International Journal of PIXE, Vol. 21, Nos.

3 & 4 (2011) 75−86

 World Scientific Publishing Company
DOI:10.1142/S0129083511002215

2 MeV-PIXE TECHNIQUE FOR COASTAL MATERIAL ANALYSIS

E. MANIKANDAN‡,§,**, BHARATH PRITHIVIRAJ†, G. KAVITHA¶,

P. MAGUDAPATHY‡ and B. RAJAMANNAN║

*
Nano-Technology & Polymer Center, B. S. Abdur Rahman University, Vandalur. Chennai-600048, India
†
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80302, USA
‡
Particle Irradiation Facility Section, MSG, IGCAR, Kalpakkam 603102, Tamil Nadu, India
§
Nanotechnology Innovation Centre, Council for Scientific and Industrial Research, Pretoria, R.S.A.
¶
PG and Research Department of Physics, A. M. Jain College, Meenambakkam, Chennai-600048, India
║
Department of Physics, Annamalai University, Annamalai Nagar, Chidambaram -608 002, India
**
maniphysics@gmail.com

Received 12 August 2011

Revised 31 December 2011

Ion beam analysis (IBA) is a group of PIXE (particle induced X-ray emission) techniques dedicated
to the analysis of material for geological sample of coastal sediment samples. Coastal/Beach samples
collected from South East Coast of Tamilnadu were analyzed by PIXE technique and obtain the
elemental composition of coastal sediments. The PIXE analysis was carried out using 1.7 MV
Tandem accelerators with the energy of 2 MeV protons at Indira Gandhi Centre for Atomic Research
(IGCAR), Kalpakkam, Tamilnadu, India. The data analysis is normally done in an interactive mode
of GUPIX analytical software computer code. The identified elements are present in the fingerprint
X-ray spectrum in the range of ppm to ppb level. Therefore in this paper, introductory results
concerning determination of concentration of chosen elements such as K, P, Ca, Ti, Fe, Cr, Co, Zn,
Mn, Ni, Cu, Rb, Sr, As, Zr, Hf, Pb and Hg of coastal sediment samples from the east coast of
Tamilnadu, India are presented. The validation of the technique is assessed using standard reference
material (SRM) NIST 1646a estuarine sediment and the result shows the good agreement with the
certified one. The results were used to assess environmental toxicity of heavy metals and radiation
hazard in the study area.

Keywords: IBA technique; PIXE analysis; GUPIX; coastal samples; NIST.

1. Introduction to IBA
Ion beam analysis (IBA) is now a matured scientific technique, which are very widely
used research areas of various nanomaterials, metallurgical-materials, environmental,
geological specimen, bio-medical science and throughout thin film science. IBA is a
cluster of techniques involving materials research analysis by MeV ion beams. When a
charged high energetic ion or particle strikes a target it triggers a variety of energy loss
mechanisms, from which we obtain information about the target material. The emitted
characteristic X-ray spectrum have shown multi-elements in a fingerprint mode. The
PIXE technique is one of the methods of elemental analysis making use of ion beams

75
76 E. Manikandan et al.

accelerated by small-sized accelerators. It allows us to quantitatively analyze the entire

