9
Research Article Preparation and Aromatic Hydrocarbon Removal Performance of Potassium Ferrate Wei Guan, Zhigang Xie, and Jia Zhang Chongqing Key Laboratory of Environmental Materials & Remediation Technologies, Chongqing University of Arts and Sciences, Chongqing 402160, China Correspondence should be addressed to Zhigang Xie; [email protected] Received 22 July 2014; Accepted 9 August 2014; Published 2 September 2014 Academic Editor: Wen Zeng Copyright © 2014 Wei Guan et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. is experiment adopts the hypochlorite oxidation method to constantly synthesize potassium ferrate. Under the condition of micropolluted source water pH and on the basis of naphthalene, phenanthrene, and pyrene as research objects, the effects of different systems to remove aromatic hydrocarbons were studied. Various oxidation systems to remove phenanthrene intermediate are analyzed and the detailed mechanisms for removal of phenanthrene are discussed. e study found that the main intermediate of potassium ferrate system to transform phenanthrene is 9,10-phenanthraquinone and its area percentage reached 82.66%; that is, 9,10-phenanthraquinone is the key entity to remove phenanthrene. 1. Introduction Ferrate is an ideal water treatment reagent. In acidic medium, ferrate redox potential is very high; in a wide pH range, its oxidation is strong, and it has strong deactivating effect on microorganisms. Ferrate in sewage purification shows excellent oxidation, adsorption, and flocculation to remove contaminants, and it has stronger sterilization effect than chlorine department oxidant [13]. Ferrate is the best oxidant replacement for chlorine source as water purification agent. In addition, ferrate as the positive active material of the green power supply has high electrode potential and capacitance [46]. is unique feature makes ferrates environmentally friendly green oxidation reagents with dual function. e ferrate crystal belongs to orthogonal crystal system. For potassium ferrate (K 2 FeO 4 ), ferrate has regular tetrahe- dron structure. Fe atom is at the center of the tetrahedron, with four oxygen atoms in the four corners of tetrahedron, presenting a slightly distorted tetrahedron structure. Ferrate is a deep purple solid, its solution has specific purple color, and maximum absorption wavelength is 510 nm. At the same time, ferrate ion has an absorption peak at 786 nm, which is also its characteristic absorption peak. e main compound in ferrate is potassium ferrate and in solid state it is dark purple powder, and melting point is 198 C. When ferrate is in dry conditions, it starts to break down at 230 C[79]. Iron (VI) ions in potassium ferrate, located in the highest valence state of iron, have strong oxidativity; also they have selectivity. ey can oxidize plenty of organics. eir oxidativity is significantly stronger than conventional water treatment oxidant, such as potassium permanganate, ozone, and hypochlorite. Under acid medium their standard electrode potential is 2.20 V; however, it is 0.72 V in alkaline condition. We can modify the ferrate cations’ structure and adjust pH value to control the oxidation activity, so as to achieve high selectivity [1014]. Heavy metal pollutants in the micropolluted water, such as cadmium and manganese, can be removed by potassium ferrate, and the removal rate reached 80%. In addition, potas- sium ferrate has good ability to remove organic compounds, such as phenols, alcohols, phenols, organic acid, organic nitrogen, and amino acid, lipid compounds containing sulfur and benzene, and some refractory compounds. At present, much domestic and foreign source water is polluted by aromatic hydrocarbon. e concentration of aromatic hydrocarbon in water is very low, but the removal efficiency of conventional water treatment technology is not ideal. Due to the special stability of the benzene ring Hindawi Publishing Corporation Journal of Spectroscopy Volume 2014, Article ID 171484, 8 pages http://dx.doi.org/10.1155/2014/171484

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Research ArticlePreparation and Aromatic Hydrocarbon RemovalPerformance of Potassium Ferrate

Wei Guan Zhigang Xie and Jia Zhang

Chongqing Key Laboratory of Environmental Materials amp Remediation Technologies Chongqing University of Arts and SciencesChongqing 402160 China

Correspondence should be addressed to Zhigang Xie xinghu2200163com

Received 22 July 2014 Accepted 9 August 2014 Published 2 September 2014

Academic Editor Wen Zeng

Copyright copy 2014 Wei Guan et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

This experiment adopts the hypochlorite oxidation method to constantly synthesize potassium ferrate Under the condition ofmicropolluted source water pH and on the basis of naphthalene phenanthrene and pyrene as research objects the effects ofdifferent systems to remove aromatic hydrocarbons were studied Various oxidation systems to remove phenanthrene intermediateare analyzed and the detailed mechanisms for removal of phenanthrene are discussed The study found that the main intermediateof potassium ferrate system to transform phenanthrene is 910-phenanthraquinone and its area percentage reached 8266 that is910-phenanthraquinone is the key entity to remove phenanthrene

1 Introduction

Ferrate is an ideal water treatment reagent In acidic mediumferrate redox potential is very high in a wide pH rangeits oxidation is strong and it has strong deactivating effecton microorganisms Ferrate in sewage purification showsexcellent oxidation adsorption and flocculation to removecontaminants and it has stronger sterilization effect thanchlorine department oxidant [1ndash3] Ferrate is the best oxidantreplacement for chlorine source as water purification agentIn addition ferrate as the positive active material of the greenpower supply has high electrode potential and capacitance[4ndash6] This unique feature makes ferrates environmentallyfriendly green oxidation reagents with dual function

The ferrate crystal belongs to orthogonal crystal systemFor potassium ferrate (K

2FeO4) ferrate has regular tetrahe-

dron structure Fe atom is at the center of the tetrahedronwith four oxygen atoms in the four corners of tetrahedronpresenting a slightly distorted tetrahedron structure Ferrateis a deep purple solid its solution has specific purple colorand maximum absorption wavelength is 510 nm At the sametime ferrate ion has an absorption peak at 786 nm which isalso its characteristic absorption peak The main compoundin ferrate is potassium ferrate and in solid state it is dark

purple powder and melting point is 198∘C When ferrate isin dry conditions it starts to break down at 230∘C [7ndash9]

Iron (VI) ions in potassium ferrate located in thehighest valence state of iron have strong oxidativity alsothey have selectivity They can oxidize plenty of organicsTheir oxidativity is significantly stronger than conventionalwater treatment oxidant such as potassium permanganateozone and hypochlorite Under acid medium their standardelectrode potential is 220V however it is 072V in alkalinecondition We can modify the ferrate cationsrsquo structure andadjust pH value to control the oxidation activity so as toachieve high selectivity [10ndash14]

Heavy metal pollutants in the micropolluted water suchas cadmium and manganese can be removed by potassiumferrate and the removal rate reached 80 In addition potas-sium ferrate has good ability to remove organic compoundssuch as phenols alcohols phenols organic acid organicnitrogen and amino acid lipid compounds containing sulfurand benzene and some refractory compounds

At present much domestic and foreign source wateris polluted by aromatic hydrocarbon The concentration ofaromatic hydrocarbon in water is very low but the removalefficiency of conventional water treatment technology isnot ideal Due to the special stability of the benzene ring

Hindawi Publishing CorporationJournal of SpectroscopyVolume 2014 Article ID 171484 8 pageshttpdxdoiorg1011552014171484

2 Journal of Spectroscopy

Table 1 Main reagents and their specifications

Number Name Chemical level Manufacturer1 Caustic potash AR ACROS2 Calcium hypochlorite AR ACROS3 Potassium nitrate AR ACROS4 Sodium sulfite AR ACROS5 Cyanoacrylate AR ACROS6 Butanol AR ACROS7 Glacial acetic acid AR ACROS8 Anhydrous ethanol AR ACROS9 Cupric nitrate AR ACROS10 Naphthalene AR ACROS11 Phenanthrene AR ACROS12 Pyrene AR ACROS

structure aromatic hydrocarbon in oxidation might generateseries of intermediates There are some potential environ-mental risks it is difficult to guarantee the safety of drinkingwater This paper completes the transformation and removalof aromatic hydrocarbons in micropolluted water in view ofthe refractory aromatic hydrocarbon inmicropolluted sourcewater and in view of potassium ferrate treatment technology

