D Grant New Deer-Turriff UK Preliminary Draft of a Research Note


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 Humic polymers are hyperactive calcification inhibitors

4-1 Anthropogenic alteration of the marine humic matter dependent calcification mechanisms 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
5. understand global warming 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 humaninduced 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-fuelderived-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-forlife 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 CO2carbonate 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. 8.31)) ; 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



Accumulated CO2 in atmosphere from fossil fuel 3.2 Pg/Year [Fossil fuel burning (of which taken up by ocean Pg/Year)] 5.5 Pg/Year 2.0

(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 preindustrial 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/earlyanthropocece-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/UAclasses/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/iceages.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 post1956 of human inputs into the sea which blocked the CaCO3 precipitation oceanic sink mechanism either by reduction in the amounts of the natural catalysts present in the 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


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 wideranging 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-ChemicalStructure-of-Humic-Substances-Revised

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.


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.

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