element from sodium (Na) to uranium (U) in the periodic table at the same time and has
many distinguished features. IBA is a cluster of techniques involving material analysis by
million electron volts (MeV) ion beams.1–3 Detecting the energy distribution of the
emitted particles or radiation performance by IBA methods can be useful in
characterizing a specimen and can provide information about elements, isotopes or
chemistry. Ion beam analysis refers to several analytical techniques, including PIXE,
particles induced gamma-ray emission (PIGE), Rutherford backscattering spectroscopy
(RBS), elastic recoil-detection analysis (ERDA) and nuclear reaction analysis (NRA).3–5
When a highly charged particles (i.e. alpha He++ or protons) ion strikes into the target
there are a variety of energy loss mechanisms, which can be used to obtain information
about the target materials. An ion can undergo a number of processes when it interacts
with matter, for example elastic and inelastic scattering with the nucleus or electrons in
the material. It can also induce radiation by interacting with bound electrons or cause
emission of secondary electron or secondary ions. Particle induced X-ray emission
(PIXE) is based on the excitation of electrons from the inner shells of the atoms, induced
by a colliding charged particle, e.g. proton or alpha particles.4 Outer shell electrons
recombine with the vacancy, and result in X-ray emission with energy characteristic of
the atom under bombardment. PIXE is an attractive technique, as it does not produce the
background continuum and is applicable to low atomic (Z) elements, multi-elemental
capable, essentially non-destructive technique and low background facilities, trace
element analysis in small samples. PIXE analysis is fast, with a spatial resolution of a few
micrometers; the absolute detection limits are at the order of 10–15 to 10–16 g. In this
method, the X-rays are emitted due to the inner-shell ionization of the atoms due to their
columbic interaction with the incident charged (particle) ions. The most commonly used
particle beam is proton in the energy ranges of 2–4 MeV, although other heavy ions have
been used for specific application. PIXE is a multi-elemental technique with a practical
use for elements heavier than sodium (Na) or aluminum (Al) upto the uranium (U) in the
periodic table. Emitted characteristic X-ray energies for elements with lower atomic
numbers are so small that they are absorbed in the detector window.6 The PIXE
techniques such as the EDX spectra which involves the X-rays from inelastic collisions
of the incident ion with the inner core electrons are easy to detect. An energy dispersive
analysis of the detector signals can reveal the identity of the different elements present in
the sample and move importantly, by measuring the charge, i.e. the number of incoming
particles, the concentration of the elements can be accurately quantified. In the PIXE
technique these characteristic X-rays are detected using semiconducting Si(Li) detector.6,7
In the past few decades, IBA techniques had been an important contribution to the
various material analyses. Trace element geochemical studies can provide significant
insight into the geologic process. There are many reviews describing the most important
features and its applications of the PIXE technique in the field of geosciences.8,9 The
recent research works have been used to detect the trace-element geochemistry to study
such as beach rock,10,11 deep sea sediments in east coast of Tamilnadu, India,11–13 soil-
 2 MeV-PIXE Technique for Coastal Material Analysis 77

contaminant sediment transport in the marine environment14,15 and lichen species.16 The
scope of this paper is to determine multi-elements including trace, major and minor
elements in the region of Pondicherry to Porto-Novo (P-P) coastal sediment samples. The
target material preparation can be applied by the standard method, with same minor
modification to treat different matrices using IBA technique.3 PIXE analysis has the
following outstanding three characteristic of the assessment of the environmental
contamination. (i) Multi-elements (including major, minor and trace level) can be
determined simultaneously without destroying the samples (ii) it needs only trace (mg or
µg) amount of samples; and (iii) a valuable sample, involving great time, effort and
expense in chemical extraction, can be analyzed by repeated procedures at various
sensitivities. In brief, chemical extraction plus PIXE are predicted to be very useful for
work in the marine environment. Sequential origin of elements from soil/sediment is a
widely applied technique in geological investigation and environmental geochemistry. A
variety of protocols have been applied using different reagent, different sequencing of
reagents, and different experimental condition.6 The primary objectives of the present
study were to estimate the multi elemental concentration from the emitted X-rays and to
assess the degree of pollution in the geological coastal sediment samples from the region
of Pondicherry to Porto-Novo, (P-P) Tamilnadu coast, India.

