New Thinking on Climate Change

By D. Grant, New Deer-Turriff AB53 6SX Scotland, U.K.
Could the anthopogenic increase in Atmospheric CO2 partly arise from the ability of fulvate to elevate the degree of supersaturation (Ω ) of CaCO3 in the sea? Is this the mechanism of the postulated “evasion factor” for a supposed lack of applicability of Henry’s Law to the equilibration of CO2 between the atmosphere and the sea?
Anthopogenically degraded soils could have released sufficient fulvate, a potent inhibitor of CaCO3 crystallization, into the sea to increase the degree of supersaturation (Ω ) of CaCO3 at the surface of the sea which would tend to increase the rate of release of CO2 from the sea into the atmosphere. 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 or even the continued existence of the human species, but that a tipping point situation may already be occurring or will occur sometime in the foreseeable future when human intervention to prevent this will then no longer be possible. Even if the combustion of fossil fuel could be drastically curtailed it is entirely possible that because this may not be the principal human activity which is causing global warming, the cessation of the use of coal and petroleum e.g. for electricity generation might only have a negligible effect on the anthropogenically induced climate change. This situation could arise if the current global warming and climate change is being mainly caused by bad agricultural practices which can drastically alter the humic matter homeostasis system of the soil and sea.

It is suggested that attempts to slow the current abnormal fast climate change processes should include procedures for reversing the degradation of agricultural soils since a significant injection of CO2 and methane into the atmosphere can arise from the degradation of the soil by agriculture (in its widest sense). Direct input of greenhouse gases from the soil could be of a similar or greater order of magnitude than that produced from the industrial scale burning of fossil fuels. A further route of anthropogenically assisted injection of CO2 into the atmosphere can arise from the degradation of topsoils which caused an increase in the fulvate content of the sea which may disturb the oceanic carbon cycle so as to increase the sea surface CO2 concentration which are sometimes stated (probably wrongly) to equilibrate with the atmospheric CO2 according to Henry’s law. Yet another mechanism by which soil degradation can affect global warming is by the release of humic matter containing (colored) dust into the atmosphere. If cosmic rays are also key players in the climate change scenario then there is also urgent need to find out which currently produced human emissions might augment such effects via depletion of the ozone layer. There could also be an negative impact of cosmic radiation on soil humic matter stability.

Consider the ocean as a CO2 sink. Has this been perturbed by human activities? Evidence from ice cores suggests that such perturbation might have started to show up even 7000 years ago. This idea is
The Ruddiman Hypothesis of Late Holocene Anthropogenic Global Warming It is worth noting at the start of any discussion of climate change that early farmers, when they first developed agriculture throughout Eurasia some 7000 years ago are likely to have damaged the topsoil humus layer principally as a result of extensive deforestation but also in a similar manner to how modern farmers now do this on a much larger scale. A real and unexplained small increase in the amount of CO2 present in the atmosphere 7000 years ago which Elsig et al. (Nature 2009 461 507-510) showed could not have come from the burning of the wood (since there was no plant matter 13C deficit in the ice core CO2 evidence) but most likely came from the sea agrees with the possibility that terrestrial fulvate runoff from agricultural soil might have increases in the degree of supersaturation (Ω ) of CaCO3 (calcite) in the sea at that time. That a very small human population is able to perturb the oceanic fulvate balance and hence cause an increased level of atmospheric CO2 further suggests that the current much larger augmentation of atmospheric CO2 occurring at the present time could also by a similar mechanism of disturbance of the carbonate balance of ocean.
Terrestrial soil derived fulvate inhibition of CaCO3 precipitation was studied as part of a wider investigation of poly-carboxylated anion of the inhibition of the seeded crystallization of CaCO3 (calcite) by the author and colleagues at the University of Aberdeen many years ago; scientific paper which was drafted following extensive discussions was delayed for publication for non-scientific reasons. This draft document with the preliminary diagrams, which were not completed professionally at the time, is now made available to the public,

vide infra.

