Atomic Spectroscopy

lecture 4
 Matrix Modifiers in ETAAS
• Matrix modifier- is a substance added to the sample to
reduce the loss of the analyte during the ashing/charring
step by making the matrix more volatile or the analyte
less volatile
 For example, the matrix modifier Ammonium nitrate, can
be added to seawater(sample) to reduce interference by
NaCl during the analysis of Manganese (Mn)
 Without a matrix modifier, signals (a strong absorption
peak) due to scattering of light caused by smoke are
observed at the analytical wavelength of Mn
 The smoke is created by heating NaCl and thus interferes
with the measurement of Mn
 Adding Ammonium nitrate (NH4NO3) to the sample
greatly reduces matrix absorption peaks
 NH4NO3 + NaCl NaNO3 + NH4Cl
 NH4Cl and NaNO3 cleanly evaporate instead of
making smoke

Another example involves the matrix modifier

Mg(NO3 )2 which raises the temperature of for
atomization of Al analyte
 At high temperature, Mg(NO3 )2 decomposes to
MgO
 Al in a sample is converted to Al2O3 during heating
 At high temp, Al2O3 decomposes to Al and O, and
then Al evaporates
 However, evaporation of Al is retarded as long as
MgO(g) is present, by virtue of the reaction
 MgO(g) + 2Al(s) ) Mg(g) + Al2O3(s)
 when MgO has evaporated, the above reaction no
longer occurs and Al2O3(s) finally decomposes and
evaporates
 A matrix modifier that raises the boiling
temperature of analyte allows a higher temperature
to be used to remove more matrix without losing
analyte
 Background correction
• Background signal arises from absorption, emission,
or scatter by the sample matrix, flame, plasma or
furnace.
• Background correction is necessary to distinguish
analyte signal from absorption, emission and optical
scattering of the sample matrix, the flame, plasma
or a white-hot furnace
 Beam chopping or electrical modulation

 Beam chopping or electrical modulation (pulsing it on

and off) is used to distinguish the signal of the flame
from the desired atomic line at the same wavelength
 Light from the lamp (HCL) is periodically blocked by a
rotating chopper
 Signal reaching the detector while the beam is blocked
must be from flame emission
 Signal reaching the detector when the beam is not
blocked is from the lamp and the flame
 The difference between these two signals is the desired
 NB: Beam chopping corrects for flame emission but
not for light scattering
 Modern spectrophotometers provide for correction
due to scattering and background absorption
 Deuterium lamps and Zeeman correction systems
are most common
 Deuterium lamp background correction
 Broad emission radiation from a D2 lamp is passed through
the flame/furnace in alternation with that from HCL
(Hollow cathode lamp)
 The monochromator bandwidth is so wide that a negligible
fraction of D2 radiation is absorbed by the analytical line
 Light from HCL is absorbed by the analyte and it is
absorbed and scattered by background
 Light from D2 is absorbed and scattered only by
background
 The difference between absorbance measured with HCL and
that measured with D2 lamp is the analyte absorbance
 Zeeman background correction
 Zeeman effect – refers to the shifting of energy levels of
atoms amd molecules in a magnetic field
 When the magnetic field is applied parallel to the optical
path/light path through a flame/furnace, the analytical
line (absorption line) is split into three (3) components
 Two are shifted to slightly lower and higher wavelengths
and one component is unshifted ( background)
 Hence, a strong magnetic field is pulsed on and off
 Sample and background are observed when the field is
off
 Background alone is observed when the field is on
 Interferences (AAS & ETAAS)

Interference- any effect that changes the signal while

analyte concentration remains unchanged

Types of interferences

Spectral interference: refers to the overlap of analyte

signals with signals due to other elements or molecules
in the sample or with signals due to the flame or furnace
 Interference from the flame/furnace can be subtracted
using D2 or Zeeman background correction
 Overlap between analytical lines of elements- choose
another wavelength for analysis
 For example, vanadium line at 3082.11 Å interferes
in Al determination on its absorption line at 3082.15
Å
 Interference avoided by Al line at 3092.7 Å instead
 High resolution spectrometers eliminate
interference from other elements by resolving
closely spaced lines
 Molecular broad band spectrum leads to
interference at many wavelengths
 Hence, a different oxidant (in FAAS)should be used
to decompose the interfering species
 E.g; Interference of Ca(OH)2 in the determination of
Ba using acetylene/air flame, could use
acetylene/nitrous oxide (hotter flame)
 Molecular spectral interferences that lead to
scattering of radiation are usually due to oxides of
Ti, Zr, W (Refractory compouds)

 N.B. Most interferences in FAAS, are corrected by

change in temperature or fuel/oxidant ration
 Chemical interferences
 It is caused by any component of the sample that
decreases the extent of atomization of the analyte
i. Formation of Compounds with Low Volatility:
 Anions forming low volatility compounds with analyte,
hence reducing rate at which analyte is atomized
 E.g. SO42- and PO43- hinders the atomization of Ca2+ by
forming nonvolatile salts (low volatility compounds)
 Aluminium (Al) lowers results in determination of
Magnesium (Mg) by formation of heat stable Al/Mg
compound
 These could be eliminated by the use of higher
temperatures, or releasing agent (these are cations
that react preferably with interferent and prevent it
from reacting with analyte)
 Releasing agents; e.g Strontium ion or lanthanum
ion,La3+ reduces interferences due to phosphate
ion (PO43- ) in determination of Ca (La3+
preferentially reacts with PO43- )
 Also Strontium and Lanthanum ions are used to
reduce effects of Al during Mg determination
 Protective Agents: prevent interference by forming
stable but volatile compounds with analyte;
 Three (3) common protective reagents; EDTA, 8 –
hydroxyquinoline, APDC
 EDTA has been used to reduce the effects of
Phosphate ion, silicon, aluminum and sulfate ion in
the determination of Ca

ii) Ionization interference;

