Paper "The Origins of Petroleum, A New Theory"

        Version 3/2/2016         

Authors: Edward L Goldmann PhD, Frank W Moore PE, and Louis H Goldmann PE

Page  of 20

The Origins of Petroleum, A New Theory

Authors: Edward L. Goldmann Ph.D.Ch.E., (AAPG 10118706), Francis W. Moore B.S.M.E., PE, and Louis H. Goldmann B.S.Cer.E., M. E. M., PE

        Abstract:

The origins of geologic petroleum have been debated for nearly as long as man has incorporated its usefulness into modern society.  We propose that prevailing theories of how ‘natural’ petroleum comes about in the earth’s crust have overlooked two important possible mechanisms:  First, the existence of methane hydrates in ocean sediments under specific conditions;  Second, the presence of uranium in these sediments, the radiolytic decay of which (and associated subsequent isotopes) supply necessary energies to promote and possibly even catalyze the conversion of methane hydrate into higher molecular weight hydrocarbon materials.  We propose nuclear and chemical models which are supported by independent works found in the literature.

In recent decades we have just begun to understand one of the unique properties of water in the formation of clathrates in the oceans, lakes, and permafrost.  When one considers how the earth’s dynamics transport methane gas, how this methane can form hydrates, how hydrogen sulfide can influence the oxidation number of uranium to a virtually insoluble material leading to non-negligible local concentration, how plate tectonics move deposits en masse, and how the radiolytic decay of uranium within these sediments can provide the ionization energy needed to polymerize methane into longer hydrocarbon chains, a new theory evolves as to how huge quantities of petroleum in the earth’s crust was formed.  The biggest open question is the rate at which any of this is occurring.  The authors’ theory will be described in detail in this session, provide a greater understanding of the petroleum formations, and will further expand the techniques for finding petroleum reserves.  

Key Words

Origin, Petroleum, Oil, Natural Gas, Methane, Clathrates

  1. Opening statement

Goldmann Moore Theory for the Origin of Petroleum

This paper will present a new theory as to the oil and natural gas deposits that exist around the world, and the link between methane hydrate and these deposits.  This theory will show that the earth has a methane cycle that results from the thermodynamic engine resulting from the temperature and pressure differences.  This energy provides the same energy that powers the water cycle of the earth also provides for a Methane Cycle, a Carbon Dioxide Cycle, and a Nitrogen Cycle.  The Methane Cycle will provide bases for the fact that natural gas and oil is always being formed on the ocean floor.  This occurs in the areas that have the correct conditions to allow the cycle to deposit the hydrocarbons in the sediments of the ocean floor.  These conditions can also occur in permafrost.  Methane hydrate and its unique properties provides a major link in this cycle.  The lack of knowledge about this material and how it contributes to the cycle has been the missing link in understanding the Methane Cycle, and the formation of natural gas and oil deposits.  The starting material is primarily methane hydrate in the sediment on the ocean floor or in the sediment in the permafrost.  As the sediments are covered and or moved due to plate tectonics, the methane hydrate warms and the methane is released.  

The conversion of methane to longer chain hydrocarbons is another step in the process.  Due to the high pressure and the high energy particles from the decay of primarily uranium and its daughter products the methane can be polymerized or cross linked in to longer chain hydrocarbons which make up crude oil and heavy crude oil.  It is no coincidence that uranium is found in significant quantities among the deposits of crude oil and oil sands.  

Earth as a processing engine

About one half of the energy from the Sun reaches the earth according to NASA and other Sources.  The Sun, Earth and moon and their movements provide the energy that powers the mighty thermodynamic engine, which makes up the weather of the earth, the tides, the winds, and the ocean currents.  This engine provides the necessary energy to power the various cycles that exists.  This energy is necessary to overpower other forces such as gravity, the rotation of the earth, and other laws of physics.  These huge flow of energies have been here since the earth was formed and then when the moon was formed.  It is very likely that this energy is also a major part of the driving forces in the movement of the earth’s magma and the movement of the earth’s tectonic plates.  

Certain Natural Gas, Crude oil, and Heavy Crude Oil in tar sands are/can be defined by the new theory.

Natural Gas and Crude oil

High methane content natural gas, crude oil deposits in sandstone layers, and limestone layers, can be defined by the Goldmann Moore Theory.  Natural Gas is primarily methane with other light hydrocarbon gases mixed in.  The hydrocarbon gases are chemically combined elements of hydrogen and carbon.  Also within the deposits are other molecules and elements that can provide evidence as to how these deposits were formed.   An example of one of these elements is helium and the amounts that exist in the sediment layers.  Also lead isotopes 206 and 207 in the deposits give an indication as to the source of the hydrocarbons.  Table 1 below provides the composition of Natural Gas in Gas Fields in Texas.

