Reaction Pathways and Mechanisms of Phot

Journal of Photochemistry and Photobiology B: Biology 67 (2002) 71–108
www.elsevier.com / locate / jphotobiol
Invited Review
Reaction pathways and mechanisms of photodegradation of pesticides

H.D. Burrows a , M. Canle L b , *, J.A. Santaballa b , S. Steenken c
a
´
Departamento de Quımica , Universidade de Coimbra, 3004 -535 Coimbra, Portugal
b
´
Departamento de Quımica ´
Fısica ˜ ´ Quımica
e Enxenerıa ´ ˜ , Rua
I, Universidade da Coruna ˜ , Galicia, Spain
´ Alejandro de la Sota 1, E-15008 A Coruna
c
¨ Strahlenchemie, D-45413 Mulheim
Max-Planck Institut f ur ¨ an der Ruhr, Germany
Received 26 March 2001; accepted 25 February 2002
Abstract
The photodegradation of pesticides is reviewed, with particular reference to the studies that describe the mechanisms of the processes
involved, the nature of reactive intermediates and final products. Potential use of photochemical processes in advanced oxidation methods
for water treatment is also discussed. Processes considered include direct photolysis leading to homolysis or heterolysis of the pesticide,
photosensitized photodegradation by singlet oxygen and a variety of metal complexes, photolysis in heterogeneous media and degradation
by reaction with intermediates generated by photolytic or radiolytic means.  2002 Elsevier Science B.V. All rights reserved.
Keywords: Pesticides; Photodegradation; Photoionization; Photocatalysis; Photosensitization; Photolysis; Hydroxyl radicals
1. Introduction worsen with the appearance of new and more sophisticated

substances.
Due to the world-wide general application of intensive The critical nature of this environmental problem has
agricultural methods during the last few decades and to the prompted the development of faster and more accurate
large-scale development of the agrochemical industry, the methods for the characterisation and quantification of the
variety and quantities of agrochemicals present in con- pesticides dispersed in the environment. These have gener-
tinental and marine natural waters has dramatically in- ally been very successful. However, until now no com-
creased. Most pesticides are resistant to chemical and / or pletely efficient methods have been developed for remedia-
photochemical degradation under typical environmental tion of contaminated waters [16].
conditions [1]. In recent years, the scientific community Advanced oxidation processes (AOPs) are at present
has shown a great concern about the possible adverse considered to have considerable potential in this area and a
effects that the presence of these pesticides in water and general survey of these can be found in the review by
food [2] may have for human health and for the equilib- Legrini et al. [17] The most efficient of these used
rium of ecosystems [3–7]. Such concern, which has nowadays involve the use of UV irradiation with light of
recently been highlighted [8,9], is supported by results an appropriate wavelength [18–21]. The method is based
from major monitoring studies already performed over 20 on the ability of UV radiation to attack and damage the
years ago [10], and confirmed by more recent inves- DNA of undesirable microorganisms. As a consequence,
tigations. Among the possible chronic effects of these photochemical processes may take place, in which differ-
compounds are carcinogenesis [11,12], neurotoxicity [13], ent transient species are generated: e 2aq (photoionization),
effects on reproduction [14] and cell development effects, radicals generated by bond homolysis or bond heterolysis,
particularly in the early stages of life [15]. With increasing etc, as well as a number of photophysical processes
global demand for vegetables, the situation does not look (fluorescence, phosphorescence, etc.) Alternatively, UV-
likely to improve. In fact, the current situation might sensitive materials may be added to give rise to photo-
sensitized oxidation, that allow the use of wavelengths that
are not absorbed by the pesticides [17]. Hydroxyl radical
*Corresponding author. Tel.: 134-981-167-000x2150; fax: 134-981-
(HO ? ) might also be generated by various different ways,
167-065.
E-mail addresses: [email protected] (H.D. Burrows), [email protected] giving rise to induced photodegradation.
(M. Canle L), [email protected] (J.A. Santaballa), steenken@mpi- The regulations for the control of the quality of water
muelheim.mpg.de (S. Steenken). for human use in the European Union clearly establishes
1011-1344 / 02 / $ – see front matter  2002 Elsevier Science B.V. All rights reserved.
PII: S1011-1344( 02 )00277-4
72 H.D. Burrows et al. / Journal of Photochemistry and Photobiology B: Biology 67 (2002) 71 – 108
the maximum admissible values of different substances in evaluate or authoritatively criticise the cited literature, but
solution [22]. Among these, pesticides are identified as hope that this review will stimulate more detailed analyses
toxic, with very low concentrations of them in general of the data in each of the particular areas discussed.
being allowed (a maximum permissible concentration for a
particular pesticide of 0.1 ppb and of 0.5 ppb for the total
load of all plaguicides). In addition, these regulations also 2. Direct photodegradation
establish maximum concentrations for the products of
degradation of pesticides [23,22]. No maximum concen- Most pesticides show UV–Vis absorption bands at
tration levels have been established in the USA, the relatively short UV wavelengths. Since sunlight reaching
regulations depending on the particular compounds, based the Earth’s surface (mainly UV-A, with varying amounts of
on the toxicological evidences available for them [24]. UV-B) contains only a very small amount of short wave-
The literature reports on pesticide photodegradation length UV radiation [32,33], the direct photodegradation of
products is relatively abundant. However, little information pesticides by sunlight is expected to be, in general, of only
is available on the reaction mechanisms involved in the limited importance. Abundant studies are available, how-
photolysis of pesticides under typical environmental con- ever, with steady state and / or laser-pulsed UV radiation.
ditions [1]. The environmental photochemistry of her- Direct irradiation will lead to the promotion of the
bicides was reviewed several years ago [25]. Similarly, the pesticides to their excited singlet states, which may then
kinetics and mechanisms of photodegradation of chloro- intersystem cross to produce triplet states. Such excited
phenol pesticides have recently been discussed [26]. states can then undergo, among other processes: (i)
Considering the environmental relevance and impor- homolysis, (ii) heterolysis or (iii) photoionization, as
tance of this problem, we review the state-of-the-art depicted in Scheme 1.
situation on the photodegradation of pesticides. These will Because of the particular relevance to the photoreactivi-
be classified in terms of the main structural groups, ty of these pesticides under sunlight, relevant references to
following a chronological order within each group. We product identification, kinetics, mechanisms and toxicity of
shall concentrate on the behaviour in solution and on solid degradation products are summarised in Table 1. More
supports. The photochemical decomposition of pesticides detailed information of photoreactivity under both solar
and herbicides on plants, on model plant systems and on and ultraviolet irradiation is given in the following sec-
soil is of fundamental importance to the situation in vivo. tions.
Some studies in this area, notably on model plant cuticles,
are presented in Section 2. However, much less detailed 2.1. Amidinohydrazone insecticides
mechanistic information is available in this case, and we
feel, that as a first approximation, it is not unreasonable to Adityachaudhury et al. [34] studied the sunlight photo-
extrapolate the behaviour from solution or solid supports to degradation of hydramethylnon h5,5-dimethylperhydro-
these systems. Most papers reviewed are from the last pyrimidin - 2 - one - 4 - trifluoromethyl - a - (4 - trifluorome-
decade, although some previous articles have also been thylstyryl) cinnamylidenehydrazonej and found three prod-
included to facilitate understanding of mechanistic path- ucts. Transformation took place within 10 h, with the rate
ways. Although the production and use of some of the of disappearance being only marginally affected by the
pesticides discussed has been discontinued, we have still acidity of the medium.
considered them, because of their possible persistence in
the environment. In identifying products, we report a 2.2. Anilide herbicides
systematic name in all cases, as some of the common
commercial names have changed through the years (CAS Tanaka et al. [35] studied the formation of biphenyls
names are given in those cases where no systematic name upon sunlight photolysis of propanil h39,49-dichloro-
has been found). In addition, we note that several excellent propionanilidej. Coupling of two herbicide molecules took
compendia are available compiling the different names and place, leading to formation of a chlorinated biphenyl, with
properties of the various different compounds [27–31]. We
have chosen to classify the photodegradation studies into
four broad categories: direct photodegradation, photosen-
sitized degradation, photocatalyzed degradation and degra-
dation by reaction with hydroxyl radical. Within each
group these are discussed in terms of general classes of
compounds. However, in some cases these categories
overlap. In such situations, we have tried to fit the work to
the field that is the authors’ main target area. Finally, our
aim in this review is to compile and annotate the main
reaction types and mechanisms. We do not attempt to Scheme 1. Possible chemical events taking place upon direct photolysis.
H.D. Burrows et al. / Journal of Photochemistry and Photobiology B: Biology 67 (2002) 71 – 108 73
Table 1
Studies on pesticides photodegradation under sunlight or simulated sunlight
Compounds Product Kinetics Mechanistic Toxicity
identification studies measurements
Amidinohydrazones [34] [34]
Anilides [35] [36–38] [39]
Avermectins [40]
Carbamates [35,41,42,34,43–46,37] [47,48] [49]
Carboxamides [50]
Chloronicotinoids [51,52]
Chlorophenols [53] [53,54]
Dicarboximides [55]
Dichloroanilines [53]
Dinitroanilines [56] [57]
Diphenylethers [58]
Halobenzonitriles [59]
Mercapto-
pyridine-N-oxides [60]
Methylisocyanate [61]
Organophosphorous
derivatives [62–65] [66,57] [67]
Oxadiazoles [58] [36]
Phenols [68] [68]
Phosphorothioates [69]
Pyrimidines [70]
Sulfonylureas [71,72] [73] [74]
Thiocarbamates [75–77] [78,38]
Thiones [79]
Triazines [80] [81,82,38] [83]
Triazinones [84]
Triazoles [85]
Ureas [86–88,35,89,90]
very low yield. Probably, the photolability of such a reduced, possibly through photodegradation. The observed
biphenyl would lead to fast degradation, so that they would reduction of toxicity was higher in bay water than in fresh
accumulate only to a very low extent. water.
The major photoproducts found upon irradiation of Recently, Mabury and Wilson [37] have investigated the
alachlor [2-chloro-29,69-diethyl-N-methoxymethylacet- photodegradation of alachlor (vide supra), butachlor hN-
anilide] with a medium pressure mercury lamp were (butoxymethyl)-2-chloro-29,69-diethyl-acetanilidej, metola-
hydroxyalachlor and a lactam, plus another three products: chlor (vide supra) and the model compound 2-chloro-N-
norchloralachlor, 29,69-diethylacetanilide and 2-hydroxy- methylacetanilide in a solar simulator, with the aim of
29,69-diethyl-N-methylacetanilide [91]. The author sug- determining the extent of monochloroacetic acid product-
gests that the mechanism proceeds via homolytic scission ion. The photodegradation followed pseudo-first order
of the C–Cl bond, followed by trapping of the radical kinetics, which was independent of the pH of the medium.
so-formed by water or intramolecular hydrogen abstrac- Photolysis in synthetic field water reduced the time of
tion. photolysis.
Albanis and Konstantinou [92] studied the photodegra- Hogenboom et al. [93] used on-line solid-phase ex-
dation of propachlor h2-chloro-N-isopropylacetanilidej and traction liquid chromatography combined with mass spec-
propanil h39,49-dichloropropionanilidej in water and soil, trometry to screen the products of photodegradation of
and found the half-lives of the compounds to be ¯1–2 alachlor (vide supra) and related structures. The structures
months in water and ¯1 month in soils. The presence of of ten photodegradation products were proposed, based on
humic substances reduced the photodegradation rate in the most likely fragmentation MS patterns. Comparison
water but led to an enhancement in soil. The major with the results of Hapeman-Somich [91] indicates a rather
photoproducts found were the hydroxy and dechlorinated complicated reaction scheme. However, it is not clear how
derivatives. many of the products resulted from secondary photolysis
Lin et al. [39] looked into the effect of simulated pathways.
sunlight on metolachlor h2-chloro-69-ethyl-N-(2-methoxy- The aqueous photodegradation of butachlor (vide supra)
1-methylethyl)acet-o-toluidinej toxicity in surface waters. by sunlight takes place with a pseudo-first order rate
They concluded that the toxicity of the herbicide is constant 0.012 h 21 (t 1 / 2 558.2 h) [36].
2.3. Bipyridinium herbicides and photo-Fries rearrangement products, with a low quan-
tum efficiency. In contrast to previous findings, these
Different authors [94,95] have shown that photolysis of authors did not observe any effect of the concentration of
paraquat [1,1-dimethyl-4,49-bipyridinium dichloride] yields starting carbamate [100].
4-carboxy-1-methypyridium ion and methylamine, with the Tanaka et al. [35] investigated the generation of bi-
mechanism involving a transient ketone or aldehyde. More phenyls upon sunlight photolysis of chlorpropham hiso-
recently [96], it has been found that irradiation of paraquat propyl 3-chlorocarbanilatej and PPG-124 h4-chlorophenyl
in the presence of oxygen, led to formation of 4,49- methylcarbamatej. The photoreactions took place via cou-
bipyridyl and 4-picolinic acid. In addition, sequential loss pling of the two insecticide molecules, leading with very
of methyl was found to lead to monoquat [1-methyl-4,49- low yield to formation of a chlorinated biphenyl. The high
bipyridinium dichloride] and 4,49-bipyridyl. The mecha- photolability of these biphenyls would lead to their fast
nism proposed for formation of 4-picolinic acid involves degradation, so that they would not accumulate signifi-
an oxidative ring cleavage of 4,49-bipyridyl or demethyla- cantly.
tion of 4-carboxy-1-methypyridium ion. If paraquat is A report has been presented of the photochemical
irradiated for longer times oxalate, succinate, malate and degradation of carbaryl (vide supra) and carbofuran h2,3-
N-formyl glycine are formed. dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamatej by
the action of sunlight and UV ( l .290 nm) in natural
2.4. Carbamate insecticides waters of Northern Greece [76]. The major photoproduct
observed from degradation of carbofuran was carbofuran–
Aly and El-Dib [97] investigated the photodecomposi- phenol, which further photodegraded. The major photo-
tion of sevin (carbaryl) h1-naphthyl methylcarbamatej, product observed from degradation of carbaryl was a-
baygon (propoxur) h2-(1-methylethoxy)phenyl methyl- naphthol. Continuous irradiation led to almost complete
carbamatej, pyrolan h3-methyl-1-phenylpyrazol-5-yl dime- degradation of the pesticide.
thylcarbamatej and dimetilane hpyrazole-1-carboxamide, The photodegradation of carbetamide h(R)-1-(ethylcar-
3-hydroxy-N,N,5-trimethyl-, dimethylcarbamatej. In the bamoyl)ethyl carbanilatej by 290 nm light has been
case of sevin and baygon the rate of photodegradation studied in water, ethanol, methanol and a water / 1%
increase with the pH of the medium, while no effect was acetone mixture [41]. The highest quantum yield of
observed for pyrolan and dimetilane. The main photo- photodegradation (¯9%) was observed in aqueous ace-
chemical event observed was the bond scission of the ester. tone. The presence of formulation additives produced, in
a-Naphtol was identified as the main photoproduct derived all cases, a decrease in the photodegradation quantum
from sevin. The order of photostability found was yield. Aniline and hydroxy phenyl carbamoyloxy 2-N-ethyl
pyrolan.dimetilane.baygon.sevin. propionamide were identified as the main photoproducts of
The photodegradation of zectran h4-dimethylamino-3,5- aqueous photodegradation.
xylyl-N-methyl carbamatej was studied in aerated and With relevance to the design and synthesis of light-
degassed cyclohexane and ethanol [98]. A photo-Fries sensitive urethanes as photoprecursors of amines, Cameron
rearrangement was proposed as the main reaction pathway. ´
and Frechet [102] proposed a heterolysis mechanism for
Kumar et al. [99] studied the 265 nm photodegradation the UV photocleavage of carbamates. They subsequently,
of azak h2,6-di-tert-butyl-4-methylphenyl-N-methylcarba- while studying the photogeneration of organic bases from
matesj in aerated or degassed ethanol. A radical mecha- carbamate derivatives, reported the existence of steric and
nism taking place via a photo-Fries rearrangement involv- electronic effects on the quantum efficiency of 254 nm
ing a cyclohexadienone intermediate was proposed. photolysis [103].
While studying the photoinduced transformation of The photodegradation of aldicarb h2-methyl-2-
ethyl-N-phenylcarbamate to ethyl o-aminobenzoate, ethyl (methylthio)propionaldehyde O-methylcarbamoyloximej,
p-amino-benzoate and aniline, Masilamani and Hutchins carbaryl (vide supra) and carbofuran (vide supra) has been
[100] found an effect of the concentration of the starting studied using the UV radiation from a high pressure
material. According to these authors, at high concen- mercury lamp and from a suntest apparatus equipped with
trations of carbamate ethyl o-aminobenzoate is predomi- a Xe arc lamp in distilled, pond and artificial water, in the
nant, while at low concentrations aniline is the only absence and presence of humic acids [42]. Aldicarb
product observed. sulfoxide and 1-naphthol, respectively, were identified as
A more recent and very detailed study of the UV the major photodegradation products from aldicarb and
photodegradation of various alkyl N-arylcarbamates in carbaryl. An unidentified major product was produced
ethyl propionate and cyclohexane has been carried out by upon photolysis of carbofuran. Photosensitizing effects,
Herweh and Hoyle [101]. These authors propose a mecha- leading to an enhancement of photodegradation were
nism involving an excited singlet state that undergoes observed with carbaryl and carbofuran when using water
homolytic cleavage of the C–N bond to a radical pair in a containing humic acids.
solvent cage. This radical pair eventually leads to amines Adityachaudhury et al. [34] studied the sunlight induced
photodegradation of carbofuran (vide supra). The authors methylpyrimidin-4-yl dimethylcarbamate and 2-

