Você está na página 1de 8

Chemosphere 54 (2004) 297304

www.elsevier.com/locate/chemosphere

Cleaning oiled shores: laboratory experiments testing


the potential use of vegetable oil biodiesels
M. Gl
oria Pereira *, Stephen M. Mudge
School of Ocean Sciences, University of Wales, Bangor, Menai Bridge, Anglesey LL59 5AB, UK
Received 7 January 2003; received in revised form 10 June 2003; accepted 19 June 2003

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,

Corresponding author. Tel.: +44-1248-382-859; fax: +441248-716-367.


E-mail address: g.pereira@bangor.ac.uk (M.G. Pereira).

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

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

cleaners with surfactants emulsify the adsorbed oil,


which can entrain adjacent waters or be transported
deeper into the shoreline substrates (Fuller et al., 2000).
The oilsolvent mixtures have a lower viscosity and
specic gravity than the adsorbed oil. The oilsolvent
mixture rises to the water surface and is collect using
conventional skimming methods (Page et al., 2000).
Shoreline cleaners are most appropriate for rocky shores
and gravel dominated environments, man made structures and sandy beaches. Low toxicity shoreline cleaning
agents may also be used in wetlands (Pezeski et al., 1995)
and mudats (Bizzell et al., 1999). However, chemical
agents and their emulsions with oil can cause toxicity in
aquatic organisms (Wu, 1981; Greenwood, 1983; Scott,
1984). Biodegradation is the ultimate fate of any oil not
collected or burned during a spill response. In situ bioremediation is also recognised as an alternative spill
response technology for the remediation of shorelines
and is recommended for use following the physical removal of bulk oil (Lee and de Mora, 1999).
Strategies for removing oil from impacted shore lines
should strike a balance between environmental impact
and benet, since aggressive shoreline clean up operations can have further deleterious eects (Foster et al.,
1990; Jahns et al., 1991; Michel et al., 1991; Michel and
Hayes, 1993).
Therefore, there is considerable interest in low-cost
eective technologies that accelerate the removal of oil
from intertidal beaches without causing equivalent or
greater damage. The success of these technologies
should be judged not simply on how quickly the oil
disappears, but also on a demonstrated reduction in
risk, i.e. on how quickly toxicity and exposure to oil are
reduced.
A promising alternative is the use of biosolvent
cleaners. Recent studies suggested that biodiesel (vegetable oil methyl esters) can be used as biological solvent
(Miller and Mudge, 1997; Von Wedel, 1997) and that
vegetable oil methyl esters biodiesel, may remove twice
the amount of oil from sand compared to conventional
shoreline cleaners (Page et al., 2000). Large quantities of
biodiesel can be produced at low-cost, making it a less
expensive countermeasure. Furthermore, vegetable oils
methyl esters are signicantly less toxic than crude oils
towards a wide-range of algae, macrophytes and animals
(Birchall et al., 1995), and are also rapidly degradable in
the environment (Louwrier, 1998; Zhang et al., 1998).
The mixture of biodieseloil at the water surface can be
collected with conventional booms and skimmers deployed in advance to collect the biodieseloil mixture,
which can then be recycled as burner fuel or reprocessed
at an oil renery.
In this study, laboratory experiments were carried
out to investigate further the potential of vegetable oil
biodiesels to clean up dierent types of oiled shore
sediments.

