Journal of Applied Geochemistry

Vol. 19, No.2 (2017). pp. 145-163

ANALYTICAL METHOD DEVELOPMENT FOR MAJOR, MINOR AND TRACE

ELEMENTS IN GEOCHEMICAL AND HYDROGEOCHEMICAL SAMPLES
P .K .Tarafder
Chemical Laboratory, Atomic Minerals Directorate for Exploration and Research, Department of Atomic Energy,
Khasmahal, Jamshedpur
E-mail:pktarafder1954@gmail.com

Abstract
During the last three decades, need based analytical methods for 15 elements of strategic importance, including uranium, thorium,
rare earth elements (REE’s), a host of major, minor and trace elements-some of which being the path finder elements for uranium-
as well as certain anions in hydro geochemical samples have been suitably developed for their accurate determination by analytical
instruments like, UV-Visible Spectrophotometer, Fluorimeter (both laser and conventional), Atomic Absorption Spectrophotometer
(flame as well as non-flame), ICP-AES, etc. Analytical method have also been developed for Fe3+,Fe2+,Ti,Nb,Mn,U,Th, rare earth
elements REE’s (total), Au, V, Mo, Zr, F-, Cl-, NO3- and NO2-, for application to geological samples. The present paper encompasses
a brief account of the methodologies developed in the present and earlier work for the rapid, selective and accurate determination of
major, minor, and trace elements in geological/hydrogeochemical samples of diverse matrices.
Keywords: Analytical method development, Major, Minor, Trace, Rare Earth Elements, Spectrophotometry, AAS, ICP-AES.

1. Introduction In addition to the above, some of the existing

While analysing a host of geological samples,
like rocks, soils, stream sediments, minerals and
hydrogeochemical samples of diverse matrices, over a
period of last 20 to 30 years in our chemical laboratory, it
was often observed that methods proposed in literature
for the determination of many of the major, minor, trace
elements as well as certain anions present in
hydrogeochemical samples, particularly by classical,
spectrophotometric, Atomic Absorption Spectrophotometric
etc, did not respond well when applied to samples having
complex matrices due to elementals interferences.
Interference due to matrix elements particularly in
spectrophotometric methods are serious when directly
applied to the complex matrices of these samples due to
which results obtained are often not accurate. Besides,
some of the age-old methods being followed, are less
sensitive, thereby limiting their application to samples
containing analytes at percentage to ppm levels. Usually
these methods cannot be applied to samples having
analytes at trace to ultra-trace levels (ng/g to pg/g). Such
shortcomings commonly associated with the methods
suggested in literature has enthused the development of
newer, robust, cost-effective sensitive, selective and need
based analytical methods in our laboratory.
methods have also been modified to suit our specific
requirements such as high selectivity, sensitivity,
precision and accuracy of determination. An account of
the endeavors made in the development of suitable and
need based analytical methods are as described below.
2. Method Developed and Modification for
Uranium Determination
2.1 Presentation of differential laser induced fluorimetry
as a reference measurement procedure for determination
of total uranium content in ores and similar matrices
The metrological principle of ‘differential
technique in laser-induced fluorimetric analysis is
discussed and recommended as a reference measurement
procedure for the determination of total uranium content
in ores and similar matrices. The estimated relative
expanded uncertainty values obtained for uranium
content in standard IAEA samples are, S 1, 0.04 g/kg, S 2,
0.06 g/kg, S 3, 0.04 g/kg, and for S 4, 0.10 g/kg, respectively.
These low uncertainty values obtained for uranium
indicate the high metrological quality obtained by using
the differential technique. This reference measurement
procedure improves the quality of an analytical result in
terms of accuracy, high precision, reliability, comparability,
and traceability. Laser-induced fluorimetry is useful for

*Orginally Presented in AGM - 2015

145
 Analytical method development...............hydrogeochemical samples

the analysis of uranium in ores, certification of reference

materials, borehole core assay and other diverse
applications in the nuclear fuel cycle. Differential
technique in spectrophotometry/laser fluorimetry has
inherently a high metrological quality (Rathore et al.,2012).
In principle, laser-induced fluorimetry is an ideal technique
for an accurate determination of uranium by the use of
appropriate fluorescence-enhancing reagents and
methodology depending upon the concentration of
uranium and the sample matrices.
2.2 Extraction of uranium with 2,3-dihydroxynaphthalene
and cetyl
2.2.1 Trimethylammonium bromide and its fluorimetric
determination in silicate rocks
The novel procedure for the extraction of
uranium has shown that UO2 2+ forms a 1:3 anionic complex
with 2,3-dihydroxynaphthalene in the pH range, 4–12. This Fig. 1. The reaction scheme of uranium with 2,3-dihydroxy
anionic complex is best extracted into ethyl acetate at a naphthalene.
pH of 11–12 under the influence of the counter cation,
cetyl trimethylammoniumbromide (Tarafder et al.,2002). 2.3 Application of differential technique in laser induced
This extraction technique has been extended for the fluorimetry: Simple and precise method for the direct
separation of uranium from silicate rock matrices during determination of uranium at percentage levels in
its determination by fluorimetry. Except for Co, Cr,Mn and mineralized rocks
Fe, most of the elements present in silicate rocks do not A simple, rapid, cost-effective, accurate and
interfere during analysis. While the interference by Co precise differential laser-induced fluorimetric method for
and Cr are suppressed by the addition of EDTA, iron is the direct determination of uranium in mineralised rocks
removed as a neutral complex with 2,3-dihydroxy at the percentage level is presented, based on the
naphthalene by prior extraction at a pH of 4–5. Results comparison of fluorescence of the standard with a sample
obtained by the application of the method compare of similar but unknown concentration on the same sample
favourably with those obtained by the conventional weight basis, by the use of H 3PO 4–NH 4H 2PO 4 as a
technique, i.e., extraction of uranium in ethyl acetate in a fluorescence enhancing reagent. The relative standard
10% HNO3 medium under the influence of Al (NO3)3 .9H2O deviation of the method was 0.3–0.5% (n=9) for 0.04 and
as a salting out agent. The extraction system under study 3.4% U 3O8 respectively. The proposed technique is
is capable of separating even ultra-trace amounts of suitable for the determination of uranium in samples
uranium quantitatively from complex matrices often containing >0.01% uranium (Rathore et al.,2001). The
present in rock samples. Besides, the method is simple, method has been evaluated using the geo-standards -SY-
rapid, cost effective and precludes the use of reagents 2 and SY-3, low grade uranium ore-IAEA reference
like nitric acid and aluminum nitrate (salting out agent) samples and core samples of diverse matrices. The results
required in bulk quantities in the conventional system. are in good agreement with published data and those
The reaction scheme is shown in Fig. 1. obtained by conventional fluorimetry and other methods.

