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Chemistry of Sea Water
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Geochemistry of the Ocean Waters

The total quantity of dissolved solids present in the waters of the oceans can be estimated by assuming an average salinity of 35 ‰ and assuming that the volume of the ocean is 1.37 × 109 km3 (p. 15). With a density in situ of 1.04 for the ocean waters, the dissolved solids amount to 5 × 1016 metric tons. This immense quantity of material would form a layer of dried salts 45 m thick over the entire earth, or 153 m thick over the present land area. The amount in tons of any element may be estimated by multiplying the value given in the first column in table 45 by 1.42 × 1012. The figures for the variable elements correspond to the higher values listed in table 36. Obviously the total amounts of even the trace elements are tremendous, and, if methods of extraction were economically feasible, the oceans would serve as an “inexhaustible” source of these substances.

Element Sea water S = 35‰ (mg/kg) Potential “supply” in 600 g of rock (mg/kg of sea water) Percentage in solution
Silicon 4 165,000 0.002
Aluminum 0.5 53,000 0.001
Iron 0.02 31,000 0.0001
Calcium 408 22,000 1.9
Sodium 10,769 17,000 65
Potassium 387 15,000 2.6
Magnesium 1,297 13,000 10
Titanium ............ 3,800 ?
Manganese 0.01 560 0.002
Phosphorus 0.1 470 0.02
Carbon 28 300 9
Sulphur 901 300 300
Chlorine 19,353 290 6700
Strontium 13 250 5
Barium 0.05 230 0.02
Rubidium 0.2 190 0.1
Fluorine 1.4 160 0.9
Chromium p 120 ?
Zirconium ............ 120 ?
Copper 0.01 60 0.02
Nickel 0.0001 60 0.0002
Vanadium 0.0003 60 0.0005
Tungsten ............ 41 ?
Lithium 0.1 39 0.2
Cerium 0.0004 26 0.002
Cobalt p 24 ?
Tin p 24 ?
Zinc 0.005 24 0.02
Yttrium 0.0003 19 0.002
Lanthanum 0.0003 11 0.003
Lead 0.004 10 0.04
Molybdenum 0.0005 9 0.005
Thorium <0.0005 6 0.01
Cesium 0.002 4 0.05
Arsenic 0.02 3 0.7
Scandium 0.00004 3 0.001
Bromine 66 3 2000
Boron 4.7 2 240
Uranium 0.015 2 0.8
Selenium 0.004 0.4 1
Cadmium p 0.3 ?
Mercury 0.00003 0.3 0.001
Iodine 0.05 0.2 25
Silver 0.0003 0.06 0.5
Gold 0.056 0.003 0.3
Radium 0.093 0.066 0.05
p = present

According to present theories, most of the solid material dissolved in the sea originated from the weathering of the crust of the earth. The problem as to the amount of rock weathered has been treated by Goldschmidt (1933) in the following way. For each square centimeter of the surface of the earth there are 278 kg of sea water; therefore, for each square centimeter the ocean water contains very nearly 3 kg of sodium. The average sodium content of igneous rocks is 2.83 per cent, and in sedimentary deposits it is 1.00 per cent. In the process of weathering, a certain amount of the material is leached away, and Goldschmidt estimates that the mass of the sedimentary deposits (Y) is 0.97 of the original igneous rocks (X) that gave rise to them. Therefore,

From this we find that for each square centimeter of the earth's surface about 160 kg of igneous rocks have been weathered. Therefore, approximately
600 g of rock have been weathered for each kilogram of water in the oceans. Of the total sodium, 65 per cent has accumulated in the sea water and 35 per cent has been deposited in sedimentary rocks. The 600 g of igneous rock have been, therefore, a potential supply of the constituent elements to the sea, although in most cases only a part of the material has actually dissolved or remained in solution. Using 600 g as the amount of rock weathered and following Goldschmidt's estimate (1937) of the composition of the earth's crust, the “supply” of elements listed in table 45 is obtained. A number of the minor constituents of rocks are not included in this tabulation. The “percentage in solution” has been obtained by dividing the amount of each element present in sea water by the potential supply. This procedure has been followed by Goldschmidt (1937).

Examination of table 45 shows that the elements may be grouped in three classes, depending upon the percentage in solution: (1) Sulphur, chlorine, bromine, and boron occur in amounts greater than those which could have been supplied by the weathering of the 600 g of rock. Goldschmidt considers that these elements were present in the primeval atmosphere as volatile compounds and that they accumulated in the ocean waters in the earliest times. (2) Calcium, sodium, potassium, magnesium, carbon, strontium, selenium, and iodine, which form relatively soluble compounds, are present in sea water in amounts greater than 1 per cent of the potential supply. (3) The remaining elements, which are present in small amounts.

It is striking that silicon, aluminum, and iron, the most abundant elements in igneous rocks (oxygen is actually the most abundant, but does not have to be considered here), are present in sea water in extremely small amounts. Thus, the relative abundance of the elements in sea water differs markedly from that in the earth's crust. With a few exceptions, all of the elements have been potentially available in much larger amounts than are actually present in solution. The relative composition of river water differs from that of sea water, and, in addition to the dissolved constituents, rivers introduce large quantities of particulate material that would pass into solution if the sea water were unsaturated with respect to these substances. Therefore, it appears that factors operating in the sea itself must control the concentrations of many of the elements that are potentially available in Iarge amounts. These factors are solubility, physical-chemical reactions, and biological activity. Our present knowledge is inadequate to designate which process or processes may control the concentration of a given element. Therefore, the following remarks will merely indicate the character of the factors that may be involved.

Certain elements may be present in such amounts that the solubility of their compounds may limit their concentration. In these eases,

additional amounts brought to the sea in solution by rivers will be removed by chemical precipitation. The quantities of other elements may be controlled by physical-chemical processes that are, however, more complex than the precipitation of some simple salt—for example, the reactions which may take place between the dissolved substances and the colloidal and particulate material introduced by rivers. Included among such processes are ionic adsorption, base exchange, and the formation of complex minerals. Such reactions may remove from solution ions that would not be precipitated in absence of colloidal or particulate material. Biological activity is undoubtedly of great importance in controlling the concentrations of many of the elements in the sea. Cyclical processes, in which elements are removed from solution but are later released by metabolic activity, need not be considered. However, a certain amount of the material built up by organisms falls to the sea bottom, becomes a permanent part of the deposits, and is therefore removed from solution. The concentration of elements carried down in this way may be considered to be at least partly controlled by the activity of marine organisms. The character of the skeletal structures and of the detrital organic matter deposited in this way is discussed in chapters VII and XX. Organisms remove from solution elements that would not otherwise precipitate, and, if conditions are such that some of this material becomes a permanent part of the sediments, it is obvious that biological activity must play an important part in controlling the composition of the water. Not only the major constituents of skeletal structures such as calcium, carbon, silicon, and so on, but nitrogen, phosphorus and many elements present in the sea in small concentrations are also accumulated by marine organisms.

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