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Limnol. Oceanogr., 37(6), 1992, 1 307-1312
0 1992, by the American   Society of Limnology   and Oceanography,   Inc.



Oxygen solubility                   in seawater: Better fitting equations
      Abstract-We examined uncertainties associ-     where Co* is the solubility of O2 per mass
   ated with the routine computation of 0, solu-     or per volume of seawater at the tempera-
   bility (C,,*) at 1 atm total pressure in pure water
                                                     ture of equilibrium (the subscript o denotes
   and seawater in equilibrium with air as a function
   of temperature and salinity. We propose for-      0,; the asterisk signifies equilibrium      with
   mulae expressing C,* (at STP, real gas) in cm3    an atmosphere of standard composition sat-
   dm-3 and pmol kg-’ in the range (tF L t z 40°C;   urated with water vapor at a total pressure,
   0 2 S 1 42%~) based on a fit to precise data      including that of the water vapor, of 1 atm),
   selected from the literature.
                                                     S is salinity in per mil, and A and B are
                                                     constant coefficients.      Clever (1982) re-
                                                     viewed the Setschenow relation. Because
   Precise and accurate values of oxygen sol- seawater is a complex multicomponent                 so-
ubility in seawater are important for esti-          lution, disagreement exists on an expression
mating oxygen utilization,       oxygen-nutrient     for, and thermodynamic        basis of, an em-
equivalent relations, air-sea gas exchange,          pirical formula for routine computation of
etc. Green ( 196 5 and references therein) re- Co* which fits the experimental data pre-
ported measurements of O2 solubility              in cisely and accurately while covering the
seawater. However, Carpenter (1966) and thermohaline range of the world ocean (Bat-
Murray and Riley (1969) obtained more                tino et al. 1983). This disagreement com-
precise results, and Benson and Krause               plicates the use and interpretation       of Co*
(1984) published yet more precise O2 sol- data.
ubility data. For limnological        work, Mor-         We examined uncertainties         associated
timer (198 1) proposed using the results of with Co* computations in seawater as func-
Benson and Krause (1980), and Miller0                 tions of temperature and salinity and eval-
(1986) recommended those of Benson and uated several formulae for its routine esti-
Krause (1984) for oceanographic work. More            mation. Our main concern is that the
recently, Sherwood et al. (199 1) have ex- formulae that have been proposed for rou-
amined O2 solubility in hypersaline solu-             tine computation of C,* in seawater do not
tions of NaCl and other salts.                        behave well at the extremes of the experi-
    In the past, 0, solubility was difficult to mental data, especially at low temperatures.
use for several purposes because it was tab-          Although no precise 0, solubility data in
ulated for integral values of temperature and seawater are available below -0.5OC, work-
salinity (or chlorinity). More recently, sev- ers use empirical formulae to extrapolate to
eral empirical formulae have been proposed            lower temperatures       (Weiss 1970; Chen
for expressing the dependence of the loga-             198 1). These formulae do not fit the data
rithm of O2 solubility on temperature and well at temperatures below - 1°C and at high
salinity (Gilbert et al. 1968; Weiss 1970). salinity. Based on the experimental values
The effect of salinity on the logarithm of O2 of Carpenter (1966) Murray and Riley
 solubility is often expressed with the em- (1969), and Benson and Krause (1984), we
pirical Setschenow relation at constant tem-          propose a high-precision      formula for esti-
 perature,                                             mating Co* (at STP, real gas) by the method
                Inc,* = A + SS,                  (1) of least-squares; it covers oceanic ranges of
                                                       temperature and salinity. This new fit is well
                                                       behaved in the temperature and salinity
                                                       ranges of the data and it does not appear to
Acknowledgments                                        deviate significantly at the extremes of tem-
   We are grateful to R. Battino, F. Millero, and an perature and salinity of the measurements.
anonymous reviewer for their comments.
   Research supported by NSF OCE 88-17359 and We provide formulae and solubility coeffi-
NOAA NA16RC0443-0 1.                                   cients for estimating Co* in seawater as a
1308                                                Notes

