Applied Catalysis B Envuonmental3 ( 1994) 335-350

ELSEVIER

Effect of Fenton and photo-Fenton reactions on the

degradation and biodegradability of 2 and
4-nitrophenols in water treatment
J. Klwla*, C. Pulgarinb, P PermgeP
Inshturde Chrmre Phystque, Ecole Polytechnrque F.4aYrale de Lausanne. CH-1015 Lousanne, Swrtzerkmd
bbzshtut

Gime a2 IEnvlronment, Luboratorre de Genre Blologlque. Ecole Polytechnrque FtWrale a2 L.ausanne,

CH-1015 Lausanne, Swrtzerland

(Received 16 November 1993,revtsed 21 January 1994,accepted 21 January 1994)

Abstract

Photo-Fenton, Fenton and biodegradation reactions have been mveshgated m &tat1 dunng the degradation of 2 and 4-mtrophenols Fenton-type reactions accelerated mtrophenols degradation in companson with duect photolysls using pyrex flasks (A > 290 nm) The mfluence of Fe+, H,Oz. hght,
temperature, reactant concentration and gas atmosphere was systematically studied Expenmental
techniques used involved total orgamc carbon determmatlon (TOC), high pressure liquid chromatography ( HPLC) , nuclear magnetic resonance (NMR) and spectroscopy (OD) A solution contammg 3 6 10e3 M of 2-mtrophenol was degraded in ca 3 h (30C) m the dark and in ca 1 h (30C)
under hght where contmuous photoproduchon of the Fenton reagent IS achieved This study shows
that the hydroxylahon of the phenol nng IS fast as compared to the slower conconutant decrease m
DOC m dark or light processes Using NMR an explanation ISproposed m terms of pathways mvolvmg
direct oxidation of the mtrophenols under study by hydroxy type radicals Chenucal insight ISprovided
why the photo-Fenton degradation observed for 2-mtrophenol proceeds at ahout half the rate than his
homologue 4-mtrophenol Blodegradabllity of 2-mtrophenol was monitored before and after photoFenton treatment by hochenucal oxygen demand (BOD) and dissolved organic carbon (JIOC) and
m&cated the formation of substances which are non-biodegradable dunng photo-Fenton pretreatment
Key words

hochenucal oxygen demand, dissolved organic carbon, nitrophenols, organic carbon, photo-Fenton,

water treatment

1. Introduction
Nltrophenols are among the most common families of persistent pollutants
waste waters Their degradation to less dangerous materials or mmerahzatlon
*Correspondmng
author
0926-3373/94/$07 00 6 1994Elsevier Science B V All nghts reserved
SSDIO926-3313

(94)00008-3

m mdustnal
IS a difficult

336

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process involving bmdegradatlon

or oxidation via natural processes [ l-31 Nltrophenols
have also been present m the degradation of pestlcldes hke parathion and mtrofen [4,5]
Recently, direct photodegradation
has been studied as a possible method for degrading
mtrophenols [5,6] Direct photolysls has not been found to be an effective method for
degrading mtrophenols using UV light m a homogeneous solution [ 5,6]
Usual methods to elunmate mtrophenols m water treatment have been homogeneous m
nature ozone, HzOz or both Also C102 has been used as an oxidant [6] Recently the
oxldatlon of benzemc rmg compounds by Fentons reagent m dark or light dnven reactions
has been used m pollutant degradauon due to the high oxldabve power (2 8 eV) of the
OH radical Only a few studies have been pubhshed using photo-Fenton or Fenton reactions
m the destruction of complex organic molecules [7-131 The hydroxide radicals OH can
also be produced m heterogeneous processes [ 3,6] In the particular case of mtrophenols,
degradation has recently been reported via TIOZ semiconductor dlsperslons [ 14-161
In the present study we also use water sewage bactena to assess the time necessary for
blologlcal degradation of 2-mtrophenol (taken as an adequate model compound)
Nltrophenols are corrosive and persistent mater&
found m sewage plants [2,3] Also more
mformatlon 1s needed to assess the rate of blologlcal degradation m waste water treatment
Until now anaerobic biodegradation
[ 171 has been studied over a long penod of time This
compound degraded at reasonable rates under aerobic condltlons [ 181 Nevertheless, the
aqueous biodegradation
(aerobic) has been reported to be of the order of seven days [ 191
The photooxldatlon half life based on OH reactions (m water) has been reported to vary
from three weeks to years [ 191 Ngtrophenols have been recognized as priority pollutants
The allowed concentrations
from 1 to 20 ppb [ 201 m lakes and fresh water reservoirs
Justifies the search for new punficatlon methods showing low cost and possible practical
value

