ENS- ENVIRONMENTAL ANALYTICAL

801 TECHNIQUES

Dr Hira Amjad
 ENS-801: ENVIRONMENTAL ANALYTICAL
TECHNIQUES (2+1)
2

Introduction; Principles of physical, chemical and microbiological analysis of

environmental pollutants, Sampling Procedure for the examination of Water,
Wastewater, Air and Solid Waste; sampling rules, sample collection and preservation.
Laboratory Techniques and Field Monitoring for parameters of importance causing
environmental pollution. Environmental Chemical Analysis; Principles for Instrumental
Techniques using Spectroscopy, Chromatography, Microscopy and X-Ray Diffraction
analyses etc. Assessment and Interpretation of Results using Statistical Tools.

Lab work:
Analyses of Water, wastewater, air and solid wastes for pollutant determination;
Instrumental analyses of pollutants using Spectroscopy, Chromatography, Microscopy
and X-Ray Diffraction analyses etc. Data Interpretation using Statistical Tools

Recommended Books:
1) Standard Methods for Examination of Water and Wastewater. L. S. Clesceri, A. E.
Greenberg, A. D. Eaton. 22th Edition. APHA publisher, USA, 2012.
2) Environmental Engineering Laboratory. Ahmed, K.A one Publishers Lahore,
Pakistan, 1998.
 Course Contents
3

 Introduction to standard methods of analysis

 Quality assurance and quality control strategies
 Sampling rules, methods for collecting surface water, ground water and wastewater
samples wastewater samples
 Methods for sample preservation and preparation for the analysis of pollutants
 Gravimetric and volumetric methods of analysis for water and wastewater pollutants
 Environmental significance and determination of water quality parameters like solids,
DO, BOD, COD, hardness, alkalinity, turbidity, Kjeldahl nitrogen, and total and fecal
coliforms using the Standard Methods
 Data management, presentation and interpretation
 Principles of instrumental analytical techniques such as liquid chromatography, AAS,
FTIR, spectrophotometry, radiometry, gas chromatography, HPLC and Oil analyses
 Application of selected instrumental techniques for the determination of pesticides,
toxic metals and other trace organics
 Use of field instruments and test kits (Field Monitoring)
Labs
1 Determination of Elemental Composition of solid Samples using XRF/LIBS
2 Determination of Total Organic Carbon (TOC) in water
3 Analysis of Organic Contaminants in Water by Gas Chromatography
4 Estimation of Optimum Coagulant Dose using Jar Test Apparatus
5 Determination of Residual Chlorine in Water
6 Determination of Water Hardness

7 Determination of Chemical Oxygen Demand (COD)

8 Determination of Biochemical Oxygen Demand (BOD)

9 Determination of Solid (TS,TDS,TSS,TVSS) in Water and Wastewater
10 Determination of Oil and Grease in Wastewater
11 Standard Coliform by MF Method
12 Determination of Nitrate-Nitrogen in Water using Spectrophotometer
13 Microscopy and X-Ray Diffraction analyses
14 Data Interpretation using Statistical Tools
 Introduction
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 What is Environmental Analytical Science/

Techniques?
A scientific discipline that develops and applies methods,
instruments and strategies to determine the nature and
concentrations of chemical constituents of the environment. It
helps in determining the concentration of harmful pollutants in
the environment.
Two major subsections:
 Qualitative analysis : What is present ?
 Determination of chemical identity of the species in the
sample.
 Quantitative analysis : How much present ?
 Determination of the amount of species or analytes.
 Introduction
6

 What is Analytical Chemistry?

 More simply: analysis is understood today as
encompassing any examination of chemical material with
the goal of eliciting information regarding its constituents:
 their character (form, quality, or pattern of chemical bonding),
 quantity (concentration, content),
 distribution (homogeneity, but also distribution with respect to
internal and external boundary surfaces), and
 structure (spatial arrangement of atoms or molecules).
 This goal is pursued using an appropriate combination of
chemical, physical, and biological methods.
 Introduction
7

 Qualitative criteria for

use in evaluating
analytical procedures
 The Analytical Protocol
8

Environmental sample analysis involves several steps, including

sample collection, sample treatment and storage, followed by
laboratory analysis
High quality of laboratory performance by
 Selecting appropriate and validate methods of sampling

 Selecting validate methods for sample preservation and

preparation
 Selecting standard methods (validated) for analysis of
samples
 Calibrating analytical instruments

 Practicing good record keeping of methods and results

 Ensuring the quality of data produced

 A typical analytical protocol used for
environmental analysis
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 Sampling
10
 Sampling
11