function of temperature and salinity in cm3              For routine computations of Co* from Eq.
dm-3 and pmol kg-l.                                      4, they fitted values in several units (at STP,
    Weiss (1970) proposed a least-squares re-            ideal gas) in the range (0 1 t 2 40°C; 0 2
gression (LSR) fit for computing O2 solu-                s 2 40%0):
bility (at STP, real gas) in seawater in the
range (- 1 2 t 1 40°C; 0 L S 2 407~) with                   Inc,*   = A, + A,T-’ + A2T-2
the experimental data of Carpenter (1966)
in the range (0.5 L t 2 36°C; 5.2 L Cl L                              + A3T-3 + A4T-4A4
207~) and Murray and Riley (1969) in the                              + S(B, + BIT-’
range (0.7 L t 2 35°C; 0 L S 1 407~):                                     + B2T -2 + B3T-3).         (5)
   Inc,*    = A, + AIT-’    + A,10 + A,T
                 + S(B, + BIT + B,T2)                        Given the high precision of the current
                                         (2)              O2 solubility data, it is not clear from Eq.
where T is temperature in Kelvin and Ai                   2, 3, and 5 that all provide the same values
and Bi are constants. Equation 2 is based                 over oceanic ranges of T and S. The uncer-
on the Van’t Hoff and the Setschenow re-                  tainty arises because certain formulae are
lations for, respectively, T and S effects.               more robust (statistical sensitivity to the ex-
Weiss indicated a root-mean-square     (rms)              perimental data). The behavior of the gas
deviation of kO.016 cm3 dm-3 from the                     solubility formulae at high and low T and
combined data of Carpenter and Murray                     S is of importance. It is critical that a gas
and Riley. Similarly, Chen (198 1) examined               solubility equation behaves well at the ex-
the same data, proposing LSR fits for Co*                 tremes of the experimental values. The Co*
in the range (0 1 t L 35.5”C; 0 L S 1 407~)               data of Carpenter, Murray and Riley, and
with an rms deviation of kO.0 15 cm3 dm-3.                Benson and Krause do not cover the whole
                                                          range of temperature of the world ocean and
   Inc,*    = A, + A,T-l          + A,10     + A,T        extrapolation is required.
                 + S(B, + BIT-‘)          + CoS2. (3)        We compared the Co* values derived from
                                                         the formulae of Weiss (Eq. 2), Chen (Eq. 3)
   Benson and Krause (1984) made mea-                    and Benson and Krause (Eq. 5) in the range
surements of the Henry’s coefficient for O2              (-2 1 t 1 40°C; 0 1 S L 42%). We con-
in seawater (K,) in the range (0.2 L t 1                 sidered temperatures greater than or equal
45°C; 0 L S L 50?&), and proposed an LSR                 to the freezing point (tF) from Fofonoff and
fit with an rms deviation from the mea-                  Millard ( 1983). Using the formulae and co-
surements of +0.08%. They expressed Co*                  efficients of Weiss (1970) and Chen (198 l),
(at STP, real gas) in mol kg- 1 as a function            we converted their Co* values from cm3
of K, at unit standard atmospheric concen-               dm-3 to pmol kg- 1 at a molar volume of
tration per unit mass of seawater:                       O2 of 22,39 1.6 cm3 mol- 1 and the equation
                                                         of state of seawater of Miller0 and Poisson
   Co* = 0.20946F(l             - P-)(1    - B,)         (198 1). The difference between the molar
             *u-o&.x       ’                             volume of O2 (at STP) as an ideal gas and
                                                   (4)
                                                         as a real gas is -0.1%. Thus, all Co* values
                                                         (at STP, real gas) were expressed in units
where P,, is the equilibrium       water vapor           independent of pressure and temperature.
pressure in air (Green and Car&t 1967) F                 A computer program was written to fit the
and M, are a salinity factor and the gram                Co* values from Eq. 4 by singular value de-
molecular mass of water, respectively (Mil-              composition in the least-squares sense. Our
lero 1982), B, is the second virial coefficient          objective was to examine the relative pre-
for O2 (Benson and Krause 1980) and the                  cision of the fit of these solubility equations
constant 0.20946 is the mole fraction of O2              over the oceanic range of T and S when Eq.
in dry air (Glueckauf 195 1).                            2, 3, and 5 were used to fit values from Eq.
   For Eq. 4, Benson and Krause (1984) in-               4. We also examined the relative precision
dicated an uncertainty of +O. 1% or better.              of these equations to estimate the data of




       -. _--.             -
                    --...-.-.
                                                     Notes                                                          1309

                                                             1.2.      ,    .   ,     .      ,   .      ,   .   ,     .
                        (01 Carpenter (1966)                                        (01 Carpenter (1966)
                        (4 Murray and Riley (1969)                                  (3 Murray and Riley (1969)            *




