Table Of ContentMatoug, Ibrahim Omar Madi (2012) Analysis of suspended solids in river
water to assess their role in metal transport.
PhD thesis.
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Analysis of Suspended Solids in River Water to Assess Their Role in
Metal Transport
IBRAHIM OMAR MADI MATOUG
Thesis submitted for the degree of Doctor of Philosophy
November 2011
Environmental, Agricultural and Analytical Chemistry
School of Chemistry
College of Science and Engineering
University of Glasgow
Glasgow G12 8QQ
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In the Name of Allah, the Most Compassionate, the Most Merciful
(cid:1)(cid:2)(cid:3)و (cid:6)(cid:7)(cid:2)(cid:8) (cid:9)ا (cid:11)(cid:2)(cid:12) (cid:13)(cid:14)(cid:15)(cid:16)
(cid:19)(cid:29)(cid:13)(cid:7)(cid:3) (cid:1)(cid:30)(cid:31) (cid:21)ا (cid:19)(cid:20)(cid:21)!(cid:3)ر (cid:11)(cid:21)إ "(cid:2)#(cid:21)ا (cid:13)(cid:7)(cid:3) (cid:11)(cid:21)إ (cid:6)(cid:7)(cid:8)(cid:2)(cid:3)(cid:9)(cid:8)(cid:4)ا (cid:1)(cid:2)(cid:11) ي(cid:13)(cid:4)ا (cid:14)(cid:15)(cid:16)ا (cid:11)(cid:21)إ (cid:23)(cid:24)(cid:25)(cid:26)(cid:14)(cid:21)ا م(cid:19)(cid:16)(cid:28)او (cid:1)(cid:2)(cid:3)(cid:4)ا ةر(cid:19)(cid:20)(cid:16) (cid:11)(cid:21)إ
My Mother and father
Love & Inspiration
(cid:14)(cid:17)او (cid:14)(cid:15)ا (cid:19)(cid:4)ا
ن(cid:19)%(cid:31)(cid:8)و &'و (cid:31) (
Abstract
The contamination by metals present in surface water causes problems to human health. The
ultimate aim of this work is to determine the role of fine suspended sediment to the transport
of metals in rivers. During the work, the ability of fine suspended sediment to carry a range of
metals in the river water in different seasons was measured in different samples.
Suspended sediment carries a substantial proportion of the metals in river water. The
distribution of suspended particles is an important factor in controlling the availability of
metals in the river water. Dissolved form, and adsorbed to the surface coating of suspended
particulate matter are two ways to transport metals in rivers. Firstly, the work was carried out
in the laboratory, using suspended sediment components, to assess metal uptake by different
components, while later studies utilized natural suspended sediment to study metal transport in
real situations. The water samples were taken for this research from tributaries of the River
Kelvin; Craigton Burn, Allander Water, Craigmaddie, Glazert Water, Bothlin Burn, Luggie
Burn, and Cameron Burn. The research tries to evaluate the concentrations of Ca, Fe, K, Mg,
Mn, and Zn in suspended particles in these tributaries. The technique used two filters 1.2 µm
and 0.2 µm to collect the suspended sediment from water samples. Some representative
samples of kaolinite, bentonite, humic acid and iron oxides were used in the laboratory based
studies to improve understanding the distribution of the heavy metals Cu, Pb and Zn between
metals sorbed on the solid phase and metal `in the solution phase. The adsorption of the heavy
metals Cu, Pb and Zn shows different response between these materials. In addition, the
experiments were carried out to measure the distribution of copper, lead, and zinc between an
aqueous phase and solid phase of mixed materials (composite) sediment.
The results demonstrate that the fluvial system is one of the major modes of dispersing and
transporting metals from soil and parent rocks. The overall results indicated that the large and
fine particle sizes carry significant metals concentrations in the river system. The investigation
of the suspended sediment phases offers additional information and understanding of the
movement and behavior of metals within river water. The concentration of the particles > 1.2
µm is higher than that in the fine particles 1.2 and 0.2 µm diameter.
