Section I - Iodine in the Soil
This page will detail some of the data that I have personally generated as well as
references that I have used to support the mechanism I have proposed in my
iodine paper. This will not be a traditional bibliography but a discussion of the
relevant data and the portions of the related papers supporting my mechanism.

Much of the data on iodine in soils came originally from the study of goiter. One
of the best  sources is from Vinogradov, (1959), THE GEOCHEMISTRY OF
RARE AND DISPERSED CHEMICAL ELEMENTS IN THE SOIL. 2nd ed.
New York: Consultants Bureau.

Page 51            "Rocks formed from massive rocks as a result of weathering
contain a large amount of iodine and, finally, the soils formed on them contain
still more."

Page 53            "The basic source of iodine in soils is iodine of the atmosphere."
" The ocean is the reservoir from which all of the iodine of the atmosphere
is drawn"

This cycle of iodine is well established with the ocean and the soils acting as the
primary reservoirs for iodine.

Page 57           "Soils are always richer in iodine than the rocks on which they
developed, frequently by a factor of 20-30."

The Chilean Iodine Education Bureau in 1956 produced the following table of
their data.
The Chilean Iodine Educational Bureau (1956)

Rock Type                     Iodine in parent material           Iodine in soil derived from parent
ppm I2                                    ppm I2               

Igneous Rocks (ALL)                  0.26                                      4.67
Basic                                0.25                                      5.09
Intermediate                         0.26                                      4.17
Acid                                 0.27                                      3.06

Sedimentary Rocks (ALL)              0.78                                      1.93
Limestones                           0.59                                      2.26
Sandstones                           0.87                                      1.83
Shales and Argillites                1.09                                      1.11

Metamorphic Rocks (ALL)              0.81                                      2.66
In this same report the CIEB reported decreasing amounts of iodine with depth. Although my
research down to about eight feet is not deep enough to establish this, I did run a number of samples
taken from shot holes that I was told came from around 90 feet. Unfortunetly I have been unable to
locate my notes on this test but I do remember the iodine concentrations where well below the soils,
in fact they were near zero.
Section II - Iodine Compounds in the Soil
Many researchers have reported that little of the iodine in soil is water soluble.
Magomedova, Zyrin, Salmanov,  (1970), IODINE IN THE SOIL AND ROCK OF
MOUNTAINOUS DAGESTAN,   Agrokhim. No. 1 117-125

Reported 1%-12% of soil iodine was soluble.
Sinitskaya, (1969), IODINE CONTENT IN THE ZEYA-BUREYA PLAIN SOILS, Uch. Zap.,
Dal'nevost. Gos. Univ. Khim. No. 27 72-88

Reported "small amounts" of soluble soil iodine.
Whitehead, (1978), STUDIES ON IODINE IN BRITISH SOILS, J. Soil Sci. 24 260-270

Reported 25% soluble soil iodine.
Below is my test of the solubility of soil iodine from various areas over a range of concentrations.
Each sample was run and rerun, soil was extracted for 24 hours with DI water and the residue was
analyzed.
Sample Location     ppm I2           ppm I2 R         H2O ext soil       Average       % extracted

Oklahoma             4.2               3.8               3.8               4.0               5
Oklahoma             2.6               2.5               2.5               2.6               4
Oklahoma             4.0               4.1               3.9               4.1               5
Oklahoma             4.6               4.2               4.1               4.4               7
Oklahoma             2.4               2.9               2.6               2.7               4
Oklahoma             1.6               1.6               1.6               1.6               0
Oklahoma             1.8               1.7               1.7               1.8               6
Oklahoma             1.7               1.8               1.7               1.8               6
Texas                1.5               1.8               1.8               1.7              -6
Texas                1.8               2.2               2.2               2.0             -10
Texas                2.8               3.2               3.2               3.0              -7
Texas                4.0               4.3               4.1               4.2               2
Texas                3.6               4.0               4.2               3.8             -11
Texas                5.1               5.1               5.4               5.1              -6
Texas                1.7               1.9               1.8               1.8               0
Texas                1.5               1.8               1.8               1.7              -6
Texas                2.1               1.9               1.9               2.0               5
Colorado             2.4               2.3               2.2               2.4               8
Colorado             2.5               2.4               2.3               2.5               8
Colorado             3.0               3.2               2.9               3.1               7
Colorado             3.4               3.2               3.2               3.3               3
Colorado             2.8               2.8               2.5               2.8              11
Colorado             3.3               3.3               3.0               3.3               9
Colorado             2.4               2.6               2.5               2.5               0
Montana              6.7               5.9               6.1               6.3               3
Montana              3.7               3.6               3.4               3.7               8
Montana              2.9               3.0               3.0               3.0               0
Montana              3.9               4.0               3.8               4.0               5
Montana              5.2               4.3               5.3               4.8             -10
Montana              3.2               3.1               2.8               3.2              12
Montana              2.7               2.7               2.5               2.7               7
Assuming the measured increases are due to analytical error the average extraction for the remaining
24 samples ranges from 0 to 12% with an average of 5.2%. This agrees with the researchers listed
above. Clearly only a small portion of the iodine in soil is in a soluble form. All of the simple ionic
combinations of iodine with the most abundant anions are soluble, only an unusual or complex ionic
structure could explain this insoluble iodine. However, the more  likely explanation is covalently
bonded organic-iodine compounds.
Raja, Babcock, (1961), ON THE SOIL CHEMISTRY OF RADIO-IODINE, Soil Sci. 91 1-5