2. Material-Methods and Target Preparation

The geographic location of sampling sites is shown in Fig. 1. The coastal sediment
samples were collected from the Pondicherry to Porto-Novo (P-P) of various sampling
sites S1 to S22 along the east coast of Tamilnadu, India. Marine/Coastal sediments are
very important accumulation site of metals in the coastal areas; therefore analysis of these
metals is important to assess the degree of pollution in the marine environment.
Presently, as the coastal areas of Tamilnadu States are in a rapid development stage of
new harbor, oil exploration, chemical industries, power plants and other large scale
industries, further assessment of dissolved trace metals, physicochemical parameter
conditions and various hydrodynamical parameter conditions acting in the region are to
be studied in detail and continuous pollution monitoring studies should be taken up for
improving the coastal environment.
These kinds of studies are required to implement the regulations from the
international conventions, which intend the trace metal input to the sea.12 Coastal
Sediment can be considered as a heterogeneous mixture of dissimilar particles. These
particles can be considered in turn as a complex assemblage of different organic and
inorganic components. Sediments receive potentially toxic elements from both natural
and wide range of anthropogenic sources, including the vehicular emissions, erosion,
domestic and industrial discharges, agricultural sources, river inputs and various chemical
waste disposals etc., from the heavy metals have been recognized as harmful for both
environment and human health when present above certain levels. Contamination with
heavy metal may lead to severe environmental problems,17 Depending on their origin,
78 E. Manikandan et al.

metal exist in different minerals forms and chemical compounds, and in different
combinations with minerals, organic and inorganic components of sediments.18 Metals
are present naturally in marine waters in both dissolved and suspended solid forms.

Fig. 1. The geographic location of sampling sites.

The trace metals are rapidly and efficiently removed from the sediments via
adsorption, precipitation, and incorporation. Many metals can also be incorporated into
marine ecosystems as the result of human activities, leading to anomalous high
concentrations in coastal sediments where anthropogenic activities are intense in the
study area.11 The polythene bags used for the samples were stored and cleaned by soaking
in nitric acid and rinsing with distilled water. The samples were allowed to dry initially in
open air and dried at 105°C for 12 hours in an oven. This method is generally needed to
treat the sediment-soil (beach rock/coastal/lagoon/effluent) samples and briefly explained
by Ravisankar and Kennedy et al.11,19 In this study collected samples, to remove one
substance from another, usually an adsorbed material from an adsorbent surface, is done
by washing it out with a solvent. The dried samples taken were first pulverized to make
 2 MeV-PIXE Technique for Coastal Material Analysis 79

the sample into the powder form. The powdered sample was thoroughly mixed with pure
graphite powder (Merck-99.99%) in the ratio 1:1 by mass (200 mg each) mixed with
glycol as a binding agent in order to avoid the charge build-up during the PIXE
experiments. The sample preparation technique similar to the one used by8,9 was followed
200 µl of 1000-ppm palladium (Pd) as solution was added to the sediment powder
sample. Palladium is used as the co-precipitant agent for quantitative efficient method. It
also acts as the internal standard and is favored for this role due to the high stability of its
chemical complexes and for its rarity in the tested specimens. Because of this element it
is unlikely to occur in our samples and has suitable lines in the appropriate energy range.
In addition, its K and L X-ray lines do not interfere with the readings of the other
fingerprint elements that concern us.7 The mixed sample was thoroughly ground,
homogenized and pressed into the uniform pellets of 15 mm diameter. The thick targets
are prepared by pressing the above mixture with 5 ton Perkin-Elmer pellet machine with
a 15 mm die. While pelletizing, both faces of the compression die were covered with thin
mylar foil to avoid the contamination during the direct contact between the powdered
sediments and faces of the die. Blank target, compressing the chemical used and the
National Institute of Standard Technology (NIST) standard reference material (SRM-
1646a) of trace element in estuarine sediments are also prepared by the same procedure
for calibrating the PIXE set up. Quantitative PIXE analysis must take into account target
thickness or better the relevance of “matrix effects”: these are essentially the energy loss
of protons in the sample (hence the variation of cross-section for the ionization processes)
and the self-absorption of the produced X-rays within the target itself. If matrix effects
are negligible the target is considered to be “thin” and the number of X-rays collected by
the Si(Li) detector.19 The surfaces of particles can also be bombarded with protons or
ions of heavier atoms. Moreover, it has to produce targets with physical features,
principally surface density and homogeneity, to optimize the resulting PIXE
measurement.20 The sensitivity of the PIXE analysis is finally determined by the signal to
noise ratio of the detected emissions. Thus, to improve sensitivity, the choice of each
experimental parameter has to assist in increasing this ratio. The first step concerns the
measurement set-up because the mass and energy of the incident particles has to be
determined. An evaluation is necessary at this point because the sensitivity is increased
by elevated X-ray production cross-section and low background, but both the X-ray
production cross-sections and low background, emissions of gamma and secondary
electron bremsstrahlung (SEB) increase with rising particle energy, while particle
bremsstrahlung (PB) decreases. Given these incident particles features, the other
background effects may be reduced with measurement conditions that take into account
of SEB angular dependence. Other ways to reduce background effects are, to use low
atomic (Z) number and thin target elements, which are suitable for limiting SEB and PB
emission.4,5 The preparation of the sample needs to avoid and or limit the collection of
undesired elements on the target; this also reduces the intensity of background radiation.
For this purpose thin targets perform better.
80 E. Manikandan et al.

