STABLE ISOTOPES ANALYSES OF CARBON-13 AND NITROGEN-15 IN RIVER SEDIMENTS

NUR ZAFIRAH BINTI ZULKIFLI

UNIVERSITI SAINS

2019

STABLE ISOTOPES ANALYSES OF CARBON-13 AND NITROGEN-15 IN SEDIMENTS

by

NUR ZAFIRAH BINTI ZULKIFLI

Thesis submitted is fulfillment of the requirements for the degree of Master of Science

March 2019

ACKNOWLEDGEMENT

Alhamdulillah, thanks to the grace of Allah, the Most Compassionate and Merciful because His consent gives me the guidance to complete this thesis.

A very invaluable appreciation and thanks to my supervisor, Dr. Muhammad

Izzuddin Syakir Bin Ishak for giving me much support and guidance throughout my research project. His guidance had helped me from the research stage until the phase of writing this thesis. I felt very overwhelmed by having a very good supervisor and mentor who gave a lot of inspiration in this research.

In addition, I would like to thank Dr. Syahidah Akmal Binti Mohammad for helping me analysed the isotope data. Next, I would also like to thank the laboratory assistants in the Industrial Technology School, who taught me ways to use the equipment and machines in the lab because without their help I might fail to carry out this experiment.

I am also grateful for having friends who were always on my side during the up and down times in completing this thesis. Many thanks to all of them and may God reward all of their good deeds. Finally, my endless gratitude is extended to my parents and lovely family for all the supports and prayers throughout my study period. Thanks to all of your prayers, this thesis is perfectly completed. Thank you.

ii

TABLE OF CONTENT

Acknowledgement ii

Table of Contents iii

List of Tables vii

List of Figures viii

List of Abbreviations and Symbols x

Abstrak xii

Abstract xiv

CHAPTER 1- INTRODUCTION

1.1 Background of Study 1

1.2 Problem Statement 3

1.3 Objectives of the Study 4

1.4 Hypothesis 5

1.5 Scope of Study 6

CHAPTER 2- LITERATURE REVIEW

2.1 Challenges Faced by Kelantan Watersheds 7

2.2 Soil Erosion and Sedimentation 7

2.2.1 The Processes of Erosion and Sedimentation 8

2.3 The Implication of Anthropogenic Activities on Watersheds 10

2.4 Hydrology and environment impact studies of Kelantan watershed 11

2.5 Sediment Tracing within Watersheds 14

2.6 The Source of Tracing Techniques in Sediments 15

iii

2.6.1 Tracing Techniques in Sediments 16

2.6.2 Stable Isotopes 18

2.6.2(a) Case Studies 20

2.6.2(b) Limitation 21

2.6.3 C/N ratio 22

2.6.3(a) Case Studies 23

2.6.3(b) Limitation 24

2.6.4 Radioisotopes 25

2.6.4(a) Case Studies 27

2.6.4(b) Limitation 28

2.6.5 Heavy Metal 28

2.6.5(a) Case Studies 30

2.6.5(b) Limitation 31

2.6.6 Magnetic Properties 34

2.6.6(a) Case Studies 33

2.6.6(b) Limitation 34

CHAPTER 3- METHODOLOGY

3.1 Study Area 36

3.1.1 Kelantan Basin 36

3.1.2 Climate and Hydrology of Kelantan Basin 40

3.2 Methodology 41

3.2.1 Experimental design 41

3.2.2 Sample Collection of River Sediments 42

iv

3.2.3 Sample Preparation 43

3.2.4 Stable Isotope Analysis 43

3.2.5 Carbon Nitrogen Ration (C/N Ratio) Analysis 47

3.2.6 Sediement Yield and WaterQuality Data 48

3.3 Statistical Analysis 49

3.3.1 Isotope Analysis 49

3.3.2 Sediment Yield Data 50

3.3.3 Water Quality Data 50

CHAPTER 4- RESULTS AND DISCUSSIONS

4.0 Introduction 51

4.1 Stable Isotope Carbon (13C) 51

4.1.1 The Temporal Distribution of Stable Carbon Isotopes (13C) in 51 Kelantan Rivers 4.1.2 The Spatial Distribution of Stable Carbon Isotopes (13C) in Kelantan 52 Rivers 4.2 Stable Isotope Nitrogen (15N) 56

4.2.1 The Temporal Distribution of Stable Nitrogen Isotopes (15N) in 56 …Kelantan Rivers 4.2.2 The Spatial Distribution of Stable Nitrogen Isotopes (15N) in 59 …Kelantan Rivers 4.3 Carbon to Nitrogen Ratio (C/N Ratio) 61

4.4 Sediment Yield in Kelantan River Networks 63

4.5 Water Quality Analysis 65

4.6 Summary 67

v

CHAPTER 5- CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion 68

5.2 Recommendations for Future Study 69

REFERENCES 70

APPENDICES 93

vi

LIST OF TABLES

Page

Table 2.1 The consequences within watershed caused by natural processes 11 and anthropogenic activities.

Table 2.2 Summaries of different sediment tracing techniques according to 16 their timeframe, scales, advantages and limitations.

Table 3.1 Point for sampling 40

Table 3.2 Experimental design 49

Table 4.1 Spatial isotopic composition of stable isotope 13C in sediment 54

Table 4.2 Spatial isotopic composition of stable isotope 15N in sediments 60

Table 4.3 Proposed factor of sediment yields in Kelantan watershed 64

Table 4.4 Factor loadings of sediment yields over two principal components 64 F1. F1 represent 99% of cumulative loading indicate significant sedimentation in Kelantan watershed for all year round. F2 showed significant role of NEM in intensifying sediment yield of Kelantan watershed.

Table 4.5 Proposed factor of water parameter in Kelantan catchment. Factor 65 loading 1, (F1) represents the anthropogenic factors & Factor loading 2, (F2) represents the key indicator of the river health.

vii

LIST OF FIGURES

Page

Figure 1.1 The cross section of sediment mechanism (in terms of isotope 5 perspective) in a river

Figure 2.1 The erosion process is driven by water (rain) agents. Water 9 droplets will cause detachment, transport and translocation of soil particles thus deposition of sediment (Hairsine & Rose, 1991).

Figure 3.1 map 38

Figure 3.2 Map of the Kelantan River and study sites 39

Figure 3.3 Kelantan rainfall data since 2013 to 2016 40

Figure 3.4 Ekman Grab Sampler 42

Figure 3.5 Tools used for sample preparation into tin capsule 44

Figure 3.6 Isotope-ratio mass spectrometry (IRMS) 44

Figure 3.7 Perkin Elmer 2400 Series II CHN Elemental Analyser 47

Figure 3.8 The process of experimental design for sediment analysis 41

Figure 3.9 Process of crimpling sample in tin capsule 45

Figure 4.1 Bar frequency 13C [‰] sediments from two different seasons; 51 the Southwest Monsoon (July) and Northeast monsoon (January)

Figure 4.2 Spatial variation in 13C in sediments in the Kelantan rivers. 53 Depletion trend towards the ocean characterized by spatial variations of 13C in sediment describe the metabolism of the watershed (Photosynthesis: enrich versus respiration: deplete) – Carbon cycle.

Figure 4.3 Bar frequency 15N [‰] sediments on two different seasons; the 56 Southwest Monsoon (July) and Northeast monsoon (January)

Figure 4.4 Nitrogen conversion and processes affecting 15N values in forest 57 ecosystem which result in enrich and deplete of the product (Source Nadelhoffer & Fry 1994; Kendall, 1998).

viii

Figure 4.5 The average value of 15N in July and January. Organic nitrogen 58 signatures are more pronounced during January.

Figure 4.6 Spatial variation in 15N in sediments in the Kelantan rivers. No 59 trend of 15N is observed across the river networks, suggesting complex nitrogen cycle superimposed by the anthropogenic activities in the watershed.

Figure 4.7 The 13C and C/N ratio of various types of terrestrial and aquatic 62 organic matters overlapping by the sediment range of Kelantan catchments

ix

LIST OF ABBREVIATIONS AND SYMBOLS

% Percentage  Delta  Plus minus  Approximately 13C Delta carbon 13 15N Delta nitrogen 15 < Less than > Greater than ‰ Parts per mill ANOVA Analysis of variance BOD Biochemical oxygen demand C/N ratio Ratio of the mass of carbon to the mass of nitrogen in a substance

C3 The plants exhibiting C3 pathway

C4 The plants exhibiting C4 pathway CAM Crassulacean acid metabolism CHN Used to measure Carbon (C), Hydrogen (H) and Nitrogen (N) COD Chemical oxygen demand DID Department of Irrigation and Drainage DO Dissolved oxygen DOE Department of Environment IRMS Isotopic Ratio Mass Spectrometer MEA Millennium ecosystem assessment mg/l Milligram per liter N Nitrogen NH3-N Ammoniacal nitrogen + Ammonium NH4 - Ammonia NO3 PCA Principal component analysis

x

pH pH meter POM Particulate organic matter SPSS Statistical Package for the Social Sciences SS Suspended solid

xi

ANALISIS ISOTOP STABIL KARBON-13 DAN NITROGEN-15 DALAM

SEDIMEN DI SUNGAI KELANTAN

ABSTRAK

Peningkatan proses pemendapan telah meningkatkan ancaman bencana alam di

Sungai Kelantan (cth: banjir). Memandangkan kesan hakisan tanah kepada pemendapan, pengenalpastian sumber hakisan adalah penting bagi pengurusan tadahan air di Kelantan.

Isotop stabil karbon dan nitrogen, bersama-sama dengan analisis nisbah C/N telah dijalankan untuk mengenal pasti sumber pendapan di sungai Kelantan. Pensampelan telah dilakukan pada bulan Julai 2015 (Monsun Barat Daya, SWM) yang mewakili musim kering dan Januari 2016 untuk musim hujan (Northeast Monsun, NEM). Sampel dianalisis dengan menggunakan Spectrometer Mass Ratio Isotopic Analysis Elementary (EA-IRMS) dan Perkin Elmer 2400 Series II CHN Elemental Analyzer. Isotop stabil 13C menunjukkan bahawa tumbuhan jenis C3 dominan di tadahan air Sungai Kelantan dengan tidak mempunyai perbezaan statistik yang ketara antara bulan Julai dan Januari. Ini menunjukkan sumber hakisan yang sama terutamanya dari pokok yang berkayu seperti pokok hutan, getah dan kelapa sawit. Nilai 15N yang berbeza dapat diperhatikan pada bahan organic tanah pada bulan Januari (NEM) yang menunjukkan pembersihan yang berlebihan (hakisan), natijah dari peranan iklim terhadap peningkatan pemendapan.

Permerhatian terhadap nisbah C/N yang dicirikan oleh sedimen di Sungai Kelantan adalah autochthonous, menunjukkan perolehan dari sumber akuatik. BOD, COD dan SS adalah parameter utama yang menentukan kualiti air Sungai Kelantan. Pemendapan diperhatikan berlaku sepanjang tahun terutamanya semasa NEM. Penemuan ini mengenalpasti bahawa aktiviti penggunaan tanah adalah aktiviti utama dalam tadahan itu, yang memerlukan

xii usaha pengawalan bagi menguruskan magnitud hakisan tanah ke tahap yang lebih kelestarian.

xiii

STABLE ISOTOPES ANALYSES OF CARBON-13 AND NITROGEN-15 IN

KELANTAN RIVER SEDIMENTS

ABSTRACT

Intensification of sedimentation process has increased the vulnerability of

Kelantan River to natural hazards (i.e., climate change and floods). Considering the impact of soil erosion to sedimentation, identification of source of erosion is important to

Kelantan watershed management. Stable isotope of carbon and nitrogen, along with C/N ratio analysis were carried out to identify the potential source of sedimentation in Kelantan watershed. Samples were collected in July 2015 (Southwest Monsoon, SWM) representing dry season and January 2016 for the wet season (Northeast Monsoon, NEM).

The samples were analyzed using Elementary Analysis Isotopic Ratio Mass Spectrometer

(EA-IRMS) and Perkin Elmer 2400 Series II CHN Elemental Analyzer. The stable isotope

13 of  C suggested that C3 type plants are dominant in Kelantan watershed with statistically no significant difference between July and January. This indicates similar source of erosion mainly from woody plant such as forest trees, rubber and oil palm. Distinct 15N signature of soil organic matter is observed during January (NEM) indicates extra washout

(erosion), suggesting the role of climate in intensifying sedimentation. Note the C/N ratio characterized by the sediments in the Kelantan River is autochthonous, exhibits an aquatic derived. BOD, COD and SS are the major parameters that determined the water quality of

Kelantan River. Sedimentation is observed to occur in all year round particularly during the NEM. These findings provide a first-order identification of major land use activities in the catchment thus, assist the mitigation effort in managing the magnitude of soil losses to a level that more sustainably sounds.

xiv

CHAPTER 1

INTRODUCTION

1.1 Background of study

This study focuses on the off-site effect of erosion, the sediment loading in river networks of Kelantan Watershed. Consequent intensifications of the sediment in the river from upstream of the watershed often reduces the capacity of river to deliver high-quality water to downstream users, and eventually increases the risk of flooding in the river basins

(Ibrahim et al., 2012; Qi et al., 2012; Saviour & Stalin 2012; Zhang et al., 2016).

The 2014 Kelantan flood disaster is a classic example where studies agreed that extensive soil erosion at the upstream areas with subsequent sedimentation on riverbed due to rampant land clearing activities is one of the main factors other than extremely heavy rainfall (Nurul Akma et al., 2015). Changing of land use for agriculture in the watershed has been reported to reach for almost 400% in 12 years period from 1988-2000

(Adnan & Atkinson, 2011). Come as no surprise, the flood disaster was called ‘Bah

Kuning’ (yellow-coloured flood) due to its high mud content transported along with the voluminous water (Baharuddin et al., 2015)

In addition, increased soil erosion and sedimentation rates can expose the array of ecosystem services provided by the watersheds to the environmental risk (i.e. ineffective nutrient cycling and degradation of water quality) (MEA 2005). Such impact on ecosystem services may demand more chemical supply to maintain the agriculture industry, thus, more pollution generated from the washout (Mahabalaleshwara & Nagabhushan, 2014;

Kuehn, 2015) (Giliba et al., 2011; Chakravarty et al., 2012).

1

Fundamentally, climate, topography, geology, soils, vegetation and land-use activities are among the main factors that determine the sediment supply in the watershed

(Rosgen 2006, Brooks et al. 2013). Excessive sediment can adversely affect the water quality of Kelantan River. To determine what constitutes excess sediment in a stream, it is necessary to recognize that soil erosion and the sedimentation processes occur naturally and, therefore, that the elemental signatures of sediment loads in the streamflow can be identified by elemental tracing techniques.

Several techniques can be utilized to trace the elemental signatures that exist in the sediments. Heavy metals analysis technique can be employed for the impact assessment of industry in the watershed. Nonetheless, if the rate of soil losses is of the research interest, radionuclide technique may be the best. In the context of this thesis, stable isotope technique is applied to characterize the isotopic variations of 13C and 15N in the sediments. Such approach allow to first-order identification of possible major source of sedimentation in Kelantan watershed. In addition, C/N ratio of the river sediment is used to elucidate the source between terrestrial and aquatic particulates.

As mentioned, carbon and nitrogen isotope has been used to determine the source of organic matter to trace the source of sedimentation in Kelantan River (Zhang et al.,

2007; Mukundan et al., 2010; Liu et al., 2017; Koszelnik et al., 2017; Derrien et al., 2018).

The discrimination of δ13C sources is derived primarily from photosynthetic pathways which results in distinct δ13C values from fractionation processes (Boutton, 1991;

Coleman & Fry, 1991 Fry, 2006; Schimel, 1993; Werth & Kuzyakov, 2010).

Considering the nitrogen cycle the isotopic value of atmospheric nitrogen is about

0‰ (Peterson & Fry, 1987) and fractionates to a range between −10‰ and +10‰

2 depending on the processes within the nitrogen cycle. In general, δ15N fractionation is complex, with a multitude of nitrogen sources and internal changes potentially altering nitrogen isotopic ratios (Shearer and Kohl, 1993; Evans, 2007; Finlay & Kendall, 2007;

Garzon-Garcia et al., 2017).

It is imperative, that, efforts are made by watershed scientist to manage the basin by conducting a reconnaissance study in identifying major land use activities in their respected watershed. The information of isotopic variations in the river sediments will provide a snapshot of major land use activities in the watershed thus, assist the watershed management to control the magnitude of soil losses to a level that more sustainably sounds.

1.2 Problem statement

Considering the impact of erosion and sedimentation in Kelantan river, characterization of 13C and 15N in rivers sediments is critical to Kelantan watershed management. The sediment samples from seven tributaries of Kelantan river were collected for characterization of 13C and 15N. Unique characteristic of stable isotopes variation, provides first order identification of isotopic composition which can be used to describe the source of sedimentation in Kelantan River.

3

1.3 Objectives of the study

The purpose of this study is to utilize the 13C and 15N to identify the source of sedimentation in Kelantan river networks. Stable isotope technique is a cost-effective approach to characterize the isotopic composition in sediments which lead to first-order identification of major sources of sedimentation issues (Smith & Blake, 2014; Collins et al., 2016; Owens et al., 2016; Jalowska et al., 2017). As well, this study is complemented by other supplementary data like water quality and sediment yield for the purpose of discussion. The study was conducted at Kelantan watershed comprises seven main rivers.

This work is a reconnaissance study on the impact of land use to the watershed and further clarifies the relations among anthropogenic activities and its impact to sediments accumulation in the Kelantan watershed.

In summary, the aim of this study is to obtain a “snapshot” of the impact of land use activities on Kelantan Watershed through specific objectives below;

1. To characterise the stable isotopic composition of 13C and 15N in Kelantan river

sediments,

2. To determine the C/N ratio of sediments in the rivers, and

3. To establish a first-order identification of major anthropogenic sources contributed

to sedimentation.

4

1.4 Hypothesis

Hypothetically, the river sediment is transported by erosion process from terrestrial part wash out down to the river during rainfall event. Climate, topography, geology, soil weathering and anthropogenic activities such as land clearing, agriculture, mining and urbanization are the factors that triggers massive erosion process (Figure 1.1).

In order to ensure the source of sediment, stable isotope analysis were conducted to identify the carbon and nitrogen isotopic composition (‰). The anthropogenic and natural signatures can be determined from the unique individual isotopic value that varies within the systematic process of carbon and nitrogen cycle (Deines, 1980; O’Leary, 1988;

Kendall & McDonnell, 1998; Kohn, 2010).

Figure 1.1: The cross section of sediment mechanism (in terms of isotope perspective) in a river

5

1.5 Scope of study

This thesis discuss a reconnaissance study of the land use impact on the Kelantan watershed using the stable isotopic technique. The result will serve as a baseline data of

13C and 15N in tropical watershed. Such information is useful for further understanding of complex and dynamic carbon and nitrogen cycle in a developing watershed.

6

CHAPTER 2

LITERATURE REVIEW

2.1 Challenges faced by Kelantan watersheds

Kelantan is located at the Northeast of Peninsular Malaysia and the state is prone to flooding due northeast monsoon setting started from November to March (MatAmin et al., 2012). Rampant land clearing has led to land degradation and soil erosion (Qi et al.,

2012; Zhang et al., 2016) where the implication is on water quality and sediment accumulation in the river networks (Ibrahim et al, 2012; Saviour & Stalin 2012).

For record, Kelantan receives about 2433 mm of rainfall per year (MNA, 2016).

The climate setting itself has led to progressive sedimentation all year round (Ansah-

Asare, 1995; Ansari et al., 2000). In fact, this has been worsen by illegal logging and agriculture activities at upstream of Kelantan watershed, accelerating the rate of erosion, in turn, results in massive sedimentation, water quality degradation and shallower river

(Ambak & Zakaria, 2010; Ibrahim et al., 2012). In the case of Kelantan catchment, the highest suspended solids were recorded at Galas, followed by Nenggiri, Lebir, Kelantan, and Pergau Rivers (Ambak & Zakaria, 2010). Shallower river due to massive sedimentation was identified as one of the risk factors which contribute to flood disaster in Kelantan watershed (Zhang et al., 2005; Robins et al., 2016; Hadi et al., 2017).

