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Abstract
A series of laboratory experiments were carried out to test the potential of vegetable oil biodiesel for the cleaning of
oiled shorelines. In batch experiments, biodiesel was shown to have a considerable capacity to dissolve crude oil, which
appears to be dependent on the type of biodiesel used. Pure vegetable oil biodiesels (rapeseed and soybean) were
signicantly more eective in the cleanup of oiled sands (up to 96%) than recycled waste cooking oil biodiesel (70%).
In microcosm and mesocosm experiments, oiled sediments were sprayed with biodiesel and subjected to simulated
tides. Microcosm experiments revealed that, of those tested, the highest ratio of biodiesel to crude oil, had the highest
eectiveness for cleaning ne sands, with ratios of 2:1 (biodiesel:crude oil) giving the best results. In the mesocosm
experiments a ratio 1:1 of soybean biodiesel to crude oil removed 80% of the oil in cobbles and ne sands, 50% in coarse
sand and 30% in gravel. Most of the oil was removed with the surface water, with only a small amount being ushed
through the sediments. Particle size and pore size were important determinants in the cleanup and mobility of crude oil
in the sediments in these static systems. It is expected that the biodiesel eectiveness should improve in the natural
environment particularly in exposed beaches with strong wave action. However, more laboratory and eld trials are
required to conrm the operational use of biodiesel as a shoreline cleaner.
2003 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel oils; Crude oil; Spill; Cleanup; Sediments; Shoreline cleaner
1. Introduction
The anthropogenic introduction of petroleum into
the marine environment is largely due to the production
and transport of crude oil and its rened products.
Marine oil spills can cause serious environmental, economical and social damage, particularly when oil accumulates on the shore. Once on shore, cleanup operations
become signicantly complicated, expensive and time
consuming. As much as 8090% of the cleanup costs of a
major spill are attributable to shoreline cleanup (Etkin,
1998). Unfortunately, oil spills frequently reach shorelines and other environmentally sensitive areas and by
then, the oil is usually several days old and weathered; it
is usually thick, often emulsied, and frequently dicult
to remove. Furthermore, it is wrought with social
political implications due to the fact that the oil is visible
in the shoreline and many coastal areas have important
economical and cultural values (Etkin, 1998). In addition, shoreline and intertidal ecosystems are complex
and susceptible to serious impacts both from oiling and
response operations.
Conventional remediation methods include physical
removal of contaminated material (Lunel et al., 1996)
and the use of chemical countermeasures (shoreline
cleaners), which are often organic solvents with or
without surfactants (Fuller et al., 2000). The shoreline
0045-6535/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0045-6535(03)00665-9
298
2. Methods
2.1. Batch experiments
The surface of a box containing ne sand (63250 lm
grain size) was contaminated with 200 ml of light Brent
crude oil. After weathering outside for 28 days, at temperatures between 7 and 12 C, the top 23 cm were
homogenised and a series of 50 g subsamples were taken
to be cleaned with dierent biodiesels (rapeseed, soybean
and waste cooking oil). Each 50 g of subsample of sand
contained a total of 1.76 0.11 g of extractable crude
oil, determined using the practical procedure described
below. A range of volumes of rapeseed (20, 30, 40, 50
and 75 ml), of soybean and waste cooking oil biodiesels
(20 and 50 ml) were added to the oiled sand. In each
case, the slurry was manually stirred for 2 min, left to
settle for another 2 min and then the biodieseloil mixture was decanted. Distilled water (250 ml) was then
added and decanted to remove any lipids oating o the
sediments. Control asks containing oiled sand, without
prior treatment with biodiesel, or biodiesel were washed
with water. All these tests were carried out in triplicate.
