Atmospheric-CO2-Induced Global Warming and Climate Change may be

Promoted by the Perturbation by Human Actions of a Carbonate Cycle

Delay Mechanism of the Sea Afforded by Dissolved Organic Matter

Transfer of Terrestrial Fulvate from Anthropogenically Degraded Topsoil into the

Sea may Increase Atmospheric CO2

This is a rough draft of a document in preparation, but because

it provides information of potentially great public interest it seems
worthwhile to post it at the present time on the internet
in this preliminary un-edited form

David Grant Ph.D. New Deer-Turriff AB53 6SX 2 Dec. 2010

Contents

Summary

1. Statement of a Hypothesis that

“Atmospheric CO2 is Determined by Marine Fulvate Status and its Origins”

2. References (including to Section 1)

3.
Fig 1. Comparison of the inorganic element contents of seawater with that of a
poly-carboxylate saccharide (heparin) [a commonly used model for
heparan sulfate the major extracellular and cell surface animal poly-
carboxylate polyanion system manager, the basis of the heparanome]

Fig. 1a Comparison of the seawater-like multi-inorganic element contents of Na

and Li commercial heparins

Fig. 1b Comparison of the seawater-like multi-inorganic elements in heparin and

geological fulvate

Fig. 1c Comparison of the inorganic element contents of seawater and

the Earth’s crust

Fig 1e Comparison of the inorganic elements in seawater and algal biomass.

4. Evidence from Comparison of the Global

Surface Warming and the Mauna Loa Atmospheric CO2 Year-on-Year
Variation Curve That Seawater Releases of CO2

Figs. 2 Comparison Between Atmospheric Carbon Dioxide Five Yearly Change,

Fossil Fuel Usage Five Year Change and Global Surface Warming Curve

4a Comparison of five year changes in atmospheric CO2 levels and

fossil fuel usage levels

4b. Discussion of major CO2 releases from the Earth’s surface heating and
cooling events

4c. The 13C Signature The C-13 Suess Effect

{Related to the Global Surface Warming Curve}
4c (8-1a2) Atmospheric O2, CO2 and δ 13
C measurements from aircraft

4c (8-1a3) Direct measurement of the δ 13

C signature of carbon respiration by bacteria
in lakes

5. Why does deglaciation lag behind increase in atmospheric CO2? (humic surface
effects?)

6. Human alteration of the bacterial population of the soil is also likely to be a major
mechanism of (humate- related) anthropogenic influence on global warming and
climate change

7. APPPENDIX
Archived Marischal College (M.C.) Manuscripts

7a.
Manuscript of a draft research communication from the former M.C. U.K. polysaccharide research
laboratory entitled:

INHIBITION OF CaCO3 (CALCITE) CRYSTALLIZATION BY HUMIC AND FULVIC ACIDS

7b.
Manuscript of a draft research communication from the former M.C. U.K. polysaccharide laboratory
entitled:

Humic Substances Inhibit Calcite Crystallization

Possible Relevance to Global Carbon Dioxide Balance

7b-1. Internet-reported research document containing information from manuscript

reproduced in 7a plus additional information
Humic Substances Inhibit Calcite Crystallization
Possible Relevance to Global Carbon Dioxide Balance
web/scribd/com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystallizn-II

8. Further references and comments

8a. L.G. Sillén. How have sea water and air got their present compositions?

8a-1 P.J. Wangersky Limnol Oceanogr 1972 17 960-962; ibid., 1969 14 929-
933

8b. Transparent Exudate Particles (TEP) at the sea surface

8c. Stable colloidal CaCO3 as a carbon sink in seawater

8d. What are Humic Substances?

8d-0. Possible roles of polyanionic substances in the evolution of life on Earth

The preferential adsorption of L-amino acids by CaCO3

8d-1 What is the Heparanome?

8e. Polymethylene-rich humates might offer a useful tool to combat global warming
and climate change
 8f. Further discussion of the Ruddiman hypothesis of late Holocene anthropogenic
global warming

8g. Further discussion of E. Suess and related contributions

Discussion of Selected Further References

8h. (8-0) P Falkowski : dominant role of the sea in atmospheric CO2 presence
8-0-1 P. Porcal et al. humic substances and climate change review
8-0-1-1 Xie J et al. CO2 adsorption by alkaline soils and its implication to the
global carbon cycle
8-0-2 D.G. Boyce DG et al., global phytoplankton decline over the past
century
8-0-2-1 M.D. Inglesias-Rodrigues M D et al. more CO2 from phytoplankton
8-0-2-1-1 A. Ridgewell and R.E. Zeebe Review of the critical role of CaCO3 in the
carbon cycle and the relevance of

8-0-2-1-1-1 The work of J.W. Morse et al., CaCO3 seeded precipitation studies
8-0-2-1-2
-1 J. Bolze et al., amorphous colloidal size CaCO3 particle formation

-2 M. Baghimejad J.B. Darymple Role of colloidal CaCO3 particles in

calcareous soils

-3 Z. Sadowki et al. Role of surfactants in regulation of amorphous

CaCO3 particle assembly

-4 The Work of G.H. Nancollas

-5 O. Bernard O et al. report

-6 Aberdeen U., M.C. papers on calcification mechanisms

8-0-2-1-2-6-1 Example of animal servo-feedback synthesis of specific

poly-carboxylate anionic polysaccharide seed crystal blocker for the
inhibition of kidney calcification

-7 E. huxleyi polysaccharide production

8-0-2-1-2 -8 The work of E.W. de Jong et al.

31
8-0-2-1-3 P NMR studies of cell wall associated calcium phosphates

8.0.3 Discussion of a paper entitled: “180 years of atmospheric CO2 gas analysis by
chemical methods”

8-1-0 D. Frank D et al., Study of ice cores from 1050 -1800

8-1 L. Endersbee ocean temperature vs. atmospheric CO2

8-1a Degradation of soil (international data)

8-1-1 Fossil fuel usage data; Atmospheric CO2 ; Keeling data; Ice core data
(used for construction of Figs. 2)

Suggested ‘landmark’ book

James Hansen
“Storms of My Grandchildren The Truth about the Coming
Catastrophe and Our last Change to Save Humanity”
8-1-1-1 Discussion of Figs. 2

8-2 B. Bond-Lamberty & A. Thomson Temperature-associated increased in the

global soil respiration record

8-3 D. Banerjee & H.W. Nesbitt dissolution of birnessite by humate

8-3-1 S. Bélanger et al. Photomineralization of terrigenous dissolved organic matter

in Arctic coastal waters 1979-2003

8-3-1-1 H. Fischer et al., ice core records of atmospheric CO2 around the last three
glaciation terminations

8.4 E. Druffel et al., Accelerator m.s. spectrometry for radiocarbon measurement

in support of carbon cycle research

8-5 W.F. Ruddiman The early anthopogenic hypothesies

Cf., J. Elsig et al. reinvestigation of δ 13C from late Holocene wood burning
(cf. 8-7-4)

8-5-1 A methane-based time scale for Vostok ice

8-5-2 Rapid climate change events following asteroid strikes

8-5-3 The Milankovitch theory of eccentricity, obliquity and precession of Earth’s

orbital related variation of received solar radiation warming

8-5-4 Role of water vapor as a greenhouse gas

8-5-5 Climate Change 2007: Working Group I: The Physical Science Basis
Aerosols

8.5.5.1 D. Grant (internet article) The Possible Role of Nucleation of Phase

Changes as the Dominant Rate Controlling Process of Anthropogenically
Induced Climate Change

8-5-5-2 S.D. Kaspani et al., Increase in black carbon concentration since

industrialization from a Mount Everest ice core

8-6 Other scientific sites accessed ‘at random’ which discuss climate change
models

8-7 Evidence from isotopic composition of atmospheric CO2 of the relative

importance of oceanic and terrestrial biosphere exchange mechanisms for
removal of CO2 from the atmosphere

8-7-1 B.D. Mario M.B. McElroy Isotopic composition of atmospheric CO2

inferred from carbon in C4 plant cellulose

8-7-2 Phosphonate herbicides and laundry detergents

8-7-3 F. Joos et al., Calcite compensation and late Holocene

CO2 surge

8-7-4 J. Elsig et al., Stable isotope constraints on Holocene carbon cycle

8.7-5 Coral reefs

8-7-6-0 J.A.D. Dickson Fossil echinoderms as monitor of Mg/Ca ratio of
Phanerozoic oceans
R.V. Demicco et al., Model of seawater composition for the Phanerozoic
C. Borremans et al., Salinity effects of the Mg/Ca and Sr.Ca in starfish
skeleton and the echinoderm relevance for paleoenvironmental
reconstructions

-1 A. Pentecost non-calcifying species. Role of calcification inhibitors.

(Relevance to global carbon cycling)

-2 F. Neuweiler et al., Fulvic control of marine calcite nucleation under

suboxic conditions

-3 M.M. Thomas et al. Adsorbed organic compounds (including

polycarboxylated polymers) dramatically inhibit the dissolution rates of
carbonate minerals in natural waters

-4 Y. Kitano D.W. Hood Organic molecule inhibition of CaCO3

crystallization

-5 Z. Amjad et al., Kinetic inhibition of calcium carbonate crystal growth in

the presence of natural and synthetic organic inhibitors

-6 J. W. Morse Review of the surface chemistry of CaCO3 minerals in

natural water

-7
P.J. Wangerski This author proposed that the adsorption of surface-active
organic compounds adsorbed onto CaCO3 (calcite) surfaces leads to the
formation of calcified organic aggregates on the sea bed. This provides
for a built-in delay mechanism with a long time constant in the carbonate
cycle mechanism of the seawater.
The presence of surface-active dissolved organic matter in seawater
also prevents the attainment of reversible thermodynamic equilibria
involving carbonate, bicarbonate and CaCO3 in such
solutions
Dissolved organic matter (fulvate) can completely coat CaCO3 crystal
surfaces and thereby totally control the carbon cycle in the sea
including by abolition of the re-dissolution of CaCO3 in deep water, a
process, which in the absence of the adsorbed fulvates is normally
expected occur at a sharp pressure/depth horizon.
The above process are suggested to be of fundamental relevance to a
fuller understanding of the global carbon cycle.
The perturbation of the above processes by human fulvate or fulvate-
mimetic input into the sea is a probable mechanism by which human
actions can affect the climate via the perturbation of the marine carbonate
cycle and the knock-on effect of this which affects the amount of CO2 in
the atmosphere.

-8 K.E. Chave E. Suess The supersaturation of CaCO3 in seawater and

seawater-like solutions is achieved via an action of the organic matter
 present there which inhibits seeded precipitation. Mg2+ also behaves
similarly but is less potent than is dissolved organic matter as an inhibitor
of CaCO3 crystallization.

8-7-7 Mechanism of Rapid Deglaciation

Discussion of Hypothesis of Denton et al.
Possible Relevance of putative fulvate control mechanism to this
9. Cosmic ray hypothesis of the origin of global warming and climate change

Personal experimental background etc. to the hypothesis

Addendum : Problems with assessing scientific information between

different branches of science

Statement of a Hypothesis (which originated at the University of

Aberdeen, Scotland, U.K.) that
Atmospheric CO2 is Influenced by Marine Fulvate Status and its
Origins
The inorganic chemistry of animal extracellular fluids, of soils, and of the sea, seems
to be determined by approximately chemically similar type of poly-carboxylate
polyanion buffers systems.
Atmospheric-CO2-induced global warming and climate change may be
promoted by the perturbation by human actions of the carbonate cycle
delay mechanism of the sea (which had previously been identified by
P.J. Wangersky) which is afforded by the amount and type of dissolved
organic matter present in seawater.

It is now suggested that polyuronic and analogous poly-carboxylated polyanionic

systems determine the degree of supersaturation (Ω ) with respect to precipitation of
the various forms of CaCO3 and of other sparing soluble salts [1] which occur in
natural waters (cf. [1-0][1-2][2].
Both seawater and blood serum putatively attain their similar non-
thermodynamic, high mineral salt supersaturation levels because they
contain similar polyanionic inhibitors of a range of crystallization
processes which would, in the absence of such inhibitors, allow the
seeded precipitation of various kinds of solid inorganic crystalline
phases to occur from such solutions [1-2][2]. The existence of
correlated “all-element” [cf. 3] inorganic element contents in human
blood serum and seawater etc. [cf. Figs. 1] is supportive evidence for
the above hypothesis.

A further hypothesis, that anthropogenic perturbation of humic matter

[1-1][1-1a] might actually determine atmospheric CO2 levels was initially
suggested to the present author from a consideration of why both blood
serum and seawater contain correlated (50+) multi-inorganic contents as
well as being similarly supersaturated with respect to the precipitation of
CaCO3.

Fulvate, a major fraction of humic matter, and the largest organic chemical system in
the biosphere, is believed to contain random distributions of poly-carboxylated [-
C(O)O-] ligand sites; a sufficiently high proportion of such sites apparently occur in
an exactly correct configuration so as to allow relatively low fulvate abundance in
natural waters to completely control the inorganic chemistry of such waters; this
includes the formation of surface complexes on seed crystals which prevents CaCO3
(calcite) (or aragonite) precipitation and also slows or prevents the re-dissolution of
CaCO3 particles in deep water.
Both of these processes are putatively enabled by the same high-affinity fulvate
CaCO3 crystal surface adsorption phenomenon which enables fulvate to behave as a
central regulator of the inorganic carbon cycle
Fulvate in the sea and natural waters can however be augmented by an input from
agriculture in such a manner as to perturb the normal level of fulvate carbon cycle
blockage which existed prior to the Anthropocene.
This perturbation is suggested to augment of the degree of supersaturation (Ω ) of
CaCO3 and CO2 in the surface waters of the sea. This is suggested to tend to
increase the rate of emission of CO2 from the sea into the atmosphere.

Both seawater and (e.g. animal extracellular) solutions, it must be

stressed are approximately similar kinds of multi-inorganic-element
containing aqueous solutions.
Since both of these types of natural aqueous systems are also highly ‘non-
ideal’ it must be supposed that their multi-inorganic ion contents are not
achieved by the operation of thermodynamic constraints and must
therefore be kinetically determined. Nevertheless, while the natural
aqueous solutions clearly exist in a state of extreme non-thermodynamic
ideality, they also show a surprisingly similar degree of ‘non-
thermodynamically orderliness’. These solutions are not merely a random
collection of dissolved ions and molecules. (Cf. [3]). However this
degree of approximate similarity which exists between e.g. human blood
serum and seawater seems more akin to a fuzzy logic than one which has
a highly defined ‘quality-control’ product specification.

The similarity between the chemical composition of seawater and of

animal matrices allows approximately linear log-log inorganic element
inter-relation plots (e.g. that shown in Fig. 1 of ref [3] and also in Figs. 1
(vide infra) [the later from information obtained from M.C. UK]).
[It should also be noted that animal tissue polyanion ligand matrices and
geological fulvates apparently become preferentially enriched in those
inorganic ions which occur in the least abundance in their (presumed)
natural bathing solutions; such a preferential enrichment of the rarest
solute components seems to occur in an analogous manner for the various
poly-carboxylate polymers, viz. the anionic polysaccharides of animals,
algae and the humate/fulvate polyanions of natural waters and their
derived geological deposits. The natural extracellular poly-carboxylate
polyanions act as nutrient sequestration antennae which create a reservoir
of the biologically-required-essential inorganic nutrient elements; they
also control how solid phases of CaCO3 is assembled from these
solutions].

In part summary to the above text: similar log-log inorganic composition

profiles (e.g. illustrated by Figs.1) can be demonstrated for the multi-
inorganic element mass-spec.-determined contents of blood serum,
human hair, the anionic polysaccharides of animals, marine algal
polysaccharides and geological fulvates.
Various ‘daughter’ matrices appear to approximately replicate the
original multi-inorganic (Haraguchi [3]) element fingerprint present in
‘parental’ seawater.
These polyanionic systems provide potent anti-calcification ‘anti-scale
protection’ for natural aqueous systems.

Further evidence that seawater and its derived biologically-related fluid inorganic
element compositions associated with the poly-carboxylate polyanion ‘smart’ buffers,
is the lack of any marked lack of relatedness between the multi-inorganic element
contents of seawater and that the surface of the whole of the Earth’s crust, cf. Fig. 1c
which lies immediately below the soil organic matter humus layer.

Alternative Introductory Text

The ability of agricultural-soil-derived-fulvate to strongly inhibit the

seeded crystallization of CaCO3 (calcite) [1] appeared to be a related
phenomenon to the existence of a potent organic matter-dependent
calcification control system in the sea which had been indicated by earlier
reports [2b] which showed that CaCO3 particles became coated (most
typically becoming deactivated following saturation coating) with
‘dissolved organic matter’ [DOM] (this is likely to corresponds to fulvate,
the water soluble poly-carboxylated polyanion fraction of humic matter).
Marine dissolved organic matter, after its adsorption onto CaCO3 particles
apparently completely prevents their re-dissolution at depth. Dissolution
had been expected to occur at a critical depth since the solubility of pure
CaCO3 was known to increase under hydrostatic pressure, causing a
higher level CaCO3 particle ‘marine snow’ to descent in the water column
until at such a depth it was thought to be required by thermodynamic laws
to re-dissolve at a precisely defined critical horizon
The (fulvate)x- (CaCO3)y complex which, however, seems to be the
correctly formulated type of CaCO3 which exists in the sea, it should be
noted, has now become a different chemical substance with distinctly
different solubility properties from the laboratory-used form of CaCO3.
[Alternative put the operation of thermodynamic processes which apply
to CaCO3 are blocked by the rate determining reactions on which they
depend; they have become sterically hindred].

The ‘primitive’ inorganic ion homeostasis adopted from the start of the
evolution of animals in the sea and provided for by the poly-carboxylated
polyanionic systems of the animal glycosaminoglycans (poly-
carboxylated, sulfated anionic polysaccharides) behave analogously and
in a closely phenomenologically-related manner to the fulvate buffer
system of natural waters. It should be further noted, however, that all of
these buffer systems probably perform their homeostasis functions in
concert with small amounts of the other inorganic polyanionic systems
such as inorganic polyphosphate which occur at all cell surfaces
throughout biota [2a] and polysilicate [2c] which occurs widely on the
surface of the Earth and was more abundant in the pre-diatom sea in
which the ancestors of animals first evolved. (The natural fulvate buffer
systems of the sea may of course also act nowadays to some extent in
concert with the carbonate, borate and poly-silicate polyanion buffer
systems). In any case these buffer systems are known to be highly
effective for the stabilization of natural water Ω CaCO3 levels as well as
for the setting up of a characteristic type of multi-inorganic seawater
fingerprint which can still be recognized in the inorganic multi-element
fingerprints of the extracellular fluids of animals, a phenomenon which is
the most well-established for human blood serum [3].

The poly-carboxylate polyanions also are likely to control the value of pH

in natural waters.
[Cf. Injection of poly-carboxylated polyanionic sacharide buffer solutions into pH5.6
atmospheric CO2 affected distilled water immediately altered to pH value to 8.2].

The achievement of constancy of inorganic ion compositions in

poly-carboxylate polyanion buffered solutions can arise by a process of
sequestration and release of bound ions by these buffer molecules as well
as by the formation of high-affinity complexes between these buffer
molecules and the active crystal growth sites on solid surfaces (which
would otherwise act as nascent seed particles).

The poly-carboylated polyanionic buffers of biological fluids prevent the

animal organisms from being compromised by unwanted crystal growth
[2]. The prevention of the precipitation of sparingly soluble Ca salts is
obviously essential for the functional integrity of organisms.
Pathological calcification (putatively as a result of defective poly-
carboxylate buffer provision) is a well-known hallmark of degenerative
diseases and aging [2].

In vitro experiments indicate that modern marine and terrestrial soil

derived fulvates are extremely potent inhibitors of CaCO3 crystallization
([1] 4b. 7a,b]). Indeed they seem to be the most potent natural
calcification inhibitors known to science.
(Man made polyacrylates, however seem to be more active initially (cf.
Amjad et al., [8-7-6])).

The ubiquitous occurrence of such uniquely effective calcification inhibitors in the

largest class of organic polymeric material in the biosphere, seems to logically
demand that this unique ability must serve some fundamental role in the global marine
homeostasis and related atmospheric climate control systems.

This means (if the idea is further substantiated) that the degree of
supersaturation (Ω ) of CaCO3 (calcite) or (aragonite) in the sea like, that
in animals and algae etc. is kinetically controlled and is not
thermodynamically determined, at least not in any straightforward way.
This kinetic control is poly-carboxylate polyanion driven.
This system can be perturbed by human actions.

This idea accords with the notion that the Earth’s biosphere (including the atmosphere)
somewhat resembles a living organism which behaves, not as a thermodynamically controlled
equilibrium system, but as an energy ‘supercharged’ system, so allowing energy to be applied
in a rapid and apparently in a ‘directed’ manner.

The buffer mechanism of natural waters also likely determines the

manner in which exchange of CO2 between the sea and the atmosphere
can occur. Increased fulvate (e.g. from the degradation of terrestrial
soils) is expected to increase the Ω of dissolved CO2 at the sea surface.
This predicts that a major injection of CO2 into the atmosphere could be
facilitated by the presence of excess fulvate in seawater. An increased
atmospheric CO2 will then be an inevitable consequence of any
inappropriate agricultural operations which lead to any diminution of the
land humus by increasing the content therein of water soluble humic
matter which can enter and then perturb the fulvate-determined marine
homeostasis system.
Evidence that such a process may actually occur in nature is provided by
the early researches of E. Suess and their predecessors who found that all
surfaces of CaCO3 particles present in the (shallow) seas studied by them
had become totally covered by a layer of strongly adsorbed organic
matter apparently derived from the abundant DOM of the sea.
Absolutely all such surfaces of CaCO3 in the sea were apparently
effectively blocked-off from being able to act according to the
conventional carbon cycle mechanism because they become completely
covered and effectively deactivated by the highly flexible fulvate
polyanion ligation system.

This means that the chemical properties of pure CaCO3 phases having
chemically clean surfaces (i.e. the pristine pure CaCO3 (calcite) most
commonly studied in the laboratory, and used to build models of the
global carbon cycle) is not even approximately of direct relevance to how
the carbon cycle actually works in practice.

The currently proposed fulvate switch mechanism of the sea can be

regarded as an extension to the entire sea of the idea that seeded
formation controls CaCO3 formation in shallow seas cf. J.W. Morse’s
work on the Bahama Bank CaCO3 precipitation system [6] but this DOM
activity also applies to deep seas up to at least 5000 meters in depth as
had been indicated by the earlier investigations of P. J. Wangerski
[1-0][8-7-6] who failed to find any sign of the expected CaCO3 re-
dissolution horizon in the N. Atlantic which he attributed to the ability of
DOM via its strong adsorption on CaCO3 surfaces to abolish the ability of
carbonate equilibria both to control the pH of the sea and to act in the
previously perceived manner of oceanic carbon recycling. The idea that
the carbonate buffer was the principal mechanism of pH regulation of the
sea had also been challenged by L.G. Sillén [8a].

In further support of the hypothesis that anthropogenic

global warming is at least to a major extent fulvate-driven, is
that a major amount of degradation of terrestrial soils (a
phenomenon which leads to the leaching of fulvate and its
transfer by rivers into the sea) seems to have become
enhanced since the start of the industrial revolution.
Indeed topsoils degradation and increase in atmospheric CO2 may have
occurred at a parallel rate since the start of the industrial revolution [8-
1a]. [This idea seems to fit the qualitative data; more detailed
international information about topsoil degradation is needed to fully
check-out this hypothesis].

It should be noted that despite the belief that the anthropogenic

degradation and erosion of global topsoils should be of even greater
environmental concern than is the loss of tropical rainforests [7][8-a], the
critical role of such terrestrial soil degradation in the mechanism of
anthropogenic global warming and climate change has not previously, as
far as is known, been properly identified.

Agricultural induced natural topsoil degradation is also likely to have

been part of the complex process by which human actions during the late
Holocene, 7000 years ago, apparently caused an increase in atmospheric
CO2 at that time. This possibility seems to be suggested by the selected
ice core records which have been discussed in depth by Ruddiman [8].
This ‘late Holocene anthropogenic warming’ might, it is now suggested,
have been caused by operation of the putative carbonate buffer system
fulvate block mechanism (as set out vide supra). The late Holocene
atmospheric warming was, according to this hypothesis, a consequence of
terrestrial soil degradation caused by deforestation and agriculture
riverine runoff which caused an increased level of marine fulvate which
resulted in increase in the value of Ω for CaCO3 and CO2 in seawater.

