COMTENTS

screen (page no,)

1
Summary of Fulvate Atmospheric CO2 Hypotheses
Plots of atmos. CO2 vs. human population and
Fossil fuel usage vs. human population
12
Discussion of Plots
18
Letter to Chem World Jun 2011
DOCUMENTS relevant to the above hypothesis :22
38
41
62
82
87
98
101
103
104
105
127
131
135
137
140
146
152
159
166
170
175
180
182
182
189
195
228
230
266
274
275
279
280
282
293
294
296
331
333
244

Paper 1 Humate/Fulvate Climate Hypothesis

1+ Further Supporting Information to paper 1
2
3
Paper 4 Clues from polyanionic animal extracellular fluid
homeostasis suggest mechanism of sea water carbonate ion
homeostasis and atmospheric CO2 regulation
References to paper 4
Paper 5 Silln Hypothesis of atmospheric CO2 regulation
Paper 6 Evidence that rapid CO2 release from the sea
actually occurs
Plimer 2009
References to paper 6
ref nos 8-1 a0 etc
Paper 7 Fulvate Hypothesis
Paper 8 The Fulvate Hypothesis discussed in terms of
the Ruddiman Hypothesis
Paper 8 Comments
..Chu
Letter Dec 3 2007 Re Natural Polyanionic Substances as
Inhibitors of Oceanic Calcification
Paper 9+ Fulvate. a smart polyanion
Paper 10 The Putative Early Anthropogenic Warming of the Sea
Hoffman 2009
Paper 11 Marischal College mid 1980s discussed ideas
References to orig. section 3-4
Paper 12 Further graphical. Population Driven Atmospheric CO 2
Pollack Theory of Water Structure
Paper 13 More on the definition of fulvate
Increasing human lifespan
Shilajit
.. the complexity of fulvic/humic acid
Paper 14 (further comment on) Fulvate-Led Sea Supersturation
Climate
Paper 15 Humic substances inhibit calcite crystallization
Marischal College research document
Paper 16 Conclusions fulvate climate
Paper 17 Further References
Paper 18 Seeing the Wood for the Trees
19 Selected refs to provide a quick intro
20 Review of the traditional viewpoint
21
Happs
22
23 Humus Water Structure and Water Activity
23+ Global miracle ?
25+ The Gaia Hypothesis
26
Postscripts
26+ Carbon Monoxide etc
27 Solomon
28 The Future of Humanity
Trivial Linearity?
Hypothesis

------HYPOTHESIS
CONTENTS
A

Humic Anion description

Introduction
PLOTS of variation of atmospheric CO2 as a function of human population
variation of fossil fuel usage as a function of human population
Five year interval comparison of atmospheric CO2, human population and fossil fuel usage

Letter to RSC Chem World Global Warming without Fossil Fuel

Further supporting information

2 Fulvate Hypothesis of Atmospheric CO2 Regulation
3 Fulvate hypothesis Nitrogen fixation and fossil fuel sulphur

oxides and fossil fuel

4 Fulvate hypothesis
5 The Silln Hypothesis of Atmospheric CO2 Regulation
6 Evidence that rapid CO2 release from the sea actually occurs
7
8 The Fulvate Hypothesis Discussed in Terms of the Ruddiman Hypothesis
9 Fulvate can be considered to be a smart polyanion
10 The Ruddiman Hypothesis
11
12 Further graphical comparison of atmospheric CO2, human population and fossil
fuel usage
13 Definition of fulvate
14 Fulvate hypothesis
15 Humic substances inhibit calcite crystallization
16 Conclusions
17 Further references of interest
18 The emperor has no clothes
RE: ANTHROPOGENIC CO2
A
LETTER RE: ANTHROPOGENIC CO2
to whom it may concern David Grant MRSC, Turriff 6 Sco.U.K.
The carbon cycle is at present not sufficiently understood in
order to make any safe predictions about how human
activities might affect atmospheric CO2 or climate. This
means that there may be serious doubt about the fossil fuel
origin of anthropogenic atmospheric CO2.
While additional research is probably needed in order to be
certain of the origin of anthropogenic atmospheric CO2, but
sufficient information exists at present to suggest that if we
restrict our initial considerations to those facts which are
most likely to be most intrinsically sound then we might
conclude that the best starting point for any CO2 assisted
anthropogenic warming deliberations are probably the
following databases:

Introduction
In order to study the human input of atmospheric CO2, we should first ask what
are the most robust primary facts which could allow us to test the commonly believed
fossil fuel hypothesis of the formation of anthropogenic CO2? It seems that these
are: the year-on year global human population, the average (remote-sensed) year-onyear average amounts of CO2 in the atmosphere and the year-on year average fossil
fuel usage rates.
Plotting the first two sets of data against each other (PLOT 1) reveals that the
carefully measured annual average (remote-sensed) atmospheric CO2 concentration
(x-axis) has increased very exactly in direct proportion to the supposedly equally
accurately determined post AD 1959 global human population data (y axis).
However, plotting the year-on-year fossil fuel usage against the year-on-year global
human population (PLOT 2) reveals a markedly different type of complex superposed
non-linear variation which is independent of the observed amount of CO2 which
appears in the atmosphere.
It seems that the usual fossil fuel hypothesis , a process of fossil fuel combustion
generation of atmospheric CO2 in which a constant proportion of the CO2 formed
remains long-term in the atmosphere, cannot explain why the amount of CO2 in the
atmosphere has accurately tracked the human population size.
A

PLOT 1

----

---- ---- ---- ---- ------- ---- ---- --PLOT 2

----

----

----

---- ----

----

----

----

----

(which also includes pre-1959 data) reveals overlapping stages of non-linear variation of increasing
fossil fuel usage (y-axis) with increasing population (x-axis); while a smoothed average curve shows a
regular variation the unsmoothed curve is highly irregular with a major break-point at AD 2000 as well as e.g.
less discontinuities at AD 1924, 1964 etc.

PLOT 3

PLOT 3 extends the 1959-2010 derived equation (1) to the entire historical
databases (including those from before the industrial revolution) so as to find
out if fossil fuel usage and atmospheric CO2 have varied in common human
population pressure determined manner as postulated by the usual fossil fuel
hypothesis of the origin of anthropogenic CO2
This superposition of the two sets of curves appears to suggest that the recorded
atmospheric CO2 contents and the corresponding recorded fossil fuel usage numbers
are actually more or less independent of each other; although both are human
pressure effects, these effects appear to have be caused separately and independently
of each other/

PLOTs A are an alternative presentation of the human population relationship

with atmospheric CO2 and fossil fuel usage.

The unsmoothed fossil fuel curve is compared with the smoothed atmospheric CO 2 curve. This further confirms the above
conclusion, namely that the overtly irregular fossil fuel variation has arisen from a different human social activity from that
which has produced the intrinsically regular observed atmospheric CO2 variation curve.

Alternatively: Plot B
Plotting the differentiated 5 year human population vs. atmospheric CO2 and fossil
fuel data (PLOT B) which magnifies the departures from a smooth dependent
variation [also discussed where it is labelled in Fig. 4-1 in the supporting documents
appended to this letter] further confirms that fossil fuel usage and anthropogenic CO2
are not accurately inter-dependent phenomena.
PLOT B
Shows the effect of differentiating (5 year differences in) the atmospheric CO2 and fossil fuel data now plotted as a function of
year or the reported surface temperature for years from AD 1740-2007 ; marked minima occur in curve a at AD 1943 and 1991
and a marked minimum I curve b at AD 1970

Discussion of Plots 1, 2, 3, A and B

While for short historical periods there might appear to have been some temporary tendency for a direct correlation
to exist between increased fossil fuel usage and an observed increase in the amount of CO 2 in the atmosphere, no
such overall historical correlation exists between the entire record of fossil fuel usage and the amount of CO 2 in the
atmosphere.

Plot 1 shows that a linear equation, y = 18.322x +258.97,

(R2=0.9921) [equation (1), where y is the atmospheric CO2 (ppm)
and x is the Earths human population (billions)] accurately
describes all of the postAD 1959 (to 2010) record of how
atmospheric CO2 has been directly correlated with the human
population. The low scatter from the least squares fit trend-line is
remarkable. It is noteworthy that the suggested (from the equation
(1) least squares fitting procedure) pre-human atmospheric CO2
baseline,
258.97 ppm CO2 is the same as that arrived at by Ruddiman from
ice core analysis. Prior to the invention of agriculture the natural
atmospheric CO2 may have been ca. 260ppm and not the
commonly-assumed pre-industrial atmospheric CO2 baseline value
of 280ppm CO2.
The 260 ppm pre-human atmospheric CO2 is identical to the value
suggested by Ruddimans ice core evaluation as well as the
trendline of the most accurately known atmospheric CO2 human
population data set (for AD 1959-2010) and also the extrapolation
shown in PLOT2 which seems to indicate that ALL of the available

atmospheric CO2 human population data can be extrapolated to the

same pre-human baseline as that predicted by equation (1).
(Alternative extrapolations shown in PLOT2 however might also
suggest an even lower value e.g. ca. 250ppm CO2 for the pre-human
baseline of atmospheric CO2 ).
Summary.
An analysis of the most accurately known data disagrees with the

commonly believed hypothesis that the same proportion of the

total CO2 emitted from the combustion of fossil fuel remains longterm year-on-year in the atmosphere. This simple fossil fuel origin
of anthropogenic CO2 hypothesis cannot account for how the
historically observed amount of CO2 in the atmosphere has varied as
a function of the human population of the Earth but can be
accurately represented by equation (1).
It seems intrinsically unlikely that a modified fossil fuel mechanism
of formation of anthropogenic CO2 e.g. a convoluted fossil fuel
combustion mechanism with variable year-on-year changes in CO2
sinks could produce a strictly linear human CO2 fingerprint in the
atmosphere. Such a model seems also unlikely to be supported by
conventional physical chemistry.
An alternative mechanism of the human injection of CO2 into the
atmosphere is therefore required. This is especially needed to
account for the lack of deviation from strict linearity in equation (1)
and needs to take account of the possibility that major amounts of
anthropogenic CO2 might first have appeared in the atmosphere
simultaneous with the first large scale agriculture and also is likely
to be produced by agriculture in the modern era, i.e. by far the
majority of the anthropogenic CO2 in the atmosphere has come from
tillage, land use changes or natural water pollution from these
activities. Some previously-unsuspected agricultural-dependent
mechanism has continued throughout human history to both inject
very large amounts of anthropogenic CO2 into the atmosphere and
also to strictly control the residual amount of that CO2 which
remains in the atmosphere.
The strict linearity of equation (1) indicates a single mechanism of
anthropogenic interference occurs in a single major CO2 sink. This is
most likely to be a perturbation of the balancing act between the
uptake and removal of CO2 from that sink.
This sink is likely to be the sea which must contain the affected
homeostatic regulator. How the amount of CO2 in the atmosphere
is set by this regulator must be subject to a direct human population
number pressure control perturbation effect. Agriculturally derived
fulvate may provide for such a control perturbation. This idea arose
from the discussion of numerous in depth laboratory experiments
conducted in the nineteen eighties in the polysaccharide research
laboratory in Marischal College, Aberdeen University.
------------------------------------------------------------------------------------------

Letter to RSC Chem World by David. Grant [AB53] MRSC, Membership No. 251231)
Submitted to RSC Chem. World in 2011.
An edited version appeared in the June edition.

-------------------------------------------------------------Joseph Needham, CO2 and Global Warming

Cf., Emissions from India & China since AD 2000; cf.
Chemistry in Britain noted in 1995 (1) that Joseph Needham, the leading Western
expert on the history of science and technology in China, who died recently, may have
saved the world from global warming.
Needham once told a colleague that Mao Tse-tung had asked his advice about whether
he should allow the Chinese people to have cars or make them stay with bicycles.
Needham was a Cambridge don, and cycled everywhere.
He told Mao this. Fine said Mao then well stick with bicycles.
Given the size of the Chinese population, this decision may have delayed global
warming by decades.
China has now become a major car-owning industrialized superpower but the kind of
marked increase in atmospheric CO2 and associated global warming predicted in 1995
article to follow from the abandonment of the use of bicycles by China has apparently
not happened.
While the year-on-year increase of atmosphere CO2 shows a direct linear relationship
[Fig. 1, cf. (2)
preamble PLOT 3]] with the size of the

human global population (i.e. it must be presumed to be anthropogenic) the same

relationship seems both to described the pre- and the post- AD 2000 data, i.e., the
amount of CO2 in the atmosphere plotted as a function of the human population has
not been directly affected by the large post- AD 2000 surge in fossil fuel usage by
China (or India). While the same CO2 human population relationship which has
apparently existed from the start of human society (cf. Fig. 1 [preamble PLOT 3])
continues to be valid, this relationship is apparently quite independent of fossil fuel
use, a circumstance which points to some other mechanism e.g., a food production
agricultural runoff alteration of the-ability-of-the-sea-to-hold- CO2 being
principally responsible for the present anthropogenic elevation of atmospheric CO2.
(1) Anon, On your bike, Chem. Brit., 1995, 31 (6) 450
(2) Fig. 1 [preamble PLOT 3] (data from CDIAC/internet) confirms the linear correlation
(reported by K. Onozaki, J. Health Sci., 2009, 55, 125) between the historical
human population sizes and the corresponding atmospheric CO2 contents which

seems to be quite independent of the less precise non-linear dependence between

the human population size and the fossil fuel usage data.
--- --- --- --- --- --- --- --- --- --- --- --- --- --- ---

Pasted-in
documents
[I have cut and pasted sections from several prior documents {inspired by personal (Marischal College) and industrial laboratory
research and related literature research information} in an attempt to assemble information in a preliminary fashion to stimulate a
public discussion of the problem of accounting for how the amount of CO2 in the atmosphere has varied for several centuries in
tandem with the size of the human population of the Earth; these documents are first and second and later insertions made in
order to write several versions of a report of the possible major scientific misinterpretation of how anthropogenic CO 2 may arise.
It contains repetitions of similar arguments and diagrams; rather than spending time in re-writing the whole as a single document
with a tedious upgrading of the diagrams at this stage it seems worthwhile simply to make available to the public the entirely
almost raw collection since the ideas presented therein because of the potential prime public interest].

Fossil fuel may erroneously have become the principal focus

of anthropogenic CO2 research.
The thinking behind the carbon footprint idea must now be
indicated to possibly lack any proper observational
evidence.
We need to find out where the
correctly defined anthropogenic atmospheric CO2 is coming
from.
This could be from the sea.
And be facilitated by the humic anion cycle.
This is a rate limiting part of the carbon cycle.
It should be noted that the detailed CO2 records show that
an season quasi sinusoidal waveform variation occurs in the
amount of CO2 in the atmosphere putatively because of a
rapid summer injection (from photosynthesis) causing a
marked CO2 maximum followed by a marked cold seasonal
CO2 removal by dissolution of a large portion of atmospheric
CO2 in the colder water (mainly of the sea).
The sea also contains abundant dissolved organic matter (DOM)(analogous to terrestrial humic matter)

The global humic matter system must be

considered a major force for bio feedback
and climate regulation.

Humic
anion
(HA) is
the
largest carbon-based polymer system of the Earth. The
traditional theory of the chemical nature of HA was that it
was lignin-like but when studied in the nineteen seventies
by non-degradative NMR methods in the Aberdeen
University (AU) Department of Soil Science in Kings College
when headed by the late Joe Tinsley and John W Parsons,
well-resolved NMR spectra of de-paramagnetized HA were
obtained for the first time (cf. The chemical structure of
humic substances Nature 1977 279 (5639) 709-10) HS was
seen to be largely aliphatic (apparently consisting of a

polyuronated carbohydrate-like matrix but this was always

associated with long polymetheylene chains. This finding
was consistent with the known high stability of polyuronides
and how man made (CH2)n with n> 30 strongly resists
biodegradation in the soil). Another characteristic feature
of HA (also studied at AU in Marischal College, in the former
polysaccharide lab. headed by Bill Long and Frank
Williamson) was that HA binds very strongly to CaCO3
crystal surfaces (which distinguishes HA from e.g. lignin
derivatives an earlier hypothesis of HA constitution). HA
also far outperforms common commercial inhibitors of
CaCO3 crystallization (scale inhibition). This unique antiCaCO3 ability of HA is potentially able to affect the
carbonate balance of the sea by blocking the seeding of
colloidal and crystalline marine CaCO3 particle formation so
allowing anthropogenic alteration of HA in the environment
and especially the creation of more water soluble fraction of
HA (fulvate, FA) to enter into a possible natural homeostatic
process of carbon cycle regulation.
Anthropogenic augmentation of FA can putatively transmit a
directly proportionate human population pressure control
over the amount of CO2 in the sea and therefore determined
the amount of CO2 in the atmosphere.
It should be noted that the HA/FA cycle also promotes both
land and sea plant fertility since HA/FA also sequesters
essential inorganic nutrients.
Humans have over the centuries sought to improve land
fertility by tillage (in which HA creates FA by oxidative
degradation) and by the application of large amounts of
manure and more recently a range of chemicals which
further perturb the HA recycling system upon which
atmospheric CO2 putatively critically depends.
One can also derive (separate) HA-chemistry-related
hypotheses which suggest how anthropogenically increased
atmospheric CO2 can also produce a range of climate change
effects via the prime anthropogenic process of HA
alteration. This anthropogenic HA connection with climate
change seem, however, to be a much less simple a problem
to resolve than is the resolution of the origin of the possible
direct correlation which exists between the formation of
anthropogenic CO2 per se and the anthropogenic alteration
Lets start with the simpler discussion:
A brief extension to climate change is attempted in the addendum at the end of
this document.
of HA.

Paper 1
The Humate/Fulvate-Led-Climate- Hypothesis Building Process
An alternative to the IPCC model of human induced climate change

Documents No 2014-12-The Fulvate

1

Contents original Section Headings Drawn up for possible former Scottish Sceptic group
{Mike Haseler} dissemination

1. What is fulvate?
2. Original Draft of a Letter to RSC Chemistry World which had discussed how CO2 seems to have
increased approximately linearly with the increasing global human population
A shorter version of this letter written in a more journalistic style eventually got published in RSC Chem
World June 2011
2-1. References to Section 2
2-1-1 The Onozaki paper

3. The above idea is introduced in a slightly

different manner
3.1. Comparison of Data Available on Year-on-Year Fossil Fuel Usage

4. The fulvate hypothesis discussed in terms of the Ruddiman Hypothesis

4.1 Fulvate can be considered to be a smart polyanion
4.2. The putative early anthropogenic warming of the sea
4-2-1 The Hofmann Paper
4.3. RW Simpson, M Salby and D Coe Contributions
4-4.The Marischal College (MC) Aberdeen U . Hypothesis

4.5.The Ruddiman early anthropogenic hypothesis combined with the MC (Aberdeen ) Hypothesis
4-5-1 The Ruddiman Hypothesis
4.-5-2. Agriculture & Humus Degradation
4.-5-3. References to sections 3 and 4
5. Further GRAPHICAL COMPARISONS OF HUMAN POPULATION DRIVEN
atmospheric CO2

6.Appendix
6-1. Humic matter modification of the Silln Sea-Atmosphere Control Model
7. Other Hypotheses
8. More on the Definition of Fulvate
8-1. Cut from a MC doc
9. Further Statement: Fulvate Led Sea Supersaturation Climate Hypothesis

10. Source of data used for plots of atmospheric CO2 and fossil
fuel usage vs. human population
11. Text of D. Grant MC 1989 and later 2001 paper
r
(Humic Substances Inhibit Calcite Crystallization)
12. Figures (draft drawings) for a precursor of the above paper
13. ACKNOWLEDGEMENTS
14. The Preincubation Effect
15. Conclusions

New Section Numbering

3+ The above ideas presented slightly differently
4. Atmospheric CO2 Marine Fulvate Status comparison of similarities in the inorganic
chemistry of animal extracellular fluid homeostasis with that of the sea
5. Ideas discussed by LG Silln
6. Evidence that rapid CO2 release from the sea actually occurs

7. Excerpt from doc New Thinking on Climate Change

8. The fulvate hypothesis discussed in terms of the Ruddiman hypothesis
9. Fulvate as a smart polyanion

14 Orig. 9 Fulvate-Led Sea Supersaturation Climate Hypothesis

15. Text of paper written in 2001 updating a MC ms from 1989 on the same subject
Humic substances inhibit calcite crystallization

Addendum
Global Warming in the Absence of Fossil Fuel
[I have inserted a number of separate documents below retaining the section head
numbering of the originals].
---- ----

---- ---

--- --- ---

--

The data plots PLOT 1 [+PLOT 3]

seem clearly to reveal an astonishing fact, namely that since
1959, when remote sensed CO2 were first accurately
recorded, atmospheric CO2 has tracked or been tracked by
the magnitude of Earths human population. This tracking
has occurred with an extreme precision. The exactness of
the pop. - atmos. CO2 tracking phenomenon seems to have
first been noted by ND Newell & L Marcus in 1987 who
reported that the then-available year-on year post-1959
atmos. CO2 and world human population data were exactly
correlated; while these data fitted best to a non-linear
equation they fitted almost as well to a linear equation.
This exact precision of the pop - atmos. CO2 tracking is
reminiscent of the ancient belief in human centred Nature
but perhaps we should now think that it is a kind of Gaia
effect. Or does it point to this being the first law of humanenvironmental interaction? A major result form some
perhaps non-thermodynamic driving force of human to the
environment engagement ?
The observed correlation surely cannot have been
fortuitous.
Its existence points to some very basic, but apparently not
currently identified process which is exerted by the human
species over the entire global environment.
We have, it seems, for decades or perhaps much longer than
this, altered the chemical composition of the entire
planetary atmosphere.
This phenomenon is now proposed to have arisen from a
constant tendency throughout socialized human history for
humans to spoil or stain those land and marine systems
which provide humans with food. The larger the human
population the greater is this stain. The human pollutants
present in the sea may be especially important since such

pollutants can be transported over thousands of miles of

ocean surface.
Continuously increased human population pressure might
also, it is now pointed out, have continuously reset the
major marine atmospheric CO2 regulation system of the
ocean.

The anthropogenic staining of the ocean might also be of

relevance to the Ruddiman Late Holocene Anthropogenic
Hypothesis.
A further consideration of the surprisingly strictly accurate
linear CO2 atmos. human population correlation, which is
most evident for the most accurately known population and
atmospheric CO2 measurements obtained after 1959, is that
the same simple linear correlation curve which describes the
post-1959 remote sensed atmospheric CO2 data (bearing in
mind the lesser accuracy) also describes much of the pre1959 atmospheric CO2 data, even possibly going all the way
back to pre-human-history. Such a linear representation of
the entire population atmospheric CO2 database is also
supported by circumstance that the least squares fit of the
most accurate straight line from the 1959-2010 data also
arrives at exactly the same pre-human atmospheric baseline
value which was reported by WF Ruddiman (and later
confirmed by J Elsig et al.) from a re-appraisal of trapped air
in ice cores which had revealed a late Holocene anomaly of
increased atmospheric CO2 for which possible major
(currently unexplained) J Elsig et al.s isotope data
indicated that came not from wood burning by early
farmers (the maximum amount which could have come from
this source being threefold too small and the observed ice
core 13C value is also wrong) but instead came from the sea
which must have been a warmed (or equivalently perturbed)
by the early farmers, a circumstance which seemed not to
be remotely credible. Elsig et al.s analysis of their new 13C
information sought to disprove the Ruddiman hypothesis
that the late Holocene CO2 surge might have been
anthropogenic. Elsig et al., did however not clearly disprove
the Ruddiman hypothesis; they simply deduced that the
extra CO2 had likely come from the sea e.g., as a by-product
of coral reef formation. In any case, how could a small
number of early farmers cause such a major sea-warming
effect? It should be remembered that Benjamin Franklin had
found that a teaspoonful of water could exert a dramatic

storm-calming effect upon a large body of water. This was

later explained by the formation of a monolayer at the water
air-phase boundary. Avogadros number is so large that any
small quantity of a surface active chemical substance which
of course contains a very large number of individual
molecules, can exert a very dramatic effect over a very
much larger system such as a large body of water, especially
if it is restricted to some critical surface layers within that
large body of water. A credible mechanism to confirm the
Ruddiman hypothesis is suggested by this analogy: a small
numbers of humans by engaging in large scale disturbances
of the soil humus, can transfer sufficient amounts of a
polymethylene containing (oil-like) natural hyperactive
surfactant (fulvate) molecules into the drainage systems
and so into sea so as to change the manner in which
atmospheric CO2 is regulated by the natural fulvate-CaCO3
regulator of the sea.
It is possible that the proposed hyperactive fulvate
surfactant polymer arises from agricultural soil following
tillage etc. This enabled the seemingly puny early farming
activity (but puny only in comparison with modern industrial
farming) to dramatically alter the chemistry and physics of
those key phase boundaries in the sea which cause a major
re-setting the surface-phase-determined marine system of
atmospheric CO2 control (e.g. that putatively provided by
colloidal CaCO3 or clay particles).
The fulvate human stain continuously produced throughout
human history e.g. by sewage plus that formed during the
agricultural oxidation of humate, it is now suggested, has
enhanced the mineral and other phase boundary binding
activity of the total natural dissolved organic matter (DOM)
of the sea.
This is putatively how an unchanging type human nutrition
linked population pressure (food production humus
degradation and human and animal waste disposal into
water) has precisely controlled the amount of atmospheric
CO2.
We continue with a system by which humans (and human
dependent species) are maintained by soil grown food.
Although the same mechanism of human control over
climate may have existed since agriculture was first
invented in the late Holocene, the unchecked acceleration of
such anthropogenic activity may also threaten the
continuation of the current comfort of the human species or
indeed its very existence. We are now able to change the
manner in which we produce food so that if we can choose if
we so wish to de-couple human population pressure from

food production and from the amount of CO2 in the

atmosphere.
In summary:
Humans can determine the composition of the atmospheric
CO2 and possibly also the global climate by resetting a
CaCO3 phase marine homeostat control system by a
mechanism which is putatively critically dependent on the
ability of degraded humic mater fulvate, to very efficiently
coat and deactivate all (active crystallization seed providing
sites on) mineral surfaces so as to allow anthropogenically
modified fulvate to dramatically alter the physical and
chemical reactivity of those CaCO3 surfaces which control
the dissolved carbonate balance of the sea. (N.b. CaCO 3 is
also the largest inorganic carbon store which provides for a
major biological influence over this store so as to create
various strong biological influences over the carbon cycle).
In other words the largest natural organic carbon system (of
humic/fulvate) cooperates with the largest natural inorganic
carbon system (of calcium carbonates) in a manner which
allows biota to control the global carbon cycle. The leading
biotic force is now the human species number.
A subsidiary control system may also be exerted over clay
particles which are also known to be peptized by
humate/fulvate.
Homo sapiens being the dominant biological force now
dictates how the natural fulvate coated CaCO3-based
colloidal chemical climate control process operates.

====================================================
FURTHER SUPPORTING INFORMATION to Paper 1
The Study of CaCO3-Fulvate Interaction by Soil Scientists which
confirmed that this interaction is critically relevant to how the
supersaturation of CaCO3 in natural waters is attained by fulvate is
exemplified by the following paper, and the references cited therein
Inskeep WP & Bloom PR
Kinetics of calcite precipitation in the presence of water-soluble organic ligands
Soil Sci Sic Am J 1986 50 1167-1172; Cf. also

1+

USGS Document downloaded from the internet on 04/03/11

Aqueous Crystal Growth and Dissolution Kinetic of Earth Surface Materials
Lists numerous reference giving information relevant to the fulvate hypothesis of
climate change, starting with Amjad Z Pugh J Reddy MM 1998 Kinetic inhibition

of calcium carbonate crystal growth in the presence of natural and synthetic

organic inhibitors, in Water Polymer , E. Amjad Z, Plenum Press New York, p 131147.
Degens ET.
Topics in Current Chemistry 64 Inorganic Biochemistry Springer Verlag
1976 p18 and refs. cited.

Suess E
Interaction of organic compounds with calcium carbonate
Geochim Cosmochim Acta 1970 34 157-168 cf. ibid. 1973 37 2435-2447
(Part II, organo-carbonate association in Recent sediments)
Morse JW. The surface chemistry of carbonate minerals in natural waters:
An overview.
Marine Chemistry 1986 20(1) 91-112; cf. p 253-254
Silln LG. How have sea water and air got their present compositions?
Chem Brit 1967 3 (7) 691-897
Pentecost A.
(Photosynthetic plants as intermediary agents between environmental HCO3-

and carbonate deposition)

Chapter 20 in Inorganic Carbon Uptake by Aquatic Photosynthetic Organisms
[WJ Lucas and JA Berry Eds] 1985 Am Soc Plant Physiol

Paper 2
Hypothesis of Atmospheric CO2 Regulation (cont.)
Supporting Inserted Document No. 2014

The Fulvate Hypothesis of Atmospheric CO2 Regulation

D. Grant Turriff UK 2014 Prelim. Draft

prelim
Draft of a paper originally prepared for Mike Haseler, B.Sc., Glasgow.

A range of texts are here offered in an attempt to draw attention to how most of
anthropogenic atmospheric CO2 could have been produced by agriculture, especially
via an anthropogenic fulvate production mechanism.
2

Contents

1. What is fulvate?
2. Original Draft of a Letter to RSC Chemistry World which had discussed how CO 2 seems to have
increased approximately linearly with the increasing global human population
A shorter version of this letter written in a more journalistic style eventually got published in RSC
Chem World June 2011 p 34-5(the published edited form of this letter did not , however, seem to
include as expected in the electronic form, the part of the text which had presented the fulvate
hypothesis which of course might have been thought to highly inappropriately challenge the now
widely accepted fossil fuel hypothesis.)
2-1. References to Section 2

2-1-1 The Onozaki paper

3. The above idea is introduced in a slightly different manner
3.1. Comparison of Data Available on Year-on-Year Fossil Fuel Usage
4. The fulvate hypothesis discussed in terms of the Ruddiman Hypothesis
4.1 Fulvate can be considered to be a smart polyanion
4.2. The putative early anthropogenic warming of the sea
4-2-1 The Hofmann Paper
4.3. RW Simpson, M Salby and D Coe Contributions

4-4.The Marischal College (MC) Aberdeen U . Hypothesis

4.5.The Ruddiman early anthropogenic hypothesis combined with the MC (Aberdeen ) Hypothesis
4-5-1 The Ruddiman Hypothesis
4.-5-2. Agriculture & Humus Degradation
4.-5-3. References to sections 3 and 4
5. Further GRAPHICAL COMPARISONS OF HUMAN POPULATION DRIVEN
atmospheric CO2
6.Appendix
6-1. Humic matter modification of the Silln Sea-Atmosphere Control Model
7. Other Hypotheses
8. More on the Definition of Fulvate
8-1. Cut from a MC doc
9. Further Statement: Fulvate Led Sea Supersaturation Climate Hypothesis
10. Source of data used for plots of atmospheric CO2 and fossil fuel usage vs. human population
11. Text of D. Grant MC 1989 and later 2001 paper
(Humic Substances Inhibit Calcite Crystallization)
12.
13.
14.
15.

Figures (draft drawings) for a precursor of the above paper

ACKNOWLEDGEMENTS
The Preincubation Effect
Conclusions

1. What is fulvate?
This class of humic matter is a polyanionic
chemical substance which is believed to be a
possible major a determinant of the carbon cycle
by fulvate both being one of the largest carbonbased chemical system in the biosphere and by
fulvate having the ability to bind strongly to
water molecules, to numerous types of ions and
to mineral surfaces.
Fulvate is a polyanionic chemical substance
having a similar but complex (and not properly
understood) overall chemical composition
worldwide; fulvate is believed to be a complex
colloidal system composed of multi-chemical
structured aggregates possessing abundant
carboxylate (CO(O)O-- anionic groups which are
apparently arranged
(almost one might have been tempted to think by
some kind of design) so as to bind very strongly
to calcium carbonate (as well as other mineral)
surfaces.

The ability of fulvate to inhibit calcification is so

outstanding that this could have been a function
which had co-evolved with life on Earth.
Fulvate occurs throughout the world in aerosols,
in the soil and in the sea; fulvate co-occurs with
a less oxidized form of fulvate termed humate
which together with fulvate comprises the
largest carbon-based chemical system on the
Earths surface. These natural polycarboylated
systems almost seem to have been designed to
bind strongly to the largest inorganic carbon
based system on the Earths surface: CaCO3 .
Fulvate is also a matrix for pro -life water and
nutrient storage and transfer to organisms, most
especially to microbial species and plants. It is also
possible that fulvate is a smart system being
responsible for various servo-feedback systems in
the biosphere roughly analogous to how
polysaccharides and their fragments can act as
hormone-like agents in plants (and more
controversially, also in animals).
Both fulvate and humate are believed to have a
related but highly complex chemical structure
consisting of a highly stable core (perhaps
degraded uronic acids of capsular polysaccharides
and mucilages etc., intertwined with oxidized lipids
with a 14C age of e.g. 1000 years) upon which a
range adsorbed molecules are attached. [Originally
the humate-fulvate core was considered to be
polyphenolic but this idea is no longer widely
believed].
Being the more hydrophilic fraction of humic matter
fulvate occurs in natural waters including the sea
where it coats and controls the activity of solid
particles including those which act as seeds for the
formation of forms of CaCO3 , a process which is
implicated as a switching or control mechanism in
the carbon cycle which likely affects how
atmospheric CO2 is regulated naturally.
Terrestrial fulvate undergoes extensive
anthropogenic alteration during intensive
agriculture. This process which is associated with

soil erosion is a serious problem worldwide. It

seems to be associated in some way with climate
change but how is not fully understood.

2.
This section contains the same graphs which have also been copied above. I repeat these
curves here since this is a historical record of my attempts to publish these data in
traditional printed form. This attempt has been only partially successful.

Original draft of a Letter to Chemistry World

This was a preliminary draft of a letter intended for RSC Chem. World; a highly truncated modified version was later published
in the RSC CW Letter pages (34-5) of the June 2011 issue. The final form of the published letter missed the principal point of
the letter namely that the fossil fuel hypothesis of the origin of the major part of the anthropogenic CO 2 in the atmosphere may be
entirely wrong.

[I am presenting Fig. 1 [PLOT3]

again here since it had been offered as supporting information in a my 2011 letter to the
Royal Society of Chemistry publication, Chemistry World]
Summary: Atmospheric CO2 seems to have increased approximately linearly in tandem
with the increasing global human population over the entire several thousand year
period of the existence of human agricultural society. Fossil fuel usage has also
increased in a human population-dependent manner but while over the same period as
CO2 has been directly linked in a linear manner to the human population, the fossil fuel
usage has shown a quite distinctly different type of non-linear variation with the human
population. Fossil fuel combustion is therefore suggested by this simple argument
(backed up by on a graphical plot of the amount of CO2 in the atmosphere and the
amount of fossil fuel usage against the global human population) not to be the primary
source of anthropogenic CO2 in the atmosphere.
A soil-related agricultural-activity-dependent mechanism is now suggested which may
explain the linear human population dependence of anthropogenic CO2.

