TRACE ANALYSIS OF SCORODITE MINERAL FOR

ITS OSMIUM AND OTHER METALS CONTENT

P.K. Tamrakar and K.S. Pitre

Department of Chemistry, Dr. Hari Singh Gour University

Sugar - 470 003 (M.P.) India

ABSTRACT

Electroanalytical methods, i.e., direct current polarography (DCP),

differential pulse polarography (DPP) and differential pulse anodic stripping
voltammetry (DPASV) were developed for the trace determination of
osmium and other metals in scorodite mineral samples. The analysis of trace
metals was performed in two different supporting electrolytes, viz. 0.1 Μ
(NH 4 ) 2 tartrate and 0.1M HCl. The results indicated the presence of T l +
(31.78), Sb3+ (374.99), Zn2+ (1.45), Fe3+ (155.90), Os8+ (1.36) and As1+ (2.40)
mg.g"' in the sample. The method of standard addition was used for
quantitative analysis. The accuracy of the methods was verified by comparing
the observed results with those obtained using atomic absorption
spectrometric (AAS) technique.

INTRODUCTION

Scorodite is an alteration product of arsenic minerals, especially

arsenopyrite. In this mineral some invaluable metals of platinum group
elements (PGE) are present at trace level with other metals.'"3 Generally in
geological materials, the concentrations of major, minor and trace elements
vary from 1 to 4 orders of magnitude. With such a large variation in
elemental abundances, it is desirable to use a technique that is highly
sensitive, especially at minor and trace levels, is specific and precise, and
yields a lot of information even in a small sample. Electroanalytical
techniques meet all these criteria. A new catalytic polarographic method for
the determination of tungsten in trace amounts in geochemical samples has
been developed by Dan et αΙ.Λ A comparative study on analysis of

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Vol. 26, No.l, 2007 Trace Analysis ofScorodite Mineral

phosphorites for its Pb and Cd content, has been done by Voulgupoulos and
his coworkers using DPASV and AAS methods and found satisfactory
results.5 Trancoso and Barros 6 used differential pulse anodic stripping
voltammetry after anion exchange separation for the determination of gold in
sulphide minerals. Some other invaluable metals i.e. Ag, Au, Pt, U, Os etc. at
trace level in geological material have been successfully analysed by
advanced electroanalytical techniques.7"10 Besides, electroanalytical
techniques are being widely used for multielemental analysis in many areas,
including geological11, biological12, industrial13, pharmaceutical14 and
15
environmental studies.
The present paper describes the determination of osmium and other
metals in scorodite mineral applying electroanalytical techniques, i.e., direct
current polarography (DCP), differential pulse polarography (DPP) and
differential pulse anodic stripping voltammetry (DPSAV).

EXPERIMENTAL

Sample

The scorodite mineral sample was collected from Chakariya village, in

the Sidhi district of Madhya Pradesh, India.

Instrumentation

Polarographic and voltammetric measurements were made on Elico

(India) Pulse polarograph model CL-90 coupled with a recorded X-Y
polarocard model LR-108. The electrode system consisted of a dropping
mercury electrode (DME) as the working electrode, a coiled platinum wire as
the auxiliary electrode and a saturated calomel electrode (SCE) as the
reference electrode. The electrochemical cell used had the provision for
inserting a bubbler for dearating the solutions by passing nitrogen gas. A
glassy carbon fibre electrode (NF 12 Sigiti Eletitiogitit, UK) was used for
DPSAV.
The pH measurements were made on a Systronics digital pH meter
(model 335).

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P.K. Tamrakar and KS. Pitre Reviews in Analytical Chemistry

Chemicals and reagents

Analytical R grade and BDH grade chemicals were used for the present
study. Stock solutions of (NH 4 ) 2 tartrate ( I M ) , HCl ( I M ) , T l + , Sb 3+ , Zn 2+ ,
Fe 3+ , 0 s 8 + and As 1+ (0.01M) were prepared by dissolving the requisite
amounts of their soluble salts in doubly distilled water. Gelatin solution
(0.1%) was prepared in hot distilled water. The solutions were standardized
and diluted as required.

