RESEARCH NOTE

Brief Statement of a New Hypothesis of Global Warming & Climate Change and its Origins
The Amount of CO2 in the Atmospheric is Probably Critically Anthropogenically Influenced by the Marine and Atmospheric Fulvate Status

by D. Grant Ph.D., New Deer-Turriff, AB53 6SX, Scotland, U.K. 5 Nov. 2010
Contents
Preamble. 1. Summary.

1a. Hypothesis of how global warming and climate change could critically depend on the mechanism by which the sea is prevented from dissolving more CO2 because of how the surface of the sea is supersaturated with respect to CO2. The organic polyanion chemistry of the sea could act both as a multi-inorganic ion buffer as well as a CO2 sink regulator. 1b. The current humic buffer and bio-protection system of the Earth may be a continuation a putative pre-biotic system of organic matter (‘pre-biotic soup’) which promoted the evolution of the first living organisms, by controlling the rate formation of CaCO3 crystals which can beneficially modulate climate and which allowed the creation of more potentially bio-friendly environments. 1c. The humic matter particles in the atmosphere may modulate the crystallization of ice crystals involved in the nucleation of cloud formation and rainfall and thereby influence climate and global warming. Humic matter in atmospheric dust is also likely to reduce the rate formation of ice crystals during surface glaciation and also to increase the rate of deglaciation by acting as a dark matter solar heat energy trap, so that global cooling and warming could be at least partly under the control of the biosphere humate matter system. 2. The putative major organic polyanion CO2 ‘servo control systems’ of the soil, the sea, and the atmosphere.

2a. The concept of the degree of supersaturation (Ω ) of sparingly soluble phases. 3. Formation of precipitates from supersaturated solutions is normally a seeded process. 3a. The glycosaminoglycans of animal extracellular space and cell surfaces putatively mimic the fulvate part of the humus/humic acid soil and seawater buffer system in the mechanisms by which they can act as multi-inorganic element buffers and crystal surface active-site capping agents. 3b. The role of marine fulvates as CaCO3 crystallization inhibitors.

4. Metallomic ‘all-element’ arrays are assembled on the surfaces of scale inhibiting polyanions. 4a. Animals have evolved improved polycarboxylate-types of putative inorganic salt solution buffer systems.

5. How the anthopogenic increase in CO2 can be linked to antropogenically altered fulvate balance of the biosphere.
6. In vitro experiments confirm that terrestrial soil fulvates are extremely potent inhibitors of CaCO3 crystallization. 6a. Possible relevance to global warming of putative fulvate inhibition of methane hydrate clathrate formation. 7. What needs to be done to halt global warming and climate change.

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

below. The text may seem to repeat itself somewhat but rather than spending the great amount of time which would be required to write a more concise thesis, it seems worthwhile at the present time to allow this new thinking about global warming and climate change to be accessed from several angles.

1. Summary
A major marine buffer system consisting of poly-carboxylate humic organic matter polymers is proposed. This putative buffer system is suggested to behave similarly to the polycarboxylated polysaccharides (including the animal heparan sulfates, the basis of the heparanomea a buffer of extracellular spaces and cell surfaces in multi-cellular animals) by acting as a multi-inorganic element collector and pH buffer and also a regulator of the degree of supersaturation (Ω ) in natural waters of CaCO3 and other sparingly soluble inorganic phases (by acting as a potent inhibitor of their crystal seeding and growth processes). This can create a situation of high supersaturation of dissolved CO2 at the surface of the sea.

A possible major mechanism by which global warming and climate change could have been caused as a result of industrialization, and which might account for at least a part of the increase in atmospheric CO2 which is currently assumed to have arisen almost entirely from fossil fuel usage, is via a process of terrestrial topsoil humus damage which is a known effect of industrial scale intensive agriculture which has induced on a a large global scale humic matter (fulvate) runoff, causing the transfer from the land into sea of large amounts of a highly potent terrestrial fulvate CaCO3 crystallization inhibitor (n.b. the amount of this transfer has putatively increased at a similar rate to the increase in atmospheric CO2 over the same period of recent human history). A further possible effect of such topsoil humus degradation is that it potentially enhances the ease with which ice crystal modulator humate/fulvate containing dust can be injected into the atmosphere. This kind of dust can potentially interfere with cloud formation and rainmaking (e.g. by inhibiting ice crystal formation in the upper troposphere) and therefore feed into climate change and global warming.
The presence of this kind of organic matter could also be a source of error in ice core CO2 estimation.

1a. Hypothesis of how global warming and climate change could critically depend on the mechanism by which the sea is prevented from dissolving more CO2 The organic polyanion chemistry of the sea can putatively act both as a multi-inorganic ion buffer as well as a controller of the CO2 sink
The top layers of the sea (at least that of the equator and part of that in temperate zones) are known commonly to be supersaturated with respect to CO2. This means that heating or

cooling of the sea can cause CO2 to be released to or absorbed from the atmosphere in a manner which shows up as discontinuities in the differentiated curve of atmospheric CO2 vs. time (e.g. the yearly average year-on year curve) of Mauna Loa data. Temperate zone seas and lakes also seem to inject CO2 into the atmosphere. It seems that the sea acts not only as a sink but also as a source of CO2 and contributes to the total amount of anthropogenic CO2 in the atmosphere at the present time which had been previously attributed entirely to the combustion fossil fuel. An important part of how the current augmentation of atmospheric CO2 and the resultant global warming and climate change is conventionally thought to be achieved is a process which relies on the operation of some unknown mechanism(s) by which the sea is currently prevented from dissolving the extra CO2 which has been injected into the atmosphere from the combustion of fossil fuels and from the degradation of soil organic matter. This ‘unknown mechanism’, it is now suggested, is afforded by the presence of the humic organic matter in the sea which causes the top layers of the sea to become supersaturated in CO2. The possible concentration of hydrophobic fractions of aliphatic humic matter (e.g. the C(O)-[CH2]n – containing polymeric material) (cf. 1-1), could act as a physical barrier able to inhibit surface transfer of gas molecules. (Cf. surfactant molecules which include pre-humate exudates of marine organisms are also known to generate sea surface foams which can reduce with gas transfer rates between the sea and the atmosphere [1, Calleja et al.]). Perhaps the most powerful mechanism of potential humic polymer interaction with marine physical chemical and biochemical processes however, is the ability of (humic) fulvic polymers to dramatically interfere with CaCO3 formation and

