pH —1

6.4 pH

By D.B. Radtke, Eurybiades Busenberg,

F.D. Wilde, and J.K. Kurklin

Page

pH ......................................................................................... pH–3

6.4.1 Equipment and supplies .............................................. 4

6.4.1.A pH buffer solutions .............................................. 6

6.4.1.B pH electrodes: maintenance, reconditioning,

cleaning, and storage ............................................ 7

6.4.2 Calibration ................................................................. 13

6.4.3 Measurement .............................................................. 18

6.4.3.A Surface water ..................................................... 19

In situ measurement .................................................. 19

Subsample measurement........................................... 20

6.4.3.B Ground water ..................................................... 22

Downhole and flowthrough-

chamber measurements ............................................ 23

Subsample measurement........................................... 25

6.4.4 Troubleshooting ......................................................... 26

6.4.5 Reporting .................................................................... 27

Tables

6.4–1. Equipment and supplies

used for measuring pH ................................................... 5

6.4–2. Troubleshooting guide for pH measurement .............. 26

U.S. Geological Survey TWRI Book 9 4/98 pH

2 — pH

pH U.S. Geological Survey TWRI Book 9 4/98

 pH —3

pH 6.4
The pH of an aqueous solution is controlled by interrelated chemi-
cal reactions that produce or consume hydrogen ions (Hem,
1985). Water pH is a useful index of the status of equilibrium
reactions in which water participates (Hem, 1985). The pH of
water directly affects physiological functions of plants and ani-
mals, and it is, therefore, an important indicator of the health of
a water system.

P pH is reported on a scale that most commonly ranges from 0

to 14 and that is directly related to the ratio of hydrogen (H+)
and hydroxyl (OH−) ion activities at a given temperature.

P A solution is considered
acidic if H+ activity is greater pH: a measure
than OH − activity (pH less
than 7 at 25°C); a solution is representing the
considered basic, or alkaline, negative base-ten
when OH– activity is greater logarithm of
than H+ activity.
hydrogen-ion activity
P Carbon dioxide (CO 2 )-free of a solution, in
water at 25°C is considered moles per liter.
neutral because activities of
H+ and OH − are equal.

U.S. Geological Survey TWRI Book 9 4/98 pH

4 — pH

6.4.1 EQUIPMENT AND SUPPLIES

The instrument system that is used to measure pH must be tested
before each field trip, and it must be cleaned soon after use. Be-
cause of the variety of pH meters and electrodes available, read
thoroughly the instruction manual provided by the manufacturer.
Every pH instrument must have a log book in which its manu-
facturer make and model, serial or property number, and all re-
pairs and calibrations are recorded.

pH can be measured either electrometrically or colorimetrically.

P The electrometric measurement method uses a hydrogen

ion electrode. This is the only technique which is approved
for measuring pH values that are to be reported or entered
into the USGS data base.

P The colorimetric method uses pH “litmus” indicators that

change color with a change in pH. The colorimetric method
is suitable only when rough estimates of pH are needed; for
example, when assessing the volume of acid or base needed
to preserve samples; or, when checking that equipment-clean-
ing solutions have been adequately neutralized prior to dis-
posal.

pH meters are sophisticated electronic instruments that require

care in handling and operation. pH instrument systems and buff-
ers must be protected from dirt and extreme heat or freezing con-
ditions while they are in the field and during storage. Keep in-
strument systems clean and dry when they are not in use. Dur-
ing field travel, protect pH meters and electrodes from being
jostled or from sudden impacts.

Some of the procedures recommended herein for

equipment operation may be out of date if
the equipment being used is different from that
described or incorporates more recent technological
advances—follow the manufacturer’s instructions.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH —5

Table 6.4–1. Equipment and supplies used for measuring pH1

[Except for the multiparameter instrument, this equipment is required also for ANC or alkalinity
determinations (see NFM 6.6); mL, milliliters; °C, degrees Celsius; mV, millivolt; µS/cm, micro-
siemens per centimeter at 25 degrees Celsius]
✓ pH meter and pH electrodes
Battery powered, solid state, with automatic temperature and slope compensa-
tion, or multiparameter instrument (possible alternative to separate pH meter
and electrode)
Range of at least 2 to 12 pH, preferably 0 to 14 pH
Accuracy of at least ±0.1 units
Temperature range of at least 0 to +45°C
Millivolt readout with accuracy of ±1.0 mV or better for instrument resolution
of 0.1 mV
Bayonet nut connector (BNC) is recommended
✓ pH electrodes, gel-filled or liquid-filled, as appropriate for study objectives and site
conditions
✓ pH electrode filling solution of appropriate composition and molarity (for liquid-
filled electrode)
✓ Thermometer, calibrated
✓ Buffer solutions, 500 mL each of pH 4, 7, and 10; temperature correction chart(s)
for buffers
✓ Stand for holding pH electrode (or stand for holding multiparameter instrument
system)
✓ Bottle, delivery (squeeze), for deionized water
✓ Deionized water, maximum conductivity of 1 µS/cm
✓ Beakers or measurement vessels, polyethylene or Teflon™ preferable, assorted,
50 to 150 mL, clean but not acid rinsed
✓ Paper tissues, disposable, soft, and lint free
✓ Flowthrough chamber for ground-water measurements (used with meter and
electrode equipment)
✓ Minnow bucket with tether or equivalent, used for temperature equilibration
of buffer solutions
✓ Antistatic spray or polish
✓ Waste disposal container
✓ Stirrer, magnetic with thin insulating pad; or stirrer, mechanical with Teflon™
coated impeller
✓ Stirrer bar, magnetic, Teflon™ coated
✓ Instrument log book for recording calibrations, maintenance, and repairs
1
Modify this list to meet the specific needs of the field effort.

