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by: Michael Reilly


Michael Reilly
GPA 3.71


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Class Notes
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This 15 page Class Notes was uploaded by Michael Reilly on Friday September 4, 2015. The Class Notes belongs to CHEM 0103 at University of California - Los Angeles taught by Staff in Fall. Since its upload, it has received 108 views. For similar materials see /class/178003/chem-0103-university-of-california-los-angeles in Chemistry at University of California - Los Angeles.




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Date Created: 09/04/15
W 1oaW 39 L Carbonqdolm Oil spills l In 1969 a Federal platform offshore Santa Barbara experienced a blowout in one of its wells an estimated 80000 barrels 3360000 gallons or oil was released into the ocean Since the tragic oil spill in Santa Barbara in 1969 about 833 barrels of oil have been spilled as a result of DOS outer continental shelf natural gas and oil operations offshore California The California nearshore and coastal areas are replete with natural seeps It is estimated that over 1000 barrels of oil each week are released into the environment from these seeps from the Coal Oil Point seeps alone almost 200 barrels a day may be entering the ocean Oil spills MURPHY OIL SPILL a 250000 barrel above ground storage tank tank 2502 was dislodged lifted and damaged in flooding associated with Hurricane Katrina At the time the tank contained 65000 barrels of mixed crude oil and released approximately 25110 barrels The released oil has impacted approximately 1700 homes in quot 7 M quot 39 an adjacent residential neighborhood an area of about one square mile Oil spills and Hurricanes Katrinas environmentally related influence 041906 87 platforms still evacuated 7 so so 1 Floating platforms Hm 2 Spilling platforms 3 Leeks of natural gas Hurricanes Rita and Katrina August September 2005 1 3 Katrina caused a huge impact on the oil production i 4 041906 shut in of oil 334019 BOPD 22 daily prod gas 13 Oil spills refinery accidents The environmental impact of oil recovery is Faxes City quotemery strongly influenced by numerous accidents U 39 Q In March 2005 a major accident in the largest refinery in the US occurred in Texas City TX Several people were killed toxic gases were spread around some ofthe Houston suburbs 6 139 More important are the numerous accidents involving tankers The most famous ofthe recent past is the Exxon Valdez 1989 Exxon Valdez oil spill The Exxon Valdez ran aground March 24 1989 on Bligh Reef in Prince V lliam Sound in the Gulf of Alaska It was carrying 126 mill barrels of crude which it had just picked up at the southern terminus of the Alaska Pipeline in the small city of Valdez M Three methods were tried in the effort to clean up the spill oBurning oMechanical Cleanup oChemical Dispersants Exxon Valdez oil spillll The oil spread quickly and some effects are still recognizable today Spread of oil mm the Exxon Valdel l v u I m M The cleanup cost Exxon about 4M they paid a 1 M fine In response the oil pollution act OPA was signed in August 1990 Oil spills and forensic chemistry Frequently small oil spills with unknown sources are encountered The ship operators did not own up to having created the problem In such cases one can analyze the oil GOMS and generally egtltacty identify the field that produced it Biomarkers are a key part of the story This may not immediately solve the crime but it moves the authorities much nearer to a solution Another example pristane C19 indicates more oxidizing conditions phytane C20 more reducing conditions phylane or Early atmosphere C02 from fermentation by prokaryotic heterotrophs eg by 6 aq gt 2C2H5OH aq 2C02 9 CH4 from metabolism by methanogenic bacteria eg by 4H2g co2g gt CH4g 2 H20 ac The total amount of carbon is shown in the table on the right side The carbon cycle Quantity Pools Gt Atmosphere 720 Oceans 38400 Total inorganic 37400 Surface layer 670 Deep layer 36730 Total organic 1000 Lithosphere Sedimentary carbonates 50000000 Kerogens 15000000 Terrestrial biosphere total 2000 Living biomass 600 1000 Dead biomass 1200 Aquatic biosphere 1 2 Fossil fuels 4130 Coal 3510 Oil 230 Gas 140 Other peat 250 DIC dissolved inorganic carbon DOC dissolved organic carbon POC particulate organic carbon The carbon cycle gt Atmosphere 750 l l Photo Dissolution