Chemosphere 95 (2014) 415–422

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Photolytic and photocatalytic degradation of surface oil

from the Deepwater Horizon spill
Sarah M. King a, Peter A. Leaf a,b, Amy C. Olson a,b, Phoebe Z. Ray a, Matthew A. Tarr a,b,⇑
a
Department of Chemistry, University of New Orleans, 2000 Lakeshore Drive, New Orleans, LA 70148, USA
b
Advanced Materials Research Institute, University of New Orleans, 2000 Lakeshore Drive, New Orleans, LA 70148, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 PAHs in oil from the Deepwater

Horizon spill are rapidly degraded by
sunlight.
 Larger PAHs photodegrade faster than
smaller PAHs.
 Absorbance of oil was photobleached
more slowly than fluorescence.
 Alkanes did not photodegrade with
up to 12 d of sunlight exposure.
 The toxicity of water in contact with
oil increased when the oil was
irradiated.

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

Article history: The photochemical behavior of Deepwater Horizon oil collected from the surface of the Gulf of Mexico
Received 13 July 2013 was studied. Thin oil films on water were subjected to simulated sunlight, and the resulting chemical
Received in revised form 30 August 2013 and optical changes were observed. Polycyclic aromatic hydrocarbons (PAHs) showed substantial photo-
Accepted 10 September 2013
degradation, with larger PAHs being more rapidly decomposed. About 60% of the fluorescence at the exci-
Available online 16 October 2013
tation and emission maxima was observed with 12 h of simulated solar irradiation equivalent to
approximately 3 d of sunlight. Synchronous scan fluorescence measurements showed 80–90% loss of lar-
Keywords:
ger PAHs with 12 h of simulated solar irradiation. Absorbance of the oil decreased by only 20% over the
Photochemistry
Oil spill
same time period. Alkanes showed no significant photochemical losses. After irradiation, the toxicity of
Petroleum water in contact with the oil significantly increased, presumably due to the release of water soluble
Photocatalyst photoproducts that were toxic. Photocatalyst addition resulted in enhanced degradation rate for PAHs,
Remediation and toxicity of the aqueous layer was altered in the presence of photocatalysts added to the oil film. Pho-
tochemistry is an important pathway for degradation of large PAHs, which are typically resistant to
biodegradation.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
The Deepwater Horizon oil spill in the Gulf of Mexico was an
enormous disruption to the entire ecosystem. It was estimated that
⇑ Corresponding author at: Department of Chemistry, University of New Orleans,
2000 Lakeshore Drive, New Orleans, LA 70148, USA. Tel.: +1 (504) 280 6323; fax: +1
(504) 280 6860.
E-mail address: mtarr@uno.edu (M.A. Tarr).
4.9 million barrels of oil flowed into the gulf over 87 d until BP
capped the well head. The impacts were widespread and a full
understanding of the long term effects is still under investigation.
To better understand the impacts that an oil spill has on an ecosys-
tem, a full knowledge is needed of the fate of the oil after it is
released.
There are several mechanisms for the degradation and disper-
sion of aquatic released oil including dissolution, emulsification,

0045-6535/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.09.060
416 S.M. King et al. / Chemosphere 95 (2014) 415–422
absorption, mixing, evaporation, biodegradation, photodegrada-
tion, and chemical reactions (McAuliffe et al., 1980; Atwood and
Ferguson, 1982; Ducreux et al., 1986; Barbosa et al., 2003; Sterling
et al., 2003, 2004). Contributions from dissolution were higher for
the Deepwater Horizon oil spill than other Gulf of Mexico oil spills
due to the depth of the well head (1500 m) and the addition of
chemical dispersants. In addition, biodegradation and photodegra-
dation have been shown to be two of the most significant degrada-
tion mechanisms in previous oil spills (Brooijmans et al., 2009;
Rojo, 2009). Initial studies reported on biodegrading bacteria in
water plumes from the Deepwater Horizon oil spill (Hazen et al.,
2010). Biodegradation has been shown to be useful for the degra-
dation of small molecules; however, it is slower in the nutrient
deficient surface waters of the open Gulf of Mexico (Dutta and
Harayama, 2000; Wrenn et al., 2006; Li et al., 2010). Furthermore,
higher molecular weight alkanes and polycyclic aromatic
hydrocarbons (PAH) are resistant to biodegradation as well as
dissolution and evaporation. For these recalcitrant compounds,
photochemical transformations become of extreme importance
as an initial step in promoting bioavailability and further
degradation.