CAUTION: Before handling pH buffers or other

chemicals, refer to Material Safety Data Sheets
(MSDS) for safety precautions. Wear eye
guards and protective clothing.

U.S. Geological Survey TWRI Book 9 4/98 pH

6 — pH

6.4.1.A pH BUFFER SOLUTIONS

pH measurements are only as accurate as the buffers used for

calibration. Use buffers that have been certified traceable to the
NIST Standard Reference Material; buffers with a pH of 4, 7, and
10 are available from QWSU.

P Note that the routine buffers obtained for measurement of

pH from 4 to 10 have a high ionic strength. For pH measure-
ments of dilute waters, obtain low ionic-strength buffers.

P Label buffer and reagent containers with the date when they
are received.

P Label every buffer with its expiration date. Copy this date
onto any container into which the buffer is transferred.

P Discard buffers on their expiration dates. The pH of the

buffers may have changed substantially because of carbon di-
oxide absorption, mold growth, or evaporation.

Take the following precautions to maximize the accuracy of

pH measurement (modified from Busenberg and Plummer,
1987):
1. Always cap buffer bottles to prevent evaporation and contami-
nation from atmospheric carbon dioxide. (In order of greatest
to least sensitivity to CO2 contamination, pH buffer 10 > 7 > 4.
Buffers are stable for the short exposure time during electrode
calibration.)

2. Never pour used buffer back into stock solution bottles. Never
insert an electrode or other material into stock solution bottles
containing buffers—always pour the buffer into a separate con-
tainer.

3. Be very careful not to contaminate the buffer with another buffer

or with other fluids (pH 4 buffer is least resistant to contamina-
tion).

4. Do not dilute buffer—for example, with water dripping from

sensors (more important for pH 7 buffer).

5. Before using buffers, bring them to the temperature of the sample

solution, and check with the buffer manufacturer for tempera-
ture-correction factors. (In order of greatest to least pH varia-
tion with temperature, buffer of pH 10 > 7 > 4.)

pH U.S. Geological Survey TWRI Book 9 4/98

 pH —7

pH ELECTRODES: MAINTENANCE, 6.4.1.B

RECONDITIONING, CLEANING, AND STORAGE
The slope and the measured potential of a new electrode should
be monitored daily for about 1 week before use (Busenberg and
Plummer, 1987). The latest instruments have microprocessors that
automatically calculate and display the slope. Some older instru-
ments have a percent-slope readout or (and) millivolt readout.
For instruments with a millivolt readout, the measured electrode
potential is calculated as the difference between millivolts mea-
sured at the known pH of two buffers. Because the theoretical
Nernst response is known, slope can be calculated from measured
potentials as follows:
E=E0–S(pH)
where
S = slope, and
E = electrode pair potential in mV.
Using two buffers of known pH (1, 2),
E1=E0–S(pH1)
and
E2=E0–S(pH2)

or E2 −E1
S=
pH1−pH2
and
E0=E2+S(pH2).

The theoretical slope is temperature dependent; the slope in mV

can be calculated as follows:
S t = 0.19841(273.15 + t)
where
t = temperature in degrees Celsius, and
St = slope at a given temperature.

Normally, electrodes drift from day to day and E0 typically varies

by ±2 mV; the slope remains fairly constant to within ±0.2 per-
cent Nernst slope after the new electrode has been conditioned.
Follow the procedures recommended by the manufacturer. Prop-
erly working electrodes commonly drift from about 0.1 to 0.2
mV per hour.

U.S. Geological Survey TWRI Book 9 4/98 pH

8 — pH
Electrode maintenance

Electrodes with gel-filled references require less maintenance than

electrodes with liquid-filled references. Follow manufacturer’s
instructions.

Deterioration of the electrode is normal, and proper maintenance

requires that electrode performance be monitored before every
water-quality field trip and again at each site. Electrodes can give
years of reliable service if maintained by following steps 1–8:

1. Do not handle the glass bulb with fingers. Oily film or scratches
on the bulb will interfere with pH measurement. Fingers leave a
protein film on the glass that decreases electrode sensitivity.

2. Inspect the electrode and electrode cable for physical damage;

for example, check for
• Scratched or broken bulb.
• Cut, frayed, or broken cable.
• Bent or broken connector.

3. Rinse electrode thoroughly with deionized water before use.

Do not wipe electrodes with paper towels or wipes—these
scratch the glass bulb. Gently blot droplets from a wet glass
electrode bulb with lens paper or soft tissue by contacting only
the droplets to soak up excess solution.

TECHNICAL NOTE: Wiping glass with paper causes a static

charge (polarization) that results in drifting, sluggish, and
erratic pH readings. It can take many minutes for the elec-
trode to return to normal operation. Clothing also can
produce a static charge that affects electrode response.

