Fuel Processing Technology 106 (2013) 366–375

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Factors affecting oxidation stability of commercially available biodiesel products

Zeyu Yang a, b,⁎, Bruce P. Hollebone b, Zhendi Wang b, Chun Yang b, Mike Landriault b
a
Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Materials Science,
South-Central University for Nationalities, Wuhan, 430,074, China
b
Emergencies Science and Technology Section (ESTS), Science and Technology Branch, Environment Canada, 335 River Road, Ottawa, ON, Canada K1A 0H3

a r t i c l e i n f o a b s t r a c t

Article history: Factors affecting oxidation stability for several commercially available biodiesels were primarily investigated
Received 15 August 2011 by acid value (AV) and induction period (IP) evaluations in this study. It was found that the measured IP at
Received in revised form 31 August 2012 different storage time points were somewhat dependent on the saturated degree of fatty acid methyl esters
Accepted 1 September 2012
(FAMEs), the corresponding measured AV scattered randomly. Generally, AV increased and IP decreased after
Available online 20 September 2012
one year of storing in a dark cold room in an air‐tight tank. Solvents (methanol, acetone and water) did not
Keywords:
show a contribution to altering IP. Metals (copper and lead) showed the strongest detrimental effects to ox-
Acid value idative stability although somewhat depending on the particle size and oxide coating thickness, however,
Induction period aluminum alloy and steel were not the case. Among the antioxidants, pyrogallol (PY) was the best in enhanc-
Oxidative stability ing IP with a concentration of less than 3000 ppm, however, tert-butylhydroquinone (TBHQ) was the best
Biodiesel after 3000 ppm, followed by propyl gallate (PG), butylated hydroxyanisole (BHA), 3,5-di-tert-butyl-4-
Metal contaminants hydroxyltoluene (BHT), and α-tocopherol. The appropriate dosage of PY was also evaluated to achieve the
Antioxidants specified IP regulated by EN-14112 for samples with copper or lead contamination.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel as an alternative diesel fuel consisting of alkyl mono-
esters of fatty acids prepared from vegetable oils or animal fats, has
attracted more and more attention because it is renewable and
environmental-friendly. However, biodiesel can be very sensitive to
oxidative and thermal degradation due to its ester chemical structure.
The first problem of biodiesel is that it undergoes oxidative degrada-
tion over time due to the presence of a significant amount of fatty
acids with double bonds. Storage stability of a fuel is its ability to re-
sist physical and chemical changes brought about by its action with
the environment. The problems arising from the deterioration of the
fuel properties of biodiesel during storage are expected to be more
severe than diesel fuel. The oxidation can result in the formation of
corrosive short chained acids and deposits that may cause increased
wearing of engine fuel pumps.
Currently, the deterioration of biodiesels under different storage con-
ditions has been investigated by evaluating several commonly-used phys-
icochemical parameters, such as, peroxide values (PV), acid value (AV),
iodine value (IV) viscosity (ν), and insoluble impurities (II) [1–3], as
⁎ Corresponding author at: Key Laboratory of Catalysis and Materials Science of the
State Ethnic Affairs Commission & Ministry of Education, College of Chemistry and Ma-
terials Science, South-Central University for Nationalities, Wuhan, 430074, China.
Tel.: + 86 27 59880491.
E-mail address: yangzeyu72@163.com (Z. Yang).
they reflect the change of fuel properties more directly compared with
the variation of chemical composition.
Rancimat test is the specified standard method for oxidation sta-
bility testing for biodiesel sample in accordance to EN-14112. The bio-
diesel standard EN-14214 calls for determining oxidative stability at
110 °C with a minimum induction time of 6 h by the Rancimat meth-
od (EN-14112) [4]. American Standard Test Method (ASTM) standard
D-6751-08 recently introduced a minimum induction period of 3 h
for biodiesel samples. However, biodiesels sourced from vegetable
oil are abundant with fatty acids with more than one double bond,
their IP values are very difficult to meet the EN-14112 and ASTM
D-6751 limits [5–7] unless antioxidants are present.
There are numerous publications on the storage oxidation stability
and factors affecting the stability of various biodiesels [5,6,8–15]. The
storage problems can be caused by the chemical composition of bio-
diesel and the storage conditions [6,8,16]. Firstly, it is well known
that fatty acid methyl esters (FAMEs) are the main chemical compo-
sition for biodiesel. The molecular structure of FAMEs can vary with
feedstocks by chain lengths, levels of unsaturation, and conformation.
Some parameters have been evaluated to represent oxidative stability
or physical property of biodiesel based on FAME composition, espe-
cially using unsaturated FAMEs [6]. For example, Knothe and Dunn
[17] reported the good correlation between IP and bis-allylic position
equivalent (BAPE, the number of doubly allylic carbons present in the
fatty oil or ester), but not for allylic position equivalent (APE, the
number of single allylic carbons present in the fatty oil or ester).
Another parameter concerned with FAME structure was expressed

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.001
 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375 367

as oxidizability (OX) by Neff et al. [18]. OX was expressed as: OX = 2. Experimental

