fenton oxidation and combined fenton-microbial treatment for remediation of crude oil contaminated...

Environmental ScienceProcesses & Impacts

PAPER

Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27

.

View Article OnlineView Journal | View Issue

aEnvironmental Chemistry laboratory, Lif

Advanced Study in Science and Technology

781 035, Assam, India. E-mail: deviarundh

Tel: + 91 0361 2270084bDepartment of Chemistry, Gauhati Univers

Cite this: Environ. Sci.: ProcessesImpacts, 2013, 15, 1913

Received 3rd April 2013Accepted 1st August 2013

DOI: 10.1039/c3em00170a

rsc.li/process-impacts

This journal is ª The Royal Society of

Fenton oxidation and combined Fenton-microbialtreatment for remediation of crude oil contaminatedsoil in Assam – India

Surabhi Buragohain,a Dibakar Chandra Dekab and Arundhuti Devi*a

The study is aimed at the remediation of soil spiked with crude oil (5%) by employing Fenton oxidation,

biological treatment and combined Fenton-biological treatment. A spiked concentration of 5% crude oil

was selected on the basis of contamination levels of 0–5% as found in the soil of upper Assam oil fields

(India). The degradation of the aliphatic fraction (C14–C28) of the crude oil was investigated by gas

chromatography. Fenton oxidation was carried out at different pH (3 to 8) in a laboratory batch reactor

and maximum oxidative degradation was observed at pH 3–5. At pH 3, single Fenton oxidation resulted

in 36 and 57% degradation in 5 and 10 days respectively. Biological treatment (with Fusarium solani)

and combined Fenton-biological treatment were carried out with a one month incubation period.

Biological treatment alone brought about 61% degradation of the crude oil while the combined

process could achieve as much as 75% degradation of the aliphatic fractions of the crude oil.

Environmental impact

Soil contamination with crude oil is a serious global problem at oil drilling sites which can cause major damage to the agricultural sector due to accidentalseepage and leakages during storage and transportation. Therefore, developing an efficient remediation technique for reclamation of soil, water and sedimentsis a great challenge for research in this eld. Our work focuses on remediation of crude oil contaminated soil by Fenton treatment, biological treatment byFusarium solani and combined Fenton-biological treatment and to nd out an efficient and economic method among them.

1 Introduction

Soil contamination due to crude oil spillage or accidental leaksis one of the most serious environmental problems in the oilproducing countries. The contamination introduces non-organic, carcinogenic and growth-inhibiting chemicals presentin the crude oil to soil. Accidental release of petroleum productsfrom pipelines and storage tanks are among the most commoncauses of soil contamination.1,2 Oil-contaminated soils or sedi-ments are complex mixtures containing many different chem-ical species with different physico-chemical properties that canshow a wide range of toxicity to biota.3,4 The natural recovery ofoil-polluted soil is slow, and serious contamination may denyfarmers of their agricultural lands for a long time.

In situ chemical oxidation (ISCO) is a promising innovativetechnology for degrading an extensive variety of hazardouswastes for the remediation of soil at waste disposal and organiccontaminant spill sites.5,6 ISCO is based on the delivery of

e Sciences Division (LSD), Institute of

(IASST), Paschim Boragaon, Guwahati –

[email protected]; Fax: +91 0361 2740659;

ity, Assam, India

Chemistry 2013

chemical oxidants to the contaminated media to destroycontaminants to end products or to convert them into morebiodegradable compounds allowing them to be degradedbiologically.

Soil contamination by crude oil is the most serious envi-ronmental problem in the oil-producing provinces. This is wellillustrated in the Niger Delta communities of southern Nigeria.It is an accepted fact, even by the culpable oil companies thatthe Niger Delta soil is “soaked” with crude oil.7 Efforts havebeen made towards reclamation of the crude oil-inundated soilthrough natural attenuation as well as bioremediation andother methods.8,9 Crude oil is a repository of hydrocarbons andother organic compounds and soil contaminated with crude oilcan be effectively managed through the use of chemicaloxidants for converting the higher hydrocarbons to innocuoussimple compounds or through complete mineralization.Common oxidants, used for the purpose, include: hydrogenperoxide, potassium or sodium persulfate, potassium orsodium dichromate, potassium permanganate, etc.10–12 Amongthem, Fenton reagent has emerged as a very powerful oxidizingagent.13,14 In Fenton's process, hydrogen peroxide (H2O2) isdecomposed by iron(II) to form hydroxyl radicals (_OH), astrong, nonspecic oxidant that reacts with most organiccompounds at near-diffusion controlled rates.15,16 It is a low

