Measurement of

Water Quality
 Quantitative measurements of pollutants are necessary before water pollution can be controlled.

Some pollutants are generally present at low concentrations,

and very accurate methods of detection are required.

A complete volume of analytical techniques used in water and wastewater engineering is compiled as
Standard Methods for the Examination o f Water and Wastewater.*

Many water pollutants are measured in terms of milligrams of the substance per litre of water (mg/L). In older
publications pollutant concentrations are expressed as parts per million (ppm), a weight/weight parameter. If the
liquid involved is water, ppm is identical with mg/L, since one litre (L) of water weighs 1000 grams (g). For
pollutants present in very low concentrations (<10 mg/L), ppm is approximately equal to mg/L. However, because
of the possibility that some wastes have specific gravity different from water, mg/L is preferred to ppm. A third
commonly used parameter is percent, a weight/weight relationship. Note that 10,000 ppm = 1% and is equal to
10,000 mg/L only when 1 mL = 1 g.

Most tests may be performed on a water sample taken from the stream. The process by which the sample is
obtained, however, may greatly influence the result.

*American Public Health Association, “Standard Methods for the Examination of Water and Wastewater,” 20th ed., Water Pollution Control Federation,
American Water Works Association (1996). (look up for updated publication)
 SAMPLING

The process of obtaining a sample may change the measurement.

Most tests may be performed on a water sample taken from the stream. The process by which
the sample is obtained, however, may greatly influence the result. The three basic types of
samples are: grab, composite, and flow weighted composite.

The grab sample, as the name implies, measures water quality at only one sampling point, The
composite sample is obtained by taking a series of grab samples and mixing them together.
The flow weighted composite is obtained by taking each sample so that the volume of the
sample is proportional to the flow at that time.
 DISSOLVED OXYGEN (DO)

The most important measure of water quality is the dissolved oxygen

(DO). Oxygen, although poorly soluble in water, is fundamental to
aquatic life. Without free DO, streams and lakes become
uninhabitable to gill-breathing aquatic organisms. Dissolved oxygen
is inversely proportional to temperature, and the maximum oxygen
that can be dissolved in water at most ambient temperatures is about
10 mg/L. The saturation value decreases rapidly with increasing
water temperature, as shown in Table 4-1.

The amount of oxygen dissolved in water is usually measured either

with an oxygen probe or by iodometric titration. The latter method is
the Winkler test for DO, developed about 100 years ago and the
standard against which all other measurements are compared.

𝑪𝒈 = 𝑲𝑷𝒈
The simplest (and historically the first) probe is shown in the
Figure. The principle of operation is that of a galvanic cell. If lead
and silver electrodes are put into an electrolyte solution with a
microammeter between, the reaction at the lead electrode will be:

Pb + 2 𝐎𝐇 − → PbO + 𝐇𝟐 𝐎 + 2 𝐞−

At the lead electrode (the cathode), electrons are liberated that

travel through the microammeter to the silver electrode (the
anode), where the following reaction takes place:

2 𝐞− + 1Τ2 𝐎𝟐 + 𝐇𝟐 𝐎 → 2 𝐎𝐇 −

The reaction will not take place unless free dissolved oxygen DO
Schematic diagram of a galvanic
is available, in which case the microammeter will not register any
cell oxygen probe
current.
 BIOCHEMICAL OXYGEN DEMAND

The rate at which oxygen is used by available microorganisms in

consuming the available organic compounds, is perhaps even more
important than the determination of DO.

The rate of oxygen use is commonly referred to as biochemical oxygen

demand (BOD).
BOD is not a specific pollutant but rather a measure of the amount of
oxygen required by bacteria and other microorganisms engaged in
stabilizing decomposable organic matter.

The BOD test is usually carried out in standard BOD bottles (about 300- A BOD bottle, made of a special
nonreactive glass and supplied with a
mL volume) as shown to the right: ground-glass stopper.

