1 Calculating the conductivity of natural waters

2 Rich Pawlowicz∗

3 Sept 26 2007

4 Running head: Conductivity of natural waters

∗
Dept. of Earth and Ocean Sciences, University of British Columbia 6339 Stores Rd., Vancouver, British
Columbia, Canada, V6T 1Z4. email: rich@eos.ubc.ca, tel: 604-822-1356
1 Abstract

2 An algorithm is developed to compute the conductivity of lake and dilute ocean water

3 from measured chemical composition at arbitrary temperature and pressure. The complex

4 mixed electrolyte is considered as a sum of binary electrolytes rather than a sum of ions.

5 Effects of ion association are included and it is found that pairing effects are important in

6 natural freshwaters. Bounds on the accuracy of the algorithm for specific classes of binary

7 electrolytes are assessed and it is estimated that the algorithm has an overall accuracy of bet-

8 ter than 2% for salinities less than about 4 g L−1 . Comparison with seawater conductivities is

9 much better than 1%, but predicted conductivities of some published analyses of river waters

10 are about 3% too high. Some of this difference may be due to a lack of data on ion pairing

11 effects between bivalent metals and bicarbonate but may also result from uncertainties in

12 the measured chemical composition and measured conductivity. An iterative procedure in-

13 corporating this algorithm is used to compute reference conductivity at 25◦ C and salinity

14 from in situ measurements of conductivity in waters where only relative amounts of ions are

15 known. It is found that the conversion to reference conductivity is reasonably independent

16 (to within about 1%) of the ionic composition for most world river waters, but is somewhat

17 different than that for KCl solutions. However, derived salinities are quite sensitive to the

18 composition, and the ratio of ionic salinity to reference conductivity varies between 0.6 and

19 0.9 mg L−1 (µS cm−1 )−1 .

2
1 Acknowledgements

2 Discussions with Roger Pieters, Bernard Laval, and the comments of an anonymous reviewer

3 greatly improved this work, which was supported by the Natural Sciences and Engineering Re-

4 search Council of Canada through grant 194270-04.

3
1 Introduction

2 The salinity (mass of dissolved salts per unit mass of solution) of seawater has for many

3 years been operationally estimated by measurements of its conductivity, and empirical equations

4 exist to convert between the two (Lewis, 1980). As a practical matter this is possible because the

5 relative ratios of the ionic constituents are similar enough in all oceans that similar conductivities

6 yield similar salinities (with an error ≪ 0.1%). The situation is somewhat different in freshwater

7 systems. Dissolved ions are present in amounts large enough that a conductivity (in the range of 5

8 to 7000 µS cm−1 ) can be easily measured, but as the relative ratios of these ions can vary widely

9 a conversion to salinity is not straightforward. However, once salinity is available, density and

10 a number of other thermodynamic properties can be computed using standard parameterizations

11 which are for many purposes insensitive to exact composition (Chen and Millero, 1986). A

12 standard practise is to convert measurements of conductivity κ (µS cm−1 ) at a temperature T (◦ C)

13 to a reference conductivity κ25 at a fixed temperature of 25◦ C using the approximate temperature

14 dependence of a typical electrolyte:

κ
κ25 = (1)
1 + 0.0191∆T

15 where ∆T = T − 25 is the temperature anomaly from 25◦ C (Clesceri et al., 1998, hereafter

16 SMEWW). Note that most freshwater has T < 5◦ C. Reference conductivity is then converted to

17 a measure of total dissolved solids (TDS, mg L−1 ) using a relationship such as

TDS = 0.65κ25 (2)

4
1 (Snoeyink and Jenkins, 1980), where the scale factor for different systems is known to vary

2 between 0.55 and 0.9 mg L−1 (µS cm−1 )−1 in general usage (SMEWW), and as high as 1.4 in

3 meromictic saline lakes (Hall and Northcote, 1986). The error arising from eqn. (1) when applied

4 to natural waters is not known, and the error arising from eqn. (2) could be as much as 30%. Ac-

5 curate determinations of salinity, which are required in many deep and weakly stratified systems

6 where salinity is an important contributor to density, and also in those of more exotic chemistry,

7 require some knowledge of the ionic composition and/or are restricted to specific systems for

8 which empirical governing relationships can be determined. SMEWW present a semi-empirical

9 method for relating salinity and κ25 (i.e. determining eqn. 2) by summing up infinite dilution

10 conductivities for all constituents and then scaling by a specified function of ionic strength. This

11 provides good results for North American fresh waters. Sorensen and Glass (1987) assumed

12 constancy of the product of viscosity and a power of conductivity (a modified Walden product)

13 and developed a pH-dependent formula for adjusting conductivities for lakes in Minnesota, Wis-

14 consin, and Michigan (i.e. to avoid eqn. 1). McManus et al. (1992) avoided both problems by

15 developing an empirical equation directly relating measured conductivity to salinity in Crater

16 Lake. This was done by fitting a polynomial to simultaneous measurements of conductivity and

17 temperature from two dilutions of lake water over a range of temperatures (similar to the method

18 used for seawater). Wüest et al. (1996), hereafter W96, presented a general parameterization

19 for predicting the conductivity of lake water from measurements of ionic composition and used

20 this to develop polynomial relationships between measured conductivities and salinity for Lake

21 Malawi. A similar approach that requires some speciation information a priori was described by

22 Talbot et al. (1990).

23 In general little information has been presented about the general reliability and limitations

5
1 of the different approaches (although they proved useful in the particular cases considered), nor

2 have they been formally developed. The physical chemistry of limnological conductivity is still

3 poorly understood (Hall and Northcote, 1986). Below we review existing theory, and then for-

4 mally develop and assess an algorithm for predicting the conductivity of natural waters of known

5 composition at arbitrary temperature and pressure, and for determining reference conductivity,

6 using principles of physical chemistry. The algorithm has two novel features: first, the com-

7 plex electrolyte is considered as a sum of binary electrolytes rather than a sum of ions, and

8 second, the effects of ion association (as well as relaxation and electrophoresis) are included

9 in the parametrization of binary electrolytes. All numerical parameters (other than pressure de-

10 pendence) are determined from basic chemical data. We also outline a procedure for estimating

11 salinity from measured conductivities using our algorithm. Comparisons are made to previous

12 formulations and the accuracy of the algorithm is evaluated using predictions of freshwater and

13 dilute seawater conductivities.

