Optimizing photo-Fenton like process for the removal of diesel fuel from the aqueous phase
© Dehghani et al.; licensee BioMed Central Ltd. 2014
Received: 13 June 2013
Accepted: 17 May 2014
Published: 23 May 2014
In recent years, pollution of soil and groundwater caused by fuel leakage from old underground storage tanks, oil extraction process, refineries, fuel distribution terminals, improper disposal and also spills during transferring has been reported. Diesel fuel has created many problems for water resources. The main objectives of this research were focused on assessing the feasibility of using photo-Fenton like method using nano zero-valent iron (nZVI/UV/H2O2) in removing total petroleum hydrocarbons (TPH) and determining the optimal conditions using Taguchi method.
The influence of different parameters including the initial concentration of TPH (0.1-1 mg/L), H2O2 concentration (5-20 mmole/L), nZVI concentration (10-100 mg/L), pH (3-9), and reaction time (15-120 min) on TPH reduction rate in diesel fuel were investigated. The variance analysis suggests that the optimal conditions for TPH reduction rate from diesel fuel in the aqueous phase are as follows: the initial TPH concentration equals to 0.7 mg/L, nZVI concentration 20 mg/L, H2O2 concentration equals to 5 mmol/L, pH 3, and the reaction time of 60 min and degree of significance for the study parameters are 7.643, 9.33, 13.318, 15.185 and 6.588%, respectively. The predicted removal rate in the optimal conditions was 95.8% and confirmed by data obtained in this study which was between 95-100%.
In conclusion, photo-Fenton like process using nZVI process may enhance the rate of diesel degradation in polluted water and could be used as a pretreatment step for the biological removal of TPH from diesel fuel in the aqueous phase.
In recent years, pollution of soil and groundwater caused by fuel leakage from old underground storage tank, refineries, fuel distribution terminals, improper disposal and also spills during transferring, has been reported[1–3]. The accidental spills of more than 2 million tons of refined oil products per year into the environment are a worldwide problem. Large amounts of benzene, toluene, ethyl benzene, and xylenes (BTEX) have been detected in polluted water resources. The leaching of petroleum hydrocarbons such as diesel fuel into water resources causes many serious environmental problems. Diesel fuel consists of a complex compound including paraffin, olefins, aliphatic hydrocarbons, as well as a lesser amount of aromatic compounds and includes molecules containing sulfur, nitrogen and metal oxides. The toxicity of diesel fuel is mostly due to BTEX aromatic hydrocarbons. The carcinogen property of diesel fuel is due to C10 and C20 alkenes and alkylated benzene. Therefore, developing an efficient method for the removal of diesel fuel from contaminated water resources is very crucial. Different physical, chemical, and biological techniques have been used to degrade the contaminated soils and water[6–10]. The aromatic hydrocarbons with high toxic nature cannot be degraded simply by conventional treatment methods. Most conventional techniques such as evaporation, oil phase separation, filtration, dissolved air flotation, coagulation, flocculation, absorption, and ultrafiltration only transfer pollutions from one media to another[12, 13]. Therefore, another method should be developed to remove hydrocarbon pollutions. In other words, these methods do not remove the pollutants, but generally produce highly concentrated wastes in lower volume. In addition, these methods have lower efficiency in removing smaller oil droplets and emulsions. Nowadays, biological and bioremediation techniques are used to treat polluted soils and sewages, but these methods need improvement for enhancing the enzymatic activity in microbial population. Therefore, it is very important to use advanced methods in order to remove oily compounds from groundwater resources. Advanced oxidation processes (AOPs) is an efficient environment-friendly method in which hydroxyl radicals (OH°) are used to oxidize recalcitrant organic pollutants and convert them to harmless end-products such as H2O and CO2[17, 18].
Previous studies in Iran have reported soil and water pollution caused by petroleum compounds near Shiraz, Esfahan and Tehran refineries. Since Fars (in Southern part of Iran) enjoys a top rank in oil refinery, storage, and distribution of oil products in the country in recent years, there is a concern regarding the effect of petroleum hydrocarbons in water resources on people's health and the environment. Therefore, the objectives of the study were to (i) evaluate the feasibility of using photo-Fenton like method (nZVI/UV/H2O2) in removing total petroleum hydrocarbons (TPH) and (ii) determine the optimal conditions using Taguchi method so that the standard limit can be achieved by further complementary treatment.
Materials and methods
Chemicals and analytical method
In this research, regular diesel fuel from a gas station in Shiraz was used as a pollutant model. Water-oil emulsion was prepared using emulsifier SDS. Nano zero-valent iron (nZVI) was supplied by Iran Oil Industry Research Center. The rest of the chemicals were purchased from Merck (Germany). UV lamp, 125 Kw, 247.3 nm wave length, (ARDA, Netherland) was used as the radiation source.
Diesel fuel (commercial grade) at the concentration of 100 mL was added gradually to 1 liter of distilled water using 2.5 mL of 0.1 g/L SDS as emulsifier. The water-diesel emulsion was mixed using Jar test at the speed of 200 rpm for 24 h. In order to separate non-dispersed diesel in oil-water emulsion, the solution was kept at rest for 1 h. Then, the emulsion was transferred to a separator funnel and the supernatant was removed and the rest was collected and passed through Whatman filter paper (20 μm in diameter). The prepared emulsion was used as stock solution and different concentrations 0.1-1 mg/L were prepared by diluting with distilled water.
Parameters and the selected levels of photo-Fenton like treatment process (nZVI/UV/H 2 O 2 ) for the reduction of TPH from diesel fuel in the aqueous phase
Concentration TPH (mg/L)
nZVI Concentration (mg/L)
H2O2 Concentration (mmole/L)
Reaction time (min)
Taguchi’s statistical method and Qualitek-4 (QT4) software were used for the experimental design. Using this software, 16 tests were designed randomly to reduce the errors. Two replications were done for each sample. TPH reduction rate was analyzed using QT4 software. The most effective parameters for removing diesel fuel from the aqueous phase, the rate of efficiency, and the level of precision, and optimal conditions were determined.
Test conditions and reactor specifications
Results and Discussion
The effects of nZVI particles concentration
The effects of reaction time
The effect of H2O2 concentration
The effects of initial TPH concentration
Our results suggest that the photo-Fenton like process (nZVI/UV/H2O2) can be used as a pre-treatment step for the biological removal of TPH from diesel fuel in the aqueous phase. In the conventional photo-Fenton like methods, high concentrations of ferrous salts were used. Therefore, the large amount of ferrous sludge was formed. The current study revealed that a lower amount of Fe is needed and the nZVI particles can be reused in a magnetic field. The variance analysis suggests that the optimal conditions for TPH reduction rate from diesel fuel in the aqueous phase using photo-Fenton like method (nZVI/UV/H2O2) are as follows: the initial TPH concentration equals to 0.7 mg/L, nZVI concentration 20 mg/L, H2O2 concentration equals to 5 mmol/L, pH 3, and the reaction time of 60 min and degree of significance for the study parameters are 7.643, 9.33, 13.318, 15.185 and 6.588 percent, respectively. The predicted removal rate in optimal conditions was 95.8%, confirmed by the results of our study which was between 95-100%.
This article is extracted from the Master's thesis and the authors appreciate the Deputy of Research and Technology of Shiraz University of Medical Sciences for its financial support for the research project of 91-6170.
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