Preparation of sample solution

Finely pulverized scorodite mineral sample ( l g ) was heated with 50ml of

conc. H N 0 3 until the volume of the solution reduced to small volume. The
undissolved residue was separated from the solution and treated with 10ml of
conc. HF. Then the volume of the sample solution was made up to 100ml by
doubly distilled water.

Preparation of analyte and recording of the

polarograms/voltammograms

T o 10 ml of the sample solution, 10ml of 1M(NH 4 ) 2 tartrate / HCl as

supporting electrolyte and 1 ml of 0.1% gelatin as a maximum suppressor
were added and the final volume was made up to 100ml with doubly distilled
water. The pH of the test solution was first adjusted to 9.0±0.1 and then
9.510.1 in case of 0.1 Μ (NH 4 ) 2 tartrate and 0.2 ± 0.1 in case of 0.1M HCl
supporting electrolyte. The analyte were placed separately in Polarographic
cell equipped with the electrode assembly as specified above. Pure nitrogen
gas was passed through the test solution for 15 min at the beginning of the
experiment. The polarograms and voltammograms were then recorded with
the instrumental parameters indicated in Table 1. For DPASV the deposition
time was 60s and the resting period was 5s.

RESULTS AND DISCUSSION

The direct current polarograms and differential pulse polarograms (Fig.

1A&B) of the scorodite mineral sample in 0.1M (NH 4 ) 2 tartrate at pH = 9.0
± 0 . 1 showed four well defined waves/peaks with Eiri/Ef = - 0.48V/-0.50V,

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Vol. 26, No.l, 2007 Trace Analysis ofScorodite Mineral

-0.94V/-0.94V, -1.22V/-1.26V and -1.48V/-1.50V vs SCE indicating the

presence of ΤΓ, Sb1+, Zn2+ and Fe3+ in the sample. The differential pulse
anodic stripping voltammogram (Fig. 1C) of the sample in 0.1 Μ (NH 4 ) 2
tratrate also produced four distinct peaks with £ P =-0.46V, -0.90V, -1.20V
and -1.46V vs SCE corresponding to the presence of Tl + , Sb1+, Zn2+ and Fe3+
in the sample. The direct current polarograms and differential pulse
polarograms (Fig. 2A&B) in 0.1 Μ (NH4)2 tartrate at pH = 9.5 ± 0.1
produced a well defined wave/ peak with £v/£ p =-0.26/-0.30V vs SCE,
indicating the presence of Os8+ in the sample. The differential pulse anodic
stripping voltammogram (Fig. 2C) of the sample in 0.1 Μ (NH4)2 tartrate also
produced a well defined peak with £ p =-0.24V vs SCE, revealing the presence
of Os8+ in the sample.

Table 1
Instrumental Parameters

Parameters Value
Initial applied voltage 0.0 V vs SCE
Sensitivity ΙμΑ/V
C C Compensation 5
I R Compensation 4
Height of Hg 140.0 cm
Time Constant 10 ms
Pulse amplitude 50 mV
Drop time 0.5 s.
Acquisition Fast
Scan rate 12 mV.s"1
O/P zero 0
Temperature 25 ± 20°C

On Polarocard
X-Axis 100mV.cm."'/200mV.cm."1
Y-Axis 0.2 μΑ.αη."'/0.5 μΑ. cm."1

To investigate the presence of other trace metals in the sample the

polarograms and voltammograms were recorded in 0.1 Μ HCl supporting
electrolyte. The direct current polarograms and differential pulse polarograms
(Fig. 3A&B) in 0.1 Μ HCl showed one well defined wave/peak with £ v /£ p =

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P.K. Tamrakar and KS. Pitre Reviews in Analytical Chemistry

-0.72V/-0.74V vs SCE, indicating the presence of As 1+ in the sample. The

differential pulse anodic stripping voltammogram (Fig. 3C) of the sample in
0.1M HCl also produced one well-defined peak with £ p =-0.72V vs SCE,
reveling the presence of As 3+ in the sample.
To confirm the presence of the said metal ions in the sample a known
quantity of standard solution of each metal ion was added to the analyte and
then polarograms and voltammograms were recorded under the identical
experimental conditions. An increase in wave and peak height of each metal
ion signal was observed without any change in half wave and peak potential
values.

in

\ *»

- Ι βΟ ν

Ifx f "Mi

hi
1 \/
V

ZOOmv
• vcH.TAee •

Fig.l: (A), (B), (C)

(A) Direct current polarogram,
(B) Differential pulse polarogram,
(C) Differential pulse anodic stripping voltammogram of scorodite
mineral in 0.1M ammonium tartrate +0.001% gelatin. pH 9.0 ± 0.1.