The format of this thesis;-
Chapter (1) Introduction. This chapter introduces background information that is important to
the research, such as the choice of metals, the suspended particulates, and the relationship
between them. Chapter (2). This chapter describes the method used to prepare suspended
sediment of the components; the sampling sites and the sampling techniques, and the sample
3
preparation and analysis process. Chapter (3). This chapter describes the different filter paper
materials used in this study, and describes the analytical methods that were common with the
different filter papers in the experiment. Chapter (4). This chapter describes the distribution of
the heavy metals Cu, Pb and Zn between sorption in the solid phase and in the solution phase
for single adsorbent system material and for a mixed adsorbent system. Chapter (5) This
chapter explores the role of suspended sediment in the transport of metals in tributaries of the
River Kelvin. Chapter (6) contains the Conclusion and suggestion for future work.
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Table of contents
Abstract 3
Table of Contents 5
List of Figures 8
List of Tables 12
Acknowledgement 15
Declaration....................................................................................................................................17
ABBREVIATIONS......................................................................................................................18
Chapter 1.......................................................................................................................................19
1.1 Metals in the Environment........................................................................................19
1.1.1 Sources of metals..............................................................................................19
1.1.2 Metals in the air.................................................................................................22
1.1.3 Metals in soil.....................................................................................................23
1.1.4 Metals in water..................................................................................................24
1.1.5 Metals in river systems......................................................................................24
1.2 The nature of suspended particles in rivers...............................................................26
1.2.1 The origin of suspended particles.....................................................................26
1.2.2 Physical characteristics of the suspended particles...........................................27
1.2.3 Particle transport in rivers.................................................................................30
1.3 The role of suspended particles in the transport of metals........................................32
1.3.1 Metals in suspended sediment...........................................................................32
1.4 Environmetal chemistry of metals studied................................................................33
1.4.1 Calcium.............................................................................................................33
1.4.2 Copper...............................................................................................................34
1.4.3 Iron....................................................................................................................34
1.4.4 Lead...................................................................................................................35
1.4.5 Magnesium........................................................................................................36
1.4.6 Manganese.........................................................................................................36
1.4.7 Potassium..........................................................................................................36
1.4.8 Zinc...................................................................................................................37
1.5 Sampling and analysis of suspended aquatic particles..............................................38
1.5.1 Water sampling methods...................................................................................38
1.5.2 Collection and concentration of suspended sediment.......................................38
1.5.3 Tangential flow filtration..................................................................................39
1.5.4 Centrifugation...................................................................................................39
1.5.5 Continuous flow centrifugation.........................................................................39
1.6 Methods for particulate fraction collection and metals analysis...............................40
1.6.1 Analytical techniques........................................................................................40
1.6.2 Flame atomic absorption spectrometry.............................................................42
1.7 Research aim and objectives.....................................................................................44
1.7.1 Aims..................................................................................................................44
1.7.2 Objective...........................................................................................................44
Chapter 2.......................................................................................................................................45
Materials and Methods..................................................................................................................45
2.1 Filtration procedures.................................................................................................45
2.1.1 Routine methods...............................................................................................45
2.1.2 Filter papers.......................................................................................................45
2.1.3 Pump.................................................................................................................45
2.1.4 Reagents............................................................................................................45
2.2 Digestion procedures.................................................................................................47
2.2.1 Aqua regia digestion for pseudo total metal concentration...............................47
2.2.2 Preparation of AAS standards solutions...........................................................48
