By Paul Ridout, Ocean Scientific International Ltd.
As published in Ocean Challenge, Vol. 9, No. 3
Mass balance equations have shown that the input of the major biologically active nutrients (nitrogen, phosphorous and silicon) to the ocean plays an important role in regulating global oceanic production. Most of these nutrients are terrestrial in origin, finding their way to the oceans via riverine and atmospheric pathways. Once in the marine system, nutrients are made available to biological organisms for primary production either through nutrient-rich water being drawn up from below, or by local regeneration resulting from cell breakdown. In surface waters of the open ocean, uptake of nutrients by organisms usually results in one or more of those nutrients becoming limiting to their growth (i.e. when the nutrient is used up, production ceases). However, coastal and estuarine waters are increasingly subject to anthropogenic input stress, whereby frequent input of nutrients as run-off from agricultural land results in artificially prolonged algal growth. In either case, the need for high-quality measurement of nutrients is driven by economic factors associated with climate change, depleted fisheries, eutrophication and aquatic ecosystems being out of balance.
Nutrients are measured using a variety of wet chemistry techniques, which generate a colour reaction measurable with a colorimeter or spectrophotometer. The technique involves adding a reagent (or reagents) to the seawater sample, allowing a colour to develop and then measuring the intensity of the colour against blanks and standards. Manual methods usually allow the colour to develop fully before measurement, whereas most automated methods (e.g. segmented flow analysis, flow injection analysis) provide partial colour development with time controls. Concentrations of nutrients are measured in optical cells (static or flowthrough), using a spectrophotometer tuned to defined wavelengths.
Quality assurance is an essential part of any chemical analysis. The measurement of nutrients in seawater has posed a number of difficulties, particularly in terms of matrix* interference and calibration. Ocean Scientific International (OSIL), who produce the IAPSO seawater standards for Practical Salinity, have been working for some years to develop seawater calibration standards for dissolved nutrients. This article describes that development and the current availability of reference materials and standards.
*The term ‘matrix’ refers to the chemical components of a sample (normally dissolved). Matrix interference results when these dissolved components of the sample affect the response of analytical instruments. If standards are made up in simple solutions, they often are not truly comparable with the samples being analysed.
Certified Reference Materials
The International Council for Exploration of the Seas (ICES) has drawn attention to an urgent need for the development of certified reference seawater for dissolved nutrients. Unfortunately, this occurred almost a decade ago at the meeting of the IOC-IAEA-UNEP Group of Experts on Standards and Reference Materials (GESREM) and to date, no such material has appeared.
A certified reference material (CRM) is a material or substance, one or more properties of which are sufficiently well established and certified to be used for the calibration of an apparatus. In many laboratories, a CRM is analysed, as a sample, to determine the accuracy of analysis as part of a quality assurance scheme. In the case of nutrients, the ideal CRM would be a natural seawater, which has been analysed for, dissolved nutrients by more than one method, with confidence limits provided for the nutrients in question.
One of the main problems encountered in the production of a CRM, has been the stability of the product. Biological and chemical activity can lead to changes in nutrient concentrations over short periods of time. Various forms of chemical preservatives have been used, including organic solvents, formalin, potassium cyanide, sodium fluoride, various acids and mercuric chloride. Most fixatives / preservatives prevent growth of biological organisms, thereby stabilising the solution. Some chemicals that lower the pH (e.g. acids) also serve to maintain some components in solution.
The use of additives is generally undesirable as it changes the matrix of the reference. In addition, mercuric chloride, the most commonly used poison, is known to degrade the efficiency of the cadmium reduction columns on some nitrate analysers. There are also problems associated with the handling and transport of solutions containing such toxic compounds. As a result, some workers have investigated the use of heat as a means of preserving nutrient concentrations in seawater. Uncertified reference materials have been produced for dissolved nutrients in seawater by the Quasimeme Project (see Further Reading). These materials, which comprise seawaters spiked with nutrient salts, are provided as part of a laboratory performance study. The Quasimeme Project preserves mixed nutrients in seawater by autoclaving the samples.
Although reference materials are important in quality assurance, the preparation of working standards is a fundamental component of any chemical analysis. OSIL has been studying the feasibility of producing commercially available working standards for nutrients in seawater. A number of products were already available from other sources, but none offered a natural seawater matrix at salinity 35.
The need for nutrient standards
The need for seawater nutrient standards has intensified in recent years, with international programmes such as WOCE requiring high-quality nutrient data to be collected at sea. Most shipboard analyses are carried out using automated chemistry systems, which measure nutrients colorimetrically. The kinetics of the chemistry of these techniques, and often the ultimate colour intensities, are generally affected by the presence of seawater matrix salts. Elimination of these salt effects requires that working calibration solutions be prepared in natural low nutrient seawater (LNS) rather than in demineralised water. The WOCE protocol produced by Gordon and colleagues (see Further Reading) stated a preference for the production of working standards in natural low nutrient seawater (LNS), but recognised that artificial seawater may suffice when LNS is unavailable. In continuous-flow analysis, LNS can also be used as a refractive index (RI) blank. This is to correct for a false positive absorbance signal generated by refraction effects within the flow cell when saline samples are run with a demineralised water baseline and inter-sample wash.
Low Nutrient Seawater
The first requirement of a standard for nutrients in seawater, is the seawater matrix itself. It must be significantly lower in nutrients than the required standard concentration. This is particularly difficult for open ocean measurements where analyte levels can be lower than 1 µm because of depletion by plankton. Low Nutrient Seawater (LNS) can be prepared naturally or artificially. OSIL regularly collects relatively large quantities of seawater from the mid-Atlantic Ocean in order to operate the IAPSO Standard Seawater Service, and has investigated methods for depleting the nutrient content.
Chemical removal, using co-precipitation techniques with iron and aluminium compounds, was found to be effective in terms of nutrient depletion, but the subsequent removal of the precipitate proved difficult and costly. Biological depletion using an inoculum of plankton to create an artificial ‘bloom’ in the bulk seawater was occasionally successful, but was unreliable due to the difficulty of controlling conditions for growth. As a result, OSIL has now standardised on a practice of measuring each batch of bulk seawater for dissolved nutrients and reserving the batches with very low concentrations for bottling. This LNS has the advantage of being depleted naturally which, combined with our processing /bottling regime, gives rise to a very stable product. The LNS fulfils all the needs of a seawater matrix for the preparation of standards, carrier solution and RI blank.
Initial attempts to produce ‘mixed’ nutrient standards in LNS gave rise to problems of preservation. Although we were able to stabilise the product using mercuric chloride, this was considered undesirable by many users, for the reasons described earlier. Another problem that arose was defining the most useful working concentrations of the nutrients. It became obvious that it would be commercially uneconomical to produce the wide range of standards necessary to meet all user needs.
The problems described above led to the production of a range of marine nutrient standard kits (MNSK). These comprise concentrates of single nutrients in deionised water, together with bottles of Low Nutrient Seawater (LNS) (see Table 1 and photograph below).
Table 1 Marine Nutrient Standard Kits
The user dilutes the concentrate with the LNS to provide working standards. This method overcomes problems with preservatives, as the concentrates of single nutrients in deionised water, and the LNS, are stable for long periods. However, once diluted, the working standards should be used immediately after preparation. The concentrate method also allows the users to define their own working concentration range, thereby overcoming the need for a wide range of products. Although confidence limits are given for nutrient levels in the concentrates and the LNS, the final working standard concentration is dependent on the dilution made by the user.
Although our standards may be used as working calibration standards, many laboratories make up their own standards using nutrient salts, and incorporate our standards as quality assurance (QA) samples. As a result of requests by users, we now offer Performance Evaluation (PE) samples for dissolved nutrients and salinity. These PE samples are supplied, ‘unknown’, to analysts who include them in a normal analysis run. After analysis, the measured value for each PE sample is forwarded to our laboratory where a certificate is issued showing the true value and the analytical error.
The need for a certified reference material still exists for nutrients in seawater. However, data quality for marine nutrients can be improved by the careful selection of standards, carrier solutions and performance evaluation samples.
Aminot, A., Kerouel, R. (1991) Autoclaved sea water as a reference material for the determination of nitrate and phosphate in seawater. Anal. Chim. Acta, 248, 227-83.
Gordon, L.I., Jennings Jnr., J.C., Ross, A.A., Krest, J.M. (1992) A suggested protocol for continuous flow automated analysis of seawater nutrients. WHPO, Methods Manual.
Kirkwood, D.S. (1992) Stability of solutions of nutrient salts during storage. Mar.Chem., 38, 151-64.
McElroy, M.B. (1983) Marine biological controls on atmospheric CO2 and climate. Nature, 302; 328-9.
Topping, G (Ed.) (1997) Quasimeme quality measurement for marine monitoring. Review of the EU Project 1993-1996. Mar. Poll. Bull., 31, 1-6
Salinity is one of the most measured parameters in oceanography. The importance of high quality salinity data has long been recognised in open ocean studies and more recently in coastal and estuarine processes. Many of the data are collected using in-situ instrumentation but the measurement of salinity in the laboratory also remains an important and widely used technique. This article describes the methodology used in the high precision, accurate measurement of Practical Salinity in the laboratory.
Why do we Measure Salinity?
In recent years salinity data has provided important information in the study of climate change. Large transects of the ocean using Conductivity, Temperature and Depth (CTD) profiles have helped to improve the understanding of ocean circulation and water mass movements which are critical factors in the influence of global weather. Improving our knowledge of sea surface salinity also leads to a better estimation of the global hydrological cycle and will aid in the prediction of possible climate change events such as the reversal of the North Atlantic Deep Flow.
Salinity measurement continues to play an important role in other aspects of oceanography. The passage of sound in seawater is dependent on the density and hence the salinity of that water. Activities involving SONAR devices rely, at some stage, on an accurate measurement of salinity in order to obtain meaningful data. Such applications include seabed mapping, submarine detection and bathymetry.
It should be remembered that salinity data are also important in coastal and estuarine waters. Being a natural parameter, which changes significantly with every tidal cycle, salinity can play a useful role in assessing the dynamics of a coastal or estuarine location. Such applications are used, for example, to predict the fate of effluents from industry or sediments during dredging operations.
