Detection and determination of manganese

concentration in water using a fiber Bragg

grating coupled with nanotechnology
Jyoti F. Akki,1 Anandkumar S. Lalasangi,1 Konduri G. Manohar,2
Prasad Raikar,3 Talabatulla Srinivas,4 and Uday S. Raikar1,*
1
2

Department of Physics, Karnatak University, Dharwad-580003, Karnataka, India

Laser & Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai-400085, India
3

KLE Societys College of Engineering & Technology, Belgaum, India

Electrical Communication Engineering Department, Indian Institute of Science, Bengaluru-560012, Karnataka, India
*Corresponding author: usraykar_kud@yahoo.co.in
Received 31 May 2011; revised 20 August 2011; accepted 8 September 2011;
posted 12 September 2011 (Doc. ID 148458); published 2 November 2011

Through this paper we experimentally demonstrate the fabrication of a fiber Bragg grating (FBG)
chemical sensor to detect and determine the manganese concentration in water and compare our results
with sophisticated spectroscopic methods, such as atomic absorption spectrometry and the inductively
coupled plasma method. Here we propose a simple method to develop a thin layer of gold nanoparticles
above the etched grating region to enhance the sensitivity of the reflected spectrum of the FBG. By doing
so, we achieve a sensitivity of 1:26 nm=parts per million in determining the trace level of Mn in water.
Proper reagents are used to detect manganese in water. 2011 Optical Society of America
OCIS codes: 230.0250, 230.1150, 230.2285, 060.2370, 060.3735.

1. Introduction

Manganese is one of the most abundant metals in

Earths crust, usually occurring along with iron.
Since it is chemically active, it is found in the form
of chemical compounds rather than in elemental
form. Manganese can exist in 11 oxidative states;
the most environmentally and biologically important
manganese compounds are Mn4
or Mn7
. Mn is an
element essential to humans, animals, and plants for
proper functioning of some enzymes and hormones.
Manganese is supplied to the body mostly through
food. However, it can also enter the body through
drinking water. Generally, manganese is present in
water in the form of manganous ion (Mn2
). Despite
the fact that there are some very effective natural
mechanisms that filter out dissolved chemicals and
0003-6935/11/326033-06$15.00/0
2011 Optical Society of America

gases from the ground water, these salts can still occur in large dissolved concentrations. Manganese
content in water produces unpleasant dark stains
due to oxidation on every surface with which it comes
into contact, even at low concentrations. Because of
the precipitated manganese deposits collected in pipelines, tap water may contain black sediment and
turbidity [1]. Higher concentrations of Mn in water
may bring about various health-related problems
in both animals and plants. Adverse neurological
effects [decreased performance in school and in neurobehavioral examinations of the World Health
Organization (WHO) core test battery] were reported
in 11- to 13-year-old children, who were exposed to
excess manganese through ingestion of contaminated water and from wheat fertilized with sewage
water [25]. Long-term studies concluded that progressive increase in the manganese concentration
in drinking water is associated with a higher prevalence of neurological problems of chronic manganese
10 November 2011 / Vol. 50, No. 32 / APPLIED OPTICS

6033

poisoning [6]. It is found from research on animals

that the higher concentration of manganese input
(via food or water) brings about many complications,
such as neurotoxicity and reproductive problems.
The WHO recommends a limit of 0:05 mg=l manganese in consumer usable water, although this may
vary with local circumstances.
There are many methods to analyze the presence
of manganese in water, such as atomic absorption
spectrometry (AAS), inductively coupled plasma
(ICP), flow injection analysis, or spectrofluorimetry.
In this paper, we present a very sensitive and precise
method to analyze the concentration of manganese in
water, based on optical fiber grating technology
coupled with nanotechnology.
Fiber gratings have become key components of
fiber-optic devices and applications. Fiber gratings
with periodic refractive index modulation of few micrometers (less than 100 m) are popularly known as
fiber Bragg gratings (FBGs). FBGs behave as filters
by reflecting a spectrally narrowband portion of the
incoming broadband light [7] and have found applications in optical telecommunication networks and
in sensor technologies for various parameters, such
as temperature, pressure, and displacement [811].
Based on the coherent scattering mechanism, the fiber gratings can be used as built-in fiber reflectors or
as filters for fiber-optic communications and sensors
[12]. FBGs have also been proved as promising candidates in the field of chemical sensing, as refractive
index sensors and solution concentration sensors
[1315]. In recent years, nanoparticles, especially
of noble metals, have found applications in enhancing the sensitivity of fiber-optic sensors [1618].
In the work presented here, the etched region of a
FBG is coated with a thin layer of gold (Au) nanoparticles to enhance the sensitivity of the FBG as a manganese sensor in water.
2. Theory

