Bioremoval of copper and nickel on living and non-living Euglena gracilis A Thesis Submitted in ...

94 Pages·2016·1.87 MB·English

1 Bioremoval of copper and nickel on living and non-living Euglena gracilis
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5 A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of Master
6 of Science in the Faculty of Arts and Sciences
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13 TRENT UNIVERSITY
14 Peterborough, Ontario, Canada
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21 Environmental and Life Sciences MSc. Graduate Program
22 April 2016
23 © Cameron Winters 2016
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25 Abstract
26 Bioremoval of Copper and Nickel on living and non-living Euglena gracilis
27 Cam Winters 2016
28 This study assesses the ability of a unicellular protist, Euglena gracilis, to remove
29 Cu and Ni from solution in mono- and bi-metallic systems. Living Euglena cells and
30 non-living Euglena biomass were examined for their capacity to sorb metal ions.
31 Adsorption isotherms were used in batch systems to describe the kinetic and equilibrium
32 characteristics of metal removal. In living systems results indicate that the sorption
33 reaction occurs quickly (<30 min) in both Cu (II) and Ni (II) mono-metallic systems and
34 adsorption follows a pseudo-second order kinetics model for both metals. Sorption
35 capacity and intensity was greater for Cu than Ni (p < 0.05) and were described by the
36 Freundlich model. In bi-metallic systems sorption of both metals appears equivalent. In
37 non-living systems sorption occurred quickly (10-30 min) and both Cu and Ni
38 equilibrium uptake increased with a concurrent increase of initial metal concentrations.
39 The pseudo-first-order model was applied to the kinetic data and the Langmuir and
40 Freundlich models effectively described single-metal systems. The biosorption capacity
41 of Cu (II) and) was 3x times greater than that of Ni (II). Sorption of one metal in the
42 presence of relatively high concentrations of the other metal was supressed. Generally,
43 it was found that living Euglena remove Cu and Ni more efficiently than non-living
44 Euglena biomass in both mono- and bi-metallic systems. It is anticipated that this work
45 should contribute to the identification of baseline uptake parameters and capacities for Cu
46 and Ni by Euglena as well as to the increasing amount of research investigating
47 sustainable bioremediation.
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48 Keywords: biosorption, kinetics, Cu, Ni, accumulation, bioremediation, Euglena gracilis
49 Acknowledgements
50 I would like to offer my sincere thanks to my supervisor Dr. Céline Guéguen for
51 her guidance and support of this work. It has been my pleasure to work in her laboratory
52 and I am thankful for her clear perspective and valuable counsel. My thanks go also to
53 supervisory committee members Dr. Eric Sager and Dr. Neil Emery both for their time
54 and advice regarding the work. Additionally, I would like to thank Dr. Sager for his
55 friendship and guidance throughout my undergraduate and graduate studies. This work
56 would not have been possible without the assistance of Antoine Perroud whom I thank
57 for his ICPMS analysis and unfailingly good humour. I would also like to acknowledge
58 Jean- François Koprivnjak and the Water Quality Centre at Trent University for
59 assistance and expertise. My thanks also go to Noble Purification Inc. for their support
60 and encouragement of this project. Financial support from the Ontario Centre for
61 Excellence, NSERC, and the Canada Research Chair program is greatly appreciated . I
62 must also thank all my colleagues in the lab, especially Vaughn Mangal, Yong Xiang Shi,
63 and Chad Cuss for their valuable input and friendship. Finally, I thank my parents for
64 their abiding patience, love, and support over the course of this endeavour. It means
65 more than words can say, and I dedicate this work to you both.
66 Authors’ contributions
67 CW and CG developed study design and CG contributed revisions for all chapters. CW
68 collected and analyzed the data and wrote the first draft of all manuscripts. AN provided
69 technical and financial support for Chapter 2. All authors read and approved final drafts.
