Energy Sources, Part A: Recovery, Utilization, and

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Biodegradability of Biodiesel and Petrodiesel Fuels

A. Demirbaş

To cite this article: A. Demirbaş (2008) Biodegradability of Biodiesel and Petrodiesel Fuels,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 31:2, 169-174, DOI:
10.1080/15567030701521809

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Energy Sources, Part A, 31:169–174, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567030701521809

Biodegradability of Biodiesel and Petrodiesel Fuels

A. DEMIRBAŞ1
1
Sila Science, Trabzon, Turkey

Abstract In this work, biodegradation of biodiesel samples were studied. Biodiesel

is a renewable diesel fuel of domestic origin derived from a variety of fats and oils
by a transesterification reaction. It consists of the alkyl esters, usually methyl esters,
of the fatty acids. Biodiesel is one of the most interesting ways to produce renew-
able liquid fuel for transportation. Advantages of biodiesel include domestic origin,
reducing the dependency on imported petroleum, biodegradability, high flash point,
and inherent lubricity in the neat form. There are many methods for biodegradation.
The biodegradation is quantified by trapping carbon dioxide (CO2 ) formed in the
vessel during biodegradation. Among them, the CO2 evolution method is relatively
simple, economical, and environmentally safe. Comparison of the biodegradability of
biodiesel to conventional reference diesel fuel (2-D) was studied. The 2-D was used
for a comparison petroleum diesel in all of the studies. The results demonstrate that
all biodiesels assessed are biodegradable, with similar shaped curves with 80.4 to
91.2% biodegradation after 30 days, whereas the 2-D sample reached only 24.5%
biodegradation. Biodegradation is degradation caused by biological activity, partic-
ularly by enzyme action leading to significant changes in the material’s chemical
structure. The biodegradability of biodiesel is dependent on the chemical structure of
the fatty acids.

Keywords biodegradability, biodiesel, diesel fuel (2-D), renewable sources

Introduction
Biodiesel is one of the most interesting ways to produce renewable liquid fuel for
transportation. It can substitute for petrodiesel in Diesel engines (Demirbaş, 2003).
Biodiesel is a renewable, alternative diesel fuel of domestic origin derived from a variety
of fats and oils by a transesterification reaction; thus, it consists of the alkyl esters, usually
methyl esters, of the fatty acids of the parent oil or fat (Knothe et al., 2006). Biodiesel
has a heating value about 88% that of conventional petrodiesel fuel (Bala, 2005).
Advantages of biodiesel include domestic origin, reducing the dependency on im-
ported petroleum, biodegradability, high flash point, and inherent lubricity in the neat
form (Knothe et al., 2005; Mittelbach and Remschmidt, 2004). Recently, biodiesel has
become more attractive because of its environmental benefits and the fact that it is made
from renewable resources (Ma and Hanna, 1999).
As biodiesel fuels are becoming commercialized, their existence in the environment
is an area of concern since petroleum oil spills constitute a major source of contamination
of the ecosystem (Peterson et al., 1995). Among these concerns, water quality is one of the
most important issues for living systems. It is important to examine the biodegradability

Address correspondence to Professor Ayhan Demirbaş, P. K. 216, TR-61035 Trabzon, Turkey.

E-mail: [email protected]

169
170 A. Demirbaş

Table 1
Fuel economy impacts of biodiesel use

% Biodiesel in diesel fuel % Reduction in miles/gallon

20 0.9–2.1
100 4.6–10.6
Source: EPA, 2002.

of biodiesel fuels and their biodegradation rates in natural waterways in case they enter the
aquatic environment in the course of their use or disposal. Chemicals from biodegradation
of biodiesel can be released into the environment. With the increasing interest in biodiesel,
the health and safety aspects are of utmost importance, including determination of their
environmental impacts in the transport, storage, or processing.
Biodiesel has demonstrated a number of promising characteristics, including reduc-
tion of exhaust emissions (Dunn, 2001). The vegetable oil fuels have not been acceptable
because they are more expensive than petroleum fuels. With recent increases in petroleum
prices and uncertainties concerning petroleum availability, there is renewed interest in
vegetable oil fuels for compression ignition engine (CIE or diesel) engines. Alternative fu-
els for CIE have become increasingly important due to increased environmental concerns
and several socioeconomic aspects. In this sense, vegetable oils and animal fats represent
a promising alternative to conventional diesel fuel (Dorado et al., 2003). One of the
most common blends of biodiesel contains 20 vol% biodiesel and 80 vol% conventional
diesel. For soybean-based biodiesel at this concentration, the estimated emission impacts
for percent change in emissions of NOx , PM, HC, and CO were C20%, 10.1%, 21.1%,
and 11.0%, respectively, according to the U.S. Environmental Protection Agency (EPA,
2002). The possible impact of biodiesel on fuel economy is positive, as given in Table 1.
Biodegradation is degradation caused by biological activity, particularly by enzyme
action leading to significant changes in the material’s chemical structure. There are many
methods for biodegradation. Among them, the carbon dioxide (CO2 ) evolution method is
relatively simple, economical, and environmentally safe. Another method is to measure
the biochemical oxygen demand (BOD) with a respirometer (Piskorz and Radlein, 1999).
The aim of the study presented in this article was to determine the ultimate aerobic
biodegradability of biodiesel in order to evaluate if they could be a local environmental
hazard in accidental discharges.