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Vol. 26, No. 1, 2007 Trace Analysis ofScorodite Mineral

J \
0 10 V I
T
j ! ?
β i M
I

200mV
200tn V
- VOLTAGE - VOLTAGE -

• 0. 3 0 V

i nX
cc w
v
I
0·

200 mv
VOLTAGE —

Fig. 2: (A), (B), (C)

(A) Direct current polarogram,
(B) Differential pulse polarogram,
(C Differential pulse anodic stripping voltammogram of scorodite
mineral in 0.1 Μ ammonium tartrate+0.001% gelatin. pH 9.5 ± 0.1

After confirming the presence of the said metals in the sample, some
synthetic samples with varying concentration of the said metal ions were
prepared and their polarograms and voltammograms were recorded under the
aforesaid experimental conditions. The results showed no change in Ε υ 2 and
£ p values for the above-mentioned metal ions. The linear relationship
between the concentration of each metal ion and the corresponding wave
height/peak height was also unchanged, reconfirming the possibility of an
accurate simultaneous multielement qualitative and quantitative deter-
mination of the aforesaid metal ions in the sample. The concentration of each
metal ion (taken/found) in synthetic sample using DPP is given in Table 2.

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P.K. Tamrakar and KS. Pitre Reviews in Analytical Chemistry

ST'
sJ-A

! \
-o so ν

200 mV
VOLTAGE ——
VOLTAGE

—ι — t, Ο ν
r
SV
α: ! c
Λ

As

200 rnv
VOL Τ A G Ε —

Fig. 3: (A), (Β), (C)

(A) Direct current polarogram, (B) Differential pulse polarogram,
(C) Differential pulse anodic stripping voltammogram of scorodite
mineral in 0.1 Μ HCl + 0.001% gelatin. pH 0.2 ± 0 . 1 .

Table 2
Analysis of synthetic samples
Composition of synthetic samples (mg/100ml analyte)
Tl' 1.58 2.04 5.10 6.12
(1.57)* (2.00) (5.07) (6.10)
Sb 3+ 18.76 18.76 24.35 29.22
(18.70) (18.71) (24.35) (29.20)
Zn 2+ 0.08 0.17 0.49 0.52
(0.08) (0.16) (0.44) (0.51)
Fe 3+ 7.75 8.37 9.49 10.04
(7.73) (8.34) (9.48) (10.01)
Os x+ 0.19 0.45 0.52 0.59
(0.19) (0.43) (0.51) (0.53)
As 1+ 0.14 0.19 0.38 0.47
(0.12) (0.19) (0.35) (0.45)

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Vol. 26, No.], 2007 Trace Analysis ofScorodite Mineral

Average of four determinations.

( ) * Amount found using DPP (mg per 100ml analyte).

Minimum tried detection limits

The minimum tried detection limits of the DCP, DPP and DPASV
techniques for measurement of the individual and combined metal ions are
given in Table 3. Except for Os and As, all the metal ions in the sample could
be determined in one run. The detection limits were examined by preparing
synthetic samples. The data in Table 3 clearly reveals that the minimum tried
detection limits in both case, i.e. individual and combined, are T l + ( 2 0 . 4 ) ,
Sb 3 + (12.2), Zn 2+ (6.4), Fe 3+ (5.6), Os 8+ (19.0) and AS 3+ (7.4) μ δ . Γ ' using DCP,
it is 0.204 for T l \ 0.122 for Sb 3+ , 0.64 for Zn 2+ , 0.56 for Fe 3+ , 0.19 for Os s +
and 0.74 μ g . r , for As 3 + using DPP. The data also show that the D P A S V
method using a glassy carbon fibre electrode is highly sensitive for
determining the reported metal ions down to the nanogram level i.e. for
T l + ( 2 0 . 4 ) , Sb 3 + (12.2), Zn 2 + (12.8), Fe 3+ (2.8), Os 8+ (19.0) and A s 3 + ( 7 . 4 ) n g . r 1
in the individual and combined forms.