claim they characterized more than twenty photoproducts. (formylamino)-5,6-dimethylpyrimidin-4-yl dimethylcarba-
Only two of these were, however, were confirmed by mate. In the solid-phase 2-[(methylformyl)amino]-5,6-di-
comparison with authentic samples. methylpyrimidin-4-yl dimethylcarbamate and 2-
´
Benıtez et al. [104] studied the photooxidation of (methylamino)-5,6-dimethylpyrimidin-4-yl dimethylcarba-
aqueous solutions of propoxur (vide supra) using the mate were the observed photoproducts. The different
radiation supplied by a low-pressure mercury lamp. This wavelengths used do not seem to change the reaction
study included the effects of temperature, pH and pesticide pathways, but only affect the degradation rate. The mecha-
concentration, as well as of added O 3 [104]. As a result, a nism does not seem to be radical-mediated.
general rate equation for the direct UV photolysis was A detailed GC–MS study of the products resulting from
proposed, with the quantum yield being effectively insensi- photolysis of different carbamates by the UV radiation
tive to the pH. The process in the presence of O 3 can be produced by a medium-pressure mercury lamp has been
divided into a direct reaction with O 3 , a direct photochemi- carried out by Climent and Miranda [105,106]. The
cal process and a combination of both. An appropriate compounds studied were bendiocarb h2,3-iso-
reaction scheme has been proposed. propylidenedioxyphenyl methylcarbamatej, isoprocarb ho-
The 355 nm laser flash photolysis of N-hydroxy- cumenyl methylcarbamatej, promecarb h3-isopropyl 5-
pyridine-2-thione carbamates yielded dialkylaminyl radi- methylphenyl methylcarbamatej, ethiofencarb (vide supra),
cals which, upon protonation, produced the corresponding furathiocarb hbutyl 2,3-dihydro-2,2-dimethylbenzofuran-7-
dialkylaminium radical cations [49]. The kinetics of the yl N,N9-dimethyl-N,N9-thiodicarbamatej, fenoxycarb hethyl
reactions undergone by these aminium radical cations have 2-(4-phenoxyphenoxy)ethylcarbamatej and pirimicarb h2-
been studied and reported, as well as their acidity con- dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarba-
stants. matej. In general, photodegradation led to the corre-
The photodegradation of ethiofencarb h2- sponding phenols as main photoproducts. Photoprocesses
[(ethylthio)methyl]phenyl methylcarbamatej by UV light such as photo-Fries rearrangements, C–S or N–S bond
( l .280 nm) and natural sunlight has been studied in the cleavage or oxidative demethylation were observed, de-
presence of cyclohexane, cyclohexene and isopropanol, in pending on the structures of the compounds.
an attempt to model its photolysis on plant surfaces [44]. Mansour et al. [46] studied the photolysis of carbofuran
The efficiency of the photodegradation was higher in less (vide supra) in water and water / soil suspensions using UV
polar solvents, with the observed half-lives ranging from light of different wavelengths. The photodegradation was
75 min to more than 20 h. Different products were very slow when carbofuran was irradiated with l .290
obtained depending on the solvent and the light source: nm, but was substantially enhanced in the presence of
ethiofencarb sulfoxide was the main product of irradiation TiO 2 , H 2 O 2 or O 3 .
in cyclohexane, while photooxidation, hydrolysis and Albanis and Konstantinou [92] have studied the photo-
addition product formation was observed when the photodegradation of molinate hS-ethyl hexahydro-1H-azepine-1
lysis took place in isopropanol. carbothioatej in water and soil. The half-life of the
´
Benıtez et al. [43] studied the photodegradation of compounds was ¯1–2 months in water and ¯1 month in
aqueous solutions of carbofuran (vide supra) by the soils. The presence of humic substances reduced the
polychromatic light supplied by a high-pressure mercury photodegradation rate in water, but an enhancement was
lamp (emitting from 185 nm through to the visible region). observed in soil. The major photoproduct found was the
The authors claim that the contribution of hydroxyl keto derivative.
radicals to the degradation is negligible, since no effect of The photodecomposition of carbofuran (vide supra) by
tert-butyl alcohol was observed on the rate of degradation 254 nm UV light in water follows first-order reaction
upon direct photolysis. A simple rate equation is proposed kinetics [107]. The presence of dissolved organic matter
to describe the process and the quantum yield obtained and was found to inhibit the photodegradation of carbofuran.
correlated by an Arrhenius-type expression. The photoproducts were identified by GC–MS and 1 H
Pirisi et al. [45] have studied the photolysis of NMR. A tentative mechanism was proposed for the
pirimicarb h2-dimethylamino-5,6-dimethylpyrimidin-4-yl photodegradation. According to the authors, the carbamate
dimethylcarbamatej in water and in the solid-phase, using group is cleaved from carbofuran via C–O heterolysis,
three different light sources, a low pressure mercury lamp, yielding a phenoxide anion and an acylium cation. The
high pressure mercury lamps and sunlight, for irradiation. furan moiety of the phenoxide anion then undergoes ring
Three photoproducts were observed in solution: 2- opening in a second step, leading to a substituted catechol
[(methylformyl)amino]-5,6-dimethylpyrimidin-4-yl dime- moiety with a tert-butyl alcohol substituent. This catechol
thylcarbamate, 2-(dimethylamino)-5,6-dimethyl-1-hydro- dehydrates, yielding an alkene.
xypyrimidine and 2-(methylamino)-5,6-dimethylpyri- The photodegradation of the systemic insecticide
midin-4-yl dimethylcarbamate. This later product under- ethiofencarb (vide supra) has been studied in water,
went decomposition to yield 2-amino-5,6-di- methanol and hexane using a solar simulation unit [47].
The kinetics of photodegradation can be fitted to a first- photodegradation, and in some cases may even be the
order rate equation, independent of the nature of the dominant pathway.
medium, with the reaction rate increasing with the polarity
of the medium. The photoproducts depend on the solvents. 2.5. Carboxamide fungicides
In water, photocleavage of the C–S bond yields 2-
(methyl)phenyl-N-methylcarbamate. In the presence of humic acid the half-life of photo-
Vialaton and Richard [108] carried out a 266-nm laser degradation of carboxin h5,6-dihydro-2-methyl-N-phenyl-
flash photolysis study of the photolysis of ethiofencarb 1,4-oxathiin-3-carboxamidej was reduced by 25%. Oxy-
(vide supra). A quantum yield of 12% was estimated for carboxin h5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-
the photoconversion of ethiofencarb into its sulfoxide, carboxamide 4,4,-dioxidej photodegradation after 8 h
2-methylphenyl-methylcarbamate and to a further two increased from 10 to 25% [111,112].
unidentified products. The homolytic cleavage of the C–S UV irradiation ( l .290 nm) of prochloraz hN-propyl-N-
bond was confirmed by spectroscopic detection of benzyl [2 - (2, 4, 6 - trichlorophenoxy) - ethyl]imidazole - 1 - carbox-
radicals. The authors suggest that the mechanism of amidej in soil led to prochloraz–formylurea, which sub-
generation of the sulfoxide may result from an electron sequently hydrolysed to prochloraz–urea [50].
transfer from the triplet excited state to oxygen, yielding a
radical cation which then recombines with the superoxide 2.6. Chloronicotinoid insecticides
ion, to produce an intermediate peroxysulfoxide, eventual-
ly leading to the sulfoxide. Irradiation of imidacloprid h1-(6-chloro-3-pyridin-3-yl-
A study of the direct photolysis of propoxur (vide supra) methyl)-N-nitroimidazolidin-2-ylidenaminej in aqueous
in water, using 266 nm laser flash photolysis showed solution with 290 nm light resulted in 90% degradation
almost complete disappearance of propoxur, with forma- after 4 h [51]. The main photoproducts were identified as
tion of the corresponding photo-Fries rearrangement prod- 6-chloronicotinaldehyde, N-methylnicotinamide, 1-(6-chlo-
ucts [109]. According to the authors, the process can be ronicotinyl)imidazolidone and 6-chloro-3-pyridylmethyl-
rationalized on the basis of an initial homolytic –C(O)–O– ethylendiamine. Some minor products were also formed,
scission of the carbamate moiety from the singlet excited but not identified.
state of propoxur, with generation of 2-isopropoxyphenox- The sunlight induced photolysis of the insecticide
yl-carbamoyl radical pair. Radical recombination or escape imidacloprid (vide supra) in aqueous solution was studied
out of the cage would produce the observed photoproducts. on the surface of tomato leaves [52]. The photodegradation
No oxygen quenching was observed. was rapid, and five photoproducts were found, four of
Ibarz et al. [48] studied the aqueous photodegradation of which could be identified.
carbendazim hmethyl-2-benzimidazole carbamatej at vari- Kole et al. [56] studied the UV photolysis (240–260 nm)
ous pH values, using the radiation supplied by a mercury of imidacloprid (vide supra) in 10% acetonitrile / water.
lamp emitting between 250 and 750 nm. The process Three photoproducts were observed, and were suggested to
followed a first-order rate equation, and the rate of be formed by N–NO 2 bond cleavage, hydroxylation of the
photodegradation increased with pH and O 2 concentra- imidazolidine ring and oxidative cleavage of the methylene
tions. The quantum yields for photodegradation at different bridge. The authors sketch a possible mechanism for the
pH values were in all cases very low (less than 1%). process.
Detailed studies of the initial stages of photodegradation An additional study of the photodegradation of im-
of a variety of carbamates using laser flash photolysis idacloprid (vide supra) has been reported in HPLC grade
combined with pulse radiolysis showed the photodegrada- water and as the formulated product Confidor in tap water
tion is a biphotonic process when 308, 266 and 248 nm [113]. Several degradation products have been identified,
light is used for excitation, and monophotonic if 193 nm with 1-6-chloro-3-pyridinyl-methyl-2-imidazolidinone as
light is used. Photoionization is observed in all cases, with the main one. The photodegradation followed a first-order
very low quantum yields, as well as formation of the rate equation.
corresponding phenoxyl radicals. The observed photo-
products, detected using GC–MS and HPLC, and checked 2.7. Chlorophenol pesticides
in some cases against authentic commercial samples, were
the corresponding phenols and photo-Fries products. The Miille and Crosby [53] studied the photodegradation of
rate constants for one-electron oxidation of the carbamates pentachlorophenol by simulated sunlight in seawater. The
2
by SO ?2 ?
4 , one-electron reduction by e aq , and for HO photolysis reaction was slower in seawater, which was
addition were obtained. Structure–reactivity correlations attributed to the photonucleophilic interaction of the
have been established in order to predict the reactivity of substrate with chloride ions. Photooxidation, photonu-
other carbamates upon direct photolysis [110]. cleophilic substitution and photoreduction reactions were
However, it is worth noting that in aqueous solutions, observed. The amount of photoreduction products was
hydrolysis of carbamates may efficiently compete with higher than in distilled water, and the unstable tetrachloro-
muconic acid was isolated and identified as an intermediate Recently, Moza et al. [118] have revisited the photolysis
ring-fission photoproduct. of vinclozolin in water and methanol–water. Irradiation for
The photodegradation of MCPA h4-chloro-2- 10 min at 254 nm resulted in ¯90–95% degradation,
methylphenoxy acetic acidj was studied in distilled water while photolysis for 8 h at 290 nm resulted in 10%
and river (Thames) water, using low intensity 300–450 nm degradation, and irradiation for 8 h under artificial sunlight
UV light and sunlight [54]. Upon UV irradiation, MCPA led to 55% degradation. The main photoproducts were
photodegradation was almost negligible in distilled water, 3,5-dichlorophenyl isocyanate and 3,5-dichloroaniline,
while in river water it accelerated. Early autumn sunlight generated by ring opening of the 2,4-oxazolidine-dione.
photolysis took place with a pseudo first-order rate con-
stant k exp 5 0.009 h 21 (t 1 / 2 5 168 h). 2.10. Dinitroaniline pesticides
19
2.8. Cyclodiene insecticides F NMR was suggested as a possible analytical tool for
monitoring the sunlight photodegradation of trifluralin
Mukerjee et al. [114] reported an amine-induced ha,a,a -trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidinej wit-
stereoselective method of photodehalogenation of aldrin hout extraction, cleanup, concentration or chromatographic
h(1R,4S,4aS,5S,8R,8aR)-1,2,3,4,10,10-hexachloro-1,4,4a,5, separation procedures [119]. The major photodegradation
8,8a-hexahydro-1,4:5,8-dimethanonaphtalenej, in which products, identified by comparison with authentic samples
they obtain a mixture of two photoproducts in the propor- were a,a,a -trifluoro-2,6-dinitro-N-propyl-p-toluidine,
tion 9:1 upon irradiation with a high pressure Hg lamp. a,a,a -trifluoro-2,6-dinitro-p-toluidine and 2-ethyl-7-nitro-
5-(trifluoromethyl)benzimidazole. Different unidentified
2.9. Dicarboximide fungicides NMR peaks were attributed to labile intermediates not
generally observed with other analytical techniques.
Schwack et al. [115] examined the photodegradation of Adityachaudhury et al. [34] investigated the transforma-
vinclozolin h3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3- tion of the herbicide pendimethalin hN-(1-ethylpropyl)-3,4-
oxazolidine-2,4-dionej in various organic solvents, in an dimethyl-2,6-dinitrobenzenamine using UV light of l $
attempt to simulate the plant cuticle environment, using a 250 nm. They found that the main processes taking place
high-pressure Hg lamp. Different photoproducts were are N-dealkylation, arylmethyl oxidation, nitro group
observed depending on the solvent, indicating that the elimination and cyclization.
formation of bound residues in plant cuticles is possible, Mansour et al. [46] studying the photolysis of pen-
with the solvent molecules in the model reactions being dimethalin (vide supra) by UV light of different wave-
replaced by constituents of plant waxes and the cutin lengths in water and water / soil suspensions, found various
polymer. A similar study was carried out with iprodione conversion products, depending on the wavelength used
h3-(3,5-dichlorphenyl)-N-(1-methylethyl)-2,4-dioxo-1-im- for photolysis.
idazolidinecarboxamidej [116]. UV and sunlight induced photolysis of fluchloralin hN-
Schwack et al. [55] analysed the potential of (2-chloroethyl)-2,6-dinitro-N -propyl-4-(trifluoromethyl)-
procymidone h3-(3,5-dichlorophenyl)-1,5-dimethyl-3- anilinej in aqueous methanol (80%) yielded four photo-
azabicyclo[3.1.0]hexane-2,4-dionej to undergo photoin- products, that the authors attribute to result from N-
duced processes in the presence of different organic dealkylation, nitroreduction and cyclization pathways [56].
groups. Their objectives were to seek explanations for the A theoretical framework has been presented to under-
possible formation of bound residues in plant cuticles stand the combined effects of direct photolysis, layer
where solvent, waxes and cutin polymer molecules are thickness and transport processes on the photodegradation
present. A high pressure mercury lamp was used for of organic pollutants on soil surfaces under environmental
irradiation ( l .280 nm). Photodegradation in isopropanol conditions, using a xenon long arc lamp, equipped with
or cyclohexane led to photodehalogenation and substitution filters cutting out wavelengths below 280 nm and the IR
by solvent molecules. Photodegradation in cyclohexene led [120]. The model has been used to explain the behaviour
to substitution of Cl by a solvent molecule, the monode- of trifluralin (vide supra) on kaolinite layers of variable
halogenated procymidone resulting as photoproduct. thickness. The use of the appropriate experimental setup
Hustert and Moza [117] studied the photochemical and a mathematical model allowed the authors to de-
degradation of procymidone (vide supra) and vinclozolin termine the rate constant for direct photolysis of trifluralin
(vide supra) using a mercury lamp in the presence of soil as k 5 1.6 h 21 . From this, it was shown that 20% of the
constituents in water. The photodegradation rate in the initial amount of trifluralin was degraded without transport.
presence of humic and fulvic acids increased relative to the Miller et al. [57] developed a method based on a
situation in which they are absent. Fe 2 O 3 and TiO 2 solid-phase microextraction technique to determine the rate
photocatalyzed the disappearance of both compounds. of sunlight (simulated) photodegradation of trifluralin (vide
Dechlorination and isomerization are the major photo- supra) in the gas phase at high temperatures. The gas phase
degradation pathways. photolysis of trifluralin took place with half-lives of 22–24
min. The photodegradation rate was not affected by hO-aqueous solutions, thin films and n-hexane have been
changing the temperature from 60 to 80 8C. known for some time [62]. Photoisomerization by light of
l .350 nm was observed in the S-benzyl esters IBP and
2.11. Diphenylether herbicides inezin, but not for the S-phenyl ester edifenphos. The
photoisomerization of IBP led to a reverse P=O↔P=S
In a study of the photodegradation of methanolic isomerization. The P=O derivatives of IBP and inezin
solutions of oxyfluorfen h2-chloro-1-(3-ethoxy-4-nitro- underwent photooxidation to yield the corresponding O-
phenoxy)-4-(trifluoromethyl)benzenej, Adityachaudhury et benzyl esters. Cleavage of the P–S bond was observed,
al. [34] found 13 photoproducts. leading to formation of phenylthio radicals, which sub-
Ying and Williams [58] studied the sunlight photodegra- sequently yielded benzoic acid or sulphuric acid via
dation of the oxyfluorfen hvide supraj in detail on soil and disulphides and sulfonic acids. Reductive cleavage, photo-
in water. The photoproducts detected showed that loss of hydrolysis and transesterification via radicals were also
the nitro group, dechlorination and cyclisation were the observed.
main processes taking place. The photodegradation was Mansour et al. [67] studied the sunlight induced photo-
faster in water than in soil. degradation of parathion hO,O-diethyl O-4-nitrophenyl
phosphorothioatej in deaerated water, methanol, 2-pro-
2.12. Halobenzonitrile pesticides panol and aqueous mixtures of these. The authors suggest
that two main processes take place: a free-radical mecha-
Kochany [59] studied the photodegradation of bromox- nism in apolar solvents and a ionic breakdown in aqueous
ynil h3,5-dibromo-4-hydroxyphenyl cyanidejin aqueous solvents. The quantum yield for generation of photo-
solutions in the presence of carbonate and bicarbonate ions products was ¯0.1%. The half-life time for photodegrada-
using from a mercury–xenon lamp ( l .300 nm). A tion in water was ¯65 h at pH 7.8.
quenching effect by carbonate was observed, as well as a Wamhoff et al. [122] studied the photodegradation of
smaller quenching by bicarbonate. The main photoproducts azinphos-ethyl hO,O-diethyl-S-3,4-dihydro-4-oxobenzo[d]
found were 3-bromo-4-hydroxybenzonitrile and 4-hy- [1,2,3]triazine-3-yl-methyl)phosphorodithioatej in chloro-
droxybenzonitrile. Small amounts of other unstable or form and methanol solution using the radiation supplied by
unidentified products were detected. The results suggest a high-pressure mercury lamp. 3,4-dihydro-3-methyl-4-
that carbonate may be involved in the photodegradation of oxobenzo[d][1,2,3]triazine-3,4-dihydro-4-oxo-benzo[d]-
bromoxynil, although the nature of the processes involved [1,2,3]triazine, O,O-diethyl-o(3-methylbenzo[d][1,2,3]-
is not clear. triazine-4-yl)phosphate, N-methyl-anthranilic acid and sul-
The photodegradation has been studied of bromoxynil fur were found as photoproducts. The authors propose a
(vide supra), chlorothalonil htetrachloroisophthalonitrilej, reaction mechanism to explain the formation of the ob-
chloroxynil h3,5-dichloro-4-hydroxybenzonitrilej, dichlo- served products, starting either with a C–S or C–N bond
benil h2,6-dichlorobenzonitrilej and ioxynil h4-hydroxy- homolysis or with desulfuration by simultaneous C–S and
3,5-diodobenzonitrilej in aqueous, pH-buffered and or- P–S bond cleavages. The intermediate radicals or other
ganic solutions, using the radiation supplied by a xenon species have, however, not been detected.
lamp [121]. The quantum yields for photolysis were, Photolysis of coumaphos ho,o-diethyl-o-(3-chloro-4-
respectively, 0.0093, 0.0001, 0.0060, 0.0000 and 0.0024. methyl-coumarin-7-yl)-thiophosphatej by radiation of l .
Dichlobenil did not undergo photoreactions under the 313 nm in chloroform led to head-to-tail [212] regioselec-
conditions used. Results indicate that the photoreactivity is tive photodimerization to yield the anti-dimer. The reaction
influenced by the presence of both substituted halogen was not affected by singlet oxygen [63]. The authors
groups and hydroxy substituents. established the structure of the compound by single crystal
The main processes involved in the UV photolysis ( l $ X-ray diffraction, and concluded that the photoreactive
250 nm) of the fungicide chlorothalonil (vide supra) in part of the molecule is the coumarin ring, with the
ethanolic and methanolic aqueous solutions seems to be thiophosphoryl group being relatively stable toward UV
the homolytic cleavage of 4-C–Cl bond followed by irradiation.
alkylation of the a-radicals derived from the alcohols [56]. Esplugas et al. [123] studied the aqueous photodegrada-
4,5,7-trichloro-6-cyano-3-methyl-1(3H )-isobenzofuranone tion of parathion (vide supra) using the UV radiation
was identified as photoproduct in ethanolic solution and supplied by a mercury lamp. The rate of the process
4,5,7-trichloro-6-cyano-3,3-dihydro-1-isobenzofuranone in followed first-order kinetics, with the rate increasing with
methanolic solution. the pH of the medium. Very low quantum yields of less
than 1% were obtained, depending on the pH. Coloured
2.13. Organophosphorus pesticides compounds were obtained. The authors recommend carry-
ing out the photodegradation in alkaline medium, in order
The UV-induced photoreactions of the fungicides IBP to improve the degradation yield.
hS-benzyl O,O-di-isopropyl phosphorothioatej, edifenphos The photochemistry of the herbicide butamifos hO-ethyl
O-5-methyl-2-nitrophenyl sec-butylphosphoramidothioatej possibly by one-electron abstraction on the sulfur atom to

