RARE EARTH ELEMENTS (LANTHANIDES)
ASSESSMENT IN ROCKY SHORE ORGANISMS AND
SURFACE SEDIMENT ALONG PENINSULAR
MALAYSIA COASTAL WATERS
BY
MOHD FUAD MISKON
A thesis submitted in fulfillment of the requirement for the
degree of Doctor of Philosophy in Bioscience
Kulliyyah of Science
International Islamic University Malaysia
MARCH 2016
ABSTRACT
This study emphases on the assessment of REEs in rocky shore ecosystem along
Peninsular Malaysia coastal waters, describing their partitioning between surface
sediment and selected body parts of Saccostrea cucullata, Thais clavigera and Nerita
chameleon, and deliberating on interspecies, inter-tissue and interspatial variability.
Samples was digested using Teflon Bomb technique and concentrations of 14
naturally occurring REEs were measured using ICP-MS technique, along with
selected trace metals for additional data. The REEs fractionation patterns normalized
to chondrite or shale were remarkably similar, indicating a common source of the
REEs for the whole region, however, mean concentration suggested that east
Peninsular Malaysia provides higher REEs compared to west peninsula area.
Consistent REEs abundance patterns were found in all samples, with enrichment of
LREEs over HREEs, which implies that REEs are transported as a coherent group
through aquatic ecosystems. There are dissimilarities in the REEs abundance for each
site, but they demonstrate similarities in their REEs distribution patterns, which
propose that they are of parallel origins. The contaminant metals As, Mn, Cu, and Cd
were significantly correlated with REEs (p<0.05 and p<0.01), consequently suggests
that these metals are probably non-anthropogenic in origin as the REEs are geogenic
in origin. Quantification of anomalies calculated using values normalized to chondrite,
PAAS and NASC data presented ratios higher than unity for Ce and ratios lower than
unity for Eu in all sites. Filter feeder S. cucullata is considered to be highly potential
as a bioindicator for REEs, undoubtedly due to its feeding behaviour that is much
related to particulates as REEs sources. Consistent chondrite-normalized pattern
strongly suggests that the REEs accumulated by S. cucullata, T. clavigera and N.
chameleon are derived mostly from indigenous rocks. Results showed that the values
are considerably below the safety limit, with the exception of Ce and Nd in the soft
tissue of S. cucullata. With regards to sediment, comparative analysis resolved that the
concentration of surface sediment in this study is very low compared to limit sets.
ii
‫خالصة البحث‬
‫س ّوضث ٘زٖ اٌذساست ػٍى حمٍٍُ اٌؼٕبصش األسضٍت إٌبدسة فً اٌصخ‪ٛ‬س اٌشبطئٍت ػٍى‬
‫ط‪ٛ‬ي اٌٍّبٖ اٌسبدٍٍت ٌشبٗ جضٌشة ِبٌٍضٌب‪ ،‬حُ ‪ٚ‬صف أخشبس٘ب ِب بٍٓ اٌش‪ٚ‬اسب‬
‫اٌسطذٍت ‪ٚ‬أجضاء ِخخبسة ٌىً ِٓ ‪Thais clavigera ٚ Saccostrea cucullata‬‬
‫‪ٚ Nerita chameleon ٚ‬دساسخ‪ٙ‬ب ِٓ بٍٓ األٔ‪ٛ‬اع اٌّخخٍفت‪ٚ ،‬بٍٓ األٔسجت ‪ٚ‬اٌخببٌٓ‬
‫اٌّىبًٔ ٌ‪ٙ‬ب‪ .‬حُ اخخٍبس اٌؼٍٕبث بئسخخذاَ حمٍٕت ِضخت اٌخفٍ‪ٚ ْٛ‬بئسخخذاَ أسبؼت ػشش‬
‫حشوٍضا حذذد بشىً طبٍؼً‪ٚ .‬حُ لٍبط اٌؼٕبصش األسضٍت إٌبدسة ببسخخذاَ حمٍٕت‬
‫‪ ،ICP-MS‬جٕبب إٌى جٕب ِغ اٌّؼبدْ إٌبدسة اٌّخخبسة وبٍبٔبث إضبفٍت‪ .‬حُ حس‪ٌٛ‬ت‬