2.2 Soil erosion and sedimentation

Soil erosion can be defined as a process of material detachment from the soil surface by the act of water and/or wind (Sparovek & Jong van Lier, 1997; McConkey et

7 al., 2012) through geological time and crucial for soil formation under natural situation

(Grimm et al., 2003; Thiemann et al., 2005). Sediment refers to the soil or mineral particles transported from land by soil erosion, surface runoff, raindrop impact or stream flow, and deposited in a river channel (Chang, 2003; Peter et al., 2013; Zhang (b) et al., 2013).

Results from progressive erosion process will lead to sediment accumulation in river.

2.2.1 The processes of erosion and sedimentation

Erosion process is influenced by natural and anthropogenic factors. There are several types of erosion agents which are water, wind, ice (glacier), and gravity (Zachar,

1982, Wang et al., 2014). This study focuses on water erosion due to geological & geographical settings of Peninsular Malaysia (Ibrahim et al., 2012; Taha & Kaniraj, 2013;

Labrière et al., 2015; Holz et al., 2015). Nonetheless, human-induced factor such as poor management in development has accelerated the process. Basically, erosion consists of four main steps; rainfall, detachment, transportation, and deposition, (Figure 2.1).

Detachment is the disintegration of loose soil particles when rain drop makes the first touch with the soil. The soil particles were transported by floating, splashing, rolling and dragging and the translocation to another site (Ellison, 1948; Broz et al., 2003; Shi et al.,

2012). The soil particles were then finally deposited at some other lower slopes (Holz et al., 2015) as the soil particles were transported and deposited at the bottom of river, which is known as a sedimentation process. High accumulation of sediments in river water body can result in water deterioration, aquatic habitat damages, shallower river, and consequently an increase in flooding risk caused by the decrease in water storage capacity within the catchment area (Ling et al., 2016; Ahilan et al., 2016).

8

Rainfall Detachment Transportation Deposition

Figure 2.1: The erosion process is driven by water (rain) agents. Water droplets will

cause detachment, transport and translocation of soil particles thus deposition of

sediment (Hairsine & Rose, 1991).

Erosion process requires potential and kinetic energy as a triggering factor. Potential energy (PE) is an energy stored in an object. It results from mass (m), height difference

(h) and acceleration due to gravity (g). The potential energy is defined using the following

Equation (1) (Morgan, 1996),

푃퐸 = 푚ℎ𝑔……………………………… Equation (1)

The potential energy is converted into kinetic energy (KE), which is energy of motion. This energy involved mass (m) and velocity (v) of the agent in soil erosion. The kinetic energy formula is defined using the following Equation (2) (Morgan, 1996),

1 퐾퐸 = 푚푣2……………………………… Equation (2) 2

The degree of erosion also depends on erosivity (the energy of erosion) and friction of soil erosion (Thiemann et al., 2005). Water erosion resulting from rainfall, can be divided into four main erosion stages; splash, rill, sheet, and gully erosions (Gray & Sotir,

1996; Fang et al., 2015). Splash erosion is the earliest to occur when rain falls on the soil and also the least severe stage. Absence of vegetation will increase the rate of splash erosion compared to undisturbed area (Thomaz & Luiz, 2012; Moghadam et al., 2015).

Interestingly, according to Ryżak et al., 2015, the impact of raindrops is significantly

9 different between the first and subsequent drops of rainfall. Moreover, the detachment of soil particles due to splash erosion is strongly influenced by the surface area of the soils.

Removal process of soil surface particles due to rain drop impact and runoff is known as sheet erosion, where rill erosion occurs as the formation of the small channel cuts by the soil as the sheet erosion progresses. At this stage, it has greater impact on upland with the gravitational water flow. Absence in mitigation will result in gully erosion which potentially caused significant soils losses to adjacent water bodies (Ionita et al.,

2015).

Both erosion and sedimentation processes modify the landscape and as the processes move towards equilibrium, there may be a tendency to increase the risk of natural hazards particularly in the catchment where its population is high (Wright &

Schoellhamer, 2004). Besides flood risk, erosion and sedimentation processes may deteriorate water quality, disturb the aquatic habitat and decrease the light penetration for aquatic plant growth (Fred & Judith, 1995).

2.3 The implication of anthropogenic activities on watersheds

Land degradation occurs due to various factors, either natural or man-made factors

(Table 2.1). Rampant land clearing has had an impact on watersheds, especially erosions and deposits.

10

Table 2.1: The consequences within watershed caused by natural processes and

anthropogenic activities.

CAUSE EFFECT Weathering Water Natural process Soil degradation Wind Soil erosion Soil runoff Anthropogenic activities Landslides Land clearing/ deforestation Sedimentation Agriculture activities Deterioration water Land settlement & quality Human-induced development Shallower river Mining activities Increase flood risk Timber production

Deforestation, agriculture, mining, and development within the catchment are the major anthropogenic activities as reported by Wright & Schoellhamer 2004. If this is so, how to trace the sources and understand the priority solutions in addressing the problem?

To date, there is no stable isotope studies of 13C and 15N in Kelantan river sediment.

This study will serve as a baseline data of 13C and 15N variations in tropical river sediments.

2.4 Hydrology and environment impact studies of Kelantan watershed

There are several studies done by researchers in Kelantan watershed. One of the studies done by Anees et al., (2018) to find the soil erosion probability zones & accordingly prioritize watersheds using remote sensing and Geographic Information

System (GIS) techniques. From the study, it point that high rainfall and agricultural activities enhanced soil erosion rate on steep slopes in the catchment. Pixel-based soil

11 erosion analysis method through remote sensing and GIS was a very effective technique in finding accurate causes of soil erosion.

Besides that, in 2017, Jamaludin has develop a functional framework for hydrological applications using stream flow as the functional data. The results indicated that two stations which were Galas River and the Kelantan River (Guillemard Bridge), have a distinct flow pattern from the other stream flow stations. The flow curves of these two rivers are considered as the extreme curves because of their different shape and magnitude.

In the same of 2017, a study done in Kelantan river estuary to understand the source of pollutants. From the study it demonstrated that heavy metals mainly originated from natural weathering, erosion of rocks, soils in the catchment and enriched near the river mouth and total organic carbon can promote the enrichment of heavy metals in sediments

(Wang et al. 2017).

Based on the findings of Aini et al., (2016), the result showed that factors influence the channel morphology alterations in different season was significant due to the discharge, erosion, sedimentation and enlargement in Galas River Kelantan. Almost similar to previous study, Saadatkhah et al., (2016) done a study to assess the impact of land cover changes in the study area focused on the surface water, soil moisture and loss water from different land use classes and the possible impact of land cover alterations on the ecosystem of Kelantan river basin. The results indicated the direct increased in surface water from development area, grassland regions and agriculture areas compared with surface water from other land covered areas in the study area. The urban areas and less

12 vegetation density areas have a possibility to increase for surface water during the monsoon seasons, whereas the inter flow from forested and secondary jungle areas gives to the normal surface water.

In 2014, Basarusin et al., (2014) investigate the influence of rainfall during extreme rainfall events on the hydrological model in the Kelantan River catchment. The study managed to identify that rainfall change has a major impact to determine the runoff depth and peak discharge for the study area.

Along Kelantan watershed also have a lot of mining activities. A study done by

Yen & Rohasliney, (2013) to describe the effects of sand mining on the Kelantan River with respect to physical & chemical parameter analyses. The Kelantan River case study discovered that TSS, turbidity & nitrate contents exceed the Malaysian Interim National

Water Quality Standard (INWQS). High value of TDS, TSS, turbidity & nitrogen nutrients is caused by sand mining & upstream logging activities.

Apart from that, a finding from Dasar et al., (2009) showed heavy metals Pb, Zn,

Cu and Cd was identified at low concentration in sediment samples, except for Fe and Mn.

The presence of Fe and Mn in sediment samples likely from natural origin. Anthropogenic metal concentrations in sediment were low, demonstrating that Sungai Kelantan has not experienced extreme pollution.

13

2.5 Sediment tracing within watersheds

Tracing means finding or discovering something and can get a verdict by an investigation. Tracing sediment technique offers a practical approach to identify sources and sinks of sediments. As well, it tracks sediment movements and estimates spatial distribution of erosion and sediments rates (Kimoto et al., 2008). Sediment tracer has been used effectively on various scales from constant slope in the laboratory to large complex catchments (Kimoto et al., 2008). Sediment tracing techniques allow tracking the pathway of non-point sources pollutants from dry land and in water bodies (Kimoto et al., 2008;

Koiter et al., 2013; Walling, 2013; Mabit et al., 2014). Such techniques provides essential information of the sediments within the watershed (Belmont et al., 2014), hence, leading to better understanding on the dynamic processes occur within the watershed (i.e. alteration of earth landscape) due to anthropogenic factors (Koltun et al., 1997; Owen et al, 2005; Evans et al., 2006; Gellis & Walling, 2011; Mukundan et al., 2012; Gellis &

Mukundan, 2013; Owen et al., 2016).

Anthropogenic activities such as industrialisation, agriculture and deforestation play significant role in accelerating erosion which leads to massive sedimentation in water bodies. Industrialization signatures can be characterised from the elements in sediments which are set as possible proxies to factories, urbanization and mining processes. Such activities release pollutants from manufacturing, processing, effluent, and waste treatment plants that finally deposited in the riverbed (Soliman, 1974; Wolfe et al., 2001; O’Driscoll et al., 2010; Wantzen & Mol, 2013). Changes in land-cover related with urbanization may alter surface flow path which determine the load of runoff to stream channels, thus, in turn modify the geomorphology of channels (Wolman, 1967; O’Driscoll et al., 2010; Wantzen

14

& Mol, 2013). Agriculture activity is one of the main factors contributing to sediment and nutrient pollutions in rivers (Ulen et al., 2007, Wood et al., 2005; Gebreyesus & Kirubel,

2009). Intensive agriculture has led to soil degradation and erosion, hence, deteriorates the water quality of rivers (Ockenden et al., 2014). Most of the signatures in river sediments which potentially can be traced from sediments are pesticides, fertilisers, nutrients, and soils which have been washed out from agriculture land surface through generated runoff

(Wolfe et al., 2001; MEA, 2005; Restrepo et al., 2015). The tracing techniques used together with information of sediment yield data can provide an overview about the geomorphological process, essential for watershed management (Owen et al., 2016).

Current development has seen those techniques evolve to advanced applications in defining historical changes in sediment sources using the floodplain, dam, lake and watersheds (Collins et al., 1997; Owens & Walling, 2002a; Walling et al., 2003; Slimane et al., 2013; Pulley et al., 2015; Chen et al., 2016). The tracing technique comprises several approaches like properties study, statistical properties, analyses and the application of numerical mixing model (Owen et al., 2016). This study focuses on characterization of stable isotopic Carbon-13 and Nitrogen-15 in the river sediments. However, other techniques will be discuss as in Section 2.4.

2.6 The source of tracing techniques in sediments

There are several methods applicable to discriminate the potential sources of erosion from sediments within a catchment. This section provides a brief outline of the current tracing techniques. The main tracing technique for sediment includes; i) stables

15 isotopes, ii) C/N ratio, iii) radionuclides iv) heavy metal and v) magnetic properties

(Othman et al., 2003; Othman & Ismail, 2012; Owens et al., 2016; Guan et al., 2017).

2.6.1 Tracing techniques in sediments

Each approach demonstrates individual uniqueness in tracing the source of pollution in sediments. However it is up to researchers to pick the most appropriate technique that match their research interest (Table 2.2). Given the stable isotope has unique composite signatures due to its stability, low sampling requirement and ability to distinguish source of sediments, therefore, the technique is employed to this study.

Table 2.2: Summaries of different sediment tracing techniques according to their

timeframe, scales, advantages and limitations.

Tracing Applicable Applicable Advantage Limitation References technique timeframe special scale Isotopes Since 1954, Plot to Able to The (Wallbrink Runoff catchment distinguish chronology & Murray event; different type of 1993; centuries of land uses; sedimentatio Wallbrink estimate runoff n is crude, 1998; event based and which is Zhang et seasonal separated by al., 2007; erosion a turning Fox & year of 1963 Papanicola (main peak); ou 2007; not for Walling, serious 2013). erosion; able to distinguish cultivated and uncultivated soils, Not standalone

16

C/N ratio Man-made, Plot to Able to identify Not (Jennerjahn natural catchment source found in applicable et al., 2004; sediment Waterson, originate from 2005; allochthonous Spano et or al., 2014). autochthonous Radionuclide Man-made, Plot to Able to Need long (Wallbrink natural catchment distinguish term study, & Murray cosmogenic, cultivated, required skill 1993; natural uncultivated and staff Zhang et geogenic lands, estimate al., 2007; runoff events Walling, 2013). Heavy metals Rain event Catchment Able to Limits by (Chillrud et based; reconstruct mixed or al., 2003; seasonal; sedimentation unknown Franz et al., decades rates in sources of 2013). floodplains and each metal catchments having historic river pollution Mineral Runoff Plot to Able to Possibilities (Yu & magnetic event; catchment reconstruct of changes in Oldfield decades history of oxidation or 1989; sediment reduction Walden et sources and conditions al., 1997; discriminate Ven Der soil burned at Waal et al., different 2015). severities

Essentially, stable isotopes carbon and nitrogen as well as C/N ratio provide the information about the source of organic matter in the river sediment. For the effective management practices, we require the identification of actual sediment source to understand the possible erosion process, thus, plan for mitigation strategies in watershed management.

The combination of both methods (stable isotope carbon and nitrogen and C/N ratio) give a good compliment to each other. Through this study, stable isotope reveals the

17 type of plant (carbon isotope) and possible land use (nitrogen isotope) sources. While,

C/N ratio helps in ensuring the sources of the sediments i.e; allochthonous or autochthonous.

Another reason for stable isotope techniques and C/N ratio analysis is resource availability. Stable isotope of carbon and nitrogen analysis can be performed in Analytical

Biochemistry Research Centre (ABrC), Universiti Sains Malaysia using isotope ratio mass spectrometer (IRMS). While, C/N ratio analysis CHN Elemental Analyzer is available in

School Biology.

In brief, stable isotope carbon and nitrogen have shown a great potential sensitivity in tracing sediment sources, hence serve as the most appropriate method for identifying sediment origin in context of this study (Fox & Papanicolaou et al. 2008; Haddachi et al.,

2013).

2.6.2 Stable isotopes

Environmental isotope is a useful tool to help infer in geochemical processes

(Kendall & McDonnell, 1998). Application of tracer is very helpful in providing new insight of hydrological processes in a catchment as it gives variant of small-scale indication of catchment-scale processes (Kendall & McDonnell, 1998). Unique isotopic characteristic of individual element allow us to study their isotopically distinct ratios depending on their sources such as atmospheric, geogenic and biology. Biogeochemical cycle in particular system may determine the isotopic ratios of the sediments thus, such predictable pattern can be reconstructed (Kendall & McDonnell, 1998).

18

Stable isotopes provides composite signature due to its stability, low sampling requirements, and unique ability to distinguish soils produced from different land-uses

(Vaalgamaa et al., 2013). The advantage can be effectively used in large-scale watersheds to characterize the source of sediment movement in short time scale (Papanicolaou & Fox,

2004; Laceby et al., 2015). In most hydrological studies, common stable isotope elements are hydrogen, oxygen, nitrogen and carbon.

Stable isotope carbon (13C) and nitrogen (15N) are useful to determine source of sediments (Fox & Papanicolaou 2007; Tumbull et al., 2008; Alewell et al, 2009;

Papanicolaou et al, 2013). Stable isotope of 13C can be used for first-order identification of sediment source whether from forest cropland or grassland (C3, C4 or CAM type plants)

(Balesdent et al, 1998).

In tracing source of agriculture sediment, stable isotope of carbon (C) and nitrogen

(N) are used to infer sources of sediment (McConnachie and Petticrew, 2006; Fox and

Papanicolaou, 2007; Schindler Wildhaber et al., 2012; Laceby et al., 2015a). Stable isotopes of carbon and nitrogen fractionation within soil, are dependent upon a number of processes, such as, vegetation decomposition, fertilizer sorption, and denitrification.

These processes are altered due to soil-environmental factors, such as, vegetation type, soil moisture and temperature, concentration of soil gases, and land/crop management.

Assimilation, mineralization, volatilization, denitrification, and decomposition processes may determine the isotopic pattern of 13C and 15N whether enrich or deplete.

These processes are accompanied by fractionations, whereby plants or soil discriminate between nitrogen isotopes, tending to favour the incorporation of 14N over 15N or vice

19 versa. 15N values are typically enrich for agriculture soils as compared to forest soils under similar environments (Papanicolaou, & Fox, 2004).

The 13C value of soil reflects types of vegetation with only involve small

13 enrichment during decomposition. The difference in  C values for C3 and C4 plants induced by the unique photosynthetic pathway of each plant type results in the average

13 plant tissue of  C for C4 plant, –12‰ and C3 plants, –26‰ (Papanicolaou, & Fox, 2004).

2.6.2(a) Case studies

A previous study was conducted by Xiao & Liu, (2010) using stable isotope to identify the origin of sediment in an urban river. From the study, it demonstrated that stable isotope nitrogen value which is +8.5‰ comes from the industrial effluent. While, stable isotope carbon showed value with -27.7‰ indicating the source of C3 type plants, contributed by the growing vegetation along the river bank (Xiao & Liu, 2010).

Besides the river sediment, the 13C and 15N too, can be traced from suspended matter in water bodies in the Godavari studies, which reported transformation mechanism of organic matter in the system (Sarma et al., 2012). Significant variability of isotopic distribution was observed over the entire length of the Godavari estuary representing multiple sources of organic matter. The mean isotopic ratios for stable carbon and nitrogen are ‐25.1‰ and 8.0‰ respectively. Significant enrichment in isotopic ratios of stable isotope carbon in sediment profile (upper, ‐26.2 and lower, ‐24.9 ‰) indicates less influence of terrigeneous material towards mouth of the estuary (Sarma et al., 2012).

20

In Northeast China, carbon and nitrogen isotope were used to identify the source of organic matter sources in the watershed due to intensive agricultural activities. Based on the results, it demonstrated that isotopic of 13C ranged from −28.22‰ to −23.98‰ and 15N slightly lower +3.7 ± 2.42% in sediment, reflecting the dominance of anthropogenic C and N input within the area (Lu et al., 2010). Overall, the source of sediment can be identified based on the isotopic signatures measured in the sediment samples.

2.6.2(b) Limitation

Stable carbon and nitrogen isotope techniques involve with continuous biochemical processes such as carbon and nutrient cycling through the processes of immobilization and mineralization. Organic matter is usually categorized into three classes; active, slow and passive which are related to their stability over time. The active class signifies the pool of organic matter that is the most susceptible to microbial decomposition (<2 yr), the slow class is moderately susceptible, and the passive class is the most resistant to microbial decomposition (500 – 5000 yr) (Brady & Weil, 2001). This becomes important as the conveyance time of sediment through a river basin can vary widely from days to decades and up to centuries. Note, some of the organic matter can be lost through decomposition. As well, organic matter is composed of many different organic compounds including carbohydrates, amino acids, lignin and polyphenols, which decompose at different rates (Brady and Weil, 2001). Decompositional processes can result not only the changes in the quantity of organic matter but also in the composition which can be difficult to characterize. However, stable isotopes techniques, can be improved as researchers are looking for compound-specific stable isotope signatures that

21 target compounds which are more resistant to decay and that bind strongly to soil and sediment particles, thereby providing a more robust fingerprint analysis (Gibbs, 2008;

Blake et al., 2012; Hancock and Revill, 2013).

2.6.3 C/N ratio

The C/N ratio is defined as the ratio of total atomic carbon to total atomic nitrogen

(Papanicolaou et al., 2003) and represented by the following equation (Rogers, 2013):

C/N = (%C/%N)/ (14/12)

C/N can be described as a tool to test the ecosystem health and soil fertility. The soil in C/N ratio reflects the plant and microorganism composition, present in the soil.

Different sources of sample give different values of C/N ratio. It has been largely used as a proxy to explain the source and fate of organic matter in the environment of waters (e.g.,

Gordon and Goni, 2003; Wu et al., 2007; Zhang et al., 2007; Ramaswamy et al., 2008), and it enables to discriminate pollutant origins related with sediment organic matter (Nasir et al., 2015). In aquatic ecosystem, there exist two main sources, which are autochthonous and allochthonous. Autochthonous is an organic matter derived from aquatic parts such as phytoplankton and algae. While allochthonous is an organic matter derived from terrestrial washed out. By using C/N ratio, the source of aquatic parts can be identified between anthropogenic or natural sources (Rostad et al., 1997; Rogers, 2013).