Numerous studies have been conducted on the photodegrada-
tion of oil. In most of these studies, a mercury lamp or fluorescent
lamps were used as an irradiation source (Grzechulska et al., 2000;
Ziolli and Jardim, 2002, 2003; Yang et al., 2006). These sources do
not accurately mimic the optical spectrum of the sun. In addition,
in some of the previous studies, the oil was separated into different
fractions before irradiation (Rontani and Giral, 1990; Garrett et al.,
1998; Ziolli and Jardim, 2002). The chemical and physical interac-
tions of the different fractions were therefore not included in these
studies, thus the degradation rates and mechanisms do not neces-
sarily mimic those of actual crude oil samples in an environmental
setting. Photochemical degradation of films of oil on rocks was pre-
viously studied (Plata et al., 2008), and a recent report described
changes in optical properties of Deepwater Horizon oil, including
those believed to be due to photochemical changes (Zhou and
Guo, 2012).
A limited number of studies have been conducted on oil in the
presence of photocatalysts, and representative reports are
available (Gerischer and Heller, 1992; Rosenberg et al., 1992; Nair
et al., 1993; Berry and Mueller, 1994; Grzechulska et al., 2000;
Bessa et al., 2001; Pernyeszi and Dekany, 2001, 2003; Ziolli and
Jardim, 2002; Zhang et al., 2009; Samokhvalov, 2011). In those
studies, the samples with photocatalysts showed an increase in
the degradation rate of the different components of the oil. The
most common photocatalyst that has been studied in the degrada-
tion of oil is titanium dioxide, which has been applied to Deepwa-
ter Horizon oil in an effort to improve biodegradability of the oil
(Brame et al., 2013). In comparison to the rutile form, the anatase
form of TiO2 is more photochemically active. Anatase has a band
gap of 3.2 eV and is excited by electromagnetic radiation with
wavelengths that are shorter than 387 nm. The absorbed photon
excites an electron from the valence shell into the conduction
band, thus producing an electron–hole pair (Kannaiyan et al.,
2009). The excited electron can undergo direct reaction with a
pollutant molecule, thus reducing the pollutant (Xiao, 2012). Addi-
tionally, the excited electron can react with oxygen to produce a
superoxide anion radical (O2  ), which can then react with the pol-
lutant or with protons to form hydroperoxyl radical (HO2 ).
Through additional steps, hydroperoxyl radical can eventually
yield hydroxyl radical. The hole can diffuse to the particle surface
where it can react to degrade the organic compound either directly
or indirectly (Fox and Dulay, 1993; Nair et al., 1993; Hoffmann
et al., 1995; Ziolli and Jardim, 2002; Pernyeszi and Dekany, 2003;
D’Auria et al., 2009). In the indirect degradation pathway, the hole
at the particle’s surface reacts with a water molecule to produce
hydroxyl radical (HO). The hydroxyl radical produced is a nonspe-
cific oxidant that can degrade the pollutant.
In the present research, photodegradation of oil from the Deep-
water Horizon spill was studied. Photodegradation studies were
conducted in the absence of an added photocatalyst to gain a better
understanding of environmental behavior and with photocatalyst
to assess the ability of TiO2 to enhance oil photodegradation. Anal-
ysis of the phototransformation of crude oil was achieved using
GC–FID for alkanes and fluorescence for PAHs. In addition, Micro-
tox™ analysis was utilized to study the toxicity of the water
exposed to oil with and without photochemical treatment.
2. Materials and methods
Crude oil and water samples were collected on May 26, 2010 at
latitude 28.801 and longitude 89.119, which is approximately 47
miles northwest of the Deepwater Horizon spill site. Oil samples
collected were thick and dark brown. Water samples were col-
lected from a nearby area in the Gulf of Mexico that was not visibly
contaminated with oil. After collection the water samples were fil-
tered through pre-washed 0.2 lm polycarbonate filters to sterilize
the water and were subsequently stored at 4 °C.
Dichloromethane (DCM) and toluene were OmniSolv ultra high
purity obtained from EMD. HPLC solvent grade pentane was ob-
tained from J.T. Baker. Titanium (IV) oxide (anatase, nanopowder,
<25 nm, 99.7%), fluorene, fluroanthane, anthracene, pyrene, and
eicosane were obtained from Aldrich. Pentadecane, n-octacosane,
n-docosane, n-tetracosane, and n-triacontane were from Alfa Aesar.
Octane, nonane, decane, and dodecane were obtained from Fluka.
Microtox™ diluent, osmotic adjusting solution, reconstitution
solution, and acute reagent were obtained from SDIX. TiO2 nano-
tubes were prepared from the nanopowder following a previously
described method (Ratanatawanate et al., 2008).
