The Characterization of Algae Grown on Nutrient Removal Systems and Evaluation of Potential

241 Pages·2017·5.35 MB·English

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Dissertations Graduate College
8-2013
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Kristin Hampel
Western Michigan University, [email protected]
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Hampel, Kristin, "The Characterization of Algae Grown on Nutrient Removal Systems and Evaluation of
Potential Uses for the Resulting Biomass" (2013). Dissertations. 183.
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THE CHARACTERIZATION OF ALGAE GROWN ON NUTRIENT REMOVAL
SYSTEMS AND EVALUATION OF POTENTIAL USES FOR
THE RESULTING BIOMASS

by
Kristin Hampel

A dissertation submitted to the Graduate College
in partial fulfillment of the requirements
for the degree of Doctor of Philosophy
Chemistry
Western Michigan University
August 2013

Doctoral Committee:
John B. Miller, Ph.D., Chair
Steven B. Bertman, Ph.D.
Andre R. Venter, Ph.D.
Carla M. Koretsky, Ph.D.
THE CHARACTERIZATION OF ALGAE GROWN ON NUTRIENT REMOVAL
SYSTEMS AND EVALUATION OF POTENTIAL USES FOR
THE RESULTING BIOMASS

Kristin Hampel, Ph.D.

Western Michigan University, 2013

Eutrophication resulting from excess nutrient loads is a major environmental issue
that affects surface water quality and causes surplus primary production, thereby reducing
dissolved oxygen concentrations. A method for managing nutrients in surface waters
involves absorption of excess nutrients by deliberately cultivating benthic algal turf
biomass, then harvesting it for a variety of uses, including biofuels, soil amendments, or
feed supplements, thus coupling nutrient removal to additional economic drivers.
The goals of this work are to (1) evaluate the composition of algal biomass grown
to remove surface water nutrients, (2) compare biomass grown at different geographic
locations and in dissimilar water conditions, and (3) investigate uses for the biomass
products.
The algal biomasses harvested from a range of locations, were characterized by
measuring organic and inorganic carbon, nitrogen, phosphorus, and ash profiles. Algal
biomass grown on wastewater effluent has the highest nutrient content and lowest ash (40
wt% C, 7.0 wt% N, >1.0 wt% P, 32 wt% ash) while that grown in brackish water had the
lowest nutrient content and highest ash (10 wt% C, 1.0 wt% N, 0.13 wt% P, 79 wt% ash).
The algal turfs were also analyzed for silica and toxic metals. Silica in the algal turf was
partitioned into biogenic and terragenic origin. Algae harvested from freshwater locations
had ≤ 3.5 wt% biogenic silica while mixed fresh-salt water locations had biogenic silica
content ranging from 10-27 wt%. Metals composed 0.045 wt% to 0.075 % of the total dry
algal biomass, with relative concentrations of As > Cu ≈Cr > Co ≈ Mo > Cd.
The potential for using algal biomass as bio-ethanol feedstock was investigated by
quantifying the monosaccharides in freshwater algal turf, which include glucose,
galactose, xylose, mannose, ribose, and arabinose, varying from 2-30 % based on ash free
dry mass. The application of biochar made from algal biomass for sorption of
pharmaceuticals from water was assessed using model compounds. The order of sorption
was 2-[4-(2-methylpropyl)phenyl]propanoic acid ≈ 2,4-dinitroaniline > 2-phenylethanol
≈ 2-phenylethylamine.
Two commonly used analytical methods, the Boehm Titration and molybdenum
blue colorimetric method, were investigated for applicability to biomass analysis.
Systematic errors inherent in the methods indicate that they are inappropriate for
analyzing non-standard materials.
Copyright by
Kristin Hampel
2013
ACKNOWLEDGMENTS

I would like to express my deepest appreciation and gratitude to my advisors Dr.
John Miller and Dr. Steven Bertman, whose insight and continuous support helped guide
me throughout my studies. I would also like to thank them for being patient and giving
me the freedom to explore and develop my own ideas. Furthermore, I would like to thank
my committee members, Dr. Andre Venter and Dr. Carla Koretsky, for providing me
access to their expertise and challenging me to be a better scientist.
I would like to extend my sincere appreciation to my partner Nate for enduring
and supporting me though times of stress and frustration. I would also like to thank him
for his willingness to discuss and understand my research. Additionally, I would like to
acknowledge my mother and father for instilling in me a passion for knowledge and the
value of persistence.