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70 Table of Contents
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72 Chapter 1: General Introduction
73 1 Metal pollution ............................................................................................................ v
74 2 Ecological and Human Health Effects of Metals ........................................................ 2
75 3 Conventional Methods of Metal Remediation ............................................................. 2
76 4 Bioremediation: an alternative method for metal removal .......................................... 5
77 5 Euglena gracilis: a potential biosorbent for metal remediation ................................ 13
78 6 Thesis objectives........................................................................................................ 14
79 References ......................................................................................................................... 18
80 Chapter 2: Equilibrium and kinetic studies of Cu (II) and Ni (II) sorption and
81 accumulation on living Euglena gracilis
82 Abstract ..................................................................................................................... 26
83 1 Introduction ............................................................................................................... 27
84 2 Materials and Methods .............................................................................................. 28
85 3 Results and Discussion .............................................................................................. 34
86 4 Conclusions ............................................................................................................... 39
87 References ......................................................................................................................... 41
88 Chapter 3: Equilibrium and kinetic studies of Cu (II) and Ni (II) biosorption on non-
89 living Euglena gracilis
90 Abstract ..................................................................................................................... 51
91 1 Introduction ............................................................................................................... 52
92 2 Materials and Methods .............................................................................................. 56
93 3 Results and Discussion .............................................................................................. 60
94 4 Conclusion ................................................................................................................. 64
95 Chapter 4: General Conclusion ......................................................................................... 78
96 1 Euglena biomass characterization and toxicity ......................................................... 78
97 2 Sorption kinetics ....................................................................................................... 79
98 3 Sorption Isotherms .................................................................................................... 80
99 4 Significance of the work ........................................................................................... 83
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101 List of Figures
102 Chapter 1:
103 Figure 1: Euglena gracilis at 400x magnification
104 Figure 2: Growth curve for Euglena gracilis
105 Chapter 2:
106 Figure 1: Experimental data for EC50 toxicity assay on living E. gracilis
2+ 2+
107 for (a) Cu and (b) Ni
2+
108 Figure 2: Experimental data for Cu sorption kinetics on living E. gracilis
-1 -1
109 at initial concentrations of (a) 20 ug L and (b) 50 ug L . Curves
110 represent pseudo-second-order kinetic model.
2+
111 Figure 3: Experimental data for Ni sorption kinetics on living E. gracilis
-1 -1
112 at initial concentrations of (a) 3 mg L and (b) 100 mg L . Curves
113 represent pseudo-second-order kinetic model.
2+ 2+
114 Figure 4: Experimental data for a) Cu and b) Ni sorption equilibrium
115 on living E. gracilis. Curve represents the Freundlich model.
2+ 2+
116 Figure 5: Experimental data for Cu and Ni sorption equilibrium from
117 binary-metal solution on living E. gracilis. Error bars represent SE.
118 Chapter 3:
119 Figure 1: FTIR spectra of dried euglena biomass
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120 Figure 2: Experimental data for Cu sorption kinetics on non-living E.
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121 gracilis at initial concentrations of (a) 20 ug L and (b) 50 ug L (c) 1 mg
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122 L (d) 25 mg L . Curves represent PFO (a, c) and PSO (b, d) kinetic
123 models.
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124 Figure 3: Experimental data for Ni sorption kinetics on non-living E.
-1 -1
125 gracilis at initial concentrations of (a) 1 mg L and (b) 2 mg L (c) 4 mg
-1 -1
126 L (d) 20 mg L . Curves represent PFO (b, d) and PSO (a, c) kinetic
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2+
128 Figure 4: Experimental data for Cu sorption equilibrium on non-living E.
129 gracilis. Curves represent the Freundlich and Langmuir models.
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2+
130 Figure 5: Experimental data for Ni sorption equilibrium on non-living E.
131 gracilis. Curves represent the Freundlich and Langmuir models.
2+ 2+
132 Figure 6: Experimental data for Cu and Ni sorption equilibrium from
133 binary-metal solution on living E. gracilis. Error bars represent SE.
134 Chapter 4:
135 Figure 1: Percentage metal removal of Cu and Ni in mono-metallic and bi-
136 metallic solutions by living and non-living E. gracilis.
