Global Carbon Cycle Project ENGR 3520

Table of Contents
Introduction............ Overall Mass Balances of Carbon in Carbon Cycle..... Conclusion........... Appendices............ 1. 2. 3. 4. Increasing CO2 Accumulation in the Atmosphere Overall Mass Transfer Diagram of CO2 Level of Uncertainty Bibliography 3-9 9-10 10-13 14-17 14 15 16 17

Introduction

There has been a lot of debate about both the extent of climate change occurring on a global scale and the actual causes of that change. It has especially become crucial ever since Hurricane Sandy, a possible product of changing weather patterns that devastated hundreds of people. Hurricane Sandy is just one of many reasons why we should put climate change at the forefront of our minds (1).
Figure 1

Many scientists are convinced that there is enough evidence to support the theory that our relatively recently industrialized species and our consumption of fossil fuels is the cause of a carbon imbalance in the atmosphere. Some still believe that this change is a normal fluctuation in climate that is beyond our influence, like the many climate changes that have occurred over the earths history. The answer to this disagreement lies primarily in researching the mass transfer rates and proportions among the biosphere, atmosphere (carbon dioxide, methane, nitrous oxide, and hydrofluorocarbons or HFCs), hydrosphere, and lithosphere. The main compound that we are focused on is carbon dioxide. Scientists studying the composition of air trapped in glacial ice have documented an increase in CO2 composition only occurring in data from the past 300 years. Leading theories tie this change to the start of the industrial revolution and the beginning of a release of CO2 that had been stored in fossil fuels for thousands of years prior. Although other greenhouse gases are also key factors in the climate change, the main focus is on the carbon cycle and the obviously recognizable effect of CO2. This

report therefore places emphasis on the global carbon cycle in particular, but takes into consideration the fact that several other compounds are involved in the overall process causing climate change. The carbon cycle outlines the relationship among the atmosphere, the biosphere, lithosphere, and the hydrosphere based on the exchange of CO2. Carbon dioxide is a natural component of the atmosphere that made up approximately 275 ppm of the atmosphere before it began increasing around 300 years ago (2). The biosphere includes carbon in various forms: carbohydrates in plants and other autotrophs, organic compounds found in animals and other heterotrophs, deposits of carbon in the make-up of limestone (CaCo3) and fossil fuels, and carbon stored in soil and other organic matter. Carbon also gets stored in water in the form of dissolved carbonic acid (HCO3). The aforementioned carbon compounds get transferred between each other in varying proportions through a number of chemical processes. CO2 leaves the atmosphere as trees and other phototrophs undergo photosynthesis, where they convert CO2 to carbohydrates with energy from light. Carbon changes form in the biosphere and returns to the atmosphere as plant carbohydrates are consumed by heterotrophs, who then release CO2 through respiration or release carbon back to the biosphere as decayed organic matter as well as the lithosphere, when the skeletons of marine autotrophs fall to the ocean bottom and form limestone. Organic matter can be converted (eventually) to fossil fuels or can be burned and returned to the atmosphere. Fossil fuels (formerly organic matter) also transfer carbon to the air when burned, and limestone releases large amounts of CO2 via out-gassing by geological processes. This creates an overall cycle that could theoretically be balanced given known proportions and controllable variables.

Figure 2

This system therefore can be treated like any other mass transfer problem but on a generalized scale. Although Earth is a massive example of a traditional scientific system with an almost infinite number of variables, we can still gather useful data that helps us determine the effect of an imbalanced carbon cycle on the earth as a whole. Our atmosphere is made up mostly of nitrogen and oxygen (78.084% N2 and 20.946% O2 by volume). The rest includes argon, water, carbon dioxide, methane, nitrous oxide, ozone, other greenhouse gases, and other mostly inert gases. Carbon dioxide on average currently makes up 0.0314% of the atmosphere (by volume), which seems small but in comparison to the other components is relatively large. Only argon (0.9340% by volume), nitrogen, and oxygen contribute more. Other gases such as methane, nitrous oxide, and ozone contribute little to the overall system because they make up such a small percentage of the atmosphere (around 0.0046%). The water level fluctuates with humidity and can contribute somewhat to the greenhouse effect by

