Influence of desorption process and pH adjustement on the efficiency of O3, O3/H2O2 and O3/UV treatment of water and soil samples contaminated by crude petroleum.

The influence of the pH and the contaminant desorption/emulsification on ozone (O3), ozone-hydrogen peroxide (O3/H2O2) and ozone-photolysis (O3/UV) oxidation reactions were performed to treat crude petroleum (CP) contaminated soil and water samples. Oxidation efficiency is also related to both free radicals formation in reaction medium (which is dependent of the pH), and contaminant availability (which is dependent of the compounds solubilization or desorption processes). Thus, batch basic processes of O3/H2O2 or O3/UV were improved with sonication system and surfactant addition. In the case of O3/H2O2 process, the reactions were performed at adjusted (pH = 11) and natural pH (free pH= 4-5). The effectiveness of the improved advanced oxidation processes were evaluated through the time-course analysis of the chemical oxygen demand (COD), biochemical oxygen demand (BOD5), and total organic carbon (TOC) values. For both improved treatment processes, CP-contaminated water samples displayed higher values for TOC removal and BOD5/COD ratios than CP-contaminated soil samples. The O3/H2O2 process provided better results than the O3/UV process regarding degradation efficiency, but the former is associated with higher treatment costs due to H2O2 consumption. Overall, oxidation treatment processes increase their efficiencies when reactions are carried out associated with solubilization and desorption systems promoted by sonication/surfactant action.

Molecular level determination of water accommodated fraction with embryonic developmental toxicity generated by photooxidation of spilled oil.

In this study, developmental toxicity was increased as the oil was further degraded under natural sunlight. Detailed chemical composition of the degraded oils was examined by use of gas chromatography (GC) and (-) electrospray ionization ultrahigh resolution mass spectrometry (UHR-MS). Baseline toxicities were estimated based on chemical activities of polycyclic aromatic hydrocarbons, and it was obvious that the predicted chemical activities can not explain increased toxicity alone. However, the ultrahigh resolution mass spectral abundance of polar compounds including O3 and O4 class compounds was significantly increased as the photodegradation proceeded. Further examination of double bond equivalence values of the compounds showed that polar compounds with both non-aromatic and aromatic polar structures were increased. Statistical analysis indicates that the increased toxicity can be well explained by the increased polar compounds. Therefore, the oxygenated compounds identified in this study can play an important role in toxicity of degraded oils.

Phototoxicity Assessments of Field Sites in Barataria Bay, Louisiana, USA, and Heavily Weathered Macondo Crude Oil: 4 Years after the Deepwater Horizon Oil Spill.

The Deepwater Horizon oil spill resulted in the release of large amounts of crude oil into waters of the Gulf of Mexico (USA). A significant portion of the oil reached coastal waters and shorelines where aquatic organisms reside. Four years after the spill, oil remains in small quantities along the coast. Given the high volume of oil coupled with the high ultraviolet light intensities of the Gulf of Mexico, continued polycyclic aromatic hydrocarbon phototoxicity may be occurring in the Gulf region. The objective of the present study was to determine the potential for phototoxicity at 5 field sites (oiled, remediated, and unoiled) in Barataria Bay (LA, USA) to caged mysid shrimp and sheepshead minnows and to evaluate the phototoxic potential of field-collected oil water accommodated fractions (WAFs). Water chemistries were similar between field-collected oil WAFs and ambient waters, excluding the most oiled field site. Field bioassays indicated no phototoxic risk of heavily weathered crude oil under the highly turbid conditions present during the study. Laboratory WAFs of field-collected oil resulted in phototoxicity to mysid shrimp, suggesting a potential for phototoxicity of heavily weathered crude oil remaining in the Gulf of Mexico. Environ Toxicol Chem 2019;38:1811-1819. © 2019 SETAC.