3. Experimental Technique and PIXE Measurement

The measurements were carried out using 1.7 MV tandem accelerators available at
Particle Irradiation Facility Section (PIFS), IGCAR, Kalpakkam, India. In the “tandem”
configuration, particles are accelerated twice. For example, to obtain a proton beam, the
source produces H− ions; they are accelerated from ground potential to the positive high
voltage terminal. At the terminal, beam particles undergo a stripping process (in our case
performed by means of a continuum nitrogen flux) where some electrons (in the case of
H− ions, all the electrons) are removed from the particles and the ions change polarity; the
H+ ions are thus accelerated again toward ground potential. Hence the final energy of
protons is twice the one achievable with a single-ended accelerator with the same
terminal voltage. The targets were mounted in an irradiation chamber maintained at a
pressure of 10–6 torr and the samples were exposed to 3 mm diameter collimated to a
beam of 2 MeV protons from the 1.7 MV tandem accelerator. The distance between the
sample plane and the beryllium (Be) window of Si(Li) detector was kept at 5 cm and the
angle between the detector head and the beam direction was 135°. Beam current of
10–30 nA was maintained during the PIXE measurement. Two faces target ladder, on
which the target was mounted, was oriented at 45° to the axis. The detector was kept at
an angle 90° with respect to the beam direction and the target was oriented at 45°. The
majority of the emission resulting from the chemicals used at pre-concentration fall in the
lower energy part of the spectrum, and are attempted by suitable mylar absorbers. This
allows the detector system to operate with dead time lesser than 5% and with negligible
pile-up effects. The X-rays lose energy to the detector by pair production, the Compton
scattering effect and photoelectric effects. This energy is imparted to the free electrons in
the silicon and the lithium Si(Li). A Si(Li) detector with an active area of 30 mm2 and
with the resolution of 180 eV at 6.4 keV was used for PIXE measurements. The
characteristic X-rays from the sample passes through a 25 µm mylar window and the
traverse about 1 cm air gap before entering to the Si(Li) detector. A 100 µm mylar
absorber is kept in front of the detector to reduce the dominant low energy X-ray peaks.
An observer is placed near to the sample, suppressing X-ray of low energy. This allows
the detector to spend more time on X-rays from the elements. We are most interested in
those with higher atomic number (Z) and consequently higher X-ray energy, where the
absorber also absorbs some of bremsstrahlung (continuous background radiation). The
primary sources of bremsstrahlung are: (i) electron ejected from atom by inelastic
collision with the beam, and (ii) nuclear reaction between proton and atoms, which result
in gamma rays.1 Quantitative data analysis was performed using by GUPIX analytical
computer software package7 and its values were reported in parts per million (ppm). This
package has the provision to convert the X-ray intensities into elemental concentrations
using a standardization technique involving fundamental parameters, predetermined
instruments constants and input parameters such as solid angle, matrix iteration, layer
thickness, adding invisible element to fit etc. This provides a non-linear least squares
fitting of the spectrum, together with subsequent conversion of the fitted X-ray peak
intensities into elemental concentrations, utilizing the fundamental parameter method
 2 MeV-PIXE Technique for Coastal Material Analysis 81

(FPM) for quantitative analysis. It requires parameters of experimental geometry and

Si(Li) detector (H-parameter), chamber window thickness, energy of the incident particle,
the net charge collected, the target thickness along with the major matrix, and the
invisible element.