Environ. Sci.: Processes Impacts, 2013, 15, 1913–1920 | 1913

http://dx.doi.org/10.1039/c3em00170a

http://pubs.rsc.org/en/journals/journal/EM

http://pubs.rsc.org/en/journals/journal/EM?issueid=EM015010

Table 1 Characteristics of the crude oil used for soil contamination

Parameter Unit Value

Density at 15 �C g cm�3 0.9019Specic gravity at 60/60 �F — 0.9024API gravity (60 �F) — 25.3Pour point �C 30Plastic viscosity cps 26 at 30 �CYield value Dynes cm�2 15.5 at 30 �CWax % w/w 7.54

Environmental Science: Processes & Impacts Paper

Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27

. View Article Online

cost oxidative process and is used in a number of environ-mental applications, including pre-treatment of industrialwastewaters, the treatment of water containing dilute concen-trations of xenobiotics, and the remediation of soil andgroundwater.17–21

Palmroth et al. (2006) utilised a combined modied Fenton-biological treatment to remove PAHs from creosote oil-contaminated soil achieving a higher PAH removal in thecombined method than in the incubation alone.22 Further,in situ remediation of contaminated soil is considered to bemore cost-efficient than on-site and off-site treatment, but itdepends on the quantity and location of the soil to be treated.23

Advanced oxidation processes and biodegradation are prom-ising in situ remediation techniques. Mater et al. (2006) showedthat Fenton's reaction enhanced the biodegradability ofpetroleum compounds (BOD5/COD ratios) by a factor of up to3.8 for contaminated samples of both water and soil.17

Degradation of PAHs in soil has been one of the primeconcerns.24

The present work focuses on the oxidative degradation of thealiphatic fraction (C-14 to C-28) of the crude oil, which has notreceived much attention. Persistence of these hydrocarbons inthe soil depends on various environmental factors, includingthat of volatilization. According to Bossert and Bartha (1986),n-alkanes with n > 16 exhibit no substantial volatilization atambient temperatures although rate of volatilization is a func-tion of air and soil temperature, humidity, wind speed, soil type,moisture content, oil composition, solar radiation, and thick-ness of the oil layer.25 The present study is conned to ndingout a suitable method based on Fenton and combined Fenton-microbial treatment for remediation of crude oil contaminatedsoil with respect to the aliphatic fractions.

2 Materials and methods2.1 Chemicals

H2O2 (30%) was purchased from Merck chemicals andFeSO4$7H2O and the TPH (total petroleum hydrocarbons)standard for GC analysis was purchased from Sigma Aldrich.The crude oil used for the study was collected from GroupGathering Station 3 (GGS3) of Lakwa Oil Field operated by theOil and Natural Gas Corporation Limited (ONGCL), India.

Table 2 Characteristics of the uncontaminated soil

Parameter Value Method used

pH 6.00 � 0.03 Elico pH-meter 510Redox potential (mV) 22.9 Elico pH-meter 510Clay (%) 24.27 Hydrometer methodSilt (%) 39.02Sand (%) 36.71Na (mg kg�1) 3.4 Elico ame

photometerK (mg kg�1) 11.9SO4

2� (mg kg�1) 2.560 Turbidity methodTOC (mg kg�1) 0.817 Walkley–Black method

2.2 Soil samples

Two types of soil samples were collected, (i) a contaminated soilsample from the agricultural eld near the boundary wall of theGGS, and (ii) an uncontaminated soil sample (control) from anon-contaminated agricultural eld of the locality. Thecontaminated soil samples were collected from two depths, (a)0–15 cm, the surface soil, and (b) 15–45 cm, the sub-surface soil.The soil samples aer collection were dried in air in the shade,ground in a mortar and sieved through a 2 mm sieve. Theuncontaminated sample was articially contaminated by mix-ing with crude oil dissolved in DCM at 5% contamination. A fewof the physical and chemical properties of the crude oil used forspiking soil are given in Table 1.