Fig. 2-1 [PLOT 3]

shows a plot of the historical data for the human population of the Earth against, (a) the value
of atmospheric CO2 concentration and, (b) the annual rate of utilization of fossil fuel usage.
The dissimilarity between the population dependence of atmospheric CO 2 and fossil fuel
usage data tends to disagree with what a majority of climate scientists believe, namely that the
current value of anthropogenic atmospheric CO 2 has been principally determined since the
start of the industrial revolution some 250 years ago, by the combustion of fossil fuel (1) .
Fig. 2-1
Comparison between of the variation of atmospheric CO 2 with the human
population of the Earth and the variation of fossil fuel usage with the human population of
the
Earth---------------------------------------------------------------------------------------------------------------

Fig.2-1a [PLOT 1]
Least squares fit of the variation of the atmospheric CO2 as a function of
the human population of the Earth for the period 1959-2010
y= atmospheric CO2 ppm;
x= human population (/109) of Earth 1959-2010

When the most accurate of the human population/atmospheric CO 2 data, those for 1959-2010
(Fig.2- 1a) are considered separately, it seems that a strictly linear inter-relationship
(R2=0.9921) exists between them a. The 1959-2019 curve approximately extrapolates close to
the earlier, less accurately determined data to reach a zero human population baseline value
of 258.97 ppm which also agrees with the 260ppm value for this baseline which had been
suggested by W.F. Ruddiman (2) on the basis of a careful comparison of the ice core CO 2 data
from the last de-glaciation compared with those from earlier de-glaciations. Wood-burning by
prehistoric farmers was ruled out as a possible source of this putative prehistoric
anthropogenic atmospheric CO2 input, since this was calculated to be highly insufficient in
possible amounts. Some previously unsuspected mechanism e.g. input of CO2 into the
atmosphere from the sea arising by some unknown human activity e.g. from a direct
anthropogenic warming of the sea is needed to account for these data (2). An additional single
agriculture-related large scale emission mechanism which affected the sea and which may
have been responsible for injecting CO2 into the atmosphere throughout the history of human
society can however be suggested. This involves the degradation of the humus layers of
agricultural soils so as to cause a fulvate (water-soluble humic organic matter) runoff into the
sea which could have augmented the process of inhibition by dissolved marine organic matter
of marine CaCO3 precipitation (3). Since this mechanism is ultimately determined by humanpopulation number determined bacterial populations this may be why a linear dependence has
existed throughout human history between the atmospheric CO 2 contents and the
corresponding human population numbers.

David Grant, Ph.D.

MRSC (United Kingdom)

9 February 2011
a

[N.b. The (apparently trivial or it non-trivial?) very exact linear dependence of atmospheric
CO2 on human population was originally noted by ND Newell and L Marcus , Palaios , 1987
2 (1) 101-3; later the existence of this linear dependence of atmospheric CO 2 upon the global
human population has been partly explained in terms of human-dominance of twelve human
population-determined domesticated animal species by K. Onozaki (J Health Sci 2009 125-7;
cf. Y.T. Praire and C.M. Duarte Biogeoscience Discuss 2006 1781-9). It is now suggested
that the soil humus related bacterial mechanism discussed above will have a much greater
potential to release of CO2 into the atmosphere than does such an human plus domesticated
large animal species mechanism].

2-1. References to Section 2

(1) Anthropogenic CO2, which was formerly believed by some climate scientists to remain (by some unknown and
surely highly unlikely mechanism) in the atmosphere for several tens of years or even for thousands of years (but
this idea is now less commonly stated), and to have increased from a pre-industrial (pre-1800AD) baseline value of
ca. 280ppm to the current value of ca. 385ppm (when this paper was written) thereby promoting global warming and
climate change by the warming effects of the principal greenhouse gas CO 2. Cf. IPCC reports, e.g. Climate
Change 2007 (web.ipcc.ch/pdf/assessment-report/as4/syr/ar4_syr.pdf).
(1a) Atmospheric CO2, fossil fuel usage and global population number data are e.g. available on the internet; representative data
used for the construction of Fig. 1 were obtained respectively from: (for historical atmospheric CO 2 values)
web. cdiac.ornl.gov/ftp/trends/co2/maunolaco2 and the Vostok ice core data of Barbola et al.., listed on the same website
and (for historical fossil fuel usage values) from
web.cdiac.ornl..gov/ftp/ndp030/global..1751_2007.ems

(2)W.F. Ruddiman Rev Geophys 2007 45 RG 4001;

cf., Climate Change 2003 61 261-293

and Scientific American March 2005 48; cf., also J. Elsig Nature 2009 46 507-10
The present analysis of the data presented in Fig. 1 supports Ruddimans hypothesis that a
significant human anthropogenic CO2 augmentation effects began several thousand years ago.
It should be further noted here that J. Hansen, a major supporter of the fossil fuel hypothesis

of the anthropogenic augmentation of atmospheric CO 2 also seems to agree that Ruddimans

hypothesis is essentially correct(4) .

3 Additional Information to paper 2

Polyanions of the fulvate type are known to be outstandingly efficient calcification

inhibitors (3-1), an activity which is believed to depend on the adsorption of these
highly carboxylated polyanions onto the crystal growth sites of CaCO3 (seed)
particles, a process which also enables the total perturbation of the inorganic cycle of
the sea by human input, including the abolition of the lysocline (3-6).
It can also be easily demonstrated by in vitro experimentation {cf. Section !0
vide infra cf. ref 3-7} that agricultural fulvate is an exceedingly effective
calcification inhibitor which is capable of greatly diminishing the rate of precipitation
of CaCO3 from natural waters. It is well known that deforestation and agriculture has
led to global soil humus degradation thereby enabling a major amount of fulvate to be
transferred from the land into the sea. This would also have been a cumulative effect
over many centuries as humic matter.
(3-1)Cf., P. Zuddas et al. Gechemical Geol 2003 201 91-101; A.R. Hoch et al., Geochim Cosmochim Acta 2000 64 61-72 W.P.
Inskeep & P.R. Bloom Soil Sci Soc Amer J 1986 50 1167-1172; also Grant D et al. studies conducted at Aberdeen University in
the nineteen eighties (reported at conferences etc. but not fully in conventional peer reviewed form because of non-scientific
circumstances).
The process of high affinity adsorption of the poly-carboxylate organic matter (foulant) of colloidal and exokeletal crystal
surfaces CaCO3 stops both abiotic CaCO3 precipitation was originally discovered by Kitano(3-2) , Chave and E. Suess(3-3) and
Morse(3-4) and the re-dissolution of CaCO3 exoskeletal particles at the deep horizon was discovered by Wangersky (3-6)
(3-2) Y. Kitano Calcification and atmospheric CO2 in Biomineralization and Biological Metal Accumulation Ed. P. Westbroek
and E.W. de Jong D Reidel 1983, p. 89-98; cf. Y. Kitano and D.W. Hood Geochim Cosmochim Acta 1965 29 29-41
(3-3) K.E. Chave & E. Suess Limnol Oceanogr 1970 15 633-637; cf. E. Suess, Geochim Cosmochim Acta 1970 34 157-168;
cf. also A. Pentecost Thalasus 2004 20 45-49;
(3.4) J.W. Morse Rev Mineralogy 1983 11 227-394; cf., Carbonates in Mineralogy and Chemistry Ed R.J. Reeder Mineralogy
Soc Amer p. 227-264; cf. R.A. Berner et al., Amer J Sci 1978 278 816-837
(3.5) Cf J.R. Morse et al., Geochim Cosmochim Acta 2003 67 2819-2828
(3-6) P.J. Wangersky Limnol Oceanogr 1969 14 929-933; cf. ibid., 17 960-962 (this described the abolition of the CaCO3
dissolution horizon in the N. Atlantic; a more recent paper by P.J. Troy et al., Geochim Cosmochim Acta 2003 67 2819-21
confirmed the existence of a similar process in the N. Pacific).
(3-7) The ability of a standard Scottish agricultural soil-derived fulvate to very efficiently inhibit the crystallisation of CaCO 3
was confirmed by D. Grant, W.F. Long and F.W. Williamson (in a University of Aberdeen document, reproduced on the internet
at web.scribd/doc/46952647/Fulvate-II) by using an experimental method which had been developed by them for the accurate
determination of the alteration by additives of seeded crystallisation of CaCO 3 rate constants as previously described by D. Grant
et al. in Biochem J. 1989 259 41-45.
(4) J. Hansen et al. noted on their web document http://data.giss.nasa.gov/gistemp/gistemp2010_draft0803.pdf
that our greenhouse gas (GHG)-temperature comparison for the period of ice core dataalso show the anomalous (constant to
flat or slightly decreasing temperature) leap in GHG forcing in the post 6000-8000 years is highly unusual, indeed, unique among
the interglacial periods.
In the sea, the polysaccharides etc. from marine algae and their symbiotic bacterial mucilages degrade further into carboxylic
acid rich humic-like substances, also called fulvate (a term more usually applied to the water soluble humic matter of terrestrial
soils); these polymers are ultra-effective adsorber for inorganic crystal surfaces. This allows these substances to halt the growth
of e.g. CaCO3 crystals in the sea. This confers on marine fulvate polyanions the ability to potentially impede or even block the
inorganic carbon cycle of the sea. This mechanism may explain the inter-relationship between human population and
atmospheric CO2 and be the ultimate origin of at least part of the current anthropogenic elevation in atmospheric CO 2.
(cf. the data for atmospheric CO2 shows that this has apparently increased almost linearly with increase in human population
from pre-history times up to the present but the anthropogenic fossil fuel derived CO2 output has increased much more rapidly
than this).

2-1-1

The Onozaki Paper

Cf. The Existence of a Long-Term Linear Relationship between the Earths Human Population and the amount
of Carbon Dioxide in the Atmosphere
Evidence that a major human influence has both over the past centuries and currently continues to be
exerted most likely by a common mechanism upon the chemical composition of the atmosphere and
as a corollary to which a major human influence must be exerted upon this major planetary
atmospheric control homeostasis system (probably that of the sea) comes from the almost exact
linear dependence of the amount of carbon dioxide present in the atmosphere upon the human
population of the Earth cf. e.g. Fig. 1 cf. also K Onozaki J Health Sci 2009 55 125 ). This population is of
course critically dependent upon agriculture which consistently it seems may by a similar process
throughout human history have modified the sea surface via an input of agricultural soil-derived
humate polyanions

Cf. also 4-2-1 The Hoffmann 2009 paper vide infra

Paper 3+

3+

The above ideas are now introduced yet again

in a slightly different manner.

--------------------------------------------------------------------------------------------------------------------------------------

Hypothesis
D. Grant

Turriff 2014

Fulvate (the water soluble humic polyanionic

system, and a major carbon reservoir of the
biosphere) when transferred from degraded
agricultural land into the air and rivers and
eventually into the sea perturbs that part of the
carbon cycle control system which is exerted by
marine CaCO3 surface adsorption by dissolved
organic matter. This agricultural fulvate transferred
in ever greater amounts as the intensity of
agriculture has tended to increase to feed a
growing human population has allowed the amount
of CO2 in the atmosphere to be determined in an
exact global human population size dependent
manner. This mechanism, and not fossil fuel
combustion, is now argued to have caused the
current and historical anthropogenic increase in the
CO2 content of the atmosphere.
The remote sensed atmospheric CO2 values have
varied directly and precisely as a function of the
global human populations especially for the years
after1959 as illustrated in Fig.3-1. correlation is
now suggested to be a useful key for unlocking an
understanding of how humans might, through their

increased need for soil-based food production also

caused unintended soil humus degradation in such
a manner as to promote an increase in the amount
of CO2 ending up in the atmosphere.
The two most accurately known climate science
datasets list historical atmospheric CO2 values and
their associated human population numbers. These
numbers are accurately and very linearly interrelated. A simple comparison made by plotting one
dataset against the other is show in Fig.3-1 : the
straight line interdependence demonstrates a
surprisingly high correlation factor R2 of 0.9921 a.
This accuracy can hardly be fortuitous a.
Fig. 3-1 follows

ND Newell and L Marcus Palaios 1987, 2, 101-3 1987 seem

to have been the first (in a paper entitled Caron Dioxide and
People) to note that the steady increase of carbon dioxide

in the atmosphere has closely paralleled the growth of world

human population
value with an amazing correlation of 0.9985 for the
datasets for the 25 years prior to their 1987 paper. These
authors did not use a linear correlation however. A number
of other authors have also discussed the (near-linear)
human population atmospheric CO2 relationship (vide infra).
Newell & Marcus also noted that this nearly perfect
correlation can hardly be fortuitous. It suggests that the
rate of increase of CO2 is almost wholly dependent on
human activities with only very minor contributions from
natural causes such as volcanoes, the melting of glaciers,
and changes in oceanic circulation. It is generally agreed by
ecologists that rates of human activities, such as t he
consumption of fossil fuels and the destruction of forests
are also increasing. No matter how complex the
relationship may be, the fact remains that CO2 and the
population explosion are almost precisely correlated.

It emerges that the entire CO2 content of the

Earths atmosphere can also be correctly
described as an exact linear function of the
global human population.
The future level of anthropogenic CO2 can be
predicted from this simple relationship, e.g.
when the Earths population reaches 10
billion the atmospheric CO2 content is
predicted to be 442 ppm.
The increase in the amount of CO2 in the
Earths atmosphere, and most especially that
which has evident since 1959, is confirmed
by the data plotted in Fig. 3-1 to be an
entirely anthropogenic phenomenon.
All of the CO2 present in the atmospheric
above the pre-human baseline of 259 ppm
must, it seems, now be presumed to have
been caused entirely by human activities.
But which activities? The common
assumption is that this is fossil fuel (or
wood, peat etc.) combustion. Organic carbon

+ O2 CO2. However a similar plot of fossil

fuel usage as a function of the global human
population shows that this has varied nonlinearly, and hence this source of CO2 seems
likely not to have be directly connected with
the observed total amount of CO2 in the
atmosphere b.
But why is the amount of CO2 in the
atmosphere such an exact function of the
human population of the Earth?
Surely the observed atmospheric CO2 is
simply the difference between much larger
numbers, which describe very large negative
flows of CO2 from photosynthesis and
similarly large positive flows from CO2
generated by the respiration by marine soil
microbial and other biota. Since these flows
are believed to be at least an order of
magnitude greater in scale than e.g. the rate
of transfer from the CO2 introduced into the
atmosphere from the combustion of fossil
fuel b, it seems highly surprising that the
difference in these large fluxes should,
consistently over decades or perhaps for
much longer (vide infra), continue to obey a
simple highly accurate linear dependence
upon the human population numbers.
b) The maximum amount of fossil fuel usage which is also
very accurately known for the years after 1959 has varied
according to an entirely different human population
dependent mathematical relationship from that under which
atmospheric CO2 seems to be correlated with human
population numbers, so the fossil fuel generation of CO2
process, is obviously quite distinct from the simple linear
effect of increased population induced increase in
atmospheric CO2 cf. e.g. Fig. 3-2 and 4-1 vide infra).

The logical deduction we can make from Fig. 3- 1 is

that humans, since we first lived in organized
agriculturally supported societies, have caused an
alteration of the some critical part of the basic
mechanism by which the regulation of the carbon
cycle is achieved, most probably this was by
affecting on how CaCO3 is formed and re-dissolved
in the sea.
In order to meet an ever increasing global human
population, an ever more intensified global food
production regime has evidently been producing a
fulvate side effect: this is now suggested to be an
increased marine colloidal particle CaCO3 coverage
by strongly adsorbed land-derived fulvate organic
matter transferred by the atmosphere and rivers
into the sea.

3.1
Comparison of Data Available on Year-on-Year
Fossil Fuel Usage
The highly detailed historical data on human population,
atmospheric CO2 and fossil fuel usage which can be easily accessed
by members of the public from the internet was used for the
construction of Fig. 3-2.
The fairly exactly linear variation of atmospheric CO2 with global
population number must first of all be explained in order to explore
how humans can change the composition of the Earths atmosphere
and so alter the Earths climate. Is the exactitude of the linear
relationship between human numbers and the amount of CO2 in the
atmosphere is apparently a primary fact (almost a law) of Nature.
New Hypothesis Building
This is now needed and also needs to be tested.
For this purpose the following sketch (Fig.3-2, vide infra) which was
derived from the official data may be helpful. This compares (top
dots) the year-on year variation of atmospheric CO2 (y-axis) with the
amount of fossil fuel used (bottom dots) as a function of the global
human population (y-axis).
It seems that the amount of CO2 in the atmosphere and fossil fuel
usage have varied as separate mathematical functions of the
human population.

Fig.3-2
While the entire Earths atmospheric CO2 has been directly influenced in
the dramatically direct anthropogenic manner illustrated in Fig.1 cf. the
top curve of Fig. 3-2, the maximum possible amount of CO 2 available from
fossil fuel combustion for energy production (the middle curve of Fig. 3-2)
apparently has varied quite independently of the observed total amount of
CO2 in the atmosphere. The fossil fuel usage curve appears not to track
(except very approximately) the observed final amount of CO2 ending up
in the atmosphere.

The observed semi-chaotic, non-linear fossil fuel usage relationship

with the global human population has also been perturbed to a
much greater extent in certain time sections than others, and such
perturbations are not replicated in the small deviations from linearly
which may occur in the nearly linearly-determined anthropogenic
CO2 curve.

The possibility that fossil fuel combustion is not the direct origin of any of
the observed anthropogenic CO2 therefore seems worthy of seriously
consideration.
This idea obviously goes against the current IPCC recommendations etc.
The mechanism of formation of anthropogenic atmospheric CO 2 from fossil
fuel, the process which gives rise to the highly linear variation of
atmospheric CO2 as a function of the human population, is commonly
believed to involve a primary injection of CO 2 into the atmosphere and a
secondary partial removal of this CO2 from the atmosphere by variable
sinks. By consideration of Fig. 3-2 this can now be considered to be the
equivalent of the creation of order out of disorder (the eventual creation of
a linear function from a non-linear function). The IPCC hypothesis seems
then to require that we fully accept some kind of order being produced out
of chaotically random events (implied in observed scatter in the variation
of fossil fuel combustion vs. population relationship). When subject to the
logical arguments set out above, a final highly linear function seems to
have emerged from an intrinsically non-linear, irregular function. The
conventional IPCC view of the origin of anthropogenic CO 2 therefore
implies that the creation of atmospheric CO 2 from fossil fuel breaches the
second law of thermodynamics, i.e. it disobeys one of the most
fundamental laws of physics. Could the Earth actually interact with the
human species in such a disallowed manner so as to create order out of
chaos? Could the physical processes which are responsible for the
homeostasis servo feedback systems of the carbon cycle and its
elaboration in human social structures bring forth a smooth variation in
the amount of residual human-produced CO 2 presence in the atmosphere
even although this arises from a chaotic process consisting of constantly
varying inputs and removals of CO2 from the atmosphere? The currently
accepted model of anthropogenic CO2 seems, albeit inadvertently, to be
postulating that the natural Earth environmental control system is capable
of reverse entropy generation. Perhaps, however, this is valid evidence for
the correctness of the Gaia hypothesis that the Earth is similar to a living
organism. (Cf. the controversial idea that biology to exist at all, must
generate reverse entropy in order to allow the self assembly of more
complex systems to evolve over geological time. The complexity of
biological species have increased with the passage of time in contradiction
to the fundamental requirement of physics namely that time is
unidirectional a concept which is further enshrined in the second law of
thermodynamics which requires that entropy or disorder must always tend
to increase with time).
Of course it might be argued that the linear atmospheric CO 2 variation
with the human population is actually mainly caused by fossil fuel usage in
the Haber-Bosch and other ago-chemical industries which have directly
and proportionately enabled more food to have been produced more
cheaply and this has provoked an increase in the human population of the
Earth. The IPCC strategy to inhibit fossil fuel usage will then be able to

diminish the rate of CO2 increase because of an inhibition of fertilizer

production associated human population growth. The amount of directly
formed CO2 produced from the combustion of fossil fuel is a secondary
effect which hardly influences the total amount of observed CO 2 in the
atmosphere.
----------------------------------------------------------------------------------------------------------------------3++
Nitrogen Fixation & Fossil Fuel
The industrial nitrogen fixation which depends on use of fossil fuel derived energy has
boosted food production affects the sea in numerous different ways including by perturbing
the nitrogen cycle as well as the soil and water humic matter regulatory systems which are
postulated here to control the amount of CO2 in the atmosphere.

You are invited to write another hypothesis starting with the above concept.
And also consider
3+++
Sulphur Provision for Plant Nutrition from Fossil Fuel

Paper 4
Atmospheric CO2 is Influenced by Marine Fulvate Status
Brief Statement of The Hypothesis and its Origin
D Grant Ph.D. Nov. 2010

This hypothesis draws a comparison between some aspects of the

apparent similarities in the inorganic chemistry of animal extracellular fluid
homeostasis with that in the sea in order to suggest how organic polyanions
might provide related homeostasis functions in both aqueous systems.
The most common type of organic (humus-stored) polymers in the biosphere contain
arrays of carboxylate (-C(O)O-) anionic groups which can, it is now proposed, provide
chemically analogous buffer systems to those afforded in the extracellular
compartments of biological organism by anionic poly(uronate) saccharides.
These types of polyanionic ligands can in principle determine the inorganic
composition of e.g. the extracellular biological fluids in animals and of natural waters
including seawater by a process of sequestration and release of ions and inter alia an
ability to avidly bind to solid surfaces which it seems could control the solubility of
sparingly soluble salts and thereby to create stable buffered supersaturated inorganic
ionic and water activity systems.
It should be noted that human blood serum and seawater are both well-known
examples of the kinds of aqueous solutions which are naturally supersaturated with
regard to CaCO3 crystallization. This supersaturation is dependent on the presence of
polyanions of the above types. Both of these aqueous solutions achieve such nonthermodynamic supersaturation because they contain the aforementioned polyanionic

inhibitors of this crystallization process which apparently determined the degree of

supersaturation () with respect to precipitation of this and other sparingly soluble
salts [1].
The animal CaCO3 control system includes the specific kinds of anionic
polysaccharides which occur at all adherent cell surfaces and if effective e.g. at blood
or urinary vessel wall can promote the formation of pathological vascular plaques or
urinary system stones [2].
Further evidence that natural carboxylate-based polyanionics might act by a similar
mechanism as inorganic ion buffers in both the sea and in human blood serum is that
both of these solutions contain similar all-element [cf. 3] inorganic element
contents (allowing e.g. the construction of an approx. Linear log-log inorganic
element content inter-relation plots show up this relatedness). (The discussed
polyanion ligand matrices apparently become preferentially enriched in the inorganic
ions which occur in the least abundances in their natural bathing solutions in an
analogous manner for the anionic polysaccharides of animals, algae and the humic
matter type of polyanions, indicating that these anions act as antennae to create a
reservoir of the essential inorganic nutrients). Similar log-log inorganic composition
relatedness profiles can be demonstrated for multi-inorganic element mass-spec.determined contents data between the putative parent multi inorganic ion solutions
e.g. blood serum and the anionic polysaccharide (animal polysaccharide[4] as well as
in the marine algal polysaccharides and geological fulvates) The part of this animal
polysaccharide putative buffer system provided by heparan sulphate has apparently
been strictly conserved throughout animal evolution [4a] being present from the start
of this evolution (in the sea) and could specifically have been evolved from precursor
less effective bacterial polyuronates by the creation of a more flexible iduronate
uronic acid ligand in order to more closely mimic the inorganic ion homeostasis and
CaCO3/HCO3-/CO2 control systems of the sea which putatively could have been and
continues to be afforded to a major degree by the abundant marine fulvate organic
polyanion system which is known to continue to present there. This idea is confirmed
by in vitro experiments which show that modern marine ad terrestrial soil derived
fulvates are extremely potent inhibitors of CaCO3 crystallization [4a].
Indeed they include examples of the most potent of such inhibitors which are known
to science. This means (if the idea is further substantiated) that the degree of
supersaturation of CaCO3 in the sea like, like that in animals and algae etc. is
controlled kinetically and is not thermodynamically determined [5]. This idea accords
with the notion that the Earths biosphere (including its atmosphere) resembles
(somewhat) a living organism which would be expected to behave, not as a
thermodynamically-controlled equilibrium system, but as an energy supercharged
system allowing energy to be made available in a rapid and directed manner. Such a
circumstance putatively effects the exchange of CO2 between the sea and the
atmosphere. Increased fulvate (e.g. from the degradation of terrestrial soils) is
predicted in this model to cause an increase in atmospheric CO2 as part of the
operation of the marine homeostasis system.
This idea can be looked on as an extension of the idea that seeded formation control
CaCO3 formation in the shallow seas (cf. Morses work on the shallow sea CaCO3
precipitation system [6]).
In support of the present hypothesis is the circumstance that the degradation of
terrestrial soil (and the resultant transfer of fulvate from the land into the sea) has
been greatly increased since the industrial revolution and most especially in recent

years and indeed is thought to be of a more serious environmental concern than is the
loss of tropical rainforests [7].
This kind of intensive agriculture natural topsoil degradation is the key anthropogenic
activity which might be a part of the complex process by which human actions during
the late Holocene 7000 years ago caused an anthropogenic atmospheric CO2 increase
(this was discussed by Ruddiman [8] who however could not provide a mechanism).
The Late Holocene atmospheric CO2 ; ([n.b. other greenhouse gas principally CH4
surge (and perhaps climate change/global warming)]might have then and also now be
a consequence of terrestrial soil degradation caused by deforestation and agriculture
riverine runoff.
In order to stop excessive global warming and the resultant possible major species
extinction etc, it will be essential, if the above hypothesis is correct, in addition to the
enforcement of the cessation of the burning of fossil fuel, biomass and municipal and
industrial waste, to halt the increasing rate of anthropogenic degradation of the topsoil
and the resultant increasing associated rate of runoff of terrestrial fulvates into the sea.
References to paper 4
[1] Cf. D Grant et al. Biochem. J 1989 259 41-45
The above paper was a part of a wider investigation of the modulation of the
crystallization enabled by soluble substances added to controlled seeded crystal
initiated crystallization of CaCO3 (calcite) and BaSO4 by e.g. anionic polysaccharides
and anionic soil extracts.
This work was conducted as part of a more general polysaccharide research
programme at Aberdeen University, Scotland, UK.
Cf. web.abdn.ac.uk/~bch118/publications.march2003.doc
Partly unpublished results obtained as apart of Aberdeen University polysaccharide
group researches (recently put in the public domain at
web. scribd.com/doc/41263479/New-Thinking-on-Climate-Change-Abbrev-III
showed that some, typical agricultural soil derived fulvates to have unusually high
effectiveness for the inhibition of CaCO3 (calcite) crystallization.
This finding has been replicated for soil polymers from other locations suggesting that
it is a global soil organic matter phenomenon which has a putative wide relevance for
a fuller understanding of the global carbon cycle, anthropogenically induced climate
change and global warming.
That anionic polysaccharides or polysaccharide mimetics contribute to geological
CaCO3 deposition and the natural calcification CO2 control processes in the sea was
intimated may years ago by E Suess (Geochim. Cosmochim. Acta 1973 37 24352437) who had reviewed earlier work in this field and found important new evidence
of non-biogenic association of natural organic matter with constituents of recently
carbonated solids. The hypothesis of chemi-sorption of phosphorus and nitrogen
containing natural organic matter as being a control mechanism was suggested then.
This abiotic control of calcification seems to mimic a process by which marine
organisms calcify or inhibit calcification.
The co-association of polysaccharide-like material adsorbed onto CaCO3 particles in
geological deposits was observed e.g. by ME. Guthorpe & C .S. Sikes, Ohio J Sci.
1986 (3) 106-109.
The controlling influence of anionic polysaccharides in coccolith calcification has
been confirmed by the work of e.g. de Jong et al.

That the method of control of calcification of marine microorganisms is of possible

major relevance for the fuller understanding of the natural mechanism of control of
the global carbon cycle was discussed by A Pentecost (Thalassus 2004 20 (1) 45-49).
It is evident that the critical role of natural polyanions acting as a switch which can
interrupt calcification in the sea could be a major control system which feeds into
climate and global warming and therefore the possible anthropogenic perturbation of
this switch could be of critical influence on the current abnormal climate change and
global warming.
The atmospheric CO2 content seems (as far as the accuracy of the data allows us to
know) exactly tracked the human population of the Earth since the Late Holocene.
The information collected at Mona Loa post-1959 shows an almost exact correlation
of global atmospheric CO2 with global human population numbers. In stark contrast
the (IPCC) hypothesis that the source of atmospheric anthropogenic CO2 is fossil fuel
combustion is only a weakly and sporadically supported by the available evidence
(the putative correlation not being seen over long historical periods including the most
recent, cf. D Grant Chem. World 2011 June p. 73).
This content of the atmosphere is however dramatically affected by the human
fingerprint. Humans are the dominant biological species and this allows humans to
have an impact on the climate since the climate is partly influenced by biota.
The Mauna Loa atmospheric CO2 curve shows up a likely influence of marine CO2
transfer rates. The seawater cooling/heating of El Nino and volcanic ash events
correlated with irregularities in differentiated time variation of the remote site
atmospheric CO2 values. This effect seems to obscure the effect of changes in the rate
of fossil fuel usage which are evidently not as strongly coupled to the remote sensed
atmospheric levels of CO2 as are the seawater temperature effects. The release rate of
CO2 from the sea and the blocking of the CO2 sink by anthropogenic influences seem,
on the basis of this analysis, to be the principal contributors to the current abnormal
rates of global warming and climate change.
[2] D Grant et al., Medical Hypotheses 1992 38 49-5
[3] H Haraguchi J Anal At Spectrom 2004 19 5-14
That animal polysaccharides similar to those at blood vessel walls contain seawaterlike inorganic element contents was briefly discussed by D. Grant et al. in Biochem. J
1987 244 143-149, and more fully discussed in
web. Scribd.com/doc/26994439/Publication-2-Web.
[4] While these primitive kinds of anionic biopolymer, primitive homeostasis systems
have now evolved complex functions (e.g. for growth factor control during wound healing)
they seem also to retain their primitive tissue protection including anti-calcification functions
in modern animals (which of course have also evolved a host of additional protein-based ion
channel systems and for those with blood circulations including complex inorganic
filtering/recycling functions of specialized organs, which, however, also seem to use anionic
polysaccharides such as heparan sulphates as [an essential] part of their modus operandi.
Further evidence for a continued osmo-regulator function for the anionic cell surface animal
polysaccharide systems comes from the observation that for fifteen species of aquatic
invertebrates, the amounts of heparan sulphates and related anionic polysaccharides present in
their tissues is apparently controlled by an exact mathematical relationship between this
amount and the salinities of the different habitats of the organisms [4a], which tends to
support both the theory that multi-cellular animal evolution occurred in the sea (e.g. first

starting some 109 years BP), and that the abundant natural fulvate-type polyanions in the sea
could also have served and continue to serve some analogous critical basic homeostasis
function related to the [regulation of the ] inorganic contents of the sea [4b, cf. 5] (and by
inference also the regulation of the atmosphere which is, to a major extent, created by the
biosphere).

HB Nader et al. 1983 Comp Biochem. Physiol 1983 76 433-436

[4a] H.B. Nader et al. Carbohydr Res 1088 184 292-300
[4b] E.g. A.R. Hoch et al. Geochim Cosmochim Acta 2000 64 (10 61-72.
Cf. D. Grant web.scribd.com/doc/23967637/Humic-Substances-Inhibit-CalciteCrystlallizn-II
[5] Cf. the relevance of Henrys law to the uptake of CO2 by the sea. It should be
noted that Henrys law applies to equilibrium condition (this means that the rate of
uptake and release of CO2 are equal) and does not apply where the solvent reacts with
the solute. If, as seems likely, the CO system of the surface of the sea is kinetically and not thermodynamically-controlled,
2

then the rate of CO2 release from the sea is controlled by such kinetics. If this involves, as is here suggested, a dominant effect of
the inhibition of the seeding of CaCO3 solid phase formation, this process the dominates the ability of the sea to act as a sink for
CO2 and also is putatively the major mechanism of the control of the injection of CO 2 from the sea into the atmosphere.
Cf. e.g. a recently accessed internet discussion, one of numerous such documents, at: web.nzace.org.nz/index.asp?
pageID=241458801778, discussed Henrys law in the context of the role of the seas in provision of a sink for atmospheric CO 2,
notes that gases in our atmosphere exist in equilibrium with the sea. It is now suggested that this statement is essentially
wrong. The exchange processea between the gases in the atmosphere and the sea is a kinetically-controlled process which
centres on fulvate..

[6] J.W. Morse et al. Geochem Cosmochem Acta 2003 67 (5) 2819-2828
[7] [It should be noted that soil organic mater (which includes fulvate as a major fraction) is the largest pool of
organic carbon in the biosphere];

Terrestrial Soil Degradation

Cf. World Resources Institute Washington DC
web.wri.org/publication/content/8426.
Prior to 1990 topsoil degradation had occurred in 38% of croplands worldwide. Since
1990 losses have continued to mount year by year.
[8] W.F. Ruddiman
Reviews of Geophysics 2007 45 RG 4001;doi: 10.1029/2006RG000207;Cf. Climate
Change 2003 61 261-293; Scientific American March 2005 48 et seq.

Historical records of atmospheric CO2 and

fossil fuel usage compared as
five year differentiated curves and further compared with reported average
(4-)
surface temperature of the Earth for the years shown in Fig 4-1,

There appears to be a loose coupling between CO2 and temperature but no or very
weak correlation between these measured variables and the variations of fossil fuel
usage rates.

AD

s more likely) a moderate slowing rate of global warming [due perhaps to the
cooling effects of aerosols introduced into the global atmosphere from the massive
increase in use of coal fired power stations?] (but, it should be emphasized, it seems
that the CO2- population increase has continued to be strictly linear in exactly the
same manner as it had been before 1998 (cf. plots of atmospheric CO2 and fossil fuel
usage vs. the human population of the Earth, vide infra in inserted doc. [cf. also Fig.
4-2 in this appended document]. The massive increased use of fossil fuel has not, at
least from a preliminary visual inspection of the graphical representation of the data
plotted as a function of the average human population number, caused any marked
deflection of the historical human population-atmospheric CO2 curve. This clearly
shows that fossil fuel does not directly contribute in any clearly detectable manner to
the amount of CO2 in the atmosphere (at least as regards the accuracy with which the
year-on- year average CO2 variation is recorded). We must therefore assume, that
since the observed CO2 change does actually vary very accurately and directly with
any human population change, this population must be assumed to introduce a much
larger amount of anthropogenic CO2 into the atmosphere by processes which are quite
distinct from the simple generation of anthropogenic CO2 from the combustion of
fossil fuel.