146
 P .K .Tarafder
2.4 Guaiacol as a new reagent for the spectrophotometric
determination of uranium
Guiacol, i.e., o-hydroxyanisole, gives a distinct
color reaction with U(VI) suitable for spectrophotometric
determination of the metal. The complex formed in the
reaction has an absorption maximum at 352nm. Optimum
pH for color development ranges from 6.5 to 8.5. The molar
absorptivity and Sandel’s sensitivity of the method were
found to be 3.75x10 3 L./mol/cm and 0.063µg/cm 2 ,
respectively. Many anions and cations do not interfere
upto 100 µg/g level. The method has been made very
specific by selective extraction of U(VI) with TBP from a
mixture of different cations and anions in the presence of
60% NH 4 NO 3 as a salting out agent followed by
developing colour in the non-aqueous phase by adding
guiacol in methanol at a pH of 6.5 to 8.5. An amount as
low as 30µg of uranium (VI) per 10 ml of the solution
could be satisfactorily determined with an RSD of ±2.0%
(Tarafder et al.,1991). The method was applied to rock
samples after U(VI) had been extracted from a sample
solution into 25% TBP in hexane. Results obtained by
the new method compare very well with those of
conventional fluorimetric and radiometric assays. The
features of the method include excellent precision, rapidity,
good selectivity, and ease of performance. The reaction
scheme is shown in Fig 2.
2.5 Performance evaluation of different chemical analytical
methods for the determination of U3O8 in yellow cake
Yellow cake (Magnesium Diuranate, MgU2O7)
was separately analysed by a host of available gravimetric,
titrimetric, fluorimetric and spectrophotometric methods
such as diuranate precipitation followed by its ignition to
U3O8; homogeneous precipitation as a phosphate and its
ignition to pyrophosphate; oxine precipitation followed
by its ignition to U3O8; peroxyuranate precipitation
followed by its ignition to U3O8; redox titration with
dichromate; H2O2 spectrophotometry and pellet as well
as Laser fluorimetry, etc (Tarafder et al.,2007). The data
obtained by each method have been compared and it is
observed that the results from most methods studied
compared favorably, while those obtained by redox
titration (Florence method) were found to be incongruent.
Systematic studies carried out on the
performance of different chemical analytical methods for
147
Fig. 2. The reaction scheme of uranium
with Guaiacol.
the estimation of uranium in MgU2O7 sample are described
below.
2.6 Extraction-Fluorimetric determination of uranium in
ilmenite and columbite-tantalite
An useful method for the determination of
uranium in columbite-tantalite involves the mineral being
brought into solution by pyrophosphate fusion followed
by dissolution of the melt in conc. H2SO4 (Ghosh and
Tarafder, 2013). UO22+ ion from this solution is selectively
extracted into a suitable organic solvent as an ion-
associate formed with a O-O’ type of non-innocent ligand
2,3 dihydroxy naphthalene and cetylmethyl ammonium
bromide in an alkaline medium (pH 10-12). A suitable
aliquot was taken in a platinum dish the organic solvent
was evaporated (ethyl acetate) and the residue fused at
8000C using a flux (NaF:Na2CO3::1:4) and the fluorescence
intensity of the bead measured at room temperature using
a conventional fluorimeter.
2.7 Pre-concentration of traces of Uranium in water
samples by co-precipitation with hydrated titanium
oxide, and its ultra-trace determination by fluorimetry-
a green method
A highly useful method for pre-concentration of
uranium in water samples by co-precipitating uranium with
hydrated titanium oxide, followed by its dissolution in dil
HNO3 and determination in parts per billion level directly
by conventional fluorimetry without prior separation of
uranium has been developed. The method has been
 Analytical method development...............hydrogeochemical samples
successfully applied to a host of water samples, and the
results obtained compare favourably with those obtained
by Laser fluorimetry i.e. , down to the 0.5 ppb level of
uranium and can be determined in water samples with a
fairly good accuracy and precision. Although , the method
is not rapid , at least 10-15 water samples can be analysed
daily (Roychowdhury and Tarafder, 2013). The method is
more useful when laser intensity in Laser fluorimeters is
too low to detect the presence of uranium in water samples.
2.8 Hydrometallurgical extraction studies on carbonate
leaching of uranium from its ores, and purification of
the metal by solvent extraction in an alkaline medium
Crushed rock/ore samples(~100mesh) were
treated with Na2CO3 solution after in situ oxidation of
embedded U(IV) to U(VI) using minimum an amount of
concentrated HNO3. On vigorously agitating /shaking the
samples with excess Na2CO3 solution, about 98% uranium
could be separated by leaching the metal in the form of
the soluble anionic carbonato complex. On filtration, the
bulk of the R2O3 forming elements such as Fe(III), Th(IV),
Zr(IV), Al(III), Mn(II) and REE’s, could be removed in the
filtrate from the soluble uranium.
Further, the leached out uranium from the alkaline
leach liquor solution was purified by solvent extraction
of the ion-associate made up of the mixed carbonato-2,3
dihydroxy naphthalene (2,3 H2ND) anionic complex into
ethyl acetate with the help of cetyl trimethyl ammonium
cation (CTA+), leaving most anions and residual soluble
complexes of other matrix metal ions in the alkaline leach
liquor/filtrate (Tarafder and Ghosh, 2007). Prior single
extraction with 2,3-dihydroxynaphthalene (without using
CTA) eliminates Cu, Ni, Co, Th, Zr, REE’s and a host of
other elements.
Uranium can be isolated from ethyl acetate
medium either by stripping off the metal in water with
Conc. HNO3 followed by its precipitation with ammonium
hydroxide as a ammoniumdiuranate, and subsequently
roasting it to U3O8 or by distilling out ethyl acetate and
roasting the residue to U3O8 at 8500C. The former method
for isolation of pure uranium is more economical because
the extractant (2,3H2ND) as well as the organic solvent
can be recycled.
Based upon preliminary results obtained, it is
observed that uranium with a fairly good purity (~95%
148
pure) can be recovered by carbonate leaching followed
by 2,3 dihydroxynaphthalene-CTA solvent extraction
purification. Further detailed studies are required to be
carried out in order to examine the efficacy of the proposed
system for probable commercial application by way of
optimizing the variables for carbonate leaching of uranium
and solvent extraction from an alkaline leach liquor
medium. In order to obtain >98% purity, a second stage
purification of uranium isolated after solvent extraction is
proposed by selective precipitation of uranium with H2O2
as UO4.nH2O (n=2 or 4).
The present paper also encompasses the results
of preliminary studies carried out on the in-situ oxidation
of U(IV) to U(VI) in the sample by HNO3 treatment followed
by carbonate leaching of uranium and its purification by
ion-pair liquid-liquid extraction of anionic mixed
carbonato-2,3-dihydroxynaphthalene complex into ethyl
acetate with cetyltrimethylammonium cation. U(VI) which
is readily leachable with carbonate can be selectively
separated from U(IV) which invariably requires oxidation
to U(VI) for its leaching. This is very well brought about
by HNO3 oxidation.
2.9 Field Method for the rapid determination of traces of
uranium in rocks, soil and stream sediments by
fluorescence measurement
A rapid field method for the determination of
uranium at ppm level in rocks, soils and stream sediments
fluorimetrically has been developed. By simply eliminating
iron, which seriously interferes during the direct
determination of uranium due to quantity quenching,
uranium can be reliably determined in the field with a high
throughput of analysis (Tarafder et al, 2015). As a part of
geochemical exploration of uranium, a novel concept of
“iron to uranium ratio” has been introduced in the paper
to demonstrate the serious negative role played by iron
in the ppm level determination of uranium fluorimetrically
in silicate rocks and soils.
