BITS Pilani

K K Birla Goa Campus

EE ZG514/ SSTM ZG516: Environmental Sampling

and analytical methods
Dr. Sharad M. Sontakke
Lecture - 3 Department of Chemical Engineering
Summary of Lecture 2

Module 1 (part 2): Structure and function of pollutants, and

analysis
• Sources of organic and inorganic pollutants
• Introduction to typical analytical methods

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Contents

Module 1 (part 3): Structure and function of pollutants, and

analysis
• Sampling methods
• Analytical data collection
• Standardization and calibration
• Common errors during analysis

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Sampling

Sampling is not limited to simply going to the field and

collecting some material for analysis. This approach is
called “random sampling” and it is appropriate when there
is some knowledge about the nature of the sample source.

Although there are some guidelines (Example: guidelines by

US EPA), there is no set rule regarding the number, the
amount, and the frequency of samples/sampling.

Key questions to address are: how many samples to take?,

from where the samples will be taken?, and when the
samples will be taken?

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Team selection for environmental sampling (Planning
stage):
Environmental sampling often needs a team of experienced
field personnel (experts in collecting samples) and
analytical chemists who knows how to preserve, store, and
analyze samples.
An engineer helps in suggesting a sampling location and
required safety protocols in a process industry.
A statistician will then verify that the resulting data and
suggest if it is suitable for decision making.
A QA/QC representative will review the applicability of SOP,
determine the numbers of QA/QC samples and document
the accuracy and precision of the resulting database.
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Define a data quality objectives (DQOs):
The DQOs are defined as „„qualitative and quantitative
statements that define the appropriate type of data, and
specify the tolerable levels of potential decision errors that
will be used as basis for establishing the quality and quantity
of data needed to support decision‟‟ (EPA, 2000).

The DQOs are a written document developed before data

collection and preferably agreed to by all stakeholders.

DQOs is a process of asking questions and finding answers

with regard to: what, who, why, when, where, and how

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The number of samples to be collected highly depends on the
objectives with regards to the required data quality.

For example, sampling to monitor the water quality will be

different depending on whether the objective is analysis for
determining the trend of contaminants or mere baseline
(referencing or background).

For minimizing the error in order to meet the required data

quality, the number of samples increases significantly.

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Another important considerations for environmental
sampling strategy are: environmental variability,
expenses associated with sampling, sampling
convenience, site accessibility, availability of sampling
equipment, and other non-technical aspects (such as
political, social, local, regulation constraints, etc.)

Representative sample: “a measure of the degree to

which data accurately and precisely represent a
characteristic of a population, a parameter variation at a
sampling point, a process condition, or an environmental
condition” (US EPA).

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Obtaining a representative
sample
The representative sample corresponds to several small
portions taken from different parts of the bulk material.
These are called gross samples.

For analysis, the gross sample is usually reduced in size and

homogenized to create the laboratory sample.

In some cases, homogeneity can‟t be obtained as the sample

consist of microscopic particles of different compositions.

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Size of the gross sample:
The size of the gross sample should not be larger than
necessary to ensure convenience and economy.
It can be determined by:
(1) the tolerable uncertainty
(2) the degree of heterogeneity of the whole, and
(3) the size level at which the heterogeneity appears

Example: A well-mixed gas or liquid is heterogeneous only on

the molecular scale.
In case of soil (or other solid sample), the heterogeneity
depends on the spatial variation.
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Commonly used sampling
approaches
1. Judgmental sampling
2. Simple random sampling
3. Stratified sampling, and
4. Systematic sampling

Judgmental sampling is a non-statistically based approach,

and the other three are probabilistic sampling approach.

In Judgment sampling, the sampling locations are selected

based on professional judgment using prior information on
the sampling site, visual inspection, and/or personal
knowledge and experience.
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However, since the judgmental sampling is a non-
statistically based approach, it does not support any
statistical interpretation and therefore, it is not applicable
when the level of confidence needs to be quantified.

Simple random sampling (or random sampling), is the

arbitrary collection of samples such that each sample
unit in the population has a equal probability of being
selected.
It is important to note that the term random sample does
not imply that the haphazard selection of the samples.
Instead a procedure of randomization is applied to obtain
such a sample.
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In stratified random sampling, the sampling population is
divided into several non-overlapping strata (domain) and
a simple random sampling is employed to select sample
within each stratum.