Figure 3

increasing the atmospheres ability to take in other greenhouse gases but cannot itself be considered a part of the atmospheric composition. The other greenhouse gases (methane, nitrous oxide, and hydrofluorocarbons) make up a much smaller fraction of the overall atmospheric composition than carbon dioxide, and will be negligible for this report. The current concentration of CO2 is 391.03 ppm which has been observed to be increasing at a rate of 2 ppm a year (3). This increase in CO2 is problematic because it has not been coupled with an increase in CO2 sequestered from the atmosphere. This imbalance is the hypothesized explanation for climate change. Many people in the scientific community believe that the increased carbon dioxide level is anthropogenic (caused by humans) through the increased burning of fossil fuels and the clearing of natural autotrophs by burning and clearing rain forests. This is evidenced by the sharp increase in CO2 following the industrial revolution when humanity began adopting these practices on a scale not seen previously. The atmosphere transfers CO2 both to and from the biosphere, the hydrosphere, and the lithosphere. Carbon dioxide from the atmosphere gets converted to carbohydrates through the process of photosynthesis in plants. Photosynthesis by terrestrial plants moves about 110 billion metric tons of carbon from the atmosphere to the biota (4). However, this cannot be assumed to be the only non-negligible exit stream of carbon leaving the atmosphere in the carbon cycle. When mass balances are calculated for the relationship between carbon emitted to the atmosphere, carbon being taken back in through transpiration (photosynthetic processes), and carbon known to be accumulating, a numerical error occurs. Carbon dioxide also leaves the atmosphere at the surface of the ocean where it participates in a myriad of reactions including the formation of carbonic acid. The rate at which this occurs depends on the amount of carbon

dioxide in the atmosphere, as well as the temperature and pressure as seen in Henrys law. An overall increase in atmospheric CO2 has in resulted in about a 3 percent increase in surface waters and 0.25 percent over the full ocean depth (5). Around 88 billion tonnes of carbon is released from the surface of the world's oceans each year, with an annual uptake by the oceans of 90 billion tonnes. Consequently, the net uptake of carbon dioxide by oceans is estimated to be approximately 2 billion tonnes annually. Carbon dioxide is incorporated into the lithosphere through the sedimentation of dissolved and particulate organic carbon; sediments provide a global carbon sink of about 10 million tonnes each year (6). The most reasonable conclusion to make here is to hypothesize that there is an unknown carbon sink that takes additional carbon out of the atmosphere. Some believe this to be the result of a proportional growth in net production of phototrophs, or an unknown uptake mechanism in desert soils, or photosynthetic activity occurring in photoautotrophic plankton. It has even been suggested that a carbon sink exists external to the atmosphere, though little evidence exists to support this. Regardless, the missing carbon can be treated for mathematical purposes as one variable. Therefore, mass accumulated annually in the atmosphere is equal to the annual mass input from the biosphere, lithosphere, and hydrosphere minus the annual mass output to the biosphere and hydrosphere since the hydrospheric transfer is cyclical. This accumulation equals the input from the biosphere and lithosphere minus the output to the biosphere and the output to the undetermined sink. The overall calculations are made later in the report and a full diagram of the overall system is included in the appendices. Carbon dioxide entering the atmosphere involves a much more complex series of carbon transfers. There are several channels through which carbon is transferred from the biosphere to

the atmosphere. This is why we subdivided the general concept of the biosphere as the nonoceanic part of earth into the biosphere above the surface of the earth and the lithosphere which includes soil, fossils, volcanic activity, and ocean floor deposition. The lithosphere releases CO2 into the atmosphere from volcanoes (380 million tonnes of carbon dioxide per year) (7) and from the burning of fossil fuels used in both transportation and industry (~ 5.3 thousand million tonnes). The biosphere emits carbon dioxide from industrial sources, deforestation and land use, and respiration of both plants and animals (industrial sources account for: 100 million tonnes, deforestation: 4 billion metric tonnes per year (8), respiration: 115 billion metric tonnes). This sums up to 1.191x10^11 metric tonnes/year from the biosphere and 5.68 billion metric tonnes/year from the lithosphere, which sums to a total input stream of 1.2478x10^11 metric tonnes/year into the atmosphere. There are many additional relevant reactions that take place solely within the biosphere. Carbon enters the biosphere through autotrophic reactions, but gets converted to many other forms of stored energy. Some of the carbon forms carbohydrates which are then either consumed by heterotrophs, or decay and contribute to the carbon concentration in soil. Both plants and animals return some CO2 to the atmosphere through respiration (115 billion metric tonnes), but the rest of these organisms carbon compositions become organic matter as either waste products or decay broken down by fungal organisms (which also respire). Some of the carbon dioxide also returns to the atmosphere when organic matter is consumed (burned). This deforestation actually contributes to the increase in carbon dioxide in two ways: it adds carbon and it decreases the amount of carbon that can be extracted from the atmosphere. Deforestation is a key contribution to carbon dioxide emission because it releases 4 billion metric tonnes of CO2 per year to the

