Article

pubs.acs.org/JAFC

Chemical and Thermal Characterization of Potato Peel Waste and Its

Fermentation Residue as Potential Resources for Biofuel and
Bioproducts Production
Shaobo Liang and Armando G. McDonald*,,

Environmental Science Program, University of Idaho, Moscow, Idaho 83844-3006, United States
Department of Forest, Rangeland and Fire Science, University of Idaho, Moscow, Idaho 83844-1132, United States

ABSTRACT: The growing demand for renewable fuels has driven the interest in the utilization of alternative waste materials
such as potato peel waste (PPW) which contains fermentable carbohydrate. Fermentation of PPW using a mixed microbial
consortium yielded about 60% unreacted PPW fermentation residue (PPW-FR). The PPW and PPW-FR were characterized by a
combination of Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, gas
chromatographymass spectrometry (GC-MS), and thermogravimetric analysis (TGA) to quantify changes after fermentation.
Fermentation of PPW resulted in fermentation of starch and concentrating lignin plus suberin and lipids in PPW-FR. TGA
analysis showed that decomposition peaks diered for PPW (423 C) and PPW-FR (457 C). Pyrolysis-GC/MS showed an
increase in phenolic and long chain fatty acid compounds with a concomitant decrease in carbohydrate derived compounds in the
PPW after fermentation. Both the PPW and PPW-FR have shown potential based on properties to be converted into crude
biofuel via thermochemical processes.
KEYWORDS: potato peel waste, fermentation residue, chemical analysis, thermo gravimetric analysis

INTRODUCTION
Potatoes are the worlds fourth largest crop behind corn, rice,
and wheat and have experienced a steady growth over the last
two decades as a stable food crop and a major source of starch.1
According to data from the National Potato Council,2 United
States (U.S.) ranks fth of potato producing countries with a
production over 21.7 billion kg in 2011. A typical potato
processing plant can generate 610% potato peel waste (PPW)
from the peeling process,3 and other defect removal, trimming,
and cutting processes can generate an additional 15% waste.
This combined waste stream can pose a signicant waste
management eort, and therefore, knowing this wastes
composition will facilitate its utilization into bioproducts.
The composition of steam PPW was determined by Camire
et al.4 and shown to contain starch (25%), nonstarch
polysaccharide (30%), acid insoluble and acid soluble lignin
(20%), protein (18%), lipids (1%), and ash (6%). The lipid
fraction was shown to comprise long chain fatty acids,
triglycerides, alcohols, sterols, sterol esters, and phenolics.5
Suberin, a rubbery polyester material composed of polyaromatic and polyaliphatic domains, has been found in the cell
walls of potatoes.6 Lignin, a three-dimensional polymer made
up of phenylpropane units, has also been detected in the plant
cell wall.7
PPW has been utilized in a variety of applications and
traditionally has been used for local animal feed.4,812 Suberin
and lignin fractions have been pressure extracted from PPW to
obtain value added antioxidants and bioactive chemicals.8,9
While fermentation of PPW starch has been employed to
generate alcohols and organic acids. Arapoglou et al.10
converted PPW by sequential enzymatic hydrolysis and
fermentation using Saccharomyces cereviciae to yield ethanol.
2014 American Chemical Society

Lactic acid has also been produced from PPW using pure
cultures of Lactobacillus var. or Rhizupus var.11,12 Recently,
PPW has been directly converted to primarily lactic acid, a
useful chemical building block for the production of polylactic
acid, using undened mixed microbial culture fermentation.13,14
The advantage of using a mixed microbial system is that the
fermenters do not require expensive pure cultures or sterilized
conditions to operate, and the microbial community selfregulated to predominately lactic acid producing bacteria.13
However, a signicant amount of unreacted solid PPW
fermentation residue (PPW-FR) was obtained in the
process.10,13,14 This PPW-FR waste will also need to be
managed and forms the basis of this characterization study to
maximize its utilization. Another popular option for waste
management of PPW is by anaerobic digestion (AD) to
produce CH4 and electricity.15 However, AD systems require
large digesters based on the slow methanogenic bacterial
conversion of biomass to CH4 and unpleasant odor (namely,
H2S) generation.15 Work by Kang and Min16 has used PPW as
a novel substrate for making biobased exible lms for
packaging applications with good barrier properties.
Currently, food crops such as corn and soybean are the two
predominant biomass resources widely used for liquid
bioethanol and biodiesel production worldwide.17 However,
the controversy between food and fuel also promoted the
utilization of other noneligible biomass materials, such as
agricultural and forestry residues,18 animal manure,15 algae,19
Received:
Revised:
Accepted:
Published:
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February 19, 2014