Gel-filled electrodes do not require filling, but should not be

left in dilute water for long periods of time. (Salt can leach from
the gel into the dilute water and produce a large junction po-
tential, resulting in errors in pH measurement.)

For liquid-filled electrodes:

a. Remove salt crystal deposits from the electrode, membranes,
and junctions. Check that the reference junction is not blocked.
• Rinse off salt buildup with deionized water.
• Check that you can observe seepage of the filling solution
through the junction.
b. Always unplug the fill hole before making pH measurements,
and replug it after use. If using an electrode after it has been
in a storage solution, uncap the fill hole and suspend the elec-

pH U.S. Geological Survey TWRI Book 9 4/98

 pH —9
trode in air for about 15 minutes. This will allow the filling
solution to flush residual storage solution through the porous
reference junction and thoroughly wet it.
c. Check the filling solution level and replenish it if necessary—
it should reach the bottom of the fill hole. Filling solutions
differ in molarity and composition—always check that you are
using the correct filling solution required by the manufacturer
for a particular electrode.
d. Drain and flush the reference chamber of refillable electrodes,
and routinely refill them with the correct filling solution (see
manufacturer’s recommendations).

4. Monitor electrode response. Keep a record of electrode op-

eration in the pH meter log book. Record the Nernst slope read-
ing and the millivolt readings at pH 7 and pH 4 after calibration.
• Properly working glass electrodes should give approximately
98.0 to 99.5 percent response of that expected from the theo-
retical Nernst relation (Busenberg and Plummer, 1987). The
theoretical Nernst response is 59.16 mV/pH unit at 25°C.
• A slope of less than 94 percent signals possible electrode de-
terioration and the need to monitor closely any further de-
cline in slope percent. If possible, replace or recondition the
electrode at this point.
• Do not use an electrode with a slope of 90 percent or less.

5. Keep the electrode bulb moist and capped when not in use.
Keep a moist piece of cotton or lint-free tissue in the cap to
prevent the bulb from drying out.

Reconditioning liquid-filled electrodes

Before beginning a field trip, if you are unsure of an electrode’s

condition or have persistent problems during calibration, use the
following procedures to recondition the electrode.

1. Remove the old filling solution from the electrode—

a. Place the needle of a 1- or 3-mL syringe into the electrode
filling hole (or use other methods of removing the filling solu-
tion, such as vacuum extraction or draining).
b. Tilt the pH electrode until the filling solution is near the filling
hole and the needle tip is covered with the filling solution.
c. Pull back on the syringe plunger until the syringe is full.
d. Discharge the solution from the syringe into a waste container
and repeat steps 1(a) through (d) until all of the filling solu-
tion has been removed from the pH electrode chamber.

U.S. Geological Survey TWRI Book 9 4/98 pH

10 — pH
2. Flush the pH electrode chamber with deionized water—
a. Use a syringe or squeeze bottle to partially fill the pH elec-
trode chamber with deionized water.
b. With a syringe, remove the deionized water from the pH elec-
trode chamber.
c. As a result of changes in pressure, temperature, and evapora-
tion, crystals may form in the pH electrode chamber. If they
form, repeat steps 2(a) and (b) until all crystals have been
dissolved and removed from the pH electrode chamber.

3. Fill the electrode chamber with new filling solution—

a. Flush the electrode chamber with fresh filling solution using a
syringe or a plastic squeeze bottle.
• Partially fill the pH electrode chamber with filling solution.
• Tilt the pH electrode so that the filling solution will contact
all of the internal electrode surfaces.
• Remove and discard the filling solution to a waste container.
b. Fill the electrode chamber with fresh filling solution until the
filling-solution level is just below the fill hole. Be sure to use
the correct molarity filling solution.
c. Rinse any excess filling solution from the outside of the elec-
trode with deionized water.

Filling solutions might not be interchangeable

for different electrodes—
check manufacturer’s instructions.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 11
Electrode cleaning

Electrodes must be kept clean and the liquid junction free flow-
ing in order to produce accurate pH values. Because of the vari-
ety of electrodes available, check the manufacturer’s cleaning in-
structions.

P Rinse the outside of the electrode thoroughly with deionized

water after each use. In general, this should be the only rou-
tine cleaning needed.

P Rejuvenation procedures described by the manufacturer

should be used if an electrode becomes clogged or extremely
dirty.
— After completing rejuvenation procedures on a liquid-filled
electrode, drain, clean and refill the reference electrode cham-
ber with fresh filling solution. Replace the fill-hole plug, and
soak the electrode in storage solution overnight. Retest the
electrode. If the procedures fail to remedy the problem, dis-
card the electrode. Document electrode reconditioning or re-
placement in the instrument log book.
— Gel-filled electrodes can be rejuvenated in some instances by
placing the electrode in warm water (approximately 60°C)
for about one minute or less. This procedure rejuvenates the
junction by liquifying the salt gel.

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12 — pH
Electrode storage
Electrodes must be clean before they are stored for any length of
time.

