Photodegradation of Pesticides on Soil and Plant Surfaces

Springer-Verlag 2004
Rev Environ Contam Toxicol 182:1195
Photodegradation of Pesticides
on Plant and Soil Surfaces
Toshiyuki Katagi
Contents
I. Introduction .......................................................................................................
II. Photophysical and Photochemical Processes ...................................................
A. Photophysical Processes ..............................................................................
B. Photochemical Processes .............................................................................
III. Factors Controlling Photolysis on Plant Surfaces ...........................................
A. Environmental Factors .................................................................................
B. Illumination Conditions ...............................................................................
C. Effect of Formulation ..................................................................................
D. Anatomy of the Leaf ...................................................................................
E. Wax Chemistry .............................................................................................
F. Photoinduced Reactions ...............................................................................
IV. Factors Controlling Photolysis on Soil Surfaces .............................................
A. Soil Components ..........................................................................................
B. Environmental Factors Affecting Soil Properties .......................................
C. Mass Transport in Soil .................................................................................
D. Photic Depth in Soil ....................................................................................
E. Effects of Soil Properties on Photolysis ......................................................
F. Photophysical and Photochemical Processes of Soil Components .............
V. Atmospheric Oxygen Species ..........................................................................
VI. Experimental Design and Kinetic Analysis .....................................................
A. Light Source .................................................................................................
B. Photolysis Chambers ....................................................................................
C. Kinetic Analysis ...........................................................................................
VII. Photodegradation of Pesticides in Model Systems ..........................................
A. Soil Surface Models ....................................................................................
B. Plant Surface Models ...................................................................................
C. Photodegradation of Pesticides on Glass and Silica Gel Surfaces .............
D. Photodegradation of Pesticides in Organic Solvents and
Plant Model Systems ...............................................................................
VIII. Photodegradation of Pesticides on Soil and Clay Surfaces ............................
IX. Photodegradation of Pesticides on Plants ........................................................
Summary ....................................................................................................................
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Communicated by George W. Ware

T. Katagi
Sumitomo Chemical Co., Ltd., Environmental Health Science Laboratory, 2-1 Takatsukasa
4-Chome, Takarazuka, Hyogo 665-8555, Japan.
T. Katagi
Table Listing .............................................................................................................. 79

Appendices ................................................................................................................. 129
Directory of Pesticide Chemical Structures .............................................................. 130
References .................................................................................................................. 157
I. Introduction
Sunlight photodegradation is one of the most destructive pathways for pesticides
after their release into the environment. Plant surfaces, especially leaf surfaces,
are the first reaction environment for a pesticide molecule after application, and
spray drift would indirectly present a similar situation. Photolysis on soil surfaces becomes important when a pesticide is directly applied to soil or not significantly intercepted by plants, providing that the leaf cover does not shade the
ground from sunlight. Because the foliar interception of pesticides depends on
plant species and usually increases with their growth stage (Linders et al. 2000),
the importance of soil photolysis is considered to be lessened when plants become mature. Spray drift after pesticide application or washoff from plants by
rain is the indirect route by which a pesticide reaches the soil.
To elucidate the photodegradation profiles of pesticide in the environment,
many investigators have focused on solution photolysis in organic solvents or
in a dilute aqueous solution. The heterogeneity of soil and plant surfaces together with the capricious transmission of sunlight onto these media also makes
photolysis on them more difficult to understand. Although there are many excellent reviews on photolysis of pesticides (Roof 1982; Miller and Zepp 1983;
Choudhry and Webster 1985; Marcheterre et al. 1988; Parlar 1990; Wolfe et al.
1990; Cessna and Muir 1991; Meallier 1999; Floesser-Mueller and Schwack
2001; Burrows et al. 2002), photolysis on soil is still only partially understood
because of the limited number of investigations, whereas that on plants is mostly
speculation derived from plant metabolism studies. Under these circumstances,
photodegradation on soil and plant surfaces requires more examination, not only
experimentally but also theoretically, to reveal the mechanisms controlling photophysical and photochemical processes in pesticides on solid phases and to
apply such knowledge to better understand the dissipation profiles of pesticides
in the field.
This review first considers the background and basis of photophysics and
photochemistry relevant to the photodegradation of pesticides. Molecular excitation and deactivation processes together with subsequent chemical processes are
discussed, and reactivity toward active oxygen species is briefly summarized.
Second, constituents of soil and plant surfaces are reviewed from the point of
view of the factors controlling photodegradation, together with meteorological
factors. After reviewing the experimental design of photodegradation on these
surfaces, the analysis of experimental data in consideration of the photodegradation mechanism is discussed briefly. Based on the literature survey, both model
systems and the actual photodegradation in soil and plant systems are reviewed
for every chemical class of pesticide. The chemical structure of each pesticide1
appearing in this review, together with a corresponding number in bold type, is
provided in the Appendices.
II. Photophysical and Photochemical Processes

A. Photophysical Processes
The extent of sunlight photolysis is highly dependent on UV absorption profiles
of the pesticide, the surrounding medium, and the emission spectrum of sunlight.
Because the energy to break chemical bonds in pesticide molecules usually
ranges from 70 to 120 kcal mol1, corresponding to light at wavelengths of
250400 nm (Watkins 1974), spectral irradiance of sunlight detected near the
ground becomes important in determining the photodegradation profiles of pesticide. By passing through the atmosphere, sunlight intensity significantly decreases to about 10% in the troposphere, and no light is transmitted at wavelengths from <290 to 295 nm, mainly due to absorption by ozone (Zepp and
Cline 1977; Parlar 1990). As a result, sunlight near the ground exhibits a maximum at around 440460 nm, and its intensity at the UV region responsible
for photodegradation of pesticide becomes approximately 5%6% of the total
intensity. There are many photophysical pathways of sunlight absorption (Fig.
1) (Turro 1978; Roof 1982; Parlar 1990). When a photon passes close to a
pesticide molecule, molecular excitation occurs via interaction between the electric field of a pesticide molecule and that of light at a time scale of femtoseconds
without a change of molecular geometry (FranckCondon principle). Each photon can activate only one molecule in the ground state (S0) with a certain probability to the excited singlet state (StarkEinstein rule), and usually the lowest
excited state (S1) is involved in further photoprocesses. Generally, pesticide molecules exhibiting a UV-vis absorption spectrum at >290 nm have a substituted
aromatic moiety, sometimes being conjugated with the lone-pair electrons or the
unsaturated bonds such as carbonyl or carbamoyl group, and hence * or
n * transition takes place upon irradiation.
There are three possible photophysical pathways from the S1 state: nonradiative internal conversion, emission of fluorescence, and intersystem crossing to
the excited triplet state (T1) (see Fig. 1). The first pathway means the relaxation
from higher vibrational levels (1012 sec1) in the S1 state followed by decay to
a lower electronic state with the same multiplicity (106 1012 sec1). The second
one is a radiative deactivation process. The fluorescence spectrum is usually
close to a mirror image of that of absorption due to the FranckCondon principle but shifted to the red. The lifetime of fluorescence is very short (nanosec-
All pesticides are identified by their common name and parenthetical identification number, and
their structures are illustrated in the Appendices. Preceding the Appendices is a Directory of Pesticide Chemical Structures listing all pesticides in alphabetical order to aid the reader in locating
specific structures.
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Fig. 1. Energy state diagram.
onds to microseconds) due to the transition between states with the same multiplicity. The last pathway is a spin-forbidden process (S1 T1), followed by
slow radiationless deactivation or emission of phosphorescence. The T1 S0
process is also spin-forbidden, and hence the lifetime of phosphorescence usually becomes an order of milliseconds to 102 sec. The profiles of fluorescence
and phosphorescence spectra of pesticides, based on the literature survey, are
summarized in Table 1 (see table on page 80). Although there are many chemical classes and either a solvent system or temperature difference in measuring
spectra, their maximum wavelengths are located in the range of 280450 and
380530 nm, respectively. Based on the following equation of conversion where
E and are the energy level and the emission wavelength, respectively (Gould
1989b), the energy levels of the excited singlet (Es) and triplet (ET) states can be
estimated to be 64102 and 5475 kcal mol1 for these pesticides, respectively.
E (kcal mol 1) = 2.864 104/ (nm)
Because intersystem crossing is facilitated by the presence of heavy atoms in a
molecule, the fluorescence spectrum of a pesticide is usually difficult to measure
at room temperature, but in such cases phosphorescence can be efficiently detected instead.
The foregoing consideration can also be applied to pesticide molecules in the
solid phase, but adsorption onto these media is most likely to affect the photophysical processes. Molecular motion would be highly restricted, and interactions with these heterogeneous surfaces result in modification of their electronic
states. In this case, the reflectance spectrum of a pesticide gives more useful
information than an absorption spectrum, and this is described by the relation-
ship of Schuster and Kubelka-Munk (Parlar 1984) instead of the BeerLambert

law.
F(R) = (1 R)2/2R = K/S
The diffuse reflectance, F(R), represents the radiation penetrating into the powder and resembles the usual transmission spectrum. R is the ratio of reflectance
of a sample to that of a standard and thus the relative diffuse reflectance of an
infinitely thick layer compared to a nonabsorbing standard such as magnesium
oxide; K and S are the absorption and scattering coefficients, respectively. Adsorption can produce unequal displacement of the ground- and excited-state potential curves, which would result in a different vibronic band shape. Thus,
spectral changes by adsorption are characterized by a spectral shift, changes of
extinction coefficient, broadening of absorption bands, and appearance of new
bands (Wendlandt and Hecht 1966; Nicholls and Leermakers 1971; Parlar
1984). Examples of spectral changes by adsorption of organic molecules including pesticides to silica gel and clays, listed in Table 2 (see table on page 85),
are based on the literature survey. Both bathochromic (red) and hypsochromic
(blue) shifts on adsorption have been reported, which are considered to depend
on the type of an electronic transition. It is known that a blue shift almost always
occurs with n * transition and often a red shift with * transitions
(Nicholls and Leermakers 1971). In the case of the former transitions, the
change of a nonpolar environment to polar causes more stabilization of the
ground state via hydrogen-bonding and dipoledipole interactions than the excited state, resulting in a blue shift. For * transitions, the excited state is
more stabilized by polarization in the polar environment, resulting in a red shift.
The alteration of emission spectrum by adsorption is likely, but the corresponding information is limited. Villemure et al. (1986) have reported the significant
increase of fluorescence intensity of paraquat (225) when adsorbed onto clays.
Fluorescence with an emission maximum of 345 nm was very weak in aqueous
solution, but adsorption resulted in the increase of its intensity with a blue shift
by 20 nm. The increase of intensity is most likely to stem from an inhibition
of radiationless quenching by counteranion Cl by intercalation of molecules of
(225) into the interlayer of clays.
B. Photochemical Processes
Unless the energy of an excited-state molecule is lost as heat or emission of
light, it causes various types of chemical reactions in the excited molecule.
There are two types of photochemical reactions, well known as direct and
indirect photolysis (Roof 1982; Miller and Zepp 1983). Direct photolysis
means the photoreaction proceeds by absorbing light energy, whereas indirect
photolysis is defined as reaction of a ground-state molecule with the other excited molecule or photochemically produced reactive species. The former indirect photolysis is called photosensitization or quenching, and the latter is a photoinduced reaction with a reactive oxygen species. The average rate of direct
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photolysis in a well-mixed system can be estimated by using the GCSOLAR

program based on spectral irradiance of sunlight, absorption profiles, and quantum yield of pesticide (Leifer 1988). In contrast, when pesticide molecules exist
as deposits on soil and plant surfaces, the heterogeneous microenvironment
makes such estimation difficult. For example, many researchers have reported
the quantum yield for pesticides in solution photolysis, but the information is
very limited on solid-phase photolysis (Krieger et al. 2000; Samsonov and Pokrovskii 2001). In the case of soil photolysis, Balmer et al. (2000) introduced a
model function of light attenuation in soil with diffusion of a pesticide molecule
to better describe the dissipation profiles.
The molecule in the S1 or T1 state undergoes various chemical reactions.
Typical reactions observed in photolysis on soil and plant surfaces are summarized in Fig. 2. One of the most important photoreactions is initiated by carbonyl
n *excitation. The photoinduced cleavage of a CC bond generates the
ketyl radical (Norrish type I), or the carbonyl carbon in the excited state abstracts hydrogen from a neighboring alkyl group (Norrish type II) or a solvent
molecule. The electronic excitation also occurs at the C=C bond or aromatic
moiety, which results in cis/trans (or E/Z) geometric isomerization or R/S optical
one. The photoinduced homolytic bond cleavage is also a main reaction pathway
in photolysis. When it occurs at an ester or ketone moiety, decarboxylation or
decarbonylation proceeds in addition to the apparent photoinduced hydrolysis,
and its extent depends on solvent structure in relation to stabilization of produced radicals. The C-halogen (Cl, Br, and I) bond is known to also undergo
photoinduced cleavage. Dealkylation via oxidation with O2 or reactive oxygen
species such as the hydroxyl radical (OH) is also known. Oxidation at either
carbon or sulfur is one of the most important routes of photodegradation. The
most familiar rearrangement is thiono-thiolo for O-aryl phosphorothioate insecticides whose O-alkyl group (typically a methyl group) shifts to the P=S sulfur
atom (reaction 9a). The other is a photo-Fries rearrangement for amides and
carbamates where the ketyl radical generated via cleavage of an NC(=O) bond
mostly migrates to the o- or p-position of the phenyl ring (reaction 9b). The
formation of a new bond is typically observed for intramolecular cyclization for
organochlorine cyclodiene insecticides (reaction 10a).
Incidentally, an energy transfer can proceed between the excited donor (D*)
and acceptor (A) molecules. The spectral overlap between the emission spectrum of D* and absorption spectrum of A is prerequisite (Fig. 3), and energy
transfer proceeds efficiently when the process is spin-allowed and exothermic
(Turro 1978; Roof 1982). There are two mechanisms known for energy transfer,
coulombic and exchange interactions. The former mechanism involves the induction of a dipole oscillation in A by D* via a magnetic field and does not
require physical contact of the interacting D* and A. Forester theory indicates
that the rate of energy transfer according to this mechanism is proportional to
the spectral overlap and inversely proportional to intermolecular distance between D* and A to the sixth power. Therefore, the energy transfer efficiency is
and thus is
greatly reduced as the distance increases up to approximately 50 A
Fig. 2. Types of photoreactions.
sensitive to diffusion of D* and A. In contrast, the exchange interaction involves

a double electron substitution, that is, jump of an electron from D* to the unoccupied orbital of A and the simultaneous jump of an electron from A to the
half-occupied orbital of D* via overlap of electron clouds, which requires physical contact (collision) between D* and A. Singlet energy transfer is spin-allowed
for both long-range coulombic and short-range exchange mechanisms. However,
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Fig. 2. Continued.
because an acceptor molecule is in the S0 state, the triplet energy transfer is

basically spin-forbidden and only proceeds via a short-range exchange mechanism. The interatomic distance expected for the triplet energy transfer is esti . The longer a molecule remains in an excited state the
mated to be 1015 A
greater the probability that it will transfer energy to a suitable neighboring molecule. Therefore, the triplet energy transfer is the most common and most important type of energy transfer involved in photolysis of pesticides.
Fig. 3. Schematic description of the spectral overlap.
When photolysis on soil and plant surfaces is considered, diffusion of pesticide molecules is likely to be limited by adsorption and very high viscosity of
the medium. These situations may imply less possibility of energy transfer except for the case where pesticide molecules are located in the neighborhood of
D* or A. There are many candidates in the environment playing a role as D* or
A, and some of them are listed in Table 3 (see table on page 86) together with
synthetic chemicals. Because flavonoids and long-chain alkyl ketones are some
of the wax components in plant foliage (see Section III.E), photosensitization
by these components may be possible by taking account of the ET values of
pesticides (5475 kcal mol1). In the case of soil surface, either photosensitization or quenching by humic substances with the ET value of 6062 kcal mol1
is considered to proceed. Although concrete demonstrations by measurement are
limited, the importance of spectral overlap between pesticide and synthetic dyes
coadsorbed on clay surfaces has been reported in relation to stabilization of
photolabile pesticides (Margulies et al. 1988; El-Nahhal et al. 2001).
Among natural products, molecular oxygen (O2), whose ground state is a
triplet, is the most effective quencher. The very low lying singlet states with
approximate energy levels of 23 and 38 kcal mol1 can easily react with the
excited states of pesticides and natural products, resulting in the formation of
singlet oxygen (1O2). In addition, the other active species such as OH and ozone
(O3) are deeply involved in photoinduced reactions. It is not easy to identify
active oxygen species in photolysis on soil and plant surfaces, but the basic
reactivity of some pesticides is known (Table 4 [see table on page 88]). Sulfur
oxidation is one of the characteristic reactions. Concrete evidence on the
involvement of 1O2 was given for fenitrothion (138)2 by Verma et al. (1991),
who showed the significant decrease of oxon formation when the 1O2 scavenger
was added. Formation of peroxide at the isobutenyl moiety of pyrethroid (Fig.
2, reaction 7) was found sensitive to 1O2 scavenger (Ruzo et al. 1980, 1982) and
was greatly reduced by introduction of halogen atoms instead of the geminal
methyl groups (Holmstead et al. 1978a; Ruzo 1983). Hirahara et al. (2003)
confirmed the photoinduced formation of 1O2 in the phosphate buffer solution
of fenthion (143) without any dye by ESR (electron spin resonance) using the
spin trap reagent and supposed that (143) is a photosensitizer for O2. Several
methods, including Fentons reagent and illumination in the presence of hydrogen peroxide (H2O2), O3, Fe3+, humic substances, or a semiconductor, have been
utilized to generate OH. The oxidative desulfuration and N-dealkylation together with hydroxylation proceeded via reactions with OH. The involvement
of OH in photolysis of atrazine (185) was demonstrated by retardation of the
reaction in the presence of mannitol as a radical scavenger, and the attack at the
-position of the N-ethyl moiety was evidenced by formation of the N-acetyl
derivative. Concerning O3, aqueous ozonization has been extensively investigated (Reynolds et al. 1989) but the reaction on solid surfaces seems to be
See footnote 1, p. 3.
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limited. Spencer et al. (1980) reported the desulfuration of parathion (135) on

soil dusts and clay minerals in the presence of O3, which was recently confirmed
by Kromer et al. (1999). The sulfur atom was finally oxidized to sulfate ion
(Gunther et al. 1970). In the case of pyrethroids, ozonization of the isobutenyl
moiety was found to proceed to give the corresponding aldehyde derivatives
(Ruzo et al. 1982).
III. Factors Controlling Photolysis on Plant Surfaces

A. Environmental Factors
A number of factors such as meteorological conditions, formulation type,
sprayer characteristics, and affinity of plant surface to formulation are considered to determine the amount of pesticide attached to the surface as well as
ground cover and canopy thickness of plants (Willis and McDowell 1987).
Zongmao and Haibin (1997) extensively investigated factors controlling dissipation from tea plant surfaces for 16 pesticides. Photodegradation was found to be
one of the most important factors in dissipation process except for evaporation,
rainfall elution, and growth dilution. Both photolysis and rainfall elution were
found to play a great role in the dissipation of diflubenzuron (159) in a conifer
forest (Rodriguez et al. 2001). Garau et al. (2002) examined the extent of pesticide loss from a cellulose membrane due to evaporation and codistillation in
the presence or absence of underlying water. Evaporation, codistillation, and
photolysis all contributed to dissipation of pyrimethanil (209) and cyprodinil
(210) but with each varying to some extent, while only photolysis was the controlling factor for azoxystrobin (244) and fludioxinil (208). The existence of
tomato fruit wax mostly retarded evaporation and codistillation of pesticides and
exhibited a screening effect against sunlight. For a pesticide with higher vapor
pressure and less photoreactivity, volatilization loss became predominant in dissipation as observed for chloropyrifos (145) (Meikle et al. 1983). Through a
glass wind tunnel study for 14C-fenpropimorph (227) individually applied to
bean, sugar beet, and radish, the importance of reactive species (OH and/or O3)
in air was demonstrated (Ophoff et al. 1999). Furthermore, either soil dusts or
clay minerals enhanced oxidation of parathion (135) to its oxon in the presence
of O3 (Spencer et al. 1980). In addition to these factors, penetration of pesticide
into cuticle and biotic metabolism therein are also considered important (Bentson 1990; Katagi and Mikami 2000).
B. Illumination Conditions
Spectral irradiance of sunlight at the plant surface is most important to understand the effect of photolysis (Fig. 4). Because the window glass used in ordinary greenhouses absorbs a considerable amount of light in the UV-B region
All pesticides are identified by their common name and parenthetical identification number, and
their structures are illustrated in the Appendices. Preceding the Appendices is a Directory of Pesticide Chemical Structures listing all pesticides in alphabetical order to aid the reader in locating
specific structures.
11
Fig. 4. Photodegradation of pesticide on plant: (a) precipitation, (b) wind, (c) volatilization, (d) sunlight outdoors, (e) sunlight in the borosilicate glass greenhouse.
(280320 nm), this filtering effect is likely to reduce the overlap between the
solar emission spectrum and the near-UV absorption spectrum of many pesticides (Kleier 1994). Photodegradation was measurably reduced by covering the
Petri dish as a model of the greenhouse window (Garau et al. 2002). Fukushima
et al. (2003) examined the photolysis of 14C-fenitrothion (138) on tomato fruit
in a greenhouse with a ceiling made of quartz or borosilicate glass. The intensity
of sunlight at <360 nm was significantly reduced in the borosilicate glass greenhouse, and neither the corresponding oxon nor the S-isomer generated by photolysis in the quartz greenhouse was detected. Furthermore, transmission through
the greenhouse window is also known to be reduced by glass pollution, and its
extent was larger in the shorter wavelength region (Van Koot and Dijkhuizen
1968). The structure of greenhouse changing the intensity and spectral irradiance
of the transmitted sunlight gave an insignificant effect on dissipation of chlorpyrifos (145). Type of crop and season were the most relevant factors (Martnez
Vidal et al. 1998). Similar results were obtained for fenpropathrin (24) (Martnez
Galera et al. 1997), while degradation of methomyl (70) was found to depend
on the type of greenhouse (Gil Garcia et al. 1997).
Degradation of pesticides in the greenhouse or outdoors was compared to
examine the controlling factors in foliar dissipation. The application of pirimi-
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carb (78) to lettuce was conducted both in greenhouse and field (151; Cabras et
al. 1990). No significant differences occurred in half-lives of total carbamates,
but greater formation of these degradates was observed in the field. The comparative degradation study of parathion (135) using a growth chamber, greenhouse,
and open field with and without motorized covering exhibited more formation
of the oxon and S-isomer in the field (Joiner and Baetcke 1973). Based on these
results, the experimental conditions of growing plants should be monitored and
compared with the real environment as much as possible to investigate the most
realistic pesticide photodegradation process.
C. Effect of Formulation
Pesticide formulation is composed of an active ingredient, carrier such as clay,
surfactants as wetting and spreading agents, nonevaporating viscous stickers,
humectants, and penetrating agents such as crop oils (Hazen 2000). These additives having hydrophobic and hydrophilic parts in a molecule provided a very
complex medium for photolysis of pesticides, and their aromatic moiety becomes
a possible photosensitizer or quencher (Nutahara and Murai 1984; Thomas and
Harrison 1990). Baker et al. (1983) investigated extensively the changing nature
of epicuticular waxes on the impact of several formulations containing 14Clabeled pesticide using scanning electron microscopy, X-ray analysis, and microautoradiography. Oil formulations were found to immediately spread through
crystalline wax whereas aqueous solutions distributed most readily over smooth
surfaces. Lipophilic pesticides are partitioned favorably into the organic phase,
separating as a zone at the outer edge of the droplet residue, but hydrophilic
pesticides are concentrated in the central region. Furthermore, the fluidity of
epicuticular waxes is known to change with hydrophobicity and lipophilicity
balance of the surfactant (Hess and Foy 2000). In addition, surfactants in formulations are considered to affect either uptake of pesticide molecules across the
cuticle to plant tissues or photodegradation profiles on plant surfaces. The former phenomenon by monodispersing alcohol ethoxylates has been demonstrated
for several pesticides on barley leaves. Larger effects on diffusion coefficient
were observed for the larger-size molecule (Burghardt et al. 1998). The latter
effect was first pointed out in aqueous solution by Tanaka et al. (1979, 1981).
Instead of formation of 4-OH and N-CHO derivatives, monuron (52) in aqueous
solutions of surfactants Tergitol TMN-6 or Triton X-100 underwent dechlorination followed by dimerization and N-demethylation. Furthermore, photodegradation of 17 herbicides was found to be accelerated by the presence of these
surfactants.
Based on these results, pesticide molecules were thought to be partitioned to
hydrophobic cores of micelles where photolysis such as that in an organic solvent proceeded favorably and surfactants such as Triton X-100 having an aromatic moiety could act as a photosensitizer. Such photosensitization was also
reported when oxysorbic or plant oil concentrate was used as the surfactant
(Harrison and Wax 1985). In contrast, it is supposed that some surfactants hav-
13
ing a lower triplet excited energy than that of the pesticide can act as a quencher,
which has been demonstrated for TMN-6 and nonaethoxylated p-(1,1,3,3-tetramethylbutyl)phenol (Tanaka et al. 1986, 1991). The other possible effect by
surfactants would be stabilization of photoproduced radicals in a cage. In the
case of 2,4-D (1), a few products formed via Norrish type II or photo-Fries
mechanism were detected through photolysis in aqueous solution containing surfactant (Que Hee et al. 1979). There was no significant effect of Tween 80 or
Trion X-100 on photolysis of metsulfuron (97) and chlorimuron (101) on glass
surfaces (Thomas and Harrison 1990), whereas in the other study accelerated
photolysis was observed (Harrison and Thomas 1990). On corn leaves, similar
acceleration was observed for (97) but with no clear effect for (101). In pyrethroids, reduced photolysis on glass surfaces was reported when surfactants
where included (Megahed et al. 1987).
D. Anatomy of the Leaf
As shown in Fig. 5, leaves are covered with protective cuticles that function by
decreasing water loss and protecting the plant from infection by various pathogens. The cuticle is a complex structure consisting of a pectin layer that binds
the cutin to the epidermal cell walls and a layer of epicuticular wax on the
outside, this structure is known to depend on plant species (McFarlane 1995;
Bianchi 1995). When the stomata are open, gas molecules can diffuse in and
out and interact with a large hydrophilic area of water-covered mesophyll cells.
Most pesticides are hydrophobic molecules, and thus the large lipid-covered
surface of leaves (cuticles) forms an ideal sink for accumulation of pesticides.
The fine structure of the wax layer greatly differs between plant species and is
morphologically classified by using light microscopy into four main forms: needles, rods, granular layers and films (Baker 1982). Use of the electron microscope has revealed that the aerial surfaces of all higher plants carry a partial or
continuous coverage of amorphous wax and that formation of crystalline wax is
Fig. 5. Transverse view of the typical surface structure of plant foliage: (a,d) epidermal
cell, (b) stoma, (c) mesophyll, (e) pectin, (f) cutin and embedded waxes, (g) epicuticular
waxes.
14
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frequently superimposed on amorphous layers. Penetration through these wax

regions and the underlying cutin layer has been extensively studied, for example, by using the diffusion cell method (Schonherr and Riederer 1989).
Radiant energy of sunlight is considered to interact with the leaf structure by
absorption and scattering. As shown in Fig. 5, most leaves have a distinct layer
of long palisade parenchyma cells in the upper part of the mesophyll and more
irregularly shaped spongy parenchyma cells in the lower part. Sunlight is reflected and scattered by hairs, leaf pubescence, and the glaucous leaf surface,
and a portion of the light enters into the leaf (Robberecht and Caldwell 1980;
Holmes and Keiller 2002). This light is critically reflected internally at the cell
walls in the intercellular space as a result of the difference of refractive index
between air and water in tissues (Gates et al. 1965). Pesticides by foliar application are considered to distribute mainly on the epicuticular wax layer, but a
portion may enter into the plant directly through stomata or diffusion; thus,
depth and spectral distribution of penetrated sunlight would be important when
photodegradation is considered. Many studies have been conducted to investigate this using a fiberoptic probe (Vogelmann and Bjorn 1984). About 90% of
the penetrating monochromatic light (310 nm) was attenuated within the initial
one third of the leaf (100150 m) of Brassica napus L., mostly at the epidermal cells; polychromatic radiation (280320 nm) exhibited a relatively uniform
spectral distribution within the leaf (Bornman and Vogelmann 1991; Cen and
Bornman 1993). UV-B radiation was found to reach the epidermis and meso lenius et al. 1995). Day et al. (1994)
phyll in other measurements for this leaf (A
measured UV absorption spectra and the epidermal transmittance spectra at
280350 nm of foliage from 42 plant species and demonstrated that some flavonoids act as a UV-absorbing agent. These observations imply that pesticide molecules in the leaf can absorb some part of the radiation energy of sunlight irrespective of their location, and not only the anatomy of the leaf but also
chromophores in leaf tissue can greatly affect their photodegradation.
E. Wax Chemistry
Epicuticular waxes are basically aliphatic compounds and are readily solubilized
by organic solvents with minimal contamination by lipids from the inner cuticular layers. A mixture of chloroform and diethyl ether (1 : 1, v/v) was found to
be efficient to isolate waxes containing cyclic compounds (Baker 1982). Leaves
of many herbaceous plants carry delicate membranes with only sparse wax deposits (510 g cm2) and many weed species also have thin wax layers. Wax
deposits on rapidly expanding leaves of leek and Brassica spp. are heavier
(3060 g cm2), similar to those on leaves of many fruit crops. Wax layers on
fruits are invariably much thicker than those on the corresponding leaves (50
400 g cm2), and thick deposits were also found for pistachio and olive (60
300 g cm2). As a result, the average thickness of the cuticle varies with plant
species from 3 to 15 m (Lendzian and Kerstiens 1991). Wax chemistry, especially of epicuticular waxes, has been systematically investigated for many plant
15
species, sometimes with different growth stages, first by thin-layer chromatography (TLC) and gas chromatography (GC) of the derivatized extracts and later by
gas chromatography-mass spectrometry (GC-MS), nuclear magnetic resonance
(NMR), and infrared (IR) (Baker 1982; Walton 1990; Bianchi 1995). Waxes are
basically classified into even- and odd-carbon-numbered straight chain homologues and cyclic compounds (Baker 1982; Bianchi 1995). The first class consists dominantly of acids (C12 C18 and C20 C32), aldehydes (C22 C32), primary
alcohols (C22 C32), and alkyl esters (C36 C72). The odd-numbered homologues
are hydrocarbons (C17 C35), secondary alcohols (C21 C33), ketones (C23 C33),
-diketones (C29 C33), and hydroxy--diketones (C29 C33). The last class consists of triterpenoid acids such as ursolic and oleanolic acids, triterpenols such
as - and -amyrin, triterpenoid esters, and ketones. Among them, the following
chemicals are known to be common major constituents of epicuticular waxes:
nonacosane and hentriacontane for hydrocarbons: hexacosanol, octacosanol, and
triacontanol for primary alcohols; nonacosan-10-ol for secondary alcohols; hentriacontane-14,16-dione and tritriacontane-16,18-dione for -diketones; and ursolic acid for triterpenoids.
Typical wax constituents with major homologues for representative plants,
fruits, and leaves are briefly summarized in Table 5 (see table on page 89). In
the case of leaf waxes, composition was found to vary with not only growth
stage but also the parts of the leaf, that is adaxial and abaxial surfaces (Bukovac
et al. 1979; Baker and Hunt 1981; Riederer and Schneider 1990). Unique components such as anthraquinone in the leaf waxes of perennial rye grass (Allebone
et al. 1971), a long-chain 1,4-benzoquinone in a wide variety of leaves (Kofler
et al. 1959), and novel fatty acid esters of E- and Z-p-coumaryl alcohols in cv.
Gala apples (Whitaker et al. 2001) have been reported.
F. Photoinduced Reactions
There has been no systematic investigation on the contribution of these wax
components to photolysis of pesticides. Pirisi et al. (1998) have measured UV
absorption spectra of epicuticular waxes of nectarines, oranges, and mandarin
oranges extracted by chloroform and/or methanol. These waxes basically exhibited featureless absorption at 290400 nm with small shoulders around 320 nm,
but no clear correlation with photolysis rates of pirimicarb (78) could be detected. The wax of annual spruce needles also showed the featureless spectrum
but with significant absorption at 300400 nm (Niu et al. 2003). Furthermore,
although no absorption maximum was observed for leaf waxes of caster bean,
UV absorption at about 300 nm was observed for Scotch pine, cabbage, and
Carnauba waxes (Wuhrmann-Meyer and Wuhrmann-Meyer 1941). Concerning
each chemical class of waxes, the theory of UV absorption indicates no absorption by simple hydrocarbons, but many chemicals containing a carbonyl moiety
can absorb UV light at >290 nm (Jaffe and Orchin 1962). n-Hentriacontane, the
major component of green tobacco leaf, was shown to be transparent to the UV
region (Carruthers and Johnstone 1959). As -diketones and ,-unsaturated
16
T. Katagi
ketones (aldehydes) show UV absorption maxima around 270 nm and 320370

nm (Cookson and Dandegaonker 1955; Horn and Lamberton 1962), these components as well as anthraquinone and 1,4-benzoquinone already described are
most likely to be involved in photolysis of pesticides on plant foliage.
Triterpenoid derivatives are detected as major to dominant components of
leaf waxes, but their UV absorption maxima are usually located at 200210 nm
in hexane (Wheeler and Mateos 1956; Weizmann and Mazur 1958; Turner
1959), which may indicate less importance in photolysis of pesticides. Phenylpropanoids including flavones, flavonols, and cinnamoyl esters in higher plants
are known to exhibit UV screening effect (Cockell and Knowland 1999; Kolb
et al. 2001). These flavonoids are also known to show an antioxidant activity
(McPhail et al. 2003) similar to -diketones (Osawa 1994). Because the complex
mixture of wax components is the primary reaction medium for pesticides, it
should be kept in mind whether these components simply act as highly viscous
organic solvents or are involved in photochemistry of pesticides as photosensitizer or quencher. As an example of wax effects on photolysis, either enhancement or retardation of photolysis was reported for 14C-fenarimol (239) spread
on glass surface with extracted waxes from barley, rape, strawberry, and apple
leaves (Watkins 1987). On the bean leaf, more S-oxidation of carboxin (42)
proceeded as compared with that on a glass surface (Buchenauer 1975). Accelerated photolysis was also reported for 2,4-D (1) on Zea mays leaves (Venkatesh
and Harrison 1999).
When 14C-dieldrin (123) was applied to bean foliage with flavone, formation
of photodieldrin (124) was enhanced by a factor of 57 via triplet photosensitization (Ivie and Casida 1971b). Rotenone exhibited the strongest sensitization
and effect of 15 pesticides tested, but anthraquinone had an insignificant effect.
The chromanone moiety of rotenone common to flavone was found essential to
show its activity (Ivie and Casida 1970). Accelerated photodegradation in the
presence of flavone, triplet sensitizers, and extracts from plant was also reported
for pyridafenthion (150), naproanilide (41), and flutolanil (39), all of which
were resistant to photolysis by themselves (Tsao et al. 1989; Tsao and Eto
1990a, 1991). Chlorophyll and furanocoumarins are also possible sensitizers in
plants, affecting photodegradation profiles of pesticides (Dodge and Knox 1986;
Dixon and Wells 1987). Although a reactive species has not been identified in
most cases, either possible hydrogen abstraction from wax components by the
photoproduced radicals originating from the pesticide or formation of a covalent
bond with the unsaturated bond of waxes via a radical reaction was demonstrated by using model waxes such as cyclohexene and methyl oleate (Draper
and Casida 1985; Schwack 1988; Schynowski and Schwack 1996; Breithaupt
and Schwack 2000). Nutahara and Murai (1984) have reported the enhanced
photodegradation of many pesticides by oleic and linoleic acids, possibly via
similar mechanisms as above. Because the unsaturated alkyl chain of these compounds is known to undergo oxidation by reaction with 1O2, giving the corresponding monohydroperoxide (Nakajima and Hidaka 1993), this peroxide or its
photodegradates may alter photodegradation of pesticides.
17
Formation of possible photosensitizers on foliage has also been reported. 6Methyl-5-hepten-2-one (6-MHO) has been detected in significant amounts on
foliage of orange, oak, and pine trees together with 4-oxopentanal, geranylacetone, and acetone, whose origin is considered to be unsaturated wax components
such as sesquiterpenes and triterpenes (Fruekilde et al. 1998). By using epicuticular waxes extracted from these leaves, oxidation by O3 produced these carbonyl
compounds, possibly acting as an efficient photosensitizer on foliage. Berenbaum and Larson (1988) have reported the formation of 1O2 (4 1012 1O2
molecules cm2 sec1) by illuminating intact leaves of wild parsnip and prickly
ash. The reaction of ascorbic acid in plant cell walls with O3 was also found to
generate 1O2, and a similar reaction was found for gluthathione, methionine, and
uric acid (Chameides 1989). Kanofsky and Sima (2000) utilized chemiluminescence at 1270 nm due to 1O2 to monitor its formation under O3 from illuminated
tissue fluids prepared by vacuum infiltration technique or intact leaf of white
stonecrop. Emission of 1O2 with consumption of O3 was clearly demonstrated,
and its retardation in the presence of ascorbate oxidase showed involvement of
ascorbic acid in this reaction. Because O3 is a very familiar component of air
over vegetation, the photochemical and/or chemical generation of 1O2 may play
a substantial role in the degradation of some pesticides on foliage.
IV. Factors Controlling Photolysis on Soil Surfaces