2 Experiment Methods

21 Experiment Materials and Reagents The main reagentsand specifications used in the experiment are shown inTable 1

22 Instruments and Equipment The main instruments andrelated information used in the experiment are shown inTable 2 The infrared spectrum of potassium ferrate byFourier infrared spectrometer (FTIR) is drawn and theinfrared characteristic peaks of potassium ferrate crystalare measured Fluorescence spectrophotometer determinesthe degradation rate of the sample Gas chromatography-mass spectrometry instrument determines the intermediateof sample transformation and removal

Some small instruments used in experiments consist ofthe beaker 1000W long arc xenon lamp magnetic stirrerelectronic balance separatory funnel vacuum pump thesuction filter device and so forth

23ThePreparation of PotassiumFerrate Proper 3molL and13molL saturated potassium hydroxide solutions coolingto room temperature are prepared respectively for sub-sequent experiments 15 g calcium hypochlorite is weighedin a small beaker 25mL of 13molL potassium hydroxidesolution is added in slight agitation with a glass rod Theresulting solution is suckedwith 800-mesh filter cloth to leachimpurities such as potassium chloride collecting the yellow-green filtrate 20mL cooling saturated potassium hydroxidesolution is added with batch into the yellow-green filtrateImpurities are removed by careful control of temperaturesufficient mixing and air pump filtration and then alkaline

saturated potassium hypochlorite solution is obtained 8 gFe(NO

3)3sdot9H2O is weighed and is ground to powder and

then is added slowly into the alkaline saturated potassiumhypochlorite solution in batch with vigorous agitation Thisreaction is exothermic with the ice-bath to control reactiontemperature and stirring The oxidation reaction is fast soonthe solution turns into purple After 1-hour sufficient reaction90mL cooling saturated potassium hydroxide solution wasadded into purple-black solution The mixture is contin-uously stirred for 5min and then is allowed to stand tocool in ice-bath for 30ndash40min followed by quickly suckingfiltration with air pump The liquor is abandoned and theresulting filtered cake a crude potassium ferrate productsurvives The crude potassium ferrate product is washed 3times with 3molL potassium hydroxide solution 5mL foreach washing The resulting potassium ferrate is redissolvedand filtration is done with air pump sucking Filter cakeis withdrawn whereas the liquor is retained The liquor ispoured into distillation flask in ice-water bath with additionof 40mL cooling saturated potassium hydroxide solutionRecrystallization for 20sim30 minutes is done followed bysucking filtrationwith air pumpThe resulting filter cake is thepotassium ferrate leached with n-hexane (4 times 25mL) withpentane (4 times 25mL) with methanol (4 times 10mL) and withether (2 times 10mL) respectively The final product potassiumferrate crystal (purple-black) dried at 65∘C for 2 hoursweighed and kept in the drier is prepared for subsequent use

24 The Experiment of Potassium Ferrate to Remove AromaticHydrocarbon Self-made potassium ferrate transforms aro-matic hydrocarbon In the micropolluted water medium (pH= 71) with naphthalene phenanthrene and pyrene the abilityof potassium ferrate to transform aromatic hydrocarbons isexplored on the basis of reaction time potassium ferrateamounts and removal of aromatic hydrocarbon

On account of water quality of Chongqing Water Plantpolluted water by aromatic hydrocarbon is simulated byartificial addition of 200120583gL aromatic hydrocarbonThe pHof the water is 71 1000mL of the polluted water is taken intoa beaker with addition of different quantity of potassium fer-rate carrying out oxidation reaction withmagnetic stirrer Ata specified time point 20mL of the said solution is taken outof reaction system followed by addition of sodium sulfite astermination agentThe content of aromatics remaining in thesolution is determined by fluorescence spectrophotometer

25 The Main Testing Index and Method The removalof aromatic hydrocarbon is quantitatively determined byfluorescence spectrophotometer The exciting wavelengthand emission wavelength of three materials are as followsnaphthalene EXEM is 218332 nm phenanthrene EXEM is250362 nm and pyrene EXEM is 238372 nm respectivelyExcitation and emission slit are 5 nm scanning speed is2400 nmmin

The properties of phenanthrene oxidation intermediateare determined by gas chromatography-mass spectrometryAfter 30min reaction to attain constant state 200mL solutionis taken out from phenanthrene reaction system followed

Journal of Spectroscopy 3

Table 2 Main equipment and the respective specifications

Number Instrument name Instrument model Manufacturer1 X-ray diffractometer XD-2 SHIMADZU Japan2 UV spectrometer UV-3010 SHIMADZU Japan3 Fourier transform infrared spectrometer IRPrestige-21 SHIMADZU Japan4 Fluorescence spectrophotometer F-7000 SHIMADZU Japan5 Gas chromatograph-mass spectrometer (GC-MS) 6890N GC5973 MS SHIMADZU Japan

by introduction into 400mL separatory funnel 6 g NaCl isadded into the filtered solution When completely dissolved10mL CH

2Cl2is poured The said solution is shaken for

10min and then it was allowed to stand for 5min CH2Cl2

layer is transferred to the pear-shaped flask Additional 10mLCH2Cl2is put into the separative funnel twice 5mL for

each The solution was allowed to stand until organic layersurvives Then the organic layer is merged and transferredAnhydrous sodium sulfate is added into CH

2Cl2layer for

drying CH2Cl2layer is concentrated at low temperature in

the rotary evaporator highly pure nitrogen is bubbled intothe said layer until only 1mL of the said solution is left GC-MS analysis is applied

Gas chromatography-mass spectrometry Agilent 6890NetGC-Agilent 5973NetMS series is used chromatographiccolumn for HP-5 MS quartz capillary column (25m times025mm times 025 120583m) The pattern of input sample is branch-stream-free system carrier gas is helium gas and the flow rateis 10mLmin Temperature raising procedure is 40sim290∘C(10∘Cmin) Ionization mass spectrometry conditions are asfollows voltage is 70 eV and the scanning range is of 30sim400mz

Fourier transformed infrared spectrometer and ultra-violet-visible spectrometer are used to qualitatively charac-terize potassium ferrate

3 The Results and Discussion

31 The Characterization of Potassium Ferrate Crystal Four-ier infrared spectrometer determined the purple crystalinfrared spectrum at experimental conditions as shown inFigure 1

As can be seen in the figure there is an absorptionpeak at 808 cmminus1 which is potassium ferrate crystal FendashObond stretching vibration characteristic peak The peak isconsidered as the infrared characteristic peak of potassiumferrate Other impurity peaks in the infrared spectrogramshould be water vapor occurring in the instrument and thecharacteristics of absorption peak of the organic solvent usedin the purification elution [15 16]

Potassium Ferrate Ultraviolet-Visible Absorption SpectrumCharacteristics 00934 g purple crystal is weighed to prepare100mL of potassium ferrate solution in volumetric flaskUltraviolet-visible spectrometer is used to test the ultraviolet-visible absorption spectrum as shown in Figure 2

As can be seen in the figure there is an obvious charac-teristic absorption peak at 510 nm which is ultraviolet-visible

T(

)

Wavenumber (cmminus1)

100

808

80

60

40

20

04000 3500 3000 2500 2000 1500 1000 500

Figure 1 FTIR spectra of K2FeO4

Abso

rban

ce (A

bs)

Wavelength (nm)

4

3

2

1

0400 450 500 550 600 650

510

Figure 2 UV-Vis DRS of K2FeO4

characteristic absorption peak of potassium ferrateThe peakis also considered as the quantitative analysis wavelength

32 The Influence of Reaction Time on Aromatic HydrocarbonRemoval When the oxidant concentration of potassiumferrate is at 6mgL the removal percentage of three kindsof aromatic hydrocarbon along with the change of timeis shown in Figure 3 As can be seen in the figure thetransformation oxidation process of potassium ferrate forthree kinds of aromatic hydrocarbon mainly occurred inthe initial 5ndash10 minutes when the removal percentage of