‫أّٔبط حجضئت اٌؼٕبصش األسضٍت إٌبدسة اٌى و‪ٔٛ‬ذسٌج أ‪ ٚ‬اٌصخش اٌضٌخً ‪ٚ‬وبٔج‬
‫ِخشبب‪ٙ‬ت بشىً ٍِذ‪ٛ‬ظ‪ِّ ،‬ب ٌذي ػٍى اٌّصذس اٌّشخشن ٌٍؼٕبصش األسضٍت إٌبدسة‬
‫فً إٌّطمت وٍ‪ٙ‬ب‪ِٚ ،‬غ رٌه‪ٌ ،‬شٍش ٌبذذ إٌى أْ ِٕطمت ششق شبٗ جضٌشة ِبٌٍضٌب ٌ‪ٛ‬فش‬
‫حشاوٍض أػٍى ِٓ اٌؼٕبصش األسضٍت إٌبدسة ِمبسٔت ِغ ِٕطمت شبٗ اٌجضٌشة اٌغشبٍت‪.‬‬
‫حُ اٌؼز‪ٛ‬س ػٍى أّٔبط ح‪ٛ‬اجذ اٌؼٕبصش األسضٍت إٌبدسة رببخت فً جٍّغ اٌؼٍٕبث‪ِ ،‬غ‬
‫خص‪ٛ‬بت ‪ LREEs‬ػٍى ‪ِّ ،HREEs‬ب ٌذي ػٍى أٔٗ حُ ح‪ٛ‬صٌغ اٌؼٕبصش األسضٍت‬
‫إٌبدسة وّجّ‪ٛ‬ػت ِخّبسىت ِٓ خالي إٌظبَ اٌبٍئً اٌّبئً‪ٕ٘ .‬بن إخخالفبث فً ح‪ٛ‬اجذ‬
‫اٌؼٕبصش األسضٍت إٌبدسة فً وً ِ‪ٛ‬لغ ٌىٕ‪ٙ‬ب ِخشببت فً أّٔبط ح‪ٛ‬صٌؼ‪ٙ‬ب ِّب ٌذي ػٍى‬
‫أٔ‪ٙ‬ب ِٓ ِٕشأ ِخ‪ٛ‬اصي‪ .‬وبٔج اٌّؼبدْ اٌٍّ‪ٛ‬رت اسسٍٕسٓ‪ ،‬إٌّغٍٕض‪ ،‬إٌذبط‪،‬‬
‫‪ٚ‬اٌىبدٍِ‪ِ َٛ‬شحبطت بشىً وبٍش ِغ اٌؼٕبصش األسضٍت إٌبدسة ( ‪p<0.05 and‬‬
‫‪ ،)p<0.01‬ببٌخبًٌ ٌشٍش إٌى أْ ٘زٖ اٌّؼبدْ ً٘ ػٍى األسجخ غٍش بششٌت إٌّشأ ِزً‬
‫اٌؼٕبصش األسضٍت إٌبدسة اٌجٍ‪ٛ‬جٕه فً األصً‪ .‬اٌخذًٍٍ اٌىًّ ٌٍذبالث اٌشبرة‬
‫اٌّذس‪ٛ‬بت ببسخخذاَ لٍُ حس‪ٌٛ‬ت اٌى‪ٔٛ‬ذسٌج‪ٚ .‬لذِج بٍبٔبث ‪ٔ NASCٚ PAAS‬سب‬
‫أػٍى ِٓ اٌسٍشٌ‪ٔٚ ،َٛ‬سب ألً ِٓ ‪ Eu‬فً وبفت اٌّ‪ٛ‬الغ‪ٌ .‬ؼخبش ِششخ اٌّغزٌت ‪S.‬‬
‫‪ٌ cucullata‬ذٌٗ إِىبٍٔبث ػبٌٍت ببػخببسٖ ِؤششاث بٍ‪ٌٛٛ‬جٍت ٌٍؼٕبصش األسضٍت‬
‫إٌبدسة‪ِّ ،‬ب ٌذي ػٍى سٍ‪ٛ‬ن اٌخغزٌت اٌخً ٌ‪ٙ‬ب اسحببط وبٍش ٌٍجسٍّبث وّب فً‬
‫اٌؼٕبصشاألسضٍٗ إٌبدسٖ‪ٌٚ .‬شٍش ّٔظ حى‪ ٌٓٛ‬اٌى‪ٔٛ‬ذسٌج اٌّخٕبسك أْ اٌؼٕبصش‬
‫األسضٍت إٌبدسة اٌّخشاوّت ‪N. chameleon ٚ S. cucullata, T. clavigera‬‬
‫ِسخّذة فً ِؼظّ‪ٙ‬ب ِٓ اٌصخ‪ٛ‬س األصٍٍت‪ .‬أظ‪ٙ‬شث إٌخبئج أْ اٌمٍُ ً٘ ألً بىزٍش ِٓ‬
‫دذ اٌسالِت‪ ،‬ببسخزٕبء اٌسٍشٌ‪ٚ َٛ‬إٌٍ‪ٛ‬دٌٍّ‪ َٛ‬فً األٔسجت إٌٍٍت فً ‪S. cucullata‬‬
‫‪ٚ‬فٍّب ٌخؼٍك فً اٌش‪ٚ‬اسب‪ ،‬فمذ أظ‪ٙ‬ش اٌخذًٍٍ اٌّمبسْ ٌ‪ٙ‬زٖ اٌذساست أْ حشوٍض‬
‫اٌش‪ٚ‬اسب اٌسطذٍت ِٕخفض جذا ِمبسٔت فً اٌذذ‪ٚ‬د اٌّسّ‪ٛ‬ح فً اٌّجّ‪ٛ‬ػبث‪.‬‬
‫‪iii‬‬
APPROVAL PAGE
The thesis of Mohd Fuad Miskon has been approved by the following:
_____________________________
Kamaruzzaman Yunus
Supervisor
_____________________________
Md. Mokhlesur Rahman
Co-Supervisor
_____________________________
Md. Zahangir Alam
Internal Examiner
_____________________________
Noor Azhar Mohamed Shazili
External Examiner
_____________________________
Ahmad Ismail
External Examiner
_____________________________
Wan Mohd Azizi Wan Sulaiman
Chairman
iv
DECLARATION
I hereby declare that this dissertation is the result of my own investigations, except
where otherwise stated. I also declare that it has not been previously or concurrently
submitted as a whole for any other degrees at IIUM or other institutions.
Mohd Fuad Miskon
Signature ...........................................................
v
Date .........................................
COPYRIGHT PAG
INTERNATIONAL ISLAMIC UNIVERSITY MALAYSIA
DECLARATION OF COPYRIGHT AND AFFIRMATION OF
FAIR USE OF UNPUBLISHED RESEARCH
RARE EARTH ELEMENTS (LANTHANIDES) ASSESSMENT IN
ROCKY SHORE ORGANISMS AND SURFACE SEDIMENT
ALONG PENINSULAR MALAYSIA COASTAL WATERS
I declare that the copyright holders of this dissertation are jointly owned by the student
and IIUM.
Copyright © 2016 Mohd Fuad Miskon and International Islamic University Malaysia. All rights
reserved.
