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A new method of calculating electrical conductivity with applications to

natural waters

Article  in  Geochimica et Cosmochimica Acta · January 2012

DOI: 10.1016/j.gca.2011.10.031

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 Applied Geochemistry 26 (2011) S227–S229

Contents lists available at ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Electrical conductivity method for natural waters

R. Blaine McCleskey a,⇑, D. Kirk Nordstrom a, Joe N. Ryan b
a
US Geological Survey, 3215 Marine St., Suite E. 127, Boulder, CO 80303, USA
b
University of Colorado, 428 UCB, 1111 Engineering Drive, ECOT 441, Boulder, CO 80309-0428, USA

a r t i c l e i n f o a b s t r a c t

Article history: A new method is presented for calculating the electrical conductivity of a wide range of natural waters
Available online 26 March 2011 including acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water
impacted by municipal wastewater. The method has several advantages over previously published meth-
ods. New electrical conductivity measurements for electrolytes commonly found in natural waters pro-
vide a basis for improved calculation of ionic molal conductivities. In addition, the method is coupled to a
geochemical speciation model that is used to calculate the speciated concentrations required for accurate
conductivity calculations. The method can be used to calculate the electrical conductivity of most natural
water compositions and is accurate over a large range of effective ionic strengths (0.0004–0.7 m), temper-
ature (0–95 °C), pH (1.0–9.8), and conductivity (30–70,000 lS cm1). For the wide range of natural waters
tested in this study, transport numbers were calculated and the ions that contribute significantly to the
2 2
specific conductance were identified as H+ . Na+, Ca2+, Mg2+, NHþ +    3+ 2+
4 , K , Cl , SO4 ; HCO3 ; CO3 , F , Al , Fe ,
NO 3 and HSO4 .


Transport numbers can also be used to better predict the concentrations of ions in natural waters.
Another important application of the specific conductance method is checking the accuracy of water
analyses by coupling charge imbalance and specific conductance imbalance. Either the major cation or
anion concentrations for 50 different water samples were artificially adjusted and the constituent most
likely in error was easily identified. Considering the importance of accurate chemical analyses, the ability
to identify inaccurate determinations is critical.
Published by Elsevier Ltd.

1. Introduction method also uses speciated water analyses calculated with geo-
chemical models, rather than total solute concentrations.
Electrical conductivity is a water-quality property often mea-
sured when water samples are collected for chemical analyses.
Modern instrumentation allows rapid and reliable conductivity 2. Methods
measurements to be made in the field. Several methods have been
reported for calculating the conductivity of a natural water sample Depending on which electrolytes are present, the electrical con-
from its chemical composition (McNeal et al., 1970; Tanji and Big- ductivity increases 1–3%/°C (Robinson and Stokes, 1965); there-
gar, 1972; Rossum, 1975; Marion and Babcock, 1976; Laxen, 1977; fore, electrical conductivity is typically reported at 25 °C (j25) to
Miller et al., 1988; Pawlowicz, 2008; Visconti et al., 2010). How- standardize the effect of temperature. The j25 is calculated using
ever, existing conductivity methods for natural waters have been the following equation:
limited by the lack of conductivity data in the literature or not
j
properly accounting for the ion pairing. Consequently, the existing j25 ¼ ð1Þ
methods cannot be used to reliably calculate conductivity for a
1 þ aðT  25  CÞ
wide range of natural waters. Here a new method for calculating where j is the electrical conductivity at the solution temperature
conductivity for a wide range of natural waters is presented. The (T) in °C and a is the temperature compensation factor. The temper-
method incorporates new electrical conductivity measurements ature compensation factor is typically programmed into the con-
for electrolytes found in natural waters having ionic strengths of ductivity meter and ranges from 0.019 to 0.023 °C1. The
up to 1 m and temperatures of 5–90 °C (McCleskey, 2011). The electrical conductivity (j) of an aqueous solution can be calculated
from its chemical composition using the following equation:
X
⇑ Corresponding author. Tel.: +1 303 541 3079; fax: +1 303 541 3084. j¼ ki mi ð2Þ
E-mail address: [email protected] (R.B. McCleskey).

0883-2927/$ - see front matter Published by Elsevier Ltd.

doi:10.1016/j.apgeochem.2011.03.110
S228 R.B. McCleskey et al. / Applied Geochemistry 26 (2011) S227–S229

Table 1
Water analyses, calculated conductivity, and conductivity imbalance for a dilute mountain water, geothermal water, acid mine water, and sea water.

