D Grant New Deer-Turriff UK

Preliminary Draft of a Research Note

Title:
A Hypothesis: Anthropogenic Perturbation of Marine &
Terrestrial Humic Mattera is the Principal Cause of Global
Warming
This sequel to
web.scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystallizn-II
directs to the attention of the general scientific community as well as to climate change/global warming
scientists that anthropogenic influences can putatively cause climate to change by perturbing the
chemical composition, reactivity and amounts of humic substances present in various ecological
compartments.
There is believed to be an urgent need to slow climate change which
could damage the environment to such an extent as to put at risk the
continuation of the present type of human society but that a tipping
point may occur sometime in the foreseeable future when human
intervention to prevent this will then no longer be possible.

Literature Survey Collection of Reprints & Notes Relating to

Possible Role of Disturbance of the Marine Carbonate Buffer
System by Anthropogenic Disturbance in Marine Humic Mattera
Balance
(An old survey from a terminated research activity at the University of Aberdeen, Scotland, UK)

Contents
1. Summary
2. Introduction
2-1 Some interacting natural planetary homeostasis mechanisms
2-2 The role of the sea as a buffer for atmospheric CO2

3. Human alteration of the bacterial population of the soil is also likely to be a major mechanism
of anthropogenic climate change

4. Soil organic matter shifts into the sea as tundra etc. warm up
4-1 Anthropogenic alteration of the marine humic matter dependent calcification mechanisms
Humic polymers are hyperactive calcification inhibitors
4-2. More humic matter research is needed to avert possible anthropogenic climate change
damage since this branch of science is the key intellectual background now needed to
understand global warming
5. Direct warming effect of transfer of soil organic matter into the sea
5-1 Humic matter heat uptake and Milankovich Orbital Theory of Glacial Cycles

Usefulness of Soil Model in Politics of Climate Change Bargaining

6-1 The future of human society is at stake in various ways
6-2 The impending crisis in democratic government caused by climate change bargainins
6-3 The need for new, more credible hypotheses of global warming
6-4 Cultivation of polymethylene-rich humic matter in grassland to offset fossil fuel
combustion

7 The traditionally established roles of humic polymers

7-1 The microstructure of liquid water may be affected by humic polymers
7-2 Water vapor is a key greenhouse gas

8. Key References
8-1 CO2 from soil respiration inputs 98±12 Pg C/year into the atmosphere
Etc.

Personal experimental background etc. to the hypothesis

Addendum: Problems with assessing scientific information between different branches of

science
Footnote a

Conclusions

1. Summary
Considerable scientific evidence suggests that the actual
mechanisms of the current, possibly human-induced, adverse
climate changes and global warming are far from certain.
A novel concept for debate, now offered, is the notion that
terrestrial and marine humica matter, which putatively
provide a natural global biosphere ‘management control
(planetary homeostasis) system’, can become sufficiently
altered through human actions so as to promote the current
abnormal global warming and climate change.
The primary trigger for the cyclical climate warming and
cooling events responsible for glacial cycles perhaps seems
most likely to be the cyclical variations in the energy
received from the sun which feed into additional atmospheric
heating effects attributable to greenhouse gases (which
include {perhaps even a dominant effect of} water vapour,
methane as well as carbon dioxide). It is proposed that an
increased atmospheric content of these greenhouse gases and
others could chiefly depend on the anthropogenic alteration
of the ubiquitous environmentally-present humica substance
polyanionic chemical polymer system which is known to
contribute critically to soil fertility and marine biochemistry
and possibly also to the direct absorption of solar energy by
the sea and the land. Anthropogenic alteration of this
globally distributed natural polyanionc humica matter
polymer/aggregate system, rather than the carbon dioxide
produced by the combustion of fossil fuel, is now proposed
to be the principal trigger which can empower human
activities to induce abnormal global warming.
(N.b. there are, however, a host of other environmental advantages to
the reduction in the extraction and use of fossil fuel e.g. the reduction
of acid rain, polycyclic aromatic nanoparticle formation, heavy metal
pollution and abnormal water vapour production, so the present notion
that it is environmentally beneficial to seek alternative methods of
energy production is a scientifically sound one).

