~; ',.. :[ J .R; .,£ .;-£,:~~ IL>
PESTICIDE BIOCONCENTRATION FACTOR ESTIMA1E IN APPLES
Lourival
Costa
Paraiba
34Abstract
This work objective >'.as to estimate the bioconcentration factor (BCF) of thirty six pesticides used in the Brazilia n integrated apple production systems (lAP), in order to select priority pesticides' to be' monitored in apples. A hypcthetical apple orchard was assumed and the model applied was aa:ording to Paraiba (2007) [Pesticide bioconcertration rrodeling for fruit trees. Chemosphe re (66: 1468-147Sn The model relates BCF with plant and pesticide characteristics. The octanol-water partition coefficients rf pesticides and their deg-adation rates in the soil were lEed. The foliowing plant variables ...ere consirered: growth rate, total dry biomass, claily water transpiration rate,.and tctal volume of >'.atEr necessary to produce one kg rf fresh fruit Pff plant The pesticide stem-water partition coefficient and the transpiration str€8m concentration factor were calculated using equations that relate €8ch coEfficient wittl the octanol-watEr JErtition coEfficient The p=sticide B:F in fruits is an important indicator rf the p=sticide affinity to fruits, and helps to improve the integrated proouction systems.
Key words: Malus domestic a, fungicides, insecticides, lAP, integ-atEd production systems, fruits.
Introduction
Fruits are worldwide enjoyed
Of
people for their flavor, aroma, color, form and nutritional values and consumed in natura oras processed food. The temperate climate regions provide adequate conditions to cu~ivate several fruit species, but also favor the proliferation of many organisms that negatwely affect orct-ards and their econorrical production. For instance, a certain corriJ ination rf air temperature and hurridity induces several pathogenic fungi sp=cies to appear, causing fruit production decrease. For this reason, all
over the world's temperate regions, marketable orchards are cu~ivated with the aid of pesticides.
Brazil is arrong the world nation's greater consumers and exporters rf fresh fruits and fruit juices, bLt it is also ranked among the ten greatest pesticide users (Armas et aI., 200S~ The Brazilian government is concerned aboLt the fruit quality rffered to the internal and external market. TherEfore, the Brazilian government actions are within the exp=ctations of Brazilian and foreig n consumers of fresh fruits and derwates. As for instance, the 91/414/EK directive of the Europ€8n Economic Comrrunity (EEC) establishes which
pesticides are aLthorized for the EK use to proouce plarts and the pesticide residue limit values for ag-icu~ural vegetal products.
Therefore, the EK imposes sanitary constraints for vegetal products from internal or foreign origin, because they rrust be within
adequate requirements for the population consumption.
It is evidert tt-at the lEe rf pesticides in fruit p-oduction increases fruit yielding, and also the potential consumption of fruits and derivates. Ho...ever, consumers need to be informed aboLt the risks of consurring fruits from production fields managed wittl pesticides. In the integrated production system, a list of recommended pesticides and technical procedures for application and rronitoring are always suggested, airring at reducing risks of food and environmental cortarrination. t\evertheless, managers, technicians, adrrinistrators and researchers involved in the integrated production systems ougtt to have the know-how to estimate the pesticide currulative potential in fruits in order to monitor and suggest new technologies for a sustainable fruit production.
Mathematical models can cortribute to predict the substance uptake
Of
plants and can be lEed to indicate which substancesrrust be rronitored in vegetal product samples of Good Agricu~ural Practices Programs (GAPs). Several models have been developed with such objectives and among them the following works are mentioned: Fujisawa
et
al. (2002), Trapp et at (2003), Trar:p (2004),McKone and Maddalena (2007), Trapp, (2007) and Paraiba (2007).
An organism substance bioconcertration descrites the increase in the organism substance concertration in relation to the substance concertration in the medium The organism substance bioconcertration factor (BCF) is a nurriJer that expresses the bioconcentration process and it represents the substance partition coEfficient tetv.een the organism and the medium·tn the chemical equilibrium state, this coefficient is the quotient between the substance concertration in the organism and the medium According to Paraiba (2007), the BCF is reterrrined by the lirrit quotient between the substance concertration in the organism and the medium, when time tends to infinite A p=sticide BCF in apples is an importart indicator rf the apple-pesticide affinity and it rright allow selecting pesticides to te monitored and help to improve the integrated apple production systems.
Therefore, this work ob1'ctwe >'.as to estimate thirty six pesticide BCF in apples, used in the Brazilian integrated apple production systems (lAP) and indicate the priority pestiCides to be monitored. For that, a hypothetical apple orchard >'.as ass umed,
34ErriJrapa rv'eio ArriJiente -ErriJrapa Environment. CXP. 69 -Cep 13820-000 - SP 340, Km 127,5. Tel. XX-55-19·3311-2667; e-mail: 10urival@cnpma.erriJrapa.br; Jaguariuna. Sao Paulo, Brasil.
cu~ivatEd w~h pesticides used in the lAP system and a rrodel approach according to Paraiba (2007) was adop:ed to estirrnte BCF in a:>ples.