To increase the hydrophobicity of the TiO2 nanoparticles and to
make them more readily disperse in the oil, the photocatalysts
were coated with stearic acid. Stearic acid coating was achieved
by sonicating the oxide in an ethanol solution of stearic acid
(0.353 mM). After sonication the sample was centrifuged, the eth-
anol was removed, and the coated oxide particles were dispersed
in toluene.
Prior to exposure to simulated sunlight, 100 mg of weathered
crude oil was weighed and dissolved in a mixture of 2 mL pentane
and 100 lL toluene. For samples treated with TiO2, the photocata-
lyst dispersed in toluene was added to the mixture instead of pure
toluene. The mixture was then sonicated to fully disperse the oil
and photocatalyst. The mixture was then poured onto the surface
of 10 mL Gulf water in a 100 mL jacketed beaker (5 cm i.d.). The
sample was kept uncovered for several minutes to allow the
pentane and toluene to evaporate. The samples were then exposed
to simulated sunlight (Atlas Suntest CPS+ equipped with a 1500 W
air cooled xenon arc lamp, 765 W/m2 300–800 nm, equivalent to
1.3 solar noon AM 1.5 sunlight). During irradiation, the tops of
the jacketed beakers were covered with a piece of quartz glass,
and the samples were kept at 27 °C by circulating thermostated
water through the jacketed beakers. After irradiation the samples
were either extracted with DCM (2  10 mL) for GC–FID and fluo-
rescence analysis, or the aqueous layer was taken for Microtox™
analysis.
Oil extracts were analyzed using an Agilent 6890 GC coupled to
an auto sampler with a flame ionization detector and a
30 m  0.32 mm (i.d.) AT-1 capillary column (Agilent). The injector
and detector temperatures were set to 300 °C and 350 °C, respec-
tively, and the temperature programming was as follows: 80 °C
held for 1 min, ramp at 15 °C/min until a final temperature of
320 °C which was held for 15 min. To eliminate any variations in
 S.M. King et al. / Chemosphere 95 (2014) 415–422
GC performance and extraction efficiency, dodecane was added as
an internal standard to all samples prior to extraction with DCM.
Because the oil used in this study was weathered, no dodecane
was present in the samples prior to this addition.
Fluorescence spectra and synchronous scans were collected
with a PerkinElmer LS 55 luminescence spectrometer. Synchronous
scans on the diluted oil extracts were collected from 250 to 500 nm
with a delta lambda of 25 nm. Excitation and emission slits were
set to 2.5 and 5.0 nm, respectively. Fluorescence intensity was also
measured at the observed excitation and emission maxima of
265 nm excitation and 370 nm emission with slits set to 5.0 nm.
Microtox™ analysis was performed using a Microtox™ 500
analyzer (SDIX). The protocol used to analyze the toxicity of the
water exposed to the oil was the comparison test for marine and
estuarine samples (Ziolli and Jardim, 2002). For each day Micro-
tox™ analysis was used, the basic test was run with phenol or zinc
sulfate standards to ensure proper function of the procedure.
3. Results and discussion
The low molecular weight alkanes (C13 and smaller) were ab-
sent from the GC–FID chromatograms of the collected oil diluted
in DCM. These compounds were most likely lost in weathering of
the oil between its release from the well and its collection. The
more volatile compounds and compounds with even slight solubil-
ity in water (Belt et al., 1998; McKenna et al., 2013) either evapo-
rated or were removed by dissolution in the Gulf of Mexico water.
The optical spectrum of the irradiation source in the solar sim-
ulator used in our studies was similar to the optical spectrum of
the sun, with a slightly higher intensity. To standardize our instru-
ment, a Hamamatsu S1718 solar cell (calibrated at the National
Renewable Energy Laboratory) was used to measure the intensity
of the solar simulator. From the measured intensity, it was discov-
ered that the output of our solar simulator set at its maximum out-
put (765 W/cm2, 300–800 nm only) was equivalent to 1.26 times
the intensity of full sunlight (1000 W/m2 full spectrum AM1.5).
Based on solar irradiance data from the National Solar Radiation
Database (National Renewable Energy Laboratory, 2013) at latitude
28.85, longitude 88.35 (the nearest location to our sampling site),
the average daily amount of direct and diffuse solar radiation
Fig. 1. Appearance of oil as a function of irradiation time: (a) before irradiation, and after (b) 3 h, (c) 6 h, (d) 12 h, (e) 24 h, and (f) 48 h irradiation in a solar simulator
operating at 1.26 times full AM1.5 sunlight. Approximately 4 h of irradiation in the simulator was equivalent to one average day of sunlight in the Northern Gulf of Mexico.
417
received on a horizontal surface at this location in 2009 was
4972 W h/m2. Our solar simulator produced about 1260 W/m2.
Dividing this irradiance into the average daily insolation yields a
value of 3.95 h, representing the amount of time in our solar sim-
ulator equivalent to an average day of insolation at this location.
