Letter to the Editor: Comments related to

the publication titled uranium in ground

water from Western Haryana, India by
Balvinder Singh, V. K. Garg, Poonam
Yadav, Nawal Kishore, Vandana Pulhani,
J Radioanal Nucl Chem, DOI 10.1007/
s10967-014-3133-y, Published online: 13
April 2014
D.P.S.Rathore
Journal of Radioanalytical and
Nuclear Chemistry
An International Journal Dealing with
All Aspects and Applications of Nuclear
Chemistry

ISSN 0236-5731
Volume 302
Number 1

J Radioanal Nucl Chem (2014)

302:745-746
DOI 10.1007/s10967-014-3392-7

1 23
Your article is protected by copyright and
all rights are held exclusively by Akadmiai
Kiad, Budapest, Hungary. This e-offprint is
for personal use only and shall not be self-
archived in electronic repositories. If you wish
to self-archive your article, please use the
accepted manuscript version for posting on
your own website. You may further deposit
the accepted manuscript version in any
repository, provided it is only made publicly
available 12 months after official publication
or later and provided acknowledgement is
given to the original source of publication
and a link is inserted to the published article
on Springer's website. The link must be
accompanied by the following text: "The final
publication is available at link.springer.com.

1 23
 Author's personal copy
J Radioanal Nucl Chem (2014) 302:745746
DOI 10.1007/s10967-014-3392-7
Letter to the Editor: Comments related to the publication titled
uranium in ground water from Western Haryana, India
by Balvinder Singh, V. K. Garg, Poonam Yadav, Nawal Kishore,
Vandana Pulhani, J Radioanal Nucl Chem, DOI 10.1007/s10967-
014-3133-y, Published online: 13 April 2014
D. P. S. Rathore
Received: 28 June 2014 / Published online: 3 September 2014
 Akademiai Kiado, Budapest, Hungary 2014
Dear Editor,
I have read the above cited paper [1] very carefully.
Undersigned has been involved in the analysis of geolog-
ical materials and hydro-geochemical reconnaissance sur-
veys attached with mobile geochemical laboratories in
different parts of India for uranium exploration activities of
Atomic Minerals Directorate for Exploration and Research.
I have also contributed research papers on uranium deter-
mination in diverse matrices. Based on my experiences
gained so far, I would like to share some of my observa-
tions as follows:
The authors statement and claim on page 3 of the
manuscript under section: uranium estimation, the details
of model/make of the instrument is missing in the cited
paper [1]. As stated by them, quote For uranium quanti-
fication at ultra trace levels in water laser fluorimetry
technique is used which is based on the measurement of
fluorescence of uranium complexes in aqueous solution. In
this technique, on excitation of uranium complexes with
UV light of 337.1 nm wavelength, the complexes emit
green fluorescence, that is measured by photo multiplier
tubes (PMT) unquote. The description of the instrument
used and the procedure adopted for uranium measurement
is incorrect resulting in non-reproducible results, as stated
by them in Authors Reply in response to the comments of
Dr. Rathore Comments on uranium concentration in
groundwater in Hisar city, India [2] on their recent
This article is a response to the DOI:10.1007/s10967-014-3133-y.
D. P. S. Rathore (&)
Chemistry Laboratory, Central Region, Atomic Minerals
Directorate for Exploration & Research, Department of Atomic
Energy, Civil Line, Nagpur 440001, Maharashtra, India
e-mail: dpsr2002@yahoo.com; dpsrathore.amd@gov.in
publication in The IJOEM [3]. The authors very clearly
stated quote The uranium concentration in groundwater
was quantified using laser fluorimetry (Model UA-1,
Quantalase, Indore, India) employing standard spiking
method to avoid any matrix interference. There are stan-
dard protocols for uranium quantification that have been
reported in our earlier publications unquote and cited the
present publication as reference number 3 (Singh B., Garg
V. K., Yadav P., et al. Uranium in groundwater from
western Haryana, India. J Radioanal Nucl Chem 2014.
doi:10.1007/s10967-014-3133-y). On the contrary, the said
instrument, (Model UA-1, Quantalase, Indore, India) is not
a laser fluorimeter. This information furnished by the
authors is absolutely incorrect and highly misleading
[ I (strongly) disagree with this statement.
In laser fluorimetry (laser fluorimeter), nitrogen laser
giving UV light of 337.1 nm wavelength is the excitation
source while in the instrument, Uranium Analyser UA-1,
(Pulsed LEDs Fluorimeter) (Model UA-1, Quantalase, In-
dore, India) pulsed light emitting diodes (LEDs) is the
excitation source. In this LED based instrument, a bank of
intense Pulsed UV LEDs which excite fluorescence in
uranium complexes in the sample. A suitable sharp cut off
filter transmits only light of wavelengths shorter than
440 nm from the LEDs. Lenses appropriately arranged
focus the LED light on the sample in the cuvette. Detection
chamber houses the photomultiplier and suitable filters
which transmit the fluorescence but do not transmit the
LED light. The photomultiplier tube is kept in off mode
when the LEDs are on and is switched on for about 50 ls
after a suitable delay.
The authors have not even read the manual of the
instrument as well as the cited reference[It might
have avoided the attention of the authors that this is written in
the manual. Authors have adopted the incorrect procedure
123
 Author's personal copy
746
for the measurement of uranium as is evidenced from the