No part of this unpublished research may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means, electronic, mechanical, photocopying,
recording or otherwise without prior written permission of the copyright holder
except as provided below
1.
Any material contained in or derived from this unpublished research may
be used by others in their writing with due acknowledgement.
2.
IIUM or its library will have the right to make and transmit copies (print
or electronic) for institutional and academic purposes.
3.
The IIUM library will have the right to make, store in a retrieved system
and supply copies of this unpublished research if requested by other
universities and research libraries.
By signing this form, I acknowledged that I have read and understand the IIUM
Intellectual Property Right and Commercialization policy.
Affirmed by Mohd Fuad Miskon
……..……………………..
Signature
………………………..
Date
vi
ACKNOWLEDGEMENTS
Alhamdulillah, all praises to Allah for the strengths and His blessing. Only by His
grace and mercy this thesis has been completed.
I would like to take this opportunity to express my grateful thanks and deep
appreciation to my supervisor, Prof. Dr. Kamaruzzaman Yunus, for his invaluable
guidance and encouragement throughout my research. Not forgotten, my appreciation
to my co-supervisor, Assoc. Prof. Dr. Mokhlesur Rahman for his guidance, support
and knowledge. I am also grateful to the Deputy Dean Research and Postgraduate,
Prof. Dr. Ahmed Jalal Khan Chowdhury for his support and help towards my
postgraduate affairs.
Special thanks are extended to all the technicians, office staffs and laboratory
assistants of Kuliyyah of Science especially to Br. Ahmad Faezal for his kind
assistance during sampling session. Sincere thanks to all my friends, especially Br.
Zaini, Br. Faiz, Sr. Hafizah, Sr. Atikah and Br. Fadhli for helping me through my
research period. Also to those who indirectly contributed in this research, your help
and kindness means a lot to me.
My deepest gratitude goes to my beloved parents; Allahyarham Hj. Miskon
Kasmat and Hjh Zaiton Talkah, and my siblings, to my beloved parents-in-law; Hj.
Faudzi Ahmad and Allahyarhamah Hjh Aziah Othman for their endless love, prayers,
support and encouragement in letting me pursue my dreams.
Finally, I am greatly indebted to my beloved wife, Fikriah Faudzi for her
endless love, patience, encouragement, sacrifices and prayers throughout the study.
Also, I am grateful for the greatest gift from the Almighty Allah, my son, Muhammad
Fayyadh Aufaa, who opening up an exciting world and bringing us joy during the
stages of my research.
Thank you very much.
vii
TABLE OF CONTENTS
Abstract …………. .................................................................................................. ii
Abstract in Arabic …………………………...………………………………….....iii
Approval Page ……………………………………………………………………..iv
Declaration …………………………………………………………………………v
Copyright Page …… ................................................................................................ vi
Acknowledgements .................................................................................................. vii
List of Tables …………………………………………...………………………....xiv
List of Figures ………………….……………………………….………………....xviii
CHAPTER ONE: INTRODUCTION .................................................................. 1
1.1 Research Background ............................................................................. 1
1.2 Problem Statement .................................................................................. 4
1.3 Research Questions ................................................................................. 4
1.4 Research Scope ....................................................................................... 5
1.5 General Objectives.................................................................................. 5
1.6 Specific Objectives ................................................................................. 5
1.7 Research Hypothesis ............................................................................... 6
1.8 Significance of Research ........................................................................ 6
1.9 Limitations of Research .......................................................................... 7
1.10 Chapter Summary ................................................................................. 7
CHAPTER TWO: LITERATURE REVIEW ..................................................... 9
2.1 Background ............................................................................................. 9
2.2 Rare Earth Elements ............................................................................... 9
2.3 Rare Earth in Nature ............................................................................... 13
2.4 REEs Fate in the Environment ............................................................... 16
2.5 REEs as a Pollutant Tracer ..................................................................... 18
2.6 Rocky Shore............................................................................................ 22
2.7 Pollutant Biomonitoring Using Molluscs ............................................... 23
2.8 Molluscs as Bioindicator in Malaysia .................................................... 25
2.9 Biology of Studied Organisms................................................................ 27
2.9.1 Saccostrea cucullata (Born, 1778)................................................ 27
2.9.2 Thais clavigera (Kuster, 1860) ..................................................... 28
2.9.3 Nerita chameleon (Linnaeus, 1758) .............................................. 29
2.10 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) ................ 30
CHAPTER THREE: MATERIAL AND METHODS........................................ 35
3.1 Introduction............................................................................................. 35
3.2 Sampling Sites ........................................................................................ 36
3.3 Sampling Sites Description..................................................................... 41
3.3.1 Langkawi Island, Kedah ............................................................... 41
3.3.1.1 Pasir Tengkorak Beach ..................................................... 41
3.3.1.2 Tengah Beach ................................................................... 42
3.3.1.3 Beringin Beach ................................................................. 42
3.3.2 Pulau Sayak, Kedah ...................................................................... 43
x
3.3.3 Pulau Betong, Penang ................................................................... 43
3.3.4 Batu Feringghi, Penang ................................................................. 44
3.3.5 Teluk Senangin, Perak .................................................................. 44
3.3.6 Teluk Batik, Perak......................................................................... 45
3.3.7 Taman Tanjung, Negeri Sembilan ................................................ 46
3.3.8 Teluk Kemang, Negeri Sembilan .................................................. 46
3.3.9 Blue Lagoon, Negeri Sembilan ..................................................... 47
3.3.10 Tanjung Bidara, Malacca ............................................................ 47
3.3.11 Tanjung Kling, Malacca .............................................................. 48
3.3.12 Batu Pahat, Johor ........................................................................ 48
3.3.13 Sungai Rengit, Johor ................................................................... 49
3.3.14 Batu Layar, Johor ........................................................................ 50
3.3.15 Tanjung Balau, Johor .................................................................. 50
3.3.16 Sedili Kecil, Johor ....................................................................... 51
3.3.17 Mersing, Johor ............................................................................ 51
3.3.18 Kampung Tanjung Batu, Pahang ................................................ 52
3.3.19 Teluk Cempedak, Pahang ........................................................... 52
3.3.20 Tanjung Gelang, Pahang ............................................................. 53