4 Journal of Spectroscopy

0 5 10 15 20 25 300

20

40

60

80

100

Rem

oval

rate

()

Reaction time (min)

NaphthalenePyrenePhenanthrene

Figure 3 Influence of reaction time on aromatic hydrocarbonsconversion and removal

aromatic hydrocarbon increased rapidly as time increased Infive minutes later the removal percentage of aromatic hydro-carbon only increased slightly The result is consistent withthe degradation rule of potassium ferrate oxidation degradingBPA [17] and arsenic [18] Furthermore it can be seen thatover 80 final removal percentage of phenanthrene 37that of naphthalene and 58 that of pyrene are developedrespectivelyThis shows that potassium ferrate can effectivelytransform phenanthrene in a relatively short time Theseresults are consistent with potassium ferrate high activityand instability By comparison of three kinds of aromatichydrocarbon removal percentage it is found that potassiumferrate has high oxidation but to different samples its oxi-dation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableThe experiment results consisted of the three substancesrsquodelocalization According to the experimental results theoxidation reaction time of potassium ferrate to the threesubstances is preliminarily identified to be 20min

33 The Influence of the Amount on Aromatic Hydrocar-bon Removal Effect The influence of potassium ferrateamount on aromatic hydrocarbon removal ability is shownin Figure 4 derived frommeasurement of samples in 20minAs can be seen in Figure 4 as potassium ferrate amountincreases three kinds of aromatic hydrocarbon removal per-centage gradually increased Relatively at the same reagentamount phenanthrene has the highest removal percent-age When the potassium ferrate concentration is 10mgLphenanthrene has the highest removal percentage reaching98 pyrene andnaphthalenewere 84and61 respectivelyFurther improvement of amount of oxidant potassium ferratecannot obviously improve the removal percentage for thethree substances Removal of the aromatic hydrocarbons inmicropolluted source water therefore has the most appro-priate 10mgL potassium ferrate amount

0 2 4 6 8 10 12 140

20

40

60

80

100

Concentration of potassium ferrate (mgL)

Rem

oval

rate

()

NaphthalenePyrenePhenanthrene

Figure 4 Influence of K2FeO4concentration on aromatic hydrocar-

bons conversion and removal

Potassium ferrate has strong oxidation regardless ofbeing in acidic medium or alkaline medium The elec-trode potential is significantly higher than potassium per-manganate and potassium dichromate it can oxidize mostorganic substances In hydrolysis process potassium ferrateproduces strong oxidation hydroxyl free radicals [19] atthe same time the unstable intermediate pentavalent ironand tetravalent iron also have a strong oxidizing ability[20] The final reduction product is ferric iron Potassiumferrate removal of aromatic hydrocarbon is the outcome ofconcerted action of these strong oxidizing substances Lowconcentration potassium ferrate can transform removal ofaromatic hydrocarbon When the reaction time is 20minpotassium ferrate concentrations are 12 8 and 10mgLnaphthalene phenanthrene and pyrene removal percentagereached the maximum value that is 67 98 and 84respectively

34 Analysis of the Intermediate of Removing PhenanthreneDue to the special stability of benzene ring structure interme-diate products can be generated during the oxidation processof aromatic substancesThus the removal process of aromaticsubstances has a potential environmental risk Therefore westudied the concrete structure of intermediate by GC-MSanalysis

Following are the GC of potassium ferrate systemand mass spectrogram of some intermediates to transformphenanthrene

Figure 5 is the GC of potassium ferrate system to trans-form phenanthrene

As can be seen in the figure the retention time of phenan-threne and main potassium ferrate reaction products was12443 13375 13575 and 18139min respectively In termsof corresponding mass spectrum the peak retention time at12453min is the undegraded phenanthrene peak Compared

Journal of Spectroscopy 5

mz

Abun

danc

e

3405

345038503650

3531

51656165 9288 10419

12443

13576

1337714497

17302

18139

26e + 0725e + 0724e + 0723e + 0722e + 0721e + 072e + 07

19e + 0718e + 0717e + 0716e + 0715e + 0714e + 0713e + 0712e + 0711e + 071e + 07900000080000007000000600000050000004000000300000020000001000000

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

4130

Figure 5 The GC map of phenanthrene conversion and removal by potassium ferrate system

mz

Abun

danc

e

1781

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

630 760

890

1020

1260

1390 1520

1961

2809

Figure 6 The mass spectrogram of 12443min

with mass spectrometry retrieve library standard spectro-gram other intermediates mainly include butyl phthalate910-phenanthraquinone and diphenyl-221015840-biformaldehydeIn addition there are some significant intermediates suchas 9-fluorenone and dimethylbenzenal And the peak ofthe main production prepared by phenanthrene reactionwith potassium ferrate is at 13575min the component areapercentage accounted for 8266 Specific mass spectrumand structural formula of main products are as follows

(1) The mass spectrum peak diagram in GC of retentiontime at 12443min is as shown in Figure 6

mz

Abun

danc

e

9500

8500

7500

6500

5500

4500

3500

2500

1500

500

102030405060708090

100

110

120

130

140

150

160

170

180

190

200

210

220

230

141 291

411 571

760

930

1040

1210

1320

1490

1670

1701

1891

2052

2231

Figure 7 The mass spectrogram of 13375min

According to comparison with the spectral library spectrumstandard substance phenanthrene residue is identified inoriginal solution with 96 matching degree with the liter-atures as the following structural formula

(1)

(2) The peak mass spectrum diagram in GC as of reten-tion time at 13375min is as shown in Figure 7

According to comparison with the spectral library spec-trum standard substance this material is identified as butyl

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

2 Journal of Spectroscopy

Table 1 Main reagents and their specifications

Number Name Chemical level Manufacturer1 Caustic potash AR ACROS2 Calcium hypochlorite AR ACROS3 Potassium nitrate AR ACROS4 Sodium sulfite AR ACROS5 Cyanoacrylate AR ACROS6 Butanol AR ACROS7 Glacial acetic acid AR ACROS8 Anhydrous ethanol AR ACROS9 Cupric nitrate AR ACROS10 Naphthalene AR ACROS11 Phenanthrene AR ACROS12 Pyrene AR ACROS

structure aromatic hydrocarbon in oxidation might generateseries of intermediates There are some potential environ-mental risks it is difficult to guarantee the safety of drinkingwater This paper completes the transformation and removalof aromatic hydrocarbons in micropolluted water in view ofthe refractory aromatic hydrocarbon inmicropolluted sourcewater and in view of potassium ferrate treatment technology

2 Experiment Methods

21 Experiment Materials and Reagents The main reagentsand specifications used in the experiment are shown inTable 1

22 Instruments and Equipment The main instruments andrelated information used in the experiment are shown inTable 2 The infrared spectrum of potassium ferrate byFourier infrared spectrometer (FTIR) is drawn and theinfrared characteristic peaks of potassium ferrate crystalare measured Fluorescence spectrophotometer determinesthe degradation rate of the sample Gas chromatography-mass spectrometry instrument determines the intermediateof sample transformation and removal

Some small instruments used in experiments consist ofthe beaker 1000W long arc xenon lamp magnetic stirrerelectronic balance separatory funnel vacuum pump thesuction filter device and so forth