Short-term storage. Short-term storage methods are appropriate

only for in-service electrodes (those used daily or weekly). Stor-
age solutions for short-term storage of electrodes differ with the
type of electrode; follow the manufacturer’s recommendations.
Storage solutions can have a limited shelf life. Unless otherwise
instructed by the manufacturer, avoid storing glass hydrogen-
ion electrodes in deionized water or concentrated KCl solutions.
In the latter case, absorbed potassium reduces the glass sensitiv-
ity to hydrogen ions.
P Store liquid-filled pH electrodes upright.
P Keep liquid-filled electrodes wet to maximize their accuracy
and response time. Store them so that the bulb is fully im-
mersed in proper electrode storage solution between uses at a
field site. Before moving to the next field site, replace the
plug on the fill hole, fill the protective cap with storage solu-
tion, and cover the electrode bulb with the cap.
P Gel-filled electrodes must only soak in a solution for short
periods during measurements. Follow the manufacturer’s in-
structions for storage of gel-filled electrodes.

P Clean the connector ends and store them in a plastic bag.

Long-term storage. pH measuring systems must be stored in an

area that is clean, dry, and protected from extremely hot or cold
temperatures. For long-term storage of liquid-filled electrodes,
drain the filling solution from the electrode, rinse the outside of
the electrode with deionized water, and store the electrode dry
with a protective cap covering the bulb (put either storage or
filling solution in the cap before placing the cap on the bulb if
the manufacturer recommends that the bulb be kept moist). Clean
the electrode connector ends (with alcohol, if necessary), and
store them dry in a sealed plastic bag.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 13

CALIBRATION 6.4.2
Calibrate and check the operation of a pH instrument system at
the field site. Two pH buffers are needed to properly calibrate the
pH instrument system (pH 7 buffer and either the pH 4 or 10
buffer, depending on the anticipated sample pH). A third buffer
can be used to check instrument system performance over a larger
range. The pH of the buffer solution is temperature dependent:
pH 10 buffers change more per unit change in temperature than
do pH 4 buffers. The temperature of buffer solutions must be
known, and temperature-correction factors must be applied be-
fore calibration adjustments are made. Calibration and operat-
ing procedures differ with instrument systems—check the
manufacturer’s instructions.

Meters with microprocessors have reliable autocalibration

functions and will automatically compensate for buffer tem-
peratures and indicate Nernst slope. For such meters, follow
the manufacturer’s calibration instructions precisely—do not
take shortcuts.

P Check the records of electrode performance before each cali-

bration and field trip (see 6.4.1). Electrode response is opti-
mum between approximately 98 percent and 99.5 percent. A
slope of 94 percent indicates possible electrode deterioration.
At 90 percent slope, the electrode cannot be used.

P Calibrate or check the temperature sensor at least three times

per year, and tag the sensor with the date of District certifica-
tion. Do not use the automatic temperature compensating
function of a pH meter if it has not been District certified
within the past 4 months.

P Record calibration in the instrument log book and on field

forms at the time of instrument calibration.

Next, follow the 10 steps listed below:

1. Temperature equilibration of equipment (this is not needed if
using an automatic compensating meter).
a. Bring the pH buffers, thermometer (if necessary), container,
and electrode to the temperature of the sample.
b. Allow 15 to 30 minutes for the buffers to adjust to the sample
temperature. When making temperature corrections, use the
correction factors provided by the buffer manufacturer (tem-
perature coefficients can vary with buffer manufacturer).

U.S. Geological Survey TWRI Book 9 4/98 pH

14 — pH
• To equilibrate to stream temperature, place the buffer bottles
in a minnow bucket or mesh bag and suspend them in the
stream.
• To equilibrate to ground-water temperature, place the buffer
bottles in a mesh bag and suspend them in a bucket or
other large container (an ice chest works well) overflowing
with water being pumped from the well.

2. Inspect the pH electrode.

a. Check for damage to the electrode bulb, body, or cables.
b. Rinse any precipitate off of the electrode with deionized wa-
ter (the measurement can be affected if precipitate falls into
the buffer or sample).
c. Slide the protective sleeve up or down to uncover the filling
hole.
d. Gently shake or tap the electrode to dislodge and remove air
bubbles trapped in the sensing tip of the electrode and to
remove excess deionized water. Do not wipe the electrode.

3. Calibration rinse.
a. Rinse (with pH 7 buffer) the electrode, thermometer or auto-
matic temperature compensating (ATC) sensor, and a con-
tainer large enough to hold the sensors and buffer. Discard
the used pH buffer into a waste container.
b. Pour fresh pH 7 buffer into the buffer-rinsed container that
holds the electrode and thermometer. Allow the instruments
to equilibrate for 1 minute (if necessary), then discard the
buffer into a waste container.

4. Calibration. Steps c, d, e are not needed for autocompensating

meters.
a. Pour fresh pH 7 buffer into the container that holds the elec-
trode and thermometer or ATC sensor.
• The bulb of the pH electrode must not touch the bottom or
side of the container.
• Add enough pH buffer to cover the reference junction.
b. Swirl the sample gently or stir carefully with the electrode. If
using a magnetic stirrer, stir slowly enough so that a vortex is
not created. Place a thin piece of insulating material (styrofoam
or cardboard) between the magnetic stirrer and beaker to
prevent transfer of heat to the buffer solution.
c. Measure the temperature of the buffer solution; remove the
thermometer (it is not necessary to remove the ATC sensor).