A. Soil Components
Soil is a variable mixture of minerals, organic matter, and water, capable of
supporting plant life on the earths surface (Manahan 1994). The solid fraction
of a typical productive soil is approximately 5% organic matter, originating
from plant debris in various stages of decay, and 95% inorganic matter. Soil
usually contains air spaces and generally has a loose texture. The majority of
inorganic components (>90%) are crystalline and noncrystalline amorphous
minerals including primary and secondary minerals; the former includes quartz
and micas and the latter phyllosilicates (clay minerals), allophanes, and metal
oxides. Quartz and micas are simple SiO2 minerals whereas clay minerals are
basically aluminosilicates. Therefore, their surface property and photoreactivity
may be estimated from those of silica gel as a surrogate surface. There are three
types of hydroxyl groups existing on silica gel with a different acidity: geminal
silanol (Si(OH)2), nongeminal (SiOH), and hydrated silanol (SiOHOH2), as
demonstrated by 19Si- and H-NMR and fluorescence analysis (Thomas 1993).
Clay minerals possess layered structures consisting of silica tetrahedral and alumina octahedral sheets with a ratio of 1 : 1 or 2 : 1 (Takagi and Shichi 2000).
Kaolinite is the typical clay in the former type and pylophyllite, smectite, and
vermiculite groups constitute the latter. The isomorphous substitution of central
atoms in tetrahedral and octahedral structures with another of a lower valency
resulted in a net negative charge for clay sheets and electrostatic force via countercations, making them loosely bound to each other (Caine et al. 1999). The
presence of interlayer space thus gives a sterically constrained reaction environ-
18
T. Katagi
ment for pesticide molecules when intercalated. Iron is one of the most abundant
transition metals in soil and is considered to play a large role in photoinduced
redox reactions generating active oxygen species such as OH. Sherman (1989)
demonstrated by Mossbauer spectroscopy that most Fe3+ and Fe2+ ions were
found to occupy the octahedral sites and that some ions might occur as an
interlayer species such as a Fe2+-aquo complex in the 2 : 1 clay minerals. Instead
of the Fe3+-aquo complex, Fe(OH)2(H2O)4 would condense to form ferric hydroxy polymers.
Humic substances account for 60%70% of soil organic matter, consisting
of a series of highly acidic, yellow to black, high molecular weight polyelectrolytes and characterized by their high content of oxygen-containing functional
groups such as COOH, phenolic, aliphatic, and enolic OH and C=O, together
with amino, heterocyclic amino, imino, and sulfhydryl groups (Stevenson 1976;
Ruggiero 1999). The higher total acidity of fulvic acid (FA, 10 mEq g1) than
humic acid (HA, 7 meq g1) can be accounted for by the higher content of a
COOH group in FA. The typical content of each functional group was reported
to be 3.68.2 mEq g1 (COOH), 3.03.9 mEq g1 (phenolic OH), 2.66.1 mEq
g1 (alcoholic OH), 2.72.9 meq g1 (quinoid and ketonic C=O), and 0.60.8
mEq g1 (OCH3) (Choudhry 1984b). Similar results have been confirmed by
Senesi et al. (1989) by using several soil humic substances and Suwannee River
soil. The clay surface is usually covered with these humic substances, probably
via formation of claymetalorganic complexes. Through adsorption study of
atrazine (185), the contribution of clay surface on adsorption was proposed to
be important when organic matter content was less than 6% (Stevenson 1976).
Based on their nature, interactions with HA and FA should be primarily considered in soil photolysis of pesticides. As an adsorption isotherm, Freundlich,
Langmuir, and RothmundKornfeld equations are well known and the shape of
the related isotherm would shed light on the adsorption mechanism. Proposed
mechanisms of interactions are ionic bonding via cation exchange, hydrogen
bonding, charge-transfer interaction with a quinoid moiety embedded in a humic
structure, cation-bridged ligand exchange with humic carboxyl moiety, covalent
binding, hydrophobic adsorption, and partitioning via dipoledipole and/or van
der Waals interaction (Stevenson 1976; Senesi and Testini 1984; Senesi and
Miano 1995).
Another unique feature characteristic of soil humic substances is the presence
of stable radical species detected by ESR. Senesi and Schnitzer (1977) have
reported the ESR signal at g = 2.00322.0050 without a hyperfine splitting for
FA whose intensity increased with either chemical reduction under more acidic
conditions or UV irradiation. They proposed semiquinones or its ions as the
most likely partial structure of stable radical species. Further investigation on
various soil HAs and FAs has shown the presence of two types of ESR signals
originating from a quinhydron-type structure and a phenoxide ion (Choudhry
1981). These stable radicals would be involved in photoinduced transformation
of pesticides as well as formation of active oxygen species, especially when a
transition metal or its oxide coexists (Ruggiero 1999).
19
B. Environmental Factors Affecting Soil Properties

Many soil photolysis studies have not strictly controlled and monitored basic
soil properties, especially such as moisture, until the recent development by the
Chibs group (Misra et al. 1997; Frank et al. 2002). As stated later, the penetration depth of light into soil is known to be very limited, approximately to the
top 0.5 cm of soil surface, and so its influence is considered to be very different
from that in the bulk soil (Fig. 6). In this region, solid, solution, and vapor
phases are all in close proximity to the soilatmosphere interface under sunlight
irradiation. Miller et al. (1989) concisely reviewed the effect of sunlight on
soil properties. They introduced a simulation on a typical diurnal variation of
temperature near the soil surface (02 cm) where the temperature increased up
to near 40 C at midday with a difference of about 20 during a day. A temperature gradient even at this shallow depth can be suspected and, in fact, the measured temperature at the irradiated surface, interior, and bottom of a soil thin
layer (0.51 mm thickness) attached to a cooling bath was reported to be 31,
29.9, and 25.6 C, respectively (Moore et al. 1989). This diurnal fluctuation of
temperature results in variation of soil moisture, that is, drying of soil during
daytime and rewetting during nighttime. These variations together with sunlight
irradiation would cause some effects on microbial activity, but its details are
not known for shallow soil. Recently, Reichman et al. (2000a,b) developed a
one-dimensional nonisothermal model to examine the dynamic behaviour of a
surface-applied pesticide under outdoor conditions. By using the diurnal variation of meteorological data such as wind speed, air temperature and relative
humidity and sunlight irradiation, they have simulated changes of depth-dependent soil temperature and moisture.
C. Mass Transport in Soil
Diffusion of a pesticide molecule is considered to be basically described by
Ficks law; however, the heterogeneous character of soil results in a more com-
Fig. 6. Structure of soil surface.
20
T. Katagi
plex description of a diffusion constant (D) than that in water (Graham-Bryce

1969). Do is the diffusion coefficient in free solution and is the tortuosity
factor:
D = Do v/(Kd d + v)
where v is the volumetric water content, Kd is the linear partition coefficient,
and d is the bulk density of soil. The tortuosity factor is a diffusion ratio of
pathlength in soil to that in aqueous solution (Scott and Phillips 1973). GrahamBryce (1969) has developed diffusion cylinder methods to determine the diffusion constants of pesticides. Information on the diffusion constant of a pesticide
in soil is very limited, but it seems to range from 0.05 to 50 mm2 d1 (Table 6
[see table on page 92]). When pesticide molecules are homogeneously distributed in uniform soil, the mean movement after time t is given by (2Dt)1/2. Therefore, it would take about 2.4 hr and 12.5 d for parathion (135) and trifluralin
(232) to move through the 1-mm-thick soil thin layer. The foregoing consideration shows the importance of mass movement in photodegradation on soil surfaces, but many other factors would operate in the field. Walker and Crawford
(1970) have demonstrated that diffusion constant was inversely proportional to
soil adsorption coefficient. Smaller diffusion with a higher water content was
reported for dinitroaniline herbicides (Jacques and Harvey 1979), whereas the
opposite relationship was observed for triazines (Scott and Phillips 1972). Ehlers
et al. (1969a,b) have reported the contribution to diffusion from vapor- and
nonvapor-phase mechanisms. In contrast to soil, several investigators have reported diffusion of pesticides in plant waxes and intact cuticles using the diffusion cell method (Schonherr and Riederer 1989; Lendzian and Kerstiens 1991;
Bauer and Schonherr 1992; Schreiber and Schonherr 1993), but their diffusion
seemed much slower than in soil.
Balmer et al. (2000) conducted the photolysis of trifluralin (232) and p-nitroanisole on kaolinite thin layers under constant temperature and humidity using
UV light at 300800 nm. By kinetic analysis, assuming first-order direct photolysis and diffusion following Ficks law, greater contribution of diffusion was
demonstrated for (232) than p-nitroanisole. For niclosamide (40), photodegradation in/on air-dried soil was greatly reduced in proportion to thickness of soil
thin layer, whereas a very slight increase of photolytic half-life was observed
for the moisture-maintained soil (Frank et al. 2002). Because the photic depth
of soil is usually less than 1 mm, as described in Section IV.D, migration of
(40) to the photic zone with the aid of soil moisture was considered most likely
to account for the observation. The importance of vapor-phase transport in airdried sandy loam soil was briefly examined for aryl ketones undergoing Norrish
type II photoelimination (Kieatiwong and Miller 1992). The existence of surfactant seemed to affect the migration of pesticides in soil. Gong et al. (2001)
showed that the faster photodegradation of atrazine (185) in the soil thin layer
with sodium dodecylbenzene sulfonate and proposed that solubilization of (185)
results in greater availability for photodegradation. A similar effect by hexade-
21
cane in soil photolysis was reported for 2,3,7,8-TCDD (129) (Kieatiwong et al.
1990).
In addition, other factors such as the depth of the water table may have some
influence on pesticide movement. The upward movement of chlorsulfuron (96)
and triasulfuron (100) in a packed soil column was clearly demonstrated when
addition of water to soil surface and drying in a growth chamber were cycled
or the bottom of the column was dipped into water (Mahnken and Weber 1988).
Capillary movement of pesticide, similar to the latter case, was also reported
for norflurazon (214) and found to contribute to volatilization loss (Hubbs and
Lavy 1990). The effect of this type of upward movement on photolysis has been
confirmed for 14C-napropamide (47) in soil under sunlight at the different water
table levels (Donaldson and Miller 1996).
D. Photic Depth in Soil
Soils are highly heterogeneous and unmixed as compared with solution, and
illumination produces a light field difficult to define accurately (Wolfe et al.
1990; Senesi and Loffredo 1997). The depth of light penetration (photic depth)
in soil cannot be precisely defined but has been estimated by direct measurement
of transmitted fraction of light or using probe molecules selectively undergoing
direct or indirect photolysis. Transmission of xenon arc light through soil thin
layers with 0.17-mm thickness was measured and UV light was found to be
more than 90% attenuated (Herbert and Miller 1990). Frank et al. (2002) examined transmittance of UV light by varying the soil layer thickness from 0.5 to 4
mm. Even a 0.5-mm-thick soil layer was enough to block about 95% of the
incident light, but very slight light penetrated soil depths of 1.5 mm or greater.
There was no significant difference of transmission at three wavelengths (280,
365, and 440 nm). When soil thickness was less than 1.5 mm, more transmission
of light by a factor of 45 was observed for dry soil as compared with moist
soil, which may be accounted for by the difference in soil packing. As another
approach, Hebert and Miller (1990) utilized disulfoton (163) and flumetralin
(233) as chemical probes to estimate the photic depth in soil. Flumetralin (233)
absorbing light at wavelengths of 300500 nm undergoes direct photolysis,
whereas (163) has no UV absorption at >290 nm and only indirect photolysis
takes place, that is, oxidation to the corresponding sulfoxide via reaction with
1
O2. By using these pesticides as probes, mean photic depths were estimated to
be 0.23 and 0.28 mm for direct and indirect photolysis, respectively, in the
laboratory, with larger values obtained for the outdoor study, 0.32 and 0.62 mm,
respectively. The larger values for either indirect photolysis or outdoor study
may show contribution from diffusion of 1O2 to a deeper region of soil than
expected for light penetration and that from convective and evapotranspirative
transport of pesticide by thermal heating at the soilair interface. It is unclear
if light reduction originates from bulk attenuation or as an inner filter phenomenon by soil. If an adsorbing substrate is relatively porous and highly colored, it
would be possible for an adsorbed pesticide to be filtered from the incident
22
T. Katagi
light. Yokley et al. (1986) investigated photodegradation of pyrene and benzo on average),
[a]pyrene on silica gel, alumina, controlled pore glass (100 A
graphite, and various coal ashes by using a xenon arc lamp and reported the
importance of both adsorption to pores and UV screening. The UV screening
effect by soil was also reported for photodegradation of polyaromatics where
slower degradation was observed for soil with lower reflectance (Moore et al.
1989). Similar reduction of light has also been reported for sediments suspended
in aqueous solutions of pesticides (Miller and Zepp 1979; Oliver et al. 1979;
Zepp and Schlotzhauer 1981).
E. Effects of Soil Properties on Photolysis
Konstantinou et al. (2001) have shown the possible involvement of photosensitization based on faster photodegradation of herbicides in soil with higher organic
matter. In contrast, soil organic matter reduced the photodegradation of chlorimuron ethyl (102) (Choudhury and Dureja 1997a), triasulfuron (100) and thifensulfuron-methyl (105) (Albanis et al. 2002), and fipronil (220) (Bobe et al.
1998b), indicating involvement of either quenching or a shielding effect. For
niclosamide (40), modification of soil by addition of 3% HA was found to
reduce photodegradation (Graebing et al. 2002). An insignificant effect of organic matter on photolysis was observed for mecoprop (4) but its retardation by
soil amendment with 10% peat was detected under dry conditions, also implying
the quenching effect (Romero et al. 1998). Clay is the other important soil
component and may affect the photodegradation profiles of pesticides. Sukul
and Spiteller (2001) reported the linear relationship between photolytic half-life
of metalaxyl (37) and clay percentage in soil. Because (37) does not have any
significant UV absorption at >290 nm, photolysis was considered via indirect
photolysis, and the lower rate in soil with a higher clay percentage was likely
to originate from more intercalation of (37) into the intralattice structure of clay
where the incident light was screened.
Surface pH was an important factor, and such a pH effect would be operative
for acid-labile pesticides such as sulfonylurea herbicides (Schroeder 1997). One
of the other important factors to control photolysis would be soil moisture content. Faster photodegradation was detected in moistened than air-dried soils for
alachlor (34) (Fang 1977), imidazolinone herbicides (Curran et al. 1992), and
florasulam (48) (Krieger et al. 2000), and photoinduced hydrolysis and/or migration of pesticides to the photic zone of the soil thin layer might operate in these
cases. Enhancement of photolysis with soil moisture was observed for mecoprop
(4), but at higher moisture the photodegradation rates decreased (Romero et al.
1998). The significant decrease of photolysis rates in moistened soil was reported for fenpropathrin (24), which originated mainly from the increase of
surface pH on soil with moisture (Katagi 1993b). As clearly seen from these
examples, there are different mechanisms affecting photolysis with change of
soil moisture, and thus it is not easy to estimate its effect a priori.
23
F. Photophysical and Photochemical Processes of Soil Components

Soil is a heterogeneous system where clay minerals are coated with humic substances and metal (hydr)oxides and the various photochemical reactions such as
photosensitization, quenching, and photoinduced reaction proceed (Fig. 7).
Humic Substances and Intact Soils There are many excellent reviews on photoprocesses of soil and aquatic humic substances (Zepp et al. 1981; Choudhry
1984a; Zepp 1988, 1991; Hoigne et al. 1989; Cooper 1989; Frimmel 1994).
UV-vis spectra of various HA and FA exhibited mostly featureless absorption
with their tail extending up to 500600 nm. The primary photoprocess is excitation to the short-lived (1 nsec) singlet states (Fig. 8). These excited states can
react with a pesticide molecule via a diffusional or static bimolecular process,
and the latter would play a greater role on soil surfaces. Zepp et al. (1985)
estimated the triplet energy of most humic substances to be around 60 kcal mol1
(250 kJ mole1) by using photoisomerization of 1,3-pentadiene as an index. It
depends on the energy level of triplet states of humic substances as compared
with that of a pesticide molecule which process predominates, sensitization or
quenching. Many pesticides are known to undergo photosensitized degradation
by humic substances (Jensen-Korte et al. 1987), whereas aqueous photodegradation of imazapyr (229) was slowed in the presence of HA due to the UV screening effect (Elazzouzi et al. 1999). In the photoinduced E/Z isomerization of four
alkyl cinnamates having a different association ability toward Fluka HA, only
2-fold increase in the rate of isomerization was observed for the cinnamate
Fig. 7. Photoreactions on soil surface: (A) sensitization, (B) quenching, (C) photoinduced
reaction, (D) adsorption/desorption, (E) spectral change, (F) inner-filter effect. P: pesticide; D: degradate(s); HS: humic substances; M: metal (oxides: hydroxides etc.).
24
T. Katagi
Fig. 8. Photophysical and photochemical processes of humic substances. HS: humic substances; RH: substrate.
having a 40-fold-higher affinity to HA (Van Noort et al. 1988), indicating that

the associated form was hardly available for triplet energy transfer.
The presence of reactive excited triplet states has been suggested for humic
substances through investigation of photoinduced degradation of cumene and
benzene (Kotzias et al. 1986). Because diffusion of pesticide molecules is considered to be restricted on soil surfaces, the possible reactions of a pesticide
molecule with an excited triplet of humic substances are transfer of electron or
hydrogen instead of direct energy transfer. These processes have been demonstrated for aqueous humic substances in photodegradation of the several methyl
and methoxy phenols (Canonica et al. 1995; Aguer and Richard 1996a). They
proposed an aromatic ketone moiety as a reactive site model in humic substances that underwent electron or hydrogen transfer via its excited n-* state.
Their contribution as well as energy transfer has been examined by using urea
herbicides including fenuron (51) and monuron (52) (Aguer and Richard 1996b;
Richard et al. 1997; Aguer and Richard 1999; Gerecke et al. 2001). Aguer et al.
(2001) showed the higher reactivity of HA fractions with a smaller molecular
size in photolysis of (51). They also demonstrated that soil FA having a smaller
specific absorption coefficient shows a higher activity, but that no meaningful
correlation is detected for HAs (Aguer et al. 2002). The weak photoinductive
efficiency of highly absorbing humic substances implied that the majority of
absorbing components had no photoinductive effect. There may be various small
organic molecules existing except for humic substances, and therefore they may
be involved in photolytic processes on soil. Kieber and Blough (1990) showed
the possible photoinduced formation of various carbon-centered radicals that
may react with pesticides under some photolytic conditions on soil surfaces.
Humic substances are known to react with O2 via energy or electron transfer
process to generate the very reactive 1O2, OH, superoxide anion (O2), and
25
peroxide radical species (see Fig. 7). The contribution of each process was
roughly estimated for dissolved organic matter on an excited singlet state basis
(Zepp 1991). Thermal deactivation was a dominant process (97%99%), and
only 1%3% of energy would be transferred to an excited triplet state, most of
which was involved in formation of 1O2. In an aqueous solution of HA, Takahashi et al. (1988) confirmed the formation of OH, O2H, and 1O2 in the presence of O2 by ESR measurements using spin-trapping reagents. Nanosecond
laser spectroscopic methods were applied, and two short-lived transients from
four illuminated natural waters were estimated to be an excited triplet state of a
quinoid structure of humic substances and hydrated electron (eaq) (Fischer et al.
1985, 1987; Power et al. 1987; Zepp et al. 1987). Photoinduced generation of
eaq from natural waters also has been confirmed by its conversion to OH with
N2O (Thomas-Smith and Blough 2001), and the steady-state concentration of
eaq was estimated to be approximately 1.1 1017 M (Breugem et al. 1986).
Because eaq quickly reacts with water molecules to give O2 and O2H if generated (Hoigne et al. 1989), its importance would be greatly lessened, especially
on soil surfaces.
The steady-state concentration of 1O2 in natural water has been estimated to
be 1014 1012 M (Zepp et al. 1977; Wolfe et al. 1981; Haag and Hoigne 1986).
The quantum yield of the photoinduced generation of 1O2 from aqueous solutions of soil HA and FA was estimated by both ESR and chemical analysis
using furoin (1,2-dimethyl-2-hydroxyethanone) to be 0.395.5 103 (Aguer et
al. 1997). On soil surfaces, Gohre and Miller (1983) first demonstrated photoinduced formation of 1O2 by using tetramethylethylene and 2,5-dimethylfuran as
chemical probes. Gohre and Miller (1985) demonstrated that nontransition metal
oxide powders such as silica gel, aluminum oxide, and magnesium oxide catalyze the formation of 1O2. They proposed the reaction of an exciton bound to a
defect on a solid surface with adsorbed oxygen via transfer of electronic energy,
and no correlation between 1O2 generation and the content of soil organic matter
was reported (Gohre et al. 1986). The existence of 1O2 was supported by observation of chemiluminescence at 615650 nm possibly due to 1O2 dimoles, but
recently a direct spectrophotometric method for the very weak chemiluminescence at 1270 nm (1O2 3O2, spin-forbidden process) has been developed
(Rodgers 1987; Kanofsky 2000).
The reaction types of photosensitized oxidation via 1O2 can be classified into
formation of endo-peroxide, ene reaction giving allyl hydroperoxide, and formation of 1,2-dioxetane (Foote 1968a,b; Wilkinson and Brummer 1981). The
thioether-containing pesticides on soil were found to be transformed to the corresponding sulfoxide by sunlight exposure most likely via reaction with 1O2
(Gohre and Miller 1986). The other example was photoinduced degradation of
bioresmethrin, 1R-trans isomer of (15), whose degradation was clearly reduced
in the presence of -carotene as an efficient 1O2 quencher (Clements and Wells
1992). The enhanced degradation of 2-dimethylamino-5,6-dimethylpyrimidin-4ol in D2O inhibited by sodium azide also showed involvement of 1O2 in its
degradation, possibly attacking the 5,6-double bond (Dixon and Wells 1983).
26
T. Katagi
Under exposure to sunlight, OH is photochemically generated via (1) reaction of humic substances in the excited triplet with water, (2) dissociation of
nitrate ion followed by protonation, and (3) degradation of H2O2 formed by
reaction of eaq with water (Hoigne et al. 1989; Zepp 1991); in addition, coexistence of metal cations such as ferric ion with humic substances was considered
to play a great role in generating OH via (4) the photo-Fenton reaction. The
second mechanism is considered to be predominant in the aquatic environment,
but investigation has demonstrated that about half of OH is generated via
photo-Fenton reaction, and an O2-independent pathway also exists (Vaugham
and Blough 1998). Among these four mechanisms, the first and last procedures
are considered to be more important to soil photodegradation. Photoinduced
formation of OH was confirmed in photolysis of 2,6-dimethoxyphenol with soil
extracts by ESR (Suflita et al. 1981). Many investigations on OH-generating
ability of metalhumate complex through the Fenton or HaberWeiss mechanism have been reported. Paciolla et al. (1999) demonstrated the intrinsic ability
of Fe3+ or Cu2+ HA complexes to generate OH from H2O2 in darkness. Mossbauer spectroscopy of this complex showed that about 5% of iron ion was present as Fe2+, indicating involvement of the above mechanisms.
Fukushima and Tatsumi (1999) studied the photocatalytic activity of the
Fe3+ soil humate complex giving OH and H2O2 at >370 nm. Photoinduced oneelectron transfer from HA to O2 followed by protonation was considered to yield
O2H, which was then disproportioned into H2O2 and O2. They demonstrated
that the majority of Fe3+ was complexed with the HA fraction in a higher molecular weight and that the substrates were incorporated into the molecular skeleton
of HA through photolysis (Fukushima et al. 2000, 2001; Fukushima and Tatsumi 2001). Similar photo-Fenton reactions can be considered for small organic
molecules (Zepp et al. 1992; Balmer and Sulzberger 1999). Because soil components such as humic substances and silicate surface can trap a peroxy radical
(Pohlman and Mill 1983), contribution from the aforementioned processes may
be lessened on soil surfaces.
As described, H2O2 is an another important reactive oxygen species in the
environment whose generated humic substances are known to be deeply involved, and its steady-state concentration in an aquatic environment is estimated
to be 105 107 M (Draper and Crosby 1983; Cooper 1989). H2O2 on soil surfaces would be degraded by various interactions with soil components or react
with a pesticide molecule under sunlight irradiation. Petigara et al. (2002) investigated the degradation processes of H2O2 in soils and revealed the possible
involvement of three pathways: a metal-catalyzed HarberWeiss reaction, twoelectron process achieved by catalase, and a peroxidic-type reaction. OH was
fluorometrically determined using spin-trapping reagent and fluorescamine
(Vaugham and Blough 1998). Retarded loss of H2O2 by autoclaving or addition
of sodium azide or formaldehyde showed that 65%75% of loss was due to
abiotic processes on soil particles. Among minerals, goethite was found more
reactive in generation of OH than hematite. The photoinduced reaction of H2O2
with pesticide was not reported on soil surfaces, but aqueous photolysis of the
27
several pesticides in the presence of H2O2 clearly showed involvement of photogenerated OH as evidenced by product analysis (Draper and Crosby 1981,
1984).
Clays The flat organosilicate sheets with reactive edges give a unique reaction
environment on clay. Furthermore, a geometric constraint by pore or sheet structures in clay may alter the photochemistry of pesticides (Thomas 1993). A clay
surface may exhibit a cage effect for radicals generated via photoinduced homolytic cleavage of a bond similarly observed for benzyl derivatives on silica gel
(Avnir et al. 1981). As one of the basic properties on clay surfaces, it should be
noted that the sites possessing a high Brnsted acidity may show catalysis on
some pesticides (Caine et al. 1999). Using these properties, Takagi and Shichi
(2000) reviewed organic photochemistry in/on the clay surface. The efficient
transfer of electron or excited energy occurs between molecules adsorbed on
clay surfaces, and ferric ion as an impurity in clay may act as an efficient
quencher. Spectral shift by adsorption, steric constraint, and hydrogen bonding
are known to result in the different profiles for photoinduced isomerization of
styrene derivatives, Norrish type I and II reactions of aromatic ketones, and
photo-Fries rearrangement of carbamates.
One-electron transfer from an adsorbed chemical to clay is known for thianthrene on laponite, as evidenced by ESR (Mao and Thomas 1993). A similar
photoinduced electron transfer to laponite, silica gel, and silica-alumina was
reported for pyrene (Liu et al. 1994). Extent of a cation radical formation was
found to gradually decrease at above 340 nm, indicating the existence of variable active sites having a different capacity of accepting electrons. There is also
evidence that ferric ion included in montmorillonite clay as an impurity acts as
an electron mediator between excited 10-methylacridinium hexafluorophosphate
and iodide as an acceptor (Theng et al. 1997). The other type of electron transfer
is directed from clay surface to adsorbed species such as O2 and transition metal
ions in clay is considered to be deeply involved, as already described.
Various kinds of energy transfer on clay have been investigated. Detailed
analysis of difference IR spectra implied the possible interaction of bioresmethrin, 1R-trans isomer of (15), with methyl green (MG) on clay surfaces, and
photostabilization of bioresmethrin by MG could be accounted for by an efficient energy transfer (Margulies et al. 1985, 1987, 1993). Margulies et al. (1988)
have reported the red shift of absorption spectrum when NMH (242) was adsorbed on montmorillonite. Its photostablity was improved by coadsorption of
thioflavin (TFT) or MG and its extent was greater in the former dye. The UVvis absorption maximum of TFT (410 nm) was closer to that of (242) compared
to MG (630 nm), implying more efficient energy transfer from (242) to TFT.
The interaction of (242) with clay surface was considered to take place at the
cyclic enamine moiety of (242) as estimated by difference IR spectrum. Furthermore, the direct energy transfer to clay surface was also reported for (242)
(Rosen and Margulies 1991). Less photostabilization of (242) adsorbed to nontronite than hectorite and montmorillonite could be accounted for by the differ-
28
T. Katagi
ent contents of Fe3+ (29.46%, 0.26%, and 3.72% as Fe2O3, respectively), which
acted as a quencher via a charge-transfer mechanism. Efficient overlap of the
emission with the absorption spectrum is indispensable for this energy transfer,
which has been well established for norflurazon (214) coadsorbed with TFT on
montmorillonite (Undabeytia et al. 2000). They also proposed the photoinduced
generation of OH by montmorillonite accelerating its degradation. The involvement of reactive oxygen species in photodegradation of pesticides on clay surfaces has been reported for tolclofos-methyl (142), esfenvalerate (28), and PBacid (243) (Katagi 1990, 1991, 1992). A simple organic cation such as
benzyltrimethyl-ammonium has been demonstrated to modify adsorption of
alachlor (34) to a clay surface, leading to its protection against photolysis (ElNahhal et al. 1999). The IR spectral shift of carbonyl and C(aromatic)-N bonds
to lower and higher wave numbers, respectively, indicated the possible interaction of carbonyl oxygen with an exchangeable countercation on the clay surface
through a water bridge (Nir et al. 2000). The red shift of the UV absorption
spectrum (-*) of phenyltrimethylammonium was observed when coadsorbed
to montmorillonite, indicating the interaction between the phenyl rings of (34)
and the organic cation.
In addition, clay surfaces also give a steric constraint on an adsorbed pesticide molecule (Margulies et al. 1993; El-Nahhal et al. 2001). Photostabilization
of trifluralin (232) was realized by adsorption to montmorillonite, but the addition of TFT did not give further improvement (Margulies et al. 1992). Difference IR spectra clearly demonstrated interaction of one nitro group of (232)
with the clay interface. It is known that (232) undergoes photo-induced cyclization between nitro nitrogen and the C1 carbon of the N-propyl moiety to give
benzimidazole derivatives (see Fig. 2, reaction 10b). Because the intramolecular
cyclization requires a conformational change of the N-propyl moiety, which is
restricted by adsorption to the clay, the observed photostabilization is most
likely to be accounted for by imposition of a steric constraint on (232).
Metal Oxides and Hydroxides Transition metals such as iron and manganese
exist in the environment as their oxides, hydroxides, and sulfides or impurities
in clay being substituted with aluminum ions. These compounds can become
quenchers of an excited energy and catalytic sites by acting as an electron mediator. It has been reported on silica gel that dye-sensitized photooxidation of
bromacil (198) by 1O2 is significantly reduced by addition of FeO, Fe2O3, Fe3O4,
or FeO(OH), which can be accounted for by an electron transfer from the excited dyes or energy transfer from 1O2 (Riter et al. 1990). In addition, as represented by titanium dioxide, some materials also can act as semiconductors where
the photoexcited valence band electron reduces an organic chemical and the
accompaning hole oxidizes (Balkaya 2003). Irradiation at >340 nm accelerated
degradation of (185) in the presence of typical semiconductors TiO2, ZnO, and
WO3 to give N-dealkylated derivatives possibly via oxidation by OH, whereas
-Fe2O3 and Al2O3 did not show any photocatalytic action (Pelizzetti et al.
1993). Further examination was conducted by Lackhoff and Niessner (2002) to
29
estimate such a photocatalytic activity for environmental particles. Both TiO2

and ZnO exhibited a significant acceleration of degradation by a factor of 30
300, but much less activity was detected only for the other oxides such as
SrTiO3, Fe2O3, and FeTiO3. Fine particles from natural sand, soot, and ash did
not show any meaningful acceleration compared with direct photolysis, which
would be due to less occurrence of photocatalytic Ti (<1%) in these materials.
Only very weak photocatalytic activity was observed for three soils when (185)
was irradiated at >340 nm in aqueous suspension (Pelizzetti et al. 1993).
Similar trends of photocatalysis were briefly reported for dicarboximide fungicides (Hustert and Moza 1997) and azo dyes (Hustert and Moza 1994). In
contrast, the direct reaction with a positive hole was proposed for photolysis of
2,6-dimethylphenol in aqueous suspension of goethite (-FeOOH) (Mazellier
and Bolte 2000). Not only the surfaces of these metal (hydro)oxides but also
species dissolved from the surface are considered to show catalytic acitivity in
generating active oxygen species. Voelker et al. (1997) demonstrated this in the
mixture of lepidocrocite (-FeOOH) and FA, and Fenton-like degradation of
H2O2 has also been reported for goethite (Chen and Watts 2000). Many iron
species are considered to exist in an aqueous phase after dissolution, and
Fe(OH)2+ species have been found most efficient in generating OH under irradiation (Feng and Nansheng 2000). When H2O2 is enzymatically or abiotically
formed in soil, OH is likely to be produced via Fenton-like reaction as demonstrated by ESR (Huling et al. 1998). These reactions may occur in real soil and
contribute, at least in part, to photodegradation of pesticides. In contrast to iron
species, manganese oxides seem to show much less photocatalytic activity (Bertino and Zepp 1991; Lee and Huang 1995).
V. Atmospheric Oxygen Species

Reaction with oxygen species in air at a solidair interface is considered to be
another important degradation pathway for pesticides deposited on soil and plant
surfaces. In the troposphere, O2 is the most abundant reactive species from its
biradical structure in the ground state and is involved in either autooxidation or
coupling with radical species to give the corresponding peroxy species. The
other important species are O3 and OH because of their high reactivity (Crosby
1983; Marcheterre et al. 1988). In fact, their possible contribution to degradation
of pesticides has been demonstrated on plant foliage (Spear et al. 1978; Ophoff
et al. 1999) and soil surfaces (Spencer et al. 1980; Kromer et al. 1999). 1O2 is
also the other candidate, but its contribution may be limited to its specific reactivity toward a thiol moiety and C=C double bonds (Wilkinson and Brummer
1981; Larson and Marley 1999). The formation and decline processes of these
reactive species in air are known to be very complex (Prinn 1994). O3 in the
troposphere originates from that in the stratosphere formed by direct photolysis
of O2 or reaction between O2 and singlet oxygen atom O(1D) and dissipates via
UV photolysis to O(1D) or reaction with NO. OH is mainly generated via reaction between O(1D) and H2O and deactivated by reaction with air pollutants
30
T. Katagi
such as CH4, SO2, and CO. The lifetime of O3 and OH in air is estimated to be
3 105 sec and 2.7 sec, respectively.
Concentrations of O3 and OH are significantly low and known to vary with
many factors such as climate, geographical features, vegetation, and pollution
by human activities. The monthly mean value of troposheric O3 was 3550
ppb in the western North Atlantic (Oltmans and Levy 1992). The yearly mean
concentration at 13 stations in the United States was about 30 ppb with a seasonal variation, the maximum value (8090 ppb) being detected in spring (Singh
et al. 1978). The diurnal variation was also reported, and the maximum concentration was observed in the morning due to low photochemical destruction (Oltmans 1981). Logan (1999) found that rural sites downwind of urban areas might
have particularly high values of O3 in the middle of the day; 4070 ppb in
summer and 2030 ppb in winter. The steady-state concentration of OH was
estimated to be 56 105 molecules cm3 (Crutzen 1982). Direct measurements
have been conducted by using laser long-path absorption or laser-induced fluorescence method based on the X2 ( = 0) A2+ ( = 0) transition of OH.
The former method gave the OH concentration of 4.3 (0.4) 106 molecules
cm3 in a sunny period but less in the nighttime (<1.5 106 molecules cm3)
(Dorn et al. 1995). The latter method showed similar values (3.46 106 molecules cm3) in May and June (Holland et al. 1995). As laser irradiation also
produces OH from the coexisting O3 as an artifact, ion-assisted mass spectrometry using 34SO2 has been applied (Crosley 1995). Estimated values in Colorado
were 24 106 molecules cm3 smaller than expected from a photochemical
model, which could be accounted for by the presence of a quencher such as
isoprene (2 ppb) in air. In other places, 110 106 molecules cm3 was correctly
estimated.
O3 and gaseous pollutants in air are considered to be sorbed to plants and
soil surfaces, and such deposition is one of the important factors controlling
their air concentrations. In the case of plant foliage, not only the direct interaction of O3 and OH via sorption or reaction with epicuticular waxes but also
reaction with epidermal and mesophyll cells and substomatal cavities after passage through stomata is considered to play a role (Runeckles 1992; Cape 1997).
The soil surface also acted as a sink of O3 (Turner et al. 1974; Fontan et al.
1992; Cieslik and Labatut 1997). The uptake of O3 by plants was considered to
be mainly through stomata, and its flux over the vegetation was monitored (Eastman et al. 1981). As a result, the deposition velocity over maize (max., 0.84 cm
sec1) was found to be about twice as large as that over grass, suggesting that
the size of the stomatal aperture may be the predominant mechanism in O3
uptake. Wet and dry O3 deposition via stomatal or nonstomatal mechanisms
have been studied in conjunction with aerodynamics over vegetation (Fowler
et al. 2001; Zhang et al. 2002). Kerstiens and Lendzion (1989) examined nonstomatal deposition of O3 using isolated cuticle from various plant leaves and
demonstrated that its permeance via leaf is highly dependent on plant species
and that either dust or hairs on leaf surface provides more degradation sites for
O3. Based on these considerations, atmospheric conditions, especially for the
31
concentration of O3 and OH, should also be taken into account when photodegradation pathways of pesticides on plant and soil surfaces are examined.
VI. Experimental Design and Kinetic Analysis