August 4, 2014
August 5, 2014
August 5, 2014
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Figure 1. Schematic diagram of PPW and PPW-FR sample generation and analytical procedures.

and food processing wastes.20 PPW and more recently PPW-FR

are promising carbon rich waste resources for producing value
added biofuels and bioproducts. Onal et al.21 used steam
pyrolysis of PPW (at 500 C) to generate >25% bio-oil and
contained signicant amounts of aliphatics that could be used
in transportation fuels. Biochar from pyrolyzed PPW, another
coproduct, was shown to remove heavy metals from aqueous
solutions.22 These approaches to utilize PPW will minimize
waste streams, reduce the carbon footprint, mitigate greenhouse
gases, and generate a range of bioproducts.
The aim of this study is to characterize the chemical and
thermal properties of PPW and PPW-FR, an uncharacterized
bioresource, in order to target possible thermochemical
processes, such as pyrolysis, for conversions of these wastes
into biofuel and bioproducts. A combination of characterization
techniques was employed, and the results of this study can be
used in future work to evaluate the pyrolysis based biofuel and
bioproduct production from PPW and PPW-FR.

slurry that was drawn o and using a retention time of 2 days and solid
loading of 40 g L1 was kept constant. Sampling was conducted after 4
weeks running to obtain a steady state, and the PPW-FR was collected
over a 34 week period, then recovered by centrifugation, and freezedried for subsequent analyses. A detailed characterization ow process
is shown in Figure 1. All of the results in this study were calculated on
a dry weight basis biomass and measured in triplicate.
Compositional and Caloric Analyses. Freeze-dried samples
(45 g) were Soxhlet extracted with CH2Cl2 (150 mL) for 16 h
according to ASTM D 1108-9623 and the extractives (lipids) were
determined gravimetrically. The lignin and suberin complex was
divided into acid insoluble and acid soluble fractions, and the analyses
were performed on extractive free samples according to ASTM D
1106-9624 and Schoening and Johansson,25 respectively. Carbohydrate
analysis was performed on the 2-stage acid-hydrolyzates according to
ASTM E 1758-01.26 More specically, the dried sample (200 mg) was
incubated in 72% H2SO4 (2 mL) for 1 h at 30 C, then diluted into 4%
H2SO4, and subjected to secondary hydrolysis in an autoclave (117
KPa and 121 C) for 30 min. The hydrolyzate was ltered to obtain
acid insoluble (Klason lignin + suberin) residue content gravimetrically. The hydrolysis ltrate was made up to 250 mL and an aliquot
portion taken to determine acid soluble lignin (+ suberin complex)
fraction content at 205 nm using an absorption coecient of 110 L g1
cm1 (Beckman DU640 spectrometer). An aliquot portion of the
hydrolyzate (5 mL) was transferred to a centrifuge tube to which
internal standard (inositol, 1 mL, 0.5 mg mL1) and PbCO3 (0.16 g)
were added, mixed well, centrifuged, and the supernatant (4 mL)
deionized (column of Amberlite IR-120 H+ (0.5 mL) and Amberlite
IRA35 OH (0.5 mL) resins) and ltered (0.45 m) into HPLC vials.
Monosaccharides were the quantied by HPLC using two RPM
columns in series (7.8 mm 30 cm, Phenomenex) at 85 C equipped
with a dierential refractive index detector (Waters Associates model
2414) on elution with 0.5 mL min1 water. Starch content was
estimated by an enzymatic hydrolysis assay according to AACC
method 76-1127 using glucoamylase (Sigma-Aldrich) and the sugars
analyzed by HPLC. More specically, the sample (0.50 g) was
dissolved in water (25 mL) and heated to 135 C for 1 h, cooled,
acetate buer (pH 4.8, 2.5 mL) and glucoamylase (5 mL, 150 IU)

MATERIALS AND METHODS

Sample Preparation. The PPW (Russet Burbank) sample was

collected from a potato processing plant (J.R. Simplot Company,
Nampa, ID) over a 2 h period in May 2012, and the sample was mixed
thoroughly and stored frozen for fermentation studies using a
consistent feed stock and a portion freeze-dried for subsequent
analysis. Hybrid poplar (Populus deltoides Populus tremuloides)
sample was obtained from Greenwood Resources (Portland, OR) and
Wiley milled to <0.5 mm particle size.
The fermentation process primarily produced lactic acid and to a
lesser extent ethanol, and acetic acid from PPW was described by
Liang.13,14 A 1 L glass bottle with an air-lock was used as a reactor,
operated in sequencing batch mode with moderate mixing speed and
at 35 C. The fermenter was inoculated with 5% mixed microbial
cultures (sewage sludge from Moscow Wastewater Treatment Plant,
Idaho) only at the rst day running. Gelatinized PPW (boiled for 30
min and cooled down) was fed daily with the same amount of mixed
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added to the solution, incubated at 55 C for 2 h, and analyzed by

