RESEARCH NOTE

Brief Statement of a New Hypothesis of Global Warming &

Climate Change and its Origins
The Amount of CO2 in the Atmospheric is Probably Critically Anthropogenically Influenced by the
Marine and Atmospheric Fulvate Status
by
D. Grant Ph.D., New Deer-Turriff, AB53 6SX, Scotland, U.K.
5 Nov. 2010
Contents
Preamble.

1. Summary.

1a. Hypothesis of how global warming and climate change could critically depend on the
mechanism by which the sea is prevented from dissolving more CO2 because of how the
surface of the sea is supersaturated with respect to CO2.
The organic polyanion chemistry of the sea could act both as a multi-inorganic ion buffer
as well as a CO2 sink regulator.

1b. The current humic buffer and bio-protection system of the Earth may be a continuation a
putative pre-biotic system of organic matter (‘pre-biotic soup’) which promoted the
evolution of the first living organisms, by controlling the rate formation of CaCO3
crystals which can beneficially modulate climate and which allowed the creation of more
potentially bio-friendly environments.

1c. The humic matter particles in the atmosphere may modulate the crystallization of ice
crystals involved in the nucleation of cloud formation and rainfall and thereby influence
climate and global warming.
Humic matter in atmospheric dust is also likely to reduce the rate formation of ice
crystals during surface glaciation and also to increase the rate of deglaciation by acting
as a dark matter solar heat energy trap, so that global cooling and warming could be at
least partly under the control of the biosphere humate matter system.

2. The putative major organic polyanion CO2 ‘servo control systems’ of the soil, the sea,
and the atmosphere.

2a. The concept of the degree of supersaturation (Ω ) of sparingly soluble phases.

3. Formation of precipitates from supersaturated solutions is normally a seeded process.

3a. The glycosaminoglycans of animal extracellular space and cell surfaces putatively mimic
the fulvate part of the humus/humic acid soil and seawater buffer system in the
mechanisms by which they can act as multi-inorganic element buffers and crystal surface
active-site capping agents.

3b. The role of marine fulvates as CaCO3 crystallization inhibitors.

4. Metallomic ‘all-element’ arrays are assembled on the surfaces of scale inhibiting
polyanions.

4a. Animals have evolved improved polycarboxylate-types of putative

inorganic salt solution buffer systems.

5. How the anthopogenic increase in CO2 can be linked to antropogenically altered

fulvate balance of the biosphere.

6. In vitro experiments confirm that terrestrial soil fulvates

are extremely potent inhibitors of CaCO3 crystallization.

6a. Possible relevance to global warming of putative fulvate inhibition of methane hydrate
clathrate formation.

7. What needs to be done to halt global warming and climate change.

Preamble
A New Hypothesis of Anthropogenic Global Warming &
Climate Change
It is proposed that anthropogenic augmentation of
atmospheric CO2 can arise as a result of a side effect of
industrial scale agriculture via the transfer from the land to
the sea of large amounts of terrestrial-derived-soil-humus
fulvate which inhibits the ability of the sea to act as a sink for
atmospheric CO2 including via the mechanism of seed particle
growth site deactivation which blocks the formation of
calcium carbonate crystal growth. This blocks the ability of
the sea to act as a C sink and causes the sea surface to become
supersaturated in CO2 . This causes CO2 to be injected from
the seas into the atmosphere.
A related hypothesis suggests that topsoil degradation also
affects the nucleation of cloud formation by a related
mechanism by which fulvate inhibits the formation of ice
crystals.
A more detailed statement of this ‘new hypothesis’ of what the
‘real’ marine buffer system consists of, the experimental
background to it [cf. ref.1], and the ongoing scientific
discussions which have led to it, demand a more formal setting
than seems appropriate to this preliminary document.
Nevertheless the above hypothesis is presented in some detail
below. The text may seem to repeat itself somewhat but rather
than spending the great amount of time which would be required
to write a more concise thesis, it seems worthwhile at the
present time to allow this new thinking about global warming
and climate change to be accessed from several angles.

1. Summary
A major marine buffer system consisting of poly-carboxylate
humic organic matter polymers is proposed. This putative
buffer system is suggested to behave similarly to the poly-
carboxylated polysaccharides (including the animal heparan
sulfates, the basis of the heparanomea a buffer of extracellular
spaces and cell surfaces in multi-cellular animals) by acting as a
multi-inorganic element collector and pH buffer and also a
regulator of the degree of supersaturation (Ω ) in natural waters
of CaCO3 and other sparingly soluble inorganic phases (by
acting as a potent inhibitor of their crystal seeding and growth
processes). This can create a situation of high supersaturation
of dissolved CO2 at the surface of the sea.
A possible major mechanism by which global warming and climate
change could have been caused as a result of industrialization, and
which might account for at least a part of the increase in atmospheric
CO2 which is currently assumed to have arisen almost entirely from
fossil fuel usage, is via a process of terrestrial topsoil humus damage
which is a known effect of industrial scale intensive agriculture which
has induced on a a large global scale humic matter (fulvate) runoff,
causing the transfer from the land into sea of large amounts of a
highly potent terrestrial fulvate CaCO3 crystallization inhibitor (n.b.
the amount of this transfer has putatively increased at a similar rate to
the increase in atmospheric CO2 over the same period of recent
human history).

A further possible effect of such topsoil humus degradation is that it

potentially enhances the ease with which ice crystal modulator
humate/fulvate containing dust can be injected into the atmosphere.
This kind of dust can potentially interfere with cloud formation and
rainmaking (e.g. by inhibiting ice crystal formation in the upper
troposphere) and therefore feed into climate change and global
warming.
The presence of this kind of organic matter could also be a source of error in ice core CO2 estimation.

1a. Hypothesis of how global warming and

climate change could critically depend on the
mechanism by which the sea is prevented from
dissolving more CO2

The organic polyanion chemistry of the sea can

putatively act both as a multi-inorganic ion buffer
as well as a controller of the CO2 sink
The top layers of the sea (at least that of the equator and part of
that in temperate zones) are known commonly to be
supersaturated with respect to CO2. This means that heating or
cooling of the sea can cause CO2 to be released to or absorbed
from the atmosphere in a manner which shows up as
discontinuities in the differentiated curve of atmospheric CO2 vs.
time (e.g. the yearly average year-on year curve) of Mauna Loa
data. Temperate zone seas and lakes also seem to inject CO2
into the atmosphere. It seems that the sea acts not only as a sink
but also as a source of CO2 and contributes to the total amount
of anthropogenic CO2 in the atmosphere at the present time
which had been previously attributed entirely to the combustion
fossil fuel.
An important part of how the current augmentation of
atmospheric CO2 and the resultant global warming and climate
change is conventionally thought to be achieved is a process
which relies on the operation of some unknown mechanism(s)
by which the sea is currently prevented from dissolving the extra
CO2 which has been injected into the atmosphere from the
combustion of fossil fuels and from the degradation of soil
organic matter.

