Atomic Absorption

Spectrophotometry
Andi Suhendi
 The Death of Napoleon
 For 200 years controversy has surrounded
Napoleon's death.
 In 1995, the FBI used Graphite Furnace Atomic
Absorption Spectroscopy to investigate the
theory that Napoleon Bonaparte was murdered
via arsenic poisoning, by examining preserved
samples of hair from Napoleon himself. Results
showed high concentrations of arsenic, thus
supporting the theory that Napoleon was
murdered.
 Only until a thorough investigation in 2007 came
to the conclusion that he died from stomach
cancer, was the controversy finally laid to rest.
Who fired the
murder weapon ?
3
 Gunshot residue (GSR)
• Bullets contain “primer” and
“propellant” which result in GSR on the
firing hand

• Swabbing hands with mild acid will

release barium (Ba) and antimony (Sb)

• Measure by Atomic Absorption

4
 Introduction
• Molecular spectrophotometry : UV, Vis, Fluoresence
• Atomic spectrophotometry : AAS, AES, ICP
• AAS, an analytical technique that measures the
concentrations of elements. It makes use of the
absorption of light by these elements in order to
measure their concentration.
• AAS is standard instruments for the determination of
metal elements, widely applied of samples, such as
agriculture chemical, clinical and biochemistry,
minerals, food and drugs, environmental and other.
• First introduced in 1955, commercially available since
1959.
Principle of the Atomic Absorption
Method
• Atomized elements each absorb energy of a
wavelength that is peculiar to that element.
• The atomic absorption method uses as its
light source a hollow cathode lamp which
emits light of a wavelength that is peculiar to
each element.
• Elements within a solution are heated in a
flame or electrically (2000K to 3000K) and
subsequently determined using the fact that
the degree of absorption will vary with its
concentration.
Hubungan antara jumlah atom dalam keadaan
tereksitasi dan dalam keadaan azas
Persamaan Boltzmann

Nj = Banyaknya atom dalam keadaan tereksitasi

No = Banyaknya atom dalam keadaan azas
Pj & Po = Faktor statistik yang ditentukan oleh banyaknya tingkat energi
yang mempunyai energi sama pada tingkat kwantum
Pj = Jumlah keadaan kwantum dengan energi yang sama pada
keadaan tereksitasi
Po = Jumlah keadaan kwantum dengan energi yang sama pada
keadaan azas
Ej = Selisih energi (erg) antara keadaan tereksitasi dan azas
K = Tetapan Boltzmann (1,38 x 10-16 erg / derajat)
T = Temperatur dalam derajat Kelvin

7
 Aplikasi
persamaan
• Apakah nyala atau energi listrik yang digunakan untuk mengatomisasi
atom TIDAK MENYEBABKAN ATOM DALAM KEADAAN
TEREKSITASI ?
Contoh : Hitunglah perbandingan jumlah atom Na dalam keadaan
tereksitasi 3p dan keadaan azas 3s pada suhu atomisasi 2500 oK, jika λ dari
3p ke 3s 5890 dan 5895 oA.
Panjang gelombang dari 3s ke 3p = 5892,5 oA atau = 5892,5 oA x 10-8
cm/oA = 1,698 x 104 cm.
Maka Ej = 1,698 x 104 cm x [1,986 x 10-16 erg cm-1]  3,372 x 10-12 erg
• Pj/Po = 6/2 (karena pada 3p ada 6 dan pada 3s ada 2 keadaan kwantum
dengan energi yang sama).
• Nj/No = 3 exp [-Ej/KT]  3 exp [- 3,372 x 10-12 /{1,380 x 10-16 x 2500}]
log Nj/3No = [- 3,372 x 10-12 /{1,380 x 10-16 x 2500}]
Nj/No = 1,7 x 10-4
Kesimpulan : Jumlah atom Na dalam keadaan tereksitasi hanya 1,7 x 10-4
atau 0,00017 kali jumlah atom Na dalam keadaan azas, atau dengan kata
lain pada 2500 oK semua atom Na dalam keadaan azas, TIDAK ADA
YANG TEREKSITASI.
 Schematic