Salinity also plays an important role in biological processes affecting algal blooms, fish movements, shellfish productivity and aquaculture.
Early Work on Salinity Measurement
Early work in measuring the saltiness of the sea involved techniques utilizing weighing after evaporation (Boyle,1693; see Birch, 1965), solvent extraction (Lavoisier, 1772) and precipitation (Bergman, 1784). It was Forchhammer (1865) who introduced the term salinity and the concept of measuring one parameter, chloride (in reality total halide), from which the salinity could be calculated. This work was supported further by Dittmar (1884) who analysed over 75 samples from the Challenger Expedition to establish the theory of ‘Constant Composition of Seawater’. Further work by Knudsen et al(1902) resulted in a new definition which stated that Salinity was “The total amount of solid material in grams contained in one kilogram of seawater when all of the carbonate has been converted to oxide, all the bromine and iodine replaced by chlorine and all the organic material oxidised”.
It was at this time that Knudsen introduced the Standard Seawater Service to supply (natural) seawater standards to workers measuring salinity. This innovative forethought has led to the high degree of comparability in salinity data from workers world-wide for over a century ( Culkin and Smed, 1979). This service is currently operated, in the UK, by Ocean Scientific International Ltd. who supply IAPSO Standard Seawater to salinity workers in over 75 countries world-wide, who depend on the reliability of this common standard (Culkin and Ridout, 1997).
These methods remained dominant until the 1950s when conductivity was introduced as a practical means to measure salinity. A conductivity based salinometer was developed for the International Ice Patrol that was capable of measuring salinity to better than 0.01 ppt (Emery and Thomson, 1998). It contained six thermostatically controlled conductivity cells and was claimed to have reached a precision of 0.003 ppt. (Cox, 1963). Various salinometers were developed during the 1950s and 1960s (eg Hamon; 1955;) and new relationships were produced for conductivity and salinity (Culkin,1979, Millero et al.,1977; Poisson et al, 1978).
In 1978 the break with chlorinity was sealed with the introduction of a new conductivity-based definition by the Joint Panel on Oceanographic Tables and Standards (JPOTS). This new definition, which is current today, states that ‘ a seawater of salinity 35 has a conductivity ratio of unity with of 32.4356 grams of Potassium Chloride in 1 kilogram of solution at 15 C and 1 atmosphere’. The standard concentration of KCL was derived from measurements carried out on one batch of Standard Seawater, weight diluted and evaporated (Lewis,1980; see Unesco Technical Papers No. 37, 1981). Also included were measurements of absolute conductivity carried out at the Institute of Oceanographic Sciences, Wormley, UK (Culkin and Smith, 1980).
The introduction of the Practical Salinity Scale 1978 (PSS78) resulted in some significant operational changes. One change has been the abolition of units due to the adoption of a scale. Previous methods had resulted in concentration units such as parts per thousand (ppt) being used but these were no longer valid. The correct way to report Practical Salinity is as a number ( eg the sample had a salinity of 35) possibly with reference to PSS78. However the move away from units has proved so difficult for some to accept that a new unit, the Practical Salinity Unit (PSU), has been unofficially introduced. In true terms of the PSS78 the PSU is not valid but it is widely used and often not rejected by journal editors.
The first version of the modern conductive salinometer was developed by Dauphinee in 1975 who produced a 4 electrode (platinum) cell located in a temperature controlled bath. This gave rise to the widely accepted ‘industry standard’ salinometers (Autosal and Portasal), produced by Guildline Instruments Ltd., which achieve a quoted accuracy of +-0.002 in Practical Salinity. This proved to be important in the World Ocean Circulation Experiment (WOCE) during the 1990s which produced the largest set ever high precision salinity data from the world oceans. This level of accuracy is now widely accepted as the desirable goal for all salinity data from the open ocean.
The quality and comparability of the millions of salinity data points accumulated over the past century depend largely on the widespread use of a single source calibration standard, IAPSO Standard Seawater (SSW). As approved by the International Association for the Physical Sciences of the Ocean (IAPSO), SSW is now used as a reference standard in the measurement of the electrical conductivity (and hence salinity) of seawater. The label value of the standard shows the Conductivity Ratio at 15 degrees C (K15) which is used to calibrate the salinometer. The expanded uncertainty of the K15 value was found to be 1x10–5, based on a coverage factor of 2 (Bacon et al, 2007 in press) which is equivalent to 0.0003 in salinity. This allows meaningful measurements to be made with an accuracy of +- 0,002 in salinity which is of particular importance when tracking micro-scale differences in ocean salinity in, for example, ocean circulation studies.
Bacon, S., F. Culkin, N. Higgs and P. Ridout, 2007: IAPSO Standard Seawater: Definition of the Uncertainty in the Calibration Procedure, and Stability of Recent Batches. J. Atmos. Oceanic Tech., in press.
Bergman, T., 1784. Physical and chemical essays (translated by Edmund Cullen) Murray, London, 2 vol.
Birch, T. (ed.), 1965. The works of Robert Boyle. Georg Olms, Hildeschiem, 6 vol.
Boyle, R., 1693. An account of the honourable Robert Boyle’s way of examining waters as to freshness and saltness. Phil. Trans. Roy. Soc. Lond., 17, 627-641.
Cox, C.A., 1963. The salinity problem. Progress in Oceanography, 1, 243-261
Culkin, F., 1979, Calibration of Standard Seawater in Electrical Conductivity., Sci. Total Environ., 49, 1-7.
Culkin, F., and Smed, J., 1979, The History of Standard Seawater, Oc eanol. Acta., 2, (3), 355-364.
Culkin, F., and Smith, N.D., 1980, Determination of the Concentration of Potassium Chloride Solution having the same Electrical Conductivity, at 15oC and Infinite Frequency, as Standard Seawater of Salinity 35.0000%0 (Chlorinity 19.37394%0).
Culkin, F., and Ridout, P. S., 1997, Stability of IAPSO Standard Seawater, J. Atmos. Oceanic. Technol., 15, 1072-1075.
Dittmar, W., 1884. Physics and Chemistry, Rept. Scient. Res. H.M.S. Challenger 1873-76, 1, 251 pp.
Emery, W.J. and R.E. Thomson, 1998. Data Analysis Methods in Physical Oceanography. Pergamon Press, New York, 634 pp.
Forchhammer G. (1865) On the composition of seawater in different parts of the ocean.
Philos. Trans. R. Soc. London. 155, 203-262.
Hamon, B.V., 1955. A temperature-salinity-depth recorder. Conseil Permanent International pour le Exploration de la Mer. Journal de Conseil, 21, 22-73.
Knudsen, M., C. Forch and S.P.L. Sorensen, 1902. Bericht uber die chemische und physikalische Untersuchung des Seewassers und die Aufstellung der neuen hydrographischen Tabellen Wiss. Meeresunters, n.f., 6, 13-184.
Lavoisier, A. 1772. Memoire sur l’usage de esprit-de-vin dans l’analyse des eaux minerales, Mem. Acad. Roy. Sci. (Paris), 1772, 555-563
Lewis, E.L., 1980. The practical salinity scale 1978 and its antecedents. J. Oceanic Engineering, 5, 3-8.
Millero F.J., Chetirkin, P., Culkin, F., 1977. The Relative Conductivity and Density of Standard Seawaters, Deep-Sea Res., 24, 315-321.
Poisson, A., Dauphinee, T., Ross, C.K., Culkin, F., 1978. The Reliability of Standard Seawater as an Electrical Conductivity Standard, Oceanol. Acta, 2, 425-433.
Unesco 1981, Background Papers and Supporting Data on the Practical Salinity Scale 1978, Unesco Technical Papers in Marine Science, No.37, Division of Marine Sciences, Unesco, Place de Fontenoy, 75700, Paris, France.
IAPSO Standard Seawater is now only available in bottles. The ampoules were phased out during 2002 and should not still be in use.
Thoroughly shake bottle before opening
To open bottle simply remove metal crimp cap and take out stopper
Use the standard immediately after opening
Salinometer standardisation with Standard Seawater should be made regularly during analysis runs to monitor machine drift. The frequency of standardisation depends on individual machine stability and the level of accuracy required. As an absolute minimum, standards should be measured at the beginning and end of each sample set.
We recommend that Standard Seawater be stored at a temperature between 8 and 25°C. It is advisable to avoid extremes of temperature, particularly freezing, as this can lead to precipitation of salts which will not readily dissolve on thawing.
Our laboratory studies have shown that IAPSO Standard Seawater, in bottles, remains in calibration for at least three years after the calibration date. Culkin & Ridout (1998) showed changes equivalent to less than 0.001 in salinity in the label value, for these new-style borosilicate bottles, after 158 weeks storage. The older style soda glass ampoules stayed within specification for at least 18 months which was the time-limit of the experiments.
As well as the 35 salinity seawater (P-Series), additional standard seawaters are available with salinities of 38 (38H-Series), 30 (30L-Series) and 10 (10L-Series). These are used in conjunction with normal Standard Seawater (P-Series) to provide additional calibration points which can improve accuracy on high and low salinity samples.
Culkin, F. and Ridout, P.S. (1998), Stability of IAPSO Standard Seawater, j.atmos. & oceanic tech., 15, 1072-1075
Preparation: Surface seawater is collected from the North Atlantic and then pumped through filters (0.2mm) into a PVC lined tank and thoroughly mixed. Once purified by filtration and UV irradiation, distilled water is added to adjust the salinity, and the water is sealed in pre-washed glass bottles (capacity ca.200cm3).
Calibration: The electrical conductivity ratio of each batch is compared to that of a defined standard potassium chloride (KCl) solution using a modified high precision salinometer.
In accordance with the recommendations of the UNESCO, ICES, SCOR, and IAPSO Joint Panel on Oceanographic Tables and Standards (UNESCO Technical Papers in Marine Science, No. 36, 1981) the Standard Seawater label displays a conductivity ratio (K15) value where:
K15 = (Conductivity of Std. Seawater at 15oC and 1atm.) /(Conductivity of KCl soln. (32.4356g/kg) at 15oC and 1 atm.)