A. Light Source
Many kinds of conventional light sources with different spectral irradiance
(Gould 1989a) have been utilized especially for photolysis studies of pesticides
(Guth 1981; Roof 1982; Miller and Zepp 1983; Parlar 1990). The spectral comparison of artificial light with natural sunlight indicates great differences (Fig.
9) (Hirt et al. 1960). The most suitable light source is a xenon arc lamp; as it
emits at <290 nm, an appropriate UV filter should be used. The glass and solution filters commonly used in photolysis studies are each characterized by transmission of light at a specific wavelength range (Gould 1989a), and glass has
been preferred because of its simplicity. The most popular filter is Pyrex (or
Duran) glass and its thickness (4 mm) is also important for effective cutoff of
the undesired shorter wavelengths (Zepp 1982). Cellulose acetate sheet is sometimes unfavorable due to its solarization. If an appropriate glass and/or solution
filter is used, the wavelength dependency of photolysis can be conveniently
estimated for better understanding of the photolytic mechanism (Schwack and
Fig. 9. Spectral irradiance of typical light sources used in photolysis studies. Graph is
based on data from Hirt et al. (1960).
32
T. Katagi
Kopf 1993; Schwack et al. 1995c). Even if natural sunlight is used, it should be
kept in mind that a reaction vessel or the glass of the greenhouse can partially
absorb sunlight.
B. Photolysis Chambers
Ebing and Schuphan (1979) introduced a closed cultivating system made of
Pyrex or Duran glass (3-mm thickness) and equipped with volatile traps under
irradiation by fluorescent tubes to examine degradation profiles of dichlofluanid
(205) with a good 14C recovery (96%99%) in soilplant (spinach, potato, and
cress) systems. A volatilization chamber elaborately designed to simulate well
real environmental conditions was developed to evaluate the dissipation profiles
of methyl parathion (136) applied to French beans (Muller et al. 1995). The
chamber was connected with an air-conditioning unit to obtain the desired temperature, humidity, and flow rate of air that passes over the plants into volatile
traps, and the ceiling of the chamber was made of a special glass transmittimg
light from a metal-halogenide lamp to simulate exposure to natural sunlight. A
similar wind tunnel apparatus was successfully introduced to estimate volatilization and degradation profiles of fenpropimorph (227) on dwarf beans, sugar
beet, and radish (Ophoff et al. 1999). However, these apparati are not readily
available and their maintenance is difficult; therefore, photodegradation of pesticides on plants has been mostly examined with metabolism studies.
Many researchers have developed an apparatus for soil photolysis that can
be classified as a rotatory reaction vessel made of glass or thin-layer plate in a
chamber (Guth 1981; Choudhry and Webster 1985; Parlar 1990). The former
system was introduced to examine the mineralization of pesticides on a silica
gel surface (Parlar 1990), and its concept has been used to examine photolysis
of diuron (53) adsorbed on sand, clays, and iron oxide (Jirkovsky et al. 1997).
The latter system has been widely utilized, and its common design is illustrated
in Fig. 10, based on the literature (Klehr et al. 1983; Katagi 1990; Misra et al.
1997; Kromer et al. 1999; Balmer et al. 2000). The soil thin layer (thickness <2
mm) prepared on a plate or vessel made of glass or stainless steel is attached to
the controlled temperature water bath, and sometimes a thermocouple buried in
the soil is utilized to monitor and control the soil temperature. Light intensity
and its spectral distribution are monitored by a spectroradiometer. Because either diffusion of a pesticide molecule or photodegradation profiles in or on soil
is very sensitive to soil temperature and humidity, some investigators (Misra et
al. 1997; Kromer et al. 1999; Graebing et al. 2003) have also introduced a
relative humidity sensor to the chamber equipped with a water spray nozzle and
established a computerized system to automatically control humidity.
Good material balance is indispensable for precisely evaluating the photolytic
profiles of pesticides and thus the selection of appropriate traps is very important. Not only do volatile pesticides have a higher vapor pressure, most volatiles
consist mainly of CO2 and organic degradates with a small molecular size. Air
flow under reduced pressure conditions was obtained using a suitable pump to
33
Fig. 10. Soil photolysis chamber. 1, soil thin layer (<2-mm thickness); 2, thermocouple;
3, thermometer; 4, photoprobe connected by glass fiber; 5, spectroradiometer; 6, glass
filter (Pyrex); 7, thermostat-controlled water bath; 8, circulator; 9, xenon arc lamp; 10,
power supply; 11, CO2-free humidified air; 12, traps.
avoid undesirable leakage from glass joints or seals instead of the pressurized
system. One of the traps is a liquid type, represented by aqueous alkaline solution and organic solvents and the other is a solid type, for example, ascarite,
charcoal, and porous polymers (Lewis 1976). CO2 is usually collected by using
0.10.5 M KOH or NaOH in a gas-washing bottle and quantified by precipitation as BaCO3. Monoethanolamine is also used as a trapping medium (Yamaoka
et al. 1988; Tanaka et al. 1991), and its efficiency can be improved by adding
methanol and a scintillation cocktail (Abbott et al. 1992). Ascarite has been
conveniently used to trap CO2 generated during photolysis of florasulam (48)
(Krieger et al. 2000). When CO is generated, it can be catalytically converted
to CO2 using a combustion furnace (CuO at 650 C) followed by trapping as
above (Tanaka et al. 1991) or chemically trapping as cuprous complex using an
acidic CuCl solution (Busch and Franklin 1979). Small organic volatiles are
usually collected by using nonvolatile ethylene glycol, and its low solubilizing
ability toward organic molecules can be improved, for example, by addition of
a small volume of xylene. Evaporation of an organic solvent usually causes
difficulty in its use as a trapping medium, especially for longer periods, but
cooling of the medium can improve its utility (Koshy et al. 1983). The cryogenic
technique using a dry iceacetone mixture at 78 C can also be effective
(Lewis 1976). As a solid trapping medium, acetone-washed polyurethane foam
(Kromer et al. 1999) and porous polymeric sorbent such as Amberlite XAD
resins, Chromosorb, and Tenax (Lewis 1976; Smith et al. 1995; Ophoff et al.
34
T. Katagi
1999) have been used effectively. If organic volatiles can undergo fast and specific chemical reaction in a trapping medium, it can become a useful trapping
method. Tanaka et al. (1991) used dimedone (5,5-dimethylcyclohexane-1,3dione) with a trace amount of pyridine to trap formaldehyde. For formic acid
and acetic acid, Yamaoka et al. (1988) derivatized these using p-bromophenacyl
bromide in the presence of 18-crown-6.
C. Kinetic Analysis
When the reaction environment of a pesticide varies with its movement and
adsorption, a simple first-order kinetics cannot be applied. In the foliar dissipation of pesticides, the decline curve sometimes follows a two- or three-phase
kinetics, each of which consists of a single exponential decline (first order).
These are considered to correspond to the compartment models where movement of a pesticide between each compartment can be neglected. Gunther (1969)
demonstrated the involvement of two dissipation processes for pesticides applied to citrus fruit and found that the first faster dissipation stems from surface
deposits in epicuticular waxes and the slower process from metabolism in the
rind. Similar approaches are utilized for many studies. Figure 11 shows the differences in decline profiles among simple first-order (single-phase), two- and
three-phase kinetics as examples. By considering a weight of vaporization loss
from plant surfaces in the early stage after application, Stamper et al. (1979)
analyzed crop residue data by ln-ln plots and statistically obtained the better
relationship; R = a*t3/2 (R, residue; t, days after application; a, constant). When
Ficks second law of diffusion is applied, the dissipation of a pesticide can be
approximated by y0 /(4Dt)3/2 (y0, initial deposit; D, diffusion constant), which
is in accordance with the statistical analysis. This information indicates the importance of controlling factors such as volatilization besides basic degradation
mechanisms, and such an approach has been undertaken to account for dissipation of pesticides from tea plants (Zongmao and Haibin 1997). The quantum
chemical parameters were also introduced to examine photodegradation of polychlorodibenzodioxins on laurel cherry (Chen et al. 2001), and such an approach
may be useful.
In the case of soil photolysis studies, the decline of a pesticide usually does
not follow the first-order kinetics and slows down with time, possibly due to
either adsorption to soil or movement out of a photic zone. Many investigators
have applied the single- to three-phase models, but in some cases the secondorder rate constant or Hoerl function [a * exp (b*t) * tc], where a, b, and c are
constants and t is an incubation period, has been proposed as a better relationship (Emmelin et al. 1993; Romero et al. 1998). The simpler equation based on
a meaningful physicochemical assumption is desirable in the usual analysis of
experimental data. Gustafson and Holden (1990) have focused on a spatial variability in factors affecting dissipation rate in soil such as microbial population,
light intensity, temperature, and soil properties. They assumed an infinite compartment model where each compartment with a different dissipation rate is
35
distributed with some probability and introduced the concept that the rate constants follow the distribution. The simple equation, y = (1 + b*t)a, can be
derived with a half-life of (0.5(1/a) 1)/b (y, % of the applied dose; t, time; a, b,
constants); the dissipation curve is shown in Fig. 11. Data analysis using these
approaches helps to understand not only persistence of a pesticide but also the
dissipation mechanisms involved.
VII. Photodegradation of Pesticides in Model Systems

A. Soil Surface Models
Glass, silica gel, or clay have been utilized as simple models by considering
heterogeneity and variability of soil affecting photodegradation profiles of pesticides (Hulpke et al. 1983). However, the adsorptive nature of soil cannot be
taken into account on glass. This effect may be partly realized in silica gel or
clay, but the higher reactivity of their surface originating from many types of
silanol groups and adsorbed water would give different reaction environments.
Furthermore, more tightly packing may reduce the depth of light penetration
compared with soil. Although the contribution of soil humic substances acting
as a photosensitizer, quencher, or solubilizing medium is completely neglected
in either of these models, their easier handling makes them the first useful approach to evaluate soil photolysis of pesticides. Treatment of silica gel or clay
Fig. 11. Typical decline curves. When period and percent (%) of the applied dose are
t and y, respectively, each curve can be defined as follows: single-phase, y =
exp(a*t), a = 0.139; two-phase, y = a*exp(b*t) + c*exp(d*t), a = 0.6, b = 0.139,
c = 0.4, d = 0.0139; three-phase, y = a*exp(b*t) + c*exp(d*t) + e*exp(f *t), a = 0.4,
b = 0.139, c = 0.3, d = 0.0139, e = 0.3, f = 0.00693; Gustafson, y = (1 + b*t)a, a = 1.5,
b = 0.117.
36
T. Katagi
with humic substances can be alternatively considered, but such approaches are
very limited (Schafmeier et al. 1998). The most frequently reported system is
the aqueous soil suspension (Pelizzetti et al. 1990; Mansour et al. 1997; Hustert
et al. 1999), but the excess amount of water may alter the reaction environment
or unexpectedly increase the contribution either from direct or indirect photolysis in an aqueous phase containing dissolved humic substances. Furthermore,
the filter effect by suspended matters may reduce the rate of photolysis (Zepp
and Schlotzhauer 1981), and the adsorption to soil may be underestimated for
partially water-soluble pesticides. Furthermore, even if the soil thin layer with
1- to 2-mm thickness is used, diurnal variation of soil temperature and moisture
is difficult to determine (Miller et al. 1989; Reichman et al. 2000b). These
differences would change the extent of vaporization loss of pesticide from soil
surface and misstate the rate of photoinduced dissipation by neglecting transport
of pesticide or reactive oxygen species via diffusion along with the movement
of water or air in soil (Ehlers et al. 1969b; Hubbs and Lavy 1990; Donaldson
and Miller 1996; Balmer et al. 2000). The few approaches elaborately controlling these factors have been carefully developed (Misra et al. 1997; Kromer et
al. 1999; Frank et al. 2002).
B. Plant Surface Models
The simplest model is the glass surface, but the reaction environment is very
different from the cuticular surface. From this point of view, Peacock et al.
(1994) have briefly examined an inactive polytetrafluoroethylene plate. Considering the wax chemistry described in Section III.E, many researchers have conveniently examined photodegradation of a pesticide in simple organic solvents
as surrogates of waxes, but their significantly different fluidity and simple structures should be kept in mind together with easier photoaddition of a solvent
molecule. Schwack (1988, Schwack et al. 1994) used methyl oleate and 12hydroxystearate as more elaborate models of epicuticular wax. Photolysis of
2,4-D (1) has been reported to be enhanced on Zea mays leaves and thus a more
realistic model has been considered (Venkatesch and Harrison 1999). Photodegradation of carbamate and organophosphate pesticides was examined in thin
film of epicuticular waxes extracted from a variety of citrus fruits (Cabras et al.
1997b; Pirisi et al. 1998, 2001). Schuler et al. (1998) examined photodegradation of dibenzo-p-dioxins including (129) on glass coated with waxes of laurel
cherry leaves. The photolysis rate of fenarimol (239) was dependent on plant
species (Watkins 1987). Because plant cuticles can be isolated from intact leaves
by treatment with pectinase and cellulase, Schynowski and Schwack (1996) conducted photodegradation of parathion (135) on enzymatically isolated cuticles.
C. Photodegradation of Pesticides on Glass and Silica Gel Surfaces
Glass plates (Chukwudebe et al. 1989) and silica gel (Hirayama et al. 1998)
were utilized to examine the comparative photoreactivity of various pesticides.
Any significant relationship between the photolysis rate on glass at max = 300
37
nm and the extinction coefficient of each pesticide at 295305 nm could not be

identified, but the slower degradation was observed for the thicker layer of
pesticide on glass (Chen et al. 1984). Photolysis rates were greatly reduced at
the concentration of 3.3 g cm2, corresponding to the thin-layer thickness of
. Since Kitchener (1946) reported that most of light passing through a
100 A
, this reduction was likely to
crystal is absorbed along the pathlength of 100 A
originate from light attenuation. Furthermore, the different profiles of UV absorption in the solid state from those in solution (Gab et al. 1975b; Leermakers
et al. 1966) may account, at least in part, for this insignificant relationship. In
contrast, Calumpang et al. (1984) found a good correlation between maximum
molar absorptivity in solution and photolysis rate for eight organophosphate
insecticides on silica gel. On these solid surfaces, the photoinduced homolytic
cleavage of a bond to produce radicals is considered to be one of the most
important degradation pathways. Johnston et al. (1984) studied photodegradation of azobis(isobutyronitrile) on dry silica gel by using UV light and demonstrated that some portion of radicals could escape from their original partners
by a translational motion. Avnir et al. (1981) also examined the reaction profiles
of radicals by using benzyl phenylacetate and dibenzyl ketone. By comparing
the amount of dibenzyl formed in potassium dodecanoate micelles via recombination of radicals, they concluded that radical pairs separated more easily on
silica gel surface by a translational motion. Furthermore, this trend was more
emphasized for dibenzyl ketone generating radicals via the triplet state compared with benzyl phenylacetate via the singlet state. Therefore, if the pesticide
molecule deposited on silica gel surface undergoes photoinduced homolytic
cleavage of some bond, the recombination process may be less important. The
photodegradation profiles of pesticides on glass and silica gel are summarized
in Table 7 (see table on page 94) from a survey of the existing literature.
Organochlorines Photoinduced dechlorination of pentachlorophenol (121)
gave the -radical and successively the phenoxide (Piccinini et al. 1998). The
photolytic half-life was dependent on the solvent used to prepare a thin film on
glass, and a residual amount of water was found to increase the photolysis rate.
Aldrin (122) on glass underwent epoxidation to dieldrin (123) followed by further isomerization to photodieldrin (124) (Rosen and Sutherland 1967). In the
case of endosulfan (125), the ring opening to form the diol derivative via release
of SO was a major pathway but without S-oxidation (Dureja and Mukerjee
1982). The other cyclodienes, including chlordane (128), were found to form
the corresponding cage structure derivatives (Benson et al. 1971). More epoxidation and hydroxylation of (128) on silica gel implied involvement of reactive
oxygen species on the surface formed by irradiation (Gab et al. 1975a). DDT
(130) on glass primarily underwent photoinduced homolytic cleavage of the
CCl bond at the trichloromethyl group to form DDD (132) by exposure to UV
light at 254 nm (Mosier et al. 1969). The radical mechanism was also supported
by comparative photolysis of eight 3H-diethoxy analogues of (130) on glass
(Coats et al. 1979). Relative photostability decreased by substituting the CCl3
38
T. Katagi
moiety with other groups as follows: CCl3 (130) >> CHCl2 (132) > CHCl2CH3
>> CCl(CH3)2. This order was in agreement with the stability of radical species
formed via CCl cleavage.
Organophosphorus Esters Photoinduced oxidation of the P=S moiety was observed for parathion (135) and its methyl analogue (136) on glass (El-Refai and
Hopkins 1966; Calumpang et al. 1984), together with formation of S-isomers
(Chukwudebe et al. 1989). Fenitrothion (138) on silica gel underwent oxidation
at the aryl methyl group to COOH and/or P=S moiety to the oxon together with
an ester cleavage giving the corresponding phenol (Ohkawa et al. 1974b). ODemethylation was observed for the rapid photodegradation of cyanophos (137)
on silica gel in addition to oxon formation and cleavage of the PO aryl bond
(Mikami et al. 1976). The photoinduced S-oxidation of the methylthio group to
sulfoxide was the primary reaction on glass for fenthion (143) (Cabras et al.
1997b). Hirahara et al. (2001) examined comparative photodegradation of (143)
using UV-A (320400 nm), UV-B (280320 nm), and UV-C (250260 nm)
light. Because (143) has a UV absorption at the UV-BUV-C region, the ease
of photodegradation was UV-C > UV-B > UV-A. Photoinduced dehalogenation
was additionally observed for iodofenphos (141) on glass (Walia et al. 1989b).
Similar photodegradation profiles of chlorpyrifos (145) were more quantitatively
investigated (Walia et al. 1988; Racke 1993). Although the degradation products
were not identified, Meikle et al. (1983) utilized Whatman No. 1 filter paper as
a leaf model and examined rates of either photolysis or volatilization in the
presence of carruba wax. When the aryl moiety is transformed from simple
phenyl rings to heterocycles, similar phototransformation is basically observed.
Oxidation of the P=S moiety concomitant with the P-Oaryl ester cleavage proceeded on glass for quinalophos (148) (Dureja et al. 1988) and pyridafenthion
(150) (Tsao et al. 1989). Although dioxabenzofos (183) possesses a unique cyclic structure, the photoreactions on silica gel obeyed similar mechanisms (Mikami et al. 1977b). Phoxim (152) gave the same photoproducts on glass and
tomato leaf but their chemical identification was not extensively conducted
(Makary et al. 1981).
When 14C- or 32P-phenthoate (168) on glass was exposed to sunlight, about
90% was lost by volatilization after 40 hr, and 20%35% of the residual radioactivity was due to its oxon. The volatilization loss was greatly reduced on silica
gel, with the main product being the oxon (Mikami et al. 1977b). 14C-Sulprofos
(161) was oxidized to the sulfoxide and sulfone similarly as (143) (Ivie and Bull
1976). The basic photochemistry was almost the same for propaphos (159) either on glass or silica gel and was characterized by the significant formation of
the S-oxidized derivatives (Fujii et al. 1979). Direct photolysis is considered
most unlikely for dimethoate (165), malathion (167), phorate (162), and disulfoton (163) not having chromophores in the molecules. The hydrolysis products
with a trace amount of the oxon were detected only for sunlight photolysis of
32
P-(165) (Dauterman et al. 1960). Loss of (167) from the glass surface was
mainly due to thermal vaporization (Awad et al. 1967; El-Refai and Hopkins
39
1972). Phorate (162) was only photodecomposed to the oxon at 254 nm and
thus sunlight photolysis was considered unlikely (Sharma and Gupta 1994). Insignificant involvement of direct photolysis for (163) was clearly demonstrated
by degradation only at 250260 nm by Hirahara et al. (2001). UV irradiation
of phosalone (170) on glass resulted in dechlorination and cleavage of each
bond at the PSCH2N linkage but without any P=S oxidation (Walia et al.
1989a). Edifenphos (173) exhibited slow degradation under UV irradiation (Ishizuka et al. 1973).
Stereospecific oxidation of the P=S moiety to the oxon was reported for 3HS-2571 (176) on silica gel using UV light (Mikami et al. 1977a). Katagi (1993a)
proposed, in photolysis of butamifos (177), the N-sec-butyl analogue of (176),
the photoinduced intramolecular oxidation of the P=S moiety by the adjacent
nitro group attached to the o-position of the phenyl ring, which may account for
this stereospecificity. Dureja et al. (1989) reported photoinduced oxidation of
the P=S moiety and ester cleavage for isofenphos (175) on glass. 32P-Leptophos
(181) on silica gel was photodegraded with formation of oxon, O-demethylated
and debrominated derivatives, and O-methyl phenyl thiophosphonic acid that
were finally degraded to phenyl phosphonic acid (Zayed et al. 1978). Both oxidation of the P=S moiety and ester cleavage were the main pathways for (181)
on glass (Riskallah et al. 1979) and for cyanofenphos (180) on silica gel (Mikami et al. 1976) under sunlight. These results show the insignificant differences
in photochemistry among phosphorothioates, phosphoramidothioates, and phosphonothioates. Monocrotophos (156) (Dureja 1989; Lindquist and Bull 1967),
phosphamidon (158) (Bull et al. 1967), dichlorvos (153), and trichlorfon (179)
(Derek et al. 1979) do not have any chromophore to absorb sunlight and thus
direct photolysis was most unlikely.
Pyrethroids Chen and Casida (1969) studied photodegradation of the 14Clabels of pyrethrin I (9) and allethrin (10) on glass and identified three possible
oxidation pathways. One of these was the successive oxidation of the transmethyl group of the 2-methylprop-1-enyl moiety via CH2OH and CHO and
finally to the COOH derivative; the other two pathways were formation of transcaronic acid derivative, possibly via ozonide and oxidation at 1-position of the
2-methylprop-1-enyl moiety. Involvement of oxygen species was separately
demonstrated by the increased stability in the presence of an antioxidant such
as dibutylhydroxytoluene (Abe et al. 1972). Isobe et al. (1984) reported the
photoinduced opening of the cyclopropyl ring of (10) followed by either sigmatropic rearrangement to the acrylate or oxidadtive destruction to the mixtures of
glyoxylates. Ruzo et al. (1980) detected the di--methane rearrangement of the
2-(prop-2-enyl)cyclopent-2-enone moiety of S-bioallethrin (12) on glass to form
the cyclopropyl derivatives, but the cis/trans isomerization was minimal. 14CResmethrin (15) on silica gel, glass, or filter paper underwent either epoxidation
of the 2-methylprop-1-enyl moiety or ester cleavage similarly as (10) (Ueda et
al. 1974). These unique reactions were initiated by oxidation of the furan ring,
possibly to give a cyclic ozonide-type peroxide intermediate (Fig. 12). Reduc-
40
T. Katagi
Fig. 12. Photooxidative rearrangement of resmethrin (15).
tion of this intermediate to the diol followed by rearrangement resulted in formation of the cyclopentenolone derivative, especially on silica gel. Migration of
proton or hydrogen radical from the position symmetrical to the benzyl group
or that of the benzyl cation or radical gave the hydroxylactone and benzyloxylactone derivatives, respectively.
Samsonov and Makarov (1996) examined the photostability of (15) on glass
under sunlight and found that the oxidative degradation by O2 was insensitive
to thickness of thin film and likely to be controlled by a filter effect of thin
film. Tetramethrin (23) underwent successive photooxidation at the acid moiety
similar to (10) (Chen and Casida 1969). Ruzo et al. (1982) investigated the
photodegradation of phenothrin (13) and (23) on glass and demonstrated
involvement of oxygen species such as 3O2, 1O2, and O3. The ene reaction of 1O2
(see Fig. 2, reaction 7) was confirmed by formation of 2-methyl-1-hydroperoxyprop-2-ene-1-yl and 2-methyl-1-hydroxyprop-2-ene-1-yl derivatives. For (23),
hydroxylation at the 3-position of the 3,4,5,6-tetrahydrophthaloyl moiety occurred but to a lesser extent. Although the degradation products were not reported, the very rapid photodegradation of cyphenothrin (14) was observed on
silica gel possibly via photoreactions similar to (13) (Dureja et al. 1984). In
addition to the usual photoinduced isomerization in the acid moiety together
with epoxidation, kadethrin (16) underwent opening of the 2-oxo-3-thiacyclopentylidene ring on glass (Ohsawa and Casida 1979). Trace amounts of benzyloxylactone derivatives were detected similarly to (15) but without formation of
the hydroxycyclopentenolone.
Photoinduced cis/trans isomerization mainly proceeded for deltamethrin (22)
on glass under sunlight, and neither photooxidation nor debromination was detected (Ruzo et al. 1977). Maguire (1990) reported the isomerization of 1R-cisisomer to 1S-cis-, 1R-trans-, and 1S-trans forms by chiral HPLC analysis. The
41
other reactions were ester cleavage to form the corresponding acid, -cyano-3phenoxybenzyl alcohol, and 3-phenoxybenzaldehyde together with decarboxylation (see Fig. 2, reaction 4). The dimethylacrylate derivative was also detected
at a trace amount similar to (10). Cyhalothrin (21) exhibited the similar photoreactions to (22) on glass (Ruzo et al. 1987). Tralomethrin (25) and tralocythrin
(26) were mainly phototransformed to (22) and cypermethrin (19) with their
trans-isomers, respectively (Ruzo and Casida 1981). The 1-bromo derivatives
were also formed possibly via intramolecular abstraction of hydrogen at the 1position by bromine homolytically being photodissociated. Many pyrethroids
have the 3-phenoxybenzyl or -cyano-3-phenoxybenzyl moiety, and the introduction of the cyano group has been demonstrated not to significantly affect
photoreactivity either in solution or on glass (Ruzo and Casida 1982). Holmstead et al. (1978b) reported that the main photo-reaction of fenvalerate (27) on
glass is decarboxylation. Homolytic cleavage of either (C=O)OCH or
C(=O)OCH bond has been evidenced by detection of many relevant photoproducts. By exposure to sunlight, flucythrinate (29) was photodegraded on
glass via almost the same pathways as (27) (Chattopadhyaya and Dureja 1991).
Although the NH linkage was additionally introduced to the acid moiety, almost
the same photoreactions were reported for fluvalinate (30) (Quinstad and Staiger
1984). Sunlight exposure resulted in formation of formanilide, probably due to
reaction of haloanilide with photochemically produced formaldehyde, but no
decarboxylated derivative of (30) was detected on glass. Acrinathrin (31) on
glass was photodegraded to the corresponding acid and alcohol moieties via
ester cleavage (Samsonov and Pokrovskii 2001). The predominant photodegradation process of etofenprox (32) on glass was the photooxidation of the benzyl
moiety to benzoyl, whereas the unique product formed by loss of the CH2O
moiety in solution photochemistry was not detected (Fig. 13). The benzyl radical
Fig. 13. Photodegradation of etofenprox (32).
42
T. Katagi
would be possibly formed by hydrogen abstraction, which reacted with O2 to

the hydroperoxy derivative followed by its dehydration to the benzoyl derivative
(Class et al. 1989; Tsao and Eto 1990b).
Carbamates Substituted phenyl N-methylcarbamates are commonly photodegraded via successive oxidation of the N-methyl group on glass or silica gel
(see Fig. 2, reaction 6) (Abdel-Wahab et al. 1966). Aminocarb (66) or mexacarbate (67) were photodegraded on silica gel at 254 nm to more than 10 photoproducts including the N(CH3)CHO and NHCHO derivatives (Abdel-Wahab and
Casida 1967). Because the same products were detected in photolysis of (66)
on glass at >290 nm, the oxidation process was likely to occur in the environment (Pirisi et al. 2001). This oxidation was also reported for pirimicarb (78)
on glass and cellulose plates, and involvement of OH was assumed (Pirisi et
al. 1996, 1998). Methiocarb (68) underwent photoinduced oxidation of the methylthio group on wax-coated glass to form the corresponding sulfoxide and sulfone, while it was degraded to unknowns on glass (Pirisi et al. 2001). In the
case of benfuracarb (89) on glass, the photocleavage of carbamate linkage at
the NC(=O) bond gave carbofuran (72), which was further photodegraded
to the corresponding phenol (Dureja et al. 1990). At the same time, either
N(CH3)C or N(CH3)S bond was cleaved by irradiation to form N-(2-ethoxycarbonylethyl)-N-isopropylsulfenamine and its derivative (Fig. 14). Photodegradation of benthiocarb (86) gave mainly 4-chlorobenzoic acid via the corresponding alcohol and aldehyde with insignificant S-oxidation (Ishikawa et al. 1977).
Either N-deethylation or hydroxylation at the 2-position of the phenyl ring was
a minor pathway, the latter of which was characteristic of photolysis on glass.
These photoreactions were also observed on silica gel but with a slower photodegradation rate (Cheng and Hwang 1996). Photoinduced homolytic cleavage
Fig. 14. Photodegradation of benfuracarb (89).
43
of the carbonyl CS bond gave the benzyl thiol and its dimer (Ruzo and Casida
1985). The radicals produced via cleavage of the benzylic CS bond reacted
with O2 to form the series of alcohol-to-acid derivatives or gave benzyl N,Ndiethyl carbamate or benzylamine via release of either sulfur or O=C=S, followed by recombination with the 4-chlorobenzyl radical. N-Methylcarbonyl-Nethyl derivative was also detected as a major product on glass, and involvement
of OH was proposed. Cartap (91) was thought to undergo photocleavage of the
thiocarbamate SC(=O) bond to give the radical, followed by intramolecular
cyclization to nereistoxin on either glass or silica gel (Tsao and Eto 1989). The
photoinduced homolytic cleavage of the carbamate C(=O)O linkage was most
likely for phenmedipham (84) on silica gel by detection of N,N-ditolylurea from
the reactive isocyanate (Emmelin et al. 1998). Schafmeier et al. (1998) reported
that the photolysis of (84) on silica gel was highly dependent on coexisting
humic substances. In the case of fenothiocarb (85), photoinduced oxidation at
sulfur mainly proceeded on silica gel, followed by cleavage of the carbamate
linkage to the very reactive intermediate sulfenic acid that was readily decomposed to 4-phenoxybutylsulfonic acid (Unai and Tomizawa 1986). Thiophanate
methyl (92) was rapidly photodegraded on glass via conversion of the CS
group to ketone and via intramolecular cyclization to MBC (93) (Soeda et al.
1972). MBC (93) was found rather stable on silica gel, but its photodegradation
was accelerated by a sensitizer such as riboflavin (Fleeker and Lacy 1977).
Amides, Anilides, and Dicarboximides Alachlor (34) underwent photoinduced
cleavage of either the NCH2 or NC(=O) bond on glass finally to the corresponding aniline, together with dechlorination and intramolecular cyclization
to the indoline derivative (Fang 1977). Similar photodegradation profiles were
reported for butachlor (36) when irradiated at 254 nm, together with the photosubstitution of Cl with OH followed by intramolecular cyclization to N-2,6diethylphenyl-2,5-dihydrooxazol-4-one (Chen and Chen 1978). These herbicides
possess insignificant absorption at >290 nm and thus the direct photolysis was
considered unlikely in the environment. Either NC(=O) or N-aryl bond of
mepronil (38) was slowly cleaved on silica gel by sunlight to form benzamide
and benzoic acid, followed by stepwise oxidation of the o-methyl group together
with p-hydroxylation at the aniline moiety, but only as a trace amount (Yumita
and Yamamoto 1982). Although photodegradation was found insignificant at 254
nm, flutolanil (39) underwent O-deisopropylation and photo-Fries rearrangement
(see Fig. 2, reaction 9b) to give 2-aminobenzophenone derivative on either silica
gel or glass (Tsao and Eto 1991). The photo-Fries rearrangement of amides at
254 nm has been reported on dry silica gel by Abdal-Malik and de Mayo (1984),
and radical pairs formed were considered not to separate on the surface. The
photolysis mechanism on silica gel was investigated for analogues of (38) having different o-substituents (Yumita et al. 1984). They proposed involvement of
two pathways: one is the NC(=O) bond cleavage with the formed aniline
being polymerized and the other is the hydroxylation at p-position of the aniline
moiety followed by cleavage of the N-aryl bond. Carboxin (42) exhibited rapid
44
T. Katagi
photodegradation on glass, probably via oxidation at the oxathiine sulfur to sulfoxide and sulfone (Buchenauer 1975). Niclosamide (40) underwent extensive
photodegradation either on glass or silica gel to chlorosalicylic acid via cleavage
of the NC(=O) bond (Schultz and Harman 1978). In contrast, naproanilide
(41) exhibited homolytic cleavage of the CHO bond or photooxidation at the
methine carbon to form 2-hydroxypropananilide at >254 nm on glass (Tsao and
Eto 1990a). Unique photoreactions were observed for isoxaben (46) on silica
gel (Mamouni et al. 1992). The N-O bond in the isoxazole ring was first photocleaved and recyclized to the three-membered azirine derivative whose ring was
again opened at the C-C bond to form the oxazole derivative (Fig. 15). It was
considered that these compounds converted to each other under irradiation, and
the azirine and oxazole derivatives were photodegraded to 2,6-dimethoxybenzamide followed by reduction to the corresponding benzonitrile. Concerning
imide pesticides, Sumida et al. (1973) examined the photolysis of experimental
fungicide DDOD (113) on glass but without detailed information on degradates.
Ureas Diflubenzuron (59) was photodegraded on glass or silica gel to 4-chlorophenyl isocyanate and 2,6-dichlorobenzamide, indicating involvement of photoinduced cleavage of the central C-N bond via NH hydrogen abstraction by the
excited-state carbonyl oxygen in the six-membered ring transition state (Ruzo
et al. 1974). Almost half of 14C-(59) was lost from silica gel during 28 d with
trace formation of unknowns (Bull and Ivie 1976). Diafenthiuron (57) was rapidly photodegraded on Teflon sheets to give the corresponding urea through
carbodiimide by reaction with 1O2 (Drabek et al. 1992). Chlorsulfuron (96) on
Fig. 15. Photoinduced rearrangement of isoxaben (46).
45
silica gel exhibited slow photodegradation to give the corresponding aminotriazine and benzenesulfonamide derivatives via cleavage of the sulfonylurea
bridge (Herrmann et al. 1985). UV spectrum of (96) in methanol did not show
any absorbance at >290 nm and no bathochromic shift was observed by adsorption onto silica gel, implying involvement of indirect photolysis such as the
reaction with OH. Very insignificant photodegradation on glass was reported
for the few sulfonylurea herbicides, and the presence of surfactants in formulation may play a great role in its indirect photolysis in the real environment
(Thomas and Harrison 1990; Harrison and Thomas 1990). Photoinduced cleavage of either bond at the NHC(=O)N(CH3)-triazine moiety or contraction
of the sulfonylurea bridge was reported for tribenuron-methyl (99) on glass
(Bhattacharjee and Dureja 2002).
Azoles and Triazines Rapid photodegradation of triadimefon (188) was observed on glass, and the cleavage either of O-CH or CHC(=O) bond gave the
corresponding 1N-substituted 1,2,4-traizole derivatives (Nag and Dureja 1996).
Especially under UV light, 1-(4-chlorophenoxy)-1-(1H-1,2,4-triazol-1-yl)-2,2dimethylpropane was identified as a main photoproduct, suggesting that a concerted process involving simultaneous combination with loss of CO might proceed rather than simple coupling of the discrete free radicals after loss of the
CO moiety. Triadimenol (189) underwent dechlorination and cleavage of either
CH-Oaryl or C-N bond when irradiated on glass (Clark and Watkins 1986).
Diniconazole-M (190) showed photoinduced E/Z isomerization followed by intramolecular cyclization between 5-positions of the 2,4-dichlorophenyl and
1,2,4-triazolyl rings (Sharma and Chibber 1997). The secondary alcohol moiety
of this cyclized product was oxidized to the corresponding ketone, and successive opening of the hetero ring gave the isoquinoline derivative (Fig. 16). Photoinduced cleavage of the C-triazole bond eliminating 1,2,4-triazole was observed
for propiconazole (191) on glass (Dureja et al. 1987a). Fluotrimazole (195) ex-
Fig. 16. Photoinduced isomerization of diniconazole-M (190) followed by cyclization.
46
T. Katagi
hibited the similar homolytic cleavage of the C-triazole bond on glass followed
by reaction with water to give the corresponding triphenylmethanol (Clark et al.
1983). The photolytic stability of triazine herbicides on glass was briefly studied
in comparison with their solution photolysis (Chen et al. 1984).
Miscellaneous Direct photolysis was found to be of minor importance for 2,4D (1) in accordance with its insignificant UV absorption at >300 nm (Venkatesh
and Harrison 1999). In contrast, the dimethylamino derivative of MCPA (3) was
photochemically produced from the countercation N,N-dimethylamine (Crosby
and Bowers 1985). In the presence of trace water, (3) was considered to be
photodegraded via dechlorination, decarboxylation, and oxidation to many small
molecules. Significant photodegradation of trifluralin (232) by exposure to sunlight was demonstrated by reduced herbicidal activity, but no information on
the degradation pathway was given (Wright and Warren 1965). 14C-Fluchloralin
(236) on silica gel and glass was photodegraded via either release of the chloroethyl group or intramolecular cyclization between the nitro group and 1-position
of the N-propyl moiety to give benzimidazole derivatives together with the unusual formation of the quinoxaline derivative (Nilles and Zabik 1974). This
type of reductive cyclization seems common to dinitroaniline herbicides, as also
demonstrated by photodegradation of pendimethalin (238) on glass (Dureja and
Walia 1989). Rapid photodegradation of isoprothiolane (204) on silica gel involved a dithiolane ring cleavage, ester hydrolysis, decarboxylation, heterocycles formation such as dithietane and trithiolane and sulfur liberation, and finally
the accumulation of S8 was observed (Chou et al. 1980). 14C-Methoprene (246)
quickly dissipated on glass by photolysis and volatilization (Quinstad et al.
1975). The main photoreaction was E/Z isomerization at 2-ene position to give
50 : 50 mixture of (2E,4E) and (2Z,4E) isomers. 7-Methoxycitronellal was identified as one of the main volatiles and considered to be formed via oxidation at
5-position. Sethoxydim (223) was found very unstable, and N-deethoxylated
was the only derivative identified (Campbell and Penner 1985a). Soeda et al.
(1979) investigated the photodegradation of 14C-alloxydim (224) on silica gel
and found that the main pathway was N-deallyloxylation similar to (223), and
(224) also underwent Beckmann rearrangement to give two types of oxo-tetrahydrobenzoxazole derivatives but in lesser amounts.
Bentazone (200) possessing fairly strong absorption at around 300 nm undergoes direct photolysis (Nilles and Zabik 1975). 14C-(200) was lost from a silica
gel surface mainly due to volatilization, whereas photoinduced oxidation of the
NH moiety proceeded on glass followed by elimination of SO2 to give N-isopropyl-o-nitrosobenzoylamine and the successive oxidation to the nitro derivative.
For buprofezin (222) on glass, the few types of ring opening were caused by
sunlight, resulting in formation of ureas and thioureas (Datta and Walia 1997).
Thiabendazole (212) showed very slow sunlight photodegradation on glass via
opening of the thiazole ring to benzimidazole-2-carboxamide and benzimidazole
(Jacob et al. 1975). Photooxidative breakdown of one phenyl ring was observed
for diquat (226) on silica gel, leading to formation of 1,2,3,4-tetrahydro-1-oxo-
47
pyrido[1,2-a]-5-pyradinium salt and picolinamide (Smith and Grove 1969). The