Table 3
Minimum tried detection limits.

Metal DCP DPP DPASV

Ion μί?·Γ' HR-L-' ng-Γ1
Tl+ Individual 20.4 0.204 20.4
Combined 20.4 0.204 20.4
3+
Sb Individual 12.2 0.122 12.2
Combined 12.2 0.122 12.2
Zn 2+ Individual 6.4 0.64 12.8
Combined 6.4 0.64 12.8
Fe 3+ Individual 5.6 0.56 2.8
Combined 5.6 0.56 2.8
Os K+ Individual 19.0 0.19 19.0
Combined 19.0 0.19 19.0
AS 3 + Individual 7.4 0.74 7.4
Combined 7.4 0.74 7.4

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P.K. Tamrakar and K S. Pitre Reviews in Analytical Chemistry

Table 4
Results on scorodite mineral sample for its trace metals content (mg.g" 1 )

Metal Parameter DCP DPP DPSAV

Ions Added Found Added Found Added Found
31.78 31.78 31.79
Amount
31.68 63.78 31.68 63.36 31.68 63.31
Tl + R% 99.86% 99.84% 99.74%
S.D. 0.082 0.13 0.082
C.V. 0.26% 0.41% 0.26%
Amount . 374.99 . 374.99 . 374.99
374.50 749.40 374.50 749.38 374.50 749.25
3+
Sb R% 99.98% 99.97% 99.96%
S.D. 0.080 0.091 0.071
C.V. 0.02% 0.024% 0.02%
Amount - 1.45 . 1.45 1.45
1.50 2.91 1.50 2.94 1.50 2.93
Zn 2+ R% 98.64% 99.66% 99.32%
S.D. 0.074 0.048 0.052
C.V. 5% 3.31% 3.58%
Amount - 155.90 - 155.90 155.90
156.24 311.62 156.24 311.62 156.24 311.62
Fe3+ R% 99.89% 99.83% 98.83%
S.D. 0.18 0.091 0.048
C.V. 0.12% 0.058% 0.031%
Amount - 1.36 1.36 - 1.36
1.33 2.67 1.33 2.68 1.33 2.66
Os8+ R% 99.25% 99.62% 98.88%
S.D. 0.036 0.075 0.055
c.v. 2.64 5.51% 4.04%
Amount - 2.406 - 2.40 - 2.40
2.47 4.81 2.47 4.84 2.47 4.85
As 3+ R% 98.76% 99.38% 99.59%
S.D. 0.052 0.059 0.048
C.V. 2.17% 2.45% 2.0%
Results are average o f four determinations
R % Recovery (%)
S.D. Standard Deviation
C.V.Coefficient o f Variation

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Vol. 26, No.l, 2007 Trace Analysis ofScorodite Mineral

Quantitative analysis

After ascertaining the presence of above mentioned metal ions the method
of standard addition was used for quantitative analysis. The results and
reported in Table 4. The statistical data i.e. percentage recovery, standard
deviation and coefficient of variation is also reported in this table. The
percentage recovery is almost over 9 9 % for most of the metal ions with great
accuracy of determination. The standard deviation and coefficient of
variation showed the precision and reliability of the observed data.
The final results of analysis on scorodite mineral sample are reported in
Table 5. These observed voltammetric results were compared with those
obtained using the atomic absorption spectroscopic method. The data showed
excellent agreement and demonstrate the utility of the voltammetric methods
for such analysis. Further, the voltammetric method is simple, fast and may
be recommended for possible use in an analytical laboratory.

Table 5
Final results on scorodite mineral sample and the comparison
with the results by AAS.

I
Metal Ion Amount found in mg.g"
Voltammetry AAS
Tl + 31.78 31.72
Sb3+ 374.99 374.90
Zn 2 + 1.45 1.48
Fe 3 + 155.90 155.88
Os 8 + 1.36 1.37
As 3 + 2.40 2.37

ACKNOWLEDGMENT

The authors thank Prof. V. K. Saxena, Head, Department of Chemistry,

Dr. Hari Singh Gour University, Sagar (M.P.) India for providing laboratory
facilities. One of the authors ( P K T ) is thankful to CSIR, New Delhi for the
award of Senior Research Fellowship.

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P.K Tamrakar and KS. Pitre Reviews in Analytical Chemistry

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