The BOD test was first used for measuring the oxygen consumption in a stream by filling two bottles with
stream water, measuring the DO in one bottle, and placing the other in the stream. In a few days, the second
bottle was retrieved, and the DO was measured. The difference in the oxygen levels was the BOD, or
oxygen demand, in milligrams of oxygen used per litre of sample.
 The BOD test has been standardized by requiring the test to be run in the dark at 20°C for five days.
The 5-day BOD, or 𝐁𝐎𝐃𝟓 , is the oxygen used by microorganisms in the water sample during the first
five days after sampling.

The test is begun by measuring the initial

DO at the temperature at which they will be Diluted
stored, usually at 20°C. DO is then measured in Sample
several samples every day for five days, and the B by 10

results produce curves like those shown.

The oxidation of BOD is an exponential decay

curve, as is shown for example in the Figure,
and the decay constant is usually such that most
of the BOD is oxidized in the first five days.

Sample A has an initial DO of 8 mg/L, and in five

days this drops to 2 mg/L. The BOD is 8 - 2 = 6
mg/L. Sample B also has an initial DO of 8 mg/L,
but the oxygen is used so fast that it drops to zero
by the second day. Samples like this require
repeating the 5-day BOD test after diluting the
sample by 10. The BOD of sample B is therefore: Typical oxygen uptake curves in a BOD test
8−4
BOD = 0.1 = 40 mg/L
With dilution (using water with no BOD of its own), the BOD equation becomes:

BOD = (I - F) D

where D = dilution represented as a fraction and defined as:

 Example:
Calculate the BOD5 of a water sample, given the following data:
Initial DO is saturation at Temperature of sample is 20°C
Dilution is 1:30, with seeded dilution water
Final DO of seeded dilution water is 8 mg/L
Final DO bottle with sample and seeded dilution water is 2 mg/L
Volume of BOD bottle is 300 mL

Solution:

From Table-1, DO saturation at 20°C is 9.2 mg/L; hence, this is the initial DO.
Since the BOD bottle contains 300 mL, a 1:30 dilution with seeded water contains 10 mL of sample and
290 mL of seeded dilution water, the 𝐁𝐎𝐃𝟓 is:
 Example
Three BOD bottles were prepared with sample and dilution water, as shown in the following table:
Calculate the dilution (D) for each.
Bottle Sample (mL) Dilution Water (mL)

Solution 1 3 297
Recall that the volume of a standard BOD bottle is 300 mL. 2 1.5 298.5
300
For bottle 1, the dilution, D, is: 𝐷 = = 100 3 0.75 299.5
300−297
For bottle 2 and 3 D is 200 and 400, respectively

Example

A series of BOD test were run at three different dilutions. The

results were as in the table. What is the BOD? Bottle
Initial DO (mg/L) Final DO (mg/L)
Dilution
Solution 1 100 10.0 2.5
Since for case (1) BOD = (I - F)D 2 200 10.0 6.0
Then: BOD1 = (10-2.5)(100)=750 3 400 10.0 7.5
The calculated BOD for 2 and 3 is: 800, and 1000.
BOD is a measure of oxygen use or potential use. An effluent with a high BOD can be harmful to a stream if
the oxygen consumption is great enough eventually to cause anaerobic conditions (i.e., the DO sag curve
approaches zero dissolved oxygen in the stream). Obviously, a small trickle of wastewater going into a great
river probably will have negligible effect, regardless of the mg/L of BOD involved. Similarly, a large flow
into a small stream can seriously affect the stream even though the BOD might be low. Accordingly,
American engineers often talk of “pounds of BOD,” a value calculated by multiplying the concentration by
the flow rate with a conversion factor:

lb BOD/day = [mg/L BOD] × [flow in mgd] × [8.34 lb/(mg/L)/(mil gal)]

for converting volume flows to mass flows:

[Mass flow] = [Volume flow] × [Concentration]