I0 It
Light Source Monochromator Detector Amplifier

E.g. Hollow
Fuel (e.g. acetylene)
cathode lamp Atomiser Air

Analyte solution Nebuliser, spray

chamber, and burner
Instrumentation of AAS
 Flame AA Spectrometer
Hollow cathode lamps with
characteristic emissions

Burner

Flame fuelled by (e.g.)

acetylene and air

Nebuliser and Spray Hollow cathode lamps available for over 70 elements
chamber Can get lamps containing > 1 element for determination of
multiple species 12
 Light Source
• Hollow Cathode Lamp (HCL)

• Laser
• They are intense enough to excite atoms to
higher energy levels. This allows AA and atomic
fluorescence measurements in a single
instrument.
• Electrodeless Discharge Lamps (EDL)
 Why Use HCL
• Pada serapan atom pita serapan sangat sempit (0,02-
0,05 oA)  maka TIDAK ADA MONOKROMA-
TOR atau pemilih panjang gelombang yang mampu
memberikan pita sinar yang sesempit itu.

• Sedang jika digunakan sumber yang kontinyu maka

lebar pita sinar >>> lebar pita serapan atom: sehingga
perubahan intensitas oleh penyerapan atom sangat
kecil sehingga HK LB tidak terpenuhi
• Oleh karena itu pada SSA digunakan sumber sinar
yang dapat memberikan lebar pita sinar yang sempit
sesempit pita serapan atom yaitu LKB (lampu
katoda berongga = Hollow Cathode Lamp)
Mechanism of HCL
 2. Atomiser

Flame Graphite Furnace Hydride

 1. Nebulizer:
4. The mixture flows
immediately into the
burner head.

5. It burns as a smooth,
laminar flame evenly
distributed along a narrow
slot.

1. mixes acetylene (the fuel)

and oxidant
(air or nitrous oxide). 3. The result is a heterogeneous
mixture of gases (fuel + oxidant) and
suspended aerosol (finely dispersed
sample).

2. A negative pressure is formed

at the end of the small diameter,
plastic nebulizer tube
(aspiration).
6. Liquid sample not flowing
into the flame collects in the Note:
waste. When do we use NO2 ?
 Flame atomisation:
Laminar flow burner - components
 Nebuliser: converts sample solution into aerosol
 Spray chamber: Aerosol mixed with fuel, oxidant and burned
in 5-10 cm flame
 Fuel: Acetylene or nitrous oxide
 Oxidant: Air or oxygen
 Burner head:
Laminar flow: quiet
flame and long path-
length
 But: poor sensitivity
(not very efficient
method, most of
sample lost)

18
from: Skoog
Structure of a flame

19
Table of the characteristics of various
flames
Max. flame speed (cm/s) Max. temp. (oC)

Air-Coal gas 55 1840

Air-propane 82 1925

Air-hydrogen 320 2050

Air-50% oxygen-acetylene 160 2300

Oxygen-nitrogen-acetylene 640 2815

Oxygen-acetylene 1130 3060

Oxygen-cyanogen 140 4640

Nitrous oxide-acetylene 180 2955

Nitric oxide-acetylene 90 3095

Nitrogen dioxyde-hydrogen 150 2660

Nitrous oxide-hydrogen 390 2650

 B. Graphite Furnace Atom Absorption
Spectroscopy:
• (GFAAS) Graphite Furnace Atomic Absorption
Spectroscopy and (ETAAS) Electro thermal
Atomic Absorption Spectrometry
• Advantages
 Small sample
 Formation of stable Thermal oxide (Al, Mo, Ti)
 Residual elements
 Biological samples
 Effective atomization
 Sample stay for Long time in graphite tube>>>high sensetivety
 Suitable for solid samples
 Ionic interferase rather than chemical or physical due to high
temp.
5. The monochromator isolates the light of 4. The graphite tube is
the element of interest from the permanently flushed with 1. The source of light (lamp)
background lights to the PMT. The PMT argon while it is in operation emits light with a wavelength
tube measures the change intensity. specific to the element of
interest