3.3.21 Cherating, Pahang ....................................................................... 53
3.3.22 Telaga Simpul, Terengganu ........................................................ 54
3.3.23 Teluk Kalong, Terengganu ......................................................... 54
3.3.24 Kijal, Terengganu........................................................................ 55
3.3.25 Kemasik, Terengganu ................................................................. 55
3.3.26 Kerteh, Terengganu ..................................................................... 56
3.3.27 Tanjung Jara, Terengganu ........................................................... 57
3.3.28 Chendering, Terengganu ............................................................. 57
3.3.29 Bari Kecil, Terengganu ............................................................... 58
3.3.30 Tioman Island ............................................................................. 58
3.3.30.1 Dalam Bay ...................................................................... 59
3.3.30.2 Tanjung Sekeliling .......................................................... 59
3.3.30.3 Tekek village .................................................................. 60
3.4 Sampling Design ..................................................................................... 60
3.4.1 Timed Search Method ................................................................... 61
3.4.2 Sample collection .......................................................................... 61
3.5 Studied Species ....................................................................................... 63
3.6 Sample Preparation before Digestion ..................................................... 66
3.6.1 Moisture Content in Biota ............................................................. 67
3.6.2 Conversion Factor (CF) ................................................................ 67
3.7 Digestion Procedure................................................................................ 73
3.7.1 Biological sample .......................................................................... 74
3.7.2 Sediment sample ........................................................................... 75
3.8 Sample Measurement.............................................................................. 76
3.8.1 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) ........ 76
3.8.2 Detection Limit ............................................................................. 78
3.8.3 Handling of Standard Solution...................................................... 78
3.9 Quality Control and Quality Assurance .................................................. 79
3.9.1 Laboratory Interferences ............................................................... 79
3.9.2 Procedural Blank ........................................................................... 80
3.9.3 Recovery Test ............................................................................... 80
xi
3.9.4 Calculation of REEs in Sample ..................................................... 83
3.10 Data Handling ....................................................................................... 83
3.10.1 Calculation of REE ratios ........................................................... 84
3.10.2 Normalization using Reference Value ........................................ 85
3.10.3 Quantification of REE anomalies ............................................... 86
3.10.4 Enrichment factor ........................................................................ 88
3.10.5 Statistical Analysis ...................................................................... 89
3.10.5.1 ANOVA with post hoc test ............................................. 89
3.10.5.2 Correlation analysis ........................................................ 90
3.10.5.3 Hierarchical Cluster Analysis ......................................... 90
CHAPTER FOUR: RESULTS AND DISCUSSION .......................................... 91
4.1 Introduction............................................................................................. 91
4.2 Sediment analysis ................................................................................... 92
4.2.1 REEs concentration in surface sediment ....................................... 92
4.2.2 Inter-elemental variation in sediment ........................................... 97
4.2.3 Enrichment factor in sediment ...................................................... 99
4.2.4 REEs behaviour in sediment ......................................................... 101
4.2.5 REEs normalization in sediment ................................................... 103
4.2.6 REEs anomalies quantification sediment ...................................... 108
4.3 Biota analysis .......................................................................................... 111
4.3.1 REEs concentration in S. cucullata ............................................... 111
4.3.2 REEs concentration and distribution in different tissues of T.
clavigera ....................................................................................... 116
4.3.3 REEs concentration and distribution in different tissues of N.
chameleon ..................................................................................... 126
4.3.4 REEs Behaviour ............................................................................ 136
4.3.5 REEs Anomalies ........................................................................... 140
4.4 Inter-Tissue Variation ............................................................................. 153
4.5 Interspecies Variation ............................................................................. 159
4.6 Interspatial Variation .............................................................................. 165
4.7 Assessment with Maximum Permissible Concentrations ....................... 169
CHAPTER FIVE: CONCLUSION AND RECOMMENDATION ................... 174
5.1 Conclusion .............................................................................................. 174
5.2 Recommendation .................................................................................... 176
REFERENCES ..................................................................................................... 177
APPENDIX A: CORRELATION MATRIX BETWEEN REES AND TRACE
METAL CONCENTRATIONS IN SEDIMENT ........................ 196
APPENDIX B: COEFFICIENT OF CORRELATION MATRIX BETWEEN REES
CONCENTRATIONS IN SOFT TISSUE, OPERCULUM AND
SHELL OF T. CLAVIGERA FROM PARTICULAR SAMPLING
SITES ALONG THE PENINSULAR MALAYSIA COASTAL
WATERS ..................................................................................... 197
APPENDIX C: COEFFICIENT OF CORRELATION MATRIX BETWEEN REES
CONCENTRATIONS IN SOFT TISSUE, OPERCULUM AND
SHELL OF N. CHAMELEON FROM PARTICULAR SAMPLING
xii
APPENDIX D:
APPENDIX E:
APPENDIX F:
APPENDIX G:
APPENDIX H:
APPENDIX I:
APPENDIX J:
APPENDIX K:
APPENDIX L:
APPENDIX M:
APPENDIX N:
APPENDIX O:
SITES ALONG THE PENINSULAR MALAYSIA COASTAL
WATERS ..................................................................................... 199
COEFFICIENT OF CORRELATION MATRIX BETWEEN REES
CONCENTRATIONS
IN SOFT TISSUE VS
REES
CONCENTRATION
IN
OPERCULUM
AND
REES
CONCENTRATIONS
IN SOFT TISSUE VS
REES
CONCENTRATION IN SHELL OF T. CLAVIGERA FROM
PARTICULAR SAMPLING SITES ALONG THE PENINSULAR
MALAYSIA COASTAL WATERS ........................................... 201
COEFFICIENT OF CORRELATION MATRIX BETWEEN REES
CONCENTRATIONS
IN SOFT TISSUE VS
REES
CONCENTRATION
IN
OPERCULUM
AND
REES
CONCENTRATIONS
IN SOFT TISSUE VS
REES
CONCENTRATION IN SHELL OF N. CHAMELEON FROM
PARTICULAR SAMPLING SITES ALONG THE PENINSULAR
MALAYSIA COASTAL WATERS ........................................... 202
SMARTTUNE PROGRAM RESULTS PRIOR TO EACH
MEASUREMENT WORK TO ENSURE ICP-MS IN PERFECT
CONDITION ............................................................................... 203
CALIBRATION CURVES OBTAINED FROM SERIAL MULTIELEMENT CALIBRATION STANDARD FOR REES ............ 204
TUKEY’S POST HOC TEST COMPARISONS OF ELEMENTS
CONCENTRATIONS BETWEEN SAMPLING SITES IN
SURFACE SEDIMENT .............................................................. 209
TUKEY’S POST HOC TEST COMPARISONS OF ELEMENTS
CONCENTRATIONS BETWEEN SAMPLING SITES IN S.