Crude oil was deposited onto the Gulf water to mimic the inter-
actions of the components in the water with those of the oil and
degradation products. 100 mg of the oil was used which produced
a film of oil that was approximately 60 lm thick. Photographs
were taken before and after each irradiation to document the phys-
ical changes in the oil layer throughout irradiation and are pre-
sented in Fig. 1. After 6 h of irradiation the oil layer became
leathery in appearance, and upon movement the oil layer cracked.
The oil sample irradiated for 12 h was slightly lighter in color than
the 6 h irradiated sample. The 12 h sample had a leathery appear-
ance similar to the 6 h sample. After 24 and 48 h of irradiation, sig-
nificant physical degradation of the oil was apparent.
3.1. GC results
The extent of loss of alkanes was studied via GC–FID analysis of
DCM extracts. Data for these experiments are presented in Fig. 2.
Identification of the major peaks was accomplished by comparison
to retention times of known n-alkane standards. All peaks were
normalized to dodecane (not present in the weathered oil), an
internal standard added prior to DCM extraction in order to elim-
inate possible extraction, injection, and instrument variations.
From the results it was observed that all samples that were ex-
posed to simulated sunlight exhibited extensive decreases in the
amount of C14–C17 alkanes. Because no reproducible loss of larger
alkanes was observed, we believe that the loss of C14–C17 alkanes
was due to evaporation. Although we utilized dark controls for all
experiments, the surface of the oil in irradiated samples likely
became locally heated due to radiative energy transfer, which
subsequently caused greater evaporation than observed in dark
controls. The surface temperature was measured carefully with a
thermocouple after 100 min of irradiation, yielding a temperature
of 31 °C, which indicated that irradiation of the oil caused an
increase in the surface temperature of at least 4 °C. A dark control
was held at this temperature for 12 h, and loss of C14–C17 alkanes
418 S.M. King et al. / Chemosphere 95 (2014) 415–422

determined the fraction of ambient light absorbed by the oil film

(60 lm). Fig. 3 illustrates the fraction of light absorbed vs. wave-
length prior to photodegradation and after 12 h of irradiation. At
short solar wavelengths (<340 nm), 80–99% of the radiation was
absorbed within the 60 lm oil film. At 300 nm, about 50% of the
radiation was attenuated in the first 10 lm of the film. As the oil
was exposed to simulated sunlight, the absorbance decreased to
some extent, but after 12 h of radiation, the fraction of light ab-
sorbed did not decrease substantially. For example, at 300 nm,
the fraction of light absorbed decreased from 0.997 to 0.984 and
at 350 nm it decreased from 0.837 to 0.761. The fraction of absor-
bance remaining after 12 h of irradiation is presented in Fig. 4.
Across the solar UV (300–400 nm), the loss of absorbance was rel-
atively constant. After 12 h of irradiation, the absorbance across
this region decreased on average to 0.78 ± 0.03 times that of the
Fig. 2. Fraction of alkanes remaining after 12 h of irradiation in a solar simulator. initial absorbance. Interestingly, the loss of absorbance was at its
All data points were normalized to dark controls. Error is one standard deviation for
n = 3. Approximately 4 h of irradiation in the simulator was equivalent to one
maximum at 237 nm, with a smaller maximum at 290 nm, both
average day of sunlight in the Northern Gulf of Mexico. in a region outside of the solar spectrum but corresponding to
absorbance maxima for the oil. At 237 nm, 12 h of irradiation
yielded an absorbance of 0.74 times that of the dark control,
was observed. Consequently, we believe that the loss of these com- indicating only a slight difference compared to other wavelengths.
pounds in the irradiated samples was due to evaporation. We also A greater loss at 237 and 290 nm indicates that the compounds
measured the n-C17:pristine and n-C18:phytane ratios and found that absorbed at these wavelengths were more susceptible to
no statistical difference before and after irradiation, further sug- photodegradation than other compounds in the oil. As will be
gesting that no substantial photochemical transformation occurred
for the n-alkanes (Rontani and Giral, 1987). The addition of TiO2
photocatalysts did not cause measurable differences in n-alkane
loss in experiments equivalent to approximately 12 d of full sun-
light (48 h exposure in the solar simulator), suggesting that TiO2
is ineffective at catalyzing n-alkane photodegradation under the
conditions used in this study. These results differ from that in
the study done by D’Auria et al. who studied the photodegradation
of crude oil in the presence of TiO2 using headspace gas chroma-
tography or SPME and GC–MS (D’Auria et al., 2009). Their photo-
catalyst loading was much higher (1 g photocatalyst per 100 mg
oil) compared to our study (3 mg photocatalyst per 100 mg oil).