The Silln Hypothesis of Atmospheric CO2 Regulation

Lets consider the ideas discussed by

Silln LG in 1967 in an article entitled
How have sea water and air got their present compositions?
[Chemistry in Britain 3 291-297]
This article discussed a novel phase rule rationale derived aluminosilicate multiphase mechanism of buffering of
the sea, this being suggested as a useful replacement of the conventional carbonate, long and slow stabilization
system of the marine inorganic ion composition, i.e., the CO32- and HCO2- ion contents which affect the
atmospheric CO2 .

Fig. 1 of the Silln article shows a proposed possible nine component model system
of the sea atmosphere control model:
Atmospheric CO2
Marine HCO3-- -- --- ---- ---CaCO3
-- -- -- -- -- -- -Na+ K+ Mg2+ Ca2+ H+

(M-Al-Si-)O-H phases
[Note added December 2014
Humic polyanions are known to peptize clay particles as well as to alter the chemistry and
physics of CaCO3 particles.
I have personal research experience in the study of the humic/fulvic polymer CaCO 3
system but not in the humic/fulvic polymer clay particle system. That is why I have
emphasized the role of CaCO3 as a putative control system for atmospheric CO2 in this
paper.
There may however be some major additional input of anthropogenic alteration of the
Silln mechanism of CO2 control exerted via the ability of humic/fulvic poymers to modify
the surface physics and chemistry of clay particles].

Silln asked is there true equilibrium in the real system, sea water-sediments-air?
Certainly not (but he went on to suggest that) the equilibrium model may be
sufficiently similar to the real system to make a comparison a useful first
approximation to the real system.
The above paragraph actually concerns the real world in which the neat diagrams of
chemical equilibration between molecules and ions is spoiled by the existence of
barriers to the attainment of such equilibria. For the environment, the universal
spoiler is the ubiquitous presence of humic substances in both their aqueous and
dried out environments [and furthermore humic substances are also such spoilers in
the atmosphere [THIS IS HOW THE HUMIC matter (anionic) SYSTEM putatively
CONTROLS via spoilage the natural water systems, mostly the sea,
and so the CLIMATE and how human influence upon the humic
system facilitates the most powerful human impact upon such
environments and upon the climate].
----------------- ------------- --------- ----- --------- --------- ----- ----- ----------------- ------------ ---------------Evidence that rapid CO2 release from the sea actually occurs.
The sea like lakes (cf. 8-1a-3) is likely to be consistently supersaturated in CO2
Evidence that the supersaturated CO2 of the sea is quickly injected into the atmosphere
(is perhaps surprisingly) already available form remote CO2 global atmosphere year

on year data (e.g. the curve of the atmospheric CO2 content increase since the
industrial revolution used by the IPCC) in which the coincidence in the discontinuities
with volcanic eruption ash cooling and El Nino CO2 boost effects are clearly evident
form a comparison of the most recent data.
Some major potential mechanism of quick large scale release of CO2 injection into the
atmosphere seems to responds fairly rapidly to changes in the surface temperature of
the Earth. Since the sea covers 71% of the surface of the Earth, this points to the sea
as being the origin of the extra CO2 injection.
It should also be noted that the rate of change in atmospheric CO2 and of fossil fuel
usage (which according to the current IPCC paradigm should be closely linked) are
found to vary more or less independently of each other (cf. the plots shown in Figs 1
and 2 in the original DG document) (a finding which initiated a back-checking of
internet of reports) revealed (8-1a1) [the possible significance of] an essay by R.W.
Spenser dated 1/25/2008 entitled Atmospheric CO2 Increase. Could the Ocean
Rather Than Mankind Be The Reason which discussed the impact upon in Manoa
Loa atmospheric CO2 values of sudden changes of temperature of the Earths surface
(i.e. that the amount of supposed anthropogenic CO2 injected into the atmosphere did
not accord with changes in fossil fuel burning; cf. also (8-1a-1) and the further
suggestion in the same website that the supposed 13C data of atmospheric CO2 also
can be de-treated to suggest that this 13C signature is a natural one and not a
direct anthropogenic fossil fuel or plant matter combustion CO2 fingerprint).
Another (peer reviewed) paper (8-1a-2) also hinted at a similar effect but this report is
less direct in suggesting this.
Perhaps the most thorough evaluation of the role of upper equatorial region seawater
supersaturation as a source of injection of CO2 into the atmosphere is the major study
of the variability of surface layer CO2 parameters in the Western and Central
equatorial Pacific reported by M Ishi et al. in 2004 which quantified the CO2 released
into the atmosphere from this area of the sea as being 0.6PgC/year but this value
decreased during El Nino periods to 0.2-0.4PgC/year. Some removal of CO2 from the
surface of the seas [also] occurred by CaCO3 precipitation but this process was
indicated by the results tabulated by these authors to be suppressed to high degree.
{Cf. Ian Plimer Heaven & Earth 2009 (Connor Court Ballan Australia) discussed the idea
that fossil fuel led CO2 now has taken the form of an irrational cult which seems to meet the
emotional need for a new environmental focus but this cult also is driven to fast track
untested hypotheses into law }. [Read]
There are also reported to be numerous other books which take a similar viewpoint.
Cf. e.g. Booker Christopher The Real Global Warming Disaster (Continuum, cf. Telegraph
Books UK)

It is now suggested that the 13C signature previously assumed to confirm the fossil
fuel origin of anthropogenic CO2 might to a significant extent or indeed entirely arise
from an expected large 13C depletion effect in the CO2 following bacterial use of
algal biomass carbon source (nutrient provision boosted via terrestrial fulvate
injection [viz. the anthropogenic input] feeding into the ocean surface held in TEP
foam bubble systems or via and equivalent abiotic fractionation of the stable carbon
isotopes due to kinetic and not thermodynamic pathways of carbon interchange in the
inorganic dissolved carbon and associated colloidal inorganic and organic matter
carbon pool of the ocean surface.

The sea is also likely to resemble the abundant Canadian lakes in the manner in which
bacterial respiration which includes a significant humic matter carbon source emits
significant 13C depleted signature to the atmospheric CO2 pool (cf. 8-1-a3)
(8-1a0)
M Ishii S Saito T Tokieda T Kawano K Matsumoto HY Inoue
Global Environmental Change in the Ocean and on Land
Ed. M Shiyomi et al TERRAPUB 2004
web.terrapub.co.jp/e-library/kawahata/pdf/059.pdf
(8-1ai)
Read from
Web://wattsupwiththat.com/2008/01/25/double-whammy-finding-roy-spenser-onhow-oceans-are-driving-co2/
(8-1a2)
P Sturm M Leuenberger J Moncreiff M Ramonel
Atmospheric O2, CO2 and 13C measurements from aircraft sampling over Griffin
Forest, Perthshire, UK
(8-1a3)
SL Mcallister PA del Giorgio
Direct measurement of the 13C signature of carbon respiration by bacterial in lakes:
Linkage to potential carbon sources, exosystem baseline metabolites and CO2 fluxes
Limnol Oceanogr 2008 54 (3) 1204-12-1
[These authors noted that there is now overwhelming evidence that most Northern.
temperate and boreal lakes are consistently supersaturated in CO2 and as a
consequence are a significant source of CO2 to the atmosphere].
A major source of C for the bacterial respiration production of CO2 was reported in
this paper to come from allochthonous dissolved organic carbon (i.e.
humate/fulvate);
This activity will also apply to the emission of CO2 from the sea].
The remote CO2 atmospheric increase is putatively to a major extent caused by the
proposed perturbation of the marine carbon sink resulting from anthropogenic
perturbation of the terrestrial organic carbon pool. Fossil fuel use may have some
effect however, e.g., both directly and indirectly (e.g. via the formation of acid rain).

from
7 Excerpt
D. Grant document in preparation
New Thinking on Climate Change
It should be noted that changes in atmospheric CO2 levels over five year periods
shown in Fig. 4-1 (but the global temperature and atmospheric CO2 are apparently
not correlated by any simple relationship).
The curves a and c in Fig 4- 1 seem to show up the additional global cooing effects of
fairly well-understood aerosols which are quickly redistributed globally following
volcanic eruptions; cf. the effect of Mt Pinatubo in 1991 and El Chiconin in 1983 in
the differentiated historic atmospheric CO2 levels which also seem to indicate that

CO2 is increased by the El Nino ocean heating effect (especially that of 1997-8) (cf.
also ref. 8-1-1).
This means that the atmospheric CO2 is responding quickly to temperature changes on
the Earths surface compartments especially the ocean which might indicate that
humic matter or the effects of cosmic rays are involved in this quick response.
The former seems more likely intuitively.
Again, in summary while the abnormal global warming change before 1998 is
apparently related to the range of changes in the level of CO2 in the atmosphere, the
CO2 relationship is apparently not a simple one.
There is no easily-detectable similar variation or coupling between the year-to-year
fossil fuel usage data and that of the five year-year change in atmospheric CO2.
The above, perhaps inappropriate treatment of these results obviously disagrees with
the conventional IPCC and major climate science fossil fuel hypothesis of the primary
origin of climate change.
Perhaps if the compartment of the atmosphere most affected by the industrial input of
CO2 could be separately studied such as correlation might come to light.
That such compartments exist is suggested by the similarity between maps of 14C
contents of atmospheric CO2 and the light islands visible over large super
conurbations form night time lighting seen from space (both maps are available on the
internet). The possible existence of high CO2 concentrations in some industrial or
urban areas comes from the analysis of the wealth of historical data of not-remote
atmosphere CO2 analytical data (8-0-3).
A major acknowledged problem with the conventional IPCC and major climate
science hypothesis of global warming is the existence of a major discrepancy in the
carbon balance. This missing link is the fate of the amount of fossil fuel derived
carbon which cannot be accounted for by the conventional model which assumes that
some 40% of industrial CO2 remains in the atmosphere, 30% is taken up by the sea
but there is a problem in accounting for the remainder which seems most likely to
arise form the activities of humic matter in the soil, sea and atmosphere. There is a
possible role here for alkaline soil which might act as highly effective CO2 binders ,
the possibly large sink provided by amorphous CaCO3 nanoparticles in the surfaces of
the sea and CO2 hydrate clathrates in the deep sea.
A starting point to attempt to clarify the above scenario might be to start off by
finding out why major diminution seems to have occurred over the last century in the
phytoplankton population of the ocean (8-0-2). While this has been attributed to
climate change, an alternative explanation could be the opposite influence. Abnormal
climate change might actually have been caused by the abnormal human induced
changes in the chemical composition of seawater. Indeed much of the ocean may be
some kind of sub-dead zone.
It should be noted that the amount of humic matter (dissolved organic matter) in river
and lake water has increased markedly over the most recent period of rapid global
warming and climate change suggesting that some kind of coupling may exist
between global temperature, atmospheric CO2 and humic matter status of natural

waters (cf. ref. 8-0-1). Sufficient data are, however, currently not available to confirm
that such a coupling exists.
Recap
From Fig.4- 1 (vide supra) The Global Surface Warming Curve 1880-present

We might speculate that the above global warming and smaller cooling cycles may be
at least in (a major ) part a humus led anthropogenic and because of unknown
feedback mechanisms (especially involving warming of the sea?) involving periods
each lasting decades. If human CO2 and other greenhouse gas output continues in a
business as usual manner, then around 2025 the re-start of major land surface
temperature increase may get underway so as to accelerate major human population
displacements. This, of course, is pure speculation.
But if we wish to take out an insurance policy to offset some future human population
pressure induced environmental disaster it is logically deduced that the current
pollution of the sea and not the current usage of fossil fuel against which legal
frameworks must be designed.
2-2 More on
The Role of the Sea as a Buffer for Atmospheric CO2
The functions of humic matter seem also to include a critical-for-like marine multinutrient element buffer provision (putatively the dissolved multi-inorganic element
content of the sea is created by a system of supersaturation of various salts determined
by the ability of humic matter to inhibit the formation of solid phases in addition to
CaCO3).
The higher solubility of CO2 gas in cold vs. hotter water should allow the temperature
and cold sea to provide a major buffer system for atmospheric CO2. Also the uptake
of CO2 from the atmosphere at high latitudes and its release into the atmosphere at
low latitudes. Although isotope studies seem to suggest that the transfer of CO2
produced by the combustion of fossil fuel will take e.g. n x103 year to equilibrate
with the sea, an apparent partial rapid operation of this buffer system seems also to
exist which is illustrated by the almost exact linear dependence shown between the
smoothed variation of the surface sea CO2 contents (suggested by seawater surface
temperatures) and the smoothed average recent CO2 contents of the atmosphere
deduced from published data (reported by L Endersbee (loc. cit., ref. 8-1}:
[atmospheric contents of CO2 data from January 1985 through May 2008 were found
to be linearly correlated with the global average sea surface temperature (the

anomalous increase from a recent baseline) over this period]) which could indicated
that the increase in atmospheric CO2 over this period was caused to a major extent by
the direct release of CO2 from the surface of the sea as the seawater warmed up or that
the increase in atmospheric CO2 had been affected in some way by the humic matter
control effect exerted upon the seawater CO2-carbonate buffer system which seems to
act as the natural switch which allows this CO2 release.
Humate-influenced processes in the sea might perhaps facilitate CO2 release via some
additional direct physical processes which might e.g. include and activity similar to
that of animal anionic polysaccharides which seem to bind directly to dissolved CO2;
a possible role of nanobubble associated humic polymer water structure builder which
can also be suggested {based on physical chemistry research on the effects of
nanobubbles on water structure; these effects might also apply to atmospheric humic
matter which will interact with the aerosol water molecules which can create solar
energy absorbers and cloud nucleators}.
The inorganic carbon equilibria between CO2 and HCO3- and CO32- ions and the
related solubility properties of colloidal size suspended CaCO3 forms the basis of a
possible mechanism by which the pH value of the sea is buffered, but pH may also be
enabled by humate via the uptake of H3O+ by this polyanion system.
The humate-dependent carbonate balance of the sea hypothesis can also provide
insight into how the sea removes CO2 from the atmosphere via the formation of and
precipitation of abiotic solid CaCO3 and colloidal particle generation. The small
CaCO3 particles do not sediment easily. But the larger sedimenting particles of
CaCO3 also re-dissolve at greater depth however as originally discovered in the
nineteenth century by Sir John Murray (the father of oceanography).
It should be noted that relatively shallow seas are believed to have the capacity to act
as carbon sinks via sedimentation of CaCO3 produced by abiotic precipitation as well
as from the deposition of shells of marine organism which use forms of CaCO3 as
exoskeletons. The open ocean is, however, thought not to behave in such a manner
but is believed to be more influenced by the existence of the CaCO3 re-dissolution
process which is caused by the greater CaCO3 solubility with the increased hydrostatic
pressure in deep water.
These currently held views of this distinct differences between the shallow and deep
seas as regards CaCO3, is now suggested to be incorrect.
Marine organisms are also thought to use extra-cellular polyanionics such as anionic
polysaccharides to orchestrate such calcification activities in a manner analogous to
how the humic polyanionc system may control the marine carbonate and abiotic
CaCO3 formation system. Such extracellular polysaccharides (which mimic the
actions of humic matter polyanions) will also become part of the dissolved organic
matter (DOM) pool of the sea.
The most abundant natural humic polyanion could play key roles not only on biotic
and abiotic calcification as well as in the wider CO2 atmosphere buffer system
enabled via the formation of CO2 hydrates which are stable under pressure conditions
which occur at the bottom of the sea (these are currently less well known, however
than the analogous CH4 hydrates, but they could contribute significantly to CO2
cycling under global warming conditions).

The supposed dual mechanism of CaCO3 precipitation in the shallow and deep sea
may not be accurately described as separate processes.
A major control mechanism of atmospheric CO2 may arise from humate-determined
colloidal CaCO3 formation in both zones.
A dominant natural seed particle and CaCO3 colloidal size particle stability control
system is suggested to depend on the activity of natural humate polyanions.
A re-evaluation of how the carbon cycle is accomplished seems to be needed, if, as
seems likely, the creation of a CaCO3 sink for CO2 is possibly entirely dependent on
the activity of small seed particles which trigger the formation of the phase change
which leads to the creation of a colloidal system (of CaCO3 and clay particles). The
idea that shallow sea and deep sea use different kinds of CaCO3 precipitation removal
mechanisms is now also suggested to be flawed.
Humic polyanions which include aggregates of degraded proteins and degraded
anionic polysaccharides evidently could provide for multiple biosphere controls
involving biological CaCO3 formation and its stable colloidal phase precipitation in
all compartments of the natural water-based colloidal size carbon sink systems.
The various kinds of humate [C(O)O-]n - rich polyanions present in e.g. soil humus
and in the dissolved organic matter of the sea are apparently characterized by their
uniquely enhanced abilities to inhibit the rate of seeded crystallization of CaCO3.
As a system of CaCO3 based carbon cycling has co-evolved with biota on the surface
of the Earth over geological time, this unique cross interaction between the largest
organic carbon store and the largest inorganic carbon store per se, demands the a
priori assumption be made that this cross interaction must have some major
ecological relevance and be a major factor in the mechanism by which the level of
CO2 gas in the atmosphere is buffered.
The critical interaction between humate anions and CaCO3 seed particles seems to
occur as is also the case with other man-made CaCO3 scale inhibitors which
function via the adsorption and blocking off of the active crystallization sites (cf.
Nancollas et al. loc. cit.).
It is now also suggested that humic matter will also absorb onto the colloidal spherical
amorphous colloidal-sized CaCO3 particles (cf., Bolze et al. Langmuir 2002 18 (222)
8364-9) e.g. which form when CaCl2 and Na2CO3 solutions are mixed.
That such colloidal CaCO3 occurs in the sea as the principal form of CaCO3 particle
there present, now seems to be a reasonable hypothesis (at least under the specific
shallow sea situation investigated by Morse et al.) of how the activity of carbonate is
controlled.
Using the (Nancollas method) of in vitro calcite seeded crystallization of CaCO3
calcite (e.g. studied by starting from e.g. CaCl2 + NaHCO3 solutions showed that the
activities of (standard land soil derived) humic polymers, on a weight basis, is more
than and order of magnitude greater than that of the most effective man-made
inhibitors of CaCO3 precipitation which are, e.g., widely used industrially to prevent
surface calcification of boilers or oil-field boreholes or biochemically e.g. in animals
where polycarboxylated polysaccharides are ubiquitously present at vascular and
urinary surfaces where they inhibit calcification (cf. Grant D et al. Biochem. J. 1989
259 41-45). It is therefore proposed that a similar role of calcification controls exist
throughout the terrestrial surface biosphere and that this eventually determines the
CO2 pool of the sea and elsewhere in natural waters in the biosphere. [This might
perhaps be the sought-after IPCC missing link needed to account for carbon sink in
the Earth carbon cycling system].

Calcification control is predicted to occur in all the compartments of the sea by

tandem precipitation mechanism using biological and semi-or-non-biological
processes, the former being dependent both on colloidal size biological coccolith
formation which is subject to in vivo polysaccharide plus humate but the latter semiabiotic control depends entirely on the humate polyanions which yield colloidal sized
CaCO3 particles (this abotic process is of course really a delayed biotic process since
humate is produced by biota, but under the dramatically modifying influences of
human industrial activities).
A similar mechanism which applies to both the above mechanism and is suggest to be
that which was identified by Morse to apply to the Bahama Banks in which the
process of CaCO3 precipitation is dwarfed by a much greater formation of colloidal
size nanoparticles of CaCO3 which remain suspended. This process is possibly aided
by the effect of the surfactant abilities of adsorbed humate. It should be noted that this
process is made possible because the humic matter type of polyanion occurs
abundantly worldwide in the sea and in other parts of the biosphere. This is the most
abundant type of biomolecule on earth. The ability of polyanions to stabilize such
colloidal particle systems for long periods of time is a well known phenomenon and it
is now suggested that this is afforded in the sea by the ubiquitous present of humate
anions which therefore are enabled to ultimately control the level of atmospheric CO2
and global warming.
The proposed Earth humate-centred climate control system is also somewhat
analogous to how calcifying phytoplankton species control their calcification (cf. de
Jong et al. (8-0-2-1-2).
The likelihood that deglaciation lagged behind an increase in atmospheric CO2 could
indicate that climate change arises naturally at least in part also via the heating of the
dark coloured humic matter surfaces.
It should be noted that evidence from ice cores seems to clearly show that the increase
in atmospheric CO2 which occurred during de-glaciation lags behind the global
temperature increase by 600400 years, i.e. that a primary greenhouse gas heating
effect of atmospheric CO2 is not the primary driver of global warming. This being
historically true must also be true under current conditions.
The phase lag caused by the albedo reflection properties due to ice coverage seem to
get overtaken by the increase in global warming effects which must have included that
promoted by micro and macro biota and its associated formation of dark coloured
terrestrial, marine and atmospheric humic mater during the warm periods which
preceded the glaciation (8-3-1-1) when the delayed CO2 was ultimately produced as a
consequence of the eventual warming of the principal marine (and other water rivers
and soil) sinks for CO2.
There is, however, also to be considered, the probable (additional)
effect of cosmic rays upon climate and global temperature. This should be taken
account of and may include a (small or not so small?) direct heating effect of the
absorption of energy from cosmic rays by humic matter.

Cf. Shavid NJ
Web.sciencebits.com/ice-ages
[A review of the cosmic ray hypothesis of climate change].
3. Human alteration of the bacterial population of the soil is also likely to be a major
mechanism of anthropogenic climate change.
Bacteria in terrestrial soils produce a lot of CO2.
This amount is putatively increased faster when humic matter becomes degraded by
modern agricultural practices.
This conclusion can be deduced form a recent compilation of the historical records of
soil respiration research reports.
Cf. the comments made on the recent paper by B Bond-Lamberty & S Thomson,
Nature 2010 464 579-82 ; doi:10.1038/news.2010.147.
Cf . also Fang, writing in the associated Nature News article noted that CO2 form soil
respiration now apparently inputs perhaps 98 petagrams (Pg = 1015 g= Gigaton(ne)
109 metric tons or 109 x 106 g) C /year into the atmosphere.
It should be noted that this amount/year is greater (by more than an order of
magnitude) than the total amount of CO2 believed to be produced by the
anthropogenic combustion of fossil fuels.
++++++++
This finding (which is a compilation of historical data) indicates that the complete
cessation of al burning of fossil fuels may only reduce the anthropogenic input of CO2
into the atmosphere by a relatively insignificant amount.
{Cf. insertion of additional more recent documents into the original document
3/12/14 vide infra).
4. Soil organic matter shifts into the sea as tundra etc. warm up.
The direct aboitic oxidation of (degraded) humic substances is known to be promoted
by the drying out of marsh environments a process which can also be catalysed by
trace amount of anthropogenically introduced heavy metals. This can allow direct
introduction of CO2 into the atmosphere as the climate warms up
(Cf. also ref. 8-3). Solar energy also degrades photosensitive forms of river dissolved
organic matter produced by the warming of Arctic tundra (cf. ref. 8-3-1).
4-1 Anthropogenic alteration of the marine humic matter dependent calcification
mechanisms
Cf. web. scribd.com/doc/23967637/Humic-Substances-Inhbit-Calcite-Crytallizn-II)
Cf. also document inserted at end.
4-1-1 Peptization by humic matter
Humic substances bind strongly to mineral surfaces (e.g. clay particles) thereby
putatively greatly reducing their solubility in seawater but with additional water
activity alteration power derived from the high surface area colloidal particles.
The attachment of humate to colloidal CaCO3 particles prevents their precipitation,
humate acting as a peptizing a gent. The ability of metal ions to neutralize this effect
should also be noted.
This coagulation process might contribute to how CaCO3 can be kept in suspension
and also coagulated (precipitated) (and to how humans can influence this).

Peptization of insoluble apatites is also observed when columns of this material are
put to use in attempts to fractionate anionic polysaccharides.
4-1-2 Peptization of Ice Surfaces by Humic Matter
The chemical nature of the banding which occurs in the Polar ice cores used to study
the historical record of past climate change seems to be somewhat obscure by may
conceivably be of humic matter origin.
[Snowfall and the build-up of ice sheets would then also conceivably have to some
extent at least, have been subject to the phase change modulation effects of airborne
humic mater particles].
4-2 Warming effect caused by enhanced uptake of solar radiation capture by graphitelike dark coloured (soot-like) humic matter particles
Atmospheric CO2 can in principle also be increased indirectly by the effects of
transfer of terrestrial soil organic humic mater into the sea either via the atmosphere
or via rivers. Soot-like humate types (either formed by binding of polycarboxylated
humate onto soot from fossil fuel or the separate soot like graphite like humate
occurring in some terrestrial soils) could act as effective solar energy traps and also
perform this task when such particles are transferred into the sea following terrestrial
soil degradation. This could directly increase the high latitude surface sea temperature
leading to an increased release of CO2 into the atmosphere.
5-1 Humic matter heat uptake and (Croll-)Milankovich Orbital Theory of Glacial
Cycles
It should be noted that the basic physical properties of dark coloured humic matter
(especially in surface waters) which endows it with an augmented ability to directly
absorb solar heat will speed the kinetically controlled increased supply of nutrients to
microbiota. Such an increase in the abiotic uptake of solar energy by the sea may be
part of how (Croll-)Milankovich solar energy cycles feed into the Earths climate.
It should be noted that aquatic humic substances which impart a brown or yellow
colour to natural water account for 40-0% of the seawater-dissolved organic matter
(DOM; [cf. Retamal et al., ref. 8.3-1 and Kanamura et al., ref. 8-5-1].
8-0-0 Plass GN The carbon dioxide theory of climate change Tellus 1956 8 140-154
Cf. Berner RA (Hogbom and the development of the geochemical carbon cycle
Amer J Sci 1985 295 (5) 491-495.
[This article gives the origin of current thinking about the carbon cycle; CO2 cycling
and storage in various sinks].
The findings of Berner & Morse vide infra, that humic matter is an effective
modulator of the degree of supersaturation of the crystalline forms of CaCO3 in the
sea indicates that this humic matter activity may control the carbon cycle and CO2-led
global warming to a major extent by this mechanism.
Cf . also Gunthorpe ME Sikes CS
Potent natural inhibitors of CaCO3 crystallization from chalk deposits
Ohio J Sci 1986 (3) 106-109.
[The authors suggested that polymers might have been derived from those which
control CaCO3 formation in coccoliths (cf. de Jong et al., loc. cit.)];
[The studied Selma (Alabama) chalk (0.10%) extracted {humic} matter [evidently
consisted of degraded polysaccharides + proteins) showed some threefold great an

anti-CaCO3 activity than ethane 1, hydroxyl, 1,1, bisphosphonate (a commercial antiCaCO3 agent; {the proteinaceous component in the geological humate seemed
however, to sometimes act as an accelerator of CaCO3 formation}].
8-0
Although the following articles does not mention humic matter is a useful guide to the
possible dominant role of the sea in determining the amount of CO2 in the atmosphere
Falkowski P et al. Science 2000 290 291-296.
8-0-1
Pocal et al. Humic substances-Part 7: the biogeochemistry of dissolved organic
carbon and its interaction with climate change
Environ Sci Pollut Res Int 2009 16 (6) 714DOC which includes humic matter is an important component of aquatic ecosystems
which have relevance to climate change. The authors supposed that humic matter
change arose from climate change and not vice versa. General global warming has
apparently caused an often greatly increased amount of DOM in river and lake water
in N. America and N. Europe (areas of the earth which have been subjected to the
greatest anthropogenic activity which lead to humate decomposition to fulvate).

-------------------------------------------------------------------------------------------------------------

8.

The fulvate hypothesis discussed in terms of

The Ruddiman Hypothesis.

This postulates (in its later forms) that the sea controls atmospheric CO 2 and early farmers
(as well as modern farmers) change the CO2 - holding-capacity of the sea. The mechanism
by which this is achieved could not be explained by Ruddiman.
The hypothesis that agriculture injects fulvate into the sea can, it is now suggested, be
used to support the (highly controversial) Ruddiman hypothesis.
This idea is more fully discussed in the following document
Comment on the
Atmospheric CO2
The Ruddiman Early Anthropogenic Hypothesis
D Grant Turriff

------------------------- ----- --------- ----Summary

The augmented formation through anthropogenic influences of fulvic anions (a water soluble fraction of humic
matter) could conceivably been the principal cause of the early anthropogenic augmentation of atmospheric
carbon dioxide noted by Ruddiman.
Introduction
Ruddiman pointed out that some kind of human activity coincident with the invention of agriculture in China could
have led to an atmospheric carbon dioxide surge which showed was superposed on the highly regular
alteration in carbon dioxide pattern arising from a parallel cyclical variation in solar energy output.
It seems however inconceivable that any direct human production of
carbon dioxide from a pre-industrial relatively sparse human population base could have dramatically augmented
atmospheric carbon dioxide contents.
The Ruddiman-early-anthropogenic-hypothesis of the origin of
the rapid increase in atmospheric carbon dioxide which apparently
occurred at ca.5000 years b.p., as indicated by ice core evaluations
proposed that large amounts of carbon dioxide originated directly from the widespread burning of wood made
available following extensive deforestation conducted by humans in Eurasia around that time.

However, calculation of the maximum possible amount of carbon dioxide

from such wood burning, suggested that this was much less (by a
factor of at least three; and in reality probably by a much greater
factor) than the observed increase in carbon dioxide observed at
5000yr b.p.A possible explanation of this discrepancy could have been a unexplained
simultaneous increase in the average temperature of the sea.
An alternative scenario also considering effects of human activities on the sea, now suggests a possibly more
credible oceanic change mechanism which can at least in principle account for any augmentation of
atmospheric carbon dioxide. This is the anthropogenic perturbation of a proposed oceanic carbonate/ carbon
dioxide homeostasis mechanism which depends on hyperactive natural polyanionic molecules which can
efficiently inhibit the precipitation and re-dissolution of solid calcium carbonate. Such inhibitors have long
been believed to include humic polymers such as the water soluble humic fractions which can be is leached
from the humus of degraded soils (including from soil organic damaged by deforestation).
The augmented input of such inhibitors into the oceans has apparently not been systematically studied and
therefore the appropriate quantitative data which are ideally required to assess the credibility of such a
hypothesis is currently lacking.

It has however been observed and reported sporadically that humic matter is an
outstandingly effective inhibitor of calcification in an industrial scenario, e.g., for
boiler water and borehole scale formation and quantitative laboratory results of in
vitro experimental results of the alteration of the kinetics of seeded CaCO3
crystallisation previously researched by the author are now compared with similar
studies reported elsewhere. The consensus of such studies is that the polycarboxyated
humic polymers show an outstandingly high effectiveness as CaCO3 crystallization
inhibitors and furthermore humic polymers in obtained from a variety of soil types
from widely different global sources all share this property. Furthermore the
estimated amount of humic matter currently present in dissolved or suspended states in the sea is of the
correct order of magnitude to that which is required to act effectively as an ultra-efficient crystallization inhibitor.
[Original document dated 1/24/2009 8.33 AM]

Comments on Climate Change

Possible Relevance of the Ability of Polyanionic Substances to Augment
CaCO3 Supersaturation in Natural waters.
D Grant University of Aberdeen / Address Turriff UK drdgrant@btinternet.com

It was noted in an article by S Chu entitled Carbon Capture and Sequestration in the journal Science (2009 325
1599) that Overwhelming scientific evidence shows that carbon dioxide emissions have caused the climate to
change. It was also noted that much of this CO2 comes from the burning of fossil fuel. It seems that capture and
storage of CO2 emissions from fossil fuel power plants must be aggressively pursued.
In the natural world sequestration of CO2 occurs through photosynthesis, calcification of CO2 by phytoplankton
and mineralisation in ground root systems.
It was however not mentioned in this article that a major reservoir and homeostasis system centres on the
dissolution of CO2 in natural waters and the removal CO2 therefrom by formation of insoluble CaCO3 (cf. the
formation of limestone). This process can be influenced, it is now pointed out, by anthropogenic influences. Such
influences could be the dominant ones for consideration of how to allow CO 2 to become sequestered by natural
processes.
Coccolithophores, it is believed, may play critical regulatory roles in such regulation of atmospheric CO 2.
Environmental factors are thought to influence the expressing or silencing of calcifying genes which influence the
formation of CaCO3 (ME Marsh Compar. Biochem. Physiol. (pt B) Biochem. & Mol. Biol. 2003 136 (4) 743-754).
Further research is however required to more fully understand this system.
A range of findings obtained during related researches (D. Grant et al. cf. W.F. Long
University of Aberdeen web site
http://www.abdn.ac.uk/~bch118/publications2003march.doc where the
listed publications of Prof. WF Long include in sections a and b relevant reports on the present topic; these
studies confirm that anionic polysaccharides extracted from marine algae animal anionic polysaccharides are
potent modulators of calcification processes. A hypothesis of the role of a diminution of the effectiveness of such
inhibition as promoters of degenerative disease processes was suggested from the abilities of these substances to
act as stabilisers of solution supersaturation by the inhibition of thermodynamically determined solubility of
CaCO3. A similar behaviour was evident in studies of selected standard preparation of Scottish humic materials in
the soil and natural waters. Various types anionic polymers including those formed during humification processes
to efficiently and sometimes selectively deactivate the active centres of seed crystals. It is further known that such
substances can be leached from soil under deforestation or intensive agricultural processes.
Current theories predict that anthropogenic atmospheric CO2 will require ca. 4.104 years to re-establish buffering in
the ocean (cf S. Solomon, Intergovernmental Panel On Climate Change Fig 7.12). Uncertainties in such
discussion include possible errors caused by inadequate account having been made of the influence of transport on
the tracer determined dissolution rates of CaCO3 (K. Friis et al. Global Biogeochem Cycle 2006 20 (4) Notes
GB4019.1-11).
The cyclic variation in energy of solar radiation which is suggested from ice core studies.
Of atmospheric CO2 suggested that the pre-agricultural system of regular time variation was disturbed by an
additional input from anthropogenic influences. This pre-dates the conventional notion that anthropogenic input
started with the western industrial revolution.
It was assumed that forest clearance and the burning of wood therefrom was the principal source of this CO 2.
However this seems to be less by a factor of three.
Thus the major anthropogenic effect is not direct CO2 emission.
Recent examination of stable carbon isotope ratios of this CO 2 confirms the hypothesis that it arises from
disturbance of the marine carbonate buffer system and that it was not determined from the combustion of wood (J.
Elsig et al., Nature DOI:10.1038/nature08393)
The major part of the effect can therefore be rationally be attributed to a direct influence of altered topsoil runoff
humic anionic polycarboxylate polymers into the oceans.
Such polymers have been confirmed in laboratory crystallisation ratemodification experiments to be ultra-reactive
for the inhibition of CaCO3 crystallisation.
This ability of effectively inhibit CaCO3 crystallisation seems applies to humic matter derived polymers from a
variety of widely different locations consistent with the hypothesis that this mechanism of the early anthropogenic
perturbation of atmospheric CO2 was, at least during the period of the first anthropogenic influence, the dominant
one.