                                                                       0                                        40
                                                                                Lnpero2&re           (OF)

   Fig. 1. Difference between the C,* values from Weiss   Fig. 2. As Fig. 1, but for the results of Chen (198 1).
(1970, curves), Carpenter (1966, o), and Murray and
Riley (1969, V), relative to the results of Benson and
Krause (1984).                                            (3.01 pmol kg-l), and &0.3% (kO.85 pmol
                                                          kg-l). In all cases, the discrepancy between
                                                          Co* values derived from these fits was sig-
Carpenter (1966) and Murray and Riley                     nificant at low T and high S.
(1969). In each case, we used from 2 to 10                    For low-precision   estimates of Co*, de-
 Tterms to fit the constant coefficients of Eq.           viations of I 1% are probably unimportant.
 1. Because of its empirical nature, we also              However, differences in C,,* at low T and
examined addition of S terms to the Set-                  high S are important in high-precision mea-
schenow relation. After adding a Tor S term,              surements for the following reasons. First,
we analyzed the goodness-of-fit and behav-                in recent years analytical precision in dis-
ior of the fit at the extremes of the Co* data.           solved oxygen measurements in seawater at
   Because of the behavior of the equation                sea and in the laboratory have been im-
of state of seawater, chemical concentration              proved to +O. 1% or better (Culberson et al.
units on a per-mass basis should be com-                   199 1). High precision and accuracy in mea-
pared separately from those on a per-vol-                 surements of dissolved 0, and C,* are im-
ume basis. Other than for the seawater den-               portant in the detection of ocean climatic
sity effect, systematic deviations in one set             changes where relatively small variations
of dissolved O2 concentration units apply                 might be significant. Second, water masses
in others. Figure 1 shows the relative per-               responsible for the thermohaline character-
cent deviation between the Co* values from                istics of the deep ocean have T and S ranges
Eq. 4 and those of Weiss (Eq. 2) in the range             where the greatest discrepancies occur be-
(tF 2 t 2 40°C; 0 2 S L 4Oo/oo). max-The                  tween the Co* values from Eq. 2, 3, and 5.
imum and minimum relative deviations be-                      In pure water, Eq. 1 reduces to a form
tween their Co* values were +0.7% (2.60                   dependent on T, allowing the examination
pmol kg-r) and -0.2% (0.51 pmol kg-‘),                    of solubility equations without considera-
respectively,     with an rms deviation      of           tion of S effects. Because we use the same
 + 0.3% (* 1.O1 pmol kg-l). Similarly, Fig.               C,,* values (Eq. 4), LSR method, and the
2 shows the relative deviations between the               same equation of state for seawater, any dif-
Co* values from Eq. 4 and those of Chen                   ferences between Eq. 2,3, and 5 reflect their
(Eq. 3) in the range (tF L t 1: 40°C; 0 or S              relative precision and accuracy, assuming
 2 ~O?&J).In this case, the minimum, max-                 that the data of Benson and Krause (1984)
imum, and rms deviations in the range (0                  from Eq. 4 are the most precise and accu-
 L t L 35.5”C; 0 2 S L 4O?b) were, respec-                rate. In pure water and in the range (tF L t
tively, -0.2% (0.40 pmol kg-l), + 0.9%                    1 4O”C), Eq. 2 and 3 attained an rms de-
1310                                          Notes

