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ABSTRACT
Atomic absorption spectroscopy (AAS) has emerged as a powerful analytical technique in estimating various atoms by the measurement of light energy of
specific wavelength. This employs usually three different analytical techniques such as atomic emission, atomic absorption and atomic fluorescence. The
AAS can measure even trace concentrations of various elements with higher degree of sensitivity and precision. Therefore, AAS possesses considerable
position in the modern analytical laboratories. The present review highlights the various components of atomic absorption spectrophotometer, different
types of AAS and applications of atomic absorption spectroscopy in various fields such as pharmaceuticals, food, biological, geological, metallurgical,
environmental, forensic and marine applications.
Key words: Atomic absorption spectroscopy, flame atomic absorption spectroscopy, flameless method of atomic absorption, applications.
INTRODUCTION
Atomic absorption spectroscopy measures the absorption of specific wave- over F-AAS is that F-AAS can analyze solutions only whereas GF-AAS can
length of radiation by neutral atoms which are present in the ground state and analyze solutions, slurries and solid samples[3].
gets excited. The chemical compounds are dissociated into free atoms re-
quired for the atomic absorption measurement are produced by supplying Hydride generation atomic absorption spectroscopy (HG-AAS)
enough thermal energy. Hollow cathode lamp helps in the generation of By the addition of the sodium borohydride to the sample solution produces
specific wavelength of radiation. The solution of the sample aspirated into the gaseous hydrides of the elements which are swept by an argon purge into
the flame aligned in the light beam serves the purpose of atomic absorption a heated quartz cell. As, Sb, Sn, Se, Bi, Te are the elements that are normally
spectroscopy[1]. analyzed by this technique.
Types of atomic absorption spectroscopy Cold vapor mercury atomic absorption spectroscopy (CV-AAS)
Atomic absorption spectroscopy shall be broadly classified as flame and In this method, stannous chloride is involved in the chemical reaction which
flameless methods. produces mercury atoms by chemical reduction. The volatile mercury atoms
are driven from the solution by bubbling air into the solution which is then
a) Flame atomic absorption spectroscopy (FAAS) carried by the air into an absorption cell aligned in the optical path. This
In this method, the basic principle is the measurement of the absorption of method of mercury determination is the best available technique for the
the monochromatic light by the atomic cloud i.e., neutral atoms of the analyte. determination of mercury with high sensitivity in the samples of a complex
The method of flame AAS shows advantages like rapid, simple, easily avail- nature.
able standard procedures for the determination of all metals, free from inter-
ferences and known interferences if any shall also be easily overcome and Applications of Atomic absorption spectroscopy
highly sensitive[2]. AAS was found to have a wide range of applications in the various important
areas which include;
b) Flameless method of atomic absorption
Flameless method increases the sensitivity for the low concentrations of the a.Pharmaceutical applications
analyte. Flameless technique includes; As per United States Federal Food And Drug Administration (USFDA), the
pharmaceutical products/compounds need to be completely characterized.
Graphite furnace atomic absorption spectroscopy (GF-AAS) The metals were found in all phases of the drug development process, from
The passage of high electrical current through the graphite tube in which the drug synthesis to quality control (QC), metals are used in the synthesis of
sample to be determined is placed provides the required energy for atomiza- drug substances, as an excipients in tablets, capsules, liquids and metal based
tion. This technique has more sensitivity and can be used for the determina- products are used as imaging agents and the equipment used in the manufac-
tion of analytes with concentrations 1000 times lower than that which can be turing of drug substances or compounds can be a source for the trace metals.
detected by flame atomic absorption method. The advantage of GF-AAS Various atomic absorption based techniques like AAS are often used to help
for fully characterization of the pharmaceutical products[4]. Atomic spec-
*Corresponding author. trometry enables the determination of drugs with higher sensitivity and accu-
Dedeepya Sudunagunta racy. The method is free from interference by excipients present in the drug
Department of Pharmaceutical Analysis, formulations[5].
JSS College of Pharmacy
(A Constituent College of JSS University, Mysore), A wide variety of metals and metalloids are used in the manufacture of
Rocklands, Ooty – 643 001. Tamil Nadu,India. pharmaceuticals and some are also used as the active pharmaceutical ingredi-
Sample solution
Read out device
Fig 1. Components of Atomic Absorption Spectrophotometer (AAS)
ent (API) in drug products. Palladium, platinum are commonly used cata- The micro determination of pilocarpine alkaloid can be done by AAS which
lysts in the pharmaceutical industry. Because of the potential routes of entry depends on the measurement of mercuric content of pilocarpine complex [15].
for metals and metalloids into pharmaceutical products, the pharmaceutical For the determination of ethylenediaminetetraacetic acid (EDTA) in certain
industry is interested in monitoring elements at all stages of the development dosage forms flame atomic absorption spectroscopy coupled with ion ex-
process. Element analysis using atomic spectroscopy covers not only the change technique is the adopted method [16].
