Sea sulfate

The sulfur-oxidizing bacteria. Anaerobic conditions prevail in marine sediments, in poorly stirred swamps, and around hydrothermal vents at the bottom of the sea. Sulfate-reducing bacteria form high concentrations (up to mM) of H2S (in equilibrium with HS and s2-)318-320 This provides the substrate for bacteria of the genus Thiobacillus, which are able to oxidize sulfide, elemental sulfur, thiosulfate, and sulfite to sulfate and live where the aerobic and anaerobic regions meet.311 321-323 Most of these small gram-negative... 

Prada and colleagues recently described a new indirect method for determining sulfate in natural samples, such as sea water and industrial effluents. The method is based on... 

Chemical composition data for CPM and FPM for a variety of locations are summarized in Table 5. These data illustrate several important points. First, the distributions of the PM q between CPM and FPM vary from about 0.4 to 0.7. Second, the ratio of PM q to TSP varies from 0.58 to 0.79. In general, both this ratio and the ratio of FPM to PM q tend to be higher at mral sites, but Bermuda, because of the large influence of sea salt in the CPM, is an exception. Sulfate (SO ), carbon (as organic carbon, OC, and elemental carbon, EC), and nitrate (NO3 ) compounds generally account for 70—80% of the FPM. In the eastern United States, compounds are the dominant species, although very Httie is emitted directiy into the atmosphere. Thus... 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

Ammonium chloride [12125-02-9], ammonium sulfate [7783-20-2], and diammonium phosphate [7708-28-0] have also been used for shale stabilization (102,103). Ammonium ions have essentially the same effect on shales as potassium ions but use of ammonium salts is often objectionable because of the alkaline nature of the mud. In the North Sea and northern Europe, where magnesium-bearing salt formations ate encountered, magnesium chloride [7786-30-3] is used, but in the United States it is used only on a small scale. 

Salt that is substantially free of sulfate and other impurities is the cell feed. This grade may be purchased from commercial salt suppHers or made on site by purification of cmde sea or rock salt. Dried calcium chloride or cell bath from dismanded cells is added to the bath periodically as needed to replenish calcium coproduced with the sodium. The heat required to maintain the bath ia the molten condition is suppHed by the electrolysis current. Other electrolyte compositions have been proposed ia which part or all of the calcium chloride is replaced by other salts (61—64). Such baths offer improved current efficiencies and production of cmde sodium containing relatively Htde calcium. 

The Chilean nitrate deposits are located in the north of Chile, in a plateau between the coastal range and the Andes mountains, in the Atacama desert. These deposits are scattered across an area extending some 700 km in length, and ranging in width from a few kilometers to about 50 km. Most deposits are in areas of low rehef, about 1200 m above sea level. The nitrate ore, caUche, is a conglomerate of insoluble and barren material such as breccia, sands, and clays (qv), firmly cemented by soluble oxidized salts that are predominandy sulfates, nitrates, and chlorides of sodium, potassium, and magnesium. Cahche also contains significant quantities of borates, chromates, chlorates, perchlorates, and iodates. 

Minerals of sodium sulfate occur naturally throughout the world. The deposits result from evaporation of inland seas and terminal lakes. Colder climates, such as those found ia Canada and the former Soviet Union, favor formation of mirabilite. Warmer climates, such as those found ia South America, India, Mexico, and the western United States, favor formation of thenardite. In areas where other anions and cations are present, double salts can be found of the kiads shown ia Table 2, which Hsts nearly all naturally occurring minerals containing sodium sulfate. Except for mirabilite, thenardite, and astrakanite, these mineral deposits play a minor role ia sodium sulfate production. 

The approximate composition of surface water in the Dead Sea in 1966 (49) was given as 35 g/L calcium chloride 130 g/L magnesium chloride nearly 80 g/L sodium chloride more than 10 g/L potassium chloride nearly 4 g/L bromide and about 1 g/L sulfate. At 400 m depth the bromide concentration was 6 g/L. Bromine in Israel is produced from the Hquors left from potash production and the bromide content of these Hquors is 14 g/L. 

Great Salt Lake, Utah, is the largest terminal lake in the United States. From its brine, salt, elemental magnesium, magnesium chloride, sodium sulfate, and potassium sulfate ate produced. Other well-known terminal lakes ate Qinghai Lake in China, Tu2 Golu in Turkey, the Caspian Sea and Atal skoje in the states of the former Soviet Union, and Urmia in Iran. There ate thousands of small terminal lakes spread across most countries of the world. Most of these lakes contain sodium chloride, but many contain ions of magnesium, calcium, potassium, boron, lithium, sulfates, carbonates, and nitrates. 

Economic Aspects and Uses. Total world production of potassium products is 29,000,000 tons per year (65). Potassium chloride is removed from brine at Moab, and Wendover, Utah, and at Seades Lake, California. Potassium sulfate is made from Great Salt Lake brine by Great Salt Lake Minerals Corp., which is the largest producer of solar potassium sulfate in the wodd. Combined, these U.S. faciUties stiU produce a relatively small percentage of potash fertilizers in the wodd. Production from the Dead Sea, for example, is 10 times greater than production of potassium from brines in the United States. More than 95% of all the potassium produced is used in fertilizer blends. The remainder is converted to other potassium chemicals for industdal use (see Potassium compounds). 

These bacteria are anaerobic. They may survive but not actively grow when exposed to aerobic conditions. They occur in most natural waters including fresh, brackish, and sea water. Most soils and sediments contain sulfate reducers. Sulfate or sulfite must be present for active growth. The bacteria may tolerate temperatures as high as about 176°F (80°C) and a pH from about 5 to 9. 

The primary constituents to be measured are the pH of precipitation, sulfates, nitrates, ammonia, chloride ions, metal ions, phosphates, and specific conductivity. The pH measurements help to establish reliable longterm trends in patterns of acidic precipitation. The sulfate and nitrate information is related to anthropogenic sources where possible. The measurements of chloride ions, metal ions, and phosphates are related to sea spray and wind-blown dust sources. Specific conductivity is related to the level of dissolved salts in precipitation. 

Sodium, 22 700 ppm (2.27%) is the seventh most abundant element in crustal rocks and the fifth most abundant metal, after Al, Fe, Ca and Mg. Potassium (18 400 ppm) is the next most abundant element after sodium. Vast deposits of both Na and K salts occur in relatively pure form on all continents as a result of evaporation of ancient seas, and this process still continues today in the Great Salt Lake (Utah), the Dead Sea and elsewhere. Sodium occurs as rock-salt (NaCl) and as the carbonate (trona), nitrate (saltpetre), sulfate (mirabilite), borate (borax, kemite), etc. Potassium occurs principally as the simple chloride (sylvite), as the double chloride KCl.MgCl2.6H2O (camallite) and the anhydrous sulfate K2Mg2(S04)3 (langbeinite). There are also unlimited supplies of NaCl in natural brines and oceanic waters ( 30kgm ). Thus, it has been calculated that rock-salt equivalent to the NaCl in the oceans of the world would occupy... 

Finally, sulfur occurs in many localities as the sulfates of electropositive elements (see Chapters 4 and 5) and to a lesser extent as sulfates of Al, Fe, Cu and Pb, etc. Gypsum (CaS04.2H20) and anhydrite (CaSO ) are particularly notable but are little used as a source of sulfur because of high capital and operating costs. Similarly, by far the largest untapped source of sulfur is in the oceans as the dissolved sulfates of Mg, Ca and K. It has been estimated that there are some 1.5 x 10 cubic km of water in the oceans of the world and that 1 cubic km of sea-water contains approximately 1 million tonnes of sulfur combined as sulfate. 

The enol-sulfate form (I), which is the precursor of the luciferin in the bioluminescence system of the sea pansy Renilla (Hori et al., 1972), can be readily converted into coelenterazine by acid hydrolysis. The enol-sulfate (I), dehydrocoeienterazine (D) and the coelenterazine bound by the coelenterazine-binding proteins are important storage forms for preserving unstable coelenterazine in the bodies of luminous organisms. The disulfate form of coelenterazine (not shown in Fig. 5.5) is the luciferin in the firefly squid Watasenia (Section 6.3.1). An enol-ether form of coelenterazine bound with glucopyra-nosiduronic acid has been found in the liver of the myctophid fish Diapbus elucens (Inoue et al., 1987). 

Red P is used in burning-type munitions mainly for signaling purposes. Compns consisting of red P and certain oxidants or fuels are relatively slow-burning and are sometimes used in sea markers. The chemical reactions may be quite involved. For example, the main reaction for a burning mixt of Ca sulfate and red P appears to be ... 

The evaporite source is characterized by covariation of sulfate (from gypsum) and chloride (from halite). That elements can be recycled from the ocean to land by movement of saltbearing aerosols (so-called "cyclic salts") has confused the interpretation of river flux data somewhat. While this cycling generally follows the ratio of salts in the sea, the S/Cl ratio is an exception. Taking the S/Cl ratio of the cyclic component to be 2 (based on compositional data for marine rains) and assuming that all chloride in rivers is cyclic, an upper limit for the cyclic influence can be calculated. 

In recent years, many hydrothermal solution venting and sulfide-sulfate precipitations have been discovered on the seafloor of back-arc basins and island arcs (e.g., Ishibashi and Urabe, 1995) (section 2.3). Therefore, it is widely accepted that the most Kuroko deposits have formed at back-arc basin, related to the rapid opening of the Japan Sea (Horikoshi, 1990). 

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