Phases of An Element in Seawater
 1. Solids (material that does not pass through a 0.45 mm filter)

    a. Particulate organic material (plant detritus)

    b. Particulate inorganic material (minerals)

2. Gases

    a. Conservative (N2, Ar, Xe)

    b. Nonconservative (O2 and CO2)

3. Colloids (passes through 0.45 mm filter, but is not dissolved)

    a. Organic

    b. Inorganic

4. Dissolved Solutes

    a. Inorganic solutes

      1. Major ( > 1 ppm )

      2. Minor ( < 1 ppm )

    b. Organic solutes
 


 
 

Historical Measurements of Composition of Major Components of Seawater

Bergman (1779) made the earliest chemical analysis of seawater

Marcet (1819)    was the first to suggest that the relative composition of sea salt is nearly constant (the first law of chemical oceanography)

Forchhammer (1865)  made first reliable measurements of major components on several hundred surface waters from all parts of the world.
Dittmar (1884) analyzed 70 seawater samples collected at various depths for the major oceans during the cruise of the H.M.S. Challenger (1873-1876).

Lyman and Fleming (1940) recalculated Dittmar's results using modern atomic weights

Cox and Culkin (1966)  made measurements of major components of waters collected through out the world as part of salinity study.

Riley et al. (1967) made measurements of major components of waters collected through out the world as part of salinity study.
 
 
 

Methods of Determination of
The Major Elements of Seawater
 
Chloride

Ag+ + Seawater ®  AgCl(s) + AgBr(s)

2Ag+ + CrO42-  ®  Ag2CrO44 (red solid)

Cl() = -0.050 + 15.66367R15 + 7.08943 R152 - 5.91110 R153 +  3.31363 R154 - 0.73240 R155

Sulfate

BaCl2 + Seawater  ®  BaSO4 ¯

Ca2+, et al. can co-precipitate.  Measurements relative to standard seawater of known concentration can yield very precise measurements.

Bromine
 
Ag+ + Seawater ®  AgCl(s) + AgBr(s)
AgBr (s)  + chromic acid or K2MnO4  ®  Br2 ­
Br2 +  Na2S2O3  ®  Color Change

Fluorine

Colorimetric methods or using a specific ion electrode

Bicarbonate and Carbonate

At least two parameters  pH, TA (total alkalinity) TCO2 (the total carbon dioxide) and the partial pressure of CO2 (pCO2).  More details of these measurements will be discussed later.
 
Boric acid and borate

Boron  +  mannitol ®  Complex
Converted to B(OH)3 and titrate with NaOH
Colorimetric techniques using a colored indicator  curcumin complex

Magnesium

Mg2+ +  ammonium phosphate (after the Ca2+ is removed) ®  PPT.
Mg2+   +  EDTA ®  color indicator

Calcium

Ca2+ + Oxalate ®  PPT.  weigh as CaCO3 or CaO
Ca2+  +  EGTA  ®  color change (The endpoint by Potentiometrically or colorimetrically using metallochromic indicators).

Potassium

K+  +  chloroplatinate  ® K2PtCl(insoluble in 80% ethanol)
K+  +  Na tetraphenylboron ® K tetraphenylboron (insoluble).

Sodium

Balance Equivalents and determine Na+ is by difference
 
 

Relative Composition of Major Components of Seawater
 
                                                      gi/Cl()
    Solute             A                      B                        C                          D

    Na+              0.5556             0.5555                  0.5567                 0.55661
    Mg2+           0.06695           0.06692                 0.06667               0.06626
    Ca2+            0.02106           0.02126                 0.02128               0.02127
    K+               0.0200             0.0206                   0.0206                 0.02060
    Sr2+             0.00070           0.00040                 0.00042               0.00041
    Cl-               0.99894                --                           --                   0.99891
    SO42-          0.1394                  --                      0.1400                0.14000
    HCO3-         0.00735                --                           --                  0.00552
    Br-               0.00340                --                      0.003473            0.00347
    CO32-              --                     --                            --                  0.00083
    B(OH)4-           --                     --                            --                  0.000415
    F-                     --                     --                            --                  0.000067
    B(OH)3        0.00137                        0.001002
 
      å  =           1.81484                                                                  1.81540
 

A. Dittmar as recalculated by Lyman and Fleming.
B. Cox and Culkin (1966)
C. Riley and Tongadai (1967); Morris and Riley (1966).
D. Millero (1996).