API, but also cleaning validations and fingerprinting of drugs. A variety of
pharmaceuticals have been examined for many elements, such as lead (Pb), b.Food applications
Cadmium (Cd) in commercial pediatric syrups and magnesium (Mg) distri- The accumulation of heavy metals by the marine organisms is considered to
bution in tablets. AAS based techniques have also been used to provide be the most important form of pollution of the aquatic environment, the use
indirect determinations of pharmaceuticals such as ciprofloxacin, amoxicillin of tin for studying in canning is also toxic. Mercury, arsenic, cadmium and
and diclofenac sodium. Quantification of tin in an antihelminthic powder: lead can be tolerated at extremely low concentrations, they are toxic to
Organic tin compounds such as dibutyl-n-tindilaurate in antihelminthic powder humans. In canned tuna fish mercury and arsenic levels can be determined by
which is treated for worm infestations in animals. Determination of lithium hydride generation atomic absorption spectrophotometry. Cadmium, lead
in antidepressives by flame AAS, Palladium in synthetic drugs can be done levels can be determined by graphite tube atomic absorption spectropho-
by graphite tube or furnace AAS.The material used in the dental medicine is tometry, tin levels can be determined by FAAS [17].
analyzed for the determination of zirconium by AAS[6].
The determination of the geographical origin of various food products can be
HG-AAS can be used for the determination of arsenic in the commercial enabled by the inorganic elemental analysis by AAS and often combined with
samples of injectable drugs containing high concentrations of Sb (V) based on chemometrics [18]. The elemental analysis in fish and mussel samples can be
the principle of the complexion effect for Sb of citric, oxalic and acetic acids done by using flame AAS and GF-AAS [19]. AAS was helpful in the determi-
as reaction media after the predigestion of the sample [7]. The amount of nation of lead in wines [20].The toxic metals present in Shitake mushrooms
vanadate (V) bound to human serum albumin (HSA) in infusion solutions can (Lentinus edodes) can be estimated by using AAS after the microwave diges-
be determined using ET-AAS [8]. tion using oxidizing agents such as HNO3, H2SO4, H2O2[21].
The indirect AAS determination of active components in pharmaceutical The trace elements and the toxic elements in the samples of apricots can be
preparations can be achieved by continuous liquid liquid extractor coupled determined by flame and graphite furnace atomic absorption spectrometry
on line to an atomic absorption spectrometer with substantially higher sen- after microwave assisted acid digestion [22]. Flame AAS is an analytical method
sitivity [9]. The low concentration of promazine can be determined indirectly applied for the determination of calcium, potassium, magnesium, sodium,
by the reaction of Reinecke salt with promazine which forms a reddish ion- copper, iron, zinc in the honey samples [23]. The method of GF-AAS is
association compound [10]. Flouroquinolone antibacterials like gatifloxacin, helpful in the determination of the metals at very low levels in the samples of
moxifloxacin and sparfloxacin can be estimated accurately by AAS by the tomato, pepper and in onion [24].
reaction of ammonium Reinecke to form stable precipitate of ion pair com-
plexes [11]. An indirect method based on the complexation of captopril with As infants are particularly sensitive to the toxic effects of lead, the lead
an excess of Pb(II) ion was used for the determination of captopril in phar- present in their main food i.e., milk (from human) need to be estimated for the
maceutical preparation by AAS. The produced complex can be aspirated on presence of lead. The lead present in the human milk can be estimated by
the AAS after resoluting on the cationic exchange resin [12]. electrothermal atomic absorption spectrometry [25]. Since As, Cu, Pb and
their compounds are toxic to the humans, these metals are need to be esti-
AAS can be used for the study of the presence of various proportions of mated in a distilled spirit which is produced by the fermentation of sugar
important metals along with the varied concentration of ion in the ayurvedic cane. The determination can be done by GF-AAS [26].
preparations of the metallic ions [13].
c.Biological applications
Use of the coordination complexes of platinum (II) such as cis-dichlorodiamine AAS is a powerful, mature analytical tool with which meaningful measure-
platinum as chemotherapeutic drug can induce toxic effects. The platinum ments can be done for a number of important elements in biological speci-
containing compounds can be monitored with rapid, sensitive and precise mens. Lead present in blood can be determined by GF-AAS [27]. Atomic
method like graphite furnace atomic absorption spectroscopy [14].