23ThePreparation of PotassiumFerrate Proper 3molL and13molL saturated potassium hydroxide solutions coolingto room temperature are prepared respectively for sub-sequent experiments 15 g calcium hypochlorite is weighedin a small beaker 25mL of 13molL potassium hydroxidesolution is added in slight agitation with a glass rod Theresulting solution is suckedwith 800-mesh filter cloth to leachimpurities such as potassium chloride collecting the yellow-green filtrate 20mL cooling saturated potassium hydroxidesolution is added with batch into the yellow-green filtrateImpurities are removed by careful control of temperaturesufficient mixing and air pump filtration and then alkaline

saturated potassium hypochlorite solution is obtained 8 gFe(NO

3)3sdot9H2O is weighed and is ground to powder and

then is added slowly into the alkaline saturated potassiumhypochlorite solution in batch with vigorous agitation Thisreaction is exothermic with the ice-bath to control reactiontemperature and stirring The oxidation reaction is fast soonthe solution turns into purple After 1-hour sufficient reaction90mL cooling saturated potassium hydroxide solution wasadded into purple-black solution The mixture is contin-uously stirred for 5min and then is allowed to stand tocool in ice-bath for 30ndash40min followed by quickly suckingfiltration with air pump The liquor is abandoned and theresulting filtered cake a crude potassium ferrate productsurvives The crude potassium ferrate product is washed 3times with 3molL potassium hydroxide solution 5mL foreach washing The resulting potassium ferrate is redissolvedand filtration is done with air pump sucking Filter cakeis withdrawn whereas the liquor is retained The liquor ispoured into distillation flask in ice-water bath with additionof 40mL cooling saturated potassium hydroxide solutionRecrystallization for 20sim30 minutes is done followed bysucking filtrationwith air pumpThe resulting filter cake is thepotassium ferrate leached with n-hexane (4 times 25mL) withpentane (4 times 25mL) with methanol (4 times 10mL) and withether (2 times 10mL) respectively The final product potassiumferrate crystal (purple-black) dried at 65∘C for 2 hoursweighed and kept in the drier is prepared for subsequent use

24 The Experiment of Potassium Ferrate to Remove AromaticHydrocarbon Self-made potassium ferrate transforms aro-matic hydrocarbon In the micropolluted water medium (pH= 71) with naphthalene phenanthrene and pyrene the abilityof potassium ferrate to transform aromatic hydrocarbons isexplored on the basis of reaction time potassium ferrateamounts and removal of aromatic hydrocarbon

On account of water quality of Chongqing Water Plantpolluted water by aromatic hydrocarbon is simulated byartificial addition of 200120583gL aromatic hydrocarbonThe pHof the water is 71 1000mL of the polluted water is taken intoa beaker with addition of different quantity of potassium fer-rate carrying out oxidation reaction withmagnetic stirrer Ata specified time point 20mL of the said solution is taken outof reaction system followed by addition of sodium sulfite astermination agentThe content of aromatics remaining in thesolution is determined by fluorescence spectrophotometer

25 The Main Testing Index and Method The removalof aromatic hydrocarbon is quantitatively determined byfluorescence spectrophotometer The exciting wavelengthand emission wavelength of three materials are as followsnaphthalene EXEM is 218332 nm phenanthrene EXEM is250362 nm and pyrene EXEM is 238372 nm respectivelyExcitation and emission slit are 5 nm scanning speed is2400 nmmin

The properties of phenanthrene oxidation intermediateare determined by gas chromatography-mass spectrometryAfter 30min reaction to attain constant state 200mL solutionis taken out from phenanthrene reaction system followed

Journal of Spectroscopy 3

Table 2 Main equipment and the respective specifications

Number Instrument name Instrument model Manufacturer1 X-ray diffractometer XD-2 SHIMADZU Japan2 UV spectrometer UV-3010 SHIMADZU Japan3 Fourier transform infrared spectrometer IRPrestige-21 SHIMADZU Japan4 Fluorescence spectrophotometer F-7000 SHIMADZU Japan5 Gas chromatograph-mass spectrometer (GC-MS) 6890N GC5973 MS SHIMADZU Japan

by introduction into 400mL separatory funnel 6 g NaCl isadded into the filtered solution When completely dissolved10mL CH

2Cl2is poured The said solution is shaken for

10min and then it was allowed to stand for 5min CH2Cl2

layer is transferred to the pear-shaped flask Additional 10mLCH2Cl2is put into the separative funnel twice 5mL for

each The solution was allowed to stand until organic layersurvives Then the organic layer is merged and transferredAnhydrous sodium sulfate is added into CH

2Cl2layer for

drying CH2Cl2layer is concentrated at low temperature in

the rotary evaporator highly pure nitrogen is bubbled intothe said layer until only 1mL of the said solution is left GC-MS analysis is applied

Gas chromatography-mass spectrometry Agilent 6890NetGC-Agilent 5973NetMS series is used chromatographiccolumn for HP-5 MS quartz capillary column (25m times025mm times 025 120583m) The pattern of input sample is branch-stream-free system carrier gas is helium gas and the flow rateis 10mLmin Temperature raising procedure is 40sim290∘C(10∘Cmin) Ionization mass spectrometry conditions are asfollows voltage is 70 eV and the scanning range is of 30sim400mz

Fourier transformed infrared spectrometer and ultra-violet-visible spectrometer are used to qualitatively charac-terize potassium ferrate

3 The Results and Discussion

31 The Characterization of Potassium Ferrate Crystal Four-ier infrared spectrometer determined the purple crystalinfrared spectrum at experimental conditions as shown inFigure 1

As can be seen in the figure there is an absorptionpeak at 808 cmminus1 which is potassium ferrate crystal FendashObond stretching vibration characteristic peak The peak isconsidered as the infrared characteristic peak of potassiumferrate Other impurity peaks in the infrared spectrogramshould be water vapor occurring in the instrument and thecharacteristics of absorption peak of the organic solvent usedin the purification elution [15 16]

Potassium Ferrate Ultraviolet-Visible Absorption SpectrumCharacteristics 00934 g purple crystal is weighed to prepare100mL of potassium ferrate solution in volumetric flaskUltraviolet-visible spectrometer is used to test the ultraviolet-visible absorption spectrum as shown in Figure 2

As can be seen in the figure there is an obvious charac-teristic absorption peak at 510 nm which is ultraviolet-visible

T(

)

Wavenumber (cmminus1)

100

808

80

60

40

20

04000 3500 3000 2500 2000 1500 1000 500

Figure 1 FTIR spectra of K2FeO4

Abso

rban

ce (A

bs)

Wavelength (nm)

4

3

2

1

0400 450 500 550 600 650

510

Figure 2 UV-Vis DRS of K2FeO4

characteristic absorption peak of potassium ferrateThe peakis also considered as the quantitative analysis wavelength

32 The Influence of Reaction Time on Aromatic HydrocarbonRemoval When the oxidant concentration of potassiumferrate is at 6mgL the removal percentage of three kindsof aromatic hydrocarbon along with the change of timeis shown in Figure 3 As can be seen in the figure thetransformation oxidation process of potassium ferrate forthree kinds of aromatic hydrocarbon mainly occurred inthe initial 5ndash10 minutes when the removal percentage of

4 Journal of Spectroscopy

0 5 10 15 20 25 300

20

40

60

80

100

Rem

oval

rate

()

Reaction time (min)

NaphthalenePyrenePhenanthrene

Figure 3 Influence of reaction time on aromatic hydrocarbonsconversion and removal

aromatic hydrocarbon increased rapidly as time increased Infive minutes later the removal percentage of aromatic hydro-carbon only increased slightly The result is consistent withthe degradation rule of potassium ferrate oxidation degradingBPA [17] and arsenic [18] Furthermore it can be seen thatover 80 final removal percentage of phenanthrene 37that of naphthalene and 58 that of pyrene are developedrespectivelyThis shows that potassium ferrate can effectivelytransform phenanthrene in a relatively short time Theseresults are consistent with potassium ferrate high activityand instability By comparison of three kinds of aromatichydrocarbon removal percentage it is found that potassiumferrate has high oxidation but to different samples its oxi-dation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableThe experiment results consisted of the three substancesrsquodelocalization According to the experimental results theoxidation reaction time of potassium ferrate to the threesubstances is preliminarily identified to be 20min