1914 | Environ. Sci.: Processes Impacts, 2013, 15, 1913–1920

2.3 Soil characterization

Thephysico-chemical properties of theuncontaminated (control)soil samples were determined with standard methods (APHA2005) and are given in Table 2.26 pH and redox potential weredetermined by making a soil slurry of 1 : 5 (soil–water) compo-sition (USEPAMethod 9045D).Determination of particle sizewasdone by the Buoyoucos hydrometer method.27 The soil texturewas found to be loamy as determined from the Texture triangle.28

Total exchangeable sodium and potassium were determinedwith a ame photometer. The measurement of soil organicmatter (SOM) was done as per the Walkley–Black method.

2.4 TPH contamination level of the soil

The contaminated soil samples collected at different distancesfrom the boundary wall of the GGS in all the directions (taken asan average) were tested for their contamination level withrespect to TPH (total petroleum hydrocarbons) at the actual siteby Soxhlet Extraction with DCM (dichloromethane) (Table 3).The control sample was also tested by the same method for thepresence of TPH.

2.5 Fenton treatment

All the reactions were carried out in a laboratory batch reactor. Ina set of initial experiments, Fentonoxidationwas carried outwith1 : 3, 1 : 4 and 1 : 5 soil water ratios for 10.0 g soil. Almost similardegradation results were obtained for these ratios and therefore,the subsequent sets were carried out with 1 : 5 soil water ratios,since several of the physical parameters (like pH, reductionpotential) were measured at this ratio as per standard methods.

In carrying out Fenton oxidation, 10 g of the articiallycontaminated soil was mixed with 50 ml of Milli Q water, stirred

This journal is ª The Royal Society of Chemistry 2013


Table 3 TPH contamination of the actual oil field site

Serialnumber

Distance fromthe boundarywall of the GGS (m)

Typeof soil

TPHin g/5.0g soil

Contamination(%)

1 25 Surface soil 0.1424 2.85Sub-surfacesoil

0.0201 0.40


0.0158 0.32


0.0030 0.06


0.0042 0.08


0.1868 3.74

Paper Environmental Science: Processes & Impacts

Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


for 2 hours to attain homogeneity prior to addition of thereagent. To observe the pH dependence of Fenton oxidation, thereactions were carried out at three different pHs, namely pH 3(acidic), 5 (ambient) and 8 (basic). The reaction was carried outat a catalyst : oxidant ratio of 1 : 200 (previously optimized) andthe reagent was loaded daily for ve days. The Fenton reactionwas initiated upon addition of 1 ml of 1 M H2O2 which wasprepared by diluting 30% w/v H2O2. In the second stage, thereaction was carried out at pH 3–7 at double duration to see thetime dependence and pH dependence under acidic conditions.In a third stage, the reaction was done at ve differenttemperatures (20–60 �C) for ve days at the optimum pH of theFenton reaction to observe the temperature dependence of thereaction. Also, experiments were carried out by varying theconcentration of Fe(II), keeping the concentration of hydrogenperoxide concentration constant in a separate set of experi-ments with 1, 0.1 and 0.01 M Fe(II). Each of the treatments wasdone in triplicate (average results are taken) and was repeatedwith the control sample.

2.6 Biological treatment followed by Fenton treatment

Biological treatment was carried out with a 10.0 g–50.0 mlhomogenised soil–water suspension to which mineral saltswere added for promoting F33 growth. The slurry was thensterilised and inoculation was done by adding 1 ml of sporesuspension (104 spores ml�1) of F. solani grown on a potato-dextrose broth and incubated at 28 �C for one month.