Materials and Methods
The studied pesticides and their physical-chenical properties required to estirrnte BCF a~ presented in Table 1. These data were obtained from Gebler (2004) and Girardi and Bender (2003} The pesticides' haf-life times in the soil were obtained from Hornsby
et a!. (19%) or Toniin (2000). And the ~sticide octanol-water pa,Uion coeffICients were ottained from Tomlin (2000). When calculating BCF, ~ was assumed steacty-state equilibrium into the pesticide/soil solution/plant system and that the pesticide dissipation in the soiVplant system occurred via plart grov.th, plart metabolism and pesticide degradation in the soil. BCF was estirrnted by the
Q Q,TSCF
exp~ssion BCF = , where BCF (I kg") is the pesticide bioconcertration facter in the apple, Q (I day" ha") 5
Q+k .. ,K.""" .• M
the apple-t~e daily WltEr transpiration rate, Qr(1 kg'l) is the water tctal volume required fer the plart to produce one kilogram of fresh fruit, TSCF is the transpiration st~am concentration factor cf pesticide,
k.,;s
(day") is the ~sticide dissipation rate in the soil-plant system K""""wis the ~sticide stem-water partition coefficient and M(kg ha-I) is the apple plant total dry biorrnss per hectare. 9:e1lJy-state equilibriu m of the quotiert be:ween the fruit pesticide concentration and the soil solution pesticide concentration WlS assumed to obtain equation 1 (Paraiba, 2007), The ~sticide dissipation rate in the SOil-plant system was calculated by
k
.., =
k
,
+
k. -
k"
where
1<.,
kg andks
(day") are, res~ctively, the pestiCide metatxJlism rate in the plant, the plant grONth rate, and the pesticide degradation rate in the soil. The TSCF was estirrnted from the ~sticide octanol-Wlter partition coefficient using the equation given by( -('0"",_ -2,50)')
(Burken and Schnoor, 1998)
TSCF
=
0.756
x e
2.58 ,whe~ logK_
is theIoga
r
~h
m
of pesticide crctarol-watEr part~ion coefficient and TSCF is the transpiration stream concentration factor cf pesticide, The K""",wvalue was estirrnted using a'1 equation that relates the logarithm of the octanol-Wlter partition coefficient (!<;,w) with the logarithm of the stem-water partition coefficient given by (Trapp et ai, 2001)log
Kwood,w
=-0,27
+
0,632
x l
og
K
o
w '
A frve-year-old apple orchard was supposed, with ore thousand plants per hectare and a total dry weight estirrnted in 50,000 kg ha" (M= 50,000~ Plant transpiration was estirrnted in 8,220 I day' I ha" (Q= 8,220) (300 mmyea(1 cf evapctranspiration) and an average daily plant growth rate cf 2.74xla5 day" (kg = 2. 74x1(]5) (0.Q1 per year~ According to Trapp eta!. (2003), the Wlter volume required fer apple trees to produce one kilogram of fresh fruits was estirrnted in 3.5 I kg'l (Qr= 3. 5~ The pesticide degradation rate in the soil was estirrnted from the pesticide haW-life time in this medium and using the expression
k
,
=
0.693
/
t
"2
'
The pesticide degradation rate in the plant was estimated from the pesticide haW-life time in soil and using the relation termk
,
=
k,
/
16
(Juraske eta!., 2008~ The pesticide half-life time values in the soil-plant system were estirrnted by the exrression 11/2(s-p)
=
0,693
/
k
eg<
and Jsed to evaluate the pesticide BCF in apples.(
5
1
8
'\
J
'
\
"r
Table 1. Thirty six pesticides of the integrated apple production systems (IAP) and their
res~ctive
parameters used to estimate and evaluate pesticide BCF in apples: agronorric function; chenical class; crctanol-Wlter partition coefficient (Iog!<;'w); haW-life time in soil (tl/1) and soil sorption coefficient (I<;.,).Pesticide agronorric function
chenical class 10gKow' tl/1 I<;.,§
abamectin insecticide & acaricide avermectin
4.40 28+ 36644
bitertanol fungicide
triazole 4,1 30' 20941
carbaryl insecticide
carbamate 2,36 10+ 816
chlorothalonil fungicide chloronitrile
4.00 60' 17378
chlorpyrifos fungicide
organophosphorus 3.05 30+ 2955
cyprodinil fungicide anilinopyrimidine
4,96 30· 104136
diazinon insecticide & acaricide
organophosphorus 3.81 40+ 12193
difenoconazole fungicide triazole
4.30 145' 30409 dodine fungicide guanidine 1.15 20+ 85 fenarimol fungicide pirynidine 3.60 360+ 8241 fenitrcthion insecticide organophosphorus 3.30 4+ 4710
fenPiraxirrnte acaricide pyrazole
5.01 50' 114314
fluazinam fungicide
phenylPiridinanine 3,56 62' 7649
fluquinconazole fungicide triazole
3,24 300' 4211
folpet fungicide phthalinide
2.85 4.3' 2035
imibenconazole fungicide triazole
4.94 28' 100323
kresoxim-methyl fungicide
oxininoacetatE 3.40 3' 5675
rrnlathion insecticide & acaricide
orga nopha;phorus 2,36 1 + 816
rrnncozeb fungicide
dithiocarbarrnte 1.33 70+ 119
metiram insecticide & acaricide
dithioca'rbarrnte 0.3 20+ 17
myclobutanil fungicide triazole
2.94 66' 2407
phosmet fungicide
organophosphorus 2.78 19+ 1786
prochloraz fungicide imidazole
4.10 120+ 20941
pyrazophos fungicide
phosphorcthiolate 3,80 21' 11967
pyridaben insecticide & acaricide
6,37 21' 1444442
pyrimethanil fungicide
anilinopyrimidine 2.84 54' 1997
cu~ivated w~h pesticides used in the lAP systel1\ and a rrodel approach according to Paraiba (2007) was adop:ed to estimate BCF in a.~ples.