Photo-enhanced toxicity of undispersed and dispersed weathered Macondo crude oil to Pacific (Crassostrea gigas) and eastern oyster (Crassostrea virginica) larvae.

During the Deepwater Horizon oil spill rapid natural weathering of Macondo crude oil occurred during the transport of oil to coastal areas. In response to the DWH incident, dispersant was applied to Macondo crude oil to reduce the movement of oil to coastal regions. This study aimed to assess the narcotic and phototoxicity of water-accommodated fractions (WAFs) of weathered Macondo crude oil, and chemically-enhanced WAFs of Corexit 9500 to Pacific (Crassostrea gigas) and eastern (Crassostrea virginica) oyster larvae. Phototoxic effects were observed for larval Pacific oysters exposed to combinations of oil and dispersant, but not for oil alone. Phototoxic effects were observed for larval eastern oysters exposed to oil alone and combinations of oil and dispersant. Corexit 9500 did not exhibit phototoxicity but resulted in significant narcotic toxicity for Pacific oysters. Oyster larvae may have experienced reduced survival and/or abnormal development if reproduction coincided with exposures to oil or dispersant.

Phototoxic potential of undispersed and dispersed fresh and weathered Macondo crude oils to Gulf of Mexico Marine Organisms.

Crude oils contain a mixture of hydrocarbons, including phototoxic polycyclic aromatic hydrocarbons (PAHs) that have the ability to absorb ultraviolet (UV) light. Absorption of UV light by PAHs can substantially increase their toxicity to marine organisms. The objective of the present study was to examine the potential for phototoxicity of fresh and naturally weathered Macondo crude oils alone and in combination with the dispersant Corexit 9500 to mysid shrimp (Americamysis bahia), inland silverside (Menidia beryllina), sheepshead minnow (Cyprinodon variegatus), and Gulf killifish (Fundulus grandis). Acute toxicity tests were conducted using combinations of natural or artificial sunlight and low-energy water-accommodated fractions (WAFs) of fresh and weathered Macondo crude oils collected from the Gulf of Mexico. Studies were also conducted to compare the phototoxicity resulting from natural and artificial sunlight. Fresh Macondo crude oil was more phototoxic than weathered crude oils, both in the presence and in the absence of UV light. Differences in toxicity between fresh and weathered crude oils were likely attributed to lighter-ringed PAHs in fresh crude oils. Phototoxic PAHs were relatively resistant to weathering compared with lighter-ringed PAHs. The addition of Corexit 9500 to crude oil increased toxicity compared with tests with crude oil alone, by increasing phototoxic PAH concentrations in WAFs. Macondo crude oils had the potential to be phototoxic to Gulf of Mexico marine organisms if specific light conditions and PAH concentrations were present during the Deepwater Horizon oil spill. Environ Toxicol Chem 2017;36:2640-2650. © 2017 SETAC.

Mutagenicity and cytotoxicity evaluation of photo-catalytically treated petroleum refinery wastewater using an array of bioassays.

Degradation and detoxification of petroleum refinery wastewater (PRW) was carried out by advanced oxidation processes (UV/TiO2/H2O2 and gamma radiation/H2O2). Response surface methodology (RSM) was used to optimize the independent variables. The cytotoxicity was evaluated using Allium cepa, brime shrimp and haemolytic assays; whereas mutagenicity was tested by Ames tests (TA98 and TA100 strains). Maximum reductions in COD and BOD were recorded as 78% and 87% for UV/TiO2/H2O2 and 77% and 86% for gamma ray/H2O2, respectively. Treatments with both methods at optimized conditions reduced the cytotoxicity and mutagenicity of PRW, however, UV/TiO2/H2O2 system was found slightly efficient as compared to gamma ray/H2O2. From the results, it can be concluded that AOP's can successfully be utilized for the degradation of toxic pollutants in petroleum refinery wastewater. Moreover, the bioassays used in this study offered a good reliability for checking the detoxification of treated and un-treated PRW wastewater.

