research article ozonation of indigo carmine enhanced by...

Research ArticleOzonation of Indigo Carmine Enhanced byFePimenta dioica L Merrill Particles

Teresa Torres-Blancas1 Gabriela Roa-Morales1

Carlos Barrera-Diacuteaz1 Fernando Urentildea-Nuntildeez2 Julian Cruz-Olivares1

Patricia Balderas-Hernandez1 and Reyna Natividad1

1Universidad Autonoma del Estado de Mexico (UAEMex) Centro Conjunto de Investigacion en Quımica Sustentable (CCIQS)UAEM-UNAM Carretera Toluca-Atlacomulco Km 145 50200 Toluca MEX Mexico2Instituto Nacional de Investigaciones Nuclearles (ININ) Carretera Mexico-Toluca sn 52750 LaMarquesa Ocoyoacac MEX Mexico

Correspondence should be addressed to Gabriela Roa-Morales groamuaemexmx and Reyna Natividad reynanrgmailcom

Received 2 October 2014 Accepted 17 February 2015

Academic Editor Meenakshisundaram Swaminathan

Copyright copy 2015 Teresa Torres-Blancas et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Green synthesis of metallic particles has become an economic way to improve and protect the environment by decreasing the useof toxic chemicals and eliminating dyes The synthesis of metal particles is gaining more importance due to its simplicity rapidrate of synthesis of particles and environmentally friendly The present work aims to report a novel and environmentally friendlymethod for the synthesis of iron particles using deoiled Pimenta dioica L Merrill husk as support The indigo carmine removalefficiency by ozonation and catalyzed ozonation is also presented Synthesized materials were characterized by N

2physisorption

and scanning electron microscopy (SEMEDS) By UV-Vis spectrophotometry the removal efficiency of indigo carmine was foundto be nearly 100 after only 20 minutes of treatment under pH 3 and with a catalyst loading of 1000mgLminus1 Analytical techniquessuch as determination of the total organic carbon content (TOC) and chemical oxygen demand (COD) showed that iron particlessupported on deoiled Pimenta dioica L Merrill husk can be efficiently employed to degrade indigo carmine and achieved a partialmineralization (conversion to CO

2and H

2O) of the molecule From the results can be inferred that the prepared biocomposite

increases the hydroxyl radicals generation

1 Introduction

Textile industry is the greatest consumer of high quality freshwater per kg of treated material Its production processesdue to their nature significantly contribute to pollutionsince the wastewater is a source of persistent organic pol-lutants This is reflected on high chemical oxygen demand(COD) values Textile wastewater also contains chemicalssuch as formaldehyde azo dyes dioxins and heavy metals[1ndash3] These contaminants are mostly toxic carcinogenicand persistent Dyes are mostly complex molecules and arenaturally degraded under high temperature alkaline condi-tions ultraviolet (UV) radiation and other radical initiatorsgenerating the formation of by-products many times moretoxic to the environment than the original dye [4] Thegenerated by-products are known to cause perturbations in

the aquatic life and food In addition textile dyes are designedto be resistant tomicrobial chemical thermal and photolyticdegradation and thus producing recalcitrant compounds [5]Thus an effective and economical technique for removingdyes from textile wastewaters is needed In this sense severalconventional methods for treating textile industry effluentshave been studied such as photodegradation adsorptionfiltration coagulation and biological treatments [6 7] How-ever due to the stability of the molecules of dyes some ofthese methods are not completely effective andor viable Inthis sense advanced oxidation processes (AOPs) have beenstudied in order to destroy the dye molecules decolorizethe wastewater and reduce organic pollution Among theseadvanced oxidation processes (AOPs) ozonation has drawnattention Ozonation is an effective versatile and environ-mentally sound technique that has been proven as a good

Hindawi Publishing CorporationInternational Journal of PhotoenergyVolume 2015 Article ID 608412 9 pageshttpdxdoiorg1011552015608412

2 International Journal of Photoenergy

method for color removal [8 9] It oxidizes organic pollutantsvia two pathways direct oxidation with ozone moleculesandor the generation of free-radical intermediates suchas the HO∙ radical which is a powerful effective andnonselective oxidizing agent [10 11] However the oxidationrate by ozonation is limited by the chemical and molecularstability of the pollutant [2 12ndash14] In order to enhancethe ozone oxidation capabilities the addition of metallicparticles as catalysts has been suggested [12] In this contexttransition metals are preferred since they exhibit propertiesthat promote free radicals production during the ozonationprocess Colloidal particles either alloyed or core-shelledhave attracted significant attention due to new properties thatemerge from the combination of different metals (synergisticeffect) in the nanoscale and to the consequent enhancementof the physical and chemical properties of the resulting mate-rial [15 16] The application of metallic particles supportedon solid surfaces has been previously reported [17 18] It wasfound that the substrates containing immobilized particleshave several functions in analytical chemistry In generalterms the immobilization of particles or nanoparticles ona solid substrate shows several advantages for analyticalapplications [19] Regarding advanced oxidation processesmetal-catalyzed ozonations have particularly drawn attentionfor water decontamination and therefore the use of metallicparticles is being extensively investigated [20 21] In thiscontext the main aim of this study is to test a new bio-composite material which consists of stable iron particlesusing deoiled Pimenta dioica L Merrill husk as support Theevaluation of the removal efficiency using ozonation andcatalyzed ozonation of indigo carmine is presented Allspice(Pimenta dioica L Merrill) belongs to the Myrtaceae familyMexico exports around 4500 tons per year and half the pro-duction is processed in the country During the oil extractionprocesses either through steam distillation hydrodistillationor supercritical extraction the berry oil yield ranges from30 to 45 The residue of the oil extraction processes is atleast 955 in weight reaching annually 1500 tons in MexicoExhausted allspice is a fibrous material that contains 231cellulose 85 hemicellulose and 268 lignin and is theessayed biosupport in this work [22]