[0.02(%O) + (%L) + 2(%Ln)] / 100, where O refers to methyl oleate
(cis-9, C18:1, ME), L refers to methyl linoleate (cis-9, 12, C18:2, ME)
and Ln refers to methyl linolenate (cis-9, 12, 15, C18:3, ME).
Secondly, the presence of antioxidants usually prevents radical
formation in oils and subsequent degradation. Based on this theory,
some synthetic antioxidants, such as pyrogallol, 3,4,5-trihydroxybenzoic
acid propyl ester (propyl gallate), tert-butyl hydroquinone, tert-butyl
hydroxyanisole, tert-butyl methyl-phenol, butylated hydroxytoluene
(BHT), and some natural antioxidants (e.g., tocopherols), have been
used to significantly slow down, but not entirely prevent the oxidation
of various biodiesels [3,10,15,19–21] because these chemicals can only
inhibit the oxidation process.
Thirdly, the presence of impurities (e.g., transitional metals: iron,
nickel, manganese, cobalt, and copper) and degradation products
can catalyze the formation of radicals in oils, while other impurities
can catalyze the degradation pathways of oil once radicals are formed
[5,12].
For storage conditions like exposure to air and/or light, tempera-
ture can accelerate the degradation of biodiesel [5,20,22]. Water con-
tent in biodiesel will enhance biodiesel degradation due to hydrolysis
but its effect is much less than the above two factors.
However, these researches mainly focused on home-made biodiesels.
For commercial biodiesel products, few researches reported the influence
of storage parameters (storage time, the presence of water, methanol, ac-
etone, steel, aluminum alloy and lead) on oxidative stability. The correla-
tion between oxidative stability and FAME composition for commercial
products was rarely reported either.
The objective of the present study is to select nine commercial bio-
diesel products sourced from three sources (soybean, canola oil, and
animal fat) to study the effect of storage parameters on their oxida-
tive stability. The variation of acid values and induction periods
with storage time will be investigated. The correlation between the
measured IP and FAME composition will be discussed. The impact of
several solvents (methanol, water and acetone) and metals (copper,
lead, aluminum alloy and steel) on IP is to be evaluated. Several
commonly used antioxidants to enhance the oxidative stability will
be compared for biodiesel with poor quality and simulated metal
contaminated products.
2.1. Materials and chemicals
Various metals were used to test their impact on induction periods.
They include NIST SRM 8k (Bessemer Steel (Simulated, chip form), 0.1%
Carbon), NIST SRM 1240c (Aluminum Alloy 3004, chip and disk form),
lead powder (~325 mesh), and copper granule (−10 to +40 mesh)
(Bellefonte, PA, USA). Both NIST SRM standards were purchased from
the National Institute of Standard and Technology (NIST, Gaithersburg,
MD, USA), their elemental composition is known but no size informa-
tion is available. Additionally, metals with different particle sizes, in-
cluding lead shot (~1 cm), copper shot (2−5 cm), and aluminum
powder (~325 mesh) purchased from Sigma-Aldrich, were utilized to
compare the variation of oxidative stability of biodiesels with different
metal particle sizes.
Biodiesel samples were obtained from domestic Canadian manufac-
tures, e.g., Milligans Bio-Tech. Inc. (Calgery, AB, Canada). Three of them
were sourced from tallow fat (Ban), three of them were from soybean
oil (Bsoy), and three of them are produced from canola oil (Bca), please
see Table 3 for detailed information. Where Bsoy-2, Bca-1 and Ban-1 were
sampled in December 2006, all other samples were sampled in Oct. to
Dec. 2009. These biodiesel products were stored in 10 L air‐tight steel
tanks and kept in a dark cold room (−4 °C). The initial physico-
chemical properties for five samples sampled in 2009 are shown in
Table 1 (data were not available for other four samples). It is obvious
that the initial quality for these five samples, except for Bsoy-1, satisfied
with ASTM D6751 limits. For Bsoy-1, the initial induction period is
shown to be 2.3 h; the mass of total glycerine is 0.263%, which exceeded
the maximum value of 0.24%; the mass of monoglycerides, diglycerides,
and triglycerides is 0.608, 0.382, and 0.395%, respectively, which are far
higher than the other four samples. The concentration of antioxidants
was not available; the chemical composition of FAMEs with a mass
ratio higher than 1% for all target samples is discussed in Section 3.1.
Antioxidants including α-tocopherol, propyl gallate (PG), butylated
hydroxyanisole (BHA), 3,5-di-tert-butyl-4-hydorxytoluene (BHT),
pyrogallol (PY), and tert-butylhydroxyquinone (TBHQ) were obtained
from Sigma-Aldrich (Bellefonte, PA, USA). Their chemical structures
and their physico-chemical properties are listed in Fig. 1 and Table 2,

Table 1
Initial physico-chemical properties for several representative samples.

Property (units) Test method ASTM D6751-08 limits Sample number

Bsoy-1 Bsoy-3 Bca-2 Bca-3 Ban-2

Acid value, mg KOH/g ASTM D664 0.31 0.34 0.15 0.09 0.18
Ash, sulfated, mass% ASTM D874 Max. 0.02 0.001 0 0 0 0
Determination of carbon, hydrogen, and nitrogen ASTM D5291
Carbon, mass% 76.86 77.1 77.28 77.15 76.24
Hydrogen, mass% 12.01 12.03 12.14 12.1 12.54
Cetane number ASTM D613 Min. 47 57.2 54 54.6 56.7 63.7
Cloud point, °C ASTM D5773 8.4 6.6 -1.1 -1.3 13.8
Copper corrosion ASTM D130 Max. 3 1a 1a 1a 1a 1a
Flash point, °C ASTM D93, procedure A Min. 130 144 / / 162 174
Free glycerin, mass% ASTM D6584 Max. 0.02 0.007 0.002 0.005 0.004 0.006
Total glycerin, mass% ASTM D6584 Max. 0.24 0.263 0.061 0.027 0.082 0.151
Monoglycerides, mass% ASTM D6584 0.608 0.055 0.055 0.219 0.404
Diglycerides, mass% ASTM D6584 0.382 0.177 0.043 0.075 0.225
Triglycerides, mass% ASTM D6584 0.395 0.183 0.022 0.093 0.065
Density, kg/m3, at 15 °C ASTM D4052 883.1 882.5 883.8 883.8 875.7
Specific gravity, kg/L, 60/60 °F ASTM D4052 0.8836 0.8843 0.8762
Phosphorus (P) EN 14107 modified Max. 0.001 b2.0 b2.0 b2.0 b2.0 b2.0
Carbon residue, mass% ASTM D4530 Max. 0.05 0 0.002 0.001 0.002 0
Total nitrogen, mg/L ASTM D4629 26.46 29 14 12.18 63.49
Oxidation stability, 110 °C, hours EN 14112 Min. 3 2.3 5.6 5.3 5 11.8
Total sulfur by ultraviolet fluorescence, mg/kg ASTM D5453 Max. 50000 5.7 3.2 8.6 7.5 15
Kinematic viscosity, mm2/s (cSt) clear, at 40 °C ASTM D445 1.9–6.0 4.298 / / 4.474 4.758
Water and sediment, volume% ASTM D2709 Max. 0.05 0.005 b0.005 0.005 b0.005 b0.0
368 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375

OH
OH
HO OH
HO OH

C=O
OC3H7
Pyrogallol (PY)
Propyl gallate (PG)

OH CH3
H3C OH CH3
CH3
H3C CH3
C C C

H3C
CH3 CH3

OCH3 CH3

Butylated hydroxyanisole (BHA) 3, 5-di-tert-butyl-4-hydroxytoluene (BHT)

OH
H3C
CH3
C

CH3

OH
tert-butylhydroxyquinone (TBHQ)

CH3

HO

CH3 O

CH3
a-tocopherol

Fig. 1. Chemical structures of antioxidants used in the present study.