photodegradation of fipronil (220) on silica gel, glass, and paper gave the desulfinyl derivative with trace amounts of sulfone and sulfide derivatives, possibly
via photoinduced oxidation and reduction (Hainzl and Casida 1996). The desulfinylation was assumed to occur from the hydrogen-bonded six-membered intermediate formed between NH2 and SOCF3 groups (Fig. 17). Perfluidone (206),
having sufficient UV absorption at 330 nm, underwent direct photolysis probably via photochemical breakdown of the CF3SO2NH moiety (Ketchersid and
Merkle 1975). The hydrolytic degradation of 14C-chlordimeform (207) to Nformyl-4-chloro-o-toluidine was accelerated by sunlight exposure on silica gel
(Knowles and Sen Gupta 1969). 14C-Guazatine (245) gave a very odd photoproduct on glass having a carbonyl moiety with a molecular weight greater by
28 than (245) (Sato et al. 1985b). The degradate was considered to be formed
by photooxidation of the methylene group at 4-position to the central NH moiety, followed by methylation at the adjacent methylene carbon. Stepwise dephenylation was observed for fentin acetate (241) on silica gel when exposed to
UV light, finally to an inorganic tin (Barnes et al. 1973). Photooxidation to the
benzoyl derivative was the predominant photodegradation pathway of cinmethylin (249) (Grayson et al. 1987). Imazaquin (230) and imazethapyr (231) photodecomposed on glass and silica gel, probably via decarboxylation or ring decomposition through stepwise oxidation (Basham and Lavy 1987; Goetz et al.
1990; Schroeder 1997).
Azadirachtin-A (253) underwent rapid photoisomerization at the (E)-2-methylbut-2-enoate moiety to the Z-isomer on glass (Dureja and Johnson 2000). At
least 10 primary degradates were formed from avermectin B1a (250) on glass
through sunlight irradiation, but direct photolysis was unlikely due to lack of
UV absorption at >290 nm (Crouch et al. 1991). The main pathway was insertion of oxygen at the 14- or 15-position of the macrocycle with accompanying
double-bond shift, probably via formation of an allylic hydroperoxide from 1O2
by the ene-type reaction. Oxidation at the 8-position, possibly by reaction with
O2 to form the intermediate hydroperoxide, was also observed. For avermectin
B1a analogue MAB1a (251), photolysis on glass was slightly accelerated compared to (250), but no oxidation at the most photosensitive 14- and 15-positions
was observed (Feely et al. 1992). Alternatively, photoinduced isomerization at
8- and 9-positions, oxidative N-dealkylation, and cleavage of the ether linkage
in the sugar region were observed.
D. Photodegradation of Pesticides in Organic Solvents
and Plant Model Systems
Photodegradation profiles of pesticides in organic solvents and thin films of
fatty acids as plant surface models are summarized in Table 8 (see table on page
101). Examples of photodegradation in more complex media such as thin films
prepared from the extracted epicuticular waxes or enzymatically isolated cuticles
are listed in Table 9 (see table on page 104).
Fig. 17. Various photodegradation pathways of fipronil (220).
48
T. Katagi
49
Organochlorines Photolysis of DDT (130) and methoxychlor (134) was conducted in methyl oleate as a representative of octadecanoic acids in plant cuticles (Schwack 1988). The radicals produced via homolytic dechlorination reacted at the C=C double bond of methyl oleate as well as a chlorine radical to
form stearic acid derivatives and also abstracted hydrogen from methyl oleate
to form the corresponding dichloromethyl derivatives. Dechlorination also occurs at the aryl moiety of anilazine (211) in cyclohexene with irradiation, and
the radicals produced reacted with either solvent molecules or methyl oleate
(Breithaupt and Schwack 2000). Jahn et al. (1999) confirmed the bound formation of chlorothalonil (117) on the enzymatically isolated tomato cuticles under
irradiation by using enzyme-linked immunosorbent assay. Dioxin, 2,3,7,8-TCDD
(129), underwent either dechlorination at 8-position by exposure to UV light or
rearrangement to biphenyl derivative in isooctane (Kieatiwong et al. 1990).
Schuler et al. (1998) reported the photoinduced dechlorination of (129) in a thin
wax film of laurel cherry leaves. Photoinduced homolytic dechlorination followed by reaction with unsaturated C=C bonds was most likely to occur on
plant cuticles. Endosulfan (125) exhibited photoinduced isomerization in hexane
from the -isomer to the -isomer but with loss of two chlorine atoms at the
bridged carbon (Dureja and Mukerjee 1982). Heptachlor (127) gave 1-exohydroxychlordene via substitution of Cl with a hydroxyl group, which underwent either (2 + 2) cycloaddition to the full-cage isomer or intramolecular
ene-reaction, finally forming the cyclic ketone (Parlar et al. 1978).
Organophosphorus Esters Photochemistry of this chemical class has been extensively reviewed by Floer-Muller and Schwack (2001). Schwack (1987) and
Schwack et al. (1994) examined the effect of a reaction medium on photodegradation profiles of parathion (135). UV irradiation of (135) in cyclohexene
caused reduction of the nitro group followed by addition of cyclohexene to the
nitroso group via ene-type reaction. Detection of azo and azoxy dimers of (135)
indicated involvement of stepwise photoreduction of the nitro group to amino
via nitroso and hydroxyamino groups (Fig. 18). The main product in 2-propanol
was the azoxy dimer, part of which rearranged to the 2-hydroxyazo derivative
with no detection of the azo dimer. The amounts of these dimers greatly decreased in cyclohexane containing methyl 12-hydroxystearate (ester of a cutin
acid) with predominant formation of the oxon. These findings imply that the
reaction medium is one of the most important factors controlling the photoprocess of (135), and the proton-donating ability of the solvent molecule may play
a large role. These processes were confirmed by Schynowski and Schwack
(1996) on the enzymatically isolated fruit cuticle of tomato, paprika, apple, and
grape. In the early stage of photolysis, the unstable nitroso derivative of (135)
was dominant, but the 2-hydroxyazo derivative finally gradually accumulated.
The oxon derivative and 4-nitrophenol were minor products. Dissipation rates
of (135) increased with iodine number of the fruit cuticle, showing that the
olefinic portion of cuticles plays an important role in the reaction. In contrast,
oxidation to give sulfoxide and sulfone proceeded for fenthion (143) (Leuch and
Fig. 18. Successive photoreduction of parathion (135) followed by dimerization.
50
T. Katagi
51
Bowman 1968; Minelli et al. 1996). In the thin film of fruit wax from orange,
nectarine, and olive, (143) gave the sulfoxide under sunlight with a trace amount
of the sulfone (Cabras et al. 1997b; Pirisi et al. 2001). With an increase of wax
thickness, dissipation rates slightly increased for orange and nectarine, whereas
the thickest olive wax gave the slowest degradation. These results suggest that
the component rather than the amount of wax film is one of the important factors
controlling the photodegradation. Fenitrothion (138) mainly underwent photooxidation at the aryl methyl group and the P=S moiety in methanol, hexane, and
acetone (Ohkawa et al. 1974b; Greenhalgh and Marshall 1976). Thiono-thiolo
rearrangement (see Fig. 2, reaction 9a) and denitration were minor pathways.
The difference in reaction profiles between (135) and (138) most likely originates from the adjacent orientation of nitro and methyl groups in (138) that are
known to take an aci-nitro structure via photoexcitation (Katagi 1989). The
homolytic cleavage of a C-I or C-Cl bond together with formation of the oxon
and cleavage of a P-Oaryl or P-S bond was reported for iodofenphos (141)
(Walia et al. 1989b), chlorpyrifos (145) (Walia et al. 1988), and phosalone (170)
(Walia et al. 1989a). The cis/trans isomerization could be detected for tetrachlovinphos (154) in hexane by exposure to UV light (Dureja et al. 1987b). Isofenphos (175) having a different coordination at phosphorus similarly underwent
P=S oxidation to the oxon by UV irradiation in hexane (Dureja et al. 1989).
Pyrethroids Regarding the photolabile chrysanthemic acid moiety, Ruzo and
Casida (1980) examined the excited states involved by using methyl esters of
dichloro- and dibromo-vinyl derivatives. The main reactions in methanol were
cis/trans isomerization via homolytic cleavage of C1C3 bond of the cyclopropane ring to give a biradical followed by recombination together with the reductive dehalogenation in the vinyl moiety. The isomerization is considered to arise
from carbonyl excitation to the excited triplet state, as explained by molecular
orbital calculations (Katagi et al. 1988). By energy transfer experiments using
various sensitizers, the triplet state energy for these chrysanthemates was estimated to be 60 kcal mol1. Insignificant reduction of debromination in the
presence of triplet quenchers (ET = 5053 kcal mol1) showed no involvement
of the triplet state in this process. They also examined the effect of the alcohol
moiety on photochemistry in benzene at 300 nm under sunlight by using several
pyrethroids possessing a 3-phenoxybenzyl, 3-phenylbenzyl, or 3-benzoylbenzyl
group. Intramolecular energy transfer causing enhanced cis/trans isomerization
was likely to be involved (Ruzo and Casida 1982). Photoinduced cis/trans isomerization via triplet excited state was observed for permethrin (17) in organic
solvents, finally giving the cis/trans ratio of 30/70 (Holmstead et al. 1978a).
This type of pyrethroid usually exhibits weak UV absorption around 275 nm,
essentially in n-* character, resulting from the combined transition of the carbonyl system and the lower energy band of the aromatic rings. The ester cleavage
was also the major process forming 3-phenoxybenzyl alcohol and the dichlorovinyl chrysanthemic acid. In addition to the efficient cis/trans isomerization,
cypermethrin (19) in alcohols or aqueous acetonitrile underwent photoinduced
52
T. Katagi
decarboxylation (Ruzo 1983). The cis-isomer in an argon atmosphere simply

gave the corresponding acid and benzyl cyanide while the presence of O2 significantly gave the ketolactone derivative (50%60%; in the case of the transisomer, the caronic acid instead (Fig. 19). Because Rose Bengal in methanol
could not sensitize this oxidative reaction, O3 was likely to participate instead
of 1O2. The profiles of isomerization of deltamethrin (22) was examined in hexane by Maguire (1990), and detailed analysis of the photoproducts in organic
solvents was reported by Ruzo et al. (1977). The higher photoreactivity in methanol than (17) and (19) was considered to stem from more efficient intersystem
crossing by the heavy atom effect of bromine. Photoinduced homolytic cleavage
of the ester linkage was found to occur at either the C(=O)O or OC(CN)
bond. Epimerization at the benzyl carbon occurred in alcohols as a dark reaction
via proton exchange with a solvent molecule. Tralomethrin (25) and tralocythrin
(26) in organic solvents showed similar photodegradation profiles to those on
glass (Ruzo and Casida 1981). Z-cis-Cyhalothrin (21) underwent both E/Z and
cis/trans isomerizations in hexane (Ruzo et al. 1987). The decarboxylated derivative and the corresponding acid and alcohol moieties were the primary products
detected in addition to hexadienes derived from opening of the cyclopropyl ring.
In the case of allethrin (10), di--methane rearrangement via triplet state in the
alcohol moiety (Bullivant and Pattenden 1973, 1976) and epoxidation and oxidation in the acid moiety (Ruzo et al. 1980) proceeded more favorably than
the usual ester cleavage.
Photochemistry of fenvalerate (27) is characterized by a higher efficiency of
decarboxylation (Holmstead et al. 1978b). Mikami et al. (1985a) applied the
spin-trap method in ESR and demonstrated involvement of the two radical species originating from acid and alcohol moieties of (27). For photodegradation
in hexane, no energy transfer from isobutyrophenone and quenching by 1,3cyclohexadiene showed involvement of the long-lived excited singlet state. Almost identical photodegradation profiles have been reported for flucythrinate
(29) in methanol or hexane with maximum degradation at 271 nm, indicating
the involvement of n-* excitation (Chattopadhyaya and Dureja 1991). Etofenprox (32) underwent either photooxidation at the benzyl carbon or photoinduced
homolytic cleavage of the central ether linkage followed by radical recombination to give the derivative with loss of CH2O from (32) (Class et al. 1989; Tsao
and Eto 1990b).
Carbamates The main photodegradation products of xylylcarb (63) and trimethacarb (64) were phenols via cleavage of the OC(=O) bond in ethanol
and cyclohexane (Addison et al. 1974; Kumar et al. 1974). In the case of (63),
the photo-Fries reaction proceeded only in ethanol under irradiation at >265 nm
together with a trace cleavage at the C(aryl)-O bond leading to formation of
xylene. For propoxur (65), photoinduced cleavage of the C(aryl)-O bond occurred in 2-propanol, cyclohexane, and cyclohexene without photo-Fries rearrangement. Contribution from the OC(=O) bond cleavage was less than 1%.
The main product of ethiofencarb (69) in cyclohexane and 2-propanol was the
Fig. 19. Photodegradation of cypermethrin (19).
53
54
T. Katagi
corresponding sulfoxide with a trace amount of the sulfone (in 2-propanol) (Kopf
and Schwack 1995). A unique reaction, but as a minor pathway, was oxidation
of the benzyl carbon followed by nucleophilic substitution of the thionyl moiety
by the carbamate nitrogen to form 3,4-dihydro-3-methyl-1,3-benzoxazine-2,4dione. Although the simple photoinduced cleavage of the OC(=O) bond was
observed for aminocarb (66) in organic solvents (Addison et al. 1974; Kumar
et al. 1974), oxidative N-demthylation via the N-CHO intermediate proceeded
on glass. However, this oxidation product disappeared in the presence of wax
from nectarine fruits, showing that some wax components may act as scavengers
of radicals (Pirisi et al. 2001). Similar photoreactions were detected for pirimicarb (78) at >280 nm (Schwack and Kopf 1993). In cyclohexane, the intermediate N-CHO derivative of (78) underwent either decarbonylation to the N-demethylated derivative or oxidation of the aryl methyl group at the 6-position.
Stepwise oxidation at the two aryl methyl groups at 5- and 6-positions gave the
unique 5,7-dihydro-5-oxo-furo[3,4-d]pyrimidinyl ring in cyclohexane. Nectarine
(N) and orange (Or) waxes were found to retard the photodegradation of (78)
while the mandarin orange (M) wax accelerated the reaction (Pirisi et al. 1998).
The rate of photolysis could not be correlated with UV absorbance of waxes or
to their amounts, and thus it was considered dependent on the nature of wax.
Because OH would be the promotor of formylation and N-demethylation,
waxes from N and Or should play the role of radical scavengers. In contrast,
the component of M wax was considered to act as a sensitizer. Similar to fenthion (143), the S-methyl sulfur was stepwise oxidized to the corresponding
sulfoxide and sulfone in the thin wax film from nectarine (Pirisi et al. 2001).
These results indicate that wax chemistry is very important in understanding the
photolytic behavior of pesticides after foliar application.
Dicarboximides Direct photolysis is likely to proceed for this class of fungicides having a weak shoulder of UV absorption at >290 nm due to n-* transitions. The most probable reaction is hydrogen abstraction intramolecularly (Norrish type II) or from a solvent molecule by the excited carbonyl oxygen. The
former case is known for N-phthaloylvaline methyl ester (Griesbeck and Gorner
1999) but not for dicarboximide fungicides. The latter reaction has been reported
for photolysis of folpet (107) in cyclohexene (Schwack 1990). The main reaction was the allylic addition of cyclohexene to one of the carbonyl groups to
form the corresponding carbinol with an oxetane formation via the Paterno
Buchi reaction as a minor pathway. As a unique photoreaction, the (4 + 2)1,4-cycloadition at the phenyl moiety to form the benzazepindione derivative
was detected. These reactions with the olefinic carbons indicate photoreactivity
in plant cuticles when (107) is foliarly applied. However, captan (106) exhibited
a different photoreactivity, that is, homolytic cleavage of a C-Cl bond followed
by release of the SCHCl2 group to tetrahydrophthalimide (Schwack and FloerMuller 1990). Procymidone (108), iprodione (109), and vinclozolin (110) commonly underwent photoinduced cleavage of a C-Cl bond. Successive dechlorination of (109) proceeded in 2-propanol (Schwack et al. 1995a). The addition of
55
a solvent molecule was predominant in cyclohexene whereas mono-dechlorination was the major change in cyclohexane. Procymidone (108) exhibited almost
the same photolytic profiles as (109) (Schwack et al. 1995b). In (110), solvent
addition mainly occurred at the vinyl side chain and successive dechlorination
was observed (Schwack et al. 1995c). This evidence from photodegradation in
organic solvents suggests the possible photoaddition of this class of fungicides
to wax components of plant cuticles.
Azoles Da Silva et al. (2001) revealed through flash photolysis of triadimefon
(188) in cyclohexane, together with analysis of emission spectra, that the first
excited state is n-* localized at the carbonyl group via fast conversion from * state at the 4-chlorophenoxy moiety and detected a 4-chlorophenoxy radical
at 25 nsec after a laser pulse. Product analysis showed involvement of three
main photoreactions (Nag and Dureja 1997). First was cleavage of the PhO-C
bond to give 4-chlorophenol and the corresponding triazole derivative. Either
cleavage of CHC(=O) or C-triazole bond was also observed. The third was
photoreduction of the carbonyl group to form triadimenol (189). Similar profiles
through photolysis in methanol were reported by Clark et al. (1978). Triadimenol (189) having a -* character in the first excited state also underwent
dechlorination and cleavage of CH-C(OH) or C-triazole bond (Clark and Watkins 1986). Although not detected in solution photolysis of (188), the diazirin
derivative via release of the N-CH moiety from 1,2,4-triazolyl ring was formed
from propiconazole (191) in hexane by UV irradiation (Dureja et al. 1987a).
Hexaconazole (192), fluotrimazole (195), and penconazole (193), not having the
carbonyl group are considered to undergo photolysis via -* transition at the
aromatic moieties. Photoliability of (192) was demonstrated in hexane and acetonitrile but without detailed information on degradation (Santoro et al. 2000).
Photoinduced cleavage of the C-triazole bond followed by addition of methanol
molecule was reported for (195) (Clark et al. 1983). Penconazole (193) underwent photocyclization in 2-propanol or cyclohexane between o-position of the
4-chlorophenyl ring and 5-position of the 1,2,4-triazolyl ring to form the 5H,6H(1,2,4-triazole)-[5,1a]-isoquinoline derivative (Schwack and Hartmann 1994).
Similar photocyclization of diniconazole-M (190) was reported by Sharma and
Chibber (1997). Katagi (2002a) examined this photoprocess for the racemic
mixtures of (190) by NMR and molecular orbital calculations and demonstrated
that the reaction proceeds via excited singlet state in a similar manner as reported for cis-stilbene.
Ureas In addition to the usual photoinduced cleavage of an NC(=O) bond
via carbonyl excitation to form the corresponding aniline, oxidative N-demethylation successively proceeded for isoproturon (56) in organic solvents with release of formaldehyde (Kulshrestha and Mukerjee 1986). UV irradiation of
diflubenzuron (59) in methanol caused the cleavage of the central C(=O)
NHC(=O) bond, mainly leading to formation of N-phenyl methylcarbamate and
2,6-difluorobenzamide (Ruzo et al. 1974). Chlorsulfuron (96) and metsulfuron-
56
T. Katagi
methyl (98), which have insignificant UV absorption at >290 nm, are considered
unlikely to undergo direct photolysis in the environment (Yang et al. 1999). In
contrast, chlorimuron-ethyl (102), with UV absorption at 275 nm, was rapidly
photodegraded in methanol and hexane via cleavage of either the N-C ureic or
S-N bond (Choudhury and Dureja 1997b). Contraction of the sulfonylurea bridge
was considered to follow a concerted elimination of SO2 with formation of intermediate radicals being recombined (Fig. 20). In contrast, photolysis in benzene
did not produce this derivative (Choudhury and Dureja 1997c), showing the importance of solvent polarity. Bhattacharjee and Dureja (1999) reported UV photolysis of tribenuron-methyl (99) in organic solvents proceeding via bond cleavage
around the sulfonylurea bridge including its contraction, similar to (102).
Miscellaneous Sunlight photodegradation of pendimethalin (238) was studied
in several organic solvents (Halder et al. 1989). Dureja and Walia (1989) investigated its sunlight photolysis in methanol and found 2,6-dinitro- and 2-amino6-nitro-3,4-xylidene as principal products via N-dealkylation and photoreduction, but no benzimidazole derivatives formed in aqueous photolysis could be
detected. The effect of unsaturated fatty acids and surfactants coexisting in formulation on photolysis of chinomethionat (228) was studied on glass (Nutahara
and Murai 1984). Oleic acid is one of the major fatty acids in leaf extracts of
eggplant and cucumber and accelerated photolysis of (228) as with its selfdecomposition. Similar photoacceleration was observed by addition of the various unsaturated fatty acids or polyoxylene sorbitan oleates (Tween 60, 80, 85).
Because oleic acid by itself was stable under irradiation, some photoreaction
between (228) and the C=C bond of oleic acid similar to the responses of (130),
(134), and (211) might account for these results. Draper and Casida (1985)
reported the ene-reaction of the nitroso derivative photochemically formed in
thin films from nitrofen (216) and CNP (217). The nitroso derivatives reacted
with the C=C bond of various chemicals including methyl oleate to form the
corresponding nitroxides via alkenylarylhydroxyamines being detected by ESR.
The weak ESR signal was observed for beet leaves when treated with (216) in
an extremely high level, showing the ambiguity of this reaction occurring in the
environment. The ESR signal was detected for irradiated methyl oleate film
containing (135) but not for (138), which coincides with dominant formation of
nitroso and its related derivatives from (135) but major detection of the oxidized
derivatives of (138) instead. As a model cuticle instead of organic solvents or
thin film on glass, Caboni et al. (2002) utilized cellulose membrane coated with
epicuticular waxes from olives to evaluate the extent of evaporation, codistillation, and thermodegradation of azadirachtin. In the absence of waxes, codistillation with water proceeded but dissipation of azadirachtin from wax-treated cellulose was not detected.
VIII. Photodegradation of Pesticides on Soil and Clay Surfaces

The photodegradation profiles of pesticides in/on soil and clay, based on the results of the literature survey, are summarized in Table 10 (see table on page 105).
Fig. 20. Photoinduced rearrangement (bridge contraction) of chlorimuron-ethyl (102).
57
58
T. Katagi
Organochlorines Dichlobenil (116) and chlorothalonil (117) were reported to

undergo photoinduced substitution of Cl with OH or hydration of cyano groups
in aqueous phase although they were rather resistant to photolysis in or on
soils (EPA OPPTS 1998c, 1999c). In contrast, some photodegradation has been
observed for dicamba (118) and chloramben (119). Misra et al. (1997) examined
photodegradation of 14C-(119) by varying conditions of loam soil and found that
3,5-dihydroxy- and 3-chloro-6-hydroxy-benzoic acids are detected in the intact
soil at 75% field moisture while only the deaminated derivative is formed on
air-dried soil. Moisture content might affect the extent of reactive species
formed such as OH, resulting in different product profiles. When (118) coated
on synthetic clay laponite was irradiated with UV light, decarboxylation proceeded in addition to dechlorination and hydroxylation (Aguer et al. 2000). The
photoinduced charge transfer from (118) to clay via interaction of the carbonyl
group with the clay surface was proposed as the reaction mechanism, and residual water molecules on clay were considered to play a role in inducing dechlorination and hydroxylation by polarizing either the O-CH3 or C-Cl bond. Pentachlorophenol (121) rapidly dissipated on soil thin layer by UV irradiation to
form octachlorodibenzo-p-dioxin (Liu et al. 2002). Because detailed examination of photoproducts from (121) as solution or solid has revealed that the photoinduced dechlorination primarily results in formation of free radicals whose successive reactions give dioxins (Piccinini et al. 1998), a similar radical processe
would also operate on irradiated soil surfaces. This mechanism may be accounted for with less formation of dioxins by addition of fulvic acids to soils
that can act as a scavenger of radicals. When 2,3,7,8-TCDD (129) applied to
soils was exposed to sunlight, the degradation, possibly via dechlorination, appeared only in the first 5 days but the coexistence of 1%5% hexadecane maintained constant photodegradation up to 15 d (Kieatiwong et al. 1990). These
results coincided with possible photodegradation near the soil surface and implied that hexadecane might act as a hydrocarbon film allowing solubilization
and migration of (129) from the deeper region of soil to the irradiated surface.
Detection of a trace amount of photodieldrin (124) by soil application of 14Caldrin (122) showed a possible contribution of photodegradation on the soil
surface (Klein et al. 1973). Involvement of photolysis in field dissipation of
organochlorine pesticides including (122) and (123) was demonstrated by monitoring studies in 99 fields (Suzuki and Yamato 1974). DDT (130) in/on soil was
photodegraded under sunlight to DDE (131) via dechlorination (Zayed et al.
1994). Less photoreactivity of dicofol (133) was briefly reported on soil (EPA
OPPTS 1998d).
Organophosphorus Esters Hautala (1978) reported that the apparent quantum
yield of parathion (135) was reduced on soils compared to a solution phase and
that no factors except the amount of soil appeared to correlate with the photolysis rate, indicating the importance of the screening effect by soil. As a main
product of parathion methyl (136), 4-nitrophenol was reported in an outdoor
sunlight photodegradation study (EPA OPPTS 1999e). UV irradiation alone was
59
ineffective for conversion of (135) to the oxon on soil dusts and clays, but the
existence of O3 at 50300 ppb increased its rate by a factor of 23 (Spencer et
al. 1980). Greater formation of the oxon on soil dusts having less organic matter
clearly demonstrated that the catalytic activity of clay played a large role in
photooxidation. These reaction profiles have been recently confirmed on soil
for 14C-(136) by Kromer et al. (1999). Cyanophos (137) and fenitrothion (138)
were photodegraded on soil thin layers mainly to 4-cyano- or 3-methyl-4-nitrophenol via cleavage of the P-O aryl bond, respectively (Mikami et al. 1976,
1985b). Either the corresponding oxon or O-demethylated derivative was a minor photoproduct from (137) and only the former product was identified for
(138). Fenthion (143) was photodegraded on soil thin layers to 40%80% after
4 days, and insignificant degradation was observed on glass (Gohre and Miller
1986). No information on degradates was available, but product analysis on
disulfoton (163) and methiocarb (68) suggested formation of the corresponding
sulfoxide, most likely via reaction with 1O2 produced on soil surfaces by irradiation. The fastest photodegradation in the soil with the least organic matter content might imply the involvement of clay surface.
Degradation of bromophos (140) and iodofenphos (141) on soil was slightly
enhanced by sunlight irradiation via cleavage of the P-O aryl bonds (Allmaier
and Schmid 1985; Allmaier et al. 1984). Walia et al. (1989b) reported oxidation
of the P=S moiety to oxon and stepwise dehalogenation for (141). 14C-Tolclofos-methyl (142) was photodegraded on soil via either photoinduced oxidation of the P=S moiety to the oxon followed by O-demethylation or cleavage
of the P-O aryl bond to give 2,6-dichloro-4-methylphenol (Mikami et al. 1984b).
More of the oxon was detected for soils with lesser organic matter content,
showing contribution of clay surfaces in oxidation as similarily reported for
(135) and (136). From this aspect, Katagi (1990) investigated the photoinduced
oxidation of (142) in/on clay surfaces. The UV reflectance spectrum of (142)
on kaolinite film exhibited almost the same pattern as that in 10% acetonitrile
with no reflectance above 300 nm. UV light exposure at 320 nm resulted in
rapid degradation of (142) especially for the kaolinite surface where significant
amounts of oxon were formed, clearly demonstrating involvement of indirect
photolysis. Less formation of the oxon was observed when clay was air-dried
or the study was conducted under nitrogen. MS analysis of the oxon formed in
kaolinite treated with H218O showed about 40% incorporation of 18O into the
P=O moiety. Formation of H2O2 was confirmed spectrophotometrically, but the
lack of detection of trans-diacetylacetylene from 2,5-dimethylfuran by HPLC
analysis showed the absence of 1O2 on the irradiated clays. Based on these observations, formation of the oxon could be well explained by reaction with OH
that was produced from the successive reaction with residual water molecules,
with the superoxide anion radical formed probably via photoinduced electron
transfer from clay to O2.
Photodegradation of chlorpyrifos (145) on soil at 254 nm gave the oxon and
3,5,6-trichloropyridinol as main degradates with lesser amounts of dechlorinated
derivatives (Walia et al. 1988). Burkhard and Guth (1979) have shown that
60
T. Katagi
diazinon (144) undergoes photoinduced cleavage of the P-O aryl bond on soil.
Similar results have been reported for sunlight photolysis on sandy loam soil
(EPA OPPTS 2000). Because the aqueous photolysis was of insignificant contribution in its dissipation, some kind of indirect photolysis would operate on
the soil surface. Sunlight photodegradation of quinalphos (148) on soil gave
diquinoxalin-2-thiol, diquinoxalin-2-yl sulfide, and disulfide in addition to quinoxalin-2-ol formed via the usual photoinduced cleavage of the P-O aryl bond
without formation of the oxon (Dureja et al. 1988). The photoinduced thionothiolo rearrangement of (148) followed by cleavage of the P-S aryl bond was
most probable, as reported for photodegradation on clays (Banerjee and Dureja
1999). The photolytic profiles of 14C-dioxabenzofos (183) on soil were found to
be common to other phosphorothioates (Mikami et al. 1977b). Photodegradation
of profenofos (160) on soil gave 4-bromo-2-chlorophenol and O-(4-bromo-2chlorophenyl) O-ethyl O-hydrogen phosphate (Burkhard and Guth 1979). The
latter compound was most likely to be formed by photoinduced hydrolysis, in
contrast to the O-dealkylation of other phosphorothioates.
Qualitatively, the extent of photodegradation of 14C-azinphos-methyl (169)
on soil was found to be reduced with an increase of soil depth and organic
matter (Liang and Lichtenstein 1976). Phosalone (170) mainly underwent cleavage of the SCH2-N bond and was either dechlorinated or oxon derivatives were
detected in trace amounts (Walia et al. 1989a). A similar SCH2-N bond cleavage
was reported for methidathion (171) at >290 nm but at trace amounts (Burkhard
and Guth 1979). On exposure to sunlight, 14C-phenthoate (168) was photodegraded via oxidation, cleavage of P-S or S-C bond, and hydrolysis of carboxylic
ester with formation of the -carboxybenzyl thiol (Mikami et al. 1977b). O,O,STrialkyl derivatives not possessing a chromophore are considered to be degraded
by indirect mechanism if photolysis occurs. Phorate (162) was rapidly degraded
in the field to give its sulfoxide and sulfone (Lichtenstein et al. 1973). Disulfoton (163) showed rapid photodegradation on soil with formation of the corresponding sulfoxide (Gohre and Miller 1986). Based on no effect by sterilization,
reactions of (162) and (163) with 1O2 being formed by sunlight irradiation on
soil were considered most likely. Formation of the corresponding sulfone was
reported for (163) under sunlight (EPA OPPTS 1999d). The photoinduced oxidation of the P=S moiety to the oxon was observed only for ethion (184) (EPA
OPPTS 1995c).
Bensulide (164) exhibited simple photoinduced oxidation of the P=S moiety
by UV irradiation (EPA OPPTS 1999a). Monocrotophos (156) and dicrotophos
(157) are unlikely to undergo photochemical reactions on soil due to lack of
chromophores in their molecules (Lee et al. 1989, 1990). Tetrachlovinphos
(154) was expected to undergo E/Z isomerization, but the main reactions were
O-demthylation and cleavage of the P-O vinyl linkage (Beynon and Wright
1969; Dureja et al. 1987b). Isofenphos (175) underwent photoinduced P=S oxidation to the oxon with cleavage of the P-O aryl bond, but no effect on the PN linkage was observed (Dureja et al. 1989). The same degradation profiles as
aerobic soil metabolism but with a much faster rate were reported on soil (EPA
61
OPPTS 1998f). Allmaier et al. (1984) reported via soil photolysis of ditalimfos
(178) that the main product was O,O-diethyl phosphoramidothioate, probably
by stepwise hydrolysis of the imide ring, but photoinduced cleavage of the P-N
bond as observed in aqueous photolysis was not detected. The P-C bond of
cyanofenphos (180) remained unaffected by irradiation (Mikami et al. 1976).
Although examples are limited, either the P-N or P-C bond is considered to be
resistant to photolysis on soil.
Phenoxyalkanoates and Esters The apparent quantum yield of methyl ester of
2,4-D (1) on soil was found to be 30 times lower than that in aqueous solution,
which might be accounted for by screening and/or quenching effects of soil
(Hautala 1978). The coarser the soil, the faster the sunlight photodegradation of
mecoprop (4) and its 2,4-dichlorophenyl derivative, which suggests that the
deeper penetration of light into soil facilitated their degradation (Romero et al.
1998). Their declines followed the Hoerl function (y = aebxxc) rather than the
usual first-order kinetics, and increase in moisture content enhanced the photodegradation. Therefore, the transport of these pesticides to the photic zone along
with water movement may control their photodegradation profiles. Norris et al.
(1987) reported that triclopyr (7) was degraded in pastures to give 2-methoxy3,5,6-trichloropyridine and 3,5,6-trichloropyridin-2-ol via successive decarboxylation and O-demethylation.
Pyrethroids Photoinduced isomerization was a minor pathway for soil photolysis of cis- or trans-permethrin (17) (Holmstead et al. 1978a). Sunlight irradiation had no effect on ester cleavage for both isomers, and either dechlorination
or cleavage of the cyclopropyl ring to give dimethylacrylate derivative was also
a minor pathway. Photoinduced isomerization of trans- and cis-cypermethrin
(19) was also found insignificant on soil (Takahashi et al. 1985a). The main
reaction was stepwise hydration of the -cyano group to CONH2 and COOH
and was clearly accelerated by sunlight irradiation, although this hydration was
not affected by irradiation in the other study (EPA FIFRA 1999). Photodegradation of deltamethrin (22) was briefly reported with slight contribution of photolysis on soil, and the main degradation product was the corresponding dibromovinyl chrysanthemic acid (EPA FIFRA 1999). Sunlight photodegradation was
found to be also of less importance for Z-cis-cyhalothrin (21) on soil (Ruzo et
al. 1987). In another 14C study using artificial light, formation of the -CONH2
derivative was reported (EPA FIFRA 1999). In the case of cis-tefluthrin (18),
cis/trans isomerization was reported on soil by UV irradiation although its photodegradation was rather slow (EPA FIFRA 1999). Rapid sunlight photodegradation was reported for 14C-cyfluthrin (20) with formation of 4-fluoro-3phenoxybenzaldehyde via ester hydrolysis and release of cyanide ion from the
corresponding cyanohydrin (EPA FIFRA 1999). Similar to (19), hydration of
the -cyano group to CONH2 predominantly occurred for 14C-fenpropathrin (24)
with more formation under sunlight on soil (Takahashi et al. 1985b).
62
T. Katagi
To clarify the reaction mechanism of photoinduced hydration common to