Table 1

Composition of natural gas from the western part of

the Panhandle field, the Cliffside field, and the Quinduno field

[Analyses by the U.S. Bureau of Mines (Boone, 1958)]

 

Western part of Panhandle field  1 

Cliflside field

Quinduno field

Volume percent

Methane

71.6

67.1

80.2

Ethane

5.4

3.6

7.7

Higher hydrocarbons

4.3

2.8

5.5

Carbon dioxide

0.3

0.7

0.1

Hydrogen

0.1

0.2

0.1

Nitrogen

17.4

24.8

6.3

Argon

.05-.1

.1-2

Tr.

Helium

1.11

1.79

0.14

Oxygen

Tr.

Tr.

Tr.

Ratio

He: A

10

20

 

He3:He4._

2   1.73X10-7

 

1.5X10-7

3   1.5X10-7

 

Pounds per square inch

Initial Pressure

440

730

883

1 Average of analyses from 10 wells having highest helium content.

2 From Coon (1949).

3 From Aldrich and Nier (1948)

[1]

Heavy Crude Oil in Tar Sands

Heavy crude oil deposits in tar sands are all the result of the Methane Cycle in the earlier years of the earth and continue today.  Heavy crude oils are hydrocarbons chains.  They all are chemically combined elements of hydrogen and carbon.   These petroleum deposits also have other molecules and elements that can provide evidence as to how the deposits came about. Also what is missing from these deposits can be helpful in identifying how these deposits where formed.  The lack of significant amounts of free carbon like what is found in coal is just one example.

It is almost impossible to describe exact structures of all the components in bitumen. Some chemical elements of bitumen from the Athabasca oil sands are listed in Table 2 (Nelson and Gray, 2004).

Table 2: Typical composition of Athabasca bitumen

Bitumen

 C

  H

  N

O

       S

Ni

       V

                            (wt.%)          

 (ppm)

Syncrude    

83.1

10.6

0.4

1.1

4.8

 

 

 

 

 

 

 

 

150

290

Suncor        

83.9

10.5

1.0

1.0

4.2

 

 

Classified by alkane solvent solubility, bitumen contains mainly two groups of

Organic components: asphaltenes and maltenes.  

[2]

        II.         Sources of methane and other ancillary hydrocarbons

Atmosphere

The atmosphere is a mixture of gases and each gas makes up the pressure of the atmosphere based on the percentage of the gas.  The Ideal gas Laws in its simplest form is: PV=nRT.  The gases in the atmosphere vary, but for the most part follows the ideal gas laws.  The composition is shown in Table 3.

Table 3

http://www.ux1.eiu.edu/~cfjps/1400/TBL01_0T2.JPG[3]

The percentages of these gases are well distributed and very uniform in the atmosphere just above the Ocean surface.  

Henry’s Law in physics, Henry's law is one of the gas laws formulated by William Henry in 1803. It states:

"At a constant temperature, the amount of a given gas that dissolves in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid."

P=kH C

For Oxygen O2,  H=  1.3×10-3  kH /[M/atm]   P= 0.20946 atm     C= 0.20946/ 1.3x10-3 = 161.12308

 

For CO2, H=  3.4×10-2    kH /[M/atm]             P= 0.00036 atm      C= 0.00036/=  3.4×10-2 = 0.01059

For CH4,   H= 1.4×10-3   kH /[M/atm]             P= 0.0000015 atm   C= 0.0000015/ 1.4×10-3 = 0.00107

The various gases of the atmosphere dissolve in to the ocean surface based Henry’s Laws constancies (solubility) and the temperature of the water.  The current data show that the CO2 is about 250 times higher than CH4 in air at the surface of the ocean see Figure 1 below.   The partial pressure of CO2 is much higher than the partial pressure of methane at the surface of the ocean.  Using equations for determining the solubility of CO2 and CH4 one can determine the amount of methane per volume of seawater at the ocean surface.  This amount varies based on the temperature and salinity of the seawater and can be calculated by the equations and tables describes in Wysenburg’s and Guynasso’s paper detailed below.  As the wind and waves turn and mix the upper levels then the seawater with absorbed methane is moved away from the surface and more sea water is moved to the surface to absorb more methane and other gases.  