This ‘unknown mechanism’, it is now suggested, is afforded by

the presence of the humic organic matter in the sea which causes
the top layers of the sea to become supersaturated in CO2.

The possible concentration of hydrophobic fractions of aliphatic

humic matter (e.g. the C(O)-[CH2]n – containing polymeric
material) (cf. 1-1), could act as a physical barrier able to inhibit
surface transfer of gas molecules.
(Cf. surfactant molecules which include pre-humate exudates of
marine organisms are also known to generate sea surface foams
which can reduce with gas transfer rates between the sea and the
atmosphere [1, Calleja et al.]).

Perhaps the most powerful mechanism of potential humic

polymer interaction with marine physical chemical and
biochemical processes however, is the ability of (humic) fulvic
polymers to dramatically interfere with CaCO3 formation and
thereby to alter the upstream quasi-equilibria associated with
this process.

This present research note further attempts to set out how

anthropogenic influences starting some 7000 years ago could
have altered the detailed environmental chemistry of this
putative marine organic multi-potent chemical buffer system
afforded by dissolved organic matter (fulvate) water-soluble
organic matter which exists in the sea
A chemically similar system also exists in association with
terrestrial soils [1-1].
Further chemically related systems exist inter alia in
the cell walls of marine algae [2a] and in the extracellular
spaces and cell surfaces [2, cf. 2c] of multicelluar organisms.

1b. The humic buffer and bio-protection system

may have originated on the early Earth from the need to
create a bio-friendly water activity environment

The much-studied but still not completely understood

humified organic matter system of the biosphere could have co-
evolved with early life forms on Earth as a means of securing
bio-friendly water activities.
(Cf., n.b. a pre-requisite for life is liquid water; a further
meaning of this hard fact is that all living systems are
water-‘quality’-dependent and require carefully buffered
aqueous environments specifically designed for the particular
environmental niche habitats; while the highly evolved modern
organisms have build-in systems for achieving the various
essential-to-life water activities internally, the first living
organisms in the sea were probably assisted by the prior creation
in the sea of a general system of extracellular environment
buffering which preconditioned the spontaneous generation of
early biological cells. A stable seawater system seems a
necessary precondition for this to occur and this was putatively
afforded by a pre-biotic evolution of a humic polymer system.
The poly-carboxylated humic matter organic polymer system e.g. via soil
particle injection as dust input into the atmosphere must also have
affected global warming and climate throughout geological time by being
able to directly influence the rate of glaciation via the ability of the poly-
carboxylated polymer systems of humic matter to inhibit the
crystallization of ice, a process which is also likely to impact on the
formation ice crystals required for cloud formation and hence allowing
major controls by humic chemistry to have influenced historical climate
change and global warming episodes which now includes the ability of
human actions to perturb the global humic chemistry.

The putative control of ice crystal formation afforded by humate anions

will also diminish the rate of freezing and hold up glaciation as well as,
by the ability of the dark colored humic HULIS particles (similarly to the
man-made soot particles at the present time) when deposited on the
surfaces of glaciers etc. enables these to act as a solar energy absorbers
which speed glacier melting process.

The study of internal extracellular aqueous solutions of animals

(e.g. blood serum) because their predecessors evolved in the sea
(a circumstance which agrees with the similarity in composition
between 50+ element multi-inorganic ion content of the sea and
blood serum [3]) allows clues to be gleaned about those
(‘primitive’ putative poly-carboxylate polysaccharide-based)
homeostasis systems which have been retained from the start of
animal evolution. This identifies the perhaps previously-
largely-overlooked similar mechanism afforded by the poly-
carboxylated polyanion organic molecules which ubiquitously
exist in animal fluids and in the sea).

[The presence of a variety of different types of metal binding

sites in present-day humic matter polyanions (which are now
largely derived from recycled biomolecules) seems to allow for
the collection and release of inorganic ions in such a way as to
create and buffer the type of multi inorganic aqueous solution
which exists in the sea other natural waters and in the soil. Also
in human blood serum].
[The presence of organic matter similar to the organic matter which is apparently associated
with comets could have been a critical driving force for the evolution of the earliest living
organisms by both providing a source of organic substances and inorganic ions (including the
major inorganic elements needed for polysaccharide, protein and nucleic acid formation and
also the seawater range of the trace elements) but also by acting as a shield against damaging
radiation, by being an inhibitor of ice crystal formation (being a natural antifreeze agent) and
also being a controller of normal and inhibitor of damaging calcification at the surfaces of
biological cells and later, following the evolutions of multicellular organisms by providing a
method for controlling extracellular space via the same process the control of calcification
(i.e. the formation of sparingly soluble Ca salts). The more highly evolved species such as the
earliest animals apparently improved on this system by biosynthesizing their own system of
poly-carboxylated polyanions containing more flexible carboxylate groups such as those
which are present in the animal cell surface glycosaminoglycan (the putative controller of the
activity of Ca2+ which attained an ability to flexibly regulate growth factor and growth factor
receptor activities during body and organ development as well as in wound healing; these
poly-carboxylated polyanions also continue to provide the more primitive functions afforded
by poly-carboxylated polyanionic substances viz. the setting up of a seawater like solution at
cell surfaces (being able to create a similar multi-inorganic ion solution) and also control of
the formation of CaCO3 and other sparingly soluble Ca salts [2].
The study of fulvate inhibition of CaCO3 crystallization [1] was a side experiment of a
principal line of investigation into the roles of animal poly-carboxylated polysaccharides
which had started from the need to test the pivotal hypothesis outlined in a 1979 paper by
W.F. Long and F.B. Williamson (Aberdeen University) [IRCS J Med Sci (Libr Compend) 7
429-434] which had proposed that the activity of Ca2+ e.g. for signaling in animals was
controlled by poly-carboxylated polysaccharides of the heparan sulfate class.
An extension of this hypothesis (that animal Ca activity in extracellular space is
regulated by poly-carboxylated substances) could further suggest that Ca in natural
waters including seawater, is similarly regulated; this could further mean that the
commonly held theory of the CaCO3 - dependent homeostasis of the sea and the
Earth’s climate might also be modulated analogously via poly-carboxylated
substances (such as a humic matter fulvate). These could regulate the carbon cycle
(which is believed is afforded by a pivotal relationship with seawater [Ca2+] via
atmospheric and dissolved CO2 which generates CO32- by a series of probably
kinetically-controlled but commonly approximated by the formally reversible
process/equations:
CO2 (atmospheric) ↔ CO2 (dissolved in the sea)
+ H2O ↔ CO2(H2O) [↔H2CO3] ↔ H+ + HCO3- ;
and HCO3- ↔ H+ + CO32- as well as CO32- + Ca2+ ↔ CaCO3 ↓
together with
CO3 2- + Ca2+ = CaCO3 (colloidal) )

The above processes and the equivalent ones which occur in biological
organisms and which consume or produce CO2, it should be noted, are at
best, in the real world, only partially reversible.