Terrestrial plant has a wide range of C/N ratio ranging between 10 and 40 such as gymnosperms 16.4; pteridophytes-ferns and spore plants 25.6 (Papanicolaou et al., 2003),

22 whereas, the lower C/N ratio for most microorganisms ranging between 4 and 9

(Papanicolaou et al., 2003). As the decomposition process occurs, carbon will be released due to microbial oxidation and respiration of carbon dioxide as well sequestering of nitrogen. As a result, a decrease in C/N ratio is relative to plant (Papanicolaou et al., 2003).

Terrestrial plants have higher C/N ratio compared to aquatic plants as they have an abundant carbon ring structure such as cellulose and lignin and resin give strength to the plant, while aquatic plants have lower C/N as they have less carbon ring structure thus making them more fragile (Rogers, 2013).

Potentially, C/N is a powerful tool for identifying the source of soil in a catchment

(Papanicolaou et al., 2003). It gives a new understanding about the source of organic carbon and nitrogen in the catchment. In the case of Godavari catchment, the study discovered that the major source of organic matter in the high (August) season is from the soil, whereas the other season is the autochthonous, river derived where phytoplankton is the dominant source (Balakrishna & Probst, 2005). Besides, this study revealed that the amount of organic material transported from downstream to the oceans during the high

(August) season are 3 to 91 times higher than the low (March) and moderate (November) seasons (Balakrishna & Probst, 2005).

2.6.3(a) Case studies

A study was conducted at Kuala Sungai Baru in order to identify the organic matter in the sediment by using C/N ratios. According to the result, higher C/N ratio is contributed by industrial activities where climate plays significant role in intensifying the allocthonous source i.e. agriculture wastes especially palm oil, rubber and paddy field as

23 well pig farm effluent. Such intensification has led to increase in C/N ratio to 68.04

(Hamad & Omran, 2016).

In other cases, the application of C/N ratios in this study serves as indicators to know the source of organic carbon of the mangrove ecosystem in Ba Lat Estuary. Based on the results, C/N ratios from the bottom to the surface of sediments marked the changes of the organic matter with the C/N ratios values >12 indicated terrestrial source (e.g; mangrove litter) and <12 derived from marine phytoplankton source (Tue at el., 2011).

C/N ratios is therefore an effective indicator that can be used to identify the source of organic matter in catchment sediments (Yu et al., 2010).

2.6.3(b) Limitation

The identification of organic matter originally using the composition of the C/N element is constrained by the measured ratio capability to accurately represent the source characteristics. Although the relative C/N ratio varies, the material from all sources is subject to the decomposition process which results in the absolute reduction of mass and the selective destruction of the biochemical fraction of the constituent. This effect on the

C/N ratio associated with degradation of detritus and susceptibility to bacterial decomposition. Organic matter degradation causes the alteration of C/N ratios value; the

C/N ratio value increases when sinking the algae particulate organic matter into the water body (Twichell et al., 2002), on the contrary, humification and mineralization process in terrestrial will significantly lower the C/N ratio (Sorensen, 1981; Schmidt et al., 2000;

Nasir et al., 2016).

24

2.6.4 Radioisotopes

Radioisotopes can be divided into two categories which are cosmogenic and fallout radionuclides. The cosmogenic radionuclides have been mostly used to study the origin

(Blake et al., 2002; Perg et al., 2003; Chappell et al., 2006; Povinec et al., 2015). As cosmic-ray particles interact with cosmic objects, result tracks in the minerals and produce cascades of particles, they lead to the production of radioactive and stable nuclides in the target material. Meteorites are highly natural archives of radionuclides produced by these processes and their cosmogenic components can be measured either by decay counting techniques (gamma-ray spectrometry) or, for longer lived radionuclides, with accelerator mass spectrometry (AMS) (Povinec et al., 2015). The examples of cosmogenic radionuclide are 32Si, 26Al, 10Be, 58Co and etc. (Owens et al., 2016).

The potential for using fallout radionuclides to provide information on rates and patterns of soil loss and soil redistribution has now been clearly demonstrated by a wide range of investigations undertaken in many different areas of the world (Zapata & Nguyen,

2010; Matisoff & Whiting, 2012; Walling, 2012). They were shown to be particularly valuable for distinguishing between surface and subsurface materials, since commonly concentrations are relatively higher for the surface and lower or non-existent in the subsurface (Walling, 2005). The key principle involved is that the fallout reaching the soil surface is rapidly and strongly absorbed by the surface soil and its subsequent redistribution by erosion processes directly reflects the intensity and spatial distribution of the sediment throughout those processes. The most widely used of fallout radionuclides in tracing approaches are 137Cs, 210Pb and 7Be in past studies based on scientific literature

(Walling 2003; Mabit et al. 2008a; Guzmán et al., 2013; Owens et al., 2016).

25

Most of work has focused on the use of 137Cs, anthropogenically derived, a man- made fallout radionuclide associated with the testing of atomic weapons in the 1950s and early 1960s produced in great quantities and released into the stratosphere and globally distributed (Walling, 1998, Zapata et al., 2002; Guzmán et al., 2013).

Since most of the 137Cs fallout occurred during the period extending from the late

1950s to the early 1970s, this radionuclide now affords a valuable means of documenting soil redistribution over the past 50 years. Particular advantages of the approach include, i) the ability to obtain reflective data on the basis of a single site visit and without the need to install permanent monitoring equipment and structures; ii) the ability to integrate the impact of all processes resulting in soil redistribution; iii) the spatially distributed nature of the data; and iv) provision of time-integrated average rates of soil redistribution

(Walling & Quine, 1995; Mabit et al., 2008). The ability to generate spatially distributed data has agreed with the need for such data for validating physically-based distributed soil erosion models (De Roo & Walling, 1994; He & Walling, 2003; Norouzi Banis et al.,

2004).

The 137Cs radioisotope has been used in a wide variety of depositional environments to determine erosion and sedimentation rates for medium time scales (10 of years) across a broad range of spatial scales: from hillslope (Wallbrink & Murray, 1993) and small catchment (Higgitt et al., 2000) to large basins (De Roo, 1991). By combining field measurements with model analysis, 137Cs has also been used to determine rates of water and tillage erosion (Quine et al. 1999) or to differentiate between surface, subsurface and stream bank sources (Li et al., 2003; Zhang & Walling, 2005). Other than 137Cs, 210Pb also may provide longer-term estimate (approximately 100 years) of soil redistribution

26 magnitudes (Walling & He, 1999b), while, 7Be can be applied for short-term estimation of erosion and sedimentation rates (Walling et al. 1999).

2.6.4(a) Case studies

One of the potential techniques in tracing sediment sources in agriculture site is by using fallout radionuclides. In addition, it also provides the information of sediment transport rates, storage and losses from the system (Wallbrink et al., 2002). The shorter- lived fallout radionuclide 7Be has been used effectively by Schuller et al., (2006) to quantify net soil losses and retention by buffer features following forest harvest operations. The key challenges noted by the study is to ensuring that the distribution of

7Be prior to the event was spatially uniformed, especially considering the legacy of prior erosion events, which led to the development of a methodological refinement to apply 7Be over extended time periods (Walling et al., 2009).

The 137Cs and 210Pb techniques are, however, not suitable for documenting short- term erosion rates associated with forest harvesting, because of the relatively long half- lives of these two radionuclides. Furthermore, their use for estimating medium-term erosion rates in forest areas is also likely to be compromised by the spatial variability of fallout inputs under a forest canopy and the extensive soil disturbance frequently caused by harvesting machinery and the construction of roads, skid trails, and landings. The potential for using the natural occurring fallout radionuclide 7Be to document short term soil redistribution on agricultural land has been reported by Blake et al. (1999), Walling et al. (1999), Matisoff et al. (2002), and Wilson et al. (2003).

27

Radionuclides 7Be and 210Pb were used as tracers to identify suspended solid sources and transport pathways in the storm runoff events from urban catchments. The results show that the 7Be/210Pb ratio decreased through the system suggests suspended solids at sewer outlet originated from the drainage system sediments, the rest was from the wash-off of urban ground dust during the rainfall events. The 7Be and 210Pb trace approach can give insight into the short-term source and transport of pollutant during storm runoff in urban drainage systems and it can help to develop management strategies

(Yin & Li, 2008).

2.6.4(b) Limitation

Radionuclide 7Be is limited in tracing where it is not suitable to be used for serious erosion such as gully erosion, long term erosion estimation on to distinguish between cultivated and uncultivated surface soils (Walling, 2013a). Whereas, 210Pb requires skilled and experienced staff to handle as measurement with low energy gamma spectrometry is not easy (Wallbrink & Murray, 1993; Wallbrink et al., 1998; Mabit et al., 2008; Guan et al., 2017). As well, radioisotopes are not stable and will decay over time, transforming from one element into another during radioactive decay (Meier-Augenstein, 2009).

2.6.5 Heavy metal

Heavy metal study in sediments is one of the most well-known approach particularly for environment risk assessment, i.e; toxicity, originated from multiple sources and accumulative characteristic (Zhao et al., 2017). As a matter of interest, sediment is recognized as high potential sediment sink of heavy metal & other

28 contaminants (Ip et al., 2004; Chen et al., 2012). Heavy metal contaminants caused severe stress of aquatic environment (Li & Hung 2008). Thus, tracing surface sediment is critical to access heavy metal pollution in rivers (Xu et al., 2015). Heavy metal such as Pb, Hg,

Zn and Cu are the best recorded anthropogenic contaminants because of high affinity to fine sediment (Chillrud et al., 2003; Franz et al., 2013), useful to trace the source of erosion

(Zhao et al., 2017 Singh et al., 2005).

In order to investigate the influence in the study area, the assessment of sediments contamination with heavy metal was made using the index of geoaccumulation, Igeo. This method introduced by Muller (1979), a sediment contamination index relative to global standards. The Igeo can be classified into seven grades (0–6). The highest grade, 6 reflects a 100-fold enrichment and 0 reflects the background concentration. The enrichment of heavy metal (i.e. Cd, Pb, Cu, Zn and Ni) metals may be possibly caused from natural and anthropogenic factors (Singh et al., 2005).

Sediments were analysed by using inductively coupled plasma mass spectrometer

(ICPMS) (Quinton & Catt, 2007). The results were then compared to geo-accumulation index to measure the existence and concentration of anthropogenic contaminant in sediments (Nowrouzi & Pourkhabbaz, 2014). These indexes of potential contamination are measured by the normalization of one metal concentration in the sediments with respect to the concentration of the reference element (Barbieri, 2016).

This technique is suitable for tracing industrial and agricultural signature (Quinton

& Catt, 2007; Yan et al., 2018). In fact, heavy metal can be utilized for reconstructing

29 historic river pollution by observing the rate of sedimentation in floodplains and catchment (Middelkoop, 2002; Guan et al., 2017).

2.6.5(a) Case studies

A case study in Yunnan-Guizhou, Southwest China, where the potential pollution were identified by spatial and statistical analysis, found heavy metal type; mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu) and arsenic (As) in the surface sediment. It seems that Cd most probably came from industrial activities and As was from lithogenic (natural) source. While the rest Cr, Hg and Cu originated from industrial activities (e.g., mining, smelting, mechanical manufacture and chemical industry) and the

Pb originated from traffic pollution along the roadside due to road runoff (Wu et al., 2014).

Ghaghara River, a major tributary of the River Ganga in Northern India conducted a study to know about heavy metal contamination in sediment. This study referred to the geo-accumulation index to measure the stage of sediment contamination that have adverse effects on freshwater ecology of the river. Significant high correlation shown between Co,

Cu, and Zn, suggests source of contamination input is mainly due to human settlement and agriculture activity. Hence, positive correlation between Zn, Co, Cu, Cr, and Ni indicates a natural origin of these elements in the river sediment. The strong similarity between Co, Zn, Pb, Ni, Cu, and Cd showed that these metals come from the same origin, which is likely from natural and anthropogenic input (Singh et al., 2017).

A study in Tigris River, Turkey was perfomed to evaluate the level of heavy metal contamination in the sediment. The highest concentrations of metals were found at the

30 first site due to metallic wastewater discharges from copper mine plant. The contamination factor values for Co, Cu and Zn were >6 in sediments, which denotes a very high contamination by these metals. The enrichment factor values for all metals studied except

Cr and Mn were >1.5 in the sediments of the Tigris River, suggesting the contribution of anthropogenic factor. Principal component analysis (PCA) and cluster analysis suggest that As, Cd, Co, Cr, Cu, Mn, Ni and Zn are derived from the anthropogenic sources, particularly metallic discharges of the copper mine plant (Varol, 2011).

2.6.5(b) Limitation

Based on the case studies, most sources of heavy metals were classified based on the types of elements (Varol, 2011; Wu et al., 2014; Singh et al., 2017). The elements were then compared to the possible sources that presence within or around the study location. Unfortunately, it may be limited by mixed or unknown sources of each metal

(Chillrud et al., 2003; Guan et al., 2017). This is because some of the elements might not be presence or unidentified, causing the tracing detection to be limited.

2.6.6 Magnetic properties

Magnetic properties of sediment can be trace back based on their magnetic properties which varies according to sediment type, depositional setting and provenance area. Any magnetic properties material commonly is related to electronic structure, notably the presence or absence of uncompensated electron spins, and the presence or absence of collective spin behavior (Dekkers, 1978). Besides, magnetic properties of soils are dominantly controlled by the presence, volumetric abundance, and oxidation state of iron in soils (Alekseeva et al., 2011).

31

Magnetic tracing techniques refer to approaches using magnetic properties in two different methods; 1) discriminating sediment sources through natural soil magnetic properties (Dearing et al., 2001), and 2) approach using magnetic tracing materials, incorporating them into the soil and measuring the concentration and distribution of elements in soil and sediment before and after analysis (Hatfield & Maher, 2008).

The discrimination for sediment sources based on natural soil magnetic properties is mostly referring to iron oxide such as magnetite, maghemit, hematite, goethite and pyrrohite which able to discriminate different type of soil. Major concern is about bias introduce by selective transport, however it has been addressed by identify the most likely materials which potential to be transported (Hatfield & Maher, 2008; Guzmán Díaz,

2012). For example, analyzed material screened to <63 µm, because in the radius of study catchment there showed there was no evidence of suspended sediment of a larger size

(Slattery et al., 2000). A studied done by (Maher et al., 2009), only analyzed the sample material between 250 to 355 µm, because this was the best suited for the transport process within the area. On other study, the sample has been divided into several classes; sand, clay and silt fraction sediment source study for a reservoir in Spain (Yu & Oldfield, 1994).

This method is performed to reduce the rate of error due to selective transport of the finer soil fraction that tends to be enriched in tracer concentrations.

Second approach is by incorporating magnetic tracer to the soil and the concentration can be measured based on its magnetic properties. To study detachment and deposition process, a study done by Ventura et al., (2002) applied magnetic beads covered in resin over the soil surface, and magnetic tracer allowed the identification of net detachment and deposition areas. However, the quantification rates of erosion required a

32 bigger size and densities of the tracer which strengthen the detector concentration in the sediment.

The uses of magnetic properties techniques in sediment source tracing, palaeoclimatic studies and the reconstruction of particulate pollution history are illustrated by many case studies from Britain and America (Oldfield et al., 1983). Magnetic properties are widely used to discriminate the source of sediment that entering rivers, lakes and estuaries (Walden et al., 1997; Walling 2013a, b; van der Waal et al., 2015). In the late 1980’s, mineral magnetic mineralogy is used to trace allochthonous input from basic igneous rocks, for example basalts, where the presence are likely to give rise to high magnetic concentrations in the sediment record (Oldfield et al., 1983). The mineral magnetic in the sediment appears to be strongly influenced by dissolution of magnetic minerals. This may have significant implications for interpreting the geochemical records retained within the sediments (Foster et al., 1998).

Currently, this technique has been successfully used in tracing source of burned sites or wildfire (Blake et al., 2006; Hatfield & Maher, 2008). In this sites, fine-grained ferrimagnetic minerals were found accumulated in the soil surface (Longworth et al.,

1979; Smith et al. 2013). During soil burning, oxidation or reduction process can convert less magnetic ion oxyhydroxides into more magnetic minerals (Clement et al., 2011). The mineral magnetic characteristic has shown a good potential in discriminating soil burned at different stages with respect to unburned soils. A study done in South African Karoo shown a good discrimination between the sedimentary sources (soils and subsurface material) and dolerite soils due to the much higher magnetism of dolerite soils (Pulley &

Rowntree 2016).

33

2.6.6(a) Case studies

A case study in the agriculture site of the Isle of Man (British Isles) shows that, the soil surface contains a large range of magnetic concentrations, magnetic mineralogy, and magnetic domain size characteristics, enabling significant differences to be identified between soil categories. It is inferred that the mineral magnetic measurements are a viable approach to distinguish Manxsoil categories and indicate the potential of mineral magnetic methodologies as a means of establishing soil categories (Booth et al., 2005).

A study done by Charlesworth et al., (2000) show mineral magnetic measurements allow the quick and non-destructive characterisation of environmental materials in solid deposits to trace the sediments. They have been very successful in a wide variety of environments and climatic conditions. Their success has mainly been in terms of discriminating between sediments with very different magnetic characteristics such as topsoil and subsoil in relatively undisturbed catchments.

A case study in Shanghai demonstrated the enrichment of magnetic particles of the urban topsoil in Baoshan District is considerably highest in industrial and roadside areas, while the correlation between magnetic properties in the agricultural soil is the lowest hence, it indicated that the magnetic techniques can be used for monitoring soil contamination in urban area (Jiang et al., 2010).

2.6.6(b) Limitation

The applicability of sediment source tracing using environmental magnetism has been shown in a number of studies (Thompson & Morton, 1979; Walling et al., 1979;

34

Bradshaw & Thompson, 1985; Oldfield et al., 1985; Stott, 1986; Yu & Oldfield, 1989).

These studies mainly relied on matching the mineral magnetic characteristics of sediments in a sink in river with those from the most likely source materials in terrestrial and soil surface. A limitation of this approach is that the sediment is not compatible with possible source that was compared. In a large catchment, the potential number of sources to be characterized may not be considerable, making it difficult to use this method for routine catchment investigations (Caitcheon, 1993).

In addition, mineral magnetic properties have been shown to discriminate soil burned at different severities as well as unburned areas, however, recent research by Blake et al. (2006) demonstrated that there was a lack of dimensionality in the data that limited their use in sediment fingerprinting (also see Smith et al., 2013). Particle-size also exhibits a strong influence on the magnetic properties of sediment and needs to be taken into consideration in the characterization and interpretation of these properties (Oldfield and

Yu, 1994; Hatfield and Maher, 2009). In many cases, the relationship between particle size and measures of mineral magnetic properties are complex (Foster et al., 1998; Blake et al., 2006; Oldfield et al., 2009) and this complexity can make it difficult to discriminate between sources and make comparisons between sources and sediments as a result of differences in particle size distributions (Koiter et al., 2013).

35

CHAPTER 3

METHODOLOGY

3.1 Study area

3.1.1 Kelantan Basin

The study area covers the catchment around Kelantan state which is located in the northeast of Peninsular Malaysia that lies between 4° 40’ and 6° 12’ North and 101° 20’ and 102° 20’ East (Figure 3.1). It is the second largest river in Peninsular Malaysia

(Ahmad et al., 2009). The Kelantan water catchment is about 248 km long and the zone comprises an area about 11,900 km² (Ibbitt et al., 2002; Yen & Rohasline, 2013). The length of the catchment is approximately 150 km long and 140 km breadth (Ibbitt et al.,

2002). The river drains from north-east of Peninsular Malaysia and tributaries forms at forested mountains which consists of caves and limestone outcrops (Ahmad et al., 2009).

The depth of the river is up to 18 meters in localised area and Mount Korbu is the highest point of Kelantan river, about 183 meters above the sea level (Mohtar et al., 2017).

The Kelantan river flow through several districts includes Gua Musang, Kuala

Krai, Tanah Merah, and end at the river mouth, (Ahmad et al., 2009;

Mohtar et al., 2017). Besides, Kelantan receives water from two tributaries which are

Pergau and Galas river at the confluence located approximately 10 km away from Kuala

Krai town (Mohtar et al., 2017). Kelantan catchment serves many purpose to the local people especially to those who stay along the river such as drinking water, agriculture irrigation and fishing (Ahmad et al., 2009). Further, Kelantan river actives in sand mining activities. As recorded, there are about 128 on going sand mining along Kelantan river

(Ambak et al., 2010). These mining activities cause the degradation of water quality especially on its turbidity as increase in suspended solids and siltation (Ambak & Zakaria,

36

2010; Mohtar et al., 2017).