has been studied using a 500-W xenon arc lamp [65]. An form a radical cation which would subsequently react with
intramolecular oxygen transfer from the nitro group to the oxygen. 3-Methyl 4-methyl thiophenol was also formed by
P=S moiety was observed. The nitroso-oxon derivative P–O bond cleavage. The photodegradation in carbonate /
formed was photodegraded to various polar compounds. bicarbonate radical matrixes took place faster than by
The photodegradation of butamifos and its photoproducts direct photolysis.
was found to be rapid and efficient. Miller et al. [57] developed a method based on the
The photodegradation of chlorpyrifos hO,O-diethyl O- analytical technique of solid-phase microextraction to
3,5,6-trichloro-2-pyridyl phosphorothioatej and fena- determine the rate of sunlight (simulated) photodegradation
miphos hethyl 4-methylthio-m-tolyl isopropyl- of chlorpyrifos (vide supra) in gas phase at high tempera-
phosphoramidatej by simulated sunlight in water / methanol tures.
(2–4%) has been studied [64]. Fenamiphos degraded more The effect of visible and UV(A–C) light on fenthion
readily than chlorpyrifos. The major photoproducts were (vide supra) and disulfoton ho,o-diethyl S-2-ethylthioethyl
3,5,6-trichloro-2-pyridinol and fenamiphos sulphoxide, re- phosphorodithioatej was studied. Visible light did not
spectively. Under the same conditions, the extent of induced photodegradation, that took place with UV light.
photodegradation of vamidothion hO,O-dimethyl S-2-(1- The photodegradation process was faster in aqueous
methylcarbamoylethylthio)ethyl phosphorothioatej after 6 solution than in solid-phase, probably due to the presence
h of irradiation was only 2%. the dissolved oxygen in the former. Under the same
Barcelo´ et al. [83] studied the photodegradation of the conditions, fenthion (vide supra) is more readily degraded
insecticide fenitrothion hphosphorothioic acid O,O-di- than disulfoton (vide supra). The corresponding sulfoxides
methyl-O-(3-methyl-4-nitro-phenyl) esterj in a 20% were identified as photolysis products, which are photo-
methanolic solution, using a high-pressure mercury lamp. stable in environmental conditions [128].
Attempts were made to use a suntest apparatus for the Recently a general review on the photochemical trans-
photolysis, but the photodegradation rate was too slow. formations of organophosphorus insecticides has been
Oxidation of the P=S group to trimethyl phosphate was the published, focusing on environmental problems and cover-
main photolytic pathway, although products of solvolysis ing from the late 1960s to 2000 [129].
and isomerization (O,O,S-trimethyl phosphorothioate and
the S-methyl isomer of fenitrothion) were also observed. A 2.14. Oxadiazole herbicides
further tentative photodegradation mechanism was pro-
posed. These authors subsequently revisited the photo- Ying and Williams [58] studied the sunlight photodegra-
degradation of fenitrothion under similar conditions [124], dation of the oxadiazone h3-[2,4-dichloro-5-(1-methyl-
and identified 21 photoproducts, arising from oxidation, ethoxy)phenyl] - 5 - (1, 1 - dimethylethyl) - 1, 3, 4-oxadiazol-
isomerization, denitration and solvolysis. A tentative 2-(3H )-onej on soil and water. Three photoproducts were
photodegradation scheme was proposed. isolated and identified, showing that loss of chlorine was
Mok et al. [66] carried out a comparative study of the the main process taking place. The photodegradation was
quantum yields of direct photolysis of 16 different organo- faster in water than in soil.
phosphorus pesticides and their phenolic derivatives in The aqueous photodegradation of oxadiazone (ronstar)
aqueous solution. The solutions were irradiated at 254 and h5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-
313 nm, and a significant correlation was found between oxadiazol-2(3H )-onej by sunlight takes place with a
both sets of quantum yields. Similarly, a significant pseudo-first order rate constant 0.0245 h 21 (t 1 / 2 528.5 h)
correlation was found between the quantum yields of the [36].
studied organophosphorus pesticides and those of their
phenolic derivatives. 2.15. Phenol-based pesticides
Niessner et al. [125] studied the aqueous photodegrada-
tion of parathion-methyl hO,O-dimethyl O-(4-nitro- The aqueous photodegradation of mecoprop h(R,S)-2-(4-
phenyl)phosphorothioatej by UV light at a pilot plant for chloro-o-tolyloxy)propionic acidj by 254 nm and poly-
drinking water treatment in the presence of O 2 and using a chromatic light was studied. The main products were
combination of O 2 / O 3 . The photodegradation rate in- found to be 2-methyl-phenol, 2-methyl-cyclohexadie-2,5-
creased when using this latter combination with respect to ene-1,4-dione, 2-methyl-methoxybenzene, 2-methyl-1,4-
O2. dihydroxybenzene and 2-methyl-4-chlrophenol [130], sug-
In two separate papers, Mabury and co-workers gesting a radical-mediated mechanism.
[126,127] have recently described the role of the CO ?2 3 A fast photodegradation of aqueous solutions of 2,4-D
radical anion in the sunlight induced degradation of h2,4-dichlorophenoxyacetic acidj by UV radiation has been
fenthion hO,O-dimethyl O-[3-methyl-4-(methylthio)- observed, with more than 99% of the starting material
phenyl] phosphorothioatej in natural waters. The major decomposing within the first hour of treatment [131]. The
degradation pathway was through fenthion sulfoxide, authors suggest that the main processes taking place
involve C–Cl and C–O bond homolysis, with a subsequent light. The effect of added humic acids was lower than that
cascade of various free radical reactions. However, none of of river water components.
these radical intermediates were detected. The photoreactions of potasan hO,O-diethyl-O-(4-
Climent and Miranda [132] studied by GC–MS and methyl-2-oxo-2H -1-benzopyran-7-yl)-phosphorothioatej
GC–FTIR the aqueous photodegradation of dichlorprop have been studied upon UV irradiation by light of l .313
h2-(2,4-dichlorophenoxy)propionic acidj and 2-naphtoxy- nm in chloroform and / or methanol alone and under
acetic acid, using a medium-pressure mercury lamp. conditions where singlet oxygen may be present [69]. The
Photolysis of dichlorprop under oxygen led to 2-chloro- main photoproducts found were 2-oxo-2H-1-benzopyran-
phenol, 2,4-dichlorophenol, 4-chlorophenol, 2,4-dich- phosphate, 7-ethoxy-4-methyl-2-oxo-sH-1-benzopyran and
lorophenyl acetate, 2-(4-chloro-2-hydroxyphenoxy)- a 3,39-bipotasan dehydrodimer. The authors propose a
propionic acid and 2-(2-chlorophenoxy)propionic acid. mechanism involving homolytic cleavage of the 7-O–P
Under Ar, the first three of these products and the last one bond to generate intermediate radicals which further react.
were also obtained, plus 2,4-dichlorophenyl ethyl ether. In
the case of 2-naphtoxyacetic acid under oxygen atmos- 2.18. Pyrazole insecticides
phere, b-naphtol and minor amounts of 2-hydroxy-1-nap-
htaldehyde and naphtho-[2,1-b]furan-2(1H )-one were the The photodegradation of fipronil h(6)-5-amino-1-(2,6-
observed products, while only the first and last were dichloro - a, a, a - trifluoro - p - tolyl) - 4 - trifluoromethyl - sul-
observed under Ar atmosphere. finylpyrazole-3-carbonitrilej has been studied in acidic
A mechanistic study of the photodegradation of the aqueous solution and on the surface of Niger and Mediter-
lampricide (3-trifluoromethyl-4-nitrophenol) was carried ranean soils by the radiation supplied by a xenon lamp
out, with irradiation at 365 nm [68]. The main photo- [133]. The degradation in aqueous solution followed first-
product found was trifluoroacetic acid. The mechanistic order kinetics, and the observed photoproducts were 5-
study was extended to various trifluoromethylated phenols, amino-4-cyano-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-
and it was shown that the nature of the substituents, the 4-phenyl)pyrazole and 5-amino-3-cyano-1-(2,6-dichloro-4-
substitution pattern and the acidity of the medium strongly (trifluoromethyl)-phenyl)pyrazole-4-sulfonic acid, corre-
affected the photodegradation process. The half-life times sponding to desulfinylation and oxidation processes, re-
found for photodegradation were 22 and 91.7 h, at pH spectively. The authors suggest that the mechanism is
values of 9 and 7, respectively, with corresponding yields probably radical in nature, the primary photoproduct is the
of trifluoroacetic acid of 5.1 and 17.8%. Photodegradation corresponding sulfone and from there those products are
of trifluoromethylquinone led quantitatively to trifluoro- formed by simultaneous reactions. The mechanism was not
acetic acid. elucidated, however. The photodegradation in soils led to
the formation of 4-(trifluoromethyl)pyrazole, with the
2.16. Phenylamide pesticides degree of photodegradation being inversely proportional to
fipronil adsorption.
The photolysis of the fungicides metalaxyl (vide supra), Crosby et al. [134] studied the photolysis of fipronil
benalaxyl hmethyl N-phenylacetyl-N-(2,6-xylyl)-DL-alani- (vide supra) in aqueous solution to produce desthio-fi-
natej and furalaxyl hmethyl N-(2-furoyl)-N-(2,6-xylyl)-DL- pronil. The need for a sulfone intermediate has not been
alaninatej in water was studied with different UV lamps clarified, and the products of photodegradation not iden-
emitting between 254 and 290 nm [45]. The authors tified. Desthio-fipronil was formed directly and underwent
propose a relatively complex mechanism involving two photodechlorination, substitution of chlorine by trifluoro-
C–N bond scissions taking place via consecutive or methyl, and pyrazole ring cleavage.
parallel / consecutive processes. The bond cleavage is pro-
posed to take place homolytically, leading to neutral 2.19. Pyrimidine pesticides
nitrogen-centered radicals, that have not been detected.
The metalaxyl hmethyl N-(2-methoxyacetyl)-N-(2,6- Mateus et al. [135] investigated the photophysics and
xylyl)-DL-alaninatej photodegradation after 8 h was ob- photochemistry of the fungicide fenarimol ha -(2-chloro-
served to increase by 6–20% [111,112]. phenyl)-a -(4-chlorophenyl)-5-pyrimidine methanolj. The
photophysical studies suggest that the lowest excited
2.17. Phosphorothioate insecticides singlet state has predominantly n,p * character, and a small
singlet–triplet splitting. Halides were found to quench
Mansour et al. [46] studied the photolysis of diazinon fenarimol fluorescence. The photodegradation of fenarimol
hO,O-diethyl O-[6-methyl-2-(1-methylethyl)-4-pyrimi- seems not to involve dechlorination. More recently, the
dinyl] phosphorothioatej by UV light of different wave- same authors studied the kinetics and mechanism of
lengths in water and water / soil suspensions. Diazinon photodegradation of fenarimol in natural water and the
degraded faster in river water than in distilled water, and effect of salt solutions, using both sunlight and light of 313
this rate enhancement was higher upon exposure to sun- nm [70]. The rate of photodegradation was found to
decrease with increasing salinity. Fluorescence quenching gated [137]. Photodegradation products were clearly iden-
studies with halide and non-halide salts were carried out, tified, although hydrolysis was faster than photolysis.
and the correlation of the so-obtained rates with halide ion Chowdhury and co-workers [56,138] studied the UV-
oxidation potentials suggests involvement of an electron induced photodegradation of metsulfuron h2-(4-methoxy-6-
transfer mechanism. This may be used to improve / reduce methyl-1,3,5-triazin-2-yl-carbamoylsulfamoyl)benzoic acid
the fungicide photodegradability. in water. They found that ¯50% of the herbicide was
Adityachaudhury et al. [56] studied the UV (240–260 degraded within 15 h. They detected three photoproducts
nm) and sunlight photolysis of fenarimol (vide supra) in and proposed a mechanism involving hydrolytic cleavage
aqueous methanol and isopropanol solutions. Upon 24 h of of the sulfonylurea bridge to form the corresponding
UV photolysis of methanolic solution, 2,49-dichlorobenzil phenyl sulfonyl carbamic acid and s-triazine, with the
and p-chlorobenzoic acid were identified as photoproducts, carbamic acid subsequently decarboxylating to form a
while p-chlorobenzoic acid, 2,49-dichlorobenzophenone phenyl sulfonamide and a cyclic derivative.
and o-chlorobenzoic acid were the photoproducts found in The aqueous photodegradation of tribenuron-methyl
aqueous isopropanol. Two additional unidentified photo- hmethyl 2 - [4 - methoxy - 6 - methyl - 1, 3, 5 - triazin - 2 - yl-
products were formed upon sunlight photolysis. The (methyl-amino)carbonyl]benzoatej both by sunlight and by
authors suggest a mechanism for the process. the radiation supplied by a medium-pressure mercury lamp
Recently, Bhattacharyya et al. [72] revisited the aqueous was found to take place readily [72]. The main photo-
alcoholic photodegradation of fenarimol (vide supra) by products detected were N-methyl-4-methoxy-6-methyl-
light with l $250 nm. Irradiation in an aqueous metha- 1,3,5-triazine-2-amine, methyl 2-(aminosulfonyl) benzoate,
nolic solution for a day yielded 2,49-dichlorobenzil and o-benzoic sulfimide, N-(4-methoxy-6-methyl-1,3,5-triazin-
p-chlorobenzoic acid, while in an aqueous isopropanol 2-yl)-N-methyl urea and N-(2-carbomethoxyphenyl)-N-(4-
solution p-chlorobenzoic acid, 2,49-dichlorobenzophenone methoxy-6-methyl-1,3,5-triazin-2-yl)-N9-methyl urea. The
and o-chlorobenzoic acid were found. The authors hypoth- photodegradation process followed first-order kinetics and
esize possible mechanisms for these transformations, in- the reaction rate increased with pH and with the con-
volving different C–C bond homolysis processes. centration of dissolved inorganic substances. The authors
claim that the main processes taking place are cleavage of
the sulfonylurea bridge, scission of the SO 2 –NH bond and
2.20. Sulfone herbicides
de-esterification and contraction of the sulfonylurea bridge.
Bufo et al. [73] studied the photolysis of rimsulfuron
Ming and Wamhoff [136] studied the photolysis of
h1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-ethylsulfonyl-2-
dimethipin h2,3-dihydro-5,6-dimethyl-1,4-dithi-ine 1,1,4,4-
pyridylfulfonyl)ureaj and of its commercial formulation
tetraoxidej by 254 nm UV radiation in acetonitrile and
both in water and in organic solvents, using a high-
methanol containing a small amount of water (¯0.5%).
pressure mercury lamp and solar simulator. The photolysis
The disodium salt of ethane-1,2-disulfonic acid was iden-
of the commercial formulation in organic solvents was
tified as photoproduct resulting from a,a9-cleavage follow-
faster than for pure rimsulfuron. The half-life for sunlight
ing n → p * excitation of both sulfonyl groups. 2-Butyne,
photodegradation in water ranged from 1 day at pH 5 to 9
the other fragment which should be produced from such
days at pH 9. The authors report that the rate of hydrolysis
fragmentation could not be identified, possibly, according
is comparable to that of photolysis. The observed reaction
to the authors, due to its volatility and / or rapid poly-
products are, therefore, a mixture of hydrolysis and
merization. Photolysis in acetone with longer wavelengths
photolysis products.
( l .313 nm) led to the same photoproduct.
Aqueous photodegradation of triasulfuron h1-[2-(2-
chloroethoxy)phenylsulfonyl] - 3 - (4 - methoxy - 6 - methyl-
2.21. Sulfonylurea herbicides 1,3,5-triazin-2-yl)ureaj by 254 nm radiation followed first
order kinetics [74]. The observed photoproducts were 2-
The photodegradation of chlorimuron-ethyl hethyl 2-(4- chloroethoxybenzene and (4-methoxy-6-methyl-1,3,5-tri-
chloro - 6 - methoxy - pyrimidin - 2 - yl - carbamoylsulfamoyl)- azin-2-yl)urea. Upon sunlight photolysis the reaction was
benzoatej by sunlight and UV light has been studied on a slower, yielding the same photoproducts plus 2-amino-4-
soil surface [71]. The major photoproducts arise from methoxy-6-methyltriazine and 2-(2-chloroethoxy)ben-
cleavage of the sulfonylurea bridge, but some others are zenesulfonamide. The authors suggest a mechanism to
formed by dechorination, hydrolysis and cyclization. The account for the observed photoproducts.
photodegradation follows first-order kinetics, with the
process being much faster upon UV irradiation than upon 2.22. Thiocarbamate herbicides
sunlight irradiation.
The environmental fate of flupyrsulfuron-methyl hmethyl The photodegradation of EPTC hS-ethyl dipro-
2-(4,6-dimethoxy-pyrimidin-2-yl-carbomoylsulfamoyl)-6- pylthiocarbamatej, PEBC hS-propyl butyl(ethyl)thiocar-
trifluoro-methylnicotinate monosodium saltj was investi- bamatej and cycloate hS-ethyl cyclohexyl(ethyl)-
thiocarbamatej by UV light supplied by a medium pressure thioamides and thioureas. Mechanisms involving radicals
mercury lamp in hexane has been studied [139]. The derived from C–S, S–S– and S–H bond homolysis have
observed photoproducts were the corresponding form- been put forward.
amide, dialkylamine, mercaptan and disulfide. The authors Thiobencarb (vide supra) photodegrades readily upon
hypothesise a mechanism taking place via C–S bond sunlight or UV (254 nm) photolysis [78]. The photodegra-
homolysis, with subsequent recombination and H abstrac- dation by UV light takes places much faster. It has also
tion from the solvent to yield, respectively, a disulfide and been observed that the photodegradation is faster in
a formamide. The observed disulfides could result from the aqueous solution (t 1 / 2 51.5 h with UV light, 3 days under
combination of two sulfur-centered radicals. The sunlight) or on glass (t 1 / 2 51 h) or silica gel surfaces
dialkylamines found are probably due to the photolysis of (t 1 / 2 52 h) than on a soil surface (t 1 / 2 520 h). The major
the formamides, with loss of CO, and not to the direct photoproducts found were 4-chlorobenzyl alcohol, 4-chlo-
cleavage of the thiocarbamates. No effects of the con- robenzaldehyde and 4-chlorobenzoic acid. A tentative
centration of herbicide or temperature were observed. The mechanistic scheme is proposed, including a C–S bond
authors note the increased biotoxicity of the photoproducts, cleavage process to form a 4-chlorobenzyl radical that
relative to the starting herbicides. further oxidizes successively to 4-chlorobenzyl alcohol,
Photolysis of thiobencarb hS-4-chlorobenzyl dieth- 4-chlorobenzaldehyde and 4-chlorobenzoic acid. Oxidation
ylthiocarbamatej at 300 nm in aqueous solution or in the at the S atom would yield thiobencarb sulfoxide and
form of a thin film led to 30 photoproducts, the most thiobencarb sulfone, which further decompose to the
abundant of which were thiobencarb sulfoxide, N-desethyl corresponding sulfinic and sulfonic acids, leading eventual-
thiobencarb, N-acetyl thiobencarb, 4-chlorobenzyl dieth- ly to 4-chlorobenzoic acid.
ylcarbamate, N-(4-chlorobenzyl)diethylamine and 4-chlo- Vialaton and Richard [108] carried out a 266-nm laser
robenzaldehyde [75]. The authors propose a mechanism flash photolysis study of the photolysis of thiobencarb
involving photocleavage of the C–S bond to generate the (vide supra). A quantum yield of 14% was estimated for
4-chlorobenzyl radical, which leads to 4-chlorotoluene in the photoconversion of thiobencarb into 4-chloroben-
the presence of hydrogen donors. These authors also zaldehyde, 4-chlorobenzylalcohol and 2-methylphenyl-
studied the photodegradation of diallate hS-2,3-dimethylcarbamate, with the first one being formed by
chloroallyl diisopropyl thiocarbamatej, finding it to be homolytic C–S bond cleavage, and the last two by
more photostable than thiobencarb, reacting mainly by heterolytic C–S bond cleavage. The authors suggest the
cis–trans isomerization and via radicals formed at the mechanisms involved electron transfer from a triplet
N-alkyl and S-dichloroallyl moieties. excited state to oxygen, yielding a radical cation, which
The photochemical degradation of thiram htetra- then cleaves to yield the benzaldehyde derivative.
methylthiuram disulfidej by the action of sunlight and UV
( l .290 nm) was studied in natural waters of Northern
Greece [76]. Two photoproducts were detected, but could 2.23. Triazine pesticides
not be identified. However, and in contrast with a previous
report [140], it was shown that these were not ethyl- Pape and Zabik [142] studied the 254-nm photolysis of
enethiourea or ethylenethioammonium. atrazine h6-chloro-N 2 -ethyl,N 4 -isopropyl-1,3,5-triazine-
The photodegradation of captan hN-(trichloro- 2,4-diaminej, propazine h6-chloro-N 2 ,N 4 -di-isopropyl-
methylthio)cyclohex-4-ene-1,2-dicarboximidej by the UV 1,3,5-triazine-2,4-diaminej, simazine h6-chloro-N,N9-dieth-
radiation ( l .280 nm) supplied by a high-pressure mer- yl-1,3,5-triazine-2,4-diaminej, atraton h2-ethylamino-4-iso-
cury lamp was shown to be more efficient in cyclohexene propylamino-6-methoxy-s-triazinej, prometon hN 2 ,N 4 -di-
and isopropanol than in cyclohexane [77]. The photolysis isopropyl-6-methoxy-1,3,5-triazine-2,4-diaminej, simeton
process takes place via C–Cl bond homolysis. If sufficient hN,N9-diethyl-6-methoxy-1,3,5-triazine-2,4-diaminej, ame-
hydrogen donors are present N-(dichloromethylthio)-cis-4- tryn h2-ethylamino-4-isopropylamino-6-methythio-s-tri-
cyclohexene-1,2-dicarboximide is formed, and then photo- azinej, prometyn hN 2 ,N 4 -di-isopropyl-6-methylthio)-1,3,5-
decomposes, losing thiophosgene to yield tetrahydro- triazine-2,4-diaminej and symetryn hN,N9-diethyl-6-
phtalimide. (methylthio)-1,3,5-triazine-2,4-diaminej in water and in the
The UV photolysis of sodium diethyldithiocarbamate, solvents: methanol, ethanol, n-butanol and benzene. The
thiram (vide supra), captan (vide supra), captafol hN- aqueous photolysis led to the corresponding 2-hydroxy-
(1,1,2,3-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarbox- triazines, the photolysis in methanol to the 2-methoxy-
imidej and folpet hN-[(trichloromethyl)thio]phtalimidej has triazines, etc. The yields observed were high (¯85–90%).
been studied under N 2 atmosphere, photo-oxidation in the Exceptions to this were atraton, prometon and simeton,
presence of oxygen, and by photosensitized oxidation which did not undergo photolysis in methanol, ethanol or
using a 100-W tungsten lamp, also under oxygen atmos- water. No photochemical reactions were observed at
phere [141]. Various photoproducts have been identified, wavelengths longer than 300 nm. In a subsequent paper,
including SH 2 , S 8 , SO 2 , SO 22
4 , CS 2 , amines, hydrazines, these authors studied the photolysis of 2-fluoro- and, 2-
bromo-4,6-bis(ethylamino)-s-triazine, 2-iodo-triazine ana- discussed [149]. The efficiency of atrazine removal de-
logues of atrazine, propazine and simazine and 2-azido-4- pended only on the UV radiation input. Addition of H 2 O 2
ethylamino-6-methylthio-s-triazine in water, methanol, improved the efficiency of photodegradation, but required
ethanol and n-butanol [143]. From considerations of higher UV doses. The main photoproduct identified was
thermal, photochemical and spectroscopic data, the authors hydroxyatrazine.
suggest the involvement of a Chugaev-type cyclic transi- Niessner et al. [125] studied the aqueous photodegrada-
tion state in the dealkylation of s-triazines. tion of atrazine (vide supra) by UV light in the presence of
Atrazine (vide supra) has been showed to photo- O 2 and using a combination of O 2 / O 3 at a pilot plant for
dehalogenate in aqueous solution, with subsequent photo- drinking water treatment. The photodegradation rate was
dealkylation of the hydroxylated compounds to the mono- not enhanced by the last combination with respect to O 2 .
and nonalkylated species [144]. However, in experiments carried out at large scale in field
Mamaev et al. [145] found that nitro-1,3,5-triazines may conditions the degradation of atrazine and desethylatrazine
be obtained by photooxidation of azido-1,3,5-triazines by improved with increasing O 3 dose and increasing radiant
atmospheric oxygen. power.
A laser microprobe analysis, using 266 nm laser light, Similarly, Lai et al. [150] studied the photooxidation of
was applied to study the photodegradation of atrazine (vide simazine (vide supra) by UV radiation in the presence and
supra), propazine (vide supra) and simazine (vide supra) absence of O 3 . Simazine disappearance increased with UV
[146]. The photoproducts were detected using time-of- intensity, yielding dechlorination byproducts. In contrast,
flight mass spectrometry, and the results showed that the the combination of UV radiation with O 3 led to the
main process is ring-opening, with or without chlorine generation of dealkylation, deamination and dechlorination
expulsion. byproducts.
Dore´ et al. [130] studied the aqueous phototransfor- The UV photolysis of two products of photodegradation
mations of atrazine by 254 nm and polychromatic light. of atrazine (vide supra), namely deethylatrazine and de-
The main photoproducts found upon UV photodegradation, isopropylatrazine was studied [151]. Significant reductions
identified by their mass spectra, were hydroxy atrazine, in the rate of photodegradation were observed in surface
6-chloro-N-isopropyl-2,4-diamino-1,3,5-triazine, 6-chloro- waters, which the authors attribute to the presence of
N-ethyl-2,4-diamino-1,3,5-triazine, 6-hydroxy-amino- natural radical scavengers. No attempts were made to
1,3,5-triazine, ammeline, (N,N9)-isopropyl-2,4-diamino- identify by-products of these photolysis reactions.
1,3,5-triazine, 6-chloro-2,4-diamino-1,3,5-triazine and 6- The photodegradation of ametryn (vide supra), atraton
hydroxy-N-ethyl-2,4-diamino-1,3,5-triazine. The authors (vide supra), atrazine (vide supra), propazine (vide supra),
propose a complex mechanism including oxidations, simazine (vide supra) and terbuthylazine h2-chloro,4-tert-
dealkylations and hydrolyses. The authors also suggest a butylamino,6-ethylamino,(1,3,5)-triazinej by the radiation
significant involvement of radicals in these processes. supplied by a xenon lamp were investigated in aqueous
Recently, using a medium pressure mercury lamp, and buffered solutions (pH 7–9) containing a small
´
Hequet et al. [147] estimated the half-live of atrazine percentage of acetonitrile [152]. The quantum yields for
around 5 min, the corresponding 2-hydroxy-atrazine being photodegradation were measured, and comparable values
the major photoproduct. (¯5%) found. A temperature dependence was observed
Barcelo´ et al. [83] studied the photodegradation of the for the photodegradation of terbuthylazine, which allows
herbicide propazine (vide supra) in aqueous solution, using the estimation of an activation energy ¯13 kJ mol 21 .
a suntest apparatus. According to the authors, the main Atraton showed a very low photodegradation quantum
photodegradation pathways correspond to dealkylation, yield, ¯0.2%, which shows that it can be considered not to
hydroxylation and dehalogenation, leading to deiso- be significantly photodegradable under the conditions used.
propylpropazine (deethylatrazine), hydroxypropazine and The photodegradation quantum yields in acetonitrile and
2-H analogues. A tentative photodegradation mechanism is hexane for terbuthylazine are about one half of the values
proposed. observed in water. From the observed data, half-lives for
The photodegradation of cyanazine h2-(4-chloro-6- these pesticides under sunlight can be estimated, ranging
ethylamino-1,3,5-triazin-2-yl-amino)-2-methylpropionitrilej from 39 h to 3 months.
was studied in an aqueous solution bubbled with an The photodegradation of terbuthylazine (vide supra) at
oxygen stream, using a low pressure mercury lamp emit- 254 nm and with simulated sunlight ( l .290 nm) has been
ting monochromatically at 254 nm [148]. The observed studied [153]. The corresponding 2-hydroxylated deriva-
photodegradation quantum yields ranged from 0.05 to tive is generated in a few minutes, and then undergoes a
0.10%, at temperatures between 10 and 40 8C. The authors slow dealkylation to ameline h2-hydroxy,(4,6)-diamino,
hypothesize the existence of a free-radical chain reaction (1,3,5)-triazinej.
mechanism for the photodegradation process. Mansour et al. [46] studied the photolysis of metamitron
The use of an industrial-scale UV chamber to reduce the h4-amino-3-methyl-6-phenyl-1,2,4-triazine-5(4H )-onej and
amount of atrazine in a drinking water supply has been terbuthylazine (vide supra) by UV light of different
wavelengths in water and water / soil suspensions. supra) and simazine (vide supra) in river water at different
Metamitron degraded rapidly, yielding desaminometamit- pH values and contents of dissolved organic carbon, also
ron, which was much more stable. In the case of ter- with buffered samples, under the artificial light supplied by
buthylazine, an important enhancing effect was observed fluorescent tubes (300, l ,400 nm), and upon sunlight
for humic acids, leading to products of oxidation of side photolysis. Photodegradation was initiated by a wide range
chains, such as deethylterbuthylazine. or wavelengths at pH 4, but only wavelengths lower than
The photodegradation of five non-commercial unsatu- 300 nm were able to initiate it in near-neutral media. On
rated triazines with pesticide activity was investigated in this basis, and considering the rates of hydrolysis of these
water, using a mercury lamp [154]. It was observed that pesticides at different pH values, the author estimates the
the photodegradation efficiency was enhanced by the half-life of the studied pesticides in acidic upland waters as
presence of unsaturated substituents. nearly a week, some months for lowland river and years
Albanis and Konstatinou [92], when studying the photo- for groundwaters.
degradation of atrazine (vide supra), propazine (vide supra) The antifouling agent Irgarol h2-methylthio-4-tert-
and prometryn hN,N9-bis(1-methylethyl)-6-(methylthio)- butylamino-6-cyclopropylamino-s-triazinej is rather stable
1,3,5-triazine-2,4-diaminej, found the half-life of the com- toward hydrolysis, but undergoes sunlight photodegrada-
pounds to be ¯1–2 months in water and ¯1 month in tion in aqueous solution [80], the process being much
soils. The presence of humic substances produced a faster in natural waters. Three main photoproducts were
reduction of the photodegradation rate in water and an observed, with two of them being stable even after 6
enhancement in soil. The major photoproducts found were months irradiation.
the hydroxy and dealkylated derivatives. Lin et al. [39] studied the effect of simulated sunlight on
The photodegradation of metribuzin h4-amino-6-tert- atrazine (vide supra) toxicity of surface waters, concluding
butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-onej in that the toxicity of the herbicide is reduced, possibly
water was studied using a low pressure mercury lamp through photodegradation. The observed reduction of
[155]. Desaminometribuzin, diketometribuzin and de- toxicity was higher in bay water than in fresh water.
saminodiketometribuzin were identified as photoproducts, Breithaupt and Schwack [158] studied the photoinduced
plus six other unknown metabolites resulting from side- addition of the fungicide anilazine h4,6-dichloro-N-(2-chlo-
chain degradation, some of which were very stable toward rophenyl)-1,3,5-triazin-2-aminej to cyclohexene and
photolysis. Inorganic and organic ions, such as mono- methyl oleate upon irradiation with a metal halogen lamp.
carboxylic, dicarboxylic and ketocarboxylic acids were Both olefinic compounds were used as models for plant
also formed by side-chain degradation and ring cleavage. cuticle components. Extensive reaction of anilazine with
Mansour et al. [81] studied the photodegradation of the cis-double bond of both olefins was observed. The
terbuthylazine (vide supra) in distilled water and in soil addition is considered to be radical-mediated, the initial
using simulated sunlight ( l $290 nm), in the presence and step being suggested as C–Cl bond cleavage. The conclu-
absence of humic acids. The half-life time in water, sion is drawn that photochemical reactions within the plant
without and with humic acids added were, respectively, cuticle can lead to the formation of bound-residues of
¯23 and 8 h. The photodegradation process followed anilazine with unsaturated biomolecules.
pseudo-first kinetics. Dealkylation was the main degra- Detailed studies of the first stages of photodegradation
dation pathway, the main photoproducts being desethylter- of a variety of triazines using laser flash photolysis
buthylazine and desisobutylterbuthylazine. combined with pulse radiolysis showed the photodegrada-
The photodecomposition of 4-amino-1,2,4-triazin-3,5- tion is monophotonic when 193 nm light is used for
diones and 4-amino-1,2,4-triazin-thiones in oxygenated excitation. It was not possible to observe the generation of
aqueous solutions at different pH values were studied by intermediates in the nanosecond time-scale using higher
Raschke et al. [156]. Deamination, decarboxylation and wavelengths (222, 248, 266 nm). The photodegradation,
dealkylation reactions were observed. Dealkylation was a however, certainly takes place and has been observed when
slow and non-selective process. The details of the pro- samples were exposed to 254 nm steady-state photolysis,
posed mechanisms were discussed. and the some major photoproducts identified by HPLC,
A laser flash photolysis study of the photodegradation of comparing them with authentic samples. Photoionization
s-triazine, ametryn (vide supra), desmetryn h2-iso- was observed for all compounds when photolysis was
propylamino-4-methylamino-6-methylthio-s-triazinej, pro- carried out at 193 nm, with very low quantum yields. The
metryn (vide supra) and terbutryn h2-tert-butylamino-4- rate constants for the one-electron oxidation of the tri-
2
azines with SO ?2 ?
ethylamino-6-methylthio-s-triazinej by 193 nm UV light 4 , one-electron reduction with e aq and HO
showed all the compounds underwent monophotonic addition were obtained, using both the laser flash photo-
photoionization, with yields less than 10%. No significant lysis and the pulse radiolysis techniques. The fact that HO ?
photoionization was observed when using longer wave- undergoes addition to the aromatic ring, and not one-
lenghts [157]. electron oxidation, has been proved by experiments per-
Comber [82] studied the photolysis of atrazine (vide formed with conductance detection. The one-e 2 reduction
with e 2
aq has also been studied, and the corresponding rate phenoxymethyl)-1,2,4-triazole, 1-(4-chlrophenoxy)-2,2-di-
constants obtained. Triazines have been shown to quench methyl-1-(1,2,4-triazol-1-yl)propane, 1-(1,2,4-triazol-1-
the fluorescence of excited UO 212 . The rate of decay of the yl)-3,3-dimethylbutan-2-one and 1-(4-chlorophenoxy-3,3-
laser flash photolysis generated uranyl in the presence and dimethyl-1-(1,2,4-triazol-1-yl)butan-2-ol [163]. The ob-
absence of triazines has been measured. All these results served reactions followed first order kinetics. The authors
allow to confine the one-electron reduction potential of suggest the main processes taking place upon photolysis
triazines to the interval 2.4 , E8(T ?1 /T ) , 2.7 V vs. NHE. are C1 to C2 and C1 to triazole bond cleavage, hydrolysis,
The observed photoproducts, detected using HPLC, have reduction and extrusion of C=O.
been studied upon irradiation at 254 nm, obtaining mainly Murthy et al. [85] studied the photodegradation of
the 2-hydroxy derivative and, in minor amounts, photo- triadimefon (vide supra) and epoxiconazol h(2RS,3SR)-1-
products dealkylated in the side chains bind to the amino [3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)-propyl]-
groups. Structure–reactivity correlations have been estab- 1H-1,2,4-triazolej under simulated sunlight, using a xenon
lished in order to predict the reactivity of other triazines suntest lamp. Triadimefon degraded to 21% in 72 h, and
upon direct photolysis [157,110,159–161]. epoxiconazol to 12% in 120 h. When the same pesticides
were photolyzed in soil containing 6% moisture the
observed levels of photodegradation were, respectively, 37
2.24. Triazinone herbicides
and 56% in 72 h. p-Chlorophenol was identified as
photoproduct upon photodegradation of triadimefon.
The aqueous photodegradation of metamitron h4-amino-
The photophysics and photochemistry of triadimefon
3-methyl-6-phenyl-1,2,4-triazin-5(4H )-onej by UV radia-
h1-(4-chlorophenoxy)-3, 3-dimethyl-1-(1H-1, 2, 4-triazol-1-
tion from a xenon lamp and by sunlight has been studied
yl)butan-2-onej and triadimenol h1-(4-chlorophenoxy)-3,3-
[84]. The study included UV and phosphorescence spec-
dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-olj in solution
troscopy, determination of quantum yields at different pH
have been studied. 4-Chlorophenol and 1,2,4-triazole were
values and determination of the photoproducts. No reaction
identified in both cases as major photodegradation prod-
was observed in methanol, acetonitrile and hexane, or in
ucts. The photodegradation quantum yield of triadimefon
water in the dark. The photodegradation products found in
in cyclohexane at 313 nm is 0.022, whereas triadimenol is
aqueous solution were deamino metamitron and an un-
reported as photostable under the same conditions. Flash
identified compound. The triplet energy was obtained by
photolysis experiments showed the presence of 4-chloro-
phosphorescence spectroscopy (ET ¯245 kJ mol 21 , to be
phenoxyl radicals, pointing to a mechanism via homolytic
compared with ES ¯325 kJ mol 21 ). This does not allow to
cleavage of the C–O bond of the asymentric carbon [164].
discard a possible reaction involving the triplet state. In
view of its pKa and the fact that the photodegradation
quantum yields at pH 4 and 9 were comparable (¯1.6%),
2.26. Urea-based herbicides
the participation of the hydroperoxyl radical (HO ?2 ) cannot
explain the photodegradation of metamitron. The photo-
Metobromuron h3-p-bromophenyl)-1-methoxy-1-methyl-
degradation quantum yield at pH 7 was a factor of 2
ureaj was used as a model compound to study the sunlight
higher, which the authors attributed to the influence of the
photodegradation of urea-based herbicides [86]. Upon
phosphate buffer used. The photodegradation of metamit-
exposure to sunlight for 17 days, the major photoproduct
ron is strongly dependent on the presence of oxygen. The
found was 3-( p-hydroxyphenyl)-1-methoxy-1-methylurea.
mechanism of generation of the photoproducts is unclear.
Minor products were 3-( p-bromophenyl)-1-methyurea and
p-bromophenylurea, with experimental evidence for the
2.25. Triazole fungicides existence of a dimerization product.
The sunlight photolysis of linuron h3-(3,4-dich-
In the presence of humic acid the photodegradation of lorophenyl)-1-methoxy-1-methylureaj and monuron h3-(4-
triadimefon h1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H- chlorophenyl)-1,1-dimethylureaj was studied [87]. After 2
1,2,4-triazol-1-yl)butan-2-onej changed only from 87 to months exposure, linuron yielded 13% 3-(3-chloro-4-hy-
91% after 4 h [111,112]. droxyphenyl)-1-methoxy-1-methylurea, 10% 3,4-di-
The photodegradation of folicur h1-(4-chlorophenyl-4,4- chlorophenylurea and 2% 3-(3,4-dichlorophenyl)-1-
dimethyl-3-(1H-1,2,4-triazole-1-yl)methyl)-pentan-3-olj methylurea. Upon photolysis of monuron, 3-( p-hydroxy-
by UV radiation has been studied in benzene, ether, phenyl)-1,1-dimethylurea was identified as photoproduct.
methylene chloride, methanol [162]. Two photoproducts Kotzias and Korte [88] reviewed the photochemistry of
have been observed and identified by chromatography / phenylurea herbicides and their environmental reactions.
spectroscopy and direct comparison with authentic sam- The authors conclude that substituted phenylurea her-
ples. bicides are degraded by UV and sunlight, the degradation
The photodegradation of triadimefon (vide supra) by 254 being influenced by the presence of oxygen. H abstraction
nm light on glass and soil surfaces led to 1-(4-chloro- is the main process in methanol, phenols are the main
photoproducts in water, while C–C bond scission takes replacement of halogen substituents by OH groups, (iii)
place in benzene. replacement of halogen substituents by H atoms.
Tanaka et al. [35] studied the generation of biphenyls Jirkovsky´ et al. [90] studied the photolysis of diuron
upon sunlight photolysis of monuron (vide supra), diuron h3-(3,4-dichlorophenyl)-1,1-dimethylureaj using various
h3-(3,4-dichlorophenyl)-1,1-dimethylureaj, linuron (vide different wavelengths between 254 and 350 nm. According
supra) and metobromuron h3-(4-bromophenyl)-1-methoxy- to their results, the major photoproducts resulted from a
1-methylureaj. The photoreactions proceeded via coupling photoheterolysis process followed by substitution of Cl by
of two herbicide molecules, leading to a chlorinated OH. Different photoproducts were observed depending on
biphenyl. The yields of biphenyls observed were very low, the wavelength used during the photolysis: 3-(4-chloro-3-
suggesting a high photolability that would lead to their fast hydroxyphenyl)-1,1-dimethylurea was the major product
degradation, such that they would only accumulate to a when photolysing with 254 nm, while 3-(3-chloro-4-hy-
very low extent. droxyphenyl)-1,1-dimethylurea was the main one when
The photodegradation of 1,3-dimethyl-1-(2-(3-fluoro- using 365 nm light.
benzylthio)-1,3,4-thiadiazol-5-yl)urea has been studied in Mansour et al. [46] investigated the photolysis of
methylene chloride using the UV radiation provided by a isoproturon (vide supra) by UV light of different wave-
mercury lamp has been studied in a thin film and in lengths in water and water / soil suspensions. Irradiation of
solution [165]. Two photoproducts were found and char- isoproturon in the presence of organic matter shows that
acterized. The rearrangements involved an S to N benzyl photolysis in inert atmosphere is faster, suggesting that
migration, followed by a sulfur–oxygen substitution. molecular oxygen might act as a quencher.
Tanaka et al. [89] also studied the photolysis of diuron The photolysis of chlorotoluron h3-(3-chloro-p-tolyl)-
h3-(3,4-dichlorophenyl)-1,1-dimethylureaj using UV lamps 1,1-dimethylureaj in acetonitrile, hexane and aqueous
and natural sunlight. Seven photoproducts, with similar solutions buffered to pH 4, 7 and 9, and of isoproturon
yields, were identified in both cases. (vide supra) in aqueous and buffered solutions by the
A study of the photodegradation of diuron h3-(3,4- radiation supplied by a Xe lamp were investigated [169].
dichlorophenyl)-1,1-dimethylureaj has been reported using Both herbicides were degradable by l ,240 nm, but
simulated sunlight in distilled water and artificial seawater photostable when l .240 nm. In the case of chlorotoluron
containing humic acids [166]. The main photoproduct was in aqueous solution, the main photoproduct found was
monuron h3-(4-chlorophenyl)-1,1-dimethylureaj, a product 3-(3-hydroxy-4-methyl-phenyl)-1,1-dimethylurea, while
of dechlorination. A quenching effect was observed by the the quantum yields for photodegradation were ¯0.07 in
chloride ions present in seawater, leading to retardation of aqueous and buffered solutions, ¯0.035 in acetonitrile,
the photodegradation. and 0.70 in hexane. In the case of isoproturon the quantum
The photoreduction of 1-(2-chlorobenzoyl)-3-(4-chloro- yield obtained for photodegradation was ¯0.004 in all
phenyl)urea in methanol was studied using a Xe lamp solutions.
[167]. The observed process followed in all cases first- The photodegradation of hexaflumuron h1-[3,5-dichloro-
order kinetics, with rate constants in O 2 atmosphere greater 4-(1,1,2,2,-tetrafluoroethoxy)phenyl]-3-(2,6-difluoroben-
than in N 2 atmosphere. The main photoproducts found zoyl)ureaj, teflubenzuron h1-(3,5-dichloro-2,4-difluoro-
were 2-chlorobenzamide, N-phenylmethylcarbamate, N-(4- phenyl)-3-(2,6-difluorobenzoyl)ureaj and diflubenzuron
chlorophenyl)methylcarbamate and 4-chlorophenyl urea. hN - [((4-chlorophenyl)amino)carbonyl] - 2, 6 - difluoroben-
Dore´ et al. [130] studied the aqueous photodegradation zamidej in river water buffered to pH 9.0 was studied
of isoproturon h3-(4-isopropylphenyl)-1,1-dimethylureaj [170]. Hexaflumuron was the most rapidly degraded, with
by 254 nm and polychromatic light, and found N-(4- a half-life of 8.6 and 5.0 h at pH 7 and 9, respectively.
isopropyl-hydroxyphenyl)-N9 -methylurea, N-(4-isopropyl- Diflubenzuron was the slowest to degrade, with half-life
phenyl)-N9 -dimethylurea and N-(4-isopropyl-phenyl)-N9 - times of 17 and 8 h at pH 7 and 9. Dark controls showed
acetamide as main photoproducts. The authors propose a no loss of the parent compounds over similar time periods.
complex mechanism involving hydroxylation, demethyla- The initial stages of photodegradation of various urea-
tion and deamination reactions, possibly with participation based herbicides has been studied using laser-flash photo-
or radical intermediates. lysis and pulse radiolysis. Radical cations are generated
The photochemical degradation of nine different urea- immediately after the laser pulse, and deprotonate to yield
based herbicides in aqueous solution by UV light supplied neutral radicals. The quantum yield of 193 nm photoioni-
by a low pressure mercury lamp was studied, and the main zation are ¯10%. Pulse-radiolytic one-e 2 oxidation with
photoproducts identified [168]. The quantum yields for SO ?2
4 also yields the radical cation and, after deprotona-
photodegradation ranged from 0.5% for fenuron h3-phenyl- tion, the neutral radical. Semiempirical simulations of
1,1-dimethylureaj to 13% for monuron (vide supra). The UV–Vis spectra support the experimental observations. A
observed photoproducts were formed through three differ- bathochromic displacement of the bands of the radical
ent pathways: (i) cleavage of the N–O bond in the case of cation is observed as the number of e 2 -withdrawing ring
pesticides containing an N-methoxy moiety, such as substituents increases. The extinction coefficients of the
linuron (vide supra), with formation of formaldehyde, (ii) radical cation and neutral radical are, respectively, ¯3000
and ¯2000 M 21 cm 21 . The pKa for deprotonation of the photolysis reaction took place at about the same rate in
radical cation is ¯0. The reaction with hydroxyl radical seawater and in distilled water. Photooxidation, photonu-
has also been studied, both by laser flash photolysis and cleophilic substitution and photoreduction reactions are
pulse radiolysis, and the rate constants obtained. The observed. The amount of photoreduction products was
photoproducts observed by GC–MS and HPLC, and in higher than in distilled water.
some cases checked against authentic samples, are the The photolysis of the fungicide and bactericide 2-mer-
corresponding anilines and the photo-Fries products. Fur- captobenzothiazole, and of the p-isoelectronic 2-mercap-
thermore, the rate constants for one-electron reduction with tobenzimidazole by UV radiation in benzene, toluene,
e2 ?
aq and for HO addition have been obtained. Structure– methanol, ethanol and acetonitrile by UV radiation has
reactivity correlations have been established in order to been studied [176]. The thiazole derivative yielded bis-(2-
predict the reactivity of other ureas upon direct photolysis benzothiazolyl)disulfide in benzene and toluene and bis-(2-
[171,110,172,173]. benzothiazolyl)disulfone and eventually benzothiazole sul-
phate when methanol, ethanol and acetonitrile were the
2.27. Miscellaneous solvents. The imidazole led to bis-(2-benzimidazolyl)disul-
fone and benzimidazole sulfate when methanol, ethanol
Neihof et al. [60] evaluated the sunlight photodegrada- and acetonitrile were used as solvents.
tion of the biocides mercaptopyridine-N-oxide, sodium-2- Jensen-Korte et al. [177] studied the aqueous photo-
mercaptopyridine-N-oxide, 2-(tert-butylamine)-mercap- degradation of various types of pesticides: carbamates,
topyridine-N-oxide and 2,29-dithio-bis-(pyridine-N-oxide) phosphates, pyrethroids, triazoles and ureas using a high
in artificial seawater and in aged natural seawater sterilized pressure mercury lamp. In all cases the photodegradation
by autoclaving. The biocide activity dramatically reduced rate increased in the presence of humic substances.
after 5–10 h of exposure to sunlight. UV spectral measure- Irradiation by 313 nm light supplied by a high-pressure
ments showed that pyridine-N-oxide-2-sulfonic acid was mercury lamp of 1,3-dihydro-2H-benzimidazole-2-thione,
an early photoproduct. An unidentified insoluble photo- 2(3H )-benzothiazolethione and 2-chlorobenzothiazole has
product was also observed. According to the authors, been studied in the presence of oxygen in 1% acetonitrile,
temperature, pH and salinity were not relevant variables. ethanol or benzene solutions. The main photoproducts
The rates of loss of toxicity were lower in the presence of were disulfides, 2-oxo-derivatives, benzimidazole, ben-
oxygen. zothiazole and elemental sulfur [178]. The authors discuss
The photodegradation of the fungicide isoprothiolane a possible mechanism for such processes, starting with a
hdiisopropyl 1,3-dithiolan-2-ylidnemalonatej by 254 nm S–H bond homolysis and / or oxidation due to singlet
UV light on solid particles yielded oxalic acid, oxygen formation. The intermediates, however, have not
dithiolanylidenemalonic acid, dithiolanylideneacetic acid, been detected.
2,4-bis[bis(isopropoxycarbonyl)methylene]-1,3-dithietane, The UV photolysis of thioamides was studied using low
3, 5 - bis[bis(isopropoxy - carbonyl)methylene]1, 2, 4 - tri- pressure mercury lamps under nitrogen and oxygen atmos-
thiolane and sulfur [174]. Photolysis of the methyl and phere [179]. The photoproducts found under nitrogen were
ethyl analogues yielded the corresponding photoproducts. nitriles and H 2 S, while under oxygen, nitriles, amides,
Based on product analysis, the authors propose the in- carboxylic acids, 3,5-disubstituted-1,2,4-thiadiazoles, SO 2
volvement of dithiolane ring cleavage, ester hydrolysis, and SO 422 were formed. Photodegradation of secondary
decarboxylation, dithiethane and trithiolane formation and and tertiary thioamides was negligible both in inert and
sulfur liberation. A surface effect was observed, the oxidant atmosphere. The mechanism of photolysis under
photodegradation being much more rapid on sand than on nitrogen is proposed to take place through an intermediate
a glass plate. The authors observed the same phenomena biradical, centered on the C and S, that would undergo
also with other sulfur-containing pesticides. hydrogen transfer followed by elimination of H 2 S. The
Badr et al. [175] studied the photolysis of photolysis under oxygen is explained assuming the forma-
phenylacetamide, N-benzylphenylacetamide and tion of an intermediate sulphinic acid, that could eliminate
phenylacetanilide in air using a mercury lamp. The photo- H 2 SO 3 to give a nitrile or hydrolyse to an amide or
products obtained from phenylacetamide were benzal- carboxylic acid and ammonia.
dehyde, toluene, bibenzyl, stilbene and phenanthrene. In A comparative study between fragmentation processes
addition to these, benzylamine was found upon photolysis taking place in mass spectrometry using an electron
of N-benzylphenylacetamide, and aniline, N-benzylaniline, ionization source and photodegradation processes has been
o-aminodiphenylmethane and p-aminodiphenylmethane carried out for atrazine (vide supra), simazine (vide supra)
following photolysis of phenylacetanilide. The authors and trietazine h6-chloro-N 2 ,N 2 ,N 4 -triethyl-1,3,5-triazine-
suggest the mechanism proceeds via C–N bond homolysis 2,4-diaminej [180]. Simazine showed the lowest tendency
to yield phenylacetyl and aminyl radicals, that would lead to fragmentation, and atrazine the highest. The same kind
to the observed photoproducts. of fragmentations were observed for the three compounds:
Miille and Crosby [53] studied the photodegradation of C–N bond cleavage in the lateral chains, C–Cl bond
3,4-dichloroaniline by simulated sunlight in seawater. The scission and heteroatomic ring cleavage.
Sharma and Chibber [181] studied the sunlight photo-