these pyrethroids, Katagi (1993b) examined effects of moisture content and clay
on photolysis of 14C-(24) using UV light at >290 nm. The degradation rate of
(24) was found to be highly dependent on soil moisture, and UV irradiation
only slightly enhanced the hydration. The amount of -CONH2 derivative significantly increased with decreasing soil moisture, and this reaction was enhanced when clay was used. The shift of C=O vibration in IR spectra to a
higher wavenumber in soil and clay as compared with that in KBr implied some
interaction of the cyano group but not the carbonyl oxygen with these surfaces.
Because clay surface is known to exhibit an extremely high acidity when dried,
the observed hydration of the -cyano group was considered most likely to be
acid catalyzed on clay surfaces. The inconsistency observed for the amount of
-CONH2 derivative of (19) between laboratory and outdoor studies can be
elucidated by the difference of soil moisture; less moisture in soil thin layers
kept outdoors would enhance the hydration.
Fenvalerate (27) dominantly underwent hydration of the -cyano group on
soil with a trace formation of decarboxylated derivative (Mikami et al. 1980).
Katagi (1991) reported hydration of the -cyano group and O-dephenylation of
14
C-esfenvalerate (28) on soil and clays, which was enhanced on exposure to
UV light at >300 nm. It was demonstrated by MS analysis that about half of
18
O was incorporated into the O-dephenylated derivative when photolysis was
conducted on clay prepared from H218O suspension. Because Fentons reagent
was found to give the O-dephenylated derivative of (28), OH photochemically
produced on clay surfaces was most likely to directly react with (28). Furthermore, kaolinite clay was found to catalyze hydration of (28) in the presence of
H2O2, acting as a nucleophile against the cyano carbon to finally give the CONH2 derivative. Flucythrinate (29) and fluvalinate (30) similarly underwent
hydration of the -cyano group and cleavage of the ester (Quinstad and Staiger
1984; Dureja and Chattopadhyay 1995). Most of these pyrethroids have the 3phenoxybenzyl moiety, which is usually released through photodegradation as
PBacid (243). The significant red shift in reflectance spectrum of (243) on kaolinite clay showed possible interaction with the surface. The insignificant spectral overlap the artificial light (>300 nm) implied indirect photolysis; the main
photodegradate on soil and clay was 3-hydroxybenzoic acid (3-HB). The photonucleophilic reaction by OH was unlikely because there was no reaction with
more nucleophilic cyanide ion in aqueous photolysis, and 18O incorporation into
3-HB was demonstrated by MS analysis when aqueous photolysis was carried
out in 50% H218O. Incidentally, Fentons reagent gave 3-HB as a main degradate.
These results indicated that OH photochemically produced on these surfaces
attacked the 3-position of (243) and this ipso substitution resulted in formation
of 3-HB.
Carbamates Contribution of photolysis in dissipation of propoxur (65) on soil
was considered less than that from binding to soil and volatilization (EPA OPPTS 1997b). Methiocarb (68) has a 4-methylthio moiety reactive to 1O2, and the
63
main photodegradation product was the sulfoxide on soils under sunlight (Gohre
and Miller 1986). UV irradiation of carbaryl (71) at >290 nm on soil showed
less photoreactivity than aqueous photolysis (Hautala 1978). The disappearance
of fluorescence of (71) on soil implied the efficient quenching by soil constituents, which at least in part accounted for reduction of photolysis. The photolysis profiles of carbofuran (72) were briefly examined on field plots as a main
degradate of carbosulfan (88) (Nigg et al. 1984). After an outdoor application,
(88) quickly dissipated on soil to give (72), which was rapidly degraded to give
a trace amount of the 3-keto derivative. Benfuracarb (89) was reported to be
similarly converted to (72) via cleavage of the N(CH3)-S bond on soil by UV
irradiation (Dureja et al. 1990). When 14C-benthiocarb (86) was exposed to sunlight on soil taken from a rice-growing area, the photoinduced S-oxidation to
give the sulfoxide and sulfone was observed similarly as (68) possibly via reaction with 1O2 (Cheng and Hwang 1996). A similar photooxidation of sulfur by
sunlight was reported for butyrate (87) on soil (EPA OPPTS 1993). Molinate
(90) is considered to undergo S-oxidation on soil, but faster degradation under
sunlight was reported without any information on degradation products (Konstantinou et al. 2001). The usual cleavage of carbamate linkage proceeded for
asulam (82) to give sulfanilamide as a main photodegradate on soil (EPA OPPTS 1995a). Desmedipham (83) and phenmedipham (84) have two carbamate
linkages in molecules but the C(=O)O aryl bond was found to be primarily
cleaved. The main pathway of 14C-(83) on soil was formation of ethyl (3-hydroxyphenyl)carbamate, and degradates via photo-Fries rearrangement in aqueous
photolysis could not be detected (EPA OPPTS 1996b). Maneb (94) was quickly
degraded to ETU (95) on soil (Rhodes 1977). After application of 14C-(94) and
14
C-(95) to the ground, the recovered radioactivity from soil rapidly decreased
to form ethyleneurea via S-oxidation of (95). Thiophanate-methyl (92) showed
a similar S-oxidation at one of two C=S moieties on soil exposed to sunlight
together with formation of MBC (93) (EPA OPPTS 2001). Almost quantitaive
formation of (93) was reported for benomyl (81) on soil with 2-aminobenzimidazole as a minor degradate (EPA OPPTS 2001).
Amides, Anilides, and Dicarboximides Soil organic matter was found to accelerate photolysis of propachlor (33) by sunlight irradiation (Konstantinou et al.
2001). For alachlor (34), the rate of photodegradation was enhanced by low soil
organic matter, low pH, or high water content (Fang 1977; Chesters et al. 1989).
Alachlor (34) underwent cleavage of either the NCH2 or NC(=O) bond followed by further degradation to 2,6-diethylaniline and reductive dechlorination
(Fig. 21). As a unique reaction, the intramolecular cyclization occurred between
nitrogen and o-ethyl group to give N-chloroacetyl-7-ethylindoline. Somich et al.
(1988) examined the effect of photolytic ozonation on dissipation of 14C-(34) in
soil and found that O3 caused release of more carbon dioxide from the irradiated
soil. Photolysis of metolachlor (35) on soil by artificial sunlight gave N-chloroacetyl-N-(hydroxyprop-1-en-2-yl)-2-ethyl-6-methylaniline as a main degradate
(see Fig. 21) (Chesters et al. 1989). This product was considered to be formed
Fig. 21. Comparative photodegradation pathways of alachlor (34) and metolachlor (35).
64
T. Katagi
65
via photoinduced cleavage of the O-CH3 bond. Metalaxyl (37) was slowly photodegraded on soil, but its degradation was found to be also controlled by either
microbial degradation or abiotic factors other than light (Sukul and Spiteller
2001). The slower rate of degradation was observed for soil having a larger clay
content, and light screening by adsorption of (37) into the interlayer of clay
might reduce the effect of irradiation. On air-dried soil, (37) was reported to
undergo cleavage of either the CH2-OCH3 or NC(=O) bond (Saha and Sukul
1997). Under simulated sunlight, carboxin (42) was photodegraded to give the
corresponding sulfoxide, and increased moisture content accelerated photolysis
(Murthy et al. 1998). Because insignificant photodegradation of oxycarboxin
(43) was observed under the same conditions, the main degradation pathway of
(42) was most likely to be photoinduced S-oxidation. Further photodegradation
of the sulfoxide was examined in soil suspension, and oxanilic and malonic
acids were additionally identified (Hustert et al. 1999).
Effects of soil properties such as moisture content and soil depth have been
investigated in conjunction with photolytic profiles of 14C-nicloamide (40)
(Frank et al. 2002; Graebing et al. 2002). The reactive site of (40) was the 4nitro group, which was either reduced to an amino group or substituted with
OH, and these products were finally degraded to 3-chloro-6-hydroxybenzoic
acid. NO3 added as a fertilizer, iron oxide, or humic acid was found to cause
insignificant effects on photodegradation of (40) in moistened soil, but reduced
degradation was observed in air-dried soil. Although the photodegradation pathway was not available, the importance of pesticide transport to soil surface has
been extensively studied for napropamide (47) (Miller and Donaldson 1994;
Donaldson and Miller 1996). The main metabolic pathway of florasulam (48)
in soil was O-demethylation, whose formation was accelerated by sunlight exposure, and this product was further photodegraded via stepwise opening of the
triazolopyrimidine ring (Krieger et al. 2000). Microbial degradation of 14C-(48)
was considered to dominate its dissipation in soil, but one product ASTP (8fluoro-5-methoxy[1,2,4]triazolo-[1,5c]pyrimidine-2-sulfonamide) characteristic
of soil photolysis was formed via cleavage of the NH-aryl bond. Degradation
of captan (106) was slightly enhanced by sunlight exposure on moist soil with
major degradates identified as tetrahydrophthalimide and cyclohex-4-ene-2cyano-1-carboxylic acid (EPA OPPTS 1999b). The former product was considered to be formed via cleavage of the N-S bond, whereas opening of the imide
ring followed by reduction of the amide moiety would also proceed in soil. 14CIprodione (109) exhibited a slightly rapid degradation on soil with formation of
3,5-dichloroaniline and 3-(3,5-dichlorophenyl)-2,4-dioxaimidazolinone (Fig. 22)
(EPA OPPTS 1999b). As a unique degradate, 3-(1-methyl-ethyl)-N-(3,5-dichlorophenyl)-2,4-dioxo-1-imidazolidinecarboxamide was identified, and photoinduced cleavage of the amide linkage in the ring followed by recombination of
the carbonyl radical with the N-isopropyl nitrogen was most likely to be involved. The photochemistry of famoxadone (111) on soil was briefly reported
but the characteristic reaction induced by light exposure was not clarified (Jernberg and Lee 1999).
66
T. Katagi
Fig. 22. Photoinduced rearrangement of iprodione (109).
Ureas Jirkovsky et al. (1997) reported that diuron (53) was photodegraded on
sand via N-demethylation and oxidation to the N-formyl-N-methyl derivative
with a trace formation of monuron (52). As N-demethylation of (53) was demonstrated not to require O2, it was considered that the photoinduced rearrangement of an N-methyl group to carbonyl oxygen gave the corresponding isourea
derivative, which was further hydrolyzed to the NHCH3 derivative. For the Nformyl-N-methyl derivative, the excited carbonyl group was likely to initiate
hydrogen abstraction from the N-methyl group followed by reaction with O2.
Photodegradation of linuron (54) on soil gave NHOCH3, NH2 derivatives, and
3,4-dichloroaniline (EPA OPPTS 1995d). By comparing the results in aerobic
soil metabolism, photolysis was likely to be of minor importance for (54). In
the case of isoproturon (56), the same photoreactions as (53) were observed but
with a slower degradation rate (Kulshrestha and Mukerjee 1986). The photoinduced ring rearrangement was reported for 14C-thidiazuron (58) on soil thin
layer, leading to formation of 1-phenyl-3-(1,2,5-thiadiazol-3-yl)urea (Klehr et
al. 1983). Information on benzoylurea pesticides is very limited, but the results
for photodegradation of diflubenzuron (59) on soil showed an insignificant contribution of photolysis (EPA OPPTS 1997a). Chlorsulfuron (96) was slowly
photodegraded on soil via either O-demethylation or cleavage of the sulfonylurea linkage, but acetylbiuret was not detected (Strek 1998). Similar photodegradation under sunlight was reported for chlorimuron-ethyl (102) together with
unique contraction of the sulfonylurea bridge (see Fig. 20) (Choudhury and
Dureja 1997a). Tribenuron-methyl (99) was photodegraded under sunlight via
N-demethylation with cleavage of either the S-N bond or urea moiety, but any
degradates via bridge contraction were not detected (Bhattacharjee and Dureja
2002). In contrast, photodegradation of 14C-rimsulfuron (103) on soil gave two
major degradates via bridge contraction but no acceleration of degradation by
67
sunlight exposure was observed (Schneiders et al. 1993). One of the degradates
was N-(pyrimidin-2-yl)-N-(pyridin-2-yl)urea derivative, which was considered
to be degraded to the second by release of the carbamoyl group. Involvement
of direct photolysis on sterilized soil was confirmed for triasulfuron (100) and
thifensulfuron-methyl (105) (Albanis et al. 2002).
Azoles and Triazines Triadimefon (188) underwent photoinduced cleavage of
either O-CH or CHC(=O) bond and reduction of the carbonyl group on soil
under sunlight with the decarbonylated derivative as a minor product (Nag and
Dureja 1996). Judging from its UV absorption, direct photolysis was likely to
proceed and the increase of soil moisture enhanced photodegradation (Murthy
et al. 1998). Propiconazole (191) was photodegraded on soil via cleavage of the
C-triazole bond, liberating 1,2,4-triazole. The unique ring opening was reported
for photodegradation of 14C-prochloraz (240) in both laboratory and field studies
(Hollrigl-Rosta et al. 1999). Prochloraz (240) was gradually photodegraded on
soil to give primarily the formylurea derivative of (240) followed by deformylation (Fig. 23). Atrazine (185) was found resistant to photolysis on air-dried
soils (Curran et al. 1992), although slight sunlight photodegradation of an extent
proportional to the content of soil organic matter was reported (Konstantinou et
al. 2001). Gong et al. (2001) showed that in coarser soil where light can penetrate more deeply, or upon addition of humic acid, or in moistened soil where
movement of the pesticide molecule is facilitated, an increased rate of photodegradation can occur.
Miscellaneous Photolysis seems to be of minor importance for dinitroaniline
herbicides relative to volatilization loss and thermal degradation (Wright and
Warren 1965; Parochetti and Hein 1973; Parochetti and Dec 1978). Although a
detailed photodegradation pathway on soil was not available, photolysis of trifluralin (232) on kaolinite clay was conducted to theoretically investigate the
importance of photic depth in clay and its transport within the layer (Balmer et
al. 2000). On exposure to UV light, (232) on clay was slowly decomposed with
formation of two benzimidazole derivatives. Either photoinduced cyclization between nitro nitrogen and the 1-position of an N-propyl group to give the benzimidazole or N-depropylation was most likely to occur. Cyclization was preceded
by photoinduced reduction of the nitro group to a nitroso derivative whose excited state extracted hydrogen from the C1 position of the N-alkyl group. Photodegradation of fluchloralin (236) on soil gave three benzimidazole derivatives
via similar reactions observed for (232) (Nilles and Zabik 1974). The release
of the chloroethyl moiety was observed with a unique formation of 5-nitro-7trifluoromethyl-1,4-quinoxaline. In photodegradation of ethalfluralin (237), 1Hbenzimidazole-3-oxide was additionally detected (EPA OPPTS 1995b). The existence of this product supported a reaction mechanism where the photoexcited
nitro group extracted hydrogen at the C1 position of the N-alkyl group and radical recombination followed by release of hydroxide resulted in benzimidazoleN-oxide. Insignificant degradation by exposure to sunlight was observed for
Fig. 23. Photoinduced ring opening of prochloraz (240).
68
T. Katagi
69
butralin (234) on soil (EPA OPPTS 1998b). Halder et al. (1989) reported the
photoinduced N-deethylation of pendimethalin (238) on sunlight-exposed soil;
other reactions such as photoreduction were predominant when exposed to UV
light (Dureja and Walia 1989). In contrast to these dinitroaniline herbicides,
oryzalin (235) was found to be photolabile on soil, forming many unknowns,
and bound 14C via cleavage of the C-N(C3H7)2 bond, hydrolysis of sulfonamide,
and formation of the benzimidazole derivative (EPA OPPTS 1994).
Amitrole (196) was moderately resistant to sunlight photolysis on soil but
underwent C-N bond cleavage to give 1,2,4-triazole (EPA OPPTS 1996a). Another type of photoinduced deamination via cleavage of the N-N bond was reported for metribuzin (201) in an outdoor photolysis study on soil (EPA OPPTS
1998g). Terbacil (197) underwent cleavage of the N-C(CH3)3 bond to give 5chloro-6-methyluracil (EPA OPPTS 1998h). Bentazon (200) underwent oxidative opening of the thiadiazinone ring to give N-isopropyl-2-nitrosobenzamide,
followed by oxidation to the corresponding nitro derivative (Nilles and Zabik
1975). The primary photoprocess was considered to be hydrogen abstraction at
the NH moiety to form the radical whose center would also be located at the 5and 7-position of the benzothiadiazinone ring (o- and p-position toward the
carbonyl moiety) via resonance. Norflurazon (214) showed moderate sunlight
photolysis on soil with N-demethylation being the dominant process (Schroeder
Kvien and Banks 1985). Fipronil (220) exhibited a unique photoreaction to give
the desulfinyl derivative (Bobe et al. 1998b), and the sulfone derivative was
also detected in two field dissipation studies (Bobe et al. 1998a; Fenet et al.
2001). 14C-DTP (221), the herbicidal entity of pyrazolate, mainly underwent
oxidative N-demethylation on paddy soils (Yamaoka et al. 1988).
IX. Photodegradation of Pesticides on Plants

Photodegradation profiles of pesticides on plant surfaces were reviewed based
on surface-wash analysis in plant metabolism studies, unless described otherwise, to distinguish the photochemical conversion from biotic processes. The
plant species and some experimental conditions are summarized in Table 11
(see table on page 120) for each pesticide with its half-life.
Organochlorines Each formulation of DDT (130), aldrin (122), dieldrin (123),
and endrin (126) was sprayed on apple trees in the field and the hexane rinsates
of leaves were analyzed (Harrison et al. 1967). DDT was photodegraded to
DDD (132) and 4,4-dichlorobenzophenone. Aldrin was degraded with concomitant formation of (123). The cage-type ketone and aldehyde derived from reactions at the bridged carbons were detected for (126). When (122), (123), and
(126) were applied to leaves of young bean plant or glass plates under sunlight,
similar photodegradation profiles were identified (Ivie and Casida 1971b; Ivie
et al. 1972). In the same study using apple trees, the -isomer of endosulfan
(125) was found to be a little more persistent than the -isomer with formation
of its sulfate. After application to cotton leaves in the field, the -isomer mainly
70
T. Katagi
underwent dechlorination at the bridge carbon with trace amounts of -isomer

and ring-opening products, whereas the -isomer only gave the latter (Dureja
and Mukerjee 1982). These results agreed with those seen with solution photolysis in hexane. Similar solution photochemistry was also reported for chlordane
(128) applied to cabbage leaves (Parlar et al. 1978). As shown in Fig. 24, N(-trichloromethyl-p-methoxybenzyl)-p-methoxyaniline principally underwent
photoinduced rearrangement on lettuce and bean leaves to N-phenyl--hydroxybenzylamide, which was the common photoproduct in water and on glass or
silica gel (Miller et al. 1974). Direct absorption of light caused a charge transfer
from nitrogen to the CCl3 moiety, followed by the successive release of chloride
ion and recombination to the unstable three-membered intermediate, which was
hydrolyzed to the corresponding amide.
Organophosphorus Esters This class of pesticides undergoes various transformations in plant metabolism, as reviewed by Katagi and Mikami (2000). ElRefai and Hopkins (1966) compared dissipation of parathion (135) topically
applied to garden beans or glass plates. The biphasic decay in contrast to the
simple first-order dissipation on glass implied penetration of (135) into cuticle
and tissue. A similar biphasic foliar decay was observed in residue trials in
orange groves with concomitant formation of the oxon (Popendorf and Leffingwell 1978). Formation and decay of the oxon was found to strongly correlate
with dry and stable weather, and effects of foliar dust and airborne oxidants
were suspected. Spear et al. (1978) conducted residue trials of (135) on dwarf
Eureka lemon trees in the presence or absence of O3 and soil dusts (<50 m).
They showed that the a photoinduced dust-catalyzed process is one of the most
important routes for the foliar P=S oxidation of (135). However, the presence
of soil dust on foliage might retard the decay of the oxon by its stronger adsorption to dust (Adams et al. 1977). Joiner and Baetcke (1973) scrutinized the
degradates from 14C-(135) on cotton. Although the degradates were extracted by
homogenization, the S-ethyl isomer was detected with a trace amount of the Sphenyl isomer, indicating the contribution of photolysis.
Plant metabolism studies using 14C- or 32P-labeled fenitrothion (138) in rice
(Miyamoto and Sato 1965), sugar beet, (Ohkawa et al. 1974b), and apples (Hosokawa and Miyamoto 1974) have been reported. 32P-(138) rapidly penetrated
into tissues of rice plants but information on degradation was not provided.
Analysis of methanol rinses of bean leaves showed that (138) was rapidly degraded via similar pathways as (135), but oxidation of the aryl methyl group to
COOH was characteristically detected. In the case of apple fruits, the oxon and
3-methyl-4-nitrophenol were identified as major degradates in the acetone wash,
the former of which was not detected in the homogenates. In the rinsate, the
corresponding S-isomer was also confirmed. Therefore, both oxon and S-isomer
were most likely to be photochemically produced on the surface of apple fruits,
as was also demonstrated by Fukushima et al. (2003) on tomato fruits. For 14Ccyanophos (137) on bean plants, photolysis was of minor importance (Chiba et
al. 1976). The degradation of bromophos (140) on tomato leaves was also found
Fig. 24. Photodegradation of N-(-trichloromethyl-p-methoxybenzyl)-p-methoxyaniline.
71
72
T. Katagi
to be less important than metabolism in tissues (Stiasni et al. 1969). In contrast,

fenthion (143) was very rapidly degraded on coastal bermudagrass or corn
plants with successive oxidation of the S-methyl sulfur to form the corresponding sulfoxide and sulfone (Leuch and Bowman 1968). Residue analysis of (143)
and its degradates was conducted for a citrus grove, and both sulfoxide and
sulfone were detected only in the orange peel, showing that these oxidations are
surface reactions on fruits (Minelli et al. 1996). Dechlorination of chlorpyrifos
(145) was confirmed by a trace amount through its photodegradation on the
dorsal leaves of soft shield fern by irradiation, but the main degradates were
3,5,6-trichloropyridinol and the oxon (Walia et al. 1988). Formation of the oxon
from isoxathion (151) on foliage was found insignificant, as demonstrated in
metabolism of 14C-(151) (Ando et al. 1975) and residue trials (Endo et al. 1985).
When phoxim (152) was applied outdoors to tomato plants, the surface rinse of
leaves with acetone was found to contain two unknown photoproducts more
polar than (152) (Makary et al. 1981). The corresponding oxon was confirmed
by GC analysis of corn forage treated with emulsifiable concentrate formulation
of (152) but its route of formation was ambiguous due to the harsh Soxhlet
extraction (Bowman and Leuck 1971). Ivie and Bull (1976) conducted photodegradation studies of 14C-sulprofos (161) on cotton leaves and confirmed the
predominant formation of sulfoxide and sulfone in the methanol rinse. Metabolism of 14C- and 32P-phenthoate (168) in Valencia orange leaves and fruit showed
that the main degradation pathways on the surface were P=S oxidation to the
oxon, stepwise hydrolysis at the S-C bond and carboxylate moiety to mandelic
acid, and hydrolysis of the P-S bond followed by formation of disulfide (Takade
et al. 1976). The other minor reaction, O-demethylation, was detected mostly on
orange tree leaves. Similar degradation profiles were observed for 14C-azinphosmethyl (169) in corn and bean metabolism. Extraction by homogenization only
made a site of conversion difficult to identify, but similar profiles on glass under
irradiation showed possible photodegradation on plant surfaces (Liang and Kichtenstein 1976).
32
P- and 14C-Dimethoate (165) was gradually degraded on leaves via P=S
oxidation followed by conversion of the amide moiety finally to the carboxyl
derivative of the oxon, including oxidative N-dealkylation (Dauterman et al.
1960; Lucier and Menzer 1968). Due to lack of a chromophore in (165), indirect
photolysis may account for a part of these conversions. Formothion (166) underwent rapid conversion to (165) on bean leaves but contribution of photolysis is
unclear (Sauer 1972). Malathion (167) is considered to be also resistant to direct
photolysis, and only hydrolysis of ester linkages is a dominant pathway (Awad
et al. 1967; El-Refai and Hopkins 1972; Mostafa et al. 1974). 14C-Edifenphos
(173) was slowly degraded on rice leaves, presumably via hydrolysis, and thus
the contribution of photolysis also was unlikely (Ishizuka et al. 1973). Photoinduced cis/trans isomerization was expected for mevinphos (155), but its high
volatility made it difficult to confirm this possibility (Casida et al. 1956). Hydrolysis of monocrotophos (156) and dicrotophos (157) was found only predominant
on plant surfaces without any contribution from photolysis (Lindquist and Bull
73
1967; Beynon and Wright 1972; Bull and Lindquist 1964). Bull et al. (1967)
conducted a metabolism study in cotton using the cis- and trans-isomers of 14Cand 32P-phosphamidon (158) and reported faster degradation of the cis-isomer
on foliage, which would be due to its easier hydrolysis. In contrast, photoinduced E/Z isomerization was observed for 14C-tetrachlorovinphos (154) on
leaves of cabbage, apple, bean, and rice (Beynon and Wright 1969; Dureja et
al. 1987b). Acephate (174), cyanofenphos (180), leptophos (181), and butonate
(182), having P-C and P-N bonds in their molecules, underwent either O-dealkylation or ester hydrolysis, and photolysis on plant surfaces seemed to be of
minor importance (Chiba et al. 1976; Zayed et al. 1978; Bull 1979: Derek et al.
1979).
Pyrethroids The trans- and cis-isomers of 14C-phenothrin (13) were rapidly
degraded on kidney bean and rice plants via unique ozonization of the isobutenyl side chain successively to the corresponding aldehyde and carboxylic acid
(Nambu et al. 1980); this seems to be a typical example of reaction of pesticides
with active oxygen species in air. Measurable isomerization was observed for
the aldehyde and carboxylic acid derivatives, at least in part showing involvement of photoprocess. Instead of oxidation, the cis-isomer of 14C-cypermethrin
(19) predominantly underwent cis/trans isomerization on cotton and bean leaves
grown outdoors (Cole et al. 1982). A similar phototransformation was observed
for deltamethrin (22) (Ruzo and Casida 1979; Maguire 1990). Rapid conversion
of tralomethrin (25) and tralocythrin (26) to (22) and (19) followed by isomerization to the trans-isomers was observed together with a slight epimerization
at the benzyl carbon, possibly as a dark reaction (Cole et al. 1982). Dissipation
of fenpropathrin (24) on leaves of mandarin orange was mostly due to penetration into leaf tissues (Takahashi et al. 1985b). The insignificant contribution by
photolysis was accounted for by the very slight differences in half-lives when
(24) was applied to green beans and tomatoes in winter and spring when sunlight intensity to (24) was different (Martinez Galera et al. 1997). Decarboxylation proceeded for fenvalerate (27) on cotton (Holmstead et al. 1978b) and
bean leaves (Ohkawa et al. 1980). Similar profiles have been separately reported
for metabolism in spring wheat, and the analysis of hexane rinse of leaves
clearly demonstrated that decarboxylation is a photoreaction (Lee et al. 1988).
Similar photoinduced decarboxylation via radical processes was detected for
flucythrinate (29) on French bean leaves with degradates formed via cleavage
at the O-CH bond (Chattopadhyaya and Dureja 1991).
Carbamates Metolcarb (61), xylylcarb (63), and trimethacarb (64) likely dissipated from plant foliage mainly by volatilization, with photochemical reactions
playing a minor role (Slade and Casida 1970; Ohkawa et al. 1974a). Although
the hydroxylated derivative at the methylene carbon of the isobutyl group was
confirmed for 14C-fenobucarb (62) applied to rice leaves, the trace amount detected implied that photolysis was of minor importance (Ogawa et al. 1976).
For propoxur (65), Abdel-Wahab et al. (1966) reported that its foliar application
74
T. Katagi
to garden snapbean resulted in rapid dissipation, but the degradation profiles

were not clear. They also showed stepwise sulfur oxidation at the thiomethyl
group of methiocarb (68) to its sulfoxide and sulfone. On the leaves treated with
aminocarb (66) and mexacarbate (67), the stepwise oxidation proceeded outdoors at the N,N-dimethylamino moiety, evidenced by analysis of chloroform
rinsates (Abdel-Wahab and Casida 1967). Because similar reactions were identified when silica gel was used, the oxidation reactions were likely to be photoinduced processes. Carbaryl (71) underwent hydroxylation at the 4- or 5-position
of the naphthyl moiety and N-methyl group by stem injection (Mumma et al.
1971), but its photolytic behavior on plant surfaces was unclear (Abdel-Wahab
et al. 1966). The contribution of photodegradation was not clear for carbofuran
(72), but either hydrolysis of the carbamate linkage or stepwise oxidation at
the 3-position of the 2,3-dihydrobenzofuranyl moiety proceeded on strawberry
(Archer et al. 1977). When 14C-benfuracarb (89) was applied to leaves of bush
bean, cotton, and corn, (89) was gradually degraded to (72) on leaf surfaces via
cleavage of the N(CH3)-SNRR bond (Tanaka et al. 1985). Cleavage was considered to also occur at the N(CH3)S-NRR bond, resulting in formation of the
dimer derivatives of (72) possessing Sn (n > 1) or derivatives having the chemical structure of (89) but with Sn (n > 1) linkage. Because these products were
detected predominantly on the leaf surface, photodegradation most likely accounted for this conversion. From 14C-carbosulfan (88), similar derivatives having the Sn linkage were detected only in surface rinse of leaves and fruits of
Valencia orange trees (Clay and Fukuto 1984). In addition, S-oxidation to form
the sulfone derivative of (88) occurred mainly on leaf surfaces.
Hydrolysis was the main degradation pathway in plants for oxamyl (74), and
no clear explanation about the extent of photodegradation was given (Harvey et
al. 1978). In contrast, pirimicarb (78) was known to rapidly dissipate from lettuce leaves, not only by volatilization but also by stepwise oxidation of the
N,N-dimethyl group of the pyrimidyl ring, but the extent of the photochemical
contribution was not clear (Cabras et al. 1990). Similar oxidation of the Nmethyl group was reported for fenothiocarb (85) on mandarin orange trees together with S-oxidation to the sulfoxide (Unai et al. 1986). Benomyl (81) and
thiophanate-methyl (92) are known to give the same degradate, MBC (93). MBC
(93) was only formed from (81) on leaves of several plants via release of the
N-butylcarbamoyl group (Baude et al. 1973). 14C-(92) on leaves of apple and
grape trees gave (93) as a main degradate together with the degaradate where
the two C=S groups were oxidized to carbonyls (Soeda et al. 1972). Buchenauer
et al. (1973) examined the photoreactivity of (92) in solid and aqueous phases
using UV light and found that (92) was stable as a solid but rapidly degraded
to (93) in water. Therefore, the photodegradation of (92) on plant foliage seems
to proceed in an aqueous microenvironment, probably originating from morning
dew. MBC (93) was found to be mostly photostable but degradable in the presence of a photosensitizer such as riboflavin (Fleeker and Lacy 1977). Maneb
(94) was rapidly degraded to ETU (95) on leaves of tomato and snapbean plants,
followed by further transformation to either ethyleneurea via C=S oxidation to
75
C=O or dimerization to Jaffes base (1-(2-imidazoline-2-yl)-2-imidazolinethione) (Rhodes 1977). Similar degradates were identified in aqueous photolysis,
showing that these reactions were likely to proceed via photolysis.
Amides, Imides, and Ureas Flutolanil (39) showed slow dissipation on cucumber leaves via deisopropylation at the phenyl ring followed by methylation or
hydroxylation at the 4-position of the aniline ring (Uchida et al. 1983). Conversion on plant surfaces was minimum for carboxin (42) (Buchenauer 1975). Propyzamide (45) was cyclized via reaction between carbonyl oxygen and ethynyl
carbon to form the oxazoline ring followed by its opening to N-(1,1-dimethylacetonyl)benzamide (Yih and Swithenbank 1971). Because this conversion is
known in its hydrolysis (Katagi 2002b), contribution of photolysis was questionable. Opening of its imide ring was observed for procymidone (108) on cucumber leaves but only in trace amounts (Mikami et al. 1984a). Methazole (112)
underwent either opening of the 1,2,4-oxadiazoline-3,5-dione ring to the 3methyl-1-phenylurea derivative or decarboxylation to the 2-oxo-benzimidazole
derivative, with greater amounts detected on the surface of cotton leaves (Dorough et al. 1973). The latter degradate at least was considered to be formed by
photoreaction because it was also detected in aqueous photolysis. Photoreaction
scarcely proceeded for lenacil (199) on sugar beet (Zhang et al. 1999). Diflubenzuron (59) on cotton leaves was resistant to photolysis with insignificant translocation (Bull and Ivie 1976; Mansager et al. 1979). Rodriguez et al. (2001)
identified 2,6-difluorobenzamide as a sole degradate through residue trials on
pine needles. As cumulative solar irradiation was found to correlate highly with
dissipation of (59), and 4-chloroaniline formed via hydrolysis was not detected,
photodegradation forming the corresponding benzamide and isocyanate was
considered most likely. The lack of detection of the latter degradate may be
accounted for by its high volatility. In contrast, diafenthiuron (57) exhibited
rapid photodegradation on cotton leaves (Drabek et al. 1992) and Chinese cabbage (Keum et al. 2002) via reaction of the thiourea moiety with 1O2 to carbodiimide. Tribenuron methyl (99) underwent cleavage of each bond in the sulfonylurea bridge with its contraction on wheat leaves. These processes were most
likely photoreactions because similar degradates were identified on glass plates
exposed to sunlight (Bhattacharjee and Dureja 2002). In contrast, most of 14Cthifensulfuron (104) remained unchanged in the surface rinse of soybean plants,
with trace amounts of thiophene-2-methoxycarbonyl-3-sulfonamide and the 2amino-1,3,5-triazine derivative (Brown et al. 1993).
Azoles On the leaves of marrow plants, triadimefon (188) was converted to
two diastereomers of triadimenol (189) via reduction of carbonyl group to
CHOH, but the contribution of photolysis was unclear (Clark et al. 1978). Degradation of (189) was briefly investigated on apple leaves with 1-(4-chlorophenoxy)-3,3-dimethylbutan-2-one being detected as the sole metabolite (Clark and
Watkins 1986). Because the same degradate was identified through photolysis
in methanol, its formation on foliage was likely to be a photoprocess. Although
76
T. Katagi
dissipation profiles of the other azole fungicides on grape have been investigated, their degradation pathways are not available (Cabras et al. 1997a, 1998;
Peacock et al. 1994). For fluotrimazole (195), the substitution of the 1,2,4-traizole moiety with the hydroxyl group was confirmed on leaves of barley, with
the photo-induced cleavage of C-N bond being proposed (Clark et al. 1983).
Miscellaneous Although 2,4-D (1) does not possess UV absorption >290 nm,
more of (1) was lost from Zea mays leaves by exposure to UV light >290 nm
than the dark control, and thus the possible photosensitization of either some
components in epicuticular waxes or a coexisting oxysorbic surfactant might
occur (Venkatesh and Harrison 1999). The degradation pathway was not clear
but may be estimated by the results of residue trials for triclopyr (7). When (7)
was sprayed on grasses, it was rapidly degraded to give 3,5,6-trichloro-2-pyridinol with a trace amount of 2-methoxy-3,5,6-trichloropyridine (Norris et al.
1987); this suggests the possible cleavage of O-CH2 and the following decarboxylation are involved in degradation. The photostability of 2,3,7,8-TCDD (129)
was examined on excised leaves of rubber plant under sunlight (Crosby and
Wong 1976). TCDD (129) was degraded possibly via direct photolysis because
its UV absorption maximum was at 300 nm. Although its degradation pathway
was not available, dechlorination was most probable based on the latter photodegradation studies (Schuler et al. 1998). Both dinoseb (202) and dinobuton
(203) were rapidly degraded to several unknown compounds on garden snapbean seedlings, and 5%6% of (203) was found to be converted to (202) (Matsuo and Casida 1970). In the presence of a photosensitizer such as rotenone,
these pesticides were more rapidly decomposed via oxidation, ester cleavage,
and reduction of the nitro group (Bandal and Casida 1972).
Sethoxydim (223) was degraded on grasses to eight unknown products and
the O-deethylated derivative, which were also detected in photolytic and thermal
transformation (Campbell and Penner 1985b). For alloxidim (224), the contribution of photolysis to its dissipation on sugar beet leaves was examined by Soeda
et al. (1979). Alloxidim was degraded via cleavage of the N-O bond to form
the amine derivative and Beckmann rearrangement to the two cyclized derivatives. The former main degradate was also formed either by UV photolysis on
silica gel or by catalytic reduction of (224) with 10% Pd/C in a hydrogen atmosphere, indicating photoinduced reductive dissociation was most probable on the
leaf surface. 14C-Imidacloprid (215) on tomato leaves dissipated under sunlight
via oxidation of the imidazolidinimine ring and stepwise loss of the nitroimino
group to finally form the imidazolidin-2-one derivative (Scholz and Reinhard
1999). As the dark control resulted in minimum degradation, these degradates
originated from photolysis. For fipronil (220), photochemical conversion of the
trifluoromethylsulfinyl moiety via homolytic cleavage of the S-CF3 or S-C(pyrazolyl) bond was confirmed on leaves of corn, sweet pea, and pear (Hainzl and
Casida 1996). In contrast, the main degradate in field residue trials was the
sulfone derivative with a trace of the desulfinyl derivative (Fenet et al. 2001).
The well-aerated leaf surface with higher levels of water under tropical condi-
77
tions might result in favorable photoinduced S-oxidation. Thiabendazole (212)