• Usually only a small portion of sample is subjected

to quantitative analysis, hence this laboratory
sample must be representative of the parent
sample

• Samples may be homogeneous or heterogeneous

– Homogeneous samples present no problem, a
simple ‘grab sample’ approach taken at random
will suffice
– Several samples have to be taken if parent
sample is heterogeneous
The key questions to be asked before sampling begins include the
following:

1. Have arrangements been made to obtain samples from the site (e.g.
permission from the site owner)?
2. Is specialized sampling equipment required and available?
3. How many samples and how many replicates are required?
4. Are the samples required for qualitative or quantitative analyses?
5. What chemical or physical tests are required?
6. What analytical methods and equipment are needed?
7. What mass/volume of sample is required for the analytical techniques to be
used?
8. Is there a quality assurance protocol in place?
9. What types of container are required to store the samples and do you have
enough available?
10. Do the containers require any pre-treatment/cleaning prior to use and has
this been carried out?
11. Is any sample preservation required and do you know what it is?
 Distribution of inorganic
or organic contaminants

- can be random, uniform

(homogenous), patchy,
stratified (homogenous
within sub-areas) or
present as a gradient

- preliminary testing of the

site is beneficial to
establish the likely
distribution

Different distributions of inorganic and organic

contaminants: (a) random; (b) uniform (homogeneous);
(c) patchy; (d) stratified (homogeneous within sub-areas);
(e) gradient
 Environmental Sampling Approaches:
Where and When
14

 Judgmental
Selection of sampling locations based on
professional judgment using prior
information on the sampling site, visual
inspection and/or personal knowledge
and experience

 Systematic
Systematic sampling subdivides the area
of concern by square or triangle grids
and then collect sample from nodes or a
fixed location of each grid
 Environmental Sampling Approaches:
Where and When
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 Stratified Random
Divides sampling population into several
non overlapping strata. Each strata is
more homogenous than whole
population. Strata could be temporal or
spatial and sample size can be adjusted.
 Sampling Methods
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 Manual sampling
• Minimal equipment
• Costly & time consuming
• Trained field technicians
 Automatic sampling
• Eliminate human error
• Reduce labor cost
• More frequent sampling
 Sorbent sampling
• Solid sorbents e.g. membrane type disks
 Sampling Techniques
17
Soil Sampling
Surface Water & Wastewater Sampling
Ground Water Sampling
Sampling Air
Particulate sampling: in which particles are collected on filters
 Sampling Air
Vapor/gas sampling: in which air-borne compounds are trapped on a sorbent

Air sampling: (a) a typical sorbent tube; (b) the system used to carry out measurements
 Number of Samples
23
24
25
 Sample Preservation & Storage
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 Impossible to preserve sample completely

 No single method of preservation is
satisfactory
 Sample storage before analysis
• Nature of sample changes
• Time interval b/w collection & analysis
Sample Preservation & Storage
In an ideal situation, samples should be analyzed in situ without storage and
transport to the laboratory
Methods of preservation are relatively few and are generally intended to fulfill
the following criteria
• to retard biological action
• to retard hydrolysis of chemical compounds and complexes
• to reduce volatility of constituents
• to reduce adsorption effects

Preservation methods constitute the following approaches:

• pH control
• addition of chemicals
• refrigeration

Sample container: borosilicate glass or plastic (polyethylene, polypropylene

or ‘Teflon’ (PTFE))
Polyethylene (P) or glass (G), or PTFE Teflon
MAJOR CATEGORIES OF CHEMICAL ANALYSIS
Both qualitative and quantitative analysis are divided between classical methods
involving primarily chemical reactions and simple measurements of mass and
volume, and instrumental methods that use instruments of varying degrees of
complexity and sophistication to measure quantities of analyte

Analytical
Techniques

Chemical Methods Instrumental

(Classical Method) Method

Spectroscopic Electrochemical Chromatographic

Method Method Method
Advantages of Instrumental Methods

 High Sensitivity
 Accuracy
 Small Sample can be analyzed
 Measurements obtained are Reproducible
 Fast Determination
 Complex sample can be handled easily
 Process can be made automatic
Limitations of Instrumental methods
 High Cost
 Necessary to use reference substance
 Skilled Persons are required
Solutions

A solution is a homogeneous mixture composed of a solute

and a solvent. The solute is dissolved in the solvent.
Preparation of Solutions (formulae)