The FBG is prepared by inscribing a periodic refractive index modulation in the core of an optical fiber,
with periodicity of a few micrometers. When a broadband light is injected into the FBG, light in a narrowband of wavelengths centered at a particular
wavelength known as the Bragg wavelength (B ) is
reflected because of contradirectional coupling of
the fundamental mode introduced by refractive index modulation in the core [7]. The FBG works on
the principle of Bragg reflection by reflecting wavelength B , given by
B  2neff ;

1

where neff is the effective refractive index of the core

and is the grating period.
The wavelength of the reflected light depends
mainly on the grating pitch and effective refractive
index. The change of wavelength due to the changes
in the measurand is used in FBG-based sensing
applications. A FBG is normally unaffected by the
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APPLIED OPTICS / Vol. 50, No. 32 / 10 November 2011

refractive index of the surroundings, since the reflected spectrum is the result of coupling the corebound mode with the backward propagating modes.
But in FBG-based chemical sensors, the change of
Bragg wavelength is induced by change in the chemical composition around the sensor. In order to measure small changes in composition, it is important for
the optical mode to penetrate evanescently into the
surrounding solution. To design a FBG-based chemical sensor, the fiber cladding in the grating region
should be removed by etching so that the core mode
interacts directly with the external medium. In this
configuration, the value of the effective refractive index of the waveguide mode is directly affected by the
refractive index of the medium in which the fiber is
immersed. When the optical fiber cladding is etched
to a depth until the fundamental waveguide mode is
affected, the propagation constant of the mode is
modified, as can be written as [15,19]
 0
kp nsur ncld ;

2

where 0 is the propagation constant of the mode

without etching, nsur is the refractive index of the
surrounding medium, ncld is the refractive index of
the cladding, k is the wave vector, and p is the fraction of the total power of the unperturbed fundamental mode that flows in the etched region and is,
therefore, lost to the surrounding medium. If Ap is
the area of cross section of the etched ring, then p
is given by
R
p  R

Ap

2 dA

2 dA

3

A is the area of the cross section of the unetched fiber and is the wave function of the fundamental
mode in a weakly guiding circular fiber with a step
index profile. Because of the power loss that occurs in
the etched region of the fiber, the reflected power of
the FBG decreases when the fiber radius becomes
smaller. If p1 and p2 are two values of factor p at
two different diameters of etched fiber, from Eq. (2)
the associated variation of the modified propagation
constant of the fundamental mode would be
2 1  kp1 p2 nsur ncld :

4

From the definition of propagation constant, this

equation indicates that there is a variation of the
effective refractive index of the waveguide mode,
given by
neff  n;

5

where n  nsur ncl and  p1 p2 .

Combining Eqs. (1) and (5) yields
B  2neff  2n:

6

The above equation indicates that the etching

process is associated with a variation of the Bragg
wavelength of the FBG, given by
7

When the etching process is stopped, p reaches a

final value po and Eq. (7) becomes
B  2po nsur ncl :

8

At this stage, the variation of the Bragg wavelength

of the FBG is related only to the variation of the refractive index of the surrounding medium. Unlike a
pressure, temperature, or strain sensor, in this case,
only the effective refractive index is affected, while
the grating pitch remains unchanged.

Power (in W)

B  2neff :

0.00003

0.00002

0.00001

0.00000
1545

1546

1547

1548

1549

Wavelength (in nm)

Fig. 2. Reflected spectrum of FBG.