2.10 Role of soluble organic matters particularly
orthodihydroxy phenolic types of compounds in
natural waters as potential inhibitors for
manifestation of uranyl (UO22+) fluorescence : a
preliminary study
A significant finding on the role of soluble
organic matters, particularly orthodihydroxy phenols and
 P .K .Tarafder
naphthols in the suppression/inhibition of uranium
fluorescence in water samples is reported.Most natural
water samples do contain a number of soluble organic
compounds having a capacity to form chelates/complexes
with metal ions present in these waters. The organic load
in natural water varies with the degree of pollution /
eutrophication of the water bodies. Some of the soluble
organic ligands such as phenolic compounds, amino
acids, fulvic acids, etc. form very strong complexes with
UO22+ ion which cannot come out of such complexes in
order to form the phosphate complex with a fluorescence
enhancing buffer such as fluran or pyrophosphoricacids
used to measure uranium fluorescence (Tarafder and
Mondal, 2013).This phenomenon has been thoroughly
verified in our laboratory by using a host of organic
compounds, mostly phenols and naphthols which are
expected to be present in natural water samples. Heavy
suppression of uranium fluorescence has been observed
with a number of such compounds. In line with this,
suppression of uranium fluorescence in water samples
have also been observed. After destruction of the soluble
organic compounds present in water samples, the actual
fluorescence of uranium present in these waters could be
successfully measured. Measurement of uranium
fluorescence in most of the water samples is faulty unless
prior destruction of the soluble organic compounds is
resorted to.
3. Method developed/modified for Niobium
determination
3.1 Extraction and sensitive Spectrophotometric
determination of Niobium in silicate rocks and the
columbite-tantalite mineral assemblage
A new and simple method for the separation of
niobium by solvent extraction is described. Niobium has
been determined in the form of a colored mixed-ligand
complex with 2,3-dihydroxynaphthalene and acetate ion
and applying a selective and sensitive spectrophotometric
method. Molar absorptivity was 4.6 ± 0.05 × 104 L/mol/cm
at 397 nm (λmax) and detection limit equaled to 20 ng/mL.
A comparative study on the extraction of niobium (V)
using different organic solvents has shown that
extractability, sensitivity, and selectivity of the proposed
method depend on the nature of solvents and the hetero-
ligands used (Tarafder et al, 2009). Niobium has been
149
successfully separated in the presence of Ti, V, Mo, Zr,
Ta, W, Fe, Al, Cr, U, Th, Ni, Co, Zn, Cd, Cu, and Mn,
thereby eliminating the interference by these ions during
spectrophotometric determination. The designed method
has been applied for the recovery of niobium from silicate
rocks, ores, and the columbite-tantalite mineral
assemblage. The reaction scheme is shown below.
[Nb(Citrate)]2++ 2 C10H8O2 + CH3COONa → [Nb(CH3COO)
(C10H6O2)2]+ 4H+ + Citrate3-+Na+
4. Method Developed/Modified for REE
Determination
4.1 Liquid-liquid extraction of rare earth elements (total)
using 2,3-dihydroxynaphthalene as an extractant and
its application for the determination of REE’s in rock,
soil and sediment samples by spectrophotometry
has been carried out
A simple and rapid separation procedure for the
determination of total rare earth elements (lanthanides)
including yttrium in rock, soil and sediment samples has
been developed. Lanthanides form 1:3 complex with O-O’
type bi-dentate ligand, 2,3-dihydroxynaphthalene (2,3-
H2ND) and are extracted in ethyl acetate from an aqueous
solution at a pH of >8 (Tarafder et al.,2013). Lanthanides
from organic phase are quantitatively and selectively
stripped off at a pH of 6.3 ± 0.2 followed by its
spectrophotometric determination using arsenazo-III.
The effect of different experimental parameters
such as the pH of an aqueous solution, concentration of
2,3-H2ND, electrolytes, equilibration time, stripping
agents, diverse ions etc. on the quantitative recoveries
of lanthanides were studied in detail. The percentage
recovery was checked by analyzing lanthanides in
synthetic mixtures and it was found that more than 98%
recovery of lanthanides was obtained by this method.
The accuracy of the method was ascertained by analyzing
some Certified Reference Materials (CRM) like the (SY-3)
syenite sample and the (MRG-1) gabro sample. The
lanthanide values obtained for the CRMs were in excellent
agreement with the recommended values, indicating that
the method yields fairly accurate and reproducible results
as characterized by the relative standard deviation (RSD)
of 1 to 5%(n=4) . The method was successfully applied to
 Analytical method development...............hydrogeochemical samples
silicate rock, soil and sediment samples and the reaction
scheme is shown in Fig. 3.
5. Method Developed/Modified for the
Determination of Transition Metals
5.1 The complex forming ability of O-O’ type ligands with
transition metals: introducing 2,3-dihydroxynaphthalene
as a apotential analytical reagent
O-O2 type organic compounds and their
derivatives are known to form a host of complexes in
solutions, and many of them have been isolated in solid
forms and characterized by physicochemical techniques,
including X-ray crystallography. Some of the complexes
have been shown to have biological significance (Tarafder
and Mondal, 2011). Many of the complexes of ortho-
dihydroxybenzene and -naphthalene formed in solution
with metal ions, particularly transition metals, display
distinct colors under different reaction conditions. These
colored complexes are often suitable for spectrophotometric
determinations of metals. Comparative studies carried out
on a host of complexes of metal ions with different ortho-
dihydroxybenzenes and naphthalenes reveal that the color
complexes formed of the latter are invariably more
sensitive than those formed by the former, because of
ring size and extended conjugations. Among the ortho-
dihydroxynaphthalenes studied, the one having oxygen
atoms at positions 2 and 3 of the ring [2,3-
dihydroxynaphthalene (2,3-H2ND)] has a high propensity
Fig. 3. The reaction scheme of REEs with
2,3 Dihydroxy naphthalene
(H2ND).
150
to form colored complexes with a host of metal ions suitable
for liquid-liquid extraction under different reaction
conditions. A survey of literature reveals that except for a
few scarce reports, the analytical potential of this ligand,
although it had been extensively used at in the past in the
synthesis and structural assessment of numerous
complexes with different metal ions, has not been explored
thoroughly until the recent studies in detail in our
laboratory. A non-exhaustive review on the complex
forming ability of 2,3-H2ND vis-à-vis those of its other
counterparts, with special reference to its analytical
applications has recently been published (Tarafder and
Mondal 2011) .
6. Method Developed/Modified for Iron
Determination
6.1 Optimized 1,10–Phenanthroline method for the
determination of Ferrous and Ferric Oxides in
Silicate rocks, soils and minerals
A precise, accurate and rapid method developed
for the sequential determination of FeO and Fe2O3 in
rocks, soils and some non-refractory minerals by 1,10-
phenanthroline spectrophotometry involves Fe(II) and
Fe(III) leaching from the “200 mesh sample using a mixture
of NH4HF2 and H2SO4 at 40–80 °C for 10 min. on a hot
plate. Both Fe(II) and Fe(III) could be conveniently
estimated sequentially from the same reaction mixture at
the ìg/g to percentage levels. The method is better than
the existing wet chemical methods, including the
commonly used Pratt’s titrimetric redox method, for Fe(II)
and Fe(III) determinations in rock and soil samples in
terms of precision, accuracy and rapidity (Tarafder and
Thakur, 2013). The throughput of the method is very high;
at least forty to fifty samples can be estimated easily within
a given time. The results obtained compare favourably
with those obtained by Pratt’s method, as well as the
certified/recommended values for a set of eleven certified
reference materials having FeO and Fe2O3 content in the
range of 0.21–14.63% and 0.58–8.48%, respectively. The
optimized 1,10phenanthroline method was found to be
accurate to within 0.21% m/m FeO and 0.30% m/m Fe2O3
when compared with the values of the certified reference
materials studied. The reaction scheme is shown in Fig. 4.