Combined Fenton-biological treatment was done by Fentontreatment at pH 3.0 for 5 days followed by biological treatmentfor 24 days as above. Prior to biological treatment, pH wasadjusted to 7.0 which was suitable for F33 growth.29

2.7 Crude oil extraction and analytical methods

At the end of the reaction time and incubation period taken forthe study, soil was oven dried at 40 �C and extracted in Soxhletapparatus for 16 h with DCM. The extracted oil was collectedand diluted to 1 ml with DCM which was nally used for


quantitative determination of different hydrocarbons by gaschromatography (DANI Master GC tted with a ame ionizationdetector). A DN-5 capillary column (length 30 m, i.d. 0.25 mmand lm thickness 0.25 mm) was used for separation with N2 asthe carrier gas (ow rate 1 ml min�1, oven temperature 60 �C to300 �C, hold 5 min at 60 �C, ramp 10 �C min�1, injectortemperature 380 �C, and detector temperature 400 �C). Threereplicates were analyzed for each sample. The percentagedegradation of the hydrocarbons was calculated by the formula:[(mHc � mH)/mHc] � 100, where mHc is the amount obtainedin the controlled sample and mH is the amount obtained in thetreated sample.

2.8 Monitoring hydrogen peroxide in Fenton oxidation

Aer each Fenton oxidation run, a sample of the reactionmixture was taken and made into a 1 : 5 soil–water suspension.This was then tested for the presence of Hydrogen peroxide by astandard method.30

2.9 Estimation of iron

Iron in residual soil was extracted by a standard procedure31 andmeasured by using a atomic absorption spectrophotometer(Shimadzu-7000).

3 Results and discussion3.1 Contamination level at the actual site

Determination of TPH in the oil eld soil (Table 3) showed thatthe contamination level with respect to distance from the sourcewas not uniform. This may be attributed to accidental leakage ofthe underground pipes carrying the crude oil. The contamina-tion level at thenearby sitewas found tobe in the range0–5%andthe surface soil were found to be more contaminated thanthe sub-surface soil. This is a signicant result since the topsoil is very important in the paddy elds for growing crops.No contamination was found in the control sample.

3.2 Fenton treatment

Fenton oxidation is a well known chemical treatment for envi-ronmental remediation which is very much pH sensitive.32 It isknown that there is an optimum pH for Fenton oxidation andthis is to be found out by carrying out the study at differentpHs.33,34 Comparison chromatograms of samples treated at pHs3.0, 5.0 and 8.0 with the control sample are given in Fig. 1 alongwith the GC chromatogram of the sample at zero time intervalof the Fenton oxidation. The measurements clearly show thatdegradation was satisfactory at pH 3 and pH 5, but was negli-gible at pH 8.

It is observed from the chromatograms that the intensities ofthe peaks in the higher hydrocarbons side decreased while inthe lower hydrocarbons side increased following Fentonoxidation pointing to partial mineralization of the higherhydrocarbons and conversion of the same to oxidized productswith lower molecular weight. At pH 3.0, n-tetradecane, thelowermost hydrocarbon considered in the study showed nega-tive degradation whereas at pH 5.0 both n-tetradecane and



Fig. 1 Comparative GC chromatograms for Fenton oxidation of TPH at pH 3.0 (A), pH 5.0 (B) and pH 8.0 (C) with the control, (D) GC chromatogram of sample at timezero of Fenton oxidation.


Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


n-hexadecane showed negative results. This was obviously dueto a higher rate of Fenton oxidation at pH 3.0 than at pH 5.0.There was higher degradation of n-hexadecane at pH 3.0 than atpH 5.0. The lowermost hydrocarbon considered in the study,n-tetradecane shows no positive result at any pH either pH 3 orpH 5. The pH optimum of Fenton oxidation was reported in the


acidic range by Pignatello et al. (2006) near pH 3.0 which was inconformity with the results of this study.35 The degradationpercentage of individual hydrocarbons at pH 3.0 and 5.0 areshown in Fig. 2 omitting the negative results shown for thelower hydrocarbons. The degradation found at pH 3.0 was 36%and at pH 5.0 was 26%.