2. A controlled voltage is applied at

the ends of the graphite tube, which 3. Samples are deposited in the graphite tube
is heated rapidly to high  heated to vaporize and atomize the analyte
temperatures (up to 2600°C).  atoms absorb ultraviolet or visible light and
make transitions to higher electronic energy
levels.
 Flameless Method (Graphite
Furnace)
• In an actual measurement heating is done in 3 stage.
• Drying stage (100oC)
• Ashing stage (400-1000oC)
• Atomizing stage (1400-3000oC)
Analysisi of Mercury by Cold Vapor
Method
• Free mercury atoms can exist at room temperature can
be analysed using atomic absorption without employing
flame and graphite furnace techniques at high
temperatures.
•Mercury is reduced in solution using stannous
chloride or sodium borohydride in a closed system.
•The reaction quantitatively releases mercury
(from the sample solution) and is carried by a
stream of air or argon through a quartz sample sell
placed in the light path of an AA instrument for
analysis.
• The detection limit for mercury by this cold
vapor technique is approximately 0.02 mg/L.
Hydride Generation Atomic Absorption
Spectroscopy (HGAASC.):

It’s used for elements that are forming

volatile hydrides (e.g. As, Se, pb, Sb, Te, Sn, Bi)
(HAAS) is very useful in case of interferences,
poor reproducibility, and poor detection limits.
 sample flow in the (HGAAS)

4. In the optical cell the flame is ignited automatically by 3. The liquid mixture flows
the air/C2 H 4 and the gaseous into a gas/liquid separator where
metal hydride form decomposes into the elemental form the hydride and some gaseous hydrogen are
which can absorb the purged (via a high purity inert gas) into the optical
HCL's beam. The light passes to the Mon. and then to the cell via a gas transfer line
PMT

Optical cell

Volatile Hydride
Gas liquid separator

Mixing
peristaltic reaction
pump coil
1. The metal oxyanions reacts with 2. The peristaltic pump and the flowing reagents along
Sodium Borohydride and HCl and with the tubing of specific lengths controls the time
produces a volatile hydride: H2Te, from reagent mixing and separation of
H2Se, H3As, H3Sb, etc. the volatile hydride from the
liquid and sending the sample to the optical cell.
Advantages and Disadvantages of
Flame AAS
• Advantages
– equipment relatively cheap
– easy to use (training easy compared to furnace)
– good precision
– high sample throughput
– relatively facile method development
– cheap to run
• Disadvantages
– lack of sensitivity (compared to furnace)
– problems with refractory elements
– require large sample size
– sample must be in solution 27
Advantages and Disadvantages of
Electrothermal Atomisation
• Advantages
– very sensitive for many elements
– small sample size
• Disadvantages
– poor precision
– long cycle times means a low sample throughput
– expensive to purchase and run (argon, tubes)
– requires background correction
– method development lengthy and complicated
– requires a high degree of operator skill (compared
to flame AAS)
28
 4. Monochromator
The light passes from the HCL through the
element in the sample to the monochromator.
It’s function is:
It isolates the specific light of the element of
interest from the other background lights and
transfers it to the photomultiplier tube
(detector).
 5. Photomultiplier Tube (PMT)

Before an analyte is aspirated, a measured signal is

generated by the PMT as light from the HCL
passes through the flame. When analyte atoms are
present in the flame--while the sample is
aspirated--some of that light is absorbed by those
atoms. This causes a decrease in PMT signal that is
proportional to the amount of analyte.