(A list of peer-reviewed and other published scientific studies which had been put into print at the time of the cessation of research activities has been posted on the internet by Prof. W.F. Long at web. abdn.ac.uk/~bch118/publications20003march.doc)

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

David Grant, William F. Long, Marion A. Ross, Jaqueline A. Somers and Frank B. Williamson, Department of Biochemistry, University of Aberdeen, Marischal College, Aberdeen AB9 1AS, Scotland, U.K. ABSTRACT Humic and fulvic acids strongly inhibit the crystallization of CaCO3 (calcite) These soil-derived polymers may therefore affect fertilizer efficiency in calcareous soils and influence marine carbonate and atmospheric CO2 concentrations. It is possible that the anti-calcite activity of the polymers resides in an “oxidized polyethylene”-like fraction since a uronic acid residue-containing polysaccharide fraction from soil had lower anti-calcite activity and lignin derivatives had no activity. Because of their highly heterogeneous natures, it is likely that humic and fulvic acids possess other ecologically relevant anti-crystallization activities

INTRODUCTION

Humic acid and fuvic acid are names given to colloidal organic fractions obtained from soil by defined procedures involving dispersion of samples in aqueous alkali, neutralization, separation of insoluble humic from soluble fulvic fractions, and dialysis of the fractions (Schnitzer and Khan, 1978). These heterogeneous polyanionic substances are agriculturally significant, because they stabilize soil structure and stimulate root growth (Kononova, 1966; Schnitzer and Khan, 1978). They are formed by chemical and biochemical alterations of matter chiefly of microbial origin, and typically have 14C-dated residence time in soil of about 103 years (Schnitzer and Khan, 1978). They have been characterized by their cation –exchange capacity (Pleysier et al., 1986), by mass spectroscopy (Nager et al., 1975), by ir spectroscopy (Schurukhina et al., 1973) and by nmr spectroscopy (Wilson 1984). We have described the inhibition of the crystallization of calcite by a range of anionic polysaccharides derived from animal and algal tissues (Grant et al., 1989 a, b). Such compounds may have crystallization inhibition function in vivo, and structural analogues of them are of potential use as agents for the clinical augmentation of endogenous crystallization modulatory factors. Because of the broad structural similarity between these compounds and the soilderived polymers, and because soil-derived calcium salt crystallization inhibitors may be important in the modulation of marine calcification (Morse, 1983) and in increasing fertilizer efficiency in calcareous soils (Amer et al., 1985) , we examined the effects of humic and fulvic acids on the crystallization of CaCO3 (calcite). MATERIALS AND METHODS Humic acid and fulvic acid (preparation 1) were extracted from a non-calcareous agricultural soil at Countesswells, Aberdeenshire, U.K. of 5.9% carbon content

and pH ca. 5

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

fuvic acid (preparation 2) was extracted from a polysaccharide-rich fraction of climatic peat at Cairn o’Mount, Aberdeenshire, U.K. of 56% (w/w) carbon content and pH 3.7 (Forsyth, 1946) by Soxhlet extraction with H2O. Sulphation/sulphonation of the humic acid by the method of Wood and Mora (1958) converted it into a material that was soluble in the pH 8.3 solution used for study of calcite crystallization; the effect of sulphation/sulphonation on fulvic acid (preparation 1) was also investigated. Water-soluble sulphonated lignin derivatives (REAX 88B and REAX 100M) were obtained from Westvaco, Charleston Heights, SC, U.S.A. Heparin from porcine intestinal mucosa (lot no. 46C0035) and chondroitin 4-sulphate from whale cartilage (lot no. 77CO187) were from Sigma Chemical Co Ltd., Poole U.K.; Na pyrophosphate and Na tripolyphosphate were from Monsanto Chemical Company, St Louis, MO, U.S.A. Ir spectra (Fig.1) were obtained by multiple specular reflectance in a Grubb Parsons MkIII Spectrometer using films deposited on aluminium foil mirrors. The ir spectra of humic acid (Fig.1a) and fulvic acid (preparation 1) (Fig. 1b) were similar to the previously published spectra of such materials (Shurukhina et al., 1973). The ir spectrum of fulvic acid (preparation 2) (Fig. 1c) showed narrower absorption bands, indicating more homogeneity than the other soil extracts; the positions and intensities of the bands shown in Fig. 1c are typical of uronic acidcontaining polysaccharides. The spectra of sulphated/sulphonated humic acid (Fig 1e) were similar to those of the starting materials but showed additional absorbances due to the presence of SO3- groups; the major absorbance at 1238 cm-1 was assigned to the SO2- asymmetric stretching frequency. The ir spectra of lignin-derived