That such a small human population as that which existed 7000 years ago
could exert such a marked influence on the global temperature
homeostasis system tends to confirm the hypothesis that the current much
larger human population must now be driving a much larger CO2-driven
global warming and climate change process.

In order to stop excessive climate alteration and damage to human society

and major species extinctions etc., it will be essential, if the above
hypothesis is correct, in addition to the enforcement of cessation of the
burning of fossil fuel, biomass and municipal and industrial waste, also to
diminish the anthropogenic degradation of the topsoil and the resultant
increasing associated runoff of terrestrial fulvates into the sea.
It is suggested that even if the contribution of fossil fuel to the total
anthropogenic CO2 climate change is less than is it is commonly assumed
to be it will continue to be environmentally highly useful to diminish the
use of fossil fuel not only to decrease the direct injection of
anthropogenic CO2 into the atmosphere, but also to diminish the
formation of acid rain and the formation of toxic nanoparticles of soot
and other (e.g. carcinogenic) byproducts produced during the commonly
applied fossil fuel combustion process.

If the fulvate switch model of the sea is confirmed by further work, this
would mean that the commonly currently employed models used to
predict climate and global warming are entirely inappropriate and e.g.
would also invalidate the utility of the kind of proposal made by
T. Takahashi [5a] which was based on a widely currently believed model
of the carbon cycle, which suggested that, in order to counter the
industrial production of CO2, it would be useful to inhibit the growth of
calcified organisms in the sea.

2.

References to Section 1 *
[1] See archival M.C. U.K. manuscripts in Section 7 vide infra

Cf. also
D Grant 2009, web.scribd.com/doc/23967637/Humic-Substances-Inhibti-Crystallizn-II
2010, web.scribd.com/doc /41898831/New-Thinking-on-Climate-Change-Abbrev.-III

[1-0] P.J. Wangerski Limnol Oceanogr 1969 14 929-933

Available at web. aslo.org/lo/toc/vol_14/issue_6/0928.pdf
Cf., ibid.,
K.E. Chave E. Suess ibid., 1970 15 633-637
E. Suess Geochim Cosmohim Acta 1970 34 157-168

[1-0-1] J.A. Leenheer M.M. Reddy Ann Environ Sci 2008 211-25

[1-1]
D Grant 2010,
web.scribd.com/34142473/2An-Assessment-of-Progress-in-Studies-of-the-Chemical-Structure-of-Humic-
Substances-Revised
Cf. also

[1-1a] D. Grant Nature 1977 279 709-790

{n.b. the 1H nmr spectra (but not the 13C nmr spectrum) shown here
used the now obsolete τ notation (this is 10-δ )}

[1-2] Cf. D. Grant et al., Biochem J 1989 259 41-45

The above paper was part of a wider investigation of the modulation of the crystallization
enabled by soluble substances (e.g. anionic polysaccharides and anionic soil extracts) added
to controlled seeded crystal (Nancollas procedure) initiated crystallization of CaCO3 (calcite)
and BaSO4.

[This work was conducted as part of a more general polysaccharide including marine
organism research program at Aberdeen University, Scotland, UK in a lab. headed by W.F.
Long and F.B. Williamson [these highly gifted scientists have now retired from active service
to science; it is with some regret to note that they are no longer able to perform their highly
appreciated inspired leadership].
Cf., web. abdn.ac.uk/~bch118/publications.march2003.doc which lists the
peer-reviewed and similar research publications of one of the research managers of this group
(W.F. Long); additional, partly unpublished results obtained as part of this Aberdeen
University polysaccharide group research were recently put into the public domain at
web.scribd.com/doc/41263479/New-Thinking-on-Climate-Change-Abbrev.-III
which indicated that typical agricultural soil derived fulvates have an unusually high
effectiveness for the inhibition of CaCO3(calcite) crystallization; this document is now
appended here (vide infra) [Sections 7a, cf. 7b]..
The finding that humate/fulvate is a highly effective as inhibitor of CaCO3(calcite) crystallization
has now been replicated (in other laboratories) using soil and natural water humic polymers
from other locations suggesting that a common global soil organic matter controlled
mechanism exists which has a putative wide relevance for a fuller understanding of the global
carbon cycle and also the extent of anthropogenically induced climate change and global
warming.
The poly-carboxylated fulvate organic polymer buffer, which is composed of the post mortem
rearranged molecules derived from biota, may have arisen via a tandem biological adaptation
process throughout the Earth’s biosphere to achieve these two abovementioned buffering
tasks. Perhaps the most important of these is the inhibition of the formation of various kinds
of sparingly soluble salts. This especially applies to the various forms of CaCO3. Fulvate
also blocks the re-dissolution of pre-formed CaCO3 solid phases [2b]. The latter process
could be of relevance to how the ocean responds to global warming episodes e.g. during the
last stages of deglaciation which is associated with an injection of a large amounts of CO2 into
the atmosphere [2b-1].
It should be noted that compositional inter-relatedness of the amounts of the contained (e.g.
50+ kinds of) dissolved inorganic ions present exists between seawater and human blood
serum and both of these solutions are also well-established examples of long-lived naturally
occurring CaCO3 supersaturated solutions. This requires, it perhaps needs to be re-stated, the
presence in such solutions of inhibitors of the crystallization of this substance [2]. The animal
CaCO3 (plus other sparingly soluble Ca salt) crystal inhibition control system seems to
include proteins plus polyphosphates [2a] backed up by the poly-uronic acid anionic
polysaccharides which occur at all adherent cell surfaces and if defective e.g. at blood or
urinary vessel can promote the formation of pathological vascular plaques or urinary system
stones [1-2].
That anionic polysaccharides or polysaccharide mimetics contribute to geological CaCO3
deposition and the natural calcification CO2 control processes in the sea was intimated
many years ago by E Suess and a number of even earlier authors (cf. Geochim
Cosmochim Acta 1973 37 2435-2437) who obtained experimental laboratory and field
study evidence of the occurrence of a system of ‘non-biogenic’ association between
natural organic matter and CaCO3. This organic matter coating was the basis of the
Wangerski hypothesis that the carbonate cycle of the sea has a long time constant delay
mechanism built in. This is the now suggested fulvate switch mechanism.
This abiotic seawater humic matter control of calcification mechanism was further indicated
to mimic the process by which marine organisms calcify or inhibit calcification.
The co-association of polysaccharide-like materials adsorbed onto CaCO3 particles has also been
researched by several other authors, e.g. the presence of polyanioniic polysaccharide-like materials in
geological deposits was studied by M.E. Gunthorpe & C.S.Sikes, Ohio J Sci 1986 (3) 106-109.
That anionic polysaccharides exert a controlling influence in coccolith calcification was
established by e.g.
E.W. de Jong et al., (8-0-2-1-2)
That the method of control of calcification of marine microorganism is of possible major
relevance for the fuller understanding of the natural mechanism of control of the global
carbon cycle was also fairly recently discussed by A. Pentecost (Thalassas 2004 20 (1) 45-
49).

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

[2a] M.R.W. Brown A. Kornberg PNAS 2004 101 (46) 16085-16087

[2a-1] Unpublished results of D. Grant obtained at Aberdeen University,

cf. D. Grant et al. Medical Hypothesis 1962 38 46-48

[2b]
Under modern organic matter-rich seawater conditions the dissolved
organic matter (e.g. fulvate) present in the sea becomes strongly adsorbed
onto CaCO3 particles (cf. Chave & Suess and Wangereski (8-7-6-). This
creates CaCO3 supersaturation in surface waters and also prevents
any (e.g. biotic) precipitating CaCO3 particles from becoming re-
dissolved at depth. This means that the traditional hypothesis; the
existence of a carbonate buffer system of the sea ( which depends on the
occurrence of such a re- dissolution) becomes inoperative. Direct
evidence for this effect was obtained by P. J. Wangersky (8-7-6 ) for the
lack of variation in the amount of suspended CaCO3 particles with depth
for 18 deep stations (taking samples from up to 4750 meters depth) at
points distributed over a large area of the North Atlantic.
In earlier, less comprehensive studies conducted in the Pacific Ocean
evidence was obtained that dissolution of CaCO3 particles occurred below
5700 meters depth. The amount of fulvate which is likely to vary
between different seas could evidently determine the “snow line” (where
the depth-dependent hydrostatic pressure causes any pristine
precipitating CaCO3 present in the seawater column to re-dissolve).
The traditionally-held view that the pH value of the sea is in general
buffered by the carbonate system becomes invalid in the presence of
sufficient organic matter (fulvate) which deactivates all the suspended
CaCO3. present.
[2b-1] The argument set out in [2b-1] applies to all current seas. On the
other hand the fulvate polyanions per se are chemically constituted to provide the observed
geological time scale seawater pH buffering and multi-inorganic element homeostais functions.

The carbon cycle ‘control function’ exerted by the marine fulvate

chemistry may also be highly relevant to a fuller understanding of the mechanism of glacial
period terminations which have been characterized by a relatively short warming leg the
origin of which has been a major puzzle of paleoclimatology. The most recent termination
has been indicated (G.H. Denton et al., [8-7-7]) to have depended on the input of large
amounts of water from the rapid melting ice in the North Atlantic Ocean which seems to have
led to an activation of the mechanism of release of CO2 from the deep water CaCO3 store.
The preceding discussion of the role of organic matter in this process suggests a credible
mechanism by which a reduction of organic matter content in the melt-water diluted seawater
caused the eventually removal of adsorbed fulvate which was not replaced (after a 100+ year
delay); the large input of fulvate depleted glacial melt-water permitted the re-dissolution of
the very large CaCO3 particle stores held on the in deep water seabed which via an associated
upwelling process facilitated a relatively rapid injection of CO2 from the seabed store into the
atmosphere which caused the (observed in ice core) increase of 100 ppm in CO2 caused a
secondary warming effect (e.g. some 100+ year delay) which accelerated the process of
deglaciation period via the greenhouse gas effect. This of course confirms that the initial
stimulus for warming was likely to have been the Milankovitch insolation effect, the CO2
greenhouse gas warming effect being a secondary ‘amplification’ effect.

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

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.
Examples of the correlated inorganic element contents of seawater and heparan sulfate
(heparin) and alginate are shown in Figs.1.

[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 [2])
functions in modern animals (which of course have also evolved a host of additional protein-
based ion channel systems and for those with blood circulation include complex inorganic
filtering/recycling functions of specialized organs which, however, also seem to continue to
use anionic polysaccharides such as heparan sulfates as part of their modus operandi).
Further evidence [obtained by H. Nader et al. 1983 [4a]] for the continued osmoregulator
function for the anionic cell surface animal polysaccharide systems is that for fifteen species
of aquatic invertebrates, the amounts of heparan sulfates and related anionic polysaccharides
present in their tissues, is apparently determined by a system which depends on an exact
mathematical relationship between the amount of these poly-carboxyl polyanionic surface and
extracellular space buffer molecules present, and the salinities of the habitats of the organisms
in question. This observation tends to support both the theory that multicellular animal
evolution occurred in the sea (e.g. some 109 years BP) and that those poly-carboxylated
polyanions which must have been present in the sea at the time of the appearance of the first
animals, continue to serve in present day animals for the same basic homeostasis/buffering
functions. This includes the maintenance of the inorganic element contents of those the
extracelullar fluids which have ‘evolved’ from seawater and the creation in animal
extracellular fluids a permanent state of CaCO3(calcite) supersaturation (and by inference
also may therefore exert some form of control over the content of the of the atmosphere which
is partly created by the biosphere).

[4a] H.B. Nader et al. Comp Biochem Physiol 1983 76 433-436

[4a-1] H.B. Nader et al.,Carbohydr. Res. 1988, 184, 292-300

[4b] E.g. A.R. Hoch et al., Geochim Cosmochim Acta 2000 64 (1) 61-72

Cf. D. Grant
web. scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crysatalllizn-II;
Cf. also references listed and discussed in Section 8 (vide infra)
and

[5] Cf. the relevance of Henry’s law to the uptake of CO2 by the sea. It should be noted that
Henry’s law applies to equilibrium conditions (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 CO2 system of the surface of the sea is kinetically and not thermodynamically
controlled, then the rate of CO2 release from the sea is also likely to be 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, then this process dominates the ability of the sea to
act as a sink for CO2 and also is putatively the major mechanism of injection of CO2 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=24145880178
which discusses Henry’s law in the context of the role of the seas in provision of a sink
atmospheric CO2, notes that
“gases in our atmosphere exist in equilibrium with the sea”
The above use of Henry’s Law is now suggested that this statement is essentially wrong.

It is further suggested that the conventional seawater carbonate-based alkalinity pH CO2 aragonite
calcite buffer model of the sea [cf. M Frankignoulle J Marine Systems 1994 5 111-118;
ORNL/CDIAC-74 cf. Aurelia Proyle et al. {R: Parameters of the sea (internet file)}]
(or the more complex other mineral based buffer models) have become inappropriate for present day
conditions and such oversimplified and incomplete models may no longer give a useful approximation
(e.g. in the context of climate change and global warming). Putatively, the highly non-equilibrium
conditions which may arise in the surface waters of the sea are caused by inputs into the sea of
anthropogenically oilfield spillage waste, a wide range of industrial and domestic wastes (including
biologically poorly-biodegradable molecules and polymers) sewage and very large amounts (perhaps
by far the largest anthropogenic input) soil effluent augmented by intensive industrial scale agriculture
riverine runoff. This surface water (polysaccharide-rich) organic matter is now apparently associated
with the formation of major amounts of transparent expolymer particles (TEPs ) (cf. J. Zhou et al.
Limonol Oceanography 1998 43 (8) 1860-1871) the existence of which further complicates the sea air
transfer interface.

Although isotope studies seem to suggest that the transfer of CO2 produced by the combustion of fossil
fuel will take e.g. nx103 years to equilibrate with the sea (cf. IPCC, internet), an apparent partial rapid
operation of this buffer system seems also to exist.
The atmospheric values of CO2 undergo rapid changes according to the seawater temperature as
indicated by the reported year-on year average temperature of the Earth’s surface which displays
variation following volcanic eruptions and El Nino events. Cf . Figs. 2 (vide infra).
This phenomenon is also illustrated by the apparent almost exact linear dependence which can be
shown to exist 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 as discussed by L. Endersbee {loc. cit. ref. 8-1}: [atmospheric contents of CO2 data
from January 1985 through May 2008 were found by this author to be linearly correlated with the
global average sea surface temperature (the ‘anomalous’ increase from a recent baseline) over this
period]).
The above data indicates that the increase in atmospheric CO2 over this period could have been caused
to a major extent by the direct release of CO2 from the surface of the sea as the seawater warmed up.
Alternatively the increase in atmospheric CO2 was a consequence of a putative humic matter servo
control system of the seawater CO2-carbonate buffer system which might act as natural switch for
allowing CO2 release from the surface of the sea.
Such humate-influenced processes might perhaps facilitate CO2 release from the sea via a direct
physical binding/release processes similar to those which enable analogous poly-carboxylted animal
anionic polysaccharides to bind directly to dissolved CO2 and later release this gas.
There may also be a role in the sea surface CO2 binding release system of nanobubble-associated humic
polymer assisted water-structure-building, a phenomenon which is suggested by physical chemistry
researches on the effects of nanobubbles to be of possible major relevance to the formation at
interphase boundaries of extended water cluster structures.
The above hypothetical effects might also apply to atmospheric humic matter which will interact with
the atmospheric aerosol water molecules which can create solar energy absorbers and cloud nucleators.

[5a] T. Takahashi Science 2004 305 352-353

[6] J.W. Morse et al. Geochem Cosmochem Acta 2003 67 (5) 2819-2828

[7] Terrestrial Soil Degradation.

Cf., World Resources Institute Washington USA
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.

In a 1992 UN funded global survey of the world’s soil (cf. 8-1a), it was reported that more
then a tenth of the soils surveyed has lost a substantial amount of their natural fertility over
the preceding 45 years. In Central America and Mexico 24% of the soils were found to have
been seriously damaged. This figure was 17% in Europe. This soil degradation affects the
humic matter integrity.
[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].

The widespread anthropogenic alteration of humic matter putatively leads to massive leaching
of humic matter into the rivers and sea. This can, it is now suggested, set up a store of “labile
CO2” in the surface of the sea. I.e. the creation of systemic CO2 supersaturation. This may
simply be dissolved CO2 as such, stabilized in the now widely distributed transparent
exopolymer particles (TEP) or arises from a humic matter induced disequilibrium involving
HCO3- and CO32-. It might also be from some previously unsuspected chemical store.

[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.

3.
Fig. 1.
Comparison of the inorganic element content of heparin and seawater
[n.b. heparin is a commonly used model for heparan sulfate, a major extracellular and
cell surface animal poly-carboxylate polyanion buffer system].

Fig. 1a Comparison of the seawater-like multi-inorganic-element contents of

Na and Li commercial heparins

Fig. 1b Comparison of the seawater-like multi-inorganic-elements in heparin

and geological fulvate

Fig. 1c Comparison of the multi-inorganic-element contents of seawater and of

the Earth’s crust

Fig. 1d Comparison of the multi-inorganic element contents of seawater and of

algal biomass

An approximate exponential compositional relatedness also exists between the

amounts of some ca. 50+ inorganic ions (quantifiable by mass spectrometry) present
in seawater and human blood serum [cf., Fig. 1 of ref. 3]. The molecular mechanism
basis of this chemical buffering effect which is suggested to have a similar mechanism
in other natural aqueous multi-inorganic element matrices which show the kind of
composition correlation/relatedness with seawater indicated in Figs. 1,1a,1b and 1e
seems most likely to be associated with the ubiquitous poly-carboxylated polyanionic
organic polymer buffer systems which ubiquitously occur in natural aqueous solutions;
this buffer function in animals by the glycosminoglycan poly-carboxylate polyanion
system and in the sea the humate/fulvate poly-carboxylate polyanionic system. The
latter [the humic substances organic C pool]; [cf. 1-1] comprises the largest type of
organic chemical substance in the biosphere.
Fig 1 a Heparin 'Na' cf. Heparin 'Li'

Fig 1b Comparison of Inorganic Elements in Heparin and

Geological Fulvate
Fig. 1c Comparison of Inorganic Elements in Seawater and
Earth’s Crust
Fig 1d
4. Evidence of Seawater release of CO2 from the Global Surface
Warming and the Mauna Loa Atmospheric CO2 Year-on Year
Variation Curve

It is suggested that, in addition to the combustion of fossil fuel, additional

anthropogenic activities are also currently causing an elevation of
atmospheric CO2; these may include CO2 from the direct
anthropogenic degradation of humic matter including that which had
already become extensively degraded by continued intensive
agricultural practices and which also can cause an increase in the
amount of terrestrially derived soluble (fulvate) and dispersed humic
matter which can easily be transferred into the sea.

The Mauna Loa atmospheric CO2 curve shows up a likely influence of

marine CO2 transfer rates which are putatively, according to the above
discussions, partly regulated by the poly-carboxylate polyanonic seawater
buffer and CaCO3 precipitation system which can create a system of
supersaturation (Ω ) of CO2 in surface waters and which can also
apparently respond relatively rapidly to temperature changes of the
Earth’s surface. The seawater surface temperature alteration of El Nino
and volcanic ash events seem to correlate fairly closely with irregularities
in differentiated time variation of the remote site atmospheric CO2 values
as e.g. indicated by Figs 2 (vide infra).

Some fast injection mechanism of CO2 into the atmosphere seems to respond rapidly
to changes in the temperature of the surface temperature of the Earth. Since the sea
covers 71% of the surface of the Earth, this points to the sea as the likely origin of this
extra CO2 injection.
According to the current most commonly held paradigm that fossil fuel usage causes a
major part of the current elevation of CO2, it might have been predicted that the year-
to-year variation in this CO2 source should be closely linked to the year to year
variation in the level CO2 in the atmosphere. Published data on the total world use of
fossil fuel and CO2 at Mauna Loa available on the internet, however, indicate when
compared as differentiated curves, that this predicted close linkage does not exist.
The rate of change in atmospheric CO2 does not appear to confirm closely to the idea
that the principal anthropogenic source of CO2 is fossil fuel. (There may however be
some kind of indirect loose correlation so fossil fuel is likely to be part but not all of
the anthropogenic fingerprint).
The fine structures in the variation of the rate of change in atmospheric CO2 and of
fossil fuel usage apparently actually are fairly independent of each other (cf. the plots
shown in Figs 2 vide infra).
After discovering this unexpected lack of close correlation of atmospheric CO2 data
and fossil fuel usage data, an (internet) back-checking, revealed (8-1a1) that a close
correlation between atmospheric CO2 and the average temperature of the surface of
the earth had already been noted (this having been discussed by R.W. Spenser in an
internet essay dated 1/25/2008 entitled “Atmospheric CO2 Increase. Could the
Ocean, Rather Than Mankind Be The Reason”. [(8-1a1)
Read from
http://wattssupwiththat.com/2008/01/25/double-whammy-friday-roy-spencer-on-how-oceans-are-driving-co2/]

This essay noted and discussed the apparent sensitivity of the Mauna Loa atmospheric
CO2 values to sudden changes the temperature of the Earth’s surface (and not to fossil
fuel burning) (8-1a-1). There was a further suggestion on the same website that the
supposed δ 13C data of atmospheric CO2 also can be “de-treated” to suggest that this
δ 13C signature is a ‘natural’ one and not a direct anthropogenic fossil fuel or plant
matter combustion CO2 fingerprint.
A peer reviewed paper (8-1a-2) also hints at a similar effect by the report is less direct
in suggesting this.

4a.
Figs. 2 Comparison[by a preliminary sketch diagram] of five year
changes in atmospheric CO2 levels and fossil fuel usage levels [Data
used for constructing these diagrams were obtained from sources listed
in (8-1-8)]
The effect of fossil fuel usage variations is de- coupled for the remote atmospheric levels of
CO2. This seems especially to respond to likely surface seawater temperature variation
effects. The release rate of CO2 from the sea which might be as suggested in Section 1, be
controlled by the poly-carboxylate polyanionic blocking effect on the CaCO3 sink for CO2 by
anthropogenic influences seems, on the basis of this analysis, to be a possible major primary
contributor to the current abnormal rates of global warming and climate change.
It should be noted that current thinking on how to combat possibly human-induced, adverse climate changes and
global warming has become highly focused (by IPCC and most other, but not all climate scientists) on fossil
fuel generated CO2 greenhouse gas atmospheric warming (n.b. this gas is the principal greenhouse gas which
prevents heat radiated from the surface of the earth being radiated back to space (cf. Hansen ref. 8-1-1 who is
a major advocate of the Hogbom /Arrhenius, Callendar, Plass theory)); the mechanisms of the current
increase in atmospheric CO2, are however, far from certain, including a lack of a full understanding of the
possible anthropogenic influences which might affect how the atmospheric CO2 is sequestered by the various
CO2 sinks which exist in the land and in the sea.

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

4b. Discussion of major CO2 release from the Earth’s surface heating
and cooling events
Apart from the evidence (as outlined in the previous section or the discontinuities with
volcanic eruption ash cooling and El Nino effects are clearly evident from a comparison of
the most recent data of a super-supersaturated CO2 sea surface which enables an altered rate
of injection of CO2 into the atmosphere, the straightforward measurement of sea surface CO2
also suggests this.
Cf., e.g., the data obtained by M Ishii et al. in
[M Ishii S Saito T Tokieda T Kawano K Matsumoto H Y 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]
in a study which used conventional concepts of oceanic pH, alkalinity etc. to quantify
the variability of surface layer CO2 parameters in the Western and Central equatorial
Pacific during ocean survey vessel cruises quantified the amount of CO2 released into
the atmosphere from the CO2 -supersaturated upper equatorial region seawater zone
(n.b. this hot-water source of injection of CO2 into the atmosphere is conventionally
thought to be less than the amount of CO2 taken up by colder sea water in the non-
equatorial zones). This area of the sea released CO2 into the atmosphere at a rate of as
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 was reported also to occur by
CaCO3 precipitation, but this process was indicated to be suppressed to a high degree
in accord with the operation of the fulvate block mechanism which is now proposed to
control the marine carbon cycle.

