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Procedia Engineering 32 (2012) 1123 1126

I-SEEC2011

A Biomonitoring Study: Trace Metal Elements in Perna

Viridis Shell
W. Siriproma,d , N. Chumnanveja, A. Choeysuppaketb,d, P. Limsuwanc,d
a

Faculty of Resources and Environment, Kasetsart University, Sriracha Campus, Chonburi, Thailand 20230
b
Department of Physics, Faculty of Science, Burapha University, Chonburi, Thailand, 20131
c
Department of Physics, King Mongkuts University of Technology Thonburi, Bangkok, Thailand 10140
d
Thailand Center of Excellence in Physics, ThEP Center, Commission on Higher Education, Bangkok 10400, Thailand.
Elsevier use only: Received 30 September 2011; Revised 10 November 2011; Accepted 25 November 2011.

Abstract
The aim of this research was to study the metal elements in Perna Viridis shell. Energy Dispersive X-Ray
Fluorescence (EDXRF) spectrometer was used to determine the composition of mineral and levels of the metals
element. Furthermore, the Perna Viridis shell samples were prepared in powder form and investigate the structural by
x-ray diffraction (XRD). It was found that the the Perna Viridis shell are made of both aragonite and calcite phase. In
addition, the ions in the shell samples were also studied by Electron Spin Resonance Spectroscopy (ESR).

2010 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of I-SEEC2011
Open access under CC BY-NC-ND license.

Keywords: molluscan shell; XRD; Perna Viridis; ESR

1. Introduction
Marine pollution is an environmental problem. Different activities of citizens on land, in water and in
air contribute to the contamination of seawater, sediments and organisms with potentially toxic
substances. Trace metals in coastal waters are the major part of the anthropogenic metal load of the
seawater [1]. Contaminants can be natural substances or artificially produced compounds. After discharge
into the seawater, contaminants can stay in the seawater and dissolved form or they can be removed from
the seawater column through sedimentation to the bottom sediments [2]. The bivalve shell is a complex
organic-inorganic system consisting of two valves attached by largely organic ligament. The mussel had
accumulated metallic contaminants while still alive. In this way the movement of contaminants moves

* Corresponding author. E-mail address: w.siriprom@yahoo.com.

1877-7058 2012 Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
doi:10.1016/j.proeng.2012.02.065

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W. Siriprom et al. / Procedia Engineering 32 (2012) 1123 1126

from bulk aqueous solution up to the mineral surface, its deliverance covering changes because the
dielectric constant of the seawater. Benthic molluscs used for the bio monitoring of metal contamination.
Bivalve molluscs have an ability to accumulate heavy metals to various orders of magnitude with respect
to the levels found in their environment [3]. The metal elements in Bivalve molluscs (Anadara granosa )
have been studied for the monitoring of the marine environment for nearly four decades. Since 1975, it
has been suggested that Anadara granosa should be used as an indicator organisms for monitoring the
metal element pollution of the coastal marine water on a world wide scale [4].
The studies related to trace metals control in coastal areas involve monitoring a series of trace metals in
coastal water. The aim of this study was to determine the structures of Perna Viridis shell. The
information on microstructure is one of the most significant relative data for explanation of assessment the
potentiality of using the Perna Viridis shell as bio-monitoring of metal pollution.
2. Materials and Methods
The marine bivalve molluscs (Perna Viridis) were collected from the coastal areas of Cholburi
provinces. First of all, the bivalve shell was brushed and washed with distilled water. Afterward the
samples were cleaned by soaking in dilute HCL solution. The cleaned sample was ground into fine
powder to desired sizes by sieves and labels. The powders samples were pressed into tablets for chemical
analysis to measure the trace metals in the shells. The chemical analysis and levels of the trace metals was
carried out using Energy Dispersive X-ray Fluorescence (EDXRF) spectrometer, ED2000 High
Resolution. The crystal structure was characterized by a powder X-ray diffractometer. Powder diffraction
data were recorded at room temperature using a powder diffractomter, Bruker AXS D8 Advance [CuKD
(Ni filtered) with scintillation detector; 2T range from 20-80q and step size of 0.02q]. The metal ions in the
mollusks shell were studied by ESR spectrometer. All ESR spectra of the powder samples were measured
on Bruker E 500 CW ESR spectrometer operating at X-band microwave frequency using 0.5 mT field
modulation amplitude with a time constant of 0.03 s.
3. Results and Discussion
The qualitative characteristic of Perna Viridis shell samples is presented in Fig. 1. The concentrations
of the metals Ca, Sc and Sr, have high concentrations (Table 1) are major constituents of Perna Viridis
shell, resulting in the appearance of red color in Fig. 1. The composition of minor minerals as shown in
Table 1, the highest concentration for metals (Fe, Mn, Cu, Cr, Zn and Au),
Table 1. EDXRF analysis of major constituents of Perna Viridis shell samples (wt.% for Ca and Sr; parts per million (ppm) for
others unless indicated in table)
Species/
element

Ca
(Wt%)

Sc
(Wt%)

Cr
(ppm)

Mn
(ppm)

Fe
(ppm)

Zn
(ppm)

Perna viridis

99.5

0.245

48.0

143

469

44.0

Cu
(ppm)
53.0

Sr
(Wt%)

Au
(ppm)

Pb
(ppm)

0.477

36.0

Nd

The powder x-ray diffraction patterns of Perna Viridis shell samples are shown in Fig. 2. It was found
that the phase of all Perna Viridis shell samples is a is a mixture phase of aragonite and calcite. The
mineral phases of the bivalve samples all species were identified from the diffractograms by reference to
the Joint Committee on Powder Diffraction Standard (JCPDS) numbers 00-005-0453, and 01-086-2339
correspond to aragonite phase and calcite phase respectively.

Intensity (cps)

W. Siriprom et al. / Procedia Engineering 32 (2012) 1123 1126

Energy (keV)
Fig. 1. EDXRF spectra of Perna Viridis shell samples

Intensity (a.u.)

Intensity (a.u.)

The ESR spectrum of the Perna Viridis shell samples is shown in Fig. 3. The spectrum is typical of
Mn2+ in carbonate minerals. The ESR spectra of Mn2+ deviate from the Kramers doublets split further
and the energy between successive levels. Due to the low symmetry environment The ESR spectra of the
Perna Viridis shell samples have low intensity, weak line and broad signal. While, the high intense signal
at in the center of sextet may be assignable to free inorganic radicals, the most of the irradiated natural
carbonates is CO2- , CO3-3, CO3- and SO2- species.

2T (degree)

Magnetic Field (mT)

Fig. 2. Powder XRD patterns of Perna Viridis shell samples.

Fig. 3. X-band ESR spectra of Perna Viridis shell samples

Indicating that A, Aragonite and C, Calcite

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4. Conclusions
The Perna Viridis shell shell samples obtained from the coastal area of Chonburi Province, the eastern
part of Thailand consists mainly of Ca, Sc and Sr. The information of trace element in Perna Viridis shell
samples showed a significant relative between elements of metal in the shell. The magnitude of trace
element following the order Fe > Mn > Cu > Cr> Zn > Au, except lead (Pb), in the marine environment.
In addition, the ESR spectrum of Mn2+ ion in aragonite phase is the weak line and broad signal. Another
that ESR spectroscopy can be profitably used to examine information concerning structural organization
and can provide unusual metal ion metal ions (free inorganic radicals).
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