2 Materials and Methods

21 Reagents The crushed deoiled residue of allspice wasobtained as a product of a hydrodistillation process Thiswaste was first washed with an ethanol-water solution (40ndash60 vv) in order to eliminate colored and remaining sub-stances later on it was dried at 70∘C for 24 h Once theadsorbent was cooled down it was sieved through numbers10 80 and 170 meshes obtaining particles sized 200 0177and 0088mm respectively It was then stored in a desiccatorSodium hydroxide sulfuric acid sodium borohydride ironsulfate and indigo carmine (IC) dye analytical grade werepurchased from Sigma-Aldrich Chemicals Ozone was gen-erated in situ from dry air by an ozone generator (PacificOzone Technology) with an average ozone production of0005 gdmminus3

1

3

2

4 5

76

Figure 1 Schematic of the apparatus for the ozonation reaction (1)Upflow glass bubble column reactor (2) Porous glass (gas diffuser)(3) Pacific Technology D412 ozone destroyer (4) Ozone generator(5) Dry air inlet (6) Sample valve (7) Reaction solution

22 Synthesis of Iron Particles and Iron Supported on DeoiledAllspice Husk Using porous materials is an interesting alter-native to control the stability of zero-valent particles [16] Ithas been previously reported that the employment of porousmaterials improves the stability and catalytic properties ofsupported metal particles and nanoparticles [6] In this workdeoiled allspice husk was employed as porousmaterial for thesynthesis and stabilization of metal particles The synthesisand support of iron particles on deoiled allspice husk wereas follows approximately 10 g of deoiled allspice husk (MPS)was placed in a 500mL Erlenmeyer flask and mixed with250mL of a 001M FeSO

4solution for 24 h under continuous

stirring at room temperature andN2atmosphereThen 10mL

of 01 NaOH solution was added and the resulting slurrywas kept under stirring for further half an hour After thistime 60mL of 025M NaBH

4solution was gradually added

in order to obtain the metallic particles via reaction (1) [16]After vacuum filtration the solid was washed with reagentgrade acetone and labelled as MPSFe To synthesize theunsupported iron particles (Fe-NP) 250mL of 001M FeSO

4

solution was mixed with 15mol of 01 NaOH solution and60mL of 025MNaBH

4The resulting slurry was also filtered

under vacuum and the solid was washed with reagent gradeacetone and labelled as Fe-NP

2Fe2+ + 2H2O + BH

4

minus+ 4119890minus

997888rarr 2Fe(s) + BO2

minus+ 4H+ + 2H

2(g) uarr(1)

23 Ozonation Thedifferent ozonation treatmentswere con-ducted in a 1 L upflow bubble column reactor (see Figure 1)Ozone was fed through a gas diffuser with a pore size of2 120583mAheated catalytic ozone destructor (PacificTechnologyd41202) was employed in order to destroy the excess ofozone in the outlet of the glass bubble column reactor sothere was no ozone being discharged to atmosphere Sampleswere taken at specific time intervals to be analyzed Allexperiments were carried out at room temperature (19∘C plusmn2) pH was adjusted at 30 with analytical grade sulfuric acidand sodium hydroxide and the initial IC concentration was1000mgLminus1 The assessed variables were particle size and

International Journal of Photoenergy 3

solid concentration In order to establish the IC adsorptioncapacity of the synthesized materials every one of them wasplaced into an IC solution without feeding ozone In theseexperiments the IC concentration at specific time intervalswas established by UV-Vis spectrophotometry

24 Chemical Analysis To determine the concentration ofindigo carmine at specific time intervals a spectrophotomet-ric technique was employed For such a purpose an UV-Vis Perkin Elmer Lambda 25 model spectrophotometer wasused Samples were analyzed in the range of 200 to 900 nmwith a scan rate of 960 nmsminus1 A maximum absorbance of610 nm was found and ascribed to the indigo carmine (IC)dye The degree of mineralization of indigo carmine wasdetermined by measuring the total organic carbon with aTOC-LCPHCPN Shimadzu total organic carbon analyzerThe chemical oxygen demand of the samples was determinedby using the American Public Health Association (APHA)standard procedures [23]

25 Characterization

251 Scanning ElectronMicroscopy (SEMEDS) Images wereobtained in a JEOL JSM 6510LV instrument at 15 kV with10mmWD using both secondary and backscattered electronsignals Samples were coated with a 20 nm thin film of goldusing Denton Vacuum DESK IV sputtering equipment witha gold target X-ray energy dispersive spectroscopy analyseswere performed in an Oxford PentaFetx5 that was calibratedprior to all analyses with a copper standard

252 BET Analysis Surface area and pore characteristics ofdeoiled allspice husk original (MPS) and deoiled allspice huskoriginal with iron particles (MPSFe) were determined byN2gas BET analysis (GEMINI 2360 instrument) obtained

from nitrogen adsorption at 77K The nitrogen adsorptionisothermswere recorded up to a relative pressure to assess thetotal pore volume Porosity was determined using the porevolume and density