 Ionization of analyte is usually a problem in the
analysis of alkali metals at relatively low
temperature (lowest ionization potentials) and in
the analysis of other elements at higher
temperatures
 For any metallic element M, we can write a gas a
gas-phase ionization reaction
 M(g) M+ M+ + e-
 Ionization suppressor: is an element added to a
sample to decrease the extent of ionization of the
analyte
 For example, in the analysis of potassium, a 1000
ppm CsCl is added to the sample, because cesium is
more easily ionized than potassium
 By producing a high concentration of electrons in
the flame, ionization of cesium suppresses that of
potassium
 Atomic AS
Sample Preparation;
Conventional samples should be in solution form. Acids are used for
the dissolution of a lot of matrices.
external standard/ normal /Standard calibration method;
 Most common; at least three standards (Known
concentrations of the analyte should be prepared)
 Measure absorbance of the standards and draw a calibration curve
 Title of graph should include among other such information as ;
sample analyzed, source of sample, analyte determined, technique
used, some instrumental conditions, etc.
Standard Addition Method;
Useful
i). where the sample matrix varies significantly with that of standards
ii). Limited amount of sample
 Atomic AS
Standard Addition Method;
 Hydride Generation AAS
Hydride Generation Atomization
 Due to interferences, poor reproducibility, and poor detection
limits ( when using AAS & ETAA) an alternative method for some
elements--mostly metalloids--has been developed
 Hydride generation atomic absorption spectroscopy (HGAAS) is
available via an option for many modern AAS instruments
 It "only" requires the hydride generation module
 Used for Metalloids: Antimony, Arsenic, Selenium and Tellerium

Hydride Generation System:

 Many of main parts of HGAAS system are identical to AAS: a
hollow cathode lamp, air/acetylene flame, and optical system but
include (in most systems) an optical cell
 The nebulizer required in AAS is not used in HGAAS.
 HGAAS is a continuous flow system
 Hydride Generation AAS
Functions of HGAAS parts
Hollow cathode lamp
 Provide the analytical light line for the element of interest
 Provide a constant yet intense beam of that analytical line
Hydride generation system
 Suck up (aspirate) liquid sample at a controlled rate
 Mix liquid sample with sodium borohydride and Hydrochloric acid
 Create a volatile hydride of the analyte metalloid from that reaction
 Flow that gaseous hydride into the optical cell
Optical cell and flame
 Decompose the hydride form of the metalloid from the hydride
generation module
Thereby create atoms (the elemental form) of the element of interest

Se0, Sb0, Te0, etc.

 Hydride Generation AAS

Monochromator
 Isolate analytical lines' photons passing through optical cell
 Remove scattered light of other wavelengths from optical cell
in doing this, only a narrow spectral line impinges on PMT.

Photomultiplier tube (PMT)

 As the detector, the PMT determines the intensity of photons of the
analytical line exiting the monochromator
Hydride Generation AAS System
Hydride Generation AAS - A Complete Diagram
 Hydride Generation AAS
Acidic and Oxidation State of Samples and Standards Content
• In HGAAS, acid contents of samples and standards of 10% to 50%
are common; this is much much higher than in normal AAS.
• The oxidation state of the analyte metalloid is important in
HGAAS. For instance, HGAAS analysis of selenium requires the
Se(IV) oxidation state (selenite). Se(VI), the more highly oxidized
state of the element (selenate), responds erratically and non
reproducibly in the system. Therefore, all selenium in Se
calibration standards and Se containing samples must be in the
Se(IV) form for analysis. This can be accomplished by oxidizing all
Se in the sample to selenate using a strong oxidizer such as nitric
acid or hydrogen peroxide (decomposing the excess oxidant) and
then reducing the contained selenate to selenite with boiling HCl.
After that reduction step, the final acid content is made up to the
required content before the sample is introduced into the hydride
generation module. The literature also suggests that the time from
reduction to introduction into the hydride module is important:
Shorter is best.
 HGAAS - System
• Also important is the concentration of sodium borohydride
and hydrochloric acid reagents feed into the hydride
generation reaction vessel: optimization of this is important
and may be different for different elements. Example
concentrations are 0.35% NaBH4 and 50% HCl. Note that this
acid content is not necessarily identical with the acid content
of the samples and standards themselves. The reagent acid's
content is aimed at producing a reproducible amount of
hydride in the module.
 Hydride Generation AAS

Optical Cell and Flame

Fused silica glass tube (transparent to UV vis wavelengths) and
thermally stable
Usually on top of Flame with Air/acetylene
Summary:
 Oxidation state of metalloid very crucial
 Time from reagent mixing and when hydride is separated from
liquid and sent to optical cell is important
 Concentration of sodium borohydride and hydrochloric acid
reagents fed into hydride generation vessel is important
 Only volatile hydride reaches the optical cell
 Only decomposed hydride produces elemental form