2. Experimental

2- and 4-mtrophenol
(Fluka purlss, > 99%) were used as supplied Photolysls expenments were carried out m 60 ml Pyrex flasks with A > 290 nm by means of a 80 mW/cm
(AM1 ) Hanau Suntest Lamp The electrical power of this lamp was 2 1 kVA High performance liquid chromatography
(HPLC) was carned out via a Vanan 5500 unit A
Spherlsorb slllca column (HPLC Technology 50DS-2) with water-methanol
gradient elutlon was used and the signal observed with a UV detector at A = 3 15 nm and 280 nm for 4mtrophenol and 2-mtrophenol, respectively
Total organic carbon (TOC) was monitored during degradation via a Shlmadzu-500
mstrument eqmpped with an automatic sample injector Proton nuclear magnetic resonance
(NMR) was carried out by means of a Bruker ACP-2000 Spectrometnc analysis (OD)
was performed via a Hewlett-Packard 386/2ON diode array Blologlcal oxygen degradation
(BOD) was carned out by means of a BSB Controller Model 1020 T (WTW) The unit
was thermostated at 20C and urban waste water, after a primary decanting, was used as
moculum

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337

3. Resultsand discussion

The mrtral concentrations of 2-mtrophenol durmg the course of the direct photolysls 1s
shown m the upper trace of Fig 1 (up to 24 h) The progress of the reaction was followed
using the HPLC method The yields of the reactlons were determmed from the decrease m
the pollutant HPLC peak The solution used was 3 6 10m3M of 2-mtrophenol (40 mg/80
ml) and was lrradlated in the presence of oxygen mslde a Suntest lamp at 30C Fe3+-ion
(14 low4 M) was added to this solution and the 2-mtrophenol was decreased by 27% of
the mltlal concentration over a period of 24 h As seen from Fig 1 the photolysls m the
presence of Hz02 (0 25 1O- M) m the dark and under mrradlationfurther increased the
decomposlhon of 2-mtrophenol Photolysls of acldlc solutions of Hz02 give OH radicals
as primary photoproducts [ 2 1]
H202-2

hv

OH

(1)

along with small amounts of HO* radicals

hv
H202 -H

+HOz

(2)

Since H202 absorbs up to 320 nm although very weakly at the concentrations used, the 2mtrophenols (O,N-C,H,-OH)
havmg peaks at 352,280 and 210 nm absorb up to 80% of
the incident radiation of the Suntest lamp (AM 1) down to 270 nm Under these condlhons
the u-radiated 2-mtrophenol forms a tiplet state [ 221 that reacts with H202 [ 3,8] e g
HO-&H,

-NO:

+H,O,----,

HO-C&&, -NOzH

+HOz

(3)

It was also observed that, when solutions with H202 and 2-mtrophenol were irradiated m
Fig 1, photoproducts developed, resulting m a darkemng of the solution HPLC results
have been reported to show formation of hydroqumones, benzoqumones and mtrophenols
(2-position) [ 221 Nltrocatechols were previously referred in 2-tutrophenol degradation as
due to hydroxylatlon of this compound[ 231 We did not elaborate further on mechamsfic
studies of mtermedlates present m 2-mtrophenol degradation
Fig 2 presents the beneficial effect of temperature and lrradrahon on the degradation of
2-tutrophenol Using Fe 3+ /H,O,/hght results m a greater decomposltlon of 2-mtrophenol
than can be expected by combmmg the separate elements as shown m Fig 1 The solution
used contained 3 6 10m3 M (40 mg m 80 ml) of 2-mtrophenol, 14 10e4 M of Fe3+ (4 9
mg Fe(N03)3 xHzO m 80 ml) and 0 25 10-l M HzOz (120 ~1.1180ml) Trace (a) represents the values obtamed m the dark at 30C and trace (b) the results of 2-mtrophenol
degradatron wrth the same system under light at 30C Traces ( c) and ( d) show expenmental
runs at 60 m the dark and light for the same system By mspectton it IS readily seen that a
photo-Fenton reagent generates more efficiently radicals of the OH type than m the dark
Several concentratrons were trred for the Fe3+ photommator and the concentratron used
was efficient m our process Higher concentrations of Fe 3+ did not monotomcally increase
the rate of the photo-Fenton reactron reported m Fig 2 Under the expenmental condmons
Fe3+-ion 1s known to promote decomposmon of H202 [ 131
Fe3++H