degradation of diniconazole h(E)-(RS)-1-(2,4-dichloro-
phenyl) - 4, 4 - dimethyl - 2 - (1H - 1, 2, 4 - triazol - 1 - yl)
pent-1-en-3-olj as a thin film on glass surface. The
photoproducts generated were separated and identified as
the (Z)-isomer of diniconazol, a cyclic alcohol and its
corresponding ketone, and an isoquinoline.
Mushtaq et al. [40] studied the photodegradation of
emamectin benzoate h40-deoxy-40-(epi-methylamino)aver-
mectin B 1a benzoatej in aqueous solution buffered to pH 7
and natural pond water under sunlight. Avermectins are
16-member lactones, used as insecticides. The sunlight
photodegradation in the mentioned media took place in 22
and 7 days, respectively. Upon continuous exposure to
light from a Xe lamp, photodegradation of aqueous
solutions of the pesticide, buffered to pH 7 and containing Scheme 2. Chemical events taking place upon photosensitized photolysis
1% acetonitrile or ethanol as cosolvents took place in 64.5 involving energy transfer.
and 8.5 days, respectively. A photoisomer and unknown
polar residues were found as photoproducts. The amount
of polar residues found increased with the time of irradia- pesticides, that can undergo different processes, as follow-
tion. ing direct photodegradation (Scheme 2).
Miller et al. [61] reported a big difference in the rate of Photosensitization may also involve redox processes,
photolysis of methylisocyanate which, while stable in such as the photo-Fenton reaction, where there is an initial
water, has a half-life time of less than 1 day under electron or atom transfer to produce free radicals, but the
midsummer sunlight. oxidised or reduced sensitizer undergoes subsequent re-
The influence of soil and sediment composition on the actions to regenerate the initial species [184–186,54,187].
photodegradation of napropamide h(RS)-N,N-diethyl-2-(1- Some examples of this will be given in Section 5.
naphtyloxy)propionamidej has been studied using a photo- An important advantage of photosensitized photodegra-
reactor emitting with a spectrum 300, l ,450 nm, with a dation is the possibility of using light of wavelenghts
maximum at 365 nm [182]. Soil or sediment reduced the longer than those corresponding to the absorption charac-
rate of photolysis, although no dependence on its com- teristics of the pollutants.
position was found.
Dureja et al. [183] studied the photodegradation of the 3.1. Anilide herbicides
insecticide azadirachtin hdimethyl[2aR-[2aa,3b,4b
(1aR * , 2S * , 3aS * , 6aS * , 7S * , 7aS * ), 4ab, 5a, 7aS * , 8b (E), The aqueous photodegradation of butachlor hN-(butox-
10b, 10aa, 10bb ]] - 10 - (acetyloxy) octahydro - 3, 5 - dihy- ymethyl)-2-chloro-29,69-diethyl-acetanilidej by sunlight in
droxy - 4 - methyl - 8 - [2 - methyl - 1 - oxo-2-butenyl) oxy]-4- the presence of diethylamine increased significantly rela-
(3a,6a,7,7a-tetrahydro-6a-hydroxy-7a-methyl-2,7-meth- tive to the process in its absence [36]. In this case the light
anofuro[2, 3 - b]oxireno[e]oxepin - 1a(2H ) - yl) - 1H,7H- is absorbed by the pesticide, and it is probable that, as with
naphtol[1, 8-bc: 4, 4a - c9]difuran-5, 10a(8H ) - dicarboxylatej other reactions involving excited states of aromatic mole-
upon 254 nm irradiation as a thin film on a glass surface. cules and aliphatic amines the reaction involves electron
The half-life of azadirachtin was ¯48 min, yielding an transfer [188].
isomerised (Z)-2-methylbut-2-enoate product. Irradiation
in the presence of saturated fatty acids and fatty oils led to 3.2. Carbamate insecticides
an increase in the rate of photodegradation. Conversely,
irradiation in the presence of unsaturated fatty acids such The degradation of mercaptodimethur h4-methylthio-3,5-
as oleic, linoleic and elaidic acid reduced the rate of xylyl methylcarbamatej and ethiofencarb (vide supra)
photodegradation. photosensitized by anthraquinone in an acetonitrile / water
mixture, has been studied, using a medium-pressure mer-
cury lamp as radiation source [189]. The degradations were
complete after irradiating for 0.5 and 0.8 h, respectively.
3. Photosensitized degradation For mercaptodimethur, the observed photoproducts were
3,5-dimethyl-4-methylsufinylphenol (50%) and 3,5-di-
Photosensitized photodegradation is based on the ab- methyl-4-methylthiophenol (49%) and 3,5-dimethyl-4-
sorption of light by a molecule. In one possible scenario, methylthio-2-N-methylacetamidophenol (1%). For
this can then transfer energy from its excited state to the ethiofencarb, the observed photoproducts were 2-hydroxy
benzaldehyde (55.5%), 3-methyl benzo[e] [1,3] oxazine- rates, by hydroxyl radicals produced by nitrate and nitrite,
2,4-dione (33.3%) and o-hydroxybenzaldehyde (11.3%). and by photo-oxidants generated by humates, probably
The authors hypothesise different mechanisms leading to singlet oxygen or peroxyl radicals. Tests performed using
the observed products, taking place by electron transfer combinations of these photosensitizers led to first-order
from the pesticide to the excited anthraquinone. rate constants ranging from 0.03 to 0.048 h 21 . Although
HO ? radicals tend to enhance the photooxidation, their
3.3. Chloroaromatic pesticides effect is diminished due to scavenging by humates. The
authors point out that photo-oxidants generated by humates
Julliard et al. [79] investigated the N,N,N9,N9-tetra- appear to be of greater environmental significance than
methylbenzidine photosensitized reductive dechlorination HO ? in the photodegradation of MCPA.
of chloroneb h2,5-dichloro 1,4-dimethoxybenzenej, 4,49-
DDT h1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethanej and 3.4. Imidazolinone herbicide
MCPA methyl ester h4-chloro-2-methylphenoxy methyl
acetatej, in an ethanol / water mixture using sodium sulfite The photodegradation of imazapyr h2-(4-isopropyl-4-
as sacrificial electron-donor. After 7 h of irradiation of methyl-5-oxo-2-imidazolin-2-yl)nicotinic acidj by simu-
chloroneb, 95% dechlorination was observed, with the lated sunlight was studied at pH 7 in the presence of humic
main photoproducts being 2-chloro-1,4-dimethoxybenzene acids [191]. The study was carried out at different ratios of
(80%) and 1,4-dimethoxybenzene (20%). 2 h of irradiation imazapyr to humic acid (1:0.1, 1:0.5, 1:1), and the
of 4,49-DDT led to quantitative degradation, the main concentration of remaining herbicide followed by HPLC.
photoproduct being 4,49-dichorodiphenyl dichloroethane, The photolysis followed first-order kinetics, with the
that subsequently dehalogenated. Irradiation of MCPA presence of humic substances slowing down the photo-
methyl ester for 2 h led to complete conversion, 2(2- degradation rate.
methylphenoxy)methyl ethanoate being formed. The re-
sults show that the presence of an electron donor may 3.5. Organophosphorus pesticides
increase the rate of dehalogenation of haloaromatic pes-
ticides. Barcelo´ et al. [166] studied the photodegradation of
The application of tris-2,29-bipyridylruthenium(II) per- fenitrothion (vide supra) in distilled water and artificial
oxydisulphate as a photosensitizer for the oxidative photo- seawater using a suntest apparatus to simulate sunlight.
degradation of 4-chlorophenol has been studied in detail Direct photolysis was very slow and no breakdown prod-
[190]. Tris-2,29-bipyridylruthenium(II) is water soluble, ucts were observed after 3 h of irradiation. When 20%
easy to immobilize in polymers, absorbs strongly in the acetone was added as photosensitizer, different metabolites
visible (e (450 nm)¯1.4310 4 M 21 cm 21 ) and emits fluo- were observed, which were tentatively assigned to fenit-
rescence at 620 nm. Upon photoexcitation, the excited rooxon, carboxy-fenitrothion and 3-methyl,4-nitrophenol.
state of the cation is quenched by S 2 O 822 to generate the The photodegradation of vamidothion (vide supra) by
strong oxidants Ru(bpy) 331 and SO 4?2 : simulated sunlight has been studied in water / methanol
(2–4%) with 5% acetone added as a photosensitizer [64].
3 1 hn → (Ru(bpy) 3 ) *
Ru(bpy) 21 21
The major photoproduct observed was vamidothion sulfox-
ide.
Kamiya and Kameyama [192] studied the photochemical
3 ) * 1 S 2 O 8 → Ru(bpy) 3 1 SO 4 1 SO 4
(Ru(bpy) 21 22 31 22 ?2
effects of humic materials on the degradation of various

