Conditions Known Beginning Ratio of Daughter to Parent Isotope Known zero date problem Constant Decay Rate No Leaching or Addition of Parent or Daughter Isotopes All Assumptions Valid for Billions of Years There is also a difficulty in measuring precisely very small amounts of the various isotopes Factors that governed the climate of early Earth The faint young sun Changes in the atmosphere reducing vs oxidizing The snowball earth theory Glaciation through the ages Oceancovered Earth 104 Huronian glaCIation A 1 5 20 G g A Late 2 26 Precambrian 103 E if glaciation g 5 104 5 20 C a D m X 9 2 v o 30 Solar flux 10 g E reduction 0 C 6 E 102 b 1 N o 101 c O 8 3 lt5 10 o 1 4 l i I 10 45 35 25 15 05 Time before present by 39 1 31 39i ii isra i Him Le ins vi Wagihix 5 1 CH4 Climate Feedback Loop Surface temperature CH4 production rate Greenhouse effect Capyngm a 2004 Pearson Pvenhce Haii inc Archean Climate Control Loop Copyright 2004 Pearson Prentice Hall inc CH4 production Atmospheric Surface C Haze temperature production CHMQOZ ratio H 002 loss weathering Phases of the earth s atmosphere The earlier you look in the Precambrian the less evidence there is for free oxygen In the Archaean 30 billion years ago the atmosphere was either neutral a mixture of nitrogen carbon dioxide water vapour and perhaps a little hydrogen or reducing with ammonia methane carbon dioxide water vapour and perhaps hydrogen The reducing atmosphere is thought to be the original Earth39s atmosphere by analogy the outer planets Jupiter Saturn Uranus Neptune have reducing atmospheres and this has long been thought also to represent the quotoriginalquot state of the Earth39s atmosphere This model inspired Miller in his classic 1951 experiments to study the effect of electric discharge on the molecules in the atmosphere to produce amino acids quotthe building blocks of life The development of the atmosphere is thought to involve a transition to a neutral atmosphere 30 25 billion years ago Oxygen began to evolve significantly starting about 25 billion years ago The origin of a snowball earth Controversial theory hypothesizes that earth may have been nearly frozen in the Neoproterozoic period 600 800 million years ago Glaciation near the equator on large land area Pangeaea One question is was this glaciation caused by the presence of a large land mass near the equator Evidence for glacial activity includes glacial striations left and glacial erratics above Evidence for Glaciation Glacial tillite is a sedimentary rock with variable grain size ILL Spreading ridge Subduction zone Aga Mail 200 Ennwbz l Evems Glacial Iniewats 1 quotM5 1 m5 El m 393 7 E 35339 mm Sr n iiquot Etl39 i39 39 Drganic il Burial F 5 m MEN Mascuprmammic I Numt m Ic icl Phan emz i 1G 5 quotEl 5 1i Duration Eva Fenod Epoch Glacialions in millions Mquotquot quotS f Wears years ago Plelslccens fumii our glaciations 3g m g b Miocene quotquot quot 155 53937 Dumlion N A EON GLACIATLONS ERA mm Mlllinn of O 5 Oligocene 92 WE yearsago E Q Eocene 211 g CENOZOlC es 0 V g MESOZOID use Pa39e m 3902 as 7 m m i FALEOZDlC 293 1 Cretaceous 79 Late Proterozoic Neoprolerozoio 330 glaciations u 6 144 8 iii 0 Mesopmremzoc 7m 2 Jurassic 52 5 E 2 E E O E E Triassrc 45 Paleupmtemzoic 900 Permran 35 2 Farmer 3 Hurpnjan am Hi u g glaclatlons glaciations 2 g Pennsylvanian 39 lt 2 0 2 3g LATE 500 395 CL 8 a Mississippian 35 2 U E I MlDDLE 400 a 0 9 E g Devonian 50 Z O 3 EARLY 400 EL Silunan 30 z I Late 35 omowcan Drdovicran 65 D sun glaciations lt I Cambrian 1 39 PRECAMEHlAN Copyright 2004 Pearson Prentice Hall Inc Over geologic time there have been major glaciations during the Huronian 25 billion years ago the Late Proterozoic 800 600 million years ago the Permo Carboniferous 300270 million years ago and the most recent Pleistocene 18 million years to present Geologic Time and the Major Changes in Life over the past 45 billion years we My aim nplmlasymul Duration Pemd EDOCh Glaciations in millions M39H39ons f of years years ago Quaterna Holocene Pleistocene 001 um ry Max222quot glaciations gg 16 9 Miocene 7 1amp5 5393 O E 238 N 52 