Calculation of the Na+ value for Seawater (pHSWS = 8.1)
 
            Anions                   gi/Cl                         ei (eq kg-1)

              Cl-                       0.99891                       0.545879
              SO42-                  0.1400                         0.056470
              HCO3                0.005524                     0.001754
              Br-                       0.00347                       0.000841
              CO32-                  0.000830                     0.000536
              B(OH)4-               0.000407                     0.000100
              F-                         0.000067                     0.000068
              OH-                                                        0.000008

                                                                   åe= 0.605659
 

           Cations                      gi/Cl                       ei (eq kg-1)
              Mg2+                   0.06626                      0.105634
              Ca2+                    0.02127                      0.020564
              K+                       0.02060                      0.010208
              Sr2+                     0.00041                      0.136587

                                                                     åei =    0.136588

                 e(Na)/Cl = 0.605659 - 0.136588
                              = 0.469071

                 g(Na)/Cl = e(Na)/Cl x FW
                              = 0.469071 x 22.9898/19.374
                              = 0.556614

Calculation of the Na+ value for Seawater (pHSWS = 8.1)
 
Anions                       gi/Cl                         ei (eq kg-1)

Cl-                            0.99891                       0.545879
SO42-                       0.1400                         0.056470
HCO3                     0.005524                     0.001754
Br-                            0.00347                      0.000841
CO32-                       0.000830                    0.000536
B(OH)4-                    0.000407                    0.000100
F-                              0.000067                    0.000068
OH-                                                            0.000008

                                                            åe= 0.605659
 

Cations                         gi/Cl                       ei (eq kg-1)
 Mg2+                          0.06626                   0.105634
Ca2+                            0.02127                   0.020564
K+                               0.02060                   0.010208
Sr2+                             0.00041                  0.136587

                                                      åei =    0.136588

           e(Na)/Cl = 0.605659 - 0.136588
                        = 0.469071

           g(Na)/Cl = e(Na)/Cl x FW
                        = 0.469071 x 22.9898/19.374
                        = 0.556614

Composition of One Kilogram of Natural Seawater as a Function of Chlorinity
 
 
 Species          gi/Cl             Mi             ni/Cl              ei/Cl                  niZi2/Cl
 
Na+              0.556614       22.9898       0.024211        0.024211           0.024211
Mg2+            0.066260       24.3050       0.002726        0.005452           0.010905
Ca2+             0.021270       40.0780       0.000531        0.001061           0.002123
K+                0.020600       39.0983       0.000527        0.000527           0.000527
Sr2+              0.000410       87.6200       0.000005        0.000009          0.000018
Cl-                0.998910        35.4527       0.028176        0.028176          0.028176
SO42-           0.140000        96.0636       0.001457        0.002915          0.005830
HCO3-          0.005524        61.0171       0.000091        0.000091          0.000091
Br-                0.003470        79.9040       0.000043        0.000043          0.000043
CO32-           0.000830        60.0092       0.000014        0.000028          0.000055
B(OH)4-        0.000407        78.8404       0.000005        0.000005    0.000005  F-                  0.000067        18.9984       0.000004        0.000004    0.000004
OH-               0.000007        17.0034       0.0000004      0.0000004  0.0000004

1/2 å =                                                   0.028895        0.031261    0.035994

B(OH)3         0.000996         61.8322       0.000016        0.000016

    å =           1.815402                            0.028903       0.031261
 

For average seawater S = 35, Cl = 19.374, pHSWS = 8.1, TA = 2.400 mmol kg-1,
and t = 25oC.
 
 
 
 
 

The Weight Fraction, Equivalent Fraction, and Ionic Strength Fraction of the Major Solutes in Water

Species               Xi                    Ni                         Ei                       Ii

Na+                  0.306606          0.837672            0.774485            0.672685
Mg2+                0.036499          0.094321            0.174313           0.303023
Ca2+                 0.011716          0.018362            0.033954           0.058988
K+                    0.011347          0.018229            0.016854           0.014639
Sr2+                  0.000226          0.000l62             0.000299           0.000520
Cl                   0.550242           0.974836            0.901303           0.782945
SO42-               0.077118           0.050422            0.093238           0.161999
HCO3-              0.003043           0.003132            0.002896           0.002668
Br-                    0.001911           0.001503            0.001389           0.001206
CO32-               0.000457           0.000479            0.000885           0.001112
B(OH)4-            0.000229           0.000182            0.000168           0.000119
F                     0.000039           0.000122            0.000113           0.000097
OH-                   0.000004           0.000014            0.000013           0.000012
B(OH)3              0.000552           0.000561            0.000544               -----