3. Experiment
A.

FBG Sensor Fabrication

A phase mask method involving a KrF laser (248 nm)

is employed to fabricate the FBG in a single-mode
boron codoped photosensitive fiber (from Newport
Corp., USA. Specificationsstep index profile; NA,
0:120:14; mode field diameter, 9:6 m; cladding
diameter, 125  1 m; and operating wavelength,
1550 nm). The schematic diagram is given in Fig. 1.
The grating formation can be monitored on-line, by
observing the Bragg-reflected light.
The fabricated FBG was characterized with the help
of a broadband source (JDS Uniphase, 15301600 nm,
17 mW), an optical spectrum analyzer (OSA, Proximion software), and a 3 dB coupler. The reflected
spectrum is given in Fig. 2 and is characterized in
Table 1.
As mentioned in Section 2, the FBG as such is insensitive to the surrounding refractive index with
unetched cladding in the grating region. To fabricate
the concentration sensor, the cladding at the modulated refractive index region was etched with 40%
HF solution for 1 h and the shift in the Bragg wavelength was monitored at regular intervals, as shown

in Fig. 3. The grating was washed in distilled water

after the completion of the etching process. During
the etching, a blueshift in the Bragg wavelength was
observed. Figure 4 is a schematic diagram of the FBG
illustrating the cladding removal at the grating
region by the etching process.
In order to enhance the sensitivity of the sensor,
one can coat the surface of the sensing head with nanoparticles. Many methods have been proposed to
coat nanoparticles on fibers, such as the solgel method [20], electrostatic self-assembly, dip coating, and
spin coating [16,21]. In the current work, we follow
a very simple method to coat the FBG sensor head
with gold nanoparticles. The etched portion of the
FBG was kept immersed in an aqueous colloidal solution of gold nanoparticles of 412 nm size (procured
from NanoBio Chemical, India Pvt. Ltd.) for about
4 h [transmission electron microscopy (TEM) and
scanning electron microscopy (SEM) images of Au
nanoparticles are shown in Figs. 5(a) and 5(b), respectively]. Then the fiber was removed from colloidal solution and allowed to drip out the excess liquid.
The grating head was then annealed at a temperature of 80 C for 1:5 h to develop a thin monolayer
of Au nanoparticles on the etched FBG. With the
coating of gold nanoparticles, we observed a significant enhancement in its sensitivity.
B. Chemical Sensing Scheme

Standard solutions of manganese concentrations

varying from 0.04 to 0:09 parts per million (ppm)
were prepared by dissolving manganese chloride in
distilled water. To each solution of different concentrations, reagents N; N-dimethylformamide and
potassium cyanide of appropriate volumes were
Table 1.

Fig. 1. (Color online) Phase mask setup for formation of grating.

Characterization of the FBG

Bragg wavelength
Peak power
Reflectance
FWHM

1546:96 nm
30:16 W
75%
0:2 nm

10 November 2011 / Vol. 50, No. 32 / APPLIED OPTICS

6035

1547.0

0.000025

Experimental data

0.000020

Peak Power (W)

1546.9

Bragg wavelength (nm)

Air
DMWater
0.04ppm
0.06ppm
0.09ppm
Test Sample

1546.8

1546.7

0.000015

0.000010

0.000005

1546.6

0.000000

1546.5
0

10

20

30

40

50

Fig. 3. Shift of Bragg wavelength during etching.

Core

1546

1547

Wavelength (nm)

Etching time (min)

Cladding

1545

60

Fig. 7. (Color online) FBG reflected spectra for concentrations of

Mn solution.

Cladding etched
grating region

Bragg WL
Linear Fit

1546.18

Fig. 4. (Color online) Schematic of cladding etched above the

grating region.

Bragg Wavelength (nm)

1546.16

1546.14

1546.12

1546.10

1546.08

1546.06
0.00

(a)

0.02

Fig. 5. (a) TEM image of Au nanoparticles. (b) SEM image of Au

nanoparticles.

0.04

0.06

0.08

0.10

Concentration (ppm)

(b)

Fig. 8. (Color online) Wavelength shift versus concentration of

Mn solution.
21

Power
Linear Fit

Peak Power (in microwatt)

20

Fig. 6. (Color online) Experimental setup.

19
18
17
16
15
14
13

added. These test solutions were used for measurements with our FBG-based sensor. The FBG sensor
was coupled to a broadband light source and immersed into a test tube containing the manganese solution. The spectrum of the Bragg-reflected light was
recorded on an OSA through a 3 dB coupler. Figure 6
shows a schematic diagram of the experimental arrangement. The reflected spectra were recorded for
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APPLIED OPTICS / Vol. 50, No. 32 / 10 November 2011

0.00

0.02

0.04

0.06

0.08

0.10

Concentration (in ppm)

Fig. 9. (Color online) Wavelength difference versus concentration.

different concentrations of manganese solution ranging from 0.04 to 0:09 ppm. As the concentration of
the manganese solution surrounding the sensor head

Table 2.

