Dear Sir,

I would like to point out some necessary difficulties in the field of monitoring:

1. More than any monitoring research done with or without much errors I always feel strongly that results after proper interpretation should reach the concerned people such as people living in the vicinity of a study site. And all this should be done in extremely layman representation. There is no use of a data if it is circulating just among the academicians. 

2. Statistics is a tool which is most misused like people calculating mean for a series of samples which most of the times does not represent the validity of data.

There are several such vague methodologies in all kind of research fields like bio-remediation using bacteria and fungi etc.

If we are monitoring something, there will be many tangible and intangible variables affecting and under no circumstance we can identify all these. So, error can be mitigated, but they will always be a part of any measurement.

Basically errors have been classified as: Systematic and random errors.

There are interesting papers on human errors, which are attached herewith.

Article Teaching metrology and quality in chemistry based on methods...

Article Human errors and reliability of test results in analytical chemistry

There is an interesting paper on uranium:

Article Presentation of Differential Laser-induced fluorimetry as a ...

I agree with Dr. Trevor Alan Walmsley, these are most interesting observations.

I would like to reproduce the abstract of the paper for the benefit of the readers:

Data from recent studies suggest that the highest incidence of laboratory-related errors occurs in the pre-analytical phase of laboratory testing. However, few studies have examined the frequency of errors in laboratory test selection and interpretation. A survey of physicians who use our clinical laboratory demonstrated that the largest number of test ordering errors appear to involve physicians simply ordering the wrong test. Diagnostic algorithms providing guidance for test selection in specific disorders are also used as the basis for the establishment of reflex protocols in the clinical laboratory. The provision of an expert-driven interpretation by laboratory professionals resulted in improvements both in the time to and the accuracy of diagnosis. A survey of our physician staff has shown that in the absence of such an interpretation, for patients being assessed for a coagulation disorder, approximately 75% of the cases would have involved some level of test result misinterpretation.

Clin Chem Lab Med. 2007;45(6):712-9.

"Pre-pre" and "post-post" analytical error: high-incidence patient safety hazards involving the clinical laboratory.

Laposata M1, Dighe A..

Kindly provide a link to download this most interesting publication.

:

There are other interesting Letter to Editor articles by the author.

Article Letter to Editor : Query related to publication titled “A co...

Also on uranium exploration.

Article Uranium Exploration

Comments on: Uranium Concentration in Groundwater in Hisar City, India

Thanks for sharing the question.

I am not a chemist, still, i feel we should take the help of State of the art technologies for the analysis of samples for uranium, instead of pure chemical analysis to minimize human errors. A NMR spectra can give exact information, provided a Uranium NMR spectra library is available.

http://scitation.aip.org/content/aip/journal/jcp/54/10/10.1063/1.1674649

Thanks prof sharma for giving us some new information.

Regards,

Dr.D.P.S.RATHORE

One more article has been accepted for publication in J Radioanal Nucl Chem : Letter to the Editor: Comments related to the publication titled " Uranium in ground water from Western Haryana, India" by Balvinder Singh, V.K.Garg, PoonamYadav, Nawal Kishore,Vandana Pulhani, J Radioanal Nucl Chem, DOI 10.1007/s10967-014-3133-y, Published online: 13 April 2014

I will comment on this article in depth about the human errors contributed by authors, reviewers and publishers. 

Human errors and the practices of organizing manuscript, such as, citation of irrelevant publications, citation of statements and references,  without verifying original publications, copying and pasting of irrelevant paragraphs, lack of basic knowledge on uranium measurement, etc, resulting in  non-reproducible  and highly misleading conclusions /discussion based on such results.

In my opinion, such practices should be strongly discouraged and condemned. The role of institutions/organisation, funding scientific bodies, Head of institution, reviewers, editors, publishers and  finally of readers are very important. Truely speaking, the actual peer review process starts after publication of any paper. I personally believe that every one should learn and update in knowledge. No one is perfect, human errors may happen but to identify any error , to rectify the bias  is a great challenging job.   This  is how development of science/innovation take place. The over all , the very important role of quality control and quality assurances practices are very important in all measurements /evaluations, including APAR.s ( Annual performance Appraisal Reports) of Scientists .

Dear Rathore,

You can found answer in  the researches  of Dr. Kusselman. See attach file.

Joseph

give blind ed samples and audit the results  by giving same  MOA and procedure 

it will give  some idea of errors occurring between two analyst  

I spent a significant part of my professional life to explore this problem:  How to detect errors in your own analytical results before other do it for you.

The optimal approach is to

    1) create an uncertainty budget

    2) verification of your uncertainty budget

    3) participation in proficiency testings

See e.g. Accred. Qual. Assur. 13 (2008) 217-222 

Article Proficiency testing in the light of a new rationale in metrology

True, I agree with you if any laboratory  participate honestly in any PT programme and provide all the details of steps to arrive at your results. Simply providing the average value of say seven laboratories( each laboratory processing samples in triplicate), does not guarantee reliability of a single result for any element. Documentation of all the steps are mandatory to arrive at the conclusion.

Laser fluorimetry has been widely used since more than three decades for the direct determination of uranium in water samples at ppb level. Recently, LED-fluorimeters were introduced by: Quantalase - Services

http://quantalase.in/services

Quantalase. ... Quantalase Enterprises Private Limited. 229,Vigyan Nagar Near Alpine Public School Indore, MP 452012 ph: 0731 2322707 fax: 0731 2322708

Dilip Bhawalkar ( email: [email protected])

Director at Quantalase Enterprises Pvt. Ltd.

If any expert /analytical chemist carrying out uranium determination in water samples using laser fluorimetry might have reviewed the manuscript, one can easily point out the large variation in measurement results ( Fig1. From the publication in The IJOEM.

( Garg VK, Yadav A, Singh K, et al. Uranium concentration in groundwater in Hisar city, India. Int J Occup Environ Med 2014;5:112-114). Variations at such concentration levels are practically impossible ( Using Laser Fluorimetry as stated by author citing a reference 8 , which is for different laser fluorimeter,UA-3 Uranium Analyser (Scintrex Limited, Concord, Ontario, Canada).

But, From the Author’s Reply: Stating the Model UA-1, Quantalase, Indore, In¬dia was used for uranium determination.

One can easily make out that Model UA-1, Quantalase, Indore, In¬dia instrument is not a Laser Fluorimeter and also the procedure described is incorrect.

Model UA-1, Quantalase, Indore, In¬dia instrument is a Pulsed LED-Fluorimeter

So, by reading carefully all the three papers, one can easily find out the Research misconduct /human errors by authors:

1. Author paper( Garg VK, Yadav A, Singh K, et al. Uranium concentration in groundwater in Hisar city, India. Int J Occup Environ Med 2014;5:112-114.),

2. Author’s Reply

( Rathore DPS. Comments on uranium concentration in groundwater in Hisar city, India. Int J Occup Environ Med 2014;5: Online first, available from: www.theijoem.com/ijoem/index.php/ijoem/article/ view/445. And

3. Authors paper Published in J Radioanal Nucl Chem(Singh B, Garg VK, Yadav P, et al. Uranium in ground¬water from western Haryana, India. J Radioanal Nucl Chem 2014. DOI 10.1007/s10967-014-3133-y).

I am attaching herewith copies of papers for the benefit to the readers regarding tolerance to chloride ions.

I am attaching herewith copies of papers for the benefit to the readers regarding tolerance to chloride ions.

application of laser fluorimetry to saline waters.

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 quantification 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. Ra¬thore ‘Comments on uranium concentration in groundwater in Hisar city, India’ [2] on their recent publication in The IJO¬EM [3]. The authors very clearly stated quote “ The uranium concentration in ground¬water was quantified using laser fluorim¬etry (Model UA-1, Quantalase, Indore, In¬dia) employing standard spiking method to avoid any matrix interference. There are standard protocols for uranium quantifi¬cation that have been reported in our ear¬lier publications” unquote and cited the present publication as reference number 3 (Singh B, Garg VK, Yadav P, et al. Uranium in ground¬water 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, In¬dia) 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, Indore, In¬dia) pulsed LEDs ( Light Emitting Diodes) 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 microsecs 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 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 were filtered using Whatman filter paper No. 42. Five 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 µg 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 measurement 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 Figure 1 of the ar¬ticle, the error in the measurement (error bars) should have presumably depended on the concentration of uranium—while it is not ). Halides in general are well known strong quencher for uranyl fluorescence. Moreover, the authors have wrongly stated even in their The IJO¬EM publication[3] quote” To achieve the objective of this study, 38 groundwater samples were collected from the region in 1-L pre-cleaned polyethylene bottles. Uranium analysis was performed by laser fluorimetry method as described elsewhere “ unquote and cited the publication :

Campen W, Bächmann K. Laser-induced fluores¬cence for the direct determination of small con-centrations of uranium in water. Microchimica Acta 1979;72:159-70, 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 this reference in their manuscript but it is very clear that authors have not read even this reference”.