 

Composition of 1 Kilogram of Seawater with Cl = 19.374
 

Species            g                  ni              ei              Ii

Na+              10.7838        0.46907         0.46907     0.46907
Mg2+             1.2837        0.05282         0.10563     0.21127
Ca2+              0.4121        0.01028         0.02056     0.04113
K+                 0.3991        0.01021         0.01021      0.01021
Sr2+              0.0079         0.00009         0.00018     0.00036
Cl-              19.3529         0.54588         0.54587      0.54587
SO42-           2.7124         0.02824         0.05648      0.11294
HCO3-          0.1070         0.00175         0.00175      0.00175
Br-                0.0672         0.00084         0.00084      0.00084
CO32-           0.0161        0.00027          0.00054      0.00107
F-                 0.0068         0.00068          0.00068      0.00068
B(OH)4-       0.0010         0.00010          0.00010      0.00010
OH-              0.0008        0.00008           0.00008     0.00008

        1/2å =                    0.55981           0.60566     0.69717

B(OH)3         0.0194       0.00031           0.00031

g=  35.172    n= 0.56012  m= 0.60597  I= 0.69717

a) To convert to molar units multiply by the density.  To convert to molal units divide by XH2O = 0.96483

Stoichiometry of Seawater
One Kg of Solution
 

Total Moles                             nT = 1/2 å ni + nB = 0.028903 Cl()

Total Equivalents                     eT 1/2 å ei + nB=0.031260 Cl()

Total Ionals                              IT = 1/2 å niZi2 = 0.035989 Cl()

Mean Molecular Weight         MTå NiMi = 62.793

Mean Equivalent Weight        MT' =  å EiMi' = 58.046

Total Grams per Kg                g = 1000 - 1.8154 Cl()

Total Molarity                       cT = 0.028903 Cl() x r

Total Molality                       mT = 28.890 Cl()/[1000 - 1.8154 Cl()
]
Total Normality                     NT = 0.031260 Cl() x r

Total Equivalent Molality       eT = 31.260 Cl()/[1000 - 1.8154 Cl()]

Volume Ionic Strength            IV = 0.03599 Cl() x r

Molal Ionic Strength               Im = 35.990 Cl()/[1000-1.8154 Cl()]
r is the density in g cm-3

Convert to Functions of Salinity  Using S() = 1.80655 Cl()
 

The Concept of Salinity
 

Forch, Knudsen and Sorensen defined the salinity as

"the weight in grams of dissolved inorganic salts in one kilogram of seawater, when all bromides and iodides are replaced by an equivalent quantity of chlorides, and all the carbonates are replaced by an equivalent quantity of oxides"

    2HCO3- ® [MO2] + H2O + 2CO2
    CO32-  ® [MO2] + CO2
 
Knudsen                            S() = 1.805 Cl() + 0.030
Forchhammer                    ST = 1.812 Cl()
Dittmar                             ST = 1.8056 Cl()
Lyman and Fleming          ST = 1.8148 Cl()
Millero                              ST = 1.8154 Cl()
JPOTS                              S() = 1.80655 Cl()

            Cl() = 19.374, S()  = 35.000 and ST = 35.172
 
S() = - 0.08996 + 28.2970 R15 + 12.80832 R152 - 10.67869 R153 +
           5.98624  R154 - 1.32311 R155

where  R15 = Conductance of Sample/Conductance of Standard at 15oC
 
 
 

The Practical Salinity Scale of 1978
(No UNITS!)
 
 
    A standard seawater of salinity S = 35.000 (no units or are needed) has, by definition, a conductivity ratio of 1.0 at 15oC with a KCl solution containing a mass of 32.4356 g of KCl in a mass of 1 kg of solution. The salinity dependence of the conductivity ratio was determined by measuring the conductivity (C) ratio at various temperatures of S = 35.000 seawater weight evaporated or diluted with water.