The main economy of Kelantan is mainly from agricultural industries dominated by oil palm plantation, rubber, paddy, and other cash crops (Samad et al., 2017). Oil palm shows dominant plantation from to Tanah Merah followed by rubber and coconut tree (Mohtar et al., 2017). However, rubber is recorded as the largest plantation in Kelantan with an area 131,475 Ha (Samad et al., 2017). As the river passes, large scale of paddy field is found in Pasir Mas and finishing with developed, densely populated at the downstream of Kota Bharu (Mohtar et al., 2017).

Kelantan catchment which expose with local monsoon climate receive precipitation pattern varied which ranging from 0 to 1750 mm during dry and wet month respectively (Ahmad et al., 2009). During northeast monsoon season (November to Mac),

Kelantan received extra rainfall and cause the river overflow thus create recurrent flood event which occur almost every year (Ahmad et al., 2009).

Sample collection was conducted in July 2015 (dry season) and January 2016 (wet season). Sampling was done at seven rivers compromising Berok, Betis, Nenggiri, Pergau,

Galas, Lebir and Kelantan river which represent Kelantan catchment (Figure 3.2, Table

3.1). Three sampling point for each river were identified for sediment sampling for stable isotope and C/N ratio analysis.

Three main rivers are located at the which are the Nenggiri,

Betis, and Brok rivers. The dominant land use of this area is deforestation for vegetation, native forest, and countryside residential. The next river is the Lebir river located at the

Kuala Krai district. The length of Lebir river is about 91 km and encompass 30 tributary

(Ibbitt et al., 2002; Mohtar et al., 2017). Pergau river, which is located in district, has one of the highest waterfalls in the South East Asia known as Jelawang waterfall flows

37 from Stong Mount (Mariana et al., 2005). The river merges with the Galas River. Galas river runs about 179.5 km starting from the Kelantan – borderline (Mohtar et al.,

2017). The land use of this area has cropping area and a new settlement in some parts. The

Kelantan river have two tributaries which are the Galas and Lebir rivers, which converge at Kuala Krai, approximately100 km upstream of the estuary. It drains from south to north with the total river length of 248 km (Wang et al., 2017)

Figure 3.1: Peninsular Malaysia map.

38

Figure 3.2: Map of the Kelantan River and study sites.

39

Table 3.1: Point for sampling

Location Longitude Latitude Kelantan River 102.165388 5.829161 Lebir River 102.210634 5.470653 Pergau River 101.975709 5.405519 Galas River 102.006298 5.377369 Betis River 101.789096 4.899461 Nenggiri River 101.788189 4.908424 Berok River 101.793591 4.891464

3.1.2 Climate and Hydrology of Kelantan Basin

The regional climate of the Kelantan state has temperatures ranging between 21 and 32 °C and recurrent rain throughout the year but is exposed to extra rainfall in the

Northeast Monsoon from November to March every year. The average rainfall is about

2488 mm (2013-2016) (Figure 3.3) per year and humidity is constantly high on the lowlands ranging between 82% and 86% annually (Irwan et al., 2013).

2013 2014 2015 2016 1000.0 900.0 800.0 700.0 600.0 500.0 400.0 300.0

Amount of Rainfall (mm) Rainfall of Amount 200.0 100.0 0.0 Jan Feb Mar Apr May Jun July Aug Sept Oct Nov Dec Month

Figure 3.3: Kelantan rainfall data since 2013 to 2016

40

3.2 Methodology

3.2.1 Experimental design

Selection of the sampling areas

Selection of sampling points

Collection of sediment samples at different seasons (a) Dry (b) Wet

Collection of sediment samples at different rives 1. Kelantan 2. Lebir 3. Pergau 4. Galas 5. Betis 6. Nenggiri 7. Berok

Carrying the samples to the laboratory for sample preparation (i) Isotope analysis (ii) C/N ratio

Sample analysis

Analysis of data

Figure 3.8: The process of experimental design for sediment analysis

41

3.2.2 Sample Collection of river sediments

Sample collection was carried out in July 2015 (dry season) and January 2016 (wet season). Seasonal sampling is important because extreme drought can altered stable carbon isotope up to 2‰ (Papanicolaou & Fox, 2004). This study was designed to trace the source of Kelantan river sediments obtained from the river bed. The collection of samples included seven stations in Kelantan catchments which are the Broke, Betis,

Nenggiri, Lebir, Galas, Pergau, and Kelantan Rivers. Triplicate sediments were collected from each river every seasons.

The sediment was collected at about top 10-20cm (Hancock & Revill, 2011) of river sediment approximately 100g per sediment sample by using stainless steel Ekman grab sampler (6x6x6”) stainless steel (Figure 3.4). For the shallow river the sediments were collected by using plastic shovel. The sediments were put into a zipper bag (size 16.8 cm x 14.9 cm) and sealed it. In the meanwhile the sample collection, the sediments were placed in a cold storage box containing ice cube to preserve the samples (Shanbehzadeh et al., 2014). The samples were then stored in freezer until it is ready to analyse.

Figure 3.4: Ekman Grab Sampler

42

3.2.3 Sample preparation

The samples were defrost about one to two hours prior for samples preparation. In the laboratory, 50 g of sediment samples were being washed by using 10% of hydrochloric acid to remove the carbonates (inorganic carbon) hence to identify the organic carbon sources (Kennedy et al., 2005). This step is done in fume chamber as the reaction will release carbon dioxide gas. The samples were then rinsed three times with distilled water.

The samples were then dried overnight at 80 to 90 °C to remove moisture. The subsamples were then grounded into powder form. Grinding was performed using a mortar and pestle. The samples were finally sieved through a 700µm sieve to ensure the sediment is in powder form. The grinded sediments were then put in plastic container before stored in desiccator (Hancock & Revill, 2011) to keep it dry and avoid from any humidity while waiting for next isotopes and C/N ratio analysis.

3.2.4 Stable Isotope analysis

Each sediment sample was weighed using microbalance into a small tin capsule (8 x 5 mm) (Figure 3.5) for 12mg in triplicates for each river every seasons. The sediment was transferred slowly by using small spatula (Figure 3.5) into the tin capsule. While weighing, make sure there is no unwanted residue on the microbalance as it will affect the mass of the sample. If the is leftover clean the balance by using brush (Figure 3.5). The sample was folded and compressed using tweezers (Figure 3.5) on tin capsule plate

(Figure 3.5) into a tight ball. The tight ball was then transferred into micro-plate to hold the tin capsule according to the sequence before being loaded into an auto-sampler for analysis. All the replicated samples were analysed for stable carbon (13C) and nitrogen

43

(15N) isotopic composition using Flash EA 2000 elemental analyser (ThermoScientific,

Waltham, MA) coupled to a Delta V Advantage isotope ratio mass spectrometer (Thermo,

Milan, Italy) (Figure 3.6).

(i) Tin capsule

(ii) Spatula

(iii) Tweezers

(iv) Brush

(v) Tin capsule plate

Figure 3.5: Tools used for sample preparation into tin capsule

Figure 3.6: Isotope-ratio mass spectrometry (IRMS)

44

Figure 3.9: Process of crimpling sample in tin capsule

45

For the analysis, the samples were put in autosampler. The samples dropped one by one into a furnace at temperature 1000°C in an atmospheric oxygen. The tin capsules ignites and burns exothermically. The sample is oxidizing and temperature in the combustion tube rises up to approximately 1800°C. Complete combustion product is vaporised and swept through a bed of chromium oxide (Cr2O3) at temperature 1000°C by carrier gas, helium. A 15cm layer of copper oxide followed by a layer of silver wool completes the combustion and remove any Sulphur. The product was the passed through reduction reactor containing copper wires temperature 600°C where left-over oxygen is absorbed and nitrogen oxides reduced to elemental nitrogen. Then, water is removed in a trap containing anhydrous magnesium perchlorate, Mg(ClO4)2 and carbon dioxide,

CarbosorbTM, where water is removed when carbon dioxide is the gas of interest. The gas stream passes into a gas chromatograph where components of interest are separated and then bled into a mass spectrometer where isotope species are ionized then separated in a magnetic field. This isotope species is detected separately and from their ratio. The level of carbon-13 and nitrogen-15 is calculated.

Raw isotope ratios from the analysis were normalised to the international scales using USGS-40 and USGS-41 reference materials (~0.5 mg, respectively) assayed with the unknown samples. For quality control material, Urea (IVA-Analysentechnik GmbH &

Co., Germany) was used to correct for drift. Every 12 samples were measured with known values of δ13C = -40.81‰ and δ15N = -0.49‰. Variations in the stable isotope ratios were reported as parts per thousand (‰) deviations from the internationally accepted standards which are the Vienna Pee Dee Belemnite (VPDB) for carbon and atmospheric nitrogen

(AIR) for nitrogen in the delta (δ) notation.

46

The δ notation is defined using the following Equation (1),

δ (‰) = ( Rsample / Rstandard –1)…………………………………………Equation (1)

13 12 15 14 where Rsample is the isotope ratio ( C/ C or N/ N) of the sample, and Rstandard is the isotopic ratio of the international reference materials.

3.2.5 Carbon Nitrogen Ratio (C/N Ratio) Analysis

Similar to the isotope analysis, each sediment sample was weighed into a small tin capsule (8 x 5 mm) for 2mg in triplicates. The sample was folded and compressed into a tight ball before being loaded into an auto-sampler. All the replicated samples were analysed for carbon and nitrogen composition using the Perkin Elmer 2400 Series II CHN

Elemental Analyser (Perkin Elmer) (Figure 3.7).

Figure 3.7: Perkin Elmer 2400 Series II CHN Elemental Analyser

47

The samples were introduced from an autosampler into a combustion furnace with a temperature of 925 °C. The resulting gases (CO2, NOx, and H2O) were passed through combustion and reduction columns, mixed, and separated through thermal conductivity detector (TCD) gas chromatography column (Stephen et al., 2011). Duplicated samples and soil standards were run every 10 samples for quality control. Blanks and acetanilide

(C6H5NHCOCH3) standards were run every 20 samples to ensure proper instrument operation.

The C/N ratio is defined using the following Equation (2),

푪 (%푪/%푵) 풓풂풕풊풐 = ( ퟏퟒ ……………………………………………………Equation (2) 푵 ( ) ퟏퟐ

3.2.6 Sediment yield and water quality data

The secondary data of sediment yields in Kelantan were also collected from the

Department of Irrigation and Drainage (DID) Kelantan. The data was a record of the 30- year data from 1980 to 2009. Besides that, water quality parameters were collected from the Department of Environment (DOE) for ten years starting 2004 to 2014. The parameters include COD, BOD, SS, pH, DO, and Ammoniacal nitrogen (NH3-N). These both secondary data were analysed by using the principal component analysis (PCA).

48

3.3 Statistical Analysis

3.3.1 Isotope analysis

In this study there are two treatments which are location (seven rivers) and seasons

(dry and wet season) (Table 3.2). The samples were collected from seven different rivers at two different rivers with three replication of each places. So the total number of samples were 42 sediments. This experiment was arranged in Factorial Random Complete Block

Design.

The data was analysed by using two way ANOVA because there are two treatments for this experiment. Treatment 1 is river and treatment 2 is season of the sampling is done. This means it will compare by using Duncan Multiple Range Test at 5% level of confident.

Table 3.2: Experimental design

Treatment 1: Season (S)

S1 S2 S1 S2 S1 S2

R1 R1 S1 R1 S2 R1 S1 R1 S2 R1 S1 R1 S2

R2 R2 S1 R2 S2 R2 S1 R2 S2 R2 S1 R2 S2

R3 R3 S1 R3 S2 R3 S1 R3 S2 R3 S1 R3 S2

R4 R4 S1 R4 S2 R4 S1 R4 S2 R4 S1 R4 S2

R5 R5 S1 R5 S2 R5 S1 R5 S2 R5 S1 R5 S2

Treatment 2: (R) River Treatment R6 R6 S1 R6 S2 R6 S1 R6 S2 R6 S1 R6 S2

R7 R7 S1 R7 S2 R7 S1 R7 S2 R7 S1 R7 S2

Replication (Rep.) Rep. 1 Rep. 2 Rep. 3

49

3.3.2 Sediment yield data

Sediment yield data were collected about 30 years (1979 – 2009) data from

Department of Irrigation and Drainage (DID) Kelantan. The data was analysed by using principal component analysis (PCA) from Excel, ELSTAT software to see the purposed factors.

3.3.3 Water quality data

Water quality data were collected about 10 years (2004 – 2014) data from

Department of Environment (DOE) Kelantan. The data was analysed by using principal component analysis (PCA) from Excel, ELSTAT software to see the purposed factors.

50

CHAPTER 4

RESULTS AND DISCUSSIONS

4.0 Introduction

This chapter describes and discusses the isotopic variations of 13C and 15N in sediments of Kelantan watershed, observed in SWM and NEM, both represented by July and January respectively. The discussion also includes C/N ratio of the system. As well, long-term sediments yield and water quality data were reported as complementary to the isotopic findings.

4.1 Stable isotope carbon (13C)

4.1.1 The temporal distribution of stable carbon isotopes (13C ) in Kelantan rivers

13 Figure 4.1 demonstrated that all  C values for July and January fall with the C3 type plant range (-29‰ to -24‰). The range of 13C could reflect source of sedimentation, where most of the terrestrial plant signatures (such as oil palm, rubber, forest) present within the studied locations. Temporally, the results indicated no significant difference between July and January indicating similar source of erosion marked in river sediments.

51

Plants, CAM 10

Plants, C3 Plants, C4 8

6 July January

4 Sample frequency Sample

2

0 -32 -30 -28 -26 -24 -22 -19 -17 -15 -13 -10 -8 -6 -4 -2 0 13C (‰)

Figure 4.1: Bar frequency 13C [‰] sediments from two different seasons; the

Southwest Monsoon (July) and Northeast monsoon (January)

4.1.2 The spatial distribution of stable carbon isotopes (13C ) in Kelantan rivers

The 13C values vary between -28.22‰ and -24.29‰ (Figure 4.2). In average, the most depleted values was found at the downstream which is Kelantan River, while, most enriched were manipulated by upstream river which are Betis, Nenggiri and Berok river with -24.900.98‰, -26.801.28‰ and -26.811.46‰ respectively. Whereas, Lebir

27.990.82, Pergau -27.990.84 and Galas -27.360.60 rivers almost have the same values approximately -27‰.

52

Figure 4.2: Spatial variation in 13C in sediments in the Kelantan rivers. Depletion trend towards the ocean characterized by spatial variations of 13C in sediment describe the metabolism of the watershed (Photosynthesis: enrich versus respiration: deplete) – Carbon cycle.

53

Table 4.1: Spatial isotopic composition of stable isotope 13C in sediment

Stable Isotope 13C [‰] Rivers Average Season Berok Betis Nenggiri Galas Pergau Lebir Kelantan season -25.85 -25.71 -27.19 -28.31 -28.21 -26.48 -27.42 Jul -27.05  -26.79 -24.15 -26.43 -27.07 -27.53 -27.51 -27.51 (SEM) 1.02 -28.07 -25.81 -27.84 -26.94 -27.79 -27.96 -27.48 -25.55 -23.60 -24.88 -27.75 -26.10 -28.68 -28.88 Jan -26.80  -25.56 -25.78 -24.74 -26.65 -26.72 -28.65 -28.90 (NEM) 1.76 -29.05 -24.34 -25.42 -27.42 -26.40 -28.66 -29.10

The mean of 13C at Berok samples is -26.81  1.46‰ and Betis is -24.90 ± 0.98‰

(Table 4.1). Both are located in Gua Musang district. The major type of vegetation here is rubber (Hevea brasiliensis), tapioca (Manihot esculenta), and banana (Musa spp.), which all are representing the C3 type plants (Calatayud et al., 2002; Janssens et al., 2009; Da

Matta et al., 2001). Nenggiri is the main river of Betis and Berok tributaries with the average value of the 13C in sediments was observed at -26.08 ± 1.28‰. Galas and Pergau had almost the same average of 13C in sediments, -27.36 ± 0.60‰ and - 27.12 ± 0.84‰, respectively. The convergence of these two rivers are located in Dabong at the south of

Kelantan. Rubber estate is the main land use activity, followed by small farming of banana and tapioca planted along the river bank.

Berok, Betis and Nenggiri rivers are located in Gua Musang district. Nenggiri is the main river of Betis and Berok tributaries. In average, the most enriched of 13C value is Betis followed by Berok and Nenggiri rivers. From this pattern it showed that the confluence between the two rivers has resulted in the mixing process.

Lebir River is located in the Kuala Krai district with an average of 13C was -27.99

± 0.88‰ where palm oil plantation is the main land use activity (plantation) along the

54 river bank based on the observation during sampling processed. According to Lamade et al. (2009), 13C of oil palm (Elaeis guineensis) leaves is around -27‰, which is also categorised as a C3 type plant. For Kelantan river sediments located at the downstream catchment, the mean value of 13C was - 28.22 ± 0.82‰. Small farming activities like banana, cocoa, tapioca, and rubber estate were present around the catchment area particularly along the Kelantan river. Cocoa (Theobroma cacao) (Gattward et al., 2012) also falls within the C3 type plant range.

Tabulated data demonstrated the mean value for 13C for July is -27.05  1.02‰ followed by January, -26.80  1.76‰. The results from both dry and wet seasons in

Kelantan catchment showed that the value was ranged from -29.10‰ to -23.60‰ with no significant difference (Appendix, Table A2) between the rivers suggesting similar source of erosion which contributes to river sedimentation, spatially (Kohn, 2010; Tappert et al.,

2013).

55

4.2 Stable isotope nitrogen (15N)

4.2.1 The temporal distribution of stable nitrogen isotopes (15N) in Kelantan rivers

Distinct pattern of 15N for July and January was observed and reported in Figure

4.3. The pattern indicates an overlapping trend of 15N values representing, complex fractionation caused by multiple processes (mineralisation, nitrification, plant uptake, and denitrification) of nitrogen cycle (Figure 4.4) (Heaton, 1986; Lajtha & Schlesinger, 1986;

Ryabenko, 2013) traced in sediment samples.

Organic, N 10 Plants 9 - Fertilizer, NO3 8 + Fertilizer, NH4 - 7 Animal waste, NO3 July 6 January 5

4 Sample frequency Sample 3 2 1 0 -10 -8 -6 -4 -2 0 +2 +4 +6 8 10 12 14 16 18 20 22 15N (‰)

Figure 4.3: Bar frequency 15N [‰] sediments on two different seasons; the Southwest

Monsoon (July) and Northeast monsoon (January)

Fertiliser appeared as one of the main signature in the sediment samples. Both

- + nitrate (NO3 ) and ammonia (NH4 ) were common results from the industrial fixation of

56 atmospheric nitrogen via the measurable process of isotopic fractionation, whereby 15N depleted (Gunter, 1986). Meanwhile, organic nitrogen in soil undergoes mineralisation process that causes it to fractionate. It involves steps that can fractionate it and change

15N values in favourable condition with the aid of bacterial activities (Heaton, 1986).

Figure 4.4: Nitrogen conversion and processes affecting 15N values in forest ecosystem

which result in enrich and deplete of the product (Source: Nadelhoffer & Fry 1994;

Kendall, 1998).

The existence of organic nitrogen within the soil (+0 to +7‰), plant debris (-10 to

+9‰), fertilizer ammonia and nitrate (-5 to +7‰) range in the sediments, may indicates significant erosion process in Kelantan watershed especially during Northeast monsoon

(NEM) (to be discussed in Section 4.4) (An et al., 2008; Chakravarty et al., 2012; Ickowitz et al., 2015).

57

However, statistically, no significant difference of 15N values between July and

January as the source of river networks received same source of sediments. However, organic nitrogen signatures are more pronounced during January, suggesting more washout (erosion) activity during (Figure 4.5)

Organic, N 10 9 8 7 July 6 January 5

4 Sample frequency Sample 3 2 1 0 -10 -8 -6 -4 -2 0 +2 +4 +6 8 10 12 14 16 18 20 22 15N (‰)

Figure 4.5: The average value of 15N in July and January. Organic nitrogen signatures

are more pronounced during January.