They are best thought of as being completely irreversible since

the inorganic carbon chemistry of the sea can be dominated by the rate
controlling influence of dissolved organic matter.
(Cf. P. J. Wangersky [1B] [3a-1]]).

[It should be noted that P.J. Wangersky

correctly identified the critical role played by
the binding of dissolved organic matter to
CaCO3 surfaces as being a likely prime rate
control mechanism of the marine carbon
cycle;
this is why the fulvate status of the sea and
natural waters can act as a major
determinant of the carbonate cycle of the sea
and allow the sea to be a source of
anthropogenic CO2 injection into the
atmosphere ; a wider recognition of the
importance of the late Professor P.J.
Wangersky’s discovery is merited since this
was of major relevance not only to marine
science but also to climate science].

[The above scenario also means that kinetic isotope effects will exist
which cause, e.g. a depletion in the amount of 13C in the CO2 produced
which may be injected into the atmosphere].

Fulvate could potentially achieve regulation of the amount of

CO2 in the atmosphere via seawater (the major buffer of CO2) by
a mechanism which centers on the inhibition of sparingly
soluble CaCO3 precipitation.
It should be noted that a pressure horizon which is supposed to
exist at a depth below which these particles can re-dissolve and
is thought to allow for a carbopnate-based pH buffer system of
the sea, could not be detected at any point in the N. Atlantic at
six positions ranging form 08o00'N 19o58'W to 23o 14'N 52o 38'
W [P. Wangersky [3a-1] [Limnol & Oceanogr 1972 17 (6) 960-962].
This rigorously executed survey failed to find any trace of this
horizon. This indicated that the supposed carbonate buffer
system of the sea was, at least under the conditions present in
the N. Atlantic at the time of this survey, a purely hypothetical
textbok-only concept. These results support the hypothesis that
fulvate and not carbonate provides multifunctional carbon cycle
and seawater homeostasis regulation].
A conceptually different process involving CaCO3 solid phases
in seawater is where the formation of non-precipitating colloidal
amorphous CaCO3 particles can, in principle, form a dispersed
carbon sink with long-term stability. The formation of such
CaCO3 solid phases is also more likely to be kinetically
controlled rather than being thermodynamically controlled.

The detailed mechanism of kinetic control of the seeded

crystallization of CaCO3 (calcite) was investigated by in vitro
methods by the Aberdeen U. polysaccharide group in the 1980s;
the results obtained in these studies were believed to be relevant
to a fuller understanding of the mechanism of marine carbonate
cycling. (These results have now been replicated by a number of
laboratories worldwide [3a] which confirms the notion that the
ability of the formation of CaCO3 to regulate CO2 is facilitated
by the outstanding ability of fulvate to inhibit CaCO3
crystallization and that this phenomenon plays a pivotal part of
the mechanism of anthropogenically induced climate change
[3a]).

CaCO3 formation and precipitation in the sea and other natural

aqueous solutions may be regulated by the outstanding ability of
humic polymers to bind to CaCO3 crystal surfaces and change
their thermodynamic properties (cf. the groundbreaking papers
by K.E. Chave & E. Suess and P. J. Wangersky [3a-1][1B]]
papers which might be considered the origin of the organic
matter (fulvate) marine and CaCO3 control system).
This means that various thermodynamically-determined
processes, e.g. Henry’s Law, are not, in any straightforward
way, applicable to the uptake and release of anthropogenic CO2
by the sea.

Considerable confusion appears to exists at present amongst the

scientific community regarding how thermodynamic models
which seem partially valid can be employed to model how
marine CaCO3 and CO2 pools affect the atmospheric levels of
CO2. Part of this confusion relates to if and how the 13C, 12C and
14
C isotopes could become fractionated by abiotic processes in
addition to the usual biotic processes and what is the level of
confidence to be accorded C isotope evidence that fossil fuel
derived CO2 greenhouse gas is driving the current global
warming and climate change.

1c. The humic matter particles present in the

atmosphere may modulate the crystallization of ice
crystals involved in the nucleation of cloud formation
and rainfall and thereby influence climate and global
warming. Humic matter may also modulate the rate of
formation of ice crystals on the Earth’s surface during
glaciation and increase the rate of deglaciation by
acting as a dark matter solar energy trap.

The major potential influence which the formation of

clouds and induction of rainfall exerts over climate,
climate change and global warming may, in part, be
determined by the presence of humic matter particles in
the atmosphere which, could in principle, affect the rate
of formation of the ice crystals which are believed
normally to act as phase change nucleation agents
required for cloud and rain formation. Although the
formation of ice crystal particles is normally temperature
driven, the mechanism of the influence of inhibitors on
this crystallization process is thought not intrinsically to
differ from that of the supersaturation-driven
crystallization of inorganic solids such as CaCO3
crystals, which suggests that both types of crystallization
processes may be modifiable by the humate/fulvate poly-
carboxylated polyanions (which are designated HULIS
when they occur in the atmosphere).
The ability of HULIS type poly-carboxylated
biopolymers to modulate ice crystal nucleation in the
upper troposphere has been recently confirmed by
in vitro studies which used a simple citric acid model of
HULIS; this work (by E.J. Murray et al. [2e] was
apparently an attempt to confirm that the mechanism of
cloud formation and climate change could be subject to a
possible human input by way of anthropogenic influence
on the ubiquitous atmospheric poly-carboxylated
humate/fulvate system.