Materials and Methods
The studied pesticides and their physical-cherrical properties required to estimate BCF are presented in Table L These data were obtained from Gebler (2004) and Girardi and Bender (2003~ The pesticides' haf-life times in the 9:lil were ootained from Hornsby et al. (19%) or Torrlin (2000). And the pesticide octanol-water part~ion coefficients were ottained from Tomlin (2000). When calculating BCF, ~ was assumed steady-state equilibrium into the pesticide/soil solution/plant system and that the pesticide dissipation in the soiVplant system occurred via plart groW:h, plart metabolism and pesticide degradation in the soil. SO' was estimated by the
Q QfTSCF
expression BCF = , where SO' (I kg") is the pesticide bioconcertration facter in the apple, Q (I day" ha,l) 6
Q+k .. , K-..d.,. M
the apple-tree daily Wlter transpiration rate, Q,(I kg'l) is the water tetal volume required fer the plart to produce one kilogram of fresh fruit, TSCF is the transpiration stream concentration fador ci pesticide, k..;, (day") is the pesticide dissipation rate in the 9:lil-plant systel1\ K><Dd, .. is the pesticide stem-water iErt~ion mefficient and M (kg ha-l) is the apple plant total dry biomass per hectare. 9:eiily -state equilibriu m of the quotiert bEtween the fru~ pesticide concentration and the soil solution pesticide concentration WlS assumed to obtain equation 1 (Paraiba, 2007). The pesticide dissipation rate in the 9:l11-plant system was calculated by
k
"8'
=
k
,
+ k
g
- k"
where1<.,
kg and k, (day") are, respectively, the pesticide metaoolism rate in the plant, the plant grONth rate, and the pesticide degradation rate in the soil. The TSCF was estimated from the pesticide octanol-Wlter part~ion coefficient using the equation given by( -(logK_ -2.50)' )
(Burken and Schnoor, 1998)
TSCF
=
0
,
756
x e 2.58 , where 10gKow is theIoga
r
~hm
of pesticide octanol-water part~ion crefficient and TSCF is the transpiration stream concentration factor ci pesticide. The Komd,,,,value was estimated using an equation that relates the Iogar~hm of the oetanol-Wlter part~ion coefficient (11;, .. ) w~h the logarithm of the stem-water parUion coefficient given by (Trapp et ai, 2001)l
og K
woo</,w
=
-0,27 +
0,632
x
l
og Kow'
A five-year-<Jid apple orchard was supposed, w~h one thousand plants per hectare and a total dry weight estimated in 50,000 kg ha,l (M
=
50,000~ Plant transpiration was estimated in 8,220 I day" ha'l (Q=
8,220)(300 mm year'l ci evapetranspiration) and an average daily plant growth rate ci 2,74x1(T' day,l (kg = 2. 74xl(J') (0.01 per year} Acmrding to Trapp et al. (2003), the Wlter volume required fer apple trees to produce one kilogram of fresh fru~ was estimated in 3.5 I kg,l (Q,= 3.5} The pesticide degradation rate in the soil was estimated from the pesticide haW-life time in this medium and using the expressionk
,
=
0,693
/
'l/2 . The pesticide degradation rate in the plant was estimated from the pesticide haW-life time in soil and using the relation termk
,
=
k
,
/
1
6
(Juraske et aI., 2008} The pesticide half-life time values in the soil-plant system were estimated by the exp-essiont
"
2
(s-p)
=0.693
/
k<g>
and Jsed to evaluate the pesticide BCF in apples.(
'\
5
18
l
J
Table L Thirty six pesticides of the Integrated apple production system; (lAP) and their respective parameters used to estimate and evaluate pesticide BCF in apples: agronomic function; chenical class; octanol-Wlter partition coefficient (log 11;, .. ); haW-life time in soil (tlfl) and soil sorption coefficient (K.c).