Some high latitude natural water systems are, however also likely to
resemble the equatorial hot-water seas in their ability to inject CO2 into
the atmosphere; this seem to apply to 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. 8-1a-3);
[Cf . also 4c (8-1a2)
P Sturm M Leuenberger J Moncreiff M Ramonel
Atmospheric O2, CO2 and δ 13C measurements from aircraft sampling over Griffin
Forest, Perthshire, UK]
4c (8-1a3) S L McCallister P A del Giorgio
Direct measurement of the δ 13C signature of carbon respiration by bacteria in lakes
suggested a linkage to potential carbon sources, ecosystem baseline metabolites and
CO2 fluxes
Limnol Oceanogr 2008 54 (3) 1204-1216
[These authors noted that there is now overwhelming evidence that most N. 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 equatorial sea (plus more northerly seas like the northern latitude lakes
(cf.4c 8-1a-3)) is likely to be consistently supersaturated in CO2 and therefore be
poised to inject CO2 into the atmosphere.

4c (8-1a0)

13
4c. The δ C Signature
The C-13 Suess Effect
It seems inconceivable that the well-established C-13 Suess Effect
which allows the amount of fossil fuel usage produced CO2 to be
quantified by the 14C/13C/12C isotope ratios, could in any way be subject to
some major error. [
E.g. recent study showed the need to remove the anthropogenic 13 C Suess effect
from fossil foraminifera data from the North Atlantic in order to reveal the pre-
industrial this ocean ventilation patterns by A Olsen and U Ninnemann Science 2010
330 658-659).
It is nevertheless tentatively suggested that the δ 13C signature, previously assumed to be
good evidence for fossil fuel origin of a large proportion of the increased CO2, might, to a
significantly degree, arise from an expected large δ 13C depletion effect in the CO2 following
bacterial use of algal biomass carbon source (nutrient provision boosted via terrestrial fulvate
injection [the anthopogenic input]) feeding into the ocean surface held in TEP foam bubble
systems or via an 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 remote CO2 atmospheric increase is putatively to a major extent then

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 direct and
indirect (e.g. via the formation of acid rain).
5. Why does increases in atmospheric CO2 lag behind deglaciation?:
(Humic suface effects? Loosening of the Wangersky block on the
marine carbon cycle?)
This could indicate that climate change arises naturally via 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 deglaciation lags behind global temperature increases by 600±400 years, i.e. that a primary
greenhouse gas heating effect of atmospheric CO2 is not the primary driver of global warming then and at the
present time also (cf. C. Lorius et al. Nature 1990 347 139-1145).
It should be noted however that possible errors may have occurred in the interpretation of ice core gas analysis data
may arise from the presence of natural antifreeze ingredients both inorganic and organic (e.g. humate/fulvate) in
snow. This can cause liquid water to be retained at low temperatures. Such water dissolves CO2 from gas bubbles
in contact with this phase.
[Cf. Z. Jaworowski et al. Sci Tot Environ 1992 114 227-284].

The phase lag caused by the albedo reflection properties due to ice coverage seems to have been overtaken the
increase in solar warming effect which must have included that promoted by micro and macrobiota and its
associated formation of dark colored terrestrial, marine and atmospheric humic matter during the warm periods
which preceded glaciation (8-3-1-1) when the delayed CO2 came as a consequence of the eventual warming of the
principle marine sink of CO2.
There is, however, also a possible major effect of cosmic rays on climate and global temperature to be taken
account of, which may also include a small direct heating effect of absorption of energy from cosmic rays in humic
matter.

The delay in injection of CO2 into the atmosphere could also arise from the dilution
effect of rapid meltwater input to the sea which could loosen the (P.J. Wangersky)
fulvate block on the carbon cycle by the mechanism outlined in Section 1 (vide
supra).

6. Human alteration of the bacterial population of the soil is also likely to

be a major mechanism of (humate-related) anthropogenic influence on
global warming and climate change
Bacteria in terrestrial soils produce a lot of CO2.
This amount can be increased after humic matter becomes degraded by modern agricultural practices.
This conclusion can be deduced from a recent compilation of the historical record on soil respiration research.
Cf. the comments made on the recent paper B. Bond-Lamberty & A. Thomson, Nature 2010 464 579-82,
doi:10.1038/news.2010.147.
Cf., A. Fang A in the associated Nature News article noted that
CO2 from soil respiration now apparently inputs 98±12 petagram (Pg =1015g = Gigaton(ne) = 109 metric tons or
109 x106g) C/year into the atmosphere.
It should be noted that this amount is greater (by more than an order of magnitude) than the total amount believed
to be produced by the anthropogenic combustion of fossil fuels. This finding (which was deduced from a
comprehensive compilation of the relevant historical scientific data) indicates that the complete cessation of all
burning of fossil fuels may only reduce the anthropogenic input of CO2 into the atmosphere by a relatively
insignificant amount.

8. Some further key references and comments

------------------------------------- -------------------------------
-------------------------------
7a.
The amount of CO2 in the atmosphere and resultant global warming is
probably determined by the ability of fulvate polyanions to block a
major part of the carbon cycle
In support of the above statement
the following text was obtained from a report produced following extensive
discussions and verification of the validity of the arguments supported by the cited
reference in an academic institution (Marischal College , U.K.) research project.

INHIBITION OF CaCO3 (CALCITE) CRYSTALLIZATION BY HUMIC AND FULVIC ACIDS

David Grant, William F. Long, Marion A. Ross, Jaqueline A. Somers and Frank B.

Williamson,

Department of Biochemistry, University of Aberdeen, Marischal College,

Aberdeen AB9 1AS, Scotland, U.K.

ABSTRACT

Humic and fulvic acids strongly inhibit the crystallization of CaCO3 (calcite)
These soil-derived polymers may therefore affect fertilizer efficiency in calcareous soils

and influence marine carbonate and atmospheric CO2 concentrations.

It is possible that the anti-calcite activity of the polymers resides in an

“oxidized polyethylene”-like fraction since a uronic acid residue-containing polysaccharide

fraction from soil had lower anti-calcite activity and lignin derivatives had no activity.

Because of their highly heterogeneous natures, it is likely that humic and fulvic acids possess

other ecologically relevant anti-crystallization activities

INTRODUCTION

Humic acid and fulvic acid are names given to colloidal organic fractions

obtained from soil by defined procedures involving dispersion of samples in aqueous

alkali, neutralization, separation of insoluble humic from soluble fulvic fractions,

and dialysis of the fractions (Schnitzer and Khan, 1978). These heterogeneous

polyanionic substances are agriculturally significant, because they stabilize soil

structure and stimulate root growth (Kononova, 1966; Schnitzer and Khan, 1978).

They are formed by chemical and biochemical alterations of matter chiefly of

microbial origin, and typically have 14C-dated residence time in soil of about 103

years (Schnitzer and Khan, 1978). They have been characterized by their

cation –exchange capacity (Pleysier et al., 1986), by mass spectroscopy (Nager et al.,

1975), by ir spectroscopy (Schurukhina et al., 1973) and by nmr spectroscopy (Wilson

1984).

We have described the inhibition of the crystallization of calcite by a

range of anionic polysaccharides derived from animal and algal tissues (Grant et al.,

1989 a,b). Such compounds may have crystallization inhibition function in vivo, and

structural analogues of them are of potential use as agents for the clinical

augmentation of endogenous crystallization modulatory factors. Because of the broad

structural similarity between these compounds and the soil-derived polymers, and

because soil-derived calcium salt crystallization inhibitors may be important in the

modulation of marine calcification (Morse, 1983) and in increasing fertilizer

efficiency in calcareous soils (Amer et al., 1985) , we examine the effects of humic
and fulvic acids on the crystallization of calcite.

MATERIALS AND METHODS

Humic acid and fulvic acid (preparation 1) were extracted from a non-calcareous

agricultural soil at Countesswells, Aberdeenshire, U.K. of 5.9% carbon content

and pH 5.9 (Glentworth and Muir, 1963) by the method of Ogner (1973) ;

fuvic acid (preparation 2) was extracted from a polysaccharide-rich fraction of climatic

peat at Cairn o’Mount, Aberdeenshire, U.K. of 56% (w/w) carbon content and pH 3.7

(Forsyth, 1946) by Soxhlet extraction with H2O. Sulphation/sulphonation of the

humic acid by the method of Wood and Mora (1958) converted it into a material

that was soluble in the pH 8.3 solution used for study of calcite crystallization;

the effect of sulphation/sulphonation on fulvic acid (preparation 1) was also investigated.

Water-soluble sulphonated lignin derivatives (REAX 88B and REAX 100M) were

obtained from Westvaco, Charleston Heights, SC, U.S.A. Heparin from porcine

intestinal mucosa (lot no. 46C0035) and chondroitin 4-sulphate from whale cartilage

(lot no. 77CO187) were from Sigma Chemical Co Ltd., Poole U.K.; Na pyrophosphate and

Na tripolyphosphate were from Monsanto Chemical Company, St Louis, MO, U.S.A.

Ir spectra (Fig.1) were obtained by multiple specular reflectance in a Grubb

Parsons MkIII Spectrometer using films deposited on aluminium foil mirrors. The ir

Spectra of humic acid (Fig1a) and fulvic acid (preparation 1) (Fig. 1b) were

Similar to the previously published spectra of such materials (Shurukhina et al., 1973).

The ir spectrum of fulvic acid (preparation 2) (Fig. 1c) showed narrower absorption

bands, indicating more homogeneity than the other soil extracts; the positions and

intensities of the bands shown in Fig. 1c are typical of uronic acid-containing

polysaccharides. The spectra of sulphated/sulphonated humic acid (Fig 1e) were similar to

those of the starting materials but showed additional absorbances due to the presence

of SO3- groups; the major absorbance at 1238 cm-1 was assigned to the SO2- asymmetric

stretching frequency. The ir spectra of lignin-derived materials (Fig. 1 f, g) were

similar to those of other soil-derived lignin fractions (Farmer and Morrison, 1964)

but had additional SO3- absorptions.

Crystallization studies were carried out as previously described (Grant et al.,

1989a). Briefly, this involved, for the study of calcite crystallization, the addition of

7.8 mg calcite seed crystals prepared according to the method of Reddy and

Nancollas (1971) to 60 cm3 of a solution containing CaCl2 (0.8mmol.dm-3) and NaHCO3

20 mmol.dm-3) and having a pH of 8.3 and a saturation index (Rogers et al., 1985)

of approximately 31. A similar seeded crystallization method (Liu and Nancollas, 1975)

was used for the study of BaSO4 crystallization. Crystallizations wee followed by

conductivity measurement using a Philips model PW9527 conductivity meter with a

Philips 9514/60 electrode, and also, in then case of BaSO4 crystallization studies

using a nephelometer (Evans Electroselenium Ltd., Halstead, Essex, U.K.). The

dissolution of calcite seed crystals in dilute H2SO4 solution, and the effect of

crystallization inhibitors on this process, were also followed by conductivity

measurements.

RESULTS

Figure 2 curve g shows the decrease in conductivity caused by crystallization of calcite

from a solution containing CaCl2 and NaHCO3, following addition of calcite seed

crystals to the solution. Figure 2 curves a-g show the effects of various additives on the

process. Fulvic acid (preparation 1) acted as a potent inhibitor of calcite crystallization

(Fig 2 curves a,c and g). Fulvic acid (preparation 2) was only weakly inhibitory

(Fig. 2 curve e).

Crystallization in its presence followed complex kinetics perhaps explained by the

formation of a soluble complex between Ca2+ and the polymer.

Humic acid could not be studied directly because of its insolubility at pH 8.3;

its soluble sulphated/sulphonated derivative (Fig. 2b) was of intermediate effectiveness.

The lignin derivatives under the conditions used by us, either did not affect

the process of calcite crystallization (Fig 2f) or increased its rate (Fig. 2h).

The effectiveness of the soil extracts were compared with that of other calcification

inhibitors by plotting Freundlich (1926) isotherms (Fig. 4).

The most effective soil polymers are apparently more than an order of magnitude more

active than the other calcification inhibitors studied.

Fulvic acid (preparation 1) and its sulphation/sulphonated product inhibited CaCO3

dissolution in 2.5x10-5 mol dm-3 H2SO4 solution showing a similar inhibitory

activity to sulphated polysaccharide calcification inhibitors (Fig. 5).

In related calcite crystallization experiments not reported in detail here, when

seed crystals were pre-incubated at 25o C for 30 min. with the additives, a higher

level of inhibition was achieved.

Inhibition by soil extracts of the crystallization of BaSO4 (Table I) increased

in the order: fulvic acid (preparation 1) < sulphated/sulphated fulvic acid

(preparation1) < sulphated/sulphonated humic acid.

Conductivity measurements (not shown) made in the presence of sulphated/sulphated

soil extracts, suggested that strong chemical complexing occurred between

the soil extracts and Ba2+ ions.

Table 1
Effect of Soil Organic matter Fractions and Lignin Derivative on the Crystallization
of CaCO3 (Calcite) for Homogeneous Nucleation
Additive µ g/ml % of uninhibited rate from second order rate constants

Fulvic acid No. 1 2.7 21.0

5.5 3.5
a
20. 0 ca. 0.5

100 0.0
a
Fulvic acid No 2 15.0 ca.12.5

Sulphated humic acid 20.0 0.5

Lignin derivatives

REAX 88 20.0 86.4

REAX 100M 20.0 310.0

Na tripolyphosphahte 2.0 0.5 b

Na pyrophosphate 2.0 0.5 b

Notes
a Ca2+ complexation occurs
b Inhibition occurs for only a limited period(dependent on the dose); for 2, 1, 0.5
and 0.2 micro g/ml tripolyphosphate this was 35, 30, 7 and 2 min., respectively; similar results were found with
pyrophosphate except that the periods of activity were greater) in a manner similar to that previously described for
tripolyphosphate inhibition of
BaSO4 crystallization (Liu & Nancollas, 1975).

Table Ia

Effect of Soil Organic Matter Additives on BaSO4 Crystallization

Additive micro g/ml % Uninhibited Rate from

Homogeneous Nucleation

Fulvic acid
(preparation 1) 30 3.2

Sulphated
Fulvic acid
(preparation 1) 2.5 38

Heterogeneous Nucleation (on CaCO3 (calcite) seeds)

Fulvic acid
(preparation 1) 2. 62

Sulphated fulvic acid

(preparation 1) 2 8.6

Sulphate humic acid 2 0.5

DISCUSSION

We examined the effects of modulators of CaCO3 (calcite) crystallization under controlled

Conditions, using a procedure defined by previous workers (Reddy and Nancollas, 1971).

Because the rates of crystallization observed, and the degree and type of inhibition seen in the

presence of modulators depend strongly on the experimental conditions used (especially those

which slow reactions allow interaction of seed crystals and inhibitor), caution needs to be

applied in Anaya comparison of our results with those of others examining soil fractions. The

present work, however, supports preliminary observation of Berner et al (1978) and Inskeep

and Bloom (1986a) that some humic substances derived from soil are very potent inhibitors of

CaCO3 (calcite) crystallization. Their and our results accord with the suggestion that some

water-soluble soil substances may permit high CaCO3 supersaturations in calacareous soils

(cf. Amer et al., 1982, 1983). They also support the proposal (Berner et al., 198) that soil-derived

substances may stabilize marine CaCO3 supersaturation, which varies form 2.5- to 5-5- fold,

depending on latitude (Whitfield and Watson,1983). Since the formation of marine CaCO3

is a global drain on atmospheric CO2 (Kitanto, 1983), and investigation of the natural
inhibitors of calcification may be ecologically relevant. The possible effects of human

activity on natural inhibitors might also be considered. An increased potency and/or quality

of terrestrial soil-derived crystallization inhibitors might elicit an elevation of atmospheric

CO2.

Formation and dissolution of crystalline mineral phases such as those of BaSO4, are, together

with effects on CaCO3 crystallization, important in determining seawater composition; the

present results indicate that the soil extracts studied inhibit the crystallization of BaSO4.

Because of their highly complex and heterogeneous nature, the soil-derived inhibitors

may possess a wide range of there ecologically relevant anti-crystallization activities, e.g.,

through modulation of the physical states of iron and aluminium oxyhydroxide in the soil

(Hayes and Himes, 1986).

Stimulation of root growth by soil organic matter fractions (Kononova, 1966), Schnitzer and

Khan, 1978) may, in part, be related to the ability of such humic materials to prevent the

crystallization of sparingly soluble sulphates and phosphates (Griffin and Jurinak, 1973)

which would otherwise reduce the availability of applied nutrients. Application of a synthetic

crystallization inhibitor, pyrophosphate, has been shown to prevent this (Amer and Mostafa,

1981; Amer et al., 1982; 1983).

As a result of studies involving unseeded CaCO3 crystallization, Kitano and Hood (1965)

suggested that the chelation of Ca2+ to various organic substances influences the

crystallographic form adapted by CaCO3 in the presence of these substances. Our results

suggests that the inhibitory effect of our most active soil extracts was not due to chelation by

them of Ca2+, since the inhibitory effect was not accompanied by a decrease in conductivity

immediately on addition of the inhibitor to the supersaturated solution. In contrast, addition of

ethylenediaminetetra-acetic acid (EDTA) to the supersaturated solution produced an immediate

increase in conductivity as Ca2+ was complexed, but the compound did not act as an inhibitor of the

seeded crystallization of CaCO3 (Grant et al 1989a).

Many inhibitors of CaCO3 crystallization appear to deactivate the seed crystal

surfaces upon which crystal growth occurs, perhaps by binding to these surfaces (Nancollas,

1979). Such an effect as surface adsorption accords with the Freundlich isotherms produced

in our experiments involving the soil-derived extracts, and also with the relatively non-specific
inhibition by them of the dissolution of CaCO3 under acidic conditions. Various poly-

carboxylic acids, including polysaccharides (Grant et al., 1989 a, b) and oxidised

polysaccharides (Kuriyamam et al., 1985) are inhibitors of the crystallization of CaCO3, but

are less active, by about1.5 orders of magnitude, on a weight basis, than the fulvic acid

(preparation 1) and humic acid fractions used here (Fig 4); however, the inhibitory

activity towards the dissolution of preformed CaCO3 crystals by the polysaccharide and soil-

derived inhibitors was of the same order of magnitude (Fig. 5). This suggests that the most

active soil components have particular specificity for CaCO3 crystal growth sites (which are

possibly screw dislocations in the crystal surface (Nancollas, 1979). The chemical nature of

fulvic and humic acids has not been unambiguously established but it is likely to be highly

heterogeneous and the fractions may contain plant-derived lignin. Indeed, some described

physical and chemical properties of these soil-derived substances may be due to the presence

of aromatic components including lignin (Flaig, 1964; Schnitzer and Khan, 1978; Hayes and

Himes, 1986).

The present results suggest that the crystallization inhibitory properties of the

fulvic and humic acid is not, however, due to the presence of this component no

is it due to relatively un-degraded anionic polysaccharides.

Their ir spectra (Fig. 1 of the most active humic and fulvic acid (preparation 1) are different

form the less active preparations which exhibits a polysaccharide-associated absorption at

1430cm-1 being assigned to the symmetric stretching vibration of the carboxylate groups of

uronic acid residues. This suggests that the active component of fulvic acid (preparation 1)

and perhaps of the other very active marine-derived humic acid and fulvic acid inhibitors

reported by Berner et al. (1978) may not be polysaccharide in nature.

Tentatively, we suggest that the inhibitory activity may reside in the principal major

non-polysaccharide, non-lignin component of humic and fulvic acid, e.g. the “ oxidized

polyethylene” component of these soil-derived fractions (Grant, 1977, Hayes and Himes,

1986). This consists of aliphatic, perhaps lipid-derived, polymers of general composition

(CH2)nC(O))X,(C)m(CH)(CH3)p, n>16, in which X=OH or –C< and which exhibit 13 FT and

1H nmr spectra similar to those of partly oxidised low-density polyethylenes (i.e. with a

dominant 13C chemical shift of δ = 30 which are present in virtually all soil types, being

especially abundant in the smallest particles size fractions derived form terrestrial soils (Oades

1988), and are major components of marine humic acid (Hatcher et al., 1980). They may

modulate soil aggregate structure (Chaney and Swift, 1984), perhaps by influencing soil

mineral structure through their hydrophobic character; this hydrophobic character may

contribute to the non-biodegradability of long-chain alkanes CH3(CH2)n>32CH3 in the soil

(Potts et al., 1973). It has been reported that polymethylene-rich soil-derived substances are

strongly adsorbed on crystal surfaces in hydrophobic soils (Ma’shum et al., 1988).

Some commercially used CaCO3 crystallization inhibitors, e.g. the polyphosphates

Raistrick, 1949) are effective at low concentration, but retain their effectiveness for only a short period,

perhaps because crystal over-grow of the inhibitor-bound crystal surfaces (Liu and Nancollas, 1975).

In contrast, our results as work as well as those of Berner et al. (1978); see discussion in Morse, 1983),

suggest that soil-derived inhibitors may retain their inhibitor activity indefinitely. Further work using

soil-derived fractions of defined origin and characteristics, and with carefully controlled crystallization

procedures, may reveal inhibitors of commercial potential, and may illuminate ecological relevance of

such substances.

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soils, Soil Sci. Soc. Am. J., 45 842-847

Amer, F., Khalil, M.A. and Diab, G.S. (1982) Agronomic effectiveness of pyrophosphate as an
additive to moncalcium phosphate and diammonium phosphate calcareous soils, Soil Sci. Soc. Am. J.
46 572-583

Amer, F., Mahmoud,A.A. and Sabeet, V. (1985) Zeta potential and surface area of calcium carbonate
as related to phosphate sorption, Soil Sci. Soc. Am. J., 49, 1137-1142

Berner, R.A., Westrich, J.P., Graber, R., Smith, J. and Martens, C.S. (1978) Inhibition of aragonite
precipitation from supersaturated seawater: a laboratory and field study Amer. J. Sci., 278, 816-837

Chaney, K. and Swift, R.S. (1984) The influence of organic matter on aggregate stability of some
British soils, J. Soil Sci., 35, 223-230

Farmer, V.C. and Morrison R.I. (1964) Lignin in sphagnum and phragmites and in peats derived from
these plants, Geochimica et Cosmochimica Acta, 28, 1537-1546

Flaig, W. (1964) Effects of micro-organisms in the transformation of lignin to humic substances,

Geochimica et Cosmochimica Acta, 28, 1523-1535
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constituents, Ph.D. dissertation, Univ. of Aberdeen

Freundlich, H. (1926) Colloid and Capillary Chemistry, Methuen, London

Glentworth, R. and Muir, J.W. (1963) The Soils of the Country Round Aberdeen Inverurie and
Fraserburgh, Mem. Soil Surv. Gt. Br. Scot. Edinburgh, H.M.S.O.

Grant, D. (1977) Chemical structure of humic substances, Nature, 270,709-710

Grant, D., Long, W.F. and Williamson, F.B., (1989a) Inhibition by glycosaminoglycans of CaCO3
(calcite) crystallization Biochem J. in press (added later to the original text later: this paper appeared in
Biochem J 1989 259 41-45)

Grant, D., Long, W.F. and Williamson, F.B., (1989b) Inhibition by carrageenans of CaCO3 (calcite)
crystallization; to be submitted to Biochem J.