The BOD of most domestic sewage is about 250 mg/L, although many industrial wastes run as high as 30,000
mg/L. The potential detrimental effect of an untreated dairy waste that might have a BOD of 25,000 mg/L is
quite obvious because it represents a 100 times greater effect on the oxygen levels in a stream than raw sewage.
 The reactions in a BOD bottle can be described mathematically by first writing a material balance in
terms of the dissolved oxygen, starting as always with:

Rate of DO Rate of DO Rate of DO Rate of DO

-
Rate of DO
=
IN
- + Produced Consumed
Accumulated OUT

Because the BOD bottle is a closed system and because the test is run in the dark so that there is no DO production,
the material balance reduces to:

Rate of DO Rate of DO or
Accumulated =- Consumed
 This may be assumed to be a first-order reaction. That is, the rate at which the need for oxygen is
reduced (dz/dt) is directly proportional to the amount of oxygen necessary for the decomposition to
occur (z). Integrated, this expression yields:

𝒛 = 𝒛𝟎 𝒆−𝒌𝟏 𝒕
As the microorganisms use oxygen, at any time, t, the amount
of oxygen still to be used is z (see Figure A), and the amount of
oxygen already used at any time, t, is y, or the oxygen already
demanded by the organisms (Figure B). The total amount of
oxygen that will ever by used by the microorganisms is the sum
of what has been used, y, and what is still to be used, z:

L=z+y
Substituting z = L - y into the equation yields:

BOD definitions. Note that the L used in the dissolved oxygen sag
𝑳 − 𝒚 = 𝒛𝟎 𝒆−𝒌𝟏𝒕 equation is the ultimate carbonaceous BOD.
 Or: y = L (1 - 𝒆−𝒌𝟏 𝒕 )
where
y = DO already used or demanded at any time, t (i.e., the BOD), mg/L
z = DO still required to satisfy the ultimate demand, mg/L
L = ultimate demand for oxygen, mg/L
𝒌𝟏 is time constant (deoxygenation constant)

EXAMPLE Assuming a deoxygenation constant of 0.25 𝑑 −1 , calculate the expected BOD5

if the BOD3 is 148 mg/L.

Solution
Knowing y3 and the deoxygenation coefficient, k1, the ultimate BOD, L
148 mg/L = L [1 - 𝑒 −0.25(3𝑑𝑎𝑦𝑠) ]
L = 280.49 mg/L

With the ultimate BOD and 𝒌𝟏 , the BOD at any time can be calculated:
𝑦5 = (280.49 mg/L ) x [1 - 𝑒 −0.25(5𝑑𝑎𝑦𝑠) ] = 200 mg/L
 The results of the BOD test, however, produce a curve showing the oxygen used over time.
How do we calculate the ultimate oxygen use, L, and the deoxygenation rate, k1, from such a curve?

A method devised by Thomas:

This equation is in the form of a straight line: a = b + mt

Thus, plotting a versus t, the slope (m) and intercept (b) can be obtained, and
𝒌𝟏 = 6 (m/b) L =1Τ6 𝑚𝑏2
 EXAMPLE Calculation of K1 and L
0.8

The BOD versus time data for the first five days 0.75

of a BOD test are obtained as follows:

0.7 y = 0.0212x + 0.5434
Time, t, BOD, y R² = 0.9985

(t/y)^(1/3)
days (mg/L)
(𝒕Τ𝒚)𝟏/𝟑
0.65

2 10 0.584804
0.6
4 16 0.629961
6 20 0.669433 0.55

Calculate 𝒌𝟏 and L. 0.5

0 1 2 3 4 5 6 7
Add
This
column
Time (days)

Solution
Plotting (𝑡Τ𝑦)1/3 values : 0.585, 0.630, and 0.669, as shown. From the graph, the intercept is b = 0.5434 and the
slope is m = 0.021. Thus 𝒌𝟏 = 6 (m/b) = 6 (0.0212/0.5434) = 0.23 𝑑 −1 and
L = 1Τ6 𝑚𝑏2 = 1/6 x [0.0212 (0.54342 )] = 26.62 mg/L
If we allow the reactions to proceed and measure the DO each day,
we might get a curve like that shown in the Figure. Note that some
time after five days the curve turns sharply upward.