Oligocene 99 C2 5 3q 7 L3 39 Eocene 211 548 Paleocene 102 65 Cretaceous 79 O E 3 E 144 B 3 lt1 UJ 2 Jurassic 52 206 Triassic 45 251 Copyright 2004 Pearson Prentice Hall Inc Glacial Ice H 30 EEIi 0 39 High Sealevel j j I 7 39 I 39 v IZifjizii1 3i39 239 vv I Permanent 1 quot quot i Ice 39 39 Low Seal vel 10 2 GEM Homo TM T EocuedeeocenolCret A6 0 0 54 F3300 o o o o V 8 0 8 90 0 g6 00 A L O O OO 94 33 o o o v o O o m e A amp 4 390 A A 0 g 2 quota g 3quot 3 39 CENTRAL NORTH PACIFIC 4 39 o PLANKTONIC at 1 0 39 o BENTch 3 h 39 SOUTHERN OCEAN t A PLANKTONIC o sumo 4 g 4 J 4 L l 0 IO 20 30 4O 50 60 70 AGE IOGyrs Fig 98 Tertiary oxygen isotope record of the deep sea Ccmral North Pacific Data from R G Douglas S M Savin 1975 Init Rep Deep Sea Drilling Project 32 509 Southern Oaan Den from N J Shackleton J P Kennett 1975 Init Rep Deep Sea Drilling Pmiect 29 743 None the Age Ma Mean Global Mean Global Temperature Precipitation Cold Warm Wet Quaternary Miocene 65 Cretaceous Jurassic Triassic 251 Silurian Ordovician 544 1000 Proterozoic 2000 3000 Archean 4000 4600 Copyright 2004 Pearson Prentice Hall lnc Surface earth temperatures as a function of geologic age Note the cold temperatures 600800 million years ago a Snowball earth and the warm temperatures between 250 and 65 million years ago when dinosaurs roamed the earth Also observe the cooling trend over the past 80 million years 002 concentration times present level IOISI kll J IKI I 500 400 300 Time millions of years Copyright 2004 Pearson Prentice Hall Inc 200 OO Temperature k 310 290 270 250 Maximum Minimum Present I I I I 0 30 S 60 S 90 S Latitude I 30 N Ins mwstIIII III fjIiIII39 aIm I ISII a II I Age my ago 50 100 150 200 Relative amount of 1SC PIio Pleistocene 390 Cretaceous Jurassic Triassic w Icehouse Greenhouse 37 1 L g5 7 cfquot quotquot K 9 quot f 39 9 V r 0615 a gm w Low elevalions 2 gi V J 7gt7 k 39 73 lt I V 40 m y ago 39 INDIA 60 my ago r V 7 ngh eievauons a 312 22 9 Middle eievauqns z7 19 2 3 Le Ln I on K i L Q 7 X 7 39 A DU n o e y ago High elmaliens L7 ngn ermxmns j x3 Middle sleva on Middle elevations 39 f gt LOW elevations 39 7 Low elevations Lag y a Q 22 Li 77 3134 I 7 quot 5 L K x Copyright 2004 Pearson Prentice Hall Inc Copyright 2004 Pearson Prentice Hall Inc 20001 E 1500 y15577x2 28978x13773 3 R2o96 To 12 10001 X 9 39O 8 500 E m 0 O l W if F 1 6 7 3 9 1o 11 Stomatal index Figure 3 Palaeoatmospheric C02 can be inferred from fossil leaf Sl by using this transfer function derived from Ginkgo leaves grown in greenhouse experiments5 and taken from herbarium sheets dating back to 1888 see Supplementary Information T b gt E 6000 1 A 9 a 4000 Q X 9 2 2000 a U O 0 I I c 300 200 100 0 7000 5000 I carbomsompes Boron isotopes J I I 39 3000 l x i39 i 1ooo 4 A Mass balance model 4000 300 200 100 0 Millions of years ago a b of atmospheric C02 ppmv can be compared with flanking standard error of means c Previously published curves derived from a 300 million years a Unsmoothed data using transfer sedimentary mass balance model1 thick line boron isotopic composition of marine tandard deviation of 84 reliable SI determinations of fossil foraminifera2 bold dashed line and carbon isotopic composition 0f pedogenic carbone oving average of transformed Sl determinations with dashed line Evidence for higher carbon dioxide contents in the earth s atmosphere between 250 and 65 million years ago The two lines of evidence come from plant structure number of gas exchange openings stomata and from carbon isotopes The Origin of Life The MillerUrey experiment Alternative hypotheses Determinants of life The MillerUrey Experiment l Electrodes Electrical spark llLightningi H20CHJ4 iN H3 Hzrco to vacuum pump gases primitive atmosphere 5a mpling probe Direction of water va or circulation Condenser Cold water r Sampling probe Cooled water containing organ it compounds Heat S urce The MillerUrey Experiment The experiment used water H20 methane CH4 ammonia NH3 and hydrogen H2 The chemicals were all sealed inside a sterile array of glass tubes and flasks connected together in a loop with one flask halffull of