thereby to alter the upstream quasi-equilibria associated with this process. This present research note further attempts to set out how anthropogenic influences starting some 7000 years ago could have altered the detailed environmental chemistry of this putative marine organic multi-potent chemical buffer system afforded by dissolved organic matter (fulvate) water-soluble organic matter which exists in the sea A chemically similar system also exists in association with terrestrial soils [1-1]. Further chemically related systems exist inter alia in the cell walls of marine algae [2a] and in the extracellular spaces and cell surfaces [2, cf. 2c] of multicelluar organisms. 1b. The humic buffer and bio-protection system may have originated on the early Earth from the need to create a bio-friendly water activity environment The much-studied but still not completely understood humified organic matter system of the biosphere could have coevolved with early life forms on Earth as a means of securing bio-friendly water activities. (Cf., n.b. a pre-requisite for life is liquid water; a further meaning of this hard fact is that all living systems are water-‘quality’-dependent and require carefully buffered aqueous environments specifically designed for the particular environmental niche habitats; while the highly evolved modern organisms have build-in systems for achieving the various essential-to-life water activities internally, the first living organisms in the sea were probably assisted by the prior creation in the sea of a general system of extracellular environment buffering which preconditioned the spontaneous generation of early biological cells. A stable seawater system seems a necessary precondition for this to occur and this was putatively afforded by a pre-biotic evolution of a humic polymer system.

The poly-carboxylated humic matter organic polymer system e.g. via soil particle injection as dust input into the atmosphere must also have affected global warming and climate throughout geological time by being able to directly influence the rate of glaciation via the ability of the polycarboxylated polymer systems of humic matter to inhibit the crystallization of ice, a process which is also likely to impact on the formation ice crystals required for cloud formation and hence allowing major controls by humic chemistry to have influenced historical climate change and global warming episodes which now includes the ability of human actions to perturb the global humic chemistry. The putative control of ice crystal formation afforded by humate anions will also diminish the rate of freezing and hold up glaciation as well as, by the ability of the dark colored humic HULIS particles (similarly to the man-made soot particles at the present time) when deposited on the surfaces of glaciers etc. enables these to act as a solar energy absorbers which speed glacier melting process.

The study of internal extracellular aqueous solutions of animals (e.g. blood serum) because their predecessors evolved in the sea (a circumstance which agrees with the similarity in composition between 50+ element multi-inorganic ion content of the sea and blood serum [3]) allows clues to be gleaned about those (‘primitive’ putative poly-carboxylate polysaccharide-based) homeostasis systems which have been retained from the start of animal evolution. This identifies the perhaps previouslylargely-overlooked similar mechanism afforded by the polycarboxylated polyanion organic molecules which ubiquitously exist in animal fluids and in the sea). [The presence of a variety of different types of metal binding sites in present-day humic matter polyanions (which are now largely derived from recycled biomolecules) seems to allow for the collection and release of inorganic ions in such a way as to create and buffer the type of multi inorganic aqueous solution which exists in the sea other natural waters and in the soil. Also in human blood serum].

[The presence of organic matter similar to the organic matter which is apparently associated with comets could have been a critical driving force for the evolution of the earliest living organisms by both providing a source of organic substances and inorganic ions (including the major inorganic elements needed for polysaccharide, protein and nucleic acid formation and also the seawater range of the trace elements) but also by acting as a shield against damaging radiation, by being an inhibitor of ice crystal formation (being a natural antifreeze agent) and also being a controller of normal and inhibitor of damaging calcification at the surfaces of biological cells and later, following the evolutions of multicellular organisms by providing a method for controlling extracellular space via the same process the control of calcification (i.e. the formation of sparingly soluble Ca salts). The more highly evolved species such as the earliest animals apparently improved on this system by biosynthesizing their own system of poly-carboxylated polyanions containing more flexible carboxylate groups such as those which are present in the animal cell surface glycosaminoglycan (the putative controller of the activity of Ca2+ which attained an ability to flexibly regulate growth factor and growth factor receptor activities during body and organ development as well as in wound healing; these poly-carboxylated polyanions also continue to provide the more primitive functions afforded by poly-carboxylated polyanionic substances viz. the setting up of a seawater like solution at cell surfaces (being able to create a similar multi-inorganic ion solution) and also control of the formation of CaCO3 and other sparingly soluble Ca salts [2]. The study of fulvate inhibition of CaCO3 crystallization [1] was a side experiment of a principal line of investigation into the roles of animal poly-carboxylated polysaccharides which had started from the need to test the pivotal hypothesis outlined in a 1979 paper by W.F. Long and F.B. Williamson (Aberdeen University) [IRCS J Med Sci (Libr Compend) 7 429-434] which had proposed that the activity of Ca2+ e.g. for signaling in animals was controlled by poly-carboxylated polysaccharides of the heparan sulfate class.

An extension of this hypothesis (that animal Ca activity in extracellular space is regulated by poly-carboxylated substances) could further suggest that Ca in natural waters including seawater, is similarly regulated; this could further mean that the commonly held theory of the CaCO3 - dependent homeostasis of the sea and the Earth’s climate might also be modulated analogously via poly-carboxylated substances (such as a humic matter fulvate). These could regulate the carbon cycle (which is believed is afforded by a pivotal relationship with seawater [Ca2+] via atmospheric and dissolved CO2 which generates CO32- by a series of probably kinetically-controlled but commonly approximated by the formally reversible process/equations:

CO2 (atmospheric) ↔ CO2 (dissolved in the sea) + H2O ↔ CO2(H2O) [↔H2CO3] ↔ H+ + HCO3- ; and HCO3- ↔ H+ + CO32- as well as CO32- + Ca2+ ↔ CaCO3 ↓ together with CO3 2- + Ca2+ = CaCO3 (colloidal) ) The above processes and the equivalent ones which occur in biological organisms and which consume or produce CO2, it should be noted, are at best, in the real world, only partially reversible. They are best thought of as being completely irreversible since the inorganic carbon chemistry of the sea can be dominated by the rate controlling influence of dissolved organic matter.