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 15
d. Determine the theoretical pH of the buffer from the tempera-
ture-correction tables.
e. Note and record the pH temperature readings. Adjust the
meter reading to the pH value using the “standardize” func-
tion on the meter (usually a knob or pressure pad). Record
the adjusted pH value for the 7.0 buffer and associated milli-
volt reading.
f. Remove the electrode and ATC sensor (some instruments re-
quire that the meter be switched to the standby or off posi-
tion before removing the electrode from the solution).
• Repeat the calibration steps using fresh portions of refer-
ence buffer solution until two successive readings are ob-
tained at the adjusted pH value for pH 7 buffer without fur-
ther adjustment to the system.
• Discard the used pH 7 buffer into a waste container.

5. Slope adjustment rinse.

a. Rinse the electrode and thermometer or ATC sensor thoroughly
with deionized water.
b. Rinse a clean container, electrode, and thermometer with a
second buffer (usually pH 4 or 10) that brackets the expected
pH value of the sample; discard the used buffer into a waste
container.
c. Pour the second buffer into a container holding the electrode
and thermometer or ATC sensor. Allow the temperature to
equilibrate for 1 minute, then discard the used buffer into a
waste container.

6. Slope adjustment. This step is automated in modern meters.

a. Pour a fresh portion of the second pH buffer into a container
holding the electrode and thermometer or ATC sensor.
b. Stir slowly (no vortex) or swirl manually. Follow the directions
in 4b, above.
c. Measure the temperature and pH of the buffer solution and
check the pH value of the buffer on temperature coefficient
tables. Record the pH and temperature readings.
d. Adjust the slope to the value of the second pH buffer at known
temperature. (Some meters have separate slope-adjustment
knobs, pressure pads, or other devices, whereas others have
to be adjusted by use of a temperature knob.) Record the
adjusted pH value and associated millivolt reading.

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16 — pH
e. Discard the used buffer into a waste container.
f. Repeat steps 6(a) through 6(e) using successive portions of
the buffer solution until two successive readings are obtained
without further adjustment.

7. Rinse the electrode and thermometer or ATC sensor thoroughly

with deionized water.

8. If using a noncompensating or nonautomated meter, repeat the

calibration rinse (step 3) and calibration procedures [steps 4(a)
through 4(d)] to ensure that the slope adjustments did not af-
fect the calibration adjustment.
• This step is a check only; no adjustment should be needed,
but the result should be recorded. If adjustment is needed,
repeat the entire calibration procedure.
• If adjustment is still needed, a systematic problem is likely
(see 6.4.4). Inspect the instrument system, clean the electrode
or add filling solution, or use a spare electrode or meter.

9. Calibration check rinse.

a. Rinse the electrode and thermometer or ATC sensor with deion-
ized water.
b. Rinse another clean container, electrode, and thermometer
with a third buffer (pH 4 or 10) and discard the used buffer
into a waste container.
c. Pour the third buffer into a container holding the electrode
and thermometer or ATC sensor. Allow the temperature to
equilibrate for 1 minute (if necessary), then discard the used
buffer into a waste container.

10. Calibration range check.

a. Pour a fresh portion of third pH buffer into a container hold-
ing the electrode and thermometer or ATC sensor.
b. Stir without forming a vortex or swirl slowly (see step 4b).
c. Measure the temperature of the buffer solution (remove the
liquid-filled thermometer and check the temperature-adjusted
pH value), if necessary for the meter being used.
d. The pH instrument system should read the value of the third
buffer at a known temperature within ±0.1 pH units.
• Meters reading to three or more places to the right of the
decimal may not provide better accuracy than ±0.05 units,
and their accuracy must be verified.
• If it checks, the instrument system is calibrated over a range
of pH 4 to 10 and is ready for ANC or alkalinity titrations as
well as pH measurement.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 17
• If the instrument system does not check over the entire
range, recalibrate before measuring the sample pH.
Recalibrate before an alkalinity/ANC titration if the sample
has a pH greater than 7.0.
e. Discard the used buffer into a waste container.
f. Rinse the electrode and thermometer (or ATC sensor) with
deionized water.

Never reuse buffers or put used buffer

solution back into stock container.

Calibration for low-conductivity water:

Proper calibration of pH instrument systems with standard buff-

ers does not guarantee accurate pH measurement in water with
conductivity less than 100 µS/cm. The following recommenda-
tions for pH measurement in low-conductivity water are taken
from Busenberg and Plummer (1987).

1. After calibration with pH 4, 7, and 10 buffers, check electrode

performance daily in appropriate sulfuric acid standard solution
with conductivity less than 20 µS/cm. (For solution preparation
and handling, refer to Busenberg and Plummer, 1987).
• Before using the sulfuric acid standard solution, check for con-
tamination by measuring conductivity.

2. Check electrode performance with deionized water saturated

with an analyzed nitrogen-carbon dioxide gas mixture having
a carbon dioxide mole fraction of less than 0.5 percent.
• Addition of KCl is not recommended because of the potential
for contamination and other complications.

3. Rinse the electrode at least three times, preferably with a

portion of the sample to be measured.

4. Cap the Lazaran™ reference electrode of retrofitted Hydrolab™

units with saturated KCl solution when not in use.

5. Calibrate and measure pH in quiescent (unstirred) solutions

after the sample has been homogenized by stirring.

6. Check the electrode performance (slope) before using the

percent Nernst slope and (or) millivolt readings at pH 7 and
pH 4. Keep a record of the electrode slope and millivolt
readings—they can signal electrode deterioration.

