CHAPTER 5 WATER ANALYSIS

COURSE LEARNING OUTCOMES

At the end of this chapter, students should be able to:
To understand and apply methods for different types of water analysis such
as:
- Potentiometry for ions and gases in aqueous solution

- Metals in water samples

- Inorganic anions in water

- Organic compounds in water

COURSE OUTLINES
Potentiometry for ions and gases in aqueous solution
Metals in water samples
Inorganic anions in water
Organic compounds in water
INTRODUCTION
Clean water essential to human survival
Contamination occurred due to:
Anthropogenic activities
Direct discharge of industrial waste
Domestic sewage
Pesticide run-off from agricultural land
Acid rain
Ground water contaminated by landfill leachate, oil and gas wells, leaking storage tanks
etc.

Acts and Regulations involved:

Clean Water Act (CWA), Safe Drinking Water Act (SDWA), Resource Conservation and
Recovery Act (RCRA), Toxic Substances Control Act (TSCA), Federal Insecticide, Fungicide and
Rodenticide Act (FIFRA)
TESTS & ANALYSIS
Acidity

Turbidity Oxygen Biological

Color
demand Analysis
Volatile
hydrocarbon
Inorganic non-
metallic
Odor Hardness constituents
Taste
Organic
compounds

Conductivity
Radioactivity
Pesticides Metals
analysis
POTENTIOMETRY FOR
IONS & GASES IN
AQUEOUS SOLUTION
Potentiometry analysis uses
Electrodes to measure specific ion in
solutions.
Type of electrodes use in water
analysis:
pH measurement pH electrode
Ions & hardness measurement Ions
Selective Electrode (ISE)
PH MEASUREMENT
pH Measurement using a Glass Membrane Electrode
To determine the activity of hydrogen ions in a solution
 PH ELECTRODE
Combination electrode incorporates both glass and reference electrode in
one body

Ag(s)|AgCl(s)|Cl-(aq)||H+(aq,outside) H+(aq,inside),Cl-(aq)|AgCl(s)|Ag(s)

Outer reference [H+] outside [H+] inside Inner reference

electrode (analyte solution) electrode

Glass membrane
Selectively binds H+

Electric potential is generated by [H+] difference across glass membrane

PH GLASS MEMBRANE
Glass Membrane Irregular structure of silicate lattice
Two surfaces of glass swell as they absorb water
Surfaces are in contact with [H+]

Cations (Na+) bind

oxygen in SiO4 structure
PH GLASS MEMBRANE
H+ diffuse into glass membrane and replace Na+ in hydrated gel region
Ion-exchange equilibrium
Selective for H+ because H+ is only ion that binds significantly to the hydrated gel layer

Charge is slowly carried

by migration of Na+
across glass membrane

Eelectrode 0.059 pH Potential is determined

by external [H+]
 The sorbed ions on each surface are in equilibrium with H+ ions in the
solutions.
The difference in the concentration of ions sorbed on the inner and outer
surfaces generates electric potential.

Eelectrode 0.059 pH Potential is determined

by external [H+]

Where Eelectrode = voltage measured by the pH meter

= constant that depends on type of electrode
pH = the pH of measured solution
PH ELECTRODE CALIBRATION
A pH electrode should be calibrated with two or more standard buffers
before use.
pH of the unknown should lie within the range of the standard buffers

Measured voltage is correlated

with a pH, which is then used to
measure an unknown.
ERRORS IN PH MEASUREMENTS
Standards
pH measurements cannot be more accurate than standards (0.01)

Junction potential
If ionic strengths differ between analyte and standard buffer, junction potential will differ resulting in
an error of 0.01

Junction Potential Drift

Caused by slow changes in [KCl] and [AgCl] re-calibrate!

