Published November, 2009

Making Soil OxidationReduction

Potential Measurements using Multimeters
M. C. Rabenhorst* Researchers studying the chemistry of soil systems may be interested in documenting the oxidation
Department of Environmental Science reduction potential (Eh) for a variety of purposes, and this is often accomplished by measuring the
and Technology, Eh using platinum (Pt) electrodes in conjunction with a reference electrode and a voltmeter. It has
University of Maryland been shown that Eh values obtained when using high resistance research grade instruments often are
WETLAND SOILS

College Park, MD 20742 much different from values measured using standard multimeters. This difference appears to be a
function of the input resistance, with the low resistance multimeters allowing a higher current to flow
during measurement which alters the electrochemical environment causing the voltage to drift. The
objectives of this paper are (i) to report on a device which when attached to a low resistance multimeter
facilitates the accurate measurement of soil redox potential, and (ii) to better understand the nature
of the drift observed when measurements are made using a standard multimeter. Redox potentials
were measured with Pt and calomel electrodes in soil mesocosms using a research grade voltmeter and
a standard multimeter, with and without an inexpensive device that effectively increased the input
resistance of the multimeter to 1 Tohm. The device was constructed using a TL082 wide bandwidth
dual JFET input operational amplifier which effectively raised the input resistance from 10 Mohm
to approximately 1 Tohm. When a small correction factor was applied to account for the internal
offset error from the amplifier, the Eh data recorded using the modified multimeter were essentially
identical to those collected using higher end, research grade instruments (n = 162; Y = 0.9996X
0.09; r2 = 1.0000). Depending on the pH of the system and the type of reference electrode used, and
the redox couple of interest, Eh data collected using standard multimeters could lead to erroneous
conclusions regarding whether a soil is oxidized or reduced.

R esearchers studying the chemistry of natural systems, such as

soils, sediments, or water, commonly are interested in docu-
menting the oxidationreduction (or redox) potential (Bohn,
1971). This is commonly assessed by measuring the voltage be-
tween a Pt tipped electrode and a reference electrode (such as
calomel electrode) that have been placed in the soil, and when
corrected for the reference electrodes standard voltage relative
to the standard hydrogen electrode, it is recorded as Eh ( James
and Bartlett, 2000; Patrick et al., 1996).
Various devices can be used to measure the voltage. When
long-term experiments are undertaken and repeated measure-
ments are required, voltages can be recorded automatically using a
data logger, but these computerized devices typically are expensive.
Redox potentials may also be measured simply by using a volt me-
ter. During field experimentation a portable device is required, and
while laboratory grade field instruments are available, their cost is
relatively high (commonly >$600). Therefore, many workers have
elected to make redox measurements using standard multimeters,
which are considerably less expensive (often <$50).
Soil Sci. Soc. Am. J. 73:2198-2201
doi:10.2136/sssaj2009.0040
Received 28 Jan. 2009.
*Corresponding author (mrabeno@umd.edu).
Soil Science Society of America
677 S. Segoe Rd. Madison WI 53711 USA
All rights reserved. No part of this periodical may be reproduced or
transmitted in any form or by any means, electronic or mechanical,
including photocopying, recording, or any information storage and
retrieval system, without permission in writing from the publisher.
Permission for printing and for reprinting the material contained
herein has been obtained by the publisher.
One fundamental difference between the research grade field
instruments and the less expensive multimeters is that standard
pH/volt meters have a much higher input resistance, on the order
of 200 Gohms, while the multimeters have an input resistance of
approximately 10 Mohms. It has been recently demonstrated in soil
systems, that dramatically different Eh values are often obtained
when using the high resistance research instruments compared
with the multimeters (Rabenhorst et al., 2009), and this difference
is a function of the differences in input resistance. Apparently, the
lower resistance instruments permit a greater current flow during
the voltage measurement which causes electrochemical changes in
the soil environment immediately surrounding the Pt electrode
and this causes the voltage reading to drift. This drift can some-
times take 5 to 10 min or more to stabilize during which time the
voltage measurement continues to change, sometimes by as much
as 100 to 200 mV from its starting point. In these cases, probably
the most accurate datum is the first one observed (before there is
much drift) and it has been suggested that researchers should sim-
ply record the first observation. This is an unsatisfactory solution
because the initial rate of drift can be so rapid (sometimes more
than 20 mV s1) that it is difficult to capture this first datum, and
because the measurement continues to change rapidly, there is no
opportunity to recheck the initial reading.
The objectives of this paper are (i) to report on a device
which when attached to a low resistance multimeter facilitates
the accurate measurement of soil redox potential, and (ii) to bet-
ter understand the nature of the drift observed when measure-
ments are made using a standard multimeter.