        III.         Methane Concentration, a Nucleation Model

Methane concentration

Methane has known, non-negligible solubility in water, both fresh and sea.  As the water bearing methane circulates, this provides a continuous supply of “background methane” that can preferentially lead to hydrates when local conditions indicate.  

Seawater depths from surface to 250m are typical pressure regimes as to which hydrate formation can begin.  In coastal areas, runoff water loads the local seawater with mineral particulates.  Large particles fall quickly to the bottom, but smaller particles can remain suspended for quite some time. 

Nucleation  Sites

These particles may provide for a nucleation site for hydrate to form en masse.  

Continued agglomeration of methane hydrate and particulate material eventually results in a body whose specific gravity exceeds the surrounding water, and a deposit is formed on the seabed.  Particles that either rise to the surface, or fall too deep, disassociate and no hydrate deposit materializes on the seabed.

        IV.         Sedimentation / Co-sedimentation with methane hydrate and other mixtures

Sediments of sandstone and shale

At a solubility of 22.7 milligrams of methane per liter of sea water, a rough calculation indicates that a cubic mile of seawater would contain ~94,000 metric tons of methane.   As methane is stripped from the earth's atmosphere by its bodies of water, minerals/solids are usually present in varying amounts.  The source of these materials are from such sources as coastal erosion, river silt, wave action on larger particles, current action sweeping the water body's bottoms, underwater volcanic activity,  mineral precipitation in the water, salts, water borne decaying creatures, creature skeletons, organic materials, and materials from other processes.  As physical conditions allow, this depositional buildup with methane hydrate may happen in inland ponds and lakes as well as the seas and oceans.

As the deposit of methane hydrate and sediment deposits thicken over time the pressure and temperatures on portions of the deposit increase.  Over many millions of years and as the continents shift due to plate movement, elevation changes relative to sea level occur.  It is likely that some of the deposits would come out of the water with large solid overburdens and move inland, relatively speaking.  Others would likely go deeper in the ocean and be covered more substantially.  These deposits would then slowly dry somewhat, consolidate, and heat up even more due to the thermal heating from the earth below.

Sediments of Uranium

The materials that are deposited with the methane are of particular interest.  Uranium is in seawater at a content of about 3.3 parts per billion or 3.3 milligrams per cubic meter.  Due to known depositions and characteristics of some seabed sediments[4], for our evaluation we will assume the uranium in the initial methane deposit is approximately 40 parts per million (ppm) dry bases.  This value and the process of rendering the uranium insoluble from the seawater is widely supported throughout the entire 170 pages of the referenced paper.

Table 4 Radioactive decay path for Uranium-238:

Element

Isotope/half-life

Branching

Particle & MeV* energy

Uranium-238

4.46E9 y

~100%

α 4.27

Thorium-234

24.1 d

100%

βˉ 0.273

Protactinium-234

1.18 min

~100%

βˉ 2.197

Uranium-234

2.46E5 y

100%

α 4.859

Thorium-230

7.54E4 y

~100%

α 4.770

Radium-226

1600 y

100%

α 4.871

Radon-222

3.82 d

100%

α 5.590

Polonium-218

3.1 min

~100%

α 6.115

Lead-214

26.8 min

100%

βˉ 1.024

Bismuth-214

19.9 min

~100%

βˉ 3.272

Polonium-214

164 μs

~100%

α 7.833

Lead-210

22.3 y

~100%

βˉ 0.64

Bismuth-210

5 d

~100%

βˉ 1.163

Polonium-210

138 d

~100%

α 5.407

Lead-206

NA

 

Stable 

* Million electron volts

[5]

So, after the initial U-238 decay, the cycle is completed to Lead-206 in about 323,000 years on average, based on cumulative addition of half-lives.  This 323,000 year long chain of events releases about 44 million electron volts (MeV) of energy from the alpha particles and about 8.6 MeV of energy from the beta electrons.  During this decay path chain the total energy released from a single uranium-238 atom is then about 55 MeV.

Assuming the deposit is 350 million years old (or about 8% of the U-238 half life) then one could expect about 4% of the uranium to undergo radioactive decay.  In absolute terms, about 1.6 ppm would have decayed and released energy and alpha particles into the deposit.   The alpha particles as a matter of course become helium in the deposit.  Using a one-meter cube of deposit that originally contained 1% by weight natural gas, and at a specific gravity of 2.5, the cube would weigh about 2,500 kilograms and contain about 25 kilograms of methane.   About 4 grams of uranium has decayed within the deposit over the 350 million year time period releasing about 0.54 grams of helium and 5.59 X 1023 MeV [or 5.59 X 1029 electron volts (eV)] of energy into the one-meter cube of the deposit.