Each Standard Seawater batch is directly traceable to the standard defined KCl solution.
Calculation: Conductivity ratios should be converted to Practical Salinities using the current International Oceanographic Tables, Volume 3, and the equations contained therein (UNESCO Technical Papers in Marine Science, No.39).
Salinometer calibration for measurement of oceanic samples is traditionally carried out using IAPSO Standard Seawater (salinity = 35). For measurement of samples of higher and lower salinity, OSIL produce standards at salinities of 10, 30 and 38. Salinometer linearity checks provide a useful diagnostic tool in assessing the function of a salinometer and are routinely carried out at the OSIL Service Centre. Offset values can be used to improve the accuracy of measurements made away from 35 salinity. A large offset away from the 35 salinity point can be indicative of electronics misalignment, cell ageing or temperature bath malfunction.
A typical procedure for linearity correction would be:
1) Standardise the salinometer with P-series Normal Standard Seawater (Salinity 35)
2) Measure the salinities for 38H-series, 30L-series and 10L-series Standard Seawaters
3) Calculate the difference between the measured value and the label value for each of these standards i.e. measured value-label value = salinometer offset
4) Plot a graph of offset at each salinity (a linearity curve).
5) Use the plotted offset data to correct salinity measurements away from salinity 35 e.g. in the example below at salinity 10 the offset is -0.004 in salinity, therefore add 0.004 to your measured values around 10.
NOTE: Guildline Autosal accuracy specified as better than +/- 0.002 in salinity over the working range (2-42) Guildline Portasal accuracy specified as better than +/- 0.003 in salinity over the working range (2-42)
Shelf-life : Our laboratory studies have shown that IAPSO Standard Seawater, in bottles, remains in calibration for at least three years after the calibration date. Culkin & Ridout (1998) showed changes equivalent to less than 0.001 in salinity in the label value, for these new-style borosilicate bottles, after 158 weeks storage. The older style soda glass ampoules stayed within specification for at least 18 months which was the time-limit of the experiments.
Reference: Culkin, F. and Ridout, P.S. (1998), Stability of IAPSO Standard Seawater, j.atmos. & oceanic tech., 15, 1072-1075
IAPSO Standard Seawater is the only internationally recognised calibration standard for the measurement of Practical Salinity as approved by all the major oceanographic bodies (ICES, IOC Unesco, SCOR,etc) and is endorsed by the International Association for Physical Sciences of the Ocean (IAPSO).
The current definition for Practical Salinity states: a seawater of Practical Salinity 35 has a conductivity ratio of unity at 15 degrees Centigrade (and 1 atmosphere pressure) with a potassium chloride (KCl) solution containing a mass of 32.4356 grams of KCl per kilogram of solution.
Measurements were made on weight diluted and weight evaporated Atlantic seawater to establish the Practical Salinity Scale 1978 (PSS78) which is still in use today. At that time the following points were also made…
Although the basis of the conductivity ratio is the conductivity of a defined KCl solution, in practice it is necessary to use a seawater calibrated against the KCl standard. (i.e. IAPSO standard Seawater).
Therefore, the primary standard for Practical Salinity is the defined KCl solution and the transfer standard is IAPSO Standard Seawater which is prepared only by OSIL . OSIL are ISO9002 accredited for the preparation and calibration of salinity standards, therefore all the measurements of mass, resistance and temperature are traceable to national and international standards.
It is worth noting that when the Practical Salinity Scale was introduced in 1978 the link with chlorinity was broken and salinity became a dimensionless quantity thereby eliminating any units (part per thousand etc.). The more recently introduced PSU (Practical Salinity Unit) is also invalid.
Also, all temperature measurements on the Practical Salinity Scale were made on the International Practical Temperature Scale of 1968 (IPTS68) and this remains even though a new international temperature scale was introduced in January 1990 (ITS90). There is some argument that the current definition of salinity should be changed to reflect the new temperature scale and even though the equations have been calculated by scientists from OSIL and one or two institutes, this remains unimplemented.
A check of the calibration of 10 batches of IAPSO Standard Seawater (P120-P129) against the defined KCl standard (Practical Salinity Scale 1978) showed differences of less than 0.001 in salinity (equivalent to ca. 0.00003 in K15) during storage periods of up to 96 weeks. An experimental batch stored in borosilicate bottles showed no significant difference from the seawater stored in glass ampoules over a storage period of 158 weeks.
Standard seawater (SSW) has been employed by oceanographers as a reference material in the determination of salinity for over a century. In all that time, this is the first study to determine the uncertainty of the SSW manufacturing process. SSW is calibrated in reference to carefully prepared solutions of potassium chloride (KCl). All uncertainties in the preparation and measurement of KCl solutions and of new SSW are calculated. The expanded uncertainty of the SSW conductivity ratio is found to be 1 x 10-5, based on a coverage factor of 2, at the time of manufacture. There is no discernible “within batch” variability. No significant variability of quality within or between batches of KCl is found. Measurement of SSW “offsets” from the label conductivity ratio as long as 5 yr after the SSW batch manufacture are
reported, and no significant change in label conductivity ratio for SSW batches P130 through P144 outside the expanded uncertainty of 1 x 10-5 is found. This last result is in contrast to some other studies, and herein are suggestions as to why this may be the case.
National Oceanography Centre, Southampton, Southampton, United Kingdom
Fred Culkin, Nigel Higgs, and Paul Ridout
Ocean Scientific International Ltd., Havant, United Kingdom
Atlantic Seawater is prepared from natural open-ocean water collected from the surface waters of the mid-Atlantic. It is treated with ultra-violet light and filtered to 0.2 microns to minimise microbial contamination. However this product is not classified as sterile.
The chemical composition of Atlantic Seawater will be similar to published data for open-ocean seawater (see example table below) although the concentrations of some of the minor elements may vary as a result of processing and storage.
Salinity is a key variable in the modelling and observation of ocean circulation and ocean-atmosphere fluxes of heat and water. In this paper, we examine the climatological relevance of ocean salinity, noting fundamental deficiencies in the definition of this key observable, and its lack of a secure foundation in the International System of Units, the SI. The metrological history of salinity is reviewed, problems with its current definitions and measurement practices are analysed, and options for future improvements are discussed in conjunction with the recent seawater standard TEOS-10.
This is part 2 of a series of companion papers (Feistel et al2016, Dickson et al2016, Lovell-Smithet al2016) examining metrological challenges for measurements of key climatological observables; in this paper we examine seawater salinity. Salinity is a term used to quantify the total mass of inorganic substance dissolved in pure water to form a given mass of seawater. During the last century, only two methods of measuring this total mass were successfully exploited to establish salinity scales that were officially adopted by oceanography, namely by drying a sample and weighing the residue (Forch et al1902), or by carrying out a complete chemical analysis of the sample’s composition and adding up the constituent masses (Millero et al2008). Neither method is appropriate for the frequent and regular measurements required in oceanographic studies. In addition, the two methods are also known to result in numerically different values for the same seawater (Millero et al2008), partly because of insufficient knowledge of chemical changes that occur during drying at high temperatures over several days.
Despite the problems of measuring the dissolved content directly, salinity as a conserved seawater property (IOC et al2010), now classified as an ‘Essential Climate Variable’ (GCOS 2010), is a key variable for ocean modelling and observation. In practice, salinity has therefore been officially defined until recently by specific measurement techniques applied to a proxy property. Since 1978 this proxy has been the electrical conductivity, and the technique has been a measurement of electrical conductance relative to that of a bottled standard reference material called IAPSO Standard Seawater (SSW), which is officially approved for this purpose by the International Association for the Physical Sciences of the Oceans (IAPSO). SSW in turn is calibrated relative to the conductance of a potassium chloride (KCl) solution of specified concentration. A relative conductance measurement using the same instrument for the comparison is necessary because it provides a significantly lower uncertainty than (absolute) conductivity measurements. An uncertainty level of 0.002 g kg−1 in dissolved mass fraction (i.e., a relative uncertainty of 6 × 10−5for typical seawater with a dissolved mass fraction of about 35 g kg−1) is required for routine research and monitoring purposes (SUN 1985, King et al2001, Seitz et al2011). On the other hand, the tabulated KCl conductivity standard (Pratt et al2001), which provides an electrical conductivity value traceable to the International System of Units (SI), has a larger relative uncertainty of 2 × 10−4. One problem with this operational definition is that the relative chemical composition of seawater changes slightly from place to place in the ocean, and such changes, which can measurably affect other physical properties of seawater, cannot be determined with knowledge of the proxy only.
Significant efforts have been made to ensure consistency of salinity measurements over the past century by both the use of SSW and the development of standard protocols. Unfortunately, no robust link has yet been established between any of the salinity definitions and the International System of Units (SI), despite the fact that Practical Salinity defined by the 1978 Practical Salinity Scale (Unesco 1981a) was recommended for oceanography in the context of SI units (SUN 1985, Siedler 1998). Thus there are potential problems with the long-term stability and intercomparability of salinity measurements. Here we discuss the history of oceanic salinity measurements, technical details of current practices and their deficiencies, and a suggested plan for remedying them. We begin by briefly outlining the climatological relevance of ocean salinity.
2. Climatological relevance
The concentration of dissolved substances, that is, seawater salinity, varies from place to place, and from time to time at specific places in the ocean. Salinity changes occur as a result of mixing processes in the water column and, more dramatically, by precipitation and evaporation at the surface, by freezing and melting of sea ice, and by freshwater discharge from rivers and glaciers. Much smaller changes also occur due to biogeochemical processes in the ocean related to the uptake of inorganic matter into living organisms near the surface, and its remineralization from sinking detritus at depth (Pawlowicz et al2011). Oceanic composition and salinity changes may also result from increased atmospheric CO2 (Bender 2013, see also Dickson et al2016, Part 3 of this issue).