2.2.3 Measurement.....................................................................................................48
2.2.4 Measurement of the sample..............................................................................48
2.3 Measurement procedure............................................................................................49
2.3.1 Atomic Absorption Spectrometry (AAS) Measurement...................................49
2.3.2 Detection Limit (DL)........................................................................................50
2.3.3 Flame photometry.............................................................................................50
2.4 Sampling procedures and sampling and analyses.....................................................51
2.4.1 Sampling Methods – Field sampling................................................................51
2.4.2 River Catchment................................................................................................51
2.4.3 Sample collection...................................................................................................58
2.4.4 Preparing the sample.........................................................................................58
2.4.5 Filtration using 47 mm diameter, 1.2 m m pore-size micro-fibre filters (acid
treated low metal)..............................................................................................................58
2.4.6 Filtration using 90 mm diameter, 0.2 µm pore-size nylon membrane filter.....59
2.5 Laboratory studies using defined sediment components..........................................59
2.5.1 Studies of individual components.....................................................................60
2.5.2 Studies of mixed systems..................................................................................60
Chapter 3.......................................................................................................................................62
Selection of filter papers for collection of suspended aquatic particles................................62
3.1 Introduction...............................................................................................................62
3.2 47 mm diameter, 1.2 m m pore-size micro-fibre filters..................................................63
3.2.1 Digestion and measurement..............................................................................63
3.3 125 mm diameter, 1.2 m m pore-size micro-fibre filters................................................64
3.3.1 Digestion and measurement..............................................................................64
3.3.2 Acid treatment of 125 mm diameter, 1.2 m m pore-size micro-fibre filters.......65
3.4 47 mm diameter, 1.2 m m pore-size micro-fibre filters (Acid Treated low Metal)....67
3.4.1 Digestion and measurement..............................................................................68
3.5 47 mm diameter 0.2 m m pore size Membrane Filters Nylon....................................69
3.6 90 mm diameter 0.2 m m pore size Nylon Membrane Filters........................................69
3.7 Discussion:................................................................................................................69
3.8 Conclusion................................................................................................................71
Chapter 4.......................................................................................................................................72
4.1 Introduction...............................................................................................................72
4.1.1 Heavy metal sorption behaviour of suspended kaolinite..................................73
4.1.2 Heavy metal sorption behaviour of suspended bentonite.................................76
4.1.3 Heavy metal sorption behaviour of suspended iron oxide (goethite)......................78
4.1.4 Heavy metal sorption behaviour of suspended humic acid...............................80
4.1.5 Conclusion........................................................................................................82
4.2 The model substrates mixed (composite) sample...........................................................83
4.2.1 Heavy metal sorption behaviour of suspended materials kaolinite and iron oxide
(goethite)...........................................................................................................................83
4.2.2 Heavy metal sorption behaviour of suspended materials kaolinite and bentonite...89
4.2.3 Heavy metal sorption behaviour of suspended materials kaolinite and humic acid 92
6
4.2.4 Heavy metal sorption behaviour of suspended materials bentonite and iron oxide
(goethite)...........................................................................................................................94
4.2.5 Heavy metal sorption behaviour of suspended materials bentonite and humic acid98
4.2.6 Heavy metal sorption behaviour of suspended materials iron oxide and humic acid
.........................................................................................................................................100
4.2.7 Discussion............................................................................................................103
4.2.8 Conclusion......................................................................................................104
Chapter 5.....................................................................................................................................105
5 River Water Samples...........................................................................................................105
5.1 The suspended sediment weight..............................................................................108
5.1.1 Conclusion......................................................................................................121
5.2 River Water Samples – metal concentrations in suspended sediment....................122
5.2.1 Discussion.......................................................................................................155
5.2.2 Conclusion......................................................................................................159
5.3 River Water Samples – Sediment weight per unit volume of water.......................160
5.3.1 Discussion.......................................................................................................188
5.3.2 Conclusion......................................................................................................190
6 Conclusions and Future work.............................................................................................191