 P .K .Tarafder
Fig. 4. The reaction scheme of Fe2+ with o-phenanthroline
6.2 Micelle mediated extraction of iron and its
spectrophotometric determination in silicate rocks,
minerals, soils and water samples
Iron irrespective of its valence states forms bluish
1:1 cationic, bluish-violet 1:3 neutral and purple 1:3 anionic
complexes with 2,3-dihydroxynaphthalene, at a pH of 2 -
3, 4 - 5 and 8 - 10, respectively. The cationic bluish complex
is highly insensitive and not extractable in organic
solvents. Similarly, the bluish violet 1:3 neutral complex is
of moderate sensitivity, and extractable in organic solvents
with reduced sensitivity. The purple 1:3 anionic complex
as such is not extractable in any organic solvent. However,
in the surfactant medium of the cationic surfactant
cetyltrimethylammonium bromide, it is extractable in
organic solvents with enhanced sensitivity (Tarafder and
Mondal, 2012). The 1:3 anionic complex which is
extractable in organic solvents as an ion associate in the
presence of cetyltrimethylammoniumcation is chosen for
application to silicate rocks, minerals, soils, stream
sediments, concentrates, tobacco leaves, cigarettes and
waters, for an accurate and sensitive determination of
iron owing to its facile extraction, enhanced sensitivity,
high selectivity and a better reproducibility of results. A
systematic study on the development of an extraction
spectrophotometric method for the determination of iron
in samples of diverse matrices has been carried out and
the reaction scheme is shown in Fig. 5.
6.3 Surfactant mediated extraction of iron and its
spectrophotometric determination in rocks, minerals,
soils, stream sediments and water samples
An extraction spectrophotometric method for
iron determination in rocks, minerals, soils, stream
sediments and water samples has been developed, in
which at a pH of 3-4, iron (III) forms a 1:2:1 ternary complex
151
Fig. 5. The reaction scheme of iron with 2,3-
dihydroxynaphthalene
with thiocyanate and cetyltrimethylammonium bromide
(Fe/SCN/CTAB) which is extracted into ethyl acetate. The
readily formed purple complex is suitable for extraction
spectrophotometric determination of iron in rocks and
related materials from submicrogram to milligram levels
(Tarafder and Thakur, 2005). The method is free from any
interference due to the commonly associated ions present
in the matrices of rock samples. The present method is at
least fourfold more sensitive (ε=3.2×104L/mol/cm) than
the conventional thiocyanate method and, in addition to
the enhanced sensitivity and selectivity, it has got definite
advantages over the corresponding binary thiocyanate
system in terms of substantial improvement in the stability
of the complex formed and broadening of the Beer’s law
adherence range (0–6.0 mg/l). The method has been
applied to a number of geological and hydrogeochemical
samples for the determination of iron and the results
obtained have been found to compare favourably with
those obtained by standard methods. The reaction scheme
of is shown below.
Fe3+ + 2 SCN-+ CTAB pH 3-4[Fe(SCN)2.CTAB]
(Reddish complex)
(Extraction into ethyl acetate)
6.4 A rapid spectrophotometric method for the
determination of iron in silicate rocks
A sensitive and selective spectrophotometric
method for the rapid determination of iron in silicate rocks
has been devised using the reagent, 2,3-
dihydroxynaphthalene. The molar absorptivity at 452 nm
and Sandell’s sensitivity of the method are1.1x104 L/mol/
cm and 0.005ug/cm2, respectively. The Beer’s law is obeyed
over a wide range from 0.04 to 10 ug/ mL of iron (Tarafder
and Sardana, 1999). The selectivity of the method has
been improved by extraction spectrophotometry. The
method has been applied to a number of diverse silicate
rock samples and the results obtained are found to be
 Analytical method development...............hydrogeochemical samples
favourably comparable with those obtained from 1,10-
phenanthroline methods. The method is better than that
of TIRON in terms of sensitivity and selectivity. The
reagent used here is a better variant of TIRON for iron
determination and the reaction scheme is shown in Fig. 6.
7. Method Developed/Modified for Titanium
Determination
7.1 Micelle mediated extraction of titanium and its ultra-
trace determination in silicate rocks
This highly sensitive method for extractive
spectrophotometric determination of titanium in silicate
rocks involves extraction of Titanium in the range 0–10
μg as TiO2 into benzene or toluene by the formation of a
ternary complex of the metal with thiocyanate (SCN”) and
cetyltrimethylammonium bromide (CTAB) in the ratio 1:2:2.
A deep yellowish-orange ternary complex thus formed is
suitable for the determination of titanium at a wavelength
of 421 nm. The optimum colour intensity of this ternary
complex was attained when the complex was extracted
from an aqueous solution having concentration of
thiocyanate and HCl, in the range, 1.5–2.5mol/L and 1–
5 mol/L, respectively. The molar absorptivity and Sandell’s
sensitivity of the extracted species were found to be 1.1–
1.0 × 105 L/ mol/ cm and 0.47 ng/ cm2 (with reference to
titanium), respectively, at λmax of 421 nm. Except for Fe3+,
Nb5+ and V5+, no interference was encountered during
the estimation of titanium. While up to 10 mg /L Nb and V
did not interfere in the determination of titanium, the
interference of Fe3+ was eliminated by reducing it to Fe2+
Fig. 6. The reaction scheme of Fe3+with 2,3-
dihydroxynaphthalene.
152
using a SnCl2 solution (Tarafder and Thakur,2008). The
method is highly sensitive and selective. The results
obtained for titanium estimation in a host of silicate rock
samples have been found to be highly reproducible,
accurate and favourably comparable with certified values
of reference materials studied as well as those obtained
by standard anatylical methods. The reaction scheme of
Ti with Thiocyanateis shown below.
TiO2+ + 2 SCN-+ 2CTAB → [TiO(SCN)2.2CTAB ]
(Extraction into ethyl acetate)
(deep yellowish orange)
7.2 Extractive spectrophotometric determination of
titanium in silicate rocks, soils and columbite-tantalite
mineral assemblage
2,3-Dihydroxynaphthalene forms a strong chelate
with titanium over the pH range of 4 to 9. At a pH of 4–5,
titanium is extracted into ethylacetate along with iron,
leaving behind V, Nb, Mo, and a host of elements present
in complex matrices of rock sample solutions. In the extract,
titanium is easily separated from iron after raising the pH
of the medium and re-extracting. The method is free from
any interference. The sensitivity of the method is 3.2×104
L·mol-1cm-1. The method has been applied to a number of
diverse samples including rocks and minerals with a high
precision (Mondal and Tarafder, 2004). This method has
been compared with tiron, chromotropic acid,
diantipyrilmethane (DAM) and other existing
spectrophotometric methods used in the analysis of rocks,
ores and minerals. The proposed method has definite
advantages over most otherspectrophotometric methods
in terms of sensitivity, selectivity, reproducibility and
simplicity.