3 Results and Discussion

31 Ozonation

311 Effect of Adding Unsupported and Supported Iron Parti-cles on IC Concentration Theozonation of ICwas performedin the bubble column reactor with unsupported iron particles(NP-Fe) original deoiled allspice husk (MPS) and sup-ported iron particles on deoiled allspice husk (MPSFe) Allexperiments were conducted with an initial IC concentrationof 1000mgLminus1 The initial absorption spectrum shows ICabsorption band with a maximum at 610 nm (see Figure 2)This band was monitored in the ozonation experimentsconducted with each material (NP-Fe MPS and MPSFe)Figure 2 shows that the band at 610 nmdecreases significantlyfor MPSFe at 20 minutes compared to others suggestinggreater effectiveness in the degradation of ICThe absorptionband with a maximum at 300 nm is associated with 120587 bonds

0

02

04

06

08

1

12

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)

0min IC20min NPFe20min ozone

20min MPS20min MPSFe

Figure 2 Effect of the addition of unsupported and supported ironparticles on UV-Vis spectra of indigo carmine solution after 20minutes of ozonation

lowast

lowastlowastlowast lowast lowast

lowast

lowast

lowast

lowast

lowast

0100200300400500600700800900

1000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)

MPSFeMPS

NPrsquos FeOzone

Figure 3 Effect of the material and time on IC concentration []supported on deoiled allspice husk (MPSFe) [] deoiled allspicehusk (MPS) [lowast] iron metal particles (NP-Fe) and [◻] indigocarmine (IC) only ozone

and these are decreased by 20 with the application of ozone(O3) ozoneMPS (O

3MPS) ozoneiron (O

3iron particles

NP-Fe) indicating that the molecule has not been completelydegraded These 120587 bonds are the result of breaking down theIC molecule by the action of free radicals generated duringthe ozonation process

Figure 3 shows the IC concentration profile as function oftime It can be observed that the degradation of IC is fastestwhen thematerial with the supported iron particles (MPSFe)is employed MPSFe leads to nearly complete degradationof the dye after only 20min of ozonation In heterogeneouscatalysis the positive effect of the support textural propertieson the active sites dispersion and availability is well knownIn this context hydroxo (OH) or oxo (=O) groups in


lowast

lowastlowast

lowast

lowast

960965970975980985990995

100010051010

0 20 40 60 80 100

[IC] (

mg

L)

Time (min)

MPSMPSFe

Figure 4 Effect of type of added material and time on IC concen-tration without ozone

the synthesis stage provide a greater surface area for thesynthesis of metal particles onto the material [22]

The adsorption capacity of the MPS and MPSFe mate-rials was tested in the absence of bubbling ozone Figure 4shows the results for the two types of materials None of thetwomaterials (MPS orMPSFe) shows an important capacityof adsorption during the contact time

To elucidate the produced compounds reluctant to fur-ther degradation during each treatment the UV-Vis spectraof the reacting solution as function of time were analyzed(Figure 5) It can be seen from this figure that the spectrumcorresponding to the IC has two absorption bands withmaxima at 610 and 340 nm The first band is characteristicof IC and the latter can be ascribed to auxochromes (N SO

3)

attached to the benzene ring One of the main products whenthe IC is degraded by ozonation is isatin sulfonic acid whichexhibits a maximum of absorption of 304 nm radiation Thepresence of this by-product was detected by analysis of astandard reagent grade in UV-Vis

When only ozone is applied to the IC solution it wasobserved that the maximum absorbance at 610 nm decreasesand this indicates the characteristic blue color is also decreas-ing This may be due to the loss of sulphonate group sincethis works as auxochrome and therefore increases colorintensity From Figure 6 it is evident that the addition ofMPSFe to the ozonation process decreases the concentrationof isatin sulfonic acid generated by the degradation of IC ingreater proportion than the other types of solids It is worthobserving that the support does also have a positive effect onisatin degradationThis however is considerably slower thanwhenMPSFe is employedThus the use of MPSFe not onlyenhances the IC degradation but also markedly reduces theconcentration of the main subproduct (isatin sulfonic acid)generated during the ozonation process

312 Effect of Adding Unsupported and Supported Iron Parti-cles on Total Organic Carbon and Chemical Oxygen DemandTable 1 shows that the use of MPS increases the total carbon

0

005

01

015

02

025

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)

601nm STD indigo carmineMPS t = 60minMPSFe t = 60min

NPFe t = 60minOzone t = 60min304nm STD isatinsulfonic acid (10mgL)

Figure 5 Effect of added material type on the ozonation process onUV-Vis spectra Reaction time 60 minutes

5

15

25

35

45

55

65

75

0 10 20 30 40 50 60 70

[isat

in su

lfoni

c aci

d] (m

gL)

Time (min)

MPSMPSFe

NPFeOzone

Figure 6 Effect of the tested materials on Isatin sulfonic acidconcentration

Table 1 Effect of solid material on the final total organic carboncontent

MPS-O3 MPSFe-O3 NP-Fe O3

Total organic carbon(mgLminus1) 20min 272 plusmn 5 48 plusmn 5 80 plusmn 5 202 plusmn 5