58

4.2.2 The spatial distribution of stable nitrogen isotopes (15N ) in Kelantan

rivers

Figure 4.6: Spatial variation in 15N in sediments in the Kelantan Rivers. No trend of 15N is observed across the river networks, suggesting complex nitrogen cycle superimposed by the anthropogenic activities in the watershed.

59

The 15N values vary between 0.70‰ and 3.45‰ as shown in Figure 4.6. The most depleted values are depicted at upstream river which is Nenggiri River, while, most enriched was found in Lebir river is no trends observed of nitrogen isotope variations between upstream to the downstream is observed.

The average values of 15N for Berok, Betis, Nenggiri, were 1.48  2.48‰, 2.26 

1.82‰, and 0.70  2.74‰ (Table 4.2), respectively. The upstream of Betis River flows from and merges with Berok River at the confluence of Nenggiri River. The richness of 15N indicates more nitrogen sourced mainly from anthropogenic activities

(Dolenec et al., 2006; Brahney et al., 2014). The average values of 15N for Galas, Pergau and Lebir Rivers were 1.51  2.63‰, 2.50  0.90‰, and 3.45  2.63‰, respectively.

Matured oil palm and rubber plantations are the major land use activities around these catchment areas.

Table 4.2: Spatial isotopic composition of stable isotope 15N in sediments

Stable Isotope 15N [‰] Rivers Average Season Berok Betis Nenggiri Galas Pergau Lebir Kelantan season 1.41 1.82 -1.27 1.25 3.71 -1.45 -1.98 Jul +0.65 -2.73 5.25 -3.98 -2.94 1.90 2.33 0.67 (SEM)  2.44 0.09 -0.29 1.92 0.37 1.19 4.82 1.62 3.31 2.42 2.89 3.47 3.21 4.87 4.17 Jan +3.35 2.96 2.82 2.47 4.48 2.62 5.03 4.31 (NEM)  1.02 3.82 1.54 2.19 2.42 2.40 5.14 3.81

The villages around the catchment may affect the nitrogen concentration in the sediments due to land use activities within the catchment. The 15N variations, however, showed no significant difference of 15N values between the river networks (Appendix,

60

Table A3). This reflects complex nitrogen cycles within the catchment (Lajtha &

Schlesinger, 1986; Ryabenko, 2013).

4.3 Carbon to nitrogen ratio (C/N ratio)

C/N ratio in sediments was analysed to complement the terrestrial and organic matter sources characterised by 13C and 15N (Finlay & Kendall 2007; Sanderman et al.,

2015). Figure 4.7 shows a biplot 13C and C/N ratio presenting various types of terrestrial and aquatic organic matters overlapping from sediment collections in Kelantan. Overall, about 95% of the C/N ratio was determined to fall at <12 indicating low C/N ratios in

Kelantan catchment, suggesting an autochthonous system (Tue et al., 2011). There was an absence of C3 type plant from the terrestrial source, which constituted a ratio of more than

15. However, the signature of the allochthonous component was not clearly identified, perhaps, due to the catchment settings (climate and hydrology) that may speed up the rate of decomposition process in the water body (McGill & Cole, 1981). Besides, the C/N ratio too can be changed due to the degradation of organic matter during sediment diagenesis

(Gao et al., 2012).

As organic matter comprise of two major component which are carbon and nitrogen, thus, the content of organic carbon in sediment surface is controlled by several factor such as sediment characteristics, terrestrial input and rate of microbial degradation

(Burone et al., 2003). The C/N ratio values tend to decrease over time as degradation process releases carbon dioxide (CO2) or methane (CH4), ammonia, and other microbially- associated nitrogen (Gao et al., 2012). Additionally, low C/N ratio was caused by the abundance of ammonium ions being absorbed into clay minerals (Rumolo et al., 2011).

61

Plant that contain low organic matter has higher nitrogen hence a lower the C/N ratio, therefore represent low contribution of terrigenous organic matter (soil-derived organic matter and vascular plant debris) (Faganelli et al., 1988; Gordon, & Goñi, 2003).

Phytoplankton is high in nitrogen compounds and thus, low C/N ratios in the sediments demonstrating a dominance of aquatic organic matter (Carpenter & Capone, 1983; Burone et al., 2003).

Brok Betis Nenggiri Galas Pergau Lebir Kelantan -30.00

-29.00

-28.00 Phytoplankton

-27.00

C (‰) C 13  -26.00

-25.00 (POM) material & riverine soil

Macrophytes

3 3 C

-24.00 plant sediment Algae & submerged

-23.00 0 2 4 6 8 10 12 14 -22.00 C:N ratio

Figure 4.7: The 13C and C/N ratio of various types of terrestrial and aquatic organic

matters overlapping by the sediment range of Kelantan catchments

Kelantan and Nenggiri rivers show higher C/N ratios compares to others probably encompassed of soil derived organic matter contribution also suggested of a combination between aquatic phytoplankton and terrigenous plant matter (Tiessen et al., 1984; Parton

62 et al., 1987; Goñi et al., 1998; Gordon, & Goñi, 2003), as well, because of post depositional decay in organic sedimentary might be due to rapid sedimentation process

(Sanderman et al, 2015). In average Kelantan River (downstream), demonstrated the highest C/N value as received more loading of allochthonous components from all tributaries (Bordovskiy 1965; Burone et al., 2003).

4.4 Sediment yield in Kelantan River networks

Sedimentation in the river has been one of the major problems in Kelantan watershed as it is also one of the factors that may cause the annual flood in Kelantan

(Ismail & Haghroosta, 2014; Hua et al. 2015; Nurul Akmal et al., 2015). The data collected by DID Kelantan was analysed using multivariate PCA to determine major factors which responsible for sediment accumulation in the water bodies. PCA is a technique to reduce large data by summarising them into a small variable number (Pallant, 2001;

Wuttichaikitcharoen & Babel, 2014). From this study, the data showed a concise result that occurred for almost 30 years.

PCA for sediment yield data sets (Table 4.3 & Table 4.4) showed that the main component for factor loading was characterised by two components. This explains 99% of cumulative variability described significant sedimentation in Kelantan watershed all years round (F1) where NEM (October, November, and December) (F2) played a role in intensifying sedimentation in Kelantan watershed as discussed in Figure 4.3. As well, land use activities may contribute to F1 as factor loading are significant at all months (Butt et al., 2011; Hua, 2014).

63

Table 4.3: Proposed factor of sediment yields in Kelantan watershed

Sediment yield Kelantan catchment F1 F2 Component All Oct, Nov, Dec Eigenvalue 9.66 2.31 Variability (%) 80.54 19.24 Cumulative (%) 80.54 99.77 Factor Climate Northeast Monsoon

Table 4.4: Factor loadings of sediment yields over two principal components F1.

F1 represent 99% of cumulative loading indicate significant sedimentation in Kelantan

watershed for all year round. F2 showed significant role of NEM in intensifying

sediment yield of Kelantan watershed.

Months F1 F2 Jan 0.96 Feb 0.96 Mar 0.96 Apr 0.96 May 0.97 Jun 0.96 Jul 0.97 Aug 0.99 Sep 0.89 Oct 0.67 0.74 Nov 0.72 0.70 Dec 0.66 0.75

As well, sediments yield showed significant results in Nenggiri Rivers, suggesting rampant land use activities which degraded the soil along the river banks. According to the study done by Adnan & Atkinson, 2011, land clearing at the upstream of Kelantan showing unsustainable land use activities, thus, appear as the main factors of erosion process that contribute to massive sedimentation. Note, sand mining was also identified as one of the factors of sediment intensification in Kelantan river (Syahreza et al., 2012).

64

4.5 Water quality analysis

Sediment transport had a tremendous impact on water quality of Kelantan River.

A set of water quality data provided by DOE from 2004 to 2014 was analysed using PCA to determine major factors responsible for water quality degradation in the river networks of Kelantan catchment (Berok, Betis, Galas, Kelantan, Lebir, Nenggiri, and Pergau

Rivers).

PCA result for water quality data (Table 4.5) showed the main factors that played a crucial role in determining the water quality of Kelantan catchment. It was characterised by two-factor component with Eigenvalue > 1. According to Chatfield and Collin (1980), the components with eigenvalue less than 1 should be eliminated. This explained 51% of total variance due to anthropogenic factor contributed by land use activities along the river.

Table 4.5: Proposed factor of water parameter in Kelantan catchment. Factor loading 1,

(F1) represents the anthropogenic factors & Factor loading 2, (F2) represents the key

indicator of the river health.

Water quality Kelantan catchment F1 F2 Component COD, BOD, SS pH, DO Eigenvalue 1.90 1.17 Variability (%) 31.68 19.48 Cumulative (%) 31.68 51.17 Factor Anthropogenic Anthropogenic

Factor loading 1 consists of three parameters, which are COD, BOD, and suspended solid (SS), followed by factor loading 2 which includes pH and DO. It is suggested that, COD can serve as a key parameter in determining the water quality of

65

Kelantan River, which reflect the oxygen level required to oxidise chemical substance through chemical processes (Talib & Amat, 2012). According to the Northeast Georgia

Regional Development Centre (2001), COD always show high value compared to BOD.

This is because COD measurement only requires a few hours while BOD measurement can lead up to five days. Both COD and BOD are a correlated process to each other as oxidation process that occurs during the breakdown of organic matters to a more stable form (Talib & Amat, 2012).

Hypothetically, the second factor that contributes to COD value is phosphate concentration as they are directly proportional to each other (Talib & Amat, 2012). The

COD value will be high as phosphate concentration increases. The main source of phosphorus is mainly from agriculture fertiliser, manure industrial effluent, and sewage.

The major factor that causes a high concentration of phosphorus in the river is soil erosion, especially during flood event (USGS, 2016).

Furthermore, as BOD is correlated with COD, it is suggested that the other factor that influences BOD value is organic waste and detritus from the terrestrial part, agriculture, and also urban runoff (Northeast Georgia Regional Development Centre,

2001). These are also the same contributing factors of COD. Both COD and BOD play a major role in the deterioration of Kelantan River water quality. Besides COD and BOD,

SS appears significantly in agreement with the DID result (sediment yield) as discussed in Section 4.4.

66

4.6 Summary

1. No significant statistical difference of 13C between Southwest monsoon (SWM)

and Northeast monsoon (NEM) indicating similar source of erosion (oil palm,

rubber, forest – C3 type plant) signatures marked in the sediments.

2. 15N values in the sediment indicate soil organic matter (SOM) signature more

pronounce during NEM, suggesting the role of climate in intensifying the

- anthropogenic washout into the river (i.e.; organic N, plants and fertilizer (NO3 ,

+ NH4 )).

3. PCA of sediment yield suggest the role of land use in increasing the vulnerability

of Kelantan watershed.

4. PCA of the water quality highlight the COD, BOD and SS – critical factors,

potentially caused by land use activities, which determine the water quality of

Kelantan river.

5. The C/N ratio characterized by sediments in Kelantan river is autochthonous

(aquatic derived).

6. Allochthonous (terrestrial derived) components is mainly driven by the climate

setting of the catchment and intensified by the land use activities within the

watershed.

67

CHAPTER 5

CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion

13 The stable isotope of  C suggested that C3 type plants are dominant in Kelantan watershed with no significant difference between July (Southwest monsoon) and January

(Northeast monsoon). This indicates similar source of erosion mainly from woody plant such as forest trees, rubber and oil palm. While, stable isotope of 15N indicates that soil organic matter signature is more pronounce during January suggesting more washout

(erosion) during monsoon season, suggesting the role of climate in intensifying sedimentation.

Note, the C/N ratio characterized by the sediments in Kelantan River is autochthonous, suggesting an aquatic derived. BOD, COD and SS are the major parameters that determined the water quality of Kelantan River. Sedimentation is observed to occur in all year round and pronounced during NEM.

Anthropogenic activities have tremendous impacts on the watershed ecosystem.

Inefficient management in river basin will result in massive erosion and sedimentation.

These two factors are critical in determining the water quality of river in the watershed.

Considering these factors, understanding the erosion mechanism in the watershed and its impact on nature and humanity are crucial in research priorities.

Essentially, this research will help stakeholders to develop better strategies for restoring catchment management in Kelantan watershed. Balanced ecosystem plays a significant role in servicing the humanity and other related natural disasters.

68

5.2 Recommendations for future study

This study will serve as a precursor to future study to understand the impact of anthropogenic activities on carbon and nitrogen cycles in a tropical catchment. However, the results are still tentative, thus, require further investigation as recommended below:

1. Application of use compound specific isotope analysis (CSIA) by extracting fatty

acid in the soil or sediment, leading to more specific source identification.

2. Further investigation on nitrate isotope that can help to observe biological

processes, and in the case of mixing water with anthropogenic nitrates, it is highly

potential to identify the source of contamination in the water bodies.

69

REFERENCES

Adnan, N. A., & Atkinson, P. M. (2011). Exploring the impact of climate and land use changes on streamflow trends in a monsoon catchment. International journal of climatology, 31(6), 815-831. Ahmad, A. K., Mushrifah, I., & Shuhaimi, N, M. (2009). Water quality and heavy metal concentrations in sediment of Sungai Kelantan, Kelantan, Malaysia: a baseline study. Sains Malaysiana, 38(4), 435-442.

Aini, N., Jamil, N. R., Hasan, H. H., & Yusof, F. M. (2016). River Hydro Morphology Characteristic Influenced by Seasonal Changes: A Case Study in Galas River, Kelantan.

Alekseeva, T., Alekseev, A., Xu, R. K., Zhao, A. Z., & Kalinin, P. (2011). Effect of soil acidification induced by a tea plantation on chemical and mineralogical properties of Alfisols in eastern China. Environmental geochemistry and health, 33(2), 137- 148. Alewell, C., Schaub, M., & Conen, F. (2009). A method to detect soil carbon degradation during soil erosion. Biogeosciences, 6(11), 2541-2547.

Ambak, M. A., & Zakaria, M. Z. (2010). Freshwater fish diversity in Sungai Kelantan. Journal of Sustainability Science and Management, 5(1), 13-20.

Anees, M. T., Abdullah, K., Nawawi, M. N. M., Norulaini, N. A. N., Piah, A. R. M., Fatehah, O., ... & Omar, A. K. M. (2018). Development of daily rainfall erosivity model for Kelantan state, Peninsular Malaysia. Hydrology Research, 49(5), 1434- 1451.

Ansa-Asare, O. D. (1995). Limno-chemical characterization and water quality assessment of Birim basin. Institute of Aquatic Biology Technical Report. No. 159, Accra, Ghana. 25pp. Ansa-Asare, O.D. & Asante, K.A. (2000). The water quality of Birim river in South

Ansari, A. A., Singh, I. B., & Tobschall, H. J. (2000). Role of monsoon rain on concentrations and dispersion patterns of metal pollutants in sediments and soils of the Ganga Plain, India. Environmental Geology, 39(3), 221-237.

Baharuddin, K. A., Wahab, S. F. A., Ab Rahman, N. H. N., Mohamad, N. A. N., Kamauzaman, T. H. T., Noh, A. Y. M., & Majod, M. R. A. (2015). The record- setting flood of 2014 in Kelantan: challenges and recommendations from an emergency medicine perspective and why the medical campus stood dry. The Malaysian journal of medical sciences: MJMS, 22(2), 1.

70

Balakrishna, K., & Probst, J. L. (2005). Organic carbon transport and C/N ratio variations in a large tropical river: Godavari as a case study, India. Biogeochemistry, 73(3), 457-473. Balesdent, J., Besnard, E., Arrouays, D., & Chenu, C. (1998). The dynamics of carbon in particle-size fractions of soil in a forest-cultivation sequence. Plant and Soil, 201(1), 49-57. Barbieri, M. (2016). The importance of enrichment factor (EF) and geoaccumulation index (Igeo) to evaluate the soil contamination. J Geol Geophys, 5(237), 2.

Basarudin, Z., Adnan, N. A., Latif, A. R. A., Tahir, W., & Syafiqah, N. (2014). Event- based rainfall-runoff modelling of the Kelantan River Basin. In IOP conference series: earth and environmental science (Vol. 18, No. 1, p. 012084). IOP Publishing. Belmont, P., Willenbring, J. K., Schottler, S. P., Marquard, J., Kumarasamy, K., & Hemmis, J. M. (2014). Toward generalizable sediment fingerprinting with tracers that are conservative and nonconservative over sediment routing timescales. Journal of soils and sediments, 14(8), 1479-1492.

Blake, B., Blake, A., & Lacy, W. J. (1999). "Compositions to remove heavy metals and radioactive isotopes from wastewater." U.S. Patent No. 5,880,060. Washington, DC: U.S. Patent and Trademark Office. Blake, W. H., Ficken, K. J., Taylor, P., Russell, M. A., & Walling, D. E. (2012). Tracing crop-specific sediment sources in agricultural catchments. Geomorphology, 139, 322-329. Blake, W. H., Walling, D. E., & He, Q. (2002). Using cosmogenic beryllium–7 as a tracer in sediment budget investigations. Geografiska Annaler: Series A, Physical Geography, 84(2), 89-102.

Blake, W.H., Wallbrink, P.J., Doerr, S.H., Shakesby, R.A., Humphreys, G.S., English, P., & Wilkinson, S. (2006). Using geochemical stratigraphy to indicate post-fire sediment and nutrient fluxes into a watersupply reservoir, Sydney, Australia. In Sediment dynamics and the hydromorphology of fluvial systems, Rowan JS, Duck RW, Werritty A (eds). IAHS Publication No. 306, IAHS Press: Wallingford; 363- 370.

Booth, C. A., Walden, J., Neal, A, & Smith, J.P. (2005). Use of mineral magnetic concentration data as a particle size proxy: A case study using marine, estuarine and fluvial sediments in the Camarthen Bay area, South Wales, U.K. Science of the Total Environment. 347, 241-253.

Bordovskiy O. K. (1965). Accumulation of organic matter in bottom sediments. Marine Geology 3: 33-82.

71

Boutton, T. W. (1991). Stable carbon isotope ratios of natural materials: II. Atmospheric, terrestrial, marine, and freshwater environments. Carbon isotope techniques, 1, 173.

Bradshaw, R., & Thompson, R. (1985). The use of magnetic measurements to investigate the mineralogy of Icelandic lake sediments and to study catchment processes. Boreas, 14(3), 203-215.

Brady, N. C., Weil, R. (2001). The nature and properties of soils. Pearson Education, N.J.

Brahney, J., Ballantyne, A. P., Turner, B. L., Spaulding, S. A., Otu, M., & Neff, J. C. (2014). Separating the influences of diagenesis, productivity and anthropogenic nitrogen deposition on sedimentary δ 15 N variations. Organic Geochemistry, 75, 140-150.

Brooks, K. N., P. F. Ffolliott, and J. A. Magner. (2013). Hydrology and the management of watersheds. John Wiley & Sons, Inc., New York.

Burone, L., Muniz, P., Pires-Vanin, A. N. A., Maria, S., & Rodrigues, M. (2003). Spatial distribution of organic matter in the surface sediments of Ubatuba Bay (Southeastern-Brazil). Anais da Academia Brasileira de Ciências, 75(1), 77-80.

Butt, M. J., Mahmood, R., & Waqas, A. (2011). Sediments deposition due to soil erosion in the watershed region of Mangla Dam. Environmental monitoring and assessment, 181(1-4), 419-429.

Caitcheon, G. G. (1993). Sediment source tracing using environmental magnetism: a new approach with examples from Australia. Hydrological Processes 7: 349–358.

Calatayud, P. A.; Barón, C. H.; Velásquez, H.; Arroyave, J. A.; Lamaze, T. (2002): Wild Manihot species do not possess C4 photosynthesis. Annals of botany. 89(1), 125- 127.

Carpenter, E. J. & Capone, D. J. (1983). Nitrogen in the marine environment. Stony Brook, Marine Science Research Center. 900p

Carter, J., Owens, P.N., Walling, D.E., Leeks, G.J.L., (2003). Fingerprinting suspended sediment sources in an urban river. Sci. Total Environ. 314-316, 513-534

Chakravarty, S. K. Ghosh, C. P., Suresh, A. N. Dey. Gopal Shukla. (2012). Deforestation: Causes, Effects and Control Strategies, Global Perspectives on Sustainable Forest Management. Dr. Dr. Clement A. Okia (Ed.), ISBN: 978-953-51-0569-5, InTech

Chang, M. (2003). Forest Hydrology. An Introduction to Water and Forest. CRC Press. Pg. 2-108

72

Chappell, J., Zheng, H., & Fifield, K. (2006). Yangtse River sediments and erosion rates from source to sink traced with cosmogenic 10Be: Sediments from major rivers. Palaeogeography, Palaeoclimatology, Palaeoecology, 241(1), 79-94.