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

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

control device, was inserted through a hole at the top


and another at the base of the containers to allow liquid
to be drained through the sands. These static systems
were prepared in duplicate and placed outside, at temperatures that varied between 10 and 14 C.
Five containers were prepared, 3 experimental and 2
controls. In the experimental boxes, 200 ml of untopped
light Brent crude oil was poured onto the sediments
surface as uniformly as possible, and left to weather for
one week, after which the sediments were sprayed with
biodiesel. Three volumes of rapeseed biodiesel were used
on a 1:2, 1:1 and 2:1 ratio with crude oil. Two controls
were set up, one with 200 ml of crude oil and the other
with 200 ml of rapeseed biodiesel only. The washing
eect of the tides was simulated by adding 1 l of ltered
seawater 1 h after the treatment with biodiesel (day 0)
and then 1, 2, 3, 4, and 14 days after the addition of the
biodiesel. The pH of this seawater varied between (pH
7.8 and 8.1).
Surface water (200 ml) containing the biodieseloil
mixture was drained through the top hole of the box and
the remaining water was allowed to ush through the
sediments and was drained through the hole at the base
of the container. The biodieseloil mixture was extracted
from the seawater using a treble liquidliquid extraction
with dichloromethane and a single extraction with dichloromethane:pentane (1:1).
On the 14th day after the addition of biodiesel, sediment samples were collected using a 4 cm diameter
coring device. Three samples were collected at random
(but avoiding proximity with the container walls) and
then combined to form a representative sample. The
samples were combined according to the depths 05,
510 and 1015 cm. The biodieseloil mixture was extracted from the sediments as described previously for
the batch experiments. In this experiment, the fraction of
oil in the biodieseloil mixture was not measured.

299

Fig. 1. Example of the mesocosms experiments setup.

Two liters of light Enterprise crude oil were poured over


the sediments surface, as uniformly as possibly, in each
container. The change of crude oil used in the microcosms and mesocosms experiments from light Brent to
light Enterprise crude oil was unavoidable, since we were
unable to acquire any more Brent crude oil. The crude
oil had been weathered for one month in a fume cupboard prior to its use, losing 11.2% of its initial weight.
The oil was left to weather in the mesocosms for a week,
after which 2 l of soybean biodiesel were sprayed onto
the sediments surface. The washing eects of the tide
was simulated by waterlogging the sediments with seawater 1 h after the treatment with biodiesel (day 0) and
1, 2, 3, 4, and 7 days after the addition of the biodiesel.
The pH of this seawater varied between (pH 7.8 and
8.1).
Surface and euent (ushed through the sediments)
water as well as sediment samples were collected and
extracted following the procedures described in the
previous experiments.

3. Results

2.3. Mesocosm experiments

3.1. Batch experiments

Mesocosm experiments were carried out in plastic


containers of 1200 540 240 mm, covered with transparent perspex lids, which allowed both air circulation
and sunlight penetration, at temperatures that varied
between 4 and 8 C. In each mesocosm, a slope of about
4 was constructed to simulate a beach, by placing a
wedge under one side of the container. Taps were tted
to allow the water to be drawn from the top and base of
the containers, similar to the microcosm experiments
setup (Fig. 1).
Four experimental mesocosms were prepared to test
if the eectiveness of biodiesel varies in the cleanup of
dierent types of sediment. Each container was lled to
150 mm height with cobbles, gravel, coarse and ne
sand, respectively, collected from the intertidal zone of
nearby shores.

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

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

100

removed by 30, 40, 50 and 75 ml (94.0%, 95.2%, 96.2%


and 96.5%, respectively).
As with the rapeseed oil biodiesel, there were significant dierences between using 20 or 50 ml of soybean
and waste cooking oil biodiesels, with the use of larger
volumes resulting in a more eective cleaning of the
sand. Soybean biodiesel was shown to be as eective as
rapeseed biodiesel, removing up to 95.5% of crude oil
(Fig. 2b), whereas waste cooking oil removed at most
70% of the crude oil initially present (Fig. 2b).
During this experiments it was also observed that
more waste cooking oil biodiesel (0.79 mg g1 wet
weight) was left in the sediments after the clean up operation than rapeseed and soybean biodiesel (0.39 and
0.26 mg g1 wet weight, respectively).

rapeseed
(a)