“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 author’s attention, too. I quote from their publication, cited as reference no.12 by Sahoo et al., from page 109, under the section –Analytical procedure quote “ About 5 ml of water sample was placed in a dry and clean cell and 0.5 ml of 5 % sodium pyrophosphate (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 country and the chemical constituents may vary significantly. 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 manuscript under section: Uranium estimation, quote “The accuracy of the results was verified by Inter-laboratory 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 alkalinity, among other important factors, should have also been mentioned in the report; these factors are the most significant aspects in ascertain¬ing the potential of uranium presence in water samples.

References

1. Singh, Balvinder, Garg, VK, Yadav, Poonam, Kishore, Nawal, Pulhani Vandana (2014),Uranium in ground water from Western Haryana, India, J Radioanal Nucl Chem, DOI 10.1007/s10967-014-3133-y, Published online: 13 April 2014.

2. Rathore, DPS, Garg, VK (2014) Comments on uranium concentration in groundwater in Hisar city, India. Int J Occup Environ Med, 5:169-171 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 , 5:112-114.

4. Robbins, J. C., Castledine, C. Kostiak, W., Analytical Procedures for UA-3 Uranium Analysis—

Applications Manual, Scintrex Limited, Ontario, Canada, 1985 Oct.).

5. Rathore DPS(2013), Interpretation and evaluation of the variations in the uranium, major cations and anions content of hydrogeochemical samples with reference to the time interval between sampling and analysis. Exploration and Research for Atomic Minerals, 23: 207-215.

6. Rathore DPS(2014), Uranium exploration. Curr. Sci., 106:792

My query has been published in :

Letter to the Editor: Comments related to the publication titled " Uranium in ground water from Western Haryana, India" by Balvinder Singh, V.K.Garg, PoonamYadav, Nawal Kishore,Vandana Pulhani, J Radioanal Nucl Chem, DOI 10.1007/s10967-014-3133-y, Published online: 13 April 2014

D.P.S.RATHORE

J Radioanal Nucl Chem, DOI: 10.1007/s10967-014-3392-7 ( In Press)

The  practices of organizing manuscript, citation of irrelevant publications, citation manipulation, citation of references without verifying original publications, copying and pasting of irrelevant references, without any significant improvements over existing methods, authors claim in absence of basic fundamental studies, etc,constitutes Scientific  Misconduct /human errors. It is the sole responsibility and involvement of the institution for encouraging researchers holding senior positions for such research and publication misconduct /human errors. It is very unfortunate that instead of discouraging such practices such people are rewarded with outstanding promotions /increments.

There is a need of such case studies whether such activities /mindset of people are really helpful for  fulfilling the mandate and mission or  growth of the organization/nation.  

Recent article titled “Lessons from the recent publication scams” published in Current Science, Vol.,106, No.5, 10 March, 2014, p.649,  is worth to be quoted here. In my opinion also, for the growth of science, it is important to teach ethics to researchers, and to keep a check on their work through individual institutions and departments. Such accountability can track individual scientific contributions, which would eventually, help one to stop or minimize scientific misconduct/human errors.

 In these circumstances, there is a challenging job of Reviewers,Editors, publishers, Readers, Researchers to discourage  such activities and give directions for the growth of science for their real applications.

Attaching a copy of such publication on " Simultaneous separation and preconcentration of rare earth elements on activated carbon for its determination by ICP-OES in beneficiation products"..

http://www.indianchemsoc.org/jour2013.htm.nov13.pdf

The  practices of organizing manuscript, citation of irrelevant publications, citation manipulation, citation of references without verifying original publications, copying and pasting of irrelevant references, without any significant improvements over existing methods, authors claim in absence of basic fundamental studies, etc,constitutes research misconduct/human errors. It is the sole responsibility and involvement of the institution for encouraging researchers holding senior positions for such research and publication misconduct /human errors.

Attaching a copy of publication on " Separation and Preconcentration  of rare earth elements in geological materials using used green tea leaves and their determination by ICP-OES".

This cited manuscript1 is lacking in basic fundamental studies related with sorption properties of UGTL towards individual REEs and on update of recent literature published on low cost adsorbents.There are excellent reviews published in the literature on ‘biosorption of heavy metals-an overview’  by Das et al.2, a review by Geetha  and Belagali 3 on ‘Removal of Heavy Metals and Dyes Using Low Cost Adsorbents from Aqueous Medium-, A Review’, a review byDas and Das4 on ‘Recovery of rare earth metals through biosorption: An overview’. These review articles provide an overview of past achievements and current scenario of the biosorption studies carried out using some promising biosorbents which could serve as an economical means for recovering from wastes /removal of dyes, heavy metals, rare earth metals. The experimental findings reported by different workers will provide insights into this research frontier.

Biosorption is one of the emerging biological methods having several advantages over the conventional methods. This process does not produce any chemical sludge, easy to operate and very efficient for the removal of pollutants from very dilute solutions. A major advantage is that it can be used in situ and with proper design. It may not need any industrial process operations and can be integrated with many systems5. The initial incentives for biosorption development in industrial process are the low cost of biosorbents, their high efficiency for metal removal (especially in low-concentration solutions), the biosorbent regeneration (and the potential metal recovery), the fast kinetics of adsorption and desorption, and the non-generation of secondary residues6. Rare earth metals (REMs) are a series of 17 elements. Biosorption studies of various rare earth metals namely, La, Nd, Ce, Er, Yb, Eu, Sm and Dy  using different adsorbents in batch mode have been reported as summarized in the review4.Some of the papers on removal of heavy metals(cobalt, cadmium, and zinc) from waste water using black tea waste7, sorption/removal of lead by spent tea leaf 8,9, adsorption of lead (II) on spent tea leaves of green and black tea10 and removal of copper(II) from aqueous solution using spent tea leaves as a potential sorbent11 are interesting.

As reported in the literature, the adsorption capacity is an important factor, because it determines how much sorbent is required to quantitatively concentrate the analytes from a given solution. From the available literature12, there is a decrease in adsorption of uranium on AC in the presence of fluoride, nitrate, thiosulphate and oxalate ions can be attributed to weak adsorption of the anionic complexes. Qadeer et al.13. published their studies on surface characterization and thermodynamics of adsorption of Sr2+, Ce3+, Sm3+, Gd3+,Th4+,UO22+ on activated charcoal from aqueous solution. As reported by the authors7, on page 130, Table 4.9, quote “To check the selectivity of activated charcoal for gadolinium, the adsorption of U, Er, Dy, Sm, Ce, La, Ba, Cs, Cd, Y, Sr, Rb, Zn, Cu, Co, Mn, Cr and V on activated charcoal was examined at optimum conditions for gadolinium. The results indicate that Dy, Sm, Eu, Er, U, La, Y, Ce and Ba have considerably higher values of distribution coefficient (KD). So they would coadsorb along with gadolinium on activated charcoal. Cr, Cd, Cs, Co, Ni, Zn, Mn, V, Sr, Cu and Rb have small KD values, hence they are poorly adsorbs on activated charcoal” unquote. The KD values are different for each rare earth element. Therefore, separation and preconcentration of REEs using activated charcoal system is practically impossible. Similarly, these parameters need to be studied for UGTL’s system in the presence of heavy metals and other associated major, minor and trace elements in different geological matrices. A range of major, minor and trace element including REEs should be given for ensuring the applicability of the proposed method for different geological matrices.