In addition, their irradiation times were much longer (100 h) and
they utilized a mercury arc lamp as the source of radiation. Under
those conditions, D’Auria et al. saw substantial alkane degradation
of crude oil upon the addition of TiO2.
D’Auria et al. reported that in the absence of a catalyst, linear al-
kanes did not undergo photochemical degradation after 100 h of
mercury lamp irradiation (D’Auria et al., 2009). Klein and Pilpel Fig. 3. Fraction of light absorbed by oil film 60 lm thick without irradiation (Dark)
studied the photodegradation of n-alkanes in solution with 1- and after 12 h of irradiation in a solar simulator. Approximately 4 h of irradiation in
naphthol present (Klein and Pilpel, 1973). In their studies, which the simulator is equivalent to one average day of sunlight in the Northern Gulf of
used a medium pressure mercury lamp with a filter to transmit Mexico.

UV radiation in the absorbance region of 1-naphthol, it was ob-

served that the photodegradation of the n-alkanes increased with
increasing amounts of photosensitizer present, whereas marginal
degradation occurred in the samples without 1-naphthol. Rontani
and Giral observed that branched alkanes were more susceptible
to phototransformation than linear alkanes (Rontani and Giral,
1987). Hansen reported similar results that branched alkanes were
more readily decomposed than n-alkanes (Hansen, 1975). Rontani
and Giral later reported that the extent of degradation can be con-
firmed by comparing the ratio of branched alkanes to n-alkanes
(Rontani and Giral, 1990). Since our work utilized shorter irradia-
tion times compared to these previous reports, and since we
utilized simulated sunlight that contained less UV radiation than
is provided by mercury lamps, it is reasonable that we did not
observe substantial alkane degradation.

3.2. Absorbance results

Fig. 4. Fraction of absorbance remaining vs. wavelength for oil irradiated 12 h in a
As a result of irradiation, the absorbance spectra of the oil sam- solar simulator. Approximately 4 h of irradiation in the simulator is equivalent to
ples changed. Based on the measured absorbance of the oil, we one average day of sunlight in the Northern Gulf of Mexico.
 S.M. King et al. / Chemosphere 95 (2014) 415–422
discussed below, the loss of absorbance was much less significant
than the loss of fluorescence, indicating that fluorophores in the oil
were more readily degraded than the chromophores. Non-fluores-
cent molecules have much shorter excited state lifetimes than fluo-
rescent molecules, suggesting that excited states play an important
role in photodegradation of absorbing compounds.
3.3. Fluorescence results
The fluorescence of the oil after extraction with DCM was mon-
itored as a function of irradiation time. The maximum fluorescence
from the oil was observed with an excitation wavelength of
260 nm and an emission wavelength of 375 nm. Consequently,
we utilized total fluorescence at these wavelengths as a surrogate
for total PAH concentration. Fluorescence was lost fairly rapidly
during irradiation, as illustrated in Fig. 5. At early times, we ob-
served near linear loss at an initial rate of 8.9% per hour of irradi-
ation in the solar simulator. While the system clearly does not fit
a linear model, we utilized the first 6 h of data to calculate an initial
rate as approximated by the straight line in Fig. 5a. However, we
were not able to find a suitable model to fit the full data set.
Approximately 4 h of irradiation in this solar simulator is equiva-
lent to 1 d of average sunlight in the Northern Gulf of Mexico, so
we can predict a loss of approximately 36% of total fluorescence
(ex = 260, em = 375) for a single day of sunlight for a 60 lm oil
film. The loss of fluorescence slowed with irradiation time, sug-
gesting decreased degradation of PAHs after the first day of sun-
light. First order loss was not observed, as demonstrated in
Fig. 5b. Since the light flux was constant during the entire irradia-
tion, the decrease in fluorescence decay rate was most likely due to
a rapid initial loss in the most photolabile fluorophores followed by
Fig. 5. Loss of fluorescence vs irradiation time: linear (a) and logarithmic (b) plots.
In each plot, a linear regression for the first three points is illustrated. Approx-
imately 4 h of irradiation in our simulator is equivalent to one average day of
sunlight in the Northern Gulf of Mexico.
419
successively slower loss of less photolabile fluorophores. From 24
to 48 h, the rate of loss of fluorescence was only 0.2% per hour of
irradiation. The slowing in photodegradation of fluorophores sug-
gests that a pool of non-photolabile fluorophores exists in an abun-
dance of approximately 10% of the initial fluorescence (see Fig. 5a).