2 0 2-H02

+H++Fe+

(4)

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.I Krwt et al /Applred Catalysts B Envrronmental3 (1994) 33.5-350

H202

---

-------

H202

10

dark

light

20

hoursFig 1 Photodegmdationof 2-mtrophenoldetectedby HPLC (a) Duwt photolyslsof 2-mtrophenol(40 mg/ 80

ml of H,O),(b) 4 4 mg Fe3+/80 ml solution added to the same solution, (c) addmg 100 ~1 H,OJ80 ml m the
dark and (d) same H20z added but m hght
or accordmg to the mechamsm
Fe3+ +H,O

hu

with Fe+ Ion addmonally

Fe++H

2 0 *-

OH+H+
producing

+Fe*+

(5)

OH radicals

OH+OH-+Fe3+

(6)

Fig 2 also shows the beneficial effect of temperature on the light achvated degradation
The time 1s reduced by 40% for dark processes [traces (a) and (b) ] and 50% for similar
processes under light The importance of this observation resides m the fact that 2-mtrophenol degradation could be induced by sunlight (m the 290-400 nm region) where
temperatures above 30C are available m nature under favourable conditions
Fig 2 shows that hght improves the action of the system Fe2 +-H202 (Jiiq 6) significantly
This has previously been reported [ 3,10,11,13]
The degradation of 2-mtrophenol seems
to favour the regeneration of Fe*+ -ions m reaction (6) Fe*+ produces many OH radicals,
m contrast to the dark Fenton system where Fe *+ OH = 1 1, as was recently shown for

J KIWI et al /Applted

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339

t
=
E
0
OD

minutes

Fig 2 2-Nltrophenol (14 10e4 dark and photodegradatlon wa Fenton reagent (a) 30C. dark reduction, Fe3+
(3 6 IO-? and H,Oz (0 25 10-l I) added, (b) same but under light, (c) same as (a) but at 60C dark reachon
and (d) same as trace (c) but under hght

Fenton degradation of 4-chlorophenol

[ 111 Any mtrous acid formed ~111,as a result of the
excess H202 present, be oxidized to mtnc acid Fig 2 also shows that the amount of iron
salt necessary 1s small which would mmlmlze the iron ions separation after waste water
treatment
Reactions (4)-( 6) have been camed out at an mltlal pH of 3 0 to 3 5 arriving at a final
pH of a half unit lower The final pH of all solutions decreased due to the formation of
mtrouslmmc
acid No acldlficahon was necessary since the pH of the mltlal solution was
low enough to keep the solutions homogeneous Fe3+ -ions at higher pH values exist mamly
as an msoluble oxide-hydroxide
phase At pH = 3, as used throughout this work, the Fe3+
exists as Fe(OH)*+, an hydroxy complex showing a charge transfer band with E = 2050
M- cm- at 295 nm [24]
To report the degradation values for 2-mtrophenol obtained by HPLC shown m Fig 2
we have stopped the actlon of H202 by catalase at the times indicated m each trace This
enzyme would decompose any residual H202 [25] The dlsmutatlon at H202 by catalase
occurs via the formation of an intermediate iron-peroxo complex Blank experiments did
not show any interference of catalase decomposltlon on the degradations under study

I Krwt et al /Apphed Catalysrs B Envwonmental3 (1994) 335-350

340

In the run reported m Fig 2, the overall oxldatlon of 2-mtrophenol

be expressed

by

OH radicals could

-H
OH -O,N-C6Hj

02N-CgH4-OH+
- (OW,-

mtermedlates-

COz +H,O+H+

+NO,/NO;

(7)

and the overall reaction could be wntten

C6H,N03

+6

0H(3H,02)

+ 1/202-

6C02 + 5H202 + HN03

Interestingly enough reactions 1 to 6 show that only H202 1s consumed

degradation process as seen hereby
Fe2+ +H 0
0H+Fe3
f
0H + Hz02

(8)
during the hght

+ Fe3+ + OH+OHOH + 00H+Fe2+

+H+

(9)