Sample ID Boulder Creek, Beryl Spring, Yellowstone Lemonade Creek, Yellowstone Iron Mountain, San Diego
Colorado National Park National Park California Bay
Date 6/12/2000 9/7/2003 9/7/2003 10/17/1975 1/15/2010
Measured conductivity 104 2040 1850 3220 51,500
(lS cm1)
Calculated conductivity 103 1920 2000 3240 50,700
(lS cm1)
Temperature (°C) 10.3 92 76.7 13 10.1
Field pH 8.13 6.60 2.30 2.55 7.98
Dissolved concentration (mg/L)
Ca 12 3.90 7.60 27.2 344
Mg 4.10 0.014 2.41 52.5 1250
Na 2.41 405 46.6 8.40 10,300
K 0.69 21.9 24.1 4.18 414
Cl 1.22 493 13 <0.1 17,400
SO4 7.39 71.7 675 1850 2450
HCO3 49.5 111 <1 <1 132
Fe(total) <0.002 0.008 3.58 440 <0.002
Fe(II) <0.002 0.007 3.53 400 <0.002
SiO2 13 455 513 42 4.13
NH4 <0.1 <0.1 3.36 – –
B <0.003 7.65 0.62 – 4.75
Al <0.08 0.331 13.2 89 0.349
F <0.05 22 0.8 <1 55.1
NO3 <0.05 <0.1 <0.1 – <0.1
Li <0.008 3.96 0.067 – 0.308
Sr 0.1 0.007 0.022 – 6.74
Ba 0.032 0.001 0.018 – 0.008
Br <0.05 1.6 0.276 – 62.9
Mn 0.001 0.017 0.134 1.99 <0.01
Cu <0.003 0.0008 0.0009 7.04 <0.03
Zn 0.007 <0.004 0.031 50 <0.04
Cd <0.001 0.0002 0.0004 0.389 <0.01
Pb <0.008 0.001 0.0024 <0.008 <0.08
Ni <0.002 0.002 0.005 – <0.02
As <0.03 2.47 0.043 – <0.3
DOC <0.2 0.4 0.8 <0.2 –
Charge imbalance (%) 6.1 3.0 2.5 2.0 5.8
Conductivity imbalance (%) 1.1 5.9 8.1 0.6 1.6

where ki is the ionic molal conductivity and mi is the speciated Transport numbers are useful for identifying the ions that substan-
molality (mol kg1) of the ith ion. The following equation can be tially contribute to the electrical conductivity and thus for inter-
used to reliably calculate k at various temperatures and ionic preting the electrical conductivity.
strengths:

I1=2
k ¼ ko ðTÞ  AðTÞ ð3Þ 3. Results
1 þ BI1=2
where the limiting molal conductivity, ko, and the slope, A, are func- The j25 for 1553 samples including acid mine waters, geother-
tions of temperature (T/°C) and B is an empirical constant. A series mal waters, seawater, dilute mountain waters, and river water im-
of equations will be presented that are used to compute the ionic pacted by municipal wastewater were calculated. The mean dj25
molal conductivity over a wide range of temperatures and concen- was 0.1% with a standard deviation of 5.2%. Therefore, approxi-
trations for 28 environmentally relevant ions. mately 95% of the calculated j25 were within 10% of the field mea-
The speciated molality was calculated using the U.S. Geological surement. As an example, the calculated j25 and dj25 are shown
Survey geochemical speciation code WATEQ4F (Ball and Nord- for five different natural waters having a wide range of chemistry
strom, 1991). In addition, WATEQ4F’s code was modified to calcu- (Table 1).
late j25 using the new method as well as the conductivity The transport numbers were calculated for the relevant ions
imbalance (dj25): found in the 1553 samples. Using the maximum transport number,
j25 calculated  j25 measured the ions can be grouped into three categories. The first group in-
dj25 ¼  100 ð4Þ cludes those ions that may contribute significantly (tmax > 10%) to
j25 measured
the electrical conductivity of natural waters (H+, Na+, Ca2+, Mg2+,
The relative contribution of a given ion to the overall electrical con- NHþ +  2  2  3+ 2+  
4 , K , Cl , SO4 ; HCO3 ; CO3 , F , Al , Fe , NO3 , and HSO4 ).
ductivity, given by the transport number (ti), can also be deter- The ions in this group are essential for accurate conductivity calcu-
mined using ionic molal conductivities (Eq. (3)). For natural lations. The next group includes those ions than contribute a mod-
waters, the following equation can be used to determine the trans- erate amount (2% < tmax < 10%) to the electrical conductivity of
port numbers for the individual ions: natural waters (Li+, Fe3+, Cu2+, Mn2+, Zn2+, OH, NsSO 4 , and
ki mi NaCO 3 ). The last group includes those ions that contribute very lit-
t i ¼ Pn ð5Þ tle (tmax < 2%) to the electrical conductivity of the natural waters
i¼1 ki mi
(Ba2+, Br-, Cs+, Sr2+,and KSO 4 ).
 R. Blaine McCleskey et al. / Applied Geochemistry 26 (2011) S227–S229 S229

