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Geological Survey of India

Analysis of Hydride forming Elements by VG-AAS

The National Geological mapping (NGCM) programme of the department, which was
launched since 2001 2002 FSP, demands analysis of 68 elements in various geological and
environmental samples such as sediments, soil, food plains, regolith, water, etc. at below their
crustal level of abundance under different analytical packages. We are concerned herewith the
hydride forming elements under packages D to be determined by Vapour Generation Atomic
Absorption Spectrophotometer (VG-AAS).

The package D elements comprise i.e. Arsenic (As), Antimony (Sb), Selenium (Se) and
Bismuth (Bi) are analyzed by VG-AAS technique procedure provided from CHQ Kolkata was
applied. The sample digested by the action of multi acid (NNO3 / HF / HClO4), for complete
decomposition, and finally taken in HCl acid (1:1) for analysis of above elements. The instrument
used for analysis GBC make software based Avanta model attached with vapor generation unit
HG 3000.

In the present method, NGCM samples are to be completely decomposed by the action of
HNO3/HF/HClO4 and finally taken in HCl solution for analysis with VG-AAS. The NGCM samples
contain these elements in very low amount usually in ppb level. The above elements form
hydrides with sodium borohydride. Prior to hydride formation, the elements are reduced to the
lower oxidation states by heating with moderately concentrated HCl. The sample solution and
sodium borohydride solution are allowed to mix in reaction coil of continues flow VGA where
hydrides formation taken place. The hydride vapour so formed is transported in to the heated
quartz absorption cell placed in the optical path of AAS flame. Argon is used as carrier gas, it
also helps in stripping of the hydrides from solution. The absorption is measured and
concentration is determined against the calibration curve derived similarly by passing the freshly
prepared standard solution before passing the sample solution. The method is applicable to
determine hydride forming elements at ppb level.

1 Contributed by Dr. Shailendra Chandrawanshi,


Central Region
Geological Survey of India

Fig. Systematic diagram of vapor generation assembly for hydride formation

Atomic Absorption spectrophotometer is a versatile and essential instrument for any


modern chemical laboratory. It is known for its application in the rapid and low cost analysis of a
variety of samples. Difficulty arises with the samples of complex nature like the geological
samples. The samples matrix interferes to a greater extent in the determination of element
particularly when it is present in very low quantity. The elements having their primary resonance
lines below 200 nm where the absorption by flame gases is strong, having sensitivities very low
and present in very low quantities in the geological samples are very difficult to determine by
flame AAS.

Many of group IV, V and VI (A) elements of the periodic table namely As, Sb, Se, Bi, Te,
and Ge forms covalent hydride with nascent hydrogen. The volatile hydrides formed can be
decomposed to atomic vapour without directly being introduced in a flame or by passing through
a heated quartz cell which has been utilized as an alternative approach for their estimation. This
phenomenon forms the basis of the vapour generation technique. The advantage of volatilization
of gaseous hydrides lies clearly in the separation and enrichment of the analyte elements and
thus in a reduction or even complete elimination of interference. The absorption signal is
enhanced to a greater extent due to the increased residence time in the optical path as compared
with the direct aspiration in the flame. That is more number of atoms are exposed for longer time
to give greater response. This enables to measure the quantities in ppb order with sufficient
accuracy.

2 Contributed by Dr. Shailendra Chandrawanshi,


Central Region
Geological Survey of India

Fig. - Apparatus for the Determination of hydride forming elements

The Se, Bi, As and Sb are digested using multi-acid procedure in an open Teflon vessel,
at the end of the digestion period, Se, Bi are reduced to oxidation states +4 and +3 respectively
and after analysis of Bi and Se adding of KI + ascorbic acid on the solution As and Sb are
reduced to oxidation states +3. Sodium borohydride is added to the solution in rapid formation of
the hydride as illustrated by:

NaBH4 +3H2O + HCl === H3BO3 + NaCl + 8H


Em+ + H === EHn + H2 (E = Analyte)
3NaBH4 + 4H2SeO3 === 4H2Se (g) + 3H3BO3 + 3NaOH
3NaBH4 + 4H3BiO3 === 4BiH3 (g) + 3H3BO3 + 3NaOH
3NaBH4 + 4H3AsO3 === 4AsH3 (g) + 3H3BO3 + 3NaOH
3NaBH4 + 4H3SbO3 === 4H3Sb (g) + 3H3BO3 + 3NaOH
The easily reducible metals like Au, Ag, Cu, Ni, and Co suppress hydride formation
resulting in to poorer response. Because, the metal atoms produced on reduction precipitate as
fine dispersion and catalyse the hydride formation of the own whereby, hindering the hydride
formation of the analyte atoms. This can be solved by taking higher concentration of HCl that

3 Contributed by Dr. Shailendra Chandrawanshi,


Central Region
Geological Survey of India
may keep them in solution. The effects of interference are observed as an enhancement or
depression of analyte signal. Techniques employed to minimize or compensate interferences by
using of the same nature of standard reference materials or matrix matching standard solution for
calibration of instrument.