Comparison to absorbance data shows stark differences. Irradiation
for 12 h resulted in an approximate 22% loss in absorbance, but the
same irradiation resulted in an approximate 62% loss in fluores-
cence. This result indicates that the fluorophores are much more
photolabile than the non-fluorescent chromophores. Furthermore,
a large portion of the absorbance was associated with minimally
photolabile compounds. Since PAHs are known to be highly fluo-
rescent, it is likely that the majority of the PAHs were photode-
graded, and the remaining photostable chromophores represent
either nonPAH species or PAHs that are poor fluorophores (i.e.,
those that have short excited state lifetimes). In addition, carbonyl
containing aromatics formed from photodegradation of PAHs are
less likely to be fluorescent but will still be good chromophores.
Rapid relaxation of the excited state after absorption of a photon
could protect these compounds from further photodegradation.
While fluorescence has been shown to exhibit excellent detec-
tion limits for PAHs, many PAHs have similar excitation and emis-
sion spectra, thus making the detection of individual compounds in
multiple component systems impossible with conventional fluo-
rescence without prior separation. To overcome this limitation,
Lloyd introduced synchronous fluorescence scans as a method to
characterize complex mixtures without a separation step (Lloyd,
1971).
Synchronous scans were performed on the DCM extract (a rep-
resentative plot is shown in Supporting information, Fig. S1). In our
studies we collected synchronous scan data from 250 to 500 nm,
which slightly differs from the range of 300–700 nm used by Gue-
des et al. (2006). It was observed in their studies that after 100 h of
solar irradiation, the fluorescence intensity decreased 61% and 72%
for Arabian and Colombian oil, respectively. D’Auria et al. observed
synchronous scan fluorescence emission spectra over the range
300–550 nm for crude oil from Basilicata (Southern Italy). In their
studies the highest intensity peak was observed at 396 nm, and the
fluorescence intensity decreased 20% after 100 h of irradiation with
a high pressure mercury lamp (D’Auria et al., 2008). It is difficult to
make direct comparison between irradiation with mercury lamps
and actual sunlight.
We divided the synchronous scan data into four wavelengths
representing very small (1–2 ring, 290 nm), small (2 ring,
305 nm), medium (2–3 ring, 326 nm), and large (3–4 ring,
390 nm) PAHs. Previous studies established that fluorescence
synchronous scan data can be separated into different regions that
represent different size PAHs; smaller PAH emissions are at lower
wavelengths while larger PAH emissions occur at longer wave-
lengths (Berthou et al., 1985; Nicodem et al., 2001; Patra and Mish-
ra, 2002). For all wavelengths used, a decrease in fluorescence was
observed with increasing irradiation time. This decrease was more
pronounced as the wavelength increased, indicating that the larger
PAHs were the most photolabile. The larger PAHs have a better
overlap between their absorbance spectra and the solar spectrum.
Therefore, these compounds absorb a greater amount of photons
during solar irradiation compared to smaller PAHs that absorb at
wavelengths with low solar intensity. While photochemistry is also
dependent upon quantum yield, there is generally a correlation
between the number of photons absorbed and the amount of pho-
toreaction. PAHs are capable of forming excited state singlets and
triplets that can readily transfer energy to ground state molecular
oxygen (3O2) to form singlet oxygen (1O2), which can subsequently
react with PAHs or other compounds to yield oxygenated products
(Fasnacht and Blough, 2002, 2003b,a). Since singlet oxygen is
formed in proximity to the chromophore, there is a high likelihood
420 S.M. King et al. / Chemosphere 95 (2014) 415–422
Fig. 6. Calculated first order degradation rate constants for loss of fluorescence from synchronous scans (Dk = 25 nm) at (a) 290 nm, (b) 305 nm, (c) 326 nm, and (d) 390 nm
representing very small, small, medium, and large PAHs. Irradiance in the solar simulator was 1.3 times that of AM1.5 (1000 W/m2). Presented rate constants were corrected
to correspond to AM1.5 irradiance.
that the chromophore will subsequently react with singlet oxygen.
Consequently, the more strongly absorbing large PAHs are more
likely to undergo such self-sensitization.
We also studied the loss of fluorescence with added photocata-
lysts. Using a t-test, we found the loss of fluorescence with each
added photocatalyst to be statistically different than the loss with-
out catalyst at 95% confidence (some showed 99% confidence). As
will be discussed further below, most photocatalyst experiments
exhibited enhanced PAH degradation compared to experiments
without added catalyst.