Fig. 2 Percentage degradation of individual hydrocarbons at pH 3.0 and 5.0. Fig. 4 Percentage degradation of hydrocarbons by Fenton oxidation within 5and 10 days.


Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


3.3 pH, time and temperature dependence study of Fentoncatalysis

As the Fenton oxidation showed negligible conversion at pH 8.0,the subsequent experiment on pH dependence of the Fentonreaction was conducted in the acidic range (pH 3–7). The reac-tions were continued for double the duration of the rstexperiments (i.e. for 10 days) to see the time dependence of thereaction. The pH dependence curve is shown in Fig. 3 whichshows a gradual increase in degradation with decreasing pH.The best degradation results were achieved at pH 3.0 (57%) withalmost equal and relatively better results at pH 4.0 (48%) and5.0 (46%).

In an earlier work, Goi et al. (2009)10 carried out similar typesof experiments for remediation of soil contaminated withtransformer oil under a constant H2O2/contaminant (w/w) ratioat pH 3.0 and found that there was higher removal of trans-former oil at this pH than at the natural soil pH. As a rule, it washypothesized that the acidic pH conditions of 2.0–4.0 favouredthe oxidation of organic compounds, as it is known that thedecomposition rate of hydrogen peroxide reaches themaximumin this pH range.36 This phenomenon is attributed to theprogressive hydrolysis of the ferric ion, which provides a rela-tively large catalytically active surface for contact with H2O2. Theaccelerator Fe2+ ion in H2O2 decomposition will yield morehydroxyl radicals. From the present study, it can be said that thepH range 3.0–5.0 is the most suitable pH range for Fenton

Fig. 3 pHdependence of Fenton oxidation for aliphatic hydrocarbons in crude oil.


oxidation. If we can carry out the Fenton reaction at pH 5 well,then it can overcome the limitation of carrying out the reactionunder highly acidic conditions. It is to be noted that the Assamsoil has a natural pH of 5.0–6.0.37 According to Roques (1996)and Kwon (1999), the most effective pH range for Fenton reac-tion was pH 3.0–5.0 which is in accordance with the results ofthis work.38,39

From the rst and second sets of experiments, the timedependence curves at pH 3.0 and 5.0 were obtained (Fig. 4).Reaction time is an important determinant in the case of Fentonoxidation and it was observed that Fenton reaction gave betterconversionwith an increase in reaction time.40However, it needs

Fig. 5 Percentage degradation of hydrocarbons with varying temperature.

Fig. 6 Photograph of Fusarium solanni (F33) grown on potato dextrose agarmedium under (A). Normal light and (B). Using a phase contrast microscope.




Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


to be noted thatwith increase in reaction time, the concentrationof the hydrocarbons to be oxidized also decreased and theincreased degradation must also account for this.

Temperature is one of the important factors inuencing anyreaction which necessitates the study of Fenton oxidation withvarying temperature. With an increase in temperature, the rateof the reaction increases. However, an increase in temperaturehas two opposite effects on the reaction. According to Kha-maruddin et al. (2011), although the generation of hydroxyl

Fig. 7 Comparative GC chromatograms of Fenton oxidation for 5 days (A), biologicmonth (C); with their control; red: control samples, green: treated samples.


radicals increases at a higher temperature, hydrogen peroxidealso undergoes self-accelerating decomposition.41 In line withthis observation, it was observed in this work that degradationof the hydrocarbons gradually increased with temperature up to50 �C (49%), but at 60 �C, the degradation decreased to 42%.The plot of percentage degradation in Fenton oxidation atseveral reaction temperatures is shown in Fig. 5.

The effect of varying concentration of Fe(II), keeping theconcentration of hydrogen peroxide concentration constant was

al treatment for one month (B) and combined Fenton-biological treatment for one




Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


also studied in a separate set of experiments. The results werealmost similar (32.02, 31.13 and 33.08% degradation with 1, 0.1and 0.01 M Fe(II)). Thus, a lower concentration of Fe(II) wasequally effective in Fenton oxidation of the hydrocarbons. Thisresult is important in the context of controlling iron-load of thetreated soil.