HPLC.
The ash content was determined by furnacing samples at 600 C
according to ASTM D 1102-84.28 The C, H, and N content was
determined using a CE-440 elemental analyzer (EAI Exeter
Analytical), and O content was calculated by the dierence. The
caloric values for pressed dried pellet samples (5.5 mm 6.3 mm )
were determined by bomb calorimetry (Model 1261, Parr Instruments) according to ASTM D 5865-04.29
GC-MS Analysis of CH2Cl2 Extractives and Suberin. The
CH2Cl2 extract (5.0 mg) was weighed into a 5 mL reacti-vial to which
2 mL of CH3OH/H2SO4/CHCl3 (1.7:0.3:2.0 v/v/v) was added, and
the mixture was heated for 90 min at 90 C to form fatty acid methyl
ester (FAME) derivatives.30 CHCl3 contained 1-napthalaneacetic acid
as an internal standard (50 g mL1). To the cooled mixture, water (1
mL) was added, vigorously shaken, centrifuged, the CHCl3 layer
removed, dried through anhydrous sodium sulfate, and transferred to a
GC vial. The prepared FAME derivatives were analyzed by GC-MSEI
(FOCUS-ISQ, ThermoScientic); temperature prole, 40 C (1 min)
to 320 C at 5 C min1 with injector temperature of 320 C, mass
transfer line temperature of 325 C, and ion source temperature of 240
C; GC capillary column, RTx-5MS (30 m, 0.25 mm , 0.25 m lm
thickness, Restek). The eluted compounds were identied with
authentic standards (C12, C14, C16, and C18) and by spectral
matching with the National Institute of Standards and Technology
(NIST) 2008 mass spectral library. The abundance of each compound
was referenced against the area of internal standard.
Suberin analysis was performed on samples by NaOCH3-catalyzed
methanolysis and subsequent GC-MS analysis.6 The CH2Cl2 extractive
free sample (500 mg) was reuxed in freshly prepared 12 mmol L1
NaOCH3 in dry CH3OH (50 mL) for 3 h. The reaction mixture was
ltered (glass ber paper) and the residue washed with CH3OH (25
mL) and CHCl3 (25 mL). The ltrate (1 mL) in a GC vial was
concentrated to dryness to which CH2Cl2 (containing anthracene as
internal standard (50 g mL1, 1 mL)), N,O-bis (trimethylsilyl)triuoro-acetamide containing 1% trimethylchlorosilane (50 L), and
pyridine (50 L) were added and then heated to 70 C for 30 min.
Suberin derived trimethylsilyl (TMS) derivatives were analyzed by
GC-MSEI (Focus-ISQ, ThermoScientic)); temperature prole, 40 C
(1 min) to 300 C (20 min) at 5 C min1 with an injector
temperature of 320 C, mass transfer line temperature of 300 C, and
ion source temperature of 240 C; GC capillary column, RTx-5MS (30
m, 0.25 mm , 0.25 m lm thickness, Restek). The eluted
compounds were identied with authentic standards, literature, and
by spectral matching with the NIST 2008 mass spectral library, and the
abundance of each compound was referenced against the area of
internal standard.
Spectroscopy. FTIR spectroscopic analysis was performed using
an Avatar 370 spectrophotometer (Thermo Nicolet) with an
attenuated total reection (ATR) probe (ZnSe crystal). The spectra
were ATR and baseline corrected using Omnic v7.0 software.
13
C1H HSQC NMR spectroscopy was performed on a 500 MHz
Bruker AVANCE 500 spectrometer. CH2Cl2 extractive free samples
(10 g) were extracted with water overnight and the solid residue
freeze-dried and ball-milled in a porcelain jar (0.5 L) for 14 d. The
ball-milled samples (40 mg) were dissolved in dimethyl sulfoxide
(DMSO)-d6 (1 mL) with the aid of sonication and analyzed according
to Kim et al.31
Thermogravimetric Analysis. TGA was performed on samples
(46 mg) using a TGA-7 (PerkinElmer) instrument using a
temperature program of 30 to 900 C at a heating rate of 5, 10, 20,
30, 40 K min1 under N2 (30 mL min1). TGA and dierential
thermogravimetry (DTG) data were analyzed using Pyris v8 software.
Activation energy (E) and pre-exponential factor (A) were calculated
according to ASTM E 1641-07.32 The decomposition kinetics was
assumed to be rst-order to determine E and A by the following
equations:

