Water Analysis

Key Concepts

Water is an essential resource for living systems, industrial processes, agricultural production
and domestic use.

The principal factors that are taken into consideration when determining water quality are:

 turbidity
 acidity & alkalinity
 trace elements and nutrients such as nitrogen, phosphorus, halogens (chloride and
fluoride ions), alkali metals (sodium and potassium ions), calcium and magnesium
ions.
 microorganisms
 dissolved oxygen content (DO)

Saturated Dissolved Oxygen (DO) Levels

Saturated level of DO (ppm)
Temperature (oC)
Freshwater Sea water

10 10.9 9.0
20 8.8 7.4
30 7.5 6.1
40 6.6 5.0
Example: Water Quality of a Typical Natural Aquatic System

Substance or Quality River Water Sea Water

pH 6.8 8.0

</TD< TR>
Dissolved Oxygen 6-8 ppm 6-8 ppm

</TD< TR>
Na+ 6.7 ppm 1.1 x 104 ppm

</TD< TR>
K+ 1.5 ppm 380 ppm

</TD< TR>
Ca2+ 17.5 ppm 400 ppm

</TD< TR>
Mg2+ 4.8 ppm 1.3 x 103 ppm

</TD< TR>
Cl- 4.2 ppm 1.9 x 104 ppm

</TD< TR>
 SO42-/HSO4- 17.5 ppm 2.6 x 103

</TD< TR>
CO32-/HCO3- 33.0 ppm 142 ppm

</TD< TR>
Hg2+ < 1 ppb 0.03 ppb

</TD< TR>
Cd2+ < 1 ppb 0.1 ppb

</TD< TR>
Pb2+ < 1 ppb 4-5 ppb
Tests for Water Quality

Reason for
Test Method
testing
Temperature Use an alcohol thermometer in a hard plastic cover Temperature
influences the
amount of
dissolved oxygen
in water which in
turn influences
the survival of
aquatic
organisms
(raising the
temperature of a
freshwater
stream from 20
to 30oC will
decrease the
dissolved oxygen
saturation level
from about 9.2
ppm to 7.6
ppm.).
Increasing
temperature also
increases the
rates of chemical
reactions taking
place in the
water. Increases
in temperature
are often
associated with
hot water
discharge from
power stations
and industries
that use water as
a coolant.
 Use a pH meter in a hard plastic cover, pH paper or pH measures the

pH Universal
acidity or
alkalinity of
water. pH of rain
water is about

Indicator
5.5-6.0.
Typically, natural
solution. water has pH
6.5-8.5. A pH<5
(acidic water) is
most damaging
to eggs and
larvae of aquatic
organisms. Most
aquatic life
(except for some
bacteria and
algae) cannot
survive
pH<4.Natural
alkalinity is due
to CO2(g), HCO3-,
CO32- and OH-,
carbonate rocks
such as
limestone and
dolomite increase
alkalinity.
Alkalinity is
increased by
caustic
substances from
industry (KOH,
NaOH), soil
additives in
agriculture such
as lime Ca(OH)2,
superphosphate
which is mixture
of Ca(H2PO4)2
and CaSO4, and
soaps and
detergents.
Natural acidity is
due to CO2(g),
HPO42-, H2PO4-,
H2S, Fe3+, other
acidic metal ions,
proteins &
organic acids.
Increases in
acidity can be
due to acids used
in industry, acid
mine drainage,
 acid rain.

Turbidity Use a Sechi disc or 500mL of water in a measuring Turbidity is a

cylinder standing on paper marked with a black cross. measure of water
clarity.
Suspended solids
in water can stop
light reaching
submerged
plants and can
raise water
temperature.
Suspended solids
often present in
water are mud,
clay, algae,
bacteria and
minerals such as
silica, calcium
carbonate and
ochre (iron
oxide).
Suspended solids
can be increased
by the discharge
of wastes
(domestic
sewage,
industrial and
agricultural
effluents),
leaching of
wastes (from
mines), and
agitation
(dredging or
shipping).

Total Dissolved Use an appropriate TDS meter. Freshwater meters: 0- This is a

Solids (TDS) 1990 ppm (parts per million). Dual range brackish conductivity test
water meters: 0-19,900 ppm. Salt-water meters: to of available ions
above 35,000 ppm. in the water,
including Ca2+,
Na+, K+, Fe2+,
Fe3+, HCO3- and
ions containing P,
S & N. High
levels of Na+ is
associated with
excessive salinity
and is found in
many minerals.
Potassium is
incorporated into
plant material
 and is released
into water
systems when
plant matter is
decayed or
burnt.

