Operational problems related to the preparation of the seawater

soluble fraction of crude oil

Roberta Lourenco Ziolli*
a
and Wilson F. Jardim
b
a
Departamento de Qu mica da Pontif cia Universidade Catolica do Rio de Janeiro, Rua
Marques de Sao Vicente, 225, Gavea, 22453-900 Rio de Janeiro, RJ, Brazil.
E-mail: rlziolli@rdc.puc-rio.br
b
Instituto de Qu mica, Universidade Estadual de Campinas, CP 6154, 13083-970 Campinas,
SP, Brazil. E-mail: wfjardim@iqm.unicamp.br; Fax: z55 19 3788 3135
Received 10th August 2001, Accepted 22nd October 2001
Owing to the importance of dissolution and weathering processes following oil spills, this work focused on the
operational (quantitative) aspects related to the dissolution of petroleum-derived products, as well as the
inuence of solar light on both dissolution and the photoproduction of hydrogen peroxide. Four Brazilian
crude oil samples were used to study the transfer process of organic compounds from the crude oil lm to the
aqueous phase (natural seawater) over a period of up to 45 days. Dissolved organic carbon (DOC), measured
by non-dispersive infrared spectroscopy followed by high temperature catalytic combustion, was used to follow
the partitioning between the two phases. Aqueous DOC values increased as a function of time (up to 15 days)
until equilibrium was reached at concentrations ranging from 5 to 45 mg C L
21
. The nal DOC concentration
as well as the rate of dissolution depends on the nature of the crude oil. When exposed to sunlight, the
dissolution was enhanced by up to 67.3%, and inorganic peroxides were generated in the concentration range
from 4.5 up to 8.0 mmol L
21
after 7.3 h irradiation. These results indicate that there is a need for a standard
procedure for the production of the WSF in order to generate a more reliable tool to assess the impact of oil
spills on the marine environment.
Introduction
Problems associated with oil pollution of navigable waters have
reached critical proportions. Marine waters are nowadays
constantly receiving a wide range of contaminants, some of
them in acute events. Marine pollution caused by continuous
inputs is basically associated with sewage discharge, offshore
oil drilling and from ships. The long-term ecological impact of
such input depends largely on the dispersion of the in the
seawater and on the ultimate fate of the spilled petroleum
products.
1
Following any disaster involving an oil tanker, the oil slick
is normally removed from the surface seawater by either
mechanical or absorption methods. In terms of the environ-
mental and ecological effects of the oil pollution, the degree
to which the crude oil components dissolve in the seawater
before the removal of the crude oil slick is very important.
For example, it has been established that it is the dissolved,
rather than the emulsied or the adsorbed fraction of the
oil that is acutely toxic to the marine biota. One reason for
this is that the dissolved fraction is readily ingested by
organisms at the lower end of the food chain, thereby con-
centrating and accumulating in organisms at higher trophic
levels.
2
Because of its importance, researchers have been studying
the dissolution of petroleum-derived products in water in order
to evaluate the toxicological characteristics of seawater con-
tamination caused by crude oil. The water soluble fraction
(WSF, also referred to as SWSF if dissolved in seawater) is the
organic enriched aqueous phase in contact with the oil spill.
This enrichment is caused by the dissolution of the relatively
low molecular weight compounds present in crude oils, mainly
aromatic hydrocarbons (with relatively high water solubility),
and small amounts of high molecular weight polar compounds.
However, in the literature there is no uniformity in the
experimental steps used by different authors to obtain the WSF
from a crude oil sample and the experiments are conducted in
different ways. This results in considerable difculties in
comparing experimental data. This lack of consistency may be
partially explained by the lack of a standard procedure to
ensure reliable, reproducible and comparable results. Another
important limitation is that the experimental details are often
poorly documented.
Unfortunately, there has been very little systematic experi-
mental work aimed at providing a comparison of WSF from
crude oils. This makes it both difcult and of debatable value
to use laboratory data to evaluate environmental damage or
to select mitigating strategies. Several laboratories have been
involved in the problem of preparing a WSF of a crude oil, as
presented by the National Academy of Sciences,
3
but the
solubility reported varies according to a number of key factors,
including the composition of the oil,
4,5
the ratio of the volume
of oil to the water brought into contact,
6
the mixing rate
7
and
time,
8,9
the seawater temperature,
6,10
the salinity,
6,11
the pH,
12
and to other effects, such as separation time,
8,13
ltration,
7,8
volatilisation,
14
dilution,
5,8
illumination during preparation,
15
ask dimensions,
8
etc.
The present work shows the results of the production of
WSF in seawater for four different Brazilian crude oils. The
amount of dissolved organic carbon (DOC) was monitored at
different time intervals until an equilibrium concentration
(monitored by DOC) was reached. Some experiments were
also carried out under solar light and the photoproduction
of hydrogen peroxide in the WSF was also investigated. The
results are discussed taking into consideration experimental
procedures normally found in the literature.