TABLE - 1: INSTRUMENTAL PARAMETER FOR DETECTION OF ELEMENTS.


ELEMENT Bi Se As Sb
wavelength 223.1 nm 196.0 nm 193.7 nm 217.6 nm
Slit 0.2 nm 1.0 nm 0.5 nm 0.2 nm
Lamp Current 10mA 10mA 10mA 10mA
Preread delay 45 seconds 45 seconds 45 seconds 45 seconds
time
Integration time 5 seconds 5 seconds 5 seconds 5 seconds
Replicate 3 3 3 3
Acid channel 1:1 HCl 1:1 HCl 1:1 HCl 1:1 HCl
(6M)(1ml/min) (6M)(1ml/min) (6M)(1ml/min) (6M)(1ml/min)
Reductant 0.6% (w/v) NaBH4 0.6% (w/v) NaBH4 0.6% (w/v) 0.6% (w/v) NaBH4
channel (1ml/min) (1ml/min) NaBH4 (1ml/min) (1ml/min)
0.5 (w/v) NaOH 0.5 (w/v) NaOH 0.5 (w/v) NaOH 0.5 (w/v) NaOH
Sample channel Sample solution Sample solution Sample solution Sample solution
(7ml/min) (7ml/min) (7ml/min) (7ml/min)
Argon 80-130 ml per min. 80-130 ml per min. 80-130 ml per 80-130 ml per min.
min.
LLD 0.1 ppm 0.2 ppm 1.0 ppm 0.2 ppm

PRECISION AND ACCURACY

The analytical data obtained for two SRM samples are excellent agreement with the
certified value shown in Table-2. The above method is found suitable for the analysis of Bi, Se,
As, and Sb by VGA method as the observed values of the standard reference materials are found
within the permissible limit of the certified value.
Accuracy is the measure of how close the analytical data lie to the True composition of
the sample. For an instrument, the accuracy is its capacity to give results that are free of
systematic error, meaning a good degree of exactitude. To check the accuracy of the method,
stream sediment reference samples GSS-4 and GSD-4 was analyzed and the results are
compared with the recommended values. A fantastic agreement of data with recommended
values for most of the elements shows the acceptable accuracy in Table-2

log C = log CObtained log C Recommended

TABLE 2 : PRECISION AND ACCURACY


Sl. Reference No. No. of Selenium Bismuth Arsenic Antimony

4 Contributed by Dr. Shailendra Chandrawanshi,


Central Region
Geological Survey of India
No. replicate ppm ppm ppm ppm
1 SRM - GSS-4 OV 0.68 1.17 57.8 6.27
CV 0.64 0.18 1.04 0.20 58 3 6.31.7
log C 0.026 0.051 0.0015 0.0021
2 SRM GSD-4 OV 0.26 0.69 20.3 1.8
CV 0.29 0.07 0.64 0.18 19.7 2.6 1.80.27
log C 0.047 0.033 0.013 0.00
LLD -- 0.1 0.1 1.0 0.2
Acceptable log C Within 3 times of LLD = 0.4, Above 3 times of LLD = 0.2,
values 1% to 5% = 0.2 and Above 5% = 0.1
OV = Observed Value, CV Certified Value.

CONCLUSION:

From the above precision and accuracy of the results, we may conclude that the
technique of VG-AAS for the estimation of Arsenic (As), Antimony (Sb), Selenium (Se) and
Bismuth (Bi) are the most precise and accurate technique. The excellent agreement of the results
is mainly due to the high sensitivity of VG-AAS with very low practical detection limit, i.e. 0.1 ppm
for Bi, 0.1 ppm for Se, 1.0 ppm for As and 0.2 ppm for Sb are observed with level of 95%
confidence limit on 100 fold dilution.
REFERENCES
1. Recommendation methods of Estimation of As, Sb, Bi, and Se in sediments, sioils, rocks,
water etc. Compiled, Edited and Issued by Central Chemical laboratory, Geological Survey
of India, Kolkata, 1st May, 2006.
2. Arsenic and Selenium by Flow Injection or continuous flow hydride generation AAS; Philip L.
Hangeman, Zoe Ann Brown and Eric Welsch; U.S. Geological Survey Open File Report 02
223 L.
3. Varian Associates, VGA-77 Vapour Generation
4. B. L. Shaini, R. P. Sharma and R. G. Vijay; Studies on Determination of As, Sb, Bi, Se and
Te in stream sediment and Soil samples by AAS coupled with VGA; Indian Minerals, Volume
60, No. 3 & 4 2006.
5. Essential of Medical Geology Impacts of the Natural Environment on Public Health; Editor
in Chief Oile Selinus; Elsevier Academic Press 2009.
6. Environment Chemistry; A. K. De; 3rd Edition 1996.

5 Contributed by Dr. Shailendra Chandrawanshi,


Central Region

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