Dissolved  Winkler Titration Method The Dissolved

Oxygen (DO) -Halve the water sample. Place one sample in Oxygen test
the dark (for BOD analysis). measures the
-To the other sample add 2mL MnCl2(aq) (4g current oxygen
MnCl2 dissloved in 10mL distilled water) + 2mL levels in the
alkaline iodide solution (3.3g NaOH + 2.0g KI water. The DO
dissolved in 10mL distilled water). Shake level varies with
sample. temperature. DO
-Add 2 mL concentrated HCl. Shake. The iodine levels are highest
formed is directly proportional to the dissolved in the afternoon
oxygen. due to
-Titrate 50.0mL of the above solution with photosynthesis
0.0125M sodium thiosulfate solution using and lowest just
starch as an indicator. The end-point is reached before dawn. DO
when the blue-black colour disappears. is lowered by an
increase in

 Colorimetric temperature (as

from a discharge
of hot water form

Method
a power station),
increases in
(A field kit is available aerobic oxidation
(due to increases
using a 'Smart' colorimeter)
in organic matter
from sewage or
Collect 2 water samples, 1 for DO test, 1 for BOD test. due to inorganic
Sample must be collected under water to ensure there fertilisers such as
are no trapped air bubbles. phosphates and
nitrate with
overstimulate
algal growth).
Water with
DO<1ppm is
dead.

Biochemical The first water sample from above is kept in the dark BOD measures
Oxygen Demand for 5 days at the temperature at which the sample was the rate of
(BOD) collected. Then the dissolved oxygen is determined consumption of
using the Winkler titration method as above. Subtract oxygen by
the mass of oxygen obtained an day 5 from mass of organisms in the
oxygen on day 1 to determine the BOD (mg/L). water over a 5
Unpolluted natural waters have BOD<5mg/L. Treated day period.
sewage can have BOD 20-30 mg/L. Increases in BOD
can be due to
animal and crop
wastes and
domestic
sewage.
 Untreated
domestic sewage
BOD~350 ppm
Waste water
from breweries
BOD~550 ppm
Waste water
from petroleum
refineries
BOD~850 ppm
Abattoir wastes
BOD~2,600 ppm
Pulpmill wastes
BOD~25,000
ppm

Salinity Titrate a known volume of the water sample with silver Many aquatic
nitrate solution (2.73g AgNO3 per 100mL distilled organisms can
water) using K2CrO4 as indicator. The end-point of the only survive in a
titration is given by the reddening of the silver chloride narrow range of
precipitate (AgCl(s)). Volume of AgNO3 used = chloride salt
content in g/L. concentrations
since salt
controls their
osmotic pressure.

Total Phosphate -acid digestion using concentrated H2SO4 and Total Phosphate
Test ammonium persulfate. is used as an
-Titrate using NaOH and phenolphthalein as indicator indicator of
-Use a few drops of H2SO4 to turn the solution clear pollution from
again. run-off in
-Add ammonium molybdate solution then solid ascorbic agricultural areas
acid. or domestic
-An intense blue complex of molybdenum blue is sewage.
formed which can be measured Concentrations of
0.2mg/L are

colorimetrically
Absorbency is measured at 882nm. (A field kit is
.
common.
Concentrations of
0.05mg/L
indicate the
available using a 'Smart' colorimeter) possibility of
eutrophication
(increased
nutrient
concentrations)
and algal blooms
are likely.
Natural
phosphate is due
to decayed
organic matter
and phosphate
minerals.
Total Nitrogen  Kjeldahl digestion Total Nitrogen is
test -digestion with concentrated sulfuric acid, an important
converting the nitrogen into ammonia sulfate indicator of
-Solution is then made alkaline eutrophic waters,
-liberated ammonia is distilled, and the amount especially for
determined by titration with standard acid. those
 distillation titration method for samples contaminated by
containing >1mg/L animal wastes,
 Add Nessler's reagent (100g mercuric iodide + fertiliser run-off
70g KI in 100mL distilled water, then add 160g and domestic
NaOH in 700mL distilled water, then dilute to sewage. Aquatic
1L) for samples containing <1mg/L and nitrogen is
measure absorbancy essential for the
growth of

colorimetricall organisms and is

produced in
natural processes

y
including decay
of proteins, the
at 425nm. action of
lightning, and the
action of
nitrogen-fixing
bacteria on
ammonia.