80
60
40

% of crude oil remaining

20
0
soybean

100
(b)

waste cooking oil

3.2. Microcosm experiments

80

The time series (Fig. 3a and b) depicts the amount of


biodieseloil mixture present in the surface and ushed
through water. Given that dierent amounts of biodiesel
were added to each microcosm, the data were normalised by dividing the concentration of biodieseloil
mixture extracted per ml of water, by the volume of oil
and biodiesel added to each container (Fig. 3a and b).
In the control box containing biodiesel only, up to 25
times more biodiesel was removed from the surface water
than was crude oil from the surface water in the crude oil
control container. This was expected given that biodiesel
has lower viscosity and higher buoyancy than crude oil.
The results also appear to suggest that the higher the
ratio of biodiesel to crude oil, the greater the cleaning
eectiveness of biodiesel. The ratio 2:1 (biodieseloil)
was the most eective in dissolving and releasing crude

60
40
20
0
0

20

40

60

80

Volume of biodiesel (ml)


Fig. 2. Percentage of crude oil remaining in the sands relative
to the quantity of (a) rapeseed, (b) soybean and waste cooking
oil biodiesels used in the cleanup operation.

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.

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

oil from the sands to the surface water, in a static system


(Fig. 3a). The ratio 2:1 (biodieseloil) removed in average
7 and 4.5 times more oils than the ratio 1:2 and 1:1, respectively.
The greatest amounts of crude oil and biodiesel were
removed in the rst two tidal simulations (Fig. 3a). The
implication of this observation is that the cleaning process using biodiesel could be accomplished in a relatively
short period of time after the spillage.
The water that ushed through the sand columns
(Fig. 3b) contained less biodieseloil mixture than the
surface waters (Fig. 3a). As expected, it was in the crude
oil control that more oil was drained through the sediments than in any other of the experimental containers
(7, 8 and 11 times in the ratio biodieseloil of 1:2, 1:1
and 2:1, respectively) (Fig. 3b). These data suggest that
biodiesel has a low mobility into the sediments; therefore, in a real spill, the contamination of deeper sediment layers is avoided. The sediment analysis also
highlighted the low mobility of biodiesel, as most of the
biodieseloil mixture accumulated in the upper 5 cm
(Fig. 4). In the various microcosms, only small amounts
of crude oil and biodiesel (314.5%) accumulated at
depths below 5 cm. Furthermore, the addition of bio-

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

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

Fig. 6. Crude oil and soybean biodiesel present in the cobbles, gravel, coarse and ne sand 7 days after the biodiesel addition.

and biodiesel was obtained from the water ushed


through gravel (11%) followed by cobbles (2.9%) and
nally coarse and ne sand with less than 1% of the
initial amount of crude oil and biodiesel added. Therefore, the larger the pore size, the greater the mobility of
the oils through the sediments, as it would be expected.
In general, for all substrates tested, the supercial
water contained greater amounts of biodiesel than crude
oil (5582.7%), whereas the euent water had more
crude oil than biodiesel. This agrees with the biodiesels
buoyancy being greater than that of crude oil and once
more shows the low mobility of biodiesel through the
sediments.
The analysis of the biodieseloil remaining in the
sediments showed that gravel retained more oil and
biodiesel (70%) than the other sediments tested, which
corroborates the data obtained for the water samples
(Fig. 6). The depth to which the oils mixture penetrated
depended also on the grain size, with ne and coarse
sand retaining 99.8% and 81.9% of oils at the surface,
respectively. The increase in grain size allowed a greater
vertical diusion, with only 48.4% of oil and biodiesel
remaining at the top 5 cm in the gravel. In cobbles,
93.5% of the remaining oils mixture was in the 1015 cm
depth fraction (Fig. 6).