2198 SSSAJ: Volume 73: Number 6 NovemberDecember 2009

Table 1. Soil materials used in this study were collected from A horizons of pedons at the locations specified.

Sampling
Series Classification Pedo-geomorphic setting Initial pH Organic C Texture
location
g kg1
38127 N
Berryland Sandy, siliceous, mesic Typic Alaquods Late Pleistocene Dunes 3.2 55 Loamy sand
75302 W
Coarse-loamy, siliceous, Sandy Coastal 385412 N
Downer 5.5 6 Loamy sand
semiactive, mesic Typic Hapudults Plain Sediments 76812 W
Coarse-loamy, siliceous, active, Flood Plain of the 39143 N
Indiantown 5.1 67 Silt loam
acid, mesic Cumulic Humaquepts Inner Coastal Plain 765030 W

MATERIALS AND METHODS at 2- to 3-d intervals (after the daily change in redox potential was less
Redox potentials were measured using Pt and calomel electrodes pronounced) until approximately Day 17.
in soil mesocosms using research grade voltmeters and multimeters. Typically, when the two wires that normally lead to the Pt and ref-
Measurements were also made using multimeters that were equipped erence electrodes are connected to each other (short circuited) across a
with an inexpensive device that effectively increased the input resistance volt meter or multimeter, a voltage of zero is observed. However, when
of the multimeters. Small mesocosms were made from 1-L plastic con- the system is short circuited with an amplifier included in the circuit as
tainers approximately 12 cm high that were filled with homogenized ma- shown in Fig. 1, a small but consistent deviation from zero is observed.
terial collected from the A horizons of soils identified as the three series This has been called an internal offset error and is inherent to the ampli-
Indiantown, Berryland, and Downer. The properties of the soils used are fier. An evaluation of thirteen TL082 amplifiers showed this internal
presented in Table 1. Six replicate Pt electrodes were inserted into the soil offset to range from 1 to 8 mV (mean 4 mV). The particular device
to a depth of approximately 6 cm. The mesocosms were saturated by add- used for collecting the data in this experiment had an internal offset of
ing distilled water through a 1/2 inch PVC tube that was placed in the 5 mV, and thus a correction factor was applied by subtracting this 5 mV
center of the mesocosm and permitted the soils to be saturated from the from voltages measured when using this device.
bottom. Once saturated, the mesocosms were maintained with a 1-cm
layer of water on the surface. The mesocosms were placed on a lab bench RESULTS AND DISCUSSION
where the temperature was maintained at approximately 24C. A comparison of the Eh values measured in the mesocsoms
Voltages were measured using a Beckman model PHI 260 pH/ from all three soils using the research grade voltmeter and using
voltmeter(Beckman Coulter, Inc., Fullerton, CA) and using a Radio a multimeter modified to include the amplifier device is shown
Shack model 22812 multimeter(Radio Shack Corp., Fort Worth, TX) in Fig. 2. The linear model fit to the data shows that there is
with and without a device designed to increase the input resistance of almost a perfect fit of the data. Of the 162 data points included
the instrument. The device was constructed using a TL082 wide band- in the figure (six electrodes, three soils, nine dates) the mea-
width dual JFET input operational am-
plifier and two 9-V batteries that were
configured as shown in Fig. 1 (66pacific.
com, 2007). A single throw, double pole
switch was also incorporated into the
circuitry to easily disconnect the bat-
teries (to preserve battery life) when
measurements were not being made.
When measurements were made using
the Beckman meter or when using the
multimeter with the amplifier, the volt-
ages measured showed no drift and were
recorded after 5 to 10 s. When the mul-
timeter was used without the amplifier,
the measured voltages showed a signifi-
cant drift. The rate of drift (mV min1)
is greatest at the outset, and then slowly
decreases with time. For purposes of
standardization, voltages were recorded
after 120 s, even though in most cases,
the voltages were still continuing to
change at rates ranging between 5 and
50 mV min1) (Fiedler et al., 2007).
Starting on the day the soils were satu-
Fig. 1. A device designed to increase the input resistance of a standard multimeter by using a TL082 wide
rated, measurements were taken daily bandwidth dual JFET input operational amplifier and two 9-V batteries. The effective resistance using
for the first 5d (when redox potentials this arrangement is 1 Tohm. A single throw, double pole switch is utilized to allow easy preservation of
were changing most quickly) and then battery life when measurements are not being made. Modified from 66pacific.com (2007).

