Synchrotron based X-ray fluorescence for trace elemental analysis of industrial sludge

Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 192-195

J. Environ. Treat. Tech.

ISSN: 2309-1185

Journal web link: http://www.jett.dormaj.com

https://doi.org/10.47277/JETT/9(1)195

Synchrotron based X-ray fluorescence for trace

elemental analysis of industrial sludge

Vijay Kumar Garg , Arun Lal Srivastav , Manoj Kumar Tiwari , Ajay Sharma * and

Varinder Singh Kanwar¹

Chitkara University School of Engineering and Technology, Chitkara University, Himachal Pradesh-174103, India

BL-16, Indus-2, Raja Ramana Centre for Advanced Technology, Indore, India

Received: 12/08/2020

Accepted: 01/11/2020

Published: 20/03/2021

Abstract

This research article presents the application of the synchrotron-based X-ray fluorescence (XRF) technique for the resolution of trace

elemental accumulation in industrial sludge/waste. The X-ray fluorescence using synchrotron radiation presents an expeditious

exposition of a wide scale of elements (Sodium to Uranium) together with an ingenuous sample preparation procedure. The present X-

ray fluorescence studies carried out for the paper and toothpaste industry sludge at synchrotron source (Beam Line -16), Indus-2, Raja

Ramanna Centre for Advanced Technology, Indore, India. The XRF results show very low traces of heavy metals present in paper and

toothpaste industry sludge and therefore recommend for safe and efficient reuse.

Keywords: Elemental analysis; synchrotron radiation; industrial sludge and X-ray fluorescence

sample is atomized because of the primary incident X-ray or

Introduction

gamma ray photons. The energy and intensity of the

characteristic X-rays in the XRF spectra indicate the element

present and its concentration in the sample. XRF is an

important technique of elemental analysis for distinct kind of

samples and it is an extremely responsive technique, which

follows the principle of interaction of atoms with radiation [4-

In developing countries, industrial sectors pose significant

environmental and occupational health risks to its populations.

As industries are booming and large quantities of industrial

waste and are being dumped illegally either in open or in the

nearby riverbeds. World’s urban societies are increasing

rapidly than the global population, especially in the developing

countries. Urban growth has created momentous alteration to

the ecological system by increasing waste accumulation

through human activities. The techniques which are capable to

detect the level of metallic elements to ppb limits in a variety

of environmental, biological as well as geological samples are;

6]. The principal asset of the X-ray fluorescence method over

other elemental analysis techniques is its non-destructiveness,

simultaneous multi-elemental capability, ingenuous sample

preparation and high resolution for trace elements. Daly et al.

[7] used EDXRF for elemental analysis dairy processing sludge

before its application in the agricultural fields and concluded

that the XRF method is provides rapid and accurate results.

Mashaly et al. [8] characterized the granite sludge and cement

on the basis of X-ray fluorescence and studied the feasibility of

granite sludge in cement replacement. Elemental composition

of solid residues of sewerage sludge and biomass waste were

examined using XRF [9]. Zhang et al. [10] evaluated the textile

dyeing sludge and cattle manure using XRF and their findings

provided an insight for better reutilization of waste.

Synchrotron-based XRF can be used to know both quantitative

and qualitative multi-elemental concentration in very less time



Atomic absorption spectroscopy (AAS)

Inductively coupled plasma-atomic emission spectrometry

(

ICP-AES) or inductively coupled plasma-mass

spectrometry (ICP-MS) or Inductively coupled plasma-

optical emission spectrometry (ICP-OES).

Energy-dispersive X-ray Fluorescence Spectrometry (ED-

XRF) or Wavelength dispersive XRF (WD-XRF)

Neutron activation analysis (NAA)



Particle-induced X-ray emission (PIXE)

For the last 20 years, the energy dispersive X-ray fluorescence

EDXRF) has advanced diligently. The developments made in

(

[11] and it is a non-destructive, most precise and accurate

semiconductors, digital signal processing and data simulation

have broadened the usability of the XRF method for

economical, small-size spectrometers for trace elemental

analysis in various types of samples [1-3]. X-ray fluorescence

being a non-destructive analytical method has its own

merits. XRF analysis provides the composition of a sample by

quantifying the characteristic X-rays evolved from a sample,

excited by radiations (Fig. 1). In X-ray fluorescence, individual

atoms are excited by incident photons, which in turn emit

secondary photons called as characteristic X-rays (Fig. 1a). In

XRF spectroscopy, emission of characteristic X-rays of the

method of trace element determination of all types of samples.

Furthermore, it can simultaneously determine many elements

present in a single sample [12]. In India, this facility is available

at Raja Ramanna Centre for Advanced Technology (RRCAT),

Indore. Presently this technique is being used for the trace

elemental analysis of sludge samples collected from the paper

and toothpaste industry, which is abundant in the study area.

Corresponding author: Ajay Sharma, Chitkara University School of Engineering and Technology, Chitkara University, Himachal

Pradesh-174103, India. E-mail: coe@chitkarauniversity.edu.in

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Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 192-195

synchrotron beam for a short duration of time. In the present

measurements, the sludge pellet samples were exposed to BL-

Material and method

Presently, paper and toothpaste industry sludge samples

6 at 18 keV energy. Sludge pellets with thickness of 0.2003

are gathered from an industrial area. The collected powder

samples are pelletized by uniformly mixing with cellulose to

make 13 mm diameter self-supporting targets with a smooth

surface of equal density (Fig. 2). These targets are evaluated at

the synchrotron radiation beam line-16 at RRCAT, which is

specially designed and commissioned by Department of

Atomic Energy (DAE) for XRF/TXRF (Fig. 3a). Owing to the

numerous advantages of a synchrotron-based XRF technique

the experimental set-up on the Indus-2 synchrotron light

source is equipped with a microfocus XRF beamline (BL-16).