respectively. All these antioxidants are phenolic types of antioxidants,
five of them are sourced from chemical synthesis, only α-tocopherol
can be sourced from nature. All antioxidants were dissolved in target
biodiesel with about 0.2 mL of acetone. The addition of acetone did
not show any alternation of IP values for the target biodiesel samples
(please see Section 3.3).
2.2. Analyses
2.2.1. GC/MS analysis
The fatty acid methyl ester composition of all tested biodiesels was
determined by an Agilent 6890 GC system interfaced to an Agilent
5973 mass spectrometer by triplication. In brief, a DB-225 MS GC col-
umn (30 m × 0.25 mm i. d., film thickness: 0.25 μm) obtained from
Agilent (Mississauga, ON, Canada) was employed to separate FAME
compounds. The Supelco 37 component FAME mixture with cis- and
trans-isomers (Bellefonte, PA, USA) had good separation efficiency on
the DB-225 MS column. An internal calibration method was used to de-
termine all target analytes in the present study. The oven temperature
was programmed with the following settings: initial temperature of
50 °C, held for 1 min, then increased at a rate of 7 °C/min to 185 °C,
held for 10 min, then increased at a rate of 15 °C/min to 230 °C, with
a final hold for 5 min. The temperatures of injector, transfer line, ion
source, and MS quadrupole analyzer were held at 280, 280, 230, and
150 °C, respectively. Samples were injected in splitless mode with
helium as a carrier gas at the flow rate of 1 mL/min. The mass-
selective detector (MSD) was operated at an electron impact mode
(70 eV) in selected ion monitoring (SIM) mode.
2.2.2. Determination of oxidative stability
Oxidative stability of biodiesel in the presence of different impuri-
ties (solvents, elemental metals, antioxidants, and metals plus antiox-
idants) was studied in Rancimat equipment model 743 (Herisau,
Switzerland) according to the biodiesel standard method EN-14214.
In the Rancimat method, a sample of 3 g was heated under a heating
block temperature of 110 °C, with a temperature correction factor ΔT
to be set to 1.5 °C as recommended by the test method. A constant air
flow of 10 L/h passed through the heated samples. The volatile
 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375 369

Table 2
Physico-chemical properties of used antioxidants in the present study.

Antioxidants CAS number Molecular formula Molecular weight (g/mol) Water solubility Melting point (°C) Boiling point (°C)

α-Tocopherol 59-02-9 C29H50O2 430.71 Insoluble 2.5−3.5 200−220 (0.1 mm Hg)

Propyl gallate 121-79-9 C10H12O5 212.2 / 150 Decompose
Butylated hydroxyanisole 25103-16-5 C11H16O2 180.24 Insoluble 48−55 264−270
3,5-di-tert-butyl-4-hydorxytoluene 128-37-0 C15H24O 220.35 1.1 mg/L (20 °C) 70−73 265
Pyrogallol 87-66-1 C6H6O3 126.11 / 131−134 309
Tert-butylhydroxyquinone 1948-33-0 C10H14O2 166.22 Slightly soluble 127−129 273

carboxylic acid produced during the oxidation process released into
the vessel containing 60 mL of ultra pure water together with the
air, and absorbed in the water. The variation of conductivity of
water with time was monitored by an electrode, the point that the
conductivity begins to increase rapidly is designated as the measured
IP. Data for all analytical measurements are means of triplication.
2.2.3. Acid value determination
Acid value, as described by ASTM D974-04, measures the number
of acidic functional groups in a sample by titration with potassium
hydroxide. The titration solvent was prepared by mixing toluene,
water, and anhydrous isopropyl alcohol in the volume ratio of
100:1:99. Phenolphthalein indicator solution (0.1% phenolphthalein
in a 1:1 mixture of water, free of CO2, and ethanol) was used as
indicator for titration. About 20 g of biodiesel sample together with
0.5 mL of 10 g/L of p-naphtholbenzein indicator in titration solvent
was dissolved in a 100 mL titration solvent. The standardized potassi-
um hydroxide solution was used for the titration until the appearance
of the first permanent green color persisting for at least 15 s. Each
sample was analyzed for at least three times for the determination
of average acid values.
3. Results and discussion
3.1. Analysis of biodiesel samples
Table 3 lists the fatty acid methyl ester (FAME) composition with
>1% mass percentage, acid value (expressed as mg KOH/g sample),

Table 3
Fatty acid methyl ester composition (%, mass/mass), acid value and induction periods (n = 3) of tested biodiesel samples.

Biodiesel feedstock Soybean oil Canola oil Tallow fat

Sampling time DEC10,2009 NOV24,2006 OCT11,2009 NOV242006 OCT11,2009 DEC10,2009 NOV24,2006 DEC10,2009 DEC23,2009

Biodiesel number Bsoy-1 Bsoy-2 Bsoy-3 Bca-1 Bca-2 Bca-3 Ban-1 Ban-2 Ban-3

FAME compounds Abbreviationsa Average SD Average SD Average SD Average SD Average SD Average SD Average SD Average SD Average SD

