CEB20003 (Introduction to Environmetal Engineering Techology)

EXPERIMENT 1
Determination of Heavy Metals: Lead (Pb)
by the Direct Air-Acetylene Flame Method

LECTURER: ELMY NAHIDA BINTI OTHMAN

TECHNICIAN: EN. HAIROOL
VENUE: LAB 25

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Introduction
Water is essential to human life for us to drink and for daily life activities.
Unfortunately, people always assume that the water they used everyday are safe to be
consume. This is because the water may contain trace amount of mineral matter, gases
and other substances including heavy metals. These heavy metals are toxic for us to
consume and they have a wide range of effects to us such as acute poisons and chronic
diseases. Examples of them are nickel (Ni), cadmium (Cd), copper (Cu), zinc (Zn), lead
(Pb) and arsenic (As). These heavy metals are discharged in effluents by industries that
uses these metals in their operational such as petrochemical and electroplating. Besides
that, there are many opportunities for the water to have these heavy metals as they
located underground which they come in contact with mineral deposits. Hence, it is
necessary for us to determine the concentration of the heavy metals inside the water. It
can be done by measuring the quantity of light of specific wavelength absorbed by
atoms of the elements released in a flame using an atomic absorption
spectrophotometer. Figure 1 shows an atomic absorption spectrophotometer, which
consist of an atomizer-burner to convert the element in solution to free atoms in an air
acetylene flame. This is followed by a monochromator to disperse and isolate the light
waves emitted and a photomultiplier to detect and amplify the light passing through the
monochromator. The light source is a lamp with a cathode formed of the same element
being determined since each element has characteristic wavelengths that are readily
absorbed. The light passing through the sample is separated in the monochromator into
its component wavelength. The photomultiplier then receives the only the isolated
resonance wavelength. The amount of energy at the characteristic wavelength absorbed
in the flame is proportional to concentration of the element in the sample. But then,
sample containing particulates or organic material generally require pre-treatment
before spectroscopic analysis. This is to reduce interference by organic matter and to
convert metals associated with particulates to a form that can be determined by atomic
absorption spectrometry. Nitric acid digestion is the one suitable to be use for lead (Pb)
because this method presents one approach trace levels where lead usually at very low
concentration ( 0.1 mg.-1).

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Figure 1: Simplified schematic diagram of an atomic absorption spectrophotometer

Objectives
To familiarize in general the atomic absorption spectrophotometer
To determine the concentration of lead (Pb) in water sample
To compare the concentration of heavy metal present in the water sample with
the values of Standard B

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Method
Preparation of standard 100mg/L from stock solution 1000mg/L Pb
1. The stock solution is first diluted to become 100mg/L by transferring 10mL of
1000mg/L into 100mL capacity volumetric flask.
2. Then, distilled water was added to the mark.
3. The flask was then inverted several times to properly mix the contents.

Nitric Acid Digestion Process

1. 100 mL of waste water sample was put in a beaker and heated using hot plate.
2. 5 mL of 65% concentration nitric acid, HNO3 was added to the sample in the
beaker. The beaker was covered with ribbed watch glass.
3. During the heating of the solution, 5 ml of nitric acid was gradually inserted at
interval of 20 minutes.
4. Temperature of hot plate was increased so that a gentle reflux action occurs.
Heating was continued and it was necessary to add additional amount of acid,
until digestion is complete. (After 3-4 times gradually inserting nitric acid,
observes the colour of sample is noticeably changes from dark black to light
yellow).
5. Slow down the heat to cautiously evaporate to less than 5 mL, making certain
that sample does not boil and that no area of the bottom of the container is
allowed to go dry.
6. The hot plate was turned off and the sample is left for 5 minutes for cooling.
7. Beaker walls and watch glass were washed with metal-free water, and then
filtered to remove insoluble material that could clog the nebulizer.
8. After preparation for sample, standards and blanks has been completed, the
technician operated the AAS, the standard curve was plotted and the
concentration of lead (Pb) was measured.

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Data & Result

Mixture Observation Explanation
Adding 5 m The water sample HNO3 act as an oxidizing agent where
conc. HNO3 into change its colour from zero valence Pb are oxidized and
the water sample dark black to light brought into the solution where the
every 20 minutes yellow which seems to nitric acid does not form any insoluble
while heating it. be a clear solution. compounds reacting with lead.

Table 1: Observation during the water sample undergoes nitric acid digestion

Sample Lead Concentration (mg.-1) Absorbance

Standard 1 1.00 0.02400
Standard 2 2.00 0.04800
Standard 3 3.00 0.07200
Water Sample 0.09 0.00216

Table 2: The absorbance of the sample with different lead concentration (mg.-1)

Lead Concentration (mg.-1) vs Absorbance

0.08
Standard 3
3, 0.072
0.07

0.06 Standard 2
y = 0.0240x
2, 0.048
0.05
Absorbance

0.04
Standard 1
0.03 1, 0.024

0.02 Water Sample

0.09, 0.00216
0.01
0, 0
0
0 0.5 1 1.5 2 2.5 3 3.5
Lead Concentration (mg.-1)

Figure 2: The graph of lead concentration (mg.-1) vs absorbance

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Discussions
Sample containing particulates or organic material generally require pretreatment
before spectroscopic analysis including heavy metals such as lead. Nitric acid digestion
is the one suitable to be use for lead (Pb) because this method presents one approach
trace levels where lead usually at very low concentration ( 0.1 mg.-1). For nitric acid
digestion, 5 m conc. HNO3 was added into the water sample while heating it every 20
minutes. It was observed that the water sample change its colour from dark black to
light yellow which seems to be a clear solution. According to Gaines (2016), the
chemical reaction occurred during this acid digestion is shown below.