Charlesworth, S.M., Ormerod, L.M., Lees, J.A., (2000). Tracing sediment within urban catchments usingheavy metal, mineral magnetic and radionuclide signatures. In: Foster, I.D.L. (Ed.), Tracers in Geomorphology. Wiley, Chichester, UK, pp. 345- 368.

Chatfield, C. and Collin, A. J. (1980): Introduction to Multivariate Analysis. Chapman and Hall in Association with Methuen, Inc. 733 Third Avenue, New York NY.

Chen, C. W., Chen, C.F., Dong, C. D. (2012). Distribution and Accumulation of Mercury in Sediments of Kaohsiung River Mouth, Taiwan. APCBEE Procedia.1:153–158.

Chen, H., Chen, R., Teng, Y., & Wu, J. (2016). Contamination characteristics, ecological risk and source identification of trace metals in sediments of the Le'an River (China). Ecotoxicology and environmental safety, 125, 85-92.

Chillrud, S. N., Hemming, S., Shuster, E. L., Simpson, H. J., Bopp, R. F., Ross, J. M. (2003). Stable lead isotopes, contaminant metals and radionuclides in upper Hudson River sediment cores: Implications for improved time stratigraphy and transport processes. Chemical Geology, 199, 53–70.

Clement, B. M., Javier, J., Say, J. P., & Ross, M. S. (2011). The effects of wildfires on the magnetic properties of soils in the Everglades. Earth Surface Processes and Landforms, 36, 460–466

Coleman, D.C., Fry, B., (1991). Carbon isotope techniques. In: EA, P., JM, M. (Eds.), Isotopic Techniques in Plant, Soil and Aquatic Biology. Academic Press Inc., San Diego, p. 274.

Collins, A. L., Pulley, S., Foster, I. D., Gellis, A., Porto, P., & Horowitz, A. J. (2016). Sediment source fingerprinting as an aid to catchment management: A review of the current state of knowledge and a methodological decision-tree for end-users. Journal of Environmental Management. Collins, A. L., Walling, D. E., & Leeks, G. J. L. (1997). Sediment sources in the Upper Severn catchment: a fingerprinting approach. Hydrology and Earth System Sciences Discussions, 1(3), 509-521.

Da Matta, F. M., Loos, R. A., Rodrigues, R., & Barros, R. S. (2001): Actual and potential photosynthetic rates of tropical crop species. Revista Brasileira de Fisiologia Vegetal, 13(1), 24-32.

73

Dasar, K. N., Ahmad, A., Mushrifah, I., & Shuhaimi, O. M. (2009). Water quality and heavy metal concentrations in sediment of Sungai Kelantan, Kelantan, Malaysia: a baseline study. Sains Malaysiana, 38(4), 435-442.

Dasar, K. N., Ahmad, A., Mushrifah, I., & Shuhaimi-Othman, Mohamad. (2009). Water quality and heavy metal concentrations in sediment of Sungai Kelantan, Kelantan, DE Malaysia: a baseline study. Sains Malaysiana, 38(4), 435-442. De Roo, A. P. J. & Walling, D. E. (1994) Validating the ANSWERS soil erosion model using l37Cs. In: Conserving Soil Resources: European Perspective (ed. by R. J. Rickson), 246-263. CAB International, Wallingford, UK De Roo, A. P. J. (1991). The use of 137Cs as a tracer in an erosion study in south Limburg (The Netherlands) and the influence of Chernobyl fallout. Hydrological Processes, 5(2), 215-227.

Dearing, J. A., J. A. Hannam, A. S. Anderson, and E. M. H. Wellington (2001), Magnetic, geochemical and DNA properties of highly magnetic soils in England, Geophys. J. Int., 144(1), 183–196. Deines, P. (1980) The carbon isotopic composition of diamonds: relationship to diamond shape, color, occurrence and vapor composition. Geochim Cosmochim Acta 44(7):943–961

Dekkers M.J. (1978). Magnetic properties of sediments. In: Sedimentology. Encyclopedia of Earth Science. Springer, Berlin, Heidelberg Derrien, M., Kim, M. S., Ock, G., Hong, S., Cho, J., Shin, K. H., & Hur, J. (2018). Estimation of different source contributions to sediment organic matter in an agricultural-forested watershed using end member mixing analyses based on stable isotope ratios and fluorescence spectroscopy. Science of the Total Environment, 618, 569-578.

Dolenec, T., Lojen, S., Dolenec, M., Lambasa, Z., Dobnikar, M., & Rogan, N. (2006): ^ 1^ 5N and^ 1^ 3C Enrichment in Balanus perforatus: Tracers of Municipal Particulate Waste in the Murter Sea (Central Adriatic, Croatia). Acta Chimica Slovenica, 53(4), 469. Evans R. D. (2007). Soil nitrogen isotope composition. Pp. 83–98 in Stable isotopes in ecology and environmental science (Michener R. Lajtha K., eds.). 2nd ed. Blackwell Publishers, Boston, Massachusetts. Evans, M., Warburton, J., & Yang, J. (2006). Eroding blanket peat catchments: global and local implications of upland organic sediment budgets. Geomorphology, 79(1-2), 45-57.

Faganelli J, Malej A, Pezdic J and Malacic V. (1988). C:N:P ratios and stable C isotopic ratios as indicator of sources of organic matter in the Gulf of Trieste (northern Adriatic). Oceanologia Acta 11: 377-382.

74

Fang, H., Sun, L., & Tang, Z. (2015). Effects of rainfall and slope on runoff, soil erosion and rill development: an experimental study using two loess soils. Hydrological Processes, 29(11), 2649-2658.

Finlay, J. C., & Kendall, C. (2007). Stable isotope tracing of temporal and spatial variability in organic matter sources to freshwater ecosystems. Stable isotopes in ecology and environmental science, 2, 283-333. Foster, I. D., Lees, J. A., Owens, P. N., & Walling, D. E. (1998). Mineral magnetic characterization of sediment sources from an analysis of lake and floodplain sediments in the catchments of the Old Mill reservoir and Slapton Ley, South Devon, UK. Earth Surface Processes and Landforms: The Journal of the British Geomorphological Group, 23(8), 685-703. Foster, I.D.L., Lees, J.A. (2000). Tracers in geomorphology: theory and applications in tracing fine particulate sediments. In: Foster, I.D.L. (Ed.), Tracers in Geomorphology. Wiley, Chichester, pp. 3e20.

Fox, J. F., & Papanicolaou, A. N. (2007). The use of carbon and nitrogen isotopes to study watershed erosion processes 1. JAWRA Journal of the American Water Resources Association, 43(4), 1047-1064.

Fox, J. F., & Papanicolaou, A. N. (2008). Application of the spatial distribution of nitrogen stable isotopes for sediment tracing at the watershed scale. Journal of hydrology, 358(1-2), 46-55.

Franz, C., Makeschin, F., Weiß, H., & Lorz, C. (2013). Geochemical signature and properties of sediment sources and alluvial sediments within the Lago Paranoá catchment, Brasilia DF: A study on anthropogenic introduced chemical elements in an urban river basin. Science of theTotal Environment, 452–453, 411–420.

Franz, C., Makeschin, F., Weiß, H., Lorz, C. (2014). Sediments in urban river basins: Identification of sediment sources within the Lago Paranoá catchment, Brasilia DF, Brazil – using the fingerprint approach. Sci. Total Environ. 466-467, 513–523.

Fred, T.M.; Judith, A.M. (1995). Our Changing Planet. An Introduction to Earth System Science and Global Environmental Change; Prentice-Hall: Honolulu, HI, USA. Fry, B. 2006. Stable isotope ecology. Springer, New York, New York, USA.

Gao, X., & Chen, C. T. A. (2012). Heavy metal pollution status in surface sediments of the coastal Bohai Bay. Water research, 46(6), 1901-1911.

Gao, X., Yang, Y., & Wang, C. (2012). Geochemistry of organic carbon and nitrogen in surface sediments of coastal Bohai Bay inferred from their ratios and stable isotopic signatures. Marine pollution bulletin, 64(6), 1148-1155.

75

Garzon-Garcia, A., Laceby, J. P., Olley, J. M., & Bunn, S. E. (2017). Differentiating the sources of fine sediment, organic matter and nitrogen in a subtropical Australian catchment. Science of the total environment, 575, 1384-1394.

Gattward, J. N., Almeida, A. A. F., Souza, J. O., Gomes, F. P. Kronzucker, H. J. (2012). Sodium–potassium synergism in Theobroma cacao: stimulation of photosynthesis, water‐use efficiency and mineral nutrition. Physiologia plantarum. 146(3), 350- 362.

Gebreyesus, B. & Kirubel, M. (2009). Estimating Soil Loss Using Universal Soil Loss Equation (USLE) for Soil Conservation planning at Medego Watershed, Northern Ethiopia. J. Am. Sci. 5, 58–69.

Gellis, A. C., & Mukundan, R. (2013). Watershed sediment source identification: tools, approaches, and case studies. Journal of Soils and Sediments, 13(10), 1655-1657.

Gellis, A. C., & Walling, D. E. (2011). Sediment source fingerprinting (tracing) and sediment budgets as tools in targeting river and watershed restoration programs. Stream restoration in dynamic fluvial systems: Scientific approaches, analyses, and tools, 194, 263-291.

Gibbs, M. M. (2008). Identifying source soils in contemporary estuarine sediments: a new compound-specific isotope method. Estuaries and Coasts, 31(2), 344-359.

Giliba, R. A., Mafuru, C. S., Paul, M., Kayombo, C. J., Kashindye, A. M., Chirenje, L. I., & Musamba, E. B. (2011). Human activities influencing deforestation on meru catchment forest Reserve, Tanzania. Journal of Human Ecology, 33(1), 17-20.

Gon˜i M. A., Ruttenberg K. C., and Eglinton T. I. (1998). A reassessment of the sources and importance of land-derived organic matter in surface sediments from the Gulf of Mexico. Geochim. Cosmochim. Acta 62, 3055–3075.

Gordon, E. S., & Goñi, M. A. (2003). Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico. Geochimica et Cosmochimica Acta, 67(13), 2359-2375.

Gray, D. H & Sotir, R.B. (1996). Biotechnical and Soil Bioengineering Slope Stabilization: A Practical Guide for Erosion Control. John Wiley & Sons, 27-29.

Grimm, M., Jones, R.J., Rusco, E., & Montanarella, L. (2003). Soil Erosion Risk in Italy: A Revised USLE Approach. European Soil Bureau Research Report, Office for Official Publications of the European Communities, Luxembourg, p. 23. Guan, Z., Tang, X. Y., Yang, J. E., Ok, Y. S., Xu, Z., Nishimura, T., & Reid, B. J. (2017). A review of source tracking techniques for fine sediment within a catchment. Environmental geochemistry and health, 39(6), 1221-1243.

Gunter, F. (1986). Principal of Isotope Geology. 2nd Edition. 513-520

76

Guzmán Díaz, M. G. (2012). Development of sediment tracers to study soil redistribution and sediment dynamic due to water erosion.

Guzmán, M., Malebrán, M. C., Zavala, P., Saldívar, P., & Munoz, D. (2013). Acoustic changes of the voice as signs of vocal fatigue in radio broadcasters: preliminary findings. Acta Otorrinolaringologica (English Edition), 64(3), 176-183. Haddadchi, A., Ryder, D. S., Evrard, O., & Olley, J. (2013). Sediment fingerprinting in fluvial systems: review of tracers, sediment sources and mixing models. International Journal of Sediment Research, 28(4), 560-578.

Hadi, A. A., Ghani, M. R. A., Talib, J., & Afiqah, I. N. (2017). Geomorphology and Hydrology of 2014 Kelantan Flood. In ICIPEG 2016 (pp. 655-668). Springer, Singapore.

Hairsine, P. B., & Rose, C. W. (1991). Rainfall detachment and deposition: sediment transport in the absence of flow-driven processes. Soil Science Society of America Journal, 55(2), 320-324.

Hamad, J. R., & Omran, A. (2016). Total Organic Carbon (TOC) nd Carbon/Nitrogen Ratio in Surface Sediments in Kuala Sungai Baru, Melaka. Annals of the Faculty of Engineering Hunedoara, 14(2), 137.

Hancock, G. J., & Revill, A. T. (2013). Erosion source discrimination in a rural Australian catchment using compound‐specific isotope analysis (CSIA). Hydrological processes, 27(6), 923-932. Hancock, G., & Revill, A. (2011). Land-use and Erosion Source Discrimination of Soil and Carbon Sources to the Logan and Albert Rivers in Australia using Compound Specific Isotope Analysis. CSIRO Land and Water.

Hatfield, R. G., & Maher, B. A. (2008). Suspended sediment characterization and tracing using a magnetic fingerprinting technique: Bassenthwaite Lake, Cumbria, UK. The Holocene, 18(1), 105-115.

Hatfield, R. G., & Maher, B. A. (2009). Fingerprinting upland sediment sources: particle size‐specific magnetic linkages between soils, lake sediments and suspended sediments. Earth surface processes and landforms, 34(10), 1359-1373.

He, Q., & Walling, D. E. (2003). Testing distributed soil erosion and sediment delivery models using 137Cs measurements. Hydrological Processes, 17(5), 901-916.

Heaton, T. H. (1986): Isotopic studies of nitrogen pollution in the hydrosphere and atmosphere: a review. Chemical Geology: Isotope Geoscience section, 59, 87-102.

Higgitt, D. L., Lu, X. X., & Pu, L. J. (2000). Soil erosion assessment using 137Cs: examples from contrasting environments in southern China. Tracers in Geromorphology. DL Foster (ed.). John Wiley & Sons, Chichester, UK, 165-182. 77

Holz, D. J., Williard, K. W., Edwards, P. J., & Schoonover, J. E. (2015). Soil erosion in humid regions: a review. Journal of Contemporary Water Research & Education, 154(1), 48-59.

Hu, X. F., Su, Y., Ye, R., Li, X. Q., & Zhang, G. L. (2007). Magnetic properties of the urban soils in Shanghai and their environmental implications. Catena, 70(3), 428- 436.

Hua, A. K. (2014): Monsoon Flood Disaster in Kota Bharu, Kelantan Case Study: A Comprehensive Review. Int. J. Sci. Eng. Res. ISSN (Online): 2347-3878

Hua, A. K. (2015). Adaptation and mitigation towards monsoon floods in Kota Bharu, Kelantan. Lulu. com.

Foster, I.D.L. & Lees, J.A. (2000). Tracers in geomorphology: theory and applications in tracing fine particulate sediments. pp. 3-20 Ibbitt, R., Takara, K., Desa, M.N.M., & Pawitan, H. (2002). Catalogue of Rivers for Southeast Asia and The Pacific. (Vol. 4). The UNESCO-IHP Regional Steering Committee for Southeast Asia and the Pacific, pp. 208-218

Ibrahim, A. L., Yaakub, S.Y., Khan, N. L. M., Huey, T.T. (2012). Application of Geographic Information System in Soil Erosion Prediction. The 33rd Asian Conference of Remote Sensing. 22-30 November 2012. Pattaya, Thailand.

Ickowitz, A., Slayback, D., Asanzi, P., Nasi, R. (2015). Agriculture and deforestation in the Democratic Republic of the Congo: A synthesis of the current state of knowledge. Center for International Forestry Research (CIFOR), Bogor, Indonesia.CIFOR Occasional Paper no. 119

Ionita, I., Fullen, M. A., Zgłobicki, W., & Poesen, J. (2015). Gully erosion as a natural and human-induced hazard.

Ip, C. C. M., Li, X. D., Zhang, G., Farmer, J. G., Wai, O. W. H., & Li, Y. S. (2004). Over one hundred years of trace metal fluxes in the sediments of the Pearl River Estuary, South China. Environmental Pollution, 132(1), 157-172.

Irwan, Y. M., Daut, I., Safwati, I., Irwanto, M., Gomesh, N., & Fitra, M. (2013): An estimation of solar characteristic in Kelantan using Hargreaves Model. Energy Procedia, 36, 473-478.

Ismail, W. R., & Haghroosta, T. (2014). Extreme weather and floods in Kelantan state, Malaysia in December 2014.

Jalowska, A. M., McKee, B. A., Laceby, J. P., & Rodriguez, A. B. (2017). Tracing the sources, fate, and recycling of fine sediments across a river-delta interface. Catena, 154, 95-106.

78

Jamaludin, S. (2017). Streamflow profile classification using functional data analysis: A case study on the Kelantan River Basin. In AIP Conference Proceedings (Vol. 1842, No. 1, p. 020006). AIP Publishing.

Janssens, M. J., Keutgen, N., Pohlan, J. (2009). The role of bio-productivity on bio-energy yields. Journal of Agriculture and Rural Development in the Tropics and Subtropics (JARTS), (2009). 110(1), 41-48.

Jennerjahn, T. C., Ittekkot, V., Klöpper, S., Adi, S., Nugroho, S. P., Sudiana, N., ... & Gaye-Haake, B. (2004). Biogeochemistry of a tropical river affected by human activities in its catchment: Brantas River estuary and coastal waters of Madura Strait, Java, Indonesia. Estuarine, Coastal and Shelf Science, 60(3), 503-514. Kendall, C. & McDonnell, J. J. (1998). Isotope Tracers in Catchment Hydrology. Elsevier. 804.

Kennedy, P., Kennedy, H. & Papadimitriou, S. (2005). The effect of acidification on the determination of organic carbon, total nitrogen and their stable isotopic composition in algae and marine sediment. Rapid Communications in Mass Spectrometry 19: 1063–1068.

Kimoto, A., Fares, A., & Polyakov, V. (2008). Sediment tracing techniques and their application to coastal watersheds. Coastal Watershed Management, 13, 65.

Kohn, M. J. (2010). Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo) ecology and (paleo) climate. Proceedings of the National Academy of Sciences, 107(46), 19691-19695. Koiter, A.J., Owens, P.N., Petticrew, E.L., Lobb, D.A., (2013). The behavioural characteristics of sediment properties and their implications for sediment fingerprinting as an approach for identifying sediment sources in river basins. Earth Sci. Rev. 125, 24–42. Koltun, G. F., Landers, M. N., Nolan, K. M., & Parker, R. S. (1997). Sediment transport and geomorphology issues in the water resources division. In Proceedings of the US Geological Survey (USGS) sediment workshop: expanding sediment research capabilities in today’s USGS, February 4-7, 1997, Reston, VA. and Harpers Ferry, WV.

Koszelnik, P., Gruca-Rokosz, R., & Bartoszek, L. (2017). An isotopic model for the origin of autochthonous organic matter contained in the bottom sediments of a reservoir. International Journal of Sediment Research.

Kuehn, E. (2015). Stream Bank Erosion Trends and Sediment Contributions in a Southwestern Missouri River (Doctoral dissertation, Missouri State University).

79

Labrière, N., Locatelli, B., Laumonier, Y., Freycon, V., & Bernoux, M. (2015). Soil erosion in the humid tropics: A systematic quantitative review. Agriculture, Ecosystems & Environment, 203, 127-139.

Laceby, J. P., Olley, J., Pietsch, T. J., Sheldon, F., & Bunn, S. E. (2015). Identifying subsoil sediment sources with carbon and nitrogen stable isotope ratios. Hydrological Processes, 29(8), 1956-1971.

Lajtha, K., & Schlesinger, W. H. (1986). Plant response to variations in nitrogen availability in a desert shrubland community. Biogeochemistry, 2(1), 29-37.

Lamade, E.; Setiyo, I. E.; Girard, S.; Ghashghaie, J. (2009). Changes in 13C/12C of Oil Palm Leaves to Understand Carbon Use During Their Passage from Heterotrophy to Autotrophy. Rapid communications in mass spectrometry, (2009). 23(16)

Li Y, Poesen J, Yang JC, Fu B, Zhang JH (2003) Evaluating gully erosion using 137Cs and 210Pb/137Cs ratio in a reservoir catchment. Soil Till Res 69:107–115

Liu, C., Li, Z., Dong, Y., Chang, X., Nie, X., Liu, L., ... & Peng, H. (2017). Response of sedimentary organic matter source to rainfall events using stable carbon and nitrogen isotopes in a typical loess hilly-gully catchment of China. Journal of Hydrology, 552, 376-386.