S = a0 + a1 RT1/2 + a2 RT + a3 RT3/2 + a4 RT2 + a5 RT5/2 + DS

where

DS =  [(t - 15)/ (1 + k(t-15))] b0 + b1 RT1/2 + b2 RT + b3 RT3/2  + b4RT2 + b5 RT5/2
 
        a0 =  0.0080      b0 =  0.0005
        a1 = -0.1692      b1 = -0.0056        k = 0.0162
        a2 = 25.3851      b2 = -0.0066
        a3 = 14.0941      b3 = -0.0375
        a4 = -7.0261       b4 =  0.0636
        a5 =  2.7081       b5 = -0.0144

       åai = 35.000     å bi = 0.0000

RT = C(S, t, 0)/C(35, t, 0) at atmospheric pressure (p = 0)

 
Methods of Determining Salinity
 

Conductivity
 
 

The specific conductivity is defined as

LSP= k/R = l /A R 

where R is the resistance and the cell constant k equals the distance (l) between the electrodes (usually platinum) divided by the cross-sectional area (A) of the electrodes. The equivalent conductance L is defined as the conductance of 1 gm equivalent of the electrolyte

L =  1000 LSP/N

where N is the normality [eq/liter].  Since conductance is a function of temperature, it is necessary to make the measurements at a constant or known temperature for precision's of ± 0.001 in salinity.
 

Density

S = 1.3343 (r - r0)103 + 2.155306 x 10-4 x [(r - r0)103]2 -1.171160 x 10-5
  [(r - r0)103]3
 
 
Sound Speed

S = 0.91712 (U - U0) + 7.670097 x 10-4 x (U - U0)2 - 1.107557
      x 10-5 (U - U0)3

Refractive index

S = 35.00 + 5.3302 x 10-3 Dn + 2.274 x 10-5  Dn2 + 3.9 x 106 Dn3
  + 10.59 Dn (t - 20) + 2.5 x 102 Dn2 (t - 20)2
 

Preparation of 1 Kilogram of 35.00 of Artificial Seawater
 

A. Gravimetric Salts

Salt                    grams/kg        moles/kg          M.W.

NaCl                      23.9849                0.41040                58.4428
Na2SO4                  4.0111                0.02824               142.0372
KCl                         0.6986                 0.00937                74.5550
NaHCO3                0.1722                 0.00205                84.0070
KBr                        0.1000                 0.00084               119.0060
B(OH)3                  0.0254                 0.00041                 61.8322
NaF                        0.0029                 0.00007                 41.9882
                             28.9951

B. Volumetric Salts

Salts             grams/kg          moles/kg                M.W.

MgCl2           5.0290              0.05282          95.211
CaCl2            1.1409              0.01028        110.986
SrCl2             0.0143              0.00009        158.526

Use  1 molar MgCl2 ,  CaCland  SrCl2 (standardize by  AgNO3 titration). 52.8 ml of 1 molar MgCl2 , 10.3 ml of 1 molar CaCl2 and 0.1 ml of 1 molar SrClare needed. The densities of these solutions are 1.017 g/ml and 1.013 g/ml, respectively, for MgCl2 , CaCl2 and SrClsolutions at 1 molar. The grams of water of in each solution are given by

H2 O = gSOLN - gSALT =  ml x density  - gSALT

C.  Addition of Water

gH2 O to add = 1000 - gH2 O from MgCl2 , CaCl2 and SrCl2
 
 
 

Calculation of the Salinity for Average Seawater From Composition Data
 

                          Before Evaporation          After Evaporation

                          gms HCO3-     0.1070          gms          0.0137
                          gms CO32-      0.0161          gms          0.0043
                          gms CO2         0.0005          gms          0.0000
                          gms Br          0.0672          gms Cl      0.0298
                                                 0.1908                           0.0478

gms of salts loss from
          HCO3-, CO32- and Br0.1908 - 0.0478 = 0.1430
gms of B(OH)3 lost                                          = 0.0275
total salts  lost                                                 = 0.1705

 

gT                       35.1716
Loss of salts        -0.1705
                                  35.0011

Precision in Salinity Determined by Using Various Methods
 
 
    1)  Composition Studies of major components          ±  0.01

    2)  Evaporation to dryness                                         ±  0.01

    3)  Chlorinity                                                             ±  0.002

    4) Sound Speeds                                                        ±  0.03

    5)  Density                                                                 ±  0.004

    6)  Conductivity                                                        ±  0.001
 
    7) Refractive index                                                    ±  0.05

 
 
 
Causes of Major Components Not Being Conservative
 

A. Estuaries

The total grams of salts (gT ) are given by

    gT = gR + [(35.171 - gR)/19.374]  Cl()  

where gR is the grams of river salts.