3Pb + 6H3 O+ + 2HNO3 2NO + 3Pb+2 + 10H2 O

Gaines (2016) stated that the HNO3 act as an oxidizing agent / acid combo where zero
valence lead is oxidized and brought into the solution. In addition, nitric acid does not
form any insoluble compounds with lead. Hence, the colour change from dark black to
light yellow which seems to be a clear solution. Atomic absorption spectrophotometer
(AAS) is an analytical technique that measures the concentrations of elements. Based
on Kumar and Kumar (2016), it is so sensitive that it can measure down to parts per
billion of a gram in a sample. Kumar and Kumar (2016) also stated that the technique
makes use of the wavelengths of light specifically absorbed by an element. Atoms of
different elements absorb characteristic wavelengths of light. Analysing sample to see
if it contains a particular element means using light from that element. In AAS, the
sample is atomized by converting it into ground state free atoms in vapour state and
then a beam of electromagnetic radiation emitted from excited heavy metal atoms are
passed through the vaporized sample. Some of the radiation is absorbed by the heavy
metal atoms in the sample. The greater the number of atoms there is in the vapour, the
more radiation is absorbed. Besides that, Harris (2003) stated that the amount of light
absorbed is proportional to the number of heavy metal atoms. A calibration curve is
constructed by running several samples of known heavy metal concentration under the
same conditions as the unknown. The amount of the standard absorbs is compared with
the calibration curve and this enables the calculation of the heavy metal concentration
in the unknown sample. According to Skoog et al. (1999), it is called the external
standard method.

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According to Table 2, there are three standard solutions was used to construct a
calibration curve which have the concentration of 1.00, 2.00 and 3.00 mg.-1 and the
absorbance of 0.024, 0.048 and 0.072 respectively. Hence, the unknown concentration
of lead of the water sample can be determined by using its absorbance which 0.00216.
By using the equation given for the straight line in Figure 2, the lead concentration of
the water can be calculated.

= 0.024
Where y is the absorbance of the solution
x is the lead concentration inside the sample (mg.-1)

Hence, the concentration of Lead inside the water sample are calculated to be 0.09 mg.-
1
. According to the Environmental Quality (Industrial Effluents) Regulations 2009 (PU
(A) 434), the Standard B for concentration of lead is 0.5mg.-1. By comparing this
results with Standard B, it shows that this sample is safe and acceptable in conditions
for discharge of industrial effluent for mixed effluent as it is not more than 0.5 mg.-1.
If the concentration of heavy metals is higher than the standard, this means that the
water is not safe to use. It is because heavy metals can be very harmful to health if
found in a drinking water. According to Davis and Cornwell (2008), this can cause
severe effects such as reduced development and growth, cancer, damage in organs, and
in extreme cases, death. Thus, exposure of metals like lead may cause autoimmunity,
that is a persons immune system attacks on its own cells, which can lead to rheumatoid
arthritis, kidneys disease, circulatory and nervous system disease.

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Conclusions & Recommendation

The objectives of this experiment are achieved. Atomic Absorption Spectrophotometer
is a quantitative analytical instrument that measures the concentration of elements
inside a sample. The sample will be heated in an acetylene flame so that the lead atom
is vaporized while it absorbs the electromagnetic radiation emitted to it whereby the
concentration of lead is higher when the value of absorption is larger. The external
standard method is used to plot the calibration curve where 3 standards with known
lead concentration undergoes the AAS and using this calibration curve, the
concentration of lead inside the water sample could be calculated using the straight line
equation given whereby the concentration of lead inside the water sample is 0.09 mg.-
1
. Hence, by comparing the sample with Standard B, the water is safe and acceptable in
conditions for discharge of industrial effluent for mixed effluent.

In this experiment, it is recommended that do not hesitate to add additional acid to the
sample during heating. This is because adding more will fasten the reaction of digestion
process in sample besides increasing the temperature. Next, make sure to use mineral-
free water during beaker washing because it can prevent from the sample from
contaminated with other heavy metals. By doing this, the result will be more accurate
and the sample will be free from other contaminants.

References
Davis, M.A., & Cornwell, D.A. (2008). Introduction to Environmental Engineering.
(4th Edition). New York: McGraw-Hill Education
Gaines, P. (2016). Acid Digestion of Inorganic Samples. [Online]. [Accessed 29-08-
2017]. Available from world wide web: www.inorganicventures.com/acid-
digestions-inorganic-samples.
Harris, D.C. (2003). Quantitative Chemical Analysis. (6th Edition). New York: W. H.
Freeman and Company
Kumar, K., & Kumar, N. (2016). A Study of Heavy Metal Removal by Adsorption.
IJSRD.
Skoog, D.A., West, D.M., Holler, F.J., & Crouch, S.R. (1999). Analytical Chemistry
An Introduction. (7th Edition). Singapore: Thomson Learning Inc.

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Appendix

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