JEM: 76271_10.3d 26/11/01 13:12:25 Rev 6.06e/W (Aug 31 2000) The Charlesworth Group, Hudds 01484 517077
DOI: 10.1039/b107281c J. Environ. Monit., 2001, 4, 15 1
This journal is # The Royal Society of Chemistry 2001
Materials and methods
Crude oil samples and seawater
The Brazilian crude oil samples (named A, B, C, and D for
simplicity) originated from the continental shelf of Rio de
Janeiro State (Enchova (A), an unknown eld (B) and Marlin
(D)), as well as from Rio Grande do Norte State (Terra (C)).
Seawater was collected at Sa o Sebastia o (Sa o Paulo State),
along the coastal line of the Ilha Bela channel.
Obtaining the WSF
Pyrex asks (2.0 L) with a Teon tap at the bottom were lled
with 1.5 L of seawater. Crude oil was added at a ratio of
1 : 20 v/v, and the solution was magnetically stirred for 30 min.
For experiments in the absence of light, the asks were left to
equilibrate for up to 45 days in the dark at room temperature.
The Pyrex asks remained stoppered for the entire period,
except when water samples were drawn through the Teon tap,
this was done without disturbing the oil/seawater surface.
Sampling was carried out in duplicate.
Solar light irradiation
The samples (about 1200 mL) were exposed to solar light
irradiation in Pyrex asks in batch experiments, for periods of
up to 7.3 h. The solar light intensity was measured using a
9811-56 radiometer (Cole-Parmer Instrument Co., Chicago,
IL) xed at 365 nm.
DOC analysis
The amount of DOC present in the aqueous phase samples
(about 10 mL) was measured by non-dispersive infrared
spectroscopy followed by high temperature catalytic com-
bustion, using a Shimadzu TOC 5000 Total Organic Carbon
Analyzer (Shimadzu Corporation, Kyoto, Japan).
Determination of hydrogen peroxide
Photoproduction of hydrogen peroxide was investigated
during irradiation of the WSF. Samples (about 20 mL) were
collected during radiation exposure and the determination,
including the speciation of organic and inorganic peroxide, was
carried out using a photometric method based on the peroxi-
dase catalyzed oxidation of N,N-diethyl-p-phenylenediamine.
16
Results and discussion
DOC values resulting from the dissolution of crude oil derived
products in seawater are presented in Fig. 1. For all experi-
ments monitoring the DOC, the initial values for each crude oil
sample were taken immediately after the stirring nished (time
zero), and the values plotted were corrected taking into
consideration the DOC background values present in the
seawater. The equilibrium concentration and steady state
concentration are dened here as the arithmetic average DOC
values obtained after the time required until no further
variation in the DOC concentration could be observed (up
to 45 days).
Maximum enrichment of the aqueous phase with crude oil
products was observed for the Enchova Field crude oil (A),
which reached an equilibrium concentration after 5.8 days,
producing a WSF with an average concentration of
46.8 mg C L
21
. On the other hand, minimum dissolution was
observed for the Terra Field cruse oil (C), whose WSF reached
a steady state with an average concentration of 4.9 mg C L
21
after 7 days. Dissolution from crude oil B was quite stable,
yielding an aqueous phase with an average concentration of
8.6 mg C L
21
after 17 days. However, crude oil D apparently
did not achieve a steady state in the test period used in this
work (45 days). Based upon these results, one can see that
dissolution and the resulting WSF concentrations vary
markedly and depend on the nature of the crude oil, on the
formation of emulsions and on the time of contact of the oil/
seawater surface.
It is important to emphasize that laboratory procedures to
generate the WSF of organic compounds present in crude oils,
deviate signicantly from natural conditions, where the oating
oil slick rarely remains in contact with the same water mass
for such long periods of time. This means that the equili-
brium concentrations obtained under laboratory conditions
are expected to be much higher than the ones observed in the
eld, and represent the worst-case scenario.
When the experimental procedure for the production of the
WSF from crude oil A was carried out in the dark (control) as
well as under sunlight, an increase of 67.3% in the DOC
concentration, from 15.9 (dark) up to 26.6 mg C L
21
(irra-
diated) after 7.3 h of solar exposure, was observed (Fig. 2).
Differences in the average solubilisation rate varied from
0.61 mg C L
21
h
21
in the dark sample to 2.00 mg C L
21
h
21
for the irradiated samples. Considering that the light inten-
sities observed in these experiment varied from 1.20 up to
2.70 mW cm
22
, typical for mid-south latitudes, and taking into
consideration that oil spills often occur in areas exposed to
sunlight, this data further emphasizes the need for more
realistic procedures to obtain the WSF, so the results can be
extrapolated to natural conditions. In this context, WSF
procedures incorporating photoperiodicity using articial light
as surrogate sources of irradiation have to be considered.