CUCULLATA............................................................................... 210
TUKEY’S POST HOC TEST COMPARISONS OF ELEMENTS
CONCENTRATIONS BETWEEN SAMPLING SITES IN T.
CLAVIGERA ................................................................................ 212
TUKEY’S POST HOC TEST COMPARISONS OF ELEMENTS
CONCENTRATIONS BETWEEN SAMPLING SITES IN N.
CHAMELEON ............................................................................. 214
TOTAL CONCENTRATION (µG G-1 DRY WEIGHT) OF ΣREE
IN SEDIMENT FROM PARTICULAR SAMPLING SITES
ALONG PENINSULAR MALAYSIA COASTAL WATERS .. 216
TOTAL CONCENTRATION (µG G-1 DRY WEIGHT) OF ΣREE
IN SOFT TISSUE OF S. CUCULLATA FROM PARTICULAR
SAMPLING SITES ALONG PENINSULAR MALAYSIA
COASTAL WATERS ................................................................. 217
TOTAL CONCENTRATION (µG G-1 DRY WEIGHT) OF ΣREE
IN SOFT TISSUE, OPERCULUM AND SHELL OF T.
CLAVIGERA FROM PARTICULAR SAMPLING SITES ALONG
PENINSULAR MALAYSIA COASTAL WATERS ................. 218
TOTAL CONCENTRATION (µG G-1 DRY WEIGHT) OF ΣREE
IN SOFT TISSUE, OPERCULUM AND SHELL OF N.
CHAMELEON FROM PARTICULAR SAMPLING SITES
ALONG PENINSULAR MALAYSIA COASTAL WATERS .. 220
xiii
LIST OF TABLES
Table No.
Page No.
2.1
REEs chemical properties and abundances in earth's upper crust
14
2.2
Main usages of REEs (from USEPA, 2012, Gonzales et al., 2014)
17
2.3
Maximum permissible concentration and maximum permissible
addition in surface water and sediment (Sneller et al., 2000)
21
REEs and possible interferences in ICP-MS measurement (Dulski,
1994; Dresler et al., 2007)
33
List of sampling sites and their locations determined by coordinate
along the Peninsular Malaysia coastal waters
40
3.2
Availability of study organism for each sampling site
65
3.3
Biometric data (mean and standard deviation) of S. cucullata, T.
clavigera and N. chameleon
68
Means of wet weight, dry weight, water content (%) and conversion
factor (CF) of S. cucullata, T. clavigera and N. chameleon
71
3.5
Standard running conditions of ICP-MS
77
3.6
REEs isotope measured using ICP-MS
78
3.7
Analytical results of measured BCR 668 standard reference material,
detection limit and percentage of recovery for each element (µg g-1
dry weight)
82
Analytical results of measured BCR 667 standard reference material,
the detection limit and percentage of recovery for each element (µg
g-1 dry weight)
83
Concentration of REEs in NASC, PAAS shales (Taylor and
McLennan, 1985) and chondrite (Mcdonough and Sun, 1989)
86
3.10
Contamination categories based on the enrichment factor values
89
4.1
Total concentration (µg g-1 dry weight) of ΣREE in sediment from
particular sampling sites along Peninsular Malaysia coastal waters
93
Correlation between elements in surface sediment from Peninsular
Malaysia coastal waters
98
2.4
3.1
3.4
3.8
3.9
4.2
xiv
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
Correlation matrix between REEs and trace metal concentrations in
sediment
99
Enrichment factor (EF) values calculated for sediment along
Peninsular Malaysia coastal waters
100
Concentration of light and heavy REEs and ratios of REEs in the
sediment
102
Indicator ratio of Ce/Ce*, Eu/Eu*, and (La/Yb)N in surface sediment
of particular sites from Peninsular Malaysia coastal waters using
values of PAAS, NASC and chondrite
109
Total concentration (µg g-1 dry weight) of ΣREE in soft tissue of S.
cucullata from particular sampling sites along the Peninsular
Malaysia coastal waters
112
Decreasing pattern of REEs occurrences (µg g-1 dry weight) in soft
tissue of S. cucullata from particular sampling sites along Peninsular
Malaysia coastal waters
115
Pearson’s correlation between REEs concentration in soft tissue of S.