APPENDICES............................................................................................................................210
Appendix 1..........................................................................................................................210
Appendix 2..........................................................................................................................212
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List of Figures
Figure 1-1 Natural and Anthropogenic sources of the heavy metals (Foster and Charleworth, 1996)..............20
Figure 1- 2 The kaolinite structure (White, 2006)..................................................................................................28
Figure 1-3 The bentonite structure (White, 2006)..................................................................................................29
Figure 1-4 Distribution of mineral and organic colloids as a function of size in aquatic systems (Buffle and
Leppard, 1995).................................................................................................................................................31
Figure 2-1 Pump Buchi Vac. V-511, used for prepareation of the sample...........................................................47
Figure 2-2 the tributaries of Kelvin River (SEPA, River Kelvin catchment monitoring Years; 2002-2005).....52
Figure 2-3 Craigton Burn, Allander water (Google-Image@2011 Infoterra Ltd and Blusky, GeoEye)............53
Figure 2- 4 Sampling site, left Craigton Burn, right Allander water....................................................................53
Figure 2-5 Sampling site Craigmaddie Burn (Google-Image@2011 Infoterra Ltd and Blusky, GeoEye)........54
Figure 2-6 Sampling site Craigmaddie Burn...........................................................................................................54
Figure 2- 7 Glazert water (Google-Image@2011 Infoterra Ltd and Blusky, GeoEye)........................................55
Figure 2- 8 Sampling site Glazert water..................................................................................................................55
Figure 2-9 Luggie Burn (Google-Image@2011 Infoterra Ltd and Blusky, GeoEye)...........................................56
Figure 2-10 Sampling site Luggie Burn...................................................................................................................56
Figure 2-11 Bothlin Burn (Google-Image@2011 Infoterra Ltd and Blusky, GeoEye).......................................57
Figure 2- 12 Bothlin Burn sampling site..................................................................................................................57
Figure 4-1 weight of Cu (mg) measured on soild phase and in the prediction model..........................................88
Figure 5- 2 Mass of suspended sediment (g/ l) in the > 1.2 µm and 1.2 µm - 0.2 µm diameter size fractions
from Allander water......................................................................................................................................110
Figure 5- 3 Variation of mass of suspended sediment (g/ l) with flow rate of water for the > 1.2 µm and in the
range 1.2 µm to 0.2 µm sediment from Allander Water.............................................................................111
Figure 5- 4 Mass of suspended sediment (g/ l) in the > 1.2 µm and in the 1.2 - 0.2 µm fractions from Craigton
Burn and Allander Water.............................................................................................................................112
Figure 5- 5 Mass of suspended sediment (g/ l) in the > 1.2 µm and in the range 1.2 µm to 0.2 µm from
Craigmaddie Burn.........................................................................................................................................112
Figure 5- 6 Mass of suspended sediment (g/ l) in the > 1.2 µm and in the range 1.2 – 0.2 µm diameter size
fractions from Glazert water.........................................................................................................................113
Figure 5- 7 Variation of mass of suspended sediment (g/ l) with flow rate of water for the > 1.2 µm and in the
range 1.2 µm to 0.2 µm sediment from Glazert Water...............................................................................114
Figure 5- 8 Mass of suspended sediment (g/ l) water in the > 1.2 µm and in the 1.2 – 0.2 µm fractions from
Bothlin Burn...................................................................................................................................................115
Figure 5- 9 Variation of mass of suspended sediment (g/ l) with flow rate of water for the > 1.2 µm and in the
range 1.2 µm to 0.2 µm sediment from Bothlin Burn.................................................................................115
Figure 5- 10 Mass of suspended sediment (g/ l) water in the > 1.2 µm and in the range 1.2 µm to 0.2 µm from
Luggie Burn....................................................................................................................................................116
Figure 5- 11Variation of mass of suspended sediment (g/ l) with flow rate of water for the > 1.2 µm and in the
range 1.2 µm to 0.2 µm sediment from Luggie Burn..................................................................................116
Figure 5- 12 Mass of suspended sediment (g/ l) water the > 1.2 µm and in the range 1.2 µm to 0.2 µm diameter
size fractions from Bothlin Burn and Luggie Burn.....................................................................................117
Figure 5- 13 Mass of suspended sediment (g/ l) in the > 1.2 µm diameter size fraction from Craigmaddie
Burn, Glazert water, Bothlin Burn and Luggie Burn.................................................................................118
Figure 5- 14 Mass of suspended sediment (g/ l) in the 1.2 - 0.2 µm diameter size fraction from Craigmaddie
Burn, Glazert water, Bothlin Burn and Luggie Burn.................................................................................119
Figure 5- 15 Mass of suspended sediment in litre of water in the > 1.2 µm and 1.2 – 0.2 µm diameter size
fractions from Cameron Burn (g/ l)..............................................................................................................119
Figure 5- 16 Mass of suspended sediment (g/ l) in the > 1.2 µm and in the range 1.2 – 0.2 µm diameter size
fractions near to land fill discharge to Cameron Burn...............................................................................120
Figure 5- 17 Concentrations of Ca in suspended sediment (mg /g) of > 1.2 µm diameter from Craigton Burn.
