ࡱ> {}z%` @bjbjNN w,,36&     rrr$P4B4.6L!!!'.).).).).).).$0hF3M.rZ#|!!"Z#Z#M.""b.&&&Z#"8r'.p&Z#'.&&,hZr-v C>fr$#--\x.0.3-X24%24 -24r-@!Z!@^&<"4p"!!!M.M.%d!!!.Z#Z#Z#Z# ::"""""" Summary. This document provides an overview of the history of development of a new Equation of State of Seawater (TEOS-10) and its technical advantages over the existing UNESCO standard (EOS-80). The SCOR/IAPSO Working Group 127 developed this new standard. Several IOC primary subsidiary bodies and scientific guidance panels have considered its suitability for adoption by the 25th Assembly to replace the widely used existing UNESCO standard. The 25th Assembly will be invited to resolve to adopt the new standard (paragraph 13), to ensure this resolution is carried out at the national level (paragraph 15) and to commit sufficient extrabudgetary resources to allow the secretariat to carry out an active outreach campaign including contracting the writing of, publishing, in all of the official languages of the IOC and WMO, and widely distributing a summary report of the TEOS-10 standard (paragraph 17).  History The Practical Salinity Scale, PSS-78, and the International Equation of State of Seawater (UNESCO technical papers in marine science No. 36, 1981), which expresses the density of seawater as a function of Practical Salinity, temperature and pressure, have served the oceanographic community very well for thirty years. The Joint Panel on Oceanographic Tables and Standards (JPOTS), also promulgated an algorithm for the specific heat capacity of seawater at constant pressure, an expression for the sound speed of seawater and a formula for the freezing point temperature of seawater (UNESCO technical papers in marine science No. 44, 1983). Three other algorithms supported under the auspices of JPOTS concerned the conversion between hydrostatic pressure and depth, the calculation of the adiabatic lapse rate, and the calculation of potential temperature. All these algorithms are jointly referred to here as EOS-80 for convenience because they represent oceanographic best practice from the early 1980s to the present day. In 2005 SCOR (Scientific Committee on Oceanic Research) and IAPSO (International Association for the Physical Sciences of the Ocean) established Working Group 127 on the Thermodynamics and Equation of State of Seawater (henceforth referred to as WG-127). This group has now developed a collection of algorithms that incorporate our best knowledge of seawater thermodynamics and provide rigorous methods for calculation of seawater properties, including density (henceforth referred to as TEOS-10). The International Association for the Properties of Water and Steam (IAPWS-15, Berlin, 711 September 2008) adopted the Gibbs function of seawater developed by WG-127 (IAPWS-08). The implications of adopting TEOS-10 were further considered by the GOOS Scientific Steering Committee (GSSC-IX, Perth, 2527 February 2009), the International Oceanographic Data and Information Exchange (IODE-XX, Beijing, 49 May 2009) and the Intergovernmental Committee for GOOS (I-GOOS-IX, Paris, 1012 June 2009). At the time of the writing of this working document, none of these groups had expressed opposition to adoption of TEOS-10. In 2009 the Ocean Observations and Services section of IOC carried out an expert peer-review in which numerous scientific experts from the broad international community were asked to review and comment on TEOS-10 including both its technical and scientific merit as well as its suitability for intergovernmental adoption. At the time of the writing of this working document, none of these experts had expressed opposition to adoption of TEOS-10. Technical Background In recent years the following aspects of the thermodynamics of seawater have become apparent and suggest that it is timely to redefine the thermodynamic properties of seawater. Several of the polynomial expressions of the International Equation of State of Seawater (EOS-80) are not totally consistent with each other as they do not exactly obey the thermodynamic Maxwell cross-differentiation relations. The new approach eliminates this problem. Since the late 1970s a more accurate thermodynamic description of pure water has appeared (IAPWS-95). Also more and rather accurate measurements of the properties of seawater (such as for (i) heat capacity, (ii) sound speed and (iii) the temperature of maximum density) have been made and can be incorporated into a new thermodynamic description of seawater. The impact on seawater density of the variation of the composition of seawater in the different ocean basins has become better understood. The increasing emphasis on the ocean as being an integral part of the global heat