Moreover, in view of the solubility products values of REEs fluorides14 and the conditions used by the authors (0.12 M NaF medium, pH~3) for adsorption of REEs on UGTL’s   needs further investigations on the role of UGTl’s. In my opinion, this manuscript is lacking in basic fundamental studies related with sorption properties of UGTL’s towards individual REEs, such as, source of UGTL’s, characterization of UGTL’s, equilibrium isotherm models (KDvalues), biosorption kinetics, thermodynamic parameters for adsorption, the behaviour of individual rare earths, adsorption of REEs as a function of their concentration, adsorption of REEs in the presence of different cations namely, sodium, potassium, cobalt, zinc, chromium, copper, nickel, barium, strontium, lead, cadmium, manganese, thorium, vanadium; adsorption in presence of different anions, FTIR and SEM analysis of loaded and unloaded biosorbent, etc., prior to its quantitative application in REEs separation and preconcentration studies followed by ICP-OES measurement. In view of the concern expressed as above, Authors claim is absolutely wrong and highly misleading.

In addition to, relevant and up-to-date citations of references /support to the stated statements to the published literature on tea leaves as biosorbent are missing.What is the purpose of citing irrelevant references in the text of the manuscript by simply copying and pasting all references cited in their previous publication15 on UGTL’s by Vijay Kumar,Satya Prakash and P.N.Bangroo, titled “Synthesis of immobilized used green tea leaves on silica gel and its application in separation / preconcentration of uranium and trace elements in hydrogeochemical samples”published in the journal “Exploration and Research for Atomic Minerals, Vol.,19, pp.97-101, year, 2009 (© Director, AMD, DAE, Govt. of India, ISSN-0970-9231), of course without citing this relevant publication.

About references 1-4 cited in the manuscript: Reference No.1 titled ‘Determination of ten rare-earth elements and yttrium in silicate rocks by ICP-AES without separation and preconcentration’, 2nd Ref. is on Rare earth element geochemistry, 3rd Ref. titled ‘Determination of rare earth elements and yttrium in some uranium-and thorium-rich geological materials by inductively coupled plasma emission spectrometry’ 4th titled ‘Chemical analysis-An  instrumental approach’, Reference numbers 5-15 are cited at one place: Ref. Nos 5-12 ( all 8 references), are simply cut and pasted from their previous publication on UGTL’s15, Ref.No.5 titled ‘Speciation analysis of chromium using cryptand ethers’, Ref No.6 titled ‘Speciation of Cr(III) and Cr(VI) in waters using immobilized moss and determination by ICP-MS and FAAS’, Ref.No.7 titled ‘Preconcentrative separation of chromium (VI) species from chromium(III) by coprecipitation of its ethyle xanthate complex onto naphthalene, Ref. No. 8 titled ‘On-line separation and preconcentration of chromium species in seawater’, Ref.No.9  titled ‘On-line separation and preconcentration of chromium species in seawater’, Ref no. 10 titled ‘Separation and speciation of Cr(III) and Cr(VI) with saccharomyces cerevisiae immobilized on sepiolite and determination of both species in water by FAAS’, Ref.No.11 titled ‘Uptake of chromium cations and anions by milled peat’, Ref. No.12  cited as K. Chandrasekhar, N.S. Chary, C.T. Kamala, K. Rajni Supriya, T. Rameswar Rao, Int. J. Environ. Stud. 5 (2002) 1 , is incorrect and is absolutely wrong. This reference appears to be taken from a publication in Talanta 65 (2005) 135–143, cited there as Ref. no.28. A search was made through email to authors, journal search ‘Int. J. Environ. Stud. 5 (2002) 1’ and through journal support system of Taylor & Francis Online Customer Services www.tandfonline.com Customer Services Survey and confirmed that we have unfortunately been unable to locate the article using the information supplied. Unfortunately the mentioned article (if referenced correctly) appears to be missing from our database. What is the necessity of citing such irrelevant reference? This publication is not a primary reference related to UGTL’s.  Ref.No.13 titled ‘Determination of rare earth elements in different geological matrices by ICP-AES after solid phase micro extraction on activated charcoal’, Ref.No.14 titled ‘Removal of lead,cadmium and zinc by waste tea leaves’ Ref.No.15 titled ‘ Adsorption of divalent copper, zinc, cadmium and lead by waste tea and coffee’. There is no scientific discussion /comment on references cited in the manuscript and should be cited at appropriate places to support the statements. In my opinion, only five references nos. 2,4 ,13,14 &15 are relevant and rest others are not related with the subject matter.

Such practices of organizing manuscript, citation of irrelevant publications, citation manipulation, citation of references without verifying original publications, copying and pasting of irrelevant references, without any significant improvements over existing methods, authors claim in absence of basic fundamental studies, etc,constitutes research misconduct/Human errors.

Recent article16 titled “Lessons from the recent publication scams” published in Current Science, Vol.,106, No.5, 10 March, 2014, p.649,  is worth to be quoted here. In my opinion also, for the growth of science, it is important to teach ethics to researchers, and to keep a check on their work through individual institutions and departments. Such accountability can track individual scientific contributions, which would eventually, help one to stop or minimize scientific misconduct.

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

Vijay Kumar, Sanjay Kumar, Naveen Kumar and P.N.Bangroo, J. Indian Chem. Soc., 2013, 90, 2147.

Nilanjana Das, R.Vimala and P.Karthika, Indian J. Biotechnol., 2008, 7, 159.

K.S. Geetha and S.L. Belagali, IOSR Journal of Environmental Science, Toxicology and Food Technology (IOSR-JESTFT), 2013, 4, 56.

Nilanjana Das and Devlina Das,J. Rare Earths, 2013, 31, 933.

N. Tewari, P. Vasudevan and B. K. Guha, Biochem. Eng. J., 2005, 23,185.

D. Kratochvil and B. Volesky. Trends Biotechnol., 1998, 16, 291.

R. R. Mohammed, Arab. J. Sci. Eng., 2012,37,1505.

A.Yoshita, J.L. Lu, J.H.Ye and Y.R.Liang, African J. Biotechnol., 2009, 8, 2212.

      9. R. Lavecchia, A. Pugliese and A. Zuorro,Chem. Eng. Trans, 2010,19, 73.

    10.  A. Zuorro and R.Lavecchia, Am. J. Applied Sci., 2010, 7, 153.

    11. S.K. Bajpai and A. Jain, Water S A , 2010, 36, 221.

   12. www.google.com: [PDF] adsorption of heavy metals on activated charcoal

     prr.hec.gov.pk/Chapters/3053H-4.pdf‎  and reference cited therein.

  13. R. Qadeer, J. Hanif, M. Saleem and M.afzal,Colloid and Polymer Science, 1993, 271,  83     

       and reference cited therein.

14. Hisako Itoh, Hiromitsu Hachiya, Masashi Tsuchiya,Yasuo Suzukiand Yasukazu Asano, Bull.    

  Chem. Soc.Jpn.,1984,57,1689.

15. Vijay Kumar,Satya Prakash and P.N.Bangroo, Exploration and Research for Atomic Minerals,    

     2009,19, 97.

16. A. A. Shah, Current Science, 2014, 106, 649.

There is a publication file EARFAM .pdf:

Vijay Kumar,Satya Prakash and P.N.Bangroo, titled “Synthesis of immobilized used green tea leaves on silica gel and its application in separation / preconcentration of uranium and trace elements in hydrogeochemical samples”published in the journal “Exploration and Research for Atomic Minerals, Vol.,19, pp.97-101, year, 2009 (© Director, AMD, DAE, Govt. of India, ISSN-0970-9231)

http://www.indianchemsoc.org/jour2013.htm.nov13.pdf

There should be more emphasis on training and improvement in skills.

copy of paper  on " Chemical analysis of limestone and dolomite using capillary Electrophoresis" is attached herewith.