3.4 Combined Fenton-microbial treatment

Fusarium solani was used for the bioremediation study of the oilcontaminated soil. This is one of the available fungi in thepetroleum contaminated soil in the natural environment. Somephotographs of the Fusarium solani (F33) used in this study areshown in Fig. 6. The three GC chromatograms of the samples(compared with their control samples) obtained from Fentontreatment for ve days; biological treatment for one month andcombined Fenton-biological treatment for one month are givenin Fig. 7. It shows that (i) for the Fenton treated sample, thepeak intensity increased from higher hydrocarbon to the lowerhydrocarbon side, (ii) in the biologically treated sample, peakintensity in the middle portion (medium hydrocarbons)decreased and (iii) in the sample treated with the combinedmethod, four peaks 2, 4, 5 and 6 (Fig. 7(C) and also in Fig. 7(B))in the lower hydrocarbon side gained height indicating a directimpact of biological degradation by F. solani and the intensitiesof all other peaks decreased signicantly. From the results, itcould be summarized that chemical pre-treatment enhancedthe biodegradability of higher hydrocarbons in the combinedmethod. Combined chemical-biological treatment showed anoverall degradation of 75% whereas biological treatment aloneaer one month incubation gave a degradation of 61%. Fentontreatment alone gave 34% and 57% conversion respectively aer5 and 10 days.

In a study carried out by Ran et al. (2009) on bioremediationby Fusarium solani along with a chemical and combinedmethod, it was found that the combined method gave only 25%degradation of benzo(a)pyrene.42–44 A combined Fenton-micro-bial study by Palmroth et al. (2006)22 on remediation of PAHsfrom creosote oil-contaminated soil could achieve 43–59%conversion while incubation alone gave only 22–30% degrada-tion. The present work, however, tested the degradation of onlythe aliphatic hydrocarbons in crude oil and therefore, 75%degradation was not surprising, but a remarkable result. In thisstudy no residual H2O2 concentration remained in soil aercombined Fenton-microbial treatment.

4 Conclusion

In this work, the role of Fenton oxidation as well as combinedFenton-microbial treatment for remediation of crude oilcontaminated soil with the aliphatic fraction of the crude oilwas emphasized. Fenton's reagent represents a signicant cost,so partial oxidation by Fenton oxidation is of great interestbecause microorganisms can be used in a post-oxidationtreatment process for higher mineralization. Up to 75% reme-diation was achieved from the combined method. Therefore,the use of chemical oxidation followed by biological


degradation may provide a more economical and effectiveprocess for remediation of contaminated soil rather than bychemical or biological method alone. The detailed remediationstudies showed signicant degradation of aliphatic hydrocar-bons at pH 3.0 with combined Fenton-microbial treatment. Ingeneral, remediation of soil responded most positively bydecreasing the pH from 7 to 3. Although the soil sample treatedat pH 3 showed the highest degradation, attributed to thefavourable conditions for Fenton oxidation, it is important thatequally better performance in Fenton oxidation is possible atpH 5.0, which is the ambient soil pH. Further study will revolvearound the remediation of the aromatic fraction of the crude oilby these processes so that an appropriate soil remediationtechnology can be established.

Another notable observation from the series of degradationexperiments was that an increase in the concentration of iron inFenton oxidation was almost inconsequential with respect tohydrocarbon degradation. It will be possible to optimize ironconcentration in a pilot study for reducing the level of iron inthe soil aer treatment such that the presence of excess iron inremediated soil does not create additional environmentalproblems. Iron toxicity is primarily pH related and occurs wherethe soil pH drops down sufficiently to create strongly acidicconditions with an excess of available iron. As with some othernutrients, the visible symptoms of Fe toxicity are likely to be adeciency of another nutrient. Fe toxicity can also occur in zinc-decient soil, or when the soil is in a “reduced” conditioncaused by very wet or ooded conditions. In earlier studies, itwas found that the pH of the oil eld soil remained at 5.0–7.3,and the alkaline formation water discharged by the oil eldsalso had a positive inuence on soil pH. It is therefore highlyunlikely that iron toxicity will develop aer Fenton treatment. Inthe present work, the oil eld soil was found to be appreciablyrich in iron with an Fe concentration of (i) 2.6 g kg�1 in the‘control’ soil, (ii) 3.2 g kg�1 in the crude oil mixed soil and (iii)3.6 to 4.2 g kg�1 in the residual soil aer Fenton treatment.