The intake of mercury from the diet, amalgam restorations are the two main Flame atomic absorption spectrophotometry provides a simple, rapid and
sources for the mercury in the human beings. The most often used method cost effective pre concentration method for the determination of traces of
for the determination of mercury in blood, saliva and urine was the cold gold, silver, palladium in geological samples [43].The rocks are known to con-
vapor atomic absorption spectrometry [29].Cadmium, an environmental pol- tain small amounts of platinum metals. Due to the presence of low concen-
lutant which has been linked to hypertension, atherosclerosis and congenital trations, determination of platinum in geological samples presents certain
defects can be determined in whole blood and urine by Zeeman effect flameless difficulties. The geochemical study of the platinum content in the rocks can
atomic absorption spectroscopy [30]. Flameless atomic absorption spectros- be possible by means of atomic absorption spectroscopy [44]. The trace
copy is the method of choice for the determination of aluminium in uremic determination of antimony in rocks and soils can be done by atomic absorp-
serum [31]. The magnesium content of the blood serum can be accurately tion spectrometry by extracting antimony using 6M HCl into MIBK (me-
determined by atomic absorption spectroscopy in the air acetylene flame on thyl isobutyl ketone) [45].
the solutions prepared by direct dilution of the serum with EDTA (10,000
ppm) or strontium chloride (2500 ppm) [32], the interference due to phos- Noble metals such as gold distributed in the rocks can be determined by
phate can be overcome by the addition of an oxine [33]. atomic absorption spectrometry after the extraction into aqua regia [46]. Soils
are considered as the sinks for trace elements. Mercury is shown to be
In the nephritic syndrome, primary biliary cirrhosis, there is an increase in present in high levels in agricultural soils as a consequence of the widespread
the urinary excretion of copper. Flame AAS offers the advantage of greater use of fungicides, fertilizers, seed disinfectants. GF-AAS is a more favorable
specificity and simplicity for the accurate determination of the low levels of technique for the determination [47].
copper in urine [34]. Copper in erythrocytes can be estimated by flameless
AAS [35]. Copper plays a prominent role in the growth and development of The determination of cadmium in geological materials can be done by flame
eukaryotic cells, with those cells exposed to an oxygen containing environ- AAS [48]. Atomic absorption spectrometry with electrothermal atomization
ment being particularly susceptible. Respiration, as well as the control of can be used for the determination of bismuth even in the low concentrations
transiently formed reactive byproducts of oxygen consuming processes is in the samples of geological materials [49].
highly dependent on the body’s copper content. To calculate the amount of
copper complex accompanying the sedimented liposomes, copper in the Due to the pollution, a wide variety of chemicals have been detected in soil,
mixture before and in the supernatant after ultra centrifugation can be deter- water, air there is a chance of metallic presence in the soils. The metal
mined by atomic absorption spectrometry [36]. concentrations can be analyzed by flame AAS after acid digestion [50]. Heavy
metals in soil samples can be determined by highly sensitive method such as
Metal containing compounds (e.g., organomercurials or aluminium hydrox- AAS [51]. Tin present in trace amounts in rocks, soils, and stream sediments
ide) are used as preservatives or adjuvants and are used in the process of can be determined by AAS in air acetylene flame or in nitrous oxide acetylene
purification of the biological products. Flameless methods of AAS can be flame [52].
used for the estimation of metals like aluminium, arsenic, barium, cadmium,
cobalt, chromium, mercury, lead, selenium, thallium and zinc in the biological The concentrations of heavy metals in the soils provides higher concentra-
products [37]. Gallium can also be estimated in urine, serum and tissues by the tion of metals in plants and consequently in animal and human bodies. GFAAS
usage of flameless atomic absorption spectrophotometry. The interference estimates the concentrations of lead, zinc, cadmium, copper, iron, calcium
caused by calcium chloride (CaCl2) can be prevented completely by using the and magnesium in these matrices [53]. Arsenic (As) concentrations present in
chelating agent EDTA [38]. the soils and sediments are dependent on the geological conditions and based
on the usage of pesticides etc. FAAS provides an analytical method for the
To determine the nutritional status and possible toxic levels of selenium, determination of total As concentrations [54].
study of selenium in biological samples like serum, plasma, whole blood
sensitive techniques like atomic absorption spectrometry with electro ther- e.Metallurgical applications
mal atomization (ET-AAS) which allows the direct selenium determination Analysis of metals or special strategic materials is needed in engineering,
with minimum sample treatment can be used [39]. science, biology or medicine to study the effect of the role of specific metallic
impurities introduced deliberately through manufacturing process. Atomic
To understand the therapeutic effectiveness or lack of effectiveness of gold absorption spectrometric techniques have emerged as the workhorse of any
for the treatment of rheumatoid arthritis, it is important to determine its sites modem analytical laboratory. The high sensitivity, specificity and wide work-
of action. The tissue distribution of gold can be determined by AAS which ing range have made these methods very useful for rapid analysis of solution
permits the small amount of determination of elements in complex matrices samples [55].
such as biological samples [40].