Hardness  Calcium Ions, Ca2+ Calcium ions are

-complexometric titration using EDTA a major
(ethylenediaminetetraacetic acid) at a pH of 12- contributor to
13 (at this pH Mg2+ is precipitated and not water hardness
complexed with EDTA) and are due to
-OR potentiometric techniques using selective water running
electrodes through rocks
-OR Atomic Absorption Spectroscopy containing
minerals such as

(AAS)
-OR Gravimetric Method - measure the amount
gypsum
(CaSO4.2H2O),
calcite (CaCO3),
dolomite
of CaCO3(s) precipitated by a known volume of (CaMg(CO3)2).
0.02M Na2CO3 Hard water has a

flame
noticeable taste,
produces
-OR by Flame Test - Ca2+ precipitates with
soaps which

test
inhibits lathering
and forms
a brick-red colour in a non-luminous precipitates
Bunsen flame (scale) in boilers,
 Mg2+ hot water
-complexometric titration using EDTA at pH=10 systems and
(both Ca2+ and Mg2+ will complex with EDTA at kettles.
this pH, [Mg2+] can be found by subtracting the Temporary
results of this titration from the results of the hardness (or
first titration.) 'bicarbonate
hardness') is due
 -OR potentiometric techniques using selective to Ca(HCO3)2
electrodes which deposits
-OR Atomic Absorption Spectroscopy CaCO3(s) as scale
on boiling the

(AAS) water.
Magnesium ion
levels are often
high in irrigation
water and can
cause scouring in
stock.
Ca2+ and Mg2+
can combine with
Cl- and/or SO42-
causing
permanent
hardness which
can't be removed
by boiling. Water
can be softened
by an ion
exchange process
using a solid
material such as
a resin or clay
that is capable of
exchanging Na+
or H+ for Ca2+
and Mg2+.

Microorganisms microorganisms in a water sample are counted under a Many protozoa,

microscope bacteria, viruses,
Method for finding the number of coliform organisms in algae and fungi
a water sample: are found in
natural water
 Filter a known volume of water sample through systems. Some
a filter that retains microorgnisms are pathagenic
 Transfer the filter to a sterile petri dish (typhoid, cholera
containing appropriate agar and incubate at and amoebic
o
35 C for 20-40 hours. Also incubate a control dysentry can
plate with agar only. Colonies will develop on result from
the filter wherever bacteria are retained. water-borne
 Either visually, or using a microscope, count the pathogens). The
number of coliform colonies. Express these excessive growth
values as CFU/100mL. of algae (called
'algal bloom') can
degrade water
quality because it
lowers dissolved
oxygen levels
thereby killing
other living
things.
The level of
bacterial
contamination of
 water due to
animal waste is
measured by
determining the
number of
coliform
organisms such
as E. coli

Heavy Metals  Ni2+ + dimethylglyoxime in ethanol turns pink- Heavy metals in

red concentrations
 Fe3+ + ammonium thoicyanate turns blood-red above trace
 Cu2+ + dithizone in 1,1,1-trichloroethane turns amounts are
yellow-brown generally toxic to
 Cd2+ + dithizone in 1,1,1-trichloroethane turns living things.
blue-violet Trace amounts
 Pb2+ + dithizone in 1,1,1-trichloroethane turns (<0.05 mg/L) of
brick-red Zn, Cu and Mn
Pb2+ + 2KI(aq) -----> yellow are present in
most natural


precipitate
2+
of PbI2(s)
Zn + dithizone in 1,1,1-trichloroethane turns
waters. Zn and
Cu may be
present in higher
levels in
pink irrigation areas
due to the use of
galvanised iron,
copper and brass
in in plumbing
fixtures and for
water storage. In
irrigation areas,
acceptable levels
are 0.2 mg/L for
Cu2+, and 2.0
mg/L for Zn2+
and Mn2+.

Other Ions  Al3+ + aluminon -----> pink-red

 Mg2+ + magneson I -----> light blue

 Na+ flame test -----> yellow flame



K+ flame test
+
-----> lilac flame
NH4 & NH3 + Nessler's reagent (100g mercuric iodide + 70g KI in
100mL distilled water, then add 160g NaOH in 700mL distilled
water, then dilute to 1L) -----> yellow-brown
 NO3- + conc H2SO4 + FeSO4 -----> brown ring forms at junction

 S2- + lead acetate solution -----> black deposit of

 PbS

 SO42- + BaCl2(aq) -----> white

of BaSO4(s)
precipitate