materials (Fig. 1 f, g) were similar to those of other soil-derived lignin fractions (Farmer and Morrison, 1964) but had additional SO3- absorptions. Crystallization studies were carried out as previously described (Grant et al., 1989a). Briefly, this involved, for the study of calcite crystallization, the addition of 7.8 mg calcite seed crystals prepared according to the method of Reddy and Nancollas (1971) to 60 cm3 of a solution containing CaCl2 (0.8mmol.dm-3) and NaHCO3 20 mmol.dm-3) and having a pH of 8.3 and a saturation index (Rogers et al., 1985) of approximately 31. A similar seeded crystallization method (Liu and Nancollas, 1975) was used for the study of BaSO4 crystallization. Crystallizations were followed by conductivity measurement using a Philips model PW9527 conductivity meter with a Philips 9514/60 electrode, and also, in then case of BaSO4 crystallization studies using a nephelometer (Evans Electroselenium Ltd., Halstead, Essex, U.K.). The dissolution of calcite seed crystals in dilute H2SO4 solution, and the effect of crystallization inhibitors on this process, were also followed by conductivity measurements. RESULTS Figure 2 curve g shows the decrease in conductivity caused by crystallization of calcite from a solution containing CaCl2 and NaHCO3, following addition of calcite seed crystals to the solution. Figure 2 curves a-g show the effects of various additives on the process. Fulvic acid (preparation 1) acted as a potent inhibitor of calcite crystallization (Fig 2 curves a,c and g). Fulvic acid (preparation 2) was only weakly inhibitory (Fig. 2 curve e). Crystallization in its presence followed complex kinetics perhaps explained by the formation of a soluble complex between Ca2+ and the polymer. Humic acid could not be studied directly because of its insolubility at pH 8.3;

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

The lignin derivatives under the conditions used by us, either did not affect the process of calcite crystallization (Fig 2f) or increased its rate (Fig. 2h). The effectiveness of the soil extracts were compared with that of other calcification inhibitors by plotting Freundlich (1926) isotherms (Fig. 4). The most effective soil polymers are apparently more than an order of magnitude more active than the other calcification inhibitors studied. Fulvic acid (preparation 1) and its sulphation/sulphonated product inhibited CaCO3 dissolution in 2.5x10-5 mol dm-3 H2SO4 solution showing a similar inhibitory activity to sulphated polysaccharide calcification inhibitors (Fig. 5). In related calcite crystallization experiments not reported in detail here, when seed crystals were pre-incubated at 25o C for 30 min. with the additives, a higher level of inhibition was achieved. Inhibition by soil extracts of the crystallization of BaSO4 (Table I) increased in the order: fulvic acid (preparation 1) < sulphated/sulphated fulvic acid (preparation1) < sulphated/sulphonated humic acid. Conductivity measurements (not shown) made in the presence of sulphated/sulphated soil extracts, suggested that strong chemical complexing occurred between the soil extracts and Ba2+ ions.

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

Fulvic acid No. 1

2.7 5.5 20. 0 100

21.0 3.5 ca. 0.5 0.0 ca.12.5 0.5
a a

Fulvic acid No 2 Sulphated humic acid Lignin derivatives REAX 88 REAX 100M Na tripolyphosphahte Na pyrophosphate

15.0 20.0

20.0 20.0 2.0 2.0

86.4 310.0 0.5 b 0.5 b

Notes a Ca2+ complexation occurs b Inhibition occurs for only a limited period(dependent on the dose); for 2, 1, 0.5 and 0.2 µ g/ml tripolyphosphate this was 35, 30, 7 and 2 min., respectively;

similar results were found with pyrophosphate except that the periods of activity were greater) in a manner similar to that previously described for tripolyphosphate inhibition of BaSO4 crystallization (Liu & Nancollas, 1975).

Table Ia Effect of Soil Organic Matter Additives on BaSO4 Crystallization Additive Homogeneous Nucleation Fulvic acid (preparation 1) Sulphated Fulvic acid (preparation 1) 30 3.2 µ g/ml % Uninhibited Rate from

2.5

38.