This discontinuity is due to the demand for oxygen by the

microorganisms that decompose nitrogenous organic compounds to
stable nitrate, 𝐍𝐎−
𝟑 . The curve is thus divided into nitrogenous and
carbonaceous BOD areas. Ultimate BOD, as shown in this figure,
includes both nitrogenous and carbonaceous BOD.

For streams and rivers with travel times greater than about five days,
the ultimate demand for oxygen must include the nitrogenous
demand. Although the use of BODul (carbonaceous plus Long-term BOD. Note that BODul here includes both ultimate
carbonaceous BOD (L0) and ultimate nitrogenous BOD
nitrogenous) in DO sag calculations is not strictly accurate, it is
often assumed that the ultimate BOD may be calculated as

where KN = Kjeldahl nitrogen (organic plus ammonia), in mg/L

a, b = constants
 CHEMICAL OXYGEN DEMAND

Among many drawbacks of the BOD test, the most important is that it takes five days to run. If
the organic compounds are oxidized chemically instead of biologically, the test can be shortened
considerably. Such oxidation is accomplished with the chemical oxygen demand (COD) test.

Because nearly all organic compounds are oxidized in the COD

test and only some are decomposed during the BOD test, COD
values are always higher than BOD values. One example of this
is wood pulping waste, in which compounds such as cellulose
are easily oxidized chemically (high COD) but are very slow to
decompose biologically (low BOD).
 TURBIDITY

Water that is not clear but "dirty," in the sense that light transmission is inhibited, is
considered turbid. Turbidity can be caused by many materials, some of which were
discussed earlier. In the treatment of water for drinking, turbidity is of great importance,
first because of aesthetic considerations and second because pathogenic organisms can
hide on (or in) the tiny colloidal particles.

The standard for calibrating turbidimeters is defined as:

Turbidimeters are photometers that measure the intensity of scattered light.

Opaque particles scatter light, so the scattered light measured at right angles
to a beam of incident light is proportional to the turbidity.
 COLOR AND ODOR

Color and odor are both important measurements in water treatment. Along with
turbidity they are called physical parameters of drinking water quality.
Color and odor are important from the standpoint of aesthetics. If water looks
coloured or smells bad, people instinctively avoid using it, even though it might
be perfectly safe from the public health aspect. Both color and odor may be and
often are caused by organic substances such as algae or humic compounds.
Color is measured by comparison with standards. Colored water made
with potassium chloroplatinate when tinted with cobalt chloride closely
resembles the colour of many natural waters. When multi-coloured industrial
wastes are involved, such colour measurement is meaningless.

Odor is measured by successive dilutions of the sample

with odor-free water until the odor is no longer detectable.
This test is obviously subjective and depends entirely on the
olfactory senses of the tester.
 pH
The pH of a solution is a measure of hydrogen ion concentration, which in turn is a measure of its acidity.
Pure water dissociates slightly into equal concentrations of hydrogen and hydroxyl (𝐎𝐇 − ) ions.

𝑯𝟐 𝑶 ⇔ 𝑯+ + 𝑶𝑯−
An excess of hydrogen ions makes a solution acidic, whereas a dearth of 𝑯+ ions, or an excess of hydroxyl ions,
makes it basic.
The equilibrium constant for this reaction, Kw, is the product of 𝑯+ and 𝑶𝑯− concentrations and is equal to 10−14

This relationship may be expressed as: 𝑯+ 𝑶𝑯− = 𝐾𝑤 = 10−14

where [𝑯+ ] and [𝑶𝑯− ] are the concentrations of hydrogen and hydroxyl ions, respectively, in moles per litre.
For pure water solving for concentrations 𝑯+ = 𝑶𝑯− = 10−7 moles/L