Pesticide agronomic function cherrical class
log
1<0;
tl/1Ko!
abamectin insecticide & acaricide
avermectin 4.40 28+ 36644
bitertanol fungicide triazole
4.1 30' 20941
carbaryl insecticide carbamate
2.36 10+ 816
chlorothalonil fungicide chloronitrile
4.00 60' 17378
chlorpyrifa; fungicide organopha;phorus
3.05 30+ 2955
cyprodinil fungicide
anilinopyrimidine 4.96 30' 104136
diazinon insecticide & acaricide
organopha;phorus 3.81 40+ 12193
difenoconazole fungicide triazole
4.30 145' 30409
dodine fungicide guanidine
1.15 20+ 85
fenarimol fungicide pirynidine
3.60 360+ 8241
fenitrcthion insecticide organopha;phorus
3.30 4+ 4710
fenp,troximate acaricide pyrazole
5,01 50' 114314
fluazinam fungicide
phenylp,tridinanine 3.56 62' 7649
fluquinconazole fungicide triazole
3.24 300' 4211
folpet fungicide
phthalinide 2.85 4.3' 2035
imibenconazole fungicide triazole
4.94 28' 100323
kresoxim-rrethyl fungicide oxininoacetate
3.40 3' 5675
malathion insecticide & acaricide
organopha;phorus 2.36 1 + 816
mancozeb fungicide d~hiocarbamate
1.33 70+ 119
rretiram insecticide & aca ricide
dithioca'rbamate 0.3 20+ 17
myclobutanil fungicide triazole
2.94 66' 2407
phosmet fungicide
organopha;phorus 2,78 19+ 1786
prochloraz fungicide imidazole
4.10 120+ 20941
pyrazophos fungicide
phosphorcthiolate 3.80 21' 11967
pyridaberl insecticide & acaricide
6.37 21' 1444442
pyrirrethanil fungicide anilinopyrimidine
2.84 54' 1997
;irrazine herbicide 1,3,5-triazine 2.18 60+ 583
;pirolliclofen acaricide 5.80 5.5' 498884
:ebucorazole fungicide triazole 3.70 28' 9931
:ebLfenozkE insecticide diacylhydrazine 0.83 30' 47
:hlophanate-methyl fungicide benzirridazole 1.40 10+ 136
·
:riadimefon fungicide triazole 2.77 26+ 1753
trichlorfon insecticide organophosphorus 0.51 10+ 26
triflurrizole fungicide imidazole 1.40 14+ 136
:riforine fungicide piperazine 2.20 21 + 605
"Data otlained from Tom/in (2000); +Data otlained from Hornsby et al. (J 996) § Va/vesL estirreted by
log
Koc
=0.81
x
log
Kow
+
0.1
(EUSES, 1996) .,suits and Discussion
For each pesticide listed in Table 1, the following variables were estimated: haW-life time in the soil-plant system; transpiration
eam concentration facta-; stem-water partition coefficient; and BCF in apples (Table 2~ Sixteen of the thirty si< pesticides shew
.g
K
o,
>
3.5
,
what means there is an expressive affinity between pesticide and soil organic carbon or plart woody material, aslicated
Of
the soil sorJtion coefficients and the stem-water partition coefficients (Tables 1 and 2~ Thus, the pesticides fluazinam,larimol, tebucorazole, pyrazophos, diazino", chlorothalonil, prochloraz, bitertlnol, difenoconazole, abamectin, irribencona zole, xadinil, fenpyroximate, spirodiclofen and pyridaben rright be found mainly in the soil or woody part cf plants.
According to Paraiba (2007), pesticides with
1.5
~
logK
ow
~
3.5
presert the ideal attributes for translocation from soil fruits. The fruit bioconoentration depends also on the haW-life time in the soil-plant system, becaL5e the BCF value (equation 1) is'ersefy preportioral to the pesticide degradation rate in the soil-plant system The longer the haf-life time, the iower the degradation :e in the soil-plant system and the higher the ECF. TherEfore, considering the three parameters, half-life time in the sail-plant system,
CF and K"""" ... the following pesticides can be considered priority pesticides for apple monitoring (in decreasing order): mancozeb >
lLfenozkE> simazine > fluquinconazole > dodine > metiram> fenarimol > triflurrizole > trichiorfon > myclobutanil (Table 2). These
~ also the ten pesticides with higher BCF values in apples.
Mancozebe and metiram are dithiocarbamate class pesticides and have been found in apples and vegetables (Cesnik et aI.,
06, Glidas et ai, 2004, ANVISA, 2003, Ripley et ai, 2000, Dogheim et aI., 1999, EU, 2001, IUPAC, 1994). They are recorrrrended
Of
o (2004) as priority pesticides for fruit and vegetable monitoring.Sharma and Nath (2005) analyzed 327 apple samples collected from orchards cf Himachal Pradesh, India, and found 101
mples contarrinated with dithiocarbamates, whereas 33 from 286, 20 from 246 and 9 from 97 samples were contarrinated with lanochlorides, organophosphorates and ca rba mates, respectivefy. According to Chanilerlain et al (1998), dodine is a systerric
19icide, what means it rright bioconcentrate in apple fruits. The dadine fungicide is one of the priority pesticides indicated by FAO
)04) for vegetal-originated food monitoring.