Mechanistic investigation into sunlight-facilitated photodegradation of pyrene in seawater with oil dispersants.

This study investigated the effects of 3 model oil dispersants (Corexit EC9500A, Corexit EC9527A and SPC 1000) on photodegradation of pyrene under simulated sunlight. Both Corexit dispersants enhanced photodegradation of pyrene, while SPC1000 slightly inhibited the reaction. Span 80 and Tween 85 were the key ingredients causing the effects, though the underlying mechanisms differed. Span 80 enriches pyrene in the upper layer of water column, whereas Tween 85 induces a photosensitization process. Two reactive oxygen species, 1O2 and O2-, were found responsible for pyrene photodegradation, though the presence of EC9500A suppressed the 1O2 pathway. In terms of photodegradation products, EC9500A enhanced generation of polyaromatic intermediates, i.e., phenaleno[1,9-cd][1,2]dioxine, 1-hydroxypyrene, and 1,8-pyrenequinone, but did not alter the classical photodegradation pathway. The Corexit dispersants were more prone to photochemical decomposition, with multiple by-products detected. The information aids in our understanding of the effects of dispersants on photochemical weathering of oil compositions.

Photo-enhanced toxicity of two weathered Macondo crude oils to early life stages of the eastern oyster (Crassostrea virginica).

Polycyclic aromatic hydrocarbons (PAHs) have been reported to absorb ultraviolet (UV) light, resulting in enhanced toxicity. Early developmental stages of bivalves may be particularly susceptible to photo-enhanced toxicity during oil spills. In the current study, toxicity tests were conducted with sperm and three larval ages of the eastern oyster (Crassostrea virginica) to evaluate the photo-enhanced toxicity of low-energy water-accommodated fractions (WAFs) of two weathered Macondo crude oils collected from the Deepwater Horizon incident. Larvae exposed to oil WAFs under UV-filtered light demonstrated consistently higher survival and normal development than larvae exposed to WAFs under UV light. The phototoxicity of weathered Macondo oil increased as a function of increasing UV light intensity and dose. Early developing oyster larvae were the most sensitive to photo-enhanced toxicity, whereas later shelled prodissoconch larvae were insensitive. Comparisons between two weathered crude oils demonstrated that toxicity was dependent on phototoxic PAH concentration and UV light intensity.

Influence of UVB radiation on the lethal and sublethal toxicity of dispersed crude oil to planktonic copepod nauplii.

Toxic effects of petroleum to marine zooplankton have been generally investigated using dissolved petroleum hydrocarbons and in the absence of sunlight. In this study, we determined the influence of natural ultraviolet B (UVB) radiation on the lethal and sublethal toxicity of dispersed crude oil to naupliar stages of the planktonic copepods Acartia tonsa, Temora turbinata and Pseudodiaptomus pelagicus. Low concentrations of dispersed crude oil (1 µL L(-1)) caused a significant reduction in survival, growth and swimming activity of copepod nauplii after 48 h of exposure. UVB radiation increased toxicity of dispersed crude oil by 1.3-3.8 times, depending on the experiment and measured variables. Ingestion of crude oil droplets may increase photoenhanced toxicity of crude oil to copepod nauplii by enhancing photosensitization. Photoenhanced sublethal toxicity was significantly higher when T. turbinata nauplii were exposed to dispersant-treated oil than crude oil alone, suggesting that chemical dispersion of crude oil may promote photoenhanced toxicity to marine zooplankton. Our results demonstrate that acute exposure to concentrations of dispersed crude oil and dispersant (Corexit 9500) commonly found in the sea after oil spills are highly toxic to copepod nauplii and that natural levels of UVB radiation substantially increase the toxicity of crude oil to these planktonic organisms. Overall, this study emphasizes the importance of considering sunlight in petroleum toxicological studies and models to better estimate the impact of crude oil spills on marine zooplankton.