2. Introduction
Section 2 sub summary
The chemical and physical properties of humic substances allow them to act as a principal
homeostat control system for terrestrial and marine biology and therefore any attempt to
understand anthropogenic interference in climate can be argued a priori to be a task
which is uniquely centered on humic science. Unfortunately this branch of science
remains in some disarray.
It should be noted that a worst case scenario is that human-
induced abnormal climate change could cause mass species
including human extinction. This kind of alarmist (Hanson)
hypothesis requires that a major reduction in the use of
fossil fuels be achieved since this is assumed to be the
principal cause of the current continued increase in
atmospheric carbon dioxide. The principal mechanism of
injection of this gas into the atmospheres might however
arise from agriculture rather than from the industrial scale
burning of fossil fuels. If this idea can be supported by
further research, this human activity must then become a
principal focus of attempts to slow the current abnormal fast
climate change process.
2-1 Some interacting natural planetary homeostasis
mechanisms
A generally accepted view is that the current climate of the
Earth (and perhaps also other planets) is affected (or indeed
dominated) by the amount of carbon dioxide (CO2) in the
atmosphere, but the amounts of this gas and its associated
climate-determining effects are normally held in balance
over geological time-scales by various homeostatic
mechanisms especially those afforded by seas. It is also
believed that the sea on Earth has achieved an approximate
constancy in dissolved inorganic and organic molecule
concentrations by the operation of some form of further
homeostasis control mechanism which has been in force over
geological time. A further belief, however, is that we are
currently passing through an unstable geological climatic
period during which the various natural homeostasis
mechanisms, including those which affect the sea, can be
easily disturbed by the relative puny influences which
humans are capable of. These influences are wide and varied
and have included a major disruption of the planet Earth
homeostasis/ protection ozone layer by chlorofluorocarbon
emissions. This circumstance might conceivably act as a
vivid demonstration of to what extent humans are endowed
with the ability to trigger a major global scale ecological
event including climate change disaster, by the perturbation
of some primary planetary homeostasis mechanism.
Such human influences, it is now suggested, may include the
alteration of the humic matter introduced into the rivers and
the sea by agriculture. This possibility arises because the
total biosphere humic matter pool forms the largest single
type of organic carbon in the biosphere. Agriculture is now
conducted on such a large scale that it inevitably must at
least potentially disturb this humic matter pool of the
terrestrial humic matter alone, which it should be noted,
comprises ca. twice the amount of carbon to that which
occurs in the atmosphere as CO2. It should also be noted
that the current increase in global temperature seems to be
causing an increased rate of degradation of terrestrial humic
matter (including by bacteria) which injects CO2 into the
atmosphere in amounts which greatly dwarf the fossil-fuel-
derived-CO2 produced at present or in the foreseeable future
by humans.
An even larger humic matter pool is, however, associated with
the dissolved organic matter store in the sea, which covers
71% of the Earth’s surface and can avidly dissolve CO2. The
control of marine CO2 can be shown to likely be determined
by the chemical and physical properties of this prime humic
matter pool. The water in the sea and glacial ice evidently
provides the dominant secondary to solar energy climate
control system. This can act as a multi-factorial global
buffer feedback system pH buffer systems and global CaCO3
rock formation/dissolution-calcified organisms systems
which interface with the sea (including on the seabed of
shallow seas) which also however comprises an enormous
potential source of CO2 enabling an augmentation or
alteration of the quality of the humic matter dissolved or
suspended in the sea to influence the exchange of CO2
between marine compartments and the atmosphere. The
functions of humic matter seem also to include a critical-for-
life marine multi nutrient element buffer provision
(putatively the dissolved multi-inorganic element content of
the sea is created by a system of superstauration of various
salts determined by the ability of humic matter to inhibit the
formation of solid phases in addition to CaCO3).
Human-activity-determined terrestrial soil degradation is now
proposed to lead directly to an increased degree of CaCO3
supersaturation in seawater. This, similar to the effect of an
elevation of the temperature of the surface of the surface of
the sea causes more CO2 to be emitted directly from the sea
into the atmosphere. This mechanisms can partly explain
why the increase in sea surface temperatures in recent years
show a direct correlation with the amount of CO2 in the
atmosphere over the same time period (cf. section 3 and ref.
8-1).