The oceans play an important role in redistributing heat and water over the Earth. Most of the Earth’s free water (97%) is stored in the oceans, and 75 to 90% of the Earth’s surface freshwater fluxes occur at the ocean-atmosphere interface (Durack et al2013). The oceans also export 50 to 90% of absorbed solar energy to the atmosphere in the form of latent heat associated with evaporation of water (Josey et al1999, 2013, Emery et al2006, Pierrehumbert 2010, Feistel and Ebeling 2011, Wells 2012). The related global hydrological cycle is reflected in the distribution of sea-surface salinities. Arid regions in the trade-wind belts show higher, and humid regions at the equator and at mid-latitudes lower salinities than the global average. While observations of latent heat fluxes are technically demanding and subject to large uncertainties, on the order of 20% or 30 W m−2 (Katsaros 2001, Josey et al2013, Lovell-Smith et al2016, part 4 of this issue), local long-term trends in salinity are precisely measureable indicators for climatic changes in the terrestrial water cycle and its sensitivity to global warming (Durack and Wijffels 2010, Durack et al2012, 2013, Pierce et al2012). However, surface salinity is also affected by various processes other than evaporation or precipitation (Josey et al2013).
Ocean currents also transport vast amounts of heat polewards within the ocean. Oceanic heat is most usefully quantified in thermodynamic terms defined by the Thermodynamic Equation of Seawater 2010 (TEOS-10, see McDougall 2003, IOC et al2010, McDougall et al2013, Feistel et al2016, Part 1 of this issue). As an illustration, the Gulf Stream alone carries about 1.3 PW to the North Atlantic across a zonal section along 26 °N (Bryden and Imawaki 2001), which corresponds to about 1% of the global solar irradiation, or to roughly 100 times the total human power consumption of 14 TW (Lu et al2009). While surface currents are mostly wind-driven, advection at depths below 100 m or so is almost entirely caused by pressure gradients resulting from differences in sea level and water density, and is deflected by the Coriolis force and topographic obstacles. Salinity has a strong effect on density, which is particularly relevant in cold high-latitude and deep ocean regions, and hence salinity deviations can modify heat transports. An important scientific use of measured salinity values is to estimate the density of seawater (in conjunction with the measured temperature and pressure), using an equation of state. Seawater equations of state are empirical correlations determined from careful laboratory measurements on SSW.
Typically, an increase of 0.01 g kg−1 in Absolute Salinity, SA (see section 4 for a precise definition), leads to a relative increase of 8 × 10−6 in density, ρ, as a result of the haline contraction coefficient,
which varies in the range between 0.66 at great depths and 0.83 at the surface. A relative uncertainty in the range of 1 × 10−6 to 4 × 10−6 is at the resolution limit of today’s oceanographic density measurements, see section 5.
3. Brief history
It has long been known that common salt (sodium chloride, NaCl) is the predominant solute in seawater. The concentration of halides; principally chloride, but also including bromide and iodide, can be measured by determining the mass of the precipitate or of the silver required in titration with a silver nitrate (AgNO3) solution. The chlorine equivalent of this result is termed chlorinity (Cl). Early chemical analysis (Marcet 1819, Forchhammer 1865, Dittmar 1884) revealed that the ratios to Cl of the mass fractions of the remaining major seawater solutes are, to a good approximation, the same in all oceans and at all depths, suggesting measurements of Clcould be scaled to estimate total solute. In order to do this, the Danish chemist S P L Sørensen dried nine seawater samples of known chlorinity and weighed the residue (Forch et al1902). Six of the samples came from the Baltic Sea, and one each from the North Sea, North Atlantic, and Red Sea; none came from the South Atlantic, Indian and Pacific Oceans. The correlation derived from those results,
became known as the equation that defined Knudsen Salinity, SK, expressed as the mass fraction of precipitable salt in seawater. This definition was in practical use at least until 1969 even though it was already discouraged in a 1937 standard, when chlorinity was officially chosen to be the only variable to be used in describing the salt concentration in seawater.
In this 1937 oceanographic standard (Jacobsen and Knudsen 1940, Millero et al2008), the chlorinity was formally defined by the equation,
where Ag is the ratio of the mass of pure silver necessary to precipitate the halogens in seawater, to the mass of the seawater sample. The italicized symbols Cl and Ag for mass fractions were defined in earlier oceanographic standards and are not to be confused with the chemical symbols of the elements, Cl and Ag. For historical and chemical reasons, the value of Cl resulting from equation (3) does not exactly match the mass fraction of chloride in seawater, which is 0.998 9041 × Cl (Millero et al2008). The numerical conversion factor in equation (3) was fixed in the 1937 standard in order to eliminate from the calculation of Cl any effects resulting from gradual improvements in published values for atomic weights, which had by then already caused relative changes of 5 × 10−4 (Reeburgh 1966), and to ensure long-term comparability of the measurement results. Chlorinity can be measured with an uncertainty of 0.0004 g kg−1 by the Volhard titration method, and of 0.0002 g kg−1 by direct silver-mass comparison (Carritt 1963), although routine measurements typically have an uncertainty of around 0.01 g kg−1 (Lewis and Perkin 1978).
Routine titrations were standardized using SSW, which was distributed in sealed glass ampoules labelled with a batch number and the batch chlorinity. This reference material, originally proposed by Knudsen (Knudsen 1903) was produced in Copenhagen under the direction of F Nansen from 1902 to 1908, and then by Knudsen until 1948, all under the auspices of the International Council for the Exploration of the Seas (ICES). In 1948, the Association International d’Oceanographie Physique (now IAPSO) took over the responsibility for SSW, with H. Thomsen in charge of administration, and F. Hermann (who began as Knudsen’s assistant in 1941) in charge of preparation and calibration. Hermann subsequently took over all responsibility in 1960. When Hermann retired in 1974, the responsibility and equipment for producing SSW was transferred to F Culkin at the Institute of Oceanographic Sciences, Wormley, UK, who had collaborated with Hermann on chlorinity calibrations for some years (Culkin and Smed 1979). In 1989, responsibility was transferred to a private company, Ocean Scientific International Ltd, Havant, UK, under the direction of Ridout (who began as Culkin’s assistant). Since 2000, SSW has been distributed in crimp-sealed borosilicate bottles.
The salinity offset in equation (2), which implies that Knudsen Salinity values are not conserved when mixing with pure water, is caused by the fact that six of the nine samples analysed by Sørensen were taken from the Baltic Sea, into which additional dissolved salts (primarily lime) are discharged by rivers (Millero and Kremling 1976, Feistel et al2010a). For the open ocean this awkward feature was eventually corrected by introducing the Cox Salinity SC,
which coincides with equation (2) at the standard-ocean salinity of SC = SK = 35 g kg−1(Wooster et al1969, Lyman 1969), i.e. for seawater with a chlorinity of Cl = 19.373 94 g kg−1.
Traditionally, the mass fraction unit g kg−1 was expressed as ‰ (originally by Knudsen 1901), or as ppt (meaning part per thousand), and the use of these symbols is often taken to imply that they result from a chlorinity titration. While ppt or ‰ represent the same unit as g kg−1, the SI brochure (BIPM 2006) discourages the use of these symbols in new publications (e.g., for confusion with part per trillion). Different quantities should generally be distinguished by their symbols, not their units. According to this rule, the latest salinity definition (IOC et al2010) does not require a specific unit to be used exclusively.
Beginning in the 1950s, electrical conductivity measurements with sufficient accuracy were increasingly used to characterise the dissolved ionic content of seawater, in order to replace the less convenient silver titration procedure (although the earliest recorded usage of conductance measurements for this purpose dates to the 1920s, Wenner et al1930). Conductance ratio measurements were eventually established officially as the Practical Salinity Scale 1978 (PSS-78, Unesco 1981a), which is still the world-wide reference for salinity measurements, expressed in values of Practical Salinity, SP.
Although oceanographers typically use the term ‘conductivity’ (and/or ‘conductivity ratio’) for their measurements, some careful distinctions should be made. Conductivity is a property of seawater substance, depending on its chemical composition, temperature, and pressure, but is independent of the mass, shape, or surface properties of a given seawater sample. It is constant for applied signal frequencies up to the MHz range, where ion–ion interactions begin to be important. In contrast, conductance (the inverse of electrical resistance) is a measurement value obtained from a particular instrument, which also depends on the geometry of the measurement cell and, due to polarization effects at the electrode-solution interface, on the frequency of the applied measurement signal. These polarization effects, which typically dominate at applied signal frequencies under a few kHz (Schwan 1968, Ishai et al2013), arise mainly as ions accumulate near the electrodes, inducing an extra capacitance. Considering these effects even at higher frequencies is necessary at the uncertainty levels required in oceanographic research.
Conductivity can be calculated from a measured conductance value once the cell constant of the measurement cell has been determined for a particular measurement signal, which scales the measured conductance to the conductivity, and polarization effects eliminated. Typically, cells are calibrated using a measurement standard of known conductivity (Spitzer and Seitz 2011). The calibrated measurement is then sometimes called the specific conductance instead of the conductivity, although, confusingly, limnologists usually use the term ‘specific conductance’ to refer to a calibrated measurement only after it is also temperature-corrected to a reference temperature of 25 °C. This temperature correction is usually about 2% per °C (Wetzel 2001).
In metrological laboratories, the conductivity of a primary measurement standard (e.g., of a KCl solution), traceable to the SI, is determined using a cell in which the geometry is carefully determined by dimensional measurements which are used to calculate the cell constant from first principles. In addition, polarization effects on the measurement are avoided by using impedance spectroscropy. This involves making measurements with alternating current (AC) signals of different frequencies, typically of a few kHz for conductivities typical for seawater, identifying surface polarization effects by their spectral behaviour, and correcting for them by extrapolating to infinite frequency (Pratt et al2001).
Since impedance spectroscopy is not carried out in oceanographic instruments, and they are not calibrated using a traceable standard, it is more correct to say that they measure conductance ratios. It must be emphasized that the ratio of measured conductances between two solutions differing in conductivity or composition is not necessarily equivalent to the ratio of their conductivities because of the effects of polarization. This deviation can be minimized if the two solutions are at least similar in composition.