liquid water and another flask containing a pair of electrodes The liquid water was heated to induce evaporation sparks were fired between the electrodes to simulate lightning through the atmosphere and water vapor and then the atmosphere was cooled again so that the water could condense and trickle back into the first flask in a continuous cycle The MillerUrey Experiment At the end of one week of continuous operation Miller and Urey observed that as much as 1015 of the carbon within the system was now in the form of organic compounds Two percent of the carbon had formed amino acids including 23 of the 22 that are used to make proteins in living cells with glycine as the most abundant Sugars lipids and some of the building blocks for nucleic acids were also formed Nucleic acids DNA RNA themselves were not formed As observed in all consequent experiments both lefthanded L and righthanded D optical isomers were created in a racemic mixture Three key aspects of evolution required for life j replication m G W CEEEEEED M quot 0 Copyright 2004 Pearson Prentice Hall inc Microfossils Of Early Life Although these textbook examples of microfossils have been questioned it is clear that life arose more than 2 billion years ago W Copyright 2004 Pearson Prentice Hall Inc BACTERIA ARCHAEA Haloferax EcoRima Sym Chromatium t 39 t MethanospiriIurn mltochondna 39 A robacte um Sulfolobus Methanosamma g Chlorobium P um Methanobactenum Cytaphaga Thermoprote s Mathanococcus Epulopiscium Bacillus NEE Them Um Thermococcus chloroplast Q P Methanopyrus Synechococcus Thermus Thermomicrobiurn Thermotoga Aquifex 10 change EUCARYA rosco ic multicellular organisms prinus 39 Paramecium Porphyra Dictyostelium Glardla Hexamita Vairimorpha Physarum Naegleri 6 En Encephalitozoon Eng973 tamOeba Trypanosoma Copyright 2004 Pearson Prentice Hall Inc The Tree Of Life Based on DNARNA There is a large role played by thermophilic organisms in the early life tree This may result from evolution near thermal vents H AR a HI 5 J J 239 m 392 mm 141 g The Chemistry of Climate Change Introduction Definitions Basic Science Applications Significance How is Climate Change Related to Biology Oxygen in the atmosphere comes from photosynthesis life started in a reducing atmosphere oxygen permitted development of animal life Carbon dioxide arises from biotic and abiotic sources respiration volcanoes and vents combustion of fossil fuels Carbon dioxide dissolves in the ocean and increases the acidity of the ocean The short term carbon cycle Photosynthesis removes carbon atoms from the atmosphere and turns them into food for green plants This process requires energy derived from the sun s radiation At night when plants turn off their photosynthesis and undergo respiration carbon is replaced back into the air Also when the plant dies and begins to decay much of the trapped carbon within the plant is released back into the atmosphere There is a small percentage that remains as fixed carbon Even on a time scale of years this cycle is mostly reversible meaning that at steady state there is little carbon fixed by these processes They are important however and if the biomass on earth decreases eg deforestation the net capture of 002 will decrease Carbon Cycle Calcium carbonate in sedimentary rock Roughly 75 of the carbon injected into the atmosphere by nonorganic means usually volcanoes finds its way into deposits of calcium carbonate limestone These deposits make up the largest reservoir in the carbon cycle Limestone is formed from bicarbonate HCO ions weathered and dissolved in the ocean The ions along with the skeletal remains of marine life accumulate on the ocean floor Limestone formation involves a series of chemical reactions all of which have a net effect of removing carbon dioxide from the atmosphere Weathering of limestone deposits by rain tends to return carbon atoms to shortterm reservoirs thereby replenishing the concentration of atmospheric carbon dioxide The CarbonateSilicate Cycle The carbonatesilicate cycle regulates the amount of atmospheric carbon dioxide found in the environment As