The effect of dispersed Petrobaltic oil droplet size on photosynthetically active radiation in marine environment.

Oil pollution in seawater, primarily visible on sea surface, becomes dispersed as an effect of wave mixing as well as chemical dispersant treatment, and forms spherical oil droplets. In this study, we examined the influence of oil droplet size of highly dispersed Petrobaltic crude on the underwater visible light flux and the inherent optical properties (IOPs) of seawater, including absorption, scattering, backscattering and attenuation coefficients. On the basis of measured data and Mie theory, we calculated the IOPs of dispersed Petrobaltic crude oil in constant concentration, but different log-normal size distributions. We also performed a radiative transfer analysis, in order to evaluate the influence on the downwelling irradiance Ed, remote sensing reflectance Rrs and diffuse reflectance R, using in situ data from the Baltic Sea. We found that during dispersion, there occurs a boundary size distribution characterized by a peak diameter d0 = 0.3 µm causing a maximum E d increase of 40% within 0.5-m depth, and the maximum Ed decrease of 100% at depths below 5 m. Moreover, we showed that the impact of size distribution on the "blue to green" ratios of Rrs and R varies from 24% increase to 27% decrease at the same crude oil concentration.

Differentiating the roles of photooxidation and biodegradation in the weathering of Light Louisiana Sweet crude oil in surface water from the Deepwater Horizon site.

We determined the contributions of photooxidation and biodegradation to the weathering of Light Louisiana Sweet crude oil by incubating surface water from the Deepwater Horizon site under natural sunlight and temperature conditions. N-alkane biodegradation rate constants were ca. ten-fold higher than the photooxidation rate constants. For the 2-3 ring and 4-5 ring polycyclic aromatic hydrocarbons (PAHs), photooxidation rate constants were 0.08-0.98day(-1) and 0.01-0.07day(-1), respectively. The dispersant Corexit enhanced degradation of n-alkanes but not of PAHs. Compared to biodegradation, photooxidation increased transformation of 4-5 ring PAHs by 70% and 3-4 ring alkylated PAHs by 36%. For the first time we observed that sunlight inhibited biodegradation of pristane and phytane, possibly due to inhibition of the bacteria that can degrade branched-alkanes. This study provides quantitative measures of oil degradation under relevant field conditions crucial for understanding and modeling the fate of spilled oil in the northern Gulf of Mexico.

A practical review on photooxidation of crude oil: laboratory lamp setup and factors affecting it.

After an oil spill, crude oil in the marine environment is affected by a variety of processes collectively called weathering. Photooxidation induced by ultraviolet (UV) light from the sun is one of the most significant processes of long-term weathering that changes the chemical nature of oil. Experimental studies on photooxidation in the natural environment are generally not practicable due to the variability of factors that are more readily controlled in a laboratory. The emission spectra and irradiance of artificial lamps are critical factors for simulating sunlight, and the process of acceleration should be differentiated from simulation. We present a comprehensive review of the exposure conditions affecting in vitro photooxidation studies, including the types of lamps, their spectra and irradiance levels and maintenance conditions. The importance of xenon arc, metal halide along with mercury­xenon, high-pressure mercury lamps and other lamps with respect to their spectral characteristics is discussed and the selection guide is provided. A brief discussion on other factors affecting photooxidation rates and outcomes, such as photosensitisers, photodegraders, solvents and the synergistic effects of compounds is also given.

Sunlight creates oxygenated species in water-soluble fractions of Deepwater Horizon oil.

In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid-liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O5), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O2). Higher-order oxygen classes (O5-O9) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N1) concurrent with an increased abundance of N1Ox classes after irradiation. The predominance of higher-order oxygen classes indicates that multiple photochemical pathways exist that result in oxidation of petroleum compounds.

Petroleum films exposed to sunlight produce hydroxyl radical.