Longworth, G., Becker, L.W., Thompson, R., Oldfeld, F., Dearing, J.A. & Rummery, T.A., (1979). MoÈssbauer effect and magnetic studies of secondary iron oxides in soil, J. Soil Sci., 30, 93-110. Lu, X., Mo, J., Gilliam, F. S., Zhou, G., & Fang, Y. (2010). Effects of experimental nitrogen additions on plant diversity in an old‐growth tropical forest. Global Change Biology, 16(10), 2688-2700. Mabit, L., Benmansour, M., & Walling, D. E. (2008). Comparative advantages and limitations of the fallout radionuclides 137Cs, 210Pbex and 7Be for assessing soil erosion and sedimentation. Journal of environmental radioactivity, 99(12), 1799- 1807.

Mabit, L., Benmansour, M., Abril, J. M., Walling, D. E., Meusburger, K., Iurian, A. R., ... & Alewell, C. (2014). Fallout 210Pb as a soil and sediment tracer in catchment sediment budget investigations: a review. Earth-Science Reviews, 138, 335-351.

Mahabaleshwara, H., and H. M. Nagabhushan. (2014). "A study on soil erosion and its impacts on floods and sedimentation." International Journal of Research in Engineering and Technology 3.3, 443-451.

Maher, B. A. (2009). Rain and dust: magnetic records of climate and pollution. Elements, 5(4), 229-234.

80

Mariana, A., Zuraidawati, Z., Ho, T. M., & Kulaimi, B. M. (2005). A survey of ectoparasites in Gunung Stong Forest Reserve, Kelantan, Malaysia. Southeast Asian journal of tropical medicine and public health, 36(5), 1125.

MatAmin, A. R., Ahmad, F., Mamat, M., Rivaie, M., & Abdullah, K. (2012). Sediment Variation along the East Coast of Peninsular Malaysia. Ecological Questions, 16(1), 99. Matisoff, G., & Whiting, P. J. (2012). Measuring soil erosion rates using natural (7Be, 210Pb) and anthropogenic (137Cs, 239,240 Pu) radionuclides. In Handbook of environmental isotope geochemistry (pp. 487-519). Springer, Berlin, Heidelberg.

Matisoff, G., Bonniwell, E. C., & Whiting, P. J. (2002). Soil erosion and sediment sources in an Ohio watershed using beryllium-7, cesium-137, and lead-210. Journal of Environmental Quality, 31(1), 54-61.

McConkey,, B.G. Lobb,, D.A. Li, S. Black, J.M.W. Krug, P.M. (2012). Soil Erosion on Cropland: Introduction and Trends for Canada. Canadian Biodiversity: Ecosystem Status and Trends.

McConnachie, J. L., & Petticrew, E. L. (2006). Tracing organic matter sources in riverine suspended sediment: implications for fine sediment transfers. Geomorphology, 79(1-2), 13-26.

McGill, W. B., & Cole, C. V. (1981). Comparative aspects of cycling of organic C, N, S and P through soil organic matter. Geoderma, 26(4), 267-286.

Meier‐Augenstein, W., & Kemp, H. F. (2009). Stable isotope analysis: general principles and limitations. Wiley Encyclopedia of Forensic Science.

Middelkoop, H. (2002). Reconstructing floodplain sedimentation rates from heavy metal profiles by inverse modelling. Hydrological Processes, 16(1), 47-64.

Millennium Ecosystem Assessment (MEA). (2005). Millennium Ecosystem Assessment: Ecosystem and Human Well Being: Synthesis; Island Press: Washington, DC, USA.

Moghadam, B. K., Jabarifar, M., Bagheri, M., & Shahbazi, E. (2015). Effects of land use change on soil splash erosion in the semi-arid region of Iran. Geoderma, 241, 210- 220. Mohtar, W. H. M. W., Bassa, S. A., & Porhemmat, M. (2017). Grain Size Analysis of Surface Fluvial Sediments in Rivers in Kelantan, Malaysia. Sains Malaysiana, 46(5), 685-693.

Morgan, R. P. C. (1996). Soil erosion and conservation. 2nd Ed. Longman, p. 7.

81

Mukundan, R., Radcliffe, D. E., Ritchie, J. C., Risse, L. M., & McKinley, R. A. (2010). Sediment fingerprinting to determine the source of suspended sediment in a southern Piedmont stream. Journal of environmental Quality, 39(4), 1328-1337.

Muller, G. (1979). Heavy metals in the sediment of the Rhine – Changes seity. 1971. Umsch Wiss Tech 79: 778-783.

Nadelhoffer, K. J., & Fry, B. (1994). Nitrogen isotope studies in forest ecosystems, in Stable Isotopes in Ecology and Environmental Science, edited by K. Lajtha and R.H. Michener, pp. 22-44, Blackwell Sci., Malden, Mass., 1994. Nasir, A., Tuwo, A., Lukman, M., & Usman, H. (2015). Impact of increased nutrient on the variability of chlorophyll-a in the west coast of South Sulawesi, Indonesia. International J. of Scientific and Engineering Research, 6(5), 821-826. Norouzi Banis, Y., Bathurst, J. C., & Walling, D. E. (2004). Use of caesium‐137 data to evaluate SHETRAN simulated long‐term erosion patterns in arable lands. Hydrological processes, 18(10), 1795-1809.

Northeast Georgia Regional Development Center. (2001). A Guidebook for Local Governments for Developing Regional Watershed Protection Plans Nowrouzi, M., & Pourkhabbaz, A. (2014). Application of geoaccumulation index and enrichment factor for assessing metal contamination in the sediments of Hara Biosphere Reserve, Iran. Chemical Speciation & Bioavailability, 26(2), 99-105. Nurul Akma, J., Khanan, Z., Haq, U.Y., and Bhat, I. (2015). Effects of Recent Flood on Soil Properties. Proceedings of National Geoscience Conference, Kota Bharu, 31 July-1 August 2015, Geological Society of Malaysia. O’Driscoll, M., Clinton, S., Jefferson, A., Manda, A., & McMillan, S. (2010). Urbanization effects on watershed hydrology and in-stream processes in the southern United States. Water, 2(3), 605-648. Ockenden, M. C., Deasy, C., Quinton, J. N., Surridge, B., & Stoate, C. (2014). Keeping agricultural soil out of rivers: Evidence of sediment and nutrient accumulation within field wetlands in the UK. Journal of environmental management, 135, 54- 62.

Oldfield, F., & Yu, L. (1994). The influence of particle size variations on the magnetic properties of sediments from the north‐eastern Irish Sea. Sedimentology, 41(6), 1093-1108. Oldfield, F., Barnosky, C., Leopold, E. B., & Smith, J. P. (1983). Mineral magnetic studies of lake sediments. In Paleolimnology (pp. 37-44). Springer,

Oldfield, F., Hao, Q., Bloemendal, J. A. N., Gibbs, Z. O. Ë., Patil, S., & Guo, Z. (2009). Links between bulk sediment particle size and magnetic grain‐size: general

82

observations and implications for Chinese loess studies. Sedimentology, 56(7), 2091-2106.

Oldfield, F., Maher, B. A., Donoghue, J., Pierce, J. (1985) Particlesize related, mineral magnetic source sediment linkages in the Rhode River catchment, Maryland, USA. J Geol Soc London 142:1035–1046.

O'Leary, M. H. (1988). Carbon isotopes in photosynthesis. Bioscience, 38(5), 328-336. Othman, Z., & Ismail, W. R. (2012). Using Environmental Radionuclide, 137cs to Investigate Soil Re-Distribution In An Agricultural Plot In Kalumpang, , Malaysia. Kajian Malaysia: Journal of Malaysian Studies, 30(2). Othman, Z., Ismail, W. R., & Abdul Rahman, M. T. (2003). Erosion processes and landform evolution in agricultural land–A prespective from environmental isotope measurements. Geoinformatic. , Malaysia. Owens, P. N., & Walling, D. E. (2002). Changes in sediment sources and floodplain deposition rates in the catchment of the River Tweed, Scotland, over the last 100 years: the impact of climate and land use change. Earth Surface Processes and Landforms: The Journal of the British Geomorphological Research Group, 27(4), 403-423. Owens, P. N., Batalla, R. J., Collins, A. J., Gomez, B., Hicks, D. M., Horowitz, A. J., ... & Petticrew, E. L. (2005). Fine‐grained sediment in river systems: environmental significance and management issues. River research and applications, 21(7), 693- 717.

Owens, P. N., Blake, W. H., Gaspar, L., Gateuille, D., Koiter, A. J., Lobb, D. A., ... & Woodward, J. C. (2016). Fingerprinting and tracing the sources of soils and sediments: Earth and ocean science, geoarchaeological, forensic, and human health applications. Earth-Science Reviews, 162, 1-23.

Pallant, J. (2001): SPSS Survival Manual: A Step by Step Guide to Data Analysis Using SPSS for Windows (Versions 10 and 11): SPSS Student Version 11.0 for Windows. Open University Press.

Papanicolaou, A. N., Fox, J. F., & Marshall, J. (2003). Soil fingerprinting in the Palouse Basin, USA, using stable carbon and nitrogen isotopes. International Journal of Sediment Research, 18(2), 278-284. Papanicolaou, T., & Fox, J. (2004). Tracing Sediment Sources by Using Stable Carbon and Nitrogen Isotopes: An Exploratory Research. Hydro science & Engineering College of Engineering. The University of Iowa City, Iowa, 52242-1585.

Parton, W. J., Schimel, D. S., Cole, C. V., & Ojima, D. S. (1987). Analysis of factors controlling soil organic matter levels in Great Plains Grasslands 1. Soil Science Society of America Journal, 51(5), 1173-1179.

83

Perg, L. A., Anderson, R. S., & Finkel, R. C. (2003). Use of cosmogenic radionuclides as a sediment tracer in the Santa Cruz littoral cell, California, United States. Geology, 31(4), 299-302.

Peter, F.F., Kenneth, N.B., Roberto, P.T., Pablo, G.C., Daniel, G.N. (2013). Soil Erosion and Sediment Production on Watershed Landscapes: Processes, Prevention, and Control. Peterson, B. J., & Fry, B. (1987). Stable isotopes in ecosystem studies. Annu Rev Ecol Syst 18:293–320. Povinec, P. P., Laubenstein, M., Jull, A. T., Ferrière, L., Brandstätter, F., Sýkora, I., ... & Koeberl, C. (2015). Cosmogenic radionuclides and mineralogical properties of the Chelyabinsk (LL5) meteorite: What do we learn about the meteoroid?. Meteoritics & Planetary Science, 50(2), 273-286.

Pulley, S., & Rowntree, K. (2016a). Stages in the life of a magnetic grain: Sediment source discrimination, particle size effects and spatial variability in the South African Karoo. 1087 Geoderma, 271, 134–143.

Pulley, S., Foster, I., & Antunes, P. (2015). The uncertainties associated with sediment fingerprinting suspended and recently deposited fluvial sediment in the Nene river basin. Geomorphology, 228, 303-319.

Qi, S.S., Hao, F.H., Ouyang, W., Cheng, H.G. (2012). Characterizing landscape and soil erosion dynamics under pipeline interventions in southwest China. Procedia Environ. Sci. 13, 1863–1871. Quine, T. A., Walling, D. E., Chakela, Q. K., Mandiringana, O. T., & Zhang, X. (1999). Rates and patterns of tillage and water erosion on terraces and contour strips: evidence from caesium-137 measurements. Catena, 36(1-2), 115-142. Quinton, J. N., & Catt, J. A. (2007). Enrichment of heavy metals in sediment resulting from soil erosion on agricultural fields. Environmental science & technology, 41(10), 3495-3500. Ramaswamy, V., Gaye, B., Shirodkar, P. V., Rao, P. S., Chivas, A. R., Wheeler, D., et al. (2008). Distribution and sources of organic carbon, nitrogen and their isotopic signatures in sediments from the ayeyarwady (irrawaddy) continental shelf, Northern Andaman Sea. Mar. Chem. 111, 137–150. Restrepo, J. D., Kettner, A. J., & Syvitski, J. P. (2015). Recent deforestation causes rapid increase in river sediment load in the Colombian Andes. Anthropocene, 10, 13-28.

Robins, P. E., Skov, M. W., Lewis, M. J., Giménez, L., Davies, A. G., Malham, S. K., ... & Jago, C. F. (2016). Impact of climate change on UK estuaries: A review of past trends and potential projections. Estuarine, Coastal and Shelf Science, 169, 119- 135.

84

Rogers, K. M. (2013). Using Stable Isotopes to detect land use change and nitrogen sources in aquatic systems. Assessing Nutrient Dynamics in River Basins, 129. Rosgen, D.L., 2006, Watershed Assessment of River Stability and Sediment Supply (WARSSS), Wildland Hydrology Books, Fort Collins, CO, 648 pp.

Rostad, C. E., Leenheer, J. A., & Daniel, S. R. (1997). Organic carbon and nitrogen content associated with colloids and suspended particulates from the Mississippi River and some of its tributaries. Environmental science & technology, 31(11), 3218-3225.

Rumolo, P., Barra, M., Gherardi, S., Marsella, E., & Sprovieri, M. (2011). Stable isotopes and C/N ratios in marine sediments as a tool for discriminating anthropogenic impact. Journal of Environmental Monitoring, 13(12), 3399-3408.

Ryżak, M., Bieganowski, A., & Polakowski, C. (2015). Effect of soil moisture content on the splash phenomenon reproducibility. PloS one, 10(3), e0119269.

Saadatkhah, N., Tehrani, M. H., Mansor, S., Khuzaimah, Z., Kassim, A., & Saadatkhah, R. (2016). Impact assessment of land cover changes on the runoff changes on the extreme flood events in the Kelantan River basin. Arabian Journal of Geosciences, 9(17), 687. Samad, M. N. S. A., Hanafiah, M. M., AbdulHasan, M. J., Ghazali, N. F., & Harun, S. N. (2017). Ratio of Water Withdrawal To Availability In Kelantan Watersheds Malaysia.

Sanderman, J., Krull, E., Kuhn, T., Hancock, G., McGowan, J., Maddern, T., ... & Steven, A. (2015): Deciphering sedimentary organic matter sources: Insights from radiocarbon measurements and NMR spectroscopy. Limnology and Oceanography, 60(3), 739-753.

Sarma, V. V. S. S., Arya, J., Subbaiah, C. V., Naidu, S. A., Gawade, L., Kumar, P. P., & Reddy, N. P. C. (2012). Stable isotopes of carbon and nitrogen in suspended matter and sediments from the Godavari estuary. Journal of Oceanography, 68(2), 307- 319.

Saviour, M. N., & Stalin, P. (2012). Soil and Sand Mining: Causes, Consequences and Management. IOSR Journal of Pharmacy (IOSRPHR), 2(4), 01-06.

Schimel, D.S. (1993). Theory and Application of Tracers. 3. Academic Press, Inc., San Diego. Schindler Wildhaber, Y., Liechti, R., & Alewell, C. (2012). Organic matter dynamics and stable isotope signature as tracers of the sources of suspended sediment. Biogeosciences, 9(6), 1985-1996. Schmidt, M. W. I., Knicker, H., & Kögel-Knabner, I. (2000). Organic matter accumulation in Aeh and Bhhorizons of a Podzol–chemical characterization in primary organo-

85

mineral associations. Organ. Geochem. 31, 727–734. doi: 10.1016/S0146- 6380(00)00045-0

Schuller, P., Iroumé, A., Walling, D. E., Mancilla, H. B., Castillo, A., & Trumper, R. E. (2006). Use of beryllium-7 to document soil redistribution following forest harvest operations. Journal of Environmental Quality, 35(5), 1756-1763.

Schuller, P., Walling, D.E., Sepu´lveda, A., Castillo, A., Pino, I. (2007). Changes in soil erosion associated with the shift from conventional tillage to a no-tillage system, documented using 137Cs measurements. Soil Tillage Res. 94, 183e192

Shanbehzadeh, S., Vahid Dastjerdi, M., Hassanzadeh, A., & Kiyanizadeh, T. (2014). Heavy metals in water and sediment: a case study of Tembi River. Journal of environmental and public health.

Shearer, G. Kohl, D.H. (1993). Natural Abundance of 15N: Fractional Contribution of Two Sources to a Common Sink and Use of Isotope Discrimination. In: Knowles R, Blackburn H, editors. Nitrogen Isotope Techniques. 2. Academic Press, Inc., San Diego.

Singh, H., Pandey, R., Singh, S. K., & Shukla, D. N. (2017). Assessment of heavy metal contamination in the sediment of the River Ghaghara, a major tributary of the River Ganga in Northern India. Applied Water Science, 7(7), 4133-4149.

Singh, K. P., Mohan, D., Singh, V. K., & Malik, A. (2005). Studies on distribution and fractionation of heavy metals in Gomti river sediments—a tributary of the Ganges, India. Journal of hydrology, 312(1-4), 14-27.

Slattery, M. C., Walden, J., & Burt, T. P. (2000). Use of mineral magnetic measurements to fingerprint suspended sediment sources: results from a linear mixing model. Tracers in Geomorphology. Chichester7 Wiley, 309-22.

Slimane, A. B., Raclot, D., Evrard, O., Sanaa, M., Lefèvre, I., Ahmadi, M., ... & Le Bissonnais, Y. (2013). Fingerprinting sediment sources in the outlet reservoir of a hilly cultivated catchment in Tunisia. Journal of soils and sediments, 13(4), 801- 815.

Smith, H. G., & Blake, W. H. (2014). Sediment fingerprinting in agricultural catchments: a critical re-examination of source discrimination and data corrections. Geomorphology, 204, 177-191.

Smith, H. G., Blake, W. H., & Owens, P. N. (2013). Discriminating fine sediment sources and the application of sediment tracers in burned catchments: A review. Hydrological Processes, 27, 943–958

86

Soliman, M. M. (1974). Urbanization and the processes of erosion and sedimentation in the River Nile. Effects of man on the interface of the hydrological cycle with the physical environment, (113), 123. Sorensen, L. H. (1981). Carbon-nitrogen relationships during the humification of cellulose in soils containing different amounts of clay. Soil Biol. Biochem. 13, 313–321. doi: 10.1016/0038-0717(81)90068-7

Spano, S., Belem, A. L., Doria, R. N., do Rosário Zucchi, M., de Souza, J. R. B., Costa, A. B., ... & de Azevedo, A. E. G. (2014). Aplicação de isótopos estáveis de carbono orgânico e nitrogênio e relações C/N como indicadores de fontes de matéria orgânica no complexo estuarino de Nova Viçosa-Caravelas, sul da Bahia, Brasil. Brazilian Journal of Geology, 44(1), 13-21.

Sparovek, G.; Van Lier, Q.J. (1997). Definition of tolerable soil erosion values. Revista Brasileira de Ciência do Solo, 21, 467–471.

Stott, A. P. (1986). Sediment tracing in a reservoir-catchment system using a magnetic mixing model. Physics of the Earth and Planetary Interiors, 42(1-2), 105-112.

Syahreza, S., MatJafri, M. Z., Lim, H. S., & Mustapha, M. R. (2012): Water quality assessment in Kelantan delta using remote sensing technique. In SPIE Security+ Defence (pp. 85420X-85420X). International Society for Optics and Photonics.

Taha, F. B., & Kaniraj, S. R. (2013). Study of Soil Erosion at a Site near Chemical Engineering Laboratory in UNIMAS. Journal of Civil Engineering, Science and Technology, 4(2), 1-6.

Talib, A., & Amat, M. I. (2012): Prediction of chemical oxygen demand in Dondang River using artificial neural network. International Journal of Information and Education Technology, 2(3), 259.

Tappert, R., McKellar, R. C., Wolfe, A. P., Tappert, M. C., Ortega-Blanco, J., & Muehlenbachs, K. (2013). Stable carbon isotopes of C3 plant resins and ambers record changes in atmospheric oxygen since the Triassic. Geochimica et Cosmochimica Acta, 121, 240-262.

Thiemann, S., Schütt, B., & Förch, G. (2005). Assessment of erosion and soil erosion processes–a case study from the Northern Ethiopian Highland. Topics of integrated watershed management—proceedings, 173-185.