Total carbon(mgLminus1) 20min 274 plusmn 5 50 plusmn 5 82 plusmn 5 205 plusmn 5

Inorganic carbon(mgLminus1) 20min 3 plusmn 5 1 plusmn 5 3 plusmn 5 3 plusmn 5

Initial total organic carbon = 202 plusmn 5 mgLminus1

(TOC) during the degradation of IC This can be ascribed tothe degradation of the deoiled crushed material during theozonation process Nonetheless the addition of supportediron particles to the ozonation process substantially enhancestotal organic carbon removal Table 1 shows that the use


lowast

lowast

lowast

lowast

lowast

0

50

100

150

200

250

300

350

0 5 30 60

COD

(mg

L)

Time (min)

MPS-FeMPS

OzoneNP-Fe

(a)

Indigo carmine

minusO3S

N

NN

N

O

O O

OOH

O

O

O

O

O

∙OH ∙OH

∙OH

∙OH

∙OH

∙OH

SO3

minus

H H

H

minusSO4

2minus

H2N

H2O2

H2OCO2

Isatin 5-sulfonic acid

O∙∙

N∙∙

(b)

Figure 7 (a) Effect of catalyst type on chemical oxygen demand (COD) (b) proposed indigo carmine degradation mechanism

of MPSFe not only makes IC degradation faster but alsoinhibits degradation of the support According to the analysisof total organic carbon the addition of MPSFe leads to a76 removal of TOC after only 20 minutes of treatment Atthe same reaction time ozone alone does not reduce TOC atall This can be ascribed to the ozone incapacity to furtherdegrade the isatin molecule

Figure 7 confirms that the IC oxidation degree stronglydepends on the type of added material during the ozonation

process and this is given in terms of chemical oxygen demand(COD)These results are in concordance with TOCmeasure-ments The effect of the addition of MPSFe on the removalof indigo carmine by ozonation offers a synergistic action thatincreases the rate of degradation of indigo carmine (Figure 7)The formation of reactive oxidizing species that is freeradicals (HO∙) during the ozonation process concomitantlygenerates other radicals and hydrogen peroxide Hence theuse of MPSFe introduces new reactions mainly fenton


type that positively impact the mineralization and oxidationdegree of the IC solution

The effect of the addition of MPSFe to the ozonationprocess generates a production of free radicals not governedby the reaction (2)ndash(4) The ozone reacts in solution togenerate the hydroxyl radical (HO∙) and radicals superoxide(2) which are consumed in the production of hydrogenperoxide (2)-(3)

O3+H2O 997888rarr 2HO∙ +O

2(2)

O3+HO∙ 997888rarr HO

2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)

The synthesized zero-valent particles (Fe0) are expected to bereadily oxidized However the IC degradation results suggestthat the support allows the iron particles to exhibit a catalyticeffect on the generation of free radicals (HO∙) This effectmay be related to the interaction of the iron particles withthe support surface [24 25] As consequence this catalyticcapability is rather diminishedwhen the iron particles are notsupported Actually because of previous reports [24 26 27]when the ozone is combined withMPSFe the intensificationof HO∙ production was expected The ferrous specie in thecomposite MPSFe by means of the following reactions mayproduce the ferrous specie involved in reaction

6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)

So that FeO2+ reacts with hydrogen peroxide (traces ofoxygen peroxide generated from ozone reactions (2)ndash(4)) togenerate free radicalsThen the degradation of organicmattervia free radicals as shown in the following reaction becomesplausible [12 28 29]

FeO2+ +H2O2997888rarr FeO3+ +HO∙ +OHminus (6)

Fe3+ species may be going back to Fe2+ by means of thefollowing reaction [27]

Fe3+ +H2O2997888rarr Fe2+ +HO

2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)

Therefore when adding theMPSFe to the ozonation processthis is catalyzedThis catalytic effect of Fe2+ on ozonation hasbeen previously recognized [9 12] Therefore the synergisticeffect for the generation of free radicals (HO∙ HO

2

∙) viaozonation reactions (2)ndash(4) and catalyzed ozonation reac-tions with supported iron (5)ndash(7) cannot be neglected

Under this scheme the degradation of IC towards isatinand its products has been suggested [18] to occur accordingto the mechanism depicted in Figure 7

313 Effect of Particle Size Also the effect of particle size ofthe MPSFe material was evaluated Three different particlesizes were tested 200 0177 and 0088mm The initialconcentration of IC was 1000mgLminus1 and the reaction timewas 60min The results are shown in Figure 8 and suggest

00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)

10 meshes = 2mm80 meshes = 0177mm170 meshes = 0088mm

Figure 8 Effect of particle size of supported iron particles on indigocarmine concentration profile

0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)

05 g MPSFe5g MPSFe10 g MPSFe

Figure 9 Effect catalyst loading on indigo carmine concentrationprofile

the presence of liquid-solid and intraparticle mass transportresistances that are presumably minimized when the particlesize is 0177mm (80 mesh) as a result of the best and fasterdegradation of the dye used over the others conditions testedIt is worth noticing that the effect of adsorptionwas evaluatedfor all tested materials without the presence of ozone Theresults indicated that this phenomenon is negligible for allmaterials The unsupported iron particles (NP-Fe) did notexhibit good efficiency in contrast to the supported MPSFe

314 Effect of Catalyst Concentration In order to study theeffect of this variable three experiments with their corre-sponding repetitions were conducted At all experimentsthe initial concentration of IC were 1000mgLminus1 and thereaction time was 60min Figure 9 shows the positive effect