Sodium Error
At very low [H+], electrode responds to Na+ and the apparent pH is lower than the true pH

Acid Error
At high [H+], the measured pH is higher than actual pH, glass is saturated
ERRORS IN PH MEASUREMENTS
Equilibration Time
Takes ~30s to minutes for electrode to equilibrate with solution

Hydration of glass
A dry electrode will not respond to H+ correctly

Temperature
Calibration needs to be done at same temperature of
measurement

Cleaning
Contaminates on probe will cause reading to drift until properly
cleaned or equilibrated with analyte solution Larger errors occur at high
and low pH readings
IONS SELECTIVE ELECTRODE (ISE)
ISE is used for specific ion measurements such as fluoride, chlorine, chloride,
hardness (Ca2+ and Mg2+), dissolved oxygen, ammonia, etc.

Categorized by the type of membrane used:

Solid state electrode
Liquid membrane electrode
Gas sensing electrode
SPECIFIC ION ELECTRODES
Electrode Type Concentration range Interferences
Ammonia Gas sensing 1 5 x 10-7 M Volatile amines
Chloride Solid state 1 5 x 10-5 M OH-, S-2, Br-, I-, CN-
Fluoride Solid state Saturated to 0.02 OH-
ppm
Lead (Pb+2) Solid state 0.1 10-6 M Ag+, Hg+2, Cu+2, high
Cd+2, or Fe+2
Oxygen Gas sensing 0 14 ppm -
Silver or sulphide Solid state 1 5 x 10-7 M Hg+2
Water hardness Liquid membrane 1 6 x 10-6 M Na+, Cu+2, Zn+2, Fe+2,
(Mg+2) Ni+2, Sr+2, Ba+2, K+
Calcium (Ca+2) Liquid membrane 1 5 x 10-7 M Pb+2, Na+, Hg+, H+,
Fe+2, NH4, Mg+2
ISE SOLID STATE ELECTRODE
Use solid homogeneous substance as the sensing membrane
The substance should has the affinity for the analyte ions and tends to
absorb them.
The material should have a very low solubility constant
To avoid contamination of the solution
To remain stable over a long period of time

Based on an inorganic crystal.

Example: an electrode with a membrane made of a silver sulphide pellet
can be used either for silver or sulphide measurement.
 Fluoride electrode: LaF3 crystal doped with Eu2+

F- migrates across crystal by jumping

into crystal vacancies caused by Eu2+

Potential caused by charge imbalance from migrating ion across membrane

ISE LIQUID MEMBRANE ELECTRODE
Involve ion exchange material within a solid polymeric membrane.
Exchanges the analyte ions across the membrane, which create the
potential.
Example Calcium and nitrate ions are measured using liquid
membrane electrode
Binds Ca+2 Hydrophobic counter-ion Hydrophobic solvent
Remember: ion-selective
electrodes create a potential from
a charge imbalance caused by
analyte ion migration across
membrane
ISE GAS SENSING ELECTRODE
Use to measure gases dissolved in aqueous solutions.
Membrane made from permeable polymeric material (e.g.
silicone rubber) that allowed the dissolved gas permeate
through it.
The membrane is backed with a small volume of solution
specific for each analyte.
The dissolved gas concentration in the internal filling
solution is sensed by appropriate electrode couple within the
electrode body.
Gases that can be measured: ammonia, oxygen and
carbon dioxide.
EXAMPLE 1
A solution containing about 0.001 M Ca2+ is being measured using a calcium
specific electrode. If an interference from Na+ of 2% is acceptable, what is the
maximum permissible concentration of Na+?
The selectivity factor for Calcium ion electrode for interference by sodium as
(response to Ca2+)/(response to Na+) is 630.
METALS IN WATER SAMPLES
Most often determined spectroscopically. Total content of a particular
metal can be determined via:
Atomic Absorption Spectroscopy
Inductively Coupled Plasma Emission

Specific metal ions can be determined using Uv-Vis Spectroscopy.