R (log )
E =
b
(1/T )

A = R ln(1 ) 10a
Er

(2)
1

where, R is the gas constant, 8.314 J mol K , b is the approximate

derivative given by ASTM E 1641 numerical integration constants, is
the heating rate at K min1, is the heating rate nearest the midpoint
of the experimental heating rates at K min1, T is the temperature (K)
at constant conversion, Er is the rened value of Arrhenius E, is the
conversion value of decomposition, and a is the approximation integral
taken from ASTM E 1641 of numerical integration constants.
Py-GC/MS Analysis. Samples (<0.1 mg) were injected into a
quartz capillary tube and pyrolyzed at 500 C in an inert atmosphere
(He, 0.125 MPa) using a Pyrojector II unit (SGE Analytical Science)
coupled to a GC-MSEI (FOCUS-ISQ, ThermoScientic) instrument.
The compounds were separated on a RTx-5ms (30 m 0.25 mm ,
0.25 m lm thickness, Restek) capillary column with a temperature
program of 50 to 250 C (10 min) at 5 C min1 with an injector
temperature of 255 C, a mass transfer line temperature of 255 C, and
an ion source temperature of 240 C. The eluted compounds were
identied with the NIST 2008 library matching and by their mass
spectra, and the relative abundance of each derived compound was
calculated using CO2 as internal standard.30,33
Statistical Analysis. Statistical analyses of obtained data were
conducted by SAS 9.3 (SAS Inc., Cary, NC, USA) under analysis of
variance (ANOVA) at an level of 0.05 to determine signicant
dierences between the measured properties.

RESULTS AND DISCUSSION

Chemical, Elemental, and Caloric Value Analyses.
Chemical, elemental, and caloric value analyses were
performed to obtain base chemical properties of the PPW
and PPW-FR materials and establish what classes of
components have been removed by fermentation. PPW and
PPW-FR compositions, elemental contents, and caloric values
are given in Table 1, which were signicantly dierent. The
PPW contained approximately 17% starch and 22% nonstarch
polysaccharides. It was observed that most of the starch was
consumed and converted to ethanol, acetic acid, and lactic acid
during fermentation leaving 2% residual starch and 20%
nonstarch polysaccharides in the PPW-FR.13,14 Lignin and

Table 1. Compositional, Elemental, and Caloric Value

Analyses of PPW and PPW-FR
component
carbohydrate
starch
nonstarch glucana
galactan
mannan
xylan
arabinan
nonstarch polysaccharide
lignin and suberin
acid insoluble
acid soluble
CH2Cl2 extractive
ash
C
H
N
O
caloric value (MJ kg1)

PPW (% dry basis)

PPW-FR (% dry basis)

16.83 0.52
7.75 0.68
6.91 0.10
0.75 0.07
3.52 0.21
3.53 0.06
22.46 0.79

2.07 0.13
7.79 0.31
5.31 0.14
1.35 0.07
1.47 0.10
4.44 0.08
20.36 0.08

15.94 0.04
5.70 0.20
1.98 0.15
11.05 0.07
43.78 0.15
5.96 0.12
4.06 0.01
46.21 0.28
17.37 0.38

30.31 0.20
6.68 0.00
7.68 0.00
7.47 0.00
47.81 0.01
6.41 0.04
4.02 0.08
41.78 0.05
19.19 0.03

The nonstarch glucan, galactan, mannan, xylan, and arabinan are

listed as anhydro-sugar units present in nonstarch polysaccharides.

(1)
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suberin complex content increased during fermentation from