Concentration of Mn in Test Sample as Measured Using Different Techniques

Chemical
Species

FBG Sensor
(ppm)

Atomic Absorption
Spectrometera (ppm)

Inductively Coupled
Plasmab (ppm)

WHO Permissible
Limit (ppm)

Manganese

0.0303

0.048

<0:05

0.05

a
b

Measurement was made at the USIC.

Measurement was made at MetChem Laboratories.

was changed, the changes in the Bragg-reflection

wavelength (B ), which result from the changes in
the effective refractive index of the FBG, were recorded. After each measurement, the grating region
was cleaned thoroughly with acetone before changing to a manganese solution of different concentration to avoid contamination. Figure 7 shows the
Bragg-reflected spectra of the FBG for different concentrations of Mn with reagents. The entire experiment was carried out at room temperature.
In order to determine the concentration of dissolved
manganese, we collected ground water samples from
the local area. The above steps were repeated to record the reflected spectrum ofthe FBG sensor with
ground water.
4. Results and Discussion

From the spectral response of the FBG sensor at different Mn concentrations, as shown in Fig. 7, it is observed that as the concentration of the surrounding
medium increases, the reflected spectrum shifts toward a longer wavelength. With the increase in concentration of the solution surrounding the etched
FBG, neff of the core mode increases, resulting in a
shift of B toward a longer wavelength. Figure 8 represents the graph of the Bragg wavelength (B ) as a
function of the concentration of Mn solutions. The
shift in B is linear and the linear least-square data
fit with the experimental data gives a correlation factor of 0.95859 and a RMS error of 11:937 103 nm.
The shift of Bragg wavelength was 0:104 nm, when
the Mn concentration of the solution was increased
to 0:09 ppm. The concentration of Mn in the test samples can be determined using the least-square-fit
graph of B versus concentration. From the graph,
the concentration of the test samples from the local
ground water sources is found to be 0:0303 ppm. The
sensitivity of this sensor is found to be 1:26 nm
per ppm.
There is also a linear shift in the reflected light
intensity and power at B with the surrounding
concentration, as shown in Fig. 9. In this case, the correlation factor is 0:9803 and the RMS error is
51:33 102 W. It may be understood here that the
power mentioned in Fig. 9, in Figs. 7 and 2, and elsewhere in the text, is the power measured by the OSA,
which is proportional to the actual reflected power
from the FBG. The peak intensity at the Bragg wavelength decreases with increase in the concentration of
the manganese solution. This is due to the etchinginduced multimodal propagation conditions along
the etched region [22]. Using this graph, the concentration of manganese in our test sample is found to be

0:033 ppm. A comparative study has been done using

AAS and an ICP spectrometer. The results are given
in Table 2. The concentration measurements with
AAS were made at the University Scientific Instrument Center (USIC), Karnatak University, Dharwad,
India. ICP measurements were made at MetChem
Laboratories Pvt. Ltd., Bangalore, India.
5. Conclusions

In summary, we have demonstrated a highly sensitive etched FBG sensor using BGe codoped fiber
to detect traces of Mn in drinking water. We have also
observed the enhancement in sensitivity of a chemical sensor by depositing gold nanoparticle layers on
the unclad portion of a FBG. FBG sensors can be
used for measuring the manganese compounds in
water with good sensitivity in the lower concentration range. The advantages of this type of sensor are
its simplicity in construction and ease of use. The
sensor can find many applications in pharmaceuticals and industrial units, including in food industries. By optimization of some key parameters,
such as the length of unclad fiber, refractive index
profile, and optical design, better measurement sensitivity may be achieved.
We gratefully acknowledge support by the Department of Atomic EnergyBoard of Research in Nuclear Sciences (DAE-BRNS) (BARC, Mumbai, India),
Grant No. 2006/34/22-BRNS/2801. The authors also
acknowledge Prof. Kattesh Katti and Prof. Raghuraman Kannan, University of MissouriColumbia,
Mo., USA for the courtesy of the TEM image of the
gold nanoparticles and Prof. V. J. Fulari, Shivaji
University, Kolhapur, India for providing the SEM
image of the gold nanoparticles.
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