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149 List of Tables
150 Chapter 2:
151 Table 1: Pseudo-second-order kinetics parameters for the sorption of
2+ 2+
152 Cu and Ni on living Euglena gracilis cells (±SE).
153 Table 2: Freundlich adsorption isotherm parameters for the sorption of
2+ 2+
154 Cu and Ni on living Euglena gracilis cells at pH 5.
155 Chapter 3:
156 Table 1: Kinetic model parameters for the biosorption of Cu on non-living
157 Euglena gracilis cells – pseudo-first-order model.
158 Table 2: Kinetic model parameters for the biosorption of Ni on non-living
159 Euglena gracilis cells – pseudo-first-order model.
160 Table 3: Langmuir adsorption isotherm parameters for the biosorption of
161 Cu and Ni on non-living Euglena gracilis cells at pH 5.
162 Table 4: Freundlich adsorption isotherm parameters for the biosorption of
163 Cu and Ni on non-living Euglena gracilis cells at pH 5.
164 Chapter 4:
165 Table 1: Kinetic parameters of biosorbents for Cu and Ni in mono-metallic
166 systems.
167 Table 2: Equilibrium parameters of biosorbents for Cu and Ni in mono-
168 metallic systems.
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173 1 Metal pollution
174 Globally, freshwater resources are subjected to steadily increasing demands for
175 withdrawal which are occurring concurrently with rising rates of development,
176 industrialization, and population growth. This demand has been projected to increase by
177 a factor of 55% by 2050 and the strain which this requirement will induce on existent
178 reserves of freshwater could result in greater than 40% of the global population living in
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179 areas of acute water stress by the middle of the 21 century (Miletto, 2015).
180 Additionally, that water which is put to anthropogenic uses, domestically, agriculturally
181 or industrially, may not return to natural reserves, or if so, may be contaminated or
182 degraded to an extent which serves to preclude human consumption and poses risks to
183 ecosystem health. Metal pollution is a global concern in terms of freshwater
184 contamination (ie. further reducing available stock) and has serious ramifications in both
185 the developed and developing world (Akpor and Muchie, 2010; Kumar et al., 2015;
186 Vijayaraghavan and Balasubramanian, 2015). The chemical properties of metals are
187 such that even at dilute concentrations, levels of contaminants are persistent in the
188 environment to an extent that bioaccumulation and/or biomagnification can promulgate
189 toxic effects throughout the food web including the human body (Kumar et al., 2015). It
190 is evident therefore, that a need exists to not only judiciously manage water usage, but
191 also to develop methods for the remediation of contaminated water if the expected
192 demand for this resource is to be met.
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194 2 Ecological and Human Health Effects of Metals
195 This demand for water is driven in large part by the needs of the global
196 manufacturing sector, which, by 2050, are expected to rise by 400% (Miletto, 2015). The
197 effluent produced by these industries (ie. electroplating, milling, circuit board printing,
198 petroleum refining, wood processing, mining) has been identified as a key source of
199 pollutants that enter water bodies and include metals such as arsenic, cadmium,
200 chromium, copper, cobalt, iron, lead, mercury, nickel and zinc (Barakat, 2011). Metals
201 are commonly divided into two general categories; trace elements which are required for
202 biological function but are toxic at higher concentrations (e.g. Cu, Ni, Co, Zn) and those
203 which have no known nutritional significance yet remain highly toxic (e.g. Pb, Cd, Hg,
204 Cr) (Herrera-Estrella et al., 2009). Metals which are essential to physiological function
205 are controlled via a network of intracellular biochemical processes that serve to maintain
206 an appropriate osmotic balance (Albergoni et al., 1980; Piccinni, 1989). Those metals
207 which are not involved in homeostatic maintenance (e.g. non-essential) and tend to be
208 compartmentalized within cell vesicles and/or organelles and therefore provide a pathway
209 for toxic species to bio-accumulate (Devars et al., 2000). This persistence and
210 circulation of metals in the environment pose a threat to the well-being of plant and
211 animal life and consequently, via food-web connections, to human health.
212 3 Conventional Methods of Metal Remediation
213 Rising population growth and continued extraction of natural resources ensure
214 that the discharge of metal effluent to ecosystems will remain an environmental priority
215 both in Canada and across the globe. Conventional methods of treatment of industrial
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