Seawater salinity measurement

Anfalt and Jagner [57] measured total fluoride ion concentration by means of a single-crystal fluoride selective electrode (Orion, model 94-09). Samples of seawater were adjusted to pH 6.6 with hydrochloric acid and were titrated with 0.01 M sodium fluoride with use of the semi-automatic titrator described by Jagner [28]. Equations for the graphical or computer treatment of the results are given. Calibration of the electrode for single-point potentiometric measurements at different seawater salinities is discussed. 

Salinity measurements are most often used in oceanography to determine seawater density. The conventional measure used by oceanographers for determining salinity is conductivity. This is feasible because the salt content of seawater is well defined, as is the temperature-related compressibility. As an alternative, the refractive index of water is a good descriptor of density when temperature is known or can be measured. Refractive index provides a high-precision method for determining the density of pure water. As various salts are added, the refractive index is a less exact predictor of density, although relative measurements can still be useful. 

Salinity is a measure of the salt content of seawater. Developments in analytical chemistry have led to an historical evolution of the salinity concept. Intrinsically, it would seem to be a relatively straightforward task to measure. This is true for imprecise determinations that can be quickly performed using a hand-held refractometer. The salinity affects seawater density and thus, the impetus for high precision in salinity measurements came from physical oceanographers. 

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) ... 

Estimation of Uncertainty in The determination of the total ion molal concentration of calcium from salinity measurement is relatively precise with a probable error of less than 0.3% under open ocean conditions. Dickson and Riley (37) have recently discussed the effect of analytical errors on the evaluation of the components of the aquatic carbon-dioxide system for seawater at 25°C and 1 atmosphere total pressure. Their conclusions Indicate that if alkalinity and total carbon dioxide are the measured parameters a probable combined uncertainty in the total carbonate ion molal concentration from 3 to 6 percent results, depending on Fco2 If pH and alkalinity are the measured parameters the uncertainty is approximately 4 percent. In addition to the probable error introduced by analytical precision, the absolute accuracy of the measurements introduces an error which is difficult to evaluate. The results of the GEOSECS intercalibration study (38) were indicative of this problem. A conservative guess is that accuracy introduces at least a one percent further uncertainty. It is also difficult to determine exactly what error is introduced through temperature and pressure corrections to situ conditions. For the deep sea this may introduce a further uncertainty of at least... 

For all these reasons it is essential to have a relatively rapid and accurate measurement of seawater salinity. The obvious method... 

Whereas the composition of dissolved main solid compounds in seawater is rather constant all over the oceans, the freshwater in the Baltic Sea outbalanced by river discharge is dominated by calcium bicarbonate. For this reason, significant anomalies are observed in Baltic waters from the standard composition of seawater (Nehring and Rohde, 1966), in particular in the brackish surface water, with amount increasing toward the eastern and northern margins of the Baltic Sea. Directly measured densities of Baltic water compared with density determined from the seawater equation of state with Baltic water salinity measured by chlorinity titration resulted in a deviation of up to 0.123 kg/m (Millero and Kremling, 1976). This may result in uncertainties in estimating the thermodynamic properties of Baltic water, for example, the vertical stability. 

High accuracy salinity measurements (0.002) require knowledge of the interpretation of standard seawater measurements (Section 3.5.2), and careful sampling, storage and logging (Sections 3.5.3 and 3.5.6). Along with Section 3.5.4 on the operation of the AUTOSAL, these sections describe procedures as recommended for the WOCE (see Stalcup, 1991) with some supplementary instructions and remarks added. 

Earth s oceans Salinity is a measure of the mass of salts dissolved in seawater, usually measured in grams of salt per kilogram of seawater. Most salt in the ocean is dissociated into ions. 

Most of the published evidence suggests that marine fouling cover— particularly where it is continuous and well established — reduces corrosion rates of steels . Indeed, 35%o seawater is by no means the most corrosive of saline environments towards steel. Brackish water, as found in estuarine or certain other coastal areas, is considerably more aggressive towards steel, and careful design measures should be taken to ensure that effective corrosion control is achieved in such circumstances. 

Figure 1. Schematic cartoon for idealized estuarine mixing of a dissolved component versus salinity, which serves as a conservative measure of the degree of mixing between freshwater and seawater. Redrawn after Berner and Berner (1987).

The saltiness of the ocean is defined in terms of salinity. In theory, this term is meant to represent the total number of grams of dissolved inorganic ions present in a kilogram of seawater. In practice, salinity is determined by measuring the conductivity of a sample and by calibration through empirical relationships to the International Association of Physical Sciences of the Ocean (IAPSO) Standard Sea Water. With this approach, salinity can be measured with a precision of at least 0.001 parts per thousand. This is fortunate, considering that 75% of all of the water in the ocean falls neatly between a salinity of 34 and 35. Obviously, these high-precision measurements are required to observe the small salinity variations in the ocean. 