30 as a quality control method for checking water analyses. The use of

charge imbalance (CI) is regularly used to check the quality of
20 water analyses (APHA, 1985). However, when a large charge imbal-
Anions Too High Cations Too High ance exists, there is no indication whether the error is caused by a
cation or an anion. A second constraint is helpful to identify the
10
constituent most likely in error. Considering the importance of reli-
able water-quality analyses and the time and expense of analyzing
δκ 25 (%)

0 samples, the ability to identify inaccurate determinations is impor-

tant. The dj25 is plotted against the speciated CI for the 1553 nat-
-10 ural water samples tested (Fig. 1). The dashed box in Fig. 1, where
both the dj25 and the CI are less than ±10%, is the region where
Cations Too Low Anions Too Low
-20 both the dj25 and the CI are in an acceptable range and the analyt-
ical data is likely accurate for geochemical interpretation. Samples
with erroneous chemical analyses are expected to plot outside of
-30
-30 -20 -10 0 10 20 30 the dashed box.
CI (%) To demonstrate the utility of identifying the constituent or mea-
surement most likely in error using a dj25–CI plot, the effects of arti-
Fig. 1. The conductivity imbalance (dj25) plotted against the speciated charge ficially increasing or decreasing the major anion (meq L1) were
imbalance (CI) for 1553 natural water samples.
tested for 50 samples originally having a CI and a dj25 6 ±1%
(Fig. 2). Increasing the major anion by 20% resulted in an increase
in dj25 and a decrease in CI, while decreasing the major anion by
20
Anions Too High Cations Too High 20% resulted in a decrease in dj25 and an increase in CI. Using a
dj25–CI plot, it is straightforward to identify the measurement most
increased major likely in error.
anion by 20%
10
Acknowledgements

We would like to thank Kate Campbell and Greg Brown for their
δκ 25 (%)

0
constructive comments and reviews. This study would not have
been possible without the support of the National Research Pro-
gram of the USGS. The use of trade, product, industry, or firm
names is for descriptive purposes only and does not imply
endorsement by the US Government.
-10
decreased major
anion by 20% References

Cations Too Low Anions Too Low APHA, 1985. Standard Methods for the Examination of Water and Waste Water.
-20 American Public Health Association, Inc.
-30 -20 -10 0 10 20 30 Ball, J.W., Nordstrom, D.K., 1991. User’s Manual for WATEQ4F, with Revised
CI (%) Thermodynamic Database and Test Cases for Calculating Speciation of Major,
Trace, and Redox Elements in Natural Waters. US Geol. Surv. Open-File Rep. 91–
original analyses, major anion increased by 20%, 183.
Laxen, D.P.H., 1977. A specific conductance method for quality control in water
major anion decreased by 20% analysis. Water Res. 11, 91–94.
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Soil Sci. 110, 405–414.
4. Discussion Miller, R.L., Bradford, W.L., Peters, N.E., 1988. Specific Conductance: Theoretical
Considerations and Application to Analytical Quality Control. US Geol. Surv.
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Anal. Chem. 21, 631.
Transport numbers can be useful for the geochemical interpreta- Rossum, J.R., 1975. Checking the accuracy of water analyses through the use of
tion of natural waters and can be used to better predict the concen- conductivity. J. Am. Water Works Assoc. 67, 204–205.
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soil solutions of limited salinity levels. Water Resour. Res. 8, 145–153.
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method for a wide range of natural water samples. Rossum solution electrical conductivity at 25 °C from major ion concentrations. Eur. J.
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