Heterogeneous Nucleation (on CaCO3 (calcite) seeds) Fulvic acid (preparation 1) Sulphated fulvic acid (preparation 1) Sulphate humic acid 2. 2. 2. 62. 8.6 0.5

DISCUSSION We examined the effects of modulators of CaCO3 (calcite) crystallization under controlled conditions, using a procedure defined by previous workers (Reddy and Nancollas, 1971). Because the rates of crystallization observed, and the degree and type of inhibition seen in the presence of modulators depend strongly on the experimental conditions used (especially those which slow reactions allow interaction of seed crystals and inhibitor), caution needs to be applied in any comparison of our results with those of others examining soil fractions. The present work (cf. Table I and Fig.3) , however, supports preliminary observation of Berner et al. (1978) and Inskeep and Bloom (1986a) that some humic substances derived from soil are very potent inhibitors of CaCO3 (calcite) crystallization. Their and our results accord with the suggestion that some water-soluble soil substances may permit high CaCO3 supersaturations in calacareous soils (cf. Amer et al., 1982, 1983). They also support the proposal (Berner et al., 198) that soil-derived substances may stabilize marine CaCO3 supersaturation, which varies form 2.5- to 5-5- fold, depending on latitude (Whitfield and Watson,1983). Since the formation of marine CaCO3 is a global drain on atmospheric CO2 (Kitanto, 1983), an investigation of the natural inhibitors of calcification may be ecologically relevant. The possible effects of human activity on natural inhibitors might also be considered. An increased potency and/or quality of terrestrial soil-derived crystallization inhibitors might elicit an elevation of atmospheric CO2.

Formation and dissolution of crystalline mineral phases such as those of BaSO4, are, together with effects on CaCO3 crystallization, important in determining seawater composition; the present results (cf. Table 1b) indicate that the soil extracts studied inhibit the crystallization of BaSO4. Because of their highly complex and heterogeneous nature, the soil-derived inhibitors may possess a wide range of there ecologically relevant anti-crystallization activities, e.g., through modulation of the physical states of iron and aluminium oxyhydroxide in the soil (Hayes and Himes, 1986). Stimulation of root growth by soil organic matter fractions (Kononova, 1966), Schnitzer and Khan, 1978) may, in part, be related to the ability of such humic materials to prevent the crystallization of sparingly soluble sulphates and phosphates (Griffin and Jurinak, 1973) which would otherwise reduce the availability of applied nutrients. Application of a synthetic crystallization inhibitor, pyrophosphate, has been shown to prevent this (Amer and Mostafa, 1981; Amer et al., 1982; 1983). As a result of studies involving unseeded CaCO3 crystallization, Kitano and Hood (1965) suggested that the chelation of Ca2+ to various organic substances influences the crystallographic form adapted by CaCO3 in the presence of these substances. Our results suggests that the inhibitory effect of our most active soil extracts was not due to chelation by them of Ca2+, since the inhibitory effect was not accompanied by a decrease in conductivity immediately on addition of the inhibitor to the supersaturated solution. In contrast, addition of ethylenediaminetetra-acetic acid (EDTA) to the supersaturated solution produced an immediate increase in conductivity as Ca2+ was complexed, but the compound did not act as an inhibitor of the seeded crystallization of CaCO3 (Grant et al 1989a). Many inhibitors of CaCO3 crystallization appear to deactivate the seed crystal

surfaces upon which crystal growth occurs, perhaps by binding to these surfaces (Nancollas, 1979). Such an effect as surface adsorption accords with the Freundlich isotherms produced in our experiments involving the soil-derived extracts, and also with the relatively non-specific inhibition by them of the dissolution of CaCO3 under acidic conditions. Various poly-carboxylic acids, including polysaccharides (Grant et al., 1989 a, b) and oxidised polysaccharides (Kuriyamam et al., 1985) are inhibitors of the crystallization of CaCO3, but are less active, by about1.5 orders of magnitude, on a weight basis, than the fulvic acid (preparation 1) and humic acid fractions used here (Fig 4); however, the inhibitory activity towards the dissolution of preformed CaCO3 crystals by the polysaccharide and soil-derived inhibitors was of the same order of magnitude (Fig. 5). This suggests that the most active soil components have particular specificity for CaCO3 crystal growth sites (which are possibly screw dislocations in the crystal surface (Nancollas, 1979). The chemical nature of fulvic and humic acids has not been unambiguously established but it is likely to be highly heterogeneous and the fractions may contain plant-derived lignin. Indeed, some described physical and chemical properties of these soil-derived substances may be due to the presence of aromatic components including lignin (Flaig, 1964; Schnitzer and Khan, 1978; Hayes and Himes, 1986). The present results suggest that the crystallization inhibitory properties of the fulvic and humic acid is not, however, due to the presence of this component no is it due to relatively un-degraded anionic polysaccharides. Their ir spectra (Fig. 1 of the most active humic and fulvic acid (preparation 1) are different form the less active preparations which exhibits a polysaccharide-associated absorption at 1430cm-1 being assigned to the symmetric stretching vibration of the carboxylate groups of uronic acid residues. This suggests that the active component of