Kristin Hampel

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TABLE OF CONTENTS
ACKNOWLEDGMENTS ...................................................................................... ii
LIST OF TABLES .................................................................................................. x
LIST OF FIGURES ............................................................................................... xii
LIST OF EQUATIONS .......................................................................................... xvii
CHAPTER
1 INTRODUCTION ...................................................................................... 1
1.1 Environmental Concerns ............................................................ 1
1.2 Reducing Nutrient Pollution and Mitigating Climate Change ... 4
1.3 Overview of Algae Based Nutrient Removal Technology ......... 5
1.4 Recycling of Algal Biomass ....................................................... 8
1.4.1 Food Applications .............................................................. 9
1.4.2 Animal Feed Applications ................................................. 10
1.4.3 Fertilizer Application ......................................................... 11
1.4.4 Additional Uses for Algal Biomass ................................... 12
1.5 Project Overview ........................................................................ 13
1.6 Objectives and Organization of Thesis ...................................... 20
1.7 Bibliography ............................................................................... 22
2 NUTRIENT ANALYSES OF ALGAL BIOMASS ................................... 28
2.1 Introduction ................................................................................ 28
iii
Table of Contents-Continued
CHAPTER
2.2 Experimental Details .................................................................. 30
2.3 Methods ...................................................................................... 31
2.3.1 Biomass Harvesting ........................................................... 31
2.3.2 Phosphorus Analysis by Colorimetry ................................ 32
2.3.3 Carbon, Hydrogen, and Nitrogen Analyses ....................... 35
2.3.4 Monosaccharide Analysis .................................................. 36
2.3.5 Quantitative Analyses ........................................................ 39
2.3.6 Floway Position Experiment .............................................. 39
2.3.7 Carbon Dioxide Addition Experiment ............................... 41
2.3.8 Water Analyses .................................................................. 42
2.4 Results and Discussion ............................................................... 43
2.4.1 CHN Analyses ................................................................... 43
2.4.2 Great Wicomico River Site ................................................ 48
2.4.3 York River Site .................................................................. 51
2.4.4 Lake Erie CHN Algae Analyses ........................................ 54
2.4.5 Monosaccharide Analyses ................................................. 56
2.4.6 Phosphorus Analyses ......................................................... 62
2.5 Summary .................................................................................... 69
2.6 Bibliography ............................................................................... 71

iv
Table of Contents-Continued
CHAPTER
3 SILICA, ASH, AND METAL CONTENT IN ALGAL BIOMASS .......... 74
3.1 Introduction ................................................................................ 74
3.1.1 Importance of Ash ............................................................. 74
3.1.2 Silica .................................................................................. 75
3.1.3 Metals ................................................................................. 77
3.2 Experimental Details .................................................................. 79
3.3 Methods ...................................................................................... 79
3.3.1 Ash Analyses ..................................................................... 79
3.3.2 Total Silica Analyses ......................................................... 80
3.3.3 Biogenic Silica Analyses ................................................... 81
3.3.4 Silica ICP Analyses ........................................................... 82
3.3.5 Biogenic Silica Results ...................................................... 82
3.3.6 Metal Analyses .................................................................. 83
3.3.7 Mass Balance ..................................................................... 84
3.4 Results and Discussion ............................................................... 85
3.4.1 Ash Analyses ..................................................................... 85
3.4.2 Total Silicon Dioxide Analyses ......................................... 87
3.4.3 Biogenic Silica ................................................................... 94
3.4.4 Heavy Metals ..................................................................... 101

v
Table of Contents-Continued
CHAPTER
3.4.5 Mass Balance ..................................................................... 110
3.5 Summary .................................................................................... 113
3.6 Bibliography ............................................................................... 114
4 BIOCHAR APPLICATION OF ALGAL BIOMASS ................................ 117
4.1 Introduction ................................................................................ 117
4.2 Experimental Details .................................................................. 119
4.3 Methods ...................................................................................... 120
4.3.1 Pre-treatment and Production of Biochar .......................... 120
4.3.2 Biochar Characterization ................................................... 122
4.3.3 Ash and Elemental Analyses ............................................. 124
4.3.4 Sorption Experiments ........................................................ 125
4.3.5 Quantitation ....................................................................... 128
4.3.6 Statistical Analyses ............................................................ 129
4.4 Discussion and Results ............................................................... 129
4.4.1 Biochar Characterization ................................................... 129
4.4.2 Sorption Experiments ........................................................ 136
4.5 Summary .................................................................................... 146
4.6 Bibliography ............................................................................... 147
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