Thomaz, E. L., & Luiz, J. C. (2012). Soil loss, soil degradation and rehabilitation in a degraded land area in Guarapuava (Brazil). Land Degradation & Development, 23(1), 72-81.

Thompson, R. & Morton DJ (1979) Magnetic susceptibility and particle size distribution in recent sediments of the Loch Lomond drainage basin, Scotland. J Sediment Petrol 49:801–811

87

Tiessen, H., Stewart, J. W. B., & Hunt, H. W. (1984). Concepts of soil organic matter transformations in relation to organo-mineral particle size fractions. In Biological Processes and Soil Fertility (pp. 287-295). Springer, Dordrecht.

Tue, N. T., Hamaoka, H., Sogabe, A., Quy, T. D., Nhuan, M. T., & Omori, K. (2011). The application of δ13C and C:Nratios as indicators of organic carbon sources and paleoenvironmental change of the mangrove ecosystem from Ba Lat Estuary, Red River, Vietnam. Environmental Earth Sciences, 64(5), 1475-1486. Turnbull, L., Brazier, R. E., Wainwright, J., Dixon, L., & Bol, R. (2008). Use of carbon isotope analysis to understand semi‐arid erosion dynamics and long‐term semi‐ arid land degradation. Rapid Communications in Mass Spectrometry: An International Journal Devoted to the Rapid Dissemination of Up‐to‐the‐Minute Research in Mass Spectrometry, 22(11), 1697-1702. Twichell, S. C., Meyers, P. A., and Diester-Haass, L. (2002). Significance of high C/N ratios in organic-carbon rich Neogene sediments under the Benguela Current upwelling system. Organic Geochem. 33, 715–722. doi: 10.1016/S0146- 6380(02)00042-6 Ulén, B., Bechmann, M., Fölster, J., Jarvie, H. P., & Tunney, H. (2007). Agriculture as a phosphorus source for eutrophication in the north‐west European countries, Norway, Sweden, United Kingdom and Ireland: a review. Soil use and Management, 23, 5-15.

USGS. (2016). Phosphorus and Water. http://water.usgs.gov/edu/phosphorus.html. Retrieved on 28 October 2016.

Vaalgamaa, S., Sonninen, E., Korhola, A., & Weckström, K. (2013). Identifying recent sources of organic matter enrichment and eutrophication trends at coastal sites using stable nitrogen and carbon isotope ratios in sediment cores. Journal of paleolimnology, 50(2), 191-206.

Van der Waal, B., Rowntree, K., & Pulley, S. (2015). Flood bench chronology and sediment source tracing in the upper Thina catchment, South Africa: the role of transformed landscape connectivity. Journal of Soils and Sediments, 15, 2398−2411.

Varol, M. (2011). Assessment of heavy metal contamination in sediments of the Tigris River (Turkey) using pollution indices and multivariate statistical techniques. Journal of Hazardous Materials, 195, 355-364.

Ventura, E., Nearing, M. A., Amore, E., & Norton, L. D. (2002). The study of detachment and deposition on a hillslope using a magnetic tracer. Catena, 48(3), 149-161.

88

Walden, J., Slattery, M. C., & Burt, T. P. (1997). Use of mineral magnetic measurements to fingerprint suspended sediment sources: Approaches and techniques for data analysis. Journal of Hydrology, 202, 353–372

Wallbrink, P. J., & Murray, A. S. (1993). Use of fallout radionuclides as indicators of erosion processes. Hydrological processes, 7(3), 297-304.

Wallbrink, P. J., Murray, A. S., Olley, J. M., & Olive, L. J. (1998). Determining sources and transit times of suspended sediment in the Murrumbidgee River, New South Wales, Australia, using fallout 137Cs and 210Pb. Water Resources Research, 34(4), 879-887.

Walling D.E., He Q., Blake W. (1999). Use of 7 Be and 137Cs measurements to document short- and medium-term rates of water induced soil erosion on agricultural land. Water Resources Research, 35: 3865–3874.

Walling, D. E. (1998). Use of 137Cs and other fallout radionuclides in soil erosion investigations: progress, problems and prospects. Use of 137Cs in the Study of Soil Erosion and Sedimentation, 3962.

Walling, D. E. (2003). Using environmental radionuclides as tracers in sediment budget investigations. Iahs Publication, 57-78.

Walling, D. E. (2005). Tracing suspended sediment sources in catchments and river systems. Science of the total environment, 344(1-3), 159-184.

Walling, D. E. (2012). Fallout radionuclides and the study of erosion and sedimentation. In Encyclopedia of sustainability science and technology (pp. 3705-3768). Springer, New York, NY.

Walling, D. E. (2013a). Beryllium-7: The Cinderella of Fallout Radionuclide Sediment Tracers? Hydrological Processes, 27, 830–844.

Walling, D. E. (2013b). The evolution of sediment source fingerprinting investigations in fluvial systems. Journal of Soils and Sediments, 13, 1658–1675.

Walling, D. E., & Quine, T. A. (1995). Use of fallout radionuclide measurements in soil erosion investigations. In Nuclear techniques in soil-plant studies for sustainable agriculture and environmental preservation. Proceedings of an international symposium held in Vienna, 17-21 October 1994.

Walling, D. E., He, Q., & Blake, W. (1999). Use of 7Be and 137Cs measurements to document short‐and medium‐term rates of water‐induced soil erosion on agricultural land. Water Resources Research, 35(12), 3865-3874.

89

Walling, D. E., Peart, M. R., Oldfield, F., & Thompson, R. (1979). Suspended sediment sources identified by magnetic measurements. Nature, 281(5727), 110.

Walling, D.E., He, Q., (1999b). Using fallout lead-210 measurements to estimate soil erosion on cultivated land. Soil Sci. Soc. Am. J. 63, 1404–1412.

Walling, D.E., Schuller, P., Zhang, Y., Iroumé, A., (2009). Extending the timescale for using beryllium 7 measurements to document soil redistribution by erosion. Wat. Resourc. Res. 45, Article W02418. Wang, A. J., Bong, C. W., Xu, Y. H., Hassan, M. H. A., Ye, X., Bakar, A. F. A., ... & Loh, K. H. (2017). Assessment of heavy metal pollution in surficial sediments from a tropical river-estuary-shelf system: A case study of Kelantan River, Malaysia. Marine pollution bulletin, 125(1-2), 492-500.

Wang, A. J., Bong, C. W., Xu, Y. H., Hassan, M. H. A., Ye, X., Bakar, A. F. A., ... & Loh, K. H. (2017). Assessment of heavy metal pollution in surficial sediments from a tropical river-estuary-shelf system: A case study of Kelantan River, Malaysia. Marine pollution bulletin, 125(1-2), 492-500.

Wang, Z. Y., Lee, J.H.W., Melching, C.S. (2014). River Dynamics and Integrated River Management. Springer Science & Business Media, p.53.

Wantzen, K.M.; Mol, J.H. (2013). Soil erosion from agriculture and mining: A threat to tropical stream ecosystems. Agriculture, 3, 660–683.

Waterson, E. J. (2005). Sources of sedimentary organic matter in the Mississippi River and adjacent Gulf of Mexico.

Werth, M., & Kuzyakov, Y. (2010). 13C fractionation at the root–microorganisms–soil interface: a review and outlook for partitioning studies. Soil Biology and Biochemistry, 42(9), 1372-1384.

Wilson, C. G., Matisoff, G., & Whiting, P. J. (2003). Short‐term erosion rates from a 7Be inventory balance. Earth Surface Processes and Landforms: The Journal of the British Geomorphological Research Group, 28(9), 967-977. Wolfe, A. P., Baron, J. S., & Cornett, R. J. (2001). Anthropogenic nitrogen deposition induces rapid ecological changes in alpine lakes of the Colorado Front Range (USA). Journal of Paleolimnology, 25(1), 1-7. Wolman, M.G. (1967). A cycle of sedimentation and erosion in urban river channels. Geogr. Ann. 49, 385-395. Wood, F. L., Heathwaite, A. L., & Haygarth, P. M. (2005). Evaluating diffuse and point phosphorus contributions to river transfers at different scales in the Taw catchment, Devon, UK. Journal of Hydrology, 304(1-4), 118-138.

90

Wright, S.A.; Schoellhamer, D.H. (2004). Trends in the sediment yield of the Sacramento River, California, 1957–2001. San Franc. Estuary Watershed Sci. 2, 3.

Wu, B., Wang, G., Wu, J., Fu, Q., & Liu, C. (2014). Sources of heavy metals in surface sediments and an ecological risk assessment from two adjacent plateau reservoirs. PLoS One, 9(7), e102101. Wu, Y., Zhang, J., Liu, S. M., Zhang, Z. F., Yao, Q. Z., Hong, G. H., & Cooper, L. (2007). Sources and distribution of carbon within the Yangtze River system. Estuarine, Coastal and Shelf Science, 71(1-2), 13-25.

Wuttichaikitcharoen, P., & Babel, M. S. (2014): Principal Component and Multiple Regression Analyses for the Estimation of Suspended Sediment Yield in Ungauged Basins of Northern Thailand. Water, 6(8), 2412-2435.

Xiao, H. Y., & Liu, C. Q. (2010). Identifying organic matter provenance in sediments using isotopic ratios in an urban river. Geochemical Journal, 44(3), 181-187. Yan, X., Liu, M., Zhong, J., Guo, J., & Wu, W. (2018). How human activities affect heavy metal contamination of soil and sediment in a long-term reclaimed area of the Liaohe River Delta, North China. Sustainability, 10(2), 338.

Yen, T. P., & Rohasliney, H. (2013). Status of water quality subject to sand mining in the Kelantan River, Kelantan. Tropical life sciences research, 24(1), 19.

Yin, C., & Li, L. (2008). An investigation on suspended solids sources in urban stormwater runoff using 7Be and 210 Pb as tracers. Water Science and Technology, 57(12), 1945-1950.

Yu, F., Zong, Y., Lloyd, J. M., Huang, G., Leng, M. J., Kendrick, C., ... & Yim, W. W. S. (2010). Bulk organic δ13C and C/N as indicators for sediment sources in the Pearl River delta and estuary, southern China. Estuarine, Coastal and Shelf Science, 87(4), 618-630.

Yu, L., & Oldfield, F. (1989). A multivariate mixing model for identifying sediment source from magnetic measurements. Quaternary Research, 32(2), 168-181.

Zachar, D. (1982). Soil Erosion. Volume 10 of Developments in Soil Science. Elsevier Scientific Publishing Company, 27-222. Zapata, F. (2002). Handbook for the Assessment of Soil Erosion and Sedimentation Using Environmental Radionuclides. Kluwer Academic Publishers. Dordrecht. 219pp.

Zapata, F., and M. L. Nguyen. (2010). Soil erosion and sedimentation studies using environmental radionuclides, in Environmental Radionuclides: Tracers and Timers of Terrestrial Processes, edited by K. Froehlich, pp. 295–322, Elsevier, Amsterdam.

91

Zhang, G. H., Nearing, M. A., & Liu, B. Y. (2005). Potential effects of climate change on rainfall erosivity in the Yellow River basin of China. Transactions of the ASAE, 48(2), 511-517. Zhang, J., Wu, Y., Jennerjahn, T. C., Ittekkot, V., & He, Q. (2007). Distribution of organic matter in the Changjiang (Yangtze River) Estuary and their stable carbon and nitrogen isotopic ratios: Implications for source discrimination and sedimentary dynamics. Marine Chemistry, 106(1-2), 111-126.

Zhang, R., He, J., Zhao, Y., Peng, Y., & Fu, L. (2013). Another Important Factor of Rising Sea Level: Soil Erosion. CLEAN–Soil, Air, Water, 41(2), 174-178.

Zhang, S., Fan, W., Li, Y., and Yi, Y. (2016). The influence of changes in land use and landscape patterns on soil erosion in a watershed. Science of the Total Environment 574, 34–45.

Zhang, X., Walling, D. E. (2005). Characterizing land surface erosion from cesium-137 profiles in lake and reservoir sediments. J Environ Qual 34:514–523

92

APPENDICES

Appendix A

Two way ANOVA Turkey post hoc test using SPSS

Table A1: Stable isotope carbon and nitrogen descriptive statistics between rivers.

River Mean Std. Deviation N Brok -26.8117 1.46132 6 Betis -24.8983 .98231 6 Nenggiri -26.0833 1.27462 6 Galas -27.3567 .60378 6 Carbon Pergau -27.1250 .83949 6 Lebir -27.9900 .88000 6 Kelantan -28.2150 .82024 6 Total -26.9257 1.42561 42 Brok 1.4767 2.47693 6 Betis 2.2600 1.81625 6 Nenggiri .7033 2.73572 6 Galas 1.5083 2.63288 6 Nitrogen Pergau 2.5050 .90206 6 Lebir 3.4567 2.62716 6 Kelantan 2.1000 2.49057 6 Total 2.0014 2.29927 42

Table A2: Turkey test for stable isotope carbon at different Kelantan river sediments

Tukey HSDa,b,c River N Subset a b c Kelantan 6 -28.2150 Lebir 6 -27.9900 Galas 6 -27.3567 -27.3567 Pergau 6 -27.1250 -27.1250 Brok 6 -26.8117 -26.8117 Nenggiri 6 -26.0833 -26.0833 Betis 6 -24.8983 Sig. .233 .338 .422

93

Means for groups in homogeneous subsets are displayed. Based on observed means. The error term is Mean Square (Error) = 1.035. a. Uses Harmonic Mean Sample Size = 6.000. b. The group sizes are unequal. The harmonic mean of the group sizes is used. Type I error levels are not guaranteed. c. Alpha = .05. Table A3: Turkey test for stable isotope nitrogen at different Kelantan river sediments

Tukey HSDa,b,c River N Subset a Nenggiri 6 .7033 Brok 6 1.4767 Galas 6 1.5083 Kelantan 6 2.1000 Betis 6 2.2600 Pergau 6 2.5050 Lebir 6 3.4567 Sig. .402

Means for groups in homogeneous subsets are displayed. Based on observed means. The error term is Mean Square (Error) = 5.396. a. Uses Harmonic Mean Sample Size = 6.000. b. The group sizes are unequal. The harmonic mean of the group sizes is used. Type I error levels are not guaranteed. c. Alpha = .05.

94

Table A4: Turkey test multiple comparison between locations.

Multiple Comparisons Tukey HSD Dependent (I) River (J) River Mean Std. Sig. 95% Confidence Variable Difference Error Interval (I-J) Lower Upper Bound Bound Betis -1.9133* .58723 .036 -3.7490 -.0777 Nenggiri -.7283 .58723 .873 -2.5640 1.1073 Galas .5450 .58723 .965 -1.2906 2.3806 Brok Pergau .3133 .58723 .998 -1.5223 2.1490 Lebir 1.1783 .58723 .429 -.6573 3.0140 Kelantan 1.4033 .58723 .233 -.4323 3.2390 Brok 1.9133* .58723 .036 .0777 3.7490 Nenggiri 1.1850 .58723 .422 -.6506 3.0206 Galas 2.4583* .58723 .003 .6227 4.2940 Betis Pergau 2.2267* .58723 .009 .3910 4.0623 Lebir 3.0917* .58723 .000 1.2560 4.9273 Kelantan 3.3167* .58723 .000 1.4810 5.1523 Brok .7283 .58723 .873 -1.1073 2.5640 Betis -1.1850 .58723 .422 -3.0206 .6506 Galas 1.2733 .58723 .338 -.5623 3.1090 Nenggiri Pergau 1.0417 .58723 .573 -.7940 2.8773 Lebir 1.9067* .58723 .037 .0710 3.7423 Carbon Kelantan 2.1317* .58723 .014 .2960 3.9673 Brok -.5450 .58723 .965 -2.3806 1.2906 Betis -2.4583* .58723 .003 -4.2940 -.6227 Nenggiri -1.2733 .58723 .338 -3.1090 .5623 Galas Pergau -.2317 .58723 1.000 -2.0673 1.6040 Lebir .6333 .58723 .930 -1.2023 2.4690 Kelantan .8583 .58723 .765 -.9773 2.6940 Brok -.3133 .58723 .998 -2.1490 1.5223 Betis -2.2267* .58723 .009 -4.0623 -.3910 Nenggiri -1.0417 .58723 .573 -2.8773 .7940 Pergau Galas .2317 .58723 1.000 -1.6040 2.0673 Lebir .8650 .58723 .758 -.9706 2.7006 Kelantan 1.0900 .58723 .521 -.7456 2.9256 Brok -1.1783 .58723 .429 -3.0140 .6573 Betis -3.0917* .58723 .000 -4.9273 -1.2560 Lebir Nenggiri -1.9067* .58723 .037 -3.7423 -.0710 Galas -.6333 .58723 .930 -2.4690 1.2023

95

Pergau -.8650 .58723 .758 -2.7006 .9706 Kelantan .2250 .58723 1.000 -1.6106 2.0606 Brok -1.4033 .58723 .233 -3.2390 .4323 Betis -3.3167* .58723 .000 -5.1523 -1.4810 Nenggiri -2.1317* .58723 .014 -3.9673 -.2960 Kelantan Galas -.8583 .58723 .765 -2.6940 .9773 Pergau -1.0900 .58723 .521 -2.9256 .7456 Lebir -.2250 .58723 1.000 -2.0606 1.6106 Betis -.7833 1.34109 .997 -4.9755 3.4088 Nenggiri .7733 1.34109 .997 -3.4188 4.9655 Galas -.0317 1.34109 1.000 -4.2238 4.1605 Brok Pergau -1.0283 1.34109 .987 -5.2205 3.1638 Lebir -1.9800 1.34109 .756 -6.1722 2.2122 Kelantan -.6233 1.34109 .999 -4.8155 3.5688 Brok .7833 1.34109 .997 -3.4088 4.9755 Nenggiri 1.5567 1.34109 .904 -2.6355 5.7488 Galas .7517 1.34109 .998 -3.4405 4.9438 Betis Pergau -.2450 1.34109 1.000 -4.4372 3.9472 Lebir -1.1967 1.34109 .971 -5.3888 2.9955 Kelantan .1600 1.34109 1.000 -4.0322 4.3522 Brok -.7733 1.34109 .997 -4.9655 3.4188 Betis -1.5567 1.34109 .904 -5.7488 2.6355 Galas -.8050 1.34109 .996 -4.9972 3.3872 Nenggiri Pergau -1.8017 1.34109 .827 -5.9938 2.3905 Nitrogen Lebir -2.7533 1.34109 .402 -6.9455 1.4388 Kelantan -1.3967 1.34109 .940 -5.5888 2.7955 Brok .0317 1.34109 1.000 -4.1605 4.2238 Betis -.7517 1.34109 .998 -4.9438 3.4405 Nenggiri .8050 1.34109 .996 -3.3872 4.9972 Galas Pergau -.9967 1.34109 .989 -5.1888 3.1955 Lebir -1.9483 1.34109 .770 -6.1405 2.2438 Kelantan -.5917 1.34109 .999 -4.7838 3.6005 Brok 1.0283 1.34109 .987 -3.1638 5.2205 Betis .2450 1.34109 1.000 -3.9472 4.4372 Nenggiri 1.8017 1.34109 .827 -2.3905 5.9938 Pergau Galas .9967 1.34109 .989 -3.1955 5.1888 Lebir -.9517 1.34109 .991 -5.1438 3.2405 Kelantan .4050 1.34109 1.000 -3.7872 4.5972 Brok 1.9800 1.34109 .756 -2.2122 6.1722 Lebir Betis 1.1967 1.34109 .971 -2.9955 5.3888 Nenggiri 2.7533 1.34109 .402 -1.4388 6.9455

96

Galas 1.9483 1.34109 .770 -2.2438 6.1405 Pergau .9517 1.34109 .991 -3.2405 5.1438 Kelantan 1.3567 1.34109 .948 -2.8355 5.5488 Brok .6233 1.34109 .999 -3.5688 4.8155 Betis -.1600 1.34109 1.000 -4.3522 4.0322 Nenggiri 1.3967 1.34109 .940 -2.7955 5.5888 Kelantan Galas .5917 1.34109 .999 -3.6005 4.7838 Pergau -.4050 1.34109 1.000 -4.5972 3.7872 Lebir -1.3567 1.34109 .948 -5.5488 2.8355 Based on observed means. The error term is Mean Square (Error) = 5.396. *. The mean difference is significant at the .05 level.

97