atmosphere (deforestation evaluated further in overall balance and in conclusions section of report) (6). The lithosphere gets incoming carbon from two main sources. Carbon deposits to the ocean floor form coral and other organisms that convert CO2 to CaCO3 (CO2 + H2O H2CO3; H2CO3 + 2OH- CO32- + 4H2O; Ca2++ CO32- CaCO3) (9). Carbon also fossilizes over long periods of time and converts from organic matter in the soil to fossil fuels such as coal and petroleum. Incoming carbon from organic matter accounts for 2.27 billion metric tonnes/year and incoming carbon from ocean floor deposition is approximately equal to the amount of carbon emitted to the hydrosphere from the biosphere (appx. 2.1 hundred million tonnes/year). The lithosphere is also a highly probable source of carbon storage for many other carbon-containing compounds that are not yet being utilized. The lithosphere returns some of its carbon storage to the atmosphere through the burning of fossil fuels (anthropogenic) and through volcanic activity (380 million tonnes/year) (6). Overall mass balances of carbon in carbon cycle Carbon into atmosphere (respiration + deforestation+ industrial sources + fossil fuel burning + volcanism) Carbon out of atmosphere (photosynthesis + missing carbon) = 2.0 ppm/year(2)

Carbon into biosphere (photosynthesis + organic matter transfer) - carbon out of biosphere (respiration + deforestation+ respiration + emissions to hydrosphere) = accumulated carbon (this could include missing carbon)

Carbon into lithosphere (ocean deposits + organic matter from soil) carbon out of lithosphere (volcanism + fossil fuel emissions) = accumulation

Carbon into the hydrosphere (from atmosphere + from emissions) carbon out of the hydrosphere (to atmosphere + to ocean floor) = 2 thousand million tonnes/year (6) Conclusion While the global carbon cycle is essential for life on Earth, there has been a lingering problem with the accumulation of CO2. As a greenhouse gas, carbon dioxide absorbs and emits heat. Therefore, a high concentration of CO2 would cause a change of temperature, which would in turn cause a change of the climate. There are several possible solutions for this problem. Deforestation contributes a lot to the emission of CO2. It adds to the input (CO2 accumulated in the atmosphere) and decreases the output (CO2 then being absorbed by plants). Deforestation contributes 0.4*10^13 kg/year of CO2, so reducing deforestation by 50% would be very effective in decreasing the emission of CO2. Plants take CO2 from the atmosphere for photosynthesis, a process where carbon dioxide is absorbed and utilized for energy. A single mature tree can absorb CO2 at a rate of 48 lbs/year (10) and release enough oxygen back into the atmosphere to support two human beings. Imagine if we were able to plant enough trees in order to make up for the accumulation of CO2. If only $90 could plant 900 trees in the US that means that 43,200 lbs of CO2 could be absorbed (11). Over a large time period, it could be very effective. To improve reforestation, decreasing deforestation would essentially be priceless. We could encourage the use of recycled paper compared to virgin paper. The price differences are very minimal; for instance, virgin paper is $23/case, and recycled paper with 30% post-consumer

waste is $25/case (12). There is no noticeable difference between recycled paper with 30% postconsumer waste and virgin paper. If it takes 0.6 trees to make one carton of virgin paper (13) and 100,000,000 people leaned towards recycled paper instead of virgin paper, then 60,000,000 trees would be saved, and 2.9 billion lbs of CO2 would be absorbed. As for land usage, the cost of replacing an area of a forest with a metropolis takes a very large toll on the amount of CO2 being absorbed. For instance, Los Angeles is 1215.589 sq. kilometers and produces 1.7 ton of CO2 per year (14). One acre (0.004046 km) of trees can absorb as much as 4 tons per year. What is now Los Angeles could have been 300,442 acres of trees that absorb 1,201,512.16 tons of CO2 per year, whereas 300,442 acres of Los Angeles produces 510,751.68 tons per year (15). We can also look at cellular respiration and how an opposite approach could decrease the amount of CO2 in the atmosphere for some time. One plausible way to slow down cellular respiration would be to decrease the amount of humans. Genocide is not the recommended approach. Rather, we can promote policies that encourage populations to not expand beyond our environments carrying capacity.