The photodegradation was carried out using a medium organophosphorus pesticides: bensulide hS-2-benzenesul-
pressure mercury lamp with cut-off filters to suppress the fonamidoethyl O,O-di-isopropyl phosphorodithioatej,
short wavelengths. 4-Chlorophenol undergoes rapid photo- chlorpyrifos (vide supra), diazinon (vide supra), EPN hO-
oxidation. The main photoproducts found were benzo- ethyl O-4-nitrophenyl phenylphosphonothioatej, fenitro-
quinone, 1,4-dihydroxybenzene, 4-chlorocatechol, chloride thion (vide supra), fenthion (vide supra), isofenphos
and sulphate. Prolonged irradiation leads to generation of hO-ethyl O-2-isopropoxycarbonylphenyl isopropylphos-
CO 2 and HCl. The reaction mechanism probably involves phoramidothioatej, isoxathion hO,O-diethyl O-5-phenyl-
one-electron oxidation yielding a radical cation (4-chloro- isoxazol-3-yl phosphorothioatej, malathion hdiethyl
phenol)?1 and or phenoxyl radicals. Further addition– (dimethoxythiophosphorylthio) succinatej, parathion (vide
elimination processes are proposed, eventually leading to supra) and tolchlofos-methyl hO-2,6-dichloro-p-tolyl O,O-
4-chlorodihydroxycyclohexadienyl radicals. dimethyl phosphorothioatej. The authors suggest the sen-
The photodegradation of MCPA h4-chloro-2- sitization effects of humic substances depends on the
methylphenoxy acetic acidj was studied in aqueous solu- binding affinity of pesticides to the radical source of the
tions of naturally occurring photosensitizers, using low humic material. It was also found that metal ions having
intensity 300–450 nm UV light and sunlight [54]. Upon paramagnetic property inhibit the degradation of organo-
UV irradiation, MCPA was photooxidized at significant phosphorus pesticides sensitized by humic acids [193].
A photosensitizing process was suggested to explain the overall and singlet molecular oxygen quenching processes.
enhanced degradation of iprobenfos hS-benzyl O,O-di-iso- Again, a charge-transfer mechanism, involving an initial
propyl phosphorothioatej when poly(3-octylthiophene-2,5- excited encounter complex is suggested.
diyl) films were blended with perylene and N,N,N9,N9-
tetramethylbenzidine (a cation scavenger) [194]. The effect
could be ascribed to an enhancement in O ?2 2 production. 3.9. Triazine herbicides
Cyclodextrins have been shown to have an important
enhancing effect on the rate of photodegradation of Acetone (1%) was used as a photosensitizer in a study
organophosphorus pesticides in water containing humic of the photodegradation of atrazine (vide supra), atraton
substances [193]. Such enhancing effects are attributed to (vide supra) and ametryn (vide supra) in water by light
the inclusion effects of cyclodextrins to catalyze the with l .290 nm from a medium pressure mercury lamp
interaction of pesticides with radicals generated by the [198]. The photostability increased in the order ametryn,
photosensitizing humic acids, that are trapped in the atrazine,atraton. The main photoproducts in all cases
cyclodextrins. were the corresponding de-N-alkyl and de-N,N9 -dialkyl
triazines, as well as the hydroxytriazines. The observation
3.6. Oxadiazole herbicides of two different de-N-alkyl products suggests the de-N-
alkylation to take place in two steps. Higher yields of
The aqueous photodegradation of oxadiazon (ronstar) de-N-ethyl triazines were observed than those of de-N-
h5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4- isopropyl triazines. Irradiation of ametryn yielded also
oxadiazol-2(3H )-onej by sunlight significantly increases in de(methylthio)ametryn. The reaction was strongly sensi-
the presence of diethylamine, added as a photosensitizer, tized by acetone. No breakdown products were observed
relative to the process in the absence of sensitizer [36]. for control dark reactions over 96 h, showing that the
degradation was exclusively due to photolysis.
3.7. Phenylamide fungicides The products of sensitized photooxidation of ametryn
(vide supra), atraton (vide supra), atrazine (vide supra),
Hustert and Moza [195] reported on the aqueous photo- propazine (vide supra) and simazine (vide supra) have been
degradation of carboxin h5,6-dihydro-2-methyl-1,4-oxathi- studied in water, and using sunlight irradiation [199].
ine-3-carboxanilidej and oxycarboxin h2,3-dihydro-6- Methylene blue, Rose Bengal, riboflavin and flavin mono-
methyl-5-phenylcarbamoyl-1,4-oxathi-ine 4,4-dioxidej in nucleotide were used as sensitizers. The primary photo-
the presence of humic and fulvic substances and inorganic degradation products were dealkylated s-triazines and
soil components, using both a high-pressure mercury lamp oxidation products, with a yield of ¯60%.
and a xenon lamp for irradiation. The presence of humic The photosensitized degradation of atrazine (vide supra)
and fulvic materials enhanced photodegradation, possibly was investigated in distilled water and artificial seawater
by forming reactive oxygen species such as singlet oxygen containing humic acids, using simulated sunlight [166].
and hydroxyl radicals. The main photoproduct observed The main photoproduct was hydroxyatrazine. The rate of
for both was oxanilic acid. degradation was faster in seawater, with evidence for
photosensitized degradation of hydroxyatrazine.
3.8. Pyrimidine fungicides The photodegradation of five non-commercial unsatu-
rated triazines with pesticide activity was investigated in
´ et al. [196] studied the Rose Bengal dye-sen-
Garcıa water containing a 5% acetone as photosensitizer, using a
sitized singlet oxygen-mediated photodegradation of 2- mercury lamp [154]. The observed photodegradation ef-
hydroxypyridine, 3-hydroxypiridine, 4-hydroxypiridine, 4- ficiency was higher than in the absence of acetone.
hydroxyquinoline, 8-hydroxyquinoline, 2-hydroxy- Bendig et al. [200] studied the photosensitized photo-
pyrimidine and 4-hydroxypyrimidine in water and in the catalytic oxidation of triazine herbicides by natural sun-
mixture MeOH / MeCN, aiming to use them as models for light. Tris(bipyridyl)ruthenium complexes adsorbed on
pesticides. The photooxidation quantum yields ranged TiO 2 were uses as sensitizers. The authors discuss the
from 1 to 50%, with the higher values occurring in thermodynamic and kinetic requirements for the photo-
aqueous media. The authors suggest a charge-transfer sensitized process. The efficiency of the sensitization
mechanism, involving an initial excited encounter com- seems to be related to the adsorption of the sensitizer and
plex. More recently, the same authors studied the kinetics triazines on TiO 2 .
of Rose Bengal dye-sensitized photooxidation of the model
compound 2-amino-4-hydroxy-6-methylpyrimidine in
water and in acetonitrile / water [197]. The photooxidation 3.10. Urea-based pesticides
quantum yields ranged from 0.5 to 41%, with the higher
values observed in alkaline medium. Rate constants in the Crank and Mursyidi [201] studied the Rose Bengal
range 9310 4 to 2.7310 7 M 21 s 21 are reported for the dye-sensitized singlet oxygen-mediated oxidation of thio-
ureas in ethanol, using low pressure mercury lamps 4. Photocatalytic degradation