SSSAJ: Volume 73: Number 6 NovemberDecember 2009 2199


Fig. 2. Comparison of Eh values measured in mesocsoms with three
soils over 17 d from identical Pt and reference electrodes using a
research grade voltmeter and using a multimeter modified to include
an amplifier device.
sured differences ranged from 7 to +5 mV, and the average
magnitude of the observed differences between the two was
1.1 mV (mean 0.2; Std Dev. 1.6). Anyone familiar with the
variability typically encountered in making Eh measurements
in soils will immediately recognize that the magnitude of these
differences makes them trivial. For all practical intents and
purposes, the results obtained from these two methods can be
considered to be identical.
When Eh in the mesocosms was measured using the low resis-
tance multimeters, the voltages drifted and showed distinctive pat-
terns (Fig. 3). When Eh values were high the direction of drift was
downward, while the direction of drift was upward when initial Eh
values were low and the crossover point appeared to be at an Eh of
approximately 244 mV. In fact, 244 mV was the correction factor
used for converting voltages measured using the calomel reference
electrode to Eh. Therefore, it is significant to recognize that if the
data were plotted as raw voltage readings (and not converted to
Eh), we would see that the crossover point is actually 0 V.
Fig. 3. Comparison of Eh values measured in mesocsoms with three
different soils over 17 d from identical Pt and reference electrodes
using a research grade voltmeter and using a standard multimeter.
The voltage measurements from the multimeter were recorded after
120 s. Note that the crossover point in the curve for Eh is 244 and that
all three soils behave similarly.
2200
When the raw unconverted voltage measurements are with-
in the range of approximately 100 mV of zero (or 100 mV of
Eh = 244 in Fig. 3), the data show a strong linear relationship
(Y = 0.346X, r2 = 0.95). Two observations can be made. First,
regardless of whether initial voltages (not converted to Eh) are
positive or negative, the observed drift is always toward 0. Second,
the closer the voltage is to 0, the smaller is the observed drift.
Apparently what is transpiring electrochemically in the soil, is that
the current passing through the electrodes during the measure-
ment of the voltage (due to the lower resistance of the multimeter)
is either contributing electrons to, or consuming electrons from,
the redox active species present in the soil in the vicinity of the Pt
electrode at the time of measurement. These electron transfers dur-
ing the voltage measurement presumably change the proportion of
the species in the redox couples in the soil, tending toward a more
stable state where the electrical potential (voltage) would be zero.
Because the redox status of particular mineral species is de-
pendent on pH as well as Eh, there is no simple correction that
can be applied to interpret measurements made using a standard
multimeter, and it is affected even by the type of reference elec-
trode that is used. Researchers that are focused on soil hydromor-
phology commonly are interested in redox transformations of Fe
oxi-hydroxide species. The National Technical Committee on
Hydric Soils, for example, has promoted the use of the following
empirical Eq. [1] to describe the reduction of Fe oxide species in
soils as part of their Technical Standard (NTCHS, 2000).
Eh = 595 (pH 60) [1]
When the Eh and pH plot below the line, the system is considered
reducing with respect to Fe and oxidizing if they plot above the
line (Fig. 4). On this line, an Eh value of 244 corresponds to a pH
of 5.85. Therefore, if the soil pH is <5.85 and (using a low resis-
tance multimeter not adapted with an amplifier) the measured Eh
is below 244 mV (raw voltage < 0), then we know that any voltage
drift would have been upward toward an Eh of 244 (upward to-
ward a raw voltage of 0), and the original voltage must have been
even lower (more reducing). In such cases, the Eh and pH would
plot (unambiguously) below the NTCHS Technical Standard (Fe
oxide stability) line, and therefore clearly reducing. Conversely, if
the pH is >5.85 and (using a low resistance, non-adapted multi-
meter) the measured Eh were above 244 mV, then we know that
any voltage drift would have been downward toward an Eh of 244.
In such cases the Eh and pH would plot (unambiguously) above
the NTCHS Technical Standard (Fe oxide stability) line, and thus
clearly oxidizing. However, if the measured Eh-pH data (using a
low resistance multimeter) fall within the dark gray zones in Fig.4
(between the Fe oxide stability line and an Eh of 244 mV), these
data are ambiguous to interpret. In these cases, it is possible (or
even likely) that the measured values could have drifted from one
side of the stability line across to the other side as they moved to-
ward an Eh value of 244 mV. This would lead to an error in inter-
preting the system as being oxidized vs. reduced. The same issues
would be true if one were to make redox interpretations based on
other redox boundaries such as the stability fields for particular Fe
oxide minerals like ferrihydrite or goethite, so long as data were
collected using a low resistance (not modified) multimeter.
A data set generated by a student for another purpose and col-
lected using a standard multimeter and allowing drift for approxi-
SSSAJ: Volume 73: Number 6 NovemberDecember 2009
mately 5 min is plotted in the Eh-pH
diagram (Fig. 4). Nearly one third
(32%) of the data points plot within
the ambiguous gray zones, indicating
that these points could possibly be
erroneously described as reducing or
oxidizing when they are not. It also
appears that a disproportionately
large number of the data have an Eh
very near to 244. In fact, 49% of the
Eh values are within 10 mV of 244,
33% are within 5 mV of 244, and
21% are within 2 mV of 244. Given
the large potential Eh/pH space
where these data could have fallen,
that so many of these points fall so
close to an Eh of 244 (raw voltage
of 0 V) suggests that these data had
been drifting toward a value of 0 V
for the reasons described earlier.