+ OOH + H,O

2- nltrophenol

hours

Fig 3 TOC dark degradation at 30C and 60C for a solution contammg 500 mg/l of 2-mtrophenol as a funcbon

of ume

.I KIWI et al /Applred

Catalysts B

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(1994)

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341

(pNo2
.;; ~No2+c
)

OH
k2

*OH
J

0
NO2

CO2 +

H20

J
k3

[ ahphatic compounds]

CO2 + H20
Scheme

+ CO2 +

H20

H+/NO,

Fig 3 shows the degradation of 2-mtrophenol at two different temperatures m the dark using
Fe3+ /H202 system ( 14 10e4 M Fe3+ , 0 25 10-l M H202) on the usual 3 6 10m3 M 2mtrophenol Fig 2 showed a slgmficantly higher rate of dark degradation m traces (a) 30C
and (b) 60C for 2-mtrophenol as measured by HPLC than by the total organic carbon
degradation (TOC) reported m Fig 3 From Figs 2 and 3 it 1s readdy seen that two processes
are takmg place side by side leading to degradation of 2-mtrophenol These processes could
be represented m Scheme 1 In this scheme it 1s considered that the overall rate for TOC or
(DOC) degradation at 60C m the first 2 h as seen m Fig 3 is ca 10 times faster than the

342

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Catalysts B Envrronmental3

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1ao-

28

30

i/-r IO-~

31

32

Fig 4 khemus
plot as a function of temperature for dark degradon
conditions are as m Fig 3

of 2-mtrophenol

Other expenmental

rate subsequently observed for this reactron between 2 and 5 h The rate found for k, by
HPLC m Fig 2 (disappearance of 2-mtrophenol m 2 h) 1s m agreement with the observatron
that this 1s an caster process than the observed DOC decrease of ahphattc mtermedtates m
phenol degradation [ 26,271 Therefore kt = k2 = k3 B b The mtermedtates proposed here
are consistent wtth those found when stmrlar aromatics are reacted with a well known source
of hydroxy radicals For example the photocatalytrc degradation products of halogenated
aromatic compounds are typtcally hydroxylated structures [ 28-301 From Frgs 2 and 3 it
IS seen that the DOC decrease of 2-mtrophenol and cychc mtermedrates are much faster
processes than the mmerahsatron of alrphattc mtermedtates The steps m Scheme 1 are not
balanced stotchtometrtcally
It IS meant only to show that DOC decrease 1s taking place
along with hydroxylatton of 2-mtrophenol, conststent with results presented m Figs 2 and
6 Moreover the benzophenones
are known to be unstable [28-301 and also to degrade
easily
Energies of acttvatron for 2-mtrophenol degradation m the dark (as measured by TOC)
can be estimated from dark degradation expenments carried out between 30 and 75C and
results are presented m Fig 4 Over the first hour of reaction the tangent of log k over 11
10e3 K- Indicate an apparent acttvatron energy of 9 6 k.I/mol This observation leads to
three conclustons
(a) that the Fenton treatment could be used at temperatures close to

J Krw~ et al /Applied

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343

(1994) 335-350

ambient, (b) that the thermally activated reactlons takmg place m the process are not
Important, and (c) that the vanatlons of the mltlal rate r. m the range 303-378 K follow
the Arrhemus law
Fig 5 presents the degradation m the dark at 30C of 2-mtrophenol using the same
concentrations of H,O1 and Fe3 * ions as m Fig 1, but varymg the 2-mtrophenol concentrations between 0 45 10m3M (62 5 mg/80 ml) and 3 6 lop3 M (500 mg/80 ml) The
results shown m Fig 5 indicate that for the three concentrations up to ca 1 h, the degradation
curves of TOC can be fitted wlthm expenmental error to a zero-order law This would
indicate excess H202 as a reagent determmes the kinetics of degradation and not the mltlal
amount of 2-mtrophenol The three higher concentrations degrading mltlally with about the
same slope reflect also a steady-state OH radical concentration, which 1s the active agent
during the degradation process The degradation observed by TOC m Fig 5 durmg the first
hour then follows a zero-order expression
k (mg C/l/h) = -y=k(OH)
The radicals OH either attack the substrate (reaction 8) or recombme to H202
Fig 6 presents the degradation of 4-mtrophenol as seen by HPLC usmg the mltlal
concentration of this reagent shown m the graph, 0 25 10-l h4 m H,O, and 14 10e4 M
500