2. The putative major organic polyanion

CO2 ‘servo control systems’ of the soil
and the sea

The most common type of organic (humus-stored) polymers

(this accounting for a considerably larger amount of carbon than
occurs as CO2 in the atmosphere) in the biosphere contained
arrays of poly-carboxylate (-C(O)O-) anionic plus -C(O)(CH2)n-
groups which seem to be specifically ‘designed’ to provide in
the sea a chemically analogous buffer system to that afforded by
a conceptually similar and much more-studied system of anionic
poly (uronate) saccharides, which occur at biological cell
surfaces including at the surfaces of the vasculature in humans
and other higher animals where they act to protect and buffer the
blood serum multi-inorganic element containing, seawater
mimetic, aqueous solutions [4]. This system seems to have been
carefully conserved throughout animal evolution [4a].
2a. The Concept of the Degree of Supersaturation (Ω ) of
Sparingly Soluble CaCO3 Phases
which can act as a critical determinant of supersaturation of
CO2 in the surface layers of the sea
The degree of supersaturation (Ω ) of CaCO3 in the sea like, that
in animals and algae etc., seems, to a large measure, to be
controlled kinetically and is not thermodynamically determined
[5]. This idea accords with the notion that the Earth’s biosphere
(including the atmosphere) somewhat resembles a living
organism which is expected to behave, not as a
thermodynamically-controlled equilibrium system [cf. 3a], but
as an ‘supercharged’ energy system allowing energy allowing its
application in a rapid and in a seemingly ‘directed’ manner.

3. Formation of Precipitates from Supersaturated Solutions

is Normally a Seeded Process
Seed particles capable of growing inorganic crystals e.g. of
CaCO3 occur both in the sea and in animal tissues. The CaCO3
seed crystal inhibitor system in animal vasculature is believed to
consist of anionic poly uronic acid containing polysaccharides
which prevent the formation of pathological plaques of insoluble
Ca salts at blood or urinary vessel walls [2]. In the sea, the
analogous poly-uronic acid fulvate plus exuded algal anionic
polysaccharides [cf., 2a] are likely to act similarly and constitute
a homeostat control system for the formation of CaCO3 crystal
precipitates. This creates the largest long-term stable sink for
atmospheric CO2.
3a The glycosaminoglycans of animal extracellular
space and cell surfaces putatively mimic the fulvate
part of the humus/humic acid soil and seawater
buffer system of the sea. Both of these poly-
carboxylated-polymers can act as multi-inorganic
element buffers and crystal surface active site
capping agents.

The fulvates apart from their putative role for the ‘servo
-control’ of the precipitation of CaCO3 from (the surface
layers of) the sea, seem to resemble the much-more-
researched animal glycosaminoglycans by being
functionally en-tuned (via their possession of complex
heterogeneous organic multifunctional ligand sites
(including anionic cationic and non-ionic binding sites))
to enable them to buffer the usually complex multi-
inorganic ion compositions present in the sea by a
process of simultaneous sequestration and release of
numerous types of inorganic ions.

Research into the binding of inorganic ions to

glycosaminoglycans shows that both cations and anions can
simultaneous bind to these formally highly negatively charged
polyanions which, while they can use a straightforward
electrostatic mechanism to attract positively charged counterions
(the Manning process), obviously cannot employ this kind of
simple electrostatic attraction to achieve the observed binding of
negatively charged anions which seem to bind efficiently to the
animal glycosaminoglycan polyanions via a phase change
determined non-thermodynamic-engulfment processes which in
turn depends, it is believed on the outstanding flexibility of the
natural poly-carboxylate ligand systems to alter their
conformations so as to facilitate binding of a wide range of
anions and also of different types of colloidal inorganic particles
(ions of either charge) or (cf. Borges et al. [2c]) to crystal
surfaces. The latter include the active growth centers of the
nanoscale seed particles responsible for the growth of CaCO3
crystals.

3b The Role of Marine Fulvates as CaCO3 Crystallization

Inhibitors

The anti-crystal forming active seed crystal growth site

capping inhibitor polyanionic fulvates present in the sea,
even at a relatively small concentration of ca. 0.2-2.0 ppm,
similar to those which have been reported to occur in
modern seawater (but this value may be much greater near
the surface microlayer), can completely inhibit, or act to
greatly diminish the rates precipitation of CaCO3 phases,
and even, putatively, in some circumstances, may also cause
a reversal (peptization i.e. the formation of colloids) of this
process, as well as allow the control of the rates of the
growth and dissolution of the various other sparingly soluble
salt crystalline phases which might co-exist in seawater
together with Ca2+ and the carbonate system of anions.

The abovementioned (in section 3a) glycosaminoglycan

polyanion phase change multi-purpose cation plus anion plus
inorganic particle inhibitor system can also describe the
inorganic ion and particle binding activities of fulvate anions,
which (perhaps, partly by acting in concert with a previously
proposed (e.g by Sillén, cf. R.M. Garrells & R.A. Berner [3b]])
Si-based clay mineral marine multi inorganic ion buffer system
which can attach to the fulvate), seems specifically ‘designed’
(perhaps by pre-biotic processes akin to evolution) [e.g. similar
to that discussed by D. Grant et al., in Medical Hypothesis 1992
38 49-55] to allow for the creation of bio-friendly aqueous
solutions which include the long-term stable systems of multiple
inorganic ion solutions which occur in the sea.

These organic buffer systems are themselves produced and

destroyed by a separate homeostasis system can continue to act
in concert with the terrestrial soil system over geological time-
scales.
But human activities are now putatively altering this terrestrial
system markedly and indirectly as part of this process, are also
altering the marine fulvate buffer system.

4. Metallomic ‘all-element’ arrays are assembled on

the surface of the seawater and seawater mimicking
buffer polyanions
Evidence from full element analysis determinations by mass
spectrometetry shows that both the seawater and animal tissue
polyuronate organic polymer buffer molecules can be classified
as “all-element” inorganic element matrices. These elemental
compositions can be used to construct linear log-log inorganic
element plots. This applies to seawater, human blood serum (cf.
Fig. 1of ref. [3]), human hair and nails and also geologically
deposited fulvate).
The natural polyanion ligand matrices tend however to contain
systematically larger amounts of those inorganic ions which
occur in least abundance in their natural bathing solutions which
points to a general mechanism of selective sequestration of
ultratrace elements; this phenomenon occurs in an analogous
manner for the anionic polysaccharides associated with animal
and algal cells as well for the geological fulvates. This indicates
that the natural poly-carboxlate organic polymer polyanions
behave in their parent aqueous solutions like specialized
antennae collectors of low abundance essential nutrient elements
(which include some elements, e.g., the rare earths, which have
not yet been confirmed to be required for the nutrition purposes
of commonly studied species).