CONCLUSIONS
It has been demonstrated that Fig. 4. The EhpH diagram showing the empirical line for the Fe-oxide stability fields according to the
Technical Standard of the National Technical Committee on Hydric Soils which is defined by the equation
when soil redox potentials are mea- Eh = 595 (pH60). If when a traditional multimeter is used to measure Eh, the EhpH data fall within
sured using a low resistance instru- the dark gray zones (between the TS line and an Eh of 244 mV), these data are ambiguous to interpret,
ment, such as a standard multimeter because of the possibility that the measured values could have drifted from one side of the stability line
(approximately 10 Mohms), electro- across to the other side, toward an Eh value of 244 mV. Data points were collected during a different
chemical changes in the soil environ- study using a standard multimeter and allowing drift for approximately 5 min. Note that nearly one third
(32%) of the data points plot within the ambiguous gray zones. Of 144 data points, 49% of the Eh values
ment caused by the flowing current are within 10 mV of 244, 33% are within 5 mV of 244, and 21% are within 2 mV of 244.
result in a drift in the measured redox
potential as, presumably, the propor- interpretations of data collected using low resistance meters would
tion of reduced and oxidized chemical species are changing in the lead to erroneous conclusions with regard to the redox status of the
vicinity of the Pt electrode. This observed drift is always toward a soil. When using redox data to assist in making evaluations related
raw voltage of zero, or toward an Eh of 244 mV (if a calomel refer- hydric soil or wetland assesment, care should be taken to ensure that
ence electrode is used.) When a high resistance research grade in- Eh measurements are collected and interpreted correctly.
strument is utilized (approximately 200 Gohms), the current flow
is negligible and reliable redox measurements can be obtained. By REFERENCES
using inexpensive components including a TL082 wide bandwidth 66Pacific.com. 2007. The simplest possible pH meter. Available online at
dual JFET input operational amplifier and two 9-V batteries, a http://www.66pacific.com/ph/simplest_ph.aspx (Verified 2 June 2009).
standard multimeter can be modified to have an effective input re- Bohn, H.L. 1971. Redox potentials. Soil Sci. 112:3945.
Fiedler, S., M.J. Vepraskas, and J.L. Richardson. 2007. Soil redox potential:
sistance of 1Tohm, which when a minor correction factor of a few Importance, field measurements, and observations. Adv. Agron. 94:154.
millivolts is applied to account for the internal offset error inher- James, B.R., and R.J. Bartlett. 2000. Redox phenomena. p. B169194. In M.E.
ent to the amplifier, provides Eh measurements that are essentially Sumner (ed.) Handbook of soil science. CRC Press, Boca Raton, FL.
identical to the more expensive research instruments. The magni- National Technical Committee for Hydric Soils (NTCHS). 2000. Technical
tude of the observed voltage drift can be as high as 100 to 200 mV Note 11: Technical standards for hydric soils [Online]. http://soils.usda.
gov/use/hydric/ntchs/tech_notes/index.html (Verified 2 June 2009).
and therefore can lead to significant problems of interpretation. Patrick, W.H., R.P. Gambrell, and S.P. Faulkner. 1996. Redox measurements
Depending on the type of reference electrode used, there are cer- of soils. p. 12551273. In D.L. Sparks (ed.) Methods of soil analysis.
tain zones within Eh-pH stability diagrams where readings made Part 3. SSSA Book Ser. 5. SSSA and ASA, Madison, WI.
with low resistance meters can be interpreted unambiguously as re- Rabenhorst, M.C., W.D. Hively, and B.R. James. 2009. Measurements of soil
ducing or oxidizing. There are other Eh-pH zones, however, where redox potential. Soil Sci. Soc. Am. J. 73:668674.

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