(Cf. P. J. Wangersky [1B] [3a-1]]). [It should be noted that P.J. Wangersky correctly identified the critical role played by the binding of dissolved organic matter to CaCO3 surfaces as being a likely prime rate control mechanism of the marine carbon cycle; this is why the fulvate status of the sea and natural waters can act as a major determinant of the carbonate cycle of the sea and allow the sea to be a source of anthropogenic CO2 injection into the atmosphere ; a wider recognition of the importance of the late Professor P.J. Wangersky’s discovery is merited since this was of major relevance not only to marine science but also to climate science].
[The above scenario also means that kinetic isotope effects will exist which cause, e.g. a depletion in the amount of 13C in the CO2 produced which may be injected into the atmosphere].

Fulvate could potentially achieve regulation of the amount of CO2 in the atmosphere via seawater (the major buffer of CO2) by a mechanism which centers on the inhibition of sparingly soluble CaCO3 precipitation. It should be noted that a pressure horizon which is supposed to exist at a depth below which these particles can re-dissolve and is thought to allow for a carbopnate-based pH buffer system of the sea, could not be detected at any point in the N. Atlantic at six positions ranging form 08o00'N 19o58'W to 23o 14'N 52o 38' W [P. Wangersky [3a-1] [Limnol & Oceanogr 1972 17 (6) 960-962]. This rigorously executed survey failed to find any trace of this horizon. This indicated that the supposed carbonate buffer system of the sea was, at least under the conditions present in the N. Atlantic at the time of this survey, a purely hypothetical textbok-only concept. These results support the hypothesis that

fulvate and not carbonate provides multifunctional carbon cycle and seawater homeostasis regulation]. A conceptually different process involving CaCO3 solid phases in seawater is where the formation of non-precipitating colloidal amorphous CaCO3 particles can, in principle, form a dispersed carbon sink with long-term stability. The formation of such CaCO3 solid phases is also more likely to be kinetically controlled rather than being thermodynamically controlled. The detailed mechanism of kinetic control of the seeded crystallization of CaCO3 (calcite) was investigated by in vitro methods by the Aberdeen U. polysaccharide group in the 1980s; the results obtained in these studies were believed to be relevant to a fuller understanding of the mechanism of marine carbonate cycling. (These results have now been replicated by a number of laboratories worldwide [3a] which confirms the notion that the ability of the formation of CaCO3 to regulate CO2 is facilitated by the outstanding ability of fulvate to inhibit CaCO3 crystallization and that this phenomenon plays a pivotal part of the mechanism of anthropogenically induced climate change [3a]). CaCO3 formation and precipitation in the sea and other natural aqueous solutions may be regulated by the outstanding ability of humic polymers to bind to CaCO3 crystal surfaces and change their thermodynamic properties (cf. the groundbreaking papers by K.E. Chave & E. Suess and P. J. Wangersky [3a-1][1B]] papers which might be considered the origin of the organic matter (fulvate) marine and CaCO3 control system). This means that various thermodynamically-determined processes, e.g. Henry’s Law, are not, in any straightforward way, applicable to the uptake and release of anthropogenic CO2 by the sea. Considerable confusion appears to exists at present amongst the scientific community regarding how thermodynamic models which seem partially valid can be employed to model how

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

1c. The humic matter particles present in the atmosphere may modulate the crystallization of ice crystals involved in the nucleation of cloud formation and rainfall and thereby influence climate and global warming. Humic matter may also modulate the rate of formation of ice crystals on the Earth’s surface during glaciation and increase the rate of deglaciation by acting as a dark matter solar energy trap. The major potential influence which the formation of clouds and induction of rainfall exerts over climate, climate change and global warming may, in part, be determined by the presence of humic matter particles in the atmosphere which, could in principle, affect the rate of formation of the ice crystals which are believed normally to act as phase change nucleation agents required for cloud and rain formation. Although the formation of ice crystal particles is normally temperature driven, the mechanism of the influence of inhibitors on this crystallization process is thought not intrinsically to differ from that of the supersaturation-driven crystallization of inorganic solids such as CaCO3 crystals, which suggests that both types of crystallization processes may be modifiable by the humate/fulvate polycarboxylated polyanions (which are designated HULIS when they occur in the atmosphere).

The ability of HULIS type poly-carboxylated biopolymers to modulate ice crystal nucleation in the upper troposphere has been recently confirmed by in vitro studies which used a simple citric acid model of HULIS; this work (by E.J. Murray et al. [2e] was apparently an attempt to confirm that the mechanism of cloud formation and climate change could be subject to a possible human input by way of anthropogenic influence on the ubiquitous atmospheric poly-carboxylated humate/fulvate system. 2. The putative major organic polyanion CO2 ‘servo control systems’ of the soil and the sea
The most common type of organic (humus-stored) polymers (this accounting for a considerably larger amount of carbon than occurs as CO2 in the atmosphere) in the biosphere contained arrays of poly-carboxylate (-C(O)O-) anionic plus -C(O)(CH2)ngroups which seem to be specifically ‘designed’ to provide in the sea a chemically analogous buffer system to that afforded by a conceptually similar and much more-studied system of anionic poly (uronate) saccharides, which occur at biological cell surfaces including at the surfaces of the vasculature in humans and other higher animals where they act to protect and buffer the blood serum multi-inorganic element containing, seawater mimetic, aqueous solutions [4]. This system seems to have been carefully conserved throughout animal evolution [4a].