rain falls upon the earth chemical weathering releases 002 trapped in rocks rainwater etc which is transported by rivers and streams into the oceans Here H003 mixes with marine sediments the decaying skeletons of organisms and silicate materials and settles on the ocean floor as CaCO3 or dolomite As plate tectonics move the sediment is scraped off the ocean floor and pulled down into the earth s mantel In the earth39s crust temperatures are high enough to cause CaCO3 to undergo a metamorphosis into calciumsilicate rock For each CaCO3 molecule that gets transformed a 002 molecule is released The extracted carbon is either then pushed out into the atmosphere by volcanic activity or through hydrothermal vents in the ocean floor The long term carbon cycle LongTerm Carbon Cycle weathering consumes volcanoes C02 weathering products M23 0 u d to ocean metamorphism of Shannwsygxer older sedimentary weathering consumes rocks liberates C02 30 am j r o en ocean arbonate carbc39rme d d f 2 we ermg pm 0 S p b edi entation L carried to ocean sedimentation 5 Figure 339Echematic representation of the longterm global carbon cycle showing the flows hollow arrows of carbon that ere important on timescales of more than 100 Kyr Carbon is added to the atmosphere through metamorphic degassing and volcanic activity on land and at midocean ridges Atmospheric carbon is used in the weathering of silicate minerals in atemperaturesensitive dissolution process the products of this weathering are carried by rivers to the oceans Carbonate sedimentation exracts carbon from the oceans and ties it up in the form of limestones Pelagic limestones deposited in the deep ocean can be subducted and melted Limestones deposited on continental cmst are recycled much more slowly if theyare exposed and weathered their remains mayend up as pelagic carbonates if theyget caught up in acontinental collision they can be metamorphosed liberating their 203 Formation of calcium carbonate in prehistoric times ha quot3915quot x quot39y 39 mu ff quot Aragenital TrIT39IEEIrIGld Ftl can I canlmLinEvJCAnaPEnJTniJuni anr EENLJ WEEHDUSE1 GHEENHDUE HCEHQQEE39 I G EENHDU5E39 EET HighMg Cale1m and Irma alaIJnclzlnlll Arugnmlu gnlcizu Mg comem gemsrally izwnr increasing Inward 39 39T1r239 IUII1quot General Considerations Fixation of CO2 in organic form requires an energy source In biology that energy source is the sun s radiation The formation of CaCO3 is thermodynamically favorable However the process is slow The calcium content of seawater is about 380 mgL The solubility product of calcium carbonate is KSID Ca2CO321 5 x 10399 at 298 K The concentration of CO3239 depends on pH because of the two acid equilibria co2 H20 9 HCO3 H 9 co3z 2H Carbonic Anhydrase Enzyme example Carbonic anhydrases are enzymes that catalyze the hydration of carbon dioxide and the dehydration of bicarbonate co2 H20 gt Hcoa H Carbonic anhydrase isozymes are metalloenzymes consisting of a single polypeptide chain Mr 29000 complexed to an atom of zinc They are incredibly active catalysts with a turnover rate km of about 106 reactions per second Natural biomineralization Natural biomineralization varies from organism to organism A common feature is the further catalytic step HCO3 a 0032 H m i The driving force for formation of calcium F 39 7 139 carbonate is used to make this reaction K n 39 39 occur But relatively little is known about I this step 39m It occurs in a variety of places Chickpeaseedlings 1Extraceuar mycorrhiza quot h l a 39 2ntraceuar compartments coccoiths 3Ce surface brown alga chick peas t 39 a i an m yco nhiza migi The Balance between the Atmosphere and the Ocean The most common method of CO sequestration CO2 Atmosphere Concentration 1945 270ppm 2005 350ppm 2050 550ppm How much of the carbon ends up Chemical Equilibria and the Solubility of Carbon Dioxide The independent reactions involved in solution of 002 The following are the processes that lead to 002 solutions in the ocean C02aq C02g CO2 aq H200 H aq HCO aq HCOE aq ng aq Haq For each independent net reaction there is an equilibrium constant In the Henry