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18 — pH

6.4.3 MEASUREMENT
The pH of a water sample can change significantly within hours
or even minutes after sample collection as a result of degassing
(such as loss of carbon dioxide, hydrogen sulfide, and ammo-
nia); mineral precipitation (such as formation of calcium carbon-
ate); temperature change; and other chemical, physical, and bio-
logical reactions. The electrometric method of pH measurement
described below applies to filtered or unfiltered surface water and
ground water, from fresh to saline.

The pH of a water sample must be measured

immediately in the field; laboratory-measured
pH should not be relied on in place of field-
measured pH.

Field conditions, including rain, wind, cold, dust, and direct sun-
light can cause measurement problems. To the extent possible,
shield the instrument and measurement process from the effects
of harsh weather.

P In dry, windy climates, a static charge can build up on the

face of a pH meter and cause erratic readings on the display.

P Polish the face of the display with a soft, absorbent tissue

treated with several drops of antistatic solution (such as plas-
tic polish) to minimize this interference.

TECHNICAL NOTE: Temperature has two effects on pH

measurement of a sample: it can affect electrode poten-
tial (Nernstian slope effect), and it can change hydrogen-
ion activity (chemical effect). The electrode-potential prob-
lem can be solved by using an automatic or manual tem-
perature compensator. The change in hydrogen-ion activ-
ity resulting from temperature changes in the sample can
be minimized if the electrodes, buffers, and container are
allowed to equilibrate to the same temperature.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 19

SURFACE WATER 6.4.3.A

It is generally preferable to measure pH in situ rather than on a
sample taken from a splitter or compositing device. If stream con-
ditions are such that water would pass the in situ pH sensor at a
very high rate of flow, however, streaming-potential effects could
affect the accuracy of the measurement. For such conditions, it
is preferable to withdraw a discrete sample directly from the
stream or compositing device and use the subsample measure-
ment procedures described below. The pH instrument system
should be set up on board the boat so that pH is measured at the
time of sample collection.

Standard pH measurement in flowing surface water represents

the cross-sectional mean hydrogen ion activity or median pH at
the time of observation.

To compute a mean pH for the stream: (1) Sum the products of

each subsection area, using the logarithm of the median pH de-
termined for each subsection; (2) divide the sum by the total
area of the cross section; and (3) convert back to pH by taking
the antilogarithm of the quotient.

In situ measurement

Follow the 7 steps listed below for in situ pH measurement:

1. Calibrate a pH system on site (after equilibrating the buffers
with the stream temperature, if necessary). Check the electrode
performance (see “Electrode Maintenance,” in 6.4.1) and the
calibration date of the thermometer being used.

2. Record the pH variation from a cross-sectional profile, if pos-

sible, to determine if pH is uniform at any given discharge, and
select the sampling method (NFM 6.0.2) appropriate for study
objectives.
• Flowing, shallow stream—Wade to the location(s) where pH
is to be measured.
• Stream too deep to wade—Lower a weighted pH sensor with
a calibrated temperature sensor from a bridge, cableway, or
boat. Do not attach the weight to sensor or sensor cables.
• Still-water conditions—Measure pH at multiple depths at sev-
eral points in the cross section.

U.S. Geological Survey TWRI Book 9 4/98 pH

20 — pH
3. Immerse the pH electrode and temperature sensor in the water
to the correct depth and hold them there for at least 60 sec-
onds to equilibrate them to water temperature.

4. Measure the temperature.

• If the pH instrument system contains an automatic tempera-
ture compensator (ATC), use the ATC to measure water tem-
perature.
• If the instrument system does not contain an ATC, use a sepa-
rate calibrated thermometer, adjust the meter to the sample
temperature (if necessary), and remove the thermometer.

5. Record the pH and temperature values without removing the

sensor from the water.
• Values generally stabilize quickly within ±0.05 to 0.1 standard
pH unit, depending on the instrument system.
• Record the median of the observed values.
• If readings do not stabilize after extending the measurement
period, note this difficulty on the field forms along with the
pH readings, and record the median value of the last five or
more readings.

6. EWI or EDI measurements—Proceed to the next station in the

cross section. Repeat steps 3 through 5. After all stations in the
cross section have been measured, rinse the sensors with deion-
ized water and store them.

7. Record the stream pH on the field forms:

• In still water—median of three or more sequential values.
• EDI—mean value of all subsections measured (use the me-
dian if measuring one vertical at the centroid of flow).
• EWI—mean or median of all subsections measured. (Note
that pH values must be converted to a logarithm before cal-
culating a mean value.)

Subsample measurement

When streams are fast-flowing or the water contains much sedi-

ment or algae, pH measurement of a discretely collected
subsample might be preferable to in situ measurement. Repre-
sentative samples are to be collected and split or composited ac-
cording to approved USGS methods (Wells and others, 1990). pH
measurement in fast-flowing streams should be made at the time
of collection from a boat that has been set up for such measure-
ments.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 21
P Measure pH as soon as possible after compositing the EDI or
EWI sample.

P Filter the sample if the pH continues to drift: measure pH in

the field on both unfiltered and filtered subsamples and record
both values on the field form.

P If the filtered sample provides the only stable pH value, re-

port this value as sample pH.