Flame AAS is a method which is applicable to the determination of the
AAS method gives high specificity, rapid and simple procedure with high metals like aluminium, antimony, arsenic, barium, beryllium, boron, cad-
precision and accuracy even at low concentrations in the determination of mium, calcium, chromium, cobalt, copper, iron, lead, manganese, magnesium,
chromium as chromate (Cr2O7) in organic substances such as faecal samples. molybdenum, nickel, potassium, seleniuim, silicon, sodium, strontium, tin,
As Cr2O7 is used as non toxic, non absorbed, marker substance to estimate vanadium and zinc [56].
forage intake in grazing ruminants [41].
The trace metals (Mn, Fe, Co) in the copper can be determined simulta-
The determination of aluminium by atomic absorption spectroscopy can be AAS provides a method for the determination of manganese, iron, cobalt, and
done by using either oxy acetylene or oxy hydrogen flames fed with an nickel in air and water [80]. In natural water GF-AAS with SPE technology
organic aerosol containing an aluminium complex [60]. The usage of nitrous provides inorganic speciation of As (III,V), Se (III,V) [81].
oxide acetylene flame for atomic absorption spectroscopy provides the sen-
sitive determination of beryllium, aluminium, silicon, titanium, vanadium AAS provides a better option for the qualitative analysis of water samples
and tungsten [61]. Determination of sodium by AAS provides high degree of [82]
. Exhaust gases from vehicles were filtered through cellulose filter papers
freedom from interference [62]. using catalytic converters to collect suspended particles. The filter papers
after acid digestion bring solid material into solution. The analysis for the
Among the metal ions present in water sodium, potassium, calcium and palladium, platinum and rhodium can be done by GF-AAS [83].
magnesium are determined by AAS. Elements such as tin, lead, arsenic,
selenium can be determined by hydride generation AAS after conversion into g.Forensic applications
their hydrides in HCl medium by treatment with sodium borohydride [63]. For criminalistic purposes, quantitative elemental composition of oils is
The analysis of iron in ferrous and nonferrous alloys, rocks, minerals, water, used for the differentiation between various oil samples [84]. Application of
effluents, blood and agricultural materials can be done by AAS [64]. AAS to detect multimetal traces in injured skin is a promising tool for inves-
tigation of fatalities caused by electrocution [85].
High absolute sensitivity, small sample requirement gives more attractive-
ness for the usage of flameless AAS for the determination of selenium [65]. The h.Marine applications
detection limits for the trace metals has been considerably low by flameless In marine environment, silver is recognized as a toxic element. The concentra-
AAS which can be done with very small samples [66]. AAS provides conve- tions of silver in sea water can be determined most sensitively by ET-AAS
nient, rapid, suitable method for the determination of palladium [67].The sen- [86]
. The presence of metals such as copper, zinc and nickel in the sea water
sitivity obtained for the determination of silver by AAS is as high as that of will be in very small concentrations. AAS is used for the determination of
any other alternative methods of determination[68]. metal concentrations in water from oceans [87]. AAS method can be applied
for the determination of copper, iron, lead, nickel, cadmium in sea water
The metallic elements like vanadium, nickel, iron, magnesium and sodium samples [88].
present in highly stable crude oil water emulsion can be determined by AAS
after dry ashing procedure for sample [69]. Aluminium concentrations present CONCLUSION
in the drinking water, fruit juices and soft drinks can be determined by GF- Atomic absorption spectroscopy is an important analytical technique that
AAS [70]. estimates the trace amount of metals in a faster way, more sensitive and
reliable tool in the determination of metallic elements from the biological,
The lead content of gasoline has an important modifying effect upon the environmental, pharmaceutical, food, geological and marine samples with
octane value of gasoline. AAS is used for the determination of lead in gasoline high accuracy and sensitivity. Due to its wider applications in various
which is carried out with great frequency by petroleum refining industry [71]. important fields, it serves as an essential analytical technique in various
analytical laboratories. As it is much helpful in tracing the metallic sub-
AAS is applied for the determination of traces of metals in petroleum derived stances which may be likely to be present in the pharmaceutical com-
hydrocarbons which is aided by the enhanced sensitivity [72]. Micromolar and pounds, that may be toxic in nature, it plays an essential role in the analysis
nanomolar vanadium levels can be measured by GF-AAS [73]. Magnesium in of pharmaceutical compounds as well.
silicate rocks can be determined by AAS using nitrous oxide acetylene flame
[74]
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