33 The Influence of the Amount on Aromatic Hydrocar-bon Removal Effect The influence of potassium ferrateamount on aromatic hydrocarbon removal ability is shownin Figure 4 derived frommeasurement of samples in 20minAs can be seen in Figure 4 as potassium ferrate amountincreases three kinds of aromatic hydrocarbon removal per-centage gradually increased Relatively at the same reagentamount phenanthrene has the highest removal percent-age When the potassium ferrate concentration is 10mgLphenanthrene has the highest removal percentage reaching98 pyrene andnaphthalenewere 84and61 respectivelyFurther improvement of amount of oxidant potassium ferratecannot obviously improve the removal percentage for thethree substances Removal of the aromatic hydrocarbons inmicropolluted source water therefore has the most appro-priate 10mgL potassium ferrate amount

0 2 4 6 8 10 12 140

20

40

60

80

100

Concentration of potassium ferrate (mgL)

Rem

oval

rate

()

NaphthalenePyrenePhenanthrene

Figure 4 Influence of K2FeO4concentration on aromatic hydrocar-

bons conversion and removal

Potassium ferrate has strong oxidation regardless ofbeing in acidic medium or alkaline medium The elec-trode potential is significantly higher than potassium per-manganate and potassium dichromate it can oxidize mostorganic substances In hydrolysis process potassium ferrateproduces strong oxidation hydroxyl free radicals [19] atthe same time the unstable intermediate pentavalent ironand tetravalent iron also have a strong oxidizing ability[20] The final reduction product is ferric iron Potassiumferrate removal of aromatic hydrocarbon is the outcome ofconcerted action of these strong oxidizing substances Lowconcentration potassium ferrate can transform removal ofaromatic hydrocarbon When the reaction time is 20minpotassium ferrate concentrations are 12 8 and 10mgLnaphthalene phenanthrene and pyrene removal percentagereached the maximum value that is 67 98 and 84respectively

34 Analysis of the Intermediate of Removing PhenanthreneDue to the special stability of benzene ring structure interme-diate products can be generated during the oxidation processof aromatic substancesThus the removal process of aromaticsubstances has a potential environmental risk Therefore westudied the concrete structure of intermediate by GC-MSanalysis

Following are the GC of potassium ferrate systemand mass spectrogram of some intermediates to transformphenanthrene

Figure 5 is the GC of potassium ferrate system to trans-form phenanthrene

As can be seen in the figure the retention time of phenan-threne and main potassium ferrate reaction products was12443 13375 13575 and 18139min respectively In termsof corresponding mass spectrum the peak retention time at12453min is the undegraded phenanthrene peak Compared

Journal of Spectroscopy 5

mz

Abun

danc

e

3405

345038503650

3531

51656165 9288 10419

12443

13576

1337714497

17302

18139

26e + 0725e + 0724e + 0723e + 0722e + 0721e + 072e + 07

19e + 0718e + 0717e + 0716e + 0715e + 0714e + 0713e + 0712e + 0711e + 071e + 07900000080000007000000600000050000004000000300000020000001000000

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

4130

Figure 5 The GC map of phenanthrene conversion and removal by potassium ferrate system

mz

Abun

danc

e

1781

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

630 760

890

1020

1260

1390 1520

1961

2809

Figure 6 The mass spectrogram of 12443min

with mass spectrometry retrieve library standard spectro-gram other intermediates mainly include butyl phthalate910-phenanthraquinone and diphenyl-221015840-biformaldehydeIn addition there are some significant intermediates suchas 9-fluorenone and dimethylbenzenal And the peak ofthe main production prepared by phenanthrene reactionwith potassium ferrate is at 13575min the component areapercentage accounted for 8266 Specific mass spectrumand structural formula of main products are as follows

(1) The mass spectrum peak diagram in GC of retentiontime at 12443min is as shown in Figure 6

mz

Abun

danc

e

9500

8500

7500

6500

5500

4500

3500

2500

1500

500

102030405060708090

100

110

120

130

140

150

160

170

180

190

200

210

220

230

141 291

411 571

760

930

1040

1210

1320

1490

1670

1701

1891

2052

2231

Figure 7 The mass spectrogram of 13375min

According to comparison with the spectral library spectrumstandard substance phenanthrene residue is identified inoriginal solution with 96 matching degree with the liter-atures as the following structural formula

(1)

(2) The peak mass spectrum diagram in GC as of reten-tion time at 13375min is as shown in Figure 7

According to comparison with the spectral library spec-trum standard substance this material is identified as butyl

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Journal of Spectroscopy 3

Table 2 Main equipment and the respective specifications

Number Instrument name Instrument model Manufacturer1 X-ray diffractometer XD-2 SHIMADZU Japan2 UV spectrometer UV-3010 SHIMADZU Japan3 Fourier transform infrared spectrometer IRPrestige-21 SHIMADZU Japan4 Fluorescence spectrophotometer F-7000 SHIMADZU Japan5 Gas chromatograph-mass spectrometer (GC-MS) 6890N GC5973 MS SHIMADZU Japan

by introduction into 400mL separatory funnel 6 g NaCl isadded into the filtered solution When completely dissolved10mL CH

2Cl2is poured The said solution is shaken for

10min and then it was allowed to stand for 5min CH2Cl2

layer is transferred to the pear-shaped flask Additional 10mLCH2Cl2is put into the separative funnel twice 5mL for

each The solution was allowed to stand until organic layersurvives Then the organic layer is merged and transferredAnhydrous sodium sulfate is added into CH

2Cl2layer for

drying CH2Cl2layer is concentrated at low temperature in

the rotary evaporator highly pure nitrogen is bubbled intothe said layer until only 1mL of the said solution is left GC-MS analysis is applied

Gas chromatography-mass spectrometry Agilent 6890NetGC-Agilent 5973NetMS series is used chromatographiccolumn for HP-5 MS quartz capillary column (25m times025mm times 025 120583m) The pattern of input sample is branch-stream-free system carrier gas is helium gas and the flow rateis 10mLmin Temperature raising procedure is 40sim290∘C(10∘Cmin) Ionization mass spectrometry conditions are asfollows voltage is 70 eV and the scanning range is of 30sim400mz

Fourier transformed infrared spectrometer and ultra-violet-visible spectrometer are used to qualitatively charac-terize potassium ferrate

3 The Results and Discussion

31 The Characterization of Potassium Ferrate Crystal Four-ier infrared spectrometer determined the purple crystalinfrared spectrum at experimental conditions as shown inFigure 1

As can be seen in the figure there is an absorptionpeak at 808 cmminus1 which is potassium ferrate crystal FendashObond stretching vibration characteristic peak The peak isconsidered as the infrared characteristic peak of potassiumferrate Other impurity peaks in the infrared spectrogramshould be water vapor occurring in the instrument and thecharacteristics of absorption peak of the organic solvent usedin the purification elution [15 16]

Potassium Ferrate Ultraviolet-Visible Absorption SpectrumCharacteristics 00934 g purple crystal is weighed to prepare100mL of potassium ferrate solution in volumetric flaskUltraviolet-visible spectrometer is used to test the ultraviolet-visible absorption spectrum as shown in Figure 2

As can be seen in the figure there is an obvious charac-teristic absorption peak at 510 nm which is ultraviolet-visible

T(

)

Wavenumber (cmminus1)

100

808

80

60

40

20

04000 3500 3000 2500 2000 1500 1000 500

Figure 1 FTIR spectra of K2FeO4

Abso

rban

ce (A

bs)

Wavelength (nm)

4

3

2

1

0400 450 500 550 600 650

510

Figure 2 UV-Vis DRS of K2FeO4

characteristic absorption peak of potassium ferrateThe peakis also considered as the quantitative analysis wavelength

32 The Influence of Reaction Time on Aromatic HydrocarbonRemoval When the oxidant concentration of potassiumferrate is at 6mgL the removal percentage of three kindsof aromatic hydrocarbon along with the change of timeis shown in Figure 3 As can be seen in the figure thetransformation oxidation process of potassium ferrate forthree kinds of aromatic hydrocarbon mainly occurred inthe initial 5ndash10 minutes when the removal percentage of