4. Result and Discussion

The emitted X-ray elemental concentrations of coastal sediment samples from P-P, East
Coast of Tamilnadu, India were ten sampling sites reported in Table 1. The validity of the
experimental procedures was adopted for analyzing the SRM estuarine sediment NIST-
1646a checked in the present study. The major, minor and trace elements were quantified
in this standard sample are compared with reference values shown in the Table 1.
The measured elemental concentration values are in good agreement with the
certified once. A typical PIXE spectrum obtained from the target sample is depicted in
Fig. 2 and SRM materials in Fig. 3.
The emitted (K and L) X-ray spectrum lines are in the fingerprint mode of K, P, Ca,
Ti, Fe, Cr, Co, Zn, Mn, Ni, Cu, Rb, Sr, As, Zr, Hf, Pb, Hg and Pd. The palladium (Pd)
peaks are from the internal standard used. The concentrations of elements in the samples
(Cx) are determined by comparison with calibration curves obtained from standard
solutions and intensities of Pd internal standard using the following relations:

Ks I x (1)
Cx = × Cs
KxIS
where, Ks /Kx ratio is derived from the calculation curve, Is is the number of X-ray counts
from the internal standard in the sample, Ix is the number of X-ray counts from the
elements and the Cs is the internal standard in the sample. The elemental concentrations
of the coastal sediment samples are reported in the Table 1. From the table elemental
concentration with the all the sampling points (location are shown in Fig. 3) are indicated
in bar diagram. It was observed from the table that the elements K, Fe, Mn, Ti and Zr
concentration are highest at the sampling point S4, S5, S9 and S18. This may be due to
the heavy minerals such as Ilmenite, Rutile, Almandine Garnet, Hornblende and
Magnetite etc., present in the study area and confirmed with XRD and FTIR study,9 as
revealed in the geological concentration Ca, Cr, Cu, Ni and Zn are maximum at the
sampling point S3 and S18. This may be due to the dumped wastes from various
activities of the local industries near the river mouth. The accumulation of heavy metal
due to the industrial effluents of chemicals, oil refinery packing limited, pulp-paper mills,
glass cutting and coating unit, painting company21–27 has interestingly noted that the
concentration of potassium (K) gradually increases to the sampling locations except S2
and S4. This may be due to the relative amount of Feldspar, Mica and Clay minerals9
present in the study area. The presence of Zr in the samples gives the possibilities of
heavy minerals in the study area. The highest concentration of Zircon (Zr) present in the
sampling sites is S3, S5 and S18.
82 E. Manikandan et al.

Table 1. Elemental concentration (ppm) of beach sediment samples collected from different sites S1–S10 along
the coast of Pondicherry to Portonovo (P-P), East Coast of Tamilnadu, and India by PIXE measurement.

Sampling Sites/
Elements S1 S3 S4 S5 S9 S11

Cl 1772 1922 3495 2943 2369 3423

K 270 192 245 4356 347 1483
Ca 358 1078 813 156 4534 2610
Ti 4532 6963 2255 50980 18251 706
Cr 1239 3356 1228 917 517 958
Fe 1586 906 3327 5289 4765 2952
Mn BDL 38 615 108 398 163
Ni 851 1015 712 614 569 722
Cu 175 2856 364 200 453 407
Zn 64 1895 756 186 274 691
Zr 1135 5865 5066 8628 1461 612
Hg 768 112 208 104 145 1188
Pb 438 755 1680 210 681 136
V 114 156 512 1358 484 58
Co 238 302 156 256 237 415
Hf 402 808 351 758 668 257
*BDL-below detection limit