Turriff,
United Kingdom AB53
ADDRESS DELETED as letter was not answered
USA
December 3 2007
Re: Natural Polyanionic Substances as Inhibitors of Oceanic Calcification
Dear NAME DELETED
I was a postgraduate student at Glasgow University in 1959 when I briefly worked in the Nancollas lab. Where
techniques of outstandingly accuracy had been developed for the study of seeded crytallization; I has been
engaged in a related project supervised by DS Payne.
I later used the same Nancollas seeded crystal growth methodology at Aberdeen University where I studied how
animal sulphated polysaccharides acted as effective calcification inhibitors. The behaved analogously to borehole
anti-scale inhibitors. Some of our findings and discussions appeared in Biochem. J. 1989 259 41-5 and in Med.
Hypoth. 1992 38 49-55. Some of this work was delayed for publication as it had been funded by industry. This
included samples of humic polymer fractions which had been donated by the Macaulay Institute in Aberdeen and
which were representative of the humic matter which occurs naturally in the land and also in sea (in amounts of ca.
1-2 ppm). These humic fractions were found to be outstandingly efficient calcification inhibitors when tested
using the same procedures as employed in our Biochem J studies
A problem with the assessment of the more general relevance (e.g. for climate science which was not our
expertise) was how representative were these locally obtained humic polymers for this class of soil/water polymer
in general. Over the years further studies have now reported similar results for humic polymers from other
regions. There seems now to be sufficient evidence now to suggest that most if not all humic polymers and their
main fractions are highly efficient inhibitors of oceanic CaCO 3 crystallization and will therefore influence oceanic
HCO-/CO32- /CO2 concentrations and putative also the amount of CO2 in the atmosphere and therefore are likely to
be of central relevance to the current discussion of climate change and global warming.
Anthropogenic humic matter from the land is well-known to have been depleted by intensive agriculture and
deforestation. Poorly degradable phosphonates may also augment the anti-scale activities of marine humic matter.
I enclose a draft document containing on-going side notes. I apologise if this is difficult to read but I think it
outlines the sort of paper envisaged. I would appreciate if you could add any other relevant notes or references [I
also enclose the original starting point of this draft, from 1989, together with photocopies of (the first page) of
some relevant papers].
I would greatly value you comments.
Yours sincerely
David Grant. Ph.D.
[[Original document dated 7/25/2009 8.33 AM]

9+

Fulvate can be considered to be a smart

polyanion

The most commonly known smart polyanion is DNA. Or heparan sulfate (HS) which probably equally important but less well
known to the public. We do not, however, have the same in depth understanding about fulvate as we have about DNA or HS
(which is thought to orchestrate much of multicellular animal behavior). Fulvate, may in the planetary biosphere much like HS
does in an individual animal, ultimately orchestrate water activity. Fulvate is thought to play a major role by establishing a
crystal formation homeostasis role in the sea. This is conceivably ultimately enabled by fulvate causing an alteration of water
aggregate superstructure. The dissolved organic matter fulvate is though to self-assemble from mucilages secreted by algae.
We have a fairly good preliminary knowledge e.g. from traditional wet chemical methods and also from spectroscopic
techniques of the individual alginates which end up as fulvate. Incidentally, the alginates or the equivalent bacterial capsular
polysaccharides are possible evolutionary ancestors of HS. A library of alginates of known structure being assessed for
usefulness for borehole scale formation control agents was found to behave in the tested anti-scale role precisely as could be
predicted from their known microstructures. Differences in how individual sugar uronate sequences were observed to bind to
mineral surfaces could be read off as crystallization kinetic parameters. This is how fulvate variation of microstructure may

also regulate calcification feedback processes processes in the sea. Human input into this process seems to have been enabled
by the final fulvate microstructure being susceptible to human input.

[Fulvate was traditionally defined to be any salt (usually multi-ion) form of fulvic acid, a water soluble fraction of humic acid
which is obtained from the colloidal organic fractions extracted from dispersions of soil samples by aqueous alkali,
neutralization, separation of insoluble humic from soluble fulvic fractions, and dialysis of the fractions. These heterogeneous
polyanionic substances are commonly accepted to be highly agriculturally significant, because they stabilize soil structure and
stimulate root growth. Traditional thought is that fulvate/humate is formed by chemical and biochemical alterations of chiefly
of microbially produced organic residues, and typically humic substances have revealed 14C-dated residence time in soil of
about 1000 years. They were traditionally characterized by their cation exchange capacity (CEC), by mass spectroscopy
(including by 13C) , by ir spectroscopy and by nmr spectroscopy.

10

Orig.4.2

The Putative Early Anthropogenic Warming of the Sea

D. Grant , Turriff, 18 May 2014 (With later inserted text and figures)
A comparison of the historical data for the variation for human
population of the Earth, the amount of fossil fuel used by that
population and the CO2 content of the atmosphere provides
evidence for the validity of the Ruddiman hypothesis (that
agriculture by its effect on the sea) is currently a major source of
anthropogenic CO2.

The most accurately known data from which it seems

worthwhile to consider for any discussion (and a possible a
re-evaluation of commonly held hypotheses) in the
general field of IPCC climate science are the year-on
year average values for remote-sensed atmospheric CO 2,
the human population of the Earth and the amount of CO 2
produced from fossil fuel by that population. The two
figures (Fig. 10--1, shown below) directly compare these
population, atmospheric CO2 and fossil fuel usage data by

plotting the latter two values as a function of the first, the

top curves of Fig.10-1 showing unsmoothed CO2 variation
(cf., the greater scatter which is apparent in the variation
of the oldest CO2 records), the second a smoothed curve
for the average annual fossil fuel usage million tonnes/yr,
the bottom figure showing this in terms of ~CO2
equivalents and also not smoothing the fossil fuel
variation with population as in the upper curve of Fig. 101. It is apparent that an approximate quasi-linear
correlation might be assumed to exist between part of the
fossil fuel usage and atmospheric CO2 record for the
historical period when the human population increased
from 4 to 6 billion, but both prior and post this historical
period there seems to have been no correlation between
the fossil fuel usage and the amounts of CO 2 in the
atmosphere. This suggests that a commonly believed
hypothesis, namely that since the industrial revolution
fossil fuel consumption has been the principal source of
anthropogenic CO2, may be invalid.

Fig.10-1 part 1

Fig 10-1 part 2

Recent information suggests that the average residence time of CO2 in the atmosphere
may be ca. 5 years and not the much longer time originally assumed (1).
A comparison is made of the 5 year differentiated curves for
atmospheric CO2 annual variation and fossil fuel annual usage in Fig
4-1 (which has also been posted on the web (1-1) (and pasted
below); this diagrams third curve shows the reported average
surface temperature of the earth which was only very approximately
correlated with the variation of atmospheric CO2 (and not at all with
the variation of fossil fuel usage).

Curve a, below is the 5 year difference in CO2 (ppm) and curve b fossil fuel million metric ton record five yr
differences. Curve a shows 1991 min (Mt Pinatubo eruption?) and pos 1963 (Agung) possibly also El Chichon 1982
and El Nino events (less clear). I have now left out the third curve .

Fig.4-2

later insert:

year AD 1880
1900
1920
1940
1960
1980
2000
The lack of any close coupling between these five year-on-year 5 year interval of
recorded variations seems to rule out the fossil fuel hypothesis of anthropogenic CO 2 which confirms
the similar conclusion which is apparent from a direct comparison of the undifferentiated variations
shown in Figs 2-1, 3-1 and 4-1.

--------=====
=====
--------=====
--------4-2-1

-------------

----=====
=====
-----

--------

---------

-----

The Hofmann 2009 paper

The lack of any close coupling between the year-on-year irregularities in fossil fuel usage
and the lesser irregularities in the Mona Loa CO2 records was alluded to briefly by Hofmann
et al. in 2009 (1a). These authors seem, however to have supposed that the fossil fuel
hypothesis is essentially correct, and that e.g. the linear variation of atmospheric CO 2
increase with an increasing global human population, which they also showed graphically,
simply arises from a tendency for the human fossil fuel usage rate vs. human population
variation, to be a similar linear function of time. This hypothesis is, however, it should be
noted, supported only by a selected use of the historical data. When all available relevant
data are considered together, it seems unlikely that any consistently present direct link
exists between the fossil fuel usage rates of change, that of human populations and of that
of anthropogenic CO2 content.

4.3
More on the Sea as the Major Controller of Atmospheric CO2
Cf. internet postings by
RW Simpson, M Salby and D Coe
RW Simpson, M Salby, and D Coe (in web postings etc. but. not yet in peer-reviewed articles) believe
that the IPCC fossil fuel combustion hypothesis is wholly or partially incorrect in a number of ways

and that the amount of CO2 in the atmosphere arises from a dominant role of the sea as the CO 2
reservoir. While Simpson and Salby proposed a sea warming hypothesis of CO 2 injection into the
atmosphere which is not an anthropogenic process, D Coe suggested that a fully reversibly
thermodynamic equilibrium exists between the atmospheric and the marine pools of CO 2 and that
fossil fuel derived CO2 injection into the atmosphere has perturbed this marine-atmosphere
equilibration. According to Coe, the sea does not take up, i.e. does not act as a (one way) sink for
atmospheric CO2 as proposed e.g. in the IPCC hypothesis, but engages in a completely reversible
thermodynamic equilibrium with the CO2 present in the surface water of the sea which was also
considered to be replenished by a system which ultimately links up to an infinite sink of CO 2 provided
by CaCO3 at the sea bottom. [This, however, misses out the complexities of the pressure dependent
lysocline originally found to exist by Murray in the classical oceanic researches. Coe also rejected the
validity of the use of a Revelle (fudge) factor by climate scientists since Coe believed that Henrys law
should be completely valid for atmosphere and sea surface CO exchange]. Coe discussed how
2
underwater CaCO3 in the deep sea and other CaCO3 forms present in the sea ultimately control the
amount of CO2 in the atmosphere. This comes close to older hypotheses which had suggested that
CaCO3 in colloidal particles and exoskeletons etc. control the Earths carbon cycle under an additional
control effect of the dissolved organic matter which is well known to adhere strongly to CaCO 3
surfaces and thereby dramatically alter their thermodynamic and kinetic properties. Henrys law a
central part of Coes hypothesis of anthropogenic CO2 attainment, should apply at the surface of the
sea and other natural waters only under reversible thermodynamic situations which are unlikely to
apply in such natural heterogeneous systems and also do not apply specifically where a solute reacts
with the solvent as is the case of the dissolution of CO 2 in seawater which are likely further to be
subject to the humic matter block effect arising e.g. from the hydrophobic humic-oil-like surface
coatings which seem likely to be the origin of the Revelle (fudge) factor which climatologists have
traditionally used to denote the lack of thermodynamic exchange between the atmosphere and the
ocean.
[added Dec 5 2014 Ian R Plimer Heaven and earth: global warming: the missing science
Connorcourt Publishing Victoria Australia is a 2009 references textbook which is highly critical of the
IPCC-led hypothesis of climate change on the basis of geological evidence for past climate change,
with natural cycles of warming and cooling which preceded possible human influence [cf. the postwar increase in atmospheric CO was associated with a global cooling period; overall there is no
2
evidence for any CO led global warming; this author suggests that the role of variable solar activity
2
solar wind and cosmic rays appear to be of greater impact on climate than does CO
2
This review is probably influenced by the Southern Hemisphere effect of humans being

much less than the Northern hemisphere effects.

11

orig. 4.4

A hypothesis which was discussed in the polysaccharide laboratory of Marischal College

Aberdeen, Scotland, during the mid 1980s
This hypothesis concerned (agricultural) fulvate type of humic polyanions, which have been modified by
anthropogenic food production intensity; these polymers can act as efficient surface modifiers for both CaCO

3
surfaces and sea water air interfaces. This interaction was suggested to be the critical factor (1, cf. 2) which allows
human influence (which alters their amount and microstructure) to produced the observed almost exact correlation
between atmospheric CO and the Earths human population (which is illustrated in the Figures shown at the
2
beginning of this paper).
It should be noted that ND Newell and L Marcus (3) had noted in 1987 that

For at least a quarter of a century the steady increase in CO

in the
2
atmosphere has closely paralleled the growth of the worlds human population
with an amazing correlation of .9985. This nearly perfect correlation can
hardly be fortuitous.

4.5
The Ruddiman Early Anthropogenic Hypothesis Combined with the MC
(Aberdeen) Hypothesis
4-5-1
The Ruddiman Early Anthropogenic Hypothesis
Ruddiman (4) proposed that early farmers, starting from as early as 8000 years ago (and, it might be
additionally conjectured, had engaged in similar environmental perturbation processes which have
been continued by later farmers) have caused a major injection of CO 2 gas into the atmosphere. This
agricultural CO2 is genuinely anthropogenic, but if this hypothesis is correct, it is obviously an ancient
product of human society and cannot be the fossil fuel generated CO 2 which since the industrial
revolution has been added to the much larger pool of agricultural CO 2 present most dominantly in
the atmosphere. The hypothesis that anthropogenic CO2 arises almost entirely from agriculture seems
to be supported by a direct comparison (shown above in Fig. 2) of the historical data on the year-onyear amount of CO2 in the atmosphere which seems to have varied directly (linearly) with the human
population of the Earth in a manner consistent with the Ruddiman hypothesis of anthropogenic CO 2
and in disagreement with the fossil fuel hypothesis of anthropogenic CO 2 since, while the amount of
CO2 in the atmosphere has accurately tracked the human population of the Earth, the amount of CO 2 in
the atmosphere has apparently varied quite independently of fossil fuel as a function of the human
population of the Earth. The fairly strict linear variation of atmospheric CO 2 content with the human
population extrapolates to a pre-human value of CO2 which also agrees with the value s suggested by
Ruddiman from direct ice core measurement (ca. 260ppmv)).
Ruddiman also suggested that the early anthropogenic CO2 may even have delayed the onset of the
next ice age. Wood burning (e.g. from forest clearance) was originally suggested to have been the
source of the early anthropogenic CO2 input into the atmosphere but the calculated amount was much
less than the required amount. A warmer sea was considered to most likely have been the source of
the extra CO2. This seems to rule out the hypothesis that this extra CO 2 could have been
anthropogenic. How could the sea have been warmed by a relatively small number of early farmers?
No mechanism to account for this seemed to have been available.
4.5.2
Agriculture & Humus Degradation
It is now suggested that early agriculture, in common with later agriculture, would have tended to
cause degradation of soil humus organic matter and this degradation could have always as it does at t
he present time, allow rivers to transfer various types of soil organic matter into the sea. The first large
scale agriculture 8000 years ago, then first started to transfer in larger amounts of organic matter than
the normal amounts which had been transferred was the case before the onset of soil tillage and
agriculture. This process has continued ever since and is related to the human population pressure for
food production. This could be why the human population is directly related to the amount of CO 2 in
the atmosphere and why his rule has apparently applied over the last 8000 years.
Hydrophobic surface-film-forming, land-derived soil organic molecules might credibly be seen as being
able to modify the physics not only of CaCO3 crystals etc. but also the surface layer of the sea in an
analogous manner to how

Benjamin Franklin in the eighteenth century

had first demonstrated that a teaspoonful of oil could dramatically
calm waves in a lake of an half acre size.
(Cf. also the problems associated with crude oil spillage pollution).
The possible major chemical and physical changes potentially
arising from the spreading of a surface film on water (e.g. a
Langmuir film or a Langmuir Blogett film) may include major effects produced on
natural processes such as the transfer of solar energy into and out the surface liquid phases and also a
major alteration of the physical chemical rate processes which regulate crystal formation especially
that of CaCO3 (e.g. as arises in the marine carbon cycle). The key point is that the extremely small
number of early farmers could potentially have caused a very large effect on the sea by their ability to
transfer albeit small but sufficiently large amounts of very active surface modifying soil-derived
chemical substances which could have produced an extremely large effect upon natural water system
environments including the sea. Soil humus furthermore has been indicated to contain specific
subfractions in which (potential oil-like humate polyanions are intertwined with) long chain ([putatively
lipid-derived) hydrocarbon polymetheylene-rich (CH 2)n>30. Such oil-like chains exist in normal
agricultural soils (2a); it is therefore possible that similar hydrophobic oil-like substance afforded
Langmuir monolayers have been formed from 8000 year ago until the present time at sea surfaces
and/or adsorbed at the surfaces of suspended colloidal particle surfaces are also present in the sea. A
net heating effect on the sea might arise from a more effective soil surface molecule transfer of solar
energy into the liquid phase (e.g. including more absorption coupled with less refection) or by some
other process such as the soil fulvate deactivation of those (e.g. colloidal) seed particle surfaces
(1,2a). The latter mechanisms could have contributed to the early anthropogenic increase in
atmospheric carbon dioxide. This second mechanism by which farmers might have altered the sea
may be of especial importance since these particles are considered to be an essential part of the
marine carbon pump which is enabled by the formation and precipitation of insoluble calcium
carbonate particles (and also includes a water pressure-related re-dissolution process of such particles
which is also subject to blockage by surface deactivation by organic matter). A humate surfactant
adsorption deactivation mechanism of such particles might therefore accomplish anthropogenic
slowdown of a significant part of the marine carbon removal cycle and so provide an alternative
explanation for a marine origin of the Ruddiman anthropogenic increase in atmospheric CO 2.
Early farmers in common with modern farmers most likely than have inevitably degraded the soil
humus layer in such a manner as to allow runoff into rivers of the type of organic matter which
includes molecules with hydrophobic oil-like sub-fractions which modify the physics of heat transfer at
the seawater surface and which include or are in addition to other sub fractions which can bind
extremely strongly t o calcium carbonate surfaces; the former may have been responsible for a
direct warming of the sea and the latter for a blocking part of the carbon pump of the sea. It is not at
first apparent however how such a surface oil-like soil organic matter fraction might have contributed
to the direct warming of the sea to any major extent. A possible additional mechanism by which this
might have been accomplished can however be suggested from the recent discovery that photons are
able to absorb preferentially at a polymeric form of water which can build up at a range of polyanionic
surfaces. This may include the polycarboxylated-mineral colloid structures (and which may
additionally be associated with the polymethylene units in a major fractions of soil organic matter
(2b)). This form of water structuring effect was discovered by GM Pollack (5) who also found that
photon absorption by such structures (called exclusion zone water, EZ water) allowed them to grow in
size A further aspect of the EZ phenomenon is that it could be a major previously unsuspected
important feature of biology and part of the reason why biology requires the presence of liquid water.

4-5-3 .

References to Section 3-4

(1) Web report of L S Lepori et al. (IPCF-CNR Pisa Italy paper presented at the Seventeenth
Symposium on Thermophysical Properties Fossil Fuel emissions and fossil CO 2 in the atmosphere) R
Revelle and HE Suess Tellus 1957 9 18 had considered that the half life of CO 2 in the atmosphere was
ca. 10 years. Others e.g. S Solomon et al PNAS 2009 106 1704 suggested that CO 2 remains for a much
longer time in the atmosphere. Segalstadt (cf Table I in David Coes paper 2 {web}) has collected a
list of published estimates of this value all of which are much less than that suggested by Solomon et
al. The ca. 5 yr time period is perhaps the most credible.
(1-1)web (D Grant,Turriff Scribd Fulvate II; www.scribd.com/doc/46952647/Fulvate-II 16 Jan 2011.

Cf. D Grant RCS Chem World letters 2011 June p 46-7

The climate change debate related fossil fuel and human population or soil organic matter led
climate change argument has also been appended to a treatise on autism :
web.Scribd.com/doc105367812/DRAFT1

(1a) D J Hofmann et al. Atmos Environ 2009 (12) 2084-6 {cf. web 144105[1]pdf}
(2) D Grant, (Aberdeen University) hypotheses etc.:
CaCO3 polyanion adsorption was studied for a range of marine algal polyanions by colleagues at the former polysaccharide
lab at Marischal College University of Aberdeen (cf. the list of refs posted on the web by Prof WF Long in 2003); the
present author had, as part of the program studied a range of animal derived polyanions (e.g. (2a) reported in Biochem J
1989 259 41-5 more fully discussed in D Grant et al. Med Hypoth 1992 38 49-55 Cf .also a further
development of the Med Hypoth ideas in web.scribd.com/doc.38814103/The-Role-of-Nuclearionof-Phase-Change-as-a-Dominant-Rate-Controlling-Process-in-Anthroopgenicaly-Induced-ClimateChange.
The soil-derived polyanions studied at Aberdeen U were seen as being of relevance to a Y Kitano
paper on calcification and atmospheric CO2 which had appeared in Biomineralization and Biological
Metal Accumulation Ed P Westbroek and E W de Jong, D Reider 1983 p 89-98]; the original
printout of the 1989 paper on the soil organic matter fraction studies of CaCO 3 and BaSO4 and the
Freundlich adsorption isotherms obtained has appeared on the web, ref (1).
Humic and fulvic acids as well as Mg2+ strongly inhibit* CaCO3 crystallization. This is highly relevant to
the role of CaCO3 in the global carbon cycle (and its possible perturbation by human influence as
discussed at Aberdeen U. some thirty years ago).
Cf. Also e.g. A Pentecost Thalassas 2004 20 45-9
and the publications of MM Reddy et al. (listed below) which include the following papers which report
how CaCO3 crystallization in natural water comes under the control of humate and fulvate anions and
also of Mg2+ * are also of relevance to the present discussion.
*Mg2+ release by e.g. ammonium ion generated from agricultural animal husbandry may add to the
fulvic acid from soil tillage and contribute to the overall suppression of marine CaCO 3 crystallization in
surface waters and the dissolution of CaCO3 in deep waters.
MM Reddy (Calcite growth-rate inhibition by fulvic acid and magnesium ion--Possible influence on
biogenic calcite formation) J Crystal Growth 2012 352 151-4;
Reddy and A Hoch (Calcium carbonate nucleation in an alkaline lake surface water, Pyramid Lake,
Nevada, USA) Aquat Geochem 2012 18 95-113;
AR Hoch MM Reddy and GR Aiken JA Leenheer and MM Reddy (Co-precipitation of dissolved organic
matter by calcium carbonate in Pyramid Lake Nevada) Ann Environ Sci 2008 2 11-25;
MM Reddy and AR Hoch (Calcite crystal growth rate inhibition by polycarboxylic acids) J Colloid
Interface Sci 2001 235 (2) 365-70;
MM Reddy & AR Hoch( Calcite crystal growth rate inhibition by aquatic humic substances) Adv Crystal
Growth Inhibition Technol Ed (Z) Amjad, Kluwer Academic/Plenum New York, 2000;
DE Kile DD Eberl AR Hoch and MM Reddy (An assessment of calcite crystal growth mechanism based
on crystal size distributions) Geochim Cosmochim Acta 2000 64 (17) 2937-90;
MM Reddy and A Hoch (Calcite crystal growth inhibition by humic substances with emphasis on
hydrophobic acids from the Florida Everglades) Geochim Cosmochim Acta 2000 64 (1) 61-72;
MM Reddy (Carbonate precipitation in Pyramid Lake, Nevada. Probable control by magnesium Ion)
Mineral Scale Formation and Inhibition, Ed Zahid Amjad Plenum Press New York, 1995
Cf. Z Amjad J Pugh and MM Reddy (Kinetic inhibition of calcium carbonate crystal growth I the
presence of natural and synthetic organic inhibitors) Ch 11 (p 131-147 in Water Soluble Polymers Ed
Z Amjad Plenum Press New York;
Cf .also Z Amjad (Influence of natural and synthetic additives on calcium carbonate precipitation and
crystal morphology) Tenside Surf Det 2006 43 4 184-91
(2b) D. Grant (Aberdeen University) Nature 1977 270 709-10 .
This paper indicated that humic matter contains abundant polymethylene structures (with potential
surface film forming capabilities)
The now obsolete use of tau rather than delta for proton chemical shifts should be noted here.
Cf. also D Grant web.scribd.com/doc/34142473/2An-Assesment-of-Progress-in-Studies-of-the-Chemical-Structure-of-HumicSubstnces-revised
Cf. web.scribd.com/doc/469525647/Fulvate-II; ibid. 23967637/Humic-Substances-Inhibit-Crystallizn-II; ibid. 41898831/NewThinking-on-Climate-Change (Abbrev. III); ibid. 3754439/Anthropogenic-Augmentation-of-Marine-Fulvate-amp-Climatechange; ibid 44604504/Climate-Change {accessed by searching for the Aberdeen polysaccharide lab publications formerly
available at web.abdn.ac.uk/~bch118/publications2003march.doc}

(3) ND Newell and L Marcus Palaios, 1987 2 (1) 101-3;

An early (1993) internet document by Gary W Harding entitled

Human population and global warming

web.strom.clemson, edu/becker/prtm320/commons/popco2.html
had plotted the then known data on human population and greenhouse gases in the
atmosphere prompted by concern about global warming opinioned by W Broeker,
Science 1975 1889 460.
In Table I of this article Harding gives the following log-log correlation coefficients
Population
Population
CO2
CH4
Temperature

0.990
0.991
0.718

CO2
0.996
0.992
0.716

CH4 N2O Temperature

0.984 0.977 0.916
0.994 0.974 0.942
0.949 0.945
0.728 0.829

Other discussions of this correlation have appeared at

web.columbia.edu/itc/sipa/envp/louchouarn/courses/math/MathProb2.pdf and
web faculty.washinton.edu/blewis/papers/co2/c02b.ht ml
More recently, the highly linear dependency of atmospheric CO 2 content upon the
global human population has been discussed by K Onozaki J Health Sci. 2009, 55,
125, in terms of domestic animal respiration plus fossil fuel combustion
mechanism which were considered to vary in relative importance between
different countries.
(4) W Ruddiman Climate Change 2003 61 261-293; cf. also the Wikipedia entry for William
Ruddiman which lists later relevant papers including AGU Fall Meeting San Francisco 9-13
2013;. Recent honours awarded to Ruddiman include the Lyle Medal of the Geological
Society of London for 2010. While at the time of the original publication of the Ruddiman
early anthropocene hypothesis was not thought to be credible, more recently, however, the
Ruddiman hypothesis seems to have gained a wider acceptance outside of the USA.
(5) The Water Structure Discoveries of GM Pollack et al. (which may have some
relevance for a fuller understanding of the role of fulvate in marine physics.
GM Pollack J Phys Chem B 2013 117 (25) 7843 -6 PMID 23656175 DOI
10.1021/lp352517d cf. B Chai H Yoo and GH Pollack ibid. 2009 113 (42) 13953-8; H Yoo
R Paranji GH Pollack J Phys Chem Lett 2011 2 (6) 532-6 PMID 22003430; M Rohani M
and GH Pollack Langmuir 2013 29 (22) 6556-61 PMID 23627361; R Das and GH
Pollack ibid. 2013 29 (8) 2651-8 PMID 23311934; JT Trevors and GH Pollack
Biochemie 2012 94(1) 258-62 PMID 22030900; AS Bhalero and GH Pollack J
Biophotonics 2011 4(3) 172-7 PMID 21287689; GH Pollack Int J Des Nat Ecodyn 2010 5
(10) 27-9, PMID 22977460; IS Klyuzhin F Ienna B Roeder A Wexler GH Pollack J Phys
Chem B 2010 114 (44) 14020-7, PMID 20961076
Light was reported by Polack et al. to profoundly expand the EZ water. EZ water
was also reported to be able to dramatically alter the surface tension of water so as
to facilitate along-capillary flow.
It would be of interest to study if the EZ polyanion effect alters Henrys law. Such
an alteration might be of relevance to a full explanation of the Revelle Effect the
phenomenon which is postulated by climate scientists to create a blockage in the
ability of the sea surface to act in the manner predicted by thermodynamics to
equilibrate with atmospheric CO2

12

Orig.5. Further Graphical Comparisons of Human

Population Driven
Atmospheric CO2
If we take the view that human population number is the independent variable which produces two
dependent variables (the amount of CO2 produced by the human population from the combustion of
fossil fuel and the observed amount of residual CO2 remaining in the atmosphere arising initially from
the first process) we need to consider how these three variables have more or less steadily increased
over human history as shown (by the two graphs presented below). The details of these human
population induced increases present a puzzle however: why is there a seeming irrational interrelationship between them? What single over-riding process appears be responsible for causing the
total amount of CO2 in the atmosphere to be held under some strictly surprisingly constant-overhuman-history control mechanism? This cannot be the currently accepted view that the amount of
CO2 in the atmosphere is determined principally by the burning by humans of fossil fuel from which
only part, about half, of combustion gives rise to CO2 which remains long term in the atmosphere {the
residence time of such strange CO2 molecules in the atmosphere is also thought to be some hundreds
of years an idea which runs counter to commonly understood physics as well as chemical and
biochemical logic}. It is believed that half of the fossil fuel derived CO 2 is taken up into the much larger
stream of CO2 expired by biota, into various CO2 sinks which are e.g. provided by the terrestrial
biosphere (mainly plant uptake for photosynthesis) and the sea (which also takes up CO 2 where the
uptake by photosynthetic organisms is augmented by the direct dissolution of CO 2 in seawater) but
evidently these sinks have changed in their effectiveness over time in a chaotic (weather or human
technology change related?) manner throughout human history in marked contrast to the not-chaotic
constant increase which has been observed in the residual amount of anthropogenic CO 2 which has
remained in the atmosphere over the same time period. Why has this not been affected by these
same chaotic events which have caused year-on year variation in the total amount of CO 2 produced
by humans from the combustion of fossil fuel?
Fig. 5-1. Comparing historical data for atmospheric CO 2 ppm and fossil fuel usage vs. the human
population of the Earth
Top curve : atmospheric CO2 variation with human population of Earth
Bottom curve : Fossil fuel usage variation with human population of Earth

Fig. 5-2 Subdivision of fossil fuel usage record.

----------------------------------------

---------------

---------------

-------------------

------------------

---------------------------------------------------------

Additional Note on The Pollack Theory of Water Structure

Water Layers Associated with Humate Polyanions may Facilitate Solar Energy Transfer
Part of the reason why biology requires the presence of liquid water and why polyanions are essential
to biology could extend to a Gaia-like thinking about the role of the sea in the carbon cycle; the
binding of water to humate and humate-mineral composite polyanions may be enabled by a process
discovered recently by GM Pollack (5) et al . who found that of an exclusion zone (EZ) of polymeric
water layers exists at anionic (e.g. sulphonate or sulphate and perhaps also carboxyylate) surfaces
which could additionally act as energy modulators and energy transducers; the EZ being light
sensitive, being subject to the ability of photons to dramatically build up the polymeric EZ on the
studied polyanionic surfaces. This process might be part of the mechanism by which humate
polyanions (including those derived from secondary soil organic matter plus primary marine organic
matter which also has sulfate half ester and phosphonate anionic groups) can both warm the sea and
modulate the carbon cycle of the planet and also allow human influence to enter into this process.
The Nitrogen Cycle
*A possible role of Mg2+ release by e.g. ammonium ion generated from agricultural animal husbandry
may add to the fulvate salt form from agriculture which might explain the Ruddiman hypothesis. The
disturbance of the nitrogen cycle by human action in a food product ion intensity manner (cf JN
Galloway et al. Science 2000 320 889-92) might also contribute to how a fulvate led alteration in the
CaCO3 control of the carbon cycle might arise.

Orig. 6 Appendix
6-1
Humic matter modification of the Silln Sea Atmospheric Control Model

Cf., Silln LG asked in Chemistry in Britain 1967 3 291-297

How have sea water and air got their present compositions ?
[This article discussed a novel phase rule rationale derived aluminosilicate multiphase
mechanism of buffering of the sea, this being suggested as a useful replacement for the
conventional carbonate long and slow term stabilization system of the marine inorganic ion
composition, i.e. the CO32- and HCO2- ion contents which affect atmospheric CO2.
Fig. 1 of this article shows a proposed possible nine component model system of the sea atmosphere control
model:
atmospheric

p(CO2)

---------------- ------------------

marine

[ HCO3- ]

[Cl-]

CaCO3 (solid phases)

- - - - - - - - - - - [Na+] [K+] [Mg2+] [Ca2+] [H+]

..
M-Al-Si-O-H phases

It should be noted that humic matter (which was not discussed here by Silln) can both
promote the removal by water of inorganic substances from rocks and also stabilize colloidal
dispersions of clay minerals as well as modulate the formation of CaCO 3 phases etc.; this is
as much a normal component of seawater as are the ions etc. shown in the above scheme. The
inclusion of humic matter can be considered to be a necessary component of any atmosphere
sea exchange of CO2 model including that proposed by Silln in this paper.
An interesting statement in his article is is there true equilibrium in the real system, sea
water-sediments-air? Certainly not (but) the equilibrium model may be sufficiently similar to
the real system to make a comparison a useful first approximation to the real system.
The above paragraph actually concerns the real world in which the neat diagrams of chemical
equilibration between molecules and ions is spoiled by the existence of barriers to the
attainment of such equilibria. For the environment the universal spoiler is the ubiquitous
presence of humic substances in aqueous environments.
This determines the outcome of the interactions in this diagram.
{A further almost philosophical aspect of the spoiling of thermodynamic concepts is that it
introduces a mechanism by which the second law of thermodynamics is breached by such
systems as the biosphere. Increased time does not cause breakdown to thermodynamic
entropy increase (but generates an alternative the compensation effect which seems not to be
explicable buy current theories of causation i.e. conventional physics which keeps the strict
adherence to of one-way time and light speed limitation)}.

13
Orig. 8
More on the Definition of Fulvate
[Fulvate is the name given to a State of Matter]
Additional Information
Fulvate is the traditional name given to a major
humic matter fraction of humified organic matter
which abundantly occurs in the soil. It is a key part
of soil stability and the natural fertility of soil. It
controls soil water and binds essential plant
nutrient ions. It enables rocks to be transformed
into soils. It is, more formally, that part of aqueous
sodium hydroxide extractable humic matter which
remains in solution following neutralization with
hydrochloride acid. Together with other humus
components it comprises the largest class of
organic substance in biosphere. Fulvate, like DNA
and carrageenan, heparin, etc. are natural
polyanion, but while the detailed molecular
structure of DNA, carrageenan and heparin have
been discovered, much is yet to be learned about
fulvate which although intrinsically heterogeneous,
seems to have a similar general chemical
constitution worldwide. Fulvate thought likely to be
a smart system but only the bare outlines of its
molecular heterogeneity and an imperfect
understanding of its smartness are currently
understood. Much is yet to be learned about
fulvate which seems to be a self-assembled
composite mixture of self-selected building units
drawn from the waste and decomposition products
of the biological species which live in or end up in
the soil. Natural (and now anthropogenic e.g. large
tonnage agro- or laundry -phosphonate) molecules
which resist biodegradation to the greatest extent
(e.g. restricted in the pre-human Earth to polymers
reformed from polysaccharides and lipids with long
hydrophobic polymethylene chains) are likely to
end up being intertwined internally into the fulvate
framework which is known to contain abundant

external hydrophilic carboxylate anionic groups.