7.3 Rapid spectrophotometric method (aqueous and
extractive) for the determination of titanium in silicate
rocks
A sensitive and highly selective aqueous as well
as extractive spectrophotometric method has been
developed for the determination of titanium(IV) using 2,3-
dihydroxynaphthalene (H2ND) as a chromogenic agent.
The reagent (H2ND) forms a 1:3 (TiOH3+:ligand) complex
at a pH of 4–9. The molar absorptivity and Sandell’s
sensitivity are 3.2 × 104 L/mol / cm and 0.001 ìg/cm2,
respectively at λmax 375 nm. The method has been found
to be highly selective for Ti(IV) determination in rock
 P .K .Tarafder
samples. Solvent extraction of Ti (IV) in ethylacetate
greatly improves the detection limit of this method
(Tarafder et al.,1993). The method has been successfully
applied to diverse silicate rock samples, and the results
obtained are comparable with those obtained by the Tiron
method. The reagent (H 2 ND) used in the present
investigation is a much better variant than TIRON for
titanium(IV) determination in silicate rock samples in terms
of sensitivity, selectivity, operational simplicity and
economy. The reaction scheme is shown in Fig. 7.
8. Method Developed/Modified for Chromium
Determination
8.1 An improved spectrophotometric method for chromium
(VI) determination in rocks, minerals and water
samples
A rapid, sensitive and highly selective method
for the spectrophotometric determination of sub-
microgram quantities of chromium (VI) is described. The
method is based on the determination of nitrite produced
by Cr(VI) during the oxidation of hydroxylamine (NH2OH).
Beer’s law is obeyed in the range of 0.02-10 μg/ml of Cr(VI)
(Tarafder et al.,1996). The molar absorptivity and Sandell’s
sensitivity (with reference to chromium) are 4.2 x 104 L/
mol/cm and 0.001 μg/cm2, at 540 nm (λ max). Prior
separation of chromium(VI) with trioctylamine greatly
increases selectivity of the method. The method is applied
to the determination of Cr(VI) in rocks, minerals and water
and the reaction is shown in Fig. 8.
8.2 Spectrophotometric determination of chromium in
geological samples
A method for the determination of chromium is
presented, based on the oxidation of hydroxylamine
hydrochloride to nitrous acid by chromium (VI) in an
acetic acid medium followed by diazotization of the nitrite
produced with p-aminophenylmercaptoacetic acid and
Fig. 7. The reaction scheme of Ti with 2,3-
dihydroxynaphthalene.
153
Fig. 8. The reaction scheme of Cr (IV) with hydroxylamine
and azodye formation.
subsequent coupling of the diazonium salt with N-(1-
napththyl)ethylenediaminedihydrochloride in an acidic
medium to form a stable blueish azo dye (Tarafder and
Rathore,1992). The method is suitable for the
determination of chromium(IV) from 0.04 to 1.2 mg/L in a
1.0-cm cuvette. The molar absorptivity and Sandell’s
sensitivity are 3.65 × 104 L/mol/cm and 0.0014 μg/ cm2,
respectively and the reaction is shown in Fig.9
9. Method Developed/Modified for Zirconium
Determination
9.1 A rapid spectrophotometric method for the
determination of zirconium
A new spectrophotometric method developed
for the estimation of zirconium involves, Zirconium
reacting with nitroso-resorcinol formed by the reaction
of nitrite with resorcinol in dilute hydrochloric acid
medium to produce a yellowish-orange chelate. Beer’s
Law holds in the range 1.0 to 16.0 microgram per milliliter
of zirconium. The apparent molar absorptivity and
Sandell’s sensitivity of the method at 350 nm are 6.12 x
103L/mol/cm and 0.01µg/cm2 respectively (Tarafder et al.,
1992). Effects of diverse ions on the determination of
zirconium have also been studied. The method has been
applied to samples of heavy mineral concentrates,
containing mostly zircon, and synthetic mixtures. The
reaction scheme is shown in Fig. 10.
10. Method Developed/Modified for Cerium
Determination
10.1 Detection and determination of Cerium with para-
aminophenylmercaptoacetic acid
A direct and simple method developed for the
detection and determination of cerium(IV) with p-
aminophenylmercaptoacetic acid as a reagent, requires
 Analytical method development...............hydrogeochemical samples
Fig. 9. The reaction scheme of Cr(VI) with
hydroxylamine and azo-dye formation.
Fig. 10. The reaction scheme of zirconium with
resorcinol.
154
addition of p-aminophenylmercaptoacetic acid (0.01ml)
to a mixture of sodium acetate-acetic acid buffer (0.01ml)
and polyvinylalcohol (0.01ml), placed on a spot-plate and
making of the test solution (0.01ml) (Rathore and
Tarafder,1991). An immediate violet colour stable for 30
minutes appears, indicating the presence of Ce (IV). The
limit of detection is 0.3µg Ce in 0.01ml of test solution. For
the determination of Ce (IV) an aliquot of sample solution
containing 50-2000µg Ce (IV) is mixed with the sodium
acetate-acetic acid buffer solution (5ml), polyvinyl alcohol
solution (1ml) and 0.2% p-aminophenylmercaptoacetic
acid (1ml) and shaken well and diluted to 25 ml with distilled
water.
A violet colour developes immediately and
remaines stable for 30 minutes. The absorbance was
measured at 545nm against a reagent blank. Cerium was
determined in monazite samples by the above method
and results obtained are in reasonable agreement with
those obtained by the radiochemical neutron activation
method.
11. Method Developed/Modified for Molybdenum
Determination
11.1 Spectrophotometric determination of molybdenum
in concentrates
The new method for the rapid and accurate
estimation of molybdenum in moly concentrates has Mo6+
reacting with the reagent, 2,3-dihydroxynaphthalene at a
pH of 10 to 12 to yield a yellowish-orange chelate which
absorbs the maximum (lmax) at 400 nm (Tarafder et
al.,2007). The molar absorptivity and Sandell’s Sensitivity
of the method are 1.0x104 L/mol/cm and 0.0095 mg/cm2
respectively. The standard deviation (s) and relative
standard deviation (RSD) of 1mg/L Mo for 5 replicate
analyses are ±0.015 mg/L and 1.65 % respectively. The
method has been applied to a set of 5 different samples of
moly concentrates received from UCIL, Jaduguda and
results obtained have been found to compare favourably
with those obtained by 8-Hydroxyquinoline gravimetry.
11.2 Liquid-Liquid Extraction of Molybdenum and its ultra-
trace determination by Graphite Furnace Atomic
Absorption Spectrophotometry
The highly sensitive and reliable method for the
determination of molybdenum at nanogram level in rocks,
 P .K .Tarafder
ores, minerals, soils and hydrogeochemical samples
involves liquid-liquid extraction of the metal into a suitable
organic solvent, followed by its measurement by Graphite
Furnace Atomic Absorption Spectrophotometer (Thakur
et al., 2013). Molybdenum in the sample (~200 mesh) was
isolated by NH4HF2 and H2SO4 dissolution. At a pH of 4-
6, the major matrix elements like Fe, Ti, Nb, Cu, Th, REEs
etc are removed by the solvent extraction of the complexes
of these elements with the, O-O’ type of ligand, 2,3
dihydroxynaphthalene(2,3 H2ND) leaving Mo(VI) in
aqueous solution.