4 Journal of Spectroscopy

0 5 10 15 20 25 300

20

40

60

80

100

Rem

oval

rate

()

Reaction time (min)

NaphthalenePyrenePhenanthrene

Figure 3 Influence of reaction time on aromatic hydrocarbonsconversion and removal

aromatic hydrocarbon increased rapidly as time increased Infive minutes later the removal percentage of aromatic hydro-carbon only increased slightly The result is consistent withthe degradation rule of potassium ferrate oxidation degradingBPA [17] and arsenic [18] Furthermore it can be seen thatover 80 final removal percentage of phenanthrene 37that of naphthalene and 58 that of pyrene are developedrespectivelyThis shows that potassium ferrate can effectivelytransform phenanthrene in a relatively short time Theseresults are consistent with potassium ferrate high activityand instability By comparison of three kinds of aromatichydrocarbon removal percentage it is found that potassiumferrate has high oxidation but to different samples its oxi-dation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableThe experiment results consisted of the three substancesrsquodelocalization According to the experimental results theoxidation reaction time of potassium ferrate to the threesubstances is preliminarily identified to be 20min

33 The Influence of the Amount on Aromatic Hydrocar-bon Removal Effect The influence of potassium ferrateamount on aromatic hydrocarbon removal ability is shownin Figure 4 derived frommeasurement of samples in 20minAs can be seen in Figure 4 as potassium ferrate amountincreases three kinds of aromatic hydrocarbon removal per-centage gradually increased Relatively at the same reagentamount phenanthrene has the highest removal percent-age When the potassium ferrate concentration is 10mgLphenanthrene has the highest removal percentage reaching98 pyrene andnaphthalenewere 84and61 respectivelyFurther improvement of amount of oxidant potassium ferratecannot obviously improve the removal percentage for thethree substances Removal of the aromatic hydrocarbons inmicropolluted source water therefore has the most appro-priate 10mgL potassium ferrate amount

0 2 4 6 8 10 12 140

20

40

60

80

100

Concentration of potassium ferrate (mgL)

Rem

oval

rate

()

NaphthalenePyrenePhenanthrene

Figure 4 Influence of K2FeO4concentration on aromatic hydrocar-

bons conversion and removal

Potassium ferrate has strong oxidation regardless ofbeing in acidic medium or alkaline medium The elec-trode potential is significantly higher than potassium per-manganate and potassium dichromate it can oxidize mostorganic substances In hydrolysis process potassium ferrateproduces strong oxidation hydroxyl free radicals [19] atthe same time the unstable intermediate pentavalent ironand tetravalent iron also have a strong oxidizing ability[20] The final reduction product is ferric iron Potassiumferrate removal of aromatic hydrocarbon is the outcome ofconcerted action of these strong oxidizing substances Lowconcentration potassium ferrate can transform removal ofaromatic hydrocarbon When the reaction time is 20minpotassium ferrate concentrations are 12 8 and 10mgLnaphthalene phenanthrene and pyrene removal percentagereached the maximum value that is 67 98 and 84respectively

34 Analysis of the Intermediate of Removing PhenanthreneDue to the special stability of benzene ring structure interme-diate products can be generated during the oxidation processof aromatic substancesThus the removal process of aromaticsubstances has a potential environmental risk Therefore westudied the concrete structure of intermediate by GC-MSanalysis

Following are the GC of potassium ferrate systemand mass spectrogram of some intermediates to transformphenanthrene

Figure 5 is the GC of potassium ferrate system to trans-form phenanthrene

As can be seen in the figure the retention time of phenan-threne and main potassium ferrate reaction products was12443 13375 13575 and 18139min respectively In termsof corresponding mass spectrum the peak retention time at12453min is the undegraded phenanthrene peak Compared

Journal of Spectroscopy 5

mz

Abun

danc

e

3405

345038503650

3531

51656165 9288 10419

12443

13576

1337714497

17302

18139

26e + 0725e + 0724e + 0723e + 0722e + 0721e + 072e + 07

19e + 0718e + 0717e + 0716e + 0715e + 0714e + 0713e + 0712e + 0711e + 071e + 07900000080000007000000600000050000004000000300000020000001000000

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

4130

Figure 5 The GC map of phenanthrene conversion and removal by potassium ferrate system

mz

Abun

danc

e

1781

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

630 760

890

1020

1260

1390 1520

1961

2809

Figure 6 The mass spectrogram of 12443min

with mass spectrometry retrieve library standard spectro-gram other intermediates mainly include butyl phthalate910-phenanthraquinone and diphenyl-221015840-biformaldehydeIn addition there are some significant intermediates suchas 9-fluorenone and dimethylbenzenal And the peak ofthe main production prepared by phenanthrene reactionwith potassium ferrate is at 13575min the component areapercentage accounted for 8266 Specific mass spectrumand structural formula of main products are as follows

(1) The mass spectrum peak diagram in GC of retentiontime at 12443min is as shown in Figure 6

mz

Abun

danc

e

9500

8500

7500

6500

5500

4500

3500

2500

1500

500

102030405060708090

100

110

120

130

140

150

160

170

180

190

200

210

220

230

141 291

411 571

760

930

1040

1210

1320

1490

1670

1701

1891

2052

2231

Figure 7 The mass spectrogram of 13375min

According to comparison with the spectral library spectrumstandard substance phenanthrene residue is identified inoriginal solution with 96 matching degree with the liter-atures as the following structural formula

(1)

(2) The peak mass spectrum diagram in GC as of reten-tion time at 13375min is as shown in Figure 7

According to comparison with the spectral library spec-trum standard substance this material is identified as butyl

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

4 Journal of Spectroscopy

0 5 10 15 20 25 300

20

40

60

80

100

Rem

oval

rate

()

Reaction time (min)

NaphthalenePyrenePhenanthrene

Figure 3 Influence of reaction time on aromatic hydrocarbonsconversion and removal

aromatic hydrocarbon increased rapidly as time increased Infive minutes later the removal percentage of aromatic hydro-carbon only increased slightly The result is consistent withthe degradation rule of potassium ferrate oxidation degradingBPA [17] and arsenic [18] Furthermore it can be seen thatover 80 final removal percentage of phenanthrene 37that of naphthalene and 58 that of pyrene are developedrespectivelyThis shows that potassium ferrate can effectivelytransform phenanthrene in a relatively short time Theseresults are consistent with potassium ferrate high activityand instability By comparison of three kinds of aromatichydrocarbon removal percentage it is found that potassiumferrate has high oxidation but to different samples its oxi-dation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableThe experiment results consisted of the three substancesrsquodelocalization According to the experimental results theoxidation reaction time of potassium ferrate to the threesubstances is preliminarily identified to be 20min

33 The Influence of the Amount on Aromatic Hydrocar-bon Removal Effect The influence of potassium ferrateamount on aromatic hydrocarbon removal ability is shownin Figure 4 derived frommeasurement of samples in 20minAs can be seen in Figure 4 as potassium ferrate amountincreases three kinds of aromatic hydrocarbon removal per-centage gradually increased Relatively at the same reagentamount phenanthrene has the highest removal percent-age When the potassium ferrate concentration is 10mgLphenanthrene has the highest removal percentage reaching98 pyrene andnaphthalenewere 84and61 respectivelyFurther improvement of amount of oxidant potassium ferratecannot obviously improve the removal percentage for thethree substances Removal of the aromatic hydrocarbons inmicropolluted source water therefore has the most appro-priate 10mgL potassium ferrate amount

0 2 4 6 8 10 12 140

20

40

60

80

100

Concentration of potassium ferrate (mgL)

Rem

oval

rate

()