Sunlight exposed oil films on seawater or pure water produced substantial amounts of hydroxyl radical as a result of irradiation. Oil was collected from the surface of the Gulf of Mexico following the Deepwater Horizon spill and exposed to simulated sunlight in thin films over water. Photochemical production of hydroxyl radical was measured with benzoic acid as a selective chemical probe in the aqueous layer. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. The total amount of hydroxyl radical produced in 24 h irradiations of thin oil films over Gulf of Mexico water and pure water were 3.7×10(-7) and 4.2×10(-7) moles respectively. Steady state concentrations of hydroxyl radical were measured using a competition kinetics approach. Hydroxyl radical concentrations of 1.2×10(-16) to 2.4×10(-16) M were observed for seawater and pure water under oil films. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. The addition of TiO2 nanoparticles dramatically changed the observed formation rate of hydroxyl radical in the systems with NP water at pH 3, showing increased formation rate in many cases. With photocatalyst, the steady state concentration of radical decreased, predominantly due to an increase in the hydroxyl radical scavenging rate with oxide present. This study illustrates that oil is a strong and important source of hydroxyl radical when exposed to sunlight. The fate of oil and other dissolved species following oil spills will be heavily dependent on the formation and fate of hydroxyl radical.

Robust magnetic/polymer hybrid nanoparticles designed for crude oil entrapment and recovery in aqueous environments.

Well-defined, magnetic shell cross-linked knedel-like nanoparticles (MSCKs) with hydrodynamic diameters ca. 70 nm were constructed through the co-assembly of amphiphilic block copolymers of PAA20-b-PS280 and oleic acid-stabilized magnetic iron oxide nanoparticles using tetrahydrofuran, N,N-dimethylformamide, and water, ultimately transitioning to a fully aqueous system. These hybrid nanomaterials were designed for application as sequestering agents for hydrocarbons present in crude oil, based upon their combination of amphiphilic organic domains, for aqueous solution dispersibility and capture of hydrophobic guest molecules, with inorganic core particles for magnetic responsivity. The employment of these MSCKs in a contaminated aqueous environment resulted in the successful removal of the hydrophobic contaminants at a ratio of 10 mg of oil per 1 mg of MSCK. Once loaded, the crude oil-sorbed nanoparticles were easily isolated via the introduction of an external magnetic field. The recovery and reusability of these MSCKs were also investigated. These results suggest that deployment of hybrid nanocomposites, such as these, could aid in environmental remediation efforts, including at oil spill sites, in particular, following the bulk recovery phase.

Interactions between zooplankton and crude oil: toxic effects and bioaccumulation of polycyclic aromatic hydrocarbons.

We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1) the effects of crude oil (Louisiana light sweet oil) on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in mesozooplankton communities, (2) the lethal effects of dispersant (Corexit 9500A) and dispersant-treated oil on mesozooplankton, (3) the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4) the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L(-1) in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20), dispersant (0.25 µl L(-1)) and dispersant-treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L(-1)) to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments.

Natural sunlight and residual fuel oils are an acutely lethal combination for fish embryos.

The majority of studies characterizing the mechanisms of oil toxicity in fish embryos and larvae have focused largely on unrefined crude oil. Few studies have addressed the toxicity of modern bunker fuels, which contain residual oils that are the highly processed and chemically distinct remains of the crude oil refinement process. Here we use zebrafish embryos to investigate potential toxicological differences between unrefined crude and residual fuel oils, and test the effects of sunlight as an additional stressor. Using mechanically dispersed oil preparations, the embryotoxicity of two bunker oils was compared to a standard crude oil from the Alaska North Slope. In the absence of sunlight, all three oils produced the stereotypical cardiac toxicity that has been linked to the fraction of tricyclic aromatic compounds in an oil mixture. However, the cardiotoxicity of bunker oils did not correlate strictly with the concentrations of tricyclic compounds. Moreover, when embryos were sequentially exposed to oil and natural sunlight, the bunker oils produced a rapid onset cell-lethal toxicity not observed with crude oil. To investigate the chemical basis of this differential toxicity, a GC/MS full scan analysis was used to identify a range of compounds that were enriched in the bunker oils. The much higher phototoxic potential of chemically distinct bunker oils observed here suggests that this mode of action should be considered in the assessment of bunker oil spill impacts, and indicates the need for a broader approach to understanding the aquatic toxicity of different oils.