was photodecomposed on sugar beet, possibly via oxidation to benzimidazole2-carboxamide and benzimidazole, but only in trace amounts (Jacob et al. 1975).
Photoinduced oxidation of an alkyl chain was reported for guazatine (245) on
dwarf apple trees (Sato et al. 1985a). Oxidation to ketone at the 4-position to
the NH moiety followed by methylation at the 3- or 5-position was proposed
to proceed via reaction with the hydroxyl radical or some sensitizer in wax
components.
Moye et al. (1990) investigated the degradation of 3H-, 14C-avermectin B1a
(250) in celery seedlings. By HPLC analysis of homogenization acetone extracts, the 8,9 isomer formed via photoinduced geometric isomerization at 8and 9-positions of the macrocycle was detected as a main degradate. Analysis
of methanol rinsates from cabbage plant treated with 14C-4-(epi-methylamino)4-deoxyavermectin B1a benzoate [MAB; (251)] showed that surface degradation
was mainly due to photolysis; isomerization of the 8,9-double bond, stepwise
oxidation of the N-methyl group via N-formyl to the amino group, hydroxylation
at the 8-position, and loss of the outer sugar by cleavage of the ether bond
(Wrzesinski et al. 1996). The other example is Spinosad consisting of spinosyn
A and D. Saunders and Bret (1997) utilized 14C-spinosyn A (252) for foliar or
topical application to cotton, turnip, cabbage, and apple fruits. Although no
information on the degradation pathway is available, by analogy with (251),
oxidation at double bonds, N-demthylation, and ether cleavage may occur.
Summary
Photodegradation is an abiotic process in the dissipation of pesticides where
molecular excitation by absorption of light energy results in various organic
reactions, or reactive oxygen species such as OH, O3, and 1O2 specifically or
nonspecifically oxidize the functional groups in a pesticide molecule. In the case
of soil photolysis, the heterogeneity of soil together with soil properties varying
with meteorological conditions makes photolytic processes difficult to understand. In contrast to solution photolysis, where light is attenuated by solid particles, both absorption and emission profiles of a pesticide are modified through
interaction with soil components such as adsorption to clay minerals or solubilization to humic substances. Diffusion of a pesticide molecule results in heterogeneous concentration in soil, and either steric constraint or photoinduced
generation of reactive species under the limited mobility sometimes modifies
degradation mechanisms. Extensive investigations of meteorological effects on
soil moisture and temperature as well as development of an elaborate testing
chamber controlling these factors seems to provide better conditions for researchers to examine the photodegradation of pesticides on soil under conditions
similar to the real environment. However, the mechanistic analysis of photodegradation has just begun, and there still remain many issues to be clarified. For
example, how photoprocesses affect the electronic states of pesticide molecules
on soil or how the reactive oxygen species are generated on soil via interaction
78
T. Katagi
with clay minerals and humic substances should be investigated in greater detail.
From this standpoint, the application of diffuse reflectance spectroscopy and
usage or development of various probes to trap intermediate species is highly
desired. Furthermore, only limited information is yet available on the reactions
of pesticides on soil with atmospheric chemical species. For photodegradation
on plants, the importance of an emission spectrum of the light source near its
surface was clarified. Most photochemical information comes from photolysis
in organic solvents or on glass surfaces and/or plant metabolism studies. Epicuticular waxes may be approximated by long-chain hydrocarbons as a very viscous liquid or solid, but the existing form of pesticide molecules in waxes is
still obscure. Either coexistence of formulation agents or steric constraint in the
rigid medium would cause a change of molecular excitation, deactivation, and
photodegradation mechanisms, which should be further investigated to understand the dissipation profiles of a pesticide in or on crops in the field. A thinlayer system with a coat of epicuticular waxes extracted from leaves or isolated
cuticles has been utilized as a model, but its application has been very limited.
There appear to be gaps in our knowledge about the surface chemistry and
photochemistry of pesticides in both rigid media and plant metabolism. Photodegradation studies, for example, by using these models to eliminate contribution from metabolic conversion as much as possible, should be extensively conducted in conjunction with wax chemistry, with the controlling factors being
clarified. As with soil surfaces, the effects of atmospheric oxidants should also
be investigated. Based on this knowledge, new methods of kinetic analysis or a
device simulating the fate of pesticides on these surfaces could be more rationally developed. Concerning soil photolysis, detailed mechanistic analysis of
the mobility and fate of pesticides together with volatilization from soil surfaces
has been initiated and its spatial distribution with time has been simulated with
reasonable precision on a laboratory scale. Although mechanistic analyses have
been conducted on penetration of pesticides through cuticular waxes, its combination with photodegradation to simulate the real environment is awaiting further investigation.
79
Table Listing
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
............................................................................................................
8084
............................................................................................................
85
............................................................................................................
8687
............................................................................................................
88
............................................................................................................
8991
............................................................................................................
9293
............................................................................................................ 94100
............................................................................................................ 101103
............................................................................................................
104
............................................................................................................ 105119
............................................................................................................ 120128
2,4,5-T
MCPA
Fluazifopbutyl
Pyrethrum-I
Allethrin
Cypermethrin
Esfenvalerate
Alachlor
Metolachlor
Carboxin
Naptalam
Napropamide
Diuron
Flumeturon
Phenmec
Metolcarb
Trimethacarb
Propoxur
47
53
55
60
61
64
65
2,4-D
Pesticide
2
3
6
9
10
19
28
34
35
42
44
No.
328
427
316
329
283
283
287
324
255
294
261
264
268
276
282
293
296
255
250
349
345
340
335
342
230
267
292
292
296
Ex.
309
450
338
332
321
Em.
EPA
A
EPA
EPA
EPA
E
S
M
AW
AW
A
A
A
A
E
E
EPA
Sola
Fluorescence
b
L
r
r
r
r
25
r
r
r
r
r
r
r
25
25
L
Tc
300
282
310
255
261
264
268
280
520
498
375
379
393
400
311
279
282
273
277
280
290
300
Ex.
515
528
462
431
437
481
425
510
495
480
Em.
EPA
EPA
EPA
E
SSW
EPA
SSW
S
EW
E
E
EPA
A
EPA
E
E
Sol
<0.2s
<0.2s
2.7
3.4
2.9
0.8
s
s
s
s
0.2 ms
Phosphorescence
Table 1. Wavelength of fluorescence and phosphorescence spectra of pesticides.
L
L
L
L
L
L
L
L
L
L
L
Sogliero et al. 1985

Moye and Winefordner 1965
Mueller et al. 1992
Mueller et al. 1992
Bowman and Beroza 1967a
Bowman and Beroza 1967a
Takahashi et al. 1985a
Katagi 1991
Mueller et al. 1992
Mueller et al. 1992
Aaron et al. 1979
Krause 1983
Vannelli and Schulman 1984
Murillo Pulgarin and Garca Bermejo 2002
Argauer 1980
Krause 1983
Mueller et al. 1992
Addison et al. 1977
Addison et al. 1977
Addison et al. 1977
Bowman and Beroza 1967b
Reference
80
T. Katagi
Aminocarb
Mexacarbate
Methiocarb
Carbaryl
Carbofuran
Mobam
Dimetilan
Pyrolan
Isolan
67
68
71
72
73
75
76
77
Pesticide
66
No.
Table 1. (Continued).
375
400
365
320
325
304
306
340
326
332
338
334
373
360
375
358
Em.
304
266
270
266
281
280
278
285
281
280
286
285
272
262
262
248
Ex.
E
E
E
AW
E
M
AW
E
EPA
M
AW
EPA
E
EPA
E
EPA
Sola
Fluorescence
b
25
25
25
25
r
r
25
r
r
r
L
25
25
r
25
r
Tc
285
400
290
243
257
260
295
300
282
495,530
485,510
400
460
422
400
421
253
248
290
267
262
285
270
275
288
281
Ex.
460
459
460
430
423
440
430
435
518
467,503
Em.
SSW
E
E
E
SSW
E
E
E
EPA
E
E
EPA
E
E
E
E
EPA
Sol
s
s
s
s
s
s
s
s
s
s
0.6 s
1.6 s
0.7 s
1.6 s
2.0 s
1.7 s
0.6
1.2
0.6
0.6
0.7
0.5
0.2
<0.2
2.1
2.2
Phosphorescence
r
L
L
L
r
L
L
L
L
L
L
L
L
L
L
L
L

Addison et al. 1977
Addison et al. 1977
Addison et al. 1977
Argauer 1980
Krause 1983
Argauer 1980
Krause 1983
Krause 1983
Reference
81
Folpet
Dichlorobenil
Chloramben
Picloram
DDT
DDE
DDD
Dicofol
Methoxychlor
Parathion
Fenchlorphos
Diazinon
Chlorpyrifos
116
119
120
130
131
132
133
134
135
139
144
145
Pirimicarb
Propham
Chlorpropham
Benomyl
Pesticide
107
78
79
80
81
No.
245
298
285
325
320
310
242
286
Ex.
313
405
425
380
306
300
Em.
EPA
EPA
A
A
M
AW
E
M
Sola
Fluorescence
b
L
r
r
r
r
25
r
Tc
247
295
286
308
305
306
285
320
270
270
245
265
285
270
275
360
300
275
280
402
386
480
440
489
412
450
420
425
426
415
515
386
380
515
475
395
484
Ex.
400
Em.
EPA
E
E
EPA
E
E
EPA
E
E
E
E
EPA
SSW
EW
SSS
EW
SSS
EPA
Sol
s
s
s
s
0.2 s
0.2 s
40ms
0.2 s
0.2 s
2.6 s
0.3 s
0.7
<0.2
<0.1
5.0
Phosphorescence
L
L
L
L
L
L
L
L
L
L
L
L
r
L
25
L
25
L
Argauer 1980
Krause 1983
Argauer 1980
Aaron et al. 1979
Aaron et al. 1979
Aaron et al. 1979
Aaron et al. 1979
Mueller et al. 1992
Glass 1975
Reference
82
T. Katagi
Pesticide
Coumaphos
Pyrazophos
Azinphosmethyl
Phosalone
Phosmet
Triadimefon
Triadimenol
Bentazone
Thiabendazole
Norflurazon
Oxyfluorfen
Ethoxyquin
Paraquat
Diquat
No.
147
149
169
170
172
188
189
200
212
214
218
219
225
226
420
320
450
433
340
398
350
440
446
360
345
345
310
320
420
340
380
380
359
Em.
310
285
340
260
310
294
323
360
358
282
285
310
282
287
252
290
320
320
320
Ex.
C
C
M
A
M
A
A
M
AW
A
A
A
M
AW
M
M
M
AW
EPA
Sola
18ns
0.3ps
0.7ps
Fluorescence
21
21
r
r
r
r
r
r
r
r
r
r
r
r
r
r
r
r
L
Tc
411
440
457
420
515
510
Em.
330
305
280
325
325
335
Ex.
EPA
EPA
E
SSW
E
Sol
0.8 s
0.6 s
<0.2 s
Phosphorescence
L
L
T
Argauer 1980
Krause 1983
Vannelli and Schulman
Moye and Winefordner
Argauer 1980
Argauer 1980
Argauer 1980
Krause 1983
Da Silva et al. 2001
Da Silva et al. 2001
Argauer 1980
Mueller et al. 1992
Argauer 1980
Mueller et al. 1992
Scrano et al. 1999
Argauer 1980
Krause 1983
Mueller et al. 1992
Villemure et al. 1986
Mueller et al. 1992
1965
1965
1984
1965
Reference
83
Quinomethionate
Imazaquin
Fenarimol
NAA
Warfarine
228
230
239
247
248
453
360
324
390
380
395
Em.
259
295
290
310
360
362
Ex.
A
E
M
M
M
AW
Sola
0.2 ns
Fluorescence
r
25
r
r
r
r
Tc
295
320
475
360
Ex.
418
535
Em.
SSW
SSW
Sol
Phosphorescence
Argauer 1980
Krause 1983
Mueller et al. 1992
Conceicao et al. 1997
Argauer 1980
Argauer 1980
Reference
Em. & Ex., emission and excitation wavelengths in nm.

, Not detected.
aSolvent: A (acetonitrile), AW (acetonitrile-water, 1/1), C (cyclohexane), D (diethyl ether), E (ethanol), EW (ethanol-water, 1/9), H (hexane), M (methanol), S (sodium
dodecyl sulfate micelle), EPA (diethyl ether-pentane-ethyl alcohol, 5/5/2), SSW (solid state, Whatman No. 42 paper), SSS (solid state, S&S904 filter paper).
b, lifetime.
cTemperature: r: room temperature; L: 77 K; values in C.
Pesticide
No.
84
T. Katagi
2,4-D
Fenpropathrin
Esfenvalerate
Hexachlorobenzene
Pentachlorophenol
Photo-dieldrin
DDT
Parathion
Tolclofos-methyl
Atrazine
Paraquat
NMH
PBacid
Nitrobenzene
N,N-Dimethylaniline
Ethyl pyruvate
PBB
Thiathrene
Crystal violet
1
24
28
115
121
124
130
135
142
185
225
242
243
Aqueous
N.R.
Acetonitrile
Aq. acetonitrile
Hexane
Hexane
Hexane
Hexane
N.R.
Aq. acetonitrile
Methanol
Aqueous
Aqueous
pH 2 & 7 buffer
Cyclohexane
Cyclohexane
Cyclohexane
Hexane
Cyclohexane
Solvent
595
240
278
277
218, 231 (sh)
218, 231 (sh), 305 (br)
193
235, 265 (br)
266
275, 282
226, 268
255
346
292; 279
257
257, 297
338
253
275
max (nm)
N.R.: not reported; sh: shoulder; br: broad; PBB: N-propyl p-benzoylbenzamide.
Pesticide
No.
Absorption
max (nm)
Silica gel
282
Three Japanese soils
280
Kaolinite
276
Silica gel
241, 255, 288
Silica gel/adsorbed
247, 310
Silica gel/adsorbed
264
Silica gel/adsorbed
240, 270 (br)
Silica gel
291
Kaolinite
275, 283
Silica gel
233, 268
5% Na-hectrite suspension 263
Na-montmorillonite Swy-1 360
Silica gel or kaolinite
290; 305
+ Silica gel/slurry
273
+ Silica gel/slurry
238, 276
+ Silica gel/slurry
323
Silica gel
285, 325 8sh9
Na-laponite
265, 290 (sh),
450600 (br)
Na-bentonite
545547
Medium
Reflection
Table 2. Maximum wavelengths of absorption or reflectance spectra of chemicals including pesticides.
Ghosal and Mukherjee 1972
Parlar 1990
Katagi 1993b
Katagi 1991
Gab et al. 1975b
Gab et al. 1975b
Parlar 1980
Parlar 1980
Parlar 1990
Katagi 1990
Frei and Nomura 1968
Bailey and Karickhoff 1973
Margulies et al. 1988
Katagi 1992
Leermakers et al. 1966
Pere et al. 2001
Mao and Thomas 1993
Reference
85
86
T. Katagi
Table 3. Emission profiles of photosensitizers.

Sensitizer
max
ES
ET
ISC
Reference
Acetone
300
85
78.9
0.90 0.98
Carmichael and Hug

1989; Tsao and
Eto 1994
Acetophenone
330
79
73.9
1.00
Carmichael and Hug

1989; Tsao and
Eto 1994
Xanthone
610
77.6
73.9
1.00
Carmichael and Hug

1989; Ivie and
Casida 1971a
Tsao and Eto 1994
Rotenone
290, 340
63
65
Mallet and Surette

1974; Rau and
Hormann 1981;
Ke et al. 1940
Tryptophan
460
88
64.4 65.8
Carmichael and Hug

1989; SeguraCarretero et al.
2000; NagChaudhuri and
Augenstein 1964
Anthraquinone
390
62.4
0.90
Carmichael and Hug

1989; Ivie and
Casida 1971a
Humic substances
60 62
Zepp 1985; Van

Noort et al. 1988
53 54
TOP-9EO
Tanaka et al. 1991
Riboflavin
440, 470
57.8
50
Tsao and Eto 1994;

Nag-Chaudhuri
and Augenstein
1964; Chambers
and Kearns 1969
Eosin
580
45.4
0.43
Carmichael and Hug

1989
Eosin Y
520
52.5
45.5
Chambers and
Kearns 1969
Rose bengal
44.6
0.8
Tsao and Eto 1994
Rhodamine 6G
620
43.0
0.002
Carmichael and Hug

1989
Rhodamine B
560
49.3
43.0
Chambers and
Kearns 1969
Methylene blue
420
33.0
0.52
Carmichael and Hug

1989
87
Sensitizer
max
ES
ET
ISC
Reference
Chlorophyll b
316, 450
31.1
0.81
Carmichael and Hug

1989
Chlorophyll a
460
29.4
0.53
Carmichael and Hug

1989
max: absorption maximum in nm; ES & ET: energies of excited singlet and triplet states in kcal
mole1; ISC: quantum yield of intersystem crossing; : not applicable; TOP-9EO: nonaethoxylated p-(1,1,3,3-tetramethylbutyl)phenol.
88
T. Katagi
Table 4. Reactions of pesticides with active oxygen species.
No.
Pesticide
Singlet oxygen,1O2
12 S-Bioallethrin
13 Phenothrin
17 Permethrin
23 Tetramethrin
49 Chlorthiamid
86 Benthiocarb
145 Chlorpyrifos
138 Fenitrothion
141 Iodofenphos
146 Potasan
Hydroxyl radical, HO
51 Fenuron
86 Benthiocarb
90
122
136
142
Molinate
Aldrin
Parathion-methyl
Tolclofos-methyl
185 Atrazine
243 PBacid
Ozone, O3
13 Phenothrin
23 Tetramethrin
135 Parathion
136 Parathion-methyl
Source of
active oxygen species
Bengal red B in ethanol, O2, at
360 nm
Rose bengal in acetonitrile, O2,
with sunlamp
Rose bengal in methanol, O2, with
40 W GE lamp
Rose bengal in acetonitrile, O2,
with sunlamp
Riboflavin or methylene blue in
methanol with sunlight
Eosin in methanol with F40BL
fluorescent lamp
Rose bengal in methanol, air with
600 W tungsten lamp
Methylene blue in methanol with
200 W tungsten lamp
Rose bengal in methanol, air with
600 W tungsten lamp
Methylene blue in methanol at
>313 nm
Reference
Ruzo et al. 1980
Ruzo et al. 1982
Holmstead et al. 1978a
Ruzo 1983
Ruzo et al. 1982
Rajasekharan Pillai 1977
Draper and Crosby 1981
Walia et al. 1988
Verma et al. 1991
Walia et al. 1989b
Abdou et al. 1988
Aqueous humic acid suspension at

253.7 nm
Aqueous H2O2 at >285 nm or Fentons reagent
Aqueous H2O2 at >285 nm
O3 (85200 ppb) at >290 nm
Clay aqueous suspension at >320
nm
Aqueous Fe(ClO4)3 with sunlight
Aqueous semiconductor suspension at >340 nm
Fentons reagent, N2
Aguer and Richard 1996b
Electric discharge, hexane

Electric discharge, hexane
Laboratory ozonizer (30300 ppb)
Micro-ozonizer
Laboratory ozonizer (85200 ppb)
Ruzo et al. 1982

Ruzo et al. 1982
Spencer et al. 1980
Gunther et al. 1970
Kromer et al. 1999
Draper and Crosby

Draper and Crosby
Draper and Crosby
Draper and Crosby
Kromer et al. 1999
Katagi 1990
1981
1984
1984
1984
Sanlaville et al. 1996

Larson et al. 1991
Pelizzetti et al. 1993
Katagi 1992
Eggplant
N.R.
53
Tomato
16 21/CHCl3 3050
[C29,31]
40
[C24,26,28]
Grape
N.R./light
petroleum
1
[C25,27,29,31]
15.0
[C24,26,28]
Lemon
20 40/CHCl3 22.9
[C29,31]
10.2
[C28]
3.2
ALC
12.0
[C24,26,28]
18.9
[C29]
18.2
HC
Orange
30 50/CHCl3 40.1
[C27,29,31]
Apple
989/CHCl3
<Fruits>
Marsh grapefruit
-/CHCl3
Plant species
Quantitya/Extractb
12
[C24,26,28]
43.4
[C24,26,28,30]
28.5
[C24,26,28]
34.7
ALD
47
<0.5
7
[C20,24,26]
18.7
[C24,28,30,32]
19.3
[C26,28,30,32]
69.8
[ursolic]
AC
18
[C46]
ES
Composition (% of wax) (major homologue)
Table 5. Composition of soluble cuticular waxes of fruits and leaves.
30 50 (amyrin)
5 30 (naringenin)
0.8 (ketones)
43.9 (terpenoid)
Others
Baker et al. 1975
Baker et al. 1982
Radler and Horn 1965
Baker et al. 1975
Baker et al. 1975
Belding et al. 1998
McDonald et al. 1993
Reference
89
6 27
[C29,31,33]
HC
Barley
16.1/CHCl3
1.0
[C29,31,33]
Peach
40 69/CHCl3 10
[C25,27,29,31]
Tea crabapple
30
38/CHCl3
ether (1/1)
[C29,31]
Cherry
5
24/CHCl3
ether (1/1)
[C29,31]
Grape
10
12/CHCl3
ether (1/1)
[C29,31]
Rice
60
0.426/CHCl3
[C33]
Oat
9 21/CHCl3 0.3 6.6
<Leaves>
Bitter orange
9.8/CHCl3
Plant species
Quantitya/Extractb
10
[C26,28]
80
[C26,28]
39 65
[C26]
ALD
7.0
[C26]
20
[C26,28,30]
82
[C26]
20
[C26,28,30,32]
31 55
[C26,32,34]
ALC
1.7
[C16,18,26]
2.9 4.9
<5
[C16,18]
70
[ursolic]
30
[ursolic]
20
[ursolic]
18 31
[C16,18]
AC
6.1
[C42,44,46,48]
5
[C42,44,46,48,50]
<5
[C42,44,46]
5
[C40,42,44]
20 30
[C48,50,52]
13 35
[C40,42]
ES
7
(-diketones)
Trace
(C29,31 ketones)
10 (-amyrin)
10 20 (sterol)
Others
Larsson and Svenningsson 1986

Svenningsson 1988
Bengston et al. 1978
OToole et al. 1979
Baker and Hunt 1981
Baker and Hunt 1981
Baker and Hunt 1981
Bukovac et al. 1979

Baker et al. 1979
Haas and Schonherr 1979
Reference
90
T. Katagi
Spinach
5 10/N.R.
5
[C29,31]
50
[C30]
24.5
[C1834]
>60
70
[C22,24,26]
80
[C26]
14
[C26,28,30,32]
59.4
[C32]
ALC
5
[C26,28,30]
8.6
[C2228]
9
[C28,30,32]
19.5
[C32]
ALD
<5
2.2
[C1834]
<5
[C16]
14
[C26,28,30]
4.8
[C24]
AC
20
[C42,44,46,48]
19.6
[C42,44]
10
[C38,40,42,44]
10
[C44,50]
42
[C44,46]
12.8
[C56]
ES
5.9 (C23,25 ketones)
5
(-sitosterols)
Trace
(triterpenoids)
4 (sterols)
Others
Baker and Hunt 1981
Sen 1987
Baker 1982
Baker and Hunt 1981
Baker and Hunt 1981
Avato et al. 1990
Barta and Komives 1984
Reference
in g cm2. bOrganic solvent used for extraction. or N.R.: not reported. Composition: HC: hydrocarbon; ALC: alcohol; ALD: aldehyde; AC: acid;
ES: ester.
White clover
16/CHCl3
ether (1/1)
39.0
[C27,29,31]
<5
[C29,31,33]
Sugar beet
3.9/CHCl3
ether (1/1)
Potato
5.4/CHCl3
5
[C29,31,33]
17
[C29,31,33]
3.5
[C31]
HC
Dwarf bean
0.9/CHCl3
ether (1/1)
Maize
N.R./CHCl3
Corn
N.R./CHCl3
Plant species
Quantitya/Extractb
91
92
T. Katagi
Table 6. Diffusion coefficients.

No.
Chemicals
Soil and clay

1 2,4-D
Mediuma
MCb pH OMb C
Db
Reference
Silt loam
(3/69/28)
32.5
6.4 7.1
23 6.33
Scott and Phillips

1973
33 Propachlor
Silt loam
(15/70/15)
23
7.3 2
27 2.28
Ritter et al. 1973
50 Diphenamid
Silt loam
(3/69/28)
38
6.4 7.1
24 2.59
Scott and Phillips

1972
55 Flumeturon
Silt loam
(3/69/28)
32.5
6.4 7.1
23 2.17
Scott and Phillips

1973
25
6.4 7.1
24 6.22
Scott and Phillips

1972
0.58 30 1.57
80 Chlorpropham Silt loam

(3/69/28)
114 Lindane
Silt loam
(//18)
10
123 Dieldrin
Clay loam
(14/19/67)
53RH 7.8 0.2
20 0.051
135 Parathion
Silt loam
(//20)
0.5
25 0.62.9 Gerstl et al. 1979
144 Diazinon
Silt loam
(15/70/15)
23
7.3 2
27 0.48
163 Disulfoton
Silt loam
(//18)
32.8
7.8 2.7* 20 0.13
Graham-Bryce
1969
165 Dimethoate
Silt loam
(//18)
32.8
7.8 2.7* 20 4.94
Graham-Bryce
1969
185 Atrazine
Silt loam
(15/70/15)
Silt loam
(3/69/28)
23
7.3 2
27 1.37
Ritter et al. 1973
38
6.4 7.1
24 3.70
Scott and Phillips

1972
186 Simazine
Silt loam
(3/69/28)
38
6.4 7.1
24 3.28
Scott and Phillips

1972
187 Prometone
Silt loam
(3/69/28)
38
6.4 7.1
24 7.69
Scott and Phillips

1972
194 Triticonazole
Loam clay
(15/54/29)
8.2 1.0
22 3.0
Beigel et al. 1997
232 Trifluralin
Silt loam
(17/66/17)
Silt loam
(3/69/28)
Kaolinite clay
30.4
6.7 4.8
22 0.20
38
6.4 7.1
24 0.52
Jacques and
Harvey 1979
Scott and Phillips
1972
Balmer et al. 2000
Silt loam
(17/66/17)
30.4
6.7 4.8
22 0.05
Jacques and
Harvey 1979
(941/16
67/1051)
727
25 0.87
Sadeghi et al.
1989
235 Oryzalin
Urea
28 0.003
Ehlers et al. 1969a

Farmer and Jensen
1970
Ritter et al. 1973
93
No.
Chemicals
PEG4000
Mediuma
Sandy loam
(38/47/15)
p-Nitroanisole Kaolinite
Waxes and cuticles
1 2,4-D
Barley waxes
Isolated citrus
cuticles
MCb pH OMb C
3050 2.5
Db
Reference
25 0.31.6 Barraclough and

Nye 1979
28 0.0069
Balmer et al. 2000
25 1 106 Schreiber and

Schonherr 1993
3 104 Schonherr and
Riederer 1989
Schonherr 1993
121 Pentachloropenol
Barley waxes
185 Atrazine
Isolated citrus
cuticles
189 Triadimenol
Barley waxes

Schonherr 1993
Water
23 51.8
Water
Eight
pesticides
aMedium:
9 105 Schonherr and

Riederer 1989
Scott and Phillips

1973
values in the parentheses are weight % of sand, silt, and clay in soil.
soil moisture content in %; RH: relative humidity; OM: soil organic matter content in % (*,
soil organic carbon content); D: apparent diffusion coefficient in mm2 day1.
bMC:
94
T. Katagi
Table 7. Photodegradation of pesticides on glass and silica gel surfaces.
No.
Pesticide
Carrier (Label),
App DT50
(light/dark)
Light source
(wavelength or
season, filter)
Reference
1 2,4-D
GL(14C)
N.R.
UV fluorescent lamp
(max. 356 nm)
Venkatesh and
Harrison 1999
3 MCPA
GL, 6 103
2.5 d/N.R.
Sunlight (summer)
Crosby and Bowers 1985
GL (14C), 2.6
<5 hr/>32 hr
GL, 300
N.R.
275W G.E. sunlamp
Chen and Casida

1969
Kimmel et al. 1982
10 Allethrin
GL, 4 103
N.R.
13 Phenothrin
RPR 3500 UV lamp

(> 290 nm, Pyrex
glass)
15W Fluorescence
lamp
Isobe et al. 1984
GL, 100300
N.R.
GL (10EC), 30
1000
3 hr/N.R.
Sunlight (Sept.)
Ruzo et al. 1982
Sunlight (summer)
Samsonov and
Makarov 1996
14 Cyphenothrin
SG (14C)
2 hr/N.R.
RPR 3500A UV lamp

(max. 360 nm)
Dureja et al. 1984
15 Resmethrin
SG (14C), 1017
N.R.
Sunlight
Ueda et al. 1974
16 Kadethrin
GL (14C), 35
N.R.
Sunlight
Ohsawa and
Casida 1979
22 Deltamethrin
GL (14C), 40
N.R.
Sunlight
Ruzo et al. 1977
23 Tetramethrin
GL (14C), 2.6
<5 hr/>32 hr
GL, 100300
N.R.
275W G.E. sunlamp
Chen and Casida

1969
Ruzo et al. 1982
25 Tralomethrin
GL (14C), 100
N.R.
Sunlight
Ruzo and Casida

1981
26 Tralocythrin
GL (14C), 100
N.R.
Sunlight
Ruzo and Casida

1981
27 Fenvalerate
GL, 127
4d
Sunlight (JulyAug.,
Pyrex glass)
Holmstead et al.
1978b
29 Flucythrinate
GL
11.8 hr/N.R.
UV light in a Rayonet
reactor
Chattopadhyaya
and Dureja 1991
30 Fulvalinate
GL (14C), 24
1 d/N.R.
Sunlight, outdoors
Quinstad and
Staiger 1984
Sunlight (Sept.)
95
No.
Pesticide
Carrier (Label),
App DT50
(light/dark)
31 Acrinathrin
GL, 0.310
32 Etofenprox
GL, 14
1.7 d
2.7 hr/N.R.
GL, 140
1.94 hr
Light source
(wavelength or
season, filter)
Reference
500 W high-pressure
Hg lamp
(313 nm, glass filter)
Samsonov and
Pokrovskii 2001
RPR 3000 UV lamp

(290320 nm, Pyrex
glass)
GL10 UV lamp (254
nm)
Class et al. 1989
Tsao and Eto

1990b
34 Alachlor
GL
6 hr/N.R.
Sunlight (Mar.Apr.)
Fang 1977
36 Butachlor
GL
1.5 hr/N.R.
Germicidal lamp (254

nm)
Chen and Chen

1978
38 Mepronil
SG (14C)
36 d/N.R.
SG, 25
N.R.
Sunlight (Sept.Dec.)
Yumita and Yamamoto 1982

Yumita et al. 1984
400W high-pressure
Hg lamp (max. 365
nm)
39 Flutolanil
GL, 2.5 103

N.R.
Germicidal UV lamp
(254 nm)
Tsao and Eto 1991
40 Niclosamide
SG (14C)
20.5 hr/>7 d
Long-wave lamp
(290405 nm)
Schultz and Harman 1978
41 Naproanilide
GL
N.R.
UV germicidal GL10
lamp (>254 nm)
Tsao and Eto

1990a
42 Carboxin
GL
10 hr/N.R.
Sunlight
Buchenauer 1975
46 Isoxaben
SG
N.R.
Xenon lamp (Hereaus

Suntest)
Mamouni et al.
1992
57 Diafenthiuron
TF
1 hr/N.R.
UV light
Drabek et al. 1992
RUL 3000 lamp (max.