Reported that a large fraction of iodine released into a soil was retained                                       
due to a "reaction" with organic matter.
Vingradov (1959): Page 59

"As we have repeatedly noted, the organic material ties up the iodine in soils."
Keppler, Biester, Putschew, Silk, Scholer, Muller, (2003) Organoiodine formation durning
humification in peatlands: a key process in terrestrial iodine cycling. Environ. Chem. Lett.

"transformation of iodine from its inorganic form to organoiodine ... is a key
process in the storage of iodine ... Once bound in peat iodine remains stable
for thousands of years."
Peat represents an extreme example of a reducing environment. The process of inorganic or
elemental iodine oxidizing hydrocarbons and being retained in areas of seepage, however, is the same.
I conducted the following research to investigate the iodine compounds I measure in the soil.
This research project involved measuring soil iodine concentrations after exposing the soils to
increasing heat.
---------------------------Temperatures are degrees Centigrade-----------------------------
-------------------------------------Iodine, ppm I2----------------------------------------

Sample Location    0    200    250    300    350    400    450    500    550    600   1000

Nevada            2.0   1.8    1.8    1.9    1.9    1.9    1.8    1.8    1.4    1.3    1.6
Nevada            5.1   5.9    5.4    5.6    4.8    4.7    4.2    4.1    3.9    2.8    1.3
Ontario           5.9                 5.8            4.1   3.6    2.7                  0.9
Ontario          10.0                                6.1          4.1                  1.2
Ontario          13.6                                3.3          2.2                  1.2
Ontario           4.3   4.9           4.0            3.5          2.4           1.7
Ontario          13.6   4.5           4.3            3.6          2.8           1.9
Ontario           2.3   2.1           2.1    1.2     1.3   1.3    1.2                  1.6
Ontario           3.0   2.9           2.8    2.3     2.1   2.1    1.6                  1.4
Ontario           3.6   3.9           3.8    2.8     2.3   2.1    1.4           1.3    1.2
Ontario           2.0   1.9           1.6    1.6     1.4   1.3    1.6    1.3    1.6
Ontario           4.4   4.1           3.8    2.8     2.4   2.2    1.8    1.4    1.6
Texas             3.8   3.5    3.5    3.3    3.2     2.9   2.6    2.7    2.2    1.5    0.9
Texas             4.2                 3.7            3.3          3.2           2.4    1.3
Texas             4.5                 4.5            3.6          3.3           1.8    0.9
Texas             8.1                 7.3            5.5          5.3           2.0    1.2
Texas            11.6  12.7           9.1    9.1     6.5   1.8    1.4           1.3
Colorado          4.1   4.2    4.3    4.3    4.6     4.2   4.2    4.1    3.3    2.2    1.4
Colorado         12.0                10.0            9.2          8.6           6.5    2.1
Colorado         10.0                 7.8            7.2          6.6           3.0    1.6
Colorado         13.6                 9.2            8.3          7.8                  1.8
Colorado          3.1                 2.4            2.5          2.2           2.0    1.3
Colorado          3.1                 2.9            2.6          2.6           1.7    1.4
A number of interesting things can be derived from this data set. The first is that a large percentage
of the original iodine in the high/anomalous samples is lost between 500 and 600 degrees C. A
subset of  this observation is that the iodine from Ontario, which is mostly a natural gas region, is
more volatile, disassociating between 200 and 500 degrees C, than samples from Texas, Colorado
and Nevada which are from oil regions. The loss of iodine at these relatively low temperatures is
consistent with organic based iodine, additionally the range of temperatures over which these loses
occur, argues for a variety of compounds. However, all of the samples regardless of their original
iodine concentration, or region of origin, end with a high temperature resistant iodine of around 1.5
ppm consistent with some sort of insoluble complex inorganic or refractory humic material.