The hydrogen ion concentration is so important in aqueous solutions that an pH= − log 𝐇+
easier method of expressing it has been devised. Instead of as moles as per
liter, we define a quantity pH as the negative logarithm of [𝑯+ ], so that: Or 𝐇 + = 𝟏𝟎−𝐩𝐇
For a neutral solution, [𝑯+ ] is 10−7 , or pH = 7. For larger hydrogen ion concentrations, then, the pH of the
solution is < 7. For example, if the hydrogen ion concentration is 10−4 , the pH = 4 and the solution is acidic.
In this solution, see that the hydroxyl ion concentration is 10−14 / 10−4 = 10−10 .

Since 10−4 >> 10−10 , the solution contains a large excess of 𝑯+ ions, confirming that it is indeed acidic.

A solution containing a dearth of 𝑯+ ions would have [𝑯+ ] < 10−7 , or pH > 7 and would be basic. The pH
range of dilute solutions is from 0 (very acidic; 1 mole of [𝑯+ ] ions per liter) to 14 (very alkaline).
Solutions containing more than 1 mole of H+ ions per liter have negative pH.

The measurement of pH is now almost universally by electronic means. Electrodes that are sensitive to
hydrogen ion concentration (strictly speaking, the hydrogen ion activity) convert the signal to electric
current, pH is important in almost all phases of water and wastewater treatment.

Aquatic organisms are sensitive to pH changes, and biological treatment requires either pH control or
monitoring. In water treatment as well as in disinfection and corrosion control, pH is important in
ensuring proper chemical treatment. Mine drainage often involves the formation of sulfuric acid (high
𝑯+ concentration), which is extremely detrimental to aquatic life.
 ALKALINITY
Water that has a high alkalinity can accept large doses of an acid without lowering the pH significantly.
Waters with low alkalinity, such as rainwater, can experience a drop in the pH with only a minor addition of
hydrogen ion.

In natural waters much of the alkalinity is provided by the carbonate/bicarbonate

buffering system. Carbon dioxide (CO2) dissolves in water and is in equilibrium
with the bicarbonate and carbonate ions. Any change that occurs in the
components of this equation influences the solubility of CO2.
Any change that occurs in the components of this
equation influences the solubility of CO2. If acid is
added to the water, the hydrogen ion concentration is
increased, and this combines with both the carbonate
and bicarbonate ions, driving the carbonate and
bicarbonate equilibria to the left, releasing carbon
dioxide into the atmosphere. The added hydrogen ion
is absorbed by readjustment of all the equilibria, and
the pH does not change markedly.

Only when all of the carbonate and bicarbonate ions

are depleted will the additional acid added to the
water cause a drop in pH. The effect of alkalinity on
the pH of a water sample is shown in the Figure:

Effect of alkalinity in buffering against a pH with the addition of an acid: (A) acid
added to deionized water; (B) acid added to monobasic phosphate buffer solution
 SOLIDS

Wastewater treatment is complicated by the dissolved and suspended inorganic material the wastewater
contains. In discussion of water treatment, both dissolved and suspended materials are called solids. The
separation of these solids from the water is one of the primary objectives of treatment. Strictly speaking,
in wastewater anything other than water is classified as solid.

The usual definition of solids, however, is the residue after evaporation at 103°C (slightly higher than the
boiling point of water). The solids thus measured are known as total solids.

Total solids may be divided into two fractions:

the total dissolved solids (TDS) and the total suspended solids (TSS).

Suspended solids are separated from dissolved solids by filtering the water through a filter paper;
the subtraction of this from the total weight of the filter and the dried solids caught in the filter
paper yields the weight of suspended solids, expressed in milligrams per liter.
Solids may be classified in another way: those that are volatilized at a high temperature and those that are not.
The former are known as volatile solids, the latter as fixed solids. Volatile solids are usually organic compounds.
Obviously, at 600°C, the temperature at which the combustion takes place, some of the inorganics are
decomposed and volatilized, but this is not considered a serious drawback.