In summary of this section: Similar log-log inorganic

composition relatedness profiles can be demonstrated for multi-
inorganic element mass spectroscopic determined content data
for a putative ‘parent’ multi-inorganic solution system :-
seawater, which is replicated in various daughter matrices e.g.
blood serum/animal polysaccharide [4] and marine algal
polysaccharides and geological fulvates.
---------------------------------------------------------------------------

4a. Animals have evolved improved poly-carboxylate-

types of putative inorganic salt solution buffer systems
The part of this animal polysaccharide, putative buffer system provided
by heparan sulfate, has apparently been strictly conserved throughout
animal evolution [4a] having being present from the start of this evolution
(in the sea), in which environment it specifically could have evolved from
a precursor less effective bacterial-wall-type glucuronic acid containing
polyuronatesby the evolution of an isomerase enzyme which
biosynthesizes a more flexible iduronate uronic acid based ligand system
perhaps in order to more closely mimic the hyperactive inorganic ion
homeostasis and CaCO3 / HCO3-/CO2 control systems of the sea which
putatively could have been, and continues to be afforded by the marine
fulvate organic polyanion system which is known to continue to exist in
the sea at the present there.

5. How the anthropogenic increase in CO2 can be

linked to anthropogencially altered fulvate balance of
the biosphere
Increased fulvate (e.g. produced from anthropogenic
degradation of terrestrial soils) is predicted in this model to
cause an increase atmospheric CO2 by entering the proposed
marine fulvate-based inorganic substances homeostasis system.
This idea can be looked on as an extension of the idea that
seeded formation controls CaCO3 formation in shallow seas
(cf. the J.W. Morse et al. discussion of the Bahama Bank CaCO3
precipitation system [6]).
In support of the present hypothesis that fulvate controls the
anthropogenic augmentation of atmospheric CO2, is the
circumstance that the degradation of terrestrial soils has been
greatly increased since the industrial revolution, and most
especially in recent years, and indeed this is thought to be of a
more serious environmental concern than is the loss of tropical
rainforests [7].
A putative anthropogenic 7000 years old atmospheric CO2
increase detected in the ice core evidence by Ruddiman [8]
could, like the present-day much greater un-natural increase in
atmospheric CO2 have been caused by an un-natural topsoil
degradation which is an expected consequence of terrestrial soil
degradation caused by deforestation, agriculture riverine runoff
and fulvate enrichment of the sea.

6. In vitro experiments confirm that terrestrial soil

derived fulvates are extremely potent inhibitors of
CaCO3 crystallization [3a].
Indeed the fulvate inhibitors considerably outperform all man-
made inhibitors (e.g. the bisphosphonates) which are widely
used as anti-calcification agents e.g. in detergent and toothpaste
formulations.
The ability to control the rate of CaCO3 crystallization a
circumstance which changes how the exchange of CO2 occurs
between the sea and the atmosphere therefore also effectively
could be responsible for the current anthropogenic increase in
atmospheric CO2 and the resultant global warming and climate
change produced as a result of this.

6a. Possible relevance to global warming of putative fulvate

inhibition of methane hydrate clathrate formation
The ability of natural poly-carboxylated polyanions to inhibit
the seeding of the formation of sparingly soluble crystals and
the precipitation of CaCO3 from the sea could apply equally
well to the formation of CH4 hydrate clathrate crystals (e.g.
in deep waters). This idea was suggested by C.C. Gryte [2d].
This scenario points to a possible role of the putative
intensive agriculturally determined anthopogenic alteration
in or abundance and/or ‘microstructure’ of the marine poly-
carboxylated fulvates which may perturb not only the carbon
cycle afforded by CaCO3 precipitation,
but also that afforded by CH4 hydrate clathrate crystallization
(e.g. in the deep sea) so as to result in an increased emission
of both CO2 and CH4 greenhouse gases as an eventual
outcome of agriculturally-promoted global topsoil
degradation.

7. What needs to be done to stop global warming and climate

change
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 previously
identified need for an enforcement of a diminution of the
burning of fossil fuel, biomass, cement manufacture, and
municipal/industrial waste incineration, also to halt the
increasing rate of anthropogenic degradation of the topsoil and
the resultant increase of associated runoff of terrestrial fulvates
into the sea.
References
[1] Some Possible Mechanisms of (Dissolved) Organic Matter
Inhibition of CO2 Uptake by the Sea
Preamble
The conventional model of how anthropogenic CO2 affects the sea includes the
hypothesis that buffering of the sea is achieved by the carbonate buffer system alone
and that the precipitation of CaCO3 in the sea can be represented by the equations
Ca2+ + HCO3- → H+ + CaCO3 ↓
in which the formation of CaCO3 generates H+
cf. M. Frankignoulk J Mar Syst 1994 5 111-118 and e.g.
T. Takahasi
The fate of industrial carbon dioxide
Science 2004 305 352-353.
(This does not consider the possibility that part of the buffer activity of the sea might
arise from the presence of other potential inorganic inorganic e.g. Si- containing ions
and the ubiquitously presence in the sea of dispersed and dissolved organic matter).

Different, putatively more realistic models are now proposed:

1A. PHYSICAL BARRIER MECHANISM

Sea surface microlayer CO2 exchange barrier hypothesis of
inhibition of CO2 uptake by sea

Cf. M.L1. Calleja et al.

Evidence for surface organic matter modulation of air-sea CO2 gas
exchange
Biogeosciences 2009 6 1105-1114

1B INHIBITION OF CaCO3 FORMATION & CaCO3

RE-DISSOLUTION MECHANISM
The crystallization (precipitation) of CaCO3 has been found
to be highly sensitive to organic substances which occur in
the sea which are able to block this phase change process
Cf. e.g., E. Suess
Interaction of organic compounds with calcium carbonate-I. Association
phenomena and geochemical implications
Geochim Cosmochim Acta 1970 34 157-168.

The dissolved organic matter in the sea also, by the effect

of its adsorption at crystal surfaces also prevents the re-
dissolution of CaCO3 in deep water.
This abolishes the snow line as confirmed by an extensive
survey conducted over a wide range of locations by

P.J. Wangersky Limnol Oceanogr 1969 14 929-933

[3a-1].

The N. Atlantic Ocean was found (in contradiction of

traditional oceanographic principles established in the
nineteenth century by Sir J. Murray) to have a similar
number of CaCO3 particles per unit volume present at all
levels of the sea (a large number of samples were
obtained at levels up to ca. 5000 meters depth). The
carbonate based at depth pH buffering and the long term
C recycling system of the sea had by 1969 apparently
become completely blocked by the putative anthropogenic
dissolved organic matter (fulvate) adsorption mechanism
(cf K.E. Chave & E. Suess Limnol Oceanogr 1970 15 633-
637
[3a-1]).