SSW, originally produced to standardize chlorinity titration, was then adapted to standardize the electrical conductance measurements required by PSS-78. There have been many investigations of the reliability of SSW for this purpose (Culkin and Ridout 1998, Bacon et al2000, 2007), and of apparent differences that occur in batch-to-batch comparisons (Park 1964, Mantyla 19801987, Aoyama et al2002, Kawano et al2006). For the SSW samples used to develop PSS-78, chlorinity was correlated with the dimensionless conductivity ratio K15 between SSW and a KCl solution with a solute mass fraction of 32.4356 g kg−1. This ratio was determined at 15 °C on the International Practical Temperature Scale of 1968 (IPTS-68) or 14.996 °C on the current International Temperature Scale of 1990 (ITS-90), and a pressure of one standard atmosphere. At the resulting values of K15, chlorinity was converted to Practical Salinity, SP(K15), by means of the formula (4) from which the unit ppt (or ‰) was then omitted to denote the conductivity-ratio measurement in contrast to chlorinity titration (a source of much confusion to non-specialists, who often append the officially discouraged descriptor ‘PSU’ for ‘Practical Salinity Units’ to unit-less numerical values of SP). A major reason for this decision was that ‘the numerical values of practical salinity would be similar to the numerical values of previous salinity data, when expressed in ‰’ (Unesco 1981b), that is, similar to Cox Salinity (equation (4)).
Since it was known as early as 1937 that SK (and hence also SC) numerically underestimate the real mass fraction of dissolved matter in seawater by about 0.5%, the new formal salinity variableSP was no longer considered to express a mass fraction (Unesco 1981b), although in practice it has often been used that way. For uniformity and comparability of measurement results, the use of chlorinity was discouraged in favour of SP because the stoichiometric relations that were used to derive equation (4) are violated for real ocean water, which often contains minor deviations in its chemical composition relative to that of SSW. The primary and most demanding purpose of oceanographic salinity measurements is the calculation of seawater density to estimate significant ocean currents driven by sometimes tiny horizontal pressure gradients. In real ocean waters, densities calculated using a correlation from SP turned out to be mostly closer to their true values than densities calculated from SC because changes in conductivity partially account for the effects of these minor deviations, which rarely include any halogens that would also affect chlorinity (Lewis and Perkin 1978).
Remaining errors in density calculations were considered to be mostly within the limits of accuracies thought to be attainable at the time in salinity determinations (±0.01‰). However, within a few years an uncertainty of ±0.002 was specified for open-ocean Practical Salinity measurements in the World Ocean Circulation Experiment (King et al2001); modern measurements are then at least an order of magnitude less uncertain than estimates of thermodynamic properties like density which are derived using Practical Salinities in an equation of state (Pawlowicz et al2012).
More recently, the recognition that conceptual problems with the existing Equation of State 1980 (EOS-80, Unesco 1981a) prevented the use of common thermodynamic quantities such as entropy and enthalpy in studies of oceanic heat transport led to the development of TEOS-10 (IOC et al2010). In addition to providing a better description of ‘heat’ (see Feistel et al2016, Part 1 of this issue), TEOS-10 also addressed a number of metrological and scientific issues with the existing PSS-78 definition of salinity, which will now be described in more detail.
4. Current definition and measurement practice
It has been and will remain established oceanographic practice to derive the Practical Salinity (PSS-78) of seawater from parallel in situ measurements of electrical conductance, temperature and pressure, converting these measurements to Practical Salinity by the procedures and correlation formula provided by PSS-78 (or its future update). Although the PSS-78 Practical Salinity is no longer an official definition of seawater salinity, it does represent a temperature and pressure-corrected conductance measurement which should continue to be reported and stored in national databases.
Conductance sensors are calibrated with respect to SSW samples of certified conductance ratioK15. PSS-78 is formally valid only when used with the temperature scale of 1968 (IPTS-68) over a temperature range of −2 °C to 35 °C, and it is only valid for seawater that has Practical Salinity between 2 and 42. A correction to take into account the numerical differences between IPTS-68 temperatures and current ITS-90 temperatures, which are usually less than 0.01 °C under oceanographic conditions, is implemented in TEOS-10.
The correlations provided by PSS-78 are purely empirical and were determined by statistically fitting equations to laboratory measurements over the stated range. Further corrections are known for precise measurements in more dilute seawater (Hill et al1986) and at slightly higher concentrations (Poisson and Gadhoumi 1993). The reduced accuracy of PSS-78 correlations when extrapolated to much higher temperatures and salinities has recently been investigated by Pawlowicz, (2012).
SSW is used as a reference substance in practice rather than KCl solutions because the variations of conductivity with temperature and, less significantly, with pressure are different between the two solutions, and to minimize biases from polarization effects. SSW is currently produced by a commercial organisation (Ocean Scientific International Ltd., UK, or OSIL), under the endorsement of the International Association for the Physical Sciences of the Oceans (IAPSO), and hence is also known more formally as IAPSO SSW. This IAPSO SSW consists of near-surface water that is obtained from time to time from a particular part of the North Atlantic, filtered, diluted with de-ionised water and UV-treated to remove organic material and particulate, and then bottled in airtight crimp-sealed borosilicate glassware (Bacon et al2007). It is labelled with a batch number (which has now reached P158, since numbering began in 1906). Since 1980 (batch P91), the K15 and the Practical Salinity of the batch is also indicated on the label.
The labelled K15 and Practical Salinity of IAPSO SSW is obtained by a series of conductance measurements at OSIL relative to KCl standard solutions, prepared using precise weights of Merck Suprapur® (or equivalent) KCl crystals, with the conductance ratio assumed to be equivalent to a conductivity ratio (Bacon et al2007). IAPSO SSW prepared by OSIL is the primary reference material to which all world-wide PSS-78 salinity measurement results are traceable (Seitz et al2011), although attempts have been made to produce a second SSW product, called Chinese Primary Standard Seawater, from independently created KCl solutions (Ma and Tian 2004, JCOMM 2014).
Although SSW is carefully manufactured to be a reference solution for PSS-78, it is metrologically problematic to have the definition of salinity rely on a particular measurement technique applied to a physical artefact that is derived from a natural source, changes with age, and depends on subtle details of the production process. Instead, it is more useful to separate the definition of a quantity from the set of instructions (‘mise en pratique’, see BIPM 2006) that in practice allows its measurement at the lowest level of uncertainty. Recently, as part of the development of TEOS-10, a first step was taken to move towards this separation. Instead of basing a salinity definition on a physical artefact, the best available stoichiometric data for the composition of SSW was used to define a fixed Reference Composition for seawater (given in table 1). SSW is now considered to be a physical realization of this tabulated Reference Composition, and the correlations of PSS-78 the best available estimate of the electrical properties of Reference-Composition seawater.
Table 1. Reference Composition of sea salt (Millero et al2008). The given mole fractions are exact by definition. Derived mass fractions are rounded to seven digits to the right of the period and may be subject to future updates of molar masses. Enclosed in brackets are uncertainties derived from the uncertainties of the 2005 IUPAC atomic masses (Wieser2006) that were used for the 2008 definition of sea salt. The sodium fraction is adjusted to satisfy the condition of electroneutrality.
Molar mass g mol−1
22.989 769 28(2)
18.998 403 2(5)
This redefinition in turn permitted the recalculation of the factor relating chlorinity, and in turn also Practical Salinity, to the solute mass fraction (Millero et al2008). The resulting salinity measure, obtained by adding up the mass of solutes in Reference-Composition seawater, was termed Reference-Composition Salinity, or abbreviated for convenience, Reference Salinity, SR. In SSW it can be estimated from a PSS-78 conductance measurement using:
Given the specified composition, the largest uncertainty in the relation (5) results from the uncertainty of the molar mass of naturally-occurring chlorine (Millero et al2008).
The exact mole fractions of the Reference Composition shown in table 1 are defined to provide the best estimate currently available for the stoichiometric composition of SSW; as a part of the TEOS-10 standard, it is the first officially endorsed chemical sea-salt model in the history of oceanography. Earlier seawater composition models differed slightly from it and from each other (Forchhammer 1865, Millero and Leung 1976, Millero1982, Feistel 2003). As the name suggests, it is intended as a fixed reference stoichiometry relative to which deviations found in real seawater can be described as small perturbations (Pawlowicz 2010, Feistel et al2010b, Pawlowiczet al2011). In fact the composition of bottled SSW is also suspected to vary slightly from batch to batch (Goyet et al1985), and both ocean waters and SSW contain many trace constituents (Kennish 2001) not included in the Reference Composition. However, although future work may result in more exact knowledge of the composition of SSW (of any vintage), this will not affect the definition of the TEOS-10 Reference Composition (Wright et al2011).
Consistent with table 1 and PSS-78, as expressed by equation (5), the Reference-Composition Salinity Scale (Millero et al2008) assigns a salinity of 35.165 04 g kg−1 to so-called KCl-normalised seawater. The latter term is used to describe any seawater sample (e.g., one whose chemical composition may differ from the Reference Composition) that has the same electric conductivity as a solution of potassium chloride (KCl) in pure water with the KCl mass fraction of 32.4356 g kg−1 when both are at the ITS-90 temperature t = 14.996 °C and standard atmosphere pressure, p = 101 325 Pa. Thus by definition, the Reference Salinity of a given sample remains unaltered if the pressure or temperature of the sample is changed, and is scaled by the mass fractions if pure water (assumed to have zero salinity) is added or removed. Pure water is understood to have the isotopic composition of Vienna Standard Mean Ocean Water, VSMOW (IAPWS 2001, BIPM 2006).
In order to link current practice to this definition, measured Practical Salinity values can be converted to Reference Salinity by means of equation (5). However, for seawater whose composition is slightly different from Reference Composition, the Reference Salinity thus determined will not necessarily represent the solute mass fraction accurately, nor will it always give best results for other properties of seawater (such as density) when the TEOS-10 correlations are used. Thus as far as necessary and available, corrections for sea-salt composition anomalies, denoted δSA, must be obtained by using additional information. The final (corrected) salinity value, on the Reference-Composition Salinity Scale, is called Absolute Salinity SA:
and SA is then the salinity argument to be used in TEOS-10 correlations for other properties of seawater.