0
0

Rg 5 Dark degradation of 2-mtrophenol as a function of uutml reactant concentrabon (a) 2-mtrophenol3 6 lo- 3
IU, (b) 2-mtrophenol 1 8 10-j. (c) 2-mtrophenol0 9 10m3 For other expenmental deta& see text

344

J KIWZet al / Applied Catalysrs B Envtronmental3 (1994) 335-350

50

dark 60C

light 60C

minutes

Rg 6 Dark and photodegradatlon

of 4-mtrophenol at 60C as a function of time m the presence of 4 4 mg Fe3+
and 100 ~1 H20J80 ml solutlon measured via HPLC
m Fe3+-ion
In this case only a slight Increase 1s seen for the photo-Fenton over the Fenton
reaction Under hght 4-mtrophenol degradation proceeds two times faster (30 mm) as seen
m Fig 6 than 2-mtrophenol (60 mm) m Fig 2, trace d This result 1s mterestmg, knowing
that the rates of OH attack are about the same [ 3 1] The mtro group is a known electron
withdrawing group [ 181 In a benzemc rmg the nltro wlthdrawmg effect 1s preferentially
marked m ortho and paru posltlons and m 2-mtrophenol hydroxylatlon of the 6-posltlon
leads to a dlhydroxy compound as shown below

OH

OH

OH

NO2

J Klwt et al /Applted Catalysrs B Envwonmental3 (1994) 335-350

345

In the case of hydroxylated 4-mtrophenol, the two bonds between the adjacent OH groups
might undergo easy oxldatlve sclsslon, but only one bond of this type is found m 2mtrophenol hydroxylatlon
This explams m a quantitative way the structure-reactivity
relationship for 2 and 4-mtrophenol degradation times This explains why the photo-Fenton
degradation observed for 2-mtrophenol proceeds at about half the rate than hu homologue
4-mtrophenol
The results have been presented m Fig 6 for 4-mtrophenol degradation and
are different to the photocatalytlc results presented m ref [ 101 where a different lamp and
concentrations of mltlal reagents were employed Augugharo et al [ 141, m a recent study,
also report 4-mtrophenol photodegradation using T102 suspension as a catalyst over periods
of more than 5 h
Fig 7 presents TOC results for 4-mtrophenol
(3 6 10m3 M) degradation using H,O,
0 25 10-l A4 and m trace (a) reaction m the dark with Fe3+-ion 4 4 mg/80 ml or 1 4 10e4
M In trace (b) Fe3+ -ion 1 1 mg/80 ml 1s used under light lrradlatlon and this amount is
increased m traces (c), (d) and (e) using 2 2,4 4, and 11 mg/80 cm3, respectively These
results show the Judicious choice made during this study of using 4 4 mg Fe3+-ion as
photomltlator m the photo-Fenton
4-mtrophenol could m practice not have been degraded
300

l-nitrophenol

d
0

hours

Fig 7 Degradation of 4-mtrophenol500

ml/l mmai concentration with Fenton reagent as m Fig 5 with (a) 4 4
mg Fe3+/ 80 ml m the dark, (b) 1 1 mg Fe3+ /80 ml under hght, (c) 2 2 mg Fe3+/80 ml under hght, (d) 4 4
mg Fe3+/80 ml under hght and (e) 11 mg Fe3+/80 ml under hght

J KIWIet al /Applred Catalysts B Envrronmental3 (1594) 335-350

344

T--

-- 8

- -1--.

-r--r-

4
PPH

-7-

-7-7

J KIWIet al /Applied Catalysts B Envwonmental3 (1994) 335-350

347

160

60

60

40

0
1

Days

Fig 9 Blochemtcal oxygen demand (BOD) and dissolved orgamc carbon (DOC) as a fun&on of time dormg
2-mtrophenol bmdegradatton

in a faster way (Fig 6) If a higher concentration of Fe3+-Ion would have been used The
detrimental effect of higher concentrations hmltmg the light activated process 1s due to the
enhanced light absorption m the charge transfer band of Fe( OH) *+ at higher concentrations
This m turn blocks the posslblhty for direct light absorption by 4-mtrophenol and H202 rn
the photo-Fenton system active m reactions (4-8)
Fenton degradation of a solution contammg 3 6 10e3 M 2-mtrophenol,
1 4 10e4 of
Fe3+ and 0 25 lo- M H202 was carried (like m trace d, Fig 2) Ihe products of this
reaction as a function of time were examined by H-NMR spectroscopy and are shown m
Fig 8 After 1 5 h of u-radlatlon, the signals of the aromatic protons (7 to 8 3 ppm) show a
different nature m spectrum (b) than m spectrum (a) at time 0 This IS mdlcatlve of nondestructive modlficatlon of the aromatic cycle (e g hydroxylatlon)
Concomitantly, signals