14 Theory

15 The problem of predicting the conductivity of dilute electrolytes is of general chemical in-

16 terest and much theoretical and experimental work has been carried out (e.g., Robinson and

17 Stokes, 1970; Barthel et al., 1998). It is convenient to deal with the equivalent conductivity Λ

18 ( µS cm−1 (mol L−1 )−1 ) which can be related to the measured conductivity κ of a binary elec-

19 trolyte of arbitrary concentration by:

κ = Λcne (3)

6
1 where c is the concentration (mol L−1 ) of the electrolyte, and ne = ν1 z1 = ν2 z2 . νi are the moles

2 of the ith constituent ion formed from each mole of electrolyte, and zi the algebraic valency

3 (absolute value of charge) on that ion. At low concentrations the equivalent conductivity of a

4 dissociated electrolyte can be represented by a limiting Debye-Hückel-Onsager equation of the

5 form
√
Λ = Λ◦ − (AΛ◦ + B) I. (4)

6 where Λ◦ is the infinite dilution equivalent conductivity, different for every electrolyte, and I

7 (mol L−1 ) the stoichiometric ionic strength:

N
c N
c
cX 1X
I= νi zi2 = ci zi2 (5)
2 i 2 i

8 Here ci = νi c are the ionic concentrations, and Nc = 2 the number of ionic constituents. The

9 first form for I is useful when dealing with simple electrolytes; the second will be useful when

10 dealing with natural waters (i.e. when Nc > 2). A, B are constants that can be developed from

11 theory in a dilute solution, depend on physical factors such as the viscosity and dielectric con-

12 stant, and respectively represent the leading terms in an expansion of the relaxation effect as the

13 solution rearranges behind the moving ions, and an electrophoretic effect from the viscous drag
√
14 of neighbouring moving ions. Formal expansions to higher orders of I have been developed

15 (e.g., Quint and Viallard, 1978), but the analytic forms are complex. In addition, the expansions

16 are of terms such as 1/(1 + ka′ ) where a′ is an “ionic diameter” which varies by less than a

17 factor 2 and k can be expressed as a function of other fundamental parameters. Numerically, ka′
√ √
18 is of order zi I (∼ zi2 c) which must formally be ≪ 1. Validity is thus marginal in lakewaters

7
1 for ionic constituents with a valency greater than 1 for any order of expansion. More complex

2 theoretical approaches have also been applied to less dilute systems (e.g., Anderko and Lencka,

3 1997). As a practical matter many different quasi-empirical forms parameterizing finite dilution

4 effects have been proposed (see, e.g., Robinson and Stokes (1970), Horvath (1985), or Barthel

5 et al. (1998) for summaries) to provide useful predictions at greater concentrations than those

6 modelled by eqn. (4). All of these approaches are generally limited to simple binary electrolytes

7 that dissociate into an anion and a cation and require constants which are determined from data.

8 At infinite dilution the equivalent conductivity of a binary electrolyte Λ◦ is exactly the sum

9 of infinite dilution ionic equivalent conductivities for the cation (λ◦+ ) and anion (λ◦− ):

Λ◦ = λ◦+ + λ◦− (6)

10 and so at small concentrations a modification of (3):

Nc
X
κ= ci zi λi (I) (7)
i

11 with Nc = 2 is taken as a starting point for determining the conductivity of dilute systems

12 in general, where the ionic equivalent conductivities λi are each dependent on ionic strength

13 and can be modelled by an equation which has a limiting form (4). An obvious generalization

14 proposed by W96 and Talbot et al. (1990) for natural waters is to use (7) with Nc > 2 (i.e. to add

15 together the effects of all ions present). A problem with this approach is that the conductivity

16 of some systems (notably 2:2 electrolytes like MgSO4 but also a number of 1:1 electrolytes

17 involving NO3− or ClO4− ) is somewhat less than this sum at even very small concentrations. Ion

8
1 pairing, a mechanism not included in (4), provides a self-consistent explanation for this effect.

2 Ion pairing or association occurs when oppositely charged ions are closer than a certain crit-

3 ical distance. They then act as a neutral molecule (in symmetrical electrolytes) and hence do

4 not contribute to conductivity. The standard way of dealing with this situation is to presume a

5 dissociated fraction α̃ ≤ 1, so that

2
X
κ = α̃ ci zi λi (α̃I) (8)
i

6 Parameterization of α̃ involves both an association “constant” KA for the particular ion pair

7 involved through an equilibrium of the form

Mg 2+ + SO42− ⇄ MgSO4

8 with
1 − α̃
KA = (9)
α̃2 cf 2

9 where f ≤ 1 is an activity coefficient for the ions parametrizing the deviations from ideal ther-

10 modynamic behavior of the solution (Davies, 1962). In fact both KA and f are also functions of

11 temperature and ionic strength. In very dilute solutions α̃ decreases with ionic strength, but this

12 decrease can slow or even (for ions with higher valencies) pass through a minimum at an ionic

13 strength of around 0.1–1 mol L−1 and then increase. Note that the conductivity parameteriza-

14 tion described by SMEWW also uses the activity, but applies it somewhat inappropriately as a

9
1 conductivity reduction factor for finite concentrations:

Nc
X
2
κ25 = f ci zi λ◦25
i (10)
i

2 with f (I) parameterized using the ion-independent monovalent Davies equation at 25◦ C (Davies,

3 1962) and λ◦25

i infinite dilution equivalent conductivities at 25◦ C. As we shall see, this semiem-

4 pirical procedure performs surprisingly well for lake waters, but badly for seawater of the same

5 conductivity.

6 If the electrolyte is a 2:1 system, say Mg(HCO3)2 , then ion pairs may also form but the pair

7 has a charge and can therefore contribute to conductivity:

Mg 2+ + 2HCO3− ⇄ MgHCO3+ + HCO3−

8 The theoretical basis for dealing with this situation in the standard approach is complex (Davies,

9 1962; Barthel et al., 1998) and as a practical matter, although association constants and activi-

10 ties have been estimated for the constituents of natural waters (Millero, 2001), other necessary

11 data, e.g., infinite dilution ionic equivalent conductivities for forms like MgHCO3+ , are virtually

12 nonexistent. However, noting that most ions other than H + and OH − have similar λ◦25
i (see, e.g.

13 Table 1) we can crudely estimate that the conductivity of the right hand side of this equilibrium is

14 about one half that of the left hand side solely because of the difference in the number of charges.

15 Thus pairing will still reduce the conductivity greatly.

16 To avoid the complexity and difficulties with lack of data in the standard approach, which

17 is required for investigations into chemistry but, we believe, is overly complicated for the more

10
1 practical matter of predicting conductivity to reasonable accuracy at the current state of knowl-

2 edge, our approach will therefore be to write

2
X
κ = α(I) ci zi λi (I) (11)
i

3 where α(I) ≤ 1 is now defined as an ionic-strength-dependent reduction factor for pairing and

4 speciation effects in a binary electrolyte. Its functional form (discussed below) will be assumed

5 constant for particular valency combinations, with an amplitude that is correlated with the avail-

6 able association constants when not directly available from data.

7 Materials and Procedures

8 In order to take into account ion pairing we generalize the existing theory for binary elec-

9 trolytes to one for complex electrolytes by considering the system as a weighted sum of binary

10 electrolytes formed by partitioning ions into all combinations of available anions and cations,

11 rather than a sum of ions as in eqn. (7). The weighting of the partition is by ionic equivalent

12 fractions, which was found by Anderko and Lencka (1997) to be effective in modelling ternary

13 electrolytes. We have:
N+ N− +
X X cj zj c−
k zk
κ= Λjk µS cm−1 (12)
j k
Ceq

14 where the equivalent concentration Ceq (mol L−1 ) is defined as

N+ N− N
!
c
X X 1X
Ceq = c+
j zj = c−
k zk , = ci zi (13)
j k
2 i

11
1 and can be computed from the sum of either cation or anion ionic equivalent concentrations (c+
j zj

2 or c−
k zk respectively) which are in principle identical in a neutral electrolyte. Here j subscripts

3 refer to cations with concentrations c+ −

j (mol L ), k subscripts to anions with concentrations ck ,
−1

4 Λjk is the equivalent conductivity of a binary subsystem formed from the combination of one of

5 the N+ cations and one of the N− anions, and Nc = N+ + N− .