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Proc., 37, 847-850

Hatcher, P.G. Towan, R. and Mattingly, M.A. (1981) 1H and 13C NMR of marine humic acids, Org.
Geochem., 2, 77-85

Hayes, M.H.B. and Himes, F.L. (1986) Nature and properties of humus-mineral complexes,
Interactions of Soil Minerals with Natural Organics and Microbes. Soil Sci. Soc. Amer. Special
Publication No. 17 pp103-150

Inskeep, W.P. and Bloom, P.R (1986a) Kinetics of calcite precipitation in the presence of water-
soluble organic ligands, Soil Sci. Soc. Am. J., 50, 1167-1172

Inskeep w.P. and Bloom P.R. (1986b) Calcium carbonate supersaturation in soil solutions of
calciaquolls, Soil Sci. Soc. Am. J., 80, 1431-1437

Kitano Y. (1983) Calcification and atmospheric CO2, Biomineralizaiton and Biological Metal
Accumulation. Ed. Westbroek, P and De Jong E.W., Reidel, Dordrecht, pp89-98

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crystallization of calcium carbonate, Geochimica et Cosmochimica Acta, 29, 29-41

Kononova, M. M. (1966) Soil Organic Matter, Pergamon Press, Oxford

Kuriyama, Y., Kajiwara, S. and Ozaki, F. (1985) United States Patent Specification No. 4,561,982

Liu, S.-T. and Nancollas, G.H. (1975) The crystal growth and dissolution of barium sulfate in the
presence of additives, Journal of Colloid and Interface Science, 52, 582-592

Ma’shum M., Tate M.E., Jones G.P. and Oades, J.M. (1988) Extraction and characterization of water-
repellent materials from Australian soils, J. Soil Sci., 39, 99-109

Morse, J.W. (1983) The kinetics of calcium carbonate dissolution and precipitation, Reviews in
Mineralogy, 11, 227-394

Nager, B.R. , Waight, E.S., Meuzelaar, H.L.C. and Kistemaker, P.G. (1975) Studies and the structure
and origin of soil humic acids by Curie point pyrolysis in direct combination with low-voltage mass
spectrometry, Plant and Soil, 43, 681-685

Nancollas, G.H. (1979) The growth of crystals in solution, Advances in Colloid and Interface Science,
10, 215-252

Oades, J.M. (1988) The retention of organic matter in soils, Biogeochemistry, 5, 35-70
Ogner, G. (1973) Permanganate oxidation of methylated and unmethylated fulvic acid, humic acid and
humin isolated from raw humus, Acta Chem. Scand., 27, 1601-1612

Pleysier, J., Janssens, J. and Cremers, A. (1986) A clay suspension stability end points titration method
for measuring cation exchange capacity of soils, Soil Sci. Soc. Am. J., 50, 887-891

Potts J.E., Clendinning R.A. and Ackart W.A. (1973) Proc. Symp. Degradability of Polymers and
Plastics, 27-28 Nov., 1973, Plastics Inst. London 12-1, -12-10

Raistrick, B. (1949) The influence of foreign ions on crystal growth from solution 1.

The stabilization of the supersaturation of calcium carbonate solutions by anions possessing O-P-O-P-
O chains, Disc. Faraday Soc., 5, 234-237

Reddy, M.M. and Nancollas , G.H. (1971) The crystallization of calcium carbonate I. Isotope
exchange and kinetics, J. Colloid and Interface Sci., 36, 166-172

Rogers, L.A., Tompson, Q.B., Maty, J.M. and Durrett, L.R. (1985) Oil and Gas Journal, 83 97-106

Schnitzer, M. and Khan, S.U. (1978) Humic Substances in the Environment, Marcel Dekker , New
York

Shurukhina, S.I., Shurukhin, V.V. and Tarlakov, Yu. P. (1973) Study of humus extracts by infrared
spectroscopy, Pochvovedeniye 146-149

Whitfield, M. and Watson, A.J. (1983) The influence of biomineralization on the composition of
seawater,

Biomineralization and Biological Metal Accumulation. Ed. Westbroek, P. and De Jong, E.W., Reidel,
Dordrecht, pp57-72

Wilson, M.A. (1984) Soil organic matter maps by nuclear magnetic resonance J. Soil Sci., 35, 209-
315

Wood, J.W. and Mora, P.T. (1958) Synthetic polysaccharides. III. Polyglucose sulfates, J. Amer.
Chem. Soc. 80, 3700-3702

[N.b. The following Figures were under construction but not professionally finished when the original
research project funding was terminated; the available preliminary production diagram of essential
data from are available and are now presented].

Fig. 1 of Ms. from M.C. (Figure in preparation)

Fig 1: (Ms from MC) Infrared spectra of substances studied as potential inhibitors of CaCO3 (calcite)
crystallization
See also web. scribdcom/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-III

Fig. I preparation further relevant data

Captions to Fig. 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.2 (of Ms. from M.C.)

Fig. 2 captions. Effect of additives on crystallization of CaCO3
curves (a) (c) (d) fulvic acid (prepn. 1) 100, 5.5 and 2.8 µ g/ml
(b) sulphated /sulphonated humic acid 20µ g/ml
(e) fulvic acid (prepn. 2) 15µ g/ml
(f)(g) lignin derivs. REAX 88B, REAX 100M 20µ g/ml respectively
(h) no additive.
 Fig. 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 µ 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 CaCO3
was respectively 100.0 21.0 3.5 and 0.0.
Fig. 4 (of Ms. from M.C.)

Fig. 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 µ 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 sulphate
e, heparin,
f, chondroitin 4-sulfate
(data for curves d-f were from Grant et al., 1988a).
Fig. 5 (of Ms. from M.C.)

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

CaCO3 1.6 mg/60ml 2.5x10-5 mol dm-3 H2SO4 solution; sulphated humic
acid, fulvic acid (prepn. 1); heparin; sulphated pectin

ACKNOWLEDGEMENTS
We thank Dr. M.V. Cheshire, Macaulay Institute, Aberdeen, for samples of humic and fulvic
acids, Mrs Marion Ross for preparation of sulphated 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

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
CaCO3(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.

Another report which contained some of the above results was

the following web.scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystaallizn-II
which was based on a document now reproduced here,

vide infra.
7b.
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 ca1000 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 non-calcareous 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) REAX 88B REAX 100M
498 w
532 w 533 w 521 m 533 w 511 w 513 m
558 w 551 m 554 w 557 w
624 w,b 616 m 627 w 616 w 615 m
642 s,b 640 m 644 m,b
716 w
764 w 760 w 760 w 743 m 742 m
783 s 783 s
807 m 805 m
882 m 874 w 892 m 872 s,b 855 m
964 s,b 954 m 941 m
1020 sh 1007 sh 996 m
1046 m 1049 n 1040 vs,b 1051 m 1034 sh
1107 s.b 1110 s,b 1061 sh 1052 vs
1152 s,sh 1132 m,b 1176 sh 1160 sh
1226 sh 1219 w,b 1276 w,sh 1237 s,b 1250 vs 1241 vs
1268 m 1266 sh
1386 s 1381 w,sh 1358 sh
1433 sh 1414 s,b 1431 s 1410 vs 1431 m 1436 m
1456 m
1556 w 1506 s 1503 m
1588 vs
1602 vs 1602 vs 1629 sh 1632 sh 1620 s 1609 m
1640 sh 1659 s 1686 sh
1707 sh 1716 sh 1730 sh 1737 sh 1746 sh
2110 w
2544 w 2544 m,b 2574 w 2626 sh
2940 m 2846 m, 2908 s 2959 w 2932 m 2969 m
3264 sh 3229 vs 3256 vs
3369 vs 3376 vs 3420 vs 3400 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 sulphate and
chondroitin 4 sulphate (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 sulphate half ester/ anhydrogalactose/

disacch. disacch.
(a) 380000, 0.98 0.82
(b) 750000 1.21 0.84
(c) 610000 1.28 0.60
(d) 500000 1.6 0.13
(e) 20000 2.75 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) 4.5 (d)

phosphate ca 4 (f)
ethane, hydroxy, 1,1-diphosphonate ca 20 (f)

Dequest-2041
(N,N,N’,N’ ethylenediaminetetramethylenephosphonate) ca 22 (g)
_______________________________________________________________
heparan sulphate 1.15 (e)
heparin 1.06 (e)
chondroitin 4 sulphate 0.35 (e)
__________________________________________________________________

(a) calculated from results reported by Inskeep & Bloom (1986)) ;

(b) calculated from present studies (25C)
(c) deriviativized by sulphation; (cf sulphuric 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 sulphonated
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 commerical
polyphosphate calcification inhibitors but were up to some two orders of magnitude more
effective than animal polysaccharides inhibitors such as heparin or heparan sulphate and
analogous algal coccolith sulphated 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 sulphate) and a rational dependence upon polysaccharide microstructure
evidenced (Grant et al unpublished results summarized in Table V)).

Table IV
Barium sulphate 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 13.3
Ethane hydroxy 1,1 diphosphonic acid (Grant 1979) 4.2
Scaletreat 206 1.8
Baker ML 1559 1.2
Nalfloc NAL 1285 0.9
Fulvic acid (Countesswells) 0.4
sulphated
oligosaccharide 10 0.1
Donmarn actipol

heparin 30 4

sodium - 6
tripolyphosphate
Aquarite - 9.5

Table V
Alginate microstructure dependent BaSO4 crystallization

Alginate Relative Attained

Microstructure Disaccharide chain Second order rate const after initiation
length period , min

control (none present) 100 0

random 25 59.6 0

poly G 80 36.4 ca 0
blocks

F387 24 18.8 2

poly M acid 4000 15.2 2

poly M blocks 22 14.6 1

poly
alternating 22 6.0 0.5
MG blocks

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 (sulphated) otherwise difficult to
quantify humic acid from the same soil.

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 sulphate 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 sulphates.
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. Sulphation 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).

References

New Scientist 16 May p7

Soils spoilt by farming and industry
(24% of soils are seriously degraded and two thirds of soils in Africa and Asia)

Berner RA Westrich JP Graber R Smith J Martens CS (1978)

Amer J Soil Sci 278 816-837 CHECK
(reviewed by Morse (1983)

Freundlich H (1922)
(English translation 1926)
Colloid and Capillary Chemistry p336-341
Methuen, London

Glentworth R Muir JW (1963)

The Soils of the Country Round Aberedeen, Inverurie and Fraserburgh
Mem Soil Surv Gt Br Scot Edinburgh HMSO

Grant D (1977)
Chemical structure of humic substances
Nature 270 709-710

Molecular composition of soil organic matter components using proton and 13-C NMR
techniques
International Peat Society was also discussed by D. Grant
Proc International Workshop (Braunschweig, Germany) on Properties of Organic Peat
Components, Abstract No 11.
[1-H and 13-C NMR spectra allowed classification of humus-derived organic polymers e.g.
following removal of paramagnetic ions by sodium pyrophosphate chelation. Humus
polymers were originally thought to contain condensed aromatic core structures e.g. derived
from lignin or consisting of hydrogen-bonded aggregates of low molecular weight phenolic
compounds analogous to phenol formaldehyde resins; a non-aromatic core structure similar
to polymaleic anhydride had also been postulated. Use of NMR however indicated a
degraded-carbohydrate type of core structure associated with highly branched polymethylene
structures, and generally smaller amounts of aromatic structures than previously thought to
be present in humic polymers. The amounts and microstructures of these oligomeric
polymeric organic components, which are considered to be linked by hydrogen bonds and by
metal ion crosslinks onto colloidal-size particles, including clays, varies systematically
between soil types].

Grant D (1979)
The rearrangement polymerization of phosphorus acid with acetic anhydride
Eur Polym J 15 1161-1165

Grant D Long WF Williamson FB (1987)

Infrared spectra of heparin-cation complexes
Biochem J 244 143-149

Grant D Long WF Williamson FB (1989)

Inhibition of glycosaminoglycans of CaCO3(calcite) crystallization
Biochem J 259 41-45

Grant D Long WF Williamson FB (1992)

Degenerative and inflammatory diseases may result form defects in
antimineralization mechanisms afforded by glycosaminoglycans
Medical Hypotheses 38 49-55

Hoch AR Reddy MM Aiken GR (2000)

Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids
from the Florida Everglades
Geochim Cosmochim Acta 64 61-72

Houghton RA Woodwell GM (1989)

Global climatic change
Scientific American 260 (4) 18-26

Howarth WN Pinkard FN Stacey M (1946)

Function of bacterial polysaccharides in the soil
Nature 158 836

Inskeep WP Bloom PR (1986)

Kinetics of calcite precipitation in the presence of water-soluble organic ligands
(additional index words calcium carbonate, crystal growth,
fulvic acid, calcite, supersaturation)
Soil Sci Soc Am J 50 1431-1437; cf ibid 1167-1172

Kitano Y (1983)
Calcification and atmospheric CO2
Biomineralization and Biological Accumulation
P Westbroek and EW de Jong (eds) Reidel Dordrecht cf pp 89-98

(cf also Garrels RM & Berner RA (1983)

The global carbonate-silicate sedimentary system--some feedback relations
ibid 73-87);

Kononova MM (1966)
Soil Organic Matter
Pergamon Press Oxford

Lashof DA Ahuja DR (1990)

Relative contributions of greenhouse gas emissions to global warming
Nature 344 529-531

Morse JW (1983)
The kinetics of calcium carbonate dissolution and precipitation
Reviews in Mineralogy Vol 11
Carbonates: Mineralogy and Chemistry p227et seq
R J Reeder Ed
PH Ribbe Series Ed
Mineralogical Society of America

Nagar BR Waight ES Meuzelaar HLC Kistemaker PG (1975)

Studies on the structure and origin of soil humic acids by
Curie point pyrolysis in direct combination with low-voltage mass spectrometry
Plant and Soil 43 681-685

Nancollas GH (1979)
Advances in Colloid & Interface Science 10 215-252
(cf Reddy MM Nancollas GH (1971)
The crystallization of calcium carbonate I. Isotopic exchange and kinetics
J Colloid Interface Sci 36 (2) 166-172)

Nancollas GH Kazmierczak TF Schuttringer E (1981)

A controlled composition study of calcium carbonate crystal growth: the influence of scale
inhibitors
Corrosion-NACE 32 (2) 76-81

Ogner G (1973)
Permanganate oxidation of methylated and unmethylated fulvic acid humic acid and humin
isolated from raw humus
Acta Chem Scand 27 1601-1612

Pentecost A (1985)
Photosynthetic plants as intermediary agents between environmental HCO3-
and carbonate deposition
Chapter 29 (p459-481) in
Inorganic Carbon Uptake by Aquatic Photosynthetic organisms
Eds WJ Lucas JA Berry (American Society of Plant Physiologists)

cf Borowitzka MA (1987) Calcification in algae: mechanism and the role of metabolism

CRC Critical Reviews in Plant Sciences 6(10) 1-45

Pleysier J Janssens J Cremers A (1986)

A clay suspension stability end point titration method for measuring
cation exchange capacity of soils
Soil Sci Soc Am J 50 887-891

Potts JE Clendinning RA Ackart WA (1973)

The effect of chemical structure on the biodegradability of plastics
Proc Symp Degradability of Polymers and Plastics 27-28 Nov 1973
Plastics Inst London 12-1 - 12-10
(studies reported herein show that the biodegradability of hydrocarbon chains in soil although
rapid for smaller chains becomes very slow above C30 and this circumstance evidently allows
substantial amounts of naturally formed (partly oxidized) quasi-low-density-polyethylene
humic substances to accumulate in the soil)

Schnitzer M Khan SU (1978)

Soil Organic matter
Elsevier

Suess E (1970)
Interaction of organic compounds with calcium carbonate - I.
Association phenomena and geochemical implications
Geochim Cosmochim Acta 34 157-168

Suess E (1973)
Interaction of organic compounds with calcium carbonate -II.
Organo-carbonate association in Recent sediments
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.

7b1.
Versions of the above documents have been published on the
internet
8.

Further references and comments

8a
Sillén LG
How have sea water and air got their present compositions?
Chemistry in Britain 1967 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 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
I.e. this article extends the conventional carbonate CaCO3, CO2 model of the marine
global cycle by showing that other inorganic systems likely contribute in major ways
to the buffering of the sea. Since the fulvate system can influence the surfaces of
other minerals than CaCO3 it is also likely that the manner in which other-than-CaCO3
marine buffer systems work depend on their interactions with fulvate.
An interesting statement made in this 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.

8a-1
The probable complete lack of thermodynamic equilibria in seawater was
discussed by P.J. Wangersky in a letter to Limnology & Oceanography
1972 17 (6) 960-962 available at
web.aslo.org/lo/toc/vol_17/issue_6/0960.pdf
P.J. Wangersky noted that because of complex interactions in the web of
equilibria governing the inorganic ion systems of seawater it is not
feasible, except in theory to use any of the laboratory determined
thermodynamic constants to calculate the real equilibria in seawater.
Furthermore, ion pairs will exist and have relevance to the attainment of
the composition of the sea but data relating to their formation especially
under hydrostatic pressure conditions are lacking . The phenomenon of
re-dissolution of CaCO3 in deep water seems to occur by some quite
different process from that supposed by the traditional model in that it
does not appear to occur in the water column but instead depends on
processes which occurring at the sea floor.
This paper reported a study of the precipitation of CaCO3 (calcite) and
found no re-dissolution occurred at depth. I.e. the traditional
carbonate pH buffer system of the sea is not supported by the direct
experimental work of this author. It therefore should not be used in
models of the carbon cycle. The supposed CaCO3 buffer system does not
explain the behavior of the sea. The basis of the departure from
thermodynamic behavior is because of the formation of organic matter
surface barriers on the CaCO3 (calcite) surfaces.
This is the fulvate of the present paper.
P.J. Wangersky noted that “ for the most part the incorporation of calcite
into organic aggregates and the adsorption of surface active organic
compounds on chemically or biologically precipitated calcite may
represent a delay mechanism with a long time constant built into the
carbonate cycle in seawater”.

8b
TEPs (transparent expolymer particles) at the sea surface
The selective adsorption of CO2 into transparent exopolymer particle
(TEP) stabilized bubbles which ubiquitously occur at the ocean surface
and are especially abundant following algal blooms may be at least partly
responsible for the creation of a relatively short lived CO2 pool at the
surface of the ocean which is a possible major factor in causing abnormal
augmentation of atmospheric CO2 levels.
Cf., J Zhou et al., Limnol Oceanography 1998 43 (8) 1860-1871
The formation of TEP seems to arise from sulfate acidic polysaccharide
precursors (heparan sulfate analogs) released by diatoms.

8c Stable colloidal CaCO3 as a carbon sink in seawater

(e.g. produced as a consequence of the ability of humic matter to latch
onto nanoparticles of amorphous CaCO3 and putatively stabilize solid
phase colloidal sized, very high surface area not-easily-sedimented
(precipitated) pool of hyperactive [perhaps hydrated even something
like clathrated] colloidal carbonates or ‘basic carbonates’ (which can
later, e.g., if the sea is heated, fairly easily re-release CO2 gas into the
atmosphere). Colloidal CaCO3
[Very small CaCO3 particles can stay in suspension and do not undergo sedimentation].
It is likely that humic matter will also absorb onto the colloidal spherical amorphous CaCO3 particles
which arise (cf. Bolze et al. Langmuir 2002 18 (22) 8364-9) e.g. when CaCl2 and Na2CO3 are mixed.
That such colloidal CaCO3 occur in the sea as the principal form of CaCO3 particle there present has (at
least under the specific shallow sea situation investigated by Morse et al.

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 this may also be enabled by humate via uptake of H3O+ by this
polyanion system.

The larger, potentially sediment forming, particles of CaCO3 can re-dissolve at great depth however as
was 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 from the deposition of shells of
marine organisms which use forms of CaCO3 as exoskeletons.
The open ocean is, however, thought not to behave in such a manner but is thought to be more
influenced by the existence of a CaCO3 re-dissolution process determined by the greater CaCO3
solubility which occurs with increased pressure.

The currently held view that a distinct difference exists between the shallow and deep seas in regard to
the ability of CaCO3 to serve as a sink for CO2. . This theory is now suggested to be incorrect.

While CaCO3 solid phases are de-stablized by pressure in the deep sea
CO2 hydrate clathrates are stabilized by an equivalent pressure in the deep 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 hydrate clathrates which are stable under pressure conditions (also associated with re-dissolution
of solid CaCO3) which occur at the bottom of the sea (these are currently less well known, however,
than the analogous CH4 hydrates, but they contribute significantly to CO2 cycling under global
warming conditions). This suggests that in the deep sea the type of transformation may occur. A
further hypothesis could suggest a catalytic or stoicheometric role for fulvate in this transformation
CaCO3 (solid) + nH2O + fulvate -> Ca2+ -fulvate + CO2(H2O)n

The supposed dual mechanism of CaCO3 precipitition 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 colloidal stability control system is suggested to depend on the
activity of natural humate polyanions.
Marine organisms are now thought also to use extra-cellular polyanions such as anionic
polysaccharides to orchestrate such calcification activities in a manner analogous to how the humic
polyanion system may control the marine carbonate and abiotic CaCO3 formation system. Such
extracellular polysaccharides (which mimic the actions of humic matter polyanions) are also part of the
dissolved organic matter (DOM) pool of the sea.
A re-evaluation of how the carbon cycle is accomplished seems to be needed if, as seem 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 this phase change which leads to the creation of a colloidal system. The
idea that shallow sea and deep sea both use CaCO3 different kinds of precipitation removal mechanisms
it is suggested to be flawed.
Humic polyanions which include aggregates of degraded proteins and degraded anionic
polysaccharides evidently could provide for multiple biosphere controls of biological CaCO3
formation and its stable colloidal phase “precipitation” in all compartments of the natural water
based carbon sink system.

8d
What are Humic Substances?
Humic organic matter occurs in the soil, natural waters and dust particles
in the atmosphere forms the largest organic chemical facilitator of the
biosphere (e.g. containing more than twice or more C than that
present in atmospheric CO2). This organic matter system contains
major fractions which are termed humic and fulvic acids which
consist mainly of a system of poly-carboxylated anionic organic
polymers. This polymer system acts as the primary biosystem
regulator. It effects the rate of weathering of rocks, the supply of
inorganic elements to soil natural waters including the sea where they
it can also determine the formation of new minerals by controlling the
rates and pathways of crystal formation; it binds and stabilizes soil
particles, controls the uptake and availability of water, provide a
major and minor nutrient element collector and reservoir system for
biota and thereby supports a normally approximately balanced natural
respiratory and photosynthetic global CO2cycling activity in which
the amounts cycled to and from the atmosphere are very much greater
(by one to two orders of magnitude) than the CO2 injected into the
atmosphere from fossil-fuel combustion. The ability humic matter to
control crystallization putatively acts a control system for the
precipitation of CaCO3 in the sea thereby setting the degree of
supersaturation of this substance in the seas surface which suggests a
plausible mechanism by which human actions can alter this value and
thereby affect the global carbon cycle so as to cause atmospheric
warming and climate change.
The above circumstances could suggest that the study of humic matter
and how this can be altered by anthropogenic activities should be a
primary focus of concern regarding current abnormal increase in CO2
in the atmosphere. It should be further noted that the historical rate by
which soil humus has become degraded by human actions have
dramatically increased due to the use of more intensive agricultural
methods in recent years. These anthropogenic effects (ongoing in an
accelerated fashion from the start of the industrial revolution) have
occurred in tandem to the historical rate of increase in atmospheric
CO2 over the same period of time.
Agricultural activities which can greatly increase the injection of
terrestrial humic substance into the sea can empower humans with a
facile mechanism to greatly increase the greenhouse gas CO2 content
of the atmosphere.

The humic organic matter polymer system is believed to be

formed in the soil and in natural waters by a chemical re-
synthesis (under both biotic and abiotic catalytic influences) of
secretions from living organisms and detritus from dead ones
which creates a system of colloidal chemical particles which
demonstrate a surprising degree of reproducibility in elemental
and spectroscopic (e.g. NMR) properties from various terrestrial
and marine environments. Soil organic matter is traditionally
divided into humate and fulvate polyanion fractions on the basis
of aqueous alkali solubility.
Traditionally-Established Functions of Humic Matter in the
Environment
The unusual chemical and physical properties of the anionic
organic polymeric humic substances which occur in the soils,
natural waters and the atmosphere allow them to stabilize soils,
to bind and conserve water and nutrient elements and perform a
critically important role in the biological carbon cycle system of
the Earth.

Polycarboxylated Humates
Aliphatic structures with randomly spaced carboxylated units
side-groups seem to be the most common type of chemical
structure present in humate molecules. These ligands can mimic
and sometimes greatly surpass the water and inorganic ion and
moiety binding effectiveness of carboxylated polyuronate
containing extracellular polysaccharides secreted by all types of
organisms (putatively for this purpose).

8d-0
Possible roles of polyanionic substances in the evolution
of life on Earth
The preferential adsorption of L-amino acids by CaCO3
The high specificity of fulvate CaCO3 complexation is perhaps of
relevance to a fuller understanding of the mechanism by which life
originally evolved on Earth. Cf. CaCO3 seems to selectively bind L-
over D- amino acids (Orme CA et al., Nature 2001 411 775-79; Hazen
RM et al., PNAS 2001 98 5487-5490; cf. Kojo S Symmetry 2010 2
1022-1032) which could further suggest that a pre-biotic CaCO3-organic
matter poly carboxylate polyanion complex similar to the organic matter
which apparently exist on comets and asteroids might have orchestrated
the uptake of the building blocks of life from a prebiotic soup organic
matter system which has been rigorously retained by the natural water
systems of the Earth. This mechanism is surprisingly also likely also to
have enabled human actions to alter the climate of the Earth.
The CaCO3-fulvate system has putatively evolved into a series of CaCO3-
polysaccharide systems including that of animals as discussed in the next
Section.