22% to 37% with a concomitant removal of carbohydrate. The
extractives (lipids and secondary metabolites) comprise fats,
waxes, long-chain fatty acids, and alcohols, accounting for 2 and
8%, respectively, in PPW and PPW-FR. After fermentation,
extractives accumulated in PPW-FR, which is in accordance
with the distiller dried grains from ethanol fermentation.34
A decrease of ash content from 11% to 7% was observed and
could be attributable to solubilization. Elemental composition
analysis showed a signicant dierence between the PPW-FR
and PPW. The C and H content increased, while the O content
decreased after fermentation due to the removal of
carbohydrates. The C (48%) and H (6.4%) contents in the
PPW-FR were similar to hardwood biomass (4852% C; 4.5
6.5% H) but higher than herbaceous biomass (wheat straw
(43% C; 5.0% H) and corn stover (44% C; 5.6% H)).35 A 10%
increase in caloric value was observed after biomass
fermentation (19.2 MJ kg1), and this is consistent with the
higher C/H ratio obtained by other researchers on
fermentation residues (1921 MJ kg1)36 and comparable to
that of some hardwoods (13.519.4 MJ kg1).35 These ndings
suggest that the PPW-FR could be a promising biomass
resource for biofuel production.
Compositional Analysis of Extractives and Suberin.
Lipids are an important class of compounds because they are
used in biodiesel production and therefore were characterized
to determine composition. The CH2 Cl 2 extracts were
converted to their FAME derivatives and semiquantitatively
analyzed by GC/MS, in which total 17 compounds ranging
from C12 (lauric acid) to C30 (melissic acid) were identied
(Table 2 and Figure 2). The total biomass lipid content
increased from 7.5 to 14.3 mg g1 after fermentation. Linoleic
(C18:2, 39%), palmitic (C16:0, 18%), and linolenic (C18:3,
16%) acids were the main components in PPW and were in
agreement with the results from Dobson et al.5 The levels of
linoleic, palmitic, and linolenic acids increased, respectively, by
29.7%, 70.8, and 84.3% upon fermentation. Other minor
(<10%) fatty acids were also found: lauric (C12:0), myristic
(C14:0), pentadecanoic (C15:0), heptadecenoic (C17:0),
stearic (C18:0), eicosanoic (C20:0), heneicosanoic (C21:0),
docosanoic (C22:0), tricosanoic (C23:0), tetracosanoic
(C24:0), hexacosanoic (C26:0) acids, montanic acid (C28:0),
nonacosylic acid (C29:0), and melissic acid (C30:0). Dobson et
al.5 quantied lipids, as FAMEs, in two potato species from C14
to C24 and also detected odd numbered (C15:0, C17:0, C21:0,
and C23:0) fatty acids. The total 17 fatty acids increased by
90% after fermentation, and the increasing lipids could be
produced by microorganisms during fermentation.37
We determined the abundances of the lignin and suberin
complex in the previous section at 22 and 37%, respectively, for
PPW and PPW-FR. Suberin is regarded as a major constituent
of potato cell walls,6 and a further semiquantitative analysis to
obtain a better content value and composition was necessary.
Figure 3 shows the composition of suberin, which mainly
comprised glycerol, alkanoic acids, ,-diacids, and hydroxyacids, as well as minor amounts of alkan-1-ols,
hydroxycinnamic acids, and amino acids. Similar suberin
constituents were also identied by other researchers.38,39
Glycerol was the most abundant component in suberin at 48%,
a cross-linker of the aliphatic and aromatic domains, and
content is consistent with the literature.40 Estimated suberin
content was shown to increase in PPW after fermentation from
58 to 166 mg g1 as starch levels decreased.

Table 2. FAME Derivatives of PPW and PPW-FR Extracts

no.

compound

1
2

lauric acid (C12:0)

myristic acid
(C14:0)
pentadecanoic acid
(C15:0)
palmitic acid
(C16:0)
heptadecenoic acid
(C17:0)
linoleic acid
(C18:2)
linolenic acid
(C18:3)
stearic acid (C18:0)
eicosanoic acid
(C20:0)
heneicosanoic acid
(C21:0)
docosanoic acid
(C22:0)
tricosanoic acid
(C23:0)
tetracosanoic acid
(C24:0)
hexacosanoic acid
(C26:0)
montanic acid
(C28:0)
nonacosylic acid
(C29:0)
melissic acid
(C30:0)
total

3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

retention
time (min)

M+
(m/z)

PPW
(mg/g)

PPW-FR
(mg/g)