TECHNICAL NOTE: Reported pH values are normally de-

termined on an unfiltered sample. However, large con-
centrations of suspended sediment or algae can be a source
of measurement error; slow settling of clay particles or
algal respiration can cause “drift” of an observed pH value.

Throughout collection and processing, avoid excess

aeration to prevent losses and gains of dissolved gases
(especially CO2) from solution.

1. Calibrate the pH system on site (after equilibrating buffer tem-

perature with stream temperature, if necessary). Check the elec-
trode performance (see 6.4.1).

2. Select the appropriate sampling method (see NFM 6.0) and col-
lect a representative sample.

3. Withdraw properly homogenized sample(s) from the compositing

device.
• Rinse the collection bottles three times with the sample (use
filtrate, if a filtered sample is used).
• If the samples need to be stored for a short time or if several
subsamples will be measured, collect sample aliquots in sepa-
rate field-rinsed bottles, fill them to the brim, cap them tightly,
maintain them at ambient stream temperature, and measure
pH in the field as soon as possible.

4. Rinse thoroughly with deionized water—the pH electrode, ther-

mometer or ATC sensor, stir bar, and a measurement container.
• For pH, follow the deionized water rinse of equipment with a
rinse using sample water.
• For ANC or alkalinity, rinse with deionized water only; do not
rinse with the sample when using this equipment (see NFM
6.6).

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22 — pH
5. Immerse electrode and temperature sensor in sample water for
at least 60 seconds to equilibrate to sample temperature.

6. Pour fresh aliquot of the sample water into a container holding

the electrode and thermometer. Do not let the electrode touch
the bottom or sides of container during measurement.

7. Measure and record the initial temperature. Use the ATC, if it is

available and calibrated, or use a separate calibrated thermo-
meter and adjust the meter manually to the sample tempera-
ture (if necessary).

8. Establish equilibrium between the electrode(s) and sample by

stirring slowly (no vortex) or by manual swirling.
• Do not stir if a vortex is formed that affects the electrode
performance.
• Do not use a magnetic stirrer for samples with low conductiv-
ity (less than 100 µS/cm).
• Before recording a pH value, allow the sample to reach quies-
cence.

9. Record the pH and temperature measurements on the field

forms, along with the sampling, processing, and measurement
methods used and any observed anomalies.

10. Quality control—Repeat steps 6 through 9 with at least two

fresh subsamples to check measurement precision. Subsample
values should agree within ±0.1 pH unit (or study-determined
criterion). Report the median of the values measured.

11. Rinse the electrode and temperature sensor thoroughly with

deionized water. Replace the plug on the fill hole of refillable
electrodes and follow the recommended storage procedure.

12. Discard the used sample into a waste container and dispose of
it according to regulations.

6.4.3.B GROUND WATER

Measurements reported as ground-water pH must represent aqui-

fer conditions (consult NFM 6.0 for guidance). Measure pH as
close to the source as possible, either downhole or within a
flowthrough chamber.

P Use equipment that minimizes aeration and operate equip-

ment in a manner to help mitigate losses and gains of dis-
solved gases in solution (for example, carbon dioxide).

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 23
P Although downhole measurements are likely to be most rep-
resentative of ground-water pH, proper use of pH instruments
with flowthrough chambers can yield comparable values.

P The downhole system is not practical if samples will be col-

lected after field measurements, because the instrument
should not be left in the well during sampling and the pump
should not be turned off between purging and sample collec-
tion—use a flowthrough-chamber system.

P Streaming potentials in the flowthrough chamber can result

in biased pH values. Make the final (the reported sample pH)
measurement in quiescent water.

Bailed or other methods for collecting discrete samples isolated

from their source are not recommended for the determination of
pH, although such methods are sometimes used owing to site
characteristics or study requirements. Record the method used
to obtain the sample for pH measurements on the field forms
and in the data base.

Downhole and flowthrough-

chamber measurements
1. Calibrate the pH instrument system on site.
a. If necessary, bring the buffer solutions to the temperature of
the water to be measured (discharge the well water into a
bucket while suspending the standards in a net bag; allow at
least 15 minutes for temperature equilibration; check tem-
perature of the water flowing into the bucket against that of
the buffers).
• Check that the thermometer has been District certified
within at least the past 4 months.
• Check electrode performance (see 6.4.1 and 6.4.2).
b. After calibration, rinse the pH electrode thoroughly with deion-
ized water and blot it to remove excess water. Do not wipe
the electrode.

2. Install the pH monitoring system for sample measurement (see

6.0.3 in NFM 6.0).
• Downhole system—Lower sensors to the measuring point,
followed by the pump, to monitor pH variation during purg-
ing.

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24 — pH
• Flowthrough system—Install the chamber system as close to
the well as possible and shield the chamber and tubing from
direct sunlight. Check that the electrode fill hole is open to
the atmosphere and that the reference junction is entirely
submerged. Check for and eliminate a backpressure condi-
tion.

3. During purging (see table 6.0–1 and fig. 6.0–3 in NFM 6.0):
• Keep the flow constant and laminar.
• Allow the sensors to equilibrate with the ground water for 5
minutes or more at the flow rate to be used for collecting all
of the other samples.