                [gE - gSW] 19.374
      gR  = ¾¾¾¾¾¾¾¾
                19.374 - Cl()

      gSW = ki x Cl()

where ki is the average ratio of gi/Cl for seawater.

g(E) = 0.092 + 1.80271 Cl()

B. Evaporation in isolated basins

C. Admixture with brines

D. Precipitation and dissolution

E. Submarine Volcanism

F. Exchange between atmosphere and sea

G. Anoxic Basins

H. Freezing

I. Interstitial Waters
 

Composition of Baltic Surface Waters
 

Solute     Lyman & Fleming         Best Estimate

Na+                  ---                          5.4 ± 3.8
Mg2+                  2.3                      2.9 ± 0.5
Ca2+                 15.4                    21.1 ± 0.6
K+                    --                            0  ± 0.5
Sr2+                  --                               ----
Cl-                     --                               ----
SO42-                6.1                       6.0 ± 1.0
HCO3-             49.3                     84.6 ± 4.2
Br-                    --                          0.0 ± 0.8
B(OH)4-           --                              ----
F-                     --                         0.06 ± 0.1
B(OH)3             --                         0.8 ± 0.03

Totals              72.8                  120.7 ± 11.5

gT = 0.073 + 1.8110 Cl (),  Lyman and Fleming (1900 data)

gT = 0.120 + 1.8092 Cl (), Millero (1967 data)

Composition of River Water Entering the Baltic
                                          gi(R)103, g kg-1

Ion                  Surface                    Deep                Weighted
                        Waters                    Waters               Average

Na+                  5.4 ± 8.3              5.3 ± 10.1              5.3 ± 9.3
K+                   -0.8 ± 1.5             -0.9 ± 1.8              -0.9 ± 1.7
Ca2+                21.1 ± 1.1            20.9 ± 1.3             21.0 ± 1.2
Mg2+                2.9 ± 1.3               3.0 ± 2.1               3.0 ± 1.8
HCO3-             84.6 ± 4.7             88.1 ± 4.7             86.5 ± 4.7
SO42-                6.0 ± 3.8               3.3 ± 5.0              4.4 ± 4.5
Br-                   -0.7 ± 0.2              -1.1 ± 0.6             -0.9 ± 0.4
F-                      0.06 ± 0.02           0.06 ± 0.03          0.06 ± 0.03
B(OH)3             0.8 ± 0.4               0.8 ± 0.4               0.8 ± 0.4

Total =           119.4 ± 21.3            118.5 ± 26.0            119.4 ± 24.0
 

Composition of 1 Liter of Average World River Water
 
Species              106gi             103ni         103ei          103Ii

Na+                     6.5              0.283           0.283         0.283
Mg2+                   4.1             0.169            0.337         0.674
Ca2+                  15.0             0.374            0.749         1.496
K+                       2.3             0.059            0.059         0.059
Cl-                       7.8             0.220            0.220         0.220
SO42-                11.2             0.117            0.233         0.466
HCO3-               58.4             0.950            0.950         0.950
CO32-                  ---             0.002            0.004          0.008
NO3-                    1.0            0.016            0.016         0.016
Si(OH)3O-             ---            0.005            0.005          0.005

1/2å =                                  1.086            1.428          2.089

Si(OH)4                     21.5              0.213                 0.213              --------

                            gT = 126.8    n= 1.299      e= 1.641          I= 2.089

To convert to molar units multiply by the density.  To convert to molal units divide by XH2O = 0.96483
 

Calculation of the infinite dilution equivalent
conductance of various waters at 25oC
 

                            Ei  L0ia
 
Ion               L0 i         Seawater              River              St. Lawrence
                                                                Water             River

Ca2+            59.51            46.97                  31.41                35.40
Mg2+           53.50              9.32                  12.71                13.15
Na+             50.10            38.71                    9.67                  7.24
K+               73.50             1.24                    3.06                   0.91
HCO3-         44.50             0.14                   29.79                25.19
SO42-          89.02             7.46                   13.14                 13.89
Cl-               76.35            68.77                  11.83                 18.61
NO3-           71.46              0.20                    0.81                    -

                   L0 =              127.85            112.2                114.41
 

a)  Ei is the equivalent function of species
b)  L0å Ei L0i

Sequence of Salts Formed from Evaporation of Seawater
 

Stage          Density          Wgt % liq.          Solid                        % of Total
                                                                                                        Solid
                   1.026               100
 

I                 1.140                 50                CaCO3 + MgCO3                1
II               1.214                 10                 CaSO4 (gypsum)                 3
III              1.236                3.9                NaCl (halite)                       70
IV                ---                    ---                Na-Mg-K-SO4 and             26
                                                                    KCl, MgCl2
 