Man-made mimetics of fulvate are polymaleicanhydride and polyacrylate which turns out also to
be an ultra-effect calcification inhibitors. Fulvate
seems to have been accorded by nature the role of
acting throughout the biosphere as an ultraefficient surfactant and general purpose binder of
smaller molecules and ions. Its avid binding to
surfaces allows fulvate to, e.g, control the
formation of insoluble CaCO3 phases in the natural
environment and so also to control the
atmopsheres CO2 loading. Fulvate has apparently
co-evolved with biota so as to act as a specific
high-efficiency anti-calcification agent.
Fulvate also finds uses as a broad spectrum antipathogen agent in Ayuvedic medicine. It is
believed to possess anti-viral properties.
Cf the human longevity has doubled over the last
200 years (TV News 12//1/15 cf. interview with Prof
University of Newcastle (who mentioned that
progress in medical science was partly responsible
for this).
Increased real wealth per capita enabled by fossil
fuel usage must also have contributed surely.
Obviously this increase in human lifespan has
contributed to the increase in the human
population of the Earth since AD1800 which, as
discussed above etc. is a direct linear function of
the amount of CO2 in the atmosphere.
Could there also be some unsuspected effect of
other than overt direct medical intervention being
the reason for the increased average human
lifespan ? Perhaps the antiviral activities of
additional fulvate in the environment has
diminished human pathogen effectiveness over the
last two hundred years. Perhaps atmospheric
content of some other gas (e.g. nitric oxide,
sulphate anion necessary for antioxidant and
modulation of heparan sulphate signalling or some
airborne colloid (fulvate?)

The Ayurvedic ethnic drug shilajit is considered to

be a variety of fulvate

-Orig. 8-1 Cut from a MC doc.

The following cut and pasted text from an Aberdeen U
written document is thought to be of value in giving more
insight into the complexity fulvic /humic acid.
Schnitzer and Khan (1972) noted that the chemical structure of humic acids and
related substances, important constituents of soils, peat (brown) coals and natural
waters, was largely unknown.
It seems likely that application of nuclear magnetic resonance spectroscopy
techniques in particular Fourier Transform methods will enable a much greater insight
to be obtained into the constitution of humic polymers, a subject which has remained
unresolved since they were first studied by chemical methods towards the end of the
eighteenth century (by Achard (1786), who found that aqueous alkali solution was an
efficient peptizing agent for humic acids, and that a major fraction of the solution
precipitated readily upon acidification).
Humic substances are probably the most abundant class of natural carbon-based
polymers on Earth and are of importance to plant nutrition (many essential trace
elements being bound by them) soil classification, structure and stability, as well as
being of interest for their role sin the formation of coal and mineral oil.
Humic substances undoubtedly also affect the growth of plants; the fertility of soil
must be related to some extent to the abundance and distribution of particular kinds of
humic substances. Humic substances are also important to an understanding of the
physics and chemistry of the interactions between agrochemicals and soils.
The view which is at present most widely held is that humic substances are derived
from microbial metabolites formed (BY HUMICFICATION) I.E. FERMENTAION
FOLLOWED BY FURTHER BIOTIC AND ABIOTIC DEGRADATION OF
COMPLEXES WITH INROGANIC SPECIES FROM PLANT AND ANIMAL
TISSUES BY MAINLY INIRIALY BY A DIRECT MICROBIAL DEGRADATION;
PREVIOUS THERORIES HAVE HELD THAT THE FORMAON OF LIGNINPROTEIN ,Waksman (1938) tanned protein Handely (1954) [e.g. tannin by vegetable
polyphenol tannins cf. Davies (1964)] complexes were of importance in
humification.
Plant as well as microbial enzymes however may play some role by extracellular
mechanisms.
Presently employed nomenclature of humic substances derives essentially from 18th
and 19th century usage (being based on fractionation techniques Kononova (1966).
Humic (grey and brown varieties being distinguished Springer (1959) Domke (1972))

crenic, apocrenic cf. Murzakov (1969) ulmic, fulvic Oden (1912) (having fluvanic,
fulvenic, fulvinic and lignofulvonic sub-fractions, Vilyams (1968), hymatomelanic
acid and humin are amongst the terms used.
Fulvic acid is HCl (0.1M aqueous soln.) soluble, but HCl precipitates humic saalts
from NaOH solutoins of extracted humic substances. EtOH (or Et2O) extracts
hymatomelanic acids from humic acids. Humin is the insouble organic residue (the
term is also used for that portion of the original NaOH-soluble organic matter that
cannot be redissolved after precipitation by HCl). Al2O3 gel and charcoal columns
were employed by Vilyams (1965) to separate the several fulvic fractions (listed
above), and by Forsyth (1946) to give four fractions. Two fulvic acid sub-fractions
were distinguished by Tyurin (1968).
One of the alternative systems of classification of acid, that of Kumada et al. (1967) is
based on the light absorption characteristics.
Humic acids are probably the key types of polymer structure to be solved, the other
named polymers being variants of this basic type of compound. The term humic acid
is employed in the present text in this more general sense (in common with the usage
in much of the literature on the subject) rather than as a particular sub-fraction of the
total humic polymers.
Other preparations which have also been labeled as humic acids are produced by the
action of concentrated mineral acids on sugars (likely as a result of the promotion of
dehydration/oxidation/polymerization reactions).
The formation of yet another type of synthetic humic acid-like polymers starting
from phenols (or quinones) has stimulated postulates of the formation of soil humic
acids by this mechanism to give e.g., phenol-formaldehyde resin-like products; the
initial phenols are envisaged as either being leached from green leaves, resulting from
microbial metabolites or the degradation of lignin. Ring opening polymerization of
oxidized aromatic rings could also conceivably lead to humic acid-like polymers (cf.
Ludemann et al. (1973).
Modern fractionation techniques, e.g. by the employment of dextran gel filtration, thin
layer chromatography or electrophoresis is apparently only a little more successful
[Ishiwatari (1971), Tamai (1971), Danneberg and Schaffer (1974) Cameron et al.
(1972) , Ladd (1969), Burler and Ladd (1969) and Banerjee (1974)] than the above
classical fractionation techniques in producing chemically differentiated fractions
form soil organic matter solutions, although molecular size distribution curves
(fingerprints) can be used for characterization purposes.
Classical subdivision of humus and the subdivision achieved by dextran gel filtration
five differently colored fractions, in the former case the light absorption extinction
coefficients increase with decreasing solubility (and molecular weight) whereas in the
latter case the extinction coefficient was found to decrease with increasing molecular
weight [Ladd (1969)].
It might have been anticipated, a priori, that humic acids are random heterogeneous
aggregates of carbohydrates, microbial metabolites, degraded lipids and amino acids

and contain both mixtures and complexes, inorganic soil components and various
organic polymers.
However it is commonly considered e.g. by Burges (1960) that the various fractions
produced by solvent extraction, as outlined above, represent size fractionation of a
singly polymeric chemical substance or closely related chemical substances and
furthermore that nitrogen is probably not present in the primary polymeric backbone
structure. This statement is based primarily on the reproducibility of the properties
and the difficulty of separation of identifiable compounds from humic substances.
Amino acids, amino sugars and phenols are considered to be adsorbed at the outer
surfaces or in pores of the main humic acid core polymer structure.
Seasonal variation in carbon (and nitrogen) contents of humic acids extracted from
soils was found to be much less than the variability of these elements in the soil as a
whole, this providing evidence for a consistency in the chemical nature of various
humic acid preparations.
Piccolo A
The scientific understanding of the molecular size and shape of humic substances (was critically
reviewed) in
Soil Science Nov 2001 166 (1)) 810-832
A large body of evidence shows an alternative to the traditional view of the structure of humic
substances which indicates these consist of a self assembled hydrogen bonded plus weak dispersion
forces instead of covalent linked system of small molecules derived from the degradation of dead
biological matter.
Hu et al. in 2000 using solid-state NMR and wide-angle X-ray scattering , detected crystalline domains
composed of poly(methylene) chains in several samples of SOM humus and humic acids from soil and
coal. The crystalline thickness corresponded to ca 25 CH 2 units of the crystalline hydrophobic domain;
non crystalline polymethylene also was present This is the inert part of HS. Phosphonate herbicide
might cause enhanced de-aggregation of the humic molecules (i.e. cause augmentation of fulvate
transfer to the sea).
[Cf Hu W-G et al 2000
Poly(methylene) crystallites in humic substances detected by Nuclear Magnetic resonance Environ Sci
Technol 34 530-534; this confirms the Aberdeen hypothesis of the chemical structure of HA cf Grant D
Nature 1977]

14

9. Further Statement: Fulvate-Led Sea Supersaturation

Climate Hypothesis
It should be noted that the polyuronate polysaccharides of mucilages and soil humic
matter are ubiquitously distributed natural polyuronate polyanionic humic substances
which provide the largest carbon pool in the biosphere where they provide a natural
water and nutrient element reservoir and management control (a putative major
planetary biosphere homeostasis) system. Human perturbation of this major natural
matter system could therefore potentially contribute to climate change including by
several mechanism including that in which augmentation of marine soluble humate
(fulvate) blocks or alters the rate of precipitation of CaCO3 from the seas. The seas
are supersaturated with regard to the thermodynamic precipitation of CaCO3. To
overcome this supersaturation requires the presence of (e.g. CaCO3) seed particles.
The ability of fulvate to de-activate these particles is a likely key process by which
climate change can potentially be caused by human actions. A related surfactant

property of small CaCO3 particle adsorbed fulvate is that this encourages the
formation of colloidal sized crystalline or amorphous CaCO3 nanoparticles which
remain in suspension and tend further to increase the amount of dissolved carbonate,
bicarbonate, and CO2 in the surface layers of the sea which by reverse Henrys law
equilibrates with atmospheric CO2. There may also be a role of humic polymers in
the formation of CO2 hydrate clathrates which are believed to be present in deep seas
and which represent a possible major pool of inorganic carbon. The major
anthropogenic input into marine humate is suggested to be from modern intensive
agriculture and which is associated with increasing topsoil degradation on a massive
scale worldwide. This degradation is expected to be increase the rate of formation of
water soluble fulvate runoff into rivers. Such terrestrial humic matter derived black
water in the sea in addition to the aforementioned interference with the natural CaCO3
buffering system also can directly increase the solar warming of the sea. This lightblocking effect also leads to diminished marine primary production. The light
blocking and heat absorbing effect of humic matter in dust can as well as directly
heating the surface layers of the Earth also alter the rate of cloud formation and the
incidence of intense precipitation which further lets increasing amounts of soil organic
matter reach the sea.
The largest class of organic chemical substance in the
biosphere, humic matter, is thought to influence the servo
feedback mechanisms which controls the carbon cycle of the
planet and which dictates how the atmospheric CO2 system
is regulated. The major reservoir/regulator system so
affecting the carbon cycle is most likely to be the sea which
covers some 71% of the planets surface and which has been
subject to major perturbation by inputs from human soil
based food production methods. This allows human
population pressure to directly affect the level of CO2 in the
atmosphere.
Land fulvate potentially interfaces with the sea fulvate CO2bicarbonate-carbonate system most especially affecting
CaCO3 in its various forms which provides a very large sink
system which interfaces and potentially regulates the
c
carbon cycle . Soil humus degradation, which is known to
occur under intensive agricultural conditions, and which can
create potent marine homeostasis regulation perturbation
has previously been discussed in terms (e.g. Kitano, Silln
discussed) CaCO3- - of models of oceanic and atmospheric CO2
control. Direct anthro-perturbation of these controls can
logically explain why we observe a highly linear atmospheric
CO2-human population linkage. Soil organic matter
degradation will enable the transfer into the sea of known
potent CaCO3 surface binding polyanionic (fulvates)
[polycarboxylated heterogenous highly stable natural
d
polyanions ] which are known to be capable of perturbing
the natural marine carbonate servo-control switch afforded
by CaCO3 phase changeover from thermodynamic to kinetic

control; normal marine dissolved organic matter (DOM)

allows for a surface organic matter coverage which
deactivates CaCO3 phases thus potentially re-setting the
major marine major sink and apparently allowing for natural
climate control feedback systems used before human
presence by nature for the regulation of atmospheric CO2 .
C

E.g. cf. Y Kitano Calcification and atmospheric CO2 in

Biomineralization and Biological Metal Accumulation Ed
Westbroek and E.W. de Jong D Reiderl 1983; cf. also recent three
papers by D Coe (internet )Ocean Control Theory of
anthropogenic CO2)
d

Cf. e.g. the publications of MM Reddy et al. of the US Geological

Survey ,Denver.
This former major Aberdeen U. researched fulvate mechanism
should, it is now suggested now be more fully be addressed so to
put the debate regarding human influence on climate change into
a perhaps more accurate scientific footing. This fulvate
mechanism can also explain the Ruddiman effect (the apparent
ability of early farmers to increase the amount of CO2 in the
atmosphere by altering the apparent CO2 release rate of the sea).
10.
Source of Data Used for PLOTS of atmospheric CO 2 and fossil fuel usage
vs. human population.
The databases which were used to construct the figures presented in the
above as well as the following documents were obtained from the
following official sources.
The historical global human population, fossil fuel use estimates
compilation of Mona Loa and ice core data are official published data
available on the internet.
Cf. Fischer H et al .Science 1999 283 1712-14
Keeling data web.cdiac.ornl.gov/ftp/trends/co2/maunola.co2
Ice core data
Web.cdiac.orne.gov/trends/co2/lawdome_combinded_data

15

orig11. Text of Paper written in 2001 updating a MC ms. from 1989

D Grant Humic Substances Inhibit Calcite Crystallization
An Aberdeen U. derived Hypothesis (as discussed in the polysaccharide lab of Marischal
College in the 1980s) of Fulvate-Determined Climate.
This hypothesis has been mentioned on the web but this is now difficult to access. The
following pasted document sets out the hypothesis. Some of this data was used for poster
presentations in the 1980s and also briefly mentioned in ukonline web sites during the
1990s.
The following document which has re written in 2001 and posted in the following form at on the
web in 2009 web.scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystallizn-II seems no
longer accessible. Since it is relevant to the fulvate hypothesis of climate change it seems
worthwhile to reproduce it here. The cited references are especially of central relevance to how
anthropogenic CO2 augmentation and climate change might be afforded by the degradation of
soil organic matter and the transfer of terrestrial fulvate into the sea.
--- --- --- --- --- --- --- --- --- --- --- --- --- --- --- -Humic Substances Inhibit Calcite Crystallization
Possible Relevance to Global Carbon Dioxide Balance.
D Grant (Turriff)*
drdgrant@btinternet.
Summary
Water soluble organic humus components (fulvic acids) are potent inhibitors of calcite crystallization, suggesting that
their augmentation in natural waters may contribute to global warming.
Introduction.
Soil humus, which contains environmentally stable organic polymer /colloidal materials of molecular weights up to
several million and typical showing 14-C ages of ca.1000 years, evidently formed by chemical and biochemical
alteration of plant and microbial debris, is the major reservoir of terrestrial organic compounds and provides water
and mineral holding properties important for plant nutrition, stimulates root growth (Kononova 1966) and binds
calcium carbonate in calcareous soils.
Soil humus may be depleted by the effects of augmented dissolution/dispersion by the effects of humus degradation
by intensive agriculture and increased precipitation effects following climatic change (cf. Houghton & Woodwell
1989).
Poorly-biodegradable polymethylene humic components and carbohydrate-like fractions are interlinked in humified
organic matter of agricultural soils (Grant 1977 cf. Potts et al. 1973) but more easily degradable more overtly
polysaccharide-like structures are present in water soluble fulvic acids obtained from climatic peats. The former are
likely to persist environmentally and augment marine humic materials. It is commonly also believed (e.g. Hoch et al.
2000) that lignin-derived phenolic groups could be suitable markers of land plant derived humic materials present in
the sea.
(Humic substances remain somewhat enigmatic as regards their constituent chemical structures despite numerous
attempts to achieve this knowledge, e.g., by measurement of cation exchange capacity (e.g. Pleysier et al 1986), by
mass spectroscopy (e.g. Nagar et al.1975), ir spectroscopy (e.g., Shurukhina et al. 1973) and nmr spectrosopy (e. g.,
Grant 1977; Wilson 1984). Defining properties of traditional humus fractions termed "humic acid and "fulvic acid"
(cf, e g, Schnitzer & Khan 1978 who favoured an aromatic-rich model for their core structures but the consequences
of a highly alkaline extraction protocol may have produced this type of artifact) seem to depend more on their
physical chemistry, including hydrophobicity, than any overt chemical structural differences; a further index of the
chemical structure of humus is now shown to be provided by measurement of their effects on seeded crystallization
rates.
Although marine biological activity involving photosynthesis and calcification is of major importance for consideration
of global carbon dioxide cycling (cf. Pentcost 1985), extracellular calcification inhibitors in natural water may also be
relevant (Berner et al. (1978); Morse (1983). Dissolved oceanic calcium ion and carbon dioxide are probably held in
supersaturation (greatest under tropical conditions) with respect to solid-phase calcium carbonate crystallization by
the influence of such natural humic inhibitors which deactify crystallization nuclei; the inhibitory effects of magnesium
and phosphate is apparently insufficient to account for current oceanic calcium carbonate supersaturation (Suess
1970, 1973; Berner et al. 1978; Kitano 1983, cf. Morse 1983).
Studies of the controlled seeded inhibition of crystallization of calcite and barium sulphate carried out by the author
some years ago for assessment of potential inhibitors for oil-well usage and biochemical calcification research,
revealed that soil humic polymers and their derivatives were amongst the most strongly inhibitory substances
available. A wider discussion of the results obtained in these studies now seems warranted owing to the
environmental implication of the retardation of calcium carbonate precipitation in the global system of seawater
bicarbonate/dissolved carbon dioxide which is the major holding reservoir for potential atmospheric carbon dioxide
balance. Inskeep & Bloom (1986) reported that fulvic acid, from an USA soil, efficiently inhibited calcite
crystallization, and similar inhibitory effects of various aquatic humic fractions were reported by Hoch et al. (2000).
Materials & Methods
Humic acid and fulvic acid were extracted by the traditional method (e.g. as described by Ogner (1973)) from a noncalcareous agricultural soil (Countesswells Aberdeenshire described by Glentworth & Muir 1963; pH 5.9 and 5.9%

C) and a fulvic acid type of material by Soxhlet extraction with water from climatic peat (Cairn O'Mount,
Aberdeenshire; pH 3.7 56%C).
Various commercial calcification inhibitors including phosphonates and lignin derivatives were obtained from
commercial sources.
Infrared spectra were obtained as described by Grant et al. (1987) and crystallization kinetic data obtained using
methods developed by Nancollas et al. as described by Grant al (1989).
Infrared spectra
Infrared spectra of soil extracts [(1-Countesswells agricultural soil; 2-climatic peat, 3-(1)sulphated and lignin
derivatives] were obtained on disposable aluminium foil mirrors by a specular reflection technique (Grant et al. 1987).
Table I
Infrared Spectra of Humic and Fulvic Acids Studied
Humic acid (1) Fulvic acid (1)
Fulvic acid (2) Fulvic acid (3)
532 w

716 w
764 w
882 m
964 s,b
1046 m
1107 s.b
1226 sh
1268 m
1386 s
1433 sh

533 w
558 w
6 24 w,b

521 m
551 m
616 m
42 s,b

760 w
874 w
1020 sh
1049 n
1110 s,b

533 w
627 w
760 w

807 m
892 m
1040 vs,b

1219 w,b

1152 s,sh
1276 w,sh

1414 s,b

1381 w,sh
1431 s

1707 sh
2544 w
2940 m
3369 vs

1602 vs
1640 sh
1716 sh
2110 w
2544 m,b
2846 m,
3264 sh
3376 vs

1629 sh
1659 s
1730 sh

743 m
783s

742 m
783 s

805 m
1007 sh
1051 m
1132 m,b
1237 s,b
1266 sh
1410 vs

1556 w
1602 vs

REAX 88B
REAX 100M
498 w
511 w
513 m
554 w
557 w
616 w
615 m
640 m
644 m,b

872 s,b
855 m
954 m
941 m
996 m
1034 sh
1061 sh
1052 vs
1176 sh
1160 sh
1250 vs
1241 vs
1358 sh
1431 m
1436 m
1456 m
1506 s
1503 m

1588 vs
1632 sh

1620 s

1737 sh

1746 sh

2908 s

2574 w
2959 w

3420 vs

3400 vs

1609 m
1686 sh

2626 sh
2932 m
2969 m
3229 vs
3256 vs
3529 vs

w: weak; m: medium; s: strong; b: broad; sh: shoulder; v: very

Results
Calcium carbonate (calcite) crystallization.
Accurate second order kinetic curves were obtained for seeded calcite crystallization of fulvic acid solutions after a
short initiation period. The second order rate constant declined to zero over the range 1 -100 ppm of added fulvic
acid.
Table II
Bicarbonate 10mM 25C
Fulvic acid ppm
secondary reaction ,
% uninhibited rate
0
100.0
2.7
21.0
5.5
3.5
70
(ca. 0.0)
100
0.0
The dependence of inhibitor concentration on crystallization rate obeyed the Freundlich (1922) isotherm (1)
l/n
log (go/g) = kc

(1)

(where go is the relative rate of crystallization in the absence of inhibitor and

g is the relative rate of crystallization in the presence of inhibitor) is characteristic of surface adsorption of inhibitors
on crystallization nuclei surfaces.

The value of n = 2 in the above isotherm described seeded calcite crystallization from 10-20 mM NaHCO3 solutions
for the fulvic acids (25C) as well as heparin, heparan sulfate and chondroitin 4 sulfate (studied at 25 and 37C). The
relative slopes linear Freundlich are listed in Table III.
Comparison of 70ppm marine algal anionic polysaccharides and heparin
No additive
100
Carrageenan kappa (a)
104
iota (b)
87
iota (c)
74
lambda (d)
47
_____________________________________________________________
Heparin (e)
31
MW
(a)
(b)
(c)
(d)
(e)

380000,
750000
610000
500000
20000

sulfate half ester/

disacch.
0.98
1.21
1.28
1.6
2.75

anhydrogalactose/
disacch.
0.82
0.84
0.60
0.13
0.00

Table III
Slopes of Freundlich Isotherm Plots.
______________________________________________________________
fulvic acids from various agricultural soils
10-20 (a)(b)
(sulphated humic acid)
ca. 10(b)
fulvic acid (Countesswells)
9.6(b)
fulvic acid (climatic peat)
tripolyphosphate (f)
ethane, hydroxyl, 1,1-diphosphonate

4.5 (d)
ca.4
ca. 20 (f)

Dequest-2041
(N,N,N,N ethylenediaminetetramethylenephosphonate)
ca. 22 (g)
______________________________________________________________
heparan sulfate
1.15 (e)
heparin
1.06 (e)
chondroitin 4 sulfate
0.35 (e)
______________________________________________________________
a) calculated from results reported by Inskeep & Bloom (1986)) ;
(b) calculated from present studies (25C);
(c) deriviativized by sulfation; (cf sulfuric acid extracts soluble humic matter from soils);
(e) reported by Grant et al. (1989); (also studied at 25C);
(f) Nancollas et al. 1981;
(g) Nancollas 1979.
The results of calcite dissolution experiments in the presence of inhibitors more briefly studied were similarly treated
by plotting Freundlich isotherms with similar conclusions (not discussed here).
The data listed in Table III reflect on a log(10) scale, the relative anti-crystallization effects of the substances studied;
numerically higher values indicate greater inhibitor effectiveness.
Humic acid was less easily studied since it dispersed as a colloid rather than being soluble, however it demonstrated
a high degree of anti-crystallization activity when in a sulfonated soluble form, and the Freundlich isotherm of this
material was apparently similar to that of native fulvic acid from the same soil.
The soil organic matter (polysaccharide-like) inhibitors were of similar degree of inhibitory activity (on a weight basis,
but considerably more effective on a molar basis) to commercial polyphosphate calcification inhibitors but were up to
some two orders of magnitude more effective than animal polysaccharides inhibitors such as heparin or heparan
sulfate and analogous algal coccolith sulfated polysaccharides for which the in vivo roles likely include an
inhibition/control of biological calcification (cf. Grant et al.1992).
A series of alginates of known microstructure were compared as to their anti-crystallization activities (for barium
sulfate) and a rational dependence upon polysaccharide microstructure evidenced (Grant et al., unpublished results
summarized in Table V)).
Table IV
Barium sulfate crystallization (method used - Nancollas 1979 (cf. Grant et al. 1989))
Inhibitor 20 ppm
Crystallization rate (from second order rate plot)
Control
100
REAX 88B (lignin deruived)
86.4

Climatic peat polysaccharide-rich humus extract

Ethane hydroxy 1,1 diphosphonic acid (Grant 1979)
Scaletreat 206
Baker ML 1559
Nalfloc NAL 1285
Fulvic acid (Countesswells)
sulfated
oligosaccharide
10
Donmarn actipol

13.3
4.2
1.8
1.2
0.9
0.4
0.1

heparin

30

sodium
tripolyphosphate

Aquarite

9.5

Table V
Alginate microstructure dependent BaSO4 crystallization
Alginate
Relative
Microstructure Disaccharide chain Second order rate const
length
control

(none present)

Attained
after initiation
period , min

100

random

25

59.6

poly G
blocks

80

36.4

ca 0

F387

24

18.8

4000

15.2

poly M blocks

22

14.6

poly
alternating
MG blocks

22

6.0

poly M acid

0.5

If seed crystals were pre-incubated with the inhibitor solutions a considerably greater apparent degree of inhibition
was achieved (our standard procedure used immediate crystallization rates on addition of seed crystals to start the
reactions (Grant et al. 1989)).
Discussion
The present studies were conducted with methodologies (due to Nancollas and co-workers (cf. Nancollas 1979))
believed to allow crystallization kinetic results to be optimally obtained with regard to reproducibility and significance.
It was established that the natural polyanionic fulvic acid derived from agricultural soil is a highly effective inhibitor of
calcification (in agreement with reports by Berner et al 1978, Morse 1983. Inskeep & Bloom 1986 and Hoch et al.
2000; the latter workers had found an even higher degree of calcite crystallization by some humic acids inhibition
than that indicated by our studies which may have been partly due to differences in experimental technique (lower
carbonate concentration and different mixing procedures used).
The present authors studies showed that a similar high degree of calcite crystallization inhibition was detected for
fulvic acid and a derivatized (sulfated) humate.
The effect of the studied substances on the dissolution of calcite crystals more briefly studied by similar
conductometric techniques also showed that the range of crystallization inhibitors studied also inhibited calcite
dissolution but with altered relative inhibitory efficiencies.
The natural, relatively well-defined polyanionic biopolymer, heparan sulfate is also an efficient inhibitor of calcification
when measured on a molar basis, in which a role (amongst others) it may protect blood, urinary and other tissue (cf.
Grant et al. 1992). It is noteworthy, however, that the anti-calcite crystallization efficiency of the soil-derived humic
polymers are considerably greater than that of heparin/heparan sulfates.
Inhibition of calcite crystallization likely occurs by blocking of crystal growth nuclei rather than by sequestration of the
calcium ions since conductivity changes attributable to sequestration by complexation could not be correlated with
inhibition of crystallization which process which, however, obeyed a Freundlich isotherm, characteristic of adsorption
at crystallization nuclei surfaces.
Soil-derived polymers also effectively inhibited barium sulphate crystallization but less well than heparin-type
polymers. Sulfation of the soil-derived polymers, however, improved their barium sulphate inhibitor effectiveness.
Although land-derived soil humus fractions are thought likely to contribute to oceanic carbon dioxide balance,
especially under conditions of humus depletion through intensive agricultural practices, knowledge of the relevant
quantities and oceanic distribution of such polymers as well as of other industrially-produced calcification inhibitors

(stable calcification inhibitor input analysis should include poorly biodegradable phosphonates) is currently uncertain
but should be assessed for gaining an acceptable scientific basis for international legal frameworks to limit global
warming (cf. Lasho & Ahuja 1990).
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ibid 37 2435-2447
Shurukhina SI Shurukhin V V Tarlakov Yu P (1973)
Study of humus extracts by infrared spectroscopy
Pochvovedeniye 146-149
Wilson MA (1984)
Soil organic matter maps by nuclear magnetic resonance
J Soil Sci 35 209-315
*Most recent affiliation: University of Aberdeen Department of Molecular & Cell Biology
Acknowledgements
Thanks are due to Drs FW Williamson, WF Long, Mrs M Ross and Mrs J Somers (University of Aberdeen) and DR
MV Cheshire (Macaulay Institute Aberdeen) who provided data and samples for this study.

--------------------------------------------------------------------------------------------

15- orig.12. Draft Drawings of Figures for Paper

The following Figures which were preliminary drawings of the Marishcal College (MC) fulvate study results are relevant
to the above document
Fig 15-1: (Ms from MC) Infrared spectra of substances studied as potential inhibitors of CaCO 3 (calcite) crystallization
See also web. scribdcom/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-III
Fig 15-. I preparation further relevant data

Captions to Fig. 15-1 Ir spectra (4000-400 cm-1) of the samples studied

(a) humic acid; (b) fulvic acid (preparation 1); (c) fulvic acid (preparation 2); (d) sulphated/sulphonated fulvic acid (preparation
1); (e) sulphated/sulphonated lignin REX 88B; (f) sulphated/sulphonated lignin REAX 100M

Fig. 15-2 (of Ms. from M.C.)

Fig. 15-2 captions. Effect of additives on crystallization of CaCO3

curves (a) (c) (d) fulvic acid (prepn. 1) 100, 5.5 and 2.8 g/ml
(b) sulphated /sulphonated humic acid 20g/ml
(e) fulvic acid (prepn. 2) 15g/ml
(f)(g) lignin derivs. REAX 88B, REAX 100M 20g/ml respectively
(h) no additive.

Fig.15- 3 (of Ms. from M.C.)

Effect of additives on crystallization of CaCO3
Second order rate plot of (m-mo)-1 (mi-mo)-1 vs. time, mins.
Effect of fulvic acid (prepn. 1)
Curves (a) (b) (c) (d) fulvic acid (prepn. 1) 0.00, 2.8, 5.5 and 100 g/ml respectively
m refers to the conductivity readings, mi and mo being the initial and final values

The effect of the above amount of inhibitor on the second order seeded rate of crystallization of CaCO 3 was respectively 100.0
21.0 3.5 and 0.0.
Fig.15- 4 (of Ms. from M.C.)

Fig. 15-4 captons. Freundlich (1926) Isotherm Plot

y-axis log10 [(Uninhibited second order rate constant )/(Inhibited second order rate constant)]
x-axis [Amount of added inhibitor g/ml] 0.5
Homogeneously nucleated crystallization of CaCO3 (calcite)
Comparison of fulvic acid with other inhibitors
a, water extract of soil (data from Inskeep & Bloom (1986b)
b, fulvic acid (prepn. 1)
c, fulvic acid (prepn. 2)
b*sulfated /sulfonated humic acid
d, heparan sulfate
e, heparin,
f, chondroitin 4-sulfate
(data for curves d-f were from Grant et al., 1988a).

Fig. 15-5 (of Ms. from M.C.)

Fig. 15-5 Captions. Freundlich (1926) Isotherm Plot, CaCO3 Dissolution

CaCO3 1.6 mg/60ml 2.5x10-5 mol dm-3 H2SO4 solution; sulfated humic acid, fulvic acid (prepn. 1); heparin; sulfated pectin.
15 orig.13 Acknowledgements
We thank Dr. M.V. Cheshire, Macaulay Institute, Aberdeen, for samples of humic and fulvic acids, Mrs Marion Ross for
preparation of sulfated humic acid, Mrs Jacqueline Somers for the data on the inhibition of calcite crystallization by
tripolyphosphate and pyrophosphate, the Cancer Research Campaign and the Scottish Home and Health Department for grants
supporting work in this laboratory.
The above text was re formatted from a manuscript dated 20 Feb 1988, with modifications suggested in hand written
inserts by (Prof) WF Long dated 21 Feb 1989 of a paper intended for submission to an academic journal
was one of a series of papers dealing with natural inhibitors of the crystallization of CaCO produced by
3
the Polysaccharide Research Group of the University of Aberdeen Department of Molecular and Cell Biology
(jointly headed by W.F. Long and F.BV. Williamson) in which a humic matter led anthropogenic
climate change hypothesis was briefly suggested. One of the intended series of (three plus) papers
(Grant, D. et al., Biochem J 1989, 259, 41-45) achieved being submitted prior to termination (for un-stated reasons) of
the Scottish Home and Health Department contract which had funded the work. The other manuscripts
were retained (with permission) by D. Grant (the principal author) for future publication.
This ms. reformatting was unfunded.

15-orig.14 The Pre-incubation Effect

P.s. (comment about the results reported above added later)
It should be noted that a pre-incubation of the soil humic material inhibitors with the CaCO 3(calcite) seed crystals produced a
much greater apparent inhibitor efficiency. The degree of inhibition reported in the above document corresponds to a standard
method of conducting the crystallization experiments without any pre-incubation of the seed crystals. While this procedure is of
value for attaining a highly reproducible relative effectiveness evaluation allowing the effectiveness of different chemical
inhibitors to be quantified it actually measures an absolute minimum inhibitor effectiveness related to that which occurs in
nature. I.e. while the ability of humic matter to inhibit the precipitation of CaCO3 in natural waters is likely to be much greater
than that indicated by this experimental procedure, but the relative effectiveness of humic matter compared with other kinds of
inhibitors is probably accurately recorded.
.

16

Orig.15
Conclusions

The above was not an attempt to suggest that how human influence the
climate can easily be ascertained. It is merely an attempt to discuss this
topic by starting off from what might be considered to be the most firmly
established relevant facts which seem to be available:
namely the remote sensed atmospheric CO2 concentrations and the
human population of the Earth. I have attempted to explain how soil
humus fulvate degradation may be responsible for the manner in which
humans influence the amount of CO2 in the atmosphere and so influence
the climate by allowing anthropogenic fulvate to perturb the carbonate
balance of the atmosphere, sea and land.
This contradicts the IPCC view that fossil fuel combustion is the
principal origin of anthropogenic CO2 and that this combustion needs to
be curbed in order to prevent unacceptable climate change. Because
the currently accepted IPCC recommendations for the alleviation of
global warming will cause considerable social cost it is of major public
interest to test the argument that anthropogenic CO2 might not

after all be a direct product of fossil fuel combustion product.