Table 2. Parameter estimates for twenty six pesticides of the integrated apple production system (lAP): t".;{s-p):
haW-life time in the SOil-plant system; TSCF: conoentration factor in the transpiration stream;
Kwood,w.
stem-water(
'\
520
J
l
,.
"'~:
.
(
1
"
i{~: f'~:~
!
j
!
[r
partition coefficient; and BCF: bioconcentration factor in apples.
Pesticide tJ,ds-p) TSCF' K...:xxJ,w BCF (days) (I kg') (I kg') mancozeb 0.445 4 0.3210 tebLfenozide 2 0.256 2 0.1687 sirrezine 0.727 13 0.1576 fluquinconazole 4 0.611 60 0.1407 dodine 2 0.373 0.1169 metiram 2 0.116 0.1005 fenarimol 0.473 101 0.0789 triflurrizole 9 0.473 4 0.0760 trichklrfon 0.163 0.0631 myclobutanil 23 0.701 39 0.0579 pyrimethanil < 1 0.723 33 0.0566 triforine 3 0.730 13 0.0564 thiophanate-methyl 4 0.473 4 0.0551 triadimefon 19 0.735 30 0.0310 phosmet < 1 0.733 31 0.0224 carbaryl 0.750 17 0.0222 chlorpyrifos < 1 0.672 45 0.0219 fluazinam < 1 0.489 95 0.0156 prochloraz 4 0.280 210 0.0079 diazinon 0.389 137 0.0056 difenocorazole 4 0.215 280 0.0055 chklrothalonil 0.316 181 0.0052 tebucorazole 8 0.433 117 0.0051 folpet 0.721 34 0.0045 pyrazophos 0.393 135 0.0030 malathion 3 0.750 17 0.0022 bitertO'lol 4 0.280 210 0.0020
(
521
}
;irrazine herbicide 1,3,s-triazine 2.18 60+ 583
;pirouiclofen acaricide 5.80 5.5· 498884
:ebuconazole fungicide triazole 3.70 28· 9931
:ebLfenozide insecticide diacylhydrazine 0.83 30· 47
:hiophanate-mett1y1 fungicide benzirridazole 1.40 10+ 136
:riadimefon fungicide triazole 2.77 26+ 1753
:richlorfon insecticide organophcsphonus 0.51 10+ 26
:riflurrizole fungicide imidazole 1.40 14+ 136
:riforine fungicide piperazine 2.20 21+ 60S
"Data otl:ained from Tomlin (2000); +Data otl:ained from Homsby et al (1996) § ValuesL estirreted
OJ
logK
oc
=
0.8\
x
logKow
+
0.1
(EUSES, 1996).,suits and Discussion
For each pesticide listed in Table 1, the following variables were estimated: ha~-life time in the soil-plant system; transpiration eam concentration factor; stem-water p3rt~ion coefficient; and BCF in apples (Table 2~ Sixteen of the thirty sic pesticides shoo
'g
K
ow
> 3.5
,
what means there is an expressive affin~ between pesticide and soil organic carbon or plart wood{ material, as licated by the soil sorpcion coefficients and the stem-water part[ion coefficients (Tables 1 and 2~ Thus, the pesticides fluazinam, larimol, tebuconazole, pyrazophos, diazinon, chlorothalonil, prochloraz, bitertanol, difenoconazole, abamectin, irribencona zole, xodinil, fenpyroximate, spirodiclofen and pyridaben rright be found mainly in the soil or woody part ci plants.According to Paraiba (2007), pesticides w~h
1.5
::;
l
ogK
o
w
::;
3
.
5
presert the ideal attributes for translocation from soilfru~s. The fru~ bioconcentration depends also on the half-life time in the SOil-plant system, because the BCF value (equation 1) is
'erse~ preportional to the pesticide degradation rate in the soil-plant system The longer the haf-life time, the lower the degradation
:e in the soil-plant system and the higher the OCF. Therefore, considering the three parameters, half -life time in the soil-plant system, CF and K"""".~ the following pesticides can be considered prior~ pesticides for apple mon~oring (in decreasing order): mancozeb > )lienozide > simazine > fluquinconazole > dodine > metiram> fenarimo I > triflu rrizole > trichlorfon> myclobutanil (Table 2). These
~ also the ten pesticides w~h higher BCF values in apples.
Mancozebe and metiram are d~hiocarbamate class pesticides and have been found in apples and vegEtables (Cesnik et ai,
06, Caldas et ai, 2004, ANVISA, 2003, Ripley et ai, 2000, Dogheim et ai, 1999, EU, 2001, IUPAC, 1994). They are recommended by 0(2004) as prior~y pesticides for fru~ and vegetable mon~oring.