Earth
Sampling Sites/ Crustal Deep Sea
S13 S18 S20 S22 Present
Sediment
Elements Abundance
Cl 3069 3536 3446 2628 2860 145 21000
K 563 5870 344 1392 1506 20900 25000
Ca 2621 5853 1550 3802 2337 41500 29000
Ti 2254 2621 703 106 8937 5650 4600
Cr 366 261 115 85 904 102 90
Fe 364 844 1622 1212 2286 56300 65000
Mn 343 213 327 424 292 950 6700
Ni 246 199 15 107 515 84 225
Cu 174 225 106 154 511 60 250
Zn 312 564 135 465 534 70 250
Zr 166 1530 410 328 2520 165 150
Hg 69 390 286 157 342 0.085 Nill
Pb 80 314 244 124 466 14 110
V 112 66 134 77 307 120 120
Co 67 185 102 145 210 25 74
Hf 138 97 183 244 390 3 Nill
*BDL-below detection limit
 2 MeV-PIXE Technique for Coastal Material Analysis 83

Fig. 2. A typical PIXE spectrum of coastal sediment location (S3).

Fig. 3. A typical NIST (SRM 1646a) esturine sediments sample PIXE spectra.

From Table 1, it indicates that the average values of the metal and even maximum
concentrations are lower than those for the average earths crust values. However, this
does not reject the possibility of the presence of an anthropogenic portion of metal in the
investigated samples. Considering the sampling sites S2 and S4 has the highest values of
84 E. Manikandan et al.

Ti, Cr, Zr, Pb Chromium concentration levels in the studied range from 85–3356 ppm
from the sites S3 and S22, the average values of Cr in all the sampling point are 904 ppm
and the earth’s crustal abundance value is 102 ppm. Thus the investigated sediment is
considered as polluted by Cr except the sampling site S22.
The enhancement of Cu, Ni, Cr, Zn, As, Pb and Hg indicate that they are above the
prescribed limit by Tamilnadu Pollution Control Board (TNPCB) and considerable
attention has to be taken before it rises beyond the limit. Even though the geochemical28
and statistical parameters reveal an anthropogenic origin, the situation can be reversed if
environmental laws are enforced in a proper manner. The results suggest that the coastal
areas is one of the important sources for the enrichment of dissolved trace metals in the
P-P coast south east coast of India and unbalanced conditions occur in both the
environments.

5. Conclusion
PIXE method is essentially an interdisciplinary study of environmental samples. The
PIXE technique is a versatile and valuable tool for multi-elemental analysis in the
geological species. Its main strength lies in its efficacy for trace element analysis with
spatial resolution matched to many problems in geological science. The identified
elements are present in the fingerprint X-ray spectrum in the range of ppm to ppb level.
Therefore in this paper, introductory results concerning determination of concentration of
chosen elements such as K, P, Ca, Ti, Fe, Cr, Co, Zn, Mn, Ni, Cu, Rb, Sr, As, Zr, Hf, Pb
and Hg of coastal sediment samples from the east coast of Tamilnadu, India are
presented. The validation of the technique is assessed using SRM NIST 1646a estuarine
sediment and the result shows the good agreement with the certified one. This study
provides insight into sampling methodology and ways to characterize various locations
within a coastal source. The multi elements identified in this study may not be universal
for other source locations, but provide the beginnings for an analytical database for
coastal samples. The present work studied the elemental distribution of the sediments in
the study area by ion beam techniques of PIXE. No other method can show such a
combination of sensitivity, high speed and multi element (“fingerprint” region) capacity.
This work demonstrates the PIXE technique enabling high accuracy and precision for
environmental samples. This inturn provides further on source fingerprints and hence
possible sources of trace elements in the coastal samples.

Acknowledgments
The authors wish to express thanks to Dr. K. G. M. Nair, Prof. B. K. Panigrahi, Dr. C.
David from Particle Irradiation Facility Section (PIFS) for their indeed help for PIXE
measurement/analysis. We are very much gratitude to C. S. Sundar, Director, MSG and
V. Meenashisundaram, Head, Radiation Safety Division, IGCAR, Kalpakkam,
Tamilnadu, India for their kind cooperation, invaluable help and also constant
encouragement to the PIXE work. We would like to thank Dr. R. Sakthivel and Prof. M.
Arumugam for their assistance during coastal sampling survey.
 2 MeV-PIXE Technique for Coastal Material Analysis 85

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