NaphthalenePyrenePhenanthrene

Figure 4 Influence of K2FeO4concentration on aromatic hydrocar-

bons conversion and removal

Potassium ferrate has strong oxidation regardless ofbeing in acidic medium or alkaline medium The elec-trode potential is significantly higher than potassium per-manganate and potassium dichromate it can oxidize mostorganic substances In hydrolysis process potassium ferrateproduces strong oxidation hydroxyl free radicals [19] atthe same time the unstable intermediate pentavalent ironand tetravalent iron also have a strong oxidizing ability[20] The final reduction product is ferric iron Potassiumferrate removal of aromatic hydrocarbon is the outcome ofconcerted action of these strong oxidizing substances Lowconcentration potassium ferrate can transform removal ofaromatic hydrocarbon When the reaction time is 20minpotassium ferrate concentrations are 12 8 and 10mgLnaphthalene phenanthrene and pyrene removal percentagereached the maximum value that is 67 98 and 84respectively

34 Analysis of the Intermediate of Removing PhenanthreneDue to the special stability of benzene ring structure interme-diate products can be generated during the oxidation processof aromatic substancesThus the removal process of aromaticsubstances has a potential environmental risk Therefore westudied the concrete structure of intermediate by GC-MSanalysis

Following are the GC of potassium ferrate systemand mass spectrogram of some intermediates to transformphenanthrene

Figure 5 is the GC of potassium ferrate system to trans-form phenanthrene

As can be seen in the figure the retention time of phenan-threne and main potassium ferrate reaction products was12443 13375 13575 and 18139min respectively In termsof corresponding mass spectrum the peak retention time at12453min is the undegraded phenanthrene peak Compared

Journal of Spectroscopy 5

mz

Abun

danc

e

3405

345038503650

3531

51656165 9288 10419

12443

13576

1337714497

17302

18139

26e + 0725e + 0724e + 0723e + 0722e + 0721e + 072e + 07

19e + 0718e + 0717e + 0716e + 0715e + 0714e + 0713e + 0712e + 0711e + 071e + 07900000080000007000000600000050000004000000300000020000001000000

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

4130

Figure 5 The GC map of phenanthrene conversion and removal by potassium ferrate system

mz

Abun

danc

e

1781

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

630 760

890

1020

1260

1390 1520

1961

2809

Figure 6 The mass spectrogram of 12443min

with mass spectrometry retrieve library standard spectro-gram other intermediates mainly include butyl phthalate910-phenanthraquinone and diphenyl-221015840-biformaldehydeIn addition there are some significant intermediates suchas 9-fluorenone and dimethylbenzenal And the peak ofthe main production prepared by phenanthrene reactionwith potassium ferrate is at 13575min the component areapercentage accounted for 8266 Specific mass spectrumand structural formula of main products are as follows

(1) The mass spectrum peak diagram in GC of retentiontime at 12443min is as shown in Figure 6

mz

Abun

danc

e

9500

8500

7500

6500

5500

4500

3500

2500

1500

500

102030405060708090

100

110

120

130

140

150

160

170

180

190

200

210

220

230

141 291

411 571

760

930

1040

1210

1320

1490

1670

1701

1891

2052

2231

Figure 7 The mass spectrogram of 13375min

According to comparison with the spectral library spectrumstandard substance phenanthrene residue is identified inoriginal solution with 96 matching degree with the liter-atures as the following structural formula

(1)

(2) The peak mass spectrum diagram in GC as of reten-tion time at 13375min is as shown in Figure 7

According to comparison with the spectral library spec-trum standard substance this material is identified as butyl

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Journal of Spectroscopy 5

mz

Abun

danc

e

3405

345038503650

3531

51656165 9288 10419

12443

13576

1337714497

17302

18139

26e + 0725e + 0724e + 0723e + 0722e + 0721e + 072e + 07

19e + 0718e + 0717e + 0716e + 0715e + 0714e + 0713e + 0712e + 0711e + 071e + 07900000080000007000000600000050000004000000300000020000001000000

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

4130

Figure 5 The GC map of phenanthrene conversion and removal by potassium ferrate system

mz

Abun

danc

e

1781

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

630 760

890

1020

1260

1390 1520

1961

2809

Figure 6 The mass spectrogram of 12443min

with mass spectrometry retrieve library standard spectro-gram other intermediates mainly include butyl phthalate910-phenanthraquinone and diphenyl-221015840-biformaldehydeIn addition there are some significant intermediates suchas 9-fluorenone and dimethylbenzenal And the peak ofthe main production prepared by phenanthrene reactionwith potassium ferrate is at 13575min the component areapercentage accounted for 8266 Specific mass spectrumand structural formula of main products are as follows

(1) The mass spectrum peak diagram in GC of retentiontime at 12443min is as shown in Figure 6

mz

Abun

danc

e

9500

8500

7500

6500

5500

4500

3500

2500

1500

500

102030405060708090

100

110

120

130

140

150

160

170

180

190

200

210

220

230

141 291

411 571

760

930

1040

1210

1320

1490

1670

1701

1891

2052

2231

Figure 7 The mass spectrogram of 13375min

According to comparison with the spectral library spectrumstandard substance phenanthrene residue is identified inoriginal solution with 96 matching degree with the liter-atures as the following structural formula

(1)

(2) The peak mass spectrum diagram in GC as of reten-tion time at 13375min is as shown in Figure 7

According to comparison with the spectral library spec-trum standard substance this material is identified as butyl

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

6 Journal of Spectroscopy

phthalate with 86 matching degree and its formula is asfollows

O

O

OO

(2)

This material area percentage is only 132 to showthat this material accounts for a very small proportion inthe product This kind of material can be the intermediateproduced by complex reaction of oxidation

(3) The peak mass spectrum diagram in GC of retentiontime at 13575min is as shown in Figure 8

According to comparison with the spectral library spec-trum standard substance this material is identified as 910-phenanthraquinone with 92 matching degree and itsformula is as follows

O O

(3)

This material area percentage is 8266 to show thatthis material accounts for a very high proportion in theproduct It is the main product of potassium ferrate intransformation of phenanthrene Phenanthrene ismade up ofthree benzene rings where 910-position has strong chemicalreactivity prone to oxidation In potassium ferrate oxidationsystem phenanthrene gives Fe (VI) electron to be oxidizedIn addition phenanthrene can get 98 transformation inferrate oxidation system but it cannot completely inorganicbut is turned into 910-phenanthrenequinone According tothe research results by Lawton et al [21] quinone structureis a kind of functional group more biophile than benzenering Its relatively weak biological resistance is advantageousover the biochemical conversion process It changes aromatichydrocarbon environmental durability characteristics and tosome extent reduces the environmental risk

(4) The peak mass spectrum diagram in GC of retentiontime at 18139min is as shown in Figure 9

According to comparison with the spectral library spectrumstandard substance this material is identified as diphenyl-221015840-biformaldehyde with 70 matching degree and itsformula is as follows

O

O

(4)

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

151

291

500

630 760

906

1040

1261

1390

1520

1651

1811

1941

2101

2271

2670

2809

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

Figure 8 The mass spectrogram of 13575min

mz

Abun

danc

e

20 40 60 80 100 120 140 160 180 200 220 240 260 280

9000

8000

7000

6000

5000

4000

3000

2000

1000

0

271

500

760

980

1111 1260

1520

1650

1000

1940

2100

2361

2511

2661

2911

Figure 9 The mass spectrogram of 18139min

This material area percentage is only 105 showing thatthismaterial accounts for a very small proportion in the prod-uct In the process of potassium ferrate oxidation of phenan-threne Fe (VI) to be reduced generates Fe (V) Fe (IV)and Fe (III) [22 23] through single electron transfer stepsPhenanthrene 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Sincethis is an oxidation system diphenyl-221015840-biformaldehyde iseasy to be oxidized by potassium ferrate so its proportion inproducts accounted for quite a few