Example
 NITROGEN

Organic nitrogen may be bound in high-energy compounds such as amino acids and amines. Ammonia is one of the
intermediate compounds formed during biological metabolism and, together with organic nitrogen, is considered
an indicator of recent pollution. Therefore, these two forms of nitrogen are often combined in one measure,
called Kjeldahl nitrogen, after the scientist who first suggested the analytical procedure.

Aerobic decomposition (oxidation) eventually produces nitrite (𝐍𝐎− −

𝟐 ) and finally nitrate (𝐍𝐎𝟑 ) from organically
bound nitrogen and ammonia.

These forms of nitrogen can all be measured analytically by colorimetric techniques. In colorimetry, the ion in
question combines with a reagent to form a colored compound; the color intensity is proportional to the original
concentration of the ion.
The color is measured photometrically. A photometer, illustrated in the Figure consists of a light source, a filter, the
sample, and a photocell. The filter allows only those wavelengths of light to pass through that the compounds being
measured will absorb. Light from the light source passes through the sample to the photocell, which converts light
energy into electric current.

Photometer
An intensely colored sample will absorb a considerable amount of light and allow only a limited amount of light to
pass through and thus create little current. On the other hand, a sample containing very little of the chemical in
question will be lighter in color and allow almost all of the light to pass through, and will set up a substantial current

The intensity of light transmitted by the colored solution obeys the Beer-Lambert Law:
𝐈 𝐈𝟎
= 𝐞−𝐚𝐜𝐱 , or 𝐥𝐧 = 𝐚𝐜𝐱
𝐈𝟎 𝐈

A photometer, as shown, measures the difference between the intensity of light passing through the sample (I in the
Equation) and the intensity of light passing through clear distilled water (𝐈𝟎 ). This difference may be read out as
𝐈
( ) on a logarithmic scale; 𝐥𝐧 𝐈𝐈𝟎 is called the absorbance.
𝐈𝟎
The absorbance of samples containing known ammonia concentrations is plotted against the known concentrations,
and the absorbance of an unknown sample is then compared with that of these standards.

Example
Several known samples and an unknown sample were treated with Nessler reagent (potassium mercuric iodine,
(𝐾2 𝐻𝑔𝐼4 ) , and the color was measured with a photometer. Find the ammonia concentration of the unknown sample.

A plot of ammonia concentration of the standards vs.

absorbance results in a straight line (Beer-Lambert Law is
adhered to). We may then enter this chart at 15% absorbance
(the unknown) and read the concentration of ammonia in our
unknown as 2.5 mg/L. Calculation using colorimetric standards
 PHOSPHATES

Phosphorus in wastewater may be either inorganic or organic. Although the greatest single source
of inorganic phosphorus is synthetic detergents, organic phosphorus is found in food and human
waste as well. All phosphates in nature will, by biological action, eventually revert to inorganic
forms to be used again by the plants in making high-energy material.

Total phosphates may be measured by first boiling the sample in acid solution, which
converts all the phosphates to their inorganic forms. From that point the test is colorimetric,
like the tests for nitrogen, using a chemical that when combined with phosphates produces a
color directly proportional to the phosphate concentration.
 BACTERIOLOGICAL MEASUREMENTS

A large number of infectious diseases may be transmitted by water, among them typhoid and cholera. However,
it is one thing to declare that water must not be contaminated by pathogens (disease causing organisms) and
another to determine the existence of these organisms.

How then can we measure for bacteriological quality? The answer lies in the concept of indicator organisms
that, while not particularly harmful, indicate the possible presence of bacteria that are pathogenic. The indicator
most often used is a group of microbes of the family Escherichia coli (E. coli), often called coliform bacteria,
which are organisms normal to the digestive tracts of warm blooded animals. In addition, E. coli are: