Seawater calcium concentration

Fig. 6-5. The evolution of the lagoon s waters in response to oscillations in biological productivity. The results show the adjustment of the system from an initial composition equal to that of seawater. This figure shows isotope ratios, calcium concentration, the saturation index, and productivity.

For normal seawater the calcium concentration can be calculated from salinity for most purposes (accuracy is almost always better than 1%). 

The oceans at this time can be thought of as the solution resulting from an acid leach of basaltic rocks, and because the neutralization of the volatile acid gases was not restricted primarily to land areas as it is today, much of this alteration may have occurred by submarine processes. The atmosphere at the time was oxygen deficient anaerobic depositional environments with internal CO2 pressures of about 10-2-5 atmospheres were prevalent, and the atmosphere itself may have had a CO2 pressure near lO-25 atmospheres. If so, the pH of early ocean water was lower than that of modern seawater, the calcium concentration was higher, and early global ocean water was probably saturated with respect to amorphous silica (—120 ppm). Hydrogen peroxide may have been an important oxidant and formaldehyde, an important reductant in rain water at this time (Holland et al., 1986). Table 10.5 is one estimate of seawater composition at this time. 

Calculation of Calcium and Carbonate Total Molalities. Because of the constancy of composition of seawater, the total ion calcium concentration in seawater can be calculated, in "open ocean seawater samples, directly from high precision salinity measurements, using the relationship (14) ... 

The numerator of the right side is the product of measured total concentrations of calcium and carbonate in the water—the ion concentration product (ICP). If n = 1 then the system is in equilibrium and should be stable. If O > 1, the waters are supersaturated, and the laws of thermodynamics would predict that the mineral should precipitate removing ions from solution until n returned to one. If O < 1, the waters are undersaturated and the solid CaCOa should dissolve until the solution concentrations increase to the point where 0=1. In practice it has been observed that CaCOa precipitation from supersaturated waters is rare probably because of the presence of the high concentrations of magnesium in seawater blocks nucleation sites on the surface of the mineral (e.g., Morse and Arvidson, 2002). Supersaturated conditions thus tend to persist. Dissolution of CaCOa, however, does occur when O < 1 and the rate is readily measurable in laboratory experiments and inferred from pore-water studies of marine sediments. Since calcium concentrations are nearly conservative in the ocean, varying by only a few percent, it is the apparent solubility product, and the carbonate ion concentration that largely determine the saturation state of the carbonate minerals. 

The use of Cd/Ca measurements in the tests of benthic foraminifera for deep-water nutrient reconstructions was developed in parallel with the carbon isotope method. Cadmium concentrations in seawater follow a nutrient-like distribution, while calcium concentrations simply reflect variations in salinity. The benthic foraminifera incorporate the cadmium and calcium into their shells in proportion to their presence in seawater, which allows for the reconstruction of deep-water cadmium (and thus macronutrient) distributions. 

The calcium concentration in normal seawater can be calculated from the salinity for most purposes (accuracy is almost always better than within 1%). As previously noted, care must be taken in studies of pore waters and in unusual areas such as coastal waters, carbonate banks, and lagoons where significant deviations from normal seawater concentrations can occur. 

The Michigan Basin brines very low pH helps to explain their ability to leach and react with other rocks, as is indicated by their high contents of strontium, barium and other metals, although much of the Sr and Ba probably came from the reaction with calcite. Geothermal water also probably mixed with some of the formations, as indicated by the variable presence of iodine, boron, lithium, cesium, rubidium and other rare metals. With most of the brines, the calcium concentration is somewhat higher than its magnesium equivalent in seawater end liquor from a potash deposit, and the potassium a little lower. Wilson and Long (1993) speculated that this occurred by the conversion of the clays kaolinite and smectite to illite ... 

Obtaining maximum performance from a seawater distillation unit requires minimising the detrimental effects of scale formation. The term scale describes deposits of calcium carbonate, magnesium hydroxide, or calcium sulfate that can form ia the brine heater and the heat-recovery condensers. The carbonates and the hydroxide are conventionally called alkaline scales, and the sulfate, nonalkaline scale. The presence of bicarbonate, carbonate, and hydroxide ions, the total concentration of which is referred to as the alkalinity of the seawater, leads to the alkaline scale formation. In seawater, the bicarbonate ions decompose to carbonate and hydroxide ions, giving most of the alkalinity. 

The kinetics of the formation of the magnesium hydroxide and calcium carbonate are functions of the concentration of the bicarbonate ions, the temperature, and the rate of release of CO2 from the solution. At temperatures up to 82°C, CaCO predominates, but as the temperature exceeds 93°C, Mg(OH)2 becomes the principal scale. Thus, ia seawater, there is a coasiderable teadeacy for surfaces to scale with an iacrease ia temperature. 

Another possible modification is the use of seawater as the regenerant. Even though it contains calcium and magnesium, but only 2.7 wt % NaCl, it sometimes can be purified by coagulation, filtration, and chlorination less expensively than salt can be purchased. The lower concentration reduces the regeneration efficiency by 40—50%. 

Calcium chloride is found in the marine environment. The elemental composition of seawater is 400 ppm calcium, 18,900 ppm chlorine, and many organisms and aquatic species are tolerant of these concentrations. Toxicity arises either from the invasion of freshwater in otherwise saltwater environments or possible toxic doses of calcium chloride from spills, surface mnoff, or underground percolation into typically freshwater streams or aquifers. Various agencies have guidelines for calcium and chloride in potable water (41). The European Economic Community (EEC) is the only agency to have a minimum specification for calcium in softened water. 

An increase in carbonate-ion concentration moves the equilibrium in favour of calcium carbonate deposition. Thus one secondary effect of cathodic protection in seawater is the production of OH , which favours the production of CO, , which in turn promotes the deposition of CaCOj. Cathodically protected surfaces in seawater will often develop an aragonite (CaCOj) film. This film is commonly referred to as a calcareous deposit. 

Marshall, W.L., Slusher, R. and Jones, E.V. (1964a) Solubility of calcium sulphate to lOO C in seawater and saline water concentrates and temperature-concentration limits. J. Ghent. Eng. Data, 13, 83-93. 

Spencer and Sachs [29] determined particulate aluminium in seawater by atomic absorption spectrometry. The suspended matter was collected from seawater (at least 2 litres) on a 0.45 tm membrane filter, the filter was ashed, and the residue was heated to fumes with 2 ml concentrated hydrofluoric acid and one drop of concentrated sulfuric acid. This residue was dissolved in 2 ml 2 M hydrochloric acid and the solution was diluted to give an aluminium concentration in the range 5-50 pg/1. Atomic absorption determination was carried out with a nitrous oxide acetylene flame. The effects of calcium, iron, sodium, and sulfate alone and in combination on the aluminium absorption were studied. 

The effect of calcium interference is somewhat different. At its concentration in seawater, 0.010 M, calcium ion had no effect upon chemiluminescence analysis of a 6 x 10 8 M Crm solution in the absence of bromide ion. The... 

Polarography has also been applied to the determination of potassium in seawater [535]. The sample (1 ml) is heated to 70 °C and treated with 0.1 M sodium tetraphenylborate (1 ml). The precipitated potassium tetraphenylborate is filtered off, washed with 1% acetic acid, and dissolved in 5 ml acetone. This solution is treated with 3 ml 0.1 M thallium nitrate and 1.25 ml 2M sodium hydroxide, and the precipitate of thallium tetraphenylborate is filtered off. The filtrate is made up to 25 ml, and after de-aeration with nitrogen, unconsumed thallium is determined polarographically. There is no interference from 60 mg sodium, 0.2 mg calcium or magnesium, 20 pg barium, or 2.5 pg strontium. Standard eviations at concentrations of 375, 750, and 1125 pg potassium per ml were 26.4, 26.9, and 30.5, respectively. Results agreed with those obtained by flame photometry. 

The application of the Spectroscan DC plasma emission spectrometer confirmed that for the determination of cadmium, chromium, copper, lead, nickel, and zinc in seawater the method was not sufficiently sensitive, as its detection limits just approach the levels found in seawater [731]. High concentrations of calcium and magnesium increased both the background and elemental line emission intensities. 

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