Fig 8 H-NMR spectra of 2mtrophenol

as described III Ftg 2

at reaction rimes (a) 0 h, (b) 1 5 h and (c) 2 5 h using Fenton reagent

348

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(1994) 335-350

appear correspondmg to vrnyl protons at 6 3 ppm Spectrum (c) shows that after 2 5 h of
n-radiation, the signal of the aromatic protons has completely disappeared while the ones of
ahphatlc species with electron withdrawing character at 4 1 ppm persisted Photodegradatlon
of tbe substrate would seem to occur m two steps a rapid one destroying the aromatic
groups, followed by much slower oxldatlon of the ahphatlc chams
Blochemlcal oxygen demand (BOD) for a system contammg 14 lop3 M 2-mtrophenol
and water sewage IS shown m Fig 9 The aim was to quantify the oxygen utlhzed during
the degradation of 2-mtrophenol by waste water bacteria Three bottles were taken for each
sample contammg the N, P nutrients required during the blologlcal process Water sewage
was taken after the mltlal decanting process of the Vldy (VD, Switzerland) blologlcal waste
water treatment plant This solution was further decanted after 24 h and filtered through
cotton The oxygen consumed 1s measured as indicated m the experimental part Blank

120

60

60

Days Rg 10 Bmdegmdatlon of 2-mtrophenol soluhon as reported m Rg

for 3 h For other expenmental condltlons see text

9 but applymg

photo-Fenton

pretreatment

.I KIWI et al /Applred

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349

BOD reference runs are carned out with bactena only The formula used to calculate the
BOD reported m Fig 9 1s
BOD = [ BOD measured - 0 01 (% moculum X BOD moculum) ]
( 100 - % inoculum) X 0 01
The percentage moculum was 20% The 2-mtrophenol solution used here contamed 180
mg/l or the equivalent of 92 mg C/l This solution has a chemical oxygen demand (COD)
of 318 mg 02/1 During the five-day degradation penod the dissolved oxygen carbon DOC
was followed In Fig 9 it shows a slow adaptation permd for bactenal action up to three
days Afterwards, BOD values go up from 12 mg 0*/l day to 80 mg 0*/l day and DOC
values from 6 mg C/l day to 25 mg C/l day The ratio BODJCOD obtamed 1s0 61 which
corresponds to biodegradable substances [ 18,191
Fig 10 presents the results for the same 2-mtrophenol bactena system as reported m Fig
9 m which a light pretreatment for 3 h has been applied m the presence of Fe3+-ions and
H202 as reported m Fig 2, trace (d) This was intended to test the bacterial action on
systems where the aromatic rmg of the 2-mtrophenol has been already degraded (see Fig
8) Fig 10 shows that the products formed m this case are less biodegradable than when
no photo-Fenton pretreatment was used (Fig 9) In this case the mltlal solution used had
a chemical oxygen demand (COD) of 200 mg OJl and, as shown m Fig 10, a BODS of
50 mg/l was attamed This mdlcates a BODS/COD value of 0 25 Fig 10 shows that only
15 mg C/l is blodegraded during the first day and that a stationary BOD 1s attamed and It
mamtams a steady value until the end of the experiment Therefore the photo-Fenton
treatment leads to the formation of mtermedlates not readily attacked by bactena during the
time of a BOD, expenment An accelerated bacterial action on 2-mtrophenol after photoFenton pretreatment was not observed here as reported recently for another organic pollutant
when photocatalytlc pretreatment was beneficially coupled with bacterial degradation m
water treatment [ 8,121