6 As we typically have N+ , N− ∼ 5 in lakes using (12) implies knowing the equivalent con-

7 ductivity of ∼ 25 compounds over a range of temperature, concentration, and pressure. Such

8 data is not available. Instead we write:

Λjk = (λj + λk )αjk Γ(p) (14)

9 so that we must only parameterize the equivalent conductivities for ∼ 10 individual ions, adding

10 an ion pairing reduction factor αjk for those combinations that require it, and using a general

11 pressure dependence. Note that this formulation (eqns. 12-14) can be rewritten as:

Nc
X
κ= ci zi λi (I)αi Γ(p) (15)
i

12 where αi ≤ 1 is an equivalent-fraction-weighted average of the αjk associated with all the other

13 cations for an anion and all the other anions for a cation. This shows the relationship between

14 the procedure developed here with expansions of the form (7).

15 There are many possible parameterizations for the ionic equivalent conductivities. After

12
1 testing several, we find that a simple representation of the form

λ◦i
λi = √ (16)
1 + ai zi I

is sufficiently accurate. Temperature and pressure dependence in situations other than T = 25◦ C

and p = 0 is parameterized by multiplicative terms:

λ◦i = λ◦25
i (1 + fi (∆T )) µS cm−1 (mol L−1 )−1 (17)

ai = a25
i (1 + β∆T ) (mol L−1 )−1/2 (18)

Γ(p) = 1 + γp (p)(1 + γT (∆T )) (−) (19)

2 At constant temperature and pressure there is only one parameter (ai ), usually slightly less than

3 1 in these units, that must be determined empirically for each ion, but having this term in the de-

4 nominator gives it a slightly wider range of validity than a form like (4). This form is simpler than

5 the 4-term expansions generally recommended for analysis of binary electrolytes (Barthel et al.,

6 1998) and thus cannot be valid at salinities or conductivities that are too high, but as we must

7 estimate the unknown coefficients for some important ions (like CO3− ) without sufficient data it

8 is more robust. fi are polynomials that express approximate doubling in λ◦i over temperatures

9 between 0◦ C and 35◦ C, and β a change of about 10% in ai over the same range. Pressure-related

10 changes are relatively small (of order 0.1% over 100 m) but are included for completeness. One

11 advantage of this parameterization is that the numerical parameters other than λ◦25
i are gener-

12 ally very similar. This facilitates the approximation of effects arising from more exotic ions not

13 included here, if desired.

13
1 We parameterize the pairing reduction using a gaussian curve:

√ √ 0 )2
−wjk (log I−log Ijk
αjk = 1 − Ajk e (20)

0
2 where the center Ijk and width wjk are taken to be constant for particular combinations of valen-

0
3 cies, so that only an amplitude Ajk must be specified for each ion pair. The center Ijk is larger

4 than typical ionic strengths of interest (i.e. we generally need only a monotonically increasing

5 segment of this functional form). Temperature dependence is again of the form

Ajk = A25
jk (1 + β∆T ) (21)

6 Numerical values for all ionic parameters are listed in Table 1, and those that are taken as

7 similar for all ions in Table 2. Interaction amplitudes are given in Table 3. In addition, lim, a

8 toolbox containing programs implementing these procedures (as well as all required ancillary cal-

9 culations) in MATLAB, is available from the author at http://www.eos.ubc.ca/˜rich.

10 Note that we have estimated these parameters for 24 ions and not just the 11 limnologically im-

11 portant ones in order to better assess the algorithm, and to facilitate application in waters with

12 exotic chemistry.

13 Equations (12-21) can be used to determine the conductivity of a sample with known chem-

14 ical composition at specified temperature and pressure. Salinity is found merely by summing

15 the various constituents. Alternatively, it may be useful to use measurements of conductivity

16 to estimate the salinity in a particular system. Rather than develop a second set of equations

17 specifically for this purpose we can perform this calculation by iteration. Note that salinity deter-

14
 fi = F1 ∆T + F2 ∆T 2 + F3 ∆T 3
Ion zi λ◦25
i ai F1 F2 F3
◦ −1 ◦ −2
- mS cm −1
(mol L −1 −1
) (mol L−1 )−1/2 ( C) ( C) ( C)−3
◦
2+
Ca 2 59.47 0.85 2.213 × 10 −2
9.854 × 10 −5
−1.027 × 10−6
Mg 2+ 2 53.00 0.90 1.901 × 10−2 2.096 × 10−5 -
Na+ 1 50.08 0.80 2.189 × 10 −2
9.159 × 10 −5
−1.127 × 10 −6

NH4+ 1 73.50 0.62 1.931 × 10−2 1.113 × 10−4 2.546 × 10−6

K+ 1 73.48 0.62 1.941 × 10−2 5.786 × 10−5 −1.593 × 10−7
Cl− 1 76.31 0.62 2.012 × 10 −2
6.217 × 10−5 −4.921 × 10−8
HCO3− 1 44.50 0.91 1.909 × 10−2 1.573 × 10−5 −1.320 × 10−6
NO3− 1 71.42 0.74 1.874 × 10−2 6.764 × 10−5 8.948 × 10−7
F− 1 55.40 0.80 2.089 × 10 −2
- -
CO32− 2 69.30 0.74 1.772 × 10 −2
−6.001 × 10 −5
-
SO42− 2 80.00 0.74 2.119 × 10 −2
6.746 × 10 −5
-

H+ 1 349.65 0.30 1.388 × 10−2 −3.152 × 10−5 −6.372 × 10−7

OH − 1 198.00 0.31 1.644 × 10−2 1.403 × 10−5 4.500 × 10−6

Ba2+ 2 63.60 0.83 2.084 × 10−2 8.885 × 10−5 -

Sr 2+ 2 59.40 0.84 2.096 × 10−2 7.322 × 10−5 -
Ag + 1 61.90 0.62 1.969 × 10−2 4.308 × 10−5 -
Li+ 1 38.66 0.96 2.294 × 10−2 1.313 × 10−4 4.451 × 10−7
Br − 1 78.10 0.60 1.960 × 10−2 6.678 × 10−5 4.371 × 10−7
I− 1 76.80 0.61 1.950 × 10−2 6.370 × 10−5 7.755 × 10−7
ClO4− 1 67.30 0.66 1.724 × 10−2 −2.359 × 10−5 -

Zn2+ 2 52.80 0.80 2.200 × 10−2 1.287 × 10−4 -

Cu2+ 2 53.60 0.80 2.329 × 10−2 1.676 × 10−4 -

La3+ 3 69.70 0.81 2.191 × 10−2 8.119 × 10−5 -

F e(CN6 )4+ 4 110.4 0.62 - - -
Table 1: Ion-dependent numerical parameters. Limnologically important ions are listed at the
top.