Degassing Deforestation synthesis Decay warm 70 warm 80 06 26 100 120 50 60 cold 35 cold 22 Fossil fuels Respiration 56 40 60 Rivers DOC S f t Terrestrial 0395 ur ace wa ers 1020 610 Soil and detritus Deep water 2190 38100 4 DOC 700 Volcanoes Erosion POC 30 005 018 uplift Sedimentation l Inorganic sediments 50000000 Carbonates Units are Pg 1015 gram 05 V Surface sediments 150 Sinking remineral ization Organic sediments 10000000 Fossil fuels 5000 The CO2 fixation problem Every person releases 5 tons 002 from fossil fuels year in industrial countries 1999 US gt5t Australia 5t Canada 4t Europe Japan Russia 3t of total global release from fossil fuel burning from deforestation in Southeast Asia Central America On average 50200 years of adjustment time necessary for any input Storage possibilities Temporary sinks fast but inefficient 10L Permanent sinks really slow working Ocean acidic direct dissolving in seawater CO2 H20 gt H HCO3 Ocean neutral 104 Annual emission EOR 103 Characteristic storage time years 2co2 H20 CaSiO3 gt Sio2 CaHCO32 ms fs on Leaf litter and woody biomass only 10 temporary no final storage quot6 Oceanfloor long lasting bUt inefficient 1 10 100 1000 10000 100000 1000000 Carbon storage capacity Gt The CO2 fixation problem ll Storage possibilities using Mgchlorides MgCl2 H2003 gt MgCO3 2 HCI EOR enhanced oil recovery fast but small amounts only North Dakota Sakatchewan oil field Saline aquifiers below freshwater level porous rock w salty water huge capacity done in Norway potentially in whole North Sea lower Great Lakes southern Florida NE Texas Carbon sequestration from power plants Concentrating is necessary to make the storage process economically and energetically resonable Still amines used RZNH 002 gt RZNCOZ39 H Most of the 002 is not produced from centralized units but cars Solution might be a central hydrogen electricity producing facilities Removing carbon from the atmosphere lron fertilization no efficient solution since phytoplankton does not settle in the amounts necessary Fastgrowing plants in large forests only temporary storage The increase in CO2 and global warming ATMOSPHERIC C02 VARIATIONS SINCE 1000AD I ElIIilll39lllil39llllllililzl39lllillll39lrllllilllllllltlllllgj 360 g 370 Ma39una LWOb uvammHa39wa I j Atmospherezlvlauna Loa ii In the atmosphere 3 f M in Icaapwm increased about 30 in E 340 35 quot q IZZZZIZCSEWT the past 150 years 39 39Cetawm D 340 E 320 330 55 a E Almost all of this increase g 300 3 has been the result of g 39 fossil fuel burning and the 280 consumption rate is going 2603llllll39llllllllllllllllllllll llll llllKalil lxle39l Lr1Al 1000 1200 1400 600 1800 20 1500 Year N Gruber IGPP Solar and 39 new sources V I I I Hydro 39 gonserva 0n39vo39o 5 Imuin sa villiI ll m V The lowest prOJected rate 0 I 1 1 Gets of increase I have seen 1980 2000 2020 2040 2060 Where does all the extra CO2 reside The amount of CO2 present as C02aq HCO339 and C0321 in the ocean is about 60x greater than that in the atmosphere The mass of the Earth s atmosphere is 51x1021 g Multiplying this by 280 ppm atmos CO2 concentration in 1860 we obtain 14x1018 g The atmos concentration increased by 90 ppm 32 to 370 ppm A key parameter is the residence time of CO2 in the ocean aThe ocean can be divided into a relatively thin ca 100 m deep warm surficial layer and the intermediate or deep layers that cover the remainder the mean ocean depth is 4000 m aThe residence time for CO2 in the surficial ocean is short around 13 years It does exchange with the atmosphere and a sizable fraction of the anthropogenic CO2 has entered this zone i In contrast the mean residence time of the cold deep layer of the ocean is about 1000 years Only a minor fraction of the anthropogenic CO2 has been transferred to this layer Takeup of CO2 by the ocean The pH of the present ocean is about 78 The higherthe pH the greater amount of CO2 that will dissolve For example Manahan 2000 calculates that the combined solubility of 002 H003 and 003 is 14105 M in pH 7 water but is about 100x higher in pH 11 water As CO2 dissolves in the ocean it will gradually lower the pH One recent estimate is that the growth in CO2 will ultimately lowerthe pH down to 70 Acid Mean ocean pH H2003 HCO339 c03 log concentration Alkaline l l l l l l l 3 4 5 5 7 8 9 101112 pH HZCO3 Carbonic acid readily dissociates HCO339 Bicarbonate 03 Carbonate Ion


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