17

Further References

Orig. Back to original document transcription retaining original doc.

Ref. nos.
8-0-1-1
Xie J et al.
CO2 absorption by alkaline soils and its implication to the global carbon cycle
Environ Geol 2009 56 953-961
8-0-2
Boyce DG et al
Global phytoplankton decline over the past century
Nature 2010 466 591-596
A ca. 50% decline has occurred in phytoplankton since 1899 in 80% of the ocean; this was climate sensitive. This
decline may be associated with an increased sea surface temperature.

8-0-2-1
Inglesias-Rodriguez MD et al. Science 2008 320 336-340
[Increased CO2 in the Earths atmosphere is causing phytoplankton to produce greater amounts of CaCO 3]
Cf. Bernard O ref. 8-0-2-1 vide infra {The abnormal increase in calcification of marine coccolithophore Emiliana
huxleiyi phytoplankton reported by Inglesias-Rodriguez et al. seems a possible but unconventional mechanism by
which the increased atmospheric CO2 could have led to a reduction in photosynthetic phytoplankton activity over
the last century.
[Inglesias-Rodruguiez et al. however held that the calcification and photosynthesis balanced out and were neutral
as regards their influence on atmospheric CO2.
8-0-2-1-1
Ridgewell A Zeebe RE
Web.gmacweb.env.uea.ac.ek/e114114/publication/manuscribpt_ridgewell_and_zeebe.pdf
The Role of the Global Carbonate in the Regulation and Evolution of the Earth System
Draws attention to the role of the evolution of calcareous plankton which created a mid-Mesozoic revolution in the
nature and location of carbonate deposition and the creation of a responsive deep-sea sedimentary sink for CaCO 3
which buffers ocean chemistry and atmospheric CO2, but the current increase in the latter with a putative
associated pH decrease in sea surface (believed to be unprecedented in the geological records of the last 100My)
seems to be adversely affecting those organisms so as to make uncertain the future of the preceding carbon cycle
mechanism.
Also noted is the work of Morse JW et al. Geochem Cosmochem Acta 2003 67 (5) 2819-2828 who studied CaCO 3
whiting but of mainly invisible particles { slow precipitation (from a supersaturated state)) in the Great Bahama
Bank finding that this does not occur spontaneously but depends on the presence of re-suspended e.g. aragonite
seed particles which grow calcite.
{This colloidal CaCO3 system could be further suggested to be subject to direct anthropogenic fulvate control}
The saturation horizon in the open seas where falls below the solubility product of CaCO 3 must in principal also
be altered by the same global anthropogenic fulvate control process by which human population pressure alters the
carbon cycling mechanism of the sea.
Paradoxically the blocking off of CaCO3 crystallization sites on seed particles seems to increase the effective
solubility of CaCO3 in both the surface and deep water of the sea
8-0-2-1-2
Amorphous colloidal size CaCO3 particles
Cf. Bolze J Peng B Dingenouts N Panine P Narayanan T Ballauff M
Formation and growth of amorphous colloidal CaCO3 precursor particles as detected by time-resolved SAXS
Langmuir 2002 18 (22) 8364-8369
Spherical CaCO3 particles of colloidal dimensions up to 270nm, form when CaCl 2 2H2O and Na2CO3 solutions are
mixed in a stopped flow apparatus. The particles (which are remarkably uniform in size of mass density 1.62 g
cm-3) do not easily aggregate; they are a first step in the formation of calcite demanded by thermodynamics.
However the adsorption of fulvate on these colloidal particle surfaces is predicted to inhibit the attainment of the
thermodynamically more stable phases and promote the longevity of the colloidal CaCO 3 system.
Cf. also
Role of colloidal CaCO3 particles in calcareous soils
Cf. Baghemejad M Dalrymple JB
Colloidal suspensions of calcium carbonate in soils and their likely significance in the formation of calcic
horizons.
Geoderma 1993 58 (1-2) 17-41
Role of surfactants in regulation of amorphous CaCO3 particle assembly
Cf. Z Sadowski et al.
Physiochem Probl Miner Process 2010 44 205-214
Nancollas et al. Researches on CaCO3 and BaSO4 crystallization inhibition.
Cf web. chemistry.buffalo.edu/people/faculty/nancollas/nancollaspublications
Papers no 90,92,106,110,121-4, 126m 128, 136, 138, 146, 149, 155, 157, 160, 183 196 200 203-4, 207 213 217
241 206 286 and 336 seem to be relevant to a fuller understanding to the inhibition of CaCO 3 solid phase
formation in the context of the present climate change fulvate hypothesis
Bernard O et al.
Web.biogeoscince-discuss.net/6//C3701/2009/bgd-6-C3701-2009-supplement.pdf.
Cf. possible
servo-feedback control mechanism in E. huxleyi calcification.
Cf. Long WF
Web.abdn.ac.ul/~bch118/publications2003march.doc
Cf. section a refs 33, 34, 41, 59 and 60

Section b refs. 13, 33, 35 50 and 58 and section d ref. 1.

Similar studies include
Hirokana Y et al. Mar Biotechnol 75 634-644
Okazaki M et al. ibid. 1998 6 15-22
Possible kidney polysaccharide servo-feedback control of animal kidney stone formation:
cf. Borges FT et al. Kidney Int 2005 68 1630-1648
The organism attempts for prevent pathological formation of calcium oxalate and phosphate seed crystals by
creating specifically tailored anti-seed polysaccharides structures.
It seems possible that a similar mechanism may exist in marine algae.
And even in soils where the humic polyanions could analogously become damaged under an abusive un-natural
intensive agriculture system similar to how animal anionic polysaccharides when damaged by stress give rise to
pathological stone formation; i.e. soils and animals may suffer similar types of polyanion structure determined
illnesses.
The need to carefully balance aquatic habitat salinity in invertebrate tissues is also apparently achieved by the
same types of anionic polysaccharides as find use in kidney walls; these which are produced by a range of 15
invertebrate amphibious animal organisms (living in habitats of different salinity) in a precisely mathematically
determined salinity-related quantity
Cf. Nader HB et al. Comp Biochem Physiol 1993 76 433-436.
Perhaps these polysaccharides are evolved, specialized versions of fulvates possessing primary pro-biological
water activity regulation system functions.
In E. huxleyi polysaccharide production has been reported (Kayano KU Shirawiwa Y Plant Cell Physiol 2009 50
(8) 1522-1551) to switch from coccolith associated anionic polysaccharide types produced under inorganic
phosphate depletion conditions to neutral polysaccharides produced under inorganic phosphate nutrient sufficiency
condition.
This draws attention to the status of inorganic phosphate status in seas in regard to anthropogenic inputs which
could alter the abilities of phytoplankton to at as a as a storage sink for atmospheric CO 2.
The slow release of inorganic phosphate from humic matter or produced by the slow oxidation of anthropogenic
herbicide and/or laundry detergent phosphonate (which can act as a surrogate for phosphate as signalling
molecules). It seems that marine microbiota are adapting to use of anthropogenic P (phosphonate) pollutant as a
nutrient.
Perhaps possible climate warming will become less severe when this evolution is complete!
In soil and natural water any readily available inorganic phosphate and nitrate from human industrial pollution will
become rapidly utilized by the biota there present and fail to reach the open sea unless some mechanism such as
that suggested above is in operation.
8-0-2-1-2
The work of E.W. de Jong et al.
Cf. de Jong EW van der Wal P Borman AH Vrind JP et al.,
Calcification in coccolithophorids
Biomineralization and Biological Metal Accumulation
P Westbroek and E.W. de Jong (Eds) D. Reidel, Dordrecht 1983, cf. p 291-301.
CaCO3 bio-deposition in the sea depends to a large measure on the formation of coccoliths (scales on micro algal
coocolithophorids, e.g. E. huxleyi and Hymenomonae carterae) which are composed of CaCO 3 and which form
major geological strata (e.g. in the Cretaceous). The morphology of coccoliths is species specific with a large
variation in form amongst species. This complexity seems to be determined by the complexity of the CaCO 3
morphology.
8-0-2-1-3
Weich RG Lundberg P Vogel H Jensen P
Phosphorus-31 NMR studies of cell wall-associated calcium phosphates in Ulva lactuca
Plant Physiol 1989 90 230-236
While the Ca and Mg in seawater 10 and 55 mM respectively, the inorganic phosphate in seawater is generally
only 1-3 M;
Some species such as Porphyra tenera , however, can tolerate high phosphate levels, maximum growth of this
species occurs at 400M decreasing at concentrations above 1500 M.
Local seawater pH can vary in the range 7.5-8.4, higher values occurring nearer the surface.
High phosphate plus high calcium concentrations can give rise to precipitation of sparingly soluble metal
phosphates from seawater but this can be inhibited by Mg2+ as well as polyanions such as fulvate or anionic
polysaccharides.
Where this precipitation occurs on the organism the effect is pathological.
This is a possible mechanism of the decline in phytoplankton following anthropogenic heavy metal pollution of the
sea.
8-0-3

Beck EG
180 years of atmospheric CO2 gas analysis by chemical methods
Energy & Environment 2007 18 (2)
Cf. web friendsofscince.org/assets/files/documents/CO2%20as%20Analysis-Ernst-Georg%20Beck.pdf
[While the tone of this paper is hypercritical of the IPCC hypothesis, it highlights possibly discrepancies in
attempts to correlated 13C data with fossil fuel consumption and remote site atmospheric CO 2 levels. The CO2
values at ground level can be quite different from the average over the entire atmosphere.
Correlations between temperature change and CO2 levels. There is no way of a priori assuming that increase in
temperature arises from increase in atmospheric CO2 or vice versa.
8-1-0
Frank D et al. Nature 2010 463 527
A study of ice cores from 1050-1800 which suggest that a previous estimate of a 40 ppm CO 2 per degree C can be
excluded with 95% confidence
8-1
Endersbee L
Australian Academy of Technological Sciences & Engineering (ATSE)
ATSE Focus No 151 August 2008
Carbon dioxide in the ocean
Avail at web://icecap.as/images/uploads/Focus_0808_endersbee/pdf
This author did not consider it likely that human activities had influence the smoothed ocean temperature data
which were found to be directly correlated with the observed atmospheric CO 2 contents.
Cf. Grant D
Web.scribd.com/doc/23967639/Humic-Substances-Inhibit-Calcite-Crystallizn-II
Pearce F
Soil spoilt by farming and industry
New Scientist 1992 16 May (1821)
Major soil degradation may be caused by acid rain etc.
The article was a summary of a report by Hammond A (UN World Resource Institute) The loss of soil seems to of
a more serious concern than is loss of the rainforest.
(A map showed the wide global spread of the anthropogenic soil depletion. The regions of most less resembled old
14C atmospheric levels and sky light patterns at night except that for Africa, in a line south of the Sahara desert,
soil degradation occurred to a much larger level than
did night light pollution).
Feeding the World: Disappearing Land
World Resources Institute (Washington, DC)
Overview of publications cf.
Web.wri.org/publications/content/8426.
Anthropogenic degradation of topsoil causes it to be washed or blown away. In 1990 38% of the worlds
croplands were degraded and the degradation apparently has continued to increase thereafter.
While the transfer of terrestrial fulvate to the sea is a consequence of the degradation which is here discussed, the
specific fulvate scenario and its e.g. role in climate change, is not addressed.
Fossil fuel usage data
Web.cdiac.orne.gov/ftp/ndp036/global.1751_2007.ems
Atmospheric CO2 data
Keeling data
Web.cdia.ornl.gov/ftp/trends/co2/maunoal.co2
Ice core data
Web.cduac,orne.gov/trends.co2/lawdome_combinded_dat
Historical records from the Law Domeice cores 20 year smoothed record
Cf. Hansen, James, Storms Of My Grandchildren The Truth about the Coming Catastrophe and Our Last Change
to Save Humanity
Bloomsbury, London, Berlin and New York, 2009 {Cf. the web
site:web.columbia.edu/~jehl/2008/TargetCO2_20080407.pdf which gives the similar and related information (in
the document entitled Target Atmospheric CO2: Where Should Humanity Aim?
By Hansen J et al. (multiple author).

This book suggests that historically anthropogenic CO2 underwent a stepwise increment after 1866-70 and 1955;
since the fossil fuel carbon combustion CO2 on the other hand show steps at ca. 1920, 1845 and after 2000. These
trends suggest that the human population increase and an associated more intense growth of cities which affect
clouds etc. as well as soils and seas are the key to understanding how anthropogenic CO 2 has increased. The
fulvate hypothesis seems to allow a rational explanation of the observed data. The fossil fuel usage data fail to do
this except for a very inexact part-time only correlation which does not include all the data.
Fig. 15 in the Hansen monograph shows fossil fuel CO2 emissions data from Boden et al. (CDIAC) suggesting a
linear increase from 1950-2007 and CO2 also increased over this period as shown on p 116 (Fig. 14) of this book.
However, on p.119 it is apparent that non-linear irregularities occur in the year-to year fossil fuel usage rates and
the computed CO2 injection rates. Hansen notes that Emissions increased from less than 2 GtC in 1950 to more
than 8GtC per year in the last few years (to 2008) the growth rate of emissions as ca 4.5% /year from 1950-73
slowing to ca. 1.5 % /yr between 1973-2003 but between 2003 and 2009 it averaged about 3% per year as coal use
increased rapidly especially in China.
A close look at these data suggests that fossil fuel usage and atmospheric CO 2 levels do not vary in the dependent
manner predicted by the IPCC hypothesis.
It seems furthermore that the atmospheric CO2 levels increase much more slowly after major volcanic eruptions
than expected from a major land uptake mechanism compared to the ocean but the latter uptake process as the
dominant one could it seems explain this.
[Re-written 2014-07-05
A five year differentiated pattern of year-on year increase in atmospheric CO 2 compared with a similar treatment of
fossil fuel usage suggests that irregularities in changes in the average CO 2 content of the global in the atmosphere
is independent of fossil fuel usage.
That the fossil fuel-led increase in atmospheric CO2, the IPCC hypothesis is incorrect is also perhaps more simply
demonstrated by directly plotting the remote atmospheric CO2 vs. the human population of the earth and
comparing this curve with that of fossil fuel usage vs. the human population of the earth (vide supra, inserted text).
These curves seem to vary independently of each other except for selected time periods. In general the two curves
are independent of each other. The surge in fossil fuel usage since 2000 has not been tracked by a corresponding
increase in atmospheric CO2 as would be required if the IPCC hypothesis were correct. The amount of CO 2 in the
atmosphere has continued to vary directly according to the increase in human population of the earth but not
according to how much fossil fuel is consumed by that population. This points to food production as the most
likely process which causes a precise linkage between atmospheric CO 2 and human population number.
The most rational interpretation of currently available data seems to be that anthropogenic CO 2 (which is all of the
increase atmospheric CO2 over the last 10,000 years) arises from by a common over-history human food
production effect which perturbs the oceanic CO2 atmospheric homeostasis mechanism (i.e. that which is
putatively directly fulvate-afforded).
Human assisted fulvate transfer can explain why the observed increase in atmospheric CO 2 has been very
accurately correlated with the changes in the human population of the Earth. This correlation seems to have
existed from the start of large scale agriculture several thousand years ago. The extrapolated pre- human
agriculture CO2 baseline (obtained by plotting databases if the atmospheric CO 2 level against the human
populations of the earth) is the same as that deduced by Ruddiman (loc. cit., [the early farmer atmospheric/global
warming hypothesis]) from ice core data.
The human population throughout history including at the present time is therefore enabled to re-set the oceanic
fulvate control system which determines the level of atmospheric CO 2 via those human actions which create soil
humus layer disturbances.
There may be a host of other less well studied atmospheric components apart from CO 2 which are similarly
ultimately also anthropogenic-fulvate-determined.
Return to original text
This lack of fine-tuned fossil fuel usage change with variations in the CO 2 content of the atmosphere (at lest
over recent decades) supports the hypothesis that the variation of atmospheric CO 2 contents, which seems to be
attributable to anthropogenic influences, is largely determined by the anthropogenic alteration of the ocean via the
humic mater of the soil and atmosphere which produce increased CO 2 release into the atmosphere as the Earth
warms up, rather than (the IPCC hypothesis) by the effect of increasing CO 2 arising from the direct injection of
CO2 into the atmosphere from fossil fuel combustion. It might be argued, however, that the carbon isotope
evidence strongly supports the fossil fuel combustion hypothesis. However greater uncertainties remain then is
commonly assumed to be the case in the interpretation of the isotope data. The amount of 13C depleted CO2 which
evidently has arisen in the atmospheric CO2 account for somewhat less than half of the amount of CO2 which has
been calculated form known fossil fuel usage to have been injected into the atmosphere. This fraction seems to
have remained approximately constant over the entire period of anthropogenic augmentation of atmospheric CO 2
and apparently (there is some doubt about this however) may not even show the perhaps expected increase in the
numerical fraction over the last decades when the most apparent climate change global warming process has got
underway. It should be noted that the atmospheric CO2 engages in exchanges with various other pools and these
occur at different rates. The 13C-depeleted CO2 will undergo another cycle of depletion if it is recycled via C4
plants but not if it is recycled via bacteria. Indeed the atmospheric CO 2 also exists in sub-pools. Accurate
nineteenth and early twentieth century measurement of CO 2 in the atmosphere by wet methods (which generally

are not included in global warming hypothesis building models) show values much greater (evidently due to urban
heat island effects) than the remote area values which were obtained by modern instrumentation. The value of
ground level CO2 in atmospheres which may surround the trees studied later for 13C tree ring isotope determination
could also have been substantially different from the remote atmospheric CO 2 such as that shown in Fig 1.
[By comparing the differentiated curves. Of especial interest is an apparent marked reduction in rate of CO 2
input into the atmosphere following the Pinatubo volcanic eruption in 1991 (cf. also El Chichn in 1982) and
increased global temperature and associated atmospheric CO 2 associated with the 1997-8 El Nio].
8-2
Bond-Lamberty B Thomson A
Temperature-associated increased in the global soil respiration record
Nature 2010 264 579-582
[The authors obtained evidence from numerous previously reported data including world climate data, which after
accounting for mean annual climate leaf area nitrogen deposition and changes in CO 2 measurement techniques,
revealed a previously unknown temporal pattern in global soil respiration which indicted that the air temperature
anomaly (the deviation form the 1961-1990 mean) is significantly and positively correlated with soil respiration
rates i.e. that global warming may be affected by soil respiration. (Since this phenomenon is subject to possible
and indeed likely major anthropogenic interference, a corollary to this is that anthropogenic disturbance of the soil
humic control system which affects the microbiological population of the soil could be one of the major way by
which humans might cause global warming).
The soil respiration input into the atmosphere was estimated to be 9812 Pg/year and that this had increased at 0.1
Pg C/year between 1989 and 2008. It was not certain to the authors, however, whether this process was driven by
an increased rate of carbon uptake by the soil, or by the formation of CO 2 derived from the decomposition of
recalcitrant humic mater in the soil by microorganisms using this form of carbon as an energy source. J Fang in
Nature news drew attention to the implications of the Bond-Lamberty - Thomson work, noting that soil can greatly
outperform human fossil fuel burning as the source of anthropogenic CO 2 input into the atmosphere. A further
comment by A. Charuasia (an internet comment attached to the Fang article) suggested that the observed apparent
global increase in soil CO2 emissions has arisen from the diminished soil (microbial) bio-diversity caused, in turn
by the widespread use of agrochemicals. This, it is now suggested is a useful and probably highly informed
comment.
The possible largest anthropogenic activity which is currently affecting climate would seem if the above
hypotheses were correct, to be industrial agriculture.
This further suggests that following the further research which is need to substantiate these ideas) that the target of
international concern should shift from fossil fuel restriction to soil humus conservation.
What also seem certain at the present time, is that the science of global warming is very far from proven and
understood.
8-3
Bamerjee D Nesbit HW
XPS study of dissolved birnessite by humate with constraints on reaction mechanism
Geochim Cosmochim Acta 2001 65 (11) 1703-1714
[The reaction of Mn ions with humate carboxylate groups have important implications for the biogeochemical
cycling of carbon since they produce CO2 in soils and sediments by oxidizing carboxylic, hydrocarboxylic and
dicarboxylic acid groups which are abundant in natural organic substances (cf. Stumm 1992)]
{Other studies of the possible contribution to the degradation of soil organic matter to the augmentation of
atmospheric CO2 include studies by
Liski J et al. Proc Roy Swed Acad Sci 1998 28 (2) 171 who suggested that increased environment temperature
would increase the amount of soil organic matter in boreal forest soils; however, Krischbaum MUF et al. Soil Biol
Biochem 1995 27 (6) 755-760 confirmed a more common opposite effect found by others that soil organic matter
decreased greatly following global warming and thereby provided a positive feedback to the global carbon cycle;
warming however can also increase the rate of new soil organic matter production to partly offset this (cf.
Krichbausm MUF et al. Biogeochemistry 2000 48 (1) 21-51].
8-3-1
Banager S et al.
Photo-mineralization of terrigenous dissolved organic matter in Arctic coastal waster from 1979-2003: intra-annual
variability and implications for climate change
Global Biogeochemical Cycles 2006 20 GB4005
doi:10.1029/2006GB002708
Cf. Retamal L et al.
Comparison of the optical properties of dissolved organic matter in two river-influenced coastal regions of the
Canadian Arctic Estuarine Coastal & Shelf Science 2007 72 2251-267
[It is estimated that 25% of the soil carbon lies in Arctic catchment areas and that the ongoing climate change
(which are at the most severe in the polar regions) may mobilize these stores, transporting them into the sea. The

carbon derived from Arctic rivers seems to be a major pathway from terrigenous organic matter to deep ocean
DOM.
Of especial interest was the release of CO2 from the sea following the photo-degradation of UV sensitive porphyrin
structures in un-humified terrestrial soil organic matter.
Cf.
Anesio AM et al.
Effect of humic substance photo-degradation on bacterial growth and respiration in lake water
Apply Environ Microbiol 205 71 (10) 6267-6275
This study provides a model for the behaviour of the autochthonous humic matter from algae which dominates the
DOM of the ocean.
Land derived humic mater (n.b. the term allochthonous applied to humic matter denotes residual plant matter,
e.g. often rare aromatic lignin derived residues there present) which is thought to be distinguishable from the
marine humic matter but also contain a similar micro-organism derived (often autochthonus dominant)
components. While initial incubation of UV irradiated humic matter from a range of natural land sources caused
an inhibition of bacterial growth (e.g. via the formation of reactive oxygen containing free-radicals ) longer periods
of irradiation promoted bacterial growth via a range of mechanisms including by the release of inorganic nutrient
elements, The authors confirmed that the introduction of humic matter into natural waters can produce CO 2 both
directly and indirectly via the stimulation of bacterial activity.
8-3-1-1
Fischer H et al.
Ice core records of atmospheric CO2 around the last three glaciation terminations
Science 1999 283 (5408) 17172-1714
8-4
Druffel E Southon J Trumbore S
Accelerator mass spectrometry research for radiocarbon measurement in support of carbon cycle research
Internet file:
Web .ess.uci.edu/ams/aminpage/htm
(downloaded on march 006 m also on Sept 2 2010)
Suggested that while the CO2 in the atmosphere is known to exchange dynamically with the CO 2 dissolved in three
principal reservoirs (oceans, plants and terrestrial soils) it is important to realize that scientists do not yet fully
understand the fundamental processes which control the carbon cycle. It was further noted that radiocarbon ( 14C)
is the best and often the only method to quantify the rate of exchange of carbon among the reservoirs but
inadequacy of measurement of atmospheric 14C has hindered progress in understanding of the carbon cycle
The CO2 record derived form air bubbles trapped in the Antarctic Vostok Ice Core (Barbola et al. 2000 cited by
Druffel et al.) showed that the CO2 levels fluctuated between ca. 190 and 280 ppm, The value has risen rapidly
since about 1850 and most especially after 1958 (Keeling et al. 2000) brining the atmospheric CO2 levels to
values which are higher than those present at any time in the past 400,000 years (n.b. this increase continues in
tandem with increased human population of the earth). It was noted that while ca. 30% of the increase in the past
150 years was thought to be traceable to fossil fuel burning and forest clearing for agriculture, significant changes
of atmospheric CO2 were has also been achieved in the pre-industrial and pre-human past presumably related to
shifts in global climate and obviously nothing to do with human industrial activities.
Fig 2 of the Druffel et al. article estimates the amounts of carbon in the interacting compartment of the natural
carbon cycle which potentially are subject to small imbalances etc. the origins of which are not understood.
CO2 Cycle Related Compartments as Carbon (1 Pg = 1015g)
Atmospheric CO2 760 Pg
Fossil fuel CO2 residue remaining in atmosphere
3.2 Pg / yr (old values)
from a total 5.5 Pg/year of which 2.0 Pg/year was supposed taken up by the ocean

Ocean Atmosphere Exchange 90 Pg/year

Surface Ocean
1020 Pg
Deep Ocean 38,100 Pg
Land plants and soil
2200 Pg
A 2006 powerpoint lecture for the above group avail on the web gives further details of their 14C isotope CO 2
cycling researches.
8-5
Ruddiman WF
The early anthropogenic hypothesis: challenges and responses
Rev Geophys 2007 45 RGF4001
Doi:10.1029/2006RG000207

{The original Ruddiman (2003) hypothesis was that farmers augmented the atmospheric CO2 by the burning of
wood during late Holocene forest clearance
Ruddiman discussed 18O evidence of temperature.
CH4 (cf. 8-5-1 from wetlands also might have caused late Holocene greenhouse gas warming).
Cf. Ruddiman EF Raymo ME
Quat Sci Rev 2003 141-145
CO2 leads 18O by 5000 years at 100,000 years (eccentricity) but the two signals are nearly in phase at 41,000
years (obliquity) and 23,000 years (precession).
Decreased CO2 seems to have followed human disease epidemics when agricultural land was abandoned.
Later (2009) Elsig et al. vide infra, indicated that ice core isotope data
showed that only a quarter of the extra late Holocene CO 2 could have come from the combustion of land pants
most came form the sea.
This agrees the fulvate-led anthropogenic CO2 hypothesis.
8-5-2
Water Vapour as Greenhouse Gas
Internet discussion (web.geocraft.com/WVFossils/ice-ages.html) cites and Oct 200 US Dept of energy tabulation
of greenhouse gases which include data suggesting a possible dominant role of water vapour which tends to
diminish the importance of CO2 as a cause of global warming
Cf. also Schnieder S (US National Center for Atmospheric Research Boulder Colorada, 1970s doc which
intimated that global cooling and a renewed ice age was then considered to be a major threat to humans
8-5-2
Climate Change 2007: Working Group I: The Physical Science Basis
Web.ipcc.ch/publication-and-dat.ar4/wg1/en/tssts-2-2.html.
Radiative forcing and cloud albedo. The overall understanding of the discussed sciences was poor.
Of interest was a comparison of direct radiative forcing for individual aerosol particles containing
forcing estimated effect (W m-2)
Sulphate
-0.4
Fossil fuel organic carbon -0.05
Fossil fuel black carbon +0.2
Carbon ex biomass fuel +0.03
Nitrate
-0.1
Mineral dust
-0.1
The atmospheric warming effect of black carbon and perhaps carbonaceous particles form biomass burning is
contrasted to the cooling effects of the other aerosol particles listed. Sulphate is thought to have the greatest
cooling activity.
8-5-3-1Grant D web scribd.com/doc/38734723 (the possible role of nucleation of phase change as the dominant
rate controlling process in anthropogenically induced climate change
Cf. Clarke A Kaoystub V Science 2010 329 1488-1492 which suggested that the anthropogenically modified
seed particles which are thought to be responsible for climate changing cloud formation have now become widely
distributed globally.
The effect of large cities on the adjacent and wider climate could also depend on active aerosol formation.
Virtual super-conurbations which cover some 10% of the land area of the Earth could change the climate of the
remaining 90% of the land area.
Large cities create lots of small carbonaceous particulates.
Kaspani SD et al.
Increase in black carbon concentration since industrialization from a Mount Everest ice core
web/geoegoy.cwn.ef/facstaff/huerta/g501/pdf/Kaspani-InPreparation
Black carbon (but not dust) present in this ice core record showed a threshold increase between before and after
1975 showed industrial carbonaceous particulate deposition at high altitude
Plass GN Carbon Dioxide and Climate Scientific American 1959 July p.41-47

Cf. Berner RA (1995) A.G. Hgbom and the development of the concept
of the geochemical carbon cycle Amer J Sci 295 491-95
Cf. also
The Discovery of Global Warming February 2014
www.aip.org/history/climate This 2500 list of reference covers papers to
2001, noting that the IPCC reports have by far the most complete
bibliography
8-6
Other scientific web sites (random access)
Cf. Archer D et al. Rev Geophys 2000 38 1590180
Problems discussed the circulation of the sea, iron fertilization and sediment geochemistry
The effect of humic matter on the burial rates of CaCO 3 and the effect of anaerobic chemistry upon this was
suggested (cf. Neuweler et al. vide infra) to be a possible control mechanism of other sediment including silicate
formation
The evolution of the diatoms some 250 million years BP reduced that marine Si(OH) 4 content. Soluble inorganic
Si may have been more abundant prior to this and may conceivably have assisted the early evolution of animals.
8-7 Isotopoic composition of CO2 is believed to allow the relative importance of oceanic and terrestrial exchange
mechanism for removal of CO2 from the atmosphere to be evaluated.

8-7-1
Mario BD McElroy MB
Isotopic composition of atmospheric CO2 inferred from carbon in C4 plant cellulose
Nature 1991 349 127
[The C in C4 plants preserves and isotopic record of the CO2 used in photosynthesis
Attempts to obtain 13C data from C3 plants (e.g. from tree rings) has shown up large
variation and associated uncertainties attributable to variable physiological
performance effects.
Zea mays, a C4 plant, seems to offer a superior, less variable recording system
than does tree ring or animal remains. Bacterial input into atmospheric CO2 is
believed to have a neutral effect on a13C. Transfer of CO2 from the ocean to the
atmosphere is also thought to have a relatively small effect on a13C.
An increase of 0.0027 per 109 t (Gt) occurs for transfer of this amount of C to the
atmosphere from the terrestrial biosphere.
The combustion of fossil fuel or plant matter in the other hand causes a much greater
effect, namely a decrease in 13C of ca. 0.026 . This putatively allows a13C
measurements of CO2 either directly or indirectly to indicate the contribution made by
fossil fuel to the observed increase in atmospheric CO2 contents.
It should be noted that the value of a13C declined by ca. 0.55 between 1956and
1978 (from -6.69 to -7.24 during this time when CO2 rose from 314ppm to
334ppm {by 1989 this had become 350ppm} and produced a a13C value slightly less
than -7.8 ).
It was noted in the above article that if all CO2 derived from the combustion of fossil
fuel had remained in the atmosphere, then the a13C value would have been expected
to have changed by ca. -0.025 / ppm increase in CO2; the actually observed value
of a13C measured with respect to the CO2 concentration (Siple data) was however,
suggested to be ca. -0.011 / ppm CO2 for data before 1956 i.e. only 44% of the
expected CO2 appeared in the atmosphere.

It might be of interest to attempt to subdivide the earlier form the later data as (vide
infra) these could be a tendency for a natural carbon sink to have been inhibited by
human activities which have been accelerating from ca. the year 1800- present.
This could also have been expected to have shown up differences, e.g., between data
from pre-1940 and post-1940.
Could pre-human natural carbon sinks have been much more efficient than the posthuman carbon sinks? The global temperature seems to have had a minor maximum
about 1940 (cf. Hanson loc. cit).
Could an enhanced tendency for human activities to enhance the poison outputs of
natural carbon sink systems in wartime explain the 1940 blip in the (presumed
anthropogenic) alteration of climate?
The 13C value apparently had increased to - 0/028 /ppm CO2 between the years
1956-86; this was attributed to a much increased use of fossil fuel after 1956.
Perhaps a more likely explanation of this altered relationship between 13C and
atmospheric CO2 is that the principal CO2 buffer, the sea, conceivably has suffered
some major (anthropogenic) perturbation in the most recent decades which has made
the sea somewhat less able to fulfil its natural CO2 buffering capacity.
Elsig et al. loc cit. found that (from ice core analysis) a (likely pre-human) increase in
13C of ca. 0.25 occurred during the early Holocene followed by a decrease in 13C
of ca. 0.05 in the later Holocene (the period which Ruddiman had suggested to
have experienced a 40ppm anthropogenic CO2 addition from a pre-human
atmospheric CO2 baseline of 260 ppm [the same value which is obtained from a linear
fit of the dependence of AD1959-2010 remote sensed atmospheric CO2 values]); the
small change in 13C ( a decrease of ca. 0.05 ) in the late Holocene increase in
atmospheric CO2 is therefore markedly different from modern anthropogenic CO2
alteration in the 13C of atmospheric CO2 (which obviously has a fossil fuel CO2
signature but this has most likely been taken up by the sea surface and land biomass
and recycled repeatedly, especially if the average residence time of the CO2 in the
atmosphere is 5 years and not the much longer residence time assumed by the IPCC
hypothesis) so the idea that the fossil fuel signature stays around for centuries seems
correct but this is not because the fossil fuel generated CO2 remains for a long time in
the atmosphere. The phenomenon of how the average value of 13C of atmospheric
CO2 arises is evidently more complex (cf. also Roy Spencer , loc. cit.) than the IPCC
hypothesis which considers that the 13C signature of atmospheric CO2 directly
equates a (novel chemical substance?) a persistent form of anthropogenic CO2 in the
atmosphere, a hypothesis which seems to be unlikely both from a consideration of
basic physics and chemistry but also from a simple direct comparison of how the
human population of the Earth has caused a linearly related overall CO2 presence in
the atmosphere (an exact linear variation) which is quite different from how the
historical fossil fuel use has demonstrated a non-linear and erratic variation as a
function of the Earths human population.
8-7-2
Altered inorganic ions, humic matter, oceanic pH, redox status as well as
environmentally stable phosphonate herbicides and phosphonate laundry detergent
might be amongst the drivers of oceanic disturbance which creates augmented
atmospheric CO2 via the perturbation of the natural marine CO2 buffering capacity.