As on today, even a class 12th student is familiar with the concept of hardness of water and also with EDTA. EDTA titration methods are commonly used for the determination of calcium and magnesium in water samples. The various methods/techniques used in the determination of calcium and magnesium in the ‘Certification of Standard Reference Materials’, such as Dolomitic limestone 88b, BCS No. 368 Dolomite, BCS-CRM No. 513 Limestone  etc. are well documented in certificate of analysis. Complexometric titration method is one of them for calcium and magnesium determination in such matrices.Rapid EDTA complexometric method for determination calcium and magnesium in lime and limestone products has been thoroughly investigated and is widely accepted5,6. Complexometric titration methods and various techniques of titrations are well documented in the commonly available book A.I., Vogel, A Textbook of Quantitative Inorganic Analysis.Indicators namely, Eriochrome Black T7, murexide8, calcon 9,10, the indicator of Patton and Reeder11,  calmagite12, Arsenazo I 13 are well known for complexometric titrations. Ordinarily the EDTA procedure is designed to follow routine separations, that is, single dehydration of silica and a single precipitation with NH4OH of the combined oxides of iron and aluminum. For expediency, the assays can be run directly without prior separation of the combined oxides of iron and aluminum by using the complexing action of EDTA at appropriate pH levels. As reported in ASTM-document13, Designation: C 25-06, Standard test methods for chemical analysis of limestone, quick lime and hydrated lime. The precision of this test method was tested by ten laboratories using three limestone and one dolomite reference samples. The results are summarized as follows: The overall precision (1sigma) between laboratories (reproducibility) and within laboratories (1 sigma):  for CaO are ±0.31 and ±0.24 absolute units and for MgO are ±0.28  and ±0.22 absolute units, respectively. Moreover,titration methods are regarded as absolute methods in analytical chemistry14,15.

A claim stated in the above cited manuscript, quote “The developed analytical protocol is cheaper, faster and accurate compared to the existing analytical methods using ICP-OES and AAS as it does not require any gases during analysis and avoids all types of interferences “unquote. In view of the stated facts as above in 2nd para, the claim of authors is highly misleading and absolutely incorrect.Complexometric titration methods fulfill the essential requirements of simplicity, rapidity, cost-effective, accuracy, high precision, reliability, comparability & traceability.Complexometric titration methods require no expensive instrumentation (simple glasswares, burette, pippetes, etc),  no equipment calibration and are widely recommended for the determination of calcium and magnesium at percentage level for such matrices. Surprising, there is no comment or discussion by the authors of the cited paper in their manuscript on complexometric titration methods.

As stated and discussed in this manuscript on page 2029, 2nd para, quote “capillary electrophoresis (CE) is hybrid technique ……….multispecies analysis  and also stated in 3rd para of the manuscript….” unquote.  The use of highly sensitive capillary electrophoresis technique for the chemical analysis of major concentration of calcium and magnesium content in limestone and dolomite samples is never justified.

On page 2030, of the manuscript, as stated, quote “Dilute solutions (1-30 ppm) can be easily analysed using CE with good reproducibility, but analysis of concentrated solutions often lead to peak broadening and hence poor reproducibility of the results” unquote. Moreover, from the reproducibility data reported in Table 1 and Table 3 are significantly different ( nearly twice). In Table1, reproducibility data(% RSD) for calcium as Ca  and for magnesium as Mg by CE technique are 0.9 and 1.7 , on the contrary in Table 3 , %RSD values are 1.7  ( actual figure should be 1.8) and 3.2(actual figure should be 3.29, i.e., 3.3) , respectively. This is nothing but fabrication of analytical results for comparison purposes.

In Dolomite BCS No.368 sample( All results relate to the dried (110 0C, Correct certified value of CaO, 30.8 % (average) ±0.086 (Standard Deviation) and corresponding Ca value is 22.01±0.06 (Standard Deviation),and for MgO, 20.9 (average)±0.15( standard deviation) and corresponding Mg value is 12.6 ± 0.09. As reported in the manuscript in Table 2, on page 2032, the certified values of Ca as 22.01±0.17 and Mg as 12.6±0.14, are incorrect and wrongly quoted. As per the convention, the values of major element concentrations in minerals or rocks are reported in terms of their oxides. The same convention of reporting their concentration is adopted in their certificate of analysis of CRMs. Instead, the authors of the cited paper adopted to report their analytical results in terms of elemental form. In my opinion, this is simply to fabricate the values of standard deviations with their average values of calcium and magnesium contents in CRMs for comparison purpose as reported in Table 2 and Table 3 of the manuscript and to mislead the scientific analytical community. The information available on the NML website:www.nmlindia.org, and also from the certificate of analysis, analytical  values are as follows: Limestone (No.71.1) (revalidated), Silica,0.52%, Calcium oxide, 55.10%, Magnesium oxide, 0.50%, Loss on ignition, 43.48%.  The corresponding reported certified values of Ca as 39.38% and Mg as 0.30 % in Limestone (NML CRM No.71.1) are correctly quoted. The values of associated standard deviations in Ca  ±0.29 and Mg  ± 0.09 are not available in the certificate of analysis but appears totally incorrect.( can be calculated from the different values)

As per the published literature, common trace elements including calcium and magnesium in the reference materials are commonly determined by flame–atomic absorption spectrophotometer while ICP-OES is most suitable for the determination of traces of elements forming refractory oxides, such as REEs, etc16-18. ICP and AA spectrophotometric methods suffer from chemical, physical, and spectral interferences including wavelength absorbance, inconsistencies in the introduction of the dissolved sample into the instrument, and overlapping and unresolved wavelength peaks. AAS and ICP techniques are never recommended for the analysis of calcium and magnesium at higher concentration levels due to their unacceptable high % RSD13. X-ray spectrometric methods require that the chemical and physical compositions of the sample closely match the reference materials used to calibrate the instrument, but the availability of certified reference materials is limited18.

This analytical protocol does not satisfy any of the three essential requirements of a methodology: reliability, applicability and practicability. There are contradictory and highly misleading statements. A claim stated in the manuscript by the authors is absolutely wrong.

I request that the authors of the subject article kindly further document the reliability of their findings in view of the concerns expressed herein.

Nature News Blog

Researcher’s death shocks Japan

05 Aug 2014 | 08:10 BST | Posted by David Cyranoski | Category: Uncategorized

This is extremely shocking incident. My serious concern is about Scientific Misconduct, which might have accelerated this extreme step and it is very unfortunate.

The cases of scientific misconduct are increasing day by day due to greediness of the individuals for quick gain, fame, etc. I have also raised such issues related with  five publications in vol., 90 of J. Indian Chemical Society, November,2013 and addressed to the Editor. The reply of the concerned Editor is unscientific and I would like to quote here, quote:

Dear Dr. D. P. S. Rathore,

We have reviewed your criticism and contacted Authors. Whole things are discussed in an Editorial Board and with Indian Chemical Society Administration. It is opined that Issue is dedicated to 50 years of NML, Jamsedpur India; articles had been invited and reviewed by a Reviewers Board constituted by ICS and NML. Board had decided the publishing quality of the manuscript.  So, Journal of Indian Chemical Society does not entertain any criticism on this matter and hence the matter is closed.

Thank you for your effort.

Sincerely yours

C. Sinha

Editor, Inorganic & Analytical Chemistry Section, JICS

In my opinion, this is not the scientific basis to decline my query and I (strongly) disagree with the decision of The Editor.

I have further requested to the Editor to kindly review his decision and publish my query

Any query and the author’s reply should be published as per the standard practice adopted by the Editors of international Scientific journals/publishers.If any author fails to respond or do not respond , such authors should be blacklisted and query should be published without delay with a note from the Editor.

Recently, I have tried my best through various  ‘Letter to the Editor’ publications  in this direction. It is the most challenging task of Institution involved, Reviewers, Editors, Publishers, Readers, and finally of the Experts to discourage practices of organizing such manuscripts and need to change the mind set of such persons for real scientific contributions in future research.

In my opinion, the mindset and activities of such the so-called researchers holding senior positions are highly dangerous and destructive for the growth of any organization/ or nation in fulfilling the mission and mandate, if immediate steps are not initiated..

This is for the prompt action and meaningful suggestions by the valuable readers.

There is one more such paper published on uranium: Copy of paper is attached.

Laser Induced Luminescence Method for the Determination of Soluble Uranium in Surface Soil” by P. P. Prasad, B. Narasimha Murty, R. Muthyalu and H. R. Ravindra published in  JRA 2013, 1(5): 67-76, DOI: 10.12966/jra.08.01.20

Keeping in view, the experimental procedure described in this paper for the age old pellet fluorimetry for the determination of uranium, clearly indicate that the authors have no basic knowledge of the measurement procedure. Moreover, there is no novelty in laser fluorimetric measurement procedure described by the authors. Laser fluorimetric analytical procedures for UA-3 uranium analysis are well documented in their applications manual long back in 1985 by Robbins et al. The two main references 24 and 29 cited in this publication are wrong.