CO2 can also be retained via the ocean. As seen in the flow chart, an amount of CO2 enters the ocean, and the same amount exits into the atmosphere once again. Trapping CO2 within the ocean would prevent it from adding to the atmosphere; however there may be

Figure 4

unforeseen consequences such as increased acidity. Thankfully there are phytoplankton, autotrophic creatures that absorb CO2 to create organic compounds. If 50 billion tonnes of CO2

are absorbed by the ocean (16), then an increase in phytoplankton could surely prevent a majority of CO2 from entering the atmosphere. Also, a global iron fertilization approach, which could increase carbon fixation by phytoplankton would roughly cost around $20 billion. (17) Various pathways for artificial carbon fixation are being researched and include several methods that employ solar power. The methods being researched include: homogeneous photochemical reduction of CO2, heterogeneous photochemical reduction of CO2, photoelectrochemical CO2 fixation, electrochemical reduction of CO2 using solar electric power, and solar production of hydrogen followed by hydrogenation of CO2 . These approaches have several attractive features, the least not being that they would allow for continued use of fossil fuels and infrastructure in place. In addition to this, commercial applications involving CO2 utilization in production of fuels and chemicals can be driven by a renewable resource, the sun (18). It would also be wise to put money into the research of the missing carbon. A billion tons of human-generated CO2, roughly half of the CO2 in the atmosphere, is supposedly absorbed by forests, but the amount is unaccounted for in field studies. If we can discover the location of the missing carbon, we can propose more ideas on how to hinder CO2 accumulation in the atmosphere. (19) All things considered, the best and most plausible solution for reducing carbon dioxide accumulation lies in approaching the solution from many angles. Reducing total emissions and increasing carbon uptake into the biosphere and lithosphere would maximize the amount of total accumulation we could decrease. This could be accomplished in an infinite number of possible proportional changes to the overall system. We could directly inject all the extra carbon to the

lithosphere. We could reduce all emissions entirely and wait for the trees and unknown carbon sinks to reverse the accumulation. We could plant enough new trees and stop deforesting enough to reverse the accumulation term so that we account for all emissions and let the other carbon sinks reverse the damage. If we were to plant enough trees to match our emissions (not including opportunity costs lost for land and labor), we could reverse the accumulation back to preIndustrial revolution levels in less than a year more than how long it takes for the tree to mature. This would cost around 20 billion dollars which is significantly less than what have thus far spent on one war. Even considering the effort this would entail and the drastic idea behind pouring all efforts into one reversal mechanism, this effectively demonstrates the feasibility of solving the problem of carbon dioxide accumulation. In short, it is very possible and in fact illogical not to at least attempt to repair our atmospheric carbon dioxide imbalance.

Appendix
Appendix 1. Increasing CO2 Accumulation in the Atmosphere

Appendix 2: Overall Mass Transfer Diagram

Appendix 3: Level of Uncertainty

This paper, out of necessity makes a lot of assumptions. The values are all approximate and there would be absolutely no way to gather accurate data in a system of the magnitude of a planet. Each numerical value has a margin of error. Each atmospheric value is subject to change with the immense variations in the atmosphere that inevitably occur with fluctuations in temperature, humidity, lunar cycles and many more variables. However, over the time span of year, we can assume enough certainty that the observations gathered from the overall trends are correct. We know CO2 levels are increasing and we know they could be reduced. By how much and with how much effort is subject to immense variation. But this is true of all data expanded to fit the earth as its system. Common sense can be applied to our results. In order to reduce an accumulation term you must either reduce input or increase output. Both actions combined reduce the extent to which each would need to occur. These are the basic principles of mass transfer balance and they apply to our atmosphere like they apply to any other system subject to the same scientific law of conservation of mass.