At present there are several possible methods for determining δSA. First, the anomalies can be ignored, and this may be sufficient if the required accuracy is low. Since δSA in the open ocean is generally less than 0.03 g kg−1 this would be true in many situations when the salinity is required only to determine chemical equilibrium constants through additional correlation equations. This may also be true for certain measurements in the coastal ocean where salinity variations can be large, such as for hydrophysical monitoring of the Baltic Sea (HELCOM 2014), although coastal corrections are possible, and may be an order of magnitude larger than in the open ocean (Pawlowicz 2015). Second, under the assumption that the spatial fields of oceanic salinity, carbonate system and macro-nutrients are relatively stable, this anomaly can be extracted from values tabulated for that location and depth in a global atlas following the algorithm of McDougall et al (2012). This is probably sufficient for observations taken over large areas in the open ocean. Third, the correction can be obtained by comparisons with direct density measurements performed in the laboratory (Millero et al2008, Wright et al2011). This procedure is useful for laboratory studies or in situations where water can be obtained from sampling bottles retrieved from certain depths. Finally, the anomaly can be estimated from an additional correlation equation if chemical measurements of the most variable seawater constituents in the open ocean (carbonate system and macro-nutrients) are also available (Pawlowicz et al2011).
In determining the correction, another subtle point arises concerning the precise definition of Absolute Salinity. This involves the ultimate use of the variable. As derived densities are considered to be the most important application at highest precision, the Absolute Salinity is actually defined to be the value that will result in the most accurate density when the correlations specified in TEOS-10 for calculating density are used (Wright et al2011). This is not necessarily the actual solute mass fraction, as different chemical constituents in seawater have different effects on conductivity and density (Pawlowicz et al2011). However, corrections are also available to produce the best estimate of solute mass fraction, if this is desired. In this way, TEOS-10 is the first oceanographic standard that supports systematic consideration of natural seawater composition variations.
5. Problems and deficiencies
Although TEOS-10 has many improvements over previous salinity definitions, there still remain two fundamental problems with the current definition and measurement technology of seawater salinity: (i) a lack of traceability of salinity measurement results to the SI, and (ii) an incomplete knowledge of methods to handle small deviations in the chemical composition of the dissolved salts from the Reference Composition, which regionally occur in the oceans and marginal seas and may have relevant effects on seawater properties.
5.1. Lack of traceability to the SI
At present, the electrical conductivity of seawater can be determined in an SI-traceable way to within an uncertainty of about 0.03% (Seitz et al2010), equivalent to a salinity standard uncertainty of 0.01 g kg−1 for a typical seawater of salinity 35 g kg−1. This is comparable to the stated uncertainty of 0.02% in the tabulated SI-traceable conductivity of KCl standard solutions that are often used to calibrate conductivity measurement cells in other scientific fields (Pratt et al2001). However, individual salinity-measuring instruments, known as salinometers, commercially available and in widespread oceanographic use, can demonstrate measurements with stability and reproducibility about one order of magnitude better than this. By careful calibration with SSW, different workers can routinely measure Practical Salinity with a reproducibility of better than 0.002 (0.006%), traceable to SSW, if the time elapsed between the measurements does not exceed the expiry time of SSW; and differences on this scale are found to have meaning within the limits of known ocean behaviour.
A possible concern for the future is that this reproducibility is usually observed when all parties are using the same model of salinometer. Other precision salinometers are now being developed, but as yet no systematic intercomparisons between different salinometer designs have been carried out.
Not only might instrument differences affect intercomparisons of field measurements, but the electrode-solution interaction of the KCl reference solution defined by PSS-78 differs from that of SSW. This means that two different types of measurement device may, at the very low uncertainty levels of concern here, measure a different ratio of conductances between the same KCl solution and SSW sample at the same temperature. This could affect the label values of SSW. The use of SI-traceable calibrations allow for the identification and correction of such measurement biases, but since this is not possible at present an additional uncertainty remains.
Bottled SSW ages for poorly understood reasons, and present recommendations as written on bottle labels since batch P151 are that it should be used within 3 years of calibration (OSIL 2012). Samples are archived by OSIL and their characteristics retested after storage, with little long-term variation found in Practical Salinity (Bacon et al2007). However, batch-to-batch tests carried out independently by other workers have found systematic differences between batches, and correcting for these systematic differences can sometimes improve comparisons between field measurements of ocean water bodies (Bacon et al2000, Kawano et al2006, Pang 2015). These apparent systematic differences were as large as 0.002 in SP. Recent improvements may be due to the change from soda glass ampoules to borosilicate bottles in 2000 (Bacon et al2007). Whether or not these apparent differences are inherent to SSW, or arise from handling effects as SSW is stored and shipped globally, or are statistical artefacts is as yet unresolved. Also unresolved is the question of how properties of SSW batches other than Practical Salinity may undergo systematic drifts or random changes over time.
IAPSO Standard Seawater and the KCl solution specified by PSS-78 are metrological artefacts. The stability of their properties, in particular their composition and conductivity, must be considered as uncertain at the level of uncertainty required in oceanography and climatology, in particular with respect to the multi-decadal time scales relevant for current and future oceanographic observation. Consequently, on these long time scales the comparability of measurement results for Practical Salinity cannot be guaranteed by the current traceability practice. Traceability of ocean salinity measurement results to stable SI standards is therefore highly desirable.
5.2. Composition variability
Two aspects of chemical composition require further work. These are, first, the composition of SSW, and second, the practical determination of deviations from the composition of SSW in real seawaters, and the determination of any corrections that arise from these deviations.
The best verification of the agreement of the composition given in table 1 with that of SSW would require the preparation of artificial seawater with the given solutes and pure water whose isotopic composition is specified by VSMOW. The prepared solution is expected to be consistent with SSW in density within a relative uncertainty of about 4 × 10−6 and in Practical Salinity within 0.007 (Millero et al2008). The fact that as yet no successful experiment of this type is known from the literature indicates that the composition analysis of SSW needs to be improved in the future to determine the deviations from the Reference Composition, using the most advanced chemical analysis techniques. In fact, the accuracy of measurements of seawater salinity is mainly limited at present by the uncertainty of the underlying metrological reference (e.g. uncertainty in composition, molar masses and certified SSW samples) rather than by that of the practical measurement procedures (e.g. stability and repeatability of electronic sensor readings).
The composition of real seawater varies with location and with time. It may contain significantly more or less pure water than certified samples of SSW, and the relative amounts of different solutes may also vary slightly. As previously noted, the mass fraction of dissolved solute on the Reference-Composition Salinity Scale is termed Absolute Salinity, SA, (IOC et al2010, Wright et al2011). Reference Salinity SR based on a measurement of electrical conductance using equation (5), is currently the best estimate for the Absolute Salinity of IAPSO Standard Seawater. However, the relationship between solute mass and the electrical conductivity of real seawater may differ because of these composition differences, and hence the Absolute Salinity and the Reference Salinity calculated using equation (5) may also differ. The deviation between the two salinity values, δSA, defined by equation (6) is denoted the Absolute Salinity Anomaly and serves as a measure for the solute-composition anomaly of a given sample with respect to the Reference Composition.
However, the concept of salinity has many subtle details, both in terms of its conceptual definition and in its practical determination. Defining ‘dissolved inorganic solute’ in seawater is not entirely straightforward (Millero et al2008, Pawlowicz et al2011, Wright et al2011). Also, although salinity definitions usually include only inorganic constituents, at present the practical importance of the remaining organic material (e.g. for density or other thermodynamic properties) is poorly understood (Millero et al2010).
The first issue in defining salinity involves the choice of constituents to include. Although practically every chemical element known is contained in seawater at some concentration, many of these occur at such low concentrations (such as some nutrients or trace elements) that they have little effect on a gross ‘salinity’. Traditionally, constituents that occur in concentrations of less than about 0.001 g kg−1 are neglected in definitions of salinity. However, there are several exceptions. The first is that some dissolved gases (primarily oxygen O2 and nitrogen N2) are present at somewhat higher levels, but are neglected nevertheless because they have little practical effect on seawater densities and conductivities. On the other hand, carbon dioxide (CO2) gas and the hydroxide (OH−) ion are included even though they are present at lower levels, because they are required for a simple description of the marine carbonate system that may significantly affect electrical conductivity. Finally, macro-nutrients such as nitrate and silicic acid are usually not included, although the latter can be present in concentrations of up to 0.02 g kg−1 in the deep North Pacific.
The second issue in defining salinity is that the chemical equilibria involved in the carbonate system, which includes CO2, , , B(OH)4, , and OH− (and is significantly affected by seawater pH, see Dickson et al Part 3 of this issue) are particularly problematic. At any given conditions, the equilibrium composition of these components may deviate from the Reference Composition as a result of chemical solute-solute and solute-solvent reactions, which are concentration, temperature and pressure-dependent. On the other hand, one of the most important requirements of any salinity definition is conservation with respect to dilution, warming and compression of the seawater sample. Thus, a conservative salinity measure cannot be easily defined in terms of the total mass of a varying solute (Millero et al2008, Wright et al2011, Pawlowicz et al2011). The problem becomes even more complex when additional constituents (e.g. macro-nutrients) are introduced by biogeochemical processes.
A related problem is a proper definition of seawater molality since reactions between the solute components and with solvent as well as ionic association will change the total number of dissolved particles. This is additionally complicated by the fact that any distinction between ‘associated’ and ‘dissociated’ pairs of ions is subject to arbitrary physical convention (Bjerrum1926, Falkenhagen and Ebeling 1971, Ebeling and Grigo 1982, Justice 1991). This essential point is only infrequently mentioned as a severe problem in the literature on electrolytic solutions; it is relevant also for the physically rigorous definition of pH (as discussed in Dickson et al2016, part 3 of this issue). The crossover between bound and free ions in a solution is smooth rather than stepwise as the associated/dissociated classification suggests (Robinson and Stokes 1970). An important metrological consequence is that properties of free ions in a partly dissociated solute cannot be measured directly but only derived from theoretical relations (such as Pitzer equations or mass-action laws) which implement the particular threshold assumed. Measurable quantities should not depend on that arbitrary definition.