Abbreviations

ISCO

Envir

In situ chemical oxidation
PAHs Poly aromatic hydrocarbons EPA Environment Protection Agency BOD Biological oxygen demand COD Chemical oxygen demand TPH Total petroleum hydrocarbon GC Gas chromatography GGS Group gathering station ONGCL Oil and Natural Gas Corporation Limited DCM Dichloromethane APHA American Public Health Association SOM Soil organic matter.
Acknowledgements

The authors are thankful to DST, Govt of India for nancialsupport of the work. The authors are also thankful to Polymer

on. Sci.: Processes Impacts, 2013, 15, 1913–1920 | 1919



Publ

ishe

d on

05

Aug

ust 2

013.

Dow

nloa

ded

by U

nive

rsity

of

Vic

tori

a on

26/

10/2

014

09:5

3:27


Laboratory, Physical Sciences Division; Environmental Chem-istry Laboratory, Life Science Division, IASST.

References

1 TEPA (Taiwan Environmental Protection Administration), Aresearch on the determination of the TPHs pollution levels insoil, Technical Report, Taiwan, 2003.

2 D. Sarkar, M. Ferguson, R. Datta and S. Birnbaum, Environ.Pollut., 2005, 136, 187–195.

3 A. A. Olajire, R. Altenburger, E. Kuster and W. Brack, Sci.Total Environ., 2005, 340, 123–136.

4 D. E. Nicodem, C. L. B. Guedes, R. J. Correa andM. C. Z. Fernandes, Biogeochemistry, 1997, 39, 121–138.

5 ITRC (Interstate Technology Regulatory Council), Technicaland Regulatory Guidance for In Situ Chemical Oxidation ofContaminated Soil and Groundwater, Interstate Technologyand Regulatory Council, Washington, DC, 2001.

6 ITRC (Interstate Technology Regulatory Council), Technicaland Regulatory Guidance for In Situ Chemical Oxidation ofContaminated Soil and Groundwater, Interstate Technologyand Regulatory Council, Washington, DC, 2005.

7 L. C. Osuji and O. Achugasim, J. Appl. Sci. Environ. Manage.,2010, 14, 17–20.

8 L. O. Odokuma and A. A. Dickson, Global J. Environ. Sci.,2003, 2, 29–40.

9 L. C. Osuji and O. Achugasim, Chem. Biodiversity, 2007, 4,424–430.

10 A. Goi, M. Trapido and N. Kulik, International Journal ofChemical and Biological Engineering, 2009, 2(3), 144–148.

11 H. Mohamed, G. Achami and M. Mahmound, Proceedings ofthe Canadian Geotechnical Conference Niagara Falls, Canada,2002.

12 M. Mahmoud, M. McCormick, E. W. Dicki, G. McClaymentand P. Stoke-Rees, Proceedings of the Canadian GeotechnicalConference, Montreal, 2000.

13 D. L. Sedlak and A. W. Andren, Environ. Sci. Technol., 1991,25, 777–782.

14 F. J. Potter and J. A. Roth, Hazard. Waste Hazard. Mater.,1993, 10, 151–170.

15 E. Neyens and J. Baeyens, J. Hazard. Mater., 2003, 98, 33–50.16 C. M. Kao and M. J. Wu, J. Hazard. Mater., 2000, B74, 197–

211.17 L. Mater, R. M. Sperb, L. A. S. Madureira, A. P. Rosin,

A. X. R. Correa and C. M. Radetski, J. Hazard. Mater., 2006,136, 967–971.

18 T. Hadibarata, Interdisciplinary Studies on EnvironmentalChemistry –Environmental Research in Asia, 2009, pp. 309–316.