2a. The Concept of the Degree of Supersaturation (Ω ) of Sparingly Soluble CaCO3 Phases which can act as a critical determinant of supersaturation of CO2 in the surface layers of the sea The degree of supersaturation (Ω ) of CaCO3 in the sea like, that in animals and algae etc., seems, to a large measure, to be controlled kinetically and is not thermodynamically determined [5]. This idea accords with the notion that the Earth’s biosphere (including the atmosphere) somewhat resembles a living organism which is expected to behave, not as a thermodynamically-controlled equilibrium system [cf. 3a], but as an ‘supercharged’ energy system allowing energy allowing its application in a rapid and in a seemingly ‘directed’ manner. 3. Formation of Precipitates from Supersaturated Solutions is Normally a Seeded Process Seed particles capable of growing inorganic crystals e.g. of CaCO3 occur both in the sea and in animal tissues. The CaCO3 seed crystal inhibitor system in animal vasculature is believed to consist of anionic poly uronic acid containing polysaccharides which prevent the formation of pathological plaques of insoluble Ca salts at blood or urinary vessel walls [2]. In the sea, the analogous poly-uronic acid fulvate plus exuded algal anionic polysaccharides [cf., 2a] are likely to act similarly and constitute a homeostat control system for the formation of CaCO3 crystal precipitates. This creates the largest long-term stable sink for atmospheric CO2.

3a The glycosaminoglycans of animal extracellular space and cell surfaces putatively mimic the fulvate part of the humus/humic acid soil and seawater buffer system of the sea. Both of these polycarboxylated-polymers can act as multi-inorganic element buffers and crystal surface active site capping agents. The fulvates apart from their putative role for the ‘servo -control’ of the precipitation of CaCO3 from (the surface layers of) the sea, seem to resemble the much-moreresearched animal glycosaminoglycans by being functionally en-tuned (via their possession of complex heterogeneous organic multifunctional ligand sites (including anionic cationic and non-ionic binding sites)) to enable them to buffer the usually complex multiinorganic ion compositions present in the sea by a process of simultaneous sequestration and release of numerous types of inorganic ions.
Research into the binding of inorganic ions to glycosaminoglycans shows that both cations and anions can simultaneous bind to these formally highly negatively charged polyanions which, while they can use a straightforward electrostatic mechanism to attract positively charged counterions (the Manning process), obviously cannot employ this kind of simple electrostatic attraction to achieve the observed binding of negatively charged anions which seem to bind efficiently to the

animal glycosaminoglycan polyanions via a phase change determined non-thermodynamic-engulfment processes which in turn depends, it is believed on the outstanding flexibility of the natural poly-carboxylate ligand systems to alter their conformations so as to facilitate binding of a wide range of anions and also of different types of colloidal inorganic particles (ions of either charge) or (cf. Borges et al. [2c]) to crystal surfaces. The latter include the active growth centers of the nanoscale seed particles responsible for the growth of CaCO3 crystals. 3b The Role of Marine Fulvates as CaCO3 Crystallization Inhibitors The anti-crystal forming active seed crystal growth site capping inhibitor polyanionic fulvates present in the sea, even at a relatively small concentration of ca. 0.2-2.0 ppm, similar to those which have been reported to occur in modern seawater (but this value may be much greater near the surface microlayer), can completely inhibit, or act to greatly diminish the rates precipitation of CaCO3 phases, and even, putatively, in some circumstances, may also cause a reversal (peptization i.e. the formation of colloids) of this process, as well as allow the control of the rates of the growth and dissolution of the various other sparingly soluble salt crystalline phases which might co-exist in seawater together with Ca2+ and the carbonate system of anions. The abovementioned (in section 3a) glycosaminoglycan polyanion phase change multi-purpose cation plus anion plus inorganic particle inhibitor system can also describe the inorganic ion and particle binding activities of fulvate anions, which (perhaps, partly by acting in concert with a previously proposed (e.g by Sillén, cf. R.M. Garrells & R.A. Berner [3b]]) Si-based clay mineral marine multi inorganic ion buffer system which can attach to the fulvate), seems specifically ‘designed’

(perhaps by pre-biotic processes akin to evolution) [e.g. similar to that discussed by D. Grant et al., in Medical Hypothesis 1992 38 49-55] to allow for the creation of bio-friendly aqueous solutions which include the long-term stable systems of multiple inorganic ion solutions which occur in the sea. These organic buffer systems are themselves produced and destroyed by a separate homeostasis system can continue to act in concert with the terrestrial soil system over geological timescales. But human activities are now putatively altering this terrestrial system markedly and indirectly as part of this process, are also altering the marine fulvate buffer system.

4. Metallomic ‘all-element’ arrays are assembled on the surface of the seawater and seawater mimicking buffer polyanions
Evidence from full element analysis determinations by mass spectrometetry shows that both the seawater and animal tissue polyuronate organic polymer buffer molecules can be classified as “all-element” inorganic element matrices. These elemental compositions can be used to construct linear log-log inorganic element plots. This applies to seawater, human blood serum (cf. Fig. 1of ref. [3]), human hair and nails and also geologically deposited fulvate). The natural polyanion ligand matrices tend however to contain systematically larger amounts of those inorganic ions which occur in least abundance in their natural bathing solutions which points to a general mechanism of selective sequestration of ultratrace elements; this phenomenon occurs in an analogous manner for the anionic polysaccharides associated with animal and algal cells as well for the geological fulvates. This indicates that the natural poly-carboxlate organic polymer polyanions behave in their parent aqueous solutions like specialized antennae collectors of low abundance essential nutrient elements (which include some elements, e.g., the rare earths, which have

not yet been confirmed to be required for the nutrition purposes of commonly studied species).