cucullata from particular sampling sites along the Peninsular
Malaysia coastal waters
116
Total concentration (µg g-1 dry weight) of ΣREE in soft tissue of T.
clavigera from particular sampling sites along the Peninsular
Malaysia coastal waters
118
Total concentration (µg g-1 dry weight) of ΣREE in operculum of T.
clavigera from particular sampling sites along the Peninsular
Malaysia coastal waters
121
Total concentration (µg g-1 dry weight) of ΣREE in shell of T.
clavigera from particular sampling sites along the Peninsular
Malaysia coastal waters
124
Total concentration (µg g-1 dry weight) of ΣREE in soft tissue of N.
chameleon from particular sampling sites along the Peninsular
Malaysia coastal waters
127
Total concentration (µg g-1 dry weight) of ΣREE in operculum of N.
chameleon from particular sampling sites along the Peninsular
Malaysia coastal waters
131
Total concentration (µg g-1 dry weight) of ΣREE in shell of N.
chameleon from particular sampling sites along the Peninsular
Malaysia coastal waters
134
Concentration of ΣREE, ΣLREE, ΣHREE, LREE/HREE, Ce/La,
Eu/Sm, Yb/Sm, and La/Yb in soft tissue of S. cucullata
136
xv
Mean concentration of total REEs (∑REE), ∑LREE, ∑HREE, ratios
of LREE/HREE, La/Yb, La/Sm, Ce/La, Eu/Sm and Yb/Sm in soft
tissue, operculum and shell of T. clavigera
137
Concentration of total REEs (∑REE), ∑LREE, ∑HREE, ratios of
LREE/HREE, La/Yb, La/Sm, Ce/La, Eu/Sm and Yb/Sm in soft
tissue, operculum and shell of N. chameleon
138
Indicator ratios of Ce/Ce*, Eu/Eu* and (La/Yb)N in soft tissue of
S. cucullata
142
Concentration of Ce/Ce*, Eu/Eu* and (La/Yb)N in soft tissue,
operculum and shell of T. clavigera
146
Concentration of Ce/Ce*, Eu/Eu* and (La/Yb)N in soft tissue,
operculum and shell of N. chameleon
151
Coefficient of correlation matrix between REEs concentrations in
soft tissue, operculum and shell of T. clavigera from particular
sampling sites along the Peninsular Malaysia coastal waters
153
Coefficient of correlation matrix between REEs concentrations in
soft tissue, operculum and shell of N. chameleon from particular
sampling sites along the Peninsular Malaysia coastal waters
154
Coefficient of correlation matrix between REEs concentration in soft
tissue vs REEs concentration in operculum and REEs concentration
in soft tissue vs REEs concentration in shell of T. clavigera from
particular sampling sites along the Peninsular Malaysia coastal
waters
155
Coefficient of correlation matrix REEs concentration in soft tissue vs
REEs concentration in operculum and REEs concentration in soft
tissue vs REEs concentration in shell of N. chameleon from
particular sampling sites along the Peninsular Malaysia coastal
waters
156
Mean ratios of operculum REEs to soft tissue REEs (OTR) and shell
REEs to soft tissue REEs (STR) in T. clavigera and N. chameleon
158
4.27
Bioaccumulation Factors (BAF) calculated in studied organisms
160
4.28
Available comparative reports on the BAF of REEs in aquatic organisms
162
4.29
Maximum permissible limits on selected heavy metals (in µg g-1) for
food safety set by different countries
169
Mean values of REEs concentration (in µg g-1) in wet and dry states
of soft tissue of S. cucullata, T. clavigera and N. chameleon, to
compare with permissible limits data
170
4.17
4.18
4.19
4.20
4.21
4.22
4.23
4.24
4.25
4.26
4.30
xvi
4.31
Comparison of sediment data in this study with the maximum
permissible concentration (mg kg-1 dry weight) in marine sediment
(Sneller, 2000)
xvii
172
LIST OF FIGURES
Figure No.
Page No.
2.1
The Periodic Table with REEs, in red colour, in group 3
11
2.2
The distribution pattern of REEs in soil (Markert, 1987)
15
2.3
Schematic representation of an ICP-MS instrument (LPM = L/min).
(Beauchemin, 2010)
31
Schematic representation of the sample introduction system that is
standard on most current ICP-MS instruments. (Beauchemin, 2010)
32
Map showing sampling locations along the Peninsular Malaysia
coastal waters. Sites are specified in Table 3.1
39
3.2
Rocky shore at Pasir Tengkorak Beach, Langkawi
41
3.3
Study site at Tengah Beach, Langkawi
42
3.4
Study site at Beringin Beach, Langkawi
42
3.5
Study site at Pulau Sayak, Kedah
43
3.6
Study site at Pulau Betong, Penang
43
3.7
Study site at Batu Feringghi, Penang
44
3.8
Study site at Teluk Senangin, Perak
44
3.9
Study site at Teluk Batik, Perak
45
3.10
Study site at Taman Tanjung, Negeri Sembilan
46
3.11
Study site at Teluk Kemang, Negeri Sembilan
46
3.12
Study site at Blue Lagoon, Negeri Sembilan
47
3.13
Study site at Tanjung Bidara, Malacca
47
3.14
Study site at Tanjung Kling, Malacca
48
3.15
Study site at Batu Pahat, Johor
48
3.16
Study site at Sungai Rengit, Johor
49
3.17
Study site at Batu Layar, Johor
50
2.4
3.1
xviii
3.18
Study site at Tanjung Balau, Johor
50
3.19
Study site at Sedili Kechil, Johor
51
3.20
Study site at Mersing, Johor
51
3.21
Study site at Kg. Tg. Batu, Pahang
52
3.22
Study site at Tlk. Cempedak, Pahang
52
3.23
Study site at Tg. Gelang, Pahang
53
3.24
Study site at Cherating, Pahang
53
3.25
Study site at Telaga Simpul, Terengganu
54
3.26
Study site at Tlk. Kalong, Terengganu
54
3.27
Study site at Kijal, Terengganu
55
3.28
Study site at Kemasik, Terengganu
55
3.29
Study site at Kerteh, Terengganu
56
3.30
Study site at Tg. Jara, Terengganu
57
3.31
Study site at Chendering, Terengganu
57
3.32
Study site at Bari Kechil, Terengganu
58
3.33
Study site at Dalam Bay, Tioman Island
59
3.34
Study site at Tg. Sekeliling, Tioman Island
59
3.35
Study site at Tekek, Tioman Island
60
3.36
Pictures of (1) S. cucullata (Born, 1778); (2) Soft tissue of S.