(a)

100

50

0

OCaK

Energy (keV)2 4 6 8 10

(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)

Figure 10 SEMEDS images for the synthesized materials

on IC removal when using a [MPSFe] = 1000mgLminus1 Thepresence of the MPSFe enhances the ozonation processand its concentration has a strong influence over the dyedegradationThe IC degradation rate increases when mass ofMPSFe increases and this is also an indicative of the liquid-solid mass transfer resistance being negligible It is worthpointing out that the removal of IC by adsorption onto theMPSFe particles was found to be negligible Only 18 of ICwas removed by this phenomenon

32 Materials Characterization

321 SEMEDS and Elemental Analysis SEMmicrographs ofMPS and MPSFe materials in Figure 10(a) show the parent

supports as amorphousThese remained unchanged after thedeposition of iron In the elemental analysis it was foundthat the material elements of the MPS might be acting asnatural material (peaks of C O K and Ca which are typicalelements of the natural materials) as shown in Figure 10(b)As expected iron was detected on the MPSFe sample (seeFigure 10(c)) The SEMEDS analysis allows identifying ironparticles of approximately 250 nm in size (Figure 10(d)) It isimportant to note that the increase in oxygen observed inthe MPSFe sample suggests the presence of FeO2+ speciesin contrast with the support alone (MPS) The decrease inweight percent of carbon observed in theMPSFe sample (seeTable 2) may be due to the coating of the surface by ironparticles


Table 2 Characteristics of catalytic materials

MPS MPSFeSpecific surface area (m2gminus1) 240 458Cumulative pore volume (cm3

(STP) gminus1) 055 105

Mean pore diameter (nm) 445 661Total pore volume (119901119901

119900) = 0990

(cm3gminus1) 267119864 minus 03 758119864 minus 3

Carbon 5461 1729Oxygen 4284 5965Sodium 057 2076Calcium 199 058Iron 0 172

322 N2Physisorption The results in Table 2 show that

MPSFe has a greater specific surface area This increase maybe the consequence of the chemical treatment conducted onthe husk during the catalytic system preparation

4 Conclusions

Unsupported and supported iron particles were synthesizedvia a relatively low cost method Indigo carmine removal byozonation and ozonationwith unsupported and supported Feon a biomaterial was studied MPSFe substantially improvesthe degradation of indigo carmine and of the generated sub-products during the ozonation process Catalyzed ozonationleads to attain a reaction rate twice faster than ozonationalone The use of the MPSFe allows the removal of 76 ofTOC after only 20min of ozonation It was found that thesynthesized materials did not exhibit significant adsorptionproperties

Conflict of Interests

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

Acknowledgments

The first author acknowledges the scholarship 248402 fromCONACyT to pursue her postgraduate studies PRODEPis also acknowledged for financial support through project1035135257

References

[1] C Tang and V Chen ldquoNanofiltration of textile wastewater forwater reuserdquo Desalination vol 143 no 1 pp 11ndash20 2002

[2] A Bes-Pia J A Mendoza-Roca M I Alcaina-Miranda AIborra-Clar and M I Iborra-Clar ldquoReuse of wastewater ofthe textile industry after its treatment with a combinationof physico-chemical treatment and membrane technologiesrdquoDesalination vol 149 no 1ndash3 pp 169ndash174 2002

[3] P C Vandevivere R Bianchi andW Verstraete ldquoReview treat-ment and reuse of wastewater from the textile wet-processing

industry review of emerging technologiesrdquo Journal of ChemicalTechnology amp Biotechnology vol 72 no 4 pp 289ndash302 1998

[4] K Santhy and P Selvapathy ldquoRemoval of reactive dyes fromwastewater by adsorption on coir pith activated carbonrdquo Biore-source Technology vol 97 no 11 pp 1329ndash1336 2006

[5] A D Bokare R C Chikate C V Rode and K M PaknikarldquoIron-nickel bimetallic nanoparticles for reductive degradationof azo dye Orange G in aqueous solutionrdquo Applied Catalysis BEnvironmental vol 79 no 3 pp 270ndash278 2008

[6] F Pena-Pereira R M B O Duarte and A C Duarte ldquoImmo-bilization strategies and analytical applications for metallicand metal-oxide nanomaterials on surfacesrdquo TrACmdashTrends inAnalytical Chemistry vol 40 pp 90ndash105 2012

[7] A Majcen L Marechal and B Krizanec ldquoTextile finishingindustry as an important source of organic pollutantsrdquo inOrganic Pollutants Ten Years after the Stockholm ConventionmdashEnvironmental and Analytical Update InTech 2012

[8] P Canizares R Paz C Saez and M A Rodrigo ldquoCosts ofthe electrochemical oxidation of wastewaters a comparisonwith ozonation and Fenton oxidation processesrdquo Journal ofEnvironmental Management vol 90 no 1 pp 410ndash420 2009

[9] A C Quiroz C Barrera-Dıaz G Roa-Morales P BHernandez R Romero and R Natividad ldquoWastewater ozo-nation catalyzed by ironrdquo Industrial and Engineering ChemistryResearch vol 50 no 5 pp 2488ndash2494 2011

[10] W P Kwan and B M Voelker ldquoRates of hydroxyl radical gen-eration and organic compound oxidation in mineral-catalyzedfenton-like systemsrdquo Environmental Science and Technologyvol 37 no 6 pp 1150ndash1158 2003