A high percentage of all the areas I have analyzed from North America to Argentina to  Australia to
Turkey have all displayed "background" iodine concentrations between 1.5 and  2.5 ppm I2. Based
on the literature and my research I believe that iodine exists in the soil in two primary forms and
one minor form. An insoluble, "background" compound, an insoluble covalently bonded organic
group of compounds and a small amount of iodide or iodate salt. The second, organic form is the
basis of the massive empirical  data base associating iodine enhancements with micro-seepage.
Section III - The Iodine Cycle and the Soil
The iodine cycle has been discussed in the literature with little explanation being given to why iodine
is distributed the way it is in the environment. The amount of iodine in the crust on average is
estimated at about 0.15 ppm I2. Most igneous rocks contain little or no iodine, sedimentary rock is
highly variable but is often less than 1 ppm I2 while the soils derived from highly variable regolithic
sources exhibit surprisingly consistent enhancements in iodine based mainly on their location. In fact
other than oil brines, iodine is more concentrated in soils than in any other substance.
Iodine in the environment acts, in many ways, like oxygen. Because both elements wish to fill there
outer electron shells to achieve a noble gas configuration they are continually seeking electron donors
to combine with, to oxidize. Both form diatomic molecules that are mobile in the atmosphere,
although iodine is very near it's sublimation point at normal temperatures and could not be a gas at
low temperatures high in the atmosphere. One of the prime sources of electrons in the environment
are hydrocarbons. Unlike oxygen, which lacking an ignition source can not oxidize saturated
hydrocarbons, iodine can abstract a hydrogen, given just a relatively small amount of energy,
ultraviolet and visible frequencies being adequate, forming an iodohydrocarbon. Although iodine can
replace a primary hydrogen, it is far more likely to replace a secondary or even better a tertiary
hydrogen first available in a branched chain butane. Unsaturated hydrocarbons will be replaced by
iodine on contact, with the free radical step being unnecessary. Once iodine incorporates into the
hydrocarbon the new molecule is far less volatile and drops from the atmosphere into the soil.
At normal temperatures the selectivity of this reaction will lean heavily towards secondary, tertiary
and unsaturated compounds and in fact according to:

Weininger & Stermitz (1984), ORGANIC CHEMISTRY, pp 143,

"Iodine (I2) does not react with methane to a measurable extent."

Possibly demonstrating the difficultly iodine has abstracting a primary hydrogen. Because ethane also
has only primary hydrogens the first substantial reaction with iodine likely would be propane. This is
fortunate, although an extremely dry gas deposit might not develop an iodine anomaly, most of the
gas deposits I have surveyed have produced substantial anomalies even though methane and ethane
are not contributing to the anomaly. Balanced against this is the elimination of problems due to coal
gas and biogenic methane.
This failure of iodine to react with methane was demonstrated by a survey over the Leyden gas
storage field just north of Golden, Colorado. Prior to the decommissioning of this old coal mine used
by public service to store gas, I collected samples along a road which crosses the old mine. At the
time 3 billion cu. ft. of methane was being stored at 170-250 psi as little as 600 feet below.
Distance (miles)    0           .2            .4         1.0        1.2        1.4          1.6        1.8          2.0
Iodine (ppm I2)    1.4         1.8          1.4        1.5        1.2        1.2          1.4        1.8          1.6
CASE                 3.0         2.2          6.8        3.8        2.6        2.9          4.4       24.3         5.4
      
                                                                   Gas Storage
None of the iodine values are anomalous for this area, although the CASE values are.
I will continue to add data from my  research as well as relevant information from other sources to
this section.
These general reactions are:

1/2 I2 +  RCH3 (g)         -------->   RCH2I (s)
1/2 I2  +  RCH2CH3 (g)  -------->   RCHICH3 (s)
1/2 I2  + R2CHCH3 (g)   ------->    R2CICH3 (s)
I2  + RCH=CH2 (g)      -------->   RCHICH2I (s)
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