Metals in water samples can be divided into:
Dissolved metals
Suspended metals after pass through 0.45m filter
 METHODS TO ANALYSE METALS IN WATER

AAS

Sample Digestion Separating

Preconcentrating
of metal labile metal ICP
filtration samples
the samples
species
Voltammetry

Analysis
 SAMPLE FILTRATION
To separate suspended metals from dissolved
metals.
To determine suspended metals on the filter, the
volume of water filtered must be recorded and the
filter must be stored in a clean container for further
analysis.
Polycarbonate or cellulose
acetate filters can be used
If the sample is very turbid, it is better to centrifuge
before filtering to avoid loading of fouling.
 DIGESTION OF METAL SAMPLES
Metals associated with particulates need to brought into solution before
analysing with AAS/ICP.
Nitric acid is generally the most widely used with the addition of hydrochloric,
hydrofluoric or perchloric acid to extract more difficult metals.
Can be done in Erlenmeyer flask or beaker on a hotplate, where 50 to 100 ml
of the sample is mixed with acid.
The digestion is considered complete once the sample reach clear and light in
color.
Use of microwave digestion gives more reproducible results.

PRECONCENTRATING THE SAMPLE

Necessary for very low concentration samples.
MICROWAVE DIGESTION

Rotor

Supplied with dedicated vessels (e.g. PTFE)

Closed vessel digestion minimises sample contamination
Faster, more reproducible, and safer than conventional methods
SEPARATING LABILE METAL SPECIES
Labile species free hydrated ions that easily exchanged from various
complexed forms.
These relatively free ions can be separated by sorption on chelating resin
such as Chelex 100.
 AAS
Atomic-Absorption spectrometer can be used for determination of the metal concentration in water
(Cu, Pb, Zn, Ni, Co, Mo, Cr, Mn, Cd, Ag) and soil (Cu, Pb, Zn, Ni, Co) samples. Electrothermal
and flame methods of atomization were used.
Fully operated via computer, using the software support WinLab32.
The program provides full automatic control of the device, allows us to make changes in the methods,
memorize and receive information of measurements of the particular group of elements in a desirable
form.
THE BASIC COMPONENTS OF AN ATOMIC ABSORPTION INSTRUMENT:
The light source that emits the spectrum of the element of interest;
An Absorption cell in which atoms of the sample are produced (flame, graphite furnace);
A monochromator for light dispersion;
A detector that measures the light intensity;
A display that shows the reading after it has been processed by the instrument electronics.

Light source Sample Cell Specific Light Measurement

Flame or Furnace Monochromator Detector Electronics Readout

The light source (hollow cathode lamp) emits a spectrum specific to the element of which it
is made, which is focused through the sample cell into the monochromator. The method of
heavy metal definition via Atomic-absorption spectrometer is based on the properties of
specific metal atoms to absorb specific wavelength of light. The electronics will measure
light attenuation and convert those readings to the actual metal concentration of the sample.
 Putting lamps for various metals

The lamp holder with positions for 8 source lamps allows having 8 lamps
simultaneously that are prepared for work and can pass from one element to
another.
 Process of measurements
Choose a desired method of atomization by means of the computer, with use of
software support WinLab32

1. When using the electrothermal atomization method the aliqoute part of a sample is
put in a graphite furnace of the spectometer using sampling device (autosampler)
According to the programme, heating of a sample is performed in the inert gas
(argon) stream, including drying, incineration, atomization of a sample and clean-out
of the furnaces.

2. The flame atomization method is also used. The injectoration of the analyzed
portion of the sample in the flame of a torch is performed by means of capillary. The
mix of air acetylene is used for the formation of a flame.
 REACTANTS AND EQUIPMENT ARE NECESSARY FOR
MEASUREMENTS
A nitric acid of special cleanliness
Deionized water
Adjustable pipettes
Adjustable pipette
Measuring Flasks
Gaseous Argon of high cleanliness
Gaseous Acetylene of high cleanliness
Atomic Spectroscopy Single-Element Pure Standards.

Measuring Flasks

Standards
INDUCTIVELY COUPLED PLASMA METHODS
Well suited for water analysis because all elements desired can be analysed in one run.