Methyl myristate C14:0, ME 0.6 0.0 0.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.5 0.0 1.5 0.0 1.4 0.0
Methyl palmitate C16:0, ME 13.6 0.3 9.1 0.0 8.3 0.0 3.3 0.0 3.3 0.0 3.4 0.0 18.7 0.1 20.4 0.0 19.8 0.0
Methyl palmitoleate cis-9, C16:1, 0.9 0.0 1.0 0.0 0.1 0.0 0.2 0.0 0.2 0.0 0.2 0.0 2.0 0.0 2.4 0.0 2.4 0.0
ME
Methyl stearate C18:0, ME 6.0 0.2 2.7 0.0 2.8 0.0 1.2 0.0 1.3 0.0 1.3 0.0 11.2 0.0 10.9 0.1 11.1 0.0
Methyl oleate cis-9, C18:1, 22.9 0.4 32.2 0.3 24.7 0.1 60.3 0.6 62.8 0.8 64.2 0.7 38.0 0.1 39.9 0.3 41.6 0.1
ME
cis-10, octadecenate cis-10,C18:1, 1.8 0.1 1.5 0.1 1.2 0.0 3.6 0.4 3.6 0.0 3.4 0.4 2.2 0.0 2.2 0.1 1.9 0.0
ME
cis-11, octadecenate cis-11,C18:1, 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.2
ME
Methyl linoleate cis-9,12 C18:2, 29.4 0.9 41.8 0.2 50.8 0.5 19.4 0.1 19.2 0.0 19.4 0.1 6.9 0.0 8.2 0.1 9.4 0.0
ME
Methyl linolenate cis-9,12,15, 4.4 0.1 5.1 0.1 6.6 0.0 10.5 0.0 7.4 0.1 7.5 0.0 0.6 0.0 0.5 0.0 0.7 0.0
C18:3,ME
Methyl arachidate C20:0, ME 0.1 0.0 0.2 0.0 0.2 0.0 0.4 0.0 0.4 0.0 0.4 0.0 0.1 0.0 0.1 0.0 0.1 0.0
Methyl erucate cis-11,C20:1, 0.2 0.0 0.3 0.0 0.1 0.0 1.1 0.1 1.1 0.0 1.1 0.0 0.3 0.0 0.3 0.0 0.4 0.0
ME
Methyl behenate C22:0, ME 0.2 0.0 0.1 0.0 0.2 0.0 0.2 0.0 0.2 0.0 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Methyl lignocerate C24:0, ME 0.0 0.0 0.0 0.0 0.1 0.0 0.0 0.0 0.1 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Total FAME (%) 82.7 4.2 95.2 0.5 95.2 0.7 100.5 0.5 99.9 0.7 101.6 0.3 83.5 0.0 88.2 0.3 90.4 0.4
∑SFAME 20.4 0.1 12.9 0.2 11.7 0.1 5.1 0.0 5.4 0.0 5.5 0.0 32.4 0.1 33.6 0.1 32.9 0.1
∑MUFAME 28.1 0.2 35.2 0.2 26.0 0.1 65.4 0.5 67.8 0.8 69.0 0.3 43.2 0.1 45.5 0.3 47.1 0.4
∑PUFAME 36.5 0.4 47.1 0.3 57.5 0.5 30.0 0.2 26.7 0.1 27.1 0.1 7.9 0.0 9.1 0.1 10.4 0.0
Acid value 0.31 / 0.3 0.1 0.3 / 0.3 0.0 0.15 / 0.09 / 0.45 0.1 0.18 / 0.3 0.1
(mg KOH/g
sample)b
Acid value 0.23 0.0 0.6 0.1 0.6 0.1 0.4 0.0 0.2 0.0 0.2 0.0 0.6 0.1 0.3 0.0 0.4 0.1
(mg KOH/g
sample)c
IP (hours)b 2.3 / 4.6 0.1 5.6 / 5.1 0.1 5.2 / 5.4 / 11.1 0.2 11.8 / 9.6 0.2
IP (hours)c 0.7 0.1 4.8 0.0 4.7 0.1 5.0 0.0 4.8 0.1 5.2 0.0 10.8 0.1 10.0 0.2 9.2 0.4
Kinematic viscosity, 4.298 / / / / / / / / / / / 4.474 / 4.758 / / /
mm2/s (cSt) at
40 °C