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

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

5. How the anthropogenic increase in CO2 can be linked to anthropogencially altered fulvate balance of the biosphere
Increased fulvate (e.g. produced from anthropogenic degradation of terrestrial soils) is predicted in this model to cause an increase atmospheric CO2 by entering the proposed marine fulvate-based inorganic substances homeostasis system. This idea can be looked on as an extension of the idea that seeded formation controls CaCO3 formation in shallow seas

(cf. the J.W. Morse et al. discussion of the Bahama Bank CaCO3 precipitation system [6]). In support of the present hypothesis that fulvate controls the anthropogenic augmentation of atmospheric CO2, is the circumstance that the degradation of terrestrial soils has been greatly increased since the industrial revolution, and most especially in recent years, and indeed this is thought to be of a more serious environmental concern than is the loss of tropical rainforests [7]. A putative anthropogenic 7000 years old atmospheric CO2 increase detected in the ice core evidence by Ruddiman [8] could, like the present-day much greater un-natural increase in atmospheric CO2 have been caused by an un-natural topsoil degradation which is an expected consequence of terrestrial soil degradation caused by deforestation, agriculture riverine runoff and fulvate enrichment of the sea.

6. In vitro experiments confirm that terrestrial soil derived fulvates are extremely potent inhibitors of CaCO3 crystallization [3a].
Indeed the fulvate inhibitors considerably outperform all manmade inhibitors (e.g. the bisphosphonates) which are widely used as anti-calcification agents e.g. in detergent and toothpaste formulations. The ability to control the rate of CaCO3 crystallization a circumstance which changes how the exchange of CO2 occurs between the sea and the atmosphere therefore also effectively could be responsible for the current anthropogenic increase in atmospheric CO2 and the resultant global warming and climate change produced as a result of this. 6a. Possible relevance to global warming of putative fulvate inhibition of methane hydrate clathrate formation

The ability of natural poly-carboxylated polyanions to inhibit the seeding of the formation of sparingly soluble crystals and the precipitation of CaCO3 from the sea could apply equally well to the formation of CH4 hydrate clathrate crystals (e.g. in deep waters). This idea was suggested by C.C. Gryte [2d]. This scenario points to a possible role of the putative intensive agriculturally determined anthopogenic alteration in or abundance and/or ‘microstructure’ of the marine polycarboxylated fulvates which may perturb not only the carbon cycle afforded by CaCO3 precipitation, but also that afforded by CH4 hydrate clathrate crystallization (e.g. in the deep sea) so as to result in an increased emission of both CO2 and CH4 greenhouse gases as an eventual outcome of agriculturally-promoted global topsoil degradation. 7. What needs to be done to stop global warming and climate change In order to stop excessive global warming and the resultant possible major species extinction etc., it will be essential, if the above hypothesis is correct, in addition to the previously identified need for an enforcement of a diminution of the burning of fossil fuel, biomass, cement manufacture, and municipal/industrial waste incineration, also to halt the increasing rate of anthropogenic degradation of the topsoil and the resultant increase of associated runoff of terrestrial fulvates into the sea.

References [1] Some Possible Mechanisms of (Dissolved) Organic Matter Inhibition of CO2 Uptake by the Sea
Preamble The conventional model of how anthropogenic CO2 affects the sea includes the hypothesis that buffering of the sea is achieved by the carbonate buffer system alone and that the precipitation of CaCO3 in the sea can be represented by the equations

Ca2+ + HCO3- → H+ + CaCO3 ↓ in which the formation of CaCO3 generates H+
cf. M. Frankignoulk J Mar Syst 1994 5 111-118 and e.g. T. Takahasi The fate of industrial carbon dioxide Science 2004 305 352-353. (This does not consider the possibility that part of the buffer activity of the sea might arise from the presence of other potential inorganic inorganic e.g. Si- containing ions and the ubiquitously presence in the sea of dispersed and dissolved organic matter).

Different, putatively more realistic models are now proposed:
1A. PHYSICAL BARRIER MECHANISM Sea surface microlayer CO2 exchange barrier hypothesis of inhibition of CO2 uptake by sea Cf. M.L1. Calleja et al. Evidence for surface organic matter modulation of air-sea CO2 gas exchange Biogeosciences 2009 6 1105-1114

1B

INHIBITION OF CaCO3 FORMATION & CaCO3 RE-DISSOLUTION MECHANISM The crystallization (precipitation) of CaCO3 has been found to be highly sensitive to organic substances which occur in the sea which are able to block this phase change process Cf. e.g., E. Suess Interaction of organic compounds with calcium carbonate-I. Association phenomena and geochemical implications Geochim Cosmochim Acta 1970 34 157-168. The dissolved organic matter in the sea also, by the effect of its adsorption at crystal surfaces also prevents the redissolution of CaCO3 in deep water.

This abolishes the snow line as confirmed by an extensive survey conducted over a wide range of locations by

P.J. Wangersky Limnol Oceanogr 1969 14 929-933 [3a-1].
The N. Atlantic Ocean was found (in contradiction of traditional oceanographic principles established in the nineteenth century by Sir J. Murray) to have a similar number of CaCO3 particles per unit volume present at all levels of the sea (a large number of samples were obtained at levels up to ca. 5000 meters depth). The carbonate based at depth pH buffering and the long term C recycling system of the sea had by 1969 apparently become completely blocked by the putative anthropogenic dissolved organic matter (fulvate) adsorption mechanism (cf K.E. Chave & E. Suess Limnol Oceanogr 1970 15 633637 [3a-1]). A multidisciplinary research activity headed by WF Long and FB Williamson at Marischal College, University of Aberdeen U.K., [cf. publications up to 2003 listed at www.abdn.ac.uk/~bch118/publications2003march.doc ] included studies using an experimental method developed by G.M. Nancollas (cf. Adv Colloid Interface Sci 1979 10 215-252) which identified poly-carboxylated anionic substances such as marine algal polysaccharides, animal glycosaminglycans and a range of other substances including soil derived humic matter fractions as demonstrating potent inhibitor effects on the seeded crystallization of CaCO3 (calcite) for which the latter type of polymers (which constitute the largest pool of organic carbon in the biosphere) were found, by far, to be the most active, a circumstance which could further suggest that this property might also be of major fundamental relevance to the fuller understanding of the global carbon cycle and hence could determine the rate of increase of atmospheric greenhouse gas CO2 in the atmosphere*.