fulvic acid (preparation 1) and perhaps of the other very active marine-derived humic acid and fulvic acid inhibitors reported by Berner et al. (1978) may not be polysaccharide in nature. Tentatively, we suggest that the inhibitory activity may reside in the principal major non-polysaccharide, non-lignin component of humic and fulvic acid, e.g. the “oxidized polyethylene” component of these soil-derived fractions (Grant, 1977, Hayes and Himes, 1986). This consists of aliphatic, perhaps lipid-derived, polymers of general composition (CH2)nC(O))X,(C)m(CH)(CH3)p, n>16, in which X=OH or –C< and which exhibit 13 FT and1H nmr spectra similar to those of partly oxidised low-density polyethylenes (i.e. with a dominant 13C chemical shift of δ = 30 which are present in virtually all soil types, being especially abundant in the smallest particles size fractions derived form terrestrial soils (Oades 1988), and are major components of marine humic acid (Hatcher et al., 1980). They may modulate soil aggregate structure (Chaney and Swift, 1984), perhaps by influencing soil mineral structure through their hydrophobic character; this hydrophobic character may contribute to the non-biodegradability of long-chain alkanes CH3(CH2)n>32CH3 in the soil (Potts et al., 1973). It has been reported that polymethylene-rich soilderived substances are strongly adsorbed on crystal surfaces in hydrophobic soils (Ma’shum et al., 1988). Some commercially used CaCO3 crystallization inhibitors, e.g. the polyphosphates (Raistrick, 1949) are effective at low concentration, but retain their effectiveness for only a short period, perhaps because crystal over-grow of the inhibitor-bound crystal surfaces (Liu and Nancollas, 1975). In contrast, our results as well as those of Berner et al. (1978) (see discussion in Morse, 1983), suggest that soil-

derived inhibitors may retain their inhibitor activity indefinitely. Further work using soil-derived fractions of defined origin and characteristics, and with carefully controlled crystallization procedures, may reveal inhibitors of commercial potential, and may illuminate ecological relevance of such substances.

REFERENCES Amer, F. and Mostafa, H. E. (1981) Effect of pyrophosphate on orthophosphate reactions in calcareous soils, Soil Sci. Soc. Am. J., 45 842-847 Amer, F., Khalil, M.A. and Diab, G.S. (1982) Agronomic effectiveness of pyrophosphate as an additive to moncalcium phosphate and diammonium phosphate calcareous soils, Soil Sci. Soc. Am. J. 46 572-583 Amer, F., Mahmoud,A.A. and Sabeet, V. (1985) Zeta potential and surface area of calcium carbonate as related to phosphate sorption, Soil Sci. Soc. Am. J., 49, 11371142 Berner, R.A., Westrich, J.P., Graber, R., Smith, J. and Martens, C.S. (1978) Inhibition of aragonite precipitation from supersaturated seawater: a laboratory and field study Amer. J. Sci., 278, 816-837 Chaney, K. and Swift, R.S. (1984) The influence of organic matter on aggregate stability of some British soils, J. Soil Sci., 35, 223-230 Farmer, V.C. and Morrison R.I. (1964) Lignin in sphagnum and phragmites and in peats derived from these plants, Geochimica et Cosmochimica Acta, 28, 1537-1546 Flaig, W. (1964) Effects of micro-organisms in the transformation of lignin to humic substances, Geochimica et Cosmochimica Acta, 28, 1523-1535 Forsyth, W.G.C. (1946) A fractionation of soil organic matter with special reference to the nitrogen constituents, Ph.D. dissertation, University of Aberdeen Freundlich, H. (1926) Colloid and Capillary Chemistry, Methuen, London Glentworth, R. and Muir, J.W. (1963) The Soils of the Country Round Aberdeen Inverurie and Fraserburgh, Mem. Soil Surv. Gt. Br. Scot. Edinburgh, H.M.S.O. Grant, D. (1977) Chemical structure of humic substances, Nature, 270,709-710 Grant, D., Long, W.F. and Williamson, F.B., (1989a) Inhibition by glycosaminoglycans of CaCO3 (calcite) crystallization Biochem J. in press