Appendix 4: Bibliography 1. Zeller, Tom. Obama Victory, Sandy Give Environmental Groups Hopes For Climate Change Action. Nov 2012. Web. 11 Nov. 2012 <http//www.huffingtonpost.com/2012/11/07/obamasandy-climate-change_n_2086942.html> 2. John F. Mongillo, Linda Zierdt-Warshaw, John F. Mongillo,Encyclopedia of Environmental
Science,University, Rochester Press, 2000,ISBN1573561479, 9781573561471

3. Earths CO2 Home Page. CO2 NOW. Web. 11 Nov. 2012 <http://co2now.org/> 4. Environmental Chemistry: Carbon Cycle. The Encyclopedia of Earth. May 2012. Web. 11 Nov. 2012 <http://www.eoearth.org/article/Carbon_cycle?topic=49505> 5. What is Ocean Acidification? PMEL Carbon Program. Web. 11 Nov. 2012 <http://www.pmel.noaa.gov/co2/story/What+is+Ocean+Acidification%3F> 6. "Carbon dioxide News." Carbon Dioxide: Sources, sinks and science. GreenHouse Gas Online, 29 Oct 2012. Web. 29 Oct 2012. <http://www.ghgonline.org/carbondioxide.html 7. The Slow Carbon Cycle. NASA Earth Observatory. Web. 11 Nov. 2012. <http://earthobservatory.nasa.gov/Features/CarbonCycle/page2.php> 8. Biomass Burning: Pressure State Response Indicators. Food and Agricultural Organization of the United Nations. Web. 11 Nov. 2012 <http://www.fao.org/ag/againfo/programmes/en/lead/toolbox/Indust/BioBurEA.htm> 9. "Lime Water/Carbon Dioxide Reactions."The University of Arizona Chemistry. N.p., n.d. Web. 11 Nov 2011. <http://quiz2.chem.arizona.edu/preproom/Demo Files/lime_water_carbon_dioxide.htm>. 10. Alexander, Kathleen. "Benefits of Trees In Urban Areas." Colorado Tree Coalition. N.p., n.d. Web. 11 Nov 2011. <http://www.coloradotrees.org/benefits.htm>. 11. "Greenhouse Gas Emissions." United States Statistics Division. United States Statistics Division, Jul 2010. Web. 11 Nov 2012. <http://unstats.un.org/unsd/environment/air_co2_emissions.htm>. 12. "Copy Paper: Cost, Quality & Supply."Responsible Purchasing Network. The Responsible Purchasing Network, n.d. Web. 11 Nov 2012. <http://www.responsiblepurchasing.org/purchasing_guides/copy_paper/cost_quality_supply/>.

13. "Trees Into Paper." Conservatree. Conservatree, n.d. Web. 11 Nov 2012. <http://conservatree.org/learn/EnviroIssues/TreeStats.shtml>. 14. "Cities and CO2 - Bigger is Better."Martin Prosperity Institute. Martin Prosperity Institute, 14 Oct 2009. Web. 11 Nov 2012. <http://martinprosperity.org/insights/insight/cities-and-co2bigger-is-better>.

15. "Welcome to Key to the Citys page for Los Angeles." . N.p., n.d. Web. 11 Nov 2012. <http://www.usacitiesonline.com/cacountylosangeles.htm>. 16. "Ocean plankton absorb less CO2 ." BBC News 30 Aug 2006, n. page. Web. 11 Nov. 2012. <http://news.bbc.co.uk/2/hi/science/nature/5298004.stm>. 17. "Debate: Geoengineering, iron fertilization of algae blooms." Debatepedia. N.p., n.d. Web. 10 Nov 2012. <http://debatepedia.idebate.org/en/index.php/Debate:_Geoengineering,_iron_fertilization_of_alg ae_blooms> 18. Carbon Dioxide Fixation. Department of Energy Information Bridge. Web. 11 Nov. 2012. <http://www.osti.gov/bridge/servlets/purl/752960-T3jXzX/webviewable/752960.pdf> 19. Burgermeister, Jane. "Missing carbon mystery: Case solved?." Nature Reports Climate Change. n.d. n. page. Web. 11 Nov. 2012. <http://www.nature.com/climate/2007/0708/full/climate.2007.35.html>.