A multidisciplinary research activity headed by WF Long

and FB Williamson at Marischal College, University of
Aberdeen U.K.,
[cf. publications up to 2003 listed at
www.abdn.ac.uk/~bch118/publications2003march.doc ]
included studies using an experimental method developed
by G.M. Nancollas (cf. Adv Colloid Interface Sci 1979 10
215-252) which identified poly-carboxylated anionic
substances such as marine algal polysaccharides, animal
glycosaminglycans and a range of other substances
including soil derived humic matter fractions as
demonstrating potent inhibitor effects on the seeded
crystallization of CaCO3 (calcite) for which the latter type
of polymers (which constitute the largest pool of organic
carbon in the biosphere) were found, by far, to be the
most active, a circumstance which could further suggest
that this property might also be of major fundamental
relevance to the fuller understanding of the global carbon
cycle and hence could determine the rate of increase of
atmospheric greenhouse gas CO2 in the atmosphere*.

[1]
Cf., D. Grant
Climate Change
web. scribd.com/doc/44604504/Climate-Change
New Thinking On Climate Change
web. scribd.com/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-IIII
web. scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystallizn-II
and other papers listed are web. scribd.com/Newdeersi/documents.

Cf. D. Grant Review of current progress in understanding of the chemical structure of

humic substances.
web.scribd.com/doc/34142473/2an-assessment-of-Progress-in-Studies-of-the-
Chemical-Structure-of-Humic-Substances-Revised

[1-1] D. Grant Nature 1977 270 709-710

[A now obsolete notation for the 1H nmr chemical shift scale was used in
this paper (τ which is 10-δ )]

cf. also
[1a] D. Grant et al., Biochem J 1989 259 41-45;
[Cf. also, for evidence and related discussion of how the
mechanism of counterion binding to the anionic
polysaccharide heparin is also likely to be a phase change
determined process see:
ibid., 282 601-604; 283 243-246; 287 849-853].
The above studies suggested the following hypothesis
The humic matter hypothesis of marine buffer provision
If the sea were a purely a solution of
inorganic ions
it should, in principle, be able act as a
solvent for all of the anthropogenic CO2 in the
atmosphere.
That it does not do so, it is now suggested, arises
principally because the sea contains as major constituents
(dissolved plus colloidal size dispersions of) natural poly-
carboxylated organic polymer molecules especially those
classified as humates and fulvates.
It is further pointed out that these molecules are so chemically constituted
so as to enable them to perform multifunctional buffer actions. These
include the regulation of the pH, the buffering of long-term stable
concentrations of dissolved major, trace and ultratrace inorganic ions
present in seawater as well control the rates of nucleation and growth of
CaCO3 , BaSO4 etc. crystals. This ability to control nucleation of the
formation of sparingly soluble solids can determine the individual degree
of supersaturation of individual sparingly soluble phases which might
otherwise in the absence of an inhibitor of the kinetics of their
crystallization, precipitate out from seawater. The humic polymer system
is now proposed to be responsible for a major part of the process by
which the sea attains its geological time-scale constancy of inorganic ion
content (including pH) although this is thought now to be only
approximate constant of over millions of years, it is thought normally to
achieve an almost absolute constancy over shorter periods of time.

An apparently similar ‘primitive’ chemical system buffer

dependent mechanism to that which exists in the sea is
putatively afforded by the humic poly-carboxylate polymer
system for the regulation of the composition of dissolved
inorganic ions also exists in the biological fluids of animals
where it is determined by humic polymer mimetics, the poly-
carboxylated polysaccharides [1] [2].

The degree of supersaturation (Ω ) of CaCO3

in both seawater and animal extracellular
fluids e.g. human blood serum, is putatively
determined almost entirely by the amount
and types of the poly-carboxylated-
polyanions which can act (as shown by in
vitro experimentation) as very potent crystal
seed nuclei growth blockers in these aqueous
solutions.

The presence of ‘scale-inhibitor’ substances encourages a state

of supersaturation to be set up in natural aqueous solutions
which, under unprotected conditions in the absence of chemical
regulators, would grow a range of inorganic crystal phases.
The crystal growth blockers are of especial importance for their
ability to interfere with the seeded mechanism by which the
precipitation of the sparingly soluble CaCO3 crystalline or
amorphous phases occurs.

The circumstance that CaCO3 supersaturation (Ω) could

principally be determined by the efficiency of fulvate
{anionic poly-carboxylate (–CO(O)-) plus –C(O)[CH2]n)-
(cf. D. Grant Nature 1977 270 709-710, cf., D. Grant et al.
web. scribd.com/doc/41263479/New-Thinking-on-Climate-
Change-Abrrev.-III) inhibition of the CaCO3 crystallization
and related processes, now allows for a fuller understanding
to be achieved of the ability of seawater to control the
atmospheric CO2 content as well as how this can be critically
influenced by anthropogenic mechanisms which can alter the
amount of this type of natural poly-carboxylated organic
polymer, CaCO3 crystallization modulator system present in
the sea.

[2] D. Grant et al., Medical Hypotheses 1992 38 49-55

Cf., D. Grant et al. Biochem J 1989 259 41-45
And other papers on related topics listed at
web.abdn.ac.uk/~bch118/publications2003march.doc

cf. [2a] A. Pentecost

Significance of marine algal calcification inhibitors in
the global carbon cycle
Thalassas 2004 20 (1) 45-49.
Cf.
[2c] F.T. Borges et al. (Kidney Int. 2005 68 1630-1642) have
established that specifically microstructured poly-
carboxylated polysaccharides (heparan sulfates) are
synthesized by the kidney in order to cap-off any calcium
oxalate seeds which would otherwise grow into large tissue-
damaging crystals.
[This highly evolved use of poly-carboxylated polysaccharides
for the modification of the rate of precipitation of sparing
soluble Ca salts in animals is suggested to ultimately derive
from the existence of a similar poly-carboxylated organic matter
system in the seawater in which the ancestors of humans
originally evolved and which enabled the control of the
formation of sparingly soluble Ca salts and which currently
continues to exist in the modern seas for the same purpose].

cf. [2d] C.C. Gryte Ann New York Acad Sci 1994 78 323-329
These authors likened the seeded crystallization of CH4
hydrate clathrates (e.g. that which occurs in the sea) to
calcium oxalate which are known to be inhibited in animal
fluids by the poly-carboxylated organic polymer extended
chemical family of
which fulvate is also a member which could suggest that the
formation of CH4 in the marine environment could also be
determined by the fulvate status of the sea;

cf. [2e] B.J. Murray

Inhibition of ice crystallization in highly viscous aqueous
organic acid droplets
Atmos Chem Phys 2008 8 5423-5433.

Cf., Nature Geoscience 2010 3 233-237

[This paper seems to allude to how humic matter in the
atmosphere might affect climate via its ability to inhibit ice
crystal formation].

