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March 2006
Chapter 11
pH and Alkalinity
Every estuary is part of the carbon cycle. Carbon moves from the atmosphere into
plant and animal tissue, and into water bodies. Alkalinity, acidity, carbon dioxide
(CO2), pH, total inorganic carbon, and hardness are all related and are part of the
factors. For example, the amount of carbon dioxide in the water affects (and is
Overview
This chapter discusses two additional chemical parameters of estuaries that are
Since the pH of water is critical to the survival of most aquatic plants and animals,
monitoring program. The testing is quick and easy and can establish a valuable
understood.
Testing water samples for total alkalinity measures the capacity of the water to
Every estuary is part of the carbon cycle. Carbon moves from the atmosphere
into plant and animal tissue, and into water bodies. Alkalinity, acidity, carbon
dioxide (CO2), pH, total inorganic carbon, and hardness are all related and are part
these factors. For example, the amount of carbon dioxide in the water affects (and
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Volunteer Estuary Monitoring: A Methods Manual
Chapter 11: pH and Alkalinity Unit One: Chemical Measures
pH
pH is a measure of how acidic or basic (alka rate of eggs deposited there by spawning fish.
line) a solution is. It measures the hydrogen ion Several other factors also determine the pH
(H+) activity in a solution, and is expressed as a of the water, including:
negative logarithm. The pH measurements are • bacterial activity;
given on a scale of 0.0 to 14.0 (Figure 11-1).
Pure water has a pH of 7.0 and is neutral;
• water turbulence;
water measuring under 7.0 is acidic; and that • chemical constituents in runoff flowing
above 7.0 is alkaline or basic. Most estuarine into the waterbody;
organisms prefer conditions with pH values • sewage overflows; and
ranging from about 6.5 to 8.5. • impacts from other human activities both
Values of pH are based on the logarithmic in and outside the drainage basin (e.g.,
scale, meaning that for each 1.0 change of pH, acid drainage from coal mines, accidental
acidity or alkalinity changes by a factor of ten; spills, and acid precipitation).
that is, a pH of 5.0 is ten times more acidic than
Estuarine pH levels generally average from
6.0 and 100 times more acidic than 7.0. When
7.0 to 7.5 in the fresher sections, to between 8.0
the hydrogen and hydroxyl ions are present in
and 8.6 in the more saline areas. The slightly
equal number (the neutral point), the pH of the
alkaline pH of seawater is due to the natural
solution is 7.
buffering from carbonate and bicarbonate dis
solved in the water.
The Role of pH in the Estuarine Ecosystem The pH of water is critical to the survival of
Water’s pH is affected by the minerals dis most aquatic plants and animals. Many species
solved in the water, aerosols and dust from the have trouble surviving if pH levels drop under
air, and human-made wastes as well as by 5.0 or rise above 9.0. Changes in pH can alter
plants and animals through photosynthesis and other aspects of the water’s chemistry, usually
respiration. Human activities that cause signifi to the detriment of native species. Even small
cant, short-term fluctuations in pH or long-term shifts in the water’s pH can affect the solubility
acidification of a waterbody are exceedingly of some metals such as iron and copper. Such
harmful. For instance, algal blooms that are changes can influence aquatic life indirectly; if
often initiated by an overload of nutrients can the pH levels are lowered, toxic metals in the
cause pH to fluctuate dramatically over a few- estuary’s sediment can be resuspended in the
hour period, greatly stressing local organisms. water column. This can have impacts on many
Acid precipitation in the upper freshwater aquatic species. See Chapter 12 for more infor
reaches of an estuary can diminish the survival mation on toxins. ■
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Volunteer Estuary Monitoring: A Methods Manual
Unit One: Chemical Measures Chapter 11: pH and Alkalinity
Sampling Considerations
Chapter 6 summarized several factors that cise measures are 14 Lye, sodium hydroxide (NaOH)
should be considered when determining moni required, more Oven cleaners
toring sites, where to monitor, and when to expensive elec- 13
monitor. In addition to the considerations in tronic pH meters Bleach
Chapter 6, a few additional ones specific to provide extreme- 12
monitoring pH are presented here. ly accurate read
Alkaline
ings. Test paper 11 Ammonia
When to Sample strips to obtain
pH are unsuit 10 Milk of Magnesia,
It is well-established that levels of pH fluctu
able for use in soap solutions
ate throughout the day and season, and a single
estuarine waters 9
pH measure during the day may not draw a
since they do not
very accurate picture of long-term pH condi Baking soda
provide consis 8 Sea water
tions in the estuary. Photosynthesis by aquatic
tent measure- Blood
Neutral
plants removes carbon dioxide from the water;
ments in salt 7 Distilled water
this significantly increases pH. A pH reading Saliva
water. The fol- Water
taken at dawn in an area with many aquatic
lowing sections 6
plants will be different from a reading taken six
describe the use Rain water, urine
hours later when the plants are photosynthesiz
of the two com- Boric acid, black coffee
ing. Likewise, in waters with plant life (includ 5
mon methods.