The bonding energy of the hydrogen atom to the carbon atom in methane is about 4.5 eV.  Likewise the bonding energy of a diatomic hydrogen molecule is about 4.5 eV.  A production of 2 mol% of ethane in the deposit would require about 62.5 moles of methane to be bonded together into 31.25 moles of ethane.  This would also release 31.25 moles of diatomic hydrogen into the deposit for further reaction.

Thus the reaction, 2 CH4  + energy → C2H6 + H2 

2 mol% of ethane is 31.25 moles of the 25 kg which would consume and affect 62.5 moles of methane.  62.5 moles of methane losing one hydrogen each would take 1.694 X 1026 ev of energy at a minimum.  With 5.59 X 1029 ev available due to the decay of the uranium, allows that 3.3 X 103 ev is available at 100% efficiency for each of the 4.5 ev tasks.  This means that 730 times the needed energy is available to do the disassociation of the hydrogen directly from the methane molecules.  As an alternative mechanism to release the hydrogen of the methane, particle induced X-ray emission and X-ray fluorescent emission due to the beta electrons is also available to provide the dissociation energy.  

Presuming that 2 methyl radicals combine to form an ethane, the hydrogen atoms are free to combine to form diatomic hydrogen.  Although the energies released due to these formations are significant, the energy release is ignored here.  

This nuclear radiation induced polymerization or so called “cross linking” of the methane in the deposit is the main method proposed for the formation of natural gas and oil deposits directly from methane.  The theory proposes that the polymerization will continue to form longer chain hydrocarbon compounds and produce hydrogen and helium at a minimum.  This reaction can be compared to the hardening of plastics by solar radiation where the ultraviolet light cross links plastics and makes the material brittle.  

“The amount of uranium in black shale may be directly related to the amount of organic matter present. Because the organic matter yields oil on pyrolysis, an indirect but positive relation may exist between the uranium content and oil yield of a shale.”[6]

In the Geological Service Professional Paper 356-A on page 9, show several figures that show a relationship between uranium concentration in a specific deposit and a increase in the oil yield. [7] “Chemical analyses of 81 samples of asphaltite-free drill cuttings from various parts of the Panhandle field indicate that the uranium content of the reservoir rocks (the "Brown dolomite," "Moore, County lime," and parts of the "granite wash") ranges from 1 to 5 ppm (parts per million)”[8]

        V.         Conditions/ranges

Water- fresh/salt

Methane hydrate can form in fresh water or salt water.  The solubility of methane is a little less for sea water than it is for fresh water, but the impact is small.  The average salinity for the ocean is 34.9 g/kg

Temperature

The temperatures that methane hydrate can form at are 0°C (32°F) and up to 15°C (59°F).  The higher temperature of formation requires high pressures.  See the phase diagram for the pressure temperature curve.  In Figure 2 below the temperature drops rapidly to a depth of about 1000 meters and then drops much slower but is in the range of formation of clathrates.

Pressure

The pressure that methane hydrate can form is from 18 atmospheres’ to very high pressures.  The higher the pressure the higher the temperature can be to form methane hydrate.  The average ocean temperature is 3.5 °C with a range of -2°C to 40°C.  

Ph

“On the pH scale, which runs from 0 to 14, solutions with low numbers are considered acidic and those with higher numbers are basic. Seven is neutral. Over the past 300 million years, ocean pH has been slightly basic, averaging about 8.2. Today, it is around 8.1, a drop of 0.1 pH units, representing a 25-percent increase in acidity over the past two centuries.”[9]

Time

The time for methane hydrate to form is exothermic and is not constant.  The formation of hydrate moves along and a time dependent model is required.  The pressure has an effect on the formation rate of methane hydrate.  Once the methane hydrate is formed then if the pressure is released the release of the methane is such that blocks of methane hydrate have been retrieved to atmosphere pressure and still not be totally melted or the methane released.  More work appears to be needed to better define the formation rates.  This is an area the authors believe that more new research needs to be done.  