Subsequently, Mo(VI) was reduced with
hydroxylamine hydrochloride to Mo(V) and allowed to
form a 1:2 complex with the ligand, 2,3 H2ND at a pH of 2-
4. At this very pH, the Mo(V)-2,3H2ND neutral complex
was readily extracted in ethyl or butyl acetate. Then Mo(V)
was stripped off into aqueous solution (the minimum
volume). This solution was fed into the graphite furnace
through an auto sampler and concentration of the analyte
in the sample was estimated from the calibration curve
prepared against known standards. The method was
validated by applying it on a host of rock samples
including Geological Reference Materials and water
samples. Molybdenum can be estimated up to 1 µg per
gram rock sample and 2 µg/L of a water sample with a
precision of ±5%. The reaction scheme is shown in Fig.11.
11.3 An improved and highly useful method for gravimetric
determination of Molybdenum in molybdenum
concentrates
The dried molybdenum concentrate is treated
with hydrofluoric acid and nitric acid for dissolution and
the solution thus obtained is neutralized with ammonia
and then acidified with dilute sulfuric acid. From the
acidified solution molybdenum is precipitated with 8-
Fig. 11. The reaction scheme of Mo with 2,3-
dihydroxynaphthalene.
155
hydroxyquinoline (oxine) and digested on a steam bath
filtered, washed with water and dried at 130o C. It is heated
in a muffle furnace at 600 o C for an hour, cooled and then
weighed. The product was again heated at 750 o C for
about 1 h, cooled and the constant weight was taken
(Ghosh and Tarafder, 2013). The difference of weight
(weight of the product obtained after heating at 600 o C
minus weight of the product obtained after heating at
750 o C) is the actual weight of molybdenum as MoO3. A
substantial/major modification of the earlier reported 8-
hydroxyquinoline (oxine) method for the gravimetric
determination of molybdenum has been made in this
method.
The advantages of the proposed method over
the oxine method are (i) it is free from most of the
interferences, (ii) accuracy and precision of the method
have improved substantially and (iii) the results obtained
by the application of the proposed method for different
molybdenum concentrates are reliable.
11.4 Extraction of titanium and molybdenum with 2,3-
dihydroxynaphthalene and their sequential
determination in silicate rocks, ores, minerals,
concen trates and steel samples by molecular
absorption spectroscopy
A facile liquid-liquid extraction system for
titanium and molybdenum using the 2,3-
dihydroxynaphthalene involves extractive separation and
spectrophotometric determination of titanium in the
organic solvent, n-butylacetate at pH 4-9 and the aqueous
solution being used for the extraction and
spectrophotometric determination of molybdenum. The
molar absorptivity of the Ti system (3.7 X 104 L/mol/cm)
was found to be maximum at 390nnm in n-
butylacetate.Similarly,the molar absorptivityof the Mo-
system (1.7 X 104 L/mol/ cm) was found to be maximum at
400 nm in n-butylacetate. Mo(VI) was reduced to Mo (V)
using hydroxylamine hydrochloride. Except for titanium,
which was eliminated by a prior solvent extraction of Ti-
2,3-H2ND complex at a pH of 4-9, where Mo(VI)-2,3-H2ND
complex was not extracted, no other element was found
to interfere seriously in the determination of molybdenum
(Thakur et al. 2013). The method is applicable for the
determination of titanium and molybdenum in a wide
 Analytical method development...............hydrogeochemical samples
variety of silicate rocks, ores, minerals, concentrates and
also steel samples.
12. Method Developed/Modified for Manganese
Determination
12.1 Direct and extractive GFAAS determination of ultra-
trace manganesein rocks and water samples
Direct as well as extraction-Graphite Furnace
Atomic Absorption Spectrophotometric (GFAAS)
methods for ultra-trace determination of manganese in
hydrogeochemical samples and silicate rocks, has
manganese, irrespective of its valance states, being
extracted as an ion pair of Mn-Naphthalene-2,3-diol
anionic chelate and CTA+ into ethyl acetate in the pH
range of 10 to 12.
Nano gram (ng) level of manganese has been
successfully separated from the complex matrices of
silicate rocks and hydrogeochemical samples by liquid-
liquid extraction of manganese in the form of the above
mentioned ion associate complex (Tarafder and Pradhan,
2007). The recovery of manganese has been found to be
more than 99.99%. By applying this method, manganese
has been successfully determined with a high degree of
accuracy and precision in a number of hydrogeochemical
samples, including tap water as well as silicate rock
samples.
The results obtained for manganese estimation
in these samples compare favorably with those obtained
by flame-AAS. The present work also describes the
systematic studies carried out on the optimization of
extraction variables and GFAAS parameters for the
analysis of hydrogeochemical and silicate rock samples
for the determination of manganese.
12.2 Ultra-trace determination of manganese in
hydrogeochemical samples
A novel technique is described here for the rapid
sensitive and selective determination of trace amounts of
manganese in hydrogeochemical samples involves
manganese being pre-concentrated by its co-precipitation
with hydrated iron oxide (Tarafder and Mondal, 2007).
Manganese is then quantitatively separated from iron by
solvent extraction and determined spectrophotometrically
after extracting the bluish-violet Mn(II)-2,3-
dihydroxynaphthalene anionic complex into ethyl acetate
156
under the influence of the counter cation,
cetyltrimethylammonium bromide. The molar absorptivity
of the complex at λmax 547 nm is 1.2 x 104 l.mol-1cm-1. The
method is highly effective and free from interference and
has been applied to a number of hydrogeochemical
samples and results obtained have been found to be highly
encouraging.
12.3 An improved method for the determination of
manganese in rocks, minerals, ores, soils, steel,
lloys, seabed polymetallic nodules and
environmental samples including water and effluents
A highly useful and reliable extraction
spectrophotometric method developed for the
determination of manganese in a wide variety of samples
having complex matrices is based upon the reaction
system of Mn(II) -2,3 H2ND,an O-O’ type of ligand forming
an anionic complex with manganese,irrespective of its
valence states, and readily extractable as a purple ion-
pair complex into methyl-isobutyl ketone(MIBK) under
the influence of the cationic surfactant,
cetyltrimethylammonium bromide(CTAB). The only
interference of iron by been successfully eliminated by
its prior extraction with methyl-isobutyl ketone
(Roychowdhury et al., 2013). The method is robust as
evidenced by its application to a wide variety of samples
of diverse matrices, including certified reference materials.
While most of the spectrophotometric methods, including
formaldoxime, pyridil-azo-napthol and the well-known
permanganate method where not satisfactory, when
applied to samples of complex matrices, the method
developed in our laboratory yields highly accurate results
as attested by those obtained by AAS as well as the
certified values of the CRMs.