2-2. The Role of the Sea as a Buffer for Atmospheric CO 2

The high solubility of CO2 gas in water should allow the sea to provide a
major buffer system for atmospheric CO2. 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, an apparent
partial rapid operation of this buffer system seems to be illustrated by the
almost exact linear dependence shown between the smoothed variation of
the surface sea CO2 contents (suggested by seawater surface
temperatures) and the smoothed average recent CO2 contents of the
atmosphere deduced from published data (reported by Endersbee L {loc.
cit. ref. 8-1}: [atmospheric contents of CO2 data from January 1985
through May 2008 were found to be linearly correlated with the global
average sea surface temperature (the ‘anomalous’ increase from a recent
baseline) over this period]) which could indicate that the increase in
atmospheric CO2 over this period was caused to a major extent by the
direct release of CO2 from the surface of the sea as the seawater warmed
up or that the increase in atmospheric CO2 had been affected in some way
by the humic matter control effect exerted upon the seawater CO2-
carbonate buffer system which seems to act as the natural switch which
allows this CO2 release.

The inorganic carbon equilibria between CO2 and HCO3- and CO32- ions
and the related solubility properties of CaCO3 forms the basis of the
traditional hypothesis of the mechanism by which the pH value of the sea
is buffered, but the traditional view of the carbonate balance of the sea
can also provide for a major method of removing CO2 from the
atmosphere by allowing the formation and precipitation of solid CaCO3.
Such CaCO3 re-dissolves at great depth however as originally discovered
in the nineteenth century by Sir John Murray the father of oceanography.
Relatively shallow seas nevertheless have the capacity to act as enormous
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 latter organisms are now
thought 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.
The most abundant natural polyanion of all, humic matter also could also
play a key role in biotic calcification as well as in the wider CO2
atmosphere buffer system.

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

be a major mechanism of anthropogenic 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 Bond-Lamberty B &
Thomson A Nature 2010 464 579-82, at doi:10.1038/news.2010.147.
Fang A in the asociated Naturenews article noted that
CO2 from soil respiration now apparently inputs 98±12 Pg 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 produced by the anthropogenic
combustion of fossil fuels. This finding 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.

4. Soil organic matter shifts into the sea as tundra etc. warm
up
The direct abiotic oxidation of (degraded) humic substances is
know to be promoted by the drying out of marsh environments,
a process which can also be catalyzed by trace amounts of
anthropogenically introduced heavy metals. These processes
which occur as the climate warms up can directly introduce
carbon dioxide into the environment.
(cf. ref. 8-3). Solar energy also degrades photosensitive forms
of dissolved organic matter in river water produced by warming
up Arctic tundra (cf. ref. 8-3-1).

4-1. Anthropogenic alteration of the marine humic matter dependent

calcification mechanisms
(cf. web.scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crysallizn-II ).

Humic substances bind strongly to mineral surfaces thereby

putatively greatly reducing their effective solubility in seawater.
This mechanism could be a major part of the marine geological
scale homeostasis system which controls the (all-element,
Haraguchi) inorganic ionic contents of the sea as well as
suggesting how an anthropogenic alteration in the amount and
quality of marine humic matter might perturb inorganic carbon
exchange mechanisms including marine calcite precipitation
systems (discussed above) so as to alter carbon cycling rates
which further feed into global climate and can augment sea and
air CO2 levels.