22.59
27.07

214
242

0.00
0.02

0.01
0.03

29.15

256

0.02

0.02

31.13

270

1.37

2.34

33.04

284

0.01

0.02

34.31

294

2.93

3.80

34.43

296

1.21

2.23

34.86
38.27

298
326

0.25
0.06

0.38
0.10

39.89

340

0.02

0.03

41.42

354

0.09

0.14

42.91

368

0.01

0.02

44.34

282

0.20

0.28

47.07

410

0.28

0.58

49.61

438

0.67

2.61

50.82

452

0.14

0.60

51.99

466

0.26

1.15

7.54

14.33

Spectroscopic Analysis. FTIR spectroscopy was further

used to analyze chemical functional group changes of PPW and
PPW-FR, and their spectra are shown in Figure 4. The main
characteristics were attributed to the presence of cellulose/
starch, hemicellulose, ligninsuberin complex, and protein. A
strong hydrogen bonded OH stretching band18 at 3329 cm1
and CH (CH3, CH2) stretching vibration bands at 2974,
2915, and 2849 cm1 were observed for PPW, whereas similar
characteristic bands appeared at 3339, 2917, and 2850 cm1,
respectively, for PPW-FR. Absorption ester bands for fatty acid,
hydroxy fatty acid, and diacids in lipids and suberin polymers38
were detected at 1735 cm1 (CO) and 1238 cm1 (C-OC) in PPW-FR. However, these bands were detected, at low
intensity, in PPW at 1733 and 1255 cm1 and were reective of
lower lipid and suberin contents. These results are in agreement
with the compositional analysis mentioned above. A distinct
amide I CO stretching band,41 for protein, was detected at
1609 cm1 in PPW, whereas the band was shifted to 1628 cm1
in PPW-FR. Other functional groups associated with proteins
were observed and overlapped with carbohydrate and lignin
bands at 36403040 cm1 for NH stretching and 16001500
cm1 for amide II CN stretching and NH bonding
absorptions.42
In general, the absorption bands from 1600 to 1400 cm1
derived from CC vibration of the aromatic ring were
assigned to lignin.43 Three distinct bands at 1515, 1452, and
1418 cm1 were detected in PPW-FR, while only two bands at
1514 and 1408 cm1 and a shoulder around 1450 cm1were
detected in PPW. A clear absorption band at 1370 cm1
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Figure 2. Total ion chromatogram of FAME derivatives of the CH2Cl2 extract of PPW-FR (IS, 1-naptheneacetic acid; peak numbers and identied
compounds are given in Table 2).

Figure 3. Levels of suberin derived compound classes present in PPW and PPW-FR by methanolysis (GLY, glycerol; AKA, alkanoic acids; DA,
diacids; HAA, hydroxyalkanoic acids; APA, aliphatic alcohols; HCA, hydrocinnamic acids; AA, amino acids; triplicate tests were performed).

Figure 4. FTIR spectra of PPW (A) and PPW-FR (B).

denoted as aliphatic CH stretching44 in CH3, or phenolic OH

was observed only in PPW-FR. The band at 1314 cm1 was

assigned to CH vibration. Finally, a strong band ranging from

1200 to 900 cm1 was assigned to C-O-C vibration of
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Figure 5. HSQC 1H13C NMR spectra of (A) hybrid poplar, (B) PPW, and (C) PPW-FR in DMSO-d6.

Figure 6. TGA and DTG thermograms of PPW (A) and PPW-FR (B) at dierent heating rates (5 to 40 K min1).

120/2.55.5 ppm region belong to polysaccharides, and the

C/H 100150/68 ppm region is contributed by aromatic
components. Hybrid poplar as a model lignocellulosic substrate
exhibited signicant cellulose, hemicellulose, and lignin signals,
where the anomeric C/H correlation of cellulose and xylan
appear at C/H 103/4.4 ppm for (1 4)--D-Glcp, 104/4.2
ppm for (1 6)--D-Glcp, and 102/4.3 ppm for (1 4)--DXylp. Correlations of lignin appear at C/H 104/6.7 ppm for
C2H2 and C6H6 in syringyl units, 111/7.0, 115/6.7, and
119/6.8 ppm for C2H2, C5H5, and C6H6 in the guaiacyl

pyranose sugar rings (carbohydrates) in both PPW and PPWFR samples.

2D-NMR spectroscopy was employed to nondestructively
analyze PPW and PPW-FR by fully solubilizing the samples in
DMSO following the approach by Kim et al.31 and Lu and
Ralph,45 which were developed for woody biomass. This
approach was out to trial to assess its suitability to characterize
PPW. Figure 5 shows the 2D HSQC 13C1H correlation
spectra of ball-milled hybrid poplar, PPW, and PPW-FR
samples. Most of the 1H13C correlations in the C/H 50
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Table 3. Compounds Released by Py-GC/MS of PPW and PPW-FR

relative abundance (%)
no.

compound

retention time (min)

M+ (m/z)

formula

PPW

PPW-FR

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

acetaldehyde
acetic acid
acetic anhydride
pyrrole
toluene
acetamide
2,3-butanediol
2-oxo-3-cyclopentene-1-acetaldehyde
3-methylpyrrole
3-furylmethnol
6-hydroxy-hexan-2-one
1,2,3-cyclopentanetriol
2-methyl-2-cyclopentenone
2(5H)-furanone
1,2-cyclopentanedione
1-methyl-1-cyclopenten-3-one
4-methyl-2(5H)-furanone
phenol
3-methyl-1,2-cyclopentanedione
2-methyl-phenol
3-methyl-phenol
guaiacol
3-ethyl-2-hydroxy-2-cyclopenten-1-one
2,3-dimethyl-phenol
3-ethyl-phenol
4-methyl-guaiacol
1,4:3,6-dianhydro-hexopyranose
coumaran
2-ethyl-methyl-phenol
4-ethyl-guaiacol
1,4-benzenediol
indolizine
4-vinyl-guaiacol
syringol
propioguaiacone
-hydroxydodecanoic acid
tetradecanoic acid
pentadecanoic acid
hexadecenoic acid
hexadecanoic acid
2,6,10-trimethyltetradecane
octadecyonic acid
oxacycloheptadec-8-en-2-one
eicosane
vaccenic acid
heneicosene
2-methyleicosane
eicosenoic aicd
2-methyl-eicosane
erucic acid