engine points to the need for accurate expressions for the entropy, enthalpy and internal energy of seawater so that heat fluxes can be more accurately determined in the ocean (entropy, enthalpy and internal energy were not available from EOS-80). Freezing temperature and melting heat are computed more accurately than in (EOS-80). The temperature scale has been revised from IPTS-68 to ITS-90 and revised IUPAC (International Union of Pure and Applied Chemistry) values have been adopted for the atomic weights of the elements. Absolute Salinity employed in TEOS-10, unlike Practical Salinity employed in EOS-80, is rigorously conservative and expressed in SI units To compute all thermodynamic properties of seawater it is sufficient to know one of its so-called thermodynamic potentials. It was J.W. Gibbs (1873) who discovered that: an equation giving internal energy in terms of entropy and specific volume, or more generally any finite equation between internal energy, entropy and specific volume, for a definite quantity of any fluid, may be considered as the fundamental thermodynamic equation of that fluid, as from it may be derived all the thermodynamic properties of the fluid (so far as reversible processes are concerned. The approach taken by WG-127 has been to develop a Gibbs function from which all the thermodynamic properties of seawater can be derived by purely mathematical manipulations (such as differentiation). This approach ensures that the various thermodynamic properties are self-consistent (in that they obey the Maxwell cross-differentiation relations) and complete (in that each of them can be derived from the given potential). The Gibbs function (or Gibbs potential) is a function of Absolute Salinity (rather than Practical Salinity), temperature and pressure. The use of Absolute Salinity as the salinity argument for the Gibbs function and for all other thermodynamic functions (such as density) is a major departure from present practice (EOS-80). The reason for preferring Absolute Salinity to Practical Salinity is because the thermodynamic properties of seawater are directly influenced by the mass of dissolved constituents (i.e. Absolute Salinity) whereas Practical Salinity depends only on conductivity. Consider for example exchanging a small amount of pure water with the same mass of silicate in an otherwise isolated seawater sample at constant temperature and pressure. Since silicate is non-ionic, the conductivity (and therefore Practical Salinity) is almost unchanged but the Absolute Salinity is increased. Youngs rule indicates that the density, enthalpy etc are changed due to the change in Absolute Salinity. Similarly, if a small mass of say NaCl is added and the same mass of silicate is taken out of the sample, Absolute Salinity will not have changed (and by Youngs rule the density, enthalpy etc will be almost unchanged) but the Practical Salinity will have increased. This Gibbs function of seawater has now been published in the peer-reviewed literature and has also been issued by the International Association for the Properties of Water and Steam as the Release IAPWS-08. This new approach to seawater thermodynamics is referred to collectively as the Thermodynamic Equation Of Seawater 2010, or TEOS-10 for short. A notable difference from present practice that is being recommended by WG-127 is the adoption of Absolute Salinity to be used in journals to describe the salinity of seawater and to be used as the salinity argument to algorithms that give the various thermodynamic properties of seawater. This recommendation deviates from the current practice of working with Practical Salinity and typically treating it as the best estimate of Absolute Salinity. This practice is inaccurate and should be corrected. Note however that WG-127 strongly recommends that the salinity that is reported to national oceanographic data centres remain Practical Salinity as determined on the Practical Salinity Scale of 1978 (suitably updated to ITS-90 temperatures). There are three very good reasons for continuing to store Practical Salinity rather than Absolute Salinity in such data repositories. First, Practical Salinity is an almost directly measured quantity whereas Absolute Salinity (the mass fraction of sea salt in seawater) is generally a derived quantity. That is, we calculate Practical Salinity from measurements of conductivity, temperature and pressure, whereas to date we derive Absolute Salinity from a combination of these measurements plus other measurements and correlations that are not yet well established. Calculated Practical Salinity is preferred over the actually measured in situ conductivity value because of its conservative nature