4. Record pH values at regularly spaced time intervals throughout

purging. Compare the variability of the pH values toward the
end of purging with the stability criterion:
• The stability criterion is met when five readings made at regu-
larly spaced intervals of 3 to 5 minutes or more are within 0.1
standard pH unit or less (depending on the equipment). Rou-
tine measurement must fall within the ±0.1 unit criterion.
When readings fluctuate rapidly, select the median of three or
more readings within about 60 seconds as the value recorded
for the specific time interval.
• If the criterion is not met, extend the purge period in accor-
dance with study objectives, and continue to record measure-
ments at regularly spaced time intervals. Record any difficulty
on the field forms.

5. Measure and report the pH:

• If using a flowthrough system, divert the flow from passing
into the flowthrough chamber after recording the other field
measurements. Measure the sample pH in the chamber as soon
as the water is still. Take several readings to be sure that the
system has stabilized.
• If using a downhole method, measure the sample pH after
pumping has ceased. This entails installing the downhole sen-
sors in the well after sample collection. If field measurements
only are being monitored, stop the pump (after recording the
other field-measurement values) and allow the pH to stabilize
before recording the pH value.
• Report the final value measured on a quiescent (no-flow)
sample, if the values are stable. If the stability criterion is not
met, record the range of values observed for the time interval
monitored, and report the median of the final five or more
values observed.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 25

Subsample measurement

pH measurements reported from bailed or other discrete samples

need to be identified in the data base by a description of the
sampling method used. Refer to 6.0.3.B in NFM 6.0 for use of
bailers and the subsample method.

Do not use a subsample method

if waters are reducing.

1. Calibrate the pH system on site (after equilibrating the buffers

with the ground-water temperature, if necessary). Check the
electrode performance (see sections 6.4.1 and 6.4.2).

2. Draw off a subsample through a bottom-emptying device that

fits tightly over the bottle opening.
• Quality control—Collect three subsamples to check precision.
• Rinse the sample bottles three times with sample; use filtrate
if filtered sample is used. Cap the bottles until they are ready
for use.
• If the samples need to be stored for a short time or if several
subsamples will be measured, collect the sample aliquots in
separate field-rinsed bottles, fill them to the brim, cap them
tightly, maintain them at ambient ground-water temperature,
and measure the pH as soon as possible.

3. Follow the procedures described in steps 4 through 12 for

subsample measurement of surface water (6.4.3.A).

TECHNICAL NOTE: An alternative method is to pour the

sample into an open container instead of measuring it in
a closed system. If this method is used and readings do
not stabilize within several minutes, the cause may be out-
gassing of carbon dioxide—measure the sample in a closed
system. Filter the sample if settling of charged clay par-
ticles interferes with the stability of readings.

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26 — pH

6.4.4 TROUBLESHOOTING
Contact the instrument manufacturer if the suggestions in table
6.4–2 fail to resolve the problem.

P If available, use a commercial pH electronic calibrator to check

the pH meter function.

P A large percentage of all problems encountered during pH

calibration and measurement can be attributed directly to
problems with the pH electrode—refer to 6.4.1.B.

P New electrodes are susceptible to some of the problems listed

in table 6.4–2, and they may need reconditioning before they
can be used.

P Check the voltage of the batteries. Always have good batter-

ies in instruments and carry spares.

Table 6.4–2. Troubleshooting guide for pH measurement

[M, molar; HCl, hydrochloric acid; KCl, potassium chloride; °C, degrees Celsius; ~, about]
Symptom Possible cause and corrective action
• Buffers may be contaminated or old—use fresh buffers.
Instrument system will • Faulty electrode—recondition electrode (see discussion in section
not calibrate full scale 6.4.1 on electrode maintenance, cleaning, and storage).
• Weak batteries—replace.
For liquid-filled electrodes:
• Weak filling solution—change filling solution (section 6.4.1).
• No filling solution—add fresh solution (section 6.4.1).
• Dirty tip—clean with soap solution. Do not scratch electrode tip.
• Chemical deposits—place electrode in a 0.1 M HCl solution for about
30 minutes.
• Clogged or partially clogged junction—unclog by placing electrode
Slow response time tip in 0.1 M KCl solution at 90°C for about 15 minutes.
Do not boil calomel electrodes (section 6.4.1).
• Water is cold or of low ionic strength—longer equilibration time is
needed (be patient).
• Weak batteries—replace with new batteries.
For gel-filled electrodes:
• Dirty bulb—rinse with deionized water.
• Clogged junction—liquify gel by placing electrode into warm
(~60°C) water for one minute or less.
• Loose or defective connections—tighten, clean, or replace
connections.
• Broken or defective cable—repair or replace cable.
Erratic readings • Static charge—polish face of meter with antistatic solution.
• Loose battery connection—tighten.
• Air bubbles in the electrode bulb—shake gently.
• Too much pressure in flowthrough chamber—reduce pressure.
• Weak batteries—replace with new batteries.

pH U.S. Geological Survey TWRI Book 9 4/98

 pH — 27

REPORTING 6.4.5
Report pH measurements in the data base to the nearest 0.1 stan-
dard pH unit.

P pH values to the nearest 0.05 unit can be published provided

the instrument system has been calibrated at the required
precision and accuracy.

P Report the instrument accuracy range with the published val-

ues and record the accuracy range in the data base, if pos-
sible.

P Enter the field-determined pH under the correct parameter

code on the NWQL analytical services request form and on
field forms.

U.S. Geological Survey TWRI Book 9 4/98 pH