ing planktonic algae), an increase in pH can be
expected during the growing season. For these 4 Tomatoes, grapes
Colorimetric
Acidic
reasons, it is important to monitor pH values at
Method
the same time of day if you wish to compare 3 Vinegar, wine, soft drinks, beer,
your data with previous readings. It is also Colorimetric orange juice, some acid rain
important to monitor pH values over a long means “to mea- Stomach acid 2 Lemon juice
period of time to provide useful data. The sure color.” In a
actual time to measure pH will depend on local colorimetric test 1
conditions and the monitoring goals of the method, reagents Battery acid
volunteer program. are added to a 0
water sample,
Figure 11-1. pH range
Choosing a Sampling Method and a reaction occurs which produces a color. scale.
The color can be measured visually or electron
The pH test is one of the most common
ically. This method is not suitable for water
analyses done in volunteer estuary monitoring
containing colored materials such as dissolved
programs. In general, citizen programs use one
organic compounds or excessive algae. For
of two methods to measure pH: (1) the colori
water samples that are colored, a meter is sug
metric method or (2) electronic meters. Both
gested.
require that measurements be taken in the field,
since the pH of a water sample can change Visual Method to Measure Color
quickly due to biological and chemical process Field kits cover a range of pH values. They
es. cost between $15 and $50, depending on the
Color comparator (also called “colorimetric”) range of pH values to be tested. These kits
field kits are easy to use, inexpensive, and suffi come with several color standards built into a
ciently accurate to satisfy the needs of most plastic housing unit or printed on a card. After
programs. The colorimetric method can also be adding reagents according to the instructions,
used with an electronic colorimeter. If very pre- the volunteer compares the color in the test tube
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Volunteer Estuary Monitoring: A Methods Manual
Chapter 11: pH and Alkalinity Unit One: Chemical Measures
pH Calibration Standards
Whether you use a field kit, pH meter, or colorimeter unit, calibration standards (also called
“buffer solutions”) are employed to ensure that your equipment is accurate. The standards most
commonly used are pH 4.00 (or 4.01), pH 7.00, and pH 10.00. They are available in liquid or
powder form (the powder is added to demineralized or deionized water). These pH standards
cost from $5 to $25 each, depending on the quantity of calibrations you will be conducting.
Following is information regarding buffers:
• Because buffer pH values change with temperature, the buffer solutions should be at
room temperature when you calibrate the meter. Usually you can calibrate your pH
equipment at home, a few hours before using it. Check manufacturer’s instructions.
• Do not use a buffer after its expiration date.
• Always cap the buffers during storage to prevent contamination.
• Do not reuse buffer solutions!
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Volunteer Estuary Monitoring: A Methods Manual
Unit One: Chemical Measures Chapter 11: pH and Alkalinity
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Volunteer Estuary Monitoring: A Methods Manual
Chapter 11: pH and Alkalinity Unit One: Chemical Measures
TOTAL ALKALINITY
Alkalinity (also known as “buffer capacity”) The Role of Alkalinity in the Estuarine
is a measure of the capacity of water to Ecosystem
neutralize acids. Alkaline compounds such as
bicarbonates, carbonates, and hydroxides, Measuring alkalinity is important in
remove hydrogen ions and lower the acidity determining the estuary’s ability to neutralize
of the water (thereby increasing pH). They acidic pollution from rainfall or wastewater.
usually do this by combining with the Without this acid-neutralizing capacity, any
hydrogen ions to make new compounds. acid added to a body of water would cause an
Alkalinity is influenced by rocks and soils, immediate change in pH. This buffering
salts, certain plant activities, and certain capacity of water, or its ability to resist pH
industrial wastewater discharges. Some water change, is critical to aquatic life. The
can test on the acid side of the pH scale and estuary’s capacity to neutralize acids will vary
still rank high in alkalinity! This means that, between the freshwater reaches of the estuary
while the water might be acidic, it still has a and the portions with higher salinity.
capacity to buffer, or neutralize, acids.