Notes:
a
The abbreviations of FAME compounds based on fatty acid nomenclature. ∑SFAME indicates the sum of all saturated FAMEs; ∑MUFAME indicates the sum of FAMEs with one
double bond; ∑PUFAME indicates the sum of FAMEs with more than one double bond;
b
Data were measured at DEC, 2009;
c
Data were measured at Dec, 2010.
370 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375
and induction periods (hours) of the target biodiesel products. Two se-
ries of acid values and induction period values were measured at Dec.
2009, and Dec. 2010, respectively, to investigate the effect of storage
time on the physico-chemical property of biodiesel products. It can be
seen that FAME carbon number of 18 was the most abundant one re-
gardless of the varied saturation degree, followed by carbon number
of 16, 14 and 20. This is in good agreement with many previous reports
[23,24]. In both Ban and Bca samples, methyl oleate (cis-9, C18:1, ME)
was the most abundant composition (38−64%, mass/mass), but in
Bsoy samples, methyl linoleate (cis-9, 12, C18:2, ME) was the most abun-
dant one (29−51%). The saturated FAME in animal fat sourced biodiesel
was the highest (about 33%), followed by Bsoy (12%−20%), and Bca (7%).
Biodiesels from same feedstocks showed similar FAME distribution ex-
cept for Bsoy-1 with a relatively higher saturated FAMEs, and less mono-,
poly-unsaturated, and total FAMEs compared with Bsoy-2 and Bsoy-3
samples. The total FAME mass percentages in all these samples were de-
termined to be in the range of 83−100%. The discrepancy of the total
FAME contents depends on two aspects, the initial quality and the stor-
age time. Because all these samples were not fresh biodiesels, it is
possible that some polyunsaturated FAMEs have been degraded or po-
lymerized. For Bsoy-1, headspace gas chromatography has been used
to analyze the methanol residue, however, we did not find obvious de-
tectable methanol. As mentioned in Section 2.1, the mass concentra-
tions of glycerin and glycerides are relatively high compared with
other four samples with initial properties. This may partly contribute
to the low FAME contents for Bsoy-1.
3.2. Influence of storage time on acid value and induction periods
The acid values measured at Dec. 2009 and Dec. 2010 were ob-
served to show some random array regardless of the sources of bio-
diesel, they ranged from 0.09 to 0.45, and from 0.2 to 0.6 mg KOH/g
sample, respectively. It is obvious that all acid values measured at
Dec. 2009 did not exceed the ASTM D6751 limit of 0.5 mg KOH/g
samples, even for samples sampled in 2006 (e.g., Bsoy-2, Bca-1 and
Ban-1). But almost all acid values increased after a one year storage,
three of them (Bsoy-2, Bsoy-3 and Ban-1) exceeded 0.5 mg KOH/g.
The random AV profile regardless of biodiesel sources suggests that
feedstocks show little influence on acid values, especially for fresh
biodiesel. It is true that good processing procedures can convert free
fatty acids to biodiesel either before or during the transesterification
reaction. The increase of AV with the extension suggests that the stor-
age time is a main factor contributing to the poor quality of some
samples. After a one year storage, the AVs of most soya feedstock
fuels were found to be higher than the samples with a high abun-
dance of cis-9, C18:1 ME (Table 3). This is because FAMEs with
more than one double bond are more susceptible to oxidation [2] dur-
ing storage. As seen from Table 3, the sum of FAMEs with more than
one double bond (∑PUFAME) was the most abundant composition
(47−58% by mass) in Bsoy-2 and Bsoy-3. The high abundance of unsta-
ble ∑PUFAME could result in the significant increase of acid values
during storage. Similarly, some studies showed that the quality of bio-
diesel over a longer period of storage strongly depended on the tank
material as well as contact to air or light. They found the increases in
viscosities and acid values versus the decreases in induction periods
after storing for a longer time [2,14]. The variation of AV for Bsoy-1
is out of regular expectation; this may partly result from the experi-
mental errors in measuring acid values. Additionally, acid values for
some samples at different storage time points showed some random
variation regardless of the FAME composition (e.g., Bca-2, Bca-3,
Ban-2, Ban-3). The possible presence of antioxidants in samples may
contribute to the variation of acid values with storing extension ex-
cept for FAME composition.
Similarly, induction periods at different storage time points were
also obtained with a one year gap (Table 3). The average IP values
of Ban samples were determined to be 9.2−11.8 h within a one year
storage, they ranged from 4.8 to 5.4 h for Bca samples, 4.6–5.6 h for
Bsoy-2 and Bsoy-3 samples. It is clear that IP generally decreased after a
one year storage, especially for Bsoy-1, its IP decreased from 2.3 to 0.7.
Ban samples at any measured points meet the EN-14214 minimum
limit of 6 h. All other samples, except for Bsoy-1, meet the ASTM
D-6751 minimum limit of 3 h. That is to say, the oxidative stability of
Ban is higher than the Bca and Bsoy samples. Similar IP ranges were ob-
served among Bsoy (except for Bsoy-1) and Bca samples. It seems that
the relative higher contents of saturated FAMEs (∑SFAME) counteract
with the negative influence of ∑PUFAME on oxidative stability in most
Bsoy samples, which makes most Bsoy samples to have similar IP with Bca
samples. It is well known that even small amounts of poly-unsaturated
fatty compounds containing bis-allylic carbons are supposed to strongly
decrease the IP values [17]. In conclusion, AV generally increased, and IP
generally decreased after storing for about one year.
The exception of Bsoy-1 can be explained by many assumptions.
Firstly, free fatty acids have been shown to have a significant effect on
the oxidizability of oil [17]. Miyashita and Takagi [25] have compared
the oxidation of oleic (cis-9, C18:1), linoleic (cis-9, 12, C18:2) and
linolenic (cis-9, 12, 15, C18:3) acids with their corresponding methyl
esters, the free acids were found to be far more vulnerable to be oxi-
dized. However, the measured acid values for the Bsoy-1 were lower
than the other Bsoy samples, indicating the absence of a high concentra-
tion of free fatty acids. Secondly, the effect of the addition of solvents
(methanol, acetone, and water) into biodiesels on IP values was tested
to evaluate their contribution to the quite low IP for Bsoy-1 sample, how-
ever, the IP values did not show obvious variation (data not shown
here) when altering the solvent volume ratio in the range of 1.7 to
16.7%. Thirdly, as indicated in many previous reports [5,16,17], a variety
of other factors, for example, exposure to air and/or light, temperatures
above ambient, as well as presence of extraneous materials with cata-
lytic and inhibitory effects on oxidation, possess catalytic or inhibitory
effects on oxidative stability. All these products were stored in similar
air-tight tank in a −4 °C cold room. Therefore, the initial IP of Bsoy-1 is
2.3 h indicating that without antioxidants present in the Bsoy-1 sample.
It can be concluded that Bsoy-1 was not contaminated by metals. If Bsoy-1
was contaminated by metals, the initial IP should be far less than 2.3 h.
3.3. The correlation between FAME composition and IP values
To investigate the dominant factor influencing the IP values for
various biodiesel products, the relationship of the measured IP at
two measured time points and APE/BAPE for all samples except for
Bsoy-1 was estimated. It was found that the IP values increased with
the decrease of APE and BAPE values. However, the value of the
square of correlation coefficient (r 2) is quite low (less than 0.2) for
both of them, and the impact of APE on IP values is much less than
BAPE. Similar correlation has been achieved by some previous reports
[6,17], their explanation for the low r 2 may be that the amount of nat-
ural antioxidants is different in different biodiesels, which depends
on the process of production and the process of distillation of biodie-
sel. Similarly, all biodiesels in the present study are commercially
available products, the concentrations of antioxidants were not avail-
able, which may partly contribute to the low coefficients.
For another parameter of OX, the measured IP generally increased
with the decrease of OX. However, the correlation coefficient be-
tween OX and IP values was less than 0.4. Similar to Jain's conclusion
[6], OX is not a very reliable parameter to denote IP values.
As all above parameters did not accurately describe the relation-
ship between FAME composition and IP, the sum of FAMEs based on
their saturated degree were calculated and listed in Table 3. Based
on the measured IP at different storage time points and the FAME
composition, it can be qualitatively concluded that IP generally posi-
tively proportional to the concentration of saturated FAMEs and neg-
atively proportional to the concentration of poly-unsaturated FAMEs.
The plottings of various FAMEs by saturated degree versus two series
 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375 371

of measured IP values are shown in Fig. 2. It was found that all IP values,
except for Bsoy-1, increased with the increasing of ∑SFAME. The Pear-
son Correlation analysis indicated that both variables positively corre-
late with each other with a correlation coefficient of 0.959 and p
values below 0.050. A decreasing tendency between ∑PFAME versus
IP was observed; the Pearson Correlation analysis suggested a negative
correlation with a correlation coefficient of −0.914, p b 0.05. However,
the Pearson Correlation analysis demonstrated no significant relation-
ships between ∑MUFAME and IP (p> 0.05). Additionally, the linear re-
lationship of the measured IP values versus ∑SFAME, and ∑PUFAME
(except for Bsoy-1) was fitted to mathematically describe the correla-
tion. The positive linear correlation with a square of correlation coeffi-
cient up to as high as 0.90–0.92 for IP versus ∑SFAME, and the
negative linear correlation with a square of correlation coefficient of
0.64–0.67 between IP and ∑PUFAME were observed. The good corre-
lation between IP and ∑SFAME and ∑PUFAME indicates that the
FAME composition based on saturated degree is one of the controlled
factor affecting IP values, although the information of antioxidants
was not available for these samples.
3.4. Effect of metal contaminants on oxidation stability
Sarin et al. [5] investigated the effect of several transition metal
naphthenates (iron, nickel, manganese, cobalt, and copper) on oxida-
tion stability of their own synthesized Jatropha methyl ester. They
found that copper showed the strongest catalytic effect on the
depression of induction time. Similar results have been achieved by
Knothe et al. [17] in 2003 when they tested the effect of copper,
iron, and nickel on IP of methyl oleate at 90 °C.
Currently, the commonly used tank materials for storing biodiesel
include steel and aluminum. In this study, steel and aluminum as stan-
dard reference material from NIST, were blended with varying concen-
trations in biodiesels from three feedstocks to study the catalytic effects
on IP. The influence of copper and lead was investigated as copper
showed a strong catalytic effect on oxidative stability expressed as IP
values [17] and little was known for lead. Fig. 3 shows the effect of the
above metals with varying concentration on IP values for biodiesels
sourced from three feedstocks. The IP values decreased significantly
with the addition of copper (−10 to +40 mesh) and lead (~325
mesh) from 0 to 0.5% by mass for all these three biodiesels, then they
were almost unaltered with the continuous increasing of these two
metals. A very slight decrease of IP was found when steel (SRM 8k)
and aluminum alloy (SRM 1240c) were added. It is clear that small
amounts of copper or lead had nearly the same influence on the induc-
tion period as larger amounts. Therefore, lead and copper showed sig-
nificant catalytic effects on the oxidative stability for all biodiesels.
However, the presence of steel and aluminum alloy did not show obvi-
ous catalytic or inhibited effects. t-Test showed that no significant dif-
ference (p> 0.05) was found between copper and lead, and steel and
aluminum alloy, but significant difference (pb 0.05) was observed
between copper/lead and steel/aluminum alloy. The dependence of
the induction period on copper and lead in biodiesel resulted in the ac-
celeration of free radical oxidation due to a metal-mediated initiation
reaction [5,24]. The effect of these metals on IP is similar among the dif-
ferent biodiesel products, which is independent on biodiesel sources. As