As stated on page 69, Experimental,  section3.1. Reagents, quote “Aluminium nitrate (Al(NO3)3 9 H2O) solution: To 1000 g of aluminium nitrate nonahydrate in a two litre beaker, 1000 mL of distilled water was added and the constituents were stirred thoroughly to dissolve the solid completely. This homogenized solution was transferred in to a reagent bottle for its use in the analysis” unquote. This is absolutely wrong.

                        A saturated solution of Aluminium nitrate (Al(NO3)3. 9 H2O) is used as a salting out agent, which is prepared by dissolving 1000g in 500 ml of distilled water. The final volume of this saturated solution will be 1000ml.

On the contrary, as stated in section 3.5.1(a).1 Procedure, on page70 of the manuscript quote “ To 10 mL aliquot of the centrifuged stock solution in a graduated cylinder of 50 mL capacity with lid, 10 mL ofaluminium nitrate solution, 20 mL ethyl acetate were added and after fixing the lid firmly, the graduated cylinder was shaken manually in a gentle manner for 8 minutes. Then the constituents upon allowing to stand undisturbed separate into two clear layers” unquote. This is absolutely wrong. This saturated aluminium nitrate solution in the ratio of 1 part of the sample(v/v) aliquot( in 10% nitric acid ) and 5 part of saturated aluminium nitrate(v/v) is used as a salting out agent in the standard procedure to facilitate quantitative recovery of uranium from aqueous to ethyl acetate phase.

As stated on page 69 of the manuscript, Section 3.2. Preparation of Flux, quote  “85 g of sodium carbonate was taken in a mortar and ground to a fine powder using a pestle and now 15 g of sodium fluoride was added and the mixture was again ground to make a homogeneous fine powder. This homogenized powder was used to dispense in the form of tablets of about 0.2 g into the platinum planchet using a pellet dispenser” unquote.  This is absolutely wrong.

Moreover, as stated on page 70 of the manuscript, section 3.5.1(a).1 Procedure, Fusion temperature for sodium carbonate- sodium fluoride flux as 600 0C, is incorrect and fusion is practically impossible to get a uniform melt of the flux bead.

            The optimum flux ratio for fusion is 4 part sodium carbonate to 1 part sodium fluoride fine powder and 0.4 g of this homogenized  flux powder is used for fusion at 850 0C  in muffle furnace for 2 min.

As stated in the manuscript on page 71, Section 3.5.1(b).1 Procedure, the sodium pyrophosphate buffer adjusted to pH~7 has been used as fluorescence enhancing reagent. In my opinion, a choice of an appropriate fluorescence enhancing reagent for different types of sample matrices is essential [5]. A fluorescence enhancing reagent of pH~7 is most suitable for water samples. For solid samples, an acidic buffer has distinct advantages over others, as it eliminates the problems of iron precipitation and uranium adsorption by glass.

The claims by the authors as stated above and presented in Table 5 in the manuscript( Content of soluble uranium in various soil samples as determined by (a) Laser fluorimetry involving no prior matrix separation and (b) Conventional fluorimetry involving prior matrix separation) are practically impossible, absolutely wrong,  highly misleading and has no scientific basis.

I do not know, why people are so greedy for publications?. It is simply for the sake of getting outstanding grading in APARs, Special increments and outstanding promotions through internal assessment.

There is one more such correspondence: I would like to reproduce:

My purpose is to bring to the kind notice of the Experts/Readers to kindly review and suggest various corrective measures to discourage such Scientific Misconduct/ Human errors.

From: Editors IJP

To: D P S RATHORE

Sent: Thursday, 11 July 2013 5:38 PM

Subject: INJP: Your manuscript entitled Comments on "Uranium concentration in drinking water samples using the SSNTDs"

Ref.:  Ms. No. INJP-D-13-00093R2

Comments on "Uranium concentration in drinking water samples using the SSNTDs"

Indian Journal of Physics

Dear Dr. Rathore,

Thank you for submission to our journal. You have commented on a paper that was published 5 years back, as per journal norms, we had sent this comment to the concerned authors and some of the other respected reviewers of Indian Journal of Physics. Unfortunately we have received no reports from them. We are therefore not able to consider it for being published in the Indian Journal of Physics.

Thanking you for interest in the Indian Journal of Physics and best regards,

Sincerely,

Editor-in-Chief

Indian Journal of Physics

There is one more such paper:

Laser flourimetric analysis of uranium in water from Vishakhapatnam and estimation of health risk by R. C. Bhangare, M. Tiwari, P. Y. Ajmal, S. K. Sahu, G. G. Pandit, Radiation Protection and Environment | July 2013 | Vol 36 | Issue 3,

DOI: 10.4103/0972-0464.137478 .

www.rpe.org.in

The said instrument used for uranium determination is not a laser fluorimeter. This is incorrectly stated in the manuscript.Moreover, the uranium values are reported up to three decimal places, which is incorrect. This is how the Human errors are propagated  in publications.

There is an interesting article on Human Errors in Chemical analysis:

Monte Carlo simulation of expert judgments on human errors in chemical analysis – a case study of ICP-MS

 by Ilya Kuselman, Francesca Pennecchi, Malka Epstein, Ales Fajgelj, Stephen L.R. Ellison

Talanta130(2014)462–469

Rightly said by  Ilya Kuselman:

Identification of human error requires as a professional knowledge in the measurement method, as a statisrical background. There is no any method, primary or other, which is able to garantee human error absence.

There is one more such  paper:

Studies on effective decomposition of monazite minerals by variety of phosphate fluxes for simple and direct determination of uranium by LED Fluorimeter by Leela Gopal, V.V. Hanuman and G. Chakrapani, published in J. Indian Chem. Soc.,Vol. 90, November 2013, pp. 1935-1939.

In view of the rapidity and simplicity of measurement by pulsed fluorimetry, the main emphasis was either on developing new fluorescence-enhancing reagents or on methods of measurements for different types of sample matrices. Several workers have developed methods for the determination of uranium in matrices, like rocks, soils and sediments, mineralized rocks, concentrates and other U-rich materials 4-7, in which sample matrix effects are either eliminated by dilution of sample solution to such an extent that quenching by impurities no longer influences the analysis, or the separation of the uranium from the quenchers by extraction, compensation of matrix effects by use of an internal standards (standard addition), or other methods.

Novel sample decomposition and dissolution of refractory, nonsilicate minerals like ilmenite, rutile,  columbite, tantalite  and  xenotime 8 , tin slag9, monazite10 , Th and REE-rich matrix11   have been the subject of many studies, followed by determination of REE and other accompanying elements by ICP-OES, and uranium by pulsed fluorimetry/fluorimetry.

The mineral chemistry of REE-minerals and REE-bearing minerals are well documented in the literature. Monazite and Xenotime are REE-minerals while REE-bearing minerals are Apatite, Zircon, Fluorite, Rutile and Iron oxides12. As claimed by the authors, the paper describes, quote “A simple, rapid, effective sample decomposition method is developed for the determination of uranium (U) in monazite minerals by fluorimetric (Light Emitting Diodes (LED) based) technique. The salts of sodium dihydrogen phosphate (NaH2PO4), disodium hydrogen phosphate (Na2HPO4) and tetrasodium pyrophosphate (Na4P2O7) were used to conduct studies on effective decomposition and dissolution of monazite minerals……..” unquote.

These REE-bearing minerals contains inclusions of monazite/xenotime. A separate publication and claim by authors dealing with uranium determination in monazite by pulsed fluorimetry(LED fluorimeter) has no novelty/originality/improvements in the manuscript.

The author, Chakrapani has earlier reported vide his publications (Development of Novel Flux for effective sample decomposition of Refractory samples and Field Oriented Pre-concentration methods for the determination of Twenty Nine Trace and Ultra Trace Elements in a variety of Geological Samples by Flame and Plasma Techniques for application to Geochemical Exploration of UraniumbyG. Chakrapani, Journal of Applied Geochemistry, Vol 14, No.4 (2012),pp. 447-452 and A Rapid Fusion Technique for Chemical Characterization of Monazite by ICP-OES by M. Krishnakumar and G. Chakrapani, Journal of Applied Geochemistry, Vol 15, No.4 (2013),pp. 419-425), On page no, 450, Section 5 of the publication quote “Novel sample decomposition procedure for refractory samples for direct determination of uranium” unquote and also vide his earlier publication cited as reference no.5 in the present publication in J. Indian Chem. Soc(2013).These two publications also highlighting novel sample decomposition and dissolution of refractory minerals have not been included by them in the above cited manuscript.