8d-1 What is the Heparanome?

The management system provided to animal tissue regulation by
the heparanome is analogous to the system of control of the
Earth’s biosphere afforded by humus and especially by the
major humus fraction termed ‘fulvate’ of ‘fulvic acid’.
The heparanome (the linearly encoded tissue management system of
protein activity control putatively afforded by the heparan sulfate anionic
polysaccharide patterns and their inorganic element adducts and loosely
analogous to the genome) which is associated with animal cell surfaces
and extracellular matrices provides inter alia a flexible multi-inogranic
element buffer system which may specifically have been evolved from its
precursor, less-effective inorganic surface and inorganic ion binding
bacterial polyglucuronates coincidently with the co-evolution of the first
primitive animal cells in the sea by the evolution in such cells of the
glucuronate isomerase enzyme needed to convert glucuronate into the
more flexible iduronate carboxylates which can more effectively act as
inorganic ion buffers and as calcification inhibitors. The iduronate
system seems more closely mimic the seawater fulvate inorganic ion
homeostasis and CaCO3 / HCO3-/CO2 poly-carboxylate polyanionic
control systems. Both systems have apparently been carefully conserved
form the start of life on Earth (the heparan system began with animal
evolution (in the sea) [4a-1]).

8e
Polymethylene-Rich Humates Might Offer a Useful Tool to
Combat Global Warming & Climate Change
The humate –fulvate characterization of humic matter which is
partly determined by a highly aliphatic hydophobic component.
NMR studies showed that, apart from the carboxylated structural
units, but a major fraction (often ca. a third) of humic matter
throughout the world consists of long chain (CH2)n- aliphatic
polyethylene –like structures [1a]; these soil structures are
likely to show a similar outstandingly high chemical stability in
the soil environment to that which is well known for man-made
polyethylene. The deliberate cultivation of this kind of humic
matter could therefore be a potentially useful way of achieving a
stable soil carbon sink to offset the augmentation of atmospheric
CO2 produced by the burning of fossil fuel.

8f
Further Discussion of
The Ruddiman Hypothesis of Late Holocene Anthropogenic
Global Warming

Early farmers, some 7000 years ago, possibly by damaging the topsoil
organic matter in a manner similar to how modern farmers also achieve
this, may have left an anthropogenic imprint on the atmospheric CO2
content preserved in the ice core evidence which show up as sudden
increase of up to a few tens of ppms in the amount of CO2 present.
Hansen (8-1) seems to agree with this idea in principle (ref. 8-7-6). But
the extra CO2 7000 years ago could not have come from the burning of
wood since the maximum amount of CO2 which could have come from
this source of carbon was much too small. J. Elsig et al., (8-7-4) further
showed that there was no plant matter 13δ C deficit in the ice core CO2
evidence which indicated that the extra CO2 had probably come from the
sea which agrees with the present hypothesis that terrestrial fulvate runoff
induced by agricultural soil degradation produced an increase in the
degree of supersaturation (Ω ) of CaCO3 (calcite) in the ocean. This has
an equivalent effect on CO2 release by the ocean to an increase in ocean
temperature which seems less likely to have arisen by the kind of
anthropogenic effects which the sparse human population present during
the late Holocene were capable of. That this small human population
could have easily have been capable of perturbing the oceanic fulvate
balance because of the large deforestation of Eurasia which occurred at
the time of the first spread of agriculture and hence increased atmospheric
CO2 further suggest that the current much larger augmentation of
atmospheric CO2 occurring at the present time also arises, at least in part,
from a currently underway anthropogenic disturbance of the carbonate
balance of ocean.

8g
Further discussion of Suess E
Contribution of related papers
Chave KE Suess E
Calcium carbonate saturation in seawater: Effect of dissolved
organic matter
Limnol Oceanogr 1970 14 633-637
read at web.aslo.ng/lo/toc/vol_15/issue_4/0633.pdf
The amount of dissolved organic matter in the studied seawater
was ca. 1ppm (based on carbon content) which effectively
determined the observed long-term supersaturation of CaCO3 in
seawater.
A range of seawaters, artificial seawater and aquarium waters when treated with Na2CO3
solution to raise the pH to 9.5 exhibited CaCO3 precipitation at rates which decreased
markedly with increasing dissolved organic matter content, so that precipitation was
effectively permanently inhibited at dissolved organic matter contents of ca.3-4ppm (on a C
basis =ca.14ppm on a wt. basis). This agrees fairly well with the results shown in Fig..3 of
the M.C. document (Section 7a) of a draft paper of the inhibitor effectiveness of agricultural-
soil-derived fulvate on in vitro seeded CaCO3 crystallization conducted in NaHCO3 solutions
which had been prepared using distilled water.
Rapid precipitation of CaCO3 at high pH values could only be achieved by Chave and
Suess after the organic matter had been removed from the seawater solution.
Mg2+ was also indicated to inhibit CaCO3 sedimentation but this was apparently not
the dominant factor supporting the natural marine homeostasis system.

Interaction of organic compounds with calcium carbonate-II.

Organo-carbonate association in Recent sediments
Geochim Cosmochim Acta 1973 37 2435-2447
Interaction of organic compounds with calcium carbonate-I
Ibid., 1970 34 157-168
Cf. also Kitano Y Hood DW (8-7-6)
and Kitano Y (1983)
Calcification and atmospheric CO2
(A paper in)
Biomineralization and Biological Accumulation
P. Westbroek and E.W. de Jong Eds. Reide,l Dordrecht p 89-98

Cf. also
Gunthorpe ME Sikes CS
Potent natural inhibitors of CaCO3 crystallization from chalk deposits
Ohio J Sci 1986 86 (3) 106-109
The Selma (Alabama) chalk extract which seemed to consist mainly of
(presumably degraded so that they might more accurately be described as
humic matter) 0.10% soluble matter polysaccharide-like materials but
also containing (as does humic matter) some protein-derived components
0.05% soluble matter per dry weight; the authors suggested that the
polysaccharides might be similar to those discovered to control CaCO3
formation in coccoliths by de Jong et al. (8-0-2-1-2); the anti-CaCO3
crystallization behaviour found by these authors had a similar potency
under one of the assay conditions to ethane, 1-hydroxyl,1,1-
diphosphonate [hydroxyethylidene diphosphonate (HEDP)] but the
geological organic residue still associated with the chalk CaCO3 was
apparently possibly among the most potent known material of this type,
total inhibition being observed under one experimental protocol based on
inhibition of nucleation of crystallization showed total inhibition occurred
with HEDP at 0.06 µ g/ml but with the chalk extract this occurred in the
range of concentrations between 0,025 and 0.25 µ g/ml.
A difference from commercial CaCO3 scale inhibitors, which was
attributed to the present of degraded proteinaceous materials in the chalk,
was that under certain conditions the chalk extract could also increased
the rate of CaCO3 crystallization.

Cf. the appended Aberdeen U. polysaccharide lab study of inhibitors of

CaCO3 crystallization indicated that the most active humic matter derived
polyanions extracted from soil were however were at least an order of
magnitude of greater anti-CaCO3 potency than HEDP when studied by
the Nancollas seeded crystal growth method (using the apparatus
described by Grant D. et al. in Biochem J. 1989 259 41-45.

8h. (8-0)

Falkowski P discussion of dominant role of the sea in

determining the amount of CO2 in the atmosphere

Although the following article does not mention humic matter it

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 Porcal P et al. Humic substances-Part7: the
biogeochemistry of dissolved organic carbon and its interactions
with climate change
Environ Sci Polluat Res Int 2009 16 (6) 714-714

[Dissolved organic matter (DOC) which includes humic matter, is an

important component of aquatic ecosystems which have possible
important relevance for a fuller understanding of climate change.
The authors review the literature on this topic from the pre-conception
that climate change and global warming has caused the observed
alteration in the humic matter present in natural waters (in general global
warming seem to be associated with an (often greatly) increased
dissolved humic matter [=fulvic acid] content of river and lake waters) in
N. America and N. Europe. It should be noted that these are areas of the
Earth which have been subjected to the greatest anthropogenic alteration
of humic matter via agriculture and atmospheric pollution, activities
which are known to decrease the molecular weight of humic matter and
cause it to be more soluble in water].

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

Leenheer JA Reddy MM
Co-precipitation of dissolved organic matter by calcium carbonate in
Pyramid Lake, Nevada
Annal Environ Sci 2008 2 11-25
8-0-2
Boyce DG. et al.
Global phytoplankton decline over the past century
Nature 2010 466 591-5
A decline by approximately half in phytoplankton production is indicated
to have occurred in 8/10 of ocean regions since 1899.
Fluctuations in phytoplankton were also found to be strongly correlated
with climate indices. The long-term decline in phytoplankton seemed to
be correlated with an increased sea surface temperature.
[This indicates that the increased atmospheric CO2 may have been caused
by the anthropogenic disturbance of phytoplankton populations].

8-0-2-1
Inglesias-Rodriguez M D et al., Science 2008
[Increased CO2 in the Earth’s atmosphere is causing phytoplankton to
produce greater amounts of CaCO3 with potentially wide ranging
implication for predicting the cycling of carbon in the ocean and climate
mobility].
It should be noted that other authors have disagreed with the conclusions
of this paper (cf. Bernard O ref. 8-0-2-1-1vide infra).
{The abnormal increase of calcification of marine coccolithophore
Emiliana huxleyi phytoplankton reported by Inglesias-Rodriguez et al.
seems a possible but unconventional mechanism by which the increased
atmospheric CO2 could have led to the marked observed reduction in
photosynthetic phytoplankton activity over the last century [as reported
by Boyce et al. (ref. [8-0-2])] and which, rather than the anthropogenic
injection of CO2 into the atmosphere may be the principal mechanism
which atmospheric CO2 levels have increased above their normal
interglacial homeostatic levels of ca.250ppm; it is further suggested that
such augmented phytoplankton calcification activity is caused directly by
the presence of anthropogenically augmented terrestrial humic matter in
the ocean which inhibits the normal control system of anionic
polysaccharide dependent coccolithophore calcification regulator which
tends to drive the phytoplankton internal surfaces to now act as
hyperactive seeds and following the deposition thereon of CaCO3 perhaps
also causes blocking off the sunlight and consequent reduced
photosynthetic activities which otherwise normally act as the major
reducer of seawater dissolved CO2 and therefore atmospheric CO2 to
which this and other species contribute [Inglesias-Rodriguez believed,
however, that the increased calcification of these phytoplankton was
carbon neutral since the calcification and photosynthetic activities seemed
to balance out each other as regards their influence on atmospheric
CO2]}.

8-0-2-1-1
The Critical Role of CaCO3 in the Biogeological Carbon Cycling
System
Cf. Ridgwell A Zeebe RE
web.gmacweb.env.uea.ac.ek/e114/publication/manuscript_ridgwell_and_
zeebe.pdf
The Role of the Global Carbonate in the Regulation and Evolution of the
Earth System
[This review article 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 CaCO3 which buffers ocean
chemistry and atmospheric CO2 but the current increase in atmospheric
CO2 and the associated pH decrease in surface sea which is believed to be
without precedent in the geological records over the last 100Myr seems to
be adversely affecting these organisms and makes uncertain the future of
this part of the carbon cycle.
This review also draws attention to
8-0-2-1-1-1
the work of J.W. Morse et al.
(Geochem Cosmochem Acta 2003 67 (5) 2819-2828, a study of the
CaCO3 precipitation kinetics in the Great Bahama Bank) which confirms
that CaCO3 exists in a supersaturated state in the sea water column and
that precipitation of CaCO3 does not occur spontaneously but almost
completely depends on the presence of re-suspended sediment particles
(e.g. aragonite particles which act as seeds for CaCO3 calcite
precipitation); this determines the rate of CaCO3 removal from the sea.
This is ‘whiting’ precipitation (but the majority of CaCO3 particles
formed in this process are not white (visible) but in the colloidal size
range a circumstance which could indicate that these particles sediment
very slowly and may be easily re-suspended? Could the particle size
distribution and its perturbation by anthropogenic influences be relevant
to global warming? The colloidal state CaCO3 pool may conceivably be
the “ missing link” sought to achieve the anthropogenic carbon balance)
[Cf. also the earlier work of Morse et al discussed in section
{This review also mentions the saturation horizon of the open ocean
below which Ω becomes less that the solubility product determined
value.
It should be noted, however that the binding of e.g. fulvate to CaCO3
crystals will change Ω and hence the position of this horizon to deeper
waters. Paradoxically the blocking off of CaCO3 active sites for crystal
growth by strong ligands increases the effective solubility of CaCO3 in
seawater both at the surface and in deep water.
The further question may be asked however, are there any other types of
ligands which might have been introduced by humans which could
directly increase the solubility of CaCO3 in seawater by increasing the
rate of the disintegration [such ligands would act to decrease the Ω value
of affected crystals]}.
8-0-2-1-2-1
Amorphous colloidal size CaCO3 particles

Ostwald established a general principle that unstable phases often crystallize initially in
apparent contradiction of the laws of thermodynamics. In the case of CaCO3 , amorphous
CaCO3 are believed initially to form but redissolve and reform on seed particles of more
stable phases by a process of ripening. Where surface coverage can occur e.g. in the presence
of abundant surface binding ligands such as fulvates, it is conceivable that these metastable
phases will persist.

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 270 nm form
when CaCl22H2O and NaCO3 solutions are
mixed in a stopped flow apparatus. These particles which do not
aggregate are remarkably uniform in size and have mass density of 1.62 g
cm-3 and are precursors of the thermodynamic form of calcite.
[The ability of humic polymers etc. adsorbed at the surfaces of these
particles to inhibit the attainment of the thermodynamic crystallization
seem a credible mechanism by which a stable pool of non-precipitating
CaCO3 dispersions of relevance to how the global carbon cycle, was set
up in the first place].

8-0-2-1-2-2
Role of colloidal CaCO3 particles in calcareous soils
Cf. Baghimejad M Darymple 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

8-0-2-1-2-3
Role of surfactants in regulation of amorphous CaCO3 particle
assembly
Cf. Z. Sadowki et al.
Physiochem Probl Miner Process 2010 44 205-214
8-0-2-1-2-4
The Work of G. H. Nancollas et al. on the kinetics of
crystallization of CaCO3 and BaSO4 and the effects of
inhibitors on this process
A main theme of the present research note is information obtained from
the accurate determination of the rates of seeded crystallization of CaCO3
and other sparingly soluble salts and the effects of inhibitors and
promoters of this phenomenon. This data could be relevant to the
anthropogenic alteration of atmospheric CO2 via the marine CaCO3
recycling mechanisms. Although the possible effect on climate of
oceanic CaCO3 formation was not specifically studied by G.H. Nancollas
et al, the experimental and intellectual approach to the subject of seeded
crystallization of biologically relevant sparing soluble minerals developed
by this renowned experimental physical chemist and his coworkers is
pivotal to the present hypothesis.
Of the publications by G.H. Nancollas et al. which are listed at web.
chemistry.buffalo.edu/people/faculty/nancollas/nancollaspublications, the
papers numbered 90, 92, 106,110,115,121-124,126,128, 136, 138,
146,149, 155,157, 160, 183, 196, 200, 203-4, 207,213, 217, 241, 266,
286, and 336 are suggested to be of especial relevance to a fuller
understanding of the inhibited CaCO3 solid phase formation climate
change hypothesis.

8-0-2-1-2-5

Bernard O. et al. report;

Fulvate causes an increase in CaCO3 calcite (Ω ) in natural waters – this
mechanism may determine E. huxleyi behaviour in regard to how
phytoplankton behave in relation to the natural climate control
mechanism of the sea.)
The role of degree of saturation of CaCO3 (Ω) as a possible control
factor for the calcification behaviour E. huxleyi was discussed by
O. Bernard et al. (web.biogeoscience-discuss.net/6/C3701/2009/bgd-6-
C3701-2009-supplement.pdf .
These authors drew attention to the requirement to identify the servo
control mechanism by which the calcification process is controlled in
these organisms.
Knowledge of this mechanism is needed to establish how these organisms
can affect the carbon cycle in the sea and consequently also the
atmospheric content of CO2.
8-0-2-1-2-6
Aberdeen U. papers on calcification mechanisms
It is fairly well known that algae, like humans, rely on anionic
polysaccharides to control calcification. The existence of polysaccharide
servo feedback control processes in animal species including humans was
suggested e.g. by work conducted in a former Marischal College
(Aberdeen University, U.K.) polysaccharide laboratory of which some of
the published papers are listed on the internet at
web.abdn.ac.uk/~bch118/publications2003march.doc [cf. section a refs.
33,34,41,42,59 and 60, section b refs. 13,33, 35,50 and 58 and section d
ref. 1). (Similar studies have of been undertaken in other labs e.g. as
reported by Y. Hiroakna et al. Mar Biotechnol 75 634-644 and M.
Okazaki et al. ibid., 1998 6 16-22).
8-0-2-1-2-6-1
Animal servo-feedback synthesis of specific poly-carboxylate
anionic polysaccharide seed crystal blocker for inhibition of
kidney calcification
An example from more recent studies (in another laboratory) of how the
polysaccharide servo feedback system work is illustrated by the human
kidney response to perceived thereat of imminent pathological crystal
growth insult (cf. Borges F T et al. Kidney Int 2005 68 1630-1648) in
which the organism attempts to prevent pathological formation of
calcium oxalate and calcium phosphate seed particles which could
otherwise would go to produce damaging kidney stones is by
synthesizing more effective seed particle inhibitors (this is done by
creating the correct microstructure to attach to the active crystal growth
sites evidently in response to the perceived supersaturation (Ω ) state and
chemical composition of potentially pathological crystalline phases.
It is likely that a similar servo feedback mechanism also exists in marine
algae as well as in marine invertebrates which contain complex heparan
sulphate encodes the basis of the heparanome, a ‘smart’ control
information sorting and control system the full range of tissue protection
properties of which are now emerging from polysaccharide research.
Anionic polysaccharide structure variation appears to have been adapted
for designed tissue protection. This may be why there seems to existence
an exact exponential mathematical relationship between the amounts of
heparan sulphate proteoglycans and other glycosaminoglycans present in
aquatic invertebrates and the salinity of their habitats (Nader HB et al.,
Comp Biochem Physiol 1983 76 433-436) {Evidently for the evolution of
such organisms and perhaps also for other species, the cell surface
polysaccharides must be carefully balanced against the chemical nature of
the extracellular fluids. This requirement for bio-availability using
carefully orchestrated polysaccharides may originate from the presence of
humic polyanions in earlier stages of the evolution of the ancestors of
multicellular organisms. The chemical diversity of the humic polyanion
could analogously become damaged in soils which may similarly suffer
“illness” similarly to how the extracellular polysaccharides are apparently
become damaged prior to or during pathological insults in animals
including humans}.

8-0-2-1-2-7
E. huxleyi polysaccharide production

For E. huxleyi polysaccharide production has been reported (Kayan K &

Shiraiwa Y Plant Cell Physiol 2009 59 (8) 1522-1551) to switch from
coccolith associated anionic polysaccharide produced under inorganic
phosphate depletion to neutral polysaccharide under inorganic phosphate
nutrient sufficiency.
This draws attention to the inorganic phosphate nutrient status of
seawater as part of the mechanism by which anthropogenic inputs could
alter the ability of phytoplankton to act as storage sinks for atmospheric
CO2. A possible mechanism of slowly released inorganic phosphate
sequestered in humic matter or produced by the slow oxidation of
anthropogenic herbicide or laundry detergent phosphonate which can act
as a surrogate for phosphate as a signalling molecule. (Phosphonates are
generally poorly degraded in the sea but there seems to be hint that
marine microbiota are adapting to use this P as a nutrient; (could even
the anthropogenic climate warming get less severe when this evolution is
complete!)
In soil and natural waters readily bioavailable inorganic phosphate and
nitrate will becomes rapidly utilized by the biota there present and seems
unlikely to reach the open sea requiring the presence of some additional
mechanism such as that offered in the preceding sentence.

8-0-2-1-2-8

The work of E.W. de Jong et al.

Cf. de Jong EW van der Wal P Borman AH Vrind JPM van Emburg
Westbroek P Bosch L
Calcification in coccolithophorids
Biomineralization and Biological Metal Accumulation P.Westbroek and
E.W. de Jong (eds.) D. Reidel, 1983, cf. p. 291-301

[The CaCO3 bio-deposition mechanism in the sea depends to a major

extent on the formation of coccoliths (scales on micro algae
coccolithophorids e.g. E. huxleyi and Hymenomonae carterae) which are
composed of CaCO3 and which form major geological strata (e.g. in the
Cretaceous). The morphology of coccoliths is species specific with large
variation between species. It seems likely that highly complex sulphate
ester containing anionic polysaccharides control the formation of the
coccoliths].

8-0-2-1-3
31
P NMR studies of cell wall associated calcium phosphates
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 have a relatively high concentration of
10 and 55mM respectively inorganic phosphate of seawater is generally
in the range 1-3µ M some species can tolerate higher concentrations of
this nutrient e.g. Porphyra tenera exhibits maximum growth at 400µ M
but decreased at concentrations above 1600µ M.
Local seawater pH can also vary in the range 7.5-8.4 the higher values
occurring near the surface. High phosphate plus high calcium
concentration can give rise to precipitation of metal phosphates in
seawater but this process can be inhibited by Mg2+ and various organic
substances (especially by polyanions which have a general properties of
inhibiting the precipitation sparingly soluble calcium and other alkaline
earth salts). The authors studied the occurrence of this kind of
precipitation within algal cell walls where the effect was pathological.
This type of mechanism may have led to the observed diminution of
phytoplankton in the sea and thereby have contributed to the mechanism
by which global warming has occurred following anthropogenic pollution
of the sea.

8-0-3 180 years of atmospheric CO2 gas analysis by chemical

methods
Beck E.-G.
180 years of atmospheric CO2 gas analysis by chemical methods
Energy & Environment 2007 18 (2)
cf., web. friendsof science.org/assets/files/documents/CO2%20Gas%20Analysis-Ernst-Georg%20Beck.pdf
[While the tone of this paper is somewhat too hypercritical of the IPCC
conventional climate change theory, some of the information included in
this report is worth taking account of as it highlights the possible source
of discrepancies e.g. in attempts to correlate 13δ C data with fossil fuel
consumption data and remote site atmospheric CO2 levels since it shows
that CO2 values at ground level can be quite different from the average
over the entire atmosphere.
The author also indicated that selected ‘non-IPCC’ CO2 data show up
close correlations between temperature change and CO2 levels; as with
the IPCC data one cannot a priori correctly assume which of these
parameters is the cause and which is the effect].

8-1-0
Study of ice cores from 1050-1800
Frank D et al. Nature 2010 463 527
[This study of ice cores from 1050-1800 suggested that a previous
estimate of a 40 ppm CO2 per degree C global warming can be excluded
with 95% confidence; the ice core evidence was for a 1.7-21.4 ppm CO2
per degree].

8-1 Endersbee L
Ocean temperature vs. atmospheric CO2 plots

8-1 Endersbee L.
Australian Academy of Technological Sciences & Engineering (ATSE)
ATSE Focus No 151 August 2008
Carbon dioxide in the ocean
Available at web://icecap.as/images/uploads/Focus_0808_endersbee/pdf)
It should be noted that this author did not think that human activities had influenced the smoothed
ocean temperature data which he presented and further indicated to be directly correlated with
atmospheric CO2 contents.

The strong correlation between likely surface oceanic and atmospheric

CO2 compartments can however be usefully discussed in the context of
an anthropogenic alteration of the marine carbonate balance
cf. Grant D. 2009 web.scribd.com/doc/23967639/Humic-Substances-
Inhibit-Calcite-Crystallizn-II.

8-1a
Degradation of soil (international data)
Cf., F. Pearce, Soils spoilt by farming and industry
New Scientist 1992 16 May (1821)
This article, which notes that the major soil degradation includes that
caused by acid rain (which is caused by the burning of fossil fuels) was a
resumé of a report by A. Hammond (of a UN World Resources Institute
funded survey) who is cited as saying that the findings were “far more
shocking than the loss of rainforests”
{A map of the global distribution of degraded soils given by Pearce also
appears to resemble the maps of high human population density from
night time light or from 14C in the atmosphere; a notable difference
between nightime light however is Africa where a large, seriously
degraded soil zone (in a line South of the Sahara desert) stretches across
the continent from coast to coast}.