A major advantage of stratified random sampling is that the

sample size can be adjusted depending on the variations
or the cost of sampling in various strata.
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Systematic sampling involves selecting samples
according to a specified pattern in time or space, for
example, samples collected after n number or from equal
distance or after specific time interval.

Apart from the commonly used strategies described above,

there are number of other strategies that may be useful
for environmental sampling.

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Sampling sequence

General guidelines for sequencing samples from complex

media:
1. Collect from the least to the most contaminated sampling
locations. This will help to reduce a probable cross-
contamination between the samples.
2. Collect water sample first and then sediment in order to
minimize the effects from suspended bed materials
3. If sampling at different water depths is needed, collect
surface water samples first and then proceed to a deeper
interval.
4. Collect VOCs first, followed by semi-VOCs such as
extractable organics, oil and grease, and HCs.

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Sample size

Depends on the heterogeneity and the concentration of the

component(s) for analysis.

For heterogeneous samples, a larger portion is generally

required. This larger portion of the collected sample is then
homogenized thoroughly followed by subsampling.

Taking too large or too many samples should be avoided

because storage (cold room and freezer), transportation,
and disposal costs can become a burden in such cases

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The term macro analysis is used for samples whose masses
are greater than 0.1 g.
A semi-micro analysis is performed on samples in the range
of 0.01 to 0.1 g, and samples for a micro analysis are in
the range 10-4 to 0.01 g.
For samples whose mass is less than 10-4 g, the term ultra-
micro analysis is sometimes used.

Example: analysis of a 1-g sample of soil for a suspected

pollutant would be called a macro analysis whereas, that
of a 5-mg sample of a powder suspected pollutant would be
a micro analysis.

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For water/wastewater sample:
In general, a sample size of 5 mL is required for analysis of
HCs, 100 mL for total metals, and 1 L for trace organics
such as pesticides. This sample size is typically sufficient for
one analysis.

As per the EPA guidelines, the minimum volume collected

should be three to four times the amount required for the
analysis (EPA, 1995).

For toxicity analysis, more amount (typically 20-40 L) of

sample is needed.

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For soil/sediments:
Approximately 200 g of soil is needed for characterization of
its physicochemical properties. For contaminant analysis, a
dry mass of approximately 5–100 g is sufficient.

Air samples:
The sample volume depends on the minimum chemical
concentration that can be detected and the sensitivity of the
measurement.
Approx. 10 m3 volume of air may be required to determine
ambient concentrations. However, this volume may be
lower if smoke stack emission samples are collected for the
target contaminant.
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Other important steps during sampling:
1. Handling, storage and preservation of samples
2. Selection of sample container (example: Glass, plastic or
special container; need of headspace, etc.)
3. Selection of sampling equipment

Guidelines:
• US EPA (US Environmental Protection Agency)
• APHA (American Public Health Association)
• ASTM (American Society for Testing and Materials)

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Source: GUIDELINES FOR RECOGNITION OF ENVIRONMENTAL LABORATORIES UNDER THE ENVIRONMENT
(PROTECTION) ACT, 1986, CPCB, June 2008 (https://www.cpcb.nic.in) accessed on 20 Jan 2021.

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Standardization and
calibration
Calibration and standardization are an important part of all
analytical procedures.

Calibration determines the relationship between the

measured response and the concentration of analyte. This
is usually done by the use of chemical standards.

The standards used for calibration can be prepared from

purified reagents (if available) or standardized by classical
quantitative methods.

Most analytical methods need some type of calibration.

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Comparison with Standards

Standardization can be done either by direct comparison or by

titration procedures.

Some analytical procedures involve comparing a property of

the analyte with standards such that the property being
tested matches or nearly matches that of the standard.
(Example: matching colors)

Titration is another way of standardization and most accurate

of all analytical procedures.

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In a titration, the analyte reacts with a standardized reagent
(the titrant) in a known stoichiometric manner. Usually
the amount of titrant is varied until chemical equivalence
is reached as indicated by the color change of a
chemical indicator.

For example, in the titration of the strong acid HCl with the
strong base NaOH, a standardized solution of NaOH is
used to determine the amount of HCl present. The
reaction is:

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The standardized solution of NaOH is added from a burette
until an indicator (such as phenolphthalein) changes color.
At this point, called the end point, the number of moles of
NaOH added is approximately equal to the number of
moles of HCl initially present.