[11] A H Gemeay I A Mansour R G El-Sharkawy and A BZaki ldquoKinetics and mechanism of the heterogeneous catalyzedoxidative degradation of indigo carminerdquo Journal of MolecularCatalysis A Chemical vol 193 no 1-2 pp 109ndash120 2003

[12] M Bernal R Romero G Roa C Barrera-Dıaz T Torres-Blancas and R Natividad ldquoOzonation of indigo carminecatalyzed with Fe-pillared clayrdquo International Journal of Pho-toenergy vol 2013 Article ID 918025 7 pages 2013

[13] M Faouzi P Canizares A Gadri et al ldquoAdvanced oxidationprocesses for the treatment of wastes polluted with azoic dyesrdquoElectrochimica Acta vol 52 no 1 pp 325ndash331 2006

[14] N Gandra A T Frank O Le Gendre et al ldquoPossiblesinglet oxygen generation from the photolysis of indigodyes in methanol DMSO water and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroboraterdquo Tetrahedron vol 62 no46 pp 10771ndash10776 2006

[15] R Sankar P Manikandan V Malarvizhi T Fathima K SShivashangari and V Ravikumar ldquoGreen synthesis of colloidalcopper oxide nanoparticles usingCarica papaya and its applica-tion in photocatalytic dye degradationrdquo Spectrochimica ActamdashPart A Molecular and Biomolecular Spectroscopy vol 121 pp746ndash750 2014

[16] V K Vidhu and D Philip ldquoCatalytic degradation of organicdyes using biosynthesized silver nanoparticlesrdquoMicron vol 56pp 54ndash62 2014

[17] G Carja E Husanu C Gherasim and H Iovu ldquoLayereddouble hydroxides reconstructed in NiSO4 aqueous solutionas highly efficient photocatalysts for degrading two industrialdyesrdquo Applied Catalysis B Environmental vol 107 no 3-4 pp253ndash259 2011

[18] C Flox S Ammar C Arias E Brillas A V Vargas-Zavalaand R Abdelhedi ldquoElectro-Fenton and photoelectro-Fenton


degradation of indigo carmine in acidic aqueous mediumrdquoApplied Catalysis B Environmental vol 67 no 1-2 pp 93ndash1042006

[19] XWeng Z Chen MMegharaj and R Naidu ldquoClay supportedbimetallic FeNi nanoparticles used for reductive degradationof amoxicillin in aqueous solution characterization and kinet-icsrdquo Colloids and Surfaces A Physicochemical and EngineeringAspects vol 443 pp 404ndash409 2014

[20] P Vasileva B Donkova I Karadjova and C Dushkin ldquoSynthe-sis of starch-stabilized silver nanoparticles and their applicationas a surface plasmon resonance-based sensor of hydrogenperoxiderdquo Colloids and Surfaces A Physicochemical and Engi-neering Aspects vol 382 no 1ndash3 pp 203ndash210 2011

[21] A R Khataee V Vatanpour andA R A Ghadim ldquoDecoloriza-tion of CI Acid Blue 9 solution by UVNano-TiO

2 Fenton

Fenton-like electro-Fenton and electrocoagulation processes acomparative studyrdquo Journal of Hazardous Materials vol 161 no2-3 pp 1225ndash1233 2009

[22] T Torres-Blancas G Roa-Morales C Fall C Barrera-Dıaz FUrena-Nunez and T B Pavon Silva ldquoImproving lead sorptionthrough chemical modification of de-oiled allspice husk byxanthaterdquo Fuel vol 110 pp 4ndash11 2013

[23] American Public Health Association American Water WorksAssociationWater Environment Federation Standard Methodsfor the Examination of Water andWastewater American PublicHealth Association American Water Works AssociationWaterEnvironment Federation 20th edition 1998

[24] W P Kwan and BM Voelker ldquoInfluence of electrostatics on theoxidation rates of organic compounds in heterogeneous fentonsystemsrdquo Environmental Science and Technology vol 38 no 12pp 3425ndash3431 2004

[25] P Canizares M Hernandez-Ortega M A Rodrigo C EBarrera-Dıaz G Roa-Morales and C Saez ldquoA comparisonbetween conductive-diamond electrochemical oxidation andother advanced oxidation processes for the treatment of syn-thetic melanoidinsrdquo Journal of Hazardous Materials vol 164no 1 pp 120ndash125 2009

[26] M A Al-Shamsi N R Thomson and S P Forsey ldquoIron basedbimetallic nanoparticles to activate peroxygensrdquoChemical Engi-neering Journal vol 232 pp 555ndash563 2013

[27] J De Laat H Gallard S Ancelin and B Legube ldquoComparativestudy of the oxidation of atrazine and acetone by H

2O2UV

Fe(III)UV Fe(III)H2O2UV and Fe(II) or Fe(III)H

2O2rdquo

Chemosphere vol 39 no 15 pp 2693ndash2706 1999[28] M A Garcıa-Morales G Roa-Morales C Barrera-Dıaz B

Bilyeu and M A Rodrigo ldquoSynergy of electrochemical oxida-tion using boron-doped diamond (BDD) electrodes and ozone(O3) in industrial wastewater treatmentrdquo Electrochemistry Com-

munications vol 27 pp 34ndash37 2013[29] K C Pillai T O K Kwon and I S Moon ldquoDegradation of

wastewater from terephthalic acid manufacturing process byozonation catalyzedwith Fe2+ H