emitting mainly at ¯254 nm. According to their results,
and in contrast with a previous work in which the Although different definitions have been suggested for
irradiation was carried out in pyridine [202], thiourea do photocatalysis [204–206], and a detailed discussion is
not undergo photolysis or photo-oxidation in the absence beyond the scope of this review, we use photocatalytic
of sensitizers. Thiourea was shown to react with singlet degradation to mean cyclic photoprocesses in which the
oxygen when using Rose Bengal, methylene blue and pesticides photodegrade, but spontaneous regeneration of
chlorophyll as sensitizers. The reaction was inhibited by the catalyst occurs to allow the sequence to continue
b-carotene. The photoproducts found were cyanamides, indefinitely until all the substrate is destroyed. For a
ureas, products of heterocyclic condensation and sulfur- detailed description of this field, readers are referred to two
containing fragments of the starting materials. Possible excellent multi-author volumes [207,208]. It is clear,
reaction mechanisms are suggested. however, that there will be some overlap between this
A study of the photocatalytic degradation of meto- section and that describing photosensitized processes.
bromuron h3-(4-bromophenyl)-1-methoxy-1-methylureaj
and isoproturon (vide supra) using UV/ TiO 2 showed the 4.1. Amide herbicides
rate of degradation was always lower than when using
hydroxyl radicals [203]. The solution resulting from photo- Pathirana and Maithreepala [209] examined the photo-
degradation of metobromuron was bio-recalcitrant due to degradation of 3,4-dichloropropionamide in aqueous TiO 2
accumulation of bromide intermediates, which was not the suspensions, using 365 nm light. They found acidic
case for the solution resulting from photodegradation of medium to be suitable for the degradation, that occurred
isoproturon. quantitatively via dechlorination within 5 h, yielding Cl 2 ,
H 1 , NO 23 and CO 2 . The presence of O 2 seems to be
relevant. Degradation took place also under sunlight, with
3.11. Miscellaneous 30% yield after 7 h in the absence of TiO 2 and with 70%
yield in its presence. A mechanism for the complete
The anthraquinone photosensitized degradation of perth- photodegradation was tentatively proposed.
ane h1,1-dichloro-2,2-bis(4-ethylphenyl)ethanej has been
studied in an acetonitrile / water mixture, using a medium- 4.2. Bipyridinium herbicides
pressure mercury lamp as radiation source [189]. The
degradation was complete after irradiating for 2 h. The The photocatalytic degradation of paraquat (vide supra)
observed photoproducts were 1,1-dichloro-2,2-bis(4- in water was studied using TiO 2 and a batch of six long
acetylphenyl)ethane (74%), 4-acetyl-49-ethylbenzophenone wavelength UV lamps ( l 5365 nm) [210]. Under these
(21%), 1-chloro-2,2-bis-(4-acetylphenyl)ethene (3.5%), conditions, at high pH complete photodegradation of
and 4,49-diethylbenzophenone (1.5%). The authors indi- paraquat and the reaction intermediates took place in less
cate different possible mechanisms leading to the observed than 3 h, while direct photolysis led to 60% photodegrada-
products, which are suggested to take place by electron tion.
transfer from the pesticide to the excited anthraquinone.
Mushtaq et al. [40] studied the photodegradation of 4.3. Carbamate insecticides
emamectin benzoate (vide supra) in aqueous solution
buffered to pH 7 containing 1% acetone as sensitizer. The A comparison was made of the photocatalytic degra-
sunlight photodegradation in this medium took place in 1 dation of carbetamide (vide supra) in water, using TiO 2
day, much faster than in the absence of sensitizer (see and ZnO and irradiation at l .310 nm [211]. The main
above). Upon continuous exposure to the radiation sup- photoproducts detected were hydroxylated compounds and
plied by a Xe lamp the photodegradation took place in 0.5 products of cyclization of the side chain. After a long
days, also much faster than in the absence of sensitizer. A irradiation time carbetamide underwent complete miner-
photoisomer, epoxide derivatives and unknown polar res- alization.
idues were found as photoproducts. The amount of polar Tanaka et al. [212] studied the photocatalytic degra-
residues found increased with the time of irradiation. dation of MCC hmethyl 3,4-dichlorocarbanilatej, MIPC
Different authors have described the ability of humic h2-(1-methylethyl)phenyl methylcarbamatej, MPMC h3,4-
acids as photosensitizers to promote photooxidation of dimethylphenyl methylcarbamatej, MTMC hm-tolyl
common pollutants. Canonica et al. [187] proved the methylcarbamatej and XMC h3,5-xylyl methylcarbamatej
enhanced photodegradation of electron-rich phenols in in water, using TiO 2 and irradiating with a super-high
presence of humic acids. Increased photodegradation of pressure mercury lamp. The rate of degradation is gov-
monuron and fenuron photosensitised by soil extracted erned by the adsorbability of the pesticides to TiO 2 . The
humic substances has been reported by Aguer and co- degradation was proposed to take place by successive
workers [184,182]. hydroxylation of the aromatic ring or polyhydroxylation,
leading to opening of the aromatic ring to yield oxygenated photolysis, which the authors attribute to result from a
aliphatic intermediates. The degradation was fast, with its dimerization pathway [56].
rate being dependent on the acidity of the medium.
The effect of ionic and non-ionic surfactants on the 4.7. Halobenzonitrile pesticides
degradation of carbaryl h1-naphthyl N-methylcarbamatej
has been studied using simulated solar light and catalysed The sunlight photodegradation of aqueous solutions of
by aqueous TiO 2 suspensions [213]. An inhibition of the bromoxynil (vide supra) was studied in the presence of
degradation rate was observed, depending on the surfactant TiO 2 and Na 4 W10 O 32 [217]. When the pure pesticide was
and on the acidity of the medium. The kinetics of used, TiO 2 was more efficient as a photocatalyst. When the
photodegradation followed a pseudo-first order kinetic law pesticide was used as a formulated solution, W10 O 42 32
below the critical micellar concentration, and a complex became more efficient. The authors suggest that the
behaviour above it. Carbaryl was mineralized to CO 2 , difference in reactivity can be accounted for by the
NO 2 1
3 and NH 4 . different nature of the active species involved in the
The photolysis of propoxur h2-(1-methylethoxy)phenyl photodegradation: HO ? in the case of TiO 2 and an excited
methylcarbamatej has been studied in water using 266 nm 42
polyoxometalate in the case of W10 O 32 .
laser flash photolysis in water, with 2,4,6-triphenyl
pyrylium encapsulated inside supercages of zeolite Y as
photocatalyst under conditions in which propoxur is not 4.8. Organochlorine insecticides
directly altered [214]. According to the authors, the
process could be initiated by one-electron transfer between Vidal [218] has tested the feasibility of photocatalytic
the excited 2,4,6-triphenylpyrylium cation and propoxur to oxidation of lindane h1,2,3,4,5,6-hexachlorocyclohexanej
form the corresponding 2,4,6-triphenylpyrylium radical using TiO 2 , a high pressure xenon arc lamp and a
and propoxur radical cation. parabolic reflector, and found that it is possible to reduce
99.9% of lindane levels in water in acceptable times.
4.4. Chloronicotinoid insecticides Hupka et al. [219] investigated the photocatalytic degra-
dation of lindane in water, using a medium pressure
The TiO 2 -catalyzed photodegradation of imidacloprid mercury lamp and TiO 2 / O 2 . TiO 2 was used in the form of
(vide supra) has been followed as the formulated product rutile, anatase and supported on glass hollow microspheres.
Confidor in tap water. In the presence of TiO 2 a first-order The lowest efficiency of catalysis was observed for rutile
rate equation was followed, and the observed half-life was and the highest for TiO 2 supported on glass microspheres.
144 min, longer than in the absence of TiO 2 (126 min, see 1,2,3-trichloro benzene, g-2,3,4,5,6-pentachloro-cyclohex-
Part 2) [113] 1-ene and a hexachlorocyclohexane (lindane) isomer, a-
HCH, were detected as reaction products after 150 min
4.5. Chlorophenol pesticides irradiation. Similarly, they studied the photocatalytic deg-
radation of p, p9-DDT h1,1,1-trichloro-2,2-bis(4-chloro-
Tseng and Huang [215] studied the removal of phenol; phenyl)ethanej under the same conditions, and with similar
2-, 3- and 4-chlorophenol; 2,3-, 2,4-, 2,5-, 2,6- and 3,4- results in relation to the photocatalysts. Up to ten photo-
dichlorophenol; 2,4,6-trichlorophenol and pentachloro- products were identified in this case.
phenol from water by photocatalytic oxidation using TiO 2 /
UV. The rate of photocatalyzed degradation follows first- 4.9. Organophosphorus pesticides
order kinetics, independent of the pH. The rate increases
with increase in TiO 2 concentration until a maximum of 3 The solar TiO 2 photocatalyzed mineralization of malath-
g l 21 , and then decreases. The influence of the degree of ion (vide supra) has been studied in rinse water of
chlorination was described. agricultural sprayers and in polluted well water [220]. The
The photodegradation of 2,4-dichlorophenol and penta- observed half-life was about 1 h in the presence of TiO 2
chlorophenol was studied in O 2 -free aqueous medium, in and absence of H 2 O 2 . Using polyethylene-film covered
the presence of the hole scavengers polyethyleneimine, vessels it was observed that efficient photodegradation
triethylamine, 2-propanol and ethylenediaminetetraacetic occurred in sealed systems.
acid [216]. The photodegradation of both chlorophenols The photocatalytic removal of fenitrothion (vide supra)
was inhibited by the above mentioned hole scavengers. from TiO 2 suspensions has been studied [221]. Several
intermediates of the photocatalytic photodegradation have
4.6. Dinitroaniline pesticides been identified. These subsequently underwent mineralisa-
tion into CO 2 , H 2 PO 42 , SO 422 and NO 32 .
UV and sunlight induced photolysis of fluchloralin (vide Doon and Chang [222] studied the photocatalytic degra-
supra) in aqueous methanol (80%) in the presence of TiO 2 dation of diazinon (vide supra), EPN (vide supra), malath-
yielded an additional product to those found upon direct ion (vide supra), methamidophos hO,S-dimethyl
phophoramidothioatej and phorate hO,O-diethyl S- 4.10. Phenol-based pesticides