[3] H. Haraguchi J Anal At Spectrom 2004 19 5-14

This paper reviews the relatedness of seawater and human blood
serum etc. from the perspective of the new science of
metallomics,
That animal polysaccharides similar to those at blood vessel
walls contain seawater-like inorganic element contents has been
briefly discussed by D. Grant et al.
in Biochem J 1987 244 143-149
and more fully in
Cf. web. scribd.com/doc/26994439/Publication-2-Web.
For examples of the kinds of log log plots mentioned in the text
see
web.scribd.com/doc/38734723/WRL0526
also
web.scribd.com/doc/34178257/WRL1873-with-Fig

[3a] D. Grant et al.,

(University of Aberdeen archived research manuscript)
available at
web.scribd.com/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-III

Cf, also
E.g. P. Zuddas et al. Chemical Geol 2003 201 (1-2) 91-101;
A.R. Hoch et al., Geochim Cosmochim Acta 2000 64 (1) 61-72;
W.P. Inskeep P.R. Bloom Soil Sci Soc Amer J 1986 50 1167-
1172; cf., M.E. Gunthorpe C.S. Sikes Ohio J. Sci 1986 86
106-109; J.R. Morse Rev. Mineralogy Vol. 11 Carbonates in
Mineralogy and Chemistry Ed. R.J. Reeder Mineralogy Soc
Amer p.227-264;

E. Suess
Interaction of organic compounds with calcium carbonate-I.
Association phenomena and geochemical implications
Geochim Cosmochim Acta 1970 34 157-168;
[3a-1]

P.J. Wangersky
Distribution of suspended carbonate with depth in the ocean
Limnol Oceanogr., 1969 14 929-933
Cf. ibid., 17 960-962

Cf. K.E. Chave E. Suess

Calcium carbonate saturation in seawater: effects of dissolved
organic matter
Limnol Oceanogr 1970 15 633-637

Cf. also
J.A. Leenheer M.M. Reddy
Annal Environ Sci 2008 2 11-25
Cf also
F. Neuweiler et al., Geology 2003 31 (8) 681-684

[3b]
L.G. Sillén
How have sea water and air got their present compositions?
Chem Brit 1968 3 (7) 291-297
{This paper suggests that the previously held view that that the
pH etc. of the sea is regulated by the carbonate balance system
is incorrect; a more accurate model might be based on a more
complex clay mineral pH buffer system but Sillén also noted, on
p.294 of this article, that while it was certainly highly unlikely
that the real system of sea water-sediments-air was actually a
true equilibrium, the author asks us to believe that “the
equilibrium model may be sufficiently similar to the real system
to make a comparison interesting and a useful first
approximation to the real system”}.
Cf., R. M. Garrels R.A. Berner
The Global Carbonate-Silicate Sedimentary System—Some
Feedback Relations
p.73-87 in
Biomineralization and Biological Metal Accumulation,
Ed. P. Westbroek and E.W. de Jong 1983
D. Reidel Publishing Company.

It can be argued that the current debate about the mechanism of

climate change lacks focus because it seems centrally to demand
an improved knowledge of how the sea behaves e.g. in regard to
CO2 buffering, and this requires a kinetic model such as the
poly-carboxylate polysaccharide-based buffer system that is
proposed in the present paper will allow progress to be made in
designing appropriate procedures for ameliorating
anthropogenic input of CO2 into the atmosphere. This system is
suggested to resemble the poly-carboxylate polyanionic buffers
which exist in the seawater-like extracellular fluids of animals.
The current knowledge database available on these animal
polyanionic buffer systems could allow an improved insight to
be obtained into the real buffer system which exists in the sea.

[4]
(E.g. cf.,
W.F. Long F.B. Williamson et al. researches updated in web.
scribd.com/doc/26994439/Publication-2-Web and
ibid/34178257/WRL1873-with-Fig)
[The original ‘primitive’ kind of poly-carboxylate-organic
polymer (evolved into a polysaccharide-core type) of anionic
biopolymer, homeostasis systems have now evolved yet more
complex functions (e.g. for growth factor control during wound
healing). But they seem also to retain their more ‘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 the blood circulation
includes complex inorganic filtering/recycling functions of
specialized organs which, however, also continue to use anionic
polysaccharides such as heparan sulfates as part of their modus
operandi). Such a continued-essential-for-life osmoregulator
function for the anionic cell surface poly-carboxylated (which
have been enhanced by sulfation) anionic polysaccharide
systems comes from the discovery that for fifteen species of
aquatic invertebrates, the amounts of heparan sulfates and
related anionic polysaccharides present in their tissues is
apparently determined by an exact mathematical relationship
between this amount and the salinities of the aquatic habitats of
these organisms [H.B. Nader et al. 1983 Comp Biochem
Physiol Pt B Comparative Biochem 1983 76 433-436]. These
findings tend to support the theory that the multicellular animals
evolved initially in the sea (e.g. some 109 years BP) and also that
the early animals and possibly also their non-animal
evolutionary precursors evolved an improved inorganic and
crystal inhibitory system at their cell surfaces to mimic that
which was provided in the sea by the fulvate-type polyanions
which had likely existed in the seas from its beginning and
continue to provide therein the basic inorganic homeostasis
functions related to its inorganic composition at the present time
(and by inference also to control the atmosphere which was
created in the Early Earth to a significant extent by release of
biologically produced gases from the sea).

[4a] H.B. Nader et al., Carbohydr. Res. 1988 184 292-300

[This paper indicates that the heparan sulfate system has been
carefully conserved from the time of the evolution of the first
animals in the sea until the present time].

[5] Cf. the relevance of Henry’s law to the uptake of CO2 by the
sea is central to the current debate about the origin of the current
increase in atmospheric CO2 which is causing climate change. It
should be noted that Henry’s law applies strictly only to
equilibrium conditions (this means that the rate of uptake and
release of CO2 are equal) should not be expected to apply where
the solvent reacts with the solute. If, as seems likely, that the
CO2 system of the surface of the sea is kinetically and not
thermodynamically controlled then the rate of CO2 release from
the sea is controlled by such kinetics. If this involves, as is here
suggested, a dominant influence of the inhibition of the seeding
of CaCO3 solid phase formation, then this process will
determine the ability of the sea to act as a sink for CO2.
Control of seeding is then putatively the major control
mechanism of exchange of CO2 between the sea and the
atmosphere.
Cf., e.g. a recently accessed (at: web.nzace.org.nz/……internet
discussion, one of numerous such documents)
discusses Henry’s law in the context of the role of the seas in
provision of a sink for atmospheric CO2, notes that
“gases in our atmosphere exist in equilibrium with the sea”
It is now suggested that this statement is essentially wrong.
The CO2 in the atmosphere does not exist in a straightforward
reversible thermodynamically controlled equilibrium with the
CO2 in the sea. It depends instead on the fulvate control of the
seeded nucleation of CaCO3 crystallization and re-dissolution.