2O2andUV light direct versus

indirect ozonation reactionsrdquo Applied Catalysis B Environmen-tal vol 91 no 1-2 pp 319ndash328 2009

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


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


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


method for color removal [8 9] It oxidizes organic pollutantsvia two pathways direct oxidation with ozone moleculesandor the generation of free-radical intermediates suchas the HO∙ radical which is a powerful effective andnonselective oxidizing agent [10 11] However the oxidationrate by ozonation is limited by the chemical and molecularstability of the pollutant [2 12ndash14] In order to enhancethe ozone oxidation capabilities the addition of metallicparticles as catalysts has been suggested [12] In this contexttransition metals are preferred since they exhibit propertiesthat promote free radicals production during the ozonationprocess Colloidal particles either alloyed or core-shelledhave attracted significant attention due to new properties thatemerge from the combination of different metals (synergisticeffect) in the nanoscale and to the consequent enhancementof the physical and chemical properties of the resulting mate-rial [15 16] The application of metallic particles supportedon solid surfaces has been previously reported [17 18] It wasfound that the substrates containing immobilized particleshave several functions in analytical chemistry In generalterms the immobilization of particles or nanoparticles ona solid substrate shows several advantages for analyticalapplications [19] Regarding advanced oxidation processesmetal-catalyzed ozonations have particularly drawn attentionfor water decontamination and therefore the use of metallicparticles is being extensively investigated [20 21] In thiscontext the main aim of this study is to test a new bio-composite material which consists of stable iron particlesusing deoiled Pimenta dioica L Merrill husk as support Theevaluation of the removal efficiency using ozonation andcatalyzed ozonation of indigo carmine is presented Allspice(Pimenta dioica L Merrill) belongs to the Myrtaceae familyMexico exports around 4500 tons per year and half the pro-duction is processed in the country During the oil extractionprocesses either through steam distillation hydrodistillationor supercritical extraction the berry oil yield ranges from30 to 45 The residue of the oil extraction processes is atleast 955 in weight reaching annually 1500 tons in MexicoExhausted allspice is a fibrous material that contains 231cellulose 85 hemicellulose and 268 lignin and is theessayed biosupport in this work [22]

2 Materials and Methods

21 Reagents The crushed deoiled residue of allspice wasobtained as a product of a hydrodistillation process Thiswaste was first washed with an ethanol-water solution (40ndash60 vv) in order to eliminate colored and remaining sub-stances later on it was dried at 70∘C for 24 h Once theadsorbent was cooled down it was sieved through numbers10 80 and 170 meshes obtaining particles sized 200 0177and 0088mm respectively It was then stored in a desiccatorSodium hydroxide sulfuric acid sodium borohydride ironsulfate and indigo carmine (IC) dye analytical grade werepurchased from Sigma-Aldrich Chemicals Ozone was gen-erated in situ from dry air by an ozone generator (PacificOzone Technology) with an average ozone production of0005 gdmminus3

1

3

2

4 5

76

Figure 1 Schematic of the apparatus for the ozonation reaction (1)Upflow glass bubble column reactor (2) Porous glass (gas diffuser)(3) Pacific Technology D412 ozone destroyer (4) Ozone generator(5) Dry air inlet (6) Sample valve (7) Reaction solution

22 Synthesis of Iron Particles and Iron Supported on DeoiledAllspice Husk Using porous materials is an interesting alter-native to control the stability of zero-valent particles [16] Ithas been previously reported that the employment of porousmaterials improves the stability and catalytic properties ofsupported metal particles and nanoparticles [6] In this workdeoiled allspice husk was employed as porousmaterial for thesynthesis and stabilization of metal particles The synthesisand support of iron particles on deoiled allspice husk wereas follows approximately 10 g of deoiled allspice husk (MPS)was placed in a 500mL Erlenmeyer flask and mixed with250mL of a 001M FeSO

4solution for 24 h under continuous

stirring at room temperature andN2atmosphereThen 10mL

of 01 NaOH solution was added and the resulting slurrywas kept under stirring for further half an hour After thistime 60mL of 025M NaBH

4solution was gradually added

in order to obtain the metallic particles via reaction (1) [16]After vacuum filtration the solid was washed with reagentgrade acetone and labelled as MPSFe To synthesize theunsupported iron particles (Fe-NP) 250mL of 001M FeSO

4

solution was mixed with 15mol of 01 NaOH solution and60mL of 025MNaBH

4The resulting slurry was also filtered

under vacuum and the solid was washed with reagent gradeacetone and labelled as Fe-NP

2Fe2+ + 2H2O + BH

4

minus+ 4119890minus

997888rarr 2Fe(s) + BO2

minus+ 4H+ + 2H

2(g) uarr(1)

23 Ozonation Thedifferent ozonation treatmentswere con-ducted in a 1 L upflow bubble column reactor (see Figure 1)Ozone was fed through a gas diffuser with a pore size of2 120583mAheated catalytic ozone destructor (PacificTechnologyd41202) was employed in order to destroy the excess ofozone in the outlet of the glass bubble column reactor sothere was no ozone being discharged to atmosphere Sampleswere taken at specific time intervals to be analyzed Allexperiments were carried out at room temperature (19∘C plusmn2) pH was adjusted at 30 with analytical grade sulfuric acidand sodium hydroxide and the initial IC concentration was1000mgLminus1 The assessed variables were particle size and