Over 70 elements (in principle simultaneously)

Including non-metals such as sulfur, phosphorus, and halogens (not possible with AAS)
Principle: Argon plasma generates excited atoms and ions; these emit characteristic
radiation
ICP INTRUMENTATIONS
CURRENT STANDARD PRACTICE FOR EASY METAL
(E.G. CU)
Up to 0.25 g of sample dissolved
Metal or alloy dissolves slowly in 10% HNO3, in pre-
cleaned 0.25 L PP bottle
Take 2 g aliquot, add internal standard for drift
correction and run on ICP-MS
Analysis includes a semi-quantitative mass scan
APPLICATIONS
ICP-OES used for quantitative analysis of:
Soil, sediment, rocks, minerals, air
Geochemistry
Mineralogy
Agriculture
Forestry
Forensics
Environmental sciences
Food industry

Elements not accessible using AAS

Sulfur, Boron, Phosphorus, Titanium, and Zirconium
39
VOLTAMMETRY METHOD
Electrochemical method depends upon the oxidation/reduction of a
chemical species at a very small electrode.
EXAMPLE CHROMIUM IN FRESH WATER
Refer text book book page 263.
An example of how to prepare sample containing chromium, one of labile
species.
INORGANIC ANIONS IN WATER
Ions containing nitrogen, phosphorous, sulfur and the halogens.
Examples: Nitrates and ammonia that are valuable in plant growth.
However, these inorganic anions when existed in water could cause eutrophication of lakes, resulting in
excessive weed growth.

Inorganic anions can be measure by using several colorimetric methods, ion

chromatography or specific ionic electrodes.
and more disasters
ION CHROMATOGRAPHIC ANALYSIS FOR COMMON
ANIONS
Recall back
Different affinity of the different components to stationary phase causes the
separation
This technique employs two immiscible substances- mobile phase and
stationary phase
Mobile phase -solution of gas or liquid components, works as transporter,
moves in a definite direction
Stationary phase -liquid or solid, absorbs or impedes different components
of the solution to different degrees
ION EXCHANGE CHROMATOGRAPHY
Ion exchange chromatography is a separation based on charge
Used for almost any kind of charged molecules large proteins, small
nucleotides and amino acids
Ion-exchange chromatography preserves analyte molecules on the column
based on ionic interactions
Mobile phase buffer, pH and salt concentration---opposite charged solute
ions attracted to the stationary phage by electrostatic force
Stationary phase resin is used to covalently attach anions or cations onto it

Principle: Ion Exchange Chromatography relies on charge-

charge interactions between the proteins
CATION EXCHANGE CHROMATOGRAPHY
Positively charged molecules are attracted to a negatively charged solid
support.
Commonly used cation exchange resins are S-resin, sulfate derivatives; and
CM resins, carboxylate derived ions
ANION EXCHANGE CHROMATOGRAPHY
Negatively charged molecules is attracted to a positively charged solid
support.
Commonly used anion exchange resins are Q-resin, a Quaternary amine;
and DEAE resin, DiEthylAminoEthane
THE METHODS
Samples are prepared by filtering through a 0.2 m filter to remove
particulates.
Standard injection (of desired anion) at a minimum three different
concentration.
A sample of 10 100 l is normally injected.
The minimum detection limit is 0.1 mg/l for most of the ions except for
fluoride.
The detection limit for fluoride can be further lowered by pre-concentration
or large injection volume methods.
ORGANIC COMPOUNDS IN WATER
Relates to oxygen consumption and total carbon in a river or lake
as a result of a pollution discharge.
Measured in several ways:
DO Dissolved Oxygen
BOD - Biochemical Oxygen Demand
COD - Chemical Oxygen Demand
TOC Total Organic Carbon
DISSOLVED OXYGEN
D.O.
Amount of FREE Oxygen
O2
In the Water
Required By :
FISH
MICROORGANISMS
( Bacteria)
RESPIRATION
Organic Matter Converted to:

Carbon Dioxide
and
Water

CH2O + O2 CO2 + H2O

OXYGEN DEPLETION IN STREAMS
 B.O.D.
Biochemical Oxygen Demand
The Quantity of Oxygen Used in the Biochemical
Oxidation of Organic Material.
Organic matter + O2 CO2 + H2O + new cells

Under:
Specified Time 5 Days
Specified Temperature 200 C
Specified Conditions In the Dark
In the Presence of Bacteria
Measured Volume of Wastewater is
Added to BOD Bottle.