Methane Hydrate Phase Diagram

Figure 3

http://large.stanford.edu/courses/2010/ph240/harrison1/images/f3big.gif

Figure 4                                                                                                         Figure 5

[10]

Co-deposited materials properties and influences
Minerals, salts, organics

Oxidizing/reducing

Alpha particles and their energies

The energy of alpha particles is from 4.27 MeV to 6.15 MeV during the decay of uranium from U238 to Pb206  The ionization energies from the uranium is high enough energy to cause polymerization and cross linking, especially at the high pressures.

Gamma rays and their energies

The energy of gamma rays is from uranium decay can also support polymerization and cross linking of hydrocarbons forming longer chains and larger/different molecules.  This is presented in a paper by Hamlet, Moss, Mittal, and Libby.[11] on “Polymer Production in the ᵞ Radiolysis of Methane in Liquid Argon” in JCS and a contribution from the Department of Chemistry, University of California Los Angles, California. Received September 9, 1968.

        .

Tectonic Plates

Tectonic plate movement, continental drift over the years of the earth provides for the methane hydrate formation to be moved in land or uplifted.  Once the methane hydrate is moved away from the very cold ocean floor the heat from the inner earth will warm the methane hydrate and release the methane from the ice crystal.

Gradual Alteration of the Deposit

As the sediments are moved the deposits can be altered a number of ways.  The gases are released to move to other formations which are capped by rocks that seal the gases in.  the crude oil can be moved and concentrated in pools and entrapment areas.    

        VI.         Telltales in the deposit

Hydrocarbons

Hydrocarbons are present in the atmosphere at a value of 1.5ppm.  A clathrate is formed with methane, and will form with butane and propane.  Methane is the principle gas in the forming of clathrates.  The Van Der Waals forces provide the attraction of the clathrates to the silicates that are stirred up along the shores and river outlets.  The sediments containing clathrates participate out on the ocean floor.

Helium

Helium is present in the atmosphere at a value of 5.24ppm.  A clathrate can also be formed with helium.  The density of helium Clathrates is expected to be less than a methane clathrates.  Also there is a source of helium from the decay of uranium when alpha particles are emitted.  

Nitrogen

Nitrogen is present in the atmosphere at a value of 780,840.00ppm.  the form of Nitrogen is N2.  At equilibrium the dissolved nitrogen at the surface is about 4.8x10-9 M in the sea water.  

Argon

Argon is present in the atmosphere at a value of 9,340.00ppm.  A Clathrates can also be formed with argon.  

Oxygen

Oxygen is present in the atmosphere at a value of 209,460.00ppm. The form of oxygen is O 2 .  The oxygen is absorbed into sea water and is effected by water temperature and salinity. At equilibrium the dissolved oxygen at the surface is about 0.00027 M in the sea water.

Hydrogen

Hydrogen in the free form is present in the atmosphere and is on the order of 55ppm.  Hydrogen in the ocean is a H+ ion and quickly forms ion pairs with other elements in the sea water.  

Carbon dioxide

Carbon dioxide is present in the atmosphere and varies from 175.00ppm to 377.00ppm.  The form of carbon dioxide is CO2.  The carbon dioxide is absorbed into sea water and is affected by temperature and salinity.  

“When carbon dioxide dissolves in this ocean, carbonic acid is formed. This leads to higher acidity, mainly near the surface, which has been proven to inhibit shell growth in marine animals and is suspected as a cause of reproductive disorders in some fish.”[12]

Hydrogen sulfide

Hydrogen sulfide is present in the atmosphere and can vary from .11ppb tp .33ppb, in urban areas, and generally less that <1ppb in the atmosphere.[13]  Hydrogen sulfide can be present in sea water.

Other tracing byproducts

Trace isotopes from the decay of uranium.  Uranium is estimated to be approximately 40 ppm dry basis in seawater.  Uranium is in seawater at a content of about 3.3 milligrams per cubic meter.  
Residual minerals compositions

Uranium 238 and uranium 235 remaining in the sediments, and the amount of lead from uranium that has decayed to completion.  

        VII.         Conclusion  

The Goldmann Moore Theory presented above provides a plausible theory as to the origins of the very large quantities of hydrocarbon deposits in the earth’s sediments.  The properties of methane hydrate and the amounts of energy released by the decay of uranium are the keys to the theory.  Methane hydrate provides the link to depositing large quantities of methane and uranium provides the energy to create the large deposits of crude oils from methane hydrate deposits.

The theory is based on available data and research of others.  There is still research needed in understanding the rate of formation of clathrates and the depositing mechanics.  Sampling of the methane hydrate deposits in the sediments and determining the amounts of other clathrates in these deposits will provide more information on the rates of formation.  