1.36
1.66
2.05
2.98
3.12
3.27
3.47
4.27
4.38
4.71
5.01
5.72
5.85
6.06
6.30
7.33
7.74
7.83
9.04
9.83
10.44
10.76
11.62
13.01
13.09
13.68
14.17
14.49
14.96
16.03
16.23
16.47
16.98
17.97
20.44
21.34
27.54
29.54
31.11
31.47
33.91
34.61
34.91
37.35
38.88
40.43
40.51
41.95
43.64
45.55

44
60
102
67
92
59
90
124
81
98
116
118
96
84
98
96
98
94
112
108
108
124
126
122
122
138
144
120
136
152
110
117
150
154
180
216
228
242
254
256
240
280
252
282
282
295
296
310
296
338

C2H4O
C2H4O2
C4H6O3
C4H5N
C7H8
C2H5NO
C4H10O2
C7H8O2
C5H7N
C5H6O2
C6H12O2
C5H10O3
C6H8O
C4H4O2
C5H6O2
C6H8O
C5H6O2
C6H6O
C6H8O2
C7H8O
C7H8O
C7H8O2
C7H10O2
C8H10O
C8H10O
C8H10O2
C6H8O4
C8H8O
C9H12O2
C9H12O2
C6H6O2
C8H7N
C9H10O2
C8H10O3
C10H12O3
C12H24O3
C14H28O2
C15H30O2
C16H30O2
C16H32O2
C17H36
C18H32O2
C16H28O2
C20H42
C18H34O2
C21H42
C21H44
C20H38O2
C21H44
C22H42O2

2.89
14.00
7.92
2.37
2.80
0.45
2.09
1.72
1.20
1.01
0.92
0.24
0.72
2.03
1.76
1.39
0.57
5.28
3.19
2.10
3.32
3.21
1.57
2.54
2.24
0.82
0.50
1.45
0.91
0.76
0.29
1.99
2.73
0.27
0.72
0.57
0.95
0.90
0.95
5.53
1.03
1.40
1.80
1.67
2.05
1.05
1.34
0.84
1.00
0.92

2.17
7.02
5.13
2.12
2.53
1.39
0.00
1.70
0.60
0.76
1.54
0.20
0.48
1.38
2.11
0.64
0.71
5.74
2.83
1.61
3.87
5.34
1.09
2.39
2.23
1.45
0.87
2.83
0.90
1.42
0.61
1.79
4.97
0.52
1.26
0.53
1.28
0.83
0.88
5.51
1.25
1.69
3.83
2.40
2.81
1.17
2.19
0.98
1.80
0.67

signal appears at C/H 21/2.1 ppm for the acetyl group in

polysaccharides,31 aliphatic methylenic groups (CH2)
appear at C/H 29/1.4 ppm for suberin components,39 C6
appears at C/H 61/3.8 ppm for C6H6 in cellulose and C-H
in -O-4 substructures, C5 and C4 appear at C/H 7374/
3.63.8 ppm for C5H5 and C4H4 correlations in cellulose,
and anomeric C1 appears at C/H 100/4.95.3 ppm for
anomeric C/H of (1 4)--D-Glcp and (1 6)--D-Glcp in

unit, respectively. Other clusters of C/H correlations for

polysaccharides and lignin were also observed, and the results
are in accordance with Lu and Ralph.45 In this research,
nonderivatized solution state 2D NMR was rst introduced to
analyze potato peel samples (Figure 5), and the NMR spectra
of PPW and PPW-FR samples were quite dierent from those
of hybrid poplar. The clusters of 1H13C correlations were
associated with polysaccharides, suberin, and lignin. The methyl
8427

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Journal of Agricultural and Food Chemistry

Article

starch31,45,46 and were present in both PPW and PPW-FR.