15
 Parameter Value
β 1/300 (◦ C)−1
γp (p) 9.0718 × 10−6 p − 2.8013 × 10−10 p2 (-)
γT (∆T ) −2.5751 × 10−2 ∆T + 8.46082 × 10−4 ∆T 2 (-)

0
1:1 Ijk , wjk 0.6 (mol L−1 ), 0.24 (-)
0
1:2 Ijk , wjk 0.1 (mol L−1 ), 0.32 (-)
0
2:1 Ijk , wjk 0.1 (mol L−1 ), 0.32 (-)
0
2:2 Ijk , wjk 0.2 (mol L−1 ), 0.28 (-)
0
1:4 Ijk , wjk 0.1 (mol L−1 ), 0.54 (-)

Table 2: Numerical parameters taken as similar for all ions. See text for details.

A25
jk (-) Li+ Na+ K+ Ag + NH4+ Mg 2+ Ca2+ Sr 2+ Ba2+ Zn2+ Cu2+
F− 0 0.00- 0.00- 0 0 0 0 0 0 0 0
Cl− 0.00- 0.00+ 0.00+ 0 0.00+ 0.00+ 0.00+ 0.00+ 0.00+ 0.04- 0.04
Br − 0.00- 0 0.00+ 0 0 0 0 0 0 0 0
I− 0 0.00+ 0.00+ 0 0 0 0 0 0 0 0
NO3− 0.00- 0.00- 0.00+ .010+ 0.01- 0.00- 0.01- 0.03 0.05- 0 0
ClO4− 0.00+ 0.00+ 0.02+ 0 0 0 0 0 0 0 0
HCO3− 0 0.00+ 0.00+ 0 0 0.10 0.10 0.10 0.10 0.20 0.30
SO42− .015- 0.01+ 0.02- 0.06- 0.04- 0.27- 0.32- 0.13 0.30 0.33+ 0.36+
CO32− 0.11 0.11+ 0.12+ 0.11 0.11 0.35 0.45 0.20 0.42 0.66 1.00
F e(CN6 )4− 0 0.04- 0.10+ 0 0 0 0 0 0 0 0
Table 3: Numerical parameters for ion pairing interactions. Numbers with 2 decimal places
have been estimated in some way: trailing ‘+’ are estimates from data at 25◦ C, trailing ‘-’ are
from lower quality data mostly at 18◦ C, and remaining values were estimated by correlation
and/or similarity. Single digit numbers are values set to zero in the absence of any quantifiable
information, even through some, e.g. combinations of F − and bivalent metals, are known to pair
strongly.

16
1 mination is not possible without making additional assumptions about the chemical composition

2 of the system. In the simplest case, we assume that the system is composed of dilutions or con-

3 centrations of a known chemical composition, i.e. we have concentrations ĉi (mol L−1 ) for each

4 constituent (both ionic and nonionic) in a standard composition, so that at any actual location the

5 concentrations are ci = dĉi where d is an unknown scale factor. The true salinity S ′ (in units of

6 g L−1 of solution) is:

NX
c +Nn NX
c +Nn
′
S = ci Mi = d ĉi Mi (22)
i i

7 with Mi the molar mass of a particular constituent. The sum is over both the Nc ionic and Nn

8 nonionic constituents. We note that in situ measured conductivity:

Nc
X Nc
X
κ= λi (I)αi (I)ci zi = d λi (I(d))αi (I(d))ĉizi (23)
i i

9 depends sensitively on d through a multiplicative term on the RHS, and weakly through a de-

10 pendence of λi and αi on ionic strength I which in turn depends on d. To determine d we take

11 an initial guess d0 , compute I and thence the summation on the RHS of (23), dividing the mea-

12 sured conductivity κ by this sum to generate a new estimate d1 , and then repeat until values

13 d0 , d1 , d2 , ..., dN , ... converge, which tends to happen within a few iterations. The reference con-

14 ductivity κ25 is not actually needed to determine salinity, but if required it can then be computed

15 by setting T = 25◦ C in (23) once d is known.

16 Conversion of the salinity S ′ to salinity S (g kg−1 solution) requires a determination of the

17 density ρ which itself has a salinity dependence (Chen and Millero, 1986),

S = S ′ /ρ(S, T, p) (24)

17
1 Again this can be done iteratively, substituting numerical values of S ′ for S on the RHS, com-

2 puting a new S and then resubstituting on the RHS until convergence occurs.

3 In particular situations other assumptions and/or knowledge of the system may apply. For

4 example, the system may be a mixture of two different standard compositions. The above pro-

5 cedure could be modified to estimate the mixing faction. In addition, computation of density (or

6 other derived parameters such as static stability) to a useful accuracy may sometimes depend on

7 details of the chemical composition rather than on salinity alone (e.g., W96).

8 Data sources

9 The parameterization (12-21) is carefully written to allow us to determine the unknown nu-

10 merical parameters in a straightforward way. First, we parameterize the relationships at T =

11 25◦ C and p = 0 dbar using data available from numerous sources. Values for λ◦25
i are readily

12 available for a large variety of ions and can generally be taken from a single modern source; we

13 use Lide (2007). To determine a25 25

i data is required for λi at different concentrations, sources

14 were Lide (2007), except for carbonate data from Dean (1999). As such data is provided only for

15 binary electrolytes and not individual ions (i.e. for Λ25 25 25

jk = λj + λk ) an arbitrary initial choice

16 must be made. We take a25 +

i to be identical for Cl and K . Thereafter the ionic equivalent
−

17 conductivity for all other ions was obtained by difference, e.g., λ(Na+ ) = λ(NaCl) − λ(Cl− ),

18 where we use (12-21) for λ(Cl− ). Although not obvious in the original tables, during data reduc-

19 tion a small number of points appeared to show aberrant behavior compared to trends through

20 neighbouring points. These were deleted from the analysis. An inconsistency arose with tabula-

21 tions of K2 CO3 and Na2 CO3 which were listed as being measured at 18◦ C in both Dean (1999),

18
1 Dobos (1975), and Milazzo (1963), but whose trend using (4) was more consistent with Λo at

2 25◦ C from those and other sources.

3 Coefficients for the temperature dependence fi are obtained by fitting polynomials to data

4 available in older sources for a far smaller number of ions in the range 0 − 35◦ C. Tabled values of

5 λi for a given ion are sometimes numerically different in different sources, likely by scale factors

6 due to changes in the definitions of standard physical constants and/or experimental issues, so it

7 is more satisfying to use them only to determine relative changes. For most ions we take values

8 at 7 temperatures from Robinson and Stokes (1970). Values at 3 temperatures for CO32− , HCO3−

9 and several metals were found in Dean (1999), and a few more exotic ions were listed in Horvath

10 (1985).

11 A small joint temperature/concentration dependence occurs through variations in ai . Exam-

12 ination of this joint dependency is more speculative as tabulated data is scarce. However, on

13 theoretical grounds we expect the temperature-dependency in ka′ terms to be somewhat inde-

14 pendent of the particular ions so we take a best fit for tabulated KCl data (Lide, 2007) as being

15 generally applicable.