The Callendar, IPCC and/or Hansen models of global warming

proposes a dominant greenhouse gas climate warming forcing
effect of non-condensable CO2 rather than of condensable water
vapor (cf., this well-established theory is further supported by
computations reported by A.A. Lacis et al., Science 2010 330
356-359) but the continued upgrading of this theory needs to
address ideas advanced by informed skeptical scientific
opinions, including a possible re-evaluation of ice core data.

[5a] T.V. Segalstad [ESET Oslo] accessed from

web. geocraft.com/WVFossils/Reference_Docs/Carbon_cycle_update_Segalstad.pdf
Also available via web.co2web.info/
ESFV1.pdf; cf. also document ESFVO1
and the compilation of files which are critical of the Callendar, IPCC or Hansen
hypotheses re fossil fuel being the prime cause of elevated CO2 and global warming
listed at web.folk.uio.no/tomvs/esef/esef0.htm.
A criticism of the methodologies used to obtain the ice core historical atmospheric
CO2 data (which suggest that these were probably subjected to a sufficiently rigorous
scientific review before becoming widely accepted) is give in a paper
entitled
Z. Jaworowski T.V. Segalstad N. Ono
Do glaciers tell a true atmospheric CO2 story?
Sci Tot Environ 1992 114 227-284)
[This paper discusses the occurrence of super-cooled liquid water which could have
removed CO2 from the gas compartments analyzed; this occurrence of liquid at low
temperatures could putatively in part have been caused by the presence of fulvate in
the ice].
The first Segalstad article listed above draws attention inter alia
to the large unknown “missing sink” in the anthropogenic
carbon budget.
Segalstad negatively comments on the need for mainstream
climate models to employ a purely hypothetical “evasion factor”
limit on the operation of the supposed validity of Henry’s Law
concepts for modeling the buffering of atmospheric CO2 by the
sea.

The now-proposed humate control mechanism of rate limitation

of the carbon cycle (via the fulvate determined seed nucleus
activity regulation system of the abiotic soil and seawater
carbon cycle and CO2 marine buffer system) now seems to offer
a more credible explanation of how this “evasion factor”
activity regulator of Henry’s Law is set up in the real world, and
therefore offers a more convincing argument with which to
counter skeptical comments on the credibility of the IPCC etc.
arguments for the urgent need to curb anthropogenic CO2
emissions.
It should be noted that the possible kinetic control of abiotic as
well as biological utilization and emission of CO2 casts some
doubt on the present understanding of how 13C depletion in
fossil fuel can confirm the hypothesis that the combustion of
fossil fuel has led to a major augmentation of atmospheric CO2
and associated global warming,

[6] J.W. Morse et al. Geochim Cosmochim Acta 2003 67 (5)

2819-2828

[7] Terrestrial Soil Humus Degradation.

[It should be noted that soil organic matter (which includes
fulvate as a major fraction) is the largest pool of organic carbon
in the biosphere].
This organic matter pool which could directly produce CO2 by
biotic and abiotic processes (and also cause fulvate transfer from
the land into the sea) has become altered in a perhaps
fortuitously similarly annual rate of increase to that of the
combustion of fossil fuels, and increasing by an exponential rate
in recent years seemingly by the change in traditional
agriculture which has been going on process since the start of
the industrial revolution.
Cf.,
The web document from
World Resources Institute Washington USA
Feeding the World & Disappearing Land
web. wri.org/publication/content/8426
notes that prior to 1990 topsoil degradation had occurred in 38%
of croplands worldwide and that since 1990 losses have
continued to mount year by year.

Cf. also F. Pearce

Soils spoilt by farming and industry
New Scientist 16 May 1992 Issue 1821
[The global map of soil degradation reproduced in this article
resembles maps of brightness at night except that Africa shows
up much more in the soil degradation map].

[8] W.F. Ruddiman

Reviews of Geophysics 2007 45 RG4001;
doi: 10.1029/2006RG000207;
Cf. Climate Change 2003 61 261-293;
Scientific American, March 2005 48 et seq.
That the sea was the origin of the late Holocene injection into
the atmosphere is confirmed by the 13C ice core study
reported by of J. Elsig et al. in Nature 2009 461 507-510.

Postscript
A related state of affairs to the situation in which fully reversible
processes by which CaCO3 form in the sea are outwith those
which underpin conventional thermodynamic and chemical
equilbibria relates to how the Earth’s biosphere should be
viewed : is it a machine or a quasi-organism? It should be noted
that the conventional thermodynamic laws originated from the
study of physics and astronomy as well as machines such as
steam engines but was not achieved by way of studies of
biological systems. So it is not surprising that the original
formulation of the thermodynamic laws cannot be applied easily
to biological systems. Life and biological reaction mechanisms
are to a larger extent than is commonly realized, centered on
seeded processes which control rates. This allows control of
thermodynamic driving forces and essentially changes the way
these forces behave. An easily seen example of this is that the
evolution of living organism has resulted in increasing degrees
of complexity with the passage of time, in apparent
disobedience of the second law of thermodynamics which
requires that complexity of the sort present in living organisms
should always tend to decrease with the passage of time.
The use of the perhaps the rather at first sight bizarre idea
that the Earth is a kind of living organism (Gaia) is
suggested to be a helpful idea with which to construct
models of the sea and the atmosphere in order to predict global
warming and climate change.
The above selection of arguments which led to the belief that the
sea is the major source of atmospheric CO2 has been abstracted
from a separate document.

Footnote a
The term ‘heparanome’ was coined by J. Turnbull et al., cf.
Trends Cell Biol 2001 11 (2) 75-82;
for the role of metal ions in heparanome signalling see e.g.
T.R. Rudd et al., Carbohydr Res 2008 343 2184-2193; cf., Glycobiol.
2009, 19(1) 52-57.

*Because all of the data obtained, especially those relating to soil

and marine algal polymers were not fully published during the time
when this research (which was unexpectedly halted for what were
believed to be non-scientific reasons) was conducted and that such
data could be relevant to the ongoing debate about the mechanism
of possible anthropogenically induced climate change, the archival
database of research data held by the author which is possibly
relevant to this subject has now become, after discussion with the
former co-workers where this has been possible, the subject of
recent internet postings.

Apologies for any remaining spelling and grammatical errors.