Sharma and Nath (2005) analyzed 327 apple sarrples collected from orchards ci Himachal Pradesh, India, and found 101 rrples contarrinated w~h dithiocarbamates, whereas 33 from 286, 20 from 246 and 9 from 97 sarrples were oontarrinated with lanochlorides, organophosphorates and carbamates, respedive~. Accon:ling to Charrberlain et al (19981 dodine is a systerric 19icide, what means it rright bioconcentrate in apple fru~s. The dodine fungicide is one of the priority pesticides indicated by FAD )04) for vegEtal-originated food mon~oring.
Table 2. Parameter estimates for twenty six pesticides of the integrated apple produdion system (lAP): t¥,{s-p):
half-life time in the soil-plant system; TSCF: concentration fador in the transpiration stream;
K..ood. ...
stem-water(
520 )
..
':
'
1
}:,
I:;. :,;,,'.
'~r I ,,:~r
part~ion coefficient; and BCF: bioconcentration factor in apples.
Pesticide tIP (s-p) TSCF K»OOd.w BCF
(days) (I kg") (I kg")
mancozeb 0.445 4 0.3210
tebLfenozide 2 0.256 0.1687
simazine 0.727 13 0.1576
fluquinconazole 4 0.611 60 0.1407
dodine 2 0.373 3 0.1169 metiram 2 0.116 0.1005 fenarimol 0.473 101 0.0789 triflurrizole 9 0.473 4 0.0760 trichlorfon 0.163 0.0631 myclobutanil 23 0.701 39 0.0579 pyrimethanil < 1 0.723 33 0.0566 triforine 3 0.730 13 0.0564 thiophanate-mett1y1 4 0.473 4 0.0551 triadimefon 19 0.735 30 0.0310 phosmet < 1 0.733 31 0.0224 carbaryl 2 0.750 17 0.0222 chlorpyrifcs < 1 0.672 45 0.0219 fluazinam < 1 0.489 95 0.0156 prochioraz 4 0.280 210 0.0079 diazinon 0.389 137 0.0056 difenoconazole 4 0.215 280 0.0055 chlorothalonil 0.316 181 0.0052 tebuconazole 8 0.433 117 0.0051 folpet 0.721 34 0.0045 pyrazophos 0.393 135 0,0030 malathion 3 0.750 17 0.0022 b~ertanol 4 0.280 210 0.0020
(
521
)
fen~rcxhion < 1 0.590 65 0.0018
kresox im-rrethy I 2 0.552 76 0.0011
abarrectin 0.187 324 0.0008 fenpyr(ll(imate 0.066 788 0.0002 cyprodinil 2 0.072 732 0.0001 imibenconazole 0.075 711 0.0001 spirodiclofen 0.011 2487 0.0000 pyridabm 0.002 5700 0.0000 nelusions
The BCF -bioconcertration factor -values in apples were estimated for thirty six pesticides of the integrated apple production tems (IAP). Such estimates allowed indicating the following prior~ pesticides for a~le mon~oring (in decreasing order ri BCF ues): mancozeb, tebufenozide, simazine, fluquincona:zole, dodine, rretiram, fmarimol, triflurrizole, trichlorfm and rIlfClobutanil. This ication is corroborated
Or
the apple p;!sticide mon~oring through residue analysis andit
is according to recorrmendations rilulatory international organisms. ,ferenCES
MSA. 2003. Programa de analise de residuos de ag-otaxicos em alirrentos: resultadas anal~icos de 2003. Available at :p://www.anvisa.gOl.br.1:oxicologia/residuos/reLanual_2004.p<f Acessed 2 January 2008.
mas, E. D., R. T. R. Monteiro, A. V. Armncio, R. M. L Correa, e M.A. Guercio. 2005. Usa de agrcxaxicos em cana -de-ac;Ucar na bacia do
) Corurrtlatai eo risco de polui<;ao hidrica. Quim Nova 28:975-982.
Irken, J.G., and J.L Schnoor. 1998. Predictive relationships for up:ake of organic contarTinants Or hybrid poplar trees. Environ. Sci
:chnol. 32:3379-3385.
Iidas, E.D., M.C.e. Miranda, MH.L. Concei<;iio, and e.K.R. de Souza. 2004. D~hiocartamates residues in Brazilian foed and the ,tertia I risk for consurrers. Foed Chem ToxicoL 42: 1877-1883.
~snik, H. 8., A. Gregorcic, and S. V. Bo~a. 2006. Pesticide residues in agricu~ural products ri slovene origin in 2005. Acta Chim Siov. 1:95-99.
larrberlain, K, 5. Patel, and R.H. BrorTilow. 1998. Up:ake by rods and translocatian to. shoots ri two morpholine fungicidas in tarley.
~stic. Sci. 54: 1-7.
ogheim, S.M., SAG. Alia, A.M. EI-MalSafy, and 5. Fahrllf. 1999. Mon~cring pesticide residues in Egyp:ian fru~ and vegetables in
395. J. AOAC Irt. 82:948-955.
U. 2001. Mon~oring of pesticide residues in products of plant origin in the EuropeiYI Union, Narway, Iceland and Llechtenste in. uropean commission, hea~h and cansurrer protection directcrate, Londan, England.
ujisawa, T., K. Ichise, M. Fukushima, T. Katagi and Y. Takimota. 2002 Improved uptake models af nan ionized pesticides to faliage nd seed ri craps. J. Ag-ic. Faed Chem 50:532-537.