4. Discussion and conclusions


In this study, a series of laboratory tests were conducted using biodiesel to clean oiled sediments. The data
suggest that vegetable oil biodiesels have a considerable
capacity for remobilising crude oil. The simplistic batch
tests revealed that the crude oil dissolves into the biodiesel and the mixture can be removed by water, with
only small amounts of both crude oil and biodiesel remaining in the sediments. These experiments also point
out that eectiveness can be dependent on the type of
biodiesel used and that pure vegetable oil biodiesels were
signicantly more eective in the cleanup of oiled sands
than recycled waste cooking oil biodiesel. The eectiveness of biodiesels in terms of their chemical composition was not evaluated. However, it is expected that a

wide-range of factors could be controlling the biodiesels


dierent eectiveness. Viscosity could be one of these
factors, given the dierences in viscosity between wasting cooking oil biodiesel (4.90 cSt, at 40 C) and rapeseed biodiesel (4.65 cSt, at 40 C) (Leahy, unpublished
data). Since the chemical and physical properties of the
biodiesel could inuence the degree of dissolution of
crude oil, it is important that before applying a biodiesel
to a real spill a eld trial should be carried out rst in
order to decide which biodiesel is more appropriate. It is
then possible that to attain a cleaner environment different biodiesels can be used for dierent types of oil or
for oils in dierent weathered states. However, more
work need to be carried out to determine the best biodiesel for a particular situation.
Microcosm experiments revealed that the higher the
ratio of biodiesel to crude oil, the greater the eectiveness of the biodiesel in cleaning ne sands. Yet, in the
ne sand mesocosm a ratio of 1:1 was used and this was
sucient to ensure the removal of 80% of oil in this
static system. This indicates that lower ratios of biodiesel
to crude oil could be used and still achieve a reasonable
cleanup of the shoreline. The actual biodiesel to crude
oil ratio used for a shoreline cleanup would then depend
on the level of oil removal thought necessary and would
enable optimised cost eectiveness decisions to be made.
Both micro- and mesocosm experiments described in
this study were static systems where the biodiesel was
sprayed without further treatment. It is expected that the
simulation of wave action should improve greatly the
results of the clean up operation (e.g. Page et al., 2000).
The results of the surface water in the micro and mesocosms showed that the rst simulated tide removed
most of the oil. These data are in agreement with that
obtained in eld experiments carried out in San Francisco where a single CytoSol application followed by a
passive water deluge released 60% of the trapped oil near
the high tidal zone (Von Wedel, 1997). This prompt
cleaning of the shoreline after the spill by the biodiesel
should reduce the deleterious eects on the environment
and organisms that live therein.
The high eectiveness of biodiesel in cleaning ne
sand was also manifested in the cobbles mesocosm.

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

However, biodiesel was much less eective in the


cleaning of coarse sands and gravel. The closed systems
employed in the present study precluded the incorporation of a large number of variables present in the
natural environment, with oil diusion the only way that
the oil could penetrate into the sediments. Therefore, the
type of particles and pore size were important determinants in the eectiveness of the cleanup, with ne particles and large pores facilitating the dissolution and
release of crude oil in biodiesel and formation of the oil
slick. Biodiesel has low mobility in the sandy sediments
with only small amounts of oils found in the euent
water, and most of the oils being concentrated at the top
5 cm. In the cobbles substrate, the biodiesel was still very
eective though the oil penetrated deeper into the sediments due to the larger pore size.
Control and replication of the experimental mesocosms is desired and required for an eective evaluation of biodiesel as an alternative operational cleaner.
However, these were not carried out due to time and
resources limitations of this study. Nevertheless, the
results of the mesocosm experiments provide an initial
evaluation of the potential use of biodiesels in dierent
shoreline substrates, and some inferences can be withdrawn.
The spraying of biodiesel is a low-cost operation as it
does not require skilled personnel or high technology
and biodiesel can be manufactured at low-cost. However, biodiesel will only be an alternative operational
cleaner depending if it proves to be environmentally
friendly. Biodiesel on its own appears to be easily biodegradable and not harmful to organisms (Birchall et al.,
1995; Louwrier, 1998; Zhang et al., 1998), but, very little
is known about the biodegradation and toxicity of the
by-products of the oil and biodiesel that are left in the
environment. Although its biodegradation was not
studied during this project, it appears that the biodiesel
oil mixture in the environment could be of short
persistence because the addition of biodiesel to the
sediments appears to provide a readily available carbon
source for the micro-organisms which then co-metabolise the crude oil (Mudge and Pereira, 2000). The eects
of the biodegradation of biodieseloil mixtures in the
environment should also be studied since, for example,
rapid degradation may cause deleterious oxygen depletion for fauna and ora (Pereira et al., 2002, 2003).
The laboratory tests carried out during this study
appear to suggest that biodiesel may provide an operational oil spill countermeasure strategy that is both environmentally friendly and cost eective. Laboratory
studies are valuable in testing a shoreline cleaners effectiveness, but it is dicult to replicate the conditions of
the natural environment. The true test of biodiesel performance is a full-scale oil spill in the marine environment, which is not always possible to carry out due to
the high costs involved, public sensitivity to crude oil