The definition of the Reference Composition includes neutral molecules and free ions. The molality of seawater depends on this convention and cannot be measured unambiguously without it. However, this convention is not necessarily consistent with other conventions such as those used to define ionic association constants. For example, as a result of ionic association, 2-2 electrolytes like MgSO4 are known to begin deviating at extremely small concentrations from the limiting laws that imply full dissociation (Falkenhagen et al1971). In contrast, all Mg2+ and is counted as as if they were free ions in the Reference Composition, even at the much higher concentrations that are typical for ocean waters.
In the definition of the Reference Salinity, the problem of chemical reactions in the solution was conceptually circumvented by first moving the seawater sample to a reference temperature and pressure, and then adding or removing pure water until the Practical Salinity equals 35.000 within these significant digits, counting the particles and their masses in just the way they are listed in table 1, and then correcting by the dilution factor. For real seawaters a similar invariant reference condition cannot be so easily defined because the relative composition (and conductivity) is different. Instead, the problem is dealt with in TEOS-10 by considering Reference-Composition Seawater of the same density as that of the sample (at specified reference conditions). An alternative future approach might be that only the atoms different from hydrogen and oxygen are counted as elemental salt constituents, i.e., a measure that is rigorously invariant with respect to any chemical reactions.
Finally, it is important to keep in mind that the precision of currently available measurement technology and research needs imply that uncertainties of Practical Salinity estimates may be an order of magnitude less than those of the derived estimates of thermodynamic properties (Pawlowicz et al2012), because of composition changes. Oceanographic standards prior to TEOS-10 provided no means for discussing and compensating for seawater composition anomalies. Now, in the context of TEOS-10, the increasing demands of ocean modeling and climate research have highlighted the issue of composition variations and their effects on seawater properties.
In general, theoretical considerations make it plain that a single concentration variable is insufficient to describe all the properties of a varying multi-component solution, but complete chemical analysis of seawater samples on a routine basis is impractical. In several cases it turns out that secondary measurements of a different physical property or composition variable can be used to estimate first-order corrections if the primary salinity variable is conventional Practical Salinity (Feistel et al2010b, Pawlowicz et al2011, McDougall et al2012). Several methods based on different choices for secondary measurands, such as density or carbon/nutrient concentrations, have been developed. However, since these definitions have all been developed relatively recently, there is little practical experience in judging the strengths and weaknesses of each for different applications.
6. Suggested tasks
Carrying out a full chemical analysis for the major constituents of seawater to an accuracy resolving as many as 6 significant digits is far too complicated a procedure to be used for regular salinity measurements at sea (or even in the laboratory). It has been and will remain common practice to use a suitable seawater property as a surrogate measurand, with salinity calculated from this measurement result by means of a correlation equation between salinity and this property. Consequently, the specified property correlation must be a part of the standard measurement procedure for salinity. Traceability of measurements of this property to the SI is desirable because this enables a reliable comparison of measurement results with stated uncertainties, independent of the elapsed time between the measurements.
Currently, an electrical conductance ratio with SSW is used as the measurand, and the correlation equations given by PSS-78 are incorporated into TEOS-10. As discussed in section 5, conductivity measurements are traceable to the SI but only with an uncertainty that is somewhat larger than is needed for scientific investigations of ocean general circulation. For the time being, it appears to be technically infeasible to reduce this uncertainty to a level that would satisfy oceanographic and climatological demands. Instead, today’s precision measurements are traceable to metrological artefacts (SSW and ultimately KCl solutions) with finite useful lifetimes. Although these artefacts are compared with their predecessors in a chain through time (Bacon et al2007), each comparison in the chain will increase the uncertainty. Hence, the uncertainty in comparisons between salinities traceable to these artefacts will also increase as these salinities are determined at more widely spaced times.
Figure 1 shows an estimation of the corresponding uncertainties between two salinities measured some time apart under current practices. The uncertainty of the difference between results traceable to the conductance ratio of SSW is if those are measured within the expiry time of a particular batch of SSW. Although comparison between batches is complicated by the details of the purity of different KCl batches and other technical details (Bacon et al2007), we can crudely estimate that the uncertainty will increase as (Seitz et al2011), where N is the number of years and Nsl is the assumed shelf life of SSW (somewhere between 2 and 5 years). The uncertainty will increase even beyond that of results traceable to SI conductivity standards (about ) after several decades.
To provide a smaller upper limit on the uncertainty, another property must be considered. Among the potential candidates for the representative measurand such as chlorinity, density, sound speed, refractive index or microwave emissivity (Klemas 2011), the density of seawater appears to be the most suitable for several reasons (Seitz et al2011, Wright et al2011). With the commercial availability of vibrating-tube densimeters (Kremling 1971), measurements of the deviation of seawater density from that of pure water are possible outside specialised facilities and may become a practical alternative to conductance ratio for highly accurate salinity measurements in the laboratory.
One aim of a recent European research project (EMRP 2010) was to reduce the relative uncertainty of routine density measurements with vibrating-tube densimeters to less than 2 × 10−6. This goal was achieved by optimising a substitution method (Wolf 2008, Feistel et al2010a). A relationship between density and salinity was determined in a salinity range between 2 g kg−1 and 35 g kg−1 and at temperatures between 5 °C and 35 °C with a maximum relative uncertainty in density of less than 2 × 10−6 at the lower temperatures and increasing to 2.6 × 10−6 at 35 °C. By such a method the density of seawater is traceable to the density of pure water (figure 2), which acts in this case as a reference liquid with SI-traceable density values known with a relative uncertainty of about 1 × 10−6 from the CIPM-2001 or IAPWS-95 formulations (Tanaka et al2001, Harvey et al2009), which are consistent with TEOS-10. The maximum combined relative standard uncertainty of a density measurement is then about . Consequently, the uncertainty of the difference between two density measurements is . For liquids, no routine density measurement techniques with smaller uncertainties are currently available.
Although the relative uncertainty of density measurements is much smaller than that of conductivity measurements, density changes resulting from changes in dissolved salt content are small relative to a large base value given by the density of pure water. Whereas conductivity changes by a factor of more than 16 when increasing the salinity from 2 to 42 g kg−1, density is changed only by about 3%. Therefore, the advantage of a very small uncertainty in density, which is indeed about two orders in magnitude smaller than that in conductivity, must be qualified. A relative uncertainty of 4 × 10−6 in seawater density is equivalent to an uncertainty in salinity of about 0.005 g kg−1. At this level of uncertainty, density still cannot replace conductance ratio as a basis for comparison of measurement results at very short time scales, but because it is traceable to the SI its uncertainty will not increase with time (figure 1), and it can therefore provide superior results over time scales longer than about a decade.
A suggested new concept that takes advantage of currently available density measurement technology and at the same time leaves established oceanographic practice largely unaffected is a combination of conductance ratio and density measurement (Seitz et al2011). In this concept, the salinity of SSW samples can be additionally certified (or at least checked) by density measurements in combination with the TEOS-10 equation of state. At a given reference temperature and pressure, the density of an SSW sample corresponding to a specified salinity is measured by the sample’s producer and its Practical Salinity value is calculated via the equation of state and the Reference Salinity, equation (5). This value can be compared directly with the value achieved according to the PSS-78 procedures, which will reveal possible longer-term changes in SSW properties. Recent investigations supported the validity of this procedure (EMRP2010). However, many practical aspects must still be investigated before it would be feasible to transition to obtaining salinity from density instead of from conductance ratio.
The use of density for routine salinity measurements has other advantages. Although, as for conductivity, absolute measurements are possible, it is usually easier to make measurements relative to a reference liquid. Certified reference liquids for density are usually measured by a validated density measurement apparatus (often a hydrostatic weighing apparatus) and are delivered with a certificate giving the density value together with its uncertainty and guaranteeing the traceability to SI. However, ultra-pure water, which is routinely produced in many laboratories, and has characteristics that are well known, can also be used as a reference liquid for density measurements.
Ultrapure water can be produced in a highly reproducible way by commercial apparatuses, such as by reverse osmosis or double distillation. The purity of this water can be checked by chemical analysis. An easy verification is a conductivity measurement that is implemented in many pure-water producing devices working with reverse osmosis, since the electrical conductivity will be sensitive to the presence of ions that result from the dissolution of salts or of gases such as CO2(Zhang et al2014). However, electrical conductivity measurements cannot account for all possible impurities. The presence of non-ionic elements must be checked using other techniques. The dissolution of non-conductive silicate in particular may be important if glass bottles are used for storage.
One problem may be caused by a varying content of dissolved air. The air content of ultra-pure water depends on the handling of the sample as well as on ambient air pressure and temperature; its influence on density is about 0.002 to 0.003 kg m−3 at laboratory conditions (Harvey et al2005). To avoid this problem it is strongly recommended that airless or de-gassed water, which can be produced by boiling and subsequently avoiding any open contact to air, is used. If this is impossible, an air correction can be carried out as described by Tanaka et al (2001) or by Harveyet al (2005).
Density is also sensitive to the isotopic composition of the water. The CIPM formulation of liquid water density is based on Vienna Standard Mean Ocean Water, VSMOW (IAPWS 2001, BIPM2006) which possesses a well-defined isotopic composition with regard to deuterium and 18O. The isotopic composition of pure water is known to vary geographically (Jasechko et al2013). Although this has to be checked at least once for a given location, the temporal variation is often found to be negligible. If the influence of the isotopic composition on density is on the order of 3 g m−3 or larger, it should be handled as a correction to the water density table based on VSMOW. The recommended procedure is described by Tanaka et al (2001).
With these conditions accounted for, ultra-pure water can be used worldwide as a reference liquid, avoiding the need to make absolute density measurements routinely. The density of this water is easily available from standard tables or formulations for water density, and its traceability to the SI is guaranteed by these values. Although the suggested dual conductance ratio/density certification does not necessarily require the end user of SSW to make density measurements, the capability of doing so will allow for investigations into the quality of SSW after shipping and storage, which may account for some of the discrepancies found in different analyses of salinity determination procedures (Kawano et al2006, Bacon et al2007).