35 Primary Analysis of Oxidation System Mechanism toTransform Phenanthrene In the process of potassium ferrateto oxidize phenanthrene Fe (VI) to be reduced generates Fe(V) Fe (IV) and Fe (III) [24 25] through single electrontransfer steps Phenanthrene is made up of three benzenerings of which 910-position has strong chemical reactivityprone to oxidation In potassium ferrate oxidation systemphenanthrene gives Fe (VI) electron to be oxidized Accord-ing to the single electron transfer mechanism the possiblereaction of potassium ferrate and phenanthrene is shown inFigure 10

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Journal of Spectroscopy 7

O OO∙ O∙OH OH

Figure 10 The possible way of reaction of potassium ferrate withphenanthrene

4 Conclusions

This experiment adopts the hypochlorite oxidation approachto constantly synthesize potassium ferrate The transforma-tion oxidation process of potassium ferrate for aromatichydrocarbons mainly occurred in the initial 5ndash10 min-utes Compared with aromatic hydrocarbon transformationremoval percentage it was found that potassium ferrate hashigh oxidation but to different samples its transformationoxidation ability is not the same Relatively phenanthrene ismost likely to be transformed andnaphthalene ismore stableIn potassium ferrate to remove phenanthrene in GC andin the intermediate mass spectrum analysis phenanthrenegives electron to Fe (VI) of potassium ferrate oxidationsystem so that phenanthrene oxidation occursThus possiblereaction path is proposed the quinone structure is a kind offunctional group more biophile than benzene ring Becauseof its biologically weak resistance it is advantageous to thebiochemical conversion process to conversion of aromatichydrocarbonrsquos environmental durability characteristics andto some extent to reduction of the environmental risk

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] N F Y Tam L Ke XHWang andY SWong ldquoContaminationof polycyclic aromatic hydrocarbons in surface sediments ofmangrove swampsrdquo Environmental Pollution vol 114 no 2 pp255ndash263 2001

[2] M Sanders S Sivertsen and G Scott ldquoOrigin and distributionof polycyclic aromatic hydrocarbons in surficial sediments fromthe Savannah Riverrdquo Archives of Environmental Contaminationand Toxicology vol 43 no 4 pp 438ndash448 2002

[3] R-A Doong and Y-T Lin ldquoCharacterization and distributionof polycyclic aromatic hydrocarbon contaminations in surfacesediment and water from Gao-ping River Taiwanrdquo WaterResearch vol 38 no 7 pp 1733ndash1744 2004

[4] F Lin H Ye and Y Song ldquoPreparation and electrochemi-cal properties of Li-doped BaFeO

4as electrode material for

lithium-ion batteriesrdquo Electrochemistry Communications vol 2no 6 pp 531ndash534 2001

[5] V K Sharma ldquoPotassium ferrate(VI) an environmentallyfriendly oxidantrdquo Advances in Environmental Research vol 6no 2 pp 143ndash156 2002

[6] M Alsheyab J-Q Jiang and C Stanford ldquoOn-line productionof ferrate with an electrochemical method and its potentialapplication for wastewater treatmentmdasha reviewrdquo Journal ofEnvironmental Management vol 90 no 3 pp 1350ndash1356 2009

[7] J Q Jiang S Wang and A Panagoulopoulos ldquoThe explorationof potassium ferrate(VI) as a disinfectantcoagulant in waterand wastewater treatmentrdquoChemosphere vol 63 no 2 pp 212ndash219 2006

[8] Y Y Eng V K Sharma and A K Ray ldquoFerrate(VI) greenchemistry oxidant for degradation of cationic surfactantrdquoChemosphere vol 63 no 10 pp 1785ndash1790 2006

[9] B L Yuan Y B Li X D Huang H Liu and J Qu ldquoFe(VI)-assisted photocatalytic degradating of microcystin-LR usingtitanium dioxiderdquo Journal of Photochemistry and PhotobiologyA Chemistry vol 178 no 1 pp 106ndash111 2006

[10] D Tiwari H-U Kim B-J Choi et al ldquoFerrate(VI) agreen chemical for the oxidation of cyanide in aqueouswastesolutionsrdquo Journal of Environmental Science and Health AToxicHazardous Substances amp Environmental Engineering vol42 no 6 pp 803ndash810 2007

[11] V K Sharma ldquoUse of iron(VI) and iron(V) in water andwastewater treatmentrdquo Water Science and Technology vol 49no 4 pp 69ndash74 2004

[12] J Q Jiang ldquoResearch progress in the use of ferrate(VI) for theenvironmental remediationrdquo Journal of Hazardous Materialsvol 146 no 3 pp 617ndash623 2007

[13] C Li Z X Li N Graham et al ldquoThe aqueous degradation ofbisphenol A and steroid estrogens by ferraterdquo Water Researchvol 42 no 1-2 pp 109ndash120 2008

[14] V K Sharma S K Misra and A K Ray ldquoKinetic assessmentof the potassium ferrate(VI) oxidation of antibacterial drugsulfamethoxazolerdquo Chemosphere vol 62 no 1 pp 128ndash1342006

[15] FDong Y SunM Fu ZWu and S C Lee ldquoRoom temperaturesynthesis and highly enhanced visible light photocatalytic activ-ity of porous BiOIBiOCl composites nanoplates microflowersrdquoJournal of Hazardous Materials vol 219-220 pp 26ndash34 2012

[16] F Dong Y Sun M Fu W-K Ho S C Lee and Z WuldquoNovel in situ N-doped (BiO)

2CO3hierarchical microspheres

self-assembled by nanosheets as efficient and durable visiblelight driven photocatalystrdquoLangmuir vol 28 no 1 pp 766ndash7732012

[17] X L Zhu and C W Yuan ldquoPhotocatalytic degradation ofpesticide pyridaben onTiO

2particlesrdquo Journal ofMolecular vol

229 no l-2 pp 95ndash105 2005[18] M A Rahman and M Qamar ldquoSemiconductor mediated pho-

tocatalysed degradation of a pesticide derivative acephate inaqueous suspensions of titanium dioxiderdquo Journal of AdvancedOxidation Technologies vol 9 no 1 pp 103ndash109 2006

[19] M Iwasaki M Hara H Kawada et al ldquoState of arts for bleachplant effluent closurerdquo Journal of Colloid and Interface Scieneevol 224 no 1 pp 202ndash204 2000

[20] D C Hurum A G Agrios K A Gray T Rajh and M CThurnauer ldquoExplaining the enhanced photocatalytic activity ofDegussa P25 mixed-phase TiO

2using EPRrdquo Journal of Physical

Chemistry B vol 107 no 19 pp 4545ndash4549 2003[21] L A Lawton P K J Robertson B J P A Cornish I L Marr

and M Jaspars ldquoProcesses influencing surface interaction andphotocatalytic destruction of microcystins on titanium dioxidephotocatalystsrdquo Journal of Catalysis vol 213 no 1 pp 109ndash1132003

[22] S Malato J Blanco A Vidal and C Richter ldquoPhotocatalysiswith solar energy at a pilot-plant scale an overviewrdquo AppliedCatalysis B Environmental vol 37 no 1 pp 1ndash15 2002

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

8 Journal of Spectroscopy

[23] A G Rincon C Pulgarin N Adler and P Peringer ldquoInter-action between E coli inactivation and DBP-precursorsmdashdihydroxybenzene isomersmdashin the photocatalytic process ofdrinking-water disinfection with TiO

2rdquo Journal of Photochem-

istry and Photobiology A Chemistry vol 139 no 2-3 pp 233ndash241 2001

[24] W He J Wang H Shao J Zhang and C-N Cao ldquoNovelKOH electrolyte for one-step electrochemical synthesis of highpurity solid K

2FeO4 comparison with NaOHrdquo Electrochemistry

Communications vol 7 no 6 pp 607ndash611 2005[25] B-L Yuan X-Z Li and N Graham ldquoAqueous oxidation

of dimethyl phthalate in a Fe(VI)-TiO2-UV reaction systemrdquo

Water Research vol 42 no 6-7 pp 1413ndash1420 2008

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Applied ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Theoretical ChemistryJournal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Spectroscopy

Analytical ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Quantum Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of