PMT
 Interferences in AAS

• Broadening of a spectral line, which can occur

due to a number of factors (Physical)
• Spectral: emission line of another element or
compound, or general background radiation
from the flame, solvent, or analytical sample
– Background correction can be applied
 Chemical: Formation of compounds that do
not dissociate in the flame
 Ionisation of the analyte can reduce the signal
 Matrix interferences due to differences
between surface tension and viscosity of test
solutions and standards

Another caveat: Non-linear response common in AAS

31
 Physical interference

• Flame
– Spray efficiency fluctuations due to difference in
viscosity and surface tension between the standard
and sample.
• Furnace
– Sample dispersion ;
Measurement value fluctuations due to tube
temperature distribution
– Viscosity within the graphite furnace ;
Adherence to sample tip causing errors in
collection quantity.
• Example: samples, such as blood or juice,
containing numerous organic components.
 Physical interferences:
Atomic line widths/ line shapes

• Very important in atomic spectroscopy

• Narrow lines increase precision, decrease
spectral interferences
• Lines are broadened
by several mechanisms:
– Natural broadening
– Doppler effect
– Pressure broadening

33
 Natural linewidths

 Width of an atomic spectral line is determined

by the lifetime of the excited state
 Consequence of the Heisenberg uncertainty
principle

 For example, lifetime of 10-8 seconds (10 ns)

yields peak widths of 10-5 nm

34
 Doppler Effect
Photon detector

 Due to rapid motion of atoms in gas phase

 Atom moving toward the detector absorbs / emits
radiation of shorter  than atom moving perpendicular
to detector.
 Atom moving away from the detector absorbs / emits
radiation of longer : detector perceives fewer
oscillations
 Pressure broadening
 Results from collisions of absorbing/emitting species
 With analyte atoms or combustion products of fuel

 Deactivates the excited state – shorter lifetime -

broader spectral lines
 Increases with concentration and temperature

 E.g. in flame, Na absorbance lines broadened up to

10-3 nm.
 Doppler and pressure effects broaden atomic lines by 1-
2 orders of magnitude as compared with their natural
linewidths

36
 Background correction in AAS
• particularly important in GFAAS
• Use beam chopper to distinguish the signal due to flame
from desired atomic line at the same wavelength (old
method)

Lamp and flame emission

reach detector

Only flame emission

reaches detector

Resulting signal 37
 Background correction in AAS
 High energy Deuterium background corrector

Detector

Hollow
cathode Beam
lamp combiner

Lamps are pulsed

Sample
out of phase with
each other Deuterium lamp

38
 Minimising the effect of
Matrix Interferences
• The term "matrix" refers to the sum of all compositional
characteristics of a solution, including its acid
composition
• Calibration standards
and samples must be
matrix-matched in
terms of composition,
total dissolved solids,
and acid concentration
of the solution
• Also advisable for
ICP-OES and -MS

39
Effect on K concentration on measured Sr
 Spectral interference
• Spectral absorption line overlapping with the absorption
line of the target element.
• Absorption and scattering by molecules
• Spectral absorption line overlapping with the
absorption line of the target element.
Target element Spectral line Interfering Spectral line
(nm) element (nm)
Al  V 
Ca  Ge 
Cd  As 
Co  In 
Cu  Eu 
Fe  Pt 
Ga  Mn 
Hg  Co 
Mn  Ga 
Sb  Pb 
Si  V 
Zn  Fe 
Spectral interference

• Absorption and scattering by molecules

– Molecules absorption
• Alkaline metals + Halogens = Alkali halides
(Na, K)+(F, Cl, Br, I) = (Ex: NaCl, KI)
 Chemical interference