(Differences in observed a13C values after 1956 could have been caused by a disturbance of the rate of natural
carbon cycling, especially the carbon sink systems due to anthropogenic influences, e.g. by a reduction of the
efficiency of the pre-anthropogenic oceanic carbon homeostasis system after 1956, e.g. via an augmentation post1956 of human inputs into the sea which blocked the CaCO3 precipitation oceanic sink mechanism either by
reduction in the amounts of the natural catalysts present in the ocean which can promote this process and/or by an
augmentation of the amounts of the negative catalysts (inhibitors) of this process; such alteration could include
inputs from altered biological ecology including species. Altered amounts of inorganic ion, humic matter, altered
oceanic pH and redox status; perhaps the effect could be due to the increased presence in the ocean, after 1956 of
specific chemical substances which can (as suggested by in vitro experimentation) act as ultra-efficient anticalcification agents (e.g. substances added to the ocean directly or indirectly from human activities); the most
likely of these is suggested to be the degraded soil organic mater polyanions produced form the degradation of
terrestrial humic polymers. Perhaps containing adsorbed environmentally-stable phosphorus-containing (especially
phosphonates containing P-C bonds now used in large tonnage amounts as herbicide agrochemials and laundry
detergents)).

8-7-3
Joos F et al, Global Biogeochem Cycles 2004 18 GB2002
Calcite compensation was included in a range of mechanisms which were thought
might have caused the later Holocene CO2 surge.
The possible mechanism was noted to included the marine carbonate compensation
process which is believed to occur in stages
1) terrestrial C uptake causes the [CO32-] in the ocean to increase
2) but the oceanic content of
3) Dissolved inorganic C (DIC) [CO2] + [HCO3-] + [CO32-]
and
ocean alkalinity [HCO3-] + 2[CO32-] remains unchanged
4) the perturbation in CO32- (and DIC) is transported to the deep sea leading to a
deeper saturation horizon of CaCO3 and to enhanced calcite sedimentation.
5) Pore system exchange on the ocean floor is slow, requiring e.g. 5000 years but
allows the floor to feedback to increase atmospheric CO2.
8-7-4
Cf. Elsig J Schmitt J Leuenberger D Schneider R Eyer M Leuneberger M Joos F
Fischer H Stocker TF
Stable isotope constraints on Holocene carbon cycle changes
from an Antarctic ice core
Nature 2009 46 507-510
The authors reported their recently obtained highly resolved ice core bubble 13C
record of atmospheric CO2 over the last 11,000 years.
This new study now indicated that the early Holocene increase in 13C of about 0.25
was most probably caused by a combination of C uptake of about 290 Gt (Pg) C yr
by land biosphere and C release from the ocean in response to carbonate
compensation [re-dissolution of preformed CaCO3 due to higher pressure in deep
ocean as outlined above] of the terrestrial uptake during the termination of the last
ice age {i.e. by operation of the long-term deep oceanic carbonate-based global CO2
homeostasis buffer system}; i.e. the 20 (-30?) ppm increase in atmospheric CO2 and
the small decrease in 13C of about 0.05 during the later Holocene, it was now
suggested by these authors, might be explained by the contribution form carbonate
compensation of earlier land-atmosphere uptake and coral reef formation with only a
minor contribution form a small decrease of land-biosphere carbon inventory. If the
late Holocene augmentation of CO2 had been due to (a human intervention by) the
large scale combustion of wood as had been suggested by Ruddiman, then the

reduction in 13C would have had a value an order of magnitude greater than that
found.
The attempts by these authors, using the currently believed models of global CO2
carbon cycling to account for the observed 13C values however failed; it should be
noted that they could not fully account for the historical ice core record.
A new model is evidently required. Perhaps the inclusion of the currently proposed
humic matter blocking effect on oceanic carbonate cycling and the associated surface
water HCO3- concentration increase, could be relevant.
8-7-5
The possible role of coral reefs including elevation of atmospheric CO 2 (suggested by WH Berger, Naturwiss, 1982
69 87-88) was noted in the above Elsig et al. discussion. The original coral reef hypothesis referred to a general
equation for one way calcification,
Ca2+ + 2HCO3- CaCO3 + CO2 + H2O in which the formation of CaCO3 leads to the generation of CO2. While
this seems not to have meant to refer to real coral reefs but rather to a kinetic process, later examination of real
coral reefs suggests that some of them can actually be producers of small net amounts of CO 2 (which is partly
remove by the photosynthesis which also occurs in coral reefs). This small amount of CO 2 is insignificant for
consideration of atmospheric CO2 input
Coral form CaCO3 like the skeletal calcification in animals is subject to control exerted by anionic
polysaccharides (cf. 8-7-6-0 and 8-7-6).
8-7-6-0
Dickson JAD
Fossil echinoderms as monitor of the Mg/Ca ratio of phanerozoic oceans
Science 2002 298 1222-1223
[The conventional concept is that the Mg/Ca ratio of sea water has stayed constant at 5.2 for e.g. 500 million years
was challenged by this study. It was now indicated that this value (study of echinoderms from the Cambrian and
from the Carboniferous to the Triassic indicated that the seawater Mg /Ca ratio was ca. 3.3 and from the Jurassic
the ratio was ca 1.4].

Apologies for poor document production standard

N.b. this document assembly is unfunded.

18

Seeing the Wood for the Trees. Or The Emperor Has No

Clothes

In 2014 a brief list of references on CO2 induced global

warming listed 2500 references they deal with the same
subject and seem more or less supporting the idea that CO2
is a problem for humans. This is a far shorter list of
supporting evidence in the scientific papers available to the
IPCC (believed to be around 30,000 papers or is it 80,000

papers) all of which have been vetted to the highest

scientific standard and again saying that fossil fuel usage is
the principal cause of major anthropogenic environmental
damage and that its use needs to be stopped in order to
ensure the survival of human civilization.
How could this so carefully considered evidence be so
wrongly assessed?
To be fair to IPCC the rate of fossil-fuel derived CO2 injected
into the atmosphere is of the correct order of magnitude
(but only if this CO2 remains in the atmosphere for longer
than seems likely);
while the 14C bomb labelled CO2 seems to have much too a
short life in the atmosphere but there is a possible injection
of recycled old CaCO3 marine input; a simple minded
analysis of delta13C seems also to support the fossil fuel
anthropogenic CO2 hypothesis.
My personal research database contains not widely
publicised information about how humic matter, a major
player in the C cycle, reacts very strongly with CaCO3
another major player in the C cycle. Using this phenomenon
as a starting point, an entirely new hypothesis is suggested
which can explain how anthropogenic CO2 can seem to be
injected into the atmosphere in a manner which is directly
proportional the human population pressure.
A little further digging suggests that any human group
activity seeking agreement can achieve this more easily by
scorning and vigorously suppressing any dissent. Science is
a hierarchical community similar to other human groups like
priests; scientist are not by nature liberals; they are a
group of like-mined individuals who have personal
prosperities which have been achieved because of personal
achievement in writing scientific papers in a peer-reviewed
system The more powerful scientists within this system
may sometimes think that it is justified to suppress any
information which might be damaging to their mutual
system reputations. Cf. the 2009 Heaven+Earth
monograph by a prominent critic of IPCC hypothesis (Prof IR
Plimer) draws attention to how big science can go down this
path (probably accidentally at first). Plimer, a geologist is
aware of how the Earths climate has varied widely in the
past e.g. with cycles of glaciations/deglaciations none of
which had any human input making it easy for him to
believe that climate cannot be altered in any significant way
by human agency at the present time.
The whole issue concerns how human opinion makers deal
with the basic belief systems in science aka religion. By
sacred scripts. People who more or less do not agree with
religious fundamentalism support its scientific equivalent.

The near-linear correlation between anthropogenic CO2 and

human population numbers however means that for the last
few thousand years, a very short time to geologists, all
extra CO2 over the 250ppm baseline seems to have been
very accurately of demonstrable anthropogenic origin. The
accuracy makes it hardly likely to be fortuitous (cf. Newell &
Marcus 1987 vide supra). This is not the CO2 which has been
formed by the combustion of fossil fuel. The mechanism now
put forward is thought to offer the most likely source of this
CO2. There may, in future years, come to be a need to
suppress or to augment this anthropogenic CO2.
Searching for comments on the internet on a book by I Plimer which is highly critical of the
IPCC hypotheses, shows up a large number of supporters of this type of criticism. Cf. e.g.
John Happs Open Letter to Australias chief scientist discussed lists numerous Appeals
and Petitions including one with allegedly 4000 signatures including 62 Nobel laureates,
The Oregon Petition with 31,00 accredited scientists etc. etc. Some of this information
actually supports the IPCC hypothesis.
The following text was downloaded from the internet in 3-26-14. Cf.
Critical Thinking At the Free University Are rising man-made CO2 emissions causing global
warming?
It is generally agreed that hitherto the rise in temperatures preceded the rise in CO2 levels
by an average of 800 years.
Inevitably the relationships are complex and this referenced article gives much more
detailed account of the evidence.
CO2:Ice Cores v. Plant Stomata by David Middleton
However, the IPCC and the pro-global warming lobby insist that it is now CO2 which is
driving the rise in temperature with no hard evidence to support this illogical premise.
95% of greenhouse gas is water vapour.
Studies acknowledge that rises in CO2 concentration have a warming influence effect but
that is logarithmic, i.e. the first 20 parts per million have the most effect but thereafter the
influence wanes to negligible by the time of the current 393 part per million are
reached.CO2 concentrations have been much higher in the past.
..below 150 ppm nothing would grow and wed all die. Dutch growers buy CO2 to increase
the concentration in their greenhouses to increase crop yields. So it seems perverse to
describe a basic building block of like on earth as a pollutant.

When humans became the dominant species on Earth the chemical

composition of the atmosphere became closely linked to human food
production dependent soil humus degradation. This idea can be
deduced from the data (of remote-sensed) CO2, human
population and fossil fuel usage by that population)
have been collected since 1959 which continues to
follow the trend of the less accurate earlier data,
suggest that the amount of CO2 in the atmosphere
must be mostly dependent on soil chemistry and biochemistry and
perhaps not at all (at least directly) upon fossil fuel usage.
There may be a general problem with the size of the scientific output that individual
sections of science which logically to smoothly progress in a rational manner needs to take
on board the finding across the board now no longer does this simply because it cannot
cope with the mass of available data so it inadvertently abandons the scientific method,
putting in its place a sort of fast track from hypothesis to theory system. This seems to
have occurred throughout all of official science to a varying extent.
If this is true the type of enlightenment science which started with Copernicus and Galileo
is now at an end. Amateur science such as that offered in the present paper may emerge
as the only proper science.

The rise in atmospheric CO2 which has been identified as an increase which is likely to be
less than severely damaging and may beneficial to currently sparsely human populated regions

such as in Canada.

19

Selected refs. to provide a quick intro.

See also
Effect of additives on crystallization of CaCO3
(Second order rate plot of (m-mo)-1 - (m1-mo)-1 vs. time, min.)
[ Figure in MC Aberdeen draft paper included in inserted document vide supra ]

20

For a review stating the traditional viewpoint on the above topic see e.g.
web .radix.net/~bobg/faqs/seq/CO2rise.html
which asks

Whys does atmospheric CO2 rise?

The vexing thing is that, in the global carbon cycle, the rising level of atmospheric
CO2 and the human origin of this rise are about the only two things that are known
with high certainty. Natural CO2 fluxes into and out of the atmosphere exceed the
human contribution by more than an order of magnitude. The sizes of the natural
carbon fluxes are only approximately known, because they are much harder to
measure than atmospheric CO2 and than the features pointing to a human origin of the
CO2 rise.
From its pre-industrial level of about 280ppmv around the year 1800, atmospheric
carbon dioxide rose to 315 ppmv in 1958 and to about 358ppmv in 1994 [Battle] [C
Keeling] [Schimel 96 , p43-440].
All the signs are that the CO2 rise is man-made.
*Ice cores show that during the past 1000 years until about the year 1800,
atmospheric CO2 was fairly stable at levels between 270 and 290 ppmv.
The 1994 value of 358 ppmv is higher than any CO2 level observed over the past
220,000 years.
In the Vostok and Byrd ice cores, CO2 does not exceed 300 ppmv.
A more detailed record from peat suggests a temporary peak of ~315 ppmv about
4,700 years ago, but this needs further confirmation.
*The rise of atmospheric CO2 closely parallels the emissions history form fossil fuels
and land use changes [Schimel 94, p 46-47].
*The rise of airborne CO2 falls short of the human-made CO2 emissions. Taken
together, the ocean and the terrestrial vegetation and soils must currently be net sink
of CO2 rather than a source [Melillo, p 452 [Schimel 84, p47, 55] [Schimel 95,p 79 ]
[Siegenthaler].
*Most new CO2 comes from the Northern Hemisphere. Measurements in
Antarctica show that Southern Hemisphere CO2 level lags behind by 1 to 2 years,
which reflects the interhemispheric mixing time. The ppmv-amount of the lag at a
given time has increased according to increased anthropogenic CO2 emissions,
[Schima 94, p43].
* Fossil fuels contain practically no carbon 14 and less carbon 13 than air. CO2
coming from fossil fuels should show up in the trends of 13C and 14C. Indeed, the
observed isotope trends fit CO2 emission from fossil fuels. The trends and not
compatible with a dominant CO2 source in the terrestrial biosphere or in the ocean
* The unstable carbon isotope 14C or radiocarbon makes up for roughly 1 in 10**12
carbon a toms in earths atmosphere. 14C has a half-life of about 5700 years. The
stock is replenished in the upper atmosphere by a nuclear reaction involving cosmic
rays and 14N. [Butcher, p 240-241]. Fossil fuels contain no 14C, as it decayed long
ago. Burning fossil fuels should lower the atmospheric 14C fraction (the Suess
effect). Indeed atmospheric14C measured on tree rings dropped by 2 to 2.5% from
about 1850 to 1954, when nuclear bomb test started to inject 14C into the atmosphere
[Butcher, p 256-257] [Schimel, 95. p 82]/ This 14C decline cannot be explained by a
CO2 source in the terrestrial vegetation or soils.
*The stable isotope 13C amounts to a bit over 1% of earths carbon, almost 99% is
ordinary 12C [Butcher, p 240]. Fossil fuels contain less 13C than air, because plants,
which once produced the precursors of the fossilized organic carbon compounds,
prefer 12C over 13C in photosynthesis (rather then prefer CO2 which contains a 12C
atom+ [Butcher .p 86. Indeed, the 13C fraction of the atmosphere and ocean surface
waters declined over the past decades [Butcher. P257] [C Keeling] [Quay] [Schimel
94, p42]. This fits a fossil fuel CO2 source and argues against a dominant oceanic

CO2 source. Oceanic carbon has a trifle more 13C than atmospheric carbon, but 13CO2
is heavier and less volatile than 12CO2, this CO2 source cause a simultaneous drop of
13
C in both the atmosphere and ocean?
Overall , a natural disturbance causing the recent CO2 rise is extremely unlikely.
Battle Nature 382 (1996) 231-235
Butcher Global Biogeochemical Cycles San Diego CA Academic Press
Keeling C. Nature 375 (1996)
Melillo Terrestrial biotic responses to environmental change and feedbacks to climate p. 445481 [in IPCC 95]

Quay Science 256 (1992) 71-79

Siegenthaler Nature 365 (1993) 119-125
Schimel CO2 and the carbon cycle [IPCC 94 and 95]
BUT perhaps the above ideas are wrong
AND

21
Inserted text Dec 2014-12-08 The majority of the worlds

population who are continuing to use fossil fuel in ever

greater amounts evidently seem happy enough with this
and might be thought to ignore the Kyoto Protocol and the
IPCC warnings about how fossil fuel is causing an
unprecedented increase in atmospheric CO2. Polite society
seems at least in public to support the IPCC in the same way
that football supporters support their own team and seek to
defeat all rival teams.
John Happs (an Australian geoscientist) internet document ex
www/undeceivingourselves.org IPCCs abuse of science downloaded 12-16-14
[Some of entries in this letter seem to be contradictory]
One such petition the Oregon Petition is associated with an academic scientific
appraisal of the

Environmental Effects of Increased Atmospheric Carbon Dioxide

Arthur B Robinson, Noah E. Robinson and Willie Soon
J Amer. Physicians and Surgeons 2007 12 79-90
[Cf the critical internet essay web.uwgb4/dutchs/PSEUDOSC/Gobwarm)!HTM ]
These authors present useful graphical evidence in support of the hypothesis that
fossil fuel usage is not harmful and does not cause any serious environmental damage.
They suggest the climate change is largely outside of human control being e.g.
affected by changes in solar energy output. The change in climate is however mild.
They compare of the academic studies of the historical increase in sea level and the
historical shrinking of glaciers and fossil fuel usage, finding no correlation with fossil
fuel usage. They assume that fossil fuel usage correlates with anthropogenic CO2, but
if the fulvate hypothesis is correct and fossil fuel usage generated CO2 is insignificant
the true anthropogenic CO2 may actually correlate with glacier shrinkage and sea
level increase i.e. that human actions may be at least in part actually directly causing
the global climate change and probably warming which causes glaciers to shrink and
the sea to rise.
A major part of this heating effect, however may, however be produced by adjacent
super-urban heat island anthropogenic warming which is eventually mainly produced
by fossil fuel usage. Robinson et al. give a useful graphical representation of this for
counties in California.

Is the Principal Mechanism of Human Influence over Climate, not Fossil

Fuel Use Per Se but Agricultural Food Production Induced Humus
Degradation Leading to Pollution of the Sea?
D. Grant, Ph.D., Turriff, Scotland, Dec., 2014
There is a very precise direct linearly anthropogenic atmospheric CO2 relationship
which allows us to predict that the CO2 in the atmosphere (which has a possible but
not a direct effect on global warming) will continue to increase according to a
precise historically-valid linear dependence on the increasing number of humans
who currently live on the Earth. We are the dominant species and eventually have
control over all others. But this is not a new phenomenon.
Studies of critical agricultural environmental interactions now suggests that these
greatly outperform fossil fuel combustion as the source of anthropogenic
atmospheric CO2 and therefore should become a focus for an international study
of associated possible climate changes arising from rapidly increased atmospheric
CO2.

22

Atmospheric CO2 has apparently (cf. the following plot of official human
population, atmospheric CO2 and fossil fuel usage rates) always, over

millennia, increased in directly proportion to the number of socialized

humans on the planet but fossil fuel cannot be correlated in this way. Fossil fuel

CO2 is inconsequential to global atmospheric CO2

This contradicts the current IPCC hypothesis which should now be re-evaluated.
Ten billion humans are predicted by the historical human population atmospheric
CO2 correlation to generate 442 ppm atmospheric CO2 . Cf. PLOT 3 shown at the
very start of this doc collection].

-- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- --- -- -- -- -- -The above simple plot (shown in PLOT 3) shows that a

comparison of the historical variation of atmospheric CO2
and human population data, clearly suggested that a single
mechanism of human influence currently may exist (and has
previously existed ) over the carbon cycle. All CO2 in the
atmosphere above the glacial period of low atmospheric CO2 [minimum], the prehuman baseline (which is apparently ca 260 ppm (cf. the 258.97ppm value which is
defined by the least squares fit of the 1959-2010 data shown in the bottom part of
PLOT 3) is entirely anthropogenic. This anthropogenic CO2 has, it seems, has
arisen by a single mechanism throughout all of recorded human history, and even
earlier. This mechanism cannot be the burning of fossil or other carbon-based fuel
because if such were the origin of the observed anthropogenic CO2, then it would
also require major revision of centuries of scientific research which explains how
CO2 can rapidly removed from the atmosphere including by photosynthesis. It is
immediately obvious from a comparison of the human pressure (i.e. population)
induction of atmospheric CO2 and the recorded usage of fossil fuel by that
population that these two outcomes of human pressure are independent of each
other. I.e. fossil fuel oxidation per se cannot have directly caused the observed
amount of anthropogenic CO2 to be formed.
(except if small sections of the overall curves shown in the top part of PLOT 3 were
to be compared in isolation).
Consideration of the entire database as depicted in PLOT 3 suggests that the entire
fossil fuel usage curve has no direct impact on the entire anthropogenic CO2 curve.
The data for the most recent decades show that when the large surge of fossil fuel
CO2 production from India and China has shown none of the required
corresponding deflection in the anthropogenic CO2 curve which seems to be
demanded by the IPCC hypothesis. The IPCC hypothesis is therefore wrong.
Perhaps, however, if a more refined analysis of these data were possible some effect
of fossil fuel generated CO2 upon the total anthropogenic CO2 might come to light.
Surely fossil fuel must generates at least a few percent of the total anthropogenic
CO2.
We must now, however, reconsider how (perhaps by one single non-fossil fuel
mechanism) the size of the Earths human population, has become exactly
correlated to anthropogenic CO2 in the atmosphere. How, especially since the start
of the industrial revolution, has a single, but essentially a non-fossil fuel
mechanism, caused such a dramatic increase in the amount of anthropogenic CO2
in the atmosphere?
We might note that the human population, has, over this period, as well as before,
always has to a major extent depended on the use of terrestrial soil humus for its
food supply. While the humus layer in the soil (which is also one of the major

carbon sinks for atmospheric CO2) plays a major effect in enabling human
existence, it is also known that the intensive production of food causes a significant
degradation of the humus layer. Polyanionic humic molecular aggregates become
transformed into lower molecular weight, more water-soluble fulvic acids in
amounts which putatively is directly dependent upon the intensity of the
agricultural activity. Higher human population densities tend to create more
humus degradation which in turn creates more anthropogenic CO2 in the
atmosphere.
Humus which is the basis of soil fertility has been continuously degraded by
agriculture throughout human history. While good farmers have attempted to
regenerate the humus layer, bad farmers have not done so; overall it seems there
has been a constant ratio of good/bad farming which has tended to cause a
common mechanism of anthropogenic anthropogenic CO2 increase.
It this idea is correct then the solution to possible runaway climate warming is
clear. Conserve soil humus.
Excess Fertilizer Induced Soil Humus Degradation May Control Anthropogenic
CO2 Formation both Directly (via Oxidation of Humus to CO2) and Indirectly via
the Ability of the Fulvic Acid Byproduct of Humus Degradation to Change the
Bicarbonate Content of the Sea via its Inhibition of CaCO3 Crystallization and Redissolution Switching Mechanism of Marine CO2 Released for which Fulvate Acta
as an Ultra-effective Catalyst.
An average negligence in land husbandry during historical food production per se
may therefore have led to a major human influence being directly exerted over how
the carbon cycle via the fulvate effect upon the carbonate balance of the sea: i.e..
by a common-through-geological time humate/fulvate controlled CaCO3
redistribution of soluble carbon (with a major effect of CaCO3 colloids) which has
continuously re-set of the principal CaCO3-surface activation and clay particle
dependent homeostatic (thermostat) control system {Cf. the LG Silln mechanism}
which putatively ultimately regulates the amount of atmospheric CO2. and also
feeds into climate change.
This or a similar mechanism, it is now suggested, explains why over the last several
thousand years the alteration of the amount of CO2 in the atmosphere has achieved
a truly anthropogenic global atmosphere dimension..
My treatment leaves out the dependence of human population size on fossil fuel usage since this relationship is
obscure. The human population, if considered to be a function of fossil fuel usage simply means that the
atmospheric CO2 is also a function of fossil fuel usage. This tends to confirm the IPCC hypothesis.
I have alternatively assumed that the smoothed curve b in the above PLOT 3. has a primary scientific relevance
whereas the (unknown) function which relates fossil fuel usage to atmospheric CO2 is of only secondary
relevance.
The above perhaps too-nave treatment of the least doubtful climate science-related information suggests that
while the carefully monitored increase in CO2 in the atmosphere has been truly and exactly anthropogenic, this
CO2 is not that from fossil fuel combustion.
PLOT 2 may be considered to indicate that the human population increase has arisen as a stop-start
exponential function of the use of fossil fuel. But the fossil fuel curve is complex lets say trivial.
The CO2 curve lacks such complexity. It is not trivial.
The most significant conclusions from PLOTS 1-3 is that the atmospheric CO2 seems to be a directly linear
function of the population which is not segmented and is more-or-less a constant historical increased with
population phenomenon.
The human population is also achieved by a soil- dependent mechanism. The soil links the atmosphere to
human pressure.

There exists, perhaps surprisingly, a large

body of experimental data which supports
the hypothesis that fulvate is the principal
soil facilitator of human control over the
environment and future climate change.
The pre-1959 data show a longstanding historical
relationship between the human population of the Earth and
the amount of CO2 in the Earths atmosphere which cannot
be accounted for (contrary to the first idea which might
come to mind
from a cursory look at selected parts of the total data) by
the changing amount of fossil fuel usage by these humans.
Compare curves a and b in the above plots.
The recent post 2000 massive CO2 surge in fossil fuel
derived CO2 from China and India shows up in the fossil fuel
usage vs. human population record, but this surge is not at
all apparent in the constant slope of linear course of the
overall total CO2 vs. human population curve; this seems to
confirm that

production of anthropogenic CO2

from fossil fuel must be an
insignificant part of total
anthropogenic CO2.
The anthropogenic effect on
climate is not the direct injection
into the atmosphere of extra CO2
but is a human induced
alteration of the marine
planetary atmospheric CO2
homeostatic control system
which is enabled by the unique
chemistry and physics of CaCO3
and clay particle [phases].

The apparent dramatic nature of the single global human

impact pressure control mechanism over the planets
atmospheric compartment, is a truly remarkable (should we
use the work biblical?) phenomenon which provides a more
rational target than does fossil fuel for environmental
science: we should now consider shifting the IPCC paradigm
of the need to curb fossil fuel curbing to the need for humus
conservation.
The human species must now attempt to conserve soil
humus globally and more generally attempt to protect the
sea against inappropriate anthropogenic humus pollution of
the sea.

Humus - Water
Structure and Water Activity
Analogously to how extracellular polysaccharides etc. (the glycome) is
thought to be principally concerned the regulation of water structure and reactivity,
n.b. water comprises some 70% of the mass of living organisms and water surface of
the sea comprises some 70 % of the surface of the Earth for which humate is a major
environmental water activity co-factor.
The surface of the Earth has co-evolved with biota and thus has inevitably become
quasi-biological in nature: A part of the greater biome.

23

The Driving Force of Human Pressure on the Earths Environment.

This is analogous to the driving force for chemical reactivity

Chemical Affinity

Which further is analogous to how heat is measured by temperature which defines the
tendency for a chemical reaction to occur spontaneously.
Or analogous to a force (like a pressure difference) which drives a fluid through a
conduit by flow

C in CaCO3
humic-CaCO3

C in Water in bo o-> C in humus-Water

HUMAN PRESSURE classes +

O2
multiple carbon pools

The force
derived from
pressure
difference can
be liked to the
chemical
affinity

HUMAN -Human

End product [CO2] of * (in and out) of the Atmosphere is

PRESSURE
*O2 in atmosphere
is affected by
and affects
*****
C in Water
A

C in Biota
Photosynthesis
C in Humus-Water

Water in humus

*
Formation of CaCO3
Dissolution of CaCO3

*CO2 in
Water

.. * is
(cf. IUPAC) definition) the
DeDonder Affinity, A,
= -[G/)P,T], being the reaction extent.
The re-arrangement of matter during a chemical reaction
may be regarded as the rate of the process for the , the
extent of stoicheometric alteration of chemical
concentration.
Cf. also Prigogine
= dQ/d)Q (Q is the uncompensated heat of reaction).

Cf. the rate of entropy increase= the product of thermodynamic force (=A/T) and the
thermodynamic flow (the reaction rate).
Entropy-Enthalpy Compensation Chemical Kinetics
Compensated heat (thermal energy) can be consider to drive thermally activated
chemical reactions
Compensated thermal energy can be regarded as
= H-TS
But when 0
H = TS
Compensation between allowable entropy and entropy flow may arise by a process
suggested by the above equation which widely applicable throughout physics,
chemistry and biology and must therefore apply to climate science.
This may be the ultimate origin of any anthropogenic influence over climate.

Miracle in the Global

Biosphere: the food fertilizer
carbon dioxide system of Nature
has increased exactly in tandem
with an increasing need by the
human population of the Earth for
additional soil-derived food.
Or is this simply an accidental
human damage of how the soil
naturally controls the carbon cycle?

23+

23++

1 the carefully compiled year-on-year Earths global human

populations,
2 the amount of fossil fuel used by those populations and
3. the average remote-sensed year-on-year global
atmospheric CO2 contents.
How these data simultaneously vary was plotted above in
PLOTS 1-3. These graphically depict how the average
human population of the Earth might be considered to act
as an applied force (an independent variable) which drives
two dependent variables: the amount of CO2 fossil fuel in
the atmosphere and the amount of fossil fuel used by that
human population. An odd way perhaps to consider fossil
fuel and population but the result of using the human
population as the driver of both CO2 and fossil fuel use
shows up what seems likely-to-be important result viz. that
the total amount of CO2 in the atmosphere has been an
almost exactly linear function of the Earths human
population. This correlation may have existed for
thousands of years. This obviously does not apply to fossil
fuel use.
Different mechanisms must, it seems apply to how these
proposed dependent variables are influenced by human
pressure. But does this mean that these independent
variables are also independent of each other? In reality
perhaps the fossil fuel usage should more correctly be
considered as a prime driving force. But similarly the
major fertilizer required for plant growth, the CO2 in the
atmosphere is also a true force which drives population
growth. But these forces, especially the fossil fuel usage
effect is both positive and negative and almost impossible
to sort our precisely how it may drive CO2. Setting aside
this problem for the moment consider PLOT 3 purely
intuitively. This suggests that all of athro.- atm.-CO2
completely masks the lesser amount of fossil fuel derived
CO2.

25+

The Gaia Hypothesis

25+

This (Lovelock cf. also Kitano loc. cit.) hypothesis suggests that in order to find
out if a planet supports life, we should first of all find out if the composition of
that atmosphere is what is predicted by classical thermodynamics. Such is the case
for Venus and Mars. But not for the Earth where the amount of various gases
(including CO2) deviate markedly from the thermodynamic values. Life is a nonthermodynamic process which creates environments which also are
extrathermodynamic in composition and show the kind of direct chemical correlation
with dominant species presence as is observed on Earth.
------------------------------------------------------------------------------------------------

Postscripts

The above collection of documents

supports the hypothesis that
anthropogenic climate change arises
from human damage to those humic
polymers which regulate the amount of
CO2 in the atmosphere.
26

The carefully observed fossil fuel usage rate curve

is independent of the carefully observed amount of
anthropogenic CO2 in the atmosphere.
The smoothed average annual CO2 vs. human population
diagrams also show some irregularities which reflect El Nino
sea temperature changes and one off volcanic eruption
cooling events. These irregularities can be enhanced by
differentiating the smoothed average annual CO2 vs. human
population curve. The fossil fuel usage year-on-year data
can be treated similarly,
The irregularities in the two curves do not correspond with
each other.
Is seems also that the historical sea level changes and the
shortening of most glaciers pre-date the year-on-year fossil
fuel usage rates and that there is no correlation between
these indicators of a warming of the Earths surface
temperature and the amount of fossil fuel derived CO 2
which has been injected into the atmosphere.
Concluding Remarks
Fulvate leaches out of degraded soils and adds to the marine organic matter pool. Bacteria of
the terrestrial agricultural soil is part of the human dominance of the biosphere which allows a
large number of terrestrial and marine species to be effectively controlled as regards their
biochemical input and removal of CO2 from the atmosphere in direct human activity which
has allowed human population numbers to determine the respiration and photosynthetic rates
of numerous species. These circumstances seems to be the most likely reasons for the linear
dependence between anthropogenic atmospheric CO 2 and the global human population.

# The large biosphere controlled carbon cycle sink of humus

contains various organometallic anions which comprise
arguably the largest single class of traditionally-defined
organic substance-class in the biosphere.
This major life supporting system of polyanionic aliphatic
cored (hydrophobic) polycarboxylate ligands acts as a
reservoir for inorganic nutrients and conserves water.
Humate polymers are also hyperactive-at-very-lowconcentrations. These potent surfactants also attach
strongly to the surfaces of the colloidal CaCO3 particles
which act as a servo feedback control system for the
regulation of the amount of CO2 in the atmosphere.

The humus system is also subject to augmentation by

climate upgrade but climate can and humus can also be
degraded naturally and by human intervention. Worldwide
and throughout human history there has tended to be a
consistent anthropogenic oxidative global degradation of
soil organic matter arising from the tillage of the soil (plus
excessive soil fertilization including by human and animal
sewage).
So, it might be argued, we now need to examine seriously
the hypothesis that anthropogenic climate change may arise
both directly and indirectly from an

anthropogenic alteration of the global humic

matter cycle; such an alteration is now proposed
to be the principal reason why the amount of
residual CO2 in the atmosphere directly correlates
with the size of the human presence on Earth (as
shown above in PLOT 3.
The principal mechanism by which humans can alter the Earths
climate is via oxidative soil organic matter degradation which alters the
humic matter cycle. While this general concept can be said to

have, at least amongst a small group of soil scientists, to

have been commonly agreed upon, the mechanism by which
we are enabled to accomplish this control over Nature still
has not been ascertained over the much larger group of
scientists who support the IPCC hypothesis. Governments
and their agencies have become fascinated by a fossil-fuelcentred hypothesis of human anthropogenic environmental
damage facilitated by CO2 despite the circumstance that CO2
is a critically important fertilizer needed for human food
production. This hypothesis seems not to have been
properly debated and tested by the full scientific
community.
Instead we have been stampeded into the initiation of a
legal system which is designed to curb fossil fuel usage.
This may, however, turn out if the presently suggested
hypothesis is (at least partly) correct to have almost no
direct impact upon any attempted moderation of human
induced climate change.
Altered inorganic ions, humic matter, oceanic pH, redox status and environmentally stable
phosphonate herbicides and phosphonate laundry detergent might be amongst the drivers of
oceanic disturbance which has caused an augmented atmospheric CO 2 via the perturbation of
the natural marine CO2 buffering capacity.