Over 12 h of irradiation, the loss of fluorescence as measured by
synchronous scan followed reasonably a first order decay (see Sup-
plementary material Tables S1–S4). Therefore, we calculated first
order rate constants for this decay. Fig. 6 shows the observed first
order rate constants as a function of PAH size as well as photocat-
alyst additives. For TiO2 nanoparticles at 3% loading (w/w) and for
TiO2 nanotubes at 3% and 9% loading (w/w), the observed degrada-
tion of PAHs was substantially enhanced compared to no oxide
treatments. For the very small PAHs, 9% TiO2 nanotubes showed
a 93% enhancement in observed degradation rate constant over
the no oxide irradiation. For the small PAHs, this enhancement
was 63%, for the medium PAHs it was 72%, and for the large PAHs
it was 11%. The 3% loading of nanotubes showed similar enhance-
ments except for the largest PAHs. The 3% loading of TiO2 nanopar-
ticles showed slightly smaller enhancements except for the largest
PAHs, which demonstrated an inhibition with the added
nanoparticles. The 9% loading of TiO2 nanoparticles showed no
enhancement or inhibition for all PAH sizes. TiO2 is a known pho-
tocatalyst that can produce reactive holes and electrons on its sur-
face. Furthermore, it can produce superoxide and hydroxyl radical
through mechanisms that involve water and oxygen. TiO2 is only
active in the solar UV and not in the visible spectrum. Based on
the oil absorbance data presented above, the UV radiation was
depleted in the oil layer, but the upper regions of the oil would still
have available radiation that could be absorbed by the TiO2 to re-
sult in photocatalysis. The large PAHs were the most photoactive,
and in some cases they showed inhibition in degradation with
added TiO2. This result is reasonable since the TiO2 would have
acted as a light screening agent, preventing these PAHs from
absorbing light directly and undergoing photolysis. The smaller
PAHs were less efficient at photolysis, so the light screening effect
of TiO2 would have been less important. Consequently, for all but
the largest PAHs, a net enhancement in degradation was observed
with added TiO2. The exception is the 9% loading of TiO2 nanopar-
ticles. It is likely that for this catalyst at high loading, light screen-
ing was an important factor. The better performance of the TiO2
nanotubes as a photocatalyst is likely due to their higher surface
area to volume ratio, which is expected to provide lower hole-elec-
tron recombination and hence enhanced photocatalysis. In
additional studies, we are evaluating the mechanisms of TiO2 cat-
alyzed degradation of petroleum.
The TiO2 used in this study remained in the oil layer because the
particles/tubes were surface modified with stearic acid prior to
mixing with the oil. This modification made the particles hydro-
phobic and minimized their transport into the aqueous layer. The
high viscosity of the oil also helped to keep these particles in the
oil layer despite the greater density of the particles. The tubes,
however, likely had a net density close to that of the oil since their
hollow centers were probably filled with oil.
3.4. Toxicity screening of the aqueous layer
The aqueous fraction of irradiated samples was analyzed to
evaluate the toxicity of the samples over time. To examine the
toxicity of aqueous samples exposed to the oil with and without
exposure to simulated sunlight, the emission intensity of the
luminescent bacteria Vibrio fischeri was monitored. The toxicity
of samples is reported as the % effect, which correlates to the
 S.M. King et al. / Chemosphere 95 (2014) 415–422
decrease in luminescence of the bacteria that is exposed to the tox-
in and is directly related to the amount of test bacteria killed or
inactivated. Ziolli et al. observed that the toxicity of the water sol-
uble fraction of Brazilian crude oil samples with TiO2 increased in
comparison to samples that did not contain photocatalysts after
1 d of irradiation via high pressure mercury lamps (Ziolli and
Jardim, 2002). The toxicity then decreased until 3 d when the sam-
ples were no longer toxic. The increase and subsequent decrease in
the toxicity were attributed to the formation and destruction of
degradation intermediates that were more toxic than the parent
compounds. Our studies found that after exposing water to oil
for 24 h in the dark, no toxicity was observed for the water phase
using Microtox™ analysis. The lack of toxicity is likely due to the
fact that our oil was substantially depleted of water soluble species
when it rose through 1500 m of the Gulf of Mexico and remained
on the surface of the water prior to its collection. Consequently,
during the 24 h equilibration, little of the oil dissolved in the water
and no toxicity was observed. However, all irradiated samples
showed substantial toxicity as presented in Fig. 7. These results
partially contradict the findings of Ziolli et al. because we did not
observe a decrease in the toxicity of the samples after 12 h of irra-
diation, which would equal about 3 d of natural sunlight. The dif-
ference between the two studies can be attributed to two factors.
First, Ziolli et al. used a mercury lamp, which likely provided signif-
icantly more UV radiation than sunlight. Second Ziolli et al. used
water soluble fractions rather than whole crude oil as used here.