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External Standard Calibration
In this, a series of standard solutions are prepared. These
standard solutions are used to prepare a calibration.

Generally, a graph of instrument response (example

absorbance, intensity, current, etc.) versus known analyte
concentrations (standard solutions) is used
to prepare a calibration curve (also called a working
curve).

The concentration found is then related back to the analyte

concentration in the original sample by applying
appropriate dilution factors from the sample preparation
steps.
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One can use statistical methods, such as the method of least
squares, to find the mathematical equation describing the
calibration function.
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The simplest example of a least-squares approximation
is fitting a straight line to a set of paired observations:
(x1, y1), (x2, y2), . . . , (xn, yn).
The mathematical expression for the
straight line is
y = a0 + a1x + e
‘e' is the error or residual

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BITS Pilani, K K Birla Goa Campus
BITS Pilani, K K Birla Goa Campus
Another way of deriving the same formula

coefficient of determination (R2)

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BITS Pilani, K K Birla Goa Campus
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Errors in Chemical Analysis

When we perform any measurement, it invariably include

error and uncertainty.

Errors are most commonly caused during standardization

and calibration.

It is almost impossible to perform any chemical analysis

which is completely free of errors. However, it is possible
to minimize the errors.

Suppose we analyze six solutions with each containing 20

ppm of iron and data is shown in Figure
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 Sample 1: 19.4
Sample 2: 19.5
Sample 3: 19.6
Sample 4: 19.8
Sample 5: 20.1
Sample 5: 20.3

Average or Mean = 19.7833 (How to write this in significant

digits?, what is mean?)

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The concept of a significant figure, or digit, has been
developed to formally designate the reliability of a
numerical value

The significant digits of a number are those that can be

used with confidence.

For example, if the readings are considered as 48.5 and

87324.45 then it has three and seven significant figures,
respectively.

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zeros are not always significant figures because they may
be necessary just to locate a decimal point.

0.00002018, 0.0002018, and 0.002018 all have four

significant figures (leading zero are not significant)

When trailing zeros are used in large numbers: 74,600

7.46 x 104  three significant digits

7.460 x 104  four significant digits
7.4600 x 104  five significant digits

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• For very large or infinite figures (e.g., e, , √7), computer
retains a finite number of significant figure by omission of the
remaining significant figure (round-off error)

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The Mean (also called as arithmetic mean or the average):
It is obtained as sum of replicate measurements divided by
the number of measurements.

The median is the middle result when replicate data are

arranged in increasing or decreasing order. If the data
contains even number of readings, then median is the
average value of the central pair once the data is arranged
in increasing or decreasing order.
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Example: Calculate the mean and median for the data
shown earlier

Because the set contains an even number of

measurements, the median is the average of the central
pair:

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Accuracy refers to how
closely a computed or
measured value agrees with
the true value

Precision refers to how

closely individual computed
or measured values agree
with each other

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Precision is thus, the reproducibility of measurements. It is
measure of repeatability.

Three terms are widely used to describe the precision of a

data set: (i) standard deviation (ϭ), (ii) variance (ϭ2), and
(iii) coefficient of variation (CV)

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Accuracy indicates the closeness of the measurement to
the true or accepted value and is expressed by the error.

It is expressed in terms of either absolute or relative error

Absolute error (E)

Relative error (Er)

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Types of Errors in
Experimental Data
Common error in experimental data can be broadly
categorized as:
1. Random (or indeterminate) error and
2. Systematic (or determinate) errors:

There are three types of systematic errors:

1. Instrumental errors (arise from measuring devices,
deviation in their original calibration, etc.)
2. Method errors (arise from non-ideal chemical or physical
behavior of the reagents and reactions, eg: titration)
3. Personal errors (arise from carelessness, inattention, or
personal limitations)
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Summary

In this lecture, we discussed:

• General procedure of environmental sampling
• Sampling methods and analytical data collection
• Calibration and standardization
• Common errors in analysis

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Questions

1. What is a representative sample?

2. Explain the difference between random error and
systematic error
3. What is the difference between judgment sampling and
systematic sampling?
4. What are significant digits?
5. What is mean and median?
6. What are round off errors?
7. What are the types of systematic errors?

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Plan for next lecture

In the next lecture, we will discuss:

Module 2: Spectro-chemical Analysis of pollutants
• Interaction of Radiation and Matter
• Spectroscopy and discovery of elements
• Radiation absorption

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