(Added note to original text: this appeared in Biochem. J. 1989 259 41-45)

Grant, D., Long, W.F. and Williamson, F.B., (1989b) Inhibition by carrageenans of CaCO3 (calcite) crystallization; to be submitted to Biochem J.
(Added note to original text: the submission of this paper for publication, like that of the present one was not proceeded with because of an unexpected sudden close down of the research group which at the time was thought to be temporary but it turned out to be permanent)

Griffin, R.A. and Jurinak, J.J. (1973) The interaction of phosphate with calcite, Soil Sci. Soc. Am. Proc., 37, 847-850 Hatcher, P.G. Towan, R. and Mattingly, M.A. (1981) 1H and 13C NMR of marine humic acids, Org. Geochem., 2, 77-85 Hayes, M.H.B. and Himes, F.L. (1986) Nature and properties of humus-mineral complexes, Interactions of Soil Minerals with Natural Organics and Microbes. Soil Sci. Soc. Amer. Special Publication No. 17 pp103-150 Inskeep, W.P. and Bloom, P.R (1986a) Kinetics of calcite precipitation in the presence of water-soluble organic ligands, Soil Sci. Soc. Am. J., 50, 1167-1172 Inskeep W.P. and Bloom P.R. (1986b) Calcium carbonate supersaturation in soil solutions of calciaquolls, Soil Sci. Soc. Am. J., 80, 1431-1437 Kitano Y. (1983) Calcification and atmospheric CO2, Biomineralizaiton and Biological Metal Accumulation. Ed. Westbroek, P and De Jong E.W., Reidel, Dordrecht, pp89-98 Kitano, Y. and Hood, D.W. (1965) The influence of organic material on the polymorphic crystallization of calcium carbonate, Geochimica et Cosmochimica Acta, 29, 29-41 Kononova, M. M. (1966) Soil Organic Matter, Pergamon Press, Oxford Kuriyama, Y., Kajiwara, S. and Ozaki, F. (1985) United States Patent Specification No. 4,561,982 Liu, S.-T. and Nancollas, G.H. (1975) The crystal growth and dissolution of barium sulfate in the presence of additives, Journal of Colloid and Interface Science, 52, 582592 Ma’shum M., Tate M.E., Jones G.P. and Oades, J.M. (1988) Extraction and characterization of water-repellent materials from Australian soils, J. Soil Sci., 39, 99109 Morse, J.W. (1983) The kinetics of calcium carbonate dissolution and precipitation, Reviews in Mineralogy, 11, 227-394

Nager, B.R. , Waight, E.S., Meuzelaar, H.L.C. and Kistemaker, P.G. (1975) Studies and the structure and origin of soil humic acids by Curie point pyrolysis in direct combination with low-voltage mass spectrometry, Plant and Soil, 43, 681-685 Nancollas, G.H. (1979) The growth of crystals in solution, Advances in Colloid and Interface Science, 10, 215-252 Oades, J.M. (1988) The retention of organic matter in soils, Biogeochemistry, 5, 3570 Ogner, G. (1973) Permanganate oxidation of methylated and unmethylated fulvic acid, humic acid and humin isolated from raw humus, Acta Chem. Scand., 27, 16011612 Pleysier, J., Janssens, J. and Cremers, A. (1986) A clay suspension stability end points titration method for measuring cation exchange capacity of soils, Soil Sci. Soc. Am. J., 50, 887-891 Potts J.E., Clendinning R.A. and Ackart W.A. (1973) Proc. Symp. Degradability of Polymers and Plastics, 27-28 Nov., 1973, Plastics Inst. London 12-1, -12-10 Raistrick, B. (1949) The influence of foreign ions on crystal growth from solution 1. The stabilization of the supersaturation of calcium carbonate solutions by anions possessing O-P-O-P-O chains, Disc. Faraday Soc., 5, 234-237 Reddy, M.M. and Nancollas , G.H. (1971) The crystallization of calcium carbonate I. Isotope exchange and kinetics, J. Colloid and Interface Sci., 36, 166-172 Rogers, L.A., Tompson, Q.B., Maty, J.M. and Durrett, L.R. (1985) Oil and Gas Journal, 83 97-106 Schnitzer, M. and Khan, S.U. (1978) Humic Substances in the Environment, Marcel Dekker , New York Shurukhina, S.I., Shurukhin, V.V. and Tarlakov, Yu. P. (1973) Study of humus extracts by infrared spectroscopy, Pochvovedeniye 146-149 Whitfield, M. and Watson, A.J. (1983) The influence of biomineralization on the composition of seawater, Biomineralization and Biological Metal Accumulation. Ed. Westbroek, P. and De Jong, E.W., Reidel, Dordrecht, pp57-72 Wilson, M.A. (1984) Soil organic matter maps by nuclear magnetic resonance J. Soil Sci., 35, 209-315 Wood, J.W. and Mora, P.T. (1958) Synthetic polysaccharides. III. Polyglucose sulfates, J. Amer. Chem. Soc. 80, 3700-3702