viation from Eq. 4 of & 1.2 l%, +O. 16%,           well within the experimental uncertainty of
 &0.02%, and +O.O 1% after addition of, re-         Co* measurements in the past, it became
spectively, two, three, four, and five Tterms.     evident from our analysis that a S2 term is
Additional    T terms did not significantly         significant for the dependence of Inc,* on
change the ,rms deviation of the Weiss ex-          salinity. This finding is consistent with pre-
tended equation. When Eq. 5 was used, four         vious results (Carpenter 1966; Chen 198 1;
T terms were required to obtain an rms de-          Sherwood et al. 199 1). Values of Co* in cm3
viation of + 0.0 1%. For seawater, terms must      dm-3 and pmol kg- 1 can be obtained with
be added to Eq. 1 for the salinity effect on       Eq. 8 and the solubility coefficients in Table
Inc,*. For this case, we used the original          1. The fit to Eq. 4 with Eq. 8 has rms de-
form of the Weiss (Eq. 2) and Chen (Eq. 3)         viations of +4 x 10-4cm3 dm-3 and + 1O-3
equations as well as extended forms, Eq. 6         pmol kg-l (Fig. 3) in the range (tF 1 t 2
and 7, respectively:                               40°C; 0 L S 1 42?&).
                                                       Because of the agreement in the Co* data
   Inc,*      = A, + A,T-l   + A&T   + A,T         of Carpenter and Murray and Riley (Weiss
                + A,T2 + A,T3                       1970), we examined the precision of Eq. 8
                + S(& + B,T + B2T2),         (6)   to estimate their measurements. Chlorinity
                                                   (Cl, Ym) values were converted to salinity
and
                                                   with the expression S = 1.80655 x Cl from
      Inc,*   = A, + A,T-1 + A,lnT                 Wooster et al. (1969). From this analysis,
                + A,T + A,T2 + A,T3                solubility coefficients for computing C,* in
                +S(B, + B,T-’ + B2T-2)             cm3 dm-3 and pmol kg-l can be obtained
                                                   from Table 1 and Eq. 8. The fit to the results
                + c,s2.                (7)         of Carpenter and Murray and Riley has rms
    The extended or the original equations of      deviations from their combined data of
Weiss and Chen gave greater rms deviations          50.015 cm3 dm-3 and +0.67 pmol kg-l.
when fitting values from Eq. 4 over the oce-       The rms deviations of the fit from Carpen-
anic thermohaline range than using Eq. 5.          ter’s data are kO.013 cm3 dm-3 and +0.58
This is because a T series of the form T-”         pmol kg- l, while for Murray and Riley the
fits the Inc,* values from Eq. 4 better than       rms deviations are +O.O 18 cm3 dme3 and
the Van’t Hoff relation that Weiss or Chen          +0.78 pmol kg- l. The rms deviations be-
used for the same number of coefficients.          tween the data of Carpenter and Murray and
We examined several formulae to build a            Riley from those of Benson and Krause are
high-precision LSR fit for Co* based on Eq.         20.019 cm3 dm-3 and kO.82 pmol kg-l.
4. From our analysis, Eq. 8 proved to be               We compared our fits to the data of Car-
the best expression for estimating Co* in the      penter, Murray and Riley, and Benson and
range (tF 1 t L 40°C; 0 L S 1 427~):               Krause. When comparing the results of sev-
                                                   eral workers, it is important to weight the
Inc,*    = A, + A,T, + A2TS2+ A3TS2                precision of their data. When we assigned
              + A, TS3+ A,TS4 + A, TS5             weights to the solubility data equal to their
              + S(B, + B, T, + B2TS2+ B3TS3)       respective rms deviations from the experi-
              + c(ys2                              mental data, the resulting fit is significantly
                                          (8)
                                                   influenced by those fitted C,* values with
where T, is a newly defined, scaled temper-        better precision. Although the rms of the fit
ature: T, = ln[(298.15 - t)(273.15 + t)-‘1.        to the data of Benson and Krause is con-
This temperature (T,) transformation      sig-     siderably better, it is not clear that there are
nificantly improves the rms deviation of the       significant differences in accuracy between
fit, particularly at high and low T and S. A       the Co* data of Carpenter, Murray and Riley,
logarithmic      transformation of the depen-      and Benson and Krause. For this reason, we
dent or independent variables or both is           assigned equal weights to their solubility
common in LSR of curvilinear relations.            values to combine their fitted data. From
    Though the Setschenow relation in its lin-     this analysis, Co* values in cm3 dm-3 and
ear form has been shown to hold reasonably         pmol kg-l can be obtained from the solu-
                                                     Notes



Nz      6-
   x         _
  h
‘T      4-
  2
  a
  5     2-
             _
  =
  4     o-
  'B
  B
       -2    -


       -4 -



   Fig. 3. Residual difference (pm01 kg- ‘) between the
C,* (at STP, real gas) values from Eq. 4 of Benson and
Krause (1984) and their fit with Eq. 5 and our fit with
Eq. 8 using coefficients in Table 1 in the range (tF I t
2 40°C; 0 2 S 2 40%~).Solid lines represent the re-
sidual of our fit in the same range oft and S.