The conductivity of solutions is measured as specific conductance, which may be expressed as omhos/cm or mmhos/cm at 25°C. Seawater has a specific conductance of about 50 mmhos/cm. Salinity shows a high correlation with specific conductance at low to moderate TDS levels, but the concentrations of ions in brines are so high that the relationship between concentration and conductance becomes ill-defined.64... 

The basis of this method is that when normal seawater is chlorinated at the usual levels of 1 to 10mg/l of chloride, the bromine in seawater (8.1 x 10 4 M, 65 mg/1 at salinity = 35%o) is rapidly and quantitatively oxidised to Br() and HBrO. If 50 mg/1 of bromide is added to distilled or fresh waters containing HCIO plus C1CT, then HBrO plus BrO" are both formed. The HBrO plus BrO" will in turn rapidly brominate fluorecein (9-[o-carboxyphenyl]-6-hydroxy-3-isoxanthenone) to give the pink tetrabromo derivative eosin yellow (2,4,5,7-tetrabromo-9-[o-carboxyphenyl]-6-hydroxy-3-isoxanthenone), provided the molar ratio of bromide to fluorescein is 4 1. The resultant increase in eosin can be measured visually or spectrophotometrically, and the decrease in fluo-roscein measured fluorometrically. If the molar ratio of bromide to fluoroscein is < 4 1, then the mono-, di-, and tri-bromo derivatives are formed repro-ducibly. These derivatives have extinction coefficients close to eosin and are accounted for in the standardisation. 

Spencer and Brewer [144] have reviewed methods for the determination of nitrite in seawater. Workers at WRc, UK [ 145] have described an automated procedure for the determination of oxidised nitrogen and nitrite in estuarine waters. The procedure determines nitrite by reaction with N-1 naphthyl-ethylene diamine hydrochloride under acidic conditions to form an azo dye which is measured spectrophotometrically. The reliability and precision of the procedure were tested and found to be satisfactory for routine analyses, provided that standards are prepared using water of an appropriate salinity. Samples taken at the mouth of an estuary require standards prepared in synthetic seawater, while samples taken at the tidal limit of the estuary require standards prepared using deionised water. At sampling points between these two extremes there will be an error of up to 10% unless the salinity of the standards is adjusted accordingly. In a modification of the method, nitrate is reduced to nitrite in a micro cadmium/copper reduction column and total nitrite estimated. The nitrate content is then obtained by difference. 

Khoo et al. [249] have reported on the measurement of standard potentials, hence hydrogen ion concentrations, in seawaters of salinities between 20 and 45%o at 5-40 °C. 

Howard [27] determined dissolved aluminium in seawater by the micelle-enhanced fluorescence of its lumogallion complex. Several surfactants (to enhance fluorescence and minimise interferences), used for the determination of aluminium at very low concentrations (below 0.5 pg/1) in seawaters, were compared. The surfactants tested in preliminary studies were anionic (sodium lauryl sulfate), non-ionic (Triton X-100, Nonidet P42, NOPCO, and Tergital XD), and cationic (cetyltrimethylammonium bromide). Based on the degree of fluorescence enhancement and ease of use, Triton X-100 was selected for further study. Sample solutions (25 ml) in polyethylene bottles were mixed with acetate buffer (pH 4.7, 2 ml) lumogallion solution (0.02%, 0.3 ml) and 1,10-phenanthroline (1.0 ml to mask interferences from iron). Samples were heated to 80 °C for 1.5 h, cooled, and shaken with neat surfactant (0.15 ml) before fluorescence measurements were made. This procedure had a detection limit at the 0.02 pg/1 level. The method was independent of salinity and could therefore be used for both freshwater and seawater samples. 

C-labelled cholesterol was used to test the recovery of 5-100 pg of faecal sterols from seawater (labelled coprostanol not being available). The radioactivity of the samples and eluates was measured by a two-channel liquid scintillation counter. Percentage recovery was calculated on the basis of the amount of labeled material recovered in the acetone eluant. The results indicate that column extraction efficiency is not adversely affected by the salinity of the water samples, i.e., in the range 95-97%. 

We turn our attention now to the hydrothermal brines of the Red Sea. An oceanic survey in 1963 discovered pools of hot, saline, and metal-rich brines along the axial rift of the Red Sea (Degens and Ross, 1969 Hoffmann, 1991). The dense brines pond in the rift s depressions, or deeps. The Atlantis II deep contains the largest pool, which measures 5 x 14 km and holds about 5 km3 of supersaline brine. The deep holds two layers of brine. The lower brine contains about 25 wt.% dissolved salts and exists at temperatures up to 60 °C. Table 6.8 shows the brine s average composition. A somewhat cooler, less saline water overlies the lower brine, separating it from normal seawater. 

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