Total alkalinity is measured by measuring Total Alkalinity Levels in Estuaries
the amount of acid (e.g., sulfuric acid) needed Total alkalinity of seawater averages 116
to bring the sample to a pH of 4.2. At this pH, mg/l and is greater than fresh water, which
all the alkaline compounds in the sample are can have a total alkalinity of 30 to 90 mg/l,
“used up.” The result is reported as milli depending on the watershed. The brackish
grams per liter of calcium carbonate (mg/l waters of an estuary will have total alkalinity
CaCO3). between these values. ■
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Volunteer Estuary Monitoring: A Methods Manual
Unit One: Chemical Measures Chapter 11: pH and Alkalinity
Sampling Considerations
Choosing a Sampling Method Digital titrators have counters that display
numbers. A plunger is forced into a cartridge
For total alkalinity, a double endpoint containing the reagent by turning a knob on
titration using a pH meter and a digital titrator the titrator. As the knob turns, the counter
is recommended. This can be done in the field changes in proportion to the amount of
or in the lab. If you plan to analyze alkalinity reagent used. Alkalinity is then calculated
in the field, it is recommended that you use a based on the amount used. Digital titrators
digital titrator. Another method for analyzing cost approximately $100; the reagents
alkalinity uses a buret. For volunteer programs, (chemicals) to conduct total alkalinity tests
using a digital titrator is recommended over the cost about $36. Additionally, alkalinity
buret, because digital titrators are portable, standards are needed for accuracy checks (see
economical, take less time, and have easy-to the box, “Alkalinity Calibration Standards,”
read endpoints (results). page 11-9). ■
Digital Titrator
This method involves titration, the addition Reminder!
of small, precise quantities of sulfuric acid To ensure consistently high quality data,
(the reagent) to the sample until the sample appropriate quality control measures are
reaches a certain pH (the endpoint). The necessary. See “Quality Control and
amount of acid used corresponds to the total Assessment” in Chapter 5 for details.
alkalinity of the sample.
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Volunteer Estuary Monitoring: A Methods Manual
Chapter 11: pH and Alkalinity Unit One: Chemical Measures
• reagent (sulfuric acid titration cartridge, reduce the pH by exactly 0.3 pH units (which
0.16 N); corresponds to an exact doubling of the pH) to a
pH of 4.2. However, the exact pH at which the
• standard alkalinity ampules, 0.500 N, conversion of these bases might have happened,
for accuracy check; and
or total alkalinity, is still unknown.
• bottle with deionized water to rinse pH Arriving at total alkalinity requires an equa
meter electrode. tion (given below) to extrapolate back to the
amount of sulfuric acid that was added to actu
STEP 2: Collect the sample. ally convert all the bases to carbonic acid. A
If you plan to analyze a water sample in the multiplier (0.1) then converts this to total alka
lab for alkalinity, then follow these collection linity as mg/l of calcium carbonate (CaCO3). To
and storage steps: determine the alkalinity of your sample, follow
these steps:
• Use 100 ml plastic or glass bottles.
• Samples should be warmed to room tem
• Label the bottle with site name, date, perature before analyzing.
time, data collector, and analysis to be
performed. • Insert a clean delivery tube into the 0.16N
sulfuric acid titration cartridge and attach
• Wearing gloves, plunge the bottle into the the cartridge to the titrator body.
water. Fill the bottle completely and cap
tightly. • Hold the titrator, with the cartridge tip
• Avoid excessive agitation and prolonged pointing up, over a sink or waste bottle.
exposure to air. Turn the delivery knob to eject air and a
few drops of titrant. Reset the counter to
• Place the bottle in the cooler. Samples 0 and wipe the tip.
should be analyzed as soon as possible,
but can be stored at least 24 hours by • Measure the pH of the sample using a pH
cooling to 4°C (39°F) or below. NOTE: meter. If it is less than 4.5, skip to step 3a,
Samples should be warmed to room tem page 11-9.
perature before analyzing (Hach, 1997). • Insert the delivery tube into the beaker
containing the sample. Turn the delivery
STEP 3: Measure total alkalinity. knob while magnetically stirring the
Alkalinity is usually measured using sulfuric beaker until the pH meter reads 4.5.
acid with a digital titrator. Follow the steps Record the number of digits used to
below in the field or lab. Remember to wear achieve this pH. Do not reset the counter.
latex or rubber gloves. • Continue titrating to a pH of 4.2 and
Add sulfuric acid to the water sample in mea record the number of digits.