12.4 Liquid-liquid extraction and spectrophotometric
determination of Mn (II) in geochemical samples
The new, simple, precise and sensitive method
for the extraction and spectrophotometric determination
of manganese describes manganese (II) forming a bluish-
violet anionic chelate, [MnL2]2- with 2,3-dihydroxynaphthalene
(H2L) in an alkaline medium (pH 11-12). The colour of the
anionic chelate intensifies when the compound is
extracted in to ethyl acetate as the ion-associate,
Q2[MnL2], with the counter cation cetyltrimethylammonium
(Q+) (Tarafder et al.2004). The molar absorptivity of the
 P .K .Tarafder
complex at 547 nm (λmax) is 1.2 × 104 L/mol/cm with a
detection limit of 0.04 ìg/ mL for Mn. Beer’s law is obeyed
in the concentration range from 0 to 5 ìg/mL. Zn, Cd, Cu,
Co, Ni, Al, Be, La, Ti, Zr, Y, Ta, W, U, Mo, As, Se and Bi do
not exhibit any interfere. As, Fe normally interfere, it is
removed by prior extraction at a pH of 4-5 using the same
reagent. The method has been applied for the recovery of
Mn present in silicate rocks, ores, minerals, soils, plant
ash and hydrogeochemical samples. Results compare
favourably with those obtained by oxidation of Mn with
KIO 4 to KMnO 4 and consequent determination by
spectrophotometry and AAS. The reaction is shown in
Fig. 12.
13. Method Developed/Modified for Gold
Determination
13.1 An improved method for Ultra-Trace determination
of Gold in geological samples by Graphite Furnace–
Atomic Absorption Spectrophotometry
A simple, precise, rapid and improved method
developed for the ultra trace determination of gold in
geological samples by Graphite Furnace Atomic
Absorption Spectrophotometry (GF-AAS), initial
aquaregia treatment and hydrochloric acid digestion of
the sample, after which gold passes into solution along
with other impurities (Pradhan and Tarafder,2009). The
metal is extracted into MIBK (Methyl Isobutyl Ketone)
and then stripped back into aqueous phase with HBr.
Gold is then determined by GF-AAS coupled with an auto
sampler. The RSD of this method is ± 10% at 10 µg/L
concentration level. This method has been applied to
various geological samples for gold determination.
14. Method Developed/Modified for Vanadium
Determination
14.1 Determination of vanadium in steel and geological
samples by its extraction and spectrophotometric
determination using 2,3- dihydroxynaphthalene
A new and simple method for extraction and
spectrophotometric determination of vanadium describes,
removal of Iron from the sample solution by its prior
extraction with MIBK in a concentrated HCl
medium(~6mol/L). Vanadium has been determined in the
form of a colored complex with 2,3-dihydroxynaphthalene
after its extraction into MIBK (Mondal et al., 2013). The
157
Fig. 12. The reaction scheme of Mn with 2,3-
dihydroxynaphthalene.
method is atleast 5 fold more sensitive to the BPHA
method.The molar absorptivity of the complex at 530 nm
is 1.5 x 104 L/mol/ cm. For samples having > 5 fold excess
concentration of TiO2,a prior separation of TiO2 as its
[Ti(OH)(HND)3] complex is essential and the method has
been successfully applied to different rock, soil and steel
samples as well.
15. Method developed/Modified for Aluminium
Determination
15.1 Determination of aluminum in water samples by
Graphite Furnace Atomic Absorption spectrophotometry
after pre-concentration involving co-precipitation
with iron and separation by liquid-liquid extraction
A simple and rapid separation and pre-
concentration procedure for the determination of
aluminum in water developed is based upon the co-
precipitation of traces of analyte ions along with iron (III)
hydroxide precipitate, separation of the analyte from bulk
of the iron by liquid-liquid extraction and followed by
Graphite Furnace Atomic Absorption Spectrophotometric
determination. Aluminum was precipitated along with iron
(III) hydroxide in an ammonical medium, filtered and the
residue dissolved in a minimum quantity of nitric acid
(Pradhan andTarafder, 2013). Iron present in the aqueous
solution was selectively separated by liquid-liquid
extraction of the Fe-2,3-H2ND (2,3-dihydroxynapthalene)
complex in organic solvent ethyl acetate at the pH range
of 4-5 in the presence of the cationic surfactant,
CTA+(Cetyltrimethylammonium ion), while aluminum
remained in aqueous solution at this pH. Aluminum thus
present in the aqueous phase was determined by Graphite
Furnace Atomic Absorption Spectrophotometry coupled
with an auto sampler after deuterium background
correction and using magnesium nitrate as a matrix
modifier.
 Analytical method development...............hydrogeochemical samples
The effects of different experimental variables
like furnace conditions, pH of the aqueous solution,
amount of iron added, amount of 2,3-H2ND, sample volume
and also the influence of some foreign ions were
investigated in detail on the quantitative recoveries of
analyte ions. The detection limit was found to be 1.5 ng/
ml (3 times standard deviation of blank, n=5) while the
RSD was in the range of 1-10 % of course depending on
the concentration of the analyte. The accuracy of the
method was checked by the standard addition method
and successfully applied during the analysis of water
samples.
16. Method Developed/Modified for Fluoride
Determination
16.1 Fluorimetric determination of fluoride
A novel fluorimetric method for the rapid
determination of fluoride present in minerals and
compounds in our laboratory devised is based upon
fluorescence measurement of the beads formed by fusing
UO22+ with F- in the presence of sodium and potassium
carbonate mixture at 700±300C. The fluorescence intensity
of the species formed is observed to be directly
proportional to the fluoride ion concentration in the range
from 80 to 2000 µg at a fixed concentration of UO22+, i.e.,
10 µg of U (VI). The effects of flux combinations, fusion
temperature and time, uranium concentration and diverse
ions on fluorescence intensity, have been studied in detail
by Tarafder et al., (1997). To eliminate interference due to
potential quenchers, the interfering metal ions are
separated either by fluoride distillation or by precipitation
of matrix metal ions as hydrous oxides. The method has
been successfully applied to a wide variety of inorganic
fluorocomplexes and synthetic mixtures of different
fluoride bearing minerals.
16.2 Spectrophotometric determination of fluoride in water
Alizarin Red-S, which is used routinely during
spectrophotometric determination of aluminium in silicate
rock samples, has been successfully applied to a number
of hydrogeochemical samples for the estimation of
fluoride at ppm levels. The reddish-orange complex formed
by the co-ordination of Al+3 ion with alizarin Red-S at a
pH of 3.8 is inhibited in the presence of fluoride ion over
158
a wide range (Tarafder and Mondal, 2007). By this method
F- can be estimated up to 10 µg/mL in hydrogeochemical
and environmental samples. Except for Al+3 no interfernce
was encountered during the estimation of fluoride in
hydrogeochemical and environmental samples. The
results obtained have been found to be comparable with
those obtained by the standard method.
17. Method Developed/Modified for Chloride
Determination
17.1 An improved method for the determination of chloride
in iron ore, coal, coke, mill sludge, flue dust and sinter
products by turbidimetry and validation of results
obtained by indirect atomic absorption
spectrophotometry
An improved and rapid procedure for the
determination of chloride in iron ore, mill sludge, coal,
coke, flue dust and sinter products etc. developed using
turbidimetry, shows results which were validated by
indirect atomic absorption spectrophotometry (AAS).
Chloride present in these samples was leached by 10%
(v/v) nitric acid and then determined by the above two
methods, representing the efficacy of the proposed
method vis-à-vis the AAS method (Pradhan et al.,2013).