4-2. Humic matter science is possibly the key intellectual

discipline which is now needed to be promoted in order to
combat anthropogenic induced global warming
More Humic Matter Research is Needed to Combat
Climate Change Damage

Since the worst case scenario of the current continuation of

human induced climate warming is that human society may
be irreversibly damaged, it seems worthwhile to fully probe
by more extensive research effort, the various roles of humic
matter effects suggested in this note which is based on a
literature survey directed only by preliminary laboratory
experimentation.

More humic matter research is absolute needed urgently to

achieve sufficient understanding of this buffer system in
order to design strategems which can hope to succeed in
preventing a possible irreversible anthropogenic climate
change damage.

5. Direct Warming Effect of transfer of soil organic matter

into the sea
Atmospheric CO2 can in principle also be increased indirectly
by effects of transfer of terrestrial soil organic humic matter
into the sea via the warming effect caused by enhanced
uptake of solar radiation capture. The graphite-like dark
colored humic matter particles present in some types of soil
humate could act as solar energy traps and the transfer of
such particles to the sea in rivers following terrestrial soil
degradation could directly increase the surface sea
temperature leading to increased release to the atmosphere of
the CO2 dissolved in the sea.

5-1. Humic matter heat uptake and Milankovich Orbital

Theory of Glacial Cycles
It should be noted that the basic physical properties of dark colored
humic matter (especially in the surface waters) endows it with an
augmented ability to directly absorb solar heat and thereby speed the
kinetically controlled increased supply of nutrients to microbiota, such
increase the abiotic uptake of solar energy by the sea seem, conceivably,
may also lead to the direct warming of the sea. Such promotion of
efficient heat exchange near the ocean surfaces could also be part of the
mechanism by which solar energy cycles feed into the Earth’s climate.
Marine humic substances may also act directly as major solar energy
collectors (it should be noted that the aquatic humic substances which
impart a brown or yellow colour to natural waters account for 40-60% of
the seawater-dissolved organic matter. (DOM (cf. Retamal et al. ref. 8.3-
1)) ; since this is the major marine carbon containing compartment, sea
water and lake temperatures are potentially directly influenced by solar
energy input changes which could be of relevance to a fuller
understanding of the Milankovich orbital theory of glacial cycles.
(Cf. Kanamura et al. ref. 8-5-1).

6 Usefulness of Soil Models in Politics of Climate Change Bargaining

The release of greenhouse gases following the anthropogenic degradation
of terrestrial soils could be (and have been over the period of the
dramatic rise in human population) originally have been the
principal contributor to anthropogenic- induced climate change;
the late Holocene CO2 augmentation formerly attributed to wood
burning by early farmers (the Ruddiman hypothesis vide infra) is a
possible example of the operation of this mechanism.
It is self evident that information gained from the study of humic
substances in the proposed emergency scientific research effort which is
demanded the possible impending global environmental crisis could
facilitate the political bargaining which is required to bring about the
necessary legislative controls on those human activities which may
promote global warming.
6-2 The Impending Crisis in Democratic Government Caused by Climate Change
Bargaining
An impending crisis in democratic government seems likely to
arise from the resistance which will be shown to perceived
need by the scientific community to take urgent action in the
face of resistance from alternative beliefs held by the
majority of other persons who do not have faith in the
correctness of the current mainstream scientific theories of
climate change. Such persons will especially strenuously
challenge the need for any curb on the use of fossil fuels.
This problem is exacerbated since the current assumptions of the
mechanism of global warming is thought by the majority of
the non-scientific population to be at least partly and perhaps
completely in error. It is common knowledge that climate
has been much warmer and atmospheric CO2 much higher in
past geological eras before man evolved. Furthermore the
elementary chemistry which is known by most elementary
educated persons teaches that water avidly dissolves CO2.
This evidently should allow the sea, which is well known to
cover most of the surface of the planet, to keep the
atmosphere from accumulating CO2 and explains why the
old textbook value of atmospheric CO2 content was ca. 0.03
% by volume. While this is the fourth most abundant gas in
the atmosphere, it still seems to be very small amount to
most members of the public.