ADDENDUM

The title chosen for me for this letter Chem World 2011 June p73-4 was
Global Warming in the Absence of Fossil Fuel
This title was apt. It is a useful title with which to discuss the information contained
in Fig. 1.
My 2011 June letter to the Roy Soc Chem (London) Chem World referred to how the
increase in car ownership and other effects of industrialization had greatly increased
the amount of CO2 emitted by China and India but this fossil fuel fingerprint seemed
not to have impacted on how the amount of CO2 in the atmosphere had continued to
vary linearly (as noted by Onozaki loc cit.) with the size of the Earths human
population over the decadal period. when this major new historical surge had occurred
in the use of fossil fuel. Therefore the amount of CO2 in the atmosphere commonly
believe to be responsible for anthropogneically induced climate change must have
been produced by some other mechanism than simply the combustion of fossil fuel.
The usual manner in which the human population increase has been shown to be
correlated with the rise in atmospheric CO2 is to plot both as a function of the year
number (cf. e.g. DJ Hoffman et al. 2009 loc cit).
Which shows a quasi exponential (tandem) growth for both.
When the human population is directly plotted against the amount of CO2 in the
atmosphere a direct linear correlation is however revealed. This seems intrinsically a
more instructive treatment of the results since it removes time. This indicates that the
mechanism by which humans affect atmospheric CO2 is fast on the time scale of
decades. Also if the same mechanism has existed from before the industrial revolution
as also suggested by the population vs. atmos. CO2 curve then it must be something
very basic to humans. This is most likely how we produce food using the soil.
My lab work showed the dramatic ability of fulvate to block CaCO3 crystallization.
This applies to fulvates worldwide. Fulvate also is known to be increased by the
degradation of soil organic matter which occurs during intensive agriculture.
But there has to be more. There is some way in which humans can speed up the
transfer of fulvate from the land into the sea. It may simply be tillage, but probably
also involves the adsorption of low molecular weight nitrogen ions or molecules onto
the fulvate. This ties in with another commonly believed aspect of agriculture is its
likely impact on climate to do with a concern the use of nitrogen fertilization and its
effect on river and sea pollution. (Originally the nitrogen was from human urine,
faeces and animal waste later supplemented by guano and then in the modern
industrial era by chemical fixation of nitrogen). It is generally agreed that humans
have had a major impact on the natural nitrogen cycle of the Earth and affected the
ocean to a major extent, but the details of how this could affect climate are sketchy.
How could ammonium and nitrate ions speed the transfer of fulvate from the land into
the sea? The humate/fulvate structure seems to consist of a stable 103 year average
lifetime core hydrogen bond system which adsorbs low molecular molecules and ions.
These evidently include NH4+ etc. much in the same manner that atrazine is adsorbed
(cf. refs discussed by A Piccolo, Soil Science 2001 166 (11) 810-832 ); cf. also the
well-known abilities of nitrogen metabolite de-aggregator hydrogen-bond loosening
effects of such molecules could facilitate fulvate formation from humate. This also
seems to be afforded by N-phosphonomethyl glycine herbicide. Most agrochemicals
do this?
The anthropogenic CO2 is likely accompanied by a host of other anthropogenic
molecules (again no doubt some of these being linearly dependent on the human
population and also probably heat island population cluster effects). We simply have a

much better record of CO2 than if the others probably excepting the chlorofluoro
ethanes which are subject to international treaty limitation because of the ozone
depletion effect. This will be part of how humans can change climate as ionized
radiation affects cloud formation. How humans affect climate can be seen not to be a
straightforward as the apparent directly human population control of atmospheric
CO2.
The topic of whether humans actually affect climate at all is also hotly debated
(Cf. e.g. I Plimer 2009 book Heaven & Earth postulates that climate change has had
no human input. Fig. 1 tends to disprove this hypothesis).
The usual manner of demonstrating climate change from change in e.g. the sea level
change glacier length also considers these data in terms of year number.
It appears likely that if these data were instead treated as a function of human
population pressure as in Fig 1 then it would be apparent that the true amount of
anthropogenic CO2 suggested by the Fig 1 treatment much more clearly shows up
how this correlates to e.g. glacier shrinkage. This has however been underway from
much earlier than the industrial revolution. Glacier shrinkage does not correlate
however with the amount of fossil fuel used (cf. e.g. Fig 2 in AB Robinson et al. 2006
loc cit .)
The part of my letter which had attempted to explain how the linear variation of
atmospheric CO2 arose from food production degradation of humic matter and its
transfer into the sea had been edited out of my letter correctly since this would have
been thought to be mere speculation. My background in an appropriate soil science
experimental program of course could not be known. My internet essays have now
attempted to put these ideas into the public domain.
Consider the variation of the usage of fossil fuel as a function of the
human population of the Earth throughout history. This variation can
be shown to have been non-linear. The amount of CO2 in the atmosphere
has, however, apparently continued to vary (after the major increase in recent fossil
fuel usage by China) according to the historically valid accurately linear human
population dependent inter-relationship.
This linear relationship may have existed from the very first use by humans of large
scale agriculture.
Climate Change The WAR OF THE WORLD
By D Grant New Deer Turriff UK
The supposed ability of humans to alter climate is the big issue of today.
This cold be the end game between humans and nature
The War of the Word.

26+

Future climatic events including some future global warming induced multi-species
extinction event caused by the continued increase in current human activities cannot
be predicted with sufficient accuracy in order to stimulate the present generation to
take the necessary actions which may be needed to prevent such extinction event
which ay include the demise of mankind in the relatively near future. A future Earth
which includes humans in anything like their present numbers can therefore only be
ensured, not by science but by some new kind of religion based on the assumption
that this event will definitely occur unless humanity greatly changes its current
behaviour.

The Intergovernmental Panel on Climate Change (IPCC) thinks that we must act now
to avoid a major disaster for human society. This is the new religion.
This could require a complete alteration of human behaviour with major industrial
activities being greatly reduced. It might require some new kind of political
belief/propaganda system framework to get this to happen.
It may require the end of conventional capitalism and democracy.
But how strong is the evidence that human activities are spoiling the planet?
Part of the problem in answering this question is that the necessary scientific
understanding of climate (as well as of e.g. cosmology, oceanography and soil science
etc. (1) (2) might still be insufficient to be certain of to what extent human activities
need to be modified in order to prevent major adverse effects upon the global
ecosystem which might cause in a worst case scenario, the collapse of our present
civilization, and perhaps even the end of life on Earth which might happen if the Earth
were to warm up like Venus or cool down like Mars.
We cannot know for sure how good our scientific theories are. One way to test them is
to try to reconstruct climate in the past using the climate models which are currently
thought go be correct. There is a report (3) which asserts that current models cannot
account for the much higher than present sea temperature and atmospheric carbon
dioxide levels which occurred during the Cretaceous when the sea has been suggested
to have been hotter than a hot tub. But how accurate is the science behind this report?
Commonsense dictates that much of science is likely to currently be undiscovered. At
previous times in the history of science it has always been thought by our ancestors
that their former current states of knowledge were more or less complete, but history
clearly shows us that this belief was always incorrect. We inevitably do not have a
complete understanding of how humans could affect the Earths climate.
What about religious belief? This does not need proof or debate about what
knowledge still needs t be discovered. Could a climate change religion be emerging?
This may not be such a bad thing. Is this how we might need to force humans to do
certain things which might or might not ensure their survival?
How about a religion based on Gaia the notion that the Earth is a living organism.
Much of science could be attached to this belief system.
It need not be called a religion but a Good Earth Movement.
Life on Earth is strong and has apparently has survived many near extinctions in the
past following meteor strikes (such as the 67 million year ago event which is believed
to have ended the dinosaurs). This might indicate that the sort of global warming that
seem to be occurring might be a relatively minor affair in the annals of the geological
history of the Earth. But again the geological record suggests that major species
extinction is a real possibility. And this now might include Homo sapiens
Notes
(1) The increase in atmospheric carbon dioxide, the major focus of climate change
scientists because of the forcing effect of this gas by absorbing heat from solar
radiation in the Earths atmosphere is likely to be at least partly caused by an
augmented decomposition of soil organic mater (humus). This can happen by
deforestation and also by intensive agriculture (2). The full understanding of
the science behind this is not well-established however.

(2) Other actions of humic polymers introduced not the sea form the effect of the
decomposition of land humus may also affect climate. This dark coloured
material which is relatively stable in the sea water environment could alter the
carbonate balance of the sea especially by binding to calcium carbonate seeds
needed to allow the formation of this solid thought to be an important part of
the seas homeostasis mechanism, and also cause the sea to warm up more
than it would do otherwise (by the ability of dark particles which like soot in
the atmosphere can more effectively absorb the heat from the suns rays than
can uncontaminated waster). The land humus, like sewage may also give
marine organism a good supply of nutrients leading to major disturbance of
their former stable ecosystems
Some More References
Zenghelis D American Scientist 2010 98 246-50
This article was highly critical of the content (and the apparent lack of current
engagement in direct climate scientific research by at least some of the signatories) of
a recent open letter by climate change sceptics to the UN Secretary General. A
different opinion was expressed by the authors of some recent books on climate
change according to Zeghelis who reviewed books by
Schneider SH Science As A Contact Sport: Inside the Battle to Save Earths Climate
National Geographic Books 2009
Hansen J Storms of My Grandchildren: The Truth About the Coming Climate
Catastrophe and Our Last Chance to Save Humanity Bloomsbury 2009
Hoggan J & Littlemore R Climate Cover Up The Crusade to Deny Global
Warming Greystone Books 2009
Schnieider noted that Joseph Fourier had discovered the greenhouse effect back in
1824. Ever since the possible warming effect of carbon dioxide emitted by the
burning of fossil fuel has been debated as a possible cause of climate change.
The calculations are complex and interrelated regarding ocean dynamics, cloud
feedback, ecological changes and ice and snow change. We have no choice but to
embrace this complexity and corresponding understanding
.We can never fully solve the climate prediction problem*
The problem lies, it seems not so much with getting the public to understand the
science as with the effect of political chicanery and special interests.
Cf. Zenghelis D Amer Sci 2010 98 246-50 notes that Hansen had earlier worked on
the evolution of the atmosphere of Venus which has evolved a carbon-dioxide-rich
atmosphere which is much to hot to allow life (at least as we know it) to exist there.
This could indicate that he thinks the same could happen on Earth. He believes that
modern human activities that emit greenhouse gases are sufficient to trigger a major
climate switch since although the Earth is influenced
by self-regulating, damping feedback over very long times, larger amplifying
feedbacks are dominant over historical timescales during which humanity is rapidly
changing the atmospheric balance. He thinks that two natural amplifying feedbacks
stand out. 1st : reduction in global surface reflectivity as the plane warms, ice melts
and cloud patterns change so that less solar radiation is reflected back to the surface;
2nd as the planet warms and the permafrost thaws, more greenhouse gases such a s
methane, carbon dioxide and water vapour make their way into the atmosphere. In
the past small changes in Earths tilt and orbit round the sun or volcanic activity have
set these feedback mechanisms in motion

But it was suggested that the influence of humans is much larger and the damping
feedback that in the absence of human influence might move us into a new ice age are
very small and slow so that the emission for a single chlorofluorocarbon factory might
be enough to overcome them
Hansen is alleged to favour a global carbon tax that raises money and returns it
directly to the public. There are technologies and economic incentives necessary for
effective action to be taken to limit the projected increase in global temperature to less
than two degrees Celsius thus eliminating the bulk of the perceived risk of what may
happen if no action is take.
Hogan noted that a 2005 analysis of reference journal articles from1993-2005
identified 928 articles about climate change which provide a consensus belief that
human release of greenhouse gases is causing climate change. He noted that public
perceptions that there is no such general scientific consensus. Hogan also discussed
the publications of a number of climate sceptics including Bjrn Lomberg who seems
recently to have change sides as indicated by The Guardian newspaper (UK) which
headlined on 31 Aug 2010 an article by J Jowit their environmental correspondent that
Top climate sceptic case for $100bn fund to fight warming which started with the
statement that The worlds most high profile climate change sceptic is to declare that
global warming is undoubtedly one of the chief concerns facing the word today
and a challenge humanity must confront. In a new book, it seems that Lomberg is
to list methods by which global warming could, he believes, be averted.
Another high profile sceptic is Ian Plimer (an Australian mining geology professor)
who was quoted in an other UK newspaper (The Daily Express) which on Dec. 2
2009) in a headlined article by John Ingham, noted that carbon dioxide levels have
been up to 1,000 times higher in the past. Carbon dioxide cannot be driving global
warming now. In the past there have been temperature changes greater than anything
we are measuring today. They are driven by processes that have been going on since
the beginning of time. He cited periods of warming during the Roman Empire and in
the Middle Ages when Vikings grew grapes in Greenland and cooler phases such as
the Dark Ages and the Little Ice Age from 1300-1850). And he predicted that the next
phase would cool the plant
Q Schiermeier (Nature 2010 466 (7303) 179; cf. go.Nature.com/wN2YxX), failed to
detect major errors rather than misprints in the accuracy of the IPCCs most recent
assessment (go.nature.com/DGddCM) of the risks from global warming which could
put much of the Netherlands (55% but a more accurate value seems to have been
28%) in danger of flooding via sea level rises; IPCC may have given a wrong
indication of the number of Africans projected to be exposed to water shortages due to
climate change.
(2) W Ruddimans hypotheis.
surviving. Mainstream climate scientists do not seem to agree with this hypothesis
however. Carbon dioxide isotope studies from ice air does not however support this
hypothesis which had hinged on direct carbon dioxide emissions by wood from felled
tress which the farmers had burned during the large scale deforestation of Eurasia at
that time; but these farmers could have injected sufficient humic material into the sea
so as to slightly increase its surface temperature (by the dark matter solar energy

uptake mechanism or by blocking the inorganic carbon equilibria which control

marine carbon dioxide downsizing
(3) web.physorg.com/news10978.htm/%/7C/
[*This dilemma surely needs the mindset of a religious conviction to make headway
in offsetting the possible great danger of climate change].
. *The following is a possible agricultural mechanism by which anthropogenic
atmospheric CO2 can be generated: Greater human numbers on the planet induces an
increased agricultural soil degradation which inhibits the carbonate dependent carbon
cycle control system of the sea.. I have set out this hypothesis on the internet (search
term D Grant Fulvate II scribd Turriff www.scribd.com/doc/46952657/Fulvate-II).

The above documents have attempted to explain why all of the atmospheric CO2
increase over 260ppm may be a human city-evolved function,
namely it is a phenomenon determined by Humic Substance Cycle
Alteration , and is not an immediate effect of fossil fuel
combustion.

26++

Carbon Monoxide etc.

These exists a credible

Alternative Hypothesis : Clean anthropogenic CO2 is largely bio-friendly but polluted
anthropogenic CO2 can be bio-toxic.
The idea that human society needs to get de-carbonized should be considered in
terms not of total anthropogenic CO2 but in terms of good and bad modes of
producing anthropogenic CO2.
It seems likely that most of anthropogenic CO2 (this being the additional amount
present in the atmosphere from any human influence) is benign to the biosphere.
Only inefficient burning of fossil fuel should be of concern because the incomplete
combustion of fossil fuel inevitably leads to the formation of large amounts of
airborne nanoparticulates which further sequester other industrially produced toxic
by-products.
Most anthropogenic CO2 is likely to be benign. We can conclude this because the total
amount of such CO2 can be demonstrated to dwarf the amount produced from the
combustion of fossil fuel. This conclusions is reached by the following argument: the
carefully measured year-on year average remote-sensed atmospheric CO2 values have
increased precisely in tandem with the year-on- year increases in the average Earths
human populations, indicating that all of the observed post-industrial atmospheric
CO2 increase can be correctly labelled as being anthropogenic, but exactly the same
near-linear population-CO2 correlation curve (first reported by ND Newell & N
Marcus in 1987 for post-AD1959 data) seems also to describe all the (albeit less
accurately known) pre-industrial- revolution population - CO2 data points. This
surprising discovery taken together with the finding that the recent surge in fossil fuel
usage from India + China has not produced any alteration in the previous slope of the
population-CO2 vs. population variation curve, seems to show that fossil fuel cannot

after all (despite the suggestions that this idea is proved by 13C evaluations) be the
principal (direct) source of the experimentally observed amount of anthropogenic CO2
in the atmosphere.
The majority scientific view remains centred on the notion that the current high level
anthropogenic emissions of CO2 from fossil fuel use needs to be curbed. And fast.
A major problem with getting agreement on this, however, is that we do not know to
what extent the benefit of the use of fossil fuel outweighs the possible damage to the
environment caused by such use.
Surely, however, the major environmental hazard of fossil fuel combustion is not CO2
but CO because this is formed together with highly toxic dust. Fossil fuel use
limitation should therefore concern such dust and not CO2.
It should be noted that a major differences between the combustion-formed
CO2 and its natural formation in biology (which recycles CO2 in
photosynthesis) is that the additional CO2 produced directly by the
anthropogenic industrial combustion of fossil fuels or plant materials as well
as in forest fires (which may often also be anthropogenic) is formed together
with dirty by-products consisting of carbon monoxide (CO) together with
carbonaceous (soot) particles which can sequester an additional chemical
cocktail containing thousands of other potentially harmful substances
[including toxic metals and metalloids, oxides of sulphur and nitrogen and
their anions plus organic compounds including heterocyclic substances and
organohalogens] which are separately injected into the atmosphere from
human society including from the incineration of industrial products). The
smallest of these airborne carbon rich nano-particles have the greatest surface
areas for such sequestration. These, often invisible, particles stay aloft are
transported inter-continentally. They change the climate. They affect biota.
They diminish human lifespan. Their presence should follow the globally
distributed presence of CO which is much more abundant in the Northern
Hemisphere (NH) than in the Southern Hemisphere (SH); (e.g. more than 100
to less than 60 parts per billion (ppb) being present respectively in the NH and
SH). Forest fires however seem to create the largest local concentration of
CO. Detection of CO from space has indicated hotspots of several hundred
ppb associated with S America and Africa, which has been attributed to forest
fires.
CO per se is also overtly toxic both to animals and plants. The presence of 3 ppm is
life-threatening for humans. I.e. the uptake of oxygen (respiration) becomes
completely inhibited. Smaller amounts are also thought to be deleterious to persons
who suffer form a variety of illnesses. The binding of CO to the heme iron oxygen
binding site has a plant photosynthesis metal ion catalyst centre equivalent causing
carbon monoxide also to efficiently inhibit photosynthesis.
It seems possible that the NHs several tens of parts per billion CO could inhibit
photosynthesis sufficiently to show up as a significant factor in the anthropogenic
input into atmospheric CO2 augmentation. This CO may also be a marker of the
invisible nano-particle toxic gas which is a major biohazard. So we may then
putatively distinguish good anthropogenic CO2 from bad anthropogenic CO2.
The video shown in web.visible earth.nasa.gov/view-detail.phb?id=1780 shows how
the amount of CO detected from space varies with time over the year. At some time
points the highest (200+ ppb) concentrations occur over NH zones (e.g. India and
China) as well as the Arctic.

Cf. B Barret et al. Atmos Chem Phys 2005 5 2901-14 (Global carbon monoxide
vertical distribution from spaceborne high resolution FTIR nadir measurement) [in
which Fig. 6 shows the increase of CO mixing ratio in ppbv in the far south to a
maximum of 200 at latitude ca. 38oN.
CO which has a residence time of 1-3 month in the atmosphere is believed to be
responsible for ca. 75% of the highly reactive HO radicals which promotes the
oxidising capacity of the troposphere and the concentration of greenhouse gases CH4
and O3 and thereby contributes to climate change (cf. Barret et al. citation: Daniel &
Solomon 1998).
water
Other anthropogenic pollutants. CO may complicate how CO2 dissolves in
where it produces the bicarbonate HCO2- and
carbonate CO32- anions (which reacts with the
2+
cation Ca to form CaCO3 in both colloidal and the more easily precipitated
crystalline forms the formation of which seems to be under the control of another
colloidal carbon-based polymer system which is also the largest reservoir of carbon in
the biosphere namely that of the humic anion and such processes may conceivably
further be subject to perturbation by CO and/or by the other anthropogenic
environmental inputs for which CO may co-occur in the nano-particles together
ultratrace amounts of thousands of individual types of chemicals which include the
banned substance (dioxin-like) hexachlorobenzene (HCB) which also adsorbs
strongly onto humic polymers. HCB enters the food chain where it promotes a range
of chronic inflammatory diseases in humans. HCB plus the other substances produced
anthropogenically by the incineration of trash may act in a manner similar to the
ozone layer depleting chloroflurocarbons which J. Hansen (the father of global
warming (also described as an alarmist [cf. in Storms of My Grandchildren: The
Truth About the Coming Climate Catastrophe and Our Last Chance to Save
Humanity Bloomsbury 2009]) warns may be sufficiently hyper-active to overcome
the various Earths natural climate damping feedback mechanisms so as to potentially
cause an irreversible catastrophic warming of the climate.
An opposing (even more controversial) view, that of W. Ruddiman [cf. Climate
Change 2004 61 261-93]) is that the pre-industrial land use emission of (clean)
anthropogenic CO2 + CH4 may have benefitted human society for thousands of years.
It seems that even a small number of humans by practicing agriculture cleanly have
also produced large amounts of non-toxic mixtures of greenhouse gases from land use
(changes) and that these emissions have delayed the onset of the next ice age. An
induced warming associated with agriculture has it seems, perhaps for thousands of
years, improved the human condition.
How the Human/Earth Footprint leads to a
Human Stain in the Ocean which
is the Major Cause of Atmospheric CO2 Augmentation.
Climate Change and Toxic Anthropogenic Carbon Emissions.
The Relevance to public health and greenhouse gas induced climate change
A discussion which seeks to offer an alternative to the IPCC Hypothesis.
There Exists a Fundamental Footprint of Humans on the Earth
which causes the total amount of CO2 in the Earths atmosphere to be
a linear function of the human population of the Earth.
This will require a future ten billion humans to cause the amount of CO2 in the atmosphere to reach 442ppm.
This prediction is made using the most accurately known databases at out disposal.

We need, however, first of all the explain the following.

Why is this human atmospheric CO2 correlation so exact?
Why does the same correlation apply equally well to atmospheric CO2 and
population data from the modern industrial period of human history as
to data from long before the industrial revolution?
Apologies also if the text seems to contain apparent repetition of similar ideas;
these are set out in different ways. Some of the text may also seem contradictory.
It seems to be instructive to plot the historical databases of the amount of CO2 in the
atmosphere and the amount of fossil fuel used as a function of the human
population of the Earth. This procedure shows up a pre-human baseline of ca
260ppm atmos. CO2 and possible other faults in the logic of the
commonly believed fossil fuel hypothesis of human CO2 generation
A collection of discussion documents are presented below in the form of a preliminary
draft which has not been re-edited-into-a single-document form. Apologies if this is
confusing.
This argument is perhaps the most critical to future human society which has ever
taken place in human history so it seems worth while not delaying the making of the
following argument public.
It seems that the observed amount of anthropogenic CO2 appearing in the atmosphere
disagrees with the commonly held view that fossil fuel use is the largest direct cause
of anthropogenic CO2 .

David Grant, Ph.D. December 2014

27

Current theories predict that anthropogenic atmospheric CO2 will require ca. 4.104 years to re-establish
buffering in the ocean (cf S. Solomon, Intergovernmental Panel On Climate Change Fig 7.12). Uncertainties in
such discussion include possible errors caused by inadequate account having been made of the influence of
transport on the tracer determined dissolution rates of CaCO 3 (K. Friis et al. Global Biogeochem Cycle 2006 20 (4)
Notes GB4019.1-11).
The cyclic variation in energy of solar radiation which is suggested from ice core studies.
Of atmospheric CO2 suggested that the pre-agricultural system of regular time variation was disturbed by an
additional input from anthropogenic influences. This pre-dates the conventional notion that anthropogenic input
started with the western industrial revolution.
It was assumed that forest clearance and the burning of wood therefrom was the principal source of this CO 2.
However this seems to be less by a factor of three.
Thus the major anthropogenic effect is not direct CO2 emission.
Recent examination of stable carbon isotope ratios of this CO 2 confirms the hypothesis that it arises from
disturbance of the marine carbonate buffer system and that it was not determined from the combustion of wood (J.
Elsig et al., Nature DOI:10.1038/nature08393)
The major part of the effect can therefore be rationally be attributed to a direct influence of altered topsoil runoff
humic anionic polycarboxylate polymers into the oceans.
Such polymers have been confirmed in laboratory crystallisation rate modification experiments to be ultra-reactive
for the inhibition of CaCO3 crystallisation.
This ability of effectively inhibit CaCO3 crystallisation seems applies to humic matter derived polymers from a
variety of widely different locations consistent with the hypothesis that this mechanism of the early anthropogenic
perturbation of atmospheric CO2 was, at least during the period of the first anthropogenic influence, the dominant
one.
[Original document dated 7/25/2009 9.57AM]

28

.
The Future of Humanity

To do a review of a scientific topic we must first of all ask what is its importance; if
the
answer is the future of the human society globally, is obviously as big as it gets.
This justifies trying to make an independent review.
Next what is the most well established to be accurate primary data on which to centre
the review.
This is perhaps as shown below: the perhaps highly coupled human signature of
CO2. Quasi-linear or even accurately linear in part.
The feint lower curve shows how fossil fuel consumption has also increased in a
related non-linear manner:

not necessarily fossil fuel use

While increase in the Earths human population, plotted as a function
to fossil fuel usage shows a parallel increase in the amount of CO2 in
the atmosphere a detailed analysis of this interdependence suggests that CO2 arising
from fossil fuel combustion
is not the principal source of anthropogenic CO2.
INTRODUCTION
The impact of human carbon emissions on the Earths ecosystem and especially the
climate is of current major interest, not only to the scientific community but also to
the entire human society, since the outcome of the debate currently taking place about
what remedies are required to combat the supposed danger posed by a supposedly
too-high atmospheric CO2 (arising is it commonly believed principally from human
use of fossil fuel) will inevitably have a high cost to human society so that all human
activities will have to be diminished.
A minority view is that CO2 emitted from human use of fossil fuel should be of only
minor concern requiring no legal framework for its control because humans can, in
principle, have no major effect on the planets climate, at least in comparison with
natural cycles of climate, since the geological record teaches that large increases as
well as decreases in global temperature and atmospheric CO2 have occurred long
before the evolution of humans.
The major scientific consensus seems, however, to disagree with such a view and to
favour the hypothesis that high levels of fossil fuel usage will inevitably induce a
catastrophic global warming climate change. Of relevance from a geological
perspective is that the current rate of increase in atmospheric CO2 is so unprecedented
over the last 4000,000 years that it must tend to de-stabilize the natural balance of the
Earths climate. Human industry has undoubtedly caused an unprecedented

modification of the biosphere caused by land use change of increasing intensity and
increasing per capita energy use with major likely climate change input from
urbanization and pollution of the sea. The dramatic increase in the Earths human
population, rising from one to seven billion and the increase in energy use by several
hundred fold from AD 1800 has happened during a very short geological period.
An approximate analysis of the historical trends in fossil fuel consumption and the
resultant supposed injection of CO2 into the atmosphere has suggested that a constant
fraction ca . half tends to remain long-term in the atmosphere
Cf. the following graph which shows how the increasing use of fossil fuel usage has
increased from a miniscule amount to more than 8000 metric tons/annum from the
start of the industrial revolution until the present time over which time the amount of
CO2 in the atmosphere has increased from ca 280 to ca 400 ppm. An
approximately linear human population dependent increase in fossil fuel use has been
paralleled by a corresponding increase in the amount of CO2 in the atmosphere. The
latter is however a more exact linear function of the human population than is the
fossil fuel use.
Consider the following pasted document section discussing this

A differently slanted comparison of the recorded databases of measured atmospheric

CO2 and the amount of fossil fuel consumed disagrees with the hypothesis of
dominant fossil fuel mechanism of direct injection of CO2 into the atmosphere
Cf. plots A and B below.

In PLOT A x axis is Gt fossil fuel use av/yr and PLOT B x axis is the observed
contemporary atmospheric CO2 ppm.
(A is a smoothed version of PLOT 2 vide infra)
PLOT A
Human Population in Billions

PLOT B

It is evident that while the historical CO2 atmos. vs. pop. curve is nearly linear but a separate linear section of
slightly greater rate of increase of CO2/population describes the recent billion population surge; there may be
distinguishable linear sections with discontinuities at ca. 3 and ca 5.6 billion corresponding to AD 1960 and 2000
respectively.

Nevertheless the complete historical record can be described fairly correctly as a

single linear phenomenon cf. PLOT C,
The value of CO2 on Dec. 2014, 398.78ppm occurred when the human population had reached 7.3 billion. The .3
part seems not yet to have been agreed.
The curve shown below may extrapolate linearly to this point starting from a pre-human value of ca 260ppm.

PLOT C
*The following is a possible agricultural mechanism by which anthropogenic
atmospheric CO2 can be generated in a manner consistent with the suggestion of a
common process of generation of anthropogenic CO2 throughout human history:
Greater human numbers on the planet induces an increased agricultural soil
degradation which inhibits the carbonate dependent carbon cycle control system of
the sea.. I have set out this hypothesis on the internet (search term D Grant Fulvate
II scribd Turriff
*
www.scribd.com/doc/46952657/Fulvate-II).
I have kept the original Figure numbers and also mostly kept the section headings
used in the original documents and have not attempted to create a single document at
this stage in the hypothesis building process. Apologies if this is confusing.
The above discussion

suggests that overall the historical human population-fossil fuel plot has varied
differently from that of the observed population-CO2 variation; fossil fuel use has
followed an apparently non-linear function of the historical human population (cf.
also PLOT 2 (above) while atmos. CO2 has varied as a near-linear function of the
human population.
The fossil fuel combustion process hypothesis of anthropogenic CO2 formation can
apparently be shown to require a re-assessment of its validity by the above very
simple analysis of the most accurately recorded databases.

This does not mean of course that the overall effect of fossil fuel combustion is
without negative consequences for the environment especially since fossil fuel, if not
completely converted into CO2, produces toxic by-products.
Taxing fossil fuel usage will diminish atmospheric CO2
simply because of the increased cost of food production which will tend to diminish the
human population of the Earth.
A Letter to RSC Chem. World had attempted to draw attention to the ideas presented
above i.e. how human population pressure drives atmospheric CO2 directly by a
mechanism which must be quite distinct from simply the ability of humans to inject
CO2 into the atmosphere from the combustion of fossil fuel. This was published in
June 2011 but without the comparative plots of population vs. CO2 and fossil fuel
usage and additional information which support an agricultural soil degradation
mechanism of the formation of anthropogenic CO2.
The idea that fossil fuel combustion to CO2 (which, additionally has been required to
partially remain long-term in the atmosphere) has led the observed CO2 in the
atmosphere to increase in tandem with the human population cannot be considered to
conform with the notion that the observed amount of anthropogenic CO2 in the
atmosphere is the primary product of fossil fuel combustion
Generation.
The smoothed as well as the unsmoothed fossil fuel usage curves should, according
to the IPCC hypothesis, be directly correlated with the amount of observed
atmospheric CO2.
Evidently such an exact correlation is lacking.
The IPCC hypothesis is therefore, at least in part, wrong.
Perhaps, however the observed amount of anthropogenic CO2 might be due to an
indirect route from fossil fuel combustion involving variable rates of uptake in land
and marine CO2 sinks and/or the superposed uptake and release of CO2 by a major
sink (e.g. the sea) affected by human population pressure somehow.

29

How to suggest that fossil fuel combustion does after all create all of the
anthropogenic CO2 in the atmosphere
It must be noted that a differently slanted treatment of the data which were used in the above argument can also suggest that
the amount of observed CO2 in the atmosphere could appear to be proportional to the amount of fossil fuel consumed by
human society over the preceding years cf.

PLOT4

TRIVIAL LINEARITY ?
Other hypotheses to be considered
Hypothesis Z
Fossil fuel combustion is the principal mechanism by which anthropogenic CO 2 is formed but this CO2
has also been augmented and diminished by other human actions.
The apparent linearity in human population atmospheric CO2 plots is trivial
While over the entire period of human history, an increase has occurred in the total amount of CO 2 in
the atmosphere and this increase has evidently been an almost exact linear function of the global
human population number, but the origin of this CO2 may however not be of a constant source type
but has nevertheless changed but in such a manner as to suggest a single mechanism might have
been responsible. This is however an illusion. The notion that the linearity of the curve shown in PLOT
1 is a trivial phenomenon is suggested by an academic web site posted by Columbia U (vide infra refs)
and by the numerous authors of papers who have researched the role of human population differences
in the generation of anthropogenic CO2, (these papers can be accessed using the search terms
atmospheric CO2 and human population) it is commonly assumed that numerous separate and
highly complex mechanisms are responsible for how different human societies produce different
amounts of CO2 per capita..
-------------------------------------------------------------------------------------------------------------------------------------------------------------The (trivial) plot PLOT 5 in which the x-axis is a number from 1-94 and the y axis is the amount of CO2 in the atmosphere.
This was the order of listing an adjusted temporal effect from the start of systematic fossil fuel recording shows how the
amount of CO2 in the atmosphere has increased over time and that this increase may also be fitted to a trivial linear equation
with an apparent low degree of scatter starting from an apparent pre-fossil fuel usage atmospheric CO 2 of 274.89ppm.
The listing number used increased by unity for each year after AD 1925 to 2005 but had only 20 points to represent the 175
years prior to 1925.

PLOT 5
x-axis : fossil fuel usage assigned year number
effect

30
-----------------------------------------------------------------------------------------------------------------------------------------Final Statement
Fossil fuel usage rates must however impact to some extent on atmospheric CO 2 because fossil fuel-assisted
fertilizer manufacture dependent augmentation of agricultural output can support an increased human population.
If fossil fuel is replaced by other source of energy for fertilizer production, it seems unlikely that the atmospheric
CO2 will continue to vary by other than by the previous agriculturally-determined linear human population process.

By plotting the remote-sensed atmospheric CO2 contents

against the Earths human population, support is provided
for an old Aberdeen University discussed soluble polyanion
(fulvate) mechanism of anthropogenic climate change. This
idea is now carried forward to suggest as a new approach by
which human activities might be regulated so as to prevent
unwanted climate change
There exists a vast amount of experimental information
albeit of variable quality which is available to the public for
hypothesis building in the field of anthropogenic climate
science. These include various temperature and isotope

information databases which can be probed to discuss

anthropogenic atmospheric CO2 augmentation and
associated global warming and climate change data. But
how fit for purpose are they? Ongoing debates constantly
question not only the accuracy of these data but also how
they should be interpreted.
SUMMARY
The logical deductions made from the following diagram could help to redirect human society towards
a brighter future.

The year-on year-average, remote-sensed atmospheric CO2 values

display an apparent exact tandem variation with the Earths
human population which is absent from the corresponding fossil

fuel usage curve which suggests that the continued increase in

the amount of anthropogenic CO2 in the atmosphere is
independent of the increase in the amount of CO2 produced by
from fossil fuel combustion. Indeed fossil fuel usage per se may
to a first approximation have no effect whatsoever on the
observed increase the amount of CO2 in the atmosphere.

*The observed anthropogenic atmospheric CO2 might be generated because greater

human numbers on the planet induce an increased agricultural soil degradation which
increases the natural inhibition by dissolved organic matter of the carbonate
dependent carbon cycle control system of the sea. I have set out this hypothesis on
the internet (search term D Grant Fulvate II scribd Turriff
www.scribd.com/doc/46952657/Fulvate-II).
In order for future generations to be able to control the
amount of CO2 in the atmosphere and perhaps thereby to
avert future catastrophic climate change it is essential that
the process of anthropogenic fulvate formation and
transport should be investigated as a central topic of
climate science.