4. Conclusions
This study shows efficient photo- and dark oxldatlon via Fenton-like reactions on 2 and
4-mtrophenols Since the Fe+ /Fe3+-ion concentration added is small, such processes
would not pose any problems m waste water sewage plants H202 concomitantly used m
this process 1s an ecological oxidant glvmg only oxygen and water as reaction products
Work was carried out m the pH range 2 5 to 3, the natural pH for the mtrophenols under
study Acldlty decreased durmg the degradation due to formation of HN03 mamtammg
homogeneity during the degradation process Our measurements show that light irradiation
improves the effectiveness of the Fe 3+-H,02 system Chemical degradation and photodegradation of mtrophenols 1s much quicker than blologlcal degradation by sewage bactena
By Nh4R techniques we have shown rapld rmg dearomatlzatlon with progressive hydroxylatlon of the aromatic moiety and breakage of the aromatic rmg The complete mmerahzatlon of the 4-mtrophenol (see Fig 7) with the absence of dangerous residual compounds
may allow photo-Fenton processes to be used under visible light m waste treatment plants

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References
[ 11 M Nagakawa and D Crosby, J Agr Food Chem ,22 ( 1974) 849
[2] List of Worldwide Hazardous Chermcals aud Pollutants, The Forum for Sclentltic Excellence, J B Llppmcot
Co, New York, 1990
[3] E Pehzzetti and M Schlavello (Editors), Photochermcal Conversion and Storage of Solar Energy, Kluwer,
Dordrecht, 1991
[4] P Mealher. J Nury, B Pouyet and J Bashde, Chemosphere, 12 ( 1977) 815
[5] P Ahf, P Boule and J Lemaue, J Photochem Photoblol A ,50 ( 1990) 331
[6] 0 Legnm, E Ohvelros and A M Braun, Chem Rev, 93 (1993) 671
[ 71 C Matllard, Ch Gtullard and P P~chat,Chemosphere, 24 ( 1992) 1085
[8] J I(~wI,C Pulgann, P Pennger and M Gratzel, Appl Catal B, 3 (1993) 85
[9] A Sclafam, L Palmtsano and E Dave, J Photochem Photoblol A 56 (1991) 113
[ 101 E Lipczynska-Kochany, Chemosphere, 24 (1992) 1369
[ 111 G Ruppert, R Bauer and G Hetsler, J Photochem Photoblol A , Chenustry, 73 ( 1993) 75
[ 121 J hwl, C Pulgarm, P Pennger and M Griitzel, New J Chem ,17 (1993) 487
[ 131 M Halmann, J Photochem Photoblol A, 66 ( 1992) 215
[ 141 V Augugharo, L Pahmsano, M Schlavello, A Sclafaul, L Marchese, G Martra and F Mmno, Appl Catal,
69(1991)323
[ 151 V Augugharo, M Lopez, L Palrmsano and J Sona, Appl Catal A, 101 f 1993) 7
[ 161 M Dteckmann, K Gray and P Kamat, Wat Scl Tech, 25 (1992) 277
[ 1710 OConnor and L Young, Envvon Toxlcol Chem ,8 (1989) 853
[ 181 P pitter and J Chudoba, Bmdegradablhty of Organtc Substances m the Aquattc Envuonment, CRC Press,
Boca Raton, 1990
[ 191 Ph Howard, Handbook of EnvIronmental Degradauon Rates, Lewis, Washmgton DC, 1989, pp 336-337
(201 J Patterson (EdItor), Instrumental Waste Water Treatment Technology, Butterwotth, Boston, 1985, p 3
[21] J Baxendale and J Wilson, Tram Faraday Sot ,53 ( 1957) 344
[22] E Lipczynska-Kochany. Envtron Tech01 Lett , 12 (1991) 87
[23] 0 Volkert, G Termens and D Schulte-Frohhnde, Z Phys Chem (56 ( 1967) 261
[24] B Faust and J Holgne, J Atmos Environ ,24A ( 1990) 79
[25] J Frew and P Jones, Adv Inorg Blomorg Mech ,3 ( 1984) 175
[ 261 W Barb J Baxendale, P George and K Hargrave, Tram Faraday Sot ,47 (1951) 591
[27] Ch Comnmelhs and C Pulgann, J Appl Electrochem ,58 (1991) 703
[28] H AI-Ekabl, N Serpone, E Pellzzettl, M Fox and B Draper, LangmuIr, 5 ( 1989) 250
[29] D Olhs, C Hslao, L Budlman and C Lee, J Catal 88 (1984) 89
[30] S Turchl and D Olhs, J Catal, 119 (1989) 480
[ 311 G Buxton, C Greenstock, P Helman and A Ross, J Phys Chem Ref Data, 17 ( 1988) 513