FIGURES
(Note added to original text: these Figures were under construction when the research project was shelved. These preliminary diagrams intended for professional upgrading are however available and while not being of high standard, contain the essential information referred to in the main text).

Fig. 1a Ir spectra 400-4000cm-1 of the samples studied (a) humic acid (b) fulvic acid (prepn. 1) (c) fulvic acid (prepn. 2) (d) sulphated/sulphonated humic acid (e) sulphated sulphonated fulvic acid (prepn. 1) (f) sulphated lignin REAX 88B (g) sulphated lignin REAX 100M

Fig 1 Ir spectra 400-4000cm-1 of humic matter samples studied

Fig. 2 Effect of additives on crystallization of CaCO3 curves (a) (c) (d) fulvic acid (prepn. 1) 100, 5.5 and 2.8 µ g/ml

sulphated /sulphonated humic acid 20µ g/ml (e) fulvic acid (prepn. 2) 15µ g/ml (f)(g) lignin derivs. REAX 88B, REAX 100M 20µ g/ml respectively (h) no additive
(b)

Fig. 3 Effect of additives on crystallization of CaCO3 -second order rate plots Effect of fulvic acid (prepn. 1) m refers to the conductivity readings, m(i) and m(o)obeing the initial and final values [Insert added later: It should be noted that the above results were obtained without incubating
the additives in the presence of the seed crystals. If this is done the apparent degree of effectiveness is greatly increased. While the latter situation is likely to apply to the real situation in natural waters, there was a need for conducting the experiments in a reproducible manner to allow comparison with results obtained with other inhibitors (e.g. as reported by Grant et al. in Bichem J 1989, 259, 41-45) and by other authors].

Fig. 4

Freundlich (1926) Isothem Plot Homogeneously nucleated crystallization of CaCO3 (calcite) Comparison of fulvic acid with other inhibitors a, water extract of soil (data from Inskeep & Bloom (1968b) b, fulvic acid (prepn. 1) c, fulvic acid (prepn. 2) b*sulphated /sulphonated humic acid d, heparan sulphate e, heparin, f, chondroitin 4-sulphate (data for curves d-f were from Grant et al., 1988a)

Fig. 5

Freundlich (1926) Isotherm Plot, CaCO3 Dissolution CaCO3 1.6 mg/60ml 2.5x10-5 mol dm-3 H2SO4 solution; sulphated humic acid, fulvic acid (prepn. 1); heparin; sulphated pectin ACKNOWLEDGEMENTS We thank Dr. M.V. Cheshire, Macaulay Institute, Aberdeen, for samples of humic and fulvic acids, Mrs Marion Ross for preparation Of sulphated humic acid, Mrs Jacqueline Somers for the data on the inhibition of calcite crystallization by tripolyphosphate and pyrophosphate, the Cancer Research Campaign and the Scottish Home and Health Department for grants supporting work in this laboratory.

The above text of a manuscript dated 20 Feb 1988, with modifications suggested in hand written inserts by (Prof) WF Long dated 21 Feb 1989 of a paper intended for submission to an academic journal was one of a series of papers dealing with natural inhibitors of the crystallization of CaCO produced by 3 the Polysaccharide Research Group of the University of Aberdeen Department of Molecular and Cell Biology (jointly headed by W.F. Long and F.BV. Williamson) in which a humic matter led anthropogenic climate change hypothesis is briefly suggested. One of the intended series of (three plus) papers (Grant, D. et al., Biochem J 1989, 259, 41-45) achieved being submitted prior to termination (for un-stated reasons) of the Scottish Home and Health Department contract which had funded the work. The other manuscripts were retained (with permission) by D.Grant (the principal author) for future publication

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