16 Ion pairing for bivalent metal sulphates was parameterized using data published by Tomšič

17 et al. (2002) and Bešter-Rogač et al. (2005) over a range of temperatures, as well as Lide (2007)

18 at 25◦ C. Data for some other electrolytes for which pairing effects needed to be estimated were

19 available only at a temperature of 18◦ in Dean (1999); the general quality (accuracy, number of

20 values) of this data appeared lower than that found in Lide (2007). When no conductivity data

21 was available we used correlations between fitted A25

jk and association constants in electrolytes

22 of like valency, tabulated in Smith and Martell (1976), Millero (2001), and Millero and Hawke

23 (1992), to estimate other A25

jk .

19
1 The pressure dependence was determined from measurements of the conductivity of seawater

2 with salinities in the range of 2 to 35, temperatures from 0 to 30◦ C and pressures from 0 to 4000

3 dbar (Bradshaw and Schleicher, 1980). As salinity dependence is weak over the limnological

4 range and including it would complicate the method we ignore it by extrapolating data to a

5 salinity of zero.

6 An independent data set for binary compounds at a temperature of 18◦ was taken from Dean

7 (1999) for verification of predictions. Practical accuracy was determined by comparison with

8 measured conductivities and chemical compositions of lake and river waters listed in Wetzel

9 (2001) and Hamilton (1978). For seawater comparisons we computed a salinity using equations

10 determined by Perkin and Lewis (1980) with the low-salinity correction of Hill et al. (1986) for

11 a given conductivity and temperature. We then used a salinity-dependent chemical composition

12 described by Millero (2001) to predict conductivity using our algorithm at the same temperatures.

13 This produced substantially better results than direct comparisons with an equation for conduc-

14 tivity as a function of salinity (Poisson, 1980) due to a lack of low-salinity data in derivation of

15 the latter.

16 Assessment

17 We first assess the degree to which the the available data shows the decomposition into ionic

18 conductivities (eqn. 7) to be valid when pairing does not occur, irrespective of the parametriza-

19 tions, by finding sets of 4 binary electrolytes whose equivalent conductivities should sum to zero

20 at concentrations where this is true. For example, the sum Λ(KCl) − Λ(KI) − Λ(NaCl) +

21 Λ(NaI) computed from tabulated values is less than 0.2% of Λ(KCl) at concentrations up to

20
 8
z =1
i

7 2
← Cu
2+ 2+
and Zn 3
4
6

5
4+
Fe(CN )
i

6
a25 z

4
i

CO2−
3 3

1
H+,OH− →
0
−3 −2 −1
10 10 10
Ionic Strength (mol L−1)

Figure 1: Variation of ai zi with ionic strength for 24 ions with valencies of 1 to 4. Note that
CO32− , Cu2+ , Zn2+ and F e(CN6 )4+ are not well modelled by this parameterization (curves are
neither flat nor clustered with others of similar valency), an indication that ion pairing effects are
present in the electrolytes from which the ion-specific data was derived.

1 0.1 mol L−1 , but for some other quads the residual was less than 0.4% only for concentrations

2 less than 0.01 mol L−1 . This would then represent a maximum achievable accuracy. We use such

3 comparisons to identify binary electrolytes with weakest pairing effects, and then add/subtract

4 them to estimate equivalent conductivities for particular ions at tabulated concentrations.

21
1 Ionic equivalent conductivities at finite concentrations

2 Having estimated values for λ25 25

i , we rearrange (16) to form an expression for ai zi as a

3 function of ionic strength:

 
1 λ◦25
i
a25
i zi =√ −1 (25)
I λ25
i

4 Results are shown in Figure 1 for all ions considered. Note the general clustering of lines for ions

5 of similar valencies, with clusters at equal intervals, demonstrating the validity of the dependence

6 on zi , with a few exceptions. Use of a constant a25

i is valid in regions where the curves are

7 relatively flat. The curves tend to bend downwards at higher concentrations and the effect is more

8 noticeable for higher valencies. The values in Table 1 are an average over the 3 measurements

9 for which I < 0.01 mol L−1 .

10 Curves for H + and OH − are flat but somewhat below the other monovalent species; this

11 is because their chemistry is slightly different. CO32− appears above the other trivalent species,

12 somewhat near the curve for the only ion with zi = 4, F e(CN)4+
6 . Both of these curves are

13 also not very flat but have a broad peak. This is an indicator that ion pairing is occurring in

14 the data from which these conductivities were derived. The subtractive procedure performs even
2−
15 less well for modelling 2:2 compounds. We derive a reasonable a25
i for SO4 from Na2 SO4 ,

16 but then if we try to model Zn2+ and Cu2+ (both of which are tabulated as compounds with

17 SO42− ) the curves suggest an a25

i increasing from about 6 to 12 as ionic strengths increase from

18 0.0005 to 0.01. We therefore set a25 2+ 2+

i for Cu , Zn , F
−
(for which we have no data at 25◦ C)

19 and F eCN64+ to a typical value for their valence, and also take the value for carbonate to be the

20 same as that for sulphate.

22
 0.015 Without density compensation
constant ai
0.01
temperature−compensated a
i
relative error in Λ

0.005

−0.005

−0.01
0 10 20 30 40 50
temperature (oC)

Figure 2: Relative error in predicted temperature dependence of KCl at a concentration of 0.01

mol kg−1 . Shown are the errors arising from ignoring the density correction, correcting for
density but without the temperature correction for ai , and finally from the full parameterization.

1 Temperature effects

2 Fitting polynomials for the relative temperature dependence of λ◦i is straightforward and

3 the residuals are all less than 0.3%, although this likely represents a slight overfitting (i.e. the

4 polynomial order is higher than required), which may mask inaccuracies in the data. Differences

5 in the order of the predicting polynomial arise because some ions are tabulated more extensively

6 than others so 3rd order fits are not always possible.

7 The effect of joint temperature and concentration dependence is small but systematic. Fig-

8 ure 2 shows the relative error in predicted conductivity at a variety of temperatures for a 0.01

23
 0.45
CuSO4 CuSO4
ZnSO4 ZnSO4
0.4 CaSO
MgSO4 4
K CO MgSO4
2 3
0.35 Na2CO3 Ag2SO4
K4FeCN6 (NH4)2SO4
0.3 Na FeCN K2SO4
4 6
KClO4 Ba(NO3)2
0.25 AgNO3 AgNO3
ij
1−α

0.2

0.15

0.1

0.05

0
−4 −3 −2 −1 −4 −3 −2 −1
10 10 10 10 10 10 10 10
−1 −1
Ionic Strength (mol L ) Ionic Strength (mol L )

Figure 3: Ion pairing effects for variety of binary electrolytes at a) 25◦ C and b) 18◦ C. Symbols
represent available data, and lines are estimated functional forms, fit by eye.

1 mol kg−1 KCl solution, with and without a β = 1/300 (◦ C)−1 dependence. In order to correctly

2 account for this effect it is necessary to convert to concentrations into units of mol L−1 using

3 density computed according to Chen and Millero (1986) as the systematic error from neglect-

4 ing this is larger than the joint dependence. The remaining underestimate of about 0.2% arises

5 from the a25

i parameterization. We find that an identical parameterization adequately reduces the

6 temperature dependence of pairing effects in metal sulphates and thus assume it to be general.