[Microwave thermal remediation of soil contaminated with crude oil enhanced by granular activated carbon].

The advantage of rapid, selective and simultaneous heating of microwave heating technology was taken to remediate the crude oil-contaminated soil rapidly and to recover the oil contaminant efficiently. The contaminated soil was processed in the microwave field with addition of granular activated carbon (GAC), which was used as strong microwave absorber to enhance microwave heating of the soil mixture to remove the oil contaminant and recover it by a condensation system. The influences of some process parameters on the removal of the oil contaminant and the oil recovery in the remediation process were investigated. The results revealed that, under the condition of 10.0% GAC, 800 W microwave power, 0.08 MPa absolute pressure and 150 mL x min(-1) carrier gas (N2) flow-rate, more than 99% oil removal could be obtained within 15 min using this microwave thermal remediation enhanced by GAC; at the same time, about 91% of the oil contaminant could be recovered without significant changes in chemical composition. In addition, the experiment results showed that GAC can be reused in enhancing microwave heating of soil without changing its enhancement efficiency obviously.

Photodegradation of crude oil: liquid injection and headspace solid-phase microextraction for crude oil analysis by gas chromatography with mass spectrometer detector.

The fate of crude oil under irradiation is studied. After UV irradiation, the fraction present in the highest percentage shifts from the C8-C9 fractions to C13, using gas chromatography-mass spectrometry (GC-MS) analysis in solution. An increase of the relative amount of the C13-C25 fraction is observed, while a decrease in the relative amount of the C7-C12 fractions is present. In headspace solid-phase microextraction (HS-SPME) analysis, the C8-C10 fractions represent 53% of all the compounds detected. A decrease in the relative amount of the C8-C10 fractions is observed, while C11-C15 fractions increase. The irradiation of crude oil with a solar simulator gives a mixture the analysis of which using GC-MS in solution furnishes the same type of results: the relative amounts of linear alkanes and aromatic compounds increase, while a sharp decrease in the relative amounts of branched and cyclic alkanes is observed. In the SPME analysis, a decreased relative amount of branched alkanes and alkenes, and an increase in the relative amounts of cyclic alkanes and aromatic compounds are observed. Analysis of the distribution of the compounds in all the types of compound shows that a dynamic equilibrium between different compounds and different types of compounds is present. To confirm the presence of a dynamic equilibrium, the irradiation of methylcyclohexane in the presence of 2-methylnaphthalene shows the presence in the reaction mixture of a small amount of tetradecane.

Photocatalytic degradation of spill oils on TiO(2) nanotube thin films.

The nitrogen-doped TiO(2) nanotube (N-TNT) thin films were synthesized using ZnO nanorods as the template and doped with urea at 623K. Under ultraviolet (UV) and visible light irradiation, the efficiencies for photocatalytic degradation of methylene blue is as high as 30%. About 10% of toluene (representing aromatics in the spill oils) in sea water can be photocatalytically degraded under visible light radiation for 120 min. The aliphatic model compound (1-hexadecene) has, on the contrary, a less efficiency (8%) on the N-TNT photocatalyst. On the average, under visible light radiation, the effectnesses of the N-TNT for photocatalytic degradation of model compounds in the spill oils in sea water are 0.38 mg toluene/gN-TNTh and 0.25 mg 1-hexadecene/gN-TNTh. It is expected that spill oils in the harbors or seashores can be adsorbed and photocatalytically degraded on the N-TNT thin films that are coated onto levee at the sea water surface level.