After the above procedure, the oil and biodiesel that
remained in the sediments were extracted using a treble
dichloromethane (DCM) extraction followed by soxhlet
extraction for 4 h with DCM and pentane (1:1), after
which extractable material was dissolved in hexane. The
biodieseloil in hexane was then passed through a preconditioned normal phase silica cartridge (Alltech). The
hydrocarbons of the crude oil passed through the cartridge whilst the biodiesel was retained. The biodiesel
fraction retained by the cartridge was then extracted
using chloroform. The further washing of the cartridge
with more polar solvents did not remove any signicant
amount of biodiesel. The hydrocarbon and the biodiesel
fractions were both injected in a GCMS. The GCMS
analysis neither detected any fatty acids methyl esters in
the hydrocarbon fraction nor any hydrocarbons in the
biodiesel fraction. The quantications of crude oil and
biodiesel were achieved gravimetrically.
The amount of biodieseloil removed by the water
washing was calculated from the dierence between the
extractable biodiesel and oil controls and the amount
removed after the DCM and DCM/pentane extraction.
The DCM washed approximately 90% of the remaining
extractable biodiesel and oil. After the soxhlet extraction
insignicant quantities of extractable biodieseloil remained in the sand.
2.2. Microcosm experiments
Small boxes (330 225 200 mm) with clear perspex
lids were lled to a depth of 150 mm with ne sand (63
250 lm grain size) from the intertidal zone of a nearby
beach. A length of plastic tubing, tted with a ow
299
3. Results
The control tests showed that using water only removed 15% of the crude oil from ne sands that had not
been treated with biodiesel. The eectiveness of dierent
biodiesels in dissolving the crude oil from the sandy
sediments is shown in Fig. 2. A minimum volume of 20
ml was required to cover the sand in the asks, and this
was used as a starting volume. In reality, it is expected
that much smaller biodiesel: crude oil ratios could be
used in eld trials.
Rapeseed biodiesel removed between 90% and 96.5%
of the crude oil from ne sands (Fig. 2a) and there were
signicant dierences (ANOVA; F 42:22; P < 0:001)
in the amount of crude oil removed between the smaller
and larger volumes. For example, the addition of 20 ml
of rapeseed biodiesel resulted in the removal of 90% of
crude oil, which was signicantly less than the amount
300
100
rapeseed
(a)
80
60
40
20
0
soybean
100
(b)
80
60
40
20
0
0
20
40
60
80
crude oil
0.3
(a)
crude oil
0.15
(b)
1:2 biodiesel-oil
1:2 biodiesel-oil
1:1 biodiesel-oil
1:1 biodiesel-oil
2:1 biodiesel-oil
2:1 biodiesel-oil
biodiesel
biodiesel
0.1
g ml
mg ml
-1
-1
0.2
0.05
0.1
0
0
8
Days
10
12
14
10
12
14
Days
Fig. 3. Amount (normalised) of crude oil and rapeseed biodiesel removed by (a) surface and by (b) the ushed through water from
contaminated sand columns.
0-5 cm
5-10 cm
10-15 cm
50
mg g-1
40
30
20
10
301
diesel leads to a greater recovery of oil from the sediments which preclude the penetration to deeper layers
(Miller and Mudge, 1997).
3.3. Mesocosm experiments
Soybean biodiesel was very eective in cleaning oil
from cobbles and ne sand, with the tidal simulations
removing approximately 80% of the oil and biodiesel
initially added (Table 1). However, only about 50% of
the biodieseloil mixture was released from the coarse
sand and 30% from the gravel. This suggests that for the
set up conditions and in a static system, the biodiesel
eectiveness depends on the substrate where it was applied.
The greatest amount of biodieseloil mixture
(reaching 78% for cobbles and ne sands) was removed
with the rst tide (day 0), independently of the sediments
type (Table 1, Fig. 5a). This is in agreement with the
results of the microcosm experiments and also with
those of Von Wedel (1997) using CytoSol .