7 Pairing effects

8 To determine the pairing reduction factor parameterization (Tables 2 and 3) we compare

9 predictions without pairing to measurements of the actual conductivities of various binary sub-

24
1 systems at different ionic strengths. The ratio of these two is αjk (I), and estimates of this from

2 available data are shown in Fig. 3. After some experimentation it was found that pairing data
√
3 was generally well described by one side of a gaussian curve in log I. The gaussian curve is

4 described by 3 parameters - a width, amplitude, and center. As the available data does not con-

5 strain the center very well (curves whose peaks are rightwards and above the present ones have

6 a virtually identical goodness-of-fit) it seemed more useful to set the width and center parame-

7 ters to empirical constants for each set of valencies, changing only the amplitude of the curve

8 for different ion pairs. Amplitudes are fitted by eye, with a bias towards matching the data at

9 lower ionic strengths as inaccuracies in our parameterization (16) which is used in deriving the

10 plotted points becomes large at higher strengths. The largest reductions are found for 2:2 metal

11 sulphates.

12 The available derived amplitudes correlate well with association constants (log KA ) tabulated

13 in Millero (2001) allowing us to estimate the others. We derive amplitudes for bivalent metal

14 carbonate αjk by scaling those for bivalent metal sulphates by the ratio of tabulated log KA . 1:2

15 sulphates show pairing effects of around 5% at I = 0.1 mol L−1 in spite of the lower data quality

16 at 18◦ C. This is about 20% of the effect seen in 1:2 carbonates, although in this case tabulated

17 association constants suggest that the pairing effects should be similar so correlation does not

18 seem useful here. Instead we estimate the reduction for unknown 1:2 carbonates by setting them

19 to the value found for Na2 CO3 .

20 Metal bicarbonates are a limnologically important subsystem. Association constants for

21 metal carbonates and bicarbonates are well correlated (Millero and Hawke, 1992), so we could

22 estimate the reduction amplitude by scaling the metal carbonate amplitudes by the ratio of

23 log KA , and then taking only half of this amplitude to take into account the charge on the pairs as

25
1 discussed earlier. Alternatively we note that association constants for the 1:2 metal bicarbonates

2 and Na2 CO3 are very similar, and use the same reduction. Both approaches give approximately

3 the same value but we use the latter as being somewhat safer. Note that the comparisons with

4 measured river waters discussed later can be greatly improved if we double these reduction fac-

5 tors but at present there seems to be no justification for doing so.

6 Electrolytes with NO3− and ClO4− are also slightly prone to pairing, and we see in Figure 3 a

7 decrease of a few percent at I = 0.1 mol L−1 . Cl− shows signs of pairing with Zn2+ (and hence

8 presumably with Cu2+ as well), but not with any other ion. We have limited data for F − which

9 is known to pair strongly with bivalent metals but since such combinations are not limnologically

10 important we make no correction. No information is known about the behavior of Br − and I −

11 with bivalent metals. Bivalent metal hydroxides are also known to associate reasonably strongly

12 but again we have no conductivity data.

13 Overall accuracy for binary electrolytes

14 Figure 4a-c shows the relative error in predictions of conductivity without pairing against

15 tabulated values for 30 binary electrolytes at 25◦ C. The error when pairing effects are included

16 is shown in Fig. 4f-h and is generally less than 1% for concentrations up to 0.01 mol L−1 . Three

17 points in Fig. 4a and 4f below the rest are for NaHCO3 . Interestingly the underestimate is

18 roughly constant with changing concentrations, a pattern not generally seen when other parame-

19 terization errors arose, possibly suggesting a systematic error in tabulated data. Other than these

20 anomalies the error is a mix of over- and under-estimates. We also find the prediction error for

21 a further 34 compounds whose conductivities at 18◦ C were listed in Dean (1999) (Fig. 4d-e

22 without pairing, and 4i-j with pairing effects included). A typical error is on the order of 2% for

26
 1:1 2:1/2:2 3:1/4:1 1:1 (18°C) 2:1/2:2 (18°C)
relative error in Λ

0.1

0.05

−0.05 a b c d e

1:1 2:1/2:2 3:1/4:1 1:1 (18°C) 2:1/2:2 (18°C)

0.04

0.02
relative error in Λ

−0.02

−0.04
f g h i j
−0.06
−3 −2 −1 −3 −2 −1 −3 −2 −1 −3 −2 −1 −3 −2 −1
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
−1
Concentration (mol L )

Figure 4: Relative error in our parameterizations for 65 binary electrolytes. (a)-(e) are predictions
without the pairing parameterization, (f)-(j) include pairing. Note change of vertical scale. (a,f)
1:1 electrolytes at 25◦ C. (b,g) 2:1 and 2:2 electrolytes at 25◦ C. (c,h) 3:1 and 4:1 electrolytes at
25◦ C. (d,i) 1:1 electrolytes at 18◦ C. (e,j) 2:1 and 2:2 electrolytes at 18◦ C.

27
 4
700
40 −0 −0. 0
00 .00 01
3.5 5
0
3 600
0
0.0
05

2.5 500
0
−0.005
salinity

2 3000

1.5 0
2000
1
0.01

0.5 1000
5
0 .00
0 5 10 15 20 25 30
temperature (oC)

Figure 5: Relative difference (thick lines) between conductivities predicted for seawaters of dif-
ferent salinities and temperatures using both the algorithm developed here and standard seawater
equations (see text for details). Thin lines are contours of conductivity (µS cm−1 ). Conductivity-
based salinities are unitless but are numerically close to g kg−1 .

1 concentrations up to 0.01 mol L−1 in all cases, and somewhat better than that for 1:1 electrolytes,

2 with predicted conductivities being biased downwards at highest ionic strengths. Note that many

3 of the curves appear to be shifted vertically (accounting for much of the scatter); this arises from

4 disagreement in values of λ◦i at 18◦ C derived from different sources. The comparisons in Fig. 4

5 are perhaps overly accurate as most of the data was also used in estimation of one or more of our

6 empirical parameters.

28
1 Accuracy for natural waters

2 Although the performance of our algorithm for binary electrolytes is satisfactory it is not

3 clear if similar results can be expected for more complex (e.g., natural) systems. The most

4 comprehensive measurements of natural systems are those for seawater with salinities in the

5 range of 0.005 to 42. Using the standard seawater salinity/conductivity relationship and the

6 ionic composition of seawater (ignoring the minor constituent B(OH)−

4 for which we have no

7 chemical data) we show the relative error in our algorithm in Figure 5. The difference between

8 the two is < 1% for salinities less than 3 over virtually all temperatures, (i.e. over roughly a

9 doubling in conductivity at fixed salinity), with largest errors at 0◦ C. As this bias is systematic it

10 may be due to lesser accuracy and/or scarcity of λ◦i data at low temperatures.