• Generation of non-separable compounds by

coexisting matrices
–Example : influence of PO4-, SO4-, SiO2 relative to
Ca, Mg
in flame analysis
• (generation of Ca2PO4)
• Generation of low boiling point compounds by
coexisting matrices
–Example: influence of chloride ions relative to Cd in
furnace analyses
• (generation of CdCl2)
 Matrix modifier effect
• Masking of obstructing matrices
• Influence of phosphate on Ca is masked by La
• Conversion of obstructing matrices to compounds
that easily undergo sublimation or evaporation
– Sublimation agent
• Example: removal of chloride ion by ammonium salt of nitric
acid or phosphoric acid
• Conversion of measured elements to stable oxides
or metallic intermediary compounds
– Stabilizing agent:
• Example: creation of measured element alloy using white
metals (Pd, Pt, Rh)
 The simple diagram for the AAS
4. The element in the sample
will absorb some of the light,
thus reducing its intensity

5. The
3. A beam of UV light monochromator
will be focused on the isolates the line of
sample interest

1. We set the
instrument at certain
wavelength suitable 2. The element
for a certain element in the sample
6. The detector
will be atomized
measures the change
by heat
in intensity

7. A computer data
system converts the
change in intensity into an
absorbance
 Application
of
Atomic Absorption Spectrophotometry
Elements that are highlighted in pink are
detectable by AAS
 Application of AAS

AAS

Pretreatment (dissolution) is required for solid samples.

 Pretreatment

Precautions for pretreatment:

 Dissolve all the elements into the same solution evenly.
(Check with certified reference material.)
 Ensure that elements are not lost in the solution. i.e., due to
vaporization or sedimentation (Check with recovery test.)
 Contamination : Purified water, reagent (e.g., acid), container,
environment. (Check with blank operation.)
 Ensure that the solution to be analyzed is stable for a long time
(i.e., no hydrolysis or sedimentation).
 Consider the interference effect of the reagent on the analysis
values.
 Types of Pretreatment
 Dilution
Dilute the sample with purified water, dilute acid, or organic solvents.
Examples: food products (e.g., dairy products), pharmaceuticals, and
biological samples (e.g., blood, urine).
 Dry Decomposition
– Heat the sample to a high temperature (400 to 500C), Decomposition is possible
in a short time (a few hours) and operation is simple.
– Elements with low boiling points (e.g., Hg, As, Se, Te, and Sb) will vaporize
 Wet Decomposition
– Heat the sample together with acid to a low temperature (approx. 300C).
Suitable for volatile elements.
– A long time is required for the decomposition of organic substances.
 Microwave Decomposition
– Decompose the sample at high pressure by heating it together with acid to a
temperature in the range 100 to 200C in a sealed Teflon container.
– The decomposition process is sealed; there is little vaporization of elements with
low boiling points; the decomposition time is short; there is little contamination
from the operating environment and the reagent; and only a small amount of acid
is required.
– Examples: Sediment, soil, dust, ceramics, living organisms, food products, etc.
Wet Decomposition Method

Kjeldahl flask wet decomposition method

Waste
gas
Cooling
tube

Nitric
acid

Simple method
(no cooling)

Sample+
Sulfuric acid
Heating
 Pretreatment
Microwave Decomposition
 Decompose the sample together with an acid in a sealed container.
 Decomposition possible in a short time with little vaporization or
contamination.
- Ideal for the pretreatment of trace elements and trace samples.
- Food products, living organisms, pharmaceuticals, airborne dust, soil, etc.

High-pressure Decomposition Container

Microwave Digestion
 Sample Preparation using Pressure Digestion
with Microwave heating

Digestion Vessels 1 - 12
Microwave
power Pressure
measurement

Temperature
measurement

Control by internal PC or
Tmax and Pmax Controller

Real-Time Display
 Pretreatment
Solubility of Elements in Samples
Total Content

Simple
Organic Inorganic compounds
water-soluble Simple soluble metals
compounds with low solubility
ions & compounds
Sulfides, oxides,
Carbonates, oxides, etc.
silicates, etc.