Experimental
Rapeseed, sunflower seed, soybean, and hazelnut kernel oils were used to obtain biodiesel
samples. Table 2 shows the fatty acid compositions of vegetable oil samples.
The biodegradation is quantified by trapping carbon dioxide (CO2 ) formed in the
vessel during biodegradation. In the experiments, a modified EPA evolution method was
used (EPA, 1982). The biodegradation is quantified by trapping CO2 formed in the vessel
during biodegradation.
According to the EPA method, a reservoir holding 10 ml of barium hydroxide solution
is suspended in a 2-liter Erlenmeyer flask to trap CO2 . After inoculation, the test flasks
are sparged with CO2 -free air to ensure aerobic conditions and that CO2 is trapped only
from the microorganisms metabolizing the test substrate. To obtain CO2 -free air, the
 Biodegradability of Diesel Fuels 171

Table 2
Fatty acid compositions of vegetable oil samples

Oil sample 16:0 16:1 18:0 18:1 18:2 18:3

Rapeseed 3.5 0 0.9 64.1 22.3 8.2

Sunflower seed 6.4 0.1 2.9 17.7 72.9 0
Soybean 13.9 0.3 2.1 23.2 56.2 4.3
Hazelnut kernel 4.9 0.2 2.6 83.6 8.5 0.2
Source: Demirbaş, 2005.

flask was aerated with compressed air that had been scrubbed free of CO2 by passage
through a series of three 2,000-mL bottles, each containing 1,000 mL of 5N KOH. The
flask was sealed and incubated with shaking in a dark room. CO2 -free air is passed
through the test solution, and the CO2 released from bio-oxidation of the test material
is reacted quantitatively in a solution of Ba(OH)2 . Thus, evaluated CO2 is fixed with
barium hydroxide, Ba(OH)2 . Fixed CO2 was titrated with a solution of 0.1 N HCl to the
phenolphthalein endpoint.

CaCO3 C 2HCl ! CaCl2 C CO2 C H2 O (1)

1:00 mg C 6:08 mg HCl

From Eq. (1), the stoichiometric amount of HCl is 6.80 mg (or 1.667 mL of solution of
0.l N HCl) required to titrate the CO2 evolved from biodegradation of 1.00 mg carbon
in the test substrate.
All the samples were analyzed in a 30-day period to obtain biodegradation plots.
The CO2 evolved from biodegradation was measured for 5, 10, 15, 20, 25, and 30 days
at 293–298 K. All the biodegradation tests were duplicated.

Results and Discussion

The cumulative biodegradation measured for each sample as a function of time are
plotted in Figure 1. As shown on Figure 1, all the biodiesel samples tested have very
similar biodegradation rates, with similar shaped curves and biodegradation between
80.4 to 91.2% after 30 days, whereas the reference diesel fuel (2-D) sample reached
only 24.5% biodegradation. The biodegradation degrees of the biodiesel samples from
sunflower seed, rapeseed, soybean, and hazelnut kernel oils are 91.2, 87.9, 84.7, and
80.4%, respectively, after 30 days. Among four biodiesel samples, the most biodegradable
biodiesel is sunflower seed oil methyl ester, while the lowest biodegradable biodiesel is
hazelnut kernel oil methyl ester. All biodegradation curves show high degradation rates
during the first 10 days. The biodegradabilities of several biodiesel fuels in the aquatic
environment show that all biodiesel fuels are readily biodegradable. After 28 days, all
biodiesel fuels were 77–89% biodegraded; diesel fuel was only 18% biodegraded (Zhang,
1996).
The biodegradabilities of biodiesel fuels obtained from the present study are in
good agreement with earlier observations. The reproducibility of the measurements is
satisfactory since the standard deviation between the reference samples is 5% of the
biodegradation.
172 A. Demirbaş

Figure 1. Plots for biodegradation of vegetable oil methyl esters (ME) or biodiesels and 2-D diesel
fuel.