The correlation coefficient of linear regression was 0.98,
demonstrating that both the methods are complementary
to each other.
Different experimental parameters such as choice
of the leaching agent, leaching time, effects of diverse
ions, concentration of nitric acid etc. were studied in detail.
The accuracy of the method was ascertained by estimating
chloride content in the Certified Reference Materials
(CRM) like Syenite (SY/3) and the iron ore sample (BAM
No. ECRM 687-1). Chloride values obtained for the CRM’s
were in excellent agreement with recommended values,
indicating that the method yields fairly accurate results.
The detection limit was found to be 0.05µg/ml (based on
mean plus 3 times standard deviation of blank, n=5) while
the RSD was in the range of 1-3% depending, of course
on the concentration of the analyte. The advantage of
the proposed method is that a spectrophotometer has
been used for turbidity measurements in terms of
absorbance in line with turbidimetric measurement of
 P .K .Tarafder
sulphate ion coupled with HNO3 used for leaching of
chloride instead of hot water.
18. Method Developed/Modified for Nitrite
Determination
18.1 Spectrophotometric determination of Nitrite with p-
Aminophenylmercaptoaceticacid-Chromotropic acid
A new colour reaction for the determination of
nitrite investigated, involves nitrite reacting with p-
aminophenylmercaptoacetic acid in the presence of
hydrochloric acid to form a diazonium cation, which is
subsequently coupled with chromotropic acid disodium
salt dehydrate in an alkaline medium to form a reddish azo
dye which on acidification with hydrochloric acid
produces a purple coloured product (Rathore and
Tarafder,1990). The method is suitable for the
determination of nitrite in the range 0.02-2.0µg/mL.The
optimum reaction condition for full colour development
and the effect of variables have been studied.
18.2 Spectrophotometric Determination of Nitrite ion using
the reaction with p- Aminophenylmercaptoacetic acid
–α Naphthol
A new sensitive colour reaction for nitrite
determination is presented. Nitrite reacts with p-
aminophenylmercaptoacetic acid in an hydrochloric acid
medium to form a diazonium cation, which is coupled with
α-napthol in an alkaline medium to form a reddish orange
water soluble azo dye which is stable for more than 24 hr.
Diazotisation and coupling reactions are very fast and
require no temperature control (Rathore and
Tarafder,1990). The method is suitable for the
determination of nitrite from 0.03 to 1.2 µg/mL.in a 1.0-cm
cuvette. The observed molar absorptivity and Sandell’s
sensitivity of the azo dye are 3.49 x 104l/mole/cm and
0.001µg/cm2 respectively. Interferences due to diverse ions
have been studied.
18.3 Rapid Spectrophotometric Determination of Nitrite
in water
A new colour reaction for the determination of
nitrite is reported here shows nitrite reacting with p-
aminophenylmercaptoacetic acid in an hydrochloric acid
medium to form a diazonium cation, which is
subsequently coupled with 8-hydroxyquinoline in an
159
alkaline medium to produce a reddish orange azo dye
(Rathore and Tarafder,1989).The reactions are very fast
and require no temperature control. Features of this
method include good sensitivity, rapidity, reproducibility,
freedom from pH effects, temperature independence, less
interference and ease of performance.
18.4 Spectrophotometric Determination of Nitrite in water
A sensitive and selective colour reaction for the
determination of nitrite presented here involves nitrite
reacting with p-aminophenylmercaptoacetic acid in the
presence of hydrochloric acid to form a diazonium cation,
which is subsequently coupled with N-(1-naphthyl)
ethylenediaminedihydrochloride in an acidic medium to
form a stable bluish violet azo dye. The method is suitable
for the determination of nitrite from 0.02 to 0.80µg/mL in a
1.0-cm cuvette (Tarafder and Rathore,1988). The observed
molar absorptivity and Sandell’s sensitivity of the azo
dye are 4.65 × 104 L/mol/cmand 0.001 µg/ cm2, respectively.
The method is free from most interferences and has been
applied during the study of polluted water samples, the
results obtained are comparable with those by standard
methods. The reaction scheme is shown in Fig.13
18.5 Studies on the determinative methods of nitrites in
waters and effluents
Various methods for nitrite determination by
diazotization of amines like sulphanilic acid,
sulphanilamide,ortho and para nitro aniline with nitrite in
a HCl medium and coupling of the diazonium cation with
various phenols like resorcinol, guiacoletc in an alkaline
medium and with N-(1-naphthyl) ethylenediaminedi
hydrochloride, and α-naphthyl amine in a HCl medium
were developed in our laboratory and applied to polluted
water samples and the results obtained were compared
(Tarafder and Narasimhan, 1986).
18.6 Spectrophotometric determination of Nitrite using 1-
Amino-2-Naphthol-4-Sulphonic acid
The reagent, 1 Amino-2-Naphthol-4-sulphonic
acid was diazotized in a dil. HCl medium with nitrite present
in water samples and coupled with N-(1-naphthyl)
ethylenediaminedihydrochloride(NEDA) in a dilute acidic
medium to obtain a yellowish orange azo dye suitable for
spectrophotometric determination of nitrite in water
 Analytical method development...............hydrogeochemical samples
Fig. 13. The reaction scheme of nitrite
to form azodye.
samples (Tarafder and Narasimhan ,1986). The molar
absorptivity being 1.0x 104L/mol/cm, the results obtained
for nitrite determination in polluted water samples
compared well with those obtained by the use of
sulphanilic acid-NEDA system.
19. Method Developed/Modified for Simultaneous
Nitrite and Nitrate Determination
19.1 Rapid Ultra-violet Spectrophotometric method for
simultaneous determination of Nitrate and Nitrite in
potable waters
Nitrate has been reported to get absorbed at
220nm, nitrite too absorbed gets similarly at the same
wavelength but this absorption is suppressed by about
90% by treatment with 1.0 N hydrochloric acid and
digestion for 5 minutes. This quantative nature of
supression has been exploited here to determine nitrate
and nitrite simultaneously at the same wavelength. In
step-I, a suitable aliquot containing 0-250µg of nitrate
160
and nitrite was diluted to 50ml and its absorbance at 220nm
against distilled water was measured. In step-II, the same
amount of aliquot of the sample was taken and 1.0 N
HCL(1.0ml) was added and digested for 5 minutes on a
water bath (Tarafder,1990). The solution was cooled to
room temperature and made upto 50 ml and absorbance
was measured at 220nm against distilled water as above.
This gives the value of nitrate and the difference between
the two values (Step-I minus Step-II) gives the value of
nitrite. This method has been successfully applied for
the determination of nitrate and nitrite simultaneously in
some natural waters of Shillong City, India.
20. Conclusions
The above methods developed in our laboratory
for the determination of major, minor and trace elements
have been applied to geochemical and hydrogeochemical
samples, and the results obtained have been found to
compare favorably with those obtained by standard
methods. The above cited methods have been well tested
and can be used for routine analysis of geochemical and
hydrogeochemical samples having diverse matrices.
Acknowledgements
The author is grateful to the Director, AMD for
permission to publish this paper and to Dr. G. Chakrapani,
Head, Chemistry Group for encouragement.
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Received on 17-02-16; Revised Ms accepted on 17-02-17
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