Pretreatment Methods
Dilution, Elution Wet Decomposition
Dry/Wet Decomposition
Purified water, Hydrochloric acid, Wet/High-pressure
Microwave Decomposition Decomposition
nitric acid, etc.
solvents, etc. Nitric acid, Hydrofluoric acid, nitric acid,
sulfuric acid, etc. etc.
 Example

Application of AAS
EU Regulation for Hazardous Substances
 EU Regulation for Hazardous Substances

IEC Recommendation for RoHS

RoHS : Restriction of Hazardous Substance in Electrical and Electronic equipment.

Substances Polymers Metals Electronics

PBB/PBDE : GC-MS NA GC-MS

1000 ppm
Cr6+ : 1000 ppm Colorimetric Method Spot-test Colorimetric Method
(Spectrophotometer) procedure/boiling=water- (Spectrophotometer)
Extraction procedure
(Clause8)
Hg : 1000 ppm Cold Vapor-AAS, ICP

Pb : 1000 ppm AAS, ICP AAS, ICP AAS, ICP

Cd : 100 ppm
 Preparation of circuit boards

Pre-Cutting with the

Heavy Duty Cutting Mill
, bottom sieve 6 mm

Heavy Duty Cutting Mill SM 2000

after a grinding time of 2 min.

endfineness 90 % < 125 µm

Vibratory Disc Mill RS 100

 Sample Preparation

Target Pretreatment Methods

Element Polymer Metals Electronics

Hg Microwave digestion (HNO3+ HBF4+ H2O2)

a) Common method
(HCl : HNO3 : water ; 2 : 1 : 2) Microwave digestion Step
Cd Microwave digestion
b) If containing Zr, Hf, Ti, Ta, Nb, W A (HNO3+HBF4+H2O2)
(HNO3+H2O2)
(HNO3 : HF ; 1 : 3) Microwave digestion Step B
Pb (If contain ing Si, Ti add HF)
c) If containing Sn (add HCl)
(HCl :HNO3 ; 3 : 1)
Pretreatment method, which follow by IEC 62321
 Analyzing Cadmium (Cd) in Rice
Pretreatment Using Wet Decomposition
Level suggested by FAO/WHO Codex Committee ; 0.2 ppm max. in polished rice (proposed)

Put 5 g of the sample in a beaker.

Add 30 mL of nitric acid (1+1) and 0.5 mL of sulfuric acid.
Warm on a hot plate until the violent reaction subsides.
↓
Perform thermal decomposition until the contents approach a
hardened and dried state.
When the contents turn dark brown, add 1 mL of nitric acid. Repeat this process.
When the contents turn light yellow or become transparent, expel the white
smoke of the sulfuric acid and leave to cool.
Add nitric acid.
Heat on the hot plate to dissolve the salt content.
Leave to cool.
Dilute for measurement.
 Results of Quantitative
Analysis of Cd in Rice
The following 2 methods can be used to analyze unpolished and polished rice decomposed
using acid:

Flame method Furnace method

Polished rice:
0.118 ppm

0.1 ppm
0.5 ppm

Polished rice : Unpolished rice:

0.118 ppm 0.070 ppm

Unpolished rice :
0.073 ppm
Injected amount: 10 µL
Air-C2H2 Interference inhibitor: Pd 50ppm 5 µL
Ashing: 400C; Atomization: 1,800C
 Summary of Methods for Analyzing Cd in
Rice

Comparison of Pretreatment Methods

Wet oxidation: 3 to 5 hours; Dry ashing: 5 to 10 hours;
Microwave: 1 hour; Acid extraction: 2 hours

Expected Lower Limits for Quantitative Measurement

Flame method : 0.100 ppm
Furnace method : 0.001 ppm

Comparison of Measurement Times for Each Measurement

Method (n=3)
Flame method : 30 s

Furnace method : 360 s

Atomic Spectroscopy for Metal Analysis
Practical Tips to Sampling

Erroneous Data and Methods of Compensation

• Simple solutions (e.g. water) use standard curve technique to find unknown concentration