bility coefficients in Table 1 and Eq. 8. The
rms deviations of the fits from the com-
bined measurements of Carpenter and Mur-
ray and Riley are +0.016 cm3 dme3 and
kO.72 pmol kg- l. Similarly, the rms devi-
ations of these fits from the results of Ben-
son and Krause are kO.005 cm3 dme3 and
 kO.23 pmol kg-‘.
    We examined several empirical formulae
for estimating O2 solubility at 1 atm total
pressure in pure water and seawater in equi-
librium with air as a function of tempera-
ture and salinity. From our analysis of the
data of Carpenter (1966) Murray and Riley
(1969), and Benson and Krause (1984) we
propose a new fit (Eq. 8) and solubility co-
efficients (Table 1) for the routine compu-
tation of 0, (at STP, real gas) solubility in
 seawater (tF 2 t L 40°C; 0 L S 2 42o/oo).
This new fit estimates the Co* data with
relatively high precision in the ranges of T
 and S of the experimental values and seems
 to extrapolate more reliably beyond these
 ranges than do previous formulae. Clearly,
 extrapolation    beyond the range of the ex-
 perimental data should be viewed with cau-
 tion. When relatively high precision of Co*
 is not required, it probably makes no dif-
 ference which O2 solubility formula (Weiss
  1970; Chen 198 1; Benson and Krause 1984;
 this work) is used because the Co* values
1312                                                 Notes

estimated from these formulae agree to                     FOFONOFF, N. P., AND R. C. MILLARD, JR. 1983. Al-
within an rms deviation of +0.3% (+ 1.Ol                       gorithms for computation of fundamental prop-
                                                               erties of seawater. UNESCO Tech. Pap. Mar. Sci.
pmol kg-l). The deviations in Co* at low T                     44.
and high S, between these formulae, are of                 GILBERT, W., W. PAWLEY, AND K. PARK. 1968. Car-
importance in the context of the current an-                   penter’s oxygen solubility tables and monograph
alytical precision of dissolved O2 measure-                    for seawater as a function of temperature and sa-
                                                               linity. Oregon State Univ. Coll. Oceanogr. Ref.
ments and the need to extrapolate to the                      68-3.
thermohaline range of the world ocean. For                 GLUECKAUF, E.       195 1. The composition of atmo-
routine computation of Co* in seawater, we                     spheric air, p. 3-10. In Compendium of meteorol-
recommend using Eq. 8 and the solubility                       ogy. Am. Meteorol. Sot.
coefficients in Table 1 derived from the more              GREEN,E. J. 1965. A redetermination ofthe solubility
                                                               of oxygen in seawater and some thermodynamic
precise data of Benson and Krause ( 1984)                      implications of the solubility relations. Ph.D. the-
                                Herncin E. Garcfa              sis, Mass. Inst. Technol. 137 p.
                                                           -,       AND D. E. CARRITLT. 1967. New tables for
                                 Louis I. Gordon               oxygen saturation of seawater. J. Mar. Res. 25:
                                                                140-147.
College of Oceanography                                    MILLERO, F. J. 1982. The thermodynamics of sea-
Oregon State University                                        water. Part 1. The PVT properties. Ocean Sci. Eng.
Corvallis 9733 l-5503                                          7: 403-460.
                                                                    1986. Solubility of oxygen in seawater.
References                                                    UNESCO Tech. Pap. Mar. Sci. 50.
                                                           -,     ANDA. POISSON.1981. The international one-
BAITINO, R., T. R. RETTICH,AND T. TOMINAGA. 1983.             atmosphere equation of state of seawater. Deep-
    The solubility of oxygen and ozone in liquids. J.         Sea Res. 28: 625-629.
    Phys. Chem. Ref. Data 12: 163-178.                     MORTIMER, C. H. 198 1. The oxygen content of air
          B.
BENSON, B., AND D. KRAUSE, JR. 1980. The con-                 saturated fresh waters over the ranges of temper-
    centration and isotopic fractionation of gases dis-       ature and atmospheric pressure of limnological in-
    solved in freshwater in equilibrium with the at-          terest. Mitt. Int. Ver. Theor. Angew. Limnol. 22,
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              J.
CARPENTER, H. 1966. New measurements of ox-                   centrations in hypersaline waters. Limnol. Ocean-
    ygen solubility in pure and natural water. Limnol.         ogr. 36: 235-250.
    Oceanogr. 11: 264-277.                                 WEISS,R. F. 1970. The solubility of nitrogen, oxygen
CHEN, C.-T. A. 198 1. Oxygen solubilities up to 200           and argon in water and seawater. Deep-Sea Res.
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                                                           WOOSTER, S., A. J. LEE, AND G. DIETFUCH. 1969.
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