300 nm)
Sunlight (summer)
Ruzo et al. 1974
59 Diflubenzuron GL, SG
N.R.
SG(14C), 4.0
4 wk/N.R.
Bull and Ivie 1976
66 Aminocarb
SG (14C), 400
N.R.
UV light at 253.7 nm
Abdel-Wahab and
Casida 1967
67 Mexacarbate
SG (14C, 3H), 400

N.R.
UV light at 253.7 nm
Abdel-Wahab and
Casida 1967
96
T. Katagi
No.
Pesticide
78 Pirimicarb
Carrier (Label),
App DT50
(light/dark)
GL
64 min
CE, 0.03
19 min
Light source
(wavelength or
season, filter)
Reference
125W high-pressure
Hg lamp (> 290
nm, Pyrex glass)
Sunlight (Feb.), outdoors
Pirisi et al. 1996
84 Phenmedipham
SG
15 d/144 d
UV light from Xe
lamp (Heraeus suntest)
Schafmeier et al.
1998
85 Fenothiocarb
SG (14C)
45 hr/N.R.
Sunlight (Sept.Oct.)
Unai and Tomizawa 1986
86 Benthiocarb
GL (14C)
1.7 hr/N.R.
Ishikawa et al.
1977
GL (14C), 1 104
N.R.
High-pressure Hg
lamp (max. 365
nm)
Sunlight (3.54.5 mW
cm2)
89 Benfuracarb
GL
N.R.
Low-pressure Hg
lamp (254 nm)
Dureja et al. 1990
91 Cartap
GL, 12.7
N.R.

nm)
Tsao and Eto 1989
92 Thiophanatemethyl
GL (14C), 33
2.8 d/N.R.
Sunlight (MayAug.),
outdoors
Soeda et al. 1972
93 MBC
SG (3T,14C), 5.5
N.R.
Sunlight (July)
Fleeker and Lacy

1977
96 Chlorsulfuron
SG
60 hr/N.R.
125W high-pressure
Hg lamp (>290 nm,
borosilicate glass)
Herrmann et al.
1985
99 Tribenuronmethyl
GL
7 d or 11 hr/N.R.
Sunlight (May) or UV
light (max. 254 nm)
Bhattacharjee and
Dureja 2002
GL (14C), 6.6
500 W Xenon arc

lamp
Sumida et al. 1973
113 DDOD
Cheng and Hwang

1996
8 d/>20 d
121 Pentachlorophenol
GL, 1 103
N.R.
125 W high-pressure
Hg lamp (>290 nm,
water filter)
Piccinini et al.
1998
122 Aldrin
GL
N.R.
SG
N.R.
Sunlight (JuneJuly)
Rosen and Sutherland 1967

Gab et al. 1975a
125 W high-pressure
Hg lamp (>290 nm,
Pyrex glass)
97
No.
Pesticide
Carrier (Label),
App DT50
(light/dark)
Light source
(wavelength or
season, filter)
Reference
123 Dieldrin
GL
1 hr/N.R.
GE G30T8 germicidal
lamp
Benson 1971
125 Endosulfan
GL
N.R.
Sunlight (Mar.)
Dureja and Mukerjee 1982
128 Chlordane
GL, 890
N.R.
SG
N.R.
Sunlight (summer)
Benson et al. 1971
125 W high-pressure
Hg lamp (>290 nm,
Pyrex glass)
Gab et al. 1975a
130 DDT
GL (14C)
N.R.
15W germicidal lamp

(254 nm)
Mosier et al. 1969
136 Parathionmethyl
GL (14C), 0.84
1 d/>1 d
Xe lamp in Suntest
CPS+ (>290 nm,
volatility chamber)
Kromer et al. 1999
137 Cyanophos
SG (14C)
4 d/N.R.
Sunlight (Sept.Oct.),
outdoors
Mikami et al. 1976
138 Fenitrothion
SG (14C)
15 min6 d/N.R.
172.5 W high-pressure
Hg lamp or sunlight
(Nov.)
Ohkawa et al.
1974b
141 Iodofenphos
GL
N.R.
1 kW metal halide
lamp (Applied Photophysics 9500)
Walia et al. 1989b
143 Fenthion
GL
0.021.34 hr/N.R.
Fluorescent lamp
(380750 nm), UV
light (UV-A, UV-B,
UV-C)
Hirahara et al.
2001
145 Chlorpyrifos
GL
18.7 d/N.R.
FP (14C), 1.18
3.2 d/N.R.
GL
N.R.
Low-pressure Hg
lamp (254 nm)
UV light (Pyrex glass)
Walia et al. 1988
148 Quinalphos
Meikle et al. 1983
Low-pressure UV
lamp (254 nm)
Dureja et al. 1988
150 Pyridafenthion GL, 6.4

N.R.
Black light fluorescence lamp (>300

nm)
Tsao et al. 1989
152 Phoxim
UV light (254 nm &

350 nm, uncovered
Petri dish)
Makary et al. 1981
GL
419 hr/N.R.
98
T. Katagi
No.
Pesticide
Carrier (Label),
App DT50
(light/dark)
Light source
(wavelength or
season, filter)
Reference
156 Monocrotophos
GL (32P)
5.5 d/N.R.
GL, 1.6
N.R.
Sunlight in a greenhouse.
15W germicidal lamp
(253.7 nm) or sunlight (Apr.May)
Lindquist and Bull

1967
Dureja 1989
159 Propaphos
SG, GL (14C)
1.2 hr/>72 hr
Sunlight (Apr.Aug.)
Fujii et al. 1979
161 Sulprofos
GL (14C), 53
1.1 d/N.R.
GL
5 hr/>13 hr
Sunlight (summer)
Ivie and Bull 1976

nm)
Sharma and Gupta

1994
162 Phorate
163 Disulfoton
GL
0.4143.3 hr/N.R.
Fluorescent lamp
(380750 nm), UV
light (UV-A, UV-B,
UV-C)
Hirahara et al.
2001
165 Dimethoate
GL (32P)
N.R.
Sunlight in a greenhouse.
Dauterman et al.
1960
167 Malathion
GL (F)
N.R.
UV (253.7 nm) or
fluorescent (366
nm) light
Awad et al. 1967
168 Phenthoate
GL (14C,32P)
<3 d/N.R.
SG (14C)
4 d/>8 d
Sunlight (Mar. &

Sept.)
outdoors
Takade et al. 1976
170 Phosalone
GL
8.5 d/>15 d
1 kW high-pressure
metal-halide lamp
(>300 nm)
Walia et al. 1989a
173 Edifenphos
GL (32P), 5.0
10 d/N.R.
UV light
Ishizuka et al.
1973
175 Isofenphos
GL
N.R.
Low-pressure Hg
lamp
Dureja et al. 1989
176 S-2571
SG (3T), 300
N.R.
172.5W high-pressure
Hg lamp
Mikami et al.
1977a
outdoors
Mikami et al.1976
UV light (310 nm)
Zayed et al. 1978
Sunlight
Riskallah et al.
1979
180 Cyanofenphos SG (14C)

2 d/N.R.
181 Leptophos
SG (32P)
3.4 d/N.R.
GL, 100
20 d/N.R.
Mikami et al.
1977b
99
No.
Pesticide
Carrier (Label),
App DT50
(light/dark)
Light source
(wavelength or
season, filter)
Reference
183 Dioxabenzofos
SG (14C)
2 d/>8 d
outdoors
Mikami et al.
1977b
188 Triadimefon
GL, 32
1.32.8 hr/N.R.
UV light (254 nm) or

sunlight (Sept.)
Nag and Dureja

1996
189 Triadimenol
GL, 51
N.R.
400 W medium-presClark and Watkins

sure Hg lamp (boro1986
silicate glass)
190 Diniconazole- GL, 50

M
N.R.
Sunlight (June)
Sharma and Chibber 1997
191 Propiconazole GL, 147

N.R.
195 Fluotrimazole GL, 13-50
N.R.
Sunlight
Dureja et al. 1987a
100 W medium-presClark et al. 1983

sure Hg lamp (borosilicate) or summer
sunlight
GL (14C)
>5 d/N.R.
UV lamps (300 & 350

nm)
Nilles and Zabik

1975
204 Isoprothiolane SG
3 hr/N.R.
10 W germicidal lamp
(254 nm)
Chou et al. 1980
206 Perfluidone
GL, 33.6
36 wk/N.R.
UV light (254 or 365

nm)
Ketchersid and
Merkle 1975
207 Chlordimeform
SG (14C)
N.R.
Sunlight
Knowles and Sen

Gupta 1969
212 Thiabendazole GL (14C), 19

>4 mon/N.R.
Sunlight in a greenhouse
Jacob et al. 1975
220 Fipronil
SG, GL, FP
N.R.
Sunlight
Hainzl and Casida

1996
222 Buprofezin
GL
15 d/N.R.
Sunlight (Feb.Mar.)
Datta and Walia

1997
223 Sethoxydim
GL (14C)
<1 hr/N.R.
Sunlight in a greenhouse (350 E m2

sec1)
Campbell and Penner 1985a
224 Alloxydim
SG (14C)
0.7, 4.4 hr/ N.R.
12W UV light (253.7

or 365 nm)
Soeda et al. 1979
226 Diquat
SG (14C)
N.R.
Sunlight (May June),

outdoors
Smith and Grove

1969
232 Trifluralin
GL
N.R.
Sunlight (JuneJuly)
Wright and Warren

1965
200 Bentazone
100
T. Katagi
No.
Pesticide
236 Fluchloralin
Carrier (Label),
App DT50
(light/dark)
GL (14C)
48 hr/N.R.
SG (14C)
N.R.
238 Pendimethalin GL
N.R.
Light source
(wavelength or
season, filter)
RPR UV light (300 &
350 nm, Pyrex
glass)
Reference
Nilles and Zabik
1974
Sunlight (Aug.Oct.)
Low-pressure Hg
lamp (254 nm)
Dureja and Walia

1989
241 Fentin acetate
SG (14C)
N.R.
125W high-pressure
Hg lamp (max. 365
nm)
Barns et al. 1973
245 Guazatine
GL (14C), 0.5
36 hr/N.R.
Sunlight lamp (950

E m2 sec1)
Sato et al. 1985b
246 Methoprene
GL (14C), 11
6 hr/N.R.
Sunlight (Oct.)
Quinstad et al.
1975
249 Cinmethylin
GL, 2 103
N.R.
1 kW Xe lamp (Oriel
solar simulator,
AM1 filter)
Grayson et al.
1987
250 Avermectin
B1a
GL, 0.7
23 hr/N.R.
Sunlight
Crouch et al. 1991
251 MAB1a
GL, 0.7
6.2 hr/N.R.
275 W Suntanner RS
bulb (6070 mW
cm2 h1)
Feely et al. 1992
253 AzadirachtinA
GL
48 min/N.R.
UV light (254 nm)
Dureja and Johnson 2000
Medium: Thin film of a pesticide is basically prepared from its organic solution followed by vaporization of solvent. When unspecified, nonradiolabeled pesticide was used.
F, formulation. Materials of carrier are glass (GL), silica gel (SG), filter paper (FP), cellulose
sheet (CE), and Teflon sheet (TF). Label, radiolabel; App, application rate in g cm2 if described
in the literature; N.R., not reported.
101
Table 8. Photodegradation of pesticides in organic solvent as model plant cuticles.
No.
Pesticide
Medium
DT50
Light source
(wavelength or
season, UV filter)
Reference
17 Permethrin
Methanol
11.5 hr
RPR 3000 lamp

(290320 nm)
Holmstead et al.
1978a
21 Cyhalothrin
Cyclohexane
N.R.
RPR 3000 UV lamp

(290320 nm,
Pyrex glass)
Ruzo et al. 1987
22 Deltamethrin
Hexane
2 days
Summer sunlight
(Pyrex glass, outdoors)
Sunlight
Maguire 1990
Hexane
N.R.
Ruzo et al. 1977
27 Fenvalerate
Hexane
18 min
RPR 3000 UV lamp

(290320 nm,
Pyrex glass)
Holmstead et al.
1978b
32 Etofenprox
Methanol
5.8 days
RPR 3000 UV lamp

(290320 nm,
Pyrex glass)
Class et al. 1989
59 Diflubenzuron
Methanol
N.R.
RUL 3000 lamp

Ruzo et al. 1974
(>285 nm, borosilicate glass)
63 Xylylcarb
Ethanol
22.6 hr
UV light (>265 nm)
64 Trimethacarb
Cyclohexane
N.R.
1 kW Xe-Hg lamp
Addison et al.
(>300 nm, Corning
1974
0-54 filter)
65 Propoxur
Organic solvents
1239 hr
150 W Hg lamp
Schwack and Kopf
(>280 nm, WG295
1992
filter)
66 Aminocarb
Cyclohexane
N.R.
1 kW Xe-Hg lamp
Addison et al.
(>300 nm, Corning
1974
0-54 filter)
UV light (>265 nm) Kumar et al. 1974
Ethanol
16.4 hr
Kumar et al. 1974
69 Ethiofencarb
Organic solvents
1.35.5 hr
150 W Hg lamp
Kopf and Schwack
(>280 nm, WG295
1995
filter)
78 Pirimicarb
Organic solvents
60140 min
150 W Hg lamp
Schwack and Kopf
(>280 nm, WG295
1993
filter)
96 Chlorsulfuron
Methanol
6.3 hr
20W low-pressure
Hg lamp
Yang et al. 1999
102
T. Katagi
No.
Pesticide
Medium
DT50
Light source
(wavelength or
season, UV filter)
Reference
98 Metsulfuron
methyl
Methanol
1.8 hr
20W low-pressure
Hg lamp
Yang et al. 1999
99 Tribenuron
methyl
2-Propanol
1.7 hr
125W mediumpressure Hg lamp
Bhattacharjee and
Dureja 1999
102 Chlorimuronethyl
Hexane
55.8 min
125W Mediumpressure Hg lamp

(Pyrex glass)
Choudhury and
Dureja 1997b
106 Captan
Organic solvents
37420 min
150W Hg lamp
(>280nm, WG295
filter)
Schwack and
Floer-Muller
1990
107 Folpet
Cyclohexene
N.R.
150W Hg lamp
Schwack 1990
(WG295, 305, 320,
335 & 345 filters)
108 Procymidone
Organic solvents
N.R.
150W Hg lamp
(>280nm, WG295
filter)
Schwack et al.
1995b
109 Iprodione
Organic solvents
N.R.
150W Hg lamp
(>280nm, WG295
filter)
Schwack et al.
1995a
110 Vinclozolin
Organic solvents
N.R.
150W Hg lamp
(>280nm, WG295
filter)
Schwack et al.
1995c
125 Endosulfan
Hexane
N.R.
High-pressure Hg
lamp (>300 nm)
130 DDT
Methyl oleate
N.R.
150W Hg lamp
(>280 nm)
Schwack 1988
134 Methoxychlor
Methyl oleate
N.R.
150W Hg lamp
(>280 nm)
Schwack 1988
135 Parathion
12-Hydroxystearate/TL
N.R.
2-Propanol
N.R.
UV-B Fluorescent
Schwack et al.
sunlamp (max, 315
1994
nm)
1kW Tungstenhalogen lamp
(>280 nm)
150W Hg lamp
Schwack 1987
(>280 nm, WG295
filter)
Cyclohexene
N.R.
138 Fenitrothion
Hexane
85 min
Low-pressure u.v.
Pen Ray lamp
(253.7 nm)
Greenhalgh and
Marshall 1976
103
No.
Pesticide
Medium
DT50
Light source
(wavelength or
season, UV filter)
Reference
Methanol
120 min
Low-pressure u.v.
Pen Ray lamp
(253.7 nm)
141 Iodofenphos
Hexane
N.R.
1 kW Metal halide
lamp (Applied
Photophysics
9500)
Walia et al. 1989b
145 Chlorpyrifos
Hexane
N.R.
High-pressure Hg
lamp
Walia et al. 1988
154 Tetrachlovinphos Hexane

4.5 hr
Medium-pressure Hg Dureja et al. 1987b

lamp
170 Phosalone
Hexane
N.R.
125 W High-pressure Walia et al. 1989a

Hg lamp (254360
nm)
188 Triadimefon
Methanol
N.R.
192 Hexaconazole
Hexane
23.1 hr
125 W Hg lamp,
Pyrex
Santoro et al. 2000
193 Penconazole
Organic solvents
523 hr
Tungsten halogen
lamp (WG305 or
WG320 filter)
Schwack and Hartmann 1994
195 Fluotrimazole
Methanol
N.R.
100 W mediumClark et al. 1983

pressure Hg lamp
(borosilicate glass)
211 Anilazine
Methyl oleate
N.R.
Cyclohexene
8.0 or 15.0 min
Metal halogen lamp

(WG295 filter)
Metal halogen lamp
(WG295 or WG
320 filter)
220 Fipronil
Methanol
N.R.
UV light (max. 300

Hainzl and Casida
nm, cutoff of 280
1996
290 nm)
228 Chinomethionat
Unsat. fatty acids/ Fluorescent black

TL
light
N.R.
400 W MediumClark et al. 1978

pressure Hg lamp
(borosilicate glass)
Hexane, methanol 125 W mediumNag and Dureja
2.52.8 hr
pressure Hg lamp
1997
N.R.: not reported; TL, as a thin layer.
Breithaupt and
Schwack 2000
Nutahara and
Murai 1984
104
T. Katagi
Table 9. Photodegradation of pesticides in plant waxes and cuticles.
No.
Pesticide
Wax (W),
Cuticle (C)
DT50
Light source
(wavelength, filter)
Reference
66 Aminocarb
Nectarine fruits W. 125 W Hg lamp (>290

59 min
nm, borosilicate glass)
Pirisi et al. 2001
68 Methiocarb

436 min
Pirisi et al. 2001
78 Primicarb
Nectarine fruits W.
222 min
Fruits W.
35449 min
Fruits W.
15331 min
117 Chlorothalonil Tomato fruits C.
N.R.
125 W Hg lamp (>290

125 W Hg lamp (>290
Sunlight
(MayJune, 39 N)
Simulated sunlight
(Suntest CPS+)
129 2,3,7,8-TCDD
Laurel cherry W.
49 hr
Sunlight and 300 W

high-pressure Hg
lamps
Schuler et al.
1998
135 Parathion
Fruits C.
2.113.5 hr
UV-fluorescent sunlamp
(max, 315 nm)
Schynowski and
Schwack 1996
143 Fenthion

204 min
Pirisi et al. 2001
Fruits W.
2.411.9 hr
Cabras et al.
1997b
N.R., not reported.
Sunlight
Pirisi et al. 2001

Pirisi et al. 1998
Jahn et al. 1999
#
2,4-D
Mecoprop
Triclopyr
Permethrin
Tefluthrin
Cypermethrin
17
18
19
Pesticide
Light source (wavelength or

season, filter), temp (C)
Four soils (-/4.4 7.6/-), 30 m, 33 g cm2

Acetone soln.
450W Medium-pressure
3.3 7.8 d/N.R.
Hg lamp (Pyrex glass)
Three soils (1.4 2.1/-/-), 1 mm, 0.125 g cm2
Methanol soln.
Sunlight (Oct.), outdoors
10 15 d/N.R.
Silty clay loam soils, field (1 5/-/-), -, 34 g cm2
Formulation
Sunlight
75 81 d/N.R.
Dunkirk silt loam soil (2.6/6.0/-), 0.25 mm, 0.02 g cm2
14C, N.R.
Sunlight
N.R.
Loam soil (5.0/6.5/-), -, 600 g ha1
14C, N.R.
Xe lamp (4.5 hr d1)
>31 d/N.R. 25C
Three Japanese soils (2 15/5 6/1 12), 0.5mm, 1.1g cm2
14C, diethyl ether soln.
Sunlight (Aug.), outdoors
0.6 1.9 d/>7 d
Sandy loam soil (1.8/6.9/-), -, 14C, N.R.
Sunlight
56 d/76 100 d
Application mediumb)
DT50 (light/dark)
Soil properties and application ratea)
Table 10. Photodegradation of pesticides in and on soil (clay) thin-layer surfaces.
EPA FIFRA 1999
Takahashi et al. 1985a
EPA FIFRA 1999
Holmstead et al. 1978a
Norris et al. 1987
Romero et al. 1998
Hautala 1978
Reference
105
#
Cyfluthrin
Cyhalothrin
Deltamethrin
Fenpropathrin
Fenvalerate
Esfenvalerate
20
21
22
24
27
28
Pesticide

Sandy loam soil (2.2/5.4/-), -, N.R.

Sunlight
5.3 d/97.9 d
Richvale, MSF and Kracaws types (N.R.), -, 50 g cm2
Hexane soln.
Sunlight (Jun.)
N.R.
Loam soil (5.0/6.5/-), -, 40 g ha1
14C, N.R.
Artificial light, 25C
>166 hr/N.R.
N.R.
14C, N.R.
Xe lamp, continuous
9 d/10 11 d
Kodaira light clay soil (15/5.5/11), 0.5 mm, 1.1 g cm2
Sunlight (Sept.), outdoors
1 d/>2 wk
Three Japanese soils (2 8/5.7 6.6/4 17), 1 mm, 10 ppm
14C, acetonitrile soln.
500W Xe lamp (>290 nm,
3 51 d/4 160 d
Pyrex glass), 25C
Three Japanese soils (2 15/5 6/4 12), 0.5mm, 0.6g cm2
14C, diethyl ether
Sunlight (Sept.), outdoors
1.8 18 d/>20 d
Noichi sandy clay loam soil (1.4/5.7/3.7), 2 mm, 10 ppm
14C, 1,2-dichloroethane
500W Xe lamp (>300 nm,
100 d/138 d
Pyrex glass), 25C
14C,
DT50 (light/dark)
Katagi 1991
Mikami et al. 1980
Katagi 1993b
Takahashi et al. 1985b
EPA FIFRA 1999
EPA FIFRA 1999
Ruzo et al. 1987
EPA FIFRA 1999
Reference
106
T. Katagi
#
Flucythrinate
Fluvalinate
Propachlor
Alachlor
Metolachlor
Metalaxyl
Niclosamide
29
30
33
34
35
37
40
Pesticide

Four soils (0.3 0.5/6 8.4/-), 5 mm, 7 mg cm2

Diethyl ether soln.
Sunlight (at 300 400 nm,
1 2 d/>5 d
1.6mW)
Sterilized sandy loam soil (N.R.), 3 5 mm, 1.3 g cm2
14C, N.R.
Sunlight, outdoors
1 d/N.R.
Three soils (0.9 3.5/7.0 7.5/-), 1 mm, 5 20 ppm
Methanol soln.
Sunlight (Jul.)
14 32 d/N.R.
Three Taiwan soils (1.5 2.6/5.0 6.4/-), -, 100 ppm
Acetone soln.
Sunlight (Mar. Apr.),
>8 hr/N.R.
30 35C
Silt loam soil (N.R.), -, 5.15 hg ha1
N.R.
Sunlight, 50 55C
8 d/N.R.
Four soils (0.2 4.6/5 7/60%MWHC), 5 mm, 0.5 g cm2
Aqueous soln.
Xenon lamp (>285 nm) ,25C
8 21 d/36 73 d
Two soils (0.86 1.0/6.1 7.4/-) , -, 500 ppm
N.R.
Sunlight
7.7 d/N.R.
Loamy sand soil (-/5.4/dry or 75%FMC), 2mm, 2.5ppm
Xe lamp (>290 nm,
7 14 d/18 d
Heraeus suntest), 25C
DT50 (light/dark)
Frank et al. 2002

Graebing et al. 2002
Saha and Sukul 1997
Sukul and Spiteller 2001
Chesters et al. 1989
Fang 1977
Konstantinou et al. 2001
Quinstad and Staiger 1984
Dureja and Chattopadhyay 1995
Reference
107
#
Carboxin
Napropamide
Florasulam
Monuron
Diuron
Linuron
Isoproturon
Thidiazuron
42
47
48
52
53
54
56
58
Pesticide

Scheyern soil (N.R.), 2 mm, 5 ppm

N.R.
Xe lamp (>290 nm,
29 hr/N.R.
Heraeus suntest),18C
Two soils (0.3 1.7/7.3 7.9/-), -, CH2Cl2 soln.
Sunlight
3 7 d/N.R.
Caltin silt loam soil (2.9/6.8/dry), -, 0.13 0.32 ppm
14C,
N.R. Sunlight (May Jun.)
30 d/79 d
Sand/montmorillonite and kaolinite clays, -, Diethyl ether soln.
GL20 fluorescent lamp
N.R.
(>300 nm, glass filter)
Sand/montmorillonite and kaolinite clays, -, Diethyl ether soln.
GL20 fluorescent lamp
20 100 hr/N.R.
(>300 nm, glass filter)
Silt loam soil (N.R.), -, 14C, N.R.
Xe lamp (Pyrex glass),
>15 d/N.R.
25C
Sandy loam soil (0.35/7.2/-), -, 2.5 mg/g of soil
N.R.
Low-pressure Hg lamp
N.R.
Speyer soil 2.3 (1.2/5.5/1.5), 0.5 mm, 1.5 g cm2
14C, methanol soln.
2.5kW Xe lamp (>290 nm,
0.5 hr/51 hr
WG295+Duran filter), <30C
DT50 (light/dark)
Klehr et al. 1983
Kulshrestha and Mukerjee 1986
EPA OPPTS 1995d
Jirkovsky et al. 1997
Jirkovsky et al. 1997
Krieger et al. 2000
Donaldson and Miller 1996
Murthy et al. 1998
Reference
108
T. Katagi
#
Diflubenzuron
Propoxur
Methiocarb
Carbofuran
Benomyl
Asulam
Desmedipham
Phenmedipham
59
65
68
72
81
82
83
84
Pesticide
N.R.

N.R.
Artificial light
11.3 d/3.7 d
Two soils (1.0 1.5/5.3 7.1/-), -, 0.4 0.6 ppm
14C, methanol
Medium-pressure Hg lamp
>1 d/ 200d
(>290 nm, TQ150 filter)
Four soils (4.5 7.5/5.8 6.3/dry), -, CH2Cl2soln.
Sunlight (Jun. Aug.,
7 14 d/N.R.
Kimax glass), outdoors
Orange glove soil (N.R.), -, 44.8 g cm2
2.5EC as (49)
Sunlight
N.R.
Silt loam soil (N.R.), -, 1 lb acre1
14C, N.R.
Sunlight at 25C
< 4 d/N.R.
Sandy loam soil (N.R.), -, 14C, N.R.
Xe lamp, 25 28C.
1.5 hr/83 hr
Xe lamp (3-fold irradiation
110 160 hr/>500 hr
of summer noon sunlight)
Metapunto soil (4.8/7.4/-), -, Acetonitrile soln.
Xe lamp
12 d/15 d
(Heraeus suntest)
14C,
DT50 (light/dark)
Schafmeier et al. 1998
EPA OPPTS 1996b
EPA OPPTS 1995a
EPA OPPTS 2001
Nigg et al. 1984
Gohre and Miller 1986
EPA OPPTS 1997b
EPA OPPTS 1997a
Reference
109
#
Benthiocarb
Butyrate
Carbosulfan
Benfuracarb
Molinate
Thiophanatemethyl
Maneb
Chlorsulfuron
86
87
88
89
90
92
94
96
Pesticide

Rice-growing area clay soil (1.95/4.6/-), -,acetone soln.

Sunlight
N.R.
(3.5 4.5 mW cm2)
Loam soil (N.R.), -, 14C, N.R.
Sunlight, outdoors, 25C
N.R.
Orange glove soil (N.R.), -, 44.8 g cm2
2.5 EC
Sunlight
5.9 d/N.R
Sandy loam soil (N.R.), -, 125 g cm2
N.R.
N.R.
(254 nm)
Three soils (0.9 3.5/7.0 7.5/-), 1 mm, 5 20 ppm
Methanol soln.
Sunlight (Jul.)
13 34 d/N.R.
Sandy loam soil (1.7/7.4/-), -, 14C, N.R.
Sunlight
2.9 5.5 d/10 19 d
Delaware soil (N.R.), -, 22.4 g cm2
14C, aqueous soln.
Sunlight (spring)
<1 wk/N.R.
Nora silty clay loam soil (2/8.0/-), 1 mm, 1.7 g cm2
14C, pH 7 buffer soln.
Xe lamp (>290 nm), 25 C
50 d/130 d
14C,
DT50 (light/dark)
Strek 1998
Rhodes 1977
EPA OPPTS 2001
Konstantinou et al. 2001
Dureja et al. 1990
Nigg et al. 1984
EPA OPPTS 1993
Cheng and Hwang 1996
Reference
110
T. Katagi
#
Tribenuronmethyl
Triasulfuron
Chlorimuronethyl
Rimsulfuron
Thifensulfuronmethyl
Captan
Iprodione
Famoxadone
99
100
102
103
105
106
109
111
Pesticide

Alluvial (1.2/7.5/-), 2 mm, acetone soln.

Sunlight (May) or u.v.
11 d or 11 hr/N.R.
light (max. 254 nm)
Two soils (0.9 2.3/7.0 7.1/dry) , 1 mm, 6 7 ppm
Methanol soln.
1.1kW Xe lamp (Suntest
6 15 hr/26 198 hr
CPS+, >300 nm), 20 C
Three soils (0.7 1.2/6.2 8.1/-), 2 mm, 50 ppm
N.R.
Sunlight (Apr. May),
11 21 d/N.R.
30 35 C
Sassafras sandy loam soil (1.0/6.3/-), 1mm, 0.5g cm2
Sunlight (Jun. Jul.), 25C
11 d/11 d
Two soils (0.9 2.3/7.0 7.1/dry) , 1 mm, 6 7 ppm
Methanol soln.
1.1kW Xe lamp (Suntest
7 hr/24 34 hr
CPS+, >300 nm), 20 C
Sandy loam soil (-/-/moist), -, 14C, N.R.
Sunlight
5 15 d/10 21 d
Xe lamp
7 14 d/14 21 d
N.R.
N.R.
N.R.
12 d/28 d
14C,
DT50 (light/dark)
Jernberg and Lee 1999
EPA OPPTS 1998e
EPA OPPTS 1999b
Albanis et al. 2002
Schneiders et al. 1993
Choudhury and Dureja1997a
Albanis et al. 2002
Bhattacharjee and Dureja 2002
Reference
111
#
Dicamba
Chloramben
Pentachlorophenol
Aldrin
Dieldrin
DDT
Dicofol
118
119
121
122
123
130
133
Pesticide

Laponite,-,N.R.
125W high-pressure Hg lamp
N.R.
(>290 nm, 2.2-cm water filter)
Pennsylvania loam soil (2.0/56/-), 2 mm, 3 ppm
14C, acetonitrile
Xenon lamp (Heraeus
29 109d/2 500d
Suntest CPS), 25C
Three soils (0.3 1.5/4.4 7.7/dry), 0.08 mm, 1000 ppm
Hexane soln.
300W medium-pressure
20 60 min/N.R.
Hg lamp (water filter)
UK and German soils (2 3.5/7.4 8.1/-), -, 30 g cm2
14C, EC formulation
Sunlight (April), outdoors
N.R.
Japanese soils (N.R.), -,Formulation
Sunlight, filed
N.R.
Clay loam soil (2.5/7.5/field), -, 14C, N.R.
Sunlight, outdoors
55 d/N.R.
Silt loam soil (N.R.), -,14C, N.R.
Artificial light
21 30 d/N.R.
DT50 (light/dark)
EPA OPPTS 1998d
Zayed et al. 1994
Suzuki and Yamamoto 1974
Klein et al. 1973
Liu et al. 2002
Misra et al. 1997
Aguer et al. 2000
Reference
112
T. Katagi
#
Parathionmethyl
Cyanophos
Fenitrothion
Bromophos
Iodofenphos
Tolclofosmethyl
136
137
138
140
141
142
Pesticide

Orthic livisol (1.9/7.2/-), 0.1 mm, Methanol soln.

Xe lamp in Suntest CPS+
1 d/>1 d
20.5C
Sandy loam soil (N.R.), -, >14 g cm2
14C, N.R.
Sunlight (July), outdoors
61 d/106 d
ca. 25C
Two Japanese soils (3 19/5.2 6.4/5 12), 0.5 mm, 14C, N.R.
Sunlight (Sept. Oct.),
2 d/>12 d
outdoors
Two Japanese soils (2.5 19/-/5 12), 50 m, 10 g cm2
14C, CHCl soln.
Sunlight (Jun.), outdoors
3
1 d/>12 d
Speyer standard soil 2.2 (2.6/5.8/12), -, 180 ppm
Methanol soln.
Daylight + UV-A & -B lamps
48 d/80 d
(>290 nm), 25C
Finely powdered soil (N.R.), -, Acetone soln.
1 kW metal halide lamp
N.R.
(Applied Photophysics 9500)
Methanol soln.
Daylight + UV-A & -B lamps
71 d/85 d
(>290 nm), 25C
Four Japanese soils (3 15/5 7/5 16) , 50 m, 7 g cm2
14C, CHCl soln.
Sunlight (May Jun.),
3
1 2 d/2 >15 d
outdoors
DT50 (light/dark)
Mikami et al. 1984b
Allmaier et al. 1984
Walia et al. 1989b

Allmaier and Schmid 1985

Allmaier and Schmid 1985
Mikami et al. 1985b
Mikami et al. 1976
EPA OPPTS 1999e
Kromer et al. 1999
Reference
113
#
Fenthion
Diazinon
Chlorpyrifos
Quinalphos
Tetrachlovinphos
Monocrotophos
143
144
145
148
154
156
Pesticide

Five U.S. soils (0.8 6.3/4.5 7.5/-), -, 50 200 ppm

CH2Cl2 soln.
Sunlight (May Aug.),
N.R.
outdoors
Switzerland silty loam (3.6/6.1/dry or 12%), -, 10 ppm
14C, N.R.
Xe lamp (>290 nm, u.v. filter
<1 d/<1 d
+ IR reflecting glass), 45 C
Sunlight
20 hr/ 14.7 d
Finely powdered soil (N.R.), 2 mm, 0.5% acetone soln.
17.3 d/N.R.
(254 nm)
Four Indian soils (-/5.6 8.4/-), 50 m, 7 g cm2
Chloroform soln.
Sunlight (May Jun.)
2 5 d/14 >25 d
East Anglia medium loam (-/8.0/19),-, 13 ppm
14C, acetone soln.
Subdued daylight
4 5 d/N.R.
Sandy loam soil (0.35/7.2/ -), -, 2.5 mg/g of soil
N.R.
N.R./>10 d
Sterilized sandy loam (1.3/6.4/-) soil, <1 mm, 5 ppm
14C, methanol soln.
Sunlight (Jul. Aug.)
3 d/30 d
DT50 (light/dark)
Lee et al. 1989
Dureja et al. 1987b
Beynon and Wright 1969
Dureja et al. 1988
Walia et al. 1988
EPA OPPTS 2000
Burkhard and Guth 1979
Reference
114
T. Katagi
#
Dicrotophos
Profenofos
Phorate
Disulfoton
Bensulide
Phenthoate
Azinphosmethyl
157
160
162
163
164
168
169
Pesticide

Four U.S. soils (-/5.7 6.7/-), <1 mm, 25 ppm

acetone soln.
Fluorescent lamps
N.R.
(GEP40BL, BLB), 35C
14C, N.R.
<1 d/ 1 d
Plano silt loam soil (N.R.), field, 112 g cm2
Formulation
Sunlight (May), field
<1 wk/N.R.
Sunlight
2.4 d/N.R.
Four soils (4.5 7.5/0.8 6.3/dry), -, Dichloromethane soln.
Sunlight (Aug. or Oct.,
3 d/>5 d
Kimax glass), outdoors
Sorento loam soil (N.R.), -,14C, N.R.
Xe lamp
90 d/N.R.
Two Japanese soils (3 19/5 6/5 12), 0.5 mm, 10 g cm2
3 d/>6 d
outdoors
Sandy loam soil (-/5.1/-), -, 14C, N.R.
Sunlight (April)
180 d/N.R.
14C,
DT50 (light/dark)
EPA OPPTS 1998a
Mikami et al. 1977b
EPA OPPTS 1999a
EPA OPPTS 1999d
Lichtenstein et al. 1973
Lee et al. 1989
Reference
115
#
Phosalone
Methidathion
Isofenphos
Ditalimfos
Cyanofenphos
Dioxabenzofos
Ethion
Atrazine
170
171
175
178
180
183
184
185
Pesticide

Finely powdered soil (N.R.), -, Acetone soln.

1kW high-pressure metal5 d/>15 d
halide lamp (>300 nm)
14C, N.R.
<1 d/<1 d
Sandy loam soil (0.35/7.2/-), -, 125 g cm2
N.R.
N.R.
Methanol soln.
Daylight + UV-A & -B
18 d/N.R.
lamps (>290 nm), 25C
Two Japanese soils (3 19/5.2 6.4/5 12), 0.5 mm, 14C, N.R.
2 d/>12 d
outdoors
Two Japanese soils (3 19/5 6/5 12), 0.5 mm, 10 g cm2
<1 d/>6 d
outdoors
Sterilized sandy loam soil (N.R.), -, 8.6 ppm
14C, N.R.
Sunlight
61.6 d/175.9 d
Eight soils (0.9 1.6/7.8 8.0/various), 0.2 0.5 mm, Methanol soln.
1kW medium-pressure
4 8 min/N.R.
Hg lamp
DT50 (light/dark)
Gong et al. 2001
EPA OPPTS 1995c
Mikami et al. 1977b
Mikami et al. 1976
Dureja et al. 1989
Walia et al. 1989a
Reference
116
T. Katagi
#
Triadimefon
Propiconazole
Amitrole
Terbacil
Bentazon
Metribuzin
188
191
196
197
200
201
Pesticide

Two soils (0.4 0.8/5.3 7.4/-), 2 mm, 31.8 g cm2

Acetone soln.
u.v. light (254 nm) or
9.5 22 hr/N.R.
sunlight (Sept.)
Scheyern soil (N.R.), 2 mm, 5 ppm
N.R.
Xe lamp (>290 nm,
166 hr/N.R.
Heraeus suntest), 18C
Sandy loam soil (N.R.), 3.5 mm, 0.3g cm2
Acetone soln.
Sunlight
12 d/>26 d
Xe lamp, 25C
<73 d/N.R.
Drummer silty clay loam soil (N.R.), -, 1.2 lb acre1
14C, N.R.
Xe lamp, 25C
61 d/N.R.
Montcalm sandy loam soil (N.R.), 0.5 mm, 100 g cm2
14C, CH Cl soln.
RPR u.v. light (300 &
2 2
>5 d/N.R.
350 nm)
Sunlight, outdoors, 31C
2.5 d/N./R.
DT50 (light/dark)
EPA OPPTS 1998g
Nilles and Zabik 1975
EPA OPPTS 1998h
EPA OPPTS 1996a
Dureja et al. 1987a
Murthy et al. 1998
Nag and Dureja 1996
Reference
117
#
Norflurazon
Fipronil
DTP
Trifluralin
Butralin
Oryzalin
214
220
221
232
234
235
Pesticide

Rome loam soil (2.0/6.2/-), -, 0.6 g cm2

N.R.
Sunlight, outdoors, 25 70C
8 d/N.R.
Northern Senegal soil (0.3/7.6/-), field, 0.05 0.1 g cm2
Formulation
Sunlight, field
45 d/N.R.
Two Niger soils (0.1 0.3/5.3 5.8/-) , -, 0.08 g cm2
Formulation
Sunlight (Sept. Oct.), field
1.5 d/N.R.
Banizoumbou soil (6.5/8.3/dry) soils, -, 2.5 ppm
Methanol soln.
1.8 kW Xe lamp (Suntest,
69 d/N.R.
>290 nm, u.v.filter)
Two Japanese soils (3 9/5.6 5.8/-), 0.5 mm, 3.8 g cm2
14C, aqueous soln.
Sunlight (May Jun.)
31 34 d/N.R.
N.R.
41 d/66 d
Sandy loam soil (N.R.), -, 374 ppm
14C, N.R.
Sunlight
99.6 d/112.7 d
Xe lamp
22.4 hr/N.R.
DT50 (light/dark)
EPA OPPTS 1994
EPA OPPTS 1998b
EPA OPPTS 1996c
Yamaoka et al. 1988
Bobe et al. 1998b
Bobe et al. 1998a
Fenet et al. 2001
Schroeder Kvien and Banks 1985
Reference
118
T. Katagi
Fluchloralin
Ethalfluralin
Pendimethalin
Prochloraz
236
237
238
240
Pesticide

Montcalm sandy loam soil (N.R.), 0.5 mm, 100g cm2

CH2Cl2 soln.
RPR u.v. light (300 &
N.R.
350 nm)
N.R.
14.2 d/N.R.
Kalyani alluvial soil (1.7/7.2/dry), 2mm, 28g/g of soil
Hexane soln.
Sunlight
N.R.
New Delhi sandy loam soil (3.6/6.1/-), 50 m, 7g cm2
Methanol soln.
N.R.
(254 nm)
Two soils (1.0 1.5/5.3 7.1/-), -, 0.4 0.6 ppm
14C, methanol
>1 d/ 200d
(>290 nm, TQ150 filter)
14C,
DT50 (light/dark)
Hollrigl-Rosta et al. 1999
Dureja and Walia 1989
Hadler et al. 1989
EPA OPPTS 1995b
Nilles and Zabik 1974
Reference
aSoil properties and application rate are listed in the following order as boldface: soil name (organic matter content %/pH/ moisture content %), soil layer thickness,
application rate.
bNonradiolabeled pesticide when unspecified.
- or N.R.: not reported. MHWC, maximum water holding capacity; FMC, field moisture content
119
Phenothrin
Cypermethrin
Deltamethrin
Fenpropathrin
Fenvalerate
Flucythrinate
19
22
24
27
29
2,4-D
Pesticide
13
No.
French bean leaf

3d
Kidney bean leaf

14 d
Spring wheat leaf
24 d
Cotton leaf
8d
Mandarin orange leaf

4d
Cotton leaf
1.1 wk
Bean leaf
4 d
Potato leaf
12 d
Cotton & bean leaf

24 d
Bean & rice leaf

<1 d
Corn leaf
14.6 hr
Plant species
DT50
Cole et al. 1982

Ruzo and Casida 1979
methanol soln.
Sunlight (Nov.), greenhouse
14C,
diethyl ether soln.

