Development of Salinometers

SalinityBridge1
Wenner-Smith-Soule Salinity Bridge

Salinometer is an instrument for the determination of salinity of sea water aboard ship or in the laboratory by an electrical conductivity method.

The first apparatus of this kind was constructed by the U.S. National Bureau of Standards in 1930 and is known as the Wenner-Smith-Soule Salinity Bridge. NBS engineer Frank Wenner and U.S. Coast Guard Oceanographers Ed.Smith and F.Soule introduced them in 1934 into a oceanographic practice of the International Ice Patrol Vessels. Salinity Bridge directly measured the ratio of conductivity between the standard sample and water by using two measuring contact cells. The cells were maintained at the same temperature. Salinity was calculated from the ratio of conductivity. This instrument provided measurements at least as precise as those obtained by the method of Knudsen but it was simpler and more faster to be used. The temperature has an important effect on conductivity of sea water. An increase in the temperature of 0.01°C the same effect on conductivity as an increase in salinity of 0.01. Currently the oceanographers need a precision of ±.003 or better in the deep ocean what brought the development of instruments of a higher degree of accuracy.

A.Bradshaw and K.Schleicher operating their salinometer
A.Bradshaw and K.Schleicher operating their salinometer

For example in 1956 Alvine Bradshaw and Karl Schleicher (Woods Hole Oceanographic Institution or WHOI), like in 1958 Roland Cox (National Institute of Oceanography, the U.K.), had developed laboratory salinometer made up of 2-electrodes conductivity cells in a bath of oil thermostat equipped with a heating, a refrigeration, an electronic control of temperature and a bridge of measurement of conductivity. Salinity was measured by comparing the conductivity of the taking away to be measured with that of standard sea water after balancing of the temperature of the two samples in the oil bath. These instruments were large, complex, heavy (more than 200 kg) and thus non-marketable. However they reached the necessary precision of ± 0.003. The equipment consists of the bridge-oscillator detector unit, a refrigerated oil-tight constant-temperature bath, seven conductivity cells mounted in the bath, a refrigerator unit and controls, a proportional-type temperature controller, a constant-voltage supply for the electronic parts, and a suction system for emptying the cells. The salinometer is calibrated in the laboratory by a lengthy series of measurements of Copenhagen water and other carefully prepared standard solutions whose salinities have been determined by repeated titrations. The final calibration may be expressed in graphic form at a large scale, or a salinity versus- resistance table may be computed. How often the calibration must be renewed is uncertain but should probably be done annually. When in use to measure salinities, one cell, called the reference cell, is filled with substandard sea water whose salinity has been determined by careful titration and the six measuring cells are filled with water from the samples. About 20 minutes are required to bring them to temperature equilibrium before measurement can begin. One of the measuring cells is then balanced on the bridge with the reference cell, the resistance reading is recorded and the procedure repeated with each of the six cells. Each sample is measured twice but in different cells. Salinities are obtained from the graph or tables using the resistance reading as an entering argument. The reference cell and water are compared with a standard daily or more frequently if the salinity drift requires it. When properly used the results are far more accurate than titrations at sea, salinity determinations can be made more rapidly, and the equipment can be satisfactorily operated with less-skilled personnel.

Brown
Neil Brown with his salinometer
Inductive cell of the Brown-Hamon's Salinometer
Inductive cell of the Brown-Hamon’s Salinometer

In 1961 Bruce Hamon and Neil Brown, who worked with the division of fishing and the oceanography of the Commonwealth Science and Industrial Research Organization (CSIRO) in Australia, designed a portable salinometer of an approximate weight of 15 kilogrammes. He used a thermistor and a bridge of resistances to compensate for in a precise way the effect of the temperature on the report/ratio of conductivity what avoided the use of an oil bath thermostated. This apparatus whose precision was of ± 0.003, was manufactured in great quantity. It used a sensor with induction placed in a plexiglass container. The cell containing standard water in the preceding apparatus was replaced by a branch of the bridge of measurement which it was necessary to gauge before passing the samples. In the high part of the container, an agitator allowed to maintain a good mixture quickly. Water was in contact with two thermistors. A thermistor was placed in the compensating network of the effect of temperature, the other thermistor measured the temperature of the sample with a precision of ± 0.1°C what made it possible to calculate which would have been the ratio of conductivity if measurement had been carried out with 15°C (or 20°C). It is indeed for this temperature that the equation was established – said  “equation of state of sea water” – which allows the calculation of salinity. The use of a sensor with induction in this salinometer eliminated the problems from drift existing with the cells with two electrodes. This drift is due to the impedance of polarization, identical to an electric resistance, which exists between each electrode and the sea water. The drift was reduced in an important way by using electrodes of turntable covered with passivated platinum. However, there remained a drift sufficiently important to frequently require a cleaning of the cells and a Re-calibration with standard sea water. The sensors of conductivity to induction consist of two superimposed toroidal transformers so that their central hole is aligned.

Hytech1
Bissett-Berman Hytech 6210 Portable Salinometer c.1964

 

The sea water surrounds them completely and filled the central hole so that that forms a whorl common to both transformers. An alternating voltage is applied to the one of the transformers what induces an electrical current in the sea water circuit. This current is proportional to conductivity. It is measured by the second transformer. Although these cells are more stable than the cells with two electrodes electric resistance causes minor instabilities which must be compensated by frequent calibrations.

Inductively coupled conductivity sensors consist of two toroid-shaped transformers mounted close together with their center holes aligned one above the other. Seawater completely surrounds both transformers and fills the center holes so that the seawater forms a current common to both transformers. An alternating-current voltage applied to one transformer induces an electric current in the seawater circuit proportional to conductivity. The induced current is measured by the second transformer. Although these cells are more stable than two-electrode cells, the electrical resistance the windings causes minor instability that must be compensated for by frequent recalibration.

 

 

Autosal8400A
Guildline Autosal 8400A c.1980

In 1975 Tim Dauphinee (National Research Council of Canada in Ottawa) designed a laboratory salinometer  (commercially available as the AUTOSAL) that is still widely used by oceanographers today.  AUTOSAL uses a contact four-electrode cell immersed in thermostated bath as a means of avoiding the problem of drift caused by polarization. The four-electrodes cell is exactly analogous to a four-terminal resistor. The conductance is defined as the ratio of the current through the two current electrodes to the open-circuit voltage between the two potential electrodes: Defined this way, conductance is totally independent of the polarization impedance of any of the four electrodes.

T.M.Dauphinee with Autosal8400B, 2006

 

 

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