Once these technical issues are resolved, then official adoption of a density traceability in SSW would require the cooperation of organizations like the International Bureau of Weights and Measures (BIPM), the intergovernmental organization through which Member States act together on matters related to measurement science and measurement standards (including the SI), the International Association for the Properties of Water and Steam (IAPWS), which maintain the standards underlying TEOS-10, and the International Association for the Physical Sciences of the Oceans (IAPSO) which endorses SSW. Modifications to TEOS-10, if required, would also involve the Intergovernmental Oceanographic Commission (IOC), to communicate these modifications to international ocean programs and member countries, and to observational practitioners.
The issue of variations in relative chemical composition has received attention, and TEOS-10 procedures (see section 4) include results of that work. However, there are still many unknowns, and the sensitivity of seawater density and conductivity to changes in the chemical composition of both SSW and real seawater requires further investigation. These changes may cause changes in the temperature and pressure dependencies of measured values, which could lead to problems when laboratory measurements are used to characterise in situ properties. Measurements of Baltic seawater samples (Feistel et al2010a) and numerical calculations (Pawlowicz et al2011, Wright et al2011) suggest that composition variations typical of those in nature can sometimes lead to significant errors and increased uncertainty of properties derived from conductivity measurements when using equations developed for SSW. In addition, the effect of composition variations on the density of SSW as it ages and is distributed is unknown, although preliminary results suggest that silicic acid levels may increase by dissolution from glass bottles, which will affect density but not conductivity. Marine chemists are well aware of silicate dissolution from glass bottles (Knudsen 1903, Culkin and Smed 1979, Yan et al2015), even though this process is often only indirectly mentioned in standard handbooks of marine chemistry such as Grasshoff et al (1983).
A related issue is that the types and spatial variability of relative composition changes in the real ocean are known only imperfectly. The effects of carbon and nutrient changes explain most of the available density errors observed in the open ocean if composition variations are ignored (Pawlowicz et al2011), but there have only been limited investigations of density errors and composition changes near continental shelves, near and above hydrothermal vent fields, and in regions of significant ice formation, which may involve different chemical processes. Relevant data would become more readily available in the future if direct density measurements on seawater samples become more routine, and this should be encouraged.
Finally, although more routine density measurements can be carried out on water samples, electronic in situ instrumentation would greatly increase their viability. However, electronic sensors for oceanographic in situ density measurements are not yet available, although this seems to be a solvable, mainly technical and financial, problem. There has been no widespread demand for such a sensor because density could be easily and accurately computed from salinity by standard correlation equations (although as discussed above the actual accuracy of the results was less than generally thought because the effect of composition variations was ignored before TEOS-10). A correlation equation to be used for the salinity calculation from density is formulated as an IAPWS Release (IAPWS 2008) and is part of TEOS-10. However, due to its widespread use and field-tested acceptance, conductance ratio will remain the salinity measure of choice for the foreseeable future.
The most recent definition of seawater salinity is related directly to the mass fraction of solute in seawater at specified temperature and pressure, independent of specific operational procedures. This allows for more flexibility in operational procedures to determine this mass fraction. Unhappily, the current traceability practice using PSS-78 procedures cannot be entirely replaced at the desired uncertainty level with another technique of similar accuracy that is traceable to the SI. Practical Salinity, or the corresponding conductance ratio, must still be labelled on the SSW bottles. This does have the advantage that the calibration and measurement practice of practitioners should not be affected in the immediate future.
Nevertheless, implementing a degree of traceability to the SI will significantly improve the reliability of long-term comparisons of observational data. The most promising, SI-traceable surrogate measurand is seawater density at specified temperature and pressure, converted to salinity using the TEOS-10 equation of state. The basic conceptual problems of this approach are mostly solved. However, substantial technical and institutional problems remain to be addressed before new practical implementations can be recommended to the international oceanographic community.
Finally, determining the effect of composition variations on seawater properties to some extent relies on knowing what these composition variations might be in the real ocean. Although this problem is probably solved for most of the open ocean, more observations need to be taken, especially in areas at the edges of the ‘open ocean’, to better understand composition variations that might occur there. Encouraging the routine measurement of high-precision density (through promulgation of methods and development of equipment) will help achieve this goal.
The authors thank Nigel Higgs, OSIL, for his contributions in the early stages of this paper, and the journal editor and the anonymous referees for encouraging comments and constructive suggestions. Organizations financially supporting this work include the European Metrology Research Programme (EMRP) through project ENV05, jointly funded by the EMRP participating countries within EURAMET and the European Union, the Scientific Committee on Oceanic Research (SCOR), from grant OCE-1243377 from the US National Science Foundation and from national SCOR committees, and the International Association for the Properties of Water and Steam (IAPWS), with funding from IAPWS National Committees. We also express our gratitude to Prof. Michael Kühne who as the Director of the BIPM organised the meetings with IAPWS representatives at the BIPM in August 2011 and February 2012 and inspired the writing of this series of review articles. This paper contributes to the tasks of the Joint SCOR/IAPWS/IAPSO Committee on the Properties of Seawater (JCS).
Aoyama M, Joyce T M, Kawano T and Takatsuki Y 2002 Standard seawater comparison up to P129 Deep Sea Res. I 49 1103–14
Culkin F and Smed J 1979 The history of standard seawater Oceanol. Acta 2 355–64
Dickson J, Camões M F, Spitzer P, Fisicaro P, Stoica D, Pawlowicz R and Feistel R 2016 Metrological challenges for measurements of key climatological observables. Part 3: Seawater pHMetrologia 53 R26–R39
Dittmar W 1884 Report on researches into the composition of ocean-water, collected by H.M.S. Challenger, during the years 1873–1876. The Voyage of H.M.S. Challenger Phys. Chem. 1 1–257http://escholarship.org/uc/item/38p2q583
Durack P J and Wijffels S E 2010 Fifty-year trends in global ocean salinities and their relationship to broad-scale warming J. Clim. 23 4342–62
Durack P J, Wijffels S E and Boyer T P 2013 Long-term salinity changes and implications for the global water cycle Ocean Circulation and Climate. A 21st Century Perspective ed G Siedler et al(Amsterdam: Elsevier) pp 727–57
Feistel R, Weinreben S, Wolf H, Seitz S, Spitzer P, Adel B, Nausch G, Schneider B and Wright D G 2010a Density and absolute salinity of the Baltic sea 2006–2009 Ocean Sci. 6 3–24 www.ocean-sci.net/6/3/2010/
Forch C, Knudsen M and Sørensen S P L 1902 Berichte über die konstantenbestimmungen zur aufstellung der hydrographischen tabellen Det Kongelige Danske videnskabernes selskabs skrifter 151 6. Raekke, Naturvidenskabelige og Mathematiske Afdeling XII, 1.
Forchhammer G 1865 On the composition of sea-water in the different parts of the ocean Phil. Trans. R. Soc. 155 203–62 www.jstor.org/stable/108888
IAPWS 2001 Guideline on the use of fundamental physical constants and basic constants of water. The International Association for the Properties of Water and Steam, Revision 2012.www.iapws.org
IAPWS 2008 Release on the IAPWS formulation 2008 for the thermodynamic properties of seawater. The International Association for the Properties of Water and Steam www.iapws.org
IOC, SCOR and IAPSO 2010 The International Thermodynamic Equation of Seawater—2010: Calculation and Use of Thermodynamic Properties. 196 Intergovernmental Oceanographic Commission, Manuals and Guides No. 56, UNESCO (English) www.TEOS-10.org
Ishai P B, Talary M S, Caduff A, Levy E and Feldman Y 2013 Electrode polarization in dielectric measurements: a review Meas. Sci. Technol. 24 102001
Kawano T, Aoyama M, Joyce T, Uchida H, Takatsuki Y and Fukasawa M 2006 The latest batch-to-batch difference table of standard seawater and its application to the WOCE onetime sections J. Oceanogr. 62 777–92
Lovell-Smith J W, Feistel R, Harvey A H, Hellmuth O, Bell S A, Heinonen M and Cooper J R 2016 Metrological challenges for measurements of key climatological observables. Part 4: atmospheric relative humidity Metrologia 53 R40–R59
Pang Y 2015 Final Report. JCOMM Inter-Comparison Project for Seawater Salinity Measurements January 2013–December 2014.
Park K 1964 Reliability of standard sea water as a conductivity standard Deep Sea Res. 11 85–7
Pawlowicz R 2010 A model for predicting changes in the electrical conductivity, practical salinity, and absolute salinity of seawater due to variations in relative chemical composition Ocean Sci. 6361–78
Spitzer P and Seitz S 2011 Electrolytic conductivity Handbook of Metrology and Testing 2nd edn ed H Czichos et al (New York: Springer) chapter 9.3
SUN 1985 124 The International System of Units (SI) in Oceanography Report of IAPSO Working Group on Symbols, Units and Nomenclature in Physical Oceanography (SUN). Unesco technical papers in marine science 45
Tanaka M, Girard G, Davis R, Peuto A and Bignell N 2001 Recommended table for the density of water between 0 °C and 40 °C based on recent experimental reports Metrologia 38 301–9
Unesco 1981a The Practical Salinity Scale 1978 and the International Equation of State of Seawater 1980. (Paris: Unesco) Unesco technical papers in marine science 36
Unesco 1981b Tenth report of the joint panel on oceanographic tables and standards (Sidney, B.C., Canada, 1–5 September 1980). Unesco technical papers in marine science 36, Unesco, Paris
Wells N C 2012 The Atmosphere and Ocean (Oxford: Wiley)
Wenner F, Smith E H and Soule F M 1930 Apparatus for the determination aboard ship of the salinity of sea water by the electrical conductivity method, bureau of standards J. Res. Natl. Bur. Stand. 5 711–32
Wright D G, Pawlowicz R, McDougall T J, Feistel R and Marion G M 2011 Absolute salinity, ‘density salinity’ and the reference-composition salinity scale: present and future use in the seawater standard TEOS-10 Ocean Sci. 7 1–26
Zhang B, Lin Z, Zhang X and Wang X 2014 Absolute measurement system for low electrolytic conductivity of aqueous solutions based on van der Pauw’s theory using a flow-through cellAccreditation Qual. Assur. 19 433–8