cucullata on its shell; (3) S. cucullata in the natural environment of
rocky shore; (4) T. clavigera (Kuster, 1860); (5) Operculum of T.
clavigera at the mouth of its shell; (6) Extracted shell of T.
clavigera; (7) T. clavigera in the natural environment of rocky shore;
(8) N. chameleon (Linnaeus, 1758); (9) Operculum of N. chameleon
at the mouth of its shell; (10) Extracted shell of N. chameleon; (11)
N. chameleon in the natural environment of rocky shore
64
Pictures of (12) Teflon steel jacket and Teflon vessel; (13) Teflon
vessel fits inside the Teflon steel jacket
74
Inductively Coupled Plasma-Mass Spectrometry that used for this
research
77
3.37
3.38
xix
3.39
Pictures of Standard reference material (SRM), (14) BCR 668
Mussel Tissue; (15) BCR 667 Estuarine Sediment
81
Pattern of REEs in sediment normalized to the concentration of
chondrite value
105
Pattern of REEs in sediment normalized to the concentration of
PAAS value
106
4.3
Pattern of REEs normalized to the concentration of NASC value
108
4.4
Chondrite-normalized plots for the REEs in the soft tissue of S.
cucullata from particular sites of Peninsular Malaysia coastal waters,
divided by region
141
Chondrite-normalized plots for the REEs in the soft tissue of T.
clavigera from particular sites along Peninsular Malaysia coastal
waters, divided by region
143
Chondrite-normalized plots for the REEs in the operculum of T.
clavigera from particular sites along Peninsular Malaysia coastal
waters, divided by region
144
Chondrite-normalized plots for the REEs in the shell of T. clavigera
from particular sites along Peninsular Malaysia coastal waters,
divided by region
145
Chondrite-normalized plots for the REEs in the soft tissue of N.
chameleon from particular sites along Peninsular Malaysia coastal
waters, divided by region
147
Chondrite-normalized plots for the REEs in the operculum of N.
chameleon from particular sites along Peninsular Malaysia coastal
waters, divided by region
148
Chondrite-normalized plots for the REEs in the shell of N.
chameleon from particular sites along Peninsular Malaysia coastal
waters, divided by region
149
Bioaccumulation Factor (BAF) for REEs in studies species based on
surface sediment in dry soft tissue vs. REEs
161
4.12
REEs bioavailabilities comparison across species
163
4.13
Dendrogram of the HCA on soft tissue of S. cucullata collected from
particular sites based on their ∑LREE and ∑HREE concentrations
166
Dendrogram of the HCA on soft tissue of T. clavigera collected from
particular sites based on their ∑LREE and ∑HREE concentrations
167
4.1
4.2
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.14
xx
4.15
4.16
Dendrogram of the HCA on soft tissue of N. chameleon collected
from particular sites based on their ∑LREE and ∑HREE
concentrations
167
Dendrogram of the HCA on sediment collected from particular sites
based on their ∑LREE and ∑HREE concentrations
168
xxi
CHAPTER ONE
INTRODUCTION
1.1 RESEARCH BACKGROUND
Rare Earth Elements (REEs) consist of a group of fifteen homologous metals,
lanthanides, composed with scandium (Sc) and yttrium (Y). Antagonistic to its name
suggests that they are not rare at all and could be found abundantly in the earth crust
comparable to Pb or Cd. Naturally occurring REEs show a typical pattern in
environmental samples due to its similar physical and chemical properties (Weltje et
al., 2002). This pattern will display that the odd-numbered elements will have lower
concentrations than the nearby even-numbered ones, acknowledged as Oddo-Harkins
rule (Oddo, 1914; Harkins, 1917). The logarithm of the abundance against atomic
number presented a saw-tooth pattern, which is strongly conserved as the REEs
disperse from indigenous rocks to soils and sediments, water, and eventually biota.
Research on REEs has an increasing trend in Malaysia as REEs have found
applications in high and green technology which is important in Malaysia’s aspiration
to become a high-income nation. Green technology has become significant criteria
nowadays as this technology could mitigate global warming due to climate change.
Malaysia now has been recognized as a strategic place to develop green technology
industries. Studies have highlights that mining and processing of REEs do pose risks
to health, safety and environment (Chen and Zhu, 2008; Aquino et al., 2009) but
recent technologies could manage this risk. Still, there is a need to investigate REEs
concentration in their natural environment for monitoring purpose.
REEs are used in enormous quantities in the manufacturing of industrial
products comprises lasers, computers, catalysts for the oil industry, pigments for glass
1
and plastics, and additives (Riondato et al., 2001; Cui et al., 2012). Extraction and
processing of REEs ores may produce multiple waste streams that require complicated
environmental management systems, which improper waste management may modify
the quality of the local environment (USEPA, 2011; 2012). For instance,
environmental alterations to surface soils, surface waters, and soil–plant systems have
been documented in REE mining areas of China as reviewed by Liang et al. (2014).