;ebler, L. 2004. Ba'nm d,~ infarma~i3es arrtlientais e toxicalOgicas dos agrot6xicas utilizadas
ate
a safra de 2002/2003 na p~aduc;ao Itegrada de ma~. Errtlrapa uva e vinha, Bento. Gon~wes, Rio Grand! do. Sui, Brasil. Available at.ttp://www.cnpuv.errtlrapa.br/publica/circular/ Acessed 2 January 2008.
;irardi, e.L, and R.J. Bender. 2003.
Predu~aa
integ-ada d!ma~s
no. Brasil. Errtlrapa Uva e Vinha. BentoGon~wes,
Rio Grande do. Sui Irasil. Available at http://sistemasd!producao.cnptia.errtlra~.I1'/FartesHTML/Maca/ProducaolrtegradaMaca/ Acessed 2 January 2008. iarnsby, A.G., R. Don WaLJ:hape, and A.E. Herner. 1996. Pesticide prop;!rties in the environrrent 227 p. Springer-Verlag Inc., New 'ark, USA.(
<;??
l
IUPAe. 1994. Effects ri starage and processing an pesticide residues in plant praducts. Pure A~1. Chem 66:335-356.
Juraske R. A. Ant6n, and F. Castells. 2008. Estimating haW-lives ri p;!sticides in/on vegetatian for use in mu~irredia fate and exposure
models. Chemosphere 70:1748-1755.
Paraiba L.e. 2007. Pesticide biacancentratian modelling for fru~ trees. Chemosphere 66:1468-1475.
FAO. 2004. Pesticide residues in food. p. 383. In FAO panel of experts on pesticide residues in foad and the environrrent and the
wro
core assessrrent group on pesticide residues, Rorre, Itaft, 20-29 sep:errber 2004.McKone, T.E., Maddalena, R.L 2007. Plart uptake ri organic pallutants from sail: Bioconcentration estimates based an models and
exp;!rirrents. Environrrental Toxicalagy and Chemistry 26(12):2494-2504.
Ripley, aD., L.L Lissemore, P.O. Leisheman, and MA Denarrme. 2000. Pesticide residues on fru~ and vegetables from Ontario., Canada, 1991-1995. J. AOAC Int 83:196-213.
Sharma, 1.0., andA Nath. 2005. Persistence af different pesticides in apple. Acta Hortic. 696:437-440. TorTiin, C.D.S. 2000. The pesticide manual. Farnham: Br~ish Crop Protection Council. CD-Ram
Trapp, 5. 1995. Madel for uptake ri xmabiotics into plants. p. 107-151. In Trapp, 5., and J.e. McFarlane. (ed.) Plant cantarTination: modelling and simulation of organic cherTical pracesses. CRC Press, Boca Raton, Flarida, USA.
Trapp, 5., and J.e. Mcfarlane. 1995. Plant cortarTination: modelling and simulatian of arganic cherTical processes. 254 p. CRC Press, Boca Ratm, Flarida, USA.
Trapp, 5., and M. Matthies. 1995. Genetic one-compartrrent model for uptake ri arganic cherTicals by faliar vegetation. Environ. Sci Technal. 29:2333-2338.
Trapp, 5., and M. Matthies. 1998. ChemodynarTics and environrrental modelling. 285 p. Springer, Heidelberg, Germany.
Trapp, 5., K.5.a Miglioranza, and H. Mosbaek 2001. Scrption af lipophilic organic compaunds
to
wood and implications far their environrrental fate. Erniran. Sci. Technol. 35: 1561-1566.Trapp, 5., D. Rasmussen, and L. Samsae-Petersen. 2003. Fru~ tree model for uptake ri arganic mmpounds fram sail. Sar Qsar Erniran.
Res. 14:17-26.
(
523
l
J
fen~rcthion < 1 0.590 65 0.0018
kresox im-methy I 0.552 76 0.0011
abamectin 2 0.187 324 0.0000 fenp,'raximate 0.066 788 0.0002 cyprodinil 0.072 732 0.0001 imibenconazole 0.075 711 0.0001 spirodiclofen 0.011 2487 0.0000 pyridaben 0.002 5700 0.0000 nelusions
The BCF -bioconcertration factDr -values in apples were estimated for thirty six pesticides of tre integrated apple production
tems (IAP). Such estimates allowed indicating the following prior~ pesticides for ar:IJle mon~oring (in decreasing order ct BCF
ues): mancozeb, tebufenozide, simazine, fluquincona2Dle, dodine, metiram, fenarimol, triflurrizole, trichlorfm and myclobutanil. This
ication is corroborated t1y tre apple pesticide monitoring through residue analysis and ~ is according to recommendations ct
lulatory international organisms.