“Feeding the World: Disappearing Land”

World Resources Institute (Washington USA)
Overview of publications at
web. wri.org/publication/content/8426
This article discusses the major global problem of soil degradation which
is centred on anthropogenic influence on the topsoil which causes it to be
washed or blown away. By 1990 38% of the world’s croplands had
become degraded. Since 1990 loses have continued to increase year-by-
year.

[This topsoil degradation will cause an increase of terrestrial soil organic

matter present in the sea and in the atmosphere].

8-1-1
Fossil fuel data; Atmospheric CO2 Data; Keeling Data; Ice
Core Data
Used for Construction of Figs. 2 (vide supra)

Fossil fuel data

Web.cdiac.orne.gov/ftp/ndp036/global.1751_2007.ems

Atmospheric CO2 data

Keeling data
Web.cdiac.ornl.gov/ftp/trends/co2/maunola.co2

Ice core data

Web.cdiac.orne.gov/trends/co2/lawdome_combined_dat
Historical records from the Law Dome …ice cores 20 year smoothed
record;

Cf.
James Hansen “Storms Of My Grandchildren The Truth about the
Coming Catastrophe and Our Last Chance to Save Humanity”
Bloomsbury, London, Berlin New York, 2009 {Cf. also the web site:
web.columbia.edu/~jeh1/2008/TargetCO2_20080407.pdf which
gives the similar and related information (in a document entitled “Target
Atmospheric CO2 : Where Should Humanity Aim?”
by Hansen J Sato M Kharecha P Beeling D Masson-Delmotte V
Pagani M Raymo M Royer DL and Zachos JC)

This book indicates that overall, on a historical longer timescale, the

anthropogenic CO2 in the atmosphere underwent a stepwise increment
with steps apparent at years ca. 1865-70AD and after 1955AD; the fossil
fuel C usage on the other hand shows a steps at ca. 1920, 1945 and
perhaps the start of a new large augmentation starting after ca. 2000.
These trends seem to suggest that the human population increase and
associated more intense human activities associated with the growth of
cities (which affect clouds, soils and seas etc) are the actual key driving
forces for the anthropogenic augmentation of CO2.
Cf . Fig. 16 in the Hanson monograph shows fossil fuel CO2 emissions
and the fraction of these that appears in the atmosphere; (the data were
from Boden et al. CDIAC). The emissions of CO2 computed from the
fossil fuel production data seems at first to agree with a linear increase
from 1950-2007.
(Cf., the apparent smooth curve of steadily rising (likely anthropogenic)
CO2 level over this period shown on p. 116 (Fig. 14) of this book;
It should also be noted, however, cf. p.119, that non-linear irregularities
occur in the year-to-year fossil fuel usage and associated CO2 injection
levels; viz. J. Hansen notes that “Emissions increased from less than 2
GtC in 1950 to more than 8 GtC per year in the last few years. The
growth rate of emissions was about 4.5 percent per year from 1950 to
1973. It slowed to about 1.5 percent per year between 1973 and 2003,
but between 2003 and 2008 it averaged about 3 percent per year as coal
use increased rapidly, especially in China”.
- --- --- --- --- --- --- --- --- --- --- --- --- --- --- --- --- --- --- -
The atmospheric CO2 levels seem to increase much more slowly after
major volcanic eruption than would otherwise have been the case (in
accord with the hypotheses that the atmospheric CO2 is determined to a
large extent by the oceanic temperature and that this reservoir responds
on this timescale).
The putative direct link between fossil fuel usage and atmospheric CO2
levels is not supported by a fuller analysis of these data. [Cf. Figs, 2 in
Section 4 of the present article (vide supra)].
8-1-1-1 Discussion of Figs. 2
A comparison shown in the plots Figs. 2 (vide supra) of the five year differentiated
fingerprint pattern for the year-to-year increase in atmospheric levels of CO2 detailed
measurements of which are available from remote atmospheric CO2 measured at
Mauna Loa Hawaii the CO2 indicates that the remote-site-detected alteration in
atmospheric CO2 is apparently independent of the detailed five year-to-year variation
in fossil fuel usage (cf., the fingerprint patterns are different as indicated in Fig. 1 and
Fig. 2 vide supra) but is on the other hand is apparently much more clearly correlated
with the global average temperature five year variation curve. This lack of fine tuned
fossil fuel usage change with variations in the CO2 content of the atmospheric (at least
over the recent decades) seems to support the hypothesis that the variation of
atmospheric CO2 contents, which seems to be attributable to anthropogenic
influences, could largely be determined by the anthropogenic alteration of the ocean
and the humic matter of the soil and atmosphere which produce increased CO2 release
into the atmosphere as the Earth warms up, rather than by the effect of increasing CO2
arising from the direct injection of CO2 into the atmosphere from fossil fuel
combustion. It might be argued that the carbon isotope evidence strongly supports the
fossil fuel combustion hypothesis. However greater uncertainties remain than 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
accounts for somewhat less than half of the amount of CO2 which has been calculated
from 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 CO2 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 13-C depleted 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 CO2 also exists in
sub-pools. Accurate nineteenth and early twentieth century measurement of CO2 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 atmosphere CO2 such as that shown in Fig 1.

[By comparing the differentiated curves for the year-to-year variation of fossil fuel
use, irregularities are magnified and can be compared with the observed alteration in
the trends in atmospheric CO2 increase (shown in the Keeling curve) and the
published surface weather station global surface warming records.
Other irregularities now also become apparent in the differentiated data from the
atmospheric CO2 records
Of especial interest is an apparent marked reduction in rate of CO2 input into the
atmosphere following the Pinabuto volcanic eruption in 1991 (cf. also 1982) and the
increased global temperature and associated atmospheric CO2 associated with the
1997-8 El Nino].

8-2
Bond-Lamberty B Thomson A
Temperature-associated increases in the global soil respiration
record
Nature 2010 264 579-82
[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 CO2 measurement techniques,
revealed a previously unknown temporal pattern in global soil
respiration which indicated that the air temperature anomaly (the
deviation from 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 mechanisms by which humans might cause global
warming).

The soil respiration input into the atmosphere was estimated to

be 98+12 Pg C/year and that this had increased by 0.1Pg 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 CO2 derived
from decomposition of recalcitrant humic matter including by
micro-organisms using this form of carbon as an energy source;
J. Fang in Nature news drew attention to the implications of the
Bond-Lamberty & Thomson findings that drew attention to the
apparent fact that soil may greatly outperform human fossil fuel
burning as a source of CO2 input into the atmosphere. A further
comment by A. Chaurasia (an internet comment attached to the
J. Fang Nature-news article) suggested that the observed
apparent global increase in soil CO2 emissions has arisen from a
diminution of soil (microbial) bio-diversity caused, in turn, by
the common widespread use of agrochemicals. This, it is now
suggested, is probably a highly informed and useful comment.
The possible largest anthropogenic activity which is currently
affecting climate would seem therefore, if the above hypotheses
is correct, to be industrial scale agriculture.
This further suggests that (following the further research which
is needed to substantiate these ideas) that the target of
international concern should eventually shift away from its
traditional opposition to the combustion of fossil fuel (which in
any case now seems to produce an order of magnitude less CO2
than the amount of this gas which injected into the atmosphere
from the soil, a conclusion which should however be qualified
by plant roots and not the much more highly abundant soil
bacteria being the main soil source of CO2).
What seems certain at the present time, however, is that the
science of global warming is far (perhaps even very far) from
proved and understood.

8-3
Banerjee D Nesbitt HW
XPS study of dissolution of birnessite by humate with
constraints on reaction mechanism
Geochim Cosmochim Acta 2001 65 (11) 1703-14

[The reaction of Mn ions with humate carboxylate groups may

have important implications for the biogeochemical cycling of
carbon since they produce CO2 in soils and sediments by
oxidizing carboxylic, hydocarboxylic and dicarboxylic acid
groups which are abundant in natural organic substances
(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
which suggested that increased environment temperature would
increase the amount of soil organic matter in boreal forest soils;
Kirschbaum MUF et al. Soil Biol Biochem 1995 27 (6) 753-60
have confirmed a more common opposite effect found by others
that soil organic matter decreases greatly following global
warming and thereby provides 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.
Kirschbaum MUF et al. Biogeochemistry 2000 48 (1) 21-51)}.

8-3-1
Bélanager S et al.
Photomineralization of terrigenous dissolved organic matter in
Arctic coastal waters form 1979-2003: intra-annual variability
and implication of climate change
Global Biogeochemical Cycles 2006 20 GB4005
Doi:10.1029/2006GB002708
[The present trend of ongoing contraction of sea ice cover will
greatly accelerate the photomineralization of DOM in arctic
water].
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 72 261-7
[It is estimated that >25% of the soil carbon lies in Arctic
catchment areas and 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 source of terrigenous DOM to the
deep ocean.
Of especially interest was the release of CO2 in the sea
following the photodegradation of UV sensitive relict porphyrin
structure containing terrestrial humic matter].

Cf.
Anesio A.M. et al.
Effect of humic substance photodegradation on bacterial growth
and respiration in lake water
Appl Environ Microbiol 2005 71 (10) 6267-6275
This study provides a model for the behavior of the
autochthonous humic matter from algae which dominates the
DOM of the ocean.
Land derived humic matter (n.b. the term ‘allochthonous’
applied to humic matter denotes residual plant matter e.g. often
rare aromatic lignin derived residues there present) is thought to
be distinguishable from the marine humic matter however but
contains a similar micro-organism derived (often
‘autochthonous’ dominant) components. While initially
incubation of UV irradiated humic matter from a range of
natural land sources caused 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 CO2 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) 1712-1714
----------------------------------------------------------------------------

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/mainpage.htm
(downloaded on march 2006, also on Sept 2 2010)
It was suggested that while the CO2 in the atmosphere is known
to exchange dynamically with CO2 dissolved in three reservoirs
oceans, plants and terrestrial soils, it is important to realize that
scientists do not yet fully understand the fundamental
processes which control this ‘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
reservoirs but inadequacy of measurements of atmospheric 14C
has hindered progress in understanding the ‘carbon cycle’.

The CO2 record derived from air bubbles trapped in the Vostock
Ice Core Antarctica (Barnola et al. 1999 cited by Druffel et al.)
showed that the CO2 levels fluctuated between ca. 190 and 280
ppm. This value has risen rapidly since about 1850 and
especially between 1958 and 2000 (Keeling et al. 2000)
bringing the atmospheric CO2 levels to values higher than those
present in the past 400,000 years; [n.b. this increase in
atmospheric CO2 has continued to the present time]. It was
noted that while ca. 30% of the increase in the past 150 years
can be fairly firmly traceable to human fossil fuel burning and
clearing of forests for agriculture, significant changes of
atmospheric CO2 contents also occurred in the pre-industrial and
pre-human past presumably related to shifts in global climate.

Fig.2 of the Druffel et al. article gives an estimate of the

amounts of carbon in the interacting compartments of the natural
carbon cycle which are potentially subject to relatively small
imbalances and which have for the most part still a large
uncertainty in their detailed understanding.

CO2 Cycle Related Compartments as Carbon

(1Pg = 1015g)
Atmospheric CO2 760 Pg

Accumulation of CO2 in atmosphere

from fossil fuel burning 3.2 Pg/Year
[Fossil fuel burning 5.5 Pg/Year
(of which taken up by ocean 2.0
Pg/Year)]

(Total) Ocean – Atmosphere Exchange 90 Pg/Year

Surface Ocean 1020 Pg
Deep Ocean 38,100 Pg

Land plants and soils 2200 Pg

A 2006 powerpoint lecture from the above group, available on

the internet, gives further details of their 14C isotope CO2
cycling research.
-----------------------------------------------------------------------------

8-5

Ruddiman WF
The early anthropogenic hypotheses: challenges and responses
Reviews of Geophysics 2007 45 RG4001;
doi:10.1029/2006RG000207
{The importance of this hypothesis (which suggested that the
late Holocene rise in CO2 was caused by human activities) is
that if it can be substantiated, it might give direct proof of the
extreme fragility of the current geological period climate control
system, and add weight to the urgent need to curb present-day
human (including agricultural) activities to prevent near future
adverse climate warming. The original hypothesis that farmers
had introduced CO2 from wood burning into the atmosphere did
not, however, apparently show up in a more recently carefully
examined isotope record [by J Elsig et al. (8-7-4)]. This might
suggest that the late Holocene small CO2 increase was not in any
way caused by human activities. The idea that humic matter
fulvate could have been introduced into the sea in large enough
amounts by late Holocene human deforestation activities to
affect the atmospheric CO2 seems, however, to be a credible
mechanism of how human activity could have augmented
atmospheric CO2 at that time.
The J. Elsig et al., ice core stable carbon isotope evidence
suggested that the late Holocene extra (putative anthropogenic)
CO2 was emitted from the seas.
This agrees with the fulvic run-off following deforestation
hypothesis.

[A corollary to this idea is that the current increase in

atmospheric CO2 is also to a large measure controlled by
disturbances in land fulvate/humate and the direct injection of
CO2 from fossil fuel may be a secondary effect of this].

[The above Geophysics article by Ruddiman, it should also be

noted apparently also disagrees with the views of most climate
scientists in the belief that the pre-industrial atmospheric CO2
level was lower than the 280 ppm value normally used; the
above paper continued a discussion of an earlier hypothesis
proposed by this author in 2003 that Holocene anthropogenic
effects caused alterations in atmospheric gas contents of CO2
and also CH4 (e.g. from wetland emissions) sufficient to affect
climate (they were suggested to cause a global warming effect
which prevented a recurrence of an ice-age but a later a
pandemic-induced cooling was caused by enhances mortality
and reforestation).
Only ca. 25% of the early CO2 increase anomaly could,
however, be attributed to the CO2 which might conceivably have
been produced directly by wood burning, suggesting that
additional (unknown) anthropogenic intervention effects
promoted by agriculture than the direct emission of CO2 exist
which can greatly disturb climate system feedbacks {such
effects seemed to be equivalent to what could seem to cause the
ocean to remain anomalous1y warm}].
A corollary is that anthropogenic disturbance elevation of
greenhouse gas (including CO2) contents in the atmosphere must
have been produced in planetary climate feedback systems
which, although of an unknown nature, might centrally have
involved the oceanic carbonate homeostasis mechanisms which
could therefore be sufficiently ultra-sensitive to human activity
as to show up in the low-level pre-industrial impact of oceanic
system some five thousand years ago. This further suggests that
present and future levels of human activity which occur on a
much larger scale may also critically depend on similar effects
which are additional to the direct injection of CO2 gas into the
atmosphere.

The origin of the early anthropogenic hypothesis has centered on

interpretations of ice core evidence for atmospheric composition
in order to compare and natural greenhouse gas contents of the
atmosphere for the anthropocene and pre-anthropocene periods.
This requires the selection of the most appropriate set of
interglacial period data with which to compare the present
anthropocene period data. Much debate seems to have has
ensued on the correctness of the timing used by Ruddiman to
compare of current interglacial trends in atmospheric
greenhouse gases with those predating human activities.
Ruddiman discussed in detail information on the extent of ice
coverage obtainable from δ 18O measurements (of ice as well as
biologically produced calcite and which allows the oxygen
isotopic ratios in ancient samples of these materials to estimate
the extent of ice sheets which were present at the time of their
formation which can also indirectly indicate global
temperature). The natural emission of CH4 (cf. 8-5-1) from
wetlands in response to a late Holocene climate anthropogenic
climate alteration by early agricultural activities seems to agree
more satisfactorily than does the original CO2 from wood
burning hypothesis.
Ruddiman also suggested that large human population decreases
caused by disease epidemics when agricultural land to returned
to forest show up in greenhouse gases in ice-cores.
Elsig et al. reinvestigation of δ 13C from late Holocene wood
burning
The 2009 paper by J. Elsig et al. (vide infra) which
reinvestigated the δ 13C isotope historical record of atmosphere
CO2 indicated the absence of direct input into the atmosphere
from wood burning following forest clearing.
Fulvate runoff from degraded soils into the sea causes parallel
increases of the degree of supersaturation (Ω ) of CaCO3 in the
sea which leads to an incrase of sea surface quick-release-CO2,
as discussed in the preceding Sections.
Another mechanism by which deforestation of Eurasisa could
have altered the temperature of the sea is via the large scale
creation of natural carbonaceous particle heat traps analogous to
the industrial micro-porous carbon (which can act as a solar
energy absorber) and cause sea warming near the river estuaries.
The natural occurrence of forest fires at the present time is
thought to form small graphite-like cored humic particles.

The public internet discussions available on historical archives

(cf. e.g. web sites accessed using the search term “The
anthropogenic greenhouse era began thousands of years ago”
[the title of the Ruddiman article in Climate Change 61 261-92}
cf.
web.realclimateorg/index.php/archives/2005/12/early-
anthropocece-hypothesis/) includes numerous question and
answer sessions about the Ruddiman hypothesis between
professional scientists and some probably non-scientist members
of the public) which gives a useful insight into the issues
involved and the credibility of the hypothesis in the general
scientific community as well as the growing band of internet
reading ‘citizen scientists’ and other non-scientific public.
Amongst the comments posted in 2005 were that the current
geological period is one of great climatic instability [which is in
sharp contrast to the very high climatic stability which occurred
during the Cretaceous period] which can be likened to how the
present climate resembles a small boat which in stormy waters is
in danger of capsizing if it is rocked by the occupant {rocking
slightly when sitting down is like the pre-human situation- but
the current situation is like what can happen to the stability of
the boat when the occupant rocks the boat when standing up};
another more pertinent comment for the present noted is that the
Ruddiman mechanism of producing the observed 40 ppm
increase in atmospheric CO2 by the burning of plant material
following deforestation, should have produced a large δ 1 3C
signature in the historical ice core record but this has not been
observed [however if the atmospheric CO2 had been produced
from bacteria or humic matter it would have greatly diluted such
a δ 13C signature]; the same commentator also questioned
whether Ruddiman had taken into account the oceanic carbonate
buffer system in his deliberations (which can affect the
atmospheric CO2 levels).
------------------------------------------------------------------------------
It should be noted that no commentator in the above discussion
was aware of the possible key role of humic matter in the
climate change process.
- - - - - - - - - - - - - - - - - - - - - -
An e-mail exchange with Ruddiman confirmed that he was
unaware of the possible role of humic matter runoff following
deforestation as a possible explanation of the Holocene anomaly
(e.g. via anthropogenic modulation of marine carbonate balance
and resulting atmospheric CO2 input effect).

8-5-1
A methane-based time scale for Vostok ice
Cf. also
Ruddiman EF Raymo ME
A Methane-based time scale for Vostok ice
Quaternary Science Reviews 2003 141-55
On the CH4 timescale it was found that … CO2 responses are
highly coherent with … δ 18O at the orbital period (a measure of
temperature).
CO2 leads δ 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 year (precession).

8-5-2
Rapid climate change events have occurred in the Earth’s
history following asteroid strikes (cf. the 65 million year ago
event which is supposed to have caused the extinction of the
dinosaurs as well as most other species then extant); there could
also be relevant-to-climate cyclic variation in the earth magnetic
filed, plate tectonic dependent volcanic activities (cf. the
reduction in the Earth’s surface temperature during recent
volcanic activities) as well as a more orderly superposition of
the cyclical solar energy output (cf. sunspots and solar flares, as
well as, critically, variation of the Earth’s orbital parameters
(Milankovitch eccentricity, obliquity and precession and the
associated variation in received solar energy agrees with the
periodicity of glaciations indicated from ice core air bubbles
from the last four glaciations cf. Kawamura K et al. Nature 2007
448 912-7 as well as evidence of past global climate from loess
deposits.
[Cf. the general theory of the orbital effects on climate is given
in University of Alberta Geophysics 2008, 210 Section B7.3
available on the internet at
web.-geo.phys.ualberta.ca/~unsworth/UA-
classes/210/notes210/B/210B7-2008.pdf].

8-5-3
The Milankovitch theory of eccentricity, obliquity and
precession of Earth’s orbital related variation of received solar
radiation warming
The Milankovitch theory that Northern Hemisphere summer
insolation triggered the last four deglaciations was confirmed by
Kawamura et al. who showed that orbital-scale Antarctic
climate change lags Northern Hemisphere insolation by a few
millenia and that the increase in Antarctic temperature and
atmospheric CO2 concentration during the last four terminations
occurred with the rising phase of Northern Hemisphere summer
insolation.

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

8-5-4
Role of water vapor as a greenhouse gas

An internet discussion (web.geocraft.com./WVFossils/ice-

ages.html) cites an October 2000 US Department of Energy
tabulation of greenhouse gases which includes data suggesting a
possible dominant role of water vapor tends to diminish the
relative importance of CO2 (and the possible small human
contribution to this and other greenhouse gases) as a cause of
global warming; this document also draws attention to the
concern expressed by Schneider S of the National Center for
Atmospheric Research at Boulder Colorado in the 197Os that
global cooling and a renewed ice age was then of major concern
to climate scientists.

8-5-5

IPCC Climate Change 2007: Working Group I: The Physical Science

Basis
web.ipcc.ch/publications-and-data/ar4/wg1/en/tssts-2-2.html There is
increasing data on radiative forcing effects of anthropogenic and natural
aerosols which overall are believed to produce a global cooling effect via
the cloud albedo effect but the underlying understanding of these critical-
for-global warming-models is poor.
A major problem for climate change models is that the direct radiative
forcing for individual aerosol species remains uncertain.
The estimated effects were given (W m-2) as
Sulphate - 0.4 ± 0.2
Fossil fuel derived organic carbon - 0.05 ± 0.05
Fossil fuel black carbon +0.2 ± 0.15
ex Biomass burning +0.03 ± 0.12
 Nitrate -0.1 ± 0.1
Mineral dust -0.1 ± 0.2
The atmospheric warming effect of black carbon and perhaps also
carbonaceous particles from biomass burning is contrasted to the putative
atmospheric cooling effect of the other aerosol particles of which the
largest effect is exerted by sulfate.

8-5-5-1
Cf. also document by D. Grant
The Possible Role of Nucleation of Phase Changes as the Dominant Rate
Controlling Processes in Anthropogenically Induced Climate Change
(web. scribd. com/doc/38814103/The-Role-of -Nucleation-of-Phase-
Change-as –a-Dominant-Rate-Conrolling-Processin-Anthroogenicaly-
Induced-Climate-Change
included a brief discussion of a recent report by
A. Clarke V. Kapustin Hemispheric aerosol vertical profiles

A. Clarke and V. Kapustin (Hemispheric aerosol vertical profiles:

anthropogenic impacts on optical depth and cloud nuclei, Science, 2010
329 1488-1492) which suggested that the anthropogenically modified
seed particles which are responsible for cloud formation and climate are
now widely globally distributed. This means that global cloud formation
and associated climate is also greatly influenced by anthropogenic effects.
This finding could further suggest that the formation of anthropogenically
modified seed particles could be the major mechanism of global warming
e.g. under the circumstances where anthropogenic effects can lead to an
increased rate of seeding of water aggregate phase transitions leading to
increased precipitation which could diminish the reflection by sunlight by
clouds thereby increase the temperatures of adjacent surfaces.

The effect of large cities on climate could also have a larger-than-

supposed effect on climate-altering aerosol formation.
This includes the generation of highly toxic substances (e.g. during the
incineration of carbon and chlorine atom, bromine atom or chloride or
bromide containing municipal and medical wastes which can (putatively)
have a major impact on the biosphere and resultant potential alteration in
humic matter production and degradation as well as e.g. (putatively)
inducing alteration in animal including human development).
Since large human populations in conurbations can act in the above as
well as in more apparently benign emission situations in a cooperative
manner (by larger than a power of one proportionality to the number of
humans who are responsible from such emissions) this can promote the
generation of yet higher concentrations of volatile monomeric organic
and inorganic chemical molecules and combustion-exhaust-gas-
chemically-modified aerosol particles (perhaps in a relationship like the
heat island equation) which by further reaction with humic like matter
(HULIS) etc. could allow virtual conurbation environments which extend
to ca. 10% of the Earth’s terrestrial surface to change the climate of the
remainder of the planet’s atmosphere.