Contains:
Organics
Ammonia

Bacteria
NH3
NH3
CxHYOz
 Dilution Water Added

Dilution Water Contains:

Nutrients
O2
O2 Oxygen

O2 Measure
O2 D.O. Concentration
O2
CxHYOz
O2
 Incubate 5 Days

Some Oxygen Used:

Respiration

O2 Nitrification

O2
Measure
D.O. Concentration

O2
 Measure Oxygen Loss
(Demand)

D.O. Day 1 - D.O. Day 5

= Oxygen Demand
O2

O2 (Of What Is In The Bottle)

O2
 BOD
Distilled Water
Phosphate Buffer
Magnesium Sulfate
Calcium Chloride
Ferric Chloride
Provide Essential Nutrients
Buffer pH
 DILUTION WATER
High Quality
Distilled Water No Toxics
No Organics
plus

BUFFER pH 7.2

plus
(Phosphorus
and Ammonia)
NUTRIENTS Magnesium
Calcium
Iron
DILUTION WATER PREPARATION
NEEDED VOLUME for Each Days Use
ADD NUTRIENTS (1 mL per Liter)
SATURATE WITH OXYGEN

Vacuum
Shake
(small volume)
or
Draw Vacuum
DILUTION WATER PREPARATION
NEEDED VOLUME
ADD NUTRIENTS
SATURATE WITH OXYGEN
STORE
In Incubator

ADD BUFFER
Day of Use
 B.O.D. Calculation
D.O. In - D.O. Out
= DEPLETION
= Oxygen Demand of Diluted Sample

C1 X V1 = C2 X V2
Sample Sample BOD Diluted
BOD
X Volume = Diluted X Volume

BOD Diluted Volume

BOD Sample =
Sample Volume X Diluted

Depletion
BOD Sample =
Sample Volume X 300 mL
 B.O.D. mg/L =

D.0. DEPLETION (mg/L)

X 300 mL
SAMPLE VOLUME (mL)

D.O. DEPLETION = D.O. Initial - D.O. 5-Day

Minimum Depletion - 2.0 mg/L

Minimum Residual - 1.0 mg/L
 B.O.D. Example Problem
Calculate the B.O.D.:
Initial Sample D.O. = 8.1 mg/L
5-Day Sample D.O. = 2.1 mg/L
Vol. Of Sample in 300 mL Bottle = 60 mL

B.O.D., mg/L = D.O. Depletion, mg/L X 300 mL

Volume Sample, mL

= Initial D.O. - Residual D.O. X 300 mL

Volume Sample, mLs

= 8.1 mg/L - 2.1 mg/L X 300 mL

60 mL

= 6.0 mg/L X 300 mL

60 mL

= 0.1 mg/L X 300 = 30 mg/L

 B.O.D. PRACTICE PROBLEM
Calculate the B.O.D. value to be reported for each of the samples below.
Be sure to consider the minimum depletion and residual requirements.

Sample 1 Dilution A Dilution B

mL Sample 15 30
Initial D.O., mg/L8.1 8.2
5-Day D.O., mg/L6.6 4.2
Depletion 1.5 4.0

B.O.D., mg/L = D.O. Depletion, mg/L X 300 mL

Volume Sample, mL

= 4.0 mg/L X 300 mL

30 mL

= 40 mg/L
 B.O.D. PRACTICE PROBLEM
Calculate the B.O.D. value to be reported for each of the samples below.
Be sure to consider the minimum depletion and residual requirements.

Sample 2 Dilution A Dilution B

mL Sample 15 30
Initial D.O., mg/L8.0 8.2
5-Day D.O., mg/L4.3 0.7
Depletion 3.7

B.O.D., mg/L = D.O. Depletion, mg/L X 300 mL

Volume Sample, mL

= 3.7 mg/L X 300 mL

15 mL

= 74 mg/L
B.O.D. PRACTICE PROBLEM
Sample 3 Dilution A Dilution B

mL Sample 15 30
Initial D.O., mg/L8.1 8.1
5-Day D.O., mg/L5.6 3.3
Depletion 2.5 4.8

BODA = 2.5 mg/L X 300 mL = 50 mg/L

15 mL

BODB = 4.8 mg/L X 300 mL = 48 mg/L

30 mL

50 + 48 = 49 mg/L
2
What is Chemical Oxygen Demand (COD)?