19 A. P. Murphy, W. J. Boegli, M. K. Price and C. D. Moody,Environ. Sci. Technol., 1989, 23, 166–169.

20 D. D. Gates and R. L. Siegrist, J. Environ. Eng., 1995, 121, 639–644.

21 R. J. Watts, M. D. Udell, P. A. Rauch and S. W. Leung,Hazard.Waste Hazard. Mater., 1990, 7, 335–345.

22 M. R. T. Palmroth, H. Langwaldt, T. A. Aunola, A. Goi,J. A. Puhakka and T. A. Tuhkanen, J. Chem. Technol.Biotechnol., 2006, 8, 1598–1607.


23 E. Arctander and P. Bardos, ‘Remediation Technologies’ ofthe Concerted Action Contaminated Land RehabilitationNetwork for Environmental Technologies (CLARINET),2002.

24 L. Mater, E. V. C. Rosa, J. Berto, A. X. R. Correa,P. R. Schwingel and C. M. Radetski, J. Hazard. Mater.,2007, 149, 379–386.

25 I. D. Bossert and R. Bartha, Bull. Environ. Contam. Toxicol.,1986, 37, 490–495.

26 APHA, Standard methods for examination of water andwastewater 18th Edition, Prepared and published jointlyby:American Public Health Association (APHA),AmericanWater Works Association (AWWA), WaterPollution Control Federation, 2005.

27 B. Patiram, T. N. S. Azad and T. Ramesh, Soil Testing andAnalysis: Plant, Water and Pesticide Residues, New IndiaPublishing Agency, India, 2007.

28 S. L. Chopra and J. S. Kanwar, in Analytical AgriculturalChemistry, Kalyani Publishers, 3rd edn, 1980, ch. 6,p. 183.

29 C. Ran, E. Veignie, A. Fayeulle and G. Surpateanu,Bioresour. Technol., 2009, 100, 3157–3160.

30 I. Vogel, A textbook of quantitative inorganic analysis includingelementary instrumental analysis, Longman Publisher, 3rdedn, 1969, p. 295.

31 M. L. Jackson, Soil Chemical Analysis, Prentice-Hall, India,New Delhi, 1967.

32 G. N. Achille and L. Yilian, Journal of American Science, 2010,6, 58–66.

33 C. T. Chen, A. N. Tafuri, M. Rahman and M. B. Foerst,J. Environ. Sci. Health, Part A: Toxic/Hazard. Subst. Environ.Eng., 1998, 33, 987–1008.

34 P. T. Silva, V. L. Silva, B. B. Neto and M. Simonnot, J. Hazard.Mater., 2009, 161, 967–973.

35 J. J. Pignatello, E. Oliveros and A. MacKay, Crit. Rev. Environ.Sci. Technol., 2006, 36, 1–84.

36 J. C. Lou and Y. J. Huang, Environ. Monit. Assess., 2009, 151,251–258.

37 R. J. Watts, D. R. Haller, A. P. Jones and A. L. Teel, J. Hazard.Mater., 2000, 76, 73–89.

38 H. Roques, Chemical Water Treatment, Principles and Practice,VCH Publisher, Inc., 1996.

39 B. G. Kwon, D. S. Lee, N. G. Kang and J. Y. Yoon, Water Res.,1999, 33, 2110.

40 M. Chaudhuri and E. S. Elmolla, International Conference onSustainable Building and Infrastructure (ICSBI), KualaLumpur Convention Centre, 2010.

41 P. F. Khamaruddin, M. A. Bustam and A. A. Omar,International Conference on Environment and IndustrialInnovation IPCBEE, Singapore, 2011.

42 C. Ran, O. Potin, E. Veignie, A. Sahraoui and M. Sancholle,Fusarium Solani Polycyclic Aromatic Hydrocarbons, 2000, vol.21, pp. 311–329.

43 C. Ran, E. Veignie, A. Fayeulle and G. Surpateanu,Bioresour. Technol., 2009, 100, 3157–3160.

44 E. Veignie, E. Vinogradov, I. Sadovskaya, C. Coulon andC. Ran, Advances in Microbiology, 2012, 2, 375–381.



fenton oxidation and combined fenton-microbial treatment for remediation of crude oil contaminated...

Documents