25 Characterization





31 Ozonation


0

02

04

06

08

1

12

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)




lowast


lowast

lowast

lowast

lowast

lowast

0100200300400500600700800900

1000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)

MPSFeMPS

NPrsquos FeOzone



3MPS) ozoneiron (O

3iron particles




lowast

lowastlowast

lowast

lowast

960965970975980985990995

100010051010

0 20 40 60 80 100

[IC] (

mg

L)

Time (min)

MPSMPSFe





3)




0

005

01

015

02

025

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)




5

15

25

35

45

55

65

75

0 10 20 30 40 50 60 70

[isat

in su

lfoni

c aci

d] (m

gL)

Time (min)

MPSMPSFe

NPFeOzone










lowast

lowast

lowast

lowast

lowast

0

50

100

150

200

250

300

350

0 5 30 60

COD

(mg

L)

Time (min)

MPS-FeMPS

OzoneNP-Fe

(a)

Indigo carmine

minusO3S

N

NN

N

O

O O

OOH

O

O

O

O

O

∙OH ∙OH

∙OH

∙OH

∙OH

∙OH

SO3

minus

H H

H

minusSO4

2minus

H2N

H2O2

H2OCO2


O∙∙

N∙∙

(b)









2(2)


2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)


6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)





2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)


2




00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)



0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)






(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




25 Characterization





31 Ozonation


0

02

04

06

08

1

12

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)




lowast


lowast

lowast

lowast

lowast

lowast

0100200300400500600700800900

1000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)

MPSFeMPS

NPrsquos FeOzone



3MPS) ozoneiron (O

3iron particles




lowast

lowastlowast

lowast

lowast

960965970975980985990995

100010051010

0 20 40 60 80 100

[IC] (

mg

L)

Time (min)

MPSMPSFe





3)




0

005

01

015

02

025

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)




5

15

25

35

45

55

65

75

0 10 20 30 40 50 60 70

[isat

in su

lfoni

c aci

d] (m

gL)

Time (min)

MPSMPSFe

NPFeOzone










lowast

lowast

lowast

lowast

lowast

0

50

100

150

200

250

300

350

0 5 30 60

COD

(mg

L)

Time (min)

MPS-FeMPS

OzoneNP-Fe

(a)

Indigo carmine

minusO3S

N

NN

N

O

O O

OOH

O

O

O

O

O

∙OH ∙OH

∙OH

∙OH

∙OH

∙OH

SO3

minus

H H

H

minusSO4

2minus

H2N

H2O2

H2OCO2


O∙∙

N∙∙

(b)









2(2)


2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)


6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)





2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)


2




00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)



0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)






(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


lowast

lowastlowast

lowast

lowast

960965970975980985990995

100010051010

0 20 40 60 80 100

[IC] (

mg

L)

Time (min)

MPSMPSFe





3)




0

005

01

015

02

025

200 300 400 500 600 700 800 900

Abso

rban

ce (a

u)

Wavelength (nm)




5

15

25

35

45

55

65

75

0 10 20 30 40 50 60 70

[isat

in su

lfoni

c aci

d] (m

gL)

Time (min)

MPSMPSFe

NPFeOzone










lowast

lowast

lowast

lowast

lowast

0

50

100

150

200

250

300

350

0 5 30 60

COD

(mg

L)

Time (min)

MPS-FeMPS

OzoneNP-Fe

(a)

Indigo carmine

minusO3S

N

NN

N

O

O O

OOH

O

O

O

O

O

∙OH ∙OH

∙OH

∙OH

∙OH

∙OH

SO3

minus

H H

H

minusSO4

2minus

H2N

H2O2

H2OCO2


O∙∙

N∙∙

(b)









2(2)


2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)


6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)





2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)


2




00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)



0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)






(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


lowast

lowast

lowast

lowast

lowast

0

50

100

150

200

250

300

350

0 5 30 60

COD

(mg

L)

Time (min)

MPS-FeMPS

OzoneNP-Fe

(a)

Indigo carmine

minusO3S

N

NN

N

O

O O

OOH

O

O

O

O

O

∙OH ∙OH

∙OH

∙OH

∙OH

∙OH

SO3

minus

H H

H

minusSO4

2minus

H2N

H2O2

H2OCO2


O∙∙

N∙∙

(b)









2(2)


2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)


6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)





2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)


2




00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)



0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)






(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





2(2)


2

∙+O2larrrarr O

2

∙+H+ (3)

2HO2

∙997888rarr O

2+H2O2

(4)


6H+ +O3+ FeO 997888rarr FeO2+ + 3H

2O (5)





2

∙+H+ (7)

RH +HO∙ 997888rarr R∙ +H2O (8)


2




00

2000

4000

6000

8000

10000

0 10 20 30 40 50 60 70

[IC] (

mg

L)

Time (min)



0

200

400

600

800

1000

1200

00 100 200 300 400 500 600 700

[IC] (

mg

L)

Time (min)






(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a)

100

50

0

OCaK


(b)

Energy (keV)2 4 6 8

80

60

40

20

0

O Na

AJSi

S K Ca Fe

(c)

(d)











119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






119900) = 0990





4 Conclusions




Acknowledgments


References

























2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






2 Fenton








2O2UV


2O2rdquo
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

research article ozonation of indigo carmine enhanced by...

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