Definition
The quantity of oxygen needed to chemically oxidize
the organic compound in sample, converted to carbon
dioxide and water.

Commonly used to define the strength of industrial

wastewaters
 COD: A CHEMICAL TEST
The chemical oxygen demand (COD) of
a waste is measured in terms of the
amount of potassium dichromate
(K2Cr2O7) reduced by the sample during
2 hr of reflux in a medium of boiling, 50%
H2SO4 and in the presence of a Ag2SO4
catalyst.
The oxidation of organic matter converts
dichromate to trivalent chromium.
 COD
The stoichiometry of the reaction between dichromate and organic
matter is:

2 3 a
Cn Ha Ob Cr2 O 8H nCO2 2Cr 4 H2 O
7
2
Where: 2n a b

3 6 3
 COD
The mixture is titrated with ferrous ammonium sulphate (FAS) to
measure the excess dichromate remaining in sample.

A blank sample of distilled water is carried through the same COD

testing procedure as the wastewater sample.
COD
COD test is faster than BOD analysis: used for quick
assessment of wastewater strength and treatment
performance
Like the BOD, it does not measure oxidant demand due to
nitrogeneous species
It does not distinguish between biodegradable and non-
biodegradable organic matter. As a result COD's are
always higher than BOD's.
Required Reagent!
ORGANIC CONTENT
TOC: total organic carbon
measured with a TOC analyzer
related to oxygen demand, but does not reflect the oxidation state of the
organic matter

other group parameters

oil & grease

specific organic compounds

 ORGANIC CARBON FRACTIONS
Total Carbon (TC)
|
| |
Inorganic Carbon (IC) Total Organic Carbon (TOC)
| |
| | | |
Purgeable Non-Purgeable Purgeable Organic Non-purgeable Organic
(Dissolved) (Particulate) Carbon (POC) Carbon (NPOC)
|
| |
Particulate Dissolved
(PtOC) (DOC)
 TOC
Total organic carbon analysis is a determination of organic carbon in
a sample regardless of its oxidation state or biodegradability.
Other measures of total organic matter (e.g., COD, BOD) may
respond differently to solutions of equal carbon concentration
depending on the oxygen content or the bidegradation kinetics.
For the measurement of total organic carbon, the sample is exposed
to an oxidizing environment often at very high temperatures.
With complete oxidation all carbon is converted to carbon dioxide and
swept into a detector by the carrier gas.
The oxidation process is based on the following stoichiometry:
b d b c
Ca Hb N c Od (a )O2 aCO2 H2 O N 2
4 2 2 2
TOC - PYROLYSIS INSTRUMENT
Syringe
Sample Inlet

Furnace CO2 Detector Recorder

Condensor

O2
TOC - UV/PERSULFATE INSTRUMENT
Syringe

Sample
CO2 Detector Recorder
Inlet

Condensor

UV Reactor
O2

Persulfate
Solution
TOC - THE CO2 DETECTOR
Sensing Demodulator
Chopper Cell Amplifier

IR
Reference

Source
Sample

In Out

A non-dispersive infra-red analyzer (NDIR)

 WASTEWATER QUALITY STANDARDS
Regulations in Environmental Quality (Wastewater and
Industrial Effluent), 1978:
Sets standards for wastewater discharged from wastewater
treatment plant and industrial effluent
Standard A and Standard B
STANDARD A APPLIES
The catchment areas referred to in this regulation shall be
the areas upstream of surface or above sub-surface water
supply intakes, for the purpose of human consumption
including drinking.
 STANDARD A - UPSTREAM STANDARD B - DOWNSTREAM

BOD mg/l
BOD mg/l
SS mg/l
SS mg/l
COD mg/l
COD mg/l
Oil / grease - not detectable
Oil / grease 10 mg/l

DISTRIBUTION OF
WATER SUPPLY

RAW WATER IS PUMPED

TO WATER TREATEMENT PLANT

STREAM

UPSTREAM

DOWNSTREAM
SEWAGE TREATMENT PLANT
WATER INTAKE POINT