Signals attributable to lignin at C/H 56/3.63.9 ppm
(methoxyl group) and C/H 115/6.56.8 ppm (C5H5
correlation for guaiacyl) were observed only in the PPW-FR,
which are in agreement with FTIR and Py-GC/MS data.
Unfortunately, due to the poor spectral dispersion in the NMR
spectra of PPW and PPW-FR limited chemical information was
obtained. This may be due to the complex nature of PPW
samples (containing protein, suberin, and lipids) as compared
to that of hybrid poplar. Therefore, this approach to analyze
PPW directly by NMR was not successful and may require
further optimization.
TGA/DTG Analysis. TGA analysis was performed to
examine the thermal degradation behavior of PPW and PPWFR, which will provide useful information on the pyrolysis of
these materials, such as pyrolysis temperature and decomposition kinetics. Figure 6 shows the TGA and DTG
thermograms for PPW and PPW-FR samples. Thermal
degradation of biomass can be classied into four regions: (i)
dewatering at 50130 C; (ii) evaporation of volatile
compounds due to degradation 130220 C; (iii) thermolysis/pyrolysis of polymers (depolymerization) at 220460 C;
and (iv) char formation at >460 C.47,48 Thermal decomposition of the following main constituents occurs at 280350
C for starch; 315400 C for cellulose; and 220315 C for
hemicelluloses; and starts at 250 C for lignin and 290 C for
suberin. Two distinct peaks were observed from the DTG
thermograms at 279 and 423 C for PPW and 285 and 457 C
for PPW-FR, respectively. In addition, less char/ash was seen in
the PPW-FR than PPW, which is in accordance with ash
content determination. The E before 70% of samples at 5%
conversion intervals were calculated based on ASTM methods.
Generally, the E values for PPW and PPW-FR were similar,
where decreased trends were observed in both samples after
45% conversion. However, slightly lower values were found in
PPW-FR than PPW after reached 45%. The average E and A
values were, respectively, 214 kJ mol1 and 9.18 1024 for
PPW and 209 kJ mol1 and 1.65 1022 for PPW-FR. Similar
values of E and A for the wheat straw sample were observed at
260 kJ mol1 and 2.00 1022.47 The lower E in PPW-FR
indicates that less energy is required for thermal decomposition
and suitable for pyrolysis.49
Py-GC/MS Analysis. Py-GC/MS was used as a tool to
rapidly analyze biomass samples and assess potential pyrolysis
bio-oil chemical products. Py-GC/MS products of PPW and
PPW-FR at 500 C are listed in Table 3. A total of 51 pyrolysis
products were identied with the main product being CO2
followed by acetic acid (14% for PPW and 7.0% for PPW-FR),
acetic anhydride (7.9% and 5.1%), hexadecenoic acid (5.5% and
5.5%), and phenol (5.3% and 5.7%). A range of phenolic
compounds, including guaiacyl and syringyl derivatives, were
observed totaling at 26.7% in PPW and 35% in PPW-FR. Long
chain fatty acids and alkane were derived from lipid and suberin
decomposition,30,50 and the relative percentage increased from
22% into 28% after fermentation. The carbohydrate derived
compounds decreased from 45% into 31% from PPW during
fermentation. Nitrogen containing compounds (such as
pyrrole, methylpyrrole, acetamide, and indolizine) derived
from protein were also identied with similar relative
percentages in both PPW and PPW-FR samples, which is in
agreement with the C, H, and N analyses.
In this study, we have performed a comprehensive chemical
and thermal characterization of PPW and PPW-FR to obtain

information to improve the utilization of this resource for the

production of bioproducts, via thermochemical conversion. A
signicant increase of lignin/suberin, C/H contents, and
caloric value was observed in PPW-FR as a result of
fermentation, which will provide higher levels of phenolics
and long chain hydrocarbon products after thermochemical
conversion. Thermal characterization by TGA and Py-GC/MS
analyses indicated that PPW-FR required less energy and lower
temperature for thermal conversion processes, such as
pyrolysis, and more high value chemical compounds (phenolics
and long chain fatty acids, alcohols, and hydrocarbons) can be
recovered and upgraded catalytically to transportation fuels.
The composition (high in lipids, suberin, and lignin) and
thermal properties of PPW-FR, and to a lesser extent PPW,
make it a promising renewable biomass for biofuel and
bioproducts production. Future work will explore the
thermochemical conversion of PPW and PPW-FR in an
Auger reactor to produce a crude bio-oil, fractionation of the
bio-oil into aqueous and nonaqueous fractions, and their
characterization as biofuels.

AUTHOR INFORMATION

Corresponding Author

*Tel: +1 208 885 9454. Fax: +1 208 885 6226. E-mail:

armandm@uidaho.edu.
Funding

Funding for this research was provided by the J. R. Simplot

Company.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We acknowledge Dr. Jeanne M. Shreeve for providing
elemental analysis, Dr. Alexander Blumenfeld for technical
assistance in obtaining NMR spectra, Steve Vernon from the J.
R. Simplot Company for providing potato peels, and a Waters
Technologies Corporation equipment grant for the refractive
index detector.

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