6-3 The Need for New, More Credible, Hypotheses of Global Warming
New, more credible mechanisms by which humans might cause
climate change should be formulated and debated since the
current belief that global warming is solely dependent on the
elevation of atmospheric CO2 produced by the combustion of
fossil fuel is commonly believed to be an incorrect
assumption despite the apparent strong evidence in favor of
this hypothesis.
Evidence from soil science now supports the ‘commonsense’
opinion that although fossil fuel burning may be a significant
contributor to how the atmosphere got more CO2 during
some stages of the industrial revolution, it is unlikely to be
the principal cause of the anthropogenic augmentation of
atmospheric CO2 at the present time.
6-4 How to Offer a Safety Net Which Allows the Continued Use of Fossil Fuel by
Offsetting this with Cultivation of Polymethylene Rich Humic Matter in Grassland
A method of offsetting the various climate and human health dangers
from burning of fossil fuel can be offered as part of a more general
management of planetary humic matter. Through suitable agricultural
practices it is theoretically possible to accomplish the same rate of
capture of carbon in long lived polymethylene-rich humic matter as the
rate of fossil fuel combustion which society will demand to be allowed to
continue.
A useful soil improvement method using soot from incomplete
combustion of coal, oil and gas could also help here.

7 The Traditionally-Established Roles of Humic Polymers

Humic polymers have a number of fairly well understood roles for the
stabilisation of terrestrial soil structure which includes by the mechanism
of the binding to CaCO3 surfaces and the ability to control calcification in
soils (there being related functions in natural water) they have also
important pro-biotic water binding reservoir functions in natural waters
and soils where they provide as a pool for sequestering and releasing
major and micronutrients and a related ability to promoting the
weathering of rocks; the full seawater range of inorganic elements exist
in a multi-inorganic complex system with water soluble humic polymers,
which can also demonstrate to elicit plant hormone like activities which
e.g., can stimulate root growth, humic matter can also act as a sink for
anthropgenically produced substances which include chlorinated aromatic
substances which may act in an anti-biotic fashion.
7-1 The microstructure of liquid water may be affected by humic
polymers
The basic scientific understanding of the microstructure of liquid water
and its variation with temperature is also per se of fundamental interest to
biological systems including those in the marine environment; this
includes the alteration of the cluster complexity of water structure and the
effect on this phenomenon of the ubiquitous polyanionic surfactive humic
substances which form the majority of the dissolved organic matter in the
sea [the aparent low percent by weight e.g. ca. 1% is a modest amount,
the humic matter agregate poymer molecular system adds to its extent in
space by being highly hydrated and in addition possess and enormous
internal surface area being analogus to microporous carbon or silca sol
particles in this respect ; it seems likely that such substances can cause a
major departure from solution ideality (and the applicability of reversible
thermodynamic equilibria to serve as a model for marine input into
atmospheric CO2). The recently fully published Phillipa Wiggins high
density liquid water /low density liquid water (HDW/LDW) theory (cf.
Plos ONE 3(1): e 1406.doi:10.1371/journal.pone.0001406 (2009) )
indicates that the ultimate basis of biological energy transduction
(including that involving ATP) could be directly applicable to marine
science and perhaps also to how water vapor clusters (either clean or
attached to carbon-rich or humic particles) behave in the atmosphere
since the ability of solar energy to heat the environment could especially
depend on the hydration environment of dissolved humic matter as well
as the humate present in dust present in the atmosphere (e.g. by the
provision of a system of micropores which could at least in theory, be a
major natural solar energy transducer system). The total atmophereic
water system of relevance to the greenhouse effect needs to consider the
effect of water clusters which may be associated with the nanoparticles of
humic matter, soot other small carbon containing particles from diesel
exhaust, sulphate salts, and sulphuric acid which seem to form in the
atmosphere at least partly due to human activities.

7.2 Water vapor per se is a key greenhouse gas

While the above discussion has centered on the role of CO2 as a major
greenhouse gas it should be noted that the greenhouse gas properties of
water vapor may be more important than of CO2 or the other greenhouse
gases as a source of global warming including possible anthopogenic
influence upon this.
8.