a b
12 12

8 8

4 4
0 5 1 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Sum fo SFAME (%, m/m) Sum fo SFAME (%, m/m)
Induction periods (hours)

12 12

8 8

4 4
20 30 40 50 60 70 80 20 30 40 50 60 70 80
Sum of MUFAME (%, m/m) Sum of MUFAME (%, m/m)
12 12

8 8

4 4
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Sum of PUFAME (%, m/m) Sum of PUFAME (%, m/m)

Fig. 2. Correlation of FAME composition vs. IP values. (a) Data obtained at Dec. 2009; (b) data obtained at Dec. 2010.
372 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375

6 when traces of water cause hydrolysis of the esters into alcohol and
Bsoy-2 Pb
Cu acids [2], the spiking of water into biodiesel alone and biodiesel with
5 Al lead or copper did not change IP values clearly. It is well known that
Steel
4 the high temperature (110 °C), and the abundant oxygen (10 L/h of
air flow) in the Accelerated Oxidative System accelerate the oxidative
3 rate of FAMEs. Beside oxidation caused by exposure to air (oxygen)
and high temperature, biodiesel is also potentially subject to hydrolytic
2 degradation due to the presence of water. However, the abiotic hydro-
lysis rates of FAME were found to be slower than the microbial degrada-
1 tion rates in seawater matrix, the base-catalyzed hydrolysis half-lives of
FAMEs were estimated to be 7 years at pH 7, and 70 years at pH 6
0
0 2 4 6 8 10 12 14 (25 °C) [26]. This can be used to explain the almost unaltered IP values
12 with the spiking of water into pure biodiesel. Also, the contribution of
Ban-1
water was not beneficial to dissolving metals, or the amount of
Induction period (hours)

10 dissolved metal ions was enough to catalytically oxidize FAMEs even

without the contribution from water.
8
Knothe and Dunn [17] reported that particle size and the thick-
6
ness of oxide coating contributed somewhat to the finally deter-
mined IP values. Herein, some currently produced and long term
4 stored copper and lead with different particle sizes were utilized to
test the impact of particle size and thickness of oxide coating of
2 metal on the oxidative stability of biodiesel. The measured IP values
increased slightly when particle sizes and oxide coating thickness in-
0 creased for copper/lead. However, the catalytic effects for both of
0 2 4 6 8 10 12
6 them were still more significant than the currently produced steel
Bca-1 and aluminum alloy.
5

4 3.6. Improvement of oxidation stability

3 Two types of antioxidants were generally known: chain breakers

2
1
0 oxidants contain a highly labile hydrogen that is more easily abstract-
0 2 4 6 8 10
Metal concentration (%, mass/mass)
Fig. 3. Effect of various metals on induction periods of biodiesels sourced from three
feedstocks.
mentioned in previous sections, the steel and aluminum alloy used in
this study are NIST SRM standards, therefore, steel or aluminum tanks
with similar elemental composition to SRM 8k or 1240c can be used
to store biodiesel without obvious catalytic degradation of biodiesel
products.
3.5. Other factors on oxidation stability
If lead or copper ions play a major role on the catalysis of the oxida-
tion of biodiesel, the existence of water is supposed to result in more
dissolved metal ions due to their high water solubility. In this scenario,
the synergetic effect of water plus lead or copper in decreasing IP values
should be observed. To verify this assumption, the IP values for
biodiesels spiked with various concentrations of H2O, lead (~325
mesh) or copper (−10 to +40 mesh), and H2O plus lead/copper
were compared (Fig. 4). Similar to the results in former sections, the
presence of H2O did not alter the IP values significantly from the spiking
concentration (mass/mass) of 0.05% to 10%, but a slight increase of IP
values was observed for all samples. The co-contribution of copper/
lead with water did not significantly enhance or decrease the oxidation
of different biodiesels compared with metals alone, slightly lower or
higher IP values were observed in these tests. These slight differences
can be a result of experimental errors because t-test showed no signifi-
cant difference between them (p> 0.05). Although acid can be formed
and hydroperoxide decomposers [27]. The most commonly used
chain breaking antioxidants in improving oxidation stability of bio-
diesel are phenolic and amine-types of antioxidants, which can be
sourced from both nature and chemical synthesis [5,6,12]. These anti-
12 14 ed by a peroxy radical than fatty oil or ester hydrogen. The resulting
antioxidant free radical is either stable or further reacts to form a sta-
ble molecule which is further resistant to a chain oxidation process.
Thus the chain breaking antioxidants interrupt the oxidation chain
reaction in order to enhance stability [6].
As mentioned in previous sections, the measured IP of Bsoy-1 was
close to 0.7 h in Dec. 2010, which is far less than the EN-14112 and
ASTM D-6751 limits of 6 h and 3 h. Therefore, some antioxidants
were tested to improve the IP to meet the corresponding limits. The
enhanced efficiency of various antioxidants, including TBHQ, PY, PG,
BHA, BHT and α-tocopherol, was evaluated and compared by altering
their concentration ranged from 0 to 8000 ppm. The measured IP for
Bsoy-1 with different antioxidants and spiking concentrations is com-
pared in Fig. 5(a–b).
It can be seen that the IP of Bsoy-1 increased with the increase in dos-
age of all antioxidants except for α-tocopherol. PY was found to result in
the greatest enhancement in IP when the concentration was less than
3000 ppm, however, TBHQ was the best when the concentration was
higher than 3000 ppm (Fig. 5a), followed by PG, BHA, and BHT, ranked
from high to low (Fig. 5b). The enhancement performance in IP for nat-
ural antioxidant (α-tocopherol) was not obvious, as α-tocopherol is rel-
atively weak in increasing the induction times of biodiesel compared
with β- and γ-tocopherols [28]. The IP values improved from 0.7 h to
above 6 h as required by the EN-14112 specification when the concen-
tration of PY and TBHQ was about 1500 ppm and 3000 ppm, respec-
tively. For PG, the spiking concentration should be higher than
6000 ppm; for BHA, BHT, and α-tocopherol, this cannot be satisfied
even when their concentrations were as high as 8000 ppm. The weaker
enhancement effectiveness of TBHQ with a lower concentration com-
pared with that of PY was evaluated by a repeated test. Similar results
 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375 373

