 Diminishing Fossil Fuels
• At 2006 consumption rates
 Oil – 40 years
 Coal – 200 years
 Natural Gas – 70 years
(Shafiee et al., 2008)
 Concerns over Carbon Emissions
• Carbon Dioxide a major contributor to global warming
• Global Temperatures have risen 0.9o C in the past 140 years
• Evidence temperature will rise 0.2o C each decade
(Nema et al., 2012)
(Nema et al., 2012)
 Used
to produce biodiesel and ethanol
 Does not require agricultural land
 Does not require large amounts of fresh
water
 Can be grown in waste/brackish water
 High efficiency CO2 mitigation
 Can be harvested year long
(Mascarelli, 2009)
Experimental Parameters:
 Acidification
• 5% H2SO4
 Sonication
• 2 minutes at 20 kHz, 150 W
 Thermal
• 121o C, 15 psi (103.4 kPa) for 90 min
 Microwave
• 10 W, 145o C for 5 min
 Algae
biomass blended and lyophilized
• 0.5 g dry algal mass per sample
 Treatment
• 3 replicates per treatment conditions
 Supernatant
filtered using Büchner funnel
and vacuum filter flask
 Monosaccharaide derivatization by
alditol reduction/acetylation
 Analysis by GC-MS

5.0 mL filtered supernatant
4.4 mL 0.3 M H2SO4
0.575 mL internal standard




1.0 mL solution transferred to test tube
Concentrated NH4OH added and vortex-mixed
Excess KBH4 added and vortex-mixed
Reduction allowed to proceed for 90 min at 40o C

Reduction quenched with glacial acetic acid



400 μL of alditol solution transferred to new test tubes
1-methylimidazole added and vortex-mixed
Acetic anhydride added drop-wise and vortex-mixed
Acetic Anhydride 1-Methylimidazole
Alditol
1-methyl-3-acetylimidazole
Acetate
1-Methyl-3-acetylimidazole
Alditol Acetate
1-Methylimidazole
 Reacted
for 30 min then anhydride
decomposed with D.I. water
 Extracted into dichloromethane and
stored in autosampler vials
 Samples run through HP 6890 Gas
Chromatograph with a 5973N MSD mass
selective detector and HP 7683 Series
Autosampler
Arabinose
Calibration Standard
IS
Xylose
Glucose
Mannose
Sample
Galactose


Peak areas calculated using MSD Chemstation
integrator
Calibration Standard
• Amount Ratio (AR) = Cs/CIS
• Response Ratio (RR) = Areas/AreaIS
• Relative Response Factor (RRF) = AR/RR

Samples
• Cs = RR x RRF x CIS
• mass% Ash Free Dry Mass =
[k x Cs x (sample vol)]/[massi x (1 - %ash)]
 Different
• Sulfuric
Species of Acid
 5% concentrated H2SO4 by volume (0.9 M)
• Citric
 172.92 g solid dissolved in 1.0 L (0.9 M)
• Acetic
 10% glacial acetic acid by volume (1.8 M)
 Different Temperatures
• 15 W, 5 minutes at:
 100o C
 125o C
 150o C
1
2
3
4
5
6
7
8
9
 Investigated
different combinations of acid,
sonic, thermal, and microwave treatments to
optimize saccharide release from dried algae
biomass.
 Using
these results, a new screening matrix was
created investigating different combinations of
acid species and temperatures.
A
combination of acid and heat is crucial
for effective saccharide release.
 Hydrolysis
at lower temperatures may be
nearly as effective as high temperatures
with certain acids.
Investigate the effect of more acid species
Investigate different temperature ranges
Investigate the sulfuric treatment at the
same power
Undergraduate Research & Creative Activities
Program (WMU)
Arts & Sciences Teaching and Research
Award(WMU)
 Dr. John
Miller
 Kristin Hampel
 Dr. Steve Bertman
 Dr. James Kiddle
 Dr. Nayane Udawatte
 Dr. Jesse Thompson
•
Shafiee, S.; Topal, E. When will fossil fuel reserves be diminished?
Energy Policy. 2009, Vol. 37 (1), pp 181-189
•
Nema, P.; Nema, S.; Roy, P. An overview of global climate changing
in current scenario and mitigation action. Renewable and Sustainable
Energy Reviews. 2012, Vol. 16 (4), pp 2329–2336
•
Mascarelli, A. Algae: fuel of the future? Environ. Sci. Technol., 2009,
Vol. 43 (19), pp 7160–7161
• Li, Y.; Horsman, M.; Wu, N.; Lan, C.; Dubois-Calero, N. Biofuels from
Microalgae. Nanotechnology Progress. 2008, Vol. 24 (4), pp 815-820
• Najafi, G.; Ghobadian, B.; Yusaf, T. Algae as a sustainable energy
source for biofuel production in Iran: A case study. Energy Policy. 2011,
Vol. 15 (8), pp 3870–3876
• Oltra, C. Stakeholder perceptions of biofuels from microalgae. Energy
Policy. 2011, Vol. 39 (3), pp 1774–1781