The crude oil in our studies was not entirely depleted during irra-
diation, allowing for continuous release of degradation products
over the complete irradiation period. Thus the likelihood of the
intermediates being fully degraded during our exposures was low.
The increase in toxicity observed in our studies was expected
due to the anticipated increase in solubility of the degradation
products. Many studies have investigated the products formed
during photodegradation of oil. Hansen et al. studied the photo-
degradation of thin films of crude oil fractions and found that the
major products produced were primarily aliphatic and aromatic
acids in addition to a less significant quantity of alcohols and phe-
nols (Hansen, 1975). Tjessem and Aaberg observed substantial
changes in the chemical and physical properties of photodegraded
oil (Tjessem and Aaberg, 1983). Further investigations detected
formation of ketones as degradation products (Boukir et al.,
2001; Bobinger and Andersson, 2009). Thominette and Verdu sug-
gested that PAHs are important in radical propagation of chain
reactions and that phase separation can occur due to insoluble,
high molecular weight species formed by condensation and
polymerization reactions (Thominette and Verdu, 1984b,a). These
polymers were found to be linear or branched and not cross-linked.
Fig. 7. MicrotoxTM data of the toxicity of the aqueous layer of the irradiated
samples. % Effect represents the % of bacteria killed or inactivated during incubation
for 15 min in the aqueous sample. Approximately 4 h of irradiation in our simulator
is equivalent to one average day of sunlight in the Northern Gulf of Mexico.
421
In other studies, photosensitized reactions involved in photochem-
ical transformations were indicated to be of importance for the
degradation of otherwise unreactive linear and branched alkanes
(Rontani and Giral, 1990; Ehrhardt et al., 1992). Alkane degrada-
tion products were identified to be mostly ketones and alcohols
in these explorations. In more recent work, a number of benzothio-
phene photooxidation products were identified (Bobinger and
Andersson, 2009).
Samples irradiated for 3 and 6 h containing photocatalysts
showed lower toxicity compared to the samples that contained
no oxide. The fluorescence results for TiO2 samples irradiated for
3 h indicated an increase in the degradation rate in comparison
to that of the no oxide samples. Addition of TiO2 provides
additional degradation pathways, causing a change in photodegra-
dation products. Such a change could explain the observed differ-
ences in toxicity with and without the oxide. With additional
irradiation, all the aqueous samples had similar toxicity, suggest-
ing a change in photoproducts at early and late times with the
photocatalyst present.
4. Conclusions
This project revealed several important characteristics of oil
phototransformation in thin films on water. Under environmen-
tal conditions, n-alkane photodegradation was not observed with
the equivalent of 3 d of solar irradiation. Even with added phot-
ocatalysts, no measurable decrease in n-alkane content was ob-
served. However, solar irradiation did promote the evaporative
loss of n-alkanes with 17 or fewer carbon atoms. PAH photodeg-
radation was substantial, and larger PAHs were degraded more
rapidly than smaller PAHs. The loss of PAHs was rapid in the
first few hours of irradiations (10% per hour), but decreased
to near zero after the equivalent of 6 d of irradiation. Unlike loss
in fluorescence, which decreased by 60–90% (depending on the
measurement method) after the equivalent of 3 d of irradiation,
loss of absorbance was relatively minor (20% decrease across
all wavelengths with the same irradiation time period). These re-
sults indicate that sunlight may play an important role in degra-
dation of large, biorefractory PAHs, but that other colored
material in oil is resistant to photodegradation. TiO2 photocata-
lysts substantially enhanced PAH degradation, especially for
smaller PAHs. Sunlight clearly increased the toxicity of water
in contact with the oil, presumably due to the release of toxic,
water soluble photoproducts. Additional research is needed to
understand the mechanisms involved in oil photodegradation,
the products formed, and the impact that phototransformations
have on biodegradation.
Acknowledgements
This research was supported by the National Science Founda-
tion (CHE-0611902 and CHE-1111525) and from BP/The Gulf of
Mexico Research Initiative via the Northern Gulf Institute
(10-BP-GRI-UNO-01). Amy Olson was supported by a National
Science Foundation Research Experiences for Undergraduates site
(DMR-1004869). Intensity readings for the solar simulator were
obtained with help from Scott Gordon. Undergraduate students
Aisa Carter and Anastasia Whitney and high school student
Elizabeth Balga contributed to this study. Elizabeth Balga was
supported by the Army Research Office via a sub grant from
the Academy of Applied Science (W911NF-04-1-0226). Access
to the Microtox™ 500 analyzer was provided through a loan of
equipment by SDIX and Dr. Bhaskar Kura of the University of
New Orleans.
422 S.M. King et al. / Chemosphere 95 (2014) 415–422
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2013.09.060.
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