Processing of REE compounds for petroleum refining or utilization of REE-containing
products such as gadolinium contrast agents or nanomaterials might also end up in the
discharge of REEs to the environment (Karn, 2011; Kulaksız and Bau, 2011a, 2011b).
USEPA (2012) has recognized that there is restricted evidence with regard to health
and environmental issues connected to REEs.
In a global scale, attention has been drawn due to the wide occurrence of REEs
pollution in an aquatic system. It has become a common practice to use aquatic
organisms as bioindicators in many monitoring programs throughout the world.
Goldberg et al. (1978) were the first to initiate the ``Mussel Watch Program'' in which
the bivalves were used as a surveillance tool of coastal pollution. They are often
circulated in response to concern about contamination on seafood or to employ marine
organisms as biological monitors (Oehlmann and Schulte-Oehlmann, 2003; Zhou et
al., 2008). Marine ecosystems may receive anthropogenic pollutants originating from
various sources at the surrounding area or from distant places. Yet, there are
occurrences of purely natural concentration in some cases. REEs generally enter the
environment in much more soluble form and more reactive ionic forms due to
anthropogenic rather than naturally occurring, thus producing them to be more
bioavailable (Kumar et al., 2014).
2
The increasing industrial expenditures of REEs are accompanied by growing
emissions, which primarily end up in the aquatic environment. Such occasion leads to
a need for an investigation to gain insight whether these emissions could cause effects
on aquatic biota. A study by Riondato et al. (2001) indicated that REEs tend to be
accumulated by biota and have toxic effects similar to those of Cd, Zn, and Ni. The
study of REEs distribution may also provide basic information on the geochemistry of
these elements in the coastal marine environment related to their sources. All aquatic
invertebrates are found to accumulate REEs in their tissues, regardless whether these
elements are essential to metabolism or not. Increasing emissions lead to increasing
percentage of REEs to be accumulated in biota and producing toxic effects. No
established biological functions of REEs were reported, thus, they may be considered
as non-essential elements in biota (Sneller et al., 2000; Weltje et al., 2002).
Various bivalve and gastropod species show a high presence and play an
important role as biomonitors for pollution in global monitoring programs throughout
the world (Wang et al., 2005). Molluscs exhibit greater spatial sensitivity, thus, are the
most reliable tool for identifying sources of bioavailable contamination compare to
sediments (Goldberg et al., 1978; Hamed and Emara, 2006). Much attention related to
aquatic pollution biomonitoring using molluscs has been carried out in Malaysia by
numerous researchers (Shazili et al., 1995; Amin et al., 2006; Yap et al., 2009a,
2009b; Yap et al., 2010), primarily investigating on trace or heavy metal, yet little
information exist on REEs distribution and behaviour in biota. However, in terms of
sediment study, several studies has been done (Wood et al., 2004; Sultan and Shazili,
2009; Rezaee et al., 2009; Antonina et al., 2013), presenting that REEs studies are
gaining attention to understand its behaviour in Malaysian environment.
3
1.2 PROBLEM STATEMENT
The increasing demand for REEs led to anthropogenic emission, but knowledge of the
environmental distribution of these elements in Malaysian environment is limited.
Much attention were focused on sediment while only a narrow consideration has been
paid to the REEs accumulation in tissues of living organisms, due to their direct
exposure, and related to biomagnification effects along the trophic chain. REEs
accumulation in the environment is usually considered as a good tracer of
contamination processes. Although some toxicology test has been conducted to gain
insight on bioconcentration of REEs in biological organism, the extent of REEs on the
environment and the potential health risks for species living in aquatic environment
are not well acknowledged, perhaps as a magnitude of low REEs concentrations in
living tissues and analytical difficulties associated to their determinations at ng L-1
levels. Thus, ICP-MS is considered to be most reliable technique for REEs analysis.
Determination of REEs using local bioindicator also related to human consumption.
Possible worries regarding effects of exposure to low levels of REEs on human health
have been ascending recently. It has been testified that REEs are significantly
accumulated in blood, brain and bone after entering human body.
1.3 RESEARCH QUESTIONS
i.
How ample possibility that REEs bioavailability in Saccostrea cucullata, Thais
clavigera and Nerita chameleon could attribute to prove to be suitable
bioindicator?
ii.
How far the extent of REEs accumulation in our environment with regards to
natural and anthropogenic input?
4
iii.
How considerably REEs variation could be inspected in our various rocky
shore environment features?
iv.
How complex the behaviour of REEs across organism tissues and species?
1.4 RESEARCH SCOPE
REEs measurement on selected bioindicators with specific sizes was conducted to
evaluate the bioavailability of REEs in their bodies. Sediment analysis was also taken
into account as to understand the behaviour of such elements in sediment and their
relationship with studied organisms as well. The investigation was done in various
sites characteristics such as remote and secluded area, recreational area and heavy
industry area. The possible nearby river was also identified to relate the natural or
anthropogenic input of REEs to the particular sites.
1.5 GENERAL OBJECTIVES
To investigate the distribution of REEs in selected rocky shore organisms and surface
sediment along the coastal waters of Peninsular Malaysia.
1.6 SPECIFIC OBJECTIVES
i. To determine the behaviour of REEs in term of anomalous deviation.
ii. To clarify the partitioning of REEs in different parts of studied organisms body
and relationship among them.
iii. To justify the sediment role as REEs sink to the studied organisms.
iv. To explain spatial variation related to REEs accumulation.
5