with respect to changes of temperature or pressure, or dilution with fresh water. Second, it is imperative that confusion is not created in national databases where a change in the reporting of salinity may be mishandled at some stage and later be misinterpreted as a real increase in the oceans salinity. Thirdly, the algorithm for determining the "best" estimate of Absolute Salinity is affected by composition of dissolved constituents which, while quite accurately estimated as regionally variable, is expected to be improved by continuing research and accumulative observations, and thus will undoubtedly change in the future. The more prominent advantages of the new seawater description include: The Gibbs function approach allows the calculation of internal energy, entropy, enthalpy, potential enthalpy and the chemical potentials of seawater as well as the melting heat of ice and the latent heat of vapor. These quantities were not available from the International Equation of State but are central to a proper accounting in the ocean of the heat that is transferred between the ocean, the ice cover and the atmosphere above. The thermodynamic quantities available from the new approach are totally consistent with each other. The new salinity variable, Absolute Salinity, is measured in standard SI units. Moreover the treatment of freshwater fluxes, and fluxes of mass in ocean models will be consistent with the use of Absolute Salinity, but are only approximately so for Practical Salinity. For the first time the influence of the spatially varying composition of seawater can systematically be taken into account through the use of Absolute Salinity. In the open ocean, accounting for varying composition of seawater has a non-trivial effect on the horizontal density gradient computed from the equation of state, and thereby on calculation of currents using the so-called thermal wind relation. The Reference Composition of standard seawater supports marine physiochemical studies such as the solubility of sea salt constituents, the alkalinity, the pH and the ocean acidification by rising concentrations of atmospheric CO2. TEOS-10 is valid over a wider range of salinities than EOS-80. This is particularly important in very low or high salinity regions such as estuaries, lagoons, brine seeps etc. Proposed Strategy for Future Work in Follow-up to Potential Adoption by IOC The Assembly will be invited to commit to: (i) adopt the TEOS-10 formulation of the Thermodynamics and Equation of State of Seawater to replace the existing EOS-80 UNESCO standard; and (ii) commit sufficient resources to the IOC secretariat through regular budget, extrabudgetary contributions and staff secondments in order to allow the secretariat to effectively publish and disseminate the TEOS-10 standard and to sponsor a final meeting of the SCOR/IAPSO WG-127. Though not available at the time of the writing of this working paper, it is anticipated that a Draft Resolution for consideration by the Member States of the 25th IOC Assembly will likely be one of the outcomes of the I-GOOS-IX Session (Paris, 1012 June 2009). In the event the 25th IOC Assembly resolves to replace the existing UNESCO standard algorithms for calculation of the equation of state of Seawater (EOS-80) with the proposed new standard (TEOS-10), the most important follow-up will be for Member States to ensure compliance with this resolution at the national level. In addition to government agencies, the equation of state is employed broadly in numerical models and fieldwork across a wide spectrum of the academic research community and the private sector. As a result, an active outreach campaign targeting developing countries government institutions as well as academic and private sector communities worldwide will be required in order to ensure there is broad uptake of the new standard. No IOC regular budget funding has been allocated to any activities related to the equation of state, either in the current biennium or in the plans for the 201011 biennium. As a consequence, extrabudgetary funding, on the order of US$100,000, will need to be committed by Member States as earmarked contributions to the IOC special account if the IOC secretariat is to be able to follow-up on any resolution by supporting a final meeting of WG-127 in late 2009 as well as contracting the writing of a summary publication of the TEOS-10 standard in the IOC manuals and guides series, translating it into the six official languages of the IOC and WMO, and distributing it broadly.  Gibbs, J. W., 1873: Graphical methods in the thermodynamics of fluids, Trans. Connecticut Acad. Arts and Sci.,2, 309-342.     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