11 Next, the effectiveness of the algorithm at 25◦ C for a variety of North American waters is

12 shown in Figure 6. The observational dataset is not without its own problems, which we can see

13 when first estimating the conductivity by simply summing up the infinite dilution conductivities

14 for each ion (i.e. using λi = λ◦i in eqn. 7). As this would be an upper bound (it ignores

15 all ionic interactions, and overestimates conductivity by about 16% in this dataset) it suggests

16 that at least two data points near κ25 ≈ 50 µS cm−1 are problematic. We apply our algorithm

17 without ion pairing and find it gives results almost identical to those using the algorithm of W96

18 (also shown). Thus including relaxation and electrophoresis effects reduces the overestimation

19 to about 8%. Including the ion pairing effects of bivalent metal sulphates reduces the error to

20 about 4% on average, and adding the effects of metal carbonate pairing using the full algorithm

21 reduces this to 3%, with a root-mean-square difference (RMSD) of 5%. The SMEWW algorithm

22 overestimates the conductivity by about 2% (RMSD 4%) for this particular set of freshwater data.

29
 ↑
0.25 a (0.47) b
0.015
0.2
Freshwater
0.15 0.01 I=0
25
Relative error in predicted κ

W96
0.1 No−pairing
Full
0.005
SMEWW
0.05
Seawater
0 0 I=0
W96
−0.05 No−pairing
−0.005 Full
SMEWW
−0.1

−0.01
1 2 3 2 3
10 10 10 10 10
Measured κ (µS cm−1)
25

Figure 6: Comparison between measured and predicted κ25 for 32 North American rivers (dis-
crete symbols, Hamilton, 1978), as well as for seawater for salinities of 0.1-3 (lines). Shown
are results from our full algorithm, with and without pairing effects, and without ionic-strength-
dependence, as well as the methods proposed by W96 and SMEWW. a) All points. b) Seawater
only (note change in vertical scale)

30
1 Performance of our algorithm is not as good as the comparison with binary electrolytes but much

2 of this mismatch could occur because of uncertainties in the chemical analysis. The relative

3 error Ê in κ25 arising from the chemical analysis can be estimated by normalizing the difference

4 between anion and cation sums (and by taking advantage of the fact that κ25 ≈ 105 Ceq in our

5 units for fresh waters):

P + + PN−
∆κ25 | N
j zj cj −
−
k zk ck |
Ê = = PN+ + PN− (26)
κ25 j zj cj +
−
k zk ck

6 We find Ê is about 2% here, typical for high-quality data with κ25 > 300 µS cm−1 (SMEWW).

7 In addition, laboratory measurements of κ25 , even when done properly, typically have an un-

8 certainty of at least 1 − 2%. This could account for half of the RMSD, suggesting that the

9 parametrization error is at most only a few percent.

10 We also show on this figure the error in predictions of conductivity for dilute seawater at

11 25◦ C with salinities of 0.1 to 3. As discussed earlier, agreement is very good (to better than 0.2%

12 for κ25 < 3000 µS cm−1 ). However, the limnological “tuning” of the SMEWW algorithm for

13 freshwaters is shown clearly as it underestimates the conductivity of seawaters by up to 20%.

14 Pairing related effects are small in seawater (a reduction of about 0.3%), but still substantially

15 improve the results. The error for our algorithm curves downwards with increasing conductivity

16 (which is roughly proportional to ionic strength), in the same fashion as the curves in Fig. 4,

17 whereas that of W96 curves upwards at similar conductivity.

18 To illustrate the wider utility of this algorithm we consider results for typical fresh waters.

19 Several tables describing the ionic composition of world river waters are given in Wetzel (2001).

20 Table 10-1 of that reference provides a breakdown by continent, and Table 10-2 provides a break-

31
 Full W96 SMEWW

Lake Malawi
Crater Lake
KCL
Seawater S=0.1
World (2)
Carbonate
Volcanic
Granite
Shale
Gneiss
Sandstone
World (1)
Asia
Europe
South America
Australia
North America
Africa

eqn. (1) a b c
158 160 162 164 166 101 10
2 0.5 0.6 0.7 0.8 0.9

κ25 for κ5=100 κ

25
S/κ
25

Figure 7: (a) κ25 for κ5 = 100 µS cm−1 . At top are shown results for two specific lakes (Mc-
Manus et al., 1992; Wüest et al., 1996) as well as a dilute seawater and a 1 mmol L−1 KCl
solution. Next are world average and averages by river type, followed by world average and
averages by continent (Wetzel, 2001). At bottom is the result assuming eqn. (1). Both the full
algorithm described here as well as that of W96 and SMEWW are used. (b) κ25 for same ionic
compositions. (c) Ratio of ionic salinity to κ25 for all water types.

32
1 down by the dominant rock type in the drainage. In addition, we take ionic composition of several

2 lakes from other papers. From this database we compute both ionic salinity and reference con-

3 ductivity (for this comparison we have neglected the nonionic components of salinity which can

4 be substantial and must be accounted for in practical situations). Figure 7b shows that computed

5 reference conductivity varies greatly from very small values in granitic basins to large values in

6 carbonate basins. Differences in the computed κ25 values using this algorithm and that of W96

7 can be as large as 5% but this is too small to be easily apparent in this presentation. The differ-

8 ences are more apparent when we show the ratio of salinity to reference conductivity (Fig. 7c);

9 this is equivalent to determining the numerical coefficient in eqn. (2). This ratio varies widely

10 from a low of 0.65 for African rivers and sandstone drainages to a maximum of 0.9 for carbon-

11 ate drainages. The generally lower conductivities using our algorithm results in ratios higher by

12 1-5% than those found using W96, but slightly smaller than those using SMEWW. The ratios

13 for dilute seawater and KCl solutions are around 0.5, somewhat smaller than that for most lake

14 waters.

15 Finally, in Figure 7a we illustrate the effect of differing chemical composition by computing

16 the reference conductivity for a measured conductivity of 100 µS cm−1 at T = 5◦ C for each

17 case. The computed κ25 vary between 160 and 161.6 µS cm−1 for all compositions, i.e. we

18 can consider the correction to be composition-independent to within about ±1%. Eqn. (1) per-

19 forms admirably in spite of its crudeness, predicting a numerical correction within 1% of our

20 composition-dependent corrections. Taking the composition to be pure KCl is less useful as the

21 computed reference conductivity is less than 159 µS cm−1 , but in most situations careful calibra-

22 tion would be required to differentiate between the two. Repeating the procedure for a measured

23 conductiviy of 1000 µS cm−1 results in a slightly larger variation of about 3%. It appears that

33
1 the major advantage of our algorithm is not in computing reference conductivity itself (except as

2 a quality-control measure for chemical analyses), but rather in computing the salinity (or at least

3 the numerical factor in eqn. 2). By combining the parameterization of W96 for computing con-

4 ductivity with our iterative procedure for determining reference conductivity we can sensitively

5 test the apparent difference between the two parameterizations. Their algorithm gives values

6 about 1 µS cm−1 higher in all situations except for the KCl solution (which is well-modelled).

7 The constant difference suggests a systematic bias between the two parameterizations which is

8 likely related to the form (16) as ion pairing corrections do not seem to affect the reference con-

9 ductivity calculation to any great extent. Although the calculation in SMEWW is not claimed

10 to be valid for temperatures more than a few degrees away from 25◦ C we can also apply it in

11 this case. As they also take temperature dependence to be constant for all constituents not sur-

12 prisingly the predicted reference conductivity is independent of chemical composition; it is also

13 somewhat high.