As stated in the manuscript, on page 1935, third para quote  “ Radhamani et al 5 adopted a fusion method , using a mixture of tetrasodium pyrophosphate and monosodium dihydrogen phosphate (1:1) and prepared the solution in 3% HCl to solubilise the insoluble CeIV polyphosphate. The presence of high amount of chloride quenches  the fluorescence …” unquote. This statement    quoted is not based on reference No. 5 in the above cited publication. The authors have suppressed the already reported and published information related with the determination of uranium in refractory minerals  (a publication by Chakrapani, titled  “ Novel fusion method for direct determination of uranium inilmenite, rutile,  columbite, tantalite  and  xenotime minerals by laser induced fluorimetry by R. Radhamani, P.L.Mahanta, P . Murugesan, G. Chakarani published in Journal of Radioanal. Nucl. Chem. (2010) 285: 287-292”).

At the same time, the statement quoted in the manuscript on page 1938, section, High sample throughput: quote  “Radhamani et al 8 adopted a fusion method, using a mixture of tetra sodium pyrophosphate and monosodium dihydrogen phosphate (1:1) and prepared the solution in 3% HCl to solubilise the insoluble CeIV polyphosphate”  unquote. This is the same statement as on page  1935, third para of the cited manuscript.

There is no discussion /comment about their earlier publication cited as reference no.5 in the above cited manuscript and other publications. There is nothing new information nor any  improvement in the present manuscript over their earlier published work. A Claim by the authors in the above cited publication is absolutely wrong and highly misleading.  

This is for the information to all readers:

Int workshop on human errors and quality of chemical analytical results

Ilya Kuselman to you24 minutes ago

Dear Dr. Rathore,

I would like to inform you about development of the workshop: see details at http://bioforumconf.com/workshop2015 . Please distribute this info among your collaborators, to whom it may concern.

You and your colleagues are welcome.

Best regards,

Ilya

http://bioforumconf.com/workshop2015

Dear Sir,

I would like to point out some necessary difficulties in the field of monitoring:

1. More than any monitoring research done with or without much errors I always feel strongly that results after proper interpretation should reach the concerned people such as people living in the vicinity of a study site. And all this should be done in extremely layman representation. There is no use of a data if it is circulating just among the academicians. 

2. Statistics is a tool which is most misused like people calculating mean for a series of samples which most of the times does not represent the validity of data.

There are several such vague methodologies in all kind of research fields like bio-remediation using bacteria and fungi etc.

If we are monitoring something, there will be many tangible and intangible variables affecting and under no circumstance we can identify all these. So, error can be mitigated, but they will always be a part of any measurement.

Sampling, Preservation and validated methodology are mandatory to arrive any meaningful conclusions for any monitoring programme..

One more recent publication is worth to be quoted here:

Uranium and other heavy toxic elements distribution in the drinking water samples of SW-Punjab, India,

Journal of Radiation Research and Applied Sciences 01/2015; 1. DOI: 10.1016/j.jrras.2015.01.002 

The claim by the authors is absolutely incorrect and highly misleading’’—> I (strongly) disagree with their statement in the manuscript.Interpretation and conclusions based on such unreliable results will be highly misleading.

It is very unfortunate that instead of giving a scientific reply to queries, Editor-in-Chief are encouraging Scientific misconduct:. I would like to quote the reply :

Dear Dr Rathore,

Thank you for your e-mail and please accept my apologies for the inconvenience.

Please see below comments from the Editor-in-Chief regarding your paper JRRAS-D-15-00045:

"I would like to inform you that JRRAS publish only original research articles and review articles,

Dr. Rathore submit a letter to editor and not an article, this is not accepted for publication, he can see the information to author and ethics. Also he sent comments about a published article in JRRAS, he can send these comment to the author directly and not using the system. This published article was reviewed by specialist and corrected by the author."

Should you required further assistance please visit http://support.elsevier.com. You will find 24/7 support

contact details, including live chat.

Kind regards,

Joseph Cachuela

Researcher Support

unquote.

My purpose here is to bring in to the notice of learned readers/ Expert to give their valuable comments to discourage such practices of scientific misconduct..

In my opinion, such publications should be immediately retracted.

I am attaching a copy of my comments addressed to Editor-in-Chief of the journal and also the copy of paper.

Article Uranium and other heavy toxic elements distribution in the d...

There is another publication :

Highly sensitive & low cost colorimetric method for quantifying arsenic metal

in drinking water of Malwa Punjab and comparison with ICAP-AES

Mandeep Sidhu, Parul Mahajan and Sheelendra M Bhatt*

Annals of Biological Research, 2014, 5 (3):105-109

(http://scholarsresearchlibrary.com/archive.html)

I have read this paper [1] and all the cited references in this manuscript. I would like to share some of my observations on this manuscript which may be useful for future research and a meaningful publication.

The authors claim in the abstract of the paper quote “We have developed a highly sensitive & cost effective colorimetric method for quantifying Arsenic metal in drinking water of and the result of sample analysis has been compared with ICAP-AES method” unquote. On the contrary, authors have cited reference number ‘10’ in their publication on page 106, in the Section -Determination of Arsenic. There is no update of literature survey on arsenic determination in water. There is no validation of this new developed method using recovery/standard addition method, optimization of variables ( pH, reagent concentration, λmax, nor any study of effect of foreign ions/tolerance limits and its comparison with EPA-standard method reported in the literature[2], instrument manufacturer/models, etc. Moreover, the procedure described is practically impossible, I quote from their publication on page 106, in the Section -Determination of Arsenic, quote “ An aliquot of sample solution containing 0.2-14 μg/mL of arsenic was transferred into series of test tubes. Then potassium iodide (2%, w/v) (1mL) and sulphuric acid (0.1M), (1 mL) were added and mixture was gently shaken. EDTA (0.01%), (1 mL) was added and mixture was gently shaken. This was followed by addition of CCl4 (7%, w/v), ( 1mL). The solution was kept for 5 min and made 10 mL by adding distilled water. The absorbance of pink colour was measured at 515 nm. This method involves the liberation of iodine by the reaction of arsenic with potassium iodate in acidic medium. The liberated iodine selectively oxidizes CCl4 to form pink color which have maximum absorbance at 515 nm [10]” unquote. The range quoted is 0.2-14 μg/mL of arsenic while in the abstract authors further claimed that “The liberated iodine selectively oxidizes CCl4 to form pink color which have maximum absorbance at 515 nm [10]”. This statement on the reaction ‘liberated iodine selectively oxidizes CCl4 to form pink color’ is incorrect. In addition to, the colour was developed in test tubes and not in calibrated volumetric flasks. Authors statement and claim that “Our modified colorimetric method of arsenic determination is sensitive up to 0.0167 mg/L without any interference at 515nm” -> is absolutely incorrect and highly misleading. I have strong objections to such unscientific statements.

From Table1, how the authors are able to determine arsenic concentration in water samples stated by them ranging from 0.001 to 0.073 mg/L. The authors claims are self-contradictory, highly misleading and has no scientific basis.

On page, 107, From section quote“ Water sample detection by ICAP-AES: Water samples which were collected from various regions and were send to Punjab Agriculture University, Ludhiana for accurate measurement of arsenic by ICAP-AES (Inductively Coupled Argon Plasma-Atomic Emission Spectroscopy)” unquote. The details of the instrument model, manufacturer and operating conditions are missing. From Table1 and figure1, presenting comparative analysis of data, there are large differences among them [ Sl No. 4 Kartar Singh Wala, 0.073±0.07 Arsenic ICAP-AES (mg/L) 0.044±0.98 Arsenic UV-Vis. Spectro (mg/L), Sl No. 2 Gehri Bhagi, 0.056±.06 Arsenic ICAP-AES (mg/L) ; 0.033±0.89 Arsenic UV-Vis. Spectro (mg/L)]. Such comparison of analytical data has no reliability and validity. It is very clear that authors have not even read the cited reference number ‘10’ in their publication about statistical analysis of results using paired t-test and F-test.

The reliability/quality of measurement results depend strictly on adherence to each step of measurements of the method and not simply analysed by any person or lab or any technique.