The difference between the biodegradability rates of the biodiesel samples can be
explained by the different fatty acid structures of the vegetable oils. Even if the same
chemical families of compounds are present in vegetable oils, theirs linoleic and linolenic
acid contents are significantly different. The biodegradation had a much greater effect
on the polyunsaturated fatty acids such as linoleic and linolenic acids than saturated
and monosaturated fatty acids. Fatty acids in vegetable oils are hydrocarbon chain in
ester form with oxygen atoms attached, which makes them very biologically active. The
enzymes responsible for the dehydrogenation/oxidation reactions that occur in the process
of degradation recognize oxygen atoms and attack them immediately (Zhang et al., 1998).
The biodegradability data of petroleum and bio-fuels available in the literature are
presented in Table 3. Heavy fuel oil has a low biodegradation of 11% in 28-day laboratory
studies due to its higher proportion of high molecular weight aromatics (Mulkins-Phillips
and Stewart, 1974; Walker et al., 1976). Gasoline is considerably biodegradable (28%)
after 28 days. Vegetables oils and their derived methyl esters (biodiesels) are rapidly
degraded to reach biodegradation of between 76% and 90% (Zhang et al., 1998; Mudge
and Pereira, 1999). In their studies, Zhang et al. (1998) have shown that vegetables oils
are slightly less degraded than their modified methyl ester.
Many of the vegetable oils contain polyunsaturated fatty acid chains that are meth-
ylene interrupted rather than conjugated. The double bond of unsaturated fatty acids
restricts rotation of the hydrogen atoms attached to them. Therefore, an unsaturated fatty
acid with a double bond can exist in two forms. The cis form in which the two hydrogens
are on the same “side” and the trans form in which the hydrogen atoms are on the opposite
sides.
 Biodegradability of Diesel Fuels 173

Table 3
Biodegradability data of petroleum and bio-fuels

Degradation in
Fuel sample 28 days, % References

Gasoline (91 octane) 28 Speidel et al., 2000

Heavy fuel (bunker C oil) 11 Mulkins-Phillips and Stewart,
1974; Walker et al., 1976
Refined rapeseed oil 78 Zhang et al., 1998
Refined soybean oil 76 Zhang et al., 1998
Rapeseed oil methyl ester 88 Zhang et al., 1998
Sunflower seed oil methyl ester 90 Zhang et al., 1998

Oxidation to CO2 of biodiesel results in the formation of hydroperoxides. The forma-

tion of the hydroperoxide follows a well-known peroxidation chain mechanism. Oxidative
lipid modifications occur through lipid peroxidation mechanisms in which free radicals
and reactive oxygen species abstract a methylene hydrogen atom from polyunsaturated
fatty acids, producing a carbon-centered lipid radical. Spontaneous rearrangement of the
1,4-pentadiene yields a conjugated diene, which reacts with molecular oxygen to form
a lipid peroxyl radical. Abstraction of a proton from neighboring polyunsaturated fatty
acids produces a lipid hydroperoxide (LOOH) and regeneration of a carbon-centered
lipid radical, thereby propagating the radical reaction (Browne and Armstrong, 2000).
After hydrogen is removed from such carbons, oxygen rapidly attacks, and a LOOH is
ultimately formed where the polyunsaturation has been isomerized to include a conjugated
diene. This reaction is a chain mechanism that can proceed rapidly once an initial
induction period has occurred. The greater the level of unsaturation in a fatty oil or
ester, the more susceptible it will be to oxidation. Once the LOOHs have formed, they
decompose and inter-react to form numerous secondary oxidation products, including
higher molecular weight oligomers, often called polymers.

Conclusion
Biodiesel fuels can be used as a renewable energy source to substitute conventional
petroleum diesel in compression ignition engines. Biodegradability of biodiesel was
studied in this work. When degradation is caused by biological activity, especially by
enzymatic action, it is called biodegradation. Biodegradability of biodiesel has been
proposed as a solution for the waste problem. Biodegradable fuels such as biodiesels
have an expanding range of potential applications and they are environmentally friendly.
Therefore, there is growing interest in degradable diesel fuels that degrade more rapidly
than conventional disposable.
The biodegradability results obtained for biodiesels are compared to those of petro-
diesel fuels. Biodiesel degrades about four times faster than petroleum diesel. The results
demonstrate that all biodiesels assessed are biodegradable, with similar shaped curves
with 80.4–91.2% biodegradation after 30 days, whereas the reference diesel fuel (2-D)
sample reached only 24.5% biodegradation.
174 A. Demirbaş

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