Another important environmental factor contributing to the
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Fig. 1 Dissolution of the WSF of four Brazilian crude oils (A, B, C, and
D) from a surface lm for a period of 45 days, by DOC measured using
a Shimadzu TOC 5000 Total Organic Carbon Analyzer.
Fig. 2 DOC levels when a lm of crude oil A was exposed to sunlight
for a period of 7.3 h. Average solubilisation rate was dened as the
angular coefcient of the linear regression for both dark and sunlight
data.
2 J. Environ. Monit., 2001, 4, 15
variations in both quality and quantity of the WSF is the
presence of dissolved oxygen in the water column, which might
act as a precursor for many reactive intermediate species, such
as hydrogen peroxide, in light-driven reactions. Photoproduc-
tion of peroxide was also investigated in this work and, for all
experiments, the initial peroxide concentration in the WSF of
crude oils samples was determined immediately after stirring
(time zero), and the values presented were corrected, taking
into consideration the background peroxide concentration in
the seawater. Fig. 3 presents the results of the photoproduction
of peroxides for the Enchova crude oil (A) WSF exposed to
sunlight and kept in the dark (samples obtained in the
experiment shown in Fig. 2 for DOC monitoring). The
peroxide concentration reached 4.5 mmol L
21
for the sample
exposed to sunlight after 7.3 h of irradiation whilst in the dark
no photoproduction was observed (below 0.2 mmol L
21
). Since
hydrogen peroxide is a powerful oxidant of a wide class of
organic compounds, the photoproduction of the peroxides can
also contribute to the WSF carbon pool. The real implica-
tions of this photooxidation and its effect on the crude oil
components is not clearly understood, but it certainly alters the
toxicity to the biota due to the generation of this transient
species. Although the protocols currently used for preparation
of WSF from petroleum hydrocarbons do not allow for the
generation of peroxides, this new parameter should also be
considered. Peroxide concentrations ranging from 4.5 to
7.9 mmol L
21
were observed for all the WSFs obtained from
the crude oil samples (A, B, C, and D) exposed to 5.07.3 h of
sunlight irradiation. The signicant differences in the results
can be attributed to the irradiation intensity and also to the
nature of the oils. On the other hand, no correlation was found
between the peroxide generation and the DOC values.
The above-mentioned experiments of peroxide photopro-
duction are expressed in terms of total peroxides (organic plus
inorganic peroxides). The speciation of organic and inorganic
peroxide was carried out using catalase enzyme to inhibit
inorganic peroxide formation. As shown in Fig. 4, no organic
peroxides were detected when the WSF of crude oil B was
exposed to sunlight, thus conrming that molecular oxygen
is the major species acting as electron scavenger in this
organically enriched seawater.
To better understand the role of the oil slick in the photo-
production of hydrogen peroxide, a sample of the WSF from
the Enchova crude oil (A) was exposed to sunlight. The
only difference was that in this new experiment the oil slick
was physically removed just before exposure to the sunlight.
According to Fig. 5, it can be seen that under these new
conditions the nal concentration of H
2
O
2
(2.8 mmol L
21
)
was 62% lower than the value obtained when in the presence
of the oil slick. This conrms the role of the DOC as a
precursor of H
2
O
2
in waters, once it is exposed to sunlight.
17,18
Conclusion
The development of standard protocols for producing WSFs
for oil spill research is an important issue for assessing the
environmental impacts associated with the oil industry as a
whole, from drilling to rening. Although it has been known
for some time that variations in protocols will cause signi-
cant differences in results, and also that different oils produce
different WSFs, this paper adds new parameters to the
discussion. The effects of sunlight and peroxide photoproduc-
tion are explored, pointing out the urgent need to develop more
realistic laboratory procedures for obtaining a WSF that will
incorporate the possible effects caused by such variables.
Acknowledgements
The authors are grateful to the Coordenacao de Aperfeicoamento
de Pessoal e Ensino Superior (CAPES) for nancial support
and they also thank Dr. C. Collins for revising the manuscript.
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4 J. Environ. Monit., 2001, 4, 15
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Query
Reference
Query Remarks
1
[Y1]Ref. 3: I assume you meant pages 271280
and page 661, correct? If not, please clarify
what you meant.
2 Ref. 4: Please give the location of the publisher
API.
3
Ref. 8: Please explain the text ICES CM 1980/
E 27.
4 Please indicate the name of the publisher and
their location.
5 Ref. 10: Please give the full name and location
of the publisher Applied Science.
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J. Environ. Monit., 2001, 4, 15 5