The following key reference articles were identified are briefly

abstracted and discussed below.

Key References
The information reported in the following papers and published
comments thereon supports the hypothesis that the global
warming from 1970-present is mainly driven by anthropogenic
perturbation of a variety of humic matter reservoirs in the soil as
well as those in the sea.

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 numerical value of atmospheric CO2

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-Crytallizn-II.

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
anthrogpogenic 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 ways 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 at 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
microrganisms using this form of carbon as an energy source;
Fang J in Naturenews drew attention to the implications of the
Bond-Lamberty & Thomson findings that suggest that soil may
greatly outperform human fossil fuel burning as a source of CO2
input into the atmosphere. A further comment by Chaurasia A
(an internet comment attached to the Fang Naturenews article)
suggested that the observed global increase in soil has arisen
from the diminished soil (microbial) bio-diversity caused, in
turn, by the widespread use of agrochemicals. This, it is now
suggested is a useful and probably highly informed comment.
The possible largest anthopogenic activity which is currently
affecting climate would seem, if the above hypotheses were
correct, to be industrial agriculture.
This further suggests that (following the further research which
is 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 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 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
who 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 sever 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 is the release of CO2 in the sea following
the photodegradation of UV sensitive relict porphyrin structure
containing terrestrial humic matter].
----------------------------------------------------------------------------

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
atmohpheric CO2 has continued to the present time]. It was
noted that while ca. 30% of the increase in the part 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 = 1 billion g)
Atmospheric CO2 760 Pg

Accumulated CO2 in atmosphere from fossil fuel 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
(agricultural) activities to prevent near future adverse climate
warming. The original hypothesis that farmers had introduced
CO2 from wood burning into the atmosphere which did not show
up in the more recently carefully examined isotope record might
suggest that the late Holocene small CO2 increase was not
caused by human activities. The idea that fulvate humic matter
could have been introduced into the sea in large enough amounts
by late Holocene human deforestation activities to affect the
atmospheric CO2 seems a credible mechanism of how early
human activity could show up in the ice core evidence. 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 is
a secondary effect}.
[The above Geophysics article by Ruddiman 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 anthropgenic 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 anthopocene 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 has ensued on the
validity the timing used by Ruddiman to compare of current
interglacial trends in atmospheric greenhouse gases with those
predating human activities and includes discussion of
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 is responsive to climate change and the
alteration of the time pattern of this minor greenhouse gas
produced by early agricultural activities seems to agree more
satisfactorily with the anthropogenic greenhouse hypothesis than
does the CO2 data (which fails to show up the required 13C
signature).
Further discussions of early anthropogenic effects on climate
were centered on reduction of greenhouse gases as deduced
from ice-core evidence following large human population
decreases caused by disease epidemics when agricultural land to
returned to forest. The 2009 paper by Elsig et al. (vide infra)
reinvestigated the δ 13C isotope historical record of atmosphere
CO2 which suggested that the small late Holocene climatic
warming had been caused by wood burned e.g. following forest
clearing. Large scale deforestation of Eurasisa similarly have
introduced such natural heat traps to the sea through the soil
destabilization following deforestation. This would be expected
to act like the kind of 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. Other mechanisms of anthropogenic sea CO2 release
can also be envisaged as discussed elsewhere in this article.

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 bythe 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 anthropgenic modulation of marine carbonate balance
and resulting atmospheric CO2 input effect).

8-5-1
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].
The Milankovitch theory that Northern Hemisphere summer
insolation triggered the last four deglaciations was confimed 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.

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)

-----------------------------------------------------------------------------
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.

8-6
Other scientific web sites access ‘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 discuss e.g. problems in understanding the
circulation of the sea, iron fertilization and sediment
geochemistry. 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. Neuweler et al. 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 millon
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 allows
the relative importance of oceanic and terrestrial biosphere
exchange mechanisms for removal of CO2 from the atmosphere

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 results in
a relatively small change in δ a13C for atmospheric CO2 .
[An increase of 0.0027o/oo per 109 t (Gt) C occurs 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,

causes a much greater effect namely a decrease in δ 13 of ca.
0.026o/oo.
This allows 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. 44% only 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
difference e.g. between data from pre-1940 and post-1940.
Could pre-human natural carbon sinks have been much be 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.