[(ethylthio)methyl] phosphorodithioatej, in water, assisted
by TiO 2 and using the UV radiation supplied by a medium The photocatalytic decomposition of 2,4-D (vide supra)
pressure mercury lamp. The efficiency of degradation over TiO 2 and ZnO in water has been shown to take place
followed the order phorate.methamidophos.malathion¯ with complete mineralisation to CO 2 and HCl [224]. Two
diazinon.EPN. Apparently, methamidophos and phorate mechanisms were proposed for the oxidation: oxidation
photodegrade mainly through direct photolysis, while TiO 2 with HO ? radicals and direct oxidation by holes created on
enhances the photodegradation of diazinon, malathion and the semiconductor. The rate of photodegradation increased
EPN. The use of UV/ H 2 O 2 was more effective than that of as the acidity of the medium decreased, and the presence
UV/ TiO 2 , with the combination UV/ H 2 O 2 / TiO 2 being the of Cl 2 or HCO 32 slowed down the photodegradation rate
most promising. by scavenging HO ? radicals.
Ku and Jung [223] studied the photocatalytic degra- Herrmann et al. [225] studied also the photocatalytic
dation of monocrotophos hdimethyl (E)-1-methyl-2- degradation of 2,4-D at a pilot scale under solar irradiation.
(methylcarbamoyl)vinyl phosphatej in water by UV/ TiO 2 2,4-D disappearance followed first-order kinetics and
(80% anatase, 20% rutile) irradiation at different pH eventually yielded complete mineralization products within
values, TiO 2 dosages, light intensities and dissolved a residence time of less than 1 h. The main photoproduct
oxygen levels. The presence of oxygen inhibited the of degradation of 2,4-D was 2,4-dichlorophenol.
recombination of electrons and holes, enhancing the photo- The photodegradation of 4-nitrophenol in TiO 2 aqueous
degradation of monocrotophos. An excess of oxygen had suspension has been studied as a function of the initial
no effect. The degradation was more effective in acid concentration of 4-nitrophenol, light intensity, partial
solution than in alkaline medium. Increasing the light pressure of oxygen, concentration of catalyst, pH, chloride
intensity enhanced the decomposition. concentration and temperature [226]. A kinetic expression
The use of 2,4,6-triphenylpyrylium ion encapsulated was obtained incorporating the influence of the many
within Y zeolite as a photocatalyst for the photodegrada- factors.
tion of methyl parathion hO,O-dimethyl O-4-nitrophenyl The sunlight photodegradation of aqueous solutions of
phosphorothioatej in aqueous solution has recently been phenol, 4-chlorophenol and 2,4-dichlorophenol has been
studied, using both sunlight and the radiation supplied by studied in the presence of TiO 2 and Na 4 W10 O 32 [217].
high-pressure mercury lamps [109]. It was found that the When pure pesticides were used, TiO 2 was more efficient
zeolite encapsulation stabilizes the 2,4,6-triphenylpyrylium as a photocatalyst. When the pesticides were used in
42
ion, leading to degradation efficiencies comparable to formulated solutions W10 O 32 became more efficient. The
those obtained using TiO 2 . The authors rule out the authors suggest that the difference in reactivity can be
intermediacy of singlet oxygen in the photodegradation accounted for by the different nature of the active species
process, as well as a direct photoinduced electron transfer involved in the photodegradation: with HO ? in the case of
process from 2,4,6-triphenylpyrylium ion to methyl para- TiO 2 and an excited polyoxometalate in the case of
thion. They also suggest that radicals, resulting from W10 O 42
32 .
interaction of 2,4,6-triphenylpyrylium ion with water and The photodegradation of 4-chlorophenol using light of
oxygen, are involved in the process. l .290 nm was used to model the photocatalytic prop-
Recently, Albanis et al. [38] reported on the photo- erties of industrial TiO 2 catalysts and to compare their
catalytic degradation of methyl parathion (vide supra), efficiencies [227]. Physical characteristics such as the
ethyl parathion hO,O-diethyl O-4-nitrophenyl phosphoro- particle size or the structure of the active site seem of
thioatej, methyl bromophos hO-4-bromo-2,5-dich- importance for the photocatalytic activity.
lorophenyl O,O-dimethyl phosphorothioatej, ethyl bromo- Mazellier and Bolte [228] studied the goethite (a-
phos hO-4-bromo-2,5-dichlorophenyl O,O-dimethyl phos- FeOOH) light-induced transformation of aqueous 2,6-di-
phorothioatej and dichlofenthion hO-(2,4-dichlorophenyl) methylphenol, using 365, 436 and 546 monochromatic
O,O-diethyl phosphorothioatej in aqueous TiO 2 suspen- light.The rate of disappearance of the phenol increased
sions using simulated sunlight from a xenon lamp, sup- with the concentration of oxygen. The involvement of
pressing wavelengths below 290 nm with transmission hydroxyl radicals was discarded on the basis of the lack of
filters. The observed half-life times varied from 10 to 40 influence of isopropanol. The authors suggest the phenol
min in the presence of TiO 2 , one or two orders of may react with positive holes in goethite, the electron
magnitude lower than in its absence. The major photo- being trapped by oxygen.
products of photodegradation of ethyl bromophos and Topalov et al. [229] studied the photocatalytic miner-
dichlofenthion were identified from the corresponding alization of mecoprop (vide supra) in water, using TiO 2 as
GC–MS (EI) fragmentation patterns, corresponding to photocatalyst and irradiating with a medium-pressure
oxidation and photohydrolysis pathways. The authors mercury lamp. The rate of degradation was also followed
hypothesize a mechanism for the photodegradation of using a Cl 2 selective electrode. Complete mineralization
irgarol under the above mentioned conditions. was observed, and a possible scheme suggested on the
basis of NMR spectra taken at different times. The same Bellobono et al. [234] used photocatalytic composite
authors reported also on the photodegradation of MCPA membranes immobilizing 30 wt% TiO 2 to study photo-
h4-chloro-2-methylphenoxy acetic acidj over TiO 2 . After mineralization of atrazine (vide supra) solutions saturated
15 h of irradiation the mineralization was complete. As in with ozone. Co-immobilization of m -peroxo-bis[N,N9-
the case of mecoprop, the proposed pathway of MCPA ethylene-bis(salicylideneiminato)dimethylformamide cobalt
photodegradation in the presence of TiO 2 also involves the (III)] and of a mixture of tri-(t-butyl)- and tri-(i-pro-
formation of radicals [230]. pyl)vanadate (V) led to rate enhancements of, respectively,
1.5- and 10-fold.
4.11. Pyrimidine pesticides The photodegradation of prometryn (vide supra) and
prometon (vide supra) has been followed in aqueous
The photocatalytic degradation by sunlight of solution using membranes immobilizing TiO 2 , and using
pyrimethanil hN-(4,6-dimethylpyrimidin-2-yl)anilinej was H 2 O 2 as an oxygen supplier [235]. The observed kinetics
studied in its pure form and as commercial formulation in followed a first-order equation. The quantum yields for
a preindustrial pilot plant, using TiO 2 as a photocatalyst photodegradation were rather high, 40% for prometryn and
[231]. Complete photodegradation took 230 min, without 66% for prometon. Cyanuric acid was found as photostable
total mineralization. Twenty two photoproducts were de- photoproduct.
tected, several of which were identified. Some of the major The UV photodegradation of acidified aqueous solutions
photoproducts characterized were aniline, formamide, 1,3- (pH52.4) of atrazine (vide supra) was studied in the
benzenediol and 4,6-dimethyl-2-pyrimidinamine. Two presence of TiO 2 and Na 4 W10 O 32 [236]. GC–MS, HPLC,
mechanistic routes are suggested for the photodegradation, radioactivity counting and TLC on 14 C-labelled solutions
one involving reaction of hydroxyl radicals with the were used. Both catalysts are efficient, leading to substan-
pyrimidine and benzene rings, with subsequent ring open- tial increases in the rate of photodegradation. The mecha-
ings and the other involving photoinduced hydrolysis. nisms of photodegradation in the presence of each photo-
catalyst are different. The authors suggest that in the
4.12. Thiocarbamate herbicides presence of TiO 2 , HO ? radicals are the oxidant species,
while in the case of Na 4 W10 O 32 , H ? abstraction on the
Albini et al. [232] studied the TiO 2 photocatalyzed alkyl side chains of atrazine and dehalogenation by elec-
degradation of molinate hS-ethyl azepane-1-carbothioatej, tron transfer on the dealkylated metabolites takes place.
eptam hS-ethyl dipropylcarbamothioatej, tiocarbazil hS- Neither of these photocatalysts is able to mineralise the
benzyl di-sec-butylthiocarbamatej and thiobencarb (vide aromatic ring of atrazine.
supra) in water by 340–380 nm light. They consider the ´
Hequet et al. [237] showed that porphyrin and phthalo-
process to be efficient, although the maximum quantum cyanine complexes, used as photocatalysts for the degra-
yield is ¯12%. The process is rationalized as being dation of atrazine (vide supra) are able to cleave the
initiated by hydrogen abstraction by HO ? from the N-alkyl triazine ring more efficiently than TiO 2 . The best degra-
chains, rather than from the S-alkyl ones, except in the dation half-life time found was ¯200 min, using iron
cases where this is a benzyl group. phthalocyanine as photocatalyst.
Recently, Albanis et al. [38] studied the photocatalytic
4.13. Triazine herbicides degradation of atrazine (vide supra), propazine (vide
supra), cyanazine (vide supra), prometryn (vide supra) and
Pelizzetti et al. [233] studied the TiO 2 photocatalyzed irgarol (vide supra) in aqueous TiO 2 suspensions under
degradation of atrazine (vide supra), simazine (vide supra), simulated sunlight, supplied by a xenon lamp from which
trietazine (vide supra), prometon (vide supra) and pro- wavelengths below 290 nm had been suppressed using
metryn (vide supra) by simulated sunlight in aqueous transmission filters. The observed half-life times varied
solution, using a Xe lamp. All the herbicides were rapidly from 10 to 40 min in the presence of TiO 2 , one order of
degraded. Full mineralization was not observed. Different magnitude lower than in its absence. Eleven major photo-
intermediates have been identified, cyanuric acid being the products were detected from GC–MS (EI) fragmentation
common final photoproduct of all herbicides. A mecha- patterns for irgarol, corresponding to oxidation, dealkyla-
nism is proposed for the generation of the observed tion and dechlorination pathways. The authors hypothesize
photoproducts. a mechanism for the photodegradation of irgarol under the
The solar TiO 2 photocatalyzed mineralization of at- above mentioned conditions.
razine (vide supra) has been studied in agricultural water Macounova´ et al. [238] studied the photodegradation of
and in polluted well water [220]. The observed half-life metamitron h4-amino-6-phenyl-3-methyl-1,2,4-triazin-
time was less than 1 h in the presence of TiO 2 and absence 5(4H )-onej on a plate photoreactor with immobilized TiO 2
of H 2 O 2 . The use of polyethylene-film covered vessels or as Q-TiO 2 particles. The main photoproducts found
showed that efficient photodegradation takes place in were deaminometamitron h6-phenyl-3-methyl-1,2,4-triazin-
sealed systems. 5(4H )-onej, deaminohydroymetamitron h6-(29-hydroxy-
phenyl)-3-methyl-1,2,4-triazin-5(4H )-onej and hydroxy- alization process was slow when using TiO 2 alone. The
metamitron h4-amino-6-(29-hydroxyphenyl)-3-methyl- use of S 2 O 822 as electron scavenger enhanced the photo-
1,2,4-triazin-5(4H )-onej. The proposed mechanism ac- mineralization process.
counts for the formation of the mentioned products in
terms of the coexistence of two pathways: heterogeneous
catalysis and homogeneous direct photolysis. According to 5. Degradation by reaction with the hydroxyl radical
the authors, photocatalysis is the major route when the (HO ? )
plate photoreactor is used, while the homogeneous direct
photolysis has the same weight as photocatalysis in Some of the most frequently used AOPs involve mole-
colloidal solutions of the Q-TiO 2 particles. cules that upon photolysis generate the hydroxyl radical
?
(HO ). This can be achieved by different ways, such as:
4.14. Miscellaneous
Turchi and Ollis [239] proposed different mechanisms to (i) Addition of hydrogen peroxide that undergoes
explain the reactivity with HO ? radicals in photocatalytic homolysis upon photolysis:
systems. The cases of reaction on the surface, in the fluid
and through a Rideal mechanism yielded rate equations H 2 O 2 1 hn → 2HO ?
analogous to Langmuir–Hinshelwood expressions. The
proposed model allows estimation of the photocatalytic (ii) Photolysis of ozone, either with generation of atoms of
degradation rate from data on the physical properties of the singlet oxygen that then react with water to generate
photocatalyst, knowledge of the electron-hole recombina- HO ? :
tion and trapping rates and the values of the second order O 3 1 hn → O 2 1 O ( 1 D)
?
rate constants for HO radicals.
The photocatalyzed degradation of the pesticides O ( 1 D) 1 H 2 O → 2HO ?
propyzamide h3,5-dichloro-N-(1,1-dimethyl-2-propynyl)-
benzamidej, iprobenfos (vide supra), simazine (vide supra) or which react directly with water to produce hydrogen
and fenobucarb h2-(1-methylpropyl)phenyl methylcarba- peroxide [17]:
matej irradiating poly(2,5-dihexoxy-p-phenylene) and
O 3 1 H 2 O 1 hn → H 2 O 2 1 O 2
poly(3-oxylthiophene-2,5-diyl) films was studied with a
400-W high-pressure mercury lamp [240]. Photoexcitation followed by its homolysis to generate hydroxyl radi-
of the polymer films leaves holes in the valence band and cals.
electrons in the conduction band. These electrons are (iii) Aqueous photolysis of Fe 31 , generated by oxidation of
trapped by O 2 to form O 2?2 , from which HO ? radicals can Fe 21 by H 2 O 2 :
be formed, that can react with the pesticides. Degradation
can be initiated also from the holes in the valence band. H 2 O 2 1 Fe 21 → Fe 31 1 OH 2 1 HO ?
The photocatalytic degradation of methoxychlor h1,1,1-
trichloro-2,2-bis(4-methoxyphenyl)ethanej in water was Fe 31 1 H 2 O 1 hn → Fe 21 1 HO ? 1 H 1 or
investigated by Hupka et al. [219], using a medium
pressure mercury lamp and TiO 2 / O 2 . The results were (iv) Radiolysis of water:
similar to those obtained for lindane and p, p9-DDT (vide
supra). H 2 O V H 1 1 HO ? 1 e aq 2
A comparison of the photodegradation of phenol by
direct photolysis and by TiO 2 -assisted photocatalysis was The HO ? radical can then react either by:
studied by Chun et al. [241] using various experimental electron transfer: HO 1 P → OH 1 P
? 2 ?1
conditions: l .200 nm in the presence of O 2 or N 2 or H ? abstraction: HO ? 1 PH → H 2 O 1 P ?

using O 2 / TiO 2 . Direct photolysis yielded a brownish- or addition to aromatic rings: HO ? 1 P → P–OH ?
yellow polymer, both under O 2 and in inert atmosphere.
Complete mineralization takes place under UV irradiation 5.1. Acetamide herbicides
in O 2 atmosphere or in O 2 / TiO 2 . The polymer was found
to be more difficult to degrade than the products of Brekken and Brezonik [243] studied the reaction be-
hydroxylation from TiO 2 -assisted photocatalysis. tween acetochlor h2–chloro–N–ethoxymethyl–69–
Malato et al. [242] described the use of a pre-industrial ethylaceto–o–toluididej and HO ? , assuming that the pri-
solar TiO 2 photocatalytic treatment for the photodegrada- mary source of HO ? is nitrate photolysis. The measured
tion of high pesticide content waters from rinsing of rate constant was k(HO ? 1acetochlor)57.5310 9 M 21 s 21 ,
pesticide containers. The authors used oxamyl as a model. a value that is close to the one previously reported for
Oxamyl was completely photodegraded, but the miner- alachlor, based on structure–activity relationships [244].
The reported data do not eliminate the possibility that the dose was higher than 2 g TiO 2 l 21 decreased again.
direct photolysis takes place, but indicate that it would be The system Fe 31 / H 2 O 2 was shown to be involved in the
much slower than HO ? -mediated degradation. degradation when Fe / H 2 O 2 were combined. Oxidant
oxyanions were shown to act as electron scavengers,
enhancing the degradation in the sequence ClO 2 2
5.2. Anilide herbicides 2 .IO 3 .
2 2
BrO 3 .ClO 3 . Oxygen had little effect on the photodegra-
The photo-Fenton degradation of metolachlor (vide dation process. Diethylphosphoric acid, p-nitrophenol,
supra) in water has been studied using 330–400 nm light diethylmonothiophosphoric acid, O,O-ethyl p-nitrophenyl
[245]. Apparently, irradiation at these wavelengths did not monothiophosphoric acid and oxalate were identified as
enhance the rate of degradation. intermediates, which were subsequently oxidized.
Miller et al. [57] developed a method based on the
5.3. Carbamate insecticides technique of solid-phase microextraction to determine the
rate of reaction of chlorpyrifos (vide supra) with HO ? in
´
Benıtez et al. [43] studied the aqueous photolysis of the gas phase at high temperatures. The half-life observed
carbofuran (vide supra) by the polychromatic light supplied for chlorpyrifos was 1.4 h. Changing the temperature from
by a high-pressure mercury lamp (emitting from 185 nm to 60 to 80 8C did not affect the rate of photodegradation.
far into the visible) in the presence of H 2 O 2 . Hydroxyl
radicals accelerate the degradation relative to the case in 5.6. Phenol-based pesticides
which no H 2 O 2 is added. A simple rate equation is
proposed, taking into account both the contribution of The aqueous photodegradation of 2,4-D h2,4-dichloro-
direct photolysis and that of the reaction with HO ? . phenoxyacetic acidj by UV radiation in the presence of
H 2 O 2 was faster than in its absence, with more than 98%
5.4. Chlorophenol pesticides of the starting material having disappeared within the first
10 min of treatment [131]. The authors suggest the main
Hirvonen et al. [246] studied the degradation of 2- processes taking place involve substitution of Cl by OH at
chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6- the o- and p- positions of the aromatic ring, and elimina-
trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachloro- tion of H ? from the a-methylene of phenoxyacetic acid.
phenol in aqueous solution by the HO ? radicals generated HO ? reactivity with bromoxynil (vide supra), adsorbed
by 254 nm photolysis of H 2 O 2 . Hydroxylated chloro- on highly dispersed thin layer of silicon dioxide powder,
phenols and dimeric intermediates were found as transient used as unreactive carrier, was studied [84]. The degra-
intermediates in the degradation. Eventually, a complicated dation was fast, and was mainly attributed to direct
mixture of products was obtained, and the authors suggest photolysis.
the necessity of toxicity testing to assess the detoxification Mazellier and Bolte [250] studied the degradation of
effects of the treatment. Furthermore, they consider the 3-chlorophenol by reaction with HO ? , generated via an
dechlorination degree to be insufficient. intramolecular photoredox process in iron(III) excited
The degradation of pentachlorophenol by photo-Fenton hydroxy-complexes, specially Fe(OH)21 . Monochromatic
systems has been analysed by Fukishima and Tatsumi 365 nm radiation was used as excitation source. The
[247], possible degradation pathways by such photo-Fen- quantum yields observed for 3-chlorophenol disappearance
ton systems being proposed. were in all cases rather low, ¯5%. The main reaction
products observed were 2-chlorohydroquinone, 2-chloro-
5.5. Organophosphorus pesticides benzoquinone, 3-chlorocatechol and 4-chlorocatechol.
Cernak ´ and Cernakova