Predicted Sequence of Salts Precipitated from The Evaporation of Seawater
 

                                                                                  %
Seg.      First Appearance        C.F.           H2O        I       a(H2O)       Faces
                                                                                  Left

a    G + Sol.                               3.62          27.63        2.6      0.929   pene-saline
b    A + Sol.                               9.82          10.18        6.6      0.772
c    A + H + Sol.                          0.82           9.24        7.2       0.744        saline
d    A + H + Gl + Sol.                  13.15           7.60        7.5       0.738
e                                            29.17            3.43         9.1     0.714
f    A  + H + Gl + Po + Sol.          38.50           2.60        10.1     0.697    super-saline
g   A + H + Po + Sol.                  44.76           2.23        10.7     0.685
h   A + H + Po + Ep + Sol.           73.56           1.36        13.0     0.590
      A + H + Po + Hx + Sol.           85.05           1.18        13.8     0.567
      A + H + Po + Ki + Sol.          102.40            0.98       14.9     0.498
i    A + H + Po + Ki + Car + Sol.  117.11           0.85        15.15   0.463
      A + H + Ki + Car + Sol.         159.74           0.62        15.33   0.457
      A + H + Ki + Car + Bi + Sol.   246               0.41         17.40  0.338

C.F.  is the concentration factor (C.F. = 1.0 for seawater)
is the ionic strength
a(H2O)  is the activity of water
Sol.  is the solution

Mineral AbbreviationsA, anhydrite, CaSO4; Bi, bischofite, MgCl2·H2O; Car, carnallite, KMgCl3·6H2O; Ep, epsomite, MgSO4·7H2O; G, gypsum, CaSO4·2H2O; Gl, glauberite, Na2Ca(SO4)2; H, halite, NaCl; Hx, hexahydrite, MgSO4·6H2O; Ki, kieserite, MgSO4·H2O; Po, polyhalite, K2MgCa2(SO4)4·2H2O.
 

Composition of Water with Respect
to the Different Forms of Water
 

Water                  Portion in                  Portion in              Comparable
Molecule             Total water               Heavy water           Concentration

  1H216O                          99.73                               -                                      -

  1H218O                            0.20                             73.5                                 Mg

  1H217O                            0.04                             14.7                                 Ca

  1H2H16O                         0.032                           11.8                                 K

  1H2H18O                       6 x 10-5                          0.022                              N

  1H2H17O                       1 x 10-5                          0.003                              Al

  2D216O                          3 x 10-6                          0.001                              P

  2D218O                          6 x 10-9                        2 x 10-6                            Hg

  2D217O                          1 x 10-9                        3 x 10-7                            Au
 
 
 
 

FURTHER READING
 

Aston, S .R., Estuarine Chemistry, Chapter 41, Chemical Oceanography, Vol. 7, 2nd Ed., J. P. Riley and  R. Chester, Academic Press, New York, 361-440 (1978).

Borchert, H., Principles of Oceanic Salt Deposition and Metamorphism, Chapter 19, Chemical Oceanography, Vol. 2, 1st Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 205-276 (1965).

Cox, R. A., The Physical Properties of Seawater, Chapter 3, Chemical Oceanography, Vol. 1, 1st Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 73-120 (1965).

Culkin, F., The Major Constituents, Chapter 4, Chemical Oceanography, Vol. 1, 1st Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 121-161 (1965).

Duce, R.A. , SEAREX: The Sea/Air Exchange Program, Chemical Oceanography, Vol 10, J. P. Riley, R. Chester, and R.A. Duce, Academic Press, New York, 1-14 (1989).

Grasshoff, K., M. Ehrhart and K. Kremling, Methods of Seawater Analysis,  Eds., (1983).

Riley, J. P., Analytical Chemistry of Sea Water, Chapter 21, Chemical Oceanography, Vol. 2, 1st Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 295-424 (1965).

Riley, J. P., Analytical Chemistry of Sea Water, Chapter 19, Chemical Oceanography, Vol. 3, 2nd Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 193-514 (1975).

Riley, J. P., Historical Introduction, Chapter 1, Chemical Oceanography, Vol. 1, 2nd Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 1-41 (1965).

Wallace,  C. Development of the Chlorinity-Salinity Concept, Elsivier, New York, (1974).

Whitfield, M., Electroanalytical Chemistry of Sea Water, Chapter 20, Chemical Oceanography, Vol. 4, 2nd Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 1-154 (1975).

Wilson, T. R. S., Salinity and the Major Elements of Sea Water, Chapter 6, Chemical Oceanography, Vol. 1, 2nd Ed., J. P. Riley and G. Skirrow, Academic Press, New York, 365-413 (1975).