303

spills and obvious environmental reasons. Field trials


are, nevertheless, required.

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

M.G. Pereira, S.M. Mudge / Chemosphere 54 (2004) 297304

In: Proceedings of the Nineteenth Arctic and Marine Oil


Spill Programme, Technical Seminar, Environment Canada.
Ontario, pp. 141148.
Michel, J., Hayes, M.O., 1993. Persistence and weathering of
the Exxon Valdez oil in the intertidal zone3.5 years later.
In: Proceedings of the 1993 International Oil Spill Conference, pp. 279286.
Michel, J., Hayes, M.O., Sexton, W.J., Gibeaut, J.C., Henry,
C., 1991. Trends in natural removal of the Exxon Valdez oil
spill in Prince William Sound from September 1989 to May
1990. In: Proceedings of the 1991 International Oil Spill
Conference, pp. 177180.
Miller, N.J., Mudge, S.M., 1997. The eect of biodiesel on the
rate of removal and weathering characteristics of crude oil
within articial sand columns. Spill Sci. Technol. Bull. 4,
1733.
Mudge, S.M., Pereira, G., 2000. Simulating the biodegradation of
crude oil with biodiesel. Spill Sci. Technol. Bull. 5, 353355.
Page, C., Fuller, C., Autenrieth, R., 2000. Materials balance on
an oil washed from a sandy substrate using shoreline
cleaners. In: Proceedings of the Twenty-third Arctic and
Marine Oil Spill Programme, Technical Seminar, Environment Canada. Vancouver, pp. 697708.

Pereira, M.G., Mudge, S.M., Latchford, J., 2002. Consequences


of linseed oil spills in salt marsh sediments. Mar. Pollut.
Bull. 44, 520533.
Pereira, M.G., Mudge, S.M., Latchford, J., 2003. Vegetable oil
spills on salt marsh sediments; comparison between sunower and linseed oils. Mar. Environ. Res. 56, 367385.
Pezeski, S., Delaune, R., Nyman, J., Lessard, R., Canevari, G.,
1995. Removing oil and saving oiled marsh grass using a
shoreline cleaner. In: Proceedings of the 1995 Oil Spill
Conference, pp. 203209.
Scott, B.F., 1984. Impact of oil and oildispersant mixtures on
the mixtures in freshwater ponds. Sci. Total Environ. 35,
191206.
Von Wedel, R., 1997. The CytoSol process: cleaning oiled
shorelines with a vegetable oil biosolvent. Port Technol. Int.
7, 209212.
Wu, R.S.S., 1981. Dierences in the toxicities of an oil
dispersant and a surface active agent to some marine
animals, and their implications in the choice of species in
toxicity testing. Mar. Environ. Res. 5, 157163.
Zhang, X., Peterson, C., Reece, D., Haws, R., Moller, G., 1998.
Biodegradability of biodiesel in the aquatic environment.
Trans. ASAE 41, 14231430.

Você também pode gostar