The practices of organizing manuscript, such as, citation of irrelevant publications, citation of references without verifying original publications, copying and pasting of irrelevant paragraphs, incorrect measurement procedure and non-reproducible results, lack of basic knowledge on arsenic measurement, etc, constitutes research misconduct including plagiarism, citation manipulation, research integrity and is a gross violation of publication ethics.

Recent article[3] titled “Lessons from the recent publication scams” published in Current Science, Vol.,106, No.5, 10 March, 2014, p.649, is worth to be quoted here. In my opinion also, for the growth of science, it is important to teach ethics to researchers, and to keep a check on their work through individual institutions and departments. Such accountability can track individual scientific contributions, which would eventually, help one to stop or minimize scientific misconduct.

I request the honorable Editor to kindly verify the stated facts as above and retract such publication.

I further request the Publishers and editors to take reasonable steps to identify and prevent the publication of papers where research misconduct has occurred, including plagiarism, citation manipulation, and data falsification/fabrication.t

REFERENCES

[1] Mandeep Sidhu, Parul Mahajan and Sheelendra M Bhatt, Annals of Biological Research,

2014, 5 (3),105-109.

[2] EPA -815-R-00-010, Analytical Methods Support, Document For Arsenic In Drinking

Water, (December 1999) United States Environmental Protection Agency Office of Water

Office of Ground Water and Drinking Water Standards and Risk Management Division

Targeting and Analysis Branch 401 M Street SW (4607) Washington, DC 20460.

[3] A. A. Shah, ‘Lessons from the recent publication scams’, Current Science., 2014, 106, 649.

Note: Attaching my comments and copy of publication.; also copy of another publication.

Article Isolation and Arsenic Uptake Study by Immobilized LAB Cells

Article Biosorption of Arsenic (III) from drinking water by using lo...

There is another publication:

There is another publication by authors:

International Journal of Pharmaceutical Research & Drug Development

Volume 1 Issue 1 – May 2014 66

Biosorption of Arsenic (III) from drinking

water by using low cost biosorbents derived

from peels of Oranges, Turnip and Peanut

shells

Mandeep Sidhu

Assistant Professor, Department of Biotechnology and Biosciences,

Lovely professional University, Punjab, India

Promila Sama

Associate Professor and Head, Medical Lab Technology,

BIS Institute of Science and Technology, Gagra , Moga

Jasleen Parmar

Department of Biotechnology and Biosciences,

Lovely professional University, Punjab, India

Sheelendra M Bhatt

Assistant Professor, Department of Biotechnology and Biosciences,

Lovely professional University, Punjab, India

Such publications should be retracted .

Note: this paper was published in the Ist issue and Ist volume. There after no issue of this journal published and is not traceable/ available on website.

Article Biosorption of Arsenic (III) from drinking water by using lo...

There is one such paper and my comments were published as given below:

Anomalous silver concentration in volcano-plutonic rocks

Current science (Impact Factor: 0.83). 03/2015; 108(6):1030-1031. 

Article Anomalous silver concentration in volcano-plutonic rocks

There is another publication to be quoted: Quantification and health risk assessment due to heavy metals in potable water to the population living in the vicinity of a proposed nuclear power project site in Haryana, India

Desalination and water treatment (Impact Factor: 0.99). 11/2013; DOI: 10.1080/19443994.2013.833877 

My query:::As stated by the authors:      Heavy metal quantification was done by atomic absorption spectrophotometer (Model GBC SensAA). Acetylene gas was used as fuel and air as support. An oxidising flame was used in all the cases except chromium, where reducing nitrous oxide flame was used for metal quantification. Detailed instrumental analytical conditions for the analysis of selected heavy metals are given in Table 1. To ensure the reliability of results, standards of respective metal were analyzed after each set of 15 samples. Collected water samples were analysed for eight metals, viz. Fe, Cu, Cr, Co, Cd, Pb, Ni and Zn.

Authors are advised to clarify, how they determined directly these elements in water samples and document their reliability. 

Measurement error and measurement methods that are available can be used

There are other papers on human errors: my comments on such publications are attached herewith.

Article Anomalous silver concentration in volcano-plutonic rocks

Article Uranium Exploration

There are some other publications attached herewith ( open reviews will be more useful for the researchers).

Article Uranium in Lake Sediments – a report on Didwana Salt Lake, N...

Article Playa Sediments of the Didwana Lake, Rajasthan: A New Enviro...

Researchers are advised to be very careful in citing references in their publications without reading the full text  and cross-checking of references cited therein.

About Reference No.19 :

19. D.P.S. Rathore, P.K. Tarafder, M.Kayal, and Manjeet Kumar, Anal.Chim. Acta 434, 201 (2001).,        has been cited in the following publication but without any statement or any comment :

Application of Solvent Extraction and Acid Hydrolysis

of Nb/Ta Separation Methods for the Determination of

Uranium in Geological Materials, Nb/Ta-type

Samples, and Leach Liquors by ICP-OES

*K. Satyanarayana

Chemical Laboratory, Atomic Minerals Directorate for Exploration and Research

Department of Atomic Energy

P.O. Assam Rifles, Nongmynsong, Shillong – 793 011, Meghalaya, India

and

M.A. Nayeem

Chemical Laboratory, Atomic Minerals Directorate for Exploration and Research

Department of Atomic Energy

Begumpet, Hyderabad – 500 016, India

Published in : Atomic Spectroscopy,Atomic Spectroscopy Vol. 23(3), May/June 2002, pp.77-85.

What is the use of citing references. It was brought than in to kind notice of Editor of the journal and authors also but no erratum has been issued.

Copies of both the  papers are attached herewith for ready reference.

Reported: Phosphoric acid–ammonium dihydrogenphosphate buffer was applied for analysis of hydrogeochemical samples and rock samples. Ref: B.N. Tikoo, D.S.R. Murty, Curr. Sci. 49 (1980) 861.

Our Observations: This buffer (Phosphoric acid–ammonium dihydrogenphosphate buffer) is unsuitable for water samples because of severe quenching by halides, particularly chloride.

A choice of an appropriate fluorescence enhancing reagent for different types of sample matrices is essential. A fluorescence enhancing reagent of pH ~ 7 is most suitable for water samples. For solid samples, an acidic buffer has distinct advantages over others, as it eliminates the problems of iron precipitation and uranium adsorption by glass. Different acidic phosphate buffers such as H3PO4–NH4H2PO4, H3PO4–KH2PO4 and H3PO4–NaH2PO4 were studied at a total phosphate concentration of ~1M (pH ~ 2.5) and gave similar results. The sensitivity of uranium in these buffers was found to be in the following order:

H3PO4–NH4H2PO4 ~ H3PO4–KH2PO4 > H3PO4–NaH2PO4

The present phosphoric acid–ammonium dihydrogenphosphate buffer is more selective in the presence of metal ions and found to be most suitable for rock samples of diverse matrices.

Vide my publication in : D.P.S. Rathore, P.K. Tarafder, M. Kayal and Manjeet Kumar(2001) Application of a Differential Technique in Laser-Induced Fluorimetry: Simple and a Precise Method for the Direct Determination of Uranium in Mineralised Rocks at Percentage Level, Anal.Chim.Acta 434 201- 208.

It is surprising how authors applied this method to water samples.

 The phosphoric acid–ammonium dihydrogen phosphate buffer system is more selective for uranium in the presence of metal ions and found to be most suitable for rock samples of diverse matrices. The proposed work is a unique application of the differential technique to the real samples, tested, evaluated and is applied to a large number of samples of diverse matrices from different on-going uranium projects over a period of more than 5 years in different regional chemical laboratories.

Dear @Manbir Singh

Really interesting and challenging observations.

Dear Dr. Rathore,

Thank you for the invitation.

I agree with the aforementioned view of Prof. Russo.

An additional chemical analysis may be conducted for doubtful samples.

" self-control " of action

Human errors in any area of research has significant effect on the uncertainty of the whole work. The elimination of these errors as much as possible enhance the results credibility. How to reduce these errors? By using the scientific measuring procedures using the largest degree of accuracy and attention.

Regards

Human errors are of vital importance in any new innovations and development of science.Efforts are always underway and it will continue to remain a greatest challenge for ever to devise methodologies to minimise human errors.