6 6
Bsoy-2
Bsoy-2
5 5

4 H2O 4 H2O
Cu
Pb
5%H2O+Cu
3 3 5%H2O+Pb

2 2

1 1

0 0

6 6
Bca-1 Bca-1
5 5
Induction period (hours)

4 4

3 3

2 2

1 1

0 0

12 12
Ban-1 Ban-1
10 10

8 8

6 6

4 4

2 2

0 0
0 2 4 6 8 10 0 2 4 6 8 10 12
Mass content of spiked water and metals (%, mass/mass)
Fig. 4. Effect of water plus copper/lead on the oxidative stability of different biodiesels.

were obtained (data not shown here), which indicated the good accura-
cy of the results.
Numerous studies have evaluated the effect of various antioxidants
on the oxidative stability of biodiesel [10,11,15,29]. The effectiveness
of different antioxidants varied in different situations. For example, PY
was reported to be the best sometimes [15], TBHQ [12], PG [29], or
BHA [10] was also found to be the best performer in other situations,
but α-tocopherol was always found to exhibit the least enhancement
effectiveness regardless of biodiesel sources and storage condi-
tions [10,20]. In all, the effectiveness of an antioxidant can depend on
a variety of factors, including the fatty acid profile of the oil or fat, the
amount of naturally occurring antioxidants, and storage or other condi-
tions. The performance of synthetic antioxidants is generally better than
the natural ones [10,29]. Synergistic effects are possible in the case of
co-contribution of different antioxidants [16].
3.7. Improving the oxidation stability for metal contaminated biodiesels
Just as the description in Section 3.4, the addition of metals (copper
and lead) resulted in the decreasing oxidation stability for all biodiesels
from different sources. To find the appropriate antioxidant concentra-
tion for metal contaminated samples meeting the EN-14214 minimum
limits, metal contaminated samples (Bsoy-2, Bca-1, and Ban-1) were sim-
ulated by spiking with 5% (mass/mass) of copper or lead. Then the IP for
these samples was measured by altering the PY concentration. The data
are plotted in Fig. 6 versus the PY loading amount. It is noted that the IP
374 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375

60 16
TBH a Bsoy-2 Bsoy-2
PY Bsoy-2 with 5% Pb
12 Bsoy-2 with 5%Cu
40
8

20 4

0
0
Induction period (hours)

16
Bca-1 Bca-1
Bca-1 with 5% Pb
0 2000 4000 6000 8000 10000

Induction period (hours)

12 Bca-1 with 5% Cu
8
PG
BHA
b
8
BHT
6 a-tocopherol

4
0

16
Ban-1 5%Cu
0 5% Pb

12

-2
0 2000 4000 6000 8000 10000
Antioxidants concentration (ppm) 8

Fig. 5. Influence of antioxidant concentration on the oxidation stability of Bsoy-1.