14 Discussion

15 The conductivity of natural waters depends on chemical composition. Conductivity is re-

16 duced by the effects of relaxation and electrophoresis at finite concentrations, and by ion asso-

17 ciation between certain pairs of ions. Temperature dependence is strong over the limnological

18 range but is somewhat independent of the ionic composition. Pressure dependence is smaller.

19 The formal assessment of our algorithm clearly indicates the shortcomings of existing conduc-

20 tivity parameterizations and provides guidance about the uncertainties.

21 We find that the simple temperature correction (1) is sufficient to determine reference con-

34
1 ductivity with an error of around 1% for all water types considered. Sorensen and Glass (1987)

2 previously found that accounting for ionic composition changed the correction to reference con-

3 ductivity by an average of 0.3% for lakes in Minnesota, Wisconsin, and Michigan. Conversion

4 to salinity does require a knowledge of the ionic composition.

5 Electrophoresis and relaxation effects were accounted for in parameterizations described by

6 W96 and Talbot et al. (1990). However, our formulation, which requires only one empirically-

7 derived parameter per ion to model ionic-strength-dependence, appears to provide results as

8 good as those of the former when ion association does not occur, and is valid to slightly greater

9 concentrations than the more formal theoretical expansions utilized in the latter.

10 The strategy of considering natural waters as a mix of (possibly associated) binary elec-

11 trolytes, rather than a simple sum of ions as in all other parameterizations described, gives much

12 better results in lake waters because it naturally allows ions pairing effects to be included, and

13 the weighting by equivalent fractions reduces to a sum of ions when no pairing effects occur.

14 The numerical results indicate that ion association effects are not modelled in W96, and that

15 accounting for these effects leads to a significant improvement. Although our ion association

16 parameterization is relatively crude, it is sufficient to show that ion association is important in

17 fresh waters when κ25 is greater than about 50 µS cm−1 , but rather less so in dilute seawaters

18 of even the same (approximate) salinity. Also, it is found that pairing effects in bivalent metal

19 sulphates are generally more important than those in bivalent metal carbonates in their effect on

20 reductions in conductivity. Talbot et al. (1990) accounts for changes in conductivity due to spe-

21 ciation in metal bicarbonates, but requires speciation information a priori, and does not include

22 the more important effects arising from bivalent metal sulphates. An empirical reduction factor

23 that presumably accounts for all three effects, described in SMEWW, may perform slightly better

35
1 than our algorithm for some waters, but it clearly underperforms in dilute seawaters and hence is

2 not necessarily trustworthy.

3 Both W96 and Talbot et al. (1990) include a correction for temperature assuming the sepa-

4 rability of temperature and concentration dependencies but for more precise results a small joint

5 dependence must also be accounted for, as we do here (SMEWW is valid only near 25◦ C).

6 In addition to evaluating previously described methods of computing conductivity, the al-

7 gorithms described here should have wide utility in providing better estimates of the dissolved

8 solids in freshwater and estuarine systems with a TDS of less than around 4 g L−1 , of arbitrary

9 composition. A reliable determination of the accuracy of our algorithm is limited by uncertain-

10 ties in routine chemical analysis, but it appears to be accurate to at least within a few percent on

11 average, and perhaps much better. Even if more traditional techniques for salinity determination

12 are utilized this algorithm is useful as a check on the results.

13 Comments and Recommendations

14 The largest uncertainty in the development of the conductivity algorithm is related to the

15 effects of ion pairing with nonsymmetrical (i.e. 1:2) electrolytes. Not only are the available

16 theoretical guidelines very complex, but accurate laboratory measurements of conductivity (es-

17 pecially for the important carbonate and bicarbonate subsystems) are lacking.

18 For practical reasons we have largely avoided speciation issues in developing the algorithm,

19 with the exception of the carbonic acid system. Carbonate and bicarbonate ions are each ac-

20 counted for explicitly in the conductivity calculation. However, chemical analyses often char-

21 acterize this system using measurements of total alkalinity and pH. To convert to ionic concen-

36
1 trations dissociation constants are required; Millero (1995) provides the required equations valid

2 over a range of temperatures at ocean salinities of 0-5. Approximate freshwater salinities (e.g.

3 estimated via eqn. 2), appropriately scaled to the nondimensional ocean salinity scale, may be

4 substituted. A limnological equation of state (Chen and Millero, 1986) should be used to convert

5 from units of mol kg−1 solution to the units of mol L−1 that are used here. A further issue is that

6 the carbonate and bicarbonate ionic concentrations are assumed to remain constant with changes

7 in temperature in the reference conductivity and salinity calculations. In fact the pH of a closed

8 system will increase by order 0.1 for a 10◦ C decrease in temperature and this can change the ionic

9 concentrations slightly. The dependence may be worth investigating when highest precision is

10 required.

11 References

12 Anderko, A. and M. M. Lencka (1997). Computation of electrical conductivity of multicompo-

13 nent aqueous systems in wide concentration and temperature ranges. Ind. Eng. Chem. Res. 36,

14 1932–1943.

15 Barthel, J. M. G., H. Krienke, and W. Kunz (1998). Physical Chemistry of electrolyte solutions:

16 modern aspects, Volume 5 of Topics in physical chemistry. New York: Springer.

17 Bešter-Rogač, M., V. Babič, T. M. Perger, R. Neueder, and J. Barthel (2005). Conductometric

18 study of ion association of divalent symmetric electrolytes: I. CoSO4 , NiSO4 , CuSO4 and

19 ZnSO4 in water. J. Mol. Liquids 118, 111–118.

37
1 Bradshaw, A. L. and K. E. Schleicher (1980). Electrical conductivity of seawater. IEEE J.

2 Oceanic Eng. 5(1), 50–62.

3 Chen, C. T. and F. J. Millero (1986). Precise thermodynamical properties for natural waters

4 covering only the limnological range. Limnol. Oceanogr. 31(3), 657–662.

5 Clesceri, L. S., A. E. Greenberg, and A. D. Eaton (Eds.) (1998). Standard Methods for the

6 Examination of Water and Wastewater (20th ed.). Washington: American Public Health As-

7 sociation.

8 Davies, C. W. (1962). Ion Association. London: Butterworth & Co.

9 Dean, J. A. (Ed.) (1999). Lange’s Handbook of Chemistry (15th ed.). McGraw-Hill.

10 Dobos, D. (1975). Electrochemical Data: a Handbook for Electrochemists in Industry and

11 Universities. Amsterdam: Elsevier.

12 Hall, K. J. and T. G. Northcote (1986). Conductivity-temperature standardization and dissolved

13 solids estimation in a meromictic saline lake. Can. J. Fish. Aquat. Sci. 43, 2450–2454.

14 Hamilton, C. E. (Ed.) (1978). Manual on Water (4th ed.). ASTM Special Technical Publicaion

15 442A. Philadephia: American Society for Testing and Materials.

16 Hill, K. D., T. M. Dauphinee, and D. J. Woods (1986). The extension of the Practical Salinity

17 Scale 1978 to low salinities. IEEE J. Oceanic Eng. OE-11(1), 109–112.

18 Horvath, A. L. (1985). Handbook of Aqueous Electrolyte Solutions: Physical Properties, Es-

19 timation and Correlation Methods. Ellis Horwood Series in Physical Chemistry. Chichester:

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