8-5-5-2
Increase in black carbon concentration since industrialization from a
Mount Everest ice core

Kaspani SD et al.
web.geology.cwn.ed/facstaff/huerta/g501/pdf/Kaspani-InPreparation
Black carbon (but not dust) present in this ice core record
showed a threefold increase between post 1975 and pre-1975 (to
1866) indicating that globally distributed anthropogenic
emissions occurred at high altitude distant from source.

8-6
Other scientific web sites accessed ‘at random’ which discuss
the problems associated with the current debate regarding
climate models
included “Ice age CO2 Cycles Archer et al. 2000”
[cf. Archer D et al., Rev Geophys 2000 38 159-80]
which inter alia discusses perceived problems in understanding
the circulation of the sea, iron fertilization and sediment
geochemistry. It should also be noted that the latter two topics
are potentially affected by the humic matter control system.

The effect of humic matter on burial rates of CaCO3 and the

effect of anaerobic chemistry on this (cf. Neuweiler et al.[ 8-7-6]
vide infra) it was suggested, may be a key control mechanism of
other sediment formation including silicates.
The subject of silicic acid on marine biochemistry is mentioned
by Archer et al.
Clearly this is part of the diatom nutrient requirement. [The
evolution of the diatoms some 250 million years ago is believed
to have greatly reduce the marine Si(OH)4 content. Si shows up
in animal biochemistry apparently reflecting the first evolution
of animals in the sea some 1000 million years ago].

8-7 Evidence from isotopic composition of atmospheric CO2 of

the relative importance of oceanic and terrestrial biosphere
exchange mechanism for removal of atmospheric

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 an isotopic record of the CO2 used

in photosynthesis and was suitable for studying the fate of CO2
produced from the burning of fossil fuel.
There is an ongoing problem in understanding
the relative contributions to atmospheric CO2 between the CO2
which is derived from exchange between the atmosphere and the
ocean and that which is obtained from the terrestrial components
of the biosphere.
Attempts to obtain 13δ data from C3 plants (e.g. from tree
rings) has show up large variations 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 the study of tree rings or animal
remains.

Where there is input from the bacterial C of humic matter into

atmospheric CO2 this has a neutral effect on δ a13C.
Transfer of CO2 from the ocean to the atmosphere also was
believed to result in a relatively small change in δ a13C for
atmospheric CO2 .
[An increase of 0.0027o/oo per 109 t (Gt) C was believed to occur
for transfer of this amount of C to the atmosphere from the
(terrestrial) biosphere].
The combustion of fossil fuel or plant matter, on the other hand,
was believed to cause a much greater effect namely a decrease
in δ 13 of ca. 0.026o/oo for this amount of C
This was believed to allow δ a13C measurements of CO2 either
directly or indirectly to indicate the contribution made by fossil
fuel (and much smaller amounts of wood etc.) combustion to the
observed increase in atmospheric CO2 contents.
It should be noted that the value of δ a13 declined by ca.0.55o/oo
between 1956 and 1978 (from –6.69o/oo to –7.24o/oo during this
time when CO2 rose from 314ppm to 334ppm {by 1989 this had
become 350ppm} and produced a δ a13 value slightly less than –
7.8o/oo ).

It was noted in the above cited article that if all CO2 derived
from combustion of fossil fuel had remained in the atmosphere
then the δ a13 value would have been expected to have changed
by ca. –0.025o/oo / ppm increase in CO2; the actual value of
δ a13 measured with respect to the CO2 concentration (Siple data)
was, however, suggested to be
ca. –0.011o/oo /ppm CO2 for data from before 1956
i.e. only 44% appeared in the atmosphere.

It might be of interest to attempt to subdivide the earlier from

the later data as (vide infra) there 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 would 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 post-human 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 output of natural carbon sink systems in wartime explain
the 1940 blip in the (presumed anthropogenic) alteration of
climate?

The δ 13C value apparently had increased, however,

to –0.028o/oo/ppm CO2 between the years 1956-86; these data
were attributed to a much increased use of fossil fuel after 1956.
A perhaps more likely explanation of this altered relationship
between δ 13C and atmospheric CO2 could have been due to the
principal CO2 buffer the sea which conceivably has suffered
some major (anthropogenic) perturbation in the most recent
decades which has made the sea somewhat less able to fulfill its
natural CO2 buffering capacity.

It should be noted that there is a possible, perhaps major source of error in ice core
estimations of historical atmospheric CO2 levels arising from the existence of
antifreeze (perhaps including humic matter) conditions in some of the samples studied
(cf. T.V. Segalstad internet files) which means that the amount of CO2 in bubbles
having any connection with such supercooled water will almost certainly be less that
the original value when that air was originally trapped.

8-7-2
Altered inorganic ions, humic matter oceanic pH redox status
as well as environmentally stable phosphonate herbicides and
phosphonate laundry detergents
might be amongst the drivers of oceanic disturbances which
creates augmented atmospheric CO2 via the perturbation of the
natural marine CO2 buffering capacity.

{Such differences in observed δ a13 values noted in the

preceding paragraph 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-anthropocene oceanic carbon
homeostasis system after 1956, e.g. via an augmentation post-
1956 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 oceans 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 ions, 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 anti-calcification 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 matter polyanions produced from the
degradation terrestrial humic polymers perhaps containing
adsorbed environmentally-stable phosphorus-containing
(especially phosphonates containing P-C bonds now used in
large tonnage amounts as herbicide agrochemicals 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 include 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
dissolved inorganic C (DIC) , [CO2]+ [HCO3-]+[CO32-]
and
ocean alkalinity [HCO3-] +2[CO32-] remains unchanged
3) 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.
4) Pore system exchange on the ocean floor is slow requiring
e.g. 5000 years but allows the above to feedback to increase
atmospheric CO2.

8-7-4
Cf. Elsig J Schmitt J Leuenberger D Schneider R Eyer M
Leuenberger 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 δ 13C record of atmospheric CO2 over the last
11,000 years.
This new study now indicated that the early Holocene increase in δ 13C of about 0.25o/oo was most
probably the result of a combination of C uptake of about 290 Gt (Pg) C by the 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 ppm increase in atmospheric CO2 and the small decrease in
δ 13C of about 0.05 o/oo during the later Holocene could, it was now suggested by these authors, mostly
be explained by the contribution from carbonate compensation of earlier land-biosphere uptake and
coral reef formation with only a minor contribution from a small decrease of the 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 has been suggested by Ruddiman, then the reduction in δ 13C
would have occurred with a numerical value of ca. an order of magnitude greater than that found.
The attempts by these authors, using the currently believed
(alternative to the presently proposed) models of global CO2
carbon cycling to account for the observed δ 13C values
however fails;
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 proposed humic matter blocking
effects on oceanic carbonate cycling mechanism and the
associated surface water HCO3- and CO2 aq. concentration rises,
could be of value in explaining the observed experimental data.
8-7-5
The possible role of coral reefs in causing elevation of
atmospheric CO2 (as suggested by W.H. Berger Naturwiss 1982
69 87-8) was included in the above Elsig et al. discussion.
Cf., the original “coral reef” hypothesis referred to the 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 hypothesis seems not to have meant to refer to real
coral reefs, but merely to the ‘kinetic’ process depicted in the
above equation, later examination of real coral reefs have shown
that some of them can actually be producers of small net
amounts of CO2 (nb. this CO2 is partly removed by the
photosynthesis which also occurs in coral reefs). The net
amount of CaCO3 which is produced by coral reefs is much too
small to be of great concern for introduction into the atmosphere
e.g. in order to account for the late Holocene CO2 anomaly,
being estimated to be ca –0.1Gt(Pg)C/year and hence per se is
of minor relevance to global carbon cycles and mechanism by
which atmospheric CO2 can be altered.
Nevertheless corals form CaCO3; this process is however, like
skeletal calcification in animals subject to control 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 traditional view that the Mg/Ca ratio of seawater had
stayed constant at the 5.2 value for e.g. 500 million years was
challenged.
It was indicated that this value is indicated in echinoderms from
the Cambrian and from the Carboniferous to the Triassic
indicated a seawater Mg/Ca ratio of ca. 3.3 and from the
Jurassic a value of ca. 1.4].
Subnote
The putative role of humic matter and the metallome in the
homeostasis mechanism of seawater. The role of the
heparanome –metallome cross talk in controlling animal growth
(is of relevance to the use of fossil echinoderms
for geological parameter evaluation).
While the current view of the mechanism by which seawater
attains constancy over geological time of its inorganic ion
contents, is that stated by e.g. Demicco et al., loc cit., vide infra,
which is an extension of the Spencer and Hardie (1990) model
of the major ion chemistry of seawater through Phanereozoic
time, which considers the effect of the constant influx of river
water of constant composition, the mixing of the river water
with mid-ocean ridge brines of constant composition but
variable flux as the result of variations in the rate of seafloor
spreading, coupled to the production of CaCO3 mechanism
which returns seawater to a constant saturation state; an
additional effect which has relevance for the fuller
understanding of the attainment of constancy of composition of
seawater can be suggested to arise by the unique chemical and
physical properties of the major system of organic matter which
also occurs in seawater (as dissolved or suspended organic
substances) which might act as the dominant inorganic ion
homeostasis system.
It should be noted that while geological carbonate, silicate and
related mechanisms are currently believed to control the
long-term multi-inorganic ion content of the ocean, it is also
likely that the ability of the environmentally abundant
polyanionic system of humic substances to bind inorganic ions
and inhibit the formation of sparingly soluble crystalline phases
containing these ions, could also be an important regulator of the
inorganic element content of the sea.
It should also be noted that the multi-inorganic content of the
sea is exponentially related (giving rise to an approximately
linear log-log plot) with that of human blood serum (Haraguchi,
J Anal At Spectrom 2004 19 5-14). [Cf. also Figs. 1 vide supra].
This phenomenon could be part of the reason why inorganic
ions, especially Ca2+ and Mg2+ are involved as essential
cofactors for heparan growth factor/growth actor receptor
regulation which controls the growth and wound healing of
animal organisms [cf. M. Kan et al. J Biol Chem 1996 271
21511-21516]; it should be noted that the salinity of the sea and
other natural waters is balanced in aquatic invertebrates which
require a specific amount of heparan sulfates determined by the
salinities of the aquatic habitats of the different invertebrate
species (cf., Nader et al. 2003 ref. [4a]) who intimated the
existence of an exact mathematical relationship between the
habitat salinity and the amounts of heparan sulfate and related
anionic polysaccharides in animal tissues). A similar
mechanism is also likely to occur in algae. The growth of
calcified organisms which is a major mechanism of CaCO3
formation in the sea is also believed to be controlled by
polyanions and can be affected by extracellularly present anions
as well as by the inorganic element array associated with such
polyanions. [Cf. Figs. 1 vide supra].

Demicco RV et al.
Model of seawater composition for the Phanerozoic
Geology 2005 33 (11) 877-880

Borremans C et al.
Salinity effects of the Mg/Ca and Sr/Ca in starfish skeleton and
the echinoderm relevance for paleoenvironmental
reconstructions
Geology 2009 37 (4) 351-354
[These authors note that, while in contradiction to previous
beliefs, that the incorporation of Mg and Ca into echinoderm
skeletal CaCO3 is independent of (or only weakly dependent on)
salinity (and this factor could be ignored), but the dependence of
echinoderm growth rate on Mg/Ca and Sr/Ca ratios is actually
strongly affected by the salinity of the sea (which was the prime
effector). An inverse relation between Sr/Ca ratio and
temperature (which could have arisen from physiological
regulation mechanisms which seem to be based on the Ca to a
much greater extent than the Mg or Sr ion concentrations), was
reported].

{This paper reviewed the historical background the use of the

Mg/Ca ratio in calcified marine organisms as an indicator of
ocean temperature [Clarke & Wheeler, 1922; Chave, 1954;
Weber, 1969; Dickson 2002 and Ries 2004]; this relied on the
belief that the seawater Mg/Ca is spatially constant and unlikely
to change on time scales of <1 million years due to the very long
residence times of both Mg and Ca in the oceans;
Ferguson et al. 2008 reported a strong salinity effect on the
Mg/Ca ratio in Mediterranean high- magnesium calcite
foraminiferal skeletons].
{This work seems relevant to the correlation of metallomic
matrices in surface anionic polysaccharides of animals; for
fifteen species of aquatic invertebrates a strict mathematical
correlation was detected (by Nader et al. ref. [4a]) between the
cell surface heparan sulfates and other glycosaminoglycans and
the salinities of their habitats; a parallel variation of the Mg/Ca
and Sr/Ca ratios also occurs with the pharmaceutical agent
heparin a model for the heparan sulfate system}.

It should also be noted that Ca2+ is a prime controller of heparan

sulfate growth factor and other heparan sulfate-dependent
biological activities. It is likely that such mechanisms are such
anionic polysaccharide -controlled and putatively may be
influenced by the presence of pathological induced ‘foreign’
anionic substances such as terrestrial fulvate and, in recent
years, industrially-produced phosphonate in the environment].

8-7-6
Numerous non-calcifying species, growth of which is likely to
be controlled by natural ‘smart’ polyanionic polysaccharide
morphogens seem also to be able to evade calcification
completely by the use of a similar polyanionic mechanism (cf.
Pentecost loc. cit.). The analogous polyanionic humic
(especially fulvic type) system also seems to control the
calcification processes of the sea which feed into atmospheric
CO2.
[It should be noted that most authors (e.g. Joos et al., 8-7-3)
think that thermodynamics rather than kinetics exert control the
formation of CaCO3 and atmospheric CO2. Fully reversible
thermodynamic equilibria are likely to become greatly disturbed
in the real world by the marine extracellular polyanion
secretions; such secretion are part of the DOM which
Wangerski indicated to be were responsible for surface
deactivation of CaCO3 surfaces and for the creation of a block in
the carbonate recycling system of the sea ; this phenomenon
was also identified by Pentecost (vide infra) indicated to
perform anti-calcification roles; it is further suggested that these
acting together with the more abundant humic polyanions which
accompany them in natural waters. The controlling action of the
polyanionic which occur in natural waters offer a more
realistically useful model CO2 emitting and removing systems in
the biosphere.

Pentecost A
Significance of marine algal calcification inhibitors in the
global carbon cycle
Thalassas 2004 20 (1) 45-9
[This author noted that “while the process leading to the
precipitation of calcium carbonate in algae have been well
studied over the past few decades, little attention has been given
to the possible role of nucleation inhibitors preventing
calcification in algae…..since the majority of algae have never
been observed to calcify, it is possible that nucleation
inhibitors are widespread and have an important role in algal
ecophysiology….preliminary evidence is presented for
inhibitors in members of the Chlorophyta, Phaeophyta and
Rhodophyta….seawater contains 2.5 mmol/l dissolved CO2
most present as HCO3- , the Ca2+ concentration varies little from
10.5 mmol/l and the ion activity product of Ca2+ and CO32- in
shallow seawater indicates that it is supersaturated with respect
to calcite and aragonite (e.g. Whitfield & Watson, 1983). Little
energy of activation would appear to be needed to overcome the
activation energy barrier for the nucleation of calcite or
aragonite to bring about calcification of the surface of marine
organisms. During the carbon fixation process of
photosynthesis, carbon dioxide is removed from the surrounding
seawater, increasing the CO32- ion activity, and further increasing
the {Ca2+} {CO32-} activity product” which further promotes the
likelihood of the occurrence of calcification.
[bold italics are mine; related studies of the anionic
polysaccharides extracted from marine algae as calcification
inhibitors are included in the list of papers of W.F. Long et al.
(University of Aberdeen) listed on the internet at
web.abdn.ac.uk/bch~118/publications.march 2003.doc].
[Cf. also Grant D. et al. Med Hypoth 1992 38 49-55]
{Author’s comment:
the presence of humic matter in the marine environment,
perhaps especially above a critical threshold value, is likely to
greatly change the type of equilibration processes discussed by
Joos et al. [8-7-3] vide supra};
A major departure from an exact thermodynamic model may
occur in seawater-like solutions in the presence of polyanions
which, rather than binding as simple (Manning) electrostatic
attractors, actually seem to bind via a kinetically controlled
seeded process (cf. 1992 articles by D. Grant et al. in Biochem J,
listed in: web.abdn.ac.uk/bch~118/publications.march
2003.doc);
Colloidal size SiO2 particles (e.g. introduced into the sea via
dust from land sources) may effectively accomplish such
seeding.
It is of possible interest in this context that the Sahara desert is
the largest source of mineral dust in the world and the emission
of such dust has greatly increased since the 1970s, a process
which may originally have been promoted by the type of
industrial scale agriculture which started in beginning of the 19th
century.
Cf. the similarities between the observed dust flux post-1970 (as
reported by Mulitza et al. Nature 2010 466 2010) and (cf. J.
Hansen et al. gistemp2010_draft0803 (NASA data reports of the
post-1970 continuous increase in global temperature).

Neuweiler F d’Orazio V Immenhauser Geipel G Heise K-H

Cocozza C Miano TM
Fulvic acid-like organic compounds control nucleation of
marine calcite under suboxic conditions
Geology 2003 31 (8) 681-4

[Evidence was obtained for the strong binding of humic

substances to the surface of CaCO3 (marine microcrystalline
calcite {automicrite}) from a Lower Cretaceous deep water
carbonate mound; such binding seemed to have promoted the
precipitation of the CaCO3 particles under reducing (suboxic)
conditions.

{The seeding process here might also be subject to promotion by

SiO2 and other dust particles blown off the land following soil
degradation}.

It should be noted as indicated in the introduction to this Neuweiler et al.

paper that it has previously been indicated by Berner 1968; Chave &
Suess 1970; Berner et al. 1978; Hoch et al. 2000 {cf. refs cited by
Neuweiler et al.} that the humic substances which ubiquitously are
present in present day and presumably previous geological period
aqueous environments, can both inhibit the formation of CaCO3 (or under
alternative environmental altered redox conditions) have an opposite
effect which accelerates the formation of CaCO3 as reported by a number
of other articles which were also cited by Neuweiler et al.].
Leenheer JA Reddy MM
Co-precipitation of dissolved organic matter by calcium carbonate in
Pyramid Lake , Nevada
Annal Environ Sci 2008 2 11-25

This important paper supports the hypothesis that poly-carboxylic-

polyanion DOM (fulvates) form complexes with naturally occurring
CaCO3 particles in all types of natural waters.
The importance of this work lies in the high quality analytical and spectroscopic data rather than the
interpretation of these data attempted by the authors which is suggested to be misleading.
The contents and speciation of DOM in an arid region alkaline (pH 9)
lake showed that “precipitated” CaCO3 had incorporated DOM from lake water. The DOM associated
with the CaCO3 was enriched in “poly-carboxylic proteinaceous acids and hydroxy acids” which had
been preferentially taken up by the CaCO3 particles in preference to the other chemical substances
present in the lake water.
The title of the paper and the statement in the abstract: “The mechanism of DOM co-precipitation
and/or physical incorporation in the calcium carbonate” suggests that the authors thought that the DOM
had aided the precipitation of the CaCO3. However this is speculation and is not based on experimental
observations. It is suggested to be an incorrect interpretation of the nature of the DOM CaCO3
interaction which the authors studied. It is misleading since their speculations might be interpreted as
suggesting an opposite circumstance to the likely real situation which could be that the DOM is always
a part of how natural CaCO3 particles are made more stable in natural aqueous solutions . The most
likely role of the DOM is to stabilize and not destabilize particles.
[The authors had extracted th organic matter from the lakeside CaCO3 deposits which contained 0.23%
organic matter (with a 14C age of ca. 3300 years).
The δ 13C values of DOM which was associated with the CaCO3 were reported
δ 13C (0/00) 14C age b.p.
CaCO3 rock -2.9 3886±42
colloids -8.4 3148+38
Hydrophobic DOM adsorbed at pH 1.0 -20.9 3441+37
Hydrophobic DOM dialyzed at pH 1.0 -20.9 3097+37
Amphiphilic DOM adsorbed at pH 4.9 -20.6 3480 +37

The organic matter was also studied by infrared spectroscopy and compared with the dissolved organic
matter currently present in the lake water. A preferential surface adsorption of the poly-carboxylated
polyanionic molecules present in the lake water appeared to have occurred, indicating that under the
alkaline conditions present, a similar type of poly-carboxylate fulvate adsorption on CaCO3 particles to
that which has been observed in other types of natural waters takes place.
This study had been a continuation of previous studies by the authors which had shown that dissolved
organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water.
The Aberdeen polysaccharide group manuscripts reported in Sections 7 vide supra used the the M.M.
Reddy G. M. Nancollas 1971 study of the kinetics of seeded CaCO3 formation as basis of the
experimental protocol for our study the effect of fulvate (equivalent ot dissolved organic matter) on
seeded CaCO3 (calcite) crystallization)].

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

Kitano Y Hood DW
The influence of organic material on the polymorphic
crystallization of calcium carbonate
Geochim Cosmochim Acta 1965 29 29-41

It was noted that, of the numerous factors which can control the
polymorphic crystal formations present in calcareous organisms
(calcite or aragonite or both as well as vaterite) which include
the aqueous solution temperature, the presence of inorganic
ions, CO2, carbonic anhydrase and a range of organic
substances; the latter had, prior to this study, not been
adequately studied. The authors showed that a wide range of
organic substance greatly affected the rate and form of
calcification. E.g. the natural animal sulfated polysaccharide
chondroitin sulfate and the organic matrix from oyster shells,
coral and calcareous sediment tended to promote the formation
of calcite (but organic matter from calcareous sediments
containing clay, on the other hand, promoted the formation of
aragonite). Overall consideration of the results obtained
suggested that the organic materials which inhibited the
crystallization of CaCO3 also favored the formation of calcite.

Thomas MM et al.
Adsorption of organic compounds on carbonate minerals: 3.
Influence on dissolution rates.
Chem Geol 1993 109 (1-4) 227-237
This study conducted in the context of oil reservoir performance
research indicated that those organic compounds (fatty acids and
carboxylated polymers) which adsorbed strongly on carbonate
minerals dramatically inhibited their dissolution in natural
waters.

Amjad Z Pugh J Reddy MM

Kinetic inhibition of calcium carbonate crystal growth in the
presence of natural and synthetic organic inhibitors
Ch. 11 (p.131-147) in “Water Soluble Polymers” Ed Z Amjad
Plenum Press New York
Available on the internet at
http://wwwbrr.cr.usgs.gov/projects/GWC_Crystal /Scanned_files/Kinetic-Inhibition_of_Calcium.pdf
Calcite crystallization rates were decreased to half by 0.3 ppm
tannic acid, 0.2ppm of a fulvic acid, and 0.0175ppm of a
polyacrylic acid. These results, obtained in the context of
research related to the need to improve industrial anti-
calcification agents, confirms the results of independent studies
in other laboratories which clearly show that poly-carboxylated
polyanions including fulvate are uniquely potent inhibitors of
calcite crystallization. The results which conformed to Langmuir
adsorption isotherm behavior also confirm that surface
adsorption at growth sites by the poly-carboxylated ligands is
the likely mechanism of inhibition.
This paper is highly relevant to the hypothesis that global warming and climate
change is soil-fulvate-transfer-related.
Cf. Morse JW
Chemistry of calcium carbonate minerals in natural water: An
overview
Marine Chem 1986 20 (1) 91-112 cf., a paper entitled “The kinetics of calcium
carbonate dissolution and precipitation” which appeared in Reviews in Mineralogy Vol. 11 Carbonates:
Mineralogy and Chemistry Richard J Reeder Ed. Series Ed Paul H. Ribbe Mineralogy Society of
America 1983]
[It is of curious interest that the next paper (No. 8. “Trace elements and isotopes in sedimentary
carbonates”); in this Edition of Rev Mineralogy is by Jan Veizer a later advocate of the cosmic ray
hypothesis of global warming].