[1]

Cf., D. Grant

Climate Change
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New Thinking On Climate Change
web. scribd.com/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-IIII

web. scribd.com/doc/23967637/Humic-Substances-Inhibit-Calcite-Crystallizn-II and other papers listed are web. scribd.com/Newdeersi/documents. Cf. D. Grant Review of current progress in understanding of the chemical structure of humic substances. web.scribd.com/doc/34142473/2an-assessment-of-Progress-in-Studies-of-theChemical-Structure-of-Humic-Substances-Revised

[1-1] D. Grant Nature 1977 270 709-710 [A now obsolete notation for the 1H nmr chemical shift scale was used in this paper (τ which is 10-δ )]

cf. also [1a] D. Grant et al., Biochem J 1989 259 41-45; [Cf. also, for evidence and related discussion of how the mechanism of counterion binding to the anionic polysaccharide heparin is also likely to be a phase change determined process see: ibid., 282 601-604; 283 243-246; 287 849-853]. The above studies suggested the following hypothesis The humic matter hypothesis of marine buffer provision If the sea were a purely a solution of inorganic ions it should, in principle, be able act as a solvent for all of the anthropogenic CO2 in the atmosphere. That it does not do so, it is now suggested, arises principally because the sea contains as major constituents (dissolved plus colloidal size dispersions of) natural polycarboxylated organic polymer molecules especially those classified as humates and fulvates.
It is further pointed out that these molecules are so chemically constituted so as to enable them to perform multifunctional buffer actions. These include the regulation of the pH, the buffering of long-term stable

concentrations of dissolved major, trace and ultratrace inorganic ions present in seawater as well control the rates of nucleation and growth of CaCO3 , BaSO4 etc. crystals. This ability to control nucleation of the formation of sparingly soluble solids can determine the individual degree of supersaturation of individual sparingly soluble phases which might otherwise in the absence of an inhibitor of the kinetics of their crystallization, precipitate out from seawater. The humic polymer system is now proposed to be responsible for a major part of the process by which the sea attains its geological time-scale constancy of inorganic ion content (including pH) although this is thought now to be only approximate constant of over millions of years, it is thought normally to achieve an almost absolute constancy over shorter periods of time.

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

The degree of supersaturation (Ω ) of CaCO3 in both seawater and animal extracellular fluids e.g. human blood serum, is putatively determined almost entirely by the amount and types of the poly-carboxylatedpolyanions which can act (as shown by in vitro experimentation) as very potent crystal seed nuclei growth blockers in these aqueous solutions. The presence of ‘scale-inhibitor’ substances encourages a state of supersaturation to be set up in natural aqueous solutions

which, under unprotected conditions in the absence of chemical regulators, would grow a range of inorganic crystal phases. The crystal growth blockers are of especial importance for their ability to interfere with the seeded mechanism by which the precipitation of the sparingly soluble CaCO3 crystalline or amorphous phases occurs. The circumstance that CaCO3 supersaturation (Ω) could principally be determined by the efficiency of fulvate {anionic poly-carboxylate (–CO(O)-) plus –C(O)[CH2]n)(cf. D. Grant Nature 1977 270 709-710, cf., D. Grant et al. web. scribd.com/doc/41263479/New-Thinking-on-ClimateChange-Abrrev.-III) inhibition of the CaCO3 crystallization and related processes, now allows for a fuller understanding to be achieved of the ability of seawater to control the atmospheric CO2 content as well as how this can be critically influenced by anthropogenic mechanisms which can alter the amount of this type of natural poly-carboxylated organic polymer, CaCO3 crystallization modulator system present in the sea. [2] D. Grant et al., Medical Hypotheses 1992 38 49-55 Cf., D. Grant et al. Biochem J 1989 259 41-45 And other papers on related topics listed at web.abdn.ac.uk/~bch118/publications2003march.doc cf. [2a] A. Pentecost Significance of marine algal calcification inhibitors in the global carbon cycle Thalassas 2004 20 (1) 45-49.

Cf. [2c] F.T. Borges et al. (Kidney Int. 2005 68 1630-1642) have established that specifically microstructured polycarboxylated polysaccharides (heparan sulfates) are synthesized by the kidney in order to cap-off any calcium oxalate seeds which would otherwise grow into large tissuedamaging crystals. [This highly evolved use of poly-carboxylated polysaccharides for the modification of the rate of precipitation of sparing soluble Ca salts in animals is suggested to ultimately derive from the existence of a similar poly-carboxylated organic matter system in the seawater in which the ancestors of humans originally evolved and which enabled the control of the formation of sparingly soluble Ca salts and which currently continues to exist in the modern seas for the same purpose]. cf. [2d] C.C. Gryte Ann New York Acad Sci 1994 78 323-329 These authors likened the seeded crystallization of CH4 hydrate clathrates (e.g. that which occurs in the sea) to calcium oxalate which are known to be inhibited in animal fluids by the poly-carboxylated organic polymer extended chemical family of which fulvate is also a member which could suggest that the formation of CH4 in the marine environment could also be determined by the fulvate status of the sea; cf. [2e] B.J. Murray Inhibition of ice crystallization in highly viscous aqueous organic acid droplets Atmos Chem Phys 2008 8 5423-5433. Cf., Nature Geoscience 2010 3 233-237 [This paper seems to allude to how humic matter in the atmosphere might affect climate via its ability to inhibit ice crystal formation]. [3] H. Haraguchi J Anal At Spectrom 2004 19 5-14