The beamline (BL-16) is capable of radiating monochromatic,

intense radiations in the energy span 4 to 20 keV. At the

experimental hutch, the beamline presents both micro-focused

and collimated beam modes for versatile applications. The

energy dispersive X-ray fluorescence (EDXRF) and total

reflection x-ray fluorescence (TXRF) analysis of samples up

to ppb (parts per billion) levels can be made by exposing the

gm/cm were prepared for experimentation purposes. The

experimental set-up (Fig. 3b) consists of a sample holder

inclined at 45° to the incident radiations in the reclining

divergence arrangement. The characteristic X-rays emitted

from the sludge samples were detected by a Peltier cooled

Vortex solid-state Silicon drift detector (SII Nano, USA) for

500 seconds. The detector with an energy resolution of 138 eV

at 5.9 keV (Mn Kα) X-rays was mounted at 90° to the incident

beam. The detector was lying approximately 60 mm away

from the sample surface (middle of the beam footmark). To

escalate the flux and to focus the beam size a double crystal

monochromator and a 200-micrometer slit was pressed into

the hutch, the same helped in optimizing beam strength and

mitigating the background scattering.

(a)

(b)

Fig. 1 (a) The mechanism of X-ray fluorescence and (b) the typical XRF spectrum

Fig. 2: Sludge powder and Pellet samples for XRF study

(

(b)

Fig. 3: (a) Schematic layout of the experimental set-up (b) Actual photograph of the hutch

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Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 192-195

(

(b)

Fig. 4: Fitted fluorescent characteristic X-ray spectra for (a) paper sludge (b) toothpaste sludge

Table 1: Elemental concentration (in ppm) for paper sludge and toothpaste sludge alongwith 7% experimental uncertainty

Sr. No.

Element

Paper sludge (ppm)

Toothpaste sludge (ppm)

937683 (± 65638)

88 (± 6)

801358 (± 56095)

181 (± 13)

374 (± 26)

8063 (± 564)

280 (± 20)

724 (± 51)

217 (± 15)

51827 (± 3628)

270 (± 19)

47 (± 3)

763 (± 53)

12089 (± 846)

168 (± 12)

810 (± 57)

260 (± 18)

182591 (± 12781)

1396 (± 98)

23 (± 2)

multielemental analysis of industrial waste/sludge. The

technique exhibits both qualitative and quantitative information

of trace elements present in sample in precise and accurate

manner. The present XRF results predict the dominating

concentration of Calcium in industrial sludge/waste and

therefore, can be an alternate in replacing soil in brick

manufacturing industry.

Results and discussion

Typically recorded characteristic X-ray spectra at 18 keV

is shown in Fig. 4. In order to control the characteristic

parameters of the beam line such as spectral range and

minimum detection limit etc. the sludge samples have been

exposed to radiations for 500 seconds. Fig. 4 shows fitted XRF

spectra, where solid black and red lines are the experimental

and fitted data respectively, whereas green line represents a

good estimation of the spectral background.

Acknowledgment

The XRF results (table 1) show the dominating proportion

of Calcium in both sludge samples. The concentration of

titanium, manganese, iron and zinc is more in toothpaste sludge

as compared to paper sludge, whereas the concentration

dominates for copper and lead in paper industry sludge. The

comparative high concentration of titanium, manganese in

toothpaste sludge may be due to the small percentage of their

compounds as an ingredient in the toothpaste. The present

results (table 1) show very low traces of heavy metals and a

dominating concentration of calcium in both the sludge

samples, which recommend these industrial sludge(s) for safe

and efficient recycling. Similar findings have already been

reported for elemental analysis dairy processing sludge before

its application in the agricultural fields using EDXRF [7].

Therefore, XRF based multi-elemental, qualitative and

quantitative valuable information can be considered while

recommending any sludge for reuse. The researchers are also

working on the techniques of safe disposal of these wastes

through various techniques like phytoremediation [13].

The authors would like to thank the Department of

Environment, Science & Technology, Himachal Pradesh-India

for financial support in this study vide grant no. Env. S & T

(F)/5-1/2018-8886. The authors also acknowledge the technical

assistance and guidance extended by RRCAT Indore-India to

carry on this study.

Ethical issue

Authors are aware of, and comply with, best practice in

publication ethics specifically with regard to authorship

(

avoidance of guest authorship), dual submission, manipulation

of figures, competing interests and compliance with policies on

research ethics. Authors adhere to publication requirements

that submitted work is original and has not been published

elsewhere in any language.

Competing interests

The authors declare that there is no conflict of interest that

would prejudice the impartiality of this scientific work.

Conclusion

Authors’ contribution

All authors of this study have a complete contribution for

data collection, data analyses and manuscript writing.

As is evident from the present study, synchrotron-based X-

ray fluorescence is a significant technique for non-destructive

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Journal of Environmental Treatment Techniques

2021, Volume 9, Issue 1, Pages: 192-195

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