Three classes of organic inhibitors were determined: strong

(citrate, malate, pyruvate, glycyglycerine, glycogen) moderate
(arginine, glutamate, glycine, glycoprotein, succinate, taurine
and chondroitin sulfate and weak (galactose, dextrose, alanine
and acetate)…. The most complete study of the inhibition of
calcium carbonate precipitation by organic matter was carried
out by Berner et al. (1978). Their primary concern was lack
of carbonate precipitation from supersaturated
seawater….Both synthetic organic compounds and organic-rich
pore water from Long Island Sound were used to measure the
inhibition of aragonite precipitation. Results for the synthetic
organic compounds and humic and fulvic acids reported by
Berner et al. (1978) were tabulated. Natural marine humic
substances and certain aromatic acids were found to be the
strongest inhibitors. The rate of precipitation in pore water was
also found to be strongly inhibited.
Much of the Rev Mineralogy article deals with the effect of
Mg2+ concentration on creating CaCO3 supersaturation.
Part of Table 2 Little or no inhibition Conc
mgC/liter (Rate of precipitation with additive)

/(Rate of precipitation in the absence of additive)

Aspartic acid 4.2 0.1

ca. 1.0
(similar results were obtained with
glutamic acid glycine and arginine))
Sodium stearate 108
0.8
Potassium H-phthalate
2.7 0.8
Gallic acid
0.3 0.6

0.8 <0.2
Humic acid from marine mud
0.8 0.5

6.3 0.02
Fulvic acid from pore water
1.4 0.5

2.7 0.18

[Cf. also the more recent similar work of Morse et al. discussed
in section 8-0-2-1-1].

The work of P.J. Wangerski

e.g.
Distribution of suspended carbonate with depth in the sea
Limnol Oceanogr 1969 14 929-933
[Cf. also ibid., 1972 17 960-962]
established that the traditional carbonate buffer hypothesis is not
observed under the experimental conditions investigated by this author in
the sea. Although this author’s thinking was centred on the pH buffer
the ideas discussed in this paper also apply to the multi-element buffering
capacity of seawater. A surface adsorption (essentially the fulvate switch
mechanism which is the principal focus of the present paper) which had
been previously suggested by the work of Suess et al., appears to be the
principal control mechanism of the carbon cycling system of the sea and
therefore of the largest carbon cycling component of the planetary system
appeared to be held [under what, in a highly fanciful analogy could be
equivalent to a ‘designed’ servo control switch mechanism equivalent to a
thermostat control mechanism by which the oceanic switch could feed
into atmospheric CO2 and hence affect the temperature of the Earth’s
surface]. This long time delay in the fulvate switch was suggested to
depend on microbial degradation of the surface coatings present on
CaCO3 (calcite) crystal surfaces in natural water on the sea bed.

8-7-7 Denton GH Anderson RF Toggweller JR Edwards RL Schaefer JM Putnam AE

The last glacial termination
Science 2010 328 1652-1656

Further plots (Figures in preparation)

Fig.3a 1

9.
Cosmic Ray Hypothesis of the Origin of Global Warming and
Climate Change
Cf. N.J. Shavid
web.sciencebits.com/ice-ages
[This gives a review of the cosmic ray model of climate change
which seems to be on an equal scientific merit footing to the
CO2 greenhouse gas warming theory]
----------------------------------------------------------------------------
Personal Experimental Background Etc. to the Hypothesis
This hypothesis was suggested by preliminary bench
experimental studies of the chemical nature and reactivity of
humic substances which were conducted by the author in an
academic laboratory during the nineteen seventies and
eighties, as well as by accumulated personal literature
surveys prompted by the results of these experiments. Part
of this database is now made public in this article.
If there is any truth in my humic led global warming hypothesis then the
first action which human society needs to take is to upgrade the status of
humic matter research from its present rather low level.

During participation in academic researches (in the Department of Soil Science Kings
College Aberdeen) which had been conducted to attempt to use NMR to determine the
chemical nature of humic substances and later researches (in the Department of
Molecular Cell Biology at Marischal College Aberdeen) which had aimed to probe
the role of polyanionic substances in natural biological anti-calcification tissue
protection strategies, it became apparent that the conventional soil humic matter
fractions (including some samples provided by the Macaulay Institute, Aberdeen) can
act as outstandingly efficient ligands for metal ions (the presence of Mn and Fe in
humate had hitherto prevented resolved NMR spectra from being obtained but the
slow transfer of such paramagnetic ions into tripolyphosphate granules enabled useful
NMR spectra to be obtained for the first time); a later study of the ability of humate
to block the active sites of calcite during the seeded crystallization of CaCO3 (calcite)
showed that water soluble fulvate humic fractions were two orders of magnitude more
effective on a weight basis than the polyanionic polysaccharides which were believed
to fulfill this function in vivo, e.g. at blood and urinary vessel surfaces in higher
animals or the commercially used bisphosphonates which find widespread use to
inhibit calcification in oilwell boreholes. The inhibitory ability of natural anionic
polyanions (of which humic and fulvic acids are natural examples) led to hypothesis
building regarding their possible major roles in animal tissue protection systems.
Since similar substances have been reported to occur in natural waters (as mixtures of
(e.g. algal) extracellular polysaccharides + colloidal humic matter dispersions and
dissolved fulvates) in total amounts which, although often small (e.g. ca. 0.5-2ppm)
[n.b. this low value is somewhat offset by the very high surface area of humic mater
particles] are still sufficient great (as predicted from carefully conducted in vitro
seeded crystallization rate studies) to potentially significantly alter the rate of
precipitation of CaCO3 in natural waters. This could affect those marine systems
which are believed to influence the carbon cycle both the long term (thousand year
scale) and shorter term (hundred year scale) carbon cycle and therefore affect
atmospheric CO2 levels. It is indicated that this marine carbonate buffer system
may act as a feedback control system for global climate and therefore the identified
anti-calcification behavior of humic matter is putatively the logical rate controlling
part of this process which, however could be subject to a major modulation by
numerous kinds of anthropogenic influences including the augmentation of the total
amount of terrestrial humic matter input into the sea (e.g. from intensive agriculture,
use of agrochemicals or deforestation) and also by an alteration of chemical structures
present in humic matter (e.g. phosphonate inclusion) which can be predicted to
change the potency of humic matter for acting as a marine carbonate recycling delay
switch.

While a large number of papers dealing with animal polysaccharide polyanion biochemistry had been
accepted for peer-reviewed publication at the time of cessation of these researches the humic matter
study which had been in process of being reviewed internally was not completed. Later, an updated
version of the original paper (which included references to similar results reported later in the literature,
but these authors had not noticed that their work was of relevance to climate research) was posted on
the internet at

web.scribd.com/doc/2396737/Humic-Substances-Inhibit-Calcite-Crysallizn-II

If the above anthropogenic influences on the humic matter status of

both terrestrial and marine environments were to be confirmed, then
the agriculture industry rather than the fossil fuel industry, should
perhaps become the principal focus of legislation aimed at ameliorating
the adverse climate effects of anthropogenic activities.
While major uncertainties remain in the understanding of how
anthropogenic actions can influence climate and atmospheric
CO2 levels it seems likely that primary climate changes could
result from the anthropogenic perturbation of the putative
humic matter biosphere control system which may behave in
an analogous manner, albeit in a much large sized system, to
how animal cell surface polyanions can provide for a wide-
ranging tissue protection and homeostasis system for the
animal cell and organism * .

*
cf biomedical research notes written by the author
These were meant to be rough drafts
web. ukonline.co.uk/dgrant/dg4
web.ukonline.co.uk/dgrant/dg5
web.ukonline.co.uk/dgrant/dg8
web.ukonline.co.uk/dgrant/dg2
The following is a more refined draft
web. sribd.com/doc/26994439/Publication-2-Web
Grant D et al. (University of Aberdeen researches [from about a
generation ago]) are included in the list given at
web.abdn.ac.uk/bch~118/publications2003march.doc

A number of papers on humic matter which remain relevant to

the current understanding of climate change were originally
collected by the author during the late 1970s and published in an
updated for in a web document
web.scribd.com/doc/34142473/2An-Assessment –of-Progress-in-Studies-of-the-Chemical-
Structure-of-Humic-Substances-Revised

A previous, shorter, version of the present paper is available at

web.scribd.com/doc/37544394/Anthropogenic-Augmentation-of-Marine-Fulvate-amp-
Climate-Change

The use of NMR to identify humic substance structure was found to be greatly assisted if the
paramagnetic ions were removed. This problem had previously and also later prevented the
use of this technique from giving useful information on the chemical nature of these natural
ligand systems
cf. D. Grant Nature 1977 270 709-710

The occurrence of dimethyl sulfide in the atmosphere (from marine algal emission) suggests
that scrambled alkyl sulfur capped off products might also arise in the atmosphere e.g. as a
consequence of cosmic ray induced structural reorganization.
Bivalent sulfur scrambling was the subject of a 1964 paper: Grant D Van Wazer JR J Amer
Chem Soc 86 3012-3017

Addendum
Problems With Assessing Scientific Information Between Different
Branches of Science
A possible major problem facing human society in assessment of the
quality of scientific expertise is that the subdivision of science into
numerous sub-disciplines creates barriers to understanding not just for lay
persons but also for scientists.
Science works best when it works as a unitary whole system of
understanding nature based on taking observations and measurements and
making sense of these by writing hypotheses and theories and then trying
to disprove these by further experiments so as to create new hypotheses
and theories and so on. A major problem has arisen due to the increasing
rate of production of scientific papers which makes most scientists
unfamiliar with new ideas derived from distant branches of science. Also
the increasing sub-division of fields. It is commonly found that scientists
when moving from one field to another find it difficult or even impossible
to bring with them and successfully apply tried and accepted concepts
which they were familiar with and were accepted truths in their old fields.
This extends to the processes by which the peer-review method operate
which often disallows important papers which depend on interdisciplinary
thinking from being quickly published. Experts in sub-fields are not
experts in other sub-fields and hence cannot assess the quality of inter-
scientific field contributions. These could be especially needed in the
field of global climate change. Lateral thinking which should be a central
feature of scientific thinking has become discouraged.
For climate and global warming science perhaps more than in other
branch of science, interdisciplinary information is urgently needed to
clarify and respond to anthropogenic inputs which could impact on
climate change. This unfortunately means that the belief that all is well
with how climate scientists see themselves (as suggested by PNAS 2010
doi:10.1073/pnas.1003187107) might be inappropriate and might stop
society from responding in the most appropriate manner to climate
change.

Freundlich Isotherm Plot

Relative Effectivness of Inhibitors of Seeded Crystallization of
CaCO3 (calcite) Calculated from Second Order Rate Constants
Fig. 4 log [rate(o)/(rate (m)]v f. [i] 0
of y axis, log10 [(Uninhibited rate)/(Inhibited rate)]
vs, x-axis [Inhibitor µ gml]0.5
Homogeneously nucleated crystallization of CaCO3 (calcite)
Comparison of fulvic acid with other inhibitors
a, water extract of soil (data from Inskeep & Bloom (1968b)
b, fulvic acid (prepn. 1)
c, fulvic acid (prepn. 2)
b*sulphated /sulphonated humic acid
d, heparan sulphate
e, heparin,
f, chondroitin 4-sulphate
(data for curves d-f were from Grant et al., 1988a)

Humic Matter Effect on Sillén Sea Atmospheric Model

Cf., Sillén LG
How have sea water and air got their present compositions?
Chemistry in Britain 1967 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 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 is not discussed
here by Sillén) 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 CaCO3 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 Sillén 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 thermodynamically required states but tends to
lead to increased complexity over time. A related phenomenon
which such aqueous systems seem to show is compensated
effects between sets of kinetic rate constants where the entropic
and enthalpic changes are coupled (the ‘compensation effect’)}.

Conclusions
Humic matter and functionally similar extracellular algal exudates present
in the sea and natural water could exert a critical role by acting as a
switch which can interrupt calcification in the sea and a related
mechanism of entry of CO2 into the atmosphere from the sea. This could
be a major control system which feeds into climate and global warming
and therefore any anthropogenic perturbation of this switch could be of
possible critical influence on the current abnormal climate change and
global warming scenario.

This survey of peer-reviewed literature, combined with personal research notebooks and files of
research papers stalled in draft form collected over many years suggests that the carbon cycle is
putatively controlled by the chemical and physical properties of humic matter and this can be altered in
major ways by human activities, this could mean that progress in understanding how additional
anthropogenic activities than the burning of fossil fuel might influence climate change and global
warming must a priori hinge on the attainment of a fuller understanding of humic matter.
Unfortunately this branch of science remains in some disarray. This (work-in-progress, requiring much
more editing) research offering may in the meantime offer some improvement of this situation.
An especially outstandingly high activity of terrestrial fulvate (discovered during in vitro studies of the
rate of seeded crystallization of CaCO3 (calcite)) suggested that an increasing presence of this kind of
fulvate derived from soil degradation in the surface layers of the sea could have enables human-
induced fulvates from terrestrial soils to increasingly, over the recent decades, block the cycling of CO2
between the land, the sea and the atmosphere. The occurrence of an increasing rate of the global
degradation of a high proportion of cultivated soils especially from them the time of the start of the
industrial revolution and increasing in recent years, supports this hypothesis of the origin of the recent
elevation of CO2 in the atmosphere.
The attainment of essential-to-life-supersaturation in all biological fluids and also in seawater
is apparently critically dependent upon the presence of the poly-carboxylate type of ‘smart’
buffer system. Its chemical nature is better understood in the animal fluids than it is in
seawater. It includes the poly-carboxylated organic polyanions which are also sometimes also
phosphated and sulfated and which are apparently aided by a more primitive system of
(purely inorganic) polyphosphates which apparently exist at all or most types of cell surfaces
throughout biota [2a].
*Possible Preamble to ref. 1
The current anthropogenic global warming and climate change scenario is suggested to
have partly arisen because of human actions can increase the fulvate contents of the seas
leading to an increased amount of CO2 in the top layers of the seas further leading to a
diminished ability of the sea to act as a sink for atmospheric CO2.
It should be noted that the degradation of topsoils, a process which has increased in recent
years (seemingly at a similar rate to the observed increase in atmospheric CO2) is likely to
lead to a major transfer of terrestrial fulvate from degraded agricultural soils into the sea.
It is further proposed that the pre-human seas contained e.g., ca. 0.1 ppm fulvate which
perhaps acted in some almost servo-control-feedback manner to slow but under normal
conditions did not completely stop CaCO3 precipitation. The fulvate content of some
modern seas and lakes seems now to have become so fulvate-augmented (e.g. by more than
an order of magnitude higher fulvate concentration than pre-human) that it is now
sufficiently great to completely halt the (abiotic) seeded crystallization of CaCO3, as well as
to prevent the re-dissolution of all types CaCO3 particles in deeper layers of the sea (without
which the ‘conventional model’ carbonate pH buffer system of the sea cannot function.
This scenario had been previously intimated by P.J. Wangersky [1-0] [8a-1] who had
proposed in 1969 that the ability of dissolved organic matter to inhibit CaCO3 re-dissolution
constitutes a “delay mechanism with a long time constant built into the carbonate cycle in
seawater”. This can, it is now proposed, be more aptly and simply called the ‘fulvate
block’; it includes the process of cementation of calcified aggregates by organic matter
which prevents the marine biota skeletal calcified materials from being recycled from the
sea bed.
It should be noted that anthropogenically increased fulvate also is likely to increases the
supply of nutrients to the sea and so exacerbrate algal blooms.
A variant of the fulvate block hypothesis was suggested by studies on the inhibition by
natural polyanonic substances of the seeded crystallization of CaCO3 conduced by the
author and colleagues during the 1980s.
[The original Aberdeen polysaccharide laboratory work was funded as part of a major
biomedical research effort which aimed to probe the inorganic biochemistry of
glycosaminoglycans, and included studies of the inhibition by these poly-carboxylated
polyanions of the crystallization of sparingly soluble Ca salts in biological fluids; A
previous research activity of the author (cf. Grant Nature [1-1]) had been the elucidation
of the chemical composition of humic substances, so it had seemed appropriate (with
permission) to use the available biochemical laboratory crystal growth experimental set-ups
(described in Grant et al. Biochem J [1-2]) to determine if this non-evasive and unlikely-
to-cause-decomposition-during-analysis-method could e.g. perhaps being able to
discriminate between lignin-derived and non-lignin-derived humic matter. [The possible
presence of lignin-derived humic polymers in soil organic matter had been a subject of
intense debate, but to make progress in this field it seemed to be required to use methods
which might allow structural information to be obtained without the use of the high
energies needed to volatilize materials which seemed previously to have led to artefacts
being produced from the starting humic polymers; this mis-assignment of data had
possibly indicated that lignin-like substances were important constituent of the most
common form of humic matter in apparent agreement with the results of early attempts to
use nuclear magnetic resonance for the structural analysis of humic polymers. However
exteremely poorly resolved spectra had been interpreted in this work which had also
depende o the use of an unreliable an external tetramethylsilane reference standard. This
was known to be a potential source of error. What had been assigned as a very broad
aromatic resonance could be more rationally re-assigned, if the spectrum was shifted by the
amount of the probable error introduced by the external standard, to an aliphatic
carbohydrate like substance and not a lignin-like substance inorganic adducts (with an
abundant OH resonance presence) It was found in the Aberdeen U. soil science lab. [1-1]
that NMR spectra could be greatly improved by removing the paramagnetic ions from the
soil organic matter sample by allowing their exchange from the humic matter into a
commercial sodium tripolyphosphate detergent builder. The discussion of this kind of
serious mis-interpretation of the early spectroscopic results did not, however, merit
publication owing to the rejection of this argument by a referee. The ‘correctly obtained’
NMR spectra [1-1] had failed to confirm the lignin-derived hypothesis of humic matter.
There seemed (as was learned may years later) to be a general disbelief of this result. The
measurement by controlled seeded crystallization kinetic evaluations of the crystallization
inhibitor potency of organic substances turned out to be a highly promising method for the
study of soil organic matter. While lignin derivatives were apparently poor calcification
inhibitors, the humified soil polymer extracts were found to be exceedingly active
calcification inhibitors (e.g. an agricultural soil fulvate fraction was found to be very much
more active than common commercially used calcification inhibitors [e.g.
bisphosphonates]. The dramatically effective inhibitory effect of fulvate on CaCO3
crystallization could be ascribed to the presence therein of poly-carboxylated polyanionic
chemical units which formed high affinity complexes with the growth sites of seed crystals
thereby highly efficiently facilitating the formation of permanently supersaturated CaCO3
(calcite) solutions. The fulvates also behave as effective inhibitors of the dissolution of
CaCO3 crystals. The ability of fulvate to determine activities which are believed to be
centrally involved in the carbon cycle in the sea, namely the precipitation of CaCO3 and the
dissolution of CaCO3 particles below a specific depth in the deep sea, it was conjectured,
must also surely have some major relevance to how the global natural water and carbon
cycles could be perturbed by human actions and therefore hinted at the existence of a
major global carbon cycle control system which might be of major relevance to how
anthropogenic actions can impinge on atmospheric CO2 and so induce climate change.
It was not initially thought worthwhile, however, to publish these preliminary results
immediately since the high reactivity of North East Scotland fulvate might not have applied
to fulvates from other regions of the Earth. It later became apparent however (as
suggested by the scientific literature accessed from part-time literature browsing) that good
evidence existed for a general global ultra-active fulvate carbon cycle interrupter effect.
Possibly the first relevant studies (which had predated the Aberden U. polysaccharide lab.
findings) were those of K.E. Chave and E Suess [1967] which were independently
confirmed by P.J. Wangerski in 1969 [1-0]. The latter author also intimated that
“chemically or biologically precipitated calcite may represent a delay mechanism with a
long time constant built into the carbonate cycle in seawater”.
The ability to stop CaCO3 precipitation in surface layers of the sea could interrupt the
marine/ atmospheric carbon cycle, cause an increase in CO2 injection from the sea into the
atmosphere, and stop the CaCO3 re-dissolution processes in the deep sea.
The latter could become diminished below some critical fulvate threshold concentration
e.g. similar to that present following deglaciation dilution of the seawater by the kind of
massive freshwater runoff from melting ice sheets which recent researches (G.H. Denton et
al., Science 2010 328 1652-1656) have indicated was likely mechanism by which the fast
deglaciations of the most recent termination was promoted. The link between ocean
carbonate balance and fulvate status might explain how the dilution of the ocean by rapid
ice melting by reducing the amount of natural fulvate there present which had previously
been able to perform the above surface adsorption block on the formation of new CaCO3
particles but the lesser availability of new fulvate to replace that removed by bacterial
degradation could conceivably reactivate the pressure-dependent CaCO3 crystal dissolution
processes which allows this major store of CO2 to be eventually transferred to the
atmosphere.
(This part of the long term carbonate cycle has been suggested to be the origin of the
delayed 100 ppm rise in atmospheric CO2 associated with deglaciation, arising following an
upwelling of the sea could transfer part of the long term CaCO3 store in the deep sea to the
surface which allows release of CO2 from the sea and to augment CO2 greenhouse gas
atmospheric warming effects of the gas).
The ability of humans to affect climate arises, can, at least in part, arise because fulvate
(the major water soluble organic matter humic fraction) has an outstanding ability, as
indicated by in vitro experiments, to markedly inhibit the precipitation of CaCO3 from
supersaturated solutions including seawater.

Discarded Text Store

More on Humic Matter. It Links Geology & Biology
Fulvate is suggested to provide in the sea a chemically similar buffer system to that
afforded in the extracellular compartments of biological organisms by the anionic
poly (uronate) saccharides which are present at cell surfaces and in the extracellular
fluids of animals. Such poly-carboxylated polyanion ligands completely block the
formation of precipitates which if formed in the wrong place become highly toxic to
living organisms.
via the occurrence of Ca2+ as well as CO32- ions in aqueous solutions
associated with biology (this includes the sea). A hallmark of such
solutions is there high degree of supersaturation (Ω ) with respect to
CaCO3 precipitation. Thus the largest organic pool in the biosphere is
apparently specifically structured as a ligand to enable to playing a
critical modulatory role in both the inorganic carbon and in the organic
carbon cycle. This includes an ability to determine the amount of CO2 in
the atmosphere.
Some ‘smart’ other-than-thermodynamic control system is likely to be a
major part of what constitutes any kind living system or a quasi living
system (e.g. the system which preceded the nucleic acid led current biota
of Earth).
Modern animals seem to have retained the primitive poly-carboxylate
polyanionic seawater buffer system which was present in the archaeic
seawater in which the ancestors of present day animals first evolved. This
buffer action was and is still most likely performed by the largest broad
class of chemical substance occurring in both of these aqueous solution
systems, namely poly-carboxylated polyanonic substances.
Fulvate by coating and deactivating biogenic CaCO3 particles can also
block the medium-to-long-term carbonate cycle of the sea by abolishing
the hydrostatic pressure induced CaCO3 dissolution process on which
the traditional carbonate buffer system of the sea was supposed to
depend.
Humic matter is a polyanionic substance of major importance to all
biological systems and how these systems engage in crosstalk with
geology. This includes the regulation by humate of the rates of
dissolution of rocks and of the rate of formation of crystalline phases.
However an especially strong affinity of humic matter for attachment to
the crystalline surfaces and lattices of CaCO3 (calcite) seems to be the
most important interlink between geology and biology. This close fit
between ligand spacing and crystal surface growth sites seems most
especially to describe a common terrestrial soil derived water soluble
humic matter (fulvate) [1-1][11a]. The existence of such a specific high
affinity interaction between the most abundant subfraction :
fulvate
[the largest (humic matter) organic polymer system in the biosphere]
with
CaCO3
[the most abundant inorganic carbon system of the biosphere]
points to this phenomenon having a possible central role in the long-term
homeostatis system of the Earth’s biosphere.

This idea agrees with the findings of Chaeve & Suess and Wangerski
that a CaCO3 dissolved organic matter (i.e. a fulvate) complex and not
uncomplexed CaCO3 occurs in the CaCO3 particulates which occur
abundantly in the sea.

This suggests that a chemical compoisiton “ CaCO3 (fulvate)x “

rather than “CaCO3”
is the correct formulation with which to discuss the modus operandi of
the traditional role carbonate-based pH (and other ion) buffer system of
the sea.
A similar co-occurrence of fulvate with CaCO3 also has been recently reported to
occur in the alkaline waters of arid region lakes (as indicated by Leenheer & Reddy
[1-0-1].
The CaCO3(fulvate)x system is now suggested to have a central relevance
to the mechanism by which the short and long term oceanic carbon
cycling occurs in the sea
This homeostatic control system seems however to be potentially
relatively easily perturbed by human influences. It should be noted that
whereas fulvate from normal agricultural soils or that present in normal
DOM are potent inhibitors of CaCO3 precipitation, other types of fulvate
which might arise from human activities might promote and not inhibit
the crystallization of CaCO3.

Approximately physically similar poly-carboxylate (-C(O)O-)

polysaccharide and/or protein-based polyanionic system also occur in
biological fluids