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#           Magmatic, connate, and metamorphic waters      

      June 11, 1957    

Some major types of water of “deep” origin are believed to be recognizable from their chemical and isotopic compositions. Oil-field brines dominated by sodium and calcium chlorides differ markedly from average ocean water. In general, the brines are believed to be connate in origin (“fossil” sea water) with a negligible to high proportion of meteoric water. Many brines, particularly in pre-Tertiary rocks, are much higher in salinity than sea water and are greatly enriched in calcium as well as sodium chloride. Brines near the salinity of sea water are generally higher, relative to sea water, in bicarbonate, iodine, boron, lithium, silica, ammonium, and water-soluble organic compounds, and lower in sulfate, potassium, and magnesium.

Many changes take place after sea water is entrapped in newly deposited marine sediments: (1) Iodine, silicon, boron, nitrogen, and other elements have been selectively concentrated in organisms that decompose during and after burial in sediments. Many of the elements may redissolve in the interstitial water. (2) Bacteria are active in the sediments and reduce sulfate to sulfide and produce methane, ammonia, carbon dioxide, and other products. (3) Some elements have been selectively removed from sea water by inorganic processes, such as adsorption on clays and colloidal matter. When this matter is reconstituted by diagenetic and other changes, some components are redissolved. The abundance of lithium and possibly boron and other elements may be controlled to a considerable extent by these inorganic processes. (4) The interstitial water may react chemically with enclosing sediments and produce dolomite, reconstituted clays, and other minerals. The high loss of magnesium relative to calcium in most connate waters is probably caused by such reactions.

Volcanic hot-spring waters of different compositions have been discussed in an accompanying paper (White, 1957). The most significant type is believed to be dominated by sodium chloride, and is best explained as originating from dense gases driven at high temperature and pressure from magma and containing much matter of low volatility that is in solution because of the solvent properties of high-density steam. This dense vapor is condensed in and greatly diluted by deeply circulating meteoric water. Most other types of volcanic water are believed to be derived from the sodium-chloride type.

Volcanic sodium-chloride waters are similar in many respects to connate waters but are believed to be distinguishable by relatively high lithium, fluorine, silica, boron, sulfur, CO2, arsenic, and antimony; by relatively low calcium and magnesium; and by lack of hydrocarbons, water-soluble organic compounds, and perhaps ammonia and nitrate. Relatively high boron and combined CO2 are alone not reliable indicators of a volcanic origin.

During compaction, rocks lose most of their interstitial high-chloride water; much additional water may then be lost during progressive metamorphism, and the content changes from about 5 per cent in shale to perhaps 1 per cent in gneiss. This expelled water is here called metamorphic. Because of pressure and permeability gradients, it must normally escape upward and mix with connate and meteoric water. Even though large quantities must exist, no example of metamorphic water has been positively identified.

Some thermal springs in California are high in salinity and relatively low in temperature and apparent associated heat flow. Some are clearly connate in origin. Other springs are characterized by very high combined carbon dioxide and boron, relative to chloride. Their compositions are considerably different from known connate and volcanic waters and are believed to be best explained by a metamorphic origin.

Although some major types of deep water seem to be recognizable, there is much danger of oversimplifying the problems. Many waters are no doubt mixtures of different types, and some of high salinity result from dissolution of salts by meteoric water.

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