authors statement and claim on page 3 of the manuscript
under section: uranium estimation, 2nd quote The pH of the
reagent was maintained at 7.0 by ortho-phosphoric acid.
0.1 M HCl/0.1 M NaOH was used to adjust the pH of water
samples unquote and 3rd para quote The water samples the manuscript under section: Uranium estimation, quote
were filtered using Whatman filter paper No. 42. 5 ml of 5 %
sodium pyrophosphate (pH 7.0) solution was added to 50 ml
of the water sample and pH of the mixture was adjusted at 7.0
using 0.1 M HCl. To avoid the matrix interferences, standard
spiking method was used for uranium quantification of the
water samples as reported by Sahoo et al. (12). The laser
fluorimeter was calibrated with 1.0, 3.0, 5.0 and 10.0 lg l-1
standard solution of uranium and reagent blanks were run
with water samples to ensure the accuracy of the results. All
samples were analyzed in triplicate and the presented results
are average of three measurements unquote. It is very
unfortunate that the authors are lacking in information and
update on the basic fundamentals on fluorimetric measure-
ment of uranium and adopted incorrect procedure for
adjusting final pH of the solution at 7 using 0.1 M HCl
resulting in non-reproducible results of uranium vide their
publication [3] (In Fig. 1 of the article, the error in the
measurement (error bars) should have presumably depended
on the concentration of uraniumwhile it is not). Halides in
general are well known strong quencher for uranyl fluores-
cence. Moreover, the authors have wrongly stated even in
their The IJOEM publication [3], quote To achieve the
objective of this study, 38 groundwater samples were col-
lected from the region in 1-l pre-cleaned polyethylene bot-
tles. Uranium analysis was performed by laser fluorimetry
method as described elsewhere unquote and cited the
publication:
Campen W., Bachmann K. Laser-induced fluorescence
for the direct determination of small concentrations of
uranium in water. Microchim Acta 1979;72:159170, as
reference no. 8. This reference is related with testing the
performance of UA-3 Uranium Analyzer (Scientrix Ltd,
Canada) and is irrelevant.
They have cited the reference of the author Sahoo et al.
(12) in their manuscript but it is very clear that the authors
have not read the Analytical Procedure carefully[. This
reference must have avoided the authors attention, too. I
quote from their publication, cited as reference no. 12 by
Sahoo et al., from page 109, under the sectionAnalytical
procedure quote About 5 ml of water sample was placed
in a dry and clean cell and 0.5 ml of 5 % sodium pyro-
phosphate (pH 7) was added and measured. The instrument
was calibrated with standard uranium solution of a known
concentration. Standard addition method was followed for
analysis of field samples in order to avoid the matrix effect
because the samples were from different parts of the
123
J Radioanal Nucl Chem (2014) 302:745746
country and the chemical constituents may vary signifi-
cantly. Both micropipettes and analytical balance were
used simultaneously to avoid any error in pipetting
unquote.
Further statement of the authors and claim on page 3 of
The accuracy of the results was verified by Inter-labora-
tory comparison method. Nineteen, randomly selected,
water samples were re-analyzed at Bhabha Atomic
Research Centre, Mumbai, India. The results of both the
laboratories were better than 10 % variation in the
results unquote, appears misleading. Variation of 10 %
in the uranium measurement results at 1 ppb level is
acceptable but the same is not acceptable at 10 ppb level
and so on.
In my opinion, they should have adopted the analytical
procedure as per the manual for direct analysis of uranium
in water samples using pyrophosphate as fluorescence
enhancing reagent using standard addition method. Any
additional chemical preparation of sample will introduce
contamination and high blank value. Moreover, there are
different procedures reported for different type of sample
matrix followed by laser-induced fluorimetry [4].
The presence of fluoride in the water sample might
significantly affect the uranium content [5, 6]. Water
sample pH, uranium/conductance ratio, salinity, and alka-
linity, among other important factors, should have also
been mentioned in the report; these factors are the most
significant aspects in ascertaining the potential of uranium
presence in water samples.
I request that the authors of the subject article kindly
further document the reliability of their findings in view of
the concerns expressed herein.
References
1. Singh B, Garg VK, Yadav P, Kishore N, Vandana P (2014)
Uranium in ground water from Western Haryana, India. J Radio-
anal Nucl Chem. doi:10.1007/s10967-014-3133-y
2. Rathore DPS, Garg VK (2014) Comments on uranium concentra-
tion in groundwater in Hisar city, India. Int J Occup Environ Med
5:169171 and reference cited therein
3. Garg VK, Yadav A, Singh K et al (2014) Uranium concentration in
groundwater in Hisar city, India. Int J Occup Environ Med
5:112114
4. Robbins JC, Castledine C, Kostiak W (1985) Analytical proce-
dures for UA-3 uranium analysisapplications manual. Scintrex
Limited, Concord
5. Rathore DPS (2013) Interpretation and evaluation of the variations
in the uranium, major cations and anions content of hydrogeo-
chemical samples with reference to the time interval between
sampling and analysis. Explor Res At Miner 23:207215
6. Rathore DPS (2014) Uranium exploration. Curr Sci 106:792