s Law constant the pressure is in atm concentrations are taken equal to molarities 1 molar 1 moleliter K1 PCOZ 1rnCO2 30 HcogmH rnCOZ 45 gtlt1O7 17 K3 mcogzmH mHCOg 21 x 10 Kzzm Add constraints to the system In the study of the ocean we can take the concentration of hydrogen ions and the partial pressure of carbon dioxide as known for a given state of the atmosphere and the ocean Based on the known pH and partial pressure of 002 mH 63gtlt10 9 PCOZ 38x10 4atm we can calculate the expected value of other species from the equilibria We do not need a constraint for H20 since it does not appear in the equilibrium constants Solve for concentrations We therefore have three equations snd three unknowns and we can solve for the molarities of the carbon dioxide bearing species mCOZ 2380x10 4 30127gtlt10 5 mHCOg 45gtlt107 gtltmCO2 mH 907gtlt104 17 6 Incog2 21gtlt10 gtltmHCOg mH 67gtlt10 We also know that 14 m m 10 H OH Charge balance condition In order to consider other states of the system it is necessary to consider charge conservation The hydrogen ion concentration is far below the concentrations of the negative ions There is no charge balance without additional cations We therefore determine the molarity of cations required to balance the charges due to 003239 aq H003 aq and H aq mob mOH 2mm mHcog mH 922 x 10394 The majority of these compensating ions are calcium Of the total carbon dioxide calculated 927x10394 the majority ca 907x10394 molar came from fossil carbonate eg limestone dissolved into rivers and the remainder ca 2x105 molar came from the atmosphere Determining total amounts of 002 in the ocean and the atmosphere The mass of the ocean is mocean gtlt1021kg Nair eq represents the number of moles of 002 from the atmosphere that have dissolved in the ocean Natmeq 127 x 105 molal13 x1021 kg 165 x1016kg The number of moles of 002 in the atmosphere is Force Area x Pressure 515 x 1014 m2105 Pa natmcoz XcozF0rce N 9 W82 X MW kgmoll where MW is the molecular weight of the atmosphere 0029 kgmol 38gtlt10 4 X 5 gtlt1019 X 103 29 98 67 X 1016m01es or NZn 11quot4 C 12 z 025 Summary of where what we know from the inorganic ocean Thus the inorganic ocean can dissolve only about 25 of the total carbon dioxide that is in the atmosphere In fact the there is a 40fold excess of 002 in the oceans over that in the atmosphere The discrepancy must be caused by two factors 1 Weathering ie runoff from land that brings carbonate into the ocean 2 Living organisms that capture 002 in an inorganic form shells Calculating the dependence of the ocean concentrations of 002 on increasing 002 pressure Using the current value of 380 ppm carbon dioxide in the atmosphere and the three equilibrium constants given above we can calculate H HCO3 and 0032 as a function of the partial pressure of COzg using the 3 equilibrium constants and the charge balance equation 922gtlt104 m H 15 gtlt1014PCOZ mH 635gtlt10 25PCOZ m1 10 14mH Dependence of ocean species on PCOZ This equation relates the hydrogen ion concentration in the inorganic ocean to the partial pressure of the carbon dioxide in the atmosphere The calculated hydrogen ion concentrations can be used with the carbon dioxide partial pressures to calculate the molarities of the dissolved species PCOZ mHgtlt109 mCO2gtlt105 mHCO gtlt104 mCO 2gtlt106 400 654 134 922 651 500 816 167 920 522 600 979 200 919 434 700 114 234 924 374 The ocean is saturated in CaCO3 Now to return to the question of the ocean as a significant sink for anthropogenic carbon dioxide When the species were listed CaCO3s was not included In order for it to form the system must be saturated with respect to its formation It is reported that the surface of the ocean is 232 x 103 molar in Ca2 The solubility product for calcium carbonate is 492 X 109 Ca2CO Ksp in the ocean the ion product is 232 x103 x 67 x106 155 X 108 which is greater than the solubility product ie for the simple system considered here the solution is supersaturated Saturation and States of Disequilibrium The concentration of the CaCO3 is not necessarily in Equilibrium In other words there can