1. If solute is solid
Molarity  Mol.Wt. (g)  Volume of solution (ml)
Mass of solute required (g) 
1000
Normality  Eq.Wt. (g)  Volume of solution (ml)
Mass of solute required (g) 
1000
2. If solute is pure liquid
Molarity  Mol.Wt. (g)  Volume of solution (ml)
Volume of solute required (ml) 
Density of solute (g/ml)  1000
Normality  Eq.Wt. (g)  Volume of solution (ml)
Volume of solute required (ml) 
Density of solute (g/ml)  1000

3. If solute is an impure liquid

Density of solute (g/ml)  % Purity  10
Molarity of solute (in original packing) 
Mol.Wt. (g)
Density of solute (g/ml)  % Purity  10
Normality of solute (in original packing) 
Eq.Wt. (g)

Dilution M1 x V1 = M2 x V2 or N1 x V1 = N2 x V2
To prepare a standard solution of Oxalic acid and with its help
standardize approximately 0.1M NaOH solution
Solutions Preparation

1. Oxalic Acid: Prepare 250mL 0.05M Oxalic acid solution. Oxalic acid gives a
primary standard solution. Since Oxalic acid is solid; use

Weight of Solute (g) = Molarity x Mol. Wt. of Solute (g) x Volume of Solution (mL)
1000
Wt. of Oxalic acid required (g) = 0.05 x 126 x 250 = 1.58g.
1000

Dissolve 1.58g oxalic acid in some distilled water in a 250mL flask and shake. When
whole of the oxalic acid has dissolved, fill the flask up to the mark with distilled water
2. Sodium hydroxide: Prepare 250 mL 0.1M (approx.) NaOH solution. Since NaOH
is solid; use

Weight of Solute (g)= Molarity x Mol. Wt. of Solute (g) x Volume of Solution (mL)
1000
Wt. of NaOH required (g) = 0.1 x 40 x 250 = 1g
1000
Dissolve 1g NaOH in some distilled water in a 250mL flask and shake. When whole
of the NaOH has dissolved, fill the flask up to the mark with distilled water.
 Procedure

Pipette out 10mL of the NaOH solution in conical flask, add one or two drops of
phenolphthalein as an indicator. This will give pink color to the alkali. Titrate it
against oxalic acid (from burette) till the pink color just changes to colorless.

(COOH)2.2H2O + 2NaOH (COONa)2 + 4H2O

n1= 1 mole n2= 2 moles

Calculations
Mean volume of oxalic acid used = V1 mL

Acid : Base
M1V1 = M2V2
n1 n2

Molarity of NaOH solution: M2 = M1V1 x n2

n1 V2
EXERCISE

Prepare 250mL of 0.1M NaHCO3 solution

Hint: NaHCO3 is solid

Prepare 500mL of 0.02M KMnO4 solution

Hint: KMnO4 is solid

Prepare 250mL of 0.5M HCl solution

Hint: HCl is an impure liquid

Atomic masses (g/mol): Na: 23, K: 39, Mn: 55, Cl: 35.5, O: 16, C: 12
EXERCISE
Prepare 250 mL of 0.1M NaHCO3 solution
Hint: NaHCO3 is solid; use
Weight of Solute(g) = Molarity x Mol.Wt. of Solute(g)x Volume of Solution ( mL)
1000
Wt. of NaHCO3 (g) required = 0.1M x 84.0g x 250mL
1000
Wt. of NaHCO3 (g) required = 2.1g
Take 2.1 g NaHCO3 in a 250mL measuring flask, add some distilled water and dissolve the
NaHCO3 in it. Then fill the flask up to the mark with distilled water

Prepare 500 mL of 0.02M KMnO4 solution

Hint: KMnO4 is solid ; use
Weight of Solute (g) = Molarity x Mol.Wt. of Solute(g) x Volume of Solution( mL)
1000
Wt. of KMnO4 (g) required = 0.02M x 158g x 500mL
1000
Wt. of KMnO4 (g) required = 1.58g
Take 1.58 g KMnO4in a 500mL measuring flask, add some distilled water and dissolve the
KMnO4 in it. Then fill the flask up to the mark with distilled water
EXERCISE

Prepare 250 mL of 0.5M HCl solution

Hint: HCl is an impure liquid; use
Molarity of Liquid = Density(g/mL x % Purity x 10
Mol.wt.(g)
Molarity of HCl = 1.19 g/mL x 37 x 10
36.5g/mol
Molarity of HCl = 12.0M
Dilution:
M1 x V1 = M2 x V2
Volume of HCl (mL) required = 0.5M x 250mL
12.0M
Volume of HCl (mL) required = 10.4mL
Take some distilled water in a 250 mL flask, add 10.4mL HCl in it and
shake. Fill the flask up to the mark with distilled water