The formation of clathrates in water is not a well defined process.  The capture of a gas molecule in a cage of an ice crystal and show no chemical bonding is one of the questions of just how does this happen.  Some bonds must hold the gas molecule in place while the cage is being built around the molecule.  The gas molecule is always in motion, and the authors believe more research should be done in this area.    

The various elements and isotopes in the oil and gas deposits also provide for confirming clues as to the generation of hydrocarbons from the original methane hydrate deposits.  The source deposits will contain trace amounts of the elements in the uranium decay chain for example Pb206 Pb210, Ra226, and Th230.  The polymerization of methane into long hydrocarbon chains is achievable with the energies from the uranium decay chain.  The rate of polymerization still has not been determined and should be a subject of new research.  The rates are of great importance in determining where new deposits of crude oil may be located.  The authors believe that the new research in this area will further substantiate their theory and provide a much clearer understanding of the earth’s long history.

VIII. About the authors

Edward Goldmann

Mr. Goldmann is Chemical Engineer.  He received his Bachelors of Science in Chemical Engineering from University of Washington 1997, a Master of Science in Chemical Engineering from University of Texas Austin 1999, and a Doctor of Philosophy from the University of Texas at Austin 2002.  He has worked 12 years in the solar cell industry.  

Francis Moore

Mr. Moore is a Mechanical Engineer.  He received his Bachelors of Science in Mechanical Engineering from Kansas State University 1969.  He has worked 37 years in the Nuclear Industry of which twelve years were in nuclear fuels research at the Department of Energy Hanford Site.  

Louis Goldmann

Mr. Goldmann is a Ceramic Engineer.  He received his Bachelor of Science in Ceramic Engineering from University of Washington 1967 and a Master of Engineering Management from Washington State University 1991.He has worked 3 years at a large aircraft manufacturer, 8 years at a laboratory for an open pit mine, and 28 years in the nuclear industry doing fuel manufacturing, containment design, and transportation packaging at the Department Of Energy Hanford Site.


[1] Uranium and Helium in the Panhandle Gas Field Texas, and Adjacent Areas By A. P. PIERCE, G. B. GOTT, and J. W. MYTTON With contributions by HENRY FAUL, G. E. MANGER, A. B. TANNER, A. S. ROGERS, ROSEMARY STAATZ, and BETTY SKIPP; GEOLOGICAL SURVEY PROFESSIONAL PAPER 454-G

[2] http://www.ags.gov.ab.ca/publications/REP/PDF/REP_58.PDF ; Nelson, A. and Gray, M. “The Chemical Composition of Bitumen”, University of Alberta (2004).

[3] Table from Lutgens and Tarbuck, The Atmosphere, 8th edition)

[4] “Oil Yield and Uranium Content or Black Shales” US Department of Interior, Geological Survey Professional Paper 356-A, B, C, & D, 1960, pages  1, 5, 6. 

[5] Table from”EnviromentalChemistry.com”

[6] Page 6 of Uranium Content of Black Shales By VERNON E. SWANSON URANIUM IN CARBONACEOUS ROCKS; GEOLOGICAL SURVEY PROFESSIONAL PAPER 356-A

[7] Uranium Content of Black Shales By VERNON E. SWANSON URANIUM IN CARBONACEOUS ROCKS; GEOLOGICAL SURVEY PROFESSIONAL PAPER 356-A

[8]  Uranium and Helium in the Panhandle Gas Field Texas, and Adjacent Areas By A. P. PIERCE, G. B. GOTT, and J. W. MYTTON With contributions by HENRY FAUL, G. E. MANGER, A. B. TANNER, A. S. ROGERS, ROSEMARY STAATZ, and BETTY SKIPP; GEOLOGICAL SURVEY PROFESSIONAL PAPER 454-G

[9] http://ocean.nationalgeographic.com/ocean/critical-issues-ocean-acidification/

[10] Sara E. Harrison, October 24, 2010, Submitted as coursework for Physics 240, Stanford University, Fall 2010.

[11] “Polymer Production in the ᵞ Radiolysis of Methane in Liquid Argon by Hamlet, Moss, Mittal, and Libby, in JCS and a contribution from the Department of chemisistry, University of California Los Angles, Californis. Received September 9, 1968.

[12] http://ocean.nationalgeographic.com/ocean/critical-issues-ocean-acidification/

[13] U.S. Department of Health and Human Services Public Health Service Agency for Toxic Substances and Disease Registry www.atsdr.cdc.gov