Environmentally stable phosphonate herbicides and

phosphonate laundry detergents
might be amongst the drivers of oceanic disturbances which
creates augmented atmospheric CO2
Altered inorganic ions, humic matter oceanic pH redox status
{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-anthropcene 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)}.

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.

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, more 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 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 failed; it should be noted that they could not fully
account for the historical ice core record. A new model is
evidently required.
Perhaps the inclusion of the proposed humic matter blocking
effects on oceanic carbonate cycling mechanism and the
associated surface water HCO3- concentration rise, could be of
value here.

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.
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 –0.1GtC/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 (cf. Grant et al. Med Hypoth
1992 38 49-55) which is likely to be controlled by natural
‘smart’ polyanionic polysaccharide morphogens. Numerous
non-calcifying species seem to be able to evade calcification
completely by the use of a similar polyanionic mechanism (cf.
Pentecost loc. cit.). The analogous polyanonic 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. Sillén) think that
thermodynamics rather than kinetics 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 which
Pentecost (vide infra) indicated to perform this kind of task; 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].

{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. vide supra];
A major departure from an exact thermodynamic model may
occur in seawater-like solutions in the presence of polyanions
whichrather than binding as simple (Manning) electrostatic
attractors 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.
Hansen J et al. gistemp2010_draft0803 (NASA data reports of
the post-1970 continuous increase in global temperature).
Neuweler 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 Neuweler 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
Neuweler 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 Neuweler et al.].

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

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.

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 Fig 1.
{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’)}.

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 a
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 hyothesis 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 bisphosphates 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 almost

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

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 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 operates 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.

Footnote a
Humic Matter
Humic and fulvic acids (which are components of terrestrial soils and e.g. the dissolved organic matter
of seawater) are now believed to be composed of a variety of (mainly of aliphatic C(O)O-containing
structures ) which can act as highly effective ligands for the binding of numerous types of inorganic
ions and surfaces potentially enabling them to act as both promoters and inhibitors of crystallization.
A major problem in attempting to clarify the possibility that interactions between the
ubiquitously occurring natural humic organic matter compositions and other
environmental factors could affect the climate of the Earth in a major way is that the
fundamental chemistry of humic matter and the full range of humic matter activities are
still relatively unknown.
Nevertheless it is worth restating here that humic substances are known to form the largest
biosphere pool of both land and marine carbon.
There are a number of possible mechanisms by which humic matter could influence how CO2 is
removed from the atmosphere. An important effect of humate is that it can affect the rate of CO2
uptake by affecting the efficiency of photosynthesis by plants and marine species which require
nutrients which are provided naturally by humic polymer inorganic ion adducts present in soils and
natural waters.
Terrestrial humic matter (which can be degraded by a number of anthropogenic influences) is
known to be of critical importance for the securing of soil water environments and for
providing the slow release ligands for the reservoir provision of the full range of inorganic
macro and micro nutrient elements required by biota including microbiota, for the
stabilization of soils, as well as for the binding of pesticides and other agrochemicals.

Conclusions
We might as well provisionally lay the full blame on
climate change and global warming entirely on humic
matter alterations following their perturbation by
human activities.
Global heating which is currently believed to principally arise
directly from increased atmospheric CO2 from fossil fuel
used in human domestic and industrial activities may arise
by another mechanisms including the anthropogenic
disturbance of the humic matter biosphere homeostasis
systems.
Anthropogenic perturbation of natural humic matter cycling could
significantly increase sea and land temperatures by augmenting carbon
energy sources, increasing macro and micro inorganic nutrients and
perturbing inorganic carbon homeostasis mechanisms which apply to
ocean and soil biology.