´ ´ [248] studied the application of a 5.7. Phosphorothioate insecticides
H 2 O 2 / UV (254 nm) combination for removing parathion-
methyl (vide supra) and phenitrotion hO,O-dimethyl O-4- Miller et al. [57] developed a method based on the
nitro-m-tolyl phosphorothioatej. The maximum degrada- technique of solid-phase microextraction to determine the
tion took place within the first 5 min, longer exposures did rate of reaction of diazinon (vide supra) with HO ? in the
not significantly increase the efficiency. gas phase at high temperatures. The half-life observed for
More recently, Doon and Chang [249] investigated the diazinon was 0.5 h. Changing the temperature from 60 to
photodegradation of parathion (vide supra) in water, and in 80 8C did not affect the rate of photodegradation.
the presence of TiO 2 , Fe compounds and H 2 O 2 , using a
100-W medium pressure mercury lamp. The addition of 5.8. Triazine herbicides
TiO 2 or Fe in combination with H 2 O 2 was effective to
degrade the pesticide. The authors measured the apparent Haag and Yao [244] measured the rate constants for
first-order rate constants for disappearance of parathion. reaction of HO ? radicals with different drinking water
These increased with increasing load of TiO 2 , but when contaminants, including atrazine (vide supra) and simazine
(vide supra). A variety of HO ? generation methods were ised TiO 2 . The rate constants so-obtained are k(triazine1
used, among which is the photo-Fenton method, that was HO ? )51.5310 10 , 0.95310 10 , 1.1310 10 and 1.3310 10
used with both compounds. The rate constants found were, M 21 s 21 , respectively, for ametryn, atrazine, propazine and
respectively, 2.660.4310 9 and 2.860.2310 9 M 21 s 21 . prometryn. The authors point out that the presence of a
Cernak ´ and Cernakova
´ ´ [248] studied the application of a methylthio group in the 6-position (ametryn, prometryn)
H 2 O 2 / UV combination for removing atrazine (vide supra), instead of a chlorine (atrazine, propazine) seems to induce
prometryn (vide supra), terbuthylazine (vide supra), ter- a higher reactivity.
butryne (vide supra). They observed a maximum of HO ? reactivity has been studied with simazine (vide
degradation in the first 5 min, longer exposures being supra) and terbuthylazine (vide supra) adsorbed on highly
inefficient. dispersed thin layer of silicon dioxide powder, used as
A comparison of the photochemical oxidation of at- unreactive carrier [84]. The HO ? radicals were produced by
razine by combined UV/ H 2 O 2 and other advanced oxida- photolysis of hydrogen peroxide in the gas phase with
tion methods was carried out [251]. A monochromatic sunlamps. In this way, the first-order degradation rates
light source emitting at 254 nm was used for irradiation. observed for simazine and terbuthylazine were similar
Hydroxyatrazine, N and N,N9-dealkylated, deaminated and (k HO? ¯1.1310 21 M 21 s 21 ).
hydroxyderivatives of atrazine were the major photo- Von Gunten et al. [255] recently revisited the degra-
products found. dation of atrazine (vide supra) by reaction with HO ? during
UV/ H 2 O 2 photolysis of two products of photodegrada- advanced oxidation processes, identifying the main degra-
tion of atrazine (vide supra), namely deethylatrazine and dation products: 6-amino-2-chloro-4-isopropylamino-s-tri-
deisopropylatrazine was studied [151]. Significant reduc- azine, 6-amino-2-chloro-4-ethylamino-s-triazine, 4-acet-
tions in the rate of photodegradation were observed in amido-2-chloro-6-isopropylamino-s-triazine, 4-acetamido-
surface waters, which the authors attribute to the presence 6-amino-2-chloro-s-triazine, chlorodiamino-s-triazine, 2-
of natural radical scavengers. No attempts were made to chloro-4-ethylimino-6-isopropylamino-s-triazine, 6-amino-
identify by-products of these photolysis reactions. 2-chloro-4-ethylimino-s-triazine. The rate constant for
Hapeman et al. [252] examined the reaction of HO ? reaction between atrazine and HO ? was determined as
radical reaction with atrazine (vide supra). HO ? was 3310 9 M 21 s 21 , approximately three times higher than
generated by irradiation of nitrate solutions with 290 nm those measured for the different degradation products. HO ?
light from a xenon lamp. The products found were 20% attack on the ethyl group was favoured relative to HO ?
6-amino-2-chloro-4-isopropylamino-s-triazine, 10% 6- attack on the isopropyl group.
amino-2-chloro-4-ethylamino-s-triazine, 6% 4-acetamide-
2-chloro-6-isopropylamino-s-triazine, 3% 4-acetamide-2-
chloro-6-ethylamino-s-triazine, 16% chlorodiamino-s-tri- 5.9. Uracil herbicides
azine and 3% hydroxy atrazine, at 87% atrazine conver-
sion. The reaction was found to be much faster than direct Muszkat et al. [253] studied the reaction patterns of
photolysis that, at 23% photolysis led to 14% hydroxy photooxidation of bromacil h5-bromo-3-sec-butyl-6-
atrazine and ¯9% of chloroalkyloxydized and chloro- methyluracilj in water by UV light from a mercury lamp,
dealkylated products. and showed a small effect of oxygen on the degradation
A study of the reaction patterns of photooxidation of rate, but a strong influence from the presence of H 2 O 2 .
metribuzin (vide supra) in water by the UV radiation The authors suggest the reaction is initiated by HO ?
supplied by a mercury lamp showed a pronounced effect of radicals generated by H 2 O 2 photolysis.
oxygen on the degradation rate, with a small influence
from the presence of H 2 O 2 [253]. The authors suggest that
the process starts via a reaction of excited metribuzin with 5.10. Urea-based pesticides
H 2 O 2 or O 2 .
The photo-Fenton degradation of atrazine (vide supra) in From a study of the application of a H 2 O 2 / UV (254 nm)
water, using 330–400 nm light has been studied [245]. combination for removing chlorbromuron h3-(4-bromo-3-
According to the authors, irradiation at these wavelengths chlorophenyl)-1-methoxy-1-methylureaj, linuron (vide
did not enhance the degradation of the herbicides. The supra) it was concluded that the maximum extent of
main pathways of degradation of atrazine were N-dealkyla- degradation took place within 5 min, with longer expo-
tion and dechlorination. sures being inefficient [248].
Bellobono et al. [254] used competition kinetics to The degradation of diuron h3-(3,4-dichlorophenyl)-1,1-
obtain the rate constants for reaction of ametryn (vide dimethylureaj photoinduced by Fe 31 , using different Fe 31
supra), atrazine (vide supra), propazine (vide supra) and species and exciting at 365 nm and under sunlight has been
prometryn (vide supra) with HO ? radicals at pH 7.0 on studied [256,257]. Apparently, the mechanism of photo-
photocatalytic membranes, in the presence and absence of induced degradation involves only attack by HO ? radicals,
trialkyl vanadates as photocatalytic promoters of immobil- yielding 3-(3,4-dichloro-phenyl)-1-formyl-1-methylurea as
the major degradation product, in a relatively slow process fometuron-methyl hmethyl 2-[4,6-dimethylpyrimidin-2-yl-
(t 1 / 2 ¯1–2 h to a few days depending on [Fe 31 ]). carbamoylsulfamoyl]benzoatej with photochemically gen-
erated hydroxyl radical. The obtained values suggest
indirect photolysis is most relevant in the photodegradation
5.11. Miscellaneous of the studied compounds.
Bauer et al. [264] proved the photo-Fenton method to be
Draper and Crosby [258] studied the sunlight and very powerful for treating mixtures of ten pesticides:
near-UV induced photodegradation of different classes acrinathrin hcyano(3-phenoxyphenyl)methyl 2,2-dimethyl-
of pesticides, such as thiocarbamates, chlorophenoxy 3-[3-oxo-3-[2,2,2-trifluoro-1-(trifluoromethyl)ethoxy]-1-
acids, organophosphorus pesticides, N-methylcarbamate, propenyl]cyclopropanecarboxylatej, abamectin h(10E,14E,
cyclodienes and others in the presence of dilute H 2 O 2 . HO ? 16E, 22Z)-(1R, 4S, 59S, 6S, 69R, 8R, 12S, 13S, 20R, 21R, 24S)-
radicals were found to be the major reactants, and appro- 69[(S) - sec - butyl] - 21, 24 - dihydroxy - 59, 11, 13, 22-tetra
priate reaction mechanisms have been proposed in some methyl-2-oxo-3, 7, 19-trioxatetracyclo-[15.6.1.1 4, 8 .0 20, 24 ]-
cases. pentacosa-10, 14, 16, 22-tetraene-6-spiro-29-(59, 69-dihydro-
A method has been developed for determining rates of 29H pyran)-12-yl-2, 6-dideoxy-4-O-(2, 6-dideoxy-3-O-
generation and consumption of HO ? radicals in natural methyla - L - arabino-hexopyranosyl) - 3 - O - methyl - a - L -
waters, based on measurement competition kinetics with a arabino-hexopyranosidej, endosulfan h(1,4,5,6,7,7-hexa-
trace compound, using both a high pressure mercury lamp chloro - 8, 9, 10 - trinorborn - 5 - en - 2, 3 - ylenebismethylene)
and sunlight irradiation [259]. Possible interference’s arise sulfitej, formetanate h3-dimethylaminomethyleneimino-
from the presence of nitrate in natural waters. phenyl methylcarbamatej, imidacloprid (vide supra),
The rate of aqueous photodegradation of atrazine (vide lufenuron h(RS) - 1 - [2, 5 - dichloro - 4 - (1, 1, 2, 3, 3, 3 -
supra), ametryn (vide supra), prometon and prometryn hexafluoropropoxy)-phenyl]-3-(2,6-difluorobenzoyl)ureaj,
(vide supra) using the radiation supplied by a medium- methamidofos hO,S-dimethyl phosphoramidothioatej, ox-
pressure mercury lamp was greatly enhanced by the amyl hN,N-dimethyl- 2-methylcarbamoyloxyimino-2-
addition of Fe 31 [260]. The rate enhancement is attributed (methylthio)acetamidej, propamocarb hpropyl 3-(di-
to the reaction with HO ? . Quenchers of HO ? reduced the methylamino)propylcarbamatej and pyrimethanil hN-(4,6-
rate of photodegradation. The photoproducts found were dimethylpyrimidin-2-yl)anilinej. The mixtures were used
the ones expected for a Fenton reaction. The reaction rate as a model for a plant conceived for destroying pesticides
decreased also in the absence of O 2 and in natural water. in the wastewater of a pesticide bottle recycling plant. All
Mabury and Crosby [261] studied the reactivity of HO ? the pesticides underwent degradation, some of them rather
toward ten different pesticides: atrazine (vide supra), slowly. The degradation was incomplete, a residual amount
carbaryl (vide supra), carbofuran (vide supra), 2,4-D (vide remaining in solution. Addition of oxalate accelerated the
supra), hexazinone, MCPA (vide supra), picloram h4- degradation, but did not improve the level of degradation.
amino-3,5,6-trichloropicolinic acidj, propanil (vide supra) The results seem to be better than those previously
and quinclorac h3,7-dichloro-8-quinolinecarboxylic acidj. obtained by photocatalysis in the presence of TiO 2 .
The reaction rates were estimated by competition kinetics,
using p-nitroso-N,N-dimethylaniline as a standard com-
petitor. HO ? radicals were generated by photolysis of H 2 O 2
using a 40-W fluorescent UV lamp, with a maximum in its 6. Other papers of interest
UV emission at 310 nm. The most reactive compound was
carbaryl (3.4310 9 M 21 s 21 ), and the least reactive hexa- A seminal detailed study of the photo-Fries reaction,
zinone (0.62310 9 M 21 s 21 ). However, the estimated including a comprehensive mechanistic scheme is due to
values are rather lower than those determined by Haag and Sandner et al. [265] These authors present evidence that
Yao [244] by photo-Fenton reaction. The authors estimated the photo-Fries rearrangement takes place via a 1,3-sigmat-
for the reaction of HO ? with benzoic acid a rate constant of ropic shift originating from an upper singlet state. The
3.2310 9 M 21 s 21 , to be compared with the authentic process is of most interest in relation to the photodegrada-
value of 5.9310 9 M 21 s 21 , obtained by Buxton et al. tion of pesticides such as carbamates and ureas.
[262] by pulse radiolysis. Bent and Hayon [266] studied by 265-nm laser flash
Armbrust and Reilly [263] measured the rate constants photolysis the formation and the reactivity of the triplet
for reaction of methomyl h(Z)-S-methyl N-(methylcar- state of s-triazine in acetonitrile, cyclohexane and iso-
bamoyloxy)thioacetimidatej, oxamyl hN,N-dimethyl-2- propanol. The triplet–triplet absorption spectrum showed
methylcarbamoyloxy-imino-2-(methylthio)acetamidej, ben- maximae at 245 and 303 nm, and shoulders at 345 and 450
sulfuron-methyl hmethyl 2-[(4,6-dimethoxypyrimidin-2- nm. The rate of decay in acetonitrile was ¯1.1310 6 s 21 .
yl)carbamoylsulfamoylmethyl]benzoatej, azimsulfuron h1- The triplet state was efficiently quenched by H-atom
(4,6-dimethoxypyrimidin-2-yl)-3-[1-methyl-4-(2-methyl- donors, and probably by e 2 -donors.
2H-tetrazol-5-yl)-pyrazole-5-yl]sulfonyljureaj and sul- Wells et al. [267] described the photochemistry of the
pyrimidinic fungicides dimethirimol h5-butyl-2-di- triplet radical pair in a solvent cage, that can then decay by
methylamino-6-methylpyrimidin-4-olj and ethirimol h5- three different pathways: (i) intersystem crossing to the
butyl-2-ethylamino-6-methylpyrimidin-4-olj, as well as the singlet radical pair that then forms the (2,5-dimethox-
structurally related compound 2-dimethylamino-5,6-di- yphenyl)hydrazone of 9-fluorenone, (ii) separation of the
methylpyrimidin-4-ol. The fluorescence, phosphorescence triplet radical pair, and (iii) disproportionation yielding
and other photophysical properties have also been de- 9-fluorenone ketimine and triplet (2,5-dimethoxy-
scribed. phenyl)nitrene.
Bersohn et al. [268] studied the photodissociation of Schmidt et al. [275] carried out an NMR and molecular
s-triazine at 248 and 193 nm, finding three HCN molecules mechanics study of alachlor (vide supra) conformation, and
as photoproducts. Different considerations are made about of its implications on the mechanism of photodegradation.
the dynamics of the system and of the kinetic energy The authors conclude that environmental factors affecting
distributions of the molecules at both wavelengths. the conformation of alachlor at the molecular level may
Getoff et al. [269] studied the pulse radiolysis of alter both the rate and pathway of alachlor degradation.
paraquat (vide supra) in air-free aqueous solution at The use of ferrioxalate (Fe(C 2 O 4 ) 3 )32 as mediator of
various pHs. The very fast reaction of paraquat with the sunlight photodegradation of organic pollutants in water
solvated electron took place with k(paraquat1e 2 aq )57.53 has been studied [276]. Irradiation of ferrioxalate proceeds
10 10 mol M 21 s 21 , yielding a long-lived radical cation as:
showing to absorption maximae at 392.5 and 600 nm,
respectively. Other processes undergone by paraquat have (Fe(C 2 O 4 ) 3 )32 1 hn á(Fe(C 2 O 4 ) 2 )22 1 (C 2 O 4 )?2
also been characterized.
Wardman [270] measured by pulse-radiolysis the one- (C 2 O 4 )?2 1 (Fe(C 2 O 4 ) 3 )32 → (Fe(C 2 O 4 ) 2 )22 1
electron reduction potential for various bipyridinium com-
pounds. Among them, the one-electron reduction potential (C 2 O 4 )22 1 2CO 2
21
for paraquat is E8(methyl viologen / methyl
?1
viologen )5 20.45 V vs. NHE. In the presence of H 2 O 2 , HO ? radicals are generated as in
Katagi [271] has performed quantum chemical estima- the photo-Fenton method (see above). The efficiency of
tions of the environmental fate of pesticides, expected to this process for photodegradation of organic pollutants in
be useful in making considerations about the photooxida- tap water has been shown to be at least 25 times higher
tion and photosensitized degradation of pesticides. The than using sunlight / TiO 2 / H 2 O 2 .
photoinduced decarboxylation and isomerization of pyre- The fate of peroxyl radicals in aqueous medium has
throids were successfully explained using a photolysis been recently reviewed by von Sonntag et al. [277].
index based on the change of electron population at each Peroxyl radicals are formed during drinking-water and
bond upon excitation. wastewater processing by reaction of carbon-centered
Halmann et al. [272] studied the photodegradation of radicals with dissolved O 2 , in a reaction that is irreversible
xenobiotic contaminants in water samples from a heavily in most cases. The carbon-centered radicals from which the
polluted well by sunlight, using three different combina- reaction starts are generated by reaction of HO ? with
tions of photocatalysts: TiO 2 / H 2 O 2 , Fe 31 / H 2 O 2 and dissolved organic compounds.
TiO 2 / Fe 31 / H 2 O 2 . Among these, were acetamides, ben- Heit and Braun [278] described different effects ob-
zonitriles, ureas and triazines. The third combination led to served upon VUV-irradiation (172 nm) of aqueous solu-
appreciable degradation within 3–4 h. More complete tions containing organic compounds. The observed pro-
photodegradation required long exposures. cesses are dominated by the very short lifetimes of the
Fischer and Nwankwoala [273] studied the photolysis of intermediates generated by homolysis of water.
1,2,3-triazine in hexane and methanol and in vapour phase. Braun and Oliveros [279] recently reviewed the state-of-
They found decreasing photodissociation quantum yields the art of methods for water treatment, discussing how to
as the wavelength increases, and independence of the evaluate them. The authors suggest appropriate solutions
quantum yields with the nature of the solvent and the may be found in the combination of photochemical and
presence of air in solution. Acetylene and an unidentified thermal (catalyzed) processes.
compound were the major photoproducts, indicating that Wagner et al. [280] described the use of excimer lasers
photofragmentation is not the main photodegradation for wastewater treatment; 193 nm and 248 nm excimer
pathway. This is not the case in vapour phase, were lasers were used, with the first showing higher efficiency
acetylene and HCN were they main products, suggesting a than the second.
concerted mechanism. A detailed study that is related to the photodegradation
Scaiano et al. [274] studied the laser flash photolysis of of carbamates and ureas has been carried out by Tsen-
carbamates derived from 9-fluorenone oxime. The authors talovich et al. [281], who investigated the photo-Fries
propose a mechanism involving N–O and C–N bond rearrangement of 1- and 2-naphtyl acetates using steady-
scission upon excitation and subsequent generation of a state photolysis and laser flash photolysis, and proposed a
general mechanism for the photolysis of both compounds. amine, isopropylamine, 2-isopropylamino-s-triazine, 2-
Upon irradiation, naphthyl acetates are excited into the first ethylamino-s-triazine and 2-hydroxy-4-ethylamino-6-iso-
excited singlet state, that is responsible for most of the propylamino-s-triazine were the observed products. Cleav-
generated photoproducts. This singlet state can either age of the C–Cl bond was the main process, with halogen
dissociate to yield a radical pair or undergo intersystem substitution by a hydroxyl group.
crossing to the T 2 triplet state, which can then yield the Dionysiou and co-workers [289,290] recently developed,
same radical pair as the singlet state or relax to the characterized and evaluated a rotating disk photocatalytic
unreactive T 1 triplet state within few nanoseconds. reactor for the photodegradation of organic pollutants.
The UV–Vis absorption and emission spectra of the They tested the device using 4-chlorobenzoic acid and
fungicide fenarimol in solution have been studied [282]. chlorophenols as a model compounds and a batch of low
Comparison of the spectra with those of chlorotoluenes pressure mercury tubes. The reactor exhibited advantages
and pyrimidine, as well as the effect of solvent polarity on such as immobilization of the catalyst, reactions in a thin
the absorption spectrum allowed the authors to conclude liquid film and a mixing regime close to that of an ideal
that the lowest excited singlet state is localized on the continuously stirred tank reactor. Although the photonic
pyrimidine ring, having n,p * character. Higher excited efficiency of the reactor was low in some cases, the authors
p,p * states are localized on the chlorotoluene and py- expect to be able to optimize it.
rimidine rings. A weak fluorescence from the n,p * state is Feng and Nansheng [291] reviewed the photochemistry
observed, with its quantum yield being strongly dependent of hydrolytic iron(III) species and the photoinduced degra-
on the solvent. Phosphorescence was observed at low dation of organic compounds in connection with these
temperatures, and was attributed to a triplet state with inorganic species. They show how the pH, Fe 31 con-
p,p * character. centration, wavelength and energy of irradiation source,
The use of the photo-Fenton method for degradation of and the nature of the organic compounds influence the
nitrogen-containing compounds was studied [283]. Aro- photodegradation processes. All the low-molecular weight
matic compounds degraded to a extent higher than the derivatives of Fe 31 can generate HO ? , with Fe(OH)21
aliphatic ones. In most cases nitrogen was released as being the most relevant. Hydrolytic Fe 31 polymers are
ammonia upon photodegradation. presumed to also be photoactive. The mechanisms of
Solar et al. [284] have studied the degradation aqueous action of other environmentally relevant species are dis-
chlorophenol solutions by the g-radiation obtained from a cussed.
60
Co-g-source. The results showed that 50-mM solutions The UV absorption and fluorescence maximae of 2,4,6-
were completely degraded using 600 and 1000 Gy, respec- triaryl-1,3,5-triazines show a marked bathochromic shift as
tively. the acidity of the medium increases Evidence for a simple
Leintner et al. [285] studied the degradation of aqueous protonation equilibrium came from the existence of clearly
atrazine (vide supra) from solutions containing humic defined isosbestic points. As the acidity of the medium
substances, using g-radiation obtained from a 60 Co-g- increases, the fluorescence of the unprotonated triazines is
source. The studies were carried out with continuous replaced by the much weaker fluorescence of the proton-
bubbling of N 2 , O 2 , N 2 O and N 2 O / O 2 (80:20). Atrazine ated species, which shifts to longer wavelengths. As with
was degraded both by reaction with HO ? and with e 2 aq . For many other aza-nitrogen containing heterocycles, the pKa
the radiation dose applied (¯800 Gy), HO ? and O ?2 2 were increases from 6.8 to 9 units upon excitation from 21.7 to
the most reactive species. 3.7 in the ground state to 7–11 in the lowest singlet excited
Armbrust [286] used a computerized model to compare state [292,293]. The excited state of the protonated form
the relative importance of the photochemical processes was calculated to be 37–51 kJ mol 21 lower than that of the
influencing pesticide degradation in rice paddies. Among unprotonated species.
these, indirect photodegradation processes: degradation by Lester et al. [294] reviewed the abiotic degradation of
hydroxyl and carbonate radicals, and by singlet oxygen, pyrethroids, triazines and ureas, concluding they are
have been shown to be far more important than direct susceptible of photodegradation, and that the potential for
photolysis. their photosensitised degradation is uncertain.
Esplugas et al. [287] studied the influence of H 2 O 2 and Recently, Cid et al. [295] carried out different bioassays
Fe 21 in the photodegradation using UV radiation of with two freshwater microalgal species, Chlamydomonas
nitrobenzene in aqueous solution. Both the concentration moewusii and Chlorella vulgaris, in an attempt to assess
of H 2 O 2 and Fe 21 showed great effect on the rate of the efficiency of photodegradation of paraquat (vide supra)
photodegradation, with the first being more efficient. The and isoproturon (vide supra) in water. The evolution of
major photoproducts found were nitrophenol isomers. growth and of concentration of photosynthetic pigments of
Atrazine (vide supra) was shown to be completely the above microalgae upon a 96-h treatment with the pure
destroyed in aqueous solution upon g-irradiation using herbicides, as well as with solutions of the same that had
doses of 0.1–50 kGy from a 60 Co source [288]. Ethyl- been photolysed with 248 nm light were measured. The
results show that the attempted photodegradation can effect of factors such as the acidity of the medium, salt
effectively reduce the biotoxicity of herbicides. concentrations, presence of buffers, etc. are, in general, not
properly understood. It will be difficult to model the
environmental fate of agrochemicals unless detailed mech-
7. Concluding remarks anistic studies become available, and these should be taken
as a major task and encouraged for the near future.
Photodegradation studies on pesticides have focussed on
two distinct, but not unrelated, objectives. Firstly, it is
important that for their efficacy they do not photodegrade Acknowledgements
during the time they are exercising their biocidal activity.
On the other hand, for environmental considerations it is The authors gratefully acknowledge the financial support
important that they can eventually be converted to innocu- ´ y Cultura (project
of the Spanish Ministerio de Educacion
ous, and preferable mineral, photoproducts. Direct sunlight AMB99-0325), the Conselho de Reitores das Univer-
induced photodegradation of most pesticides is a minor sidades Portuguesas (Portugal) and the Deutscher
event, which leads to the problem of their long-term Akademisher Austauschdienst (Deutschland Bundesrepub-
persistence in the environment. Instead, these are more lik) through the Acciones Integradas bilateral programs
effectively degraded by using UV light, despite the higher HP1999-0078 and HA1997-0128, as well as of the Minis-
economic cost of the process. Alternatively, photosensit- terio de Ciencia y Tecnologıa ˜ and of the Xunta
´ (Espana)
ized and photocatalytic processes are also becoming ˜ through projects PPQ2000-
de Galicia (Galicia, Espana)
popular for treating pesticide residues, although they do 0449-C02-01 and PGIDTOOMAM10303PR, respectively.
have certain drawbacks, such as the high biotoxicity of During the editorial process, both the editor and referees
some of the sensitized compounds or metal catalysts used. made useful suggestions that helped improve this review
Indirect degradation methods based on the reaction of the and must be acknowledged.
pesticides with hydroxyl radicals are also effective and
have low cost, but the reaction products produced are in
some cases as problematic or more so than the starting References
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Reaction Pathways and Mechanisms of Phot

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Journal of Photochemistry and Photobiology B: Biology 67 (2002) 71–108

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Reaction pathways and mechanisms of photodegradation of pesticides

Keywords: Pesticides; Photodegradation; Photoionization; Photocatalysis; Photosensitization; Photolysis; Hydroxyl radicals

1. Introduction worsen with the appearance of new and more sophisticated

photodegradation of carbofuran (vide supra). The authors methylpyrimidin-4-yl dimethylcarbamate and 2-

O-5-methyl-2-nitrophenyl sec-butylphosphoramidothioatej possibly by one-electron abstraction on the sulfur atom to

Sharma and Chibber [181] studied the sunlight photo-

effects of humic materials on the degradation of various

ureas in ethanol, using low pressure mercury lamps 4. Photocatalytic degradation

phophoramidothioatej and phorate hO,O-diethyl S- 4.10. Phenol-based pesticides

conditions: l .200 nm in the presence of O 2 or N 2 or H ? abstraction: HO ? 1 PH → H 2 O 1 P ?

Cernak ´ and Cernakova

[15] L.E. Gray, J.S. Ostby, W.R. Kelcee, Developmental effects of an ´

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