Radicecology pexe 562 the crust of the earth, in sea water, the * amounts of elements supplied to sea water tot rhe percentage of those supplied which are asa in ou” the composition of the material from which 3 o earth was formed may be estimated from the the dapce of the elements in the solar atmosore In this material hydrogen, helium, and peer account for 99,7 per cent of the total oxvk" of the remaining elements only iron is ©= y“ te BS 7. “ae solution. resent in relatively high (0.167 per cent) amount fo gnd contr ibutes ; 97.4 per cent of the total mass of the transition elements vanadium, manganese, iron, Had iron not been nickel, and copper, roduced in relatively large quantities, due to egbdalt, rts high nuclear binding energy, the subsequent role of iron in the formation of the earth and its Pe availability for use by organisms probably would have been Significantly reduced, Fractionation of elements occurred in the : early molten stages of the earth and, the pre- : EE E F dominant elements at this time were iron, oxygen, mignesium, and silicon (Table 1), The amount of oxygen was not sufficient to convert the cationic elements into oxides so that a major part of the tron and nickel in elemental form sank to the center forming the core, Most of the cobalt, mulybdenum, and other heavy metals were carried ‘along and a major part of the iron and other heavy r metals was thereby effectively removed from the environment which was later to be inhabited by the | biosphere (Mason, 1958), A mantle and crust solidified over the core and the latter was enrtched in sodium, aluminum, f potassium, Chlorine, calcium, phosphorus, silicon, fF and oxygen, Iron contributed only about one- p seventh and cobalt about one-one hundredth as much F of the crust as they did of the total earth, and ; in addition, nickel, sulfur, and magnesium were reduced in amount, Although the percentage of iron was reduced in the crust of the earth in relation to that in the core, it was present in ap- preciable amounts with only oxygen, silica, and aluminum being more abundant. With the formation of the hydrosphere many of the elements of the crust were redistributed. The mobility and chemical forms of iron and cobalt were and are influenced by the environmental conditions on land and in the water and were affected significantly by physical and chemical action of the atmosphere, The paths of iron and cobalt were probably from weathered rock, to fresh water, to the seas where a major part of the iron and a lesser part of the cobalt was precipitated and deposited at the bottom. In many instances the bottoms of the seas were raised to altitudes higher than the surface of sea and the cycle was repeated. Thus, leaching of the earth’s crust was an inm- Purtant factor in the distribution and deposition of iron and cobalt in both hydrosphere, 5a2 the lithosphere and In natural yater, iron is present as Feo+ ©, and Fe(OH)“+,. Iron, in the ferrous form, ae rains in solution with precipitation occuring : ter its oxidation to the ferric state. The solpoort of ferric hydroxide is dependent upon its oh ubility which, in turn, is dependent upon the tb of the medium. At pH six, ferric hydroxide is ions 100 times as soluble as at pH seven and is 1937.00 times as soluble as at pH 8.5 (Cooper, ). Iron in weakly acid streams flowing into ‘the alkalseas therefore is p.ecipitated in the slightly the ine sea water. This fact is illustrated by fresh oevations that the average iron content of na waters is about 100 times the level found in rine waters (Mason, 1958). The precipitation of iron in sea water from acidic iron wastes was described by Ketchum and Ford (1952). After the introduction of the wastes, the sea water first became green from the formation of ferrous hydroxide, Later the oxidation of the iron to ferric hydroxide resulted in a floculent red precipitate, In addition to direct observations, an estimate of the behavior of chemical elements in the oceans may be made from the geochemical balance of the elements in sea water, If the comparison is made of the total amount of the elements supplied to the seas from the lithosphere with the amounts now found in sea water, the transfer percentage for each element may be determined. The larger the transfer percentage for a given ele- ment, the more of that element has remained in solution. In Table 1 are given the amounts of several elements in sea water, the amounts sup- plied to the sea, and the percentage of each element which is in solution. Iron has the lowest transfer percentage of any of the elements with only one part in three million of that criginally supplied remaining in solution. Manganese exhibits a transfer percentage ten times and the other transition elements cobalt, nickel and copper 100 to 200 times that of tron, In absolute amounts, however, iron is present in sea water at a level about three times that of copper, five times that of vanadium, manganese and nickel, and twenty times that of cobalt. However, all of the tran- sition elements, including iron, are present in very low amounts, The role of iron in the respiratory pigments of animals may be related to the distribution of this metal in the different environments and to the levels of available oxygen, The two principal metals contained in respiratory pigments are iron and copper in that order of occurrence. The copper containing pigment (hemocyanin), probably originated mostly among plankton and free swimming forms of ancient invertebrates which inhabited marine waters containing low amounts of iron and relatively high oxygen content. The iron containing pigment (hemoglobin) probably originated and developed at about the same time in organisms that lived at the ocean bottom, especially in those organisms which burrowed in the bottom sediments, where iron was and is available in relatively high amounts and oxygen was at a reduced level (Vinogradov, 1953), In most of those animals which made the transition from salt to brackish or fresh water or onto the land mass, the respiratory pigments contain iron, The high levels of iron available to terrestrial, fresh water, and bottom dwelling marine organisms, in contrast to the reduced amounts available to free living marine organisms, probably influenced the incidence of utilization of iron by the inhabitants of the different environments. Iron, when precipitated in sea water, forms a positively charged colloid and the precipitate carries scavenged ions with it as it settles to the bottom. Many ions, including arsenic, molybdenum, nickel, vanadium, phosphorus, antimony, copper, selenium, and lead, are removed from solution by this mechanism, In addition, the manganous ion may be catalytically oxidized by a gel of ferric hydroxide hydrate and this reaction probably accounts in part, at least, for the low transfer percentage of manganese in comparison to vanadium, cobalt, nickel, and copper. The co- precipitate of manganese and iron is capable of removing additional ions from the sea water, in- cluding cobalt, zinc, thorium, tin, and silver (Arrhenius, 1959), The removal of heavy ions by ferric hydroxide is of great importance in the survival of past nom ARCHUYE® +. ” TR

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