The human errors are related with the mistakes on the part of the analyst or of the operator. These errors can be: a change of standard, an incorrect transcription of data. Establishing an appropriate protocol for the control of the quality can be a way to detect them or the automation of the analytical process.

Any errors, if noticed even after its acceptance /publication, should be rectified through additions/corrections in published article, instead of propagation of such errors further..

I request the Editor-in-Chief , of Analytical Chemistry , ACS, to take this comment seriously and publish an erratum at the earliest. In my opinion, any publication should not be simply for the sake of publication.Any new methodology should be thoroughly optimized for its potential real applications/or advancement in science.

Article Highly Sensitive and Selective Method for Detecting Ultratra...

Working Paper Comments on: Highly sensitive and selective method for detec...

Errors in analysis including human error can be difficult to detect.  To minimise error we conduct method development and validation to try to ensure that a method is accurate, precise and repeatable in multiple laboratories by multiple operators if possible.  Then during routine testing we use calibration standards, certified reference materials, in-house reference materials and always perform replicate tests on unknown samples.  When you know what result you expect from your sample then any discrepancy or variation from the normal trend can be investigated as potential human error.  I have also seen unexpected results arise from random instrumentation malfunctions, using a different type of glass volumetricware, mortar made of different material and from variations in the sample being tested that were not visually obvious.

Comments on “A facile method of synthesizing ammonia modified graphene oxide for efficient removal of uranyl ions from aqueous medium by Swati Verma and Raj Kumar Dutta, RSC Adv., 2015, 5, 77192–77203”.

D.P.S. Rathore*

Former Senior Scientist, Atomic Minerals Directorate for Exploration & Research, Department of Atomic Energy,150/8,  Shiprapath, Mansarovar, Jaipur-302020,Rajasthan, India.

Email: [email protected]

I have read the above cited paper1, references and available published literature on the above subject very carefully. Based on my experience, I would like to share my observations and comments on the above cited manuscript.

As stated in the manuscript, in section, 2.4. Batch adsorption studies, on page no.77193, quote ‘ A stock solution of 1000 mg L-1 of uranium was prepared by dissolving 2.11 g of UO2 (NO3)2. 6H2O in 1 L of DI water. Solutions of different concentrations of uranyl ions were prepared by diluting the uranium stock solution in de-ionized water’ unquote. This procedure  for the preparation of stock solution of uranium and working standard is incorrect. The reliability/validity of uranium measurement will dependent on the standards. The stock solution of uranium is always prepared in de-ionized water containing acid to prevent loss of uranium. As per the literature 2-4, the recommended primary standard is a 1000 ppm U  ( mg/l) uranyl nitrate solution made up with 5% nitric acid ( 2.11 g UO2 (NO3)2.6H2O per litre ). This is diluted x100 and a further x10 to form 10 ppm (mg/l) ( in 0.05% HNO3) and 1 ppm (mg/l )(0.005% HNO3) respectively. The concentration of uranium in this stock solution was verified using the method of Davies and Gray4.

As stated in section, 3.2. Comparative study of uranyl ion adsorption capacities of NH3-GO, GO, on page 77195 of the manuscript, quote “The common interfering cations considered in this study were Ca 2+ (75 mg L-1), Mg 2+ (30 mg L-1), K+ (50 mg L-1), Na+ (200 mg L-1), Pb 2+ (0.1 mg L-1), Fe 2+ (0.3 mg L-1) and Zn 2+ (5 mg L-1) and anions like CO3 2- (300 mg L-1), HCO3- (300 mg L-1), Cl- (250 mg L-1) and SO4 2- (200 mg L-1), where the concentrations of these interfering species are given in the bracket as per the permissible limits by Bureau of Indian Standards (BIS)42 and WHO.3” unquote.  The range of  major cations and anions in natural waters, are as given below: Ca 2+( 4-4000), Mg 2+ (1-1350), Na+ (0-10,500), K+ (1-399), HCO3- (0-1000), Cl- (1-19000), SO4 2- (0-2,700),NO3- (1-15) and also reported in the literature5. The effect of potential interferent,  Fe 3+, V 5+ and humic acid are missing. In order to demonstrate the potential applicability of the system for uranium removal in natural water, authors are advised to clearly tabulate the tolerance limits of major cations, anions  and trace elements studied for the present system.

From table1: it gives no such comparison of salient feature of analytical performance of the adsorbent. The application of the proposed adsorbent for the removal of uranium from natural water samples are needed to validate its applicability.

A comparison of analytical performance of the proposed adsorbent for uranium removal, should clearly demonstrate the analytical performance in terms of : simplicity, rapidity, ease of use, sorption capacity, kinetics of sorption, Limit of preconcentration, preconcentrations factors, stabilty of adsorbent, re-usability, eco-friendly, cost-effective, easy synthesis, etc for the real applications in natural diverse water sample matrices. Such comparison of analytical performance will give direction for future research.

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.Swati Verma and Raj Kumar Dutta , RSC Adv., 2015, 5, 77192–77203.

2. Robbins, J.C. , Castledine, C. Kostiak, W. , Analytical Procedures for UA-3 Uranium          

   Analysis—Applications Manual, Scintrex Limited, Ontario, Canada, 1985 Oct.

3. Editorial Staff, Analytical Techniques in Uranium Exploration and Ore Processing,Technical      

     Report Series no. 341, IAEA, 1982.

4. FOR THE DETERMINATION OF URANIUM

www.osti.gov/scitech/servlets/purl/335168

5.W. Davies, W. Gray, Talanta 1964, 11, 1203-1211

6. Groundwater Quality and Groundwater Pollution     

    groundwater.ucdavis.edu/files/136273.pdf

Dated: October 18, 2016.

To,

Prof. B.Mahabaleswar

Editor

Journal Geological Society of India

No.63, 12th Cross, Basappa Layout

Bangalore - 560 019

Email: [email protected],

Sub: Comments on: The Role of GIS in Spatial Modeling of Multi-disciplinary Geoscientific Data for Uranium Exploration over the Kunjar-Darjing Basin, Odisha” by Chaturvedi, Anand Kumar, Ramesh Babu Veldi , Markandeyulu Amulotu, R.Pavanaguru and Anjan Chaki published in Journal Geological Society of India, Vol.,85,June 2015, pp.657-672, Most urgent-Reminder-VI –Retraction of publication-regd

Dear Prof. B.Mahabaleswar,

This is in continuation of my email  dated 5th August, 2016 and speed post dated 7th June, 2016, 27th June, 2016 and September 13, 2016 on the above subject. I request you to kindly expedite your decision. Based on material evidence, this published manuscript should be retracted on the grounds of  plagiarism and fraud.

Dr.D.P.S.RATHORE , M.Sc., M.Phil., Ph.D., FRSC

Retd. Senior Scientist,

Atomic Minerals Directorate for Exploration and Research,

150/8, SHIPRAPATH, MANSAROVAR, JAIPUR-302020

email: [email protected]

d r

To Sweedler, Jonathan V

26 Oct at 12:26 PM

Dear Dr. Jonathan V. Sweedler,

There are similar mistakes in his earlier publication in RSC ADV., 2015, 5, 77192–77203. I have taken up this issue with the Editor of RSC Adv.

This is how, the human errors propagate from one journal to others and so on.

My serious objections are on basic /fundamental mistakes in this publication. It requires immediate attention for its rectification.

Science has no limit.

The response of your Associate Editor is highly unscientific. Now the game is over, etc. Moreover, there was no response from your side.

In these circumstances, I am compelled to post on RG.

Basic scientific facts/fundamentals can not be manipulated whether it is Detection, or determination.

Analytical Chemistry is a standard journal. Why the reviewers/ Editors are promoting unscientific activities by publishing such exploratory stage publications without thorough investigations.

Now a days, even a class 12 th students knows that Na+, K+, Mg2+,and Ca2+ concentrations are more than 1000 μg L-1 ( 1 ppm ) in water samples. Any errors, if noticed even after its acceptance /publication, should be rectified through additions/corrections in published article, instead of propagation of such errors further..

In my opinion, any publication should not be simply for the sake of publication.Any new methodology should be thoroughly optimized for its potential real applications/or advancement in science.

I request the Editor-in-chief, of Analytical Chemistry , ACS, to take this comment seriously and publish an erratum at the earliest.

Regards,

Dr.D.P.S.RATHORE