be an excess Or deficit of Ca2 and C03239 in the solution above the CaCO3 solid If there is an excess of ions in solution the solution is supersaturated If there is a deficit then the solution is subsaturated KSID Ca2CO321 If the system is not in equilbrium then there will be a driving force AG to attain equilibrium AG AGo RTan The three possible states are AG gt 0 Q Ca2 C0321 gt K Supersaturated AG 0 Q Ca2CO321 K Saturated AG lt 0 Q Ca2CO321 lt K Subsaturated The ocean as a 002 sink So could CaCOgs be a significant sink for anthropogenic humanmade carbon dioxide It has been observed that there are no large deposits of CaCOgs on the bottom of the deep ocean so the answer is probably no There are several possible explanations for this and all possibly contribute to failure of the precipitate to form or its redissolution in the deep ocean 1 002 redissolves in the deep ocean 2 Ionic activities are reduced high salt concentration 3 Surface free energy presents a barrier to precipitation Pressuredependent equilibrium There are large pressures up to nearly 1 kbar in the deep ocean One scenario is that calcium carbonate forms at the surface and sinks to depths where it redissolves because of effect of pressure on the dissolution reaction CaCO3 gt Ca2 C032 AV 62 cm3mol molar volume of reaction The molar volume water of solvation is less around the ion that around the solid or the bulk For example at 8000 m P 800 atm lnKPK AV PR lnKPK 0062 L800 atm008206298 K 20 K800 atm e20K e20492 x 109 36 x 108 Millero in Geochimica et Cosmochimica Acta 59 661 1995 Sedimentation and the Snow Line The formation of calcium carbonate as a sediment in the oceans has been occurring for billions of years This process leads to the formation of limestone sedimenary rock One can imagine CaCO3 forming white particles and settling to the bottom This is like snow in the ocean since the particles build up a layer on the ocean floor However in the deep ocean the pressure shifts the equilibrium so that this snow melts before it reaches the bottom Below about 5000 m there is no limestone on the ocean floor This part of the deep ocean is known as the abyssal plain Deep ocean carbonate concentration is still lower than bicarbonate at surface Or mCO2 36x10 8 232x10 3 155gtlt10 5 molar From which we can conclude that even if the deep ocean were saturated with calcium carbonate the resultant molality of carbonate would be 23 times that at the surface and substantially less than that of bicarbonate at the surface Ocean acidification Furthermore if calcium carbonate were precipitating in an inorganic ocean the carbonate forming reactions below would be drawn to the right constantly forming hydrogen ions and decreasing the pH HCO 2 co2 H C02aq H20 2 co2 2H unless there were some mechanism consuming hydrogen ions at the surface Thus the pH of the oceans is falling in the short term The oceans are becoming more acidic Carbon recycling in the ocean We have seen that the inorganic species alone do not explain the large quantity ca 40 times the amount in air of carbon dioxide in the sea However living organisms in the sea die and fall toward the depths As they do so they are oxidized and produce carbon dioxide and their skeletal remains often contain calcium carbonate At great depths the dissolved carbon dioxide has over time become significantly supersaturated relative to the atmosphere because the upwelling required for equilibration is slow requiring a buildup of carbon dioxide at depth before a steady state is reached Ocean Carbon Recycling At depth CaCO3 s C02aq H200 gt 2HCO aq the surface C02aq gt C02g HCOE aq gt C02 g Haq C02 aq 2H aq gt C02 g H200 Where does humanmade 002 go The ocean takes up only 25 of the carbon dioxide output by humans As a result the pH of the oceans is decreasing The pH of the ocean has decreased from 82 to 81 since the beginning of the industrial revolution On a longer time scale 002 is fixed in the ocean as CaCOg However CaCO3 precipitation is slow and the ocean supersaturated in calcium carbonate


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