This paper reviews the relatedness of seawater and human blood serum etc. from the perspective of the new science of metallomics, That animal polysaccharides similar to those at blood vessel walls contain seawater-like inorganic element contents has been briefly discussed by D. Grant et al. in Biochem J 1987 244 143-149 and more fully in Cf. web. scribd.com/doc/26994439/Publication-2-Web. For examples of the kinds of log log plots mentioned in the text see web.scribd.com/doc/38734723/WRL0526 also web.scribd.com/doc/34178257/WRL1873-with-Fig [3a] D. Grant et al., (University of Aberdeen archived research manuscript) available at
web.scribd.com/doc/41898831/New-Thinking-on-Climate-Change-Abbrev.-III

Cf, also E.g. P. Zuddas et al. Chemical Geol 2003 201 (1-2) 91-101; A.R. Hoch et al., Geochim Cosmochim Acta 2000 64 (1) 61-72; W.P. Inskeep P.R. Bloom Soil Sci Soc Amer J 1986 50 11671172; cf., M.E. Gunthorpe C.S. Sikes Ohio J. Sci 1986 86 106-109; J.R. Morse Rev. Mineralogy Vol. 11 Carbonates in Mineralogy and Chemistry Ed. R.J. Reeder Mineralogy Soc Amer p.227-264; E. Suess Interaction of organic compounds with calcium carbonate-I. Association phenomena and geochemical implications Geochim Cosmochim Acta 1970 34 157-168;

[3a-1] P.J. Wangersky Distribution of suspended carbonate with depth in the ocean Limnol Oceanogr., 1969 14 929-933 Cf. ibid., 17 960-962 Cf. K.E. Chave E. Suess Calcium carbonate saturation in seawater: effects of dissolved organic matter Limnol Oceanogr 1970 15 633-637 Cf. also J.A. Leenheer M.M. Reddy Annal Environ Sci 2008 2 11-25
Cf also F. Neuweiler et al., Geology 2003 31 (8) 681-684

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

Biomineralization and Biological Metal Accumulation, Ed. P. Westbroek and E.W. de Jong 1983 D. Reidel Publishing Company. It can be argued that the current debate about the mechanism of climate change lacks focus because it seems centrally to demand an improved knowledge of how the sea behaves e.g. in regard to CO2 buffering, and this requires a kinetic model such as the poly-carboxylate polysaccharide-based buffer system that is proposed in the present paper will allow progress to be made in designing appropriate procedures for ameliorating anthropogenic input of CO2 into the atmosphere. This system is suggested to resemble the poly-carboxylate polyanionic buffers which exist in the seawater-like extracellular fluids of animals. The current knowledge database available on these animal polyanionic buffer systems could allow an improved insight to be obtained into the real buffer system which exists in the sea. [4] (E.g. cf., W.F. Long F.B. Williamson et al. researches updated in web. scribd.com/doc/26994439/Publication-2-Web and ibid/34178257/WRL1873-with-Fig) [The original ‘primitive’ kind of poly-carboxylate-organic polymer (evolved into a polysaccharide-core type) of anionic biopolymer, homeostasis systems have now evolved yet more complex functions (e.g. for growth factor control during wound healing). But they seem also to retain their more ‘primitive’ tissue protection including anti-calcification functions in modern animals (which of course have also evolved a host of additional protein-based ion channel systems and the blood circulation includes complex inorganic filtering/recycling functions of specialized organs which, however, also continue to use anionic polysaccharides such as heparan sulfates as part of their modus operandi). Such a continued-essential-for-life osmoregulator function for the anionic cell surface poly-carboxylated (which have been enhanced by sulfation) anionic polysaccharide

systems comes from the discovery that for fifteen species of aquatic invertebrates, the amounts of heparan sulfates and related anionic polysaccharides present in their tissues is apparently determined by an exact mathematical relationship between this amount and the salinities of the aquatic habitats of these organisms [H.B. Nader et al. 1983 Comp Biochem Physiol Pt B Comparative Biochem 1983 76 433-436]. These findings tend to support the theory that the multicellular animals evolved initially in the sea (e.g. some 109 years BP) and also that the early animals and possibly also their non-animal evolutionary precursors evolved an improved inorganic and crystal inhibitory system at their cell surfaces to mimic that which was provided in the sea by the fulvate-type polyanions which had likely existed in the seas from its beginning and continue to provide therein the basic inorganic homeostasis functions related to its inorganic composition at the present time (and by inference also to control the atmosphere which was created in the Early Earth to a significant extent by release of biologically produced gases from the sea). [4a] H.B. Nader et al., Carbohydr. Res. 1988 184 292-300 [This paper indicates that the heparan sulfate system has been carefully conserved from the time of the evolution of the first animals in the sea until the present time]. [5] Cf. the relevance of Henry’s law to the uptake of CO2 by the sea is central to the current debate about the origin of the current increase in atmospheric CO2 which is causing climate change. It should be noted that Henry’s law applies strictly only to equilibrium conditions (this means that the rate of uptake and release of CO2 are equal) should not be expected to apply where the solvent reacts with the solute. If, as seems likely, that the CO2 system of the surface of the sea is kinetically and not thermodynamically controlled then the rate of CO2 release from the sea is controlled by such kinetics. If this involves, as is here

