3732 J Age. Food Chem. 2008, 56, 3732-3787
AGRICULTURAL AND
FOOD CHEMISTRY
How Can the Fipronil Insecticide Access Phloem?
1, MICHEL TissuT, AND
Asmap Aaroup, MuRIEL RAVETON,* DaLiLa AzRou-Isc
PaTRICK RAVANEL
Laboratsire dFcologie Alpine, Université Joseph Fourier, BLP. 53,
F-38041 Grenoble Cedex 09, Fraxce
Seeds of sunflower plants coated with the fipronil "4C-insectcide were allowed to grow in the
greenhouse. The distribution of the ‘“C-compounds was studied in each part of the plant after
three months, After 88 days of culture small amounts of *4C-compounds were found in the
inflorescence (0.6% of the seed deposit) which were fipronil itself or its lipophilic or hydroptilic
metabolites, The “*C-compounds wers found in each part of the inflorescence (bracts, ray and disk
florets containing pollen, akenes). The *4C-concentration in the xylem sap evaluated at this stage
|was much too low to explain the accumulated ammount in the inflorescence. Under controlled condtions
ina culture chamber, it was then demonstrated that a net phloem transfer of “*C-fipronil occurred
{rom developed leaves to growing organs. This allowed us to suppose that a similar “C-fipronil phloem
transfer could occur toward the inflorescence during its formation. A quantitative evaluation suggests
that most ofthe labeled compounds at this stage were not coming from the leaves but from the roots
land stem where storage compounds were hycrolyzed for sustaining inflorescence development.
KEYWORDS: Fipronil; suntiower; inflorescence; phloem
INTRODUCTION
yiphenyl-+(trifluorometiy! sulhinyl) pyrarote} (Figure 4) is
‘mainly used in agriculture against soil insects, stich as wire-
worms (J). The biochemical turget of this insecticide is the
‘y-ammina butyric acid gated chloride channel (2), and it has much
‘more potent activity on insects than oa mammals (3),
Fipronil is used as a seed coating formulation named Repent
TS, mosdy for maize and sunflower cultures (4). Under this
formulation, fipronil is applied in solid, crystalline form and is
fetained in the coat by formulation agents. It is then able 10
provide an efficient protection of the seed and seedling against
soil insect attacks,
At the end of the 20th century the question arose of a possible
‘damage to honey bees, die to insecticides used as seed coating,
‘mainly for sunflower (5-7). Suchhypothetical—effect required
thatthe active ingredient (2i.) be absorbed by the roots of the
coture and transported to the inflorescence where it would be
found inside pollen grains or nectar, Iter harvested by honey
bees, To produce such an effect, 4 complex transfer appeared.
to be required. It has been previously demonstrated that '$C-
fipronil was absorbed by sunflower plantlets from an aqueous
‘medium of from soil. Such uptake Was carried out by the roots
sand bound to 2 xylem transfer, the rate of which was transpire
tion dependent (8), However, such a transfer was unable 10
solely explain a possible accumulation of ai. inside the
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orescence. Therefore, the involvement of the phloem pathway
seemed necessary
‘A Large number of herbicides are known for being phloem-
‘uansported, such as aminotiazole, glyphosate, phytohormones
of the 2.4.D series, or even paraquat (0-12), However, the
physicochemical properties of these hechicides difier radically
‘rom those of the insecticides used as seed coating against soil
‘wireworms ({.e., fipronil, imidaciopad, ..),
A careful examination was therefore required to see whether
‘a phloem transport of such insecticides was possible and whether
its result was to accumulate an insecticidal activity inside pollen
‘or nectar in cultivated plants submitted to insect pollination,
‘The purpose of this report was to study these poinis in the
cease of the sunflower culture seed coated with the insecticide
fipronil. Two questions were considered: (2) Is it possible under
field conditions or in the greenhouse to detect fiproail o¢ its
insecticidal derivatives in the inflorescence or pollen of sun-
flower plants issued from fpronil-coated seeds? (b) Under
laboratory conditions, is it possible to demonstrate a phloem-
luansfer of C-fipronil from source to sink?
MATERIALS AND METHODS
Chemicals. Fipronl[S-amino--