.........................................................................................................................................................................123
8
Figure 5- 18 Concentrations of Fe, K, and Mg in suspended sediment (mg /g) of > 1.2 µm diameter from
Craigton Burn................................................................................................................................................123
Figure 5- 19 Concentrations of Mn and Zn in suspended sediment (mg /g) of > 1.2 µm diameter from
Craigton Burn................................................................................................................................................123
Figure 5- 20 Concentrations of Fe and Ca in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from
Craigton Burn................................................................................................................................................126
Figure 5- 21 Concentrations of K and Mg in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Craigton Burn................................................................................................................................................126
Figure 5- 22 Concentrations of Mn and Zn in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from
Craigton Burn................................................................................................................................................126
Figure 5- 23 Concentrations of Ca, Fe, K, and Mg in suspended sediment (mg /g) of > 1.2 µm diameter from
Allander Water...............................................................................................................................................130
Figure 5- 24 Concentrations of Mn, and Zn in suspended sediment (mg/g) of > 1.2 µm diameter from
Allander Water...............................................................................................................................................130
Figure 5- 25 Concentrations of Fe and Ca in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Allander Water...............................................................................................................................................131
Figure 5- 26 Concentrations of K, and Mg in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Allander Water...............................................................................................................................................131
Figure 5- 27 Concentrations of Mn and Zn in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from
Allander Water...............................................................................................................................................131
Figure 5- 28 Concentrations of Fe, Ca, and Mg in suspended sediment (mg/g) of > 1.2 µm diameter from
Craigmaddie Burn.........................................................................................................................................134
Figure 5- 29 Concentrations of K, Mn, and Zn in suspended sediment (mg /g) of > 1.2 µm diameter from
Craigmaddie Burn.........................................................................................................................................134
Figure 5- 30 Concentrations of Fe and Ca in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Craigmaddie Burn.........................................................................................................................................135
Figure 5- 31 Concentrations of Mg in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from Craigmaddie
Burn.................................................................................................................................................................135
Figure 5- 32 Concentrations of K, Mn, and Zn in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Craigmaddie Burn.........................................................................................................................................135
Figure 5- 33 Concentrations of Fe, Ca, and Mg in suspended sediment (mg /g) of > 1.2 µm diameter from
Glazert Water.................................................................................................................................................139
Figure 5- 34 Concentrations of K, Mn and Zn in suspended sediment (mg /g) of > 1.2 µm diameter from
Glazert Water.................................................................................................................................................139
Figure 5- 35 Concentrations of Fe in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from Glazert
Water...............................................................................................................................................................140
Figure 5- 36 Concentrations of Ca, Mg, and Mn in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from
Glazert Water.................................................................................................................................................140
Figure 5- 37 Concentrations of K, and Zn in suspended sediment (mg /g) of (1.2- 0.2 µm) diameter from
Glazert Water.................................................................................................................................................140
Figure 5- 38 Concentrations of Ca in suspended sediment (mg /g) of > 1.2 µm diameter from Bothlin Burn.
.........................................................................................................................................................................143
Figure 5- 39 Concentrations of Fe, K, and Mg in suspended sediment (mg /g) of > 1.2 µm diameter from
Bothlin Burn...................................................................................................................................................143
Figure 5- 40 Concentrations of Mn and Zn in suspended sediment (mg /g) of > 1.2 µm diameter from Bothlin
Burn.................................................................................................................................................................143
Figure 5- 41 Concentrations of Fe and Ca in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Bothlin Burn...................................................................................................................................................144
Figure 5- 42 Concentrations of Mg in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from Bothlin
Burn.................................................................................................................................................................144
Figure 5- 43 Concentrations of K, Mn and Zn in suspended sediment (mg/g) of (1.2- 0.2 µm) diameter from
Bothlin Burn...................................................................................................................................................144
Figure 5- 44 Concentrations of Fe, Ca, K, and Mg in suspended sediment (mg/g) of > 1.2 µm diameter from
Luggie Burn....................................................................................................................................................146
Figure 5- 45 Concentrations of Mn, and Zn in suspended sediment (mg/g) of > 1.2 µm diameter from Luggie
Burn.................................................................................................................................................................146
9
Description:metals sorbed on the solid phase and metal `in the solution phase. The adsorption of the heavy metals Cu, Pb and Zn shows different response between these materials. In addition, the experiments were carried out to measure the distribution of copper, lead, and zinc between an aqueous phase and