• Complex solutions (matrix) require method of standard additions

– Add small volumes higher concentration standards (change in volume is considered
negligible)
– Graph of concentration vs. absorbance
– Concentration of sample is x-intercept
– Overcomes problem of matrix effects
 Question

A series of solutions is made up by adding 0.1, 0.2, 0.3, 0.4 and 0.5 mL of a
10 mg L-1 lead standard to 100 mL aliquots of the unknown solution. The following results
were obtained:

Volume std. (mL) 0 0.1 0.2 0.3 0.4 0.5

Abs 0.27 0.37 0.53 0.65 0.75 0.88

Plot a calibration graph and determine the concentration of the unknown

Assuming constant volume of 100 mL, the concentration increase in the 5
solutions are 10, 20, 30, 40, and 50 μg L-1.
(e.g. 0.5 mL of 10 mg/L = 5 x 10-3 mg in 100 mL = 5 μg/0.1 L = 50 μg L-1)
Absorbance = (0.01235 x conc) + 0.2694
Unknown = 21.8 g μL-1 lead
Quantification
 References
• Csuros, M. and Csuros, C. (2002) Environmental Sampling and Analysis for Metals. CRC press, Boca
Raton, Fl.
• Tatro, M.E. (2000) Optical Emission Inductively Coupled Plasma in Environmental Analysis.
Encyclopedia of Analytical Chemistry, Edited by Meyers, R.A. John Wiley & Sons, West Sussex, UK.
 Questions
1. Explain: (a) The difference in the electronic configuration among various species of calcium, that is, Ca
in CaCl2, Ca0, Ca0*, and Ca2+; (b) of these species, which one(s) are desired for AAS measurement of Ca
and which one(s) are unwanted species that may cause interference for AES measurement of Ca?

2. For the following atomic absorption spectrometers – FAA and ICP-OES: (a) Sketch the schematic
diagram; (b) Describe the principles (functions) of major components.

15. Explain why NH4NO3 is added to seawater when Pb and Ca are analyzed by FGAA. (hint: removes
interference due to high salinity – show chemistry)

23. A groundwater sample is analyzed for its K by FAA using the method of standard additions. Two 500
µL aliquots of this groundwater sample are added to 10.0 mL DI water. To one portion, 10.0 µL of 10 mM
KCl is added. The net emission signals in arbitrary units are 20.2 and 75.1. What is the concentration of K
in this groundwater in mg/L? (hint: use example 9.2)

24. A 5-point calibration curve was made for the determination of Pb via FAAS. The regression equation
was: y = 0.155x + 0.0016, where y is the signal output as absorbance, and x is the Pb concentration in
mg/L.
(a) A contaminated groundwater sample was collected, diluted from 10 to 50 mL, and analyzed without
digestion. The absorbance reading was 0.203 for the sample. Calculate the concentration of Pb in this
groundwater sample.
 Questions
23. A groundwater sample is analyzed for its K by FAA using the method of standard additions.
Two 500 µL aliquots of this groundwater sample are added to 10.0 mL DI water. To one portion,
10.0 µL of 10 mM KCl is added. The net emission signals in arbitrary units are 20.2 and 75.1. What
is the concentration of K in this groundwater in mg/L? (hint: use example 9.2)

Assume x millimols (mmols) of K in 500 µL sample

Total mmols K in spiked sample = x + 10 mmol/L x 10µL x 1 L / 106 µL

= x + 1 x 10-4 mmols

Using ratio technique:

x/20.2 = (x + 1 x 10-4 mmols) / 75.1
Solve for x, x = 3.89 x 10-5 mmols in 500 µL aliquot

x = 3.89 x 10-5 mmols / 500 x 10-6 L x 1 mol/1000 mmols = 7.78 x 10-5 mols/L

7.78 x 10-5 mols/L x 39.10 g/mol x 1000 mg/g = 3.04 mg/L = 3.04 ppm