The water ushed through the sediments (Fig. 5b)
contained less biodieseloil mixture than the surface
waters (Fig. 5a). Still, the amount of oil and biodiesel
present in the euent water also varied according to the
type of sediments (Fig. 5b). The higher percentage of oil
Table 1
Percentage of crude oil and biodiesel removed by the simulated
tides from the mesocosm containing cobbles, gravel, coarse and
ne sand
Sediment
Total
removed (%)
Surface
water (%)
Percentage of
day 0, based on
total removed
Cobbles
Gravel
Coarse sand
Fine sand
80
30
47
80
77
19
46
80
78
36
59
78
0
biodiesel
crude oil
1:2
1:1
2:1
biodiesel-oil biodiesel-oil biodiesel-oil
Fig. 4. Crude oil and rapeseed biodiesel present in sandy sediments 14 days after the addition of biodiesel.
Fig. 5. Amount of crude oil and soybean biodiesel (ml) removed by the (a) surface water and (b) ushed through the sediments water
in the various mesocosm experiments containing cobbles, gravel, coarse and ne sand.
302
Fig. 6. Crude oil and soybean biodiesel present in the cobbles, gravel, coarse and ne sand 7 days after the biodiesel addition.
303
Acknowledgements
The authors would like to thank Counter Pollution
Branch, Maritime and Coastguard Agency (MCA) for
the nancial support of this project. We also will like to
acknowledge Shell Research and Technology Centre,
Thornton, who supplied the Brent crude oil and Enterprise Oil Plc, Aberdeen who supplied the Enterprise oil.
The authors would also like to thank East Durham
Biofuels Ltd., Grin Industries, Inc and SoyGold
(Doug Pickering and Bill Ayres), USA who supplied the
rapeseed oil, waste cooking oil and soybean methyl esters, respectively.
References
Birchall, C., Newman, J.R., Greaves, M.P., 1995. Degradation
and phytotoxicity of biodiesel oil. Institute of Arable Crops
Research, Long Ashton Research Station, Reading, p. 50.
Bizzell, C.J., Townsend, R.T., Bonner, J.S., Autenrieth, R.L.,
1999. Shoreline cleaner evaluation on a petroleum-impacted
wetland. In: Proceedings of the Fifth International In-Sity
and On-site Bioremediation Symposium, Phytoremediation
and Innovative Strategies for Specialized Remedial Applications, vol. 6. Battelle Press, San Diego, CA, pp. 5762.
Etkin, D.S., 1998. Financial Costs of Oil Spills Worldwide. Cutter
Information Corp., Arlington, Massachutts, USA. p. 368.
Foster, M.S., Tarpley, J.A., Dean, S.L., 1990. To clean or not
to clean: the rationale, methods, and consequences of
removing oil from temperate shores. Northwest Environ.
J. 6, 105120.
Fuller, C., Bonner, J., Dellamea, S., Ussery, P., Tissot, P.,
Louchouarn, P., 2000. Ecological evaluation of shoreline
cleaners used on mesocosms beaches. In: Proceedings of the
Twenty-third Arctic and Marine Oil Spill Programme,
Technical Seminar, Environment Canada. Vancouver, pp.
795803.
Greenwood, P.J., 1983. The inuence of an oil dispersant
Chemiserve OSE-DH on the viability of sea urchin gametes.
Combined eects of temperature, concentration and exposure time on fertilization. Aquat. Toxicol. 4, 1529.
Jahns, H.O., Braggs, J.R., Dash, L.C., Owens, E.H., 1991.
Natural cleaning of shorelines following the Exxon Valdez
spill. In: Proceedings of the 1991 International Oil Spill
Conference, pp. 167176.
Lee, K., de Mora, S., 1999. In situ bioremediation strategies for
oiled shoreline environments. Environ. Technol. 20, 783794.
Louwrier, A., 1998. Biodiesel: tomorrows liquid gold. Biologist
45, 1721.
Lunel, T., Lee, K., Swannell, R., Wodd, P., Rusin, J., Bailey,
N., Halliwell, C., Davis, L., Sommerville, M., Dobie, A.,
Mitchell, D., McDonagh, M., 1996. Shoreline clean up
during the Sea Empress incident: the role of surf washing
(clay oil occulation) dispersants and bioremediation.
304