sured amounts until the three main alkaline • Apply the following equation:
compounds (bicarbonate, carbonate, and
Alkalinity (as mg/l CaCO3) = (2a - b) x 0.1
hydroxide) are converted to carbonic acid. At
pH 10, hydroxide (if present) reacts to form Where:
water. At pH 8.3, carbonate is converted to
a = digits of titrant to reach pH 4.5
bicarbonate. At pH 4.5, all carbonate and bicar
bonate are converted to carbonic acid. Below b = digits of titrant to reach pH 4.2
this pH, the water is unable to neutralize the sul (including digits required to get
furic acid and there is a linear relationship to pH 4.5)
between the amount of sulfuric acid added to the
0.1 = digit multiplier for a 0.16 titration
sample and the change in the pH of the sample.
cartridge and a 100 ml sample
So, more sulfuric acid is added to the sample to
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Volunteer Estuary Monitoring: A Methods Manual
Unit One: Chemical Measures Chapter 11: pH and Alkalinity
Example:
Note on Data Sheet for Alkalinity
Initial pH of sample is 6.5.
Data sheets should be specialized depending on which methods
It takes 108 turns to get to a pH of 4.5. your program uses to measure each parameter—and this is true
for alkalinity, too. With the method described in this manual, your
It takes another 5 turns to get to pH 4.2,
worksheet should include places for volunteers to record the
for a total of 113 turns.
results of the various steps described.
Alkalinity = [(2 x 108) - 113] x 0.1
= 10.3 mg/l
• Record alkalinity as mg/l CaCO3 on the Alkalinity Calibration Standards
data sheet.
You will need to do an accuracy check on your alkalinity test
• Rinse the beaker with distilled water equipment before the first field sample is titrated, again about
before the next sample. halfway through the field samples, and at the final field sample. For
this, you will need an alkalinity standard. Often, these come in pre-
STEP 3a: measured glass ampules. To use, break off the tip of the glass
If the pH of your water sample, prior ampule and pour the liquid into a beaker. Then, follow the directions
to titration, is less than 4.5, proceed as follows: found under “Step 4: Perform an accuracy check.” The price for the
alkalinity standards is about $23 for 20 2-ml ampules.
• Insert the delivery tube into the
• Turn the delivery knob while swirling STEP 4: Perform an accuracy check.
the beaker until the pH meter reads This accuracy check should be performed
exactly 0.3 pH units less than the initial on the first field sample titrated, again about
pH of the sample. halfway through the field samples, and at the
• Record the number of digits used to final field sample. Check the pH meter
achieve this pH. against pH 7.00 and 4.00 buffers after every
10 samples.
• Apply the equation as before, but a = 0
and b = the number of digits required to • Snap the neck off an alkalinity ampule
reduce the initial pH exactly 0.3 pH units. standard, 0.500 N; or, if using a standard
Titrate to a pH of 0.3 units less than the back to the pH 4.2 endpoint. Record the
It takes 10 digits to get to 4.0. • Repeat using two more additions of 0.1
Enter this in the 4.2 column on the data ml of standard. Titrate to the pH 4.2 after
sheet and note that the pH endpoint is 4.0. each addition. Each 0.1 ml addition of
Alkalinity = -1.0
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Volunteer Estuary Monitoring: A Methods Manual
Chapter 11: pH and Alkalinity Unit One: Chemical Measures
STEP 5: Return the field data sheets Make sure that the data sheets are complete,
and/or samples to the lab. legible, and accurate, and that they account for
all samples. Volunteers should make a copy of
Volunteers should thoroughly clean all the completed data sheets before sending
equipment and transport the samples to the them to the designated person or agency in
designated lab. Alkalinity samples must be case the original data sheet becomes lost. ■
analyzed within 24 hours of their collection. If
Other references:
American Public Health Association (APHA), American Water Works Association, and Water
Environment Federation. 1998. Standard Methods for the Examination of Water and
Wastewater. 20th ed. L. S. Clesceri, A. E. Greenberg, A. D. Eaton (eds). Washington, DC.
Godfrey, P. J. 1988. Acid Rain in Massachusetts. University of Massachusetts Water Resources
Research Center. Amherst, MA.
U.S. Environmental Protection Agency (USEPA). 1997. Volunteer Stream Monitoring: A
Methods Manual. EPA 841-B-97-003. November. Office of Water, Washington, DC. 211 pp.
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Volunteer Estuary Monitoring: A Methods Manual