suggested, a dominant influence of the inhibition of the seeding of CaCO3 solid phase formation, then this process will determine the ability of the sea to act as a sink for CO2. Control of seeding is then putatively the major control mechanism of exchange of CO2 between the sea and the atmosphere. Cf., e.g. a recently accessed (at: web.nzace.org.nz/……internet discussion, one of numerous such documents) discusses Henry’s law in the context of the role of the seas in provision of a sink for atmospheric CO2, notes that “gases in our atmosphere exist in equilibrium with the sea” It is now suggested that this statement is essentially wrong. The CO2 in the atmosphere does not exist in a straightforward reversible thermodynamically controlled equilibrium with the CO2 in the sea. It depends instead on the fulvate control of the seeded nucleation of CaCO3 crystallization and re-dissolution. The Callendar, IPCC and/or Hansen models of global warming proposes a dominant greenhouse gas climate warming forcing effect of non-condensable CO2 rather than of condensable water vapor (cf., this well-established theory is further supported by computations reported by A.A. Lacis et al., Science 2010 330 356-359) but the continued upgrading of this theory needs to address ideas advanced by informed skeptical scientific opinions, including a possible re-evaluation of ice core data. [5a] T.V. Segalstad [ESET Oslo] accessed from
web. geocraft.com/WVFossils/Reference_Docs/Carbon_cycle_update_Segalstad.pdf Also available via web.co2web.info/ ESFV1.pdf; cf. also document ESFVO1 and the compilation of files which are critical of the Callendar, IPCC or Hansen hypotheses re fossil fuel being the prime cause of elevated CO2 and global warming listed at web.folk.uio.no/tomvs/esef/esef0.htm. A criticism of the methodologies used to obtain the ice core historical atmospheric CO2 data (which suggest that these were probably subjected to a sufficiently rigorous scientific review before becoming widely accepted) is give in a paper entitled Z. Jaworowski T.V. Segalstad N. Ono Do glaciers tell a true atmospheric CO2 story? Sci Tot Environ 1992 114 227-284)

[This paper discusses the occurrence of super-cooled liquid water which could have removed CO2 from the gas compartments analyzed; this occurrence of liquid at low temperatures could putatively in part have been caused by the presence of fulvate in the ice].

The first Segalstad article listed above draws attention inter alia to the large unknown “missing sink” in the anthropogenic carbon budget. Segalstad negatively comments on the need for mainstream climate models to employ a purely hypothetical “evasion factor” limit on the operation of the supposed validity of Henry’s Law concepts for modeling the buffering of atmospheric CO2 by the sea. The now-proposed humate control mechanism of rate limitation of the carbon cycle (via the fulvate determined seed nucleus activity regulation system of the abiotic soil and seawater carbon cycle and CO2 marine buffer system) now seems to offer a more credible explanation of how this “evasion factor” activity regulator of Henry’s Law is set up in the real world, and therefore offers a more convincing argument with which to counter skeptical comments on the credibility of the IPCC etc. arguments for the urgent need to curb anthropogenic CO2 emissions. It should be noted that the possible kinetic control of abiotic as well as biological utilization and emission of CO2 casts some doubt on the present understanding of how 13C depletion in fossil fuel can confirm the hypothesis that the combustion of fossil fuel has led to a major augmentation of atmospheric CO2 and associated global warming, [6] J.W. Morse et al. Geochim Cosmochim Acta 2003 67 (5) 2819-2828 [7] Terrestrial Soil Humus Degradation. [It should be noted that soil organic matter (which includes fulvate as a major fraction) is the largest pool of organic carbon in the biosphere].

This organic matter pool which could directly produce CO2 by biotic and abiotic processes (and also cause fulvate transfer from the land into the sea) has become altered in a perhaps fortuitously similarly annual rate of increase to that of the combustion of fossil fuels, and increasing by an exponential rate in recent years seemingly by the change in traditional agriculture which has been going on process since the start of the industrial revolution. Cf., The web document from World Resources Institute Washington USA Feeding the World & Disappearing Land web. wri.org/publication/content/8426 notes that prior to 1990 topsoil degradation had occurred in 38% of croplands worldwide and that since 1990 losses have continued to mount year by year. Cf. also F. Pearce Soils spoilt by farming and industry New Scientist 16 May 1992 Issue 1821 [The global map of soil degradation reproduced in this article resembles maps of brightness at night except that Africa shows up much more in the soil degradation map]. [8] W.F. Ruddiman Reviews of Geophysics 2007 45 RG4001; doi: 10.1029/2006RG000207; Cf. Climate Change 2003 61 261-293; Scientific American, March 2005 48 et seq. That the sea was the origin of the late Holocene injection into the atmosphere is confirmed by the 13C ice core study reported by of J. Elsig et al. in Nature 2009 461 507-510. Postscript

A related state of affairs to the situation in which fully reversible processes by which CaCO3 form in the sea are outwith those which underpin conventional thermodynamic and chemical equilbibria relates to how the Earth’s biosphere should be viewed : is it a machine or a quasi-organism? It should be noted that the conventional thermodynamic laws originated from the study of physics and astronomy as well as machines such as steam engines but was not achieved by way of studies of biological systems. So it is not surprising that the original formulation of the thermodynamic laws cannot be applied easily to biological systems. Life and biological reaction mechanisms are to a larger extent than is commonly realized, centered on seeded processes which control rates. This allows control of thermodynamic driving forces and essentially changes the way these forces behave. An easily seen example of this is that the evolution of living organism has resulted in increasing degrees of complexity with the passage of time, in apparent disobedience of the second law of thermodynamics which requires that complexity of the sort present in living organisms should always tend to decrease with the passage of time. The use of the perhaps the rather at first sight bizarre idea that the Earth is a kind of living organism (Gaia) is suggested to be a helpful idea with which to construct models of the sea and the atmosphere in order to predict global warming and climate change. The above selection of arguments which led to the belief that the sea is the major source of atmospheric CO2 has been abstracted from a separate document.
Footnote a The term ‘heparanome’ was coined by J. Turnbull et al., cf. Trends Cell Biol 2001 11 (2) 75-82; for the role of metal ions in heparanome signalling see e.g. T.R. Rudd et al., Carbohydr Res 2008 343 2184-2193; cf., Glycobiol. 2009, 19(1) 52-57. *Because all of the data obtained, especially those relating to soil and marine algal polymers were not fully published during the time when this research (which was unexpectedly halted for what were believed to be non-scientific reasons) was conducted and that such

data could be relevant to the ongoing debate about the mechanism of possible anthropogenically induced climate change, the archival database of research data held by the author which is possibly relevant to this subject has now become, after discussion with the former co-workers where this has been possible, the subject of recent internet postings.

Apologies for any remaining spelling and grammatical errors.

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