,ferences
MSA. 2003. Programa de analise de residuos de agotc><icos em alimentos: resultados analiticos de 2003. Available at
:p://www.anvisa.gov.brjl:oxicologia/residuos/reLanuaL2004.pcf Acessed 2 January 2008.
mas, E.D., R T.R Monteiro, A.V. Arrancio, RM.L Correa, e M.A. Guercio. 2005. US) de agrctc><icos em cana-de-a~ucar na bacia do
) Corumbatai eo risco de polui<;ao hidrica. Quim Nova 28:975-982.
"ken, lG., and J.L Schnoor. 1998. Predictive relationships for up:ake of organic contaninants t1y hybrid popiar trees. Environ. Sci
:chnol. 32:3379-3385.
,Idas, E.D., M.C.e. Miranda, MH.L Concei<;iio, and e.K.R de Souza. 2004. D~hiocartamates residues in Brazilian food and tre
.tertial risk for consumers. Food Chem Toxicol 42:1877-1883.
?snik, H.B., A. Gregorcic, and S.V. Bo~a. 2006. Pesticide residues in agricu~ural products ct slovene origin in 2005. Acta Chim Siov. !:95-99.
lani:>erlain, K, S Patel, and R.H. Bmnilow. 1998. Up:ake by rocts and translocation to shoots ct two morpholine fungicidas in tarley. ?stk:. Sci. 54: 1-7.
ogheim, S.M., SA.G. Alia, A.M. EI-MalSafy, and S Fahmy. 1999. Mon~a-ing pesticide residues in Egyp:ian fruits and vegEtables in
~95. J. AOAC Irt. 82:948-955.
U. 2001. Mon~oring of pesticide residues in products of plant origin in the European Union, Norway, Iceland and Liechtenstein.
uropean comnission, hea~h and consumer protection directa-ate, London, England.
ujisawa, T., K. Ichise, M. Fukushima, T. Katag\ and y, Takimoto. 2002. Improved uptake models of non ionized pesticides to foliage nd seed ct crops. 1 Agic. Food Chem 50:532-537.
ebler, L. 2004. Ba'nco d,~ informa~iies ambientais e taxicologicas dos agrotDxicos utilizados
ate
a safra de 2002/2003 na produc;iioltegrada de ma~. Embrapa uva e vinho, Bento Gon~~es, Rio Grand! do Sui, Brasil. Available at
ttp://www.cnpuv.embrapa.br/pLblica/circular/ Acessed 2 January 2008.
;irardi, e.L., and Rl Bender. 2003.
Produ~ao
integada d!ma~s
no Brasil. Embrapa Uva e Vinho. BentoGon~a~es,
Rio Grande do Su\Irasil. Available at http://sistemasd!producao.cnptia.embraJll,tr/FortesKTML/Maca/ProducaolrtegradaMaca/ Acessed 2 January 2000.
iornsby, A.G., R Don Wauchope, and A.E. Herner. 1996. Pesticide properties in the environment 227 p. Springer-Verlag Inc., New
'ork, USA. ( t;??
,
'r ~~.'
)
IUPAe. 1994. B'fects ct storage and processing on pesticide residues in plant products. Pure Ar:lJl. Crem 66:335-356.
Juraske R, A. Anton, and F. castells. 2000. Estimating ha~-lives ct pesticides in/on vegEtation for lI5e in mu~imedia fate and exposure
models. Chemosphere 70:174&1755.
Paraiba L.e. 2007. Pesticide bioconcentration modelling for fru~ trees. Chemosphere 66: 1468-1475.
FAO. 2004. l'esticide residues in food. p. 383. In FAO panel of experts on pesticide residues in food and the environment and the WI-O core assessment group on pesticide residues, Rome, Ita~, 20-29 sep:errber 2004,
McKone, T. E., Maddalena, R. L 2007. Plart uptake ct organic pollutants from soil: Bioconcentration estimates based on models and
experiments. Environmental Toxicology and Chemistry 26(12):2494-2504.
Ripiey, B.D., L.L Lissemore, P.O. Leisheman, and MA Denomme. 2000. Pesticide residues on fruits and vegetables from Ontario, Canada, 1991-1995. J. AOAC Int 83:196-213.
Sharma, I. D., andA Nath. 2005. Persistence of different pesticides in apple. Acta Hortic. 696:437 -440.
Toniin, C.D.S. 2000. The pesticide manual. Farnham: Br~ish Crop Protection Council. CD-Rom
Trapp, S 1995. Model for uptake ct xenobiotics into plants. p. 107-151. In Trapp, S, and J.e. McFarlane. (ed.) Plant contanination:
modelling and simulation of organic chemical processes. CRC Press, Boca Raton, Florida, USA.
Trapp, S, and J.e. Mcfarlane. 1995. Plant cortanination: modelling and simulation of organic chenical processes. 254 p. CRC Press,
Boca Ratm, Florida, USA.
Trapp, S, and M. Matthies. 1995. Genetic one-compartment model for uptake ct organic chenicals by foliar vegEtation. Environ. Sci