of Ban was higher than 9 (Table 3), so no data is available for pure Ban
with PY. Only Bca-1 was selected as the representative of Bca samples
as their IP values and chemical composition are similar to each other.
Clearly, IP values increased with the increment of the dosage of PY.
For Bsoy-2, the original IP was 4.8 h; it reached to 6 h when PY concen-
tration was increased to 50 ppm. For Bsoy-2 mixed with 5% Cu or Pb, the
IP decreased to less than 1 h, they increased with the increasing dosage
of PY, and reached to 6 h when PY concentration increased to 500 ppm.
For Bca-1, the original IP value was 5.0 h, it reached to 10 h when the PY
concentration increased to 50 ppm, so less than 50 ppm of PY can satis-
fy the specification of oxidation stability. Similarly, the IP values for Bca
spiked with 5% Cu or Pb decreased significantly due to the catalytic ef-
fects of both metals. When the PY concentration was about 100−
200 ppm, their IP values could satisfy the EN-14112 limit. For Ban spiked
with 5% Cu or Pb, their IP decreased from 10 h to close to 4 h. However,
they increased to above 6 h when the PY concentration was about
50 ppm.
The enhancement effectiveness of PY on copper or lead contaminat-
ed biodiesels varied with the source of biodiesels. In detail, for copper
and lead contaminated Bsoy-2, t-test showed no significant difference
(p> 0.05) between two series of data, therefore, almost similar effec-
tiveness was observed. Although visual stronger effectiveness was ob-
served for lead contaminated Bca-1 and Ban-1 compared with copper
contaminated ones, t-test showed no significant difference (p>0.05).
This visual difference can be partly attributable to experimental errors.
4. Conclusions
The factors, including solvents, metals, FAME chemical composi-
tion, and some antioxidants, affecting oxidation stability during stor-
age for several commercially available biodiesel products in Canada
4
0
0 100 200 300 400 500 600
Concentration of PY (ppm)
Fig. 6. Influence of antioxidant concentration on the oxidation stability of copper and
lead contaminated biodiesels sourced from three feedstocks.
were investigated. The results showed that the absolute acid values
were independent on FAME composition, but the variation of acid
values was kind of dependent on the feedstock of biodiesel with the
extension of storage. When oxidative stability was expressed as in-
duction periods, oxidative stability was positively correlated with
∑SFAME and negatively correlated with ∑ PUFAME in spite of the
possible interference of antioxidants. The acid values generally in-
creased, and induction periods generally decreased after a one year
storage in a dark cold room (− 4 °C) in an air‐tight tank. The presence
of pyrogallol or tert-butylhydroxyquinone showed the strongest en-
hancement of induction periods. Copper and lead showed a strong
catalytic effect on decreasing oxidative stability, but not for steel
and aluminum alloy. The solvents (methanol, acetone and water)
did not show contribution to altering the IP values. This study
shows a promising theoretical guidance for the transportation, stor-
age and usage of biodiesel products.
Acknowledgments
This work was funded by the Natural Resources Canada, under the
PERD program through POL 2.1.2 Advanced Fuels & Transportation
Emissions Reduction (AFTER), supported by the Fundamental
Research Funds for the Central Universities, South-Central University
 Z. Yang et al. / Fuel Processing Technology 106 (2013) 366–375
for Nationalities (CZZ11006) the Natural Science Foundation of
South-Central University for Nationalities (YCZZ11006). Fuel samples
were generously provided by Debbie Rosenblatt of the Emissions
Research and Measurement Division of Environment Canada from
commercial sources.
References
[1] A. Bouaid, M. Martinez, J. Aracil, Production of biodiesel from bioethanol and
Brassica carinata oil: oxidation stability study, Bioresource Technology 100
(2009) 2234–2239.
[2] A. Bouaid, M. Martinez, J. Aracil, Long storage stability of biodiesel from vegetable
and used frying oils, Fuel 86 (2007) 2596–2602.
[3] L.M. Das, D.K. Bora, S. Pradhan, M.K. Naik, S.N. Naik, Long-term storage stability of
biodiesel produced from Karanja oil, Fuel 88 (2009) 2315–2318.
[4] EN 14112, Fatty acid methyl esters (FAME)—determination of oxidation stability
(accelerated oxidation test), 2003.
[5] A. Sarin, R. Arora, N.P. Singh, M. Sharma, R.K. Malhotra, Influence of metal contami-
nants on oxidation stability of Jatropha biodiesel, Energy 34 (2009) 1271–1275.
[6] S. Jain, M.P. Sharma, Stability of biodiesel and its blends: a review, Renewable and
Sustainable Energy Reviews 14 (2010) 667–678.
[7] W. Li, W. Du, D. Liu, Y. Yao, Study on factors influencing stability of whole cell dur-
ing biodiesel production in solvent-free and tert-butanol system, Biochemical En-
gineering Journal 41 (2008) 111–115.
[8] G. Karavalakis, S. Stournas, D. Karonis, Evaluation of the oxidation stability of
diesel/biodiesel blends, Fuel 89 (2010) 2483–2489.
[9] R.O. Dunn, Effect of oxidation under accelerated conditions on fuel properties of
methyl soyate (biodiesel), Journal of the American Oil Chemists' Society 79
(2002) 915–920.
[10] R.O. Dunn, Effect of antioxidants on the oxidative stability of methyl soyate
(biodiesel), Fuel Processing Technology 86 (2005) 1071–1085.
[11] R.O. Dunn, Oxidative stability of biodiesel by dynamic mode pressurized-differential
scanning calorimetry (P-DSC), Transactions of the ASABE 49 (2006) 1633–1641.
[12] A. Sarin, R. Arora, N.P. Singh, R. Sarin, R.K. Malhotra, Oxidation stability of palm
methyl ester: effect of metal contaminants and antioxidants, Energy & Fuels 24
(2010) 2652–2656.
[13] R.L. McCormick, M. Ratcliff, L. Moens, R. Lawrence, Several factors affecting the
stability of biodiesel in standard accelerated tests, Fuel Processing Technology
88 (2007) 651–657.
375
[14] M. Mittelbach, S. Gangl, Long storage stability of biodiesel made from rapeseed and
used frying oil, Journal of the American Oil Chemists' Society 78 (2001) 573–577.
[15] M. Mittelbach, R. Schaeffer, The influence of antioxidants on the oxidation stabil-
ity of biodiesel, Journal of the American Oil Chemists' Society 80 (2003) 817–823.
[16] G. Knothe, Some aspects of biodiesel oxidative stability, Fuel Processing Technol-
ogy 88 (2007) 669–677.
[17] G. Knothe, R.O. Dunn, Dependence of oil stability index of fatty compounds on
their structure and concentration and presence of metals, Journal of the American
Oil Chemists' Society 80 (2003) 1021–1026.
[18] W.E. Neff, E. Selke, T.L. Mounts, E.N. Rinsch, M.A.M. Zeitoun, Effect of
triacylglycerol composition and structures on oxidative stability of oils from se-
lected soybean germplasm, Journal of the American Oil Chemists' Society 69
(1992) 111–118.
[19] P. Bondioli, A. Gasparoli, L.D. Bella, S. Tagliabue, Evaluation of biodiesel storage
stability using reference methods, European Journal of Lipid Science and Technol-
ogy 104 (2002) 777–784.
[20] Y.C. Liang, C.Y. May, C.S. Foon, M.A. Ngan, C.C. Hock, Y. Basiron, The effect of nat-
ural and synthetic antioxidants on the oxidative stability of palm diesel, Fuel 85
(2006) 867–870.
[21] L.S. Gang, M. Mittelbach, The impact of antioxidants on biodiesel oxidation stabil-
ity, European Journal of Lipid Science and Technology 106 (2004) 382–389.
[22] D.Y.C. Leung, B.C.P. Koo, Y. Guo, Degradation of biodiesel under different storage
conditions, Bioresource Technology 97 (2006) 250–256.
[23] R.M. Balabin, R.Z. Safieva, Biodiesel classification by base stock type (vegetable
oil) using near infrared (NIR) spectroscopy data, Analytica Chimica Acta 689
(2011) 190–197.
[24] G. Knothe, Dependence of biodiesel fuel properties on the structure of fatty acid
alkyl esters, Fuel Processing Technology 86 (2005) 1059–1070.
[25] K. Miyashita, T. Takagi, Study of the oxidative rate and prooxidant activity of free
fatty acids, Journal of the American Oil Chemists' Society 63 (1986) 1380–1384.
[26] J.A. DeMello, C.A. Carmichael, E.E. Peacock, R.K. Nelson, J. Samuel Arey, C.M.
Reddy, Biodegradation and environmental behavior of biodiesel mixtures in the
sea: an initial study, Marine Pollution Bulletin 54 (2007) 894–904.
[27] J. Pospisil, P.P. Klemchuk, Oxidation Inhibition in Organic Materials, CRC Press,
1990.
[28] A. Fröhlich, S. Schober, The influence of tocopherols on the oxidation stability of
methyl esters, Journal of the American Oil Chemists' Society 84 (2007) 579–585.
[29] S.-K. Loh, S.-M. Chew, Y.-M. Choo, Oxidative stability and storage behavior of fatty
acid methyl esters derived from used palm oil, Journal of the American Oil Chemists'
Society 83 (2006) 947–952.