Sunlight (JulySept.), outdoors
14C,
Methanol soln.
Sunlight (Apr.), greenhouse
Chattopadhyaya and Dureja 1991
Holmstead et al. 1978b
Lee et al. 1988
Ohkawa et al. 1980
14C,
methanol soln.
Sunlight (Oct.), greenhouse
14C, 0.1% EC
Sunlight (Sept.Dec.), outdoors
2.4 lb/gal EC formulation
Sunlight (mid-July)
Takahashi et al. 1985b
methanol soln.
Sunlight (Sept.), greenhouse
14C,
Maguire 1990
Cole et al. 1982
Nambu et al. 1980
14C,
diethyl ether soln.

Sunlight, greenhouse
Sunlight (JulySept.), outdoors
2.5% EC
Sunlight (summer), field
Venkatesh and Harrison 1999
References
0.25% oxysorbic surfactant

Fluorescent lamps
14C,
Application medium
Light source (season), conditions
Table 11. Surface degradation of pesticides in foliar or topical application.
120
T. Katagi
Flutolanil
Carboxin
Propyzamide
Diafenthiuron
Diflubenzuron
Metolcarb
Fenobucarb
Xylylcarb
Trimethacarb
42
45
57
59
61
62
63
64
Pesticide
39
No.
Pinto bean leaf

N.R.
Bean leaf
<1 d
Rice leaf
N.R.
Bean leaf
<1 d
Cotton leaf
31.9 d
Conifer pine needle
23 wk
Chinese cabbage leaf

4d
Cotton leaf
<3 hr
Alfalfa leaf
63.8 d
Bean leaf
<10 hr
Cucumber leaf
29.3 d
Plant species
DT50
Ogawa et al. 1976

Ohkawa et al. 1974a
Slade and Casida 1970
14C,
methanol-water (1/3) soln.

14C,
methanol soln.
14C,
ethanol soln.
Sunlight (JuneJuly), outdoors
Ohkawa et al. 1974a
Rodriguez et al. 2001
Bull and Ivie 1976
Drabek et al. 1992
methanol soln.
14C,
25% WP
Sunlight (summer), outdoors
45% oil formulation
Sunlight (Aug.Oct.), field
14C,
25 EC
Sunlight, field
SC400 formulation
Sunlight, field
Keum et al. 2002
Yih and Swithenbank 1971
14C,
acetone soln.
Sunlight, field
Buchenauer 1975
Uchida et al. 1983
References
Suspension
Sunlight
diethyl ether soln.

14C,
Application medium
121
Propoxur
Aminocarb
Mexacarbate
Methiocarb
Carbaryl
Carbofuran
Oxamyl
Pirimicarb
Benomyl
Fenothiocarb
Carbosulfan
66
67
68
71
72
74
78
81
85
88
Pesticide
65
No.
Valencia orange
36 d
Mandarin orange
1.612 d
Pinto bean leaf

N.R.
Lettuce leaf
2 d
Tobacco leaf
15 d
Strawberry
13 d
Garden snapbean leaf

2.8 d

>3 d

23 hr

4 hr

8 hr
Plant species
DT50
Abdel-Wahab and Casida 1967

Abdel-Wahab and Casida 1967
Abdel-Wahab et al. 1966
14C,
ethanol soln.
Sunlight (Aug.Sept.), outdoors
3H, 14C;
ethanol soln.
14C,
ethanol soln.
14C,
Harvey et al. 1978
14C,
Baude et al. 1973

Unai et al. 1986
Clay and Fukuto 1984
14C,
52% WP
14C, 30% EC
Sunlight (Sept.), greenhouse
14C,
EC
Sunlight (summer), field
Cabras et al. 1990
25% liquid formulation

Sunlight (May), field
0.2% Tween 20 aqueous soln.

Plant growth chamber
Archer et al. 1977
43.8% FL
Sunlight, field
ethanol soln.
References
ethanol soln.
14C,
Application medium
122
T. Katagi
Benfuracarb
Thiophanate-methyl
MBC
ETU
Tribenuron methyl
Thifen-sulfuron
Procymidone
Methazole
Aldrin
Dieldrin
92
93
95
99
104
108
112
122
123
Pesticide
89
No.
Apple tree leaf

<1 wk
Apple tree leaf

<1 wk
Cotton leaf
<1 d
Bean & cucumber leaf

23 wk
Soybean leaf
420 d
Wheat leaf
N.R.
Tomato leaf
2.1 d
Corn leaf
N.R.
Cotton leaf
N.R.
Apple tree leaf
15 d
Cotton leaf
N.R.
Plant species
DT50
Rhodes 1977
14C,
Brown et al. 1993
aqueous soln. surfactant

50% dispersible powder

Sunlight (June), field
Aldrex 30
Harrison et al. 1967
Dorough et al. 1973
14C,
aqueous soln.
Sunlight (June), outdoors
Mikami et al. 1984a
diethyl ether soln.

14C,
14C,
Bhattacharjee and Dureja 2002
Acetone soln.
80% WP
Sunlight, outdoors
Fleeker and Lacy 1977
Soeda et al. 1972
Buchenauer et al. 1973
Tanaka et al. 1985
References
10 mM HCl in 50% ethanol.

3H, 14C;
70% WP
Sunlight, outdoors
14C, 70% WP
Sunlight (MayAug.)
acetone-water (1/1)
14C,
Application medium
123
Endosulfan
Endrin
DDT
Parathion
Cyanophos
Fenitrothion
Bromophos
Fenthion
126
130
135
137
138
140
143
Pesticide
125
No.
Orange fruit, peel

3.94.8 d
Corn leaf
1 d
Tomato leaf
< 8 hr
Apple tree leaf

1.2 d
Bean leaf
<1 d
Kidney bean leaf

0.54 d
Garden bean leaf

1 d
Cotton leaf
N.R.
Apple tree leaf

<12 wk
Apple tree leaf

<1 wk
Apple tree leaf

<1 wk
Cotton leaf
N.R.
Plant species
DT50
Commercial formulation (24.2% a.i.)

Sunlight (Apr.), outdoors
50% EC
Sunlight, field
& 3T, emulsion

400 W daylight lamps in chamber
32P
0.5% emulsion
Sunlight (Oct.Nov.)
14C, ethanol soln.
Sunlight (Nov.), outdoors
14C,
benzene-hexane (4/1) + surfactant

El-Refai and Hopkins 1966
0.2% Triton X-155 + B-1956(1/1)

Fluorescent lamps, greenhouse
14C, methanol soln.
Sunlight, field
Leuch and Bowman 1968
Minelli et al. 1996
Stiasni et al. 1969
Ohkawa et al. 1974b
Hosokawa and Miyamoto 1974
Chiba et al. 1976
Joiner and Baetcke 1973
References
25% EC or 50% dispersible powder

Endrex 20
20% concentrate
0.1% hexane soln.
Sunlight (June)
Application medium
124
T. Katagi
Chlorpyrifos
Isoxathion
Phoxim
Tetrachlo-vinphos
Monocroto-phos
Dicrotophos
Phosphami-don
Sulprofos
151
152
154
156
157
158
161
Pesticide
145
No.
Cotton leaf
1d
Cotton leaf
<1 d
Cotton leaf
<1 d
Cotton leaf
<2 d
Bush apple fruit
N.R.
Apple tree leaf

2 d
Bean leaf
6d
Tomato leaf
1 d
Corn leaf
<1 d
Cabbage leaf
23 d
Soft shield fern leaf

54.3 d
Plant species
DT50
Bull et al. 1967

Ivie and Bull 1976
32P,
aqueous soln.
14C,
50% EC
Sunlight (Aug.), outdoors
Bull and Lindquist 1964
Lindquist and Bull 1967
Dureja et al. 1987b
Bowman and Leuck 1971
aqueous soln.
Laboratory
32P,
aqueous soln.
14C, acetone soln.
32P,
acetone soln.
Acetone soln.
Sunlight
14C,
5% formulation
Sunlight, field
EC
Sunlight, field
Makary et al. 1981
Ando et al. 1975
14C,
0.03% Tween 20 aqueous soln.

Walia et al. 1988
References
0.1% acetone soln.

Solar simulator (1 kW metal-halide lamp)
14C,
Application medium
125
Dimethoate
Formothion
Malathion
Phenthoate
Azinphos-methyl
Edifenphos
Acephate
166
167
168
169
173
174
Pesticide
165
No.
Cotton leaf
5.9 hr
Tobacco leaf
58 d
Rice leaf
5 d
Bean & corn leaf

1 d
Valencia orange
37 d
Broad bean leaf

N.R.
Bean leaf
2d
Cotton leaf
1.23.8 d
Bean leaf
1.2 d
Corn leaf
N.R.
Bean leaf
4 d
Bean leaf
1.7 d
Plant species
DT50
Ishizuka et al. 1973

Bull 1979
acetone soln.
Sunlight (JuneAug.)
32P,
emulsion
14C,
Yamazaki et al. 1982
Liang and Lichtenstein 1976
14C,
0.1% Triton X-100

Sunlight, field
50% WP
Takade et al. 1976
& 14C, 0.06% emulsion

Sunlight (Mar. & Sept.)
32P
Awad et al. 1967
El-Refai and Hopkins 1972
Mostafa et al. 1974
32P,
acetone soln.
Sunlight, field
Emulsion
Sunlight, field
14C, ULV or 57% EC
Sauer 1972
Lucier and Menzer 1970
Lucier and Menzer 1968
Dauterman et al. 1960
References
20% EC
Artificial light, greenhouse
14C,
emulsion
14C & 32P, aqueous soln.
Sunlight (Apr.), greenhouse
14C, aqueous soln.
32P,
Application medium
126
T. Katagi
Pesticide
Cyanofenphos
Leptophos
Butonate
Triadimefon
Triadimenol
Fluotrimazole
Lenacil
Dinoseb
Dinobuton
Imidacloprid
Fipronil
No.
180
181
182
188
189
195
199
202
203
215
220
Corn leaf
20 hr
Tomato leaf
0.71.4 d

0.3 hr

0.9 hr
Sugar beet leaf

N.R.
Barley leaf
N.R.
Apple tree leaf

N.R.
Marrow, 1st true leaf

N.R.
Bean leaf
8.3 hr
Cotton leaf
N.R.
Kidney bean leaf

2.25 wk
Plant species
DT50
Matsuo and Casida 1970

Bandal and Casida 1972
Scholz and Reinhard 1999
50% WP
14C,
ethanol soln.
Sunlight (Aug.), greenhouse
14C,
ethanol soln.
Sunlight (Aug.), greenhouse
+ 20SL formulation
Sunlight (51 N), greenhouse
Acetone soln.
Sunlight (Nov.)
Hainzl and Casida 1996

Fenet et al. 2001
Zhang et al. 1999
14C,
14C
Clark et al. 1983
Clark and Watkins 1986
Acetone-water (1/1) soln.

400W Hg lamp, greenhouse
Acetone-water (3/7) soln.

1 mM, WP
Clark et al. 1978
Derek et al. 1979
32P,
aqueous soln.
Sunlight
Zayed et al. 1978
Chiba et al. 1976
References
50% aqueous acetone

Sunlight
32P,
benzene-hexane (4/1) + surfactant

14C,
Application medium
127
Alloxydim
Guazatine
Avermectin B1a
MAB1a
Spinosyn A
224
245
250
251
252
4 plant species
1.616 d
Commercial formulation
Sunlight
Saunders and Bret 1997
Wrzesinski et al. 1996
14C,
Cabbage leaf
N.R.
EC
Sunlight, field
Moye et al. 1990
& 3H, EC formulation

Sunlight (JuneMar.), outdoors
+ 200 ppm nonionic surfactant

Sunlamps, growth chamber
14C
Sato et al. 1985a
aqueous emulsion
Sunlight (Jan.Mar.), outdoors
Celery
59 d
Soeda et al. 1979
14C,
14C,
Campbell and Penner 1985b
References
aqueous emulsion.
Fluorescence light, greenhouse
14C,
Application medium
Dwarf apple leaf

67 wk
Sugar beet leaf

3d
Navy bean leaf

1 hr
Plant species
DT50
N.R.: not reported.

Formulation: ULV: ultra-low-volume formulation; EC: emulsifiable concentrate; WP: wettable powder; FL: flowable.
Sethoxydim
Pesticide
223
No.
128
T. Katagi
129
Appendices Listing
Appendix Number
1 ................................................................................................................................
2 ................................................................................................................................
3 ................................................................................................................................
4 ................................................................................................................................
5 ................................................................................................................................
6 ................................................................................................................................
7 ................................................................................................................................
8 ................................................................................................................................
9 ................................................................................................................................
10 ................................................................................................................................
11 ................................................................................................................................
Page
136
137
139
140
141
144
145
146
148
151
152
130
T. Katagi
Directory of pesticide chemical structures.
Pesticide
Acephate
Acrinathrin
Alachlor
Aldrin
Allethrin
Alloxydim
Aminocarb
Amitrole
Anilazine
Asulam
Atrazine
Avermectin B1a
Azadirachtin-A
Azinphos-methyl
Azoxystrobin
Benfuracarb
Benomyl
Bensulide
Bentazone
Benthiocarb
Bioallethrin
Bromacil
Bromophos
Buprofezine
Butachlor
Butamifos
Butonate
Butralin
Butylate
Captan
Carbaryl
Carbofuran
Carbosulfan
Carboxin
Cartap
Chinomethionat
Chloramben
Chlordane
Chlordimeform
Chlorimuron
Chlorimuron ethyl
Chlorothalonil
Chlorpropham
Chlorpyrifos
Identification number
Appendix number
174
31
34
122
10
224
66
196
211
82
185
250
253
169
244
89
81
164
200
86
11
198
140
222
36
177
182
234
87
106
71
72
88
42
91
228
119
128
207
101
102
117
80
145
9
2
3
8
2
11
5
11
11
5
10
11
11
9
11
5
5
9
11
5
2
11
9
11
3
9
9
11
5
7
5
5
5
3
5
11
8
8
11
6
6
8
5
9
131
Directory of pesticide chemical structures (Continued).

Pesticide
Chlorsulfuron
Chlorthiamid
Cinmethylin
CNP (Chlornitrofen)
Coumaphos
Cyanofenphos
Cyanophos
Cyfluthrin
Cyhalothrin
Cypermethrin
Cyphenothrin
Cyprodinil
2,4-D
DDD
DDE
DDOD
DDT
DTP
Deltamethrin
Desmedipham
Diafenthiuron
Diazinon
Dicamba
Dichlobenil
Dichlofluanid
Dichlorvos
Diclofop-methyl
Dicofol
Dicrotophos
Dieldrin
Diflubenzuron
Dimethoate
Dimetilam
Diniconazole-M
Dinobuton
Dinoseb
Dioxabenzofos
Diphenamid
Diquat
Disulfoton
Ditalimfos
Diuron
ETU
Edifenphos
Endosulfan
Appendix number
96
49
249
217
147
180
137
20
21
19
14
210
1
132
131
113
130
221
22
83
57
144
118
116
205
153
5
133
157
123
59
165
75
190
203
202
183
50
226
163
178
53
95
173
125
6
3
11
11
9
9
9
2
2
2
2
11
1
8
8
7
8
11
2
5
4
9
8
8
11
9
1
8
9
8
4
9
5
10
11
11
9
3
11
9
9
4
5
9
8
132
T. Katagi
Pesticide
Endrin
Esfenvalerate
Ethalfluralin
Ethiofencarb
Ethion
Ethirimol
Ethoxyquin
Etofenprox
Famoxadone
Fenarimol
Fenchlorphos
Fenitrothion
Fenobucarb
Fenothiocarb
Fenpropathrin
Fenpropimorph
Fenthion
Fentin acetate
Fenuron
Fenvalerate
Fipronil
Florasulam
Fluazifop-butyl
Fluchloralin
Flucythrinate
Fludioxinil
Flumetralin
Flumeturon
Fluotrimazole
Flutolanil
Fluvalinate
Folpet
Formothion
Guazatine
Haloxyfop
Heptachlor
Hexachlorobenzene
Hexaconazole
Imazapyr
Imazaquin
Imazethapyr
Imidacloprid
Iodofenphos
Iprodione
Isofenphos
Appendix number
126
28
237
69
184
213
219
32
111
239
139
138
62
85
24
227
143
241
51
27
220
48
6
236
29
208
233
55
195
39
30
107
166
245
8
127
115
192
229
230
231
215
141
109
175
8
2
11
5
9
11
11
2
7
11
9
9
5
5
2
11
9
11
4
2
11
3
1
11
2
11
11
4
10
3
2
7
9
11
1
8
8
10
11
11
11
11
9
7
9
133

Pesticide
Isolan
Isoprothiolane
Isoproturon
Isoxaben
Isoxathion
Kadethrin
Lenacil
Leptophos
Lindane
Linuron
MAB1a
MBC
MCPA
Malathion
Maneb
Mecoprop
Mepronil
Metalaxyl
Methazole
Methidathion
Methiocarb
Methomyl
Methoprene
Methoxychlor
Metolachlor
Metolcarb
Metribuzin
Metsulfuron
Metsulfuron methyl
Mevinphos
Mexacarbate
Mobam
Molinate
Monocrotophos
Monuron
NAA
NMH
Naproanilide
Napropamide
Naptalam
Niclosamide
Nitrofen
Norflurazon
Oryzalin
Oxamyl
Appendix number
77
204
56
46
151
16
199
181
114
54
251
93
3
167
94
4
38
37
112
171
68
70
246
134
35
61
201
97
98
155
67
73
90
156
52
247
242
41
47
44
40
216
214
235
74
5
11
4
3
9
2
11
9
8
4
11
5
1
9
5
1
3
3
7
9
5
5
11
8
3
5
11
6
6
9
5
5
5
9
4
11
11
3
3
3
3
11
11
11
5
134
T. Katagi
Pesticide
Oxycarboxin
Oxyfluorfen
PBacid
Paraquat
Parathion
Parathion-methyl
Penconazole
Pendimethalin
Pentachlorophenol
Perfluidone
Permethrin
Phenmec
Phenmedipham
Phenothrin
Phenthoate
Phorate
Phosalone
Phosmet
Phosphamidon
Photo-dieldrin
Phoxim
Picloram
Pirimicarb
Potasan
Prochloraz
Procymidone
Profenofos
Prometone
Propachlor
Propaphos
Propham
Propiconazole
Propoxur
Propyzamide
Pyrazophos
Pyrethrin-I
Pyridaphenthion
Pyrimethanil
Pyrolan
Quinalophos
Resmethrin
Rimsulfuron
S-2571
S-Bioallethrin
Sethoxydim
Appendix number
43
218
243
225
135
136
193
238
121
206
17
60
84
13
168
162
170
172
158
124
152
120
78
146
240
108
160
187
33
159
79
191
65
45
149
9
150
209
76
148
15
103
176
12
223
3
11
11
11
9
9
10
11
8
11
2
5
5
2
9
9
9
9
9
8
9
8
5
9
11
7
9
10
3
9
5
10
5
3
9
2
9
11
5
9
2
6
9
2
11
135

Pesticide
Simazine
Spinosyn A
Sulprofos
2,4,5-T
2,3,7,8-TCDD
Tefluthrin
Terbacil
Tetrachlovinphos
Tetramethrin
Thiabendazole
Thiadiazuron
Thifensulfuron
Thifensulfuron methyl
Thiophanate-methyl
Tolclofos-methyl
Tralocythrin
Tralomethrin
Triadimefon
Triadimenol
Triasulfuron
Tribenuron methyl
Trichlorfon
Triclopyr
Trifluralin
Trimethacarb
Triticonazole
Vinclozoline
Warfarine
Xylylcarb
Appendix number
186
252
161
2
129
18
197
154
23
212
58
104
105
92
142
26
25
188
189
100
99
179
7
232
64
194
110
248
63
10
11
9
1
8
2
11
9
2
11
4
6
6
5
9
2
2
10
10
6
6
9
1
11
5
10
7
11
5
Pesticide
2,4-D
2,4,5-T
MCPA
Mecoprop
Diclofop-methyl
Fluazifop-butyl
Triclopyr
Haloxyfop
No.
1
2
3
4
5
6
7
8
C
C
C
C
C
C
2-N
C
X
2,4-Cl2
2,4,5-Cl3
4-Cl-2-CH3
4-Cl-2-CH3
4-(2,4-Cl2-Phenoxy)
5-CF3-2-Pyridyloxy
3,5,6-Cl3
3-Cl-5-CF3-2-Pyridyloxy
R1
Appendix 1. Chemical structures of aryloxyalkanoates.
H
H
H
CH3
CH3
CH3
H
CH3
R2
H
H
H
H
CH3
n-C4H9
H
H
R3
136
T. Katagi
Insecticide
Pyrethrin-I
Allethrin
Bioallethrin
S-Bioallethrin
Phenothrin
Cyphenothrin
Resmethrin
Kadethrin
Permethrin
Tefluthrin
Cypermethrin
Cyfluthrin
Cyhalothrin
Deltamethrin
Tetramethrin
No.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
A1
A1
A1
A1
A1
A1
A1
A2
A1
A1
A1
A1
A1
A1
A1
R1
CH3
CH3
CH3
CH3
CH3
CH3
CH3
Cl
Cl
Cl
Cl
Cl
Br
CH3
X
CH3
CH3
CH3
CH3
CH3
CH3
CH3
Cl
CF3
Cl
Cl
CF3
Br
CH3
Y
1R-trans
1RS-cis,trans
1R-trans
1R-trans
1RS-cis,trans
1RS-cis,trans
1RS-cis,trans
E-1R-cis
1RS-cis,trans
Z-1RS-cis
1RS-cis,trans
1RS-cis,trans
Z-1RS-cis
1R-cis
1RS-cis,trans
Configuration
Appendix 2. Chemical structures of pyrethroids.
B1
B1
B1
B1
B2
B2
B3
B3
B2
B2
B2
B2
B2
B2
B4
R2
H
CN
H
H
CN
CN
CN
CN
Z
Z-S
RS
RS
S
RS
RS
RS
RS
S
Configuration
CH=CH2
H
H
H
3-Phenoxy
3-Phenoxy
3-Phenoxy
2,3,5,6-Tetrafluoro-4-methyl
3-Phenoxy
4-Fluoro-3-phenoxy
3-Phenoxy
3-Phenoxy
R3
137
24
25
26
(28)/27
29
30
31
No.
Fenpropathrin
Tralomethrin
Tralocythrin
(Es)fenvalerate
Flucythrinate
Fluvalinate
Acrinathrin
Insecticide
Appendix 2. (Continued).
A3
A4
A4
A5
A5
A5
A1
R1
Br
Cl
NH
H
4-Cl
4-OCHF2
2-Cl-4-CF3
COOCH(CF3)2
1R-cis
1R-cis
(2S) 2RS
2S
2R
Z-1R-cis
Configuration
B2
B2
B2
B2
B2
B2
B2
R2
CN
CN
CN
CN
CN
CN
CN
Z
RS
S
S
(S) RS
RS
RS
S
Configuration
3-Phenoxy
3-Phenoxy
3-Phenoxy
3-Phenoxy
3-Phenoxy
3-Phenoxy
3-Phenoxy
R3
138
T. Katagi
Pesticide
Propachlor
Alachlor
Metolachlor
Butachlor
Metalaxyl
Mepronil
Flutolanil
Niclosamide
Naproanilide
Carboxin
Oxycarboxin
No.
33
34
35
36
37
38
39
40
41
42
43
H
2,6-(C2H5)2
2-C2H5-6-CH3
2,6-(C2H5)2
2,6-(CH3)2
3-O-iso-C3H7
3-O-iso-C3H7
2-Cl-4-NO2
H
H
H
R1
CH2Cl
CH2Cl
CH2Cl
CH2Cl
CH2OCH3
2-CH3Ph
2-CF3Ph
3-Cl-6-OHPh
CH(CH3)O-2-Naphthyl
A1
A2
R2
Appendix 3. Chemical structures of anilides and amides.
CH(CH3)2
CH2OCH3
CH(CH3)CH2OCH3
CH2O(CH2)3CH3
CH(CH3)COOCH3
H
H
H
H
H
H
R3
139
Pesticide
Fenuron
Monuron
Diuron
Linuron
Flumeturon
Isoproturon
Diafenthiuron
No.
51
52
53
54
55
56
57
O
O
O
O
O
O
S
X
H
4-Cl
3,4-Cl2
3,4-Cl2
3-CF3
4-iso-C3H7
2,6-(iso-C3H7)2-4-OPh
R1
CH3
CH3
CH3
OCH3
CH3
CH3
tert-C4H9
R2
Appendix 4. Chemical structures of ureas and benzoylureas.
CH3
CH3
CH3
CH3
CH3
CH3
H
R3
140
T. Katagi
Pesticide
Phenmec
Metolcarb
Fenobucarb
Xylylcarb
Trimethacarb
Propoxur
Aminocarb
Mexacarbate
Methiocarb
Ethiofencarb
Methomyl
Carbaryl
Carbofuran
Mobam
Oxamyl
Dimetilam
Pyrolan
Isolan
Pirimicarb
Propham
Chlorpropham
Benomyl
Asulam
Desmedipham
Phenmedipham
No.
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
Ph
3-ClPh
A7
A8
Ph
3-CH3Ph
R1
Appendix 5. Chemical structures of carbamates.
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CH3
CH3
CH3
CH3
H
H
H
H
H
H
R2
Ph
3-CH3Ph
2-sec-C4H9Ph
3,4-(CH3)2Ph
3,4,5 (or 2,3,5)-(CH3)3Ph
2-O-iso-C3H7Ph
3-CH3-4-N(CH3)2Ph
3,5-(CH3)2-4-N(CH3)2Ph
3,5-(CH3)2-4-SCH3Ph
2-CH2SC2H5-Ph
N=C(CH3)SCH3
Naphth-1-yl
A1
A2
N=C(SCH3)C(O)N(CH3)2
A3
A4
A5
A6
iso-C3H7
iso-C3H7
CH3
CH3
3-NHCO2C2H5Ph
3-NHCO2CH3Ph
R3
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
X
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
141
Pesticide
Fenothiocarb
Benthiocarb
Butylate
No.
85
86
87
CH3
C2H5
(CH3)2CHCH2
R1
CH3
C2H5
(CH3)2CHCH2
R2
(CH2)4OPh
CH2-4-ClPh
C2H5
R3
O
O
O
S
S
S
142
T. Katagi
143
Herbicide
Chlorsulfuron
Metsulfuron
Metsulfuron methyl
Tribenuron methyl
Triasulfuron
Chlorimuron
Chlorimuron ethyl
Rimsulfuron
Thifensulfuron
Thifensulfuron methyl
No.
96
97
98
99
100
101
102
103
104
105
C
C
C
C
C
C
C
C
A1
A2
X
C
C
C
C
C
C
C
N
R1
R2
Cl
COOH
COOCH3
COOCH3
OCH2CH2Cl
COOH
COOC2H5
SO2C2H5
Aryl
Appendix 6. Chemical structures of sulfonylureas.
N
N
N
N
N
C
C
C
N
N
Z
H
H
H
CH3
H
H
H
H
H
H
R3
OCH3
OCH3
OCH3
OCH3
OCH3
Cl
Cl
OCH3
OCH3
OCH3
R4
CH3
CH3
CH3
CH3
CH3
OCH3
OCH3
OCH3
CH3
CH3
R5
144
T. Katagi
Appendix 7. Chemical structures of cyclic dicarboximides and related pesticides.
145
Appendix 8. Chemical structures of organochlorine pesticides.
146
T. Katagi
147
Pesticide
Parathion
Parathion-methyl
Cyanophos
Fenitrothion
Fenchlorphos
Bromophos
Iodofenphos
Tolclofos-methyl
Fenthion
Diazinon
Chlorpyrifos
Potasan
Coumaphos
Quinalophos
Pyrazophos
Pyridaphenthion
Isoxathion
Phoxim
Dichlorvos
Tetrachlovinphos
Mevinphos
Monocrotophos
Dicrotophos
Phosphamidon
Propaphos
No.
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
OC2H5
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
O-nC3H7
R1
OC2H5
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OC2H5
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
O-nC3H7
R2
R3
O(4-NO2Ph)
O(4-NO2Ph)
O(4-CNPh)
O(3-CH3-4-NO2Ph)
O(2,4,5-Cl3Ph)
O(2,5-Cl2-4-BrPh)
O(2,5-Cl2-4-IPh)
O(2,6-Cl2-4-CH3Ph)
O(3-CH3-4-SCH3Ph)
A1
O(3,5,6-Cl3-pyridin-2-yl)
A2
A3
A4
A5
A6
A7
ON=C(CN)Ph
OCH=CCl2
OC(=CHCl)(2,4,5-Cl3Ph)
OC(CH3)=CHCOOCH3
OC(CH3)=CHC(O)NHCH3
OC(CH3)=CHC(O)N(CH3)2
OC(CH3)=CClC(O)N(C2H5)2
O(4-SCH3Ph)
Appendix 9. Chemical structures of organophosphorus pesticides.
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
O
O
O
O
O
O
O
148
T. Katagi
Pesticide
Profenofos
Sulprofos
Phorate
Disulfoton
Bensulide
Dimethoate
Formothion
Malathion
Phenthoate
Azinphos-methyl
Phosalone
Methidathion
Phosmet
Edifenphos
Acephate
Isofenphos
S-2571
Butamifos
Ditalimfos
Trichlorfon
Cyanofenphos
Leptophos
Butonate
No.
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
OC2H5
OC2H5
OC2H5
OC2H5
O-iso-C3H7
OCH3
OCH3
OCH3
OCH3
OCH3
OC2H5
OCH3
OCH3
OC2H5
OCH3
OC2H5
OC2H5
OC2H5
OC2H5
OCH3
OC2H5
OCH3
OCH3
R1
S-nC3H7
S-nC3H7
OC2H5
OC2H5
O-iso-C3H7
OCH3
OCH3
OCH3
OCH3
OCH3
OC2H5
OCH3
OCH3
SPh
NHC(O)CH3
NH-iso-C3H7
NH-iso-C3H7
NH-sec-C4H9
OC2H5
OCH3
O(4-CNPh)
O(2,5-Cl2-4-BrPh)
OCH3
R2
O(4-Br-2-ClPh)
O(4-SCH3)Ph
SCH2SC2H5
SCH2CH2SC2H5
SCH2CH2NHS(O)2Ph
SCH2C(O)NHCH3
SCH2C(O)N(CHO)CH3
SCH(COOC2H5)CH2COOC2H5
SCH(COOC2H5)Ph
A8
A9
A10
A11
SPh
SCH3
O(2-C(O)O-iso-C3H7Ph)
O(3-CH3-6-NO2Ph)
O(3-CH3-6-NO2Ph)
A12
CH(OH)CCl3
Ph
Ph
CH(CCl3)OC(=O)C3H7
R3
O
S
S
S
S
S
S
S
S
S
S
S
S
O
O
S
S
S
S
O
S
S
O
149
150
T. Katagi
Pesticide
Atrazine
Simazine
Prometone
No.
185
186
187
Cl
Cl
OCH3
R1
CH(CH3)2
CH2CH3
CH(CH3)2
R2
CH2CH3
CH2CH3
CH(CH3)2
R3
Appendix 10. Chemical structures of triazines and azoles.
151
Appendix 11. Chemical structures of miscellaneous pesticides.
152
T. Katagi
153
154
T. Katagi
155
156
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Springer-Verlag 2004

Rev Environ Contam Toxicol 182:1195

Communicated by George W. Ware

Table Listing .............................................................................................................. 79

II. Photophysical and Photochemical Processes

Fig. 1. Energy state diagram.

ship of Schuster and Kubelka-Munk (Parlar 1984) instead of the BeerLambert

photolysis in a well-mixed system can be estimated by using the GCSOLAR

Fig. 2. Types of photoreactions.

sensitive to diffusion of D* and A. In contrast, the exchange interaction involves

because an acceptor molecule is in the S0 state, the triplet energy transfer is

Fig. 3. Schematic description of the spectral overlap.

limited. Spencer et al. (1980) reported the desulfuration of parathion (135) on

III. Factors Controlling Photolysis on Plant Surfaces

frequently superimposed on amorphous layers. Penetration through these wax

ketones (aldehydes) show UV absorption maxima around 270 nm and 320370

IV. Factors Controlling Photolysis on Soil Surfaces

B. Environmental Factors Affecting Soil Properties

Fig. 6. Structure of soil surface.

plex description of a diffusion constant (D) than that in water (Graham-Bryce

F. Photophysical and Photochemical Processes of Soil Components

having a 40-fold-higher affinity to HA (Van Noort et al. 1988), indicating that

estimate such a photocatalytic activity for environmental particles. Both TiO2

V. Atmospheric Oxygen Species

VI. Experimental Design and Kinetic Analysis

VII. Photodegradation of Pesticides in Model Systems

nm and the extinction coefficient of each pesticide at 295305 nm could not be

Fig. 12. Photooxidative rearrangement of resmethrin (15).

Fig. 13. Photodegradation of etofenprox (32).

would be possibly formed by hydrogen abstraction, which reacted with O2 to

Fig. 14. Photodegradation of benfuracarb (89).

Fig. 15. Photoinduced rearrangement of isoxaben (46).

Fig. 16. Photoinduced isomerization of diniconazole-M (190) followed by cyclization.

pyrido[1,2-a]-5-pyradinium salt and picolinamide (Smith and Grove 1969). The

Fig. 17. Various photodegradation pathways of fipronil (220).

Fig. 18. Successive photoreduction of parathion (135) followed by dimerization.

decarboxylation (Ruzo 1983). The cis-isomer in an argon atmosphere simply

Fig. 19. Photodegradation of cypermethrin (19).

VIII. Photodegradation of Pesticides on Soil and Clay Surfaces

Fig. 20. Photoinduced rearrangement (bridge contraction) of chlorimuron-ethyl (102).

Organochlorines Dichlobenil (116) and chlorothalonil (117) were reported to

To clarify the reaction mechanism of photoinduced hydration common to

Fig. 22. Photoinduced rearrangement of iprodione (109).

Fig. 23. Photoinduced ring opening of prochloraz (240).

IX. Photodegradation of Pesticides on Plants

underwent dechlorination at the bridge carbon with trace amounts of -isomer

Fig. 24. Photodegradation of N-(-trichloromethyl-p-methoxybenzyl)-p-methoxyaniline.

to be less important than metabolism in tissues (Stiasni et al. 1969). In contrast,

to garden snapbean resulted in rapid dissipation, but the degradation profiles

tions might result in favorable photoinduced S-oxidation. Thiabendazole (212)

Table 1. Wavelength of fluorescence and phosphorescence spectra of pesticides.

Sogliero et al. 1985

Bowman and Beroza 1967b

Em. & Ex., emission and excitation wavelengths in nm.

Table 2. Maximum wavelengths of absorption or reflectance spectra of chemicals including pesticides.

Ghosal and Mukherjee 1972

Table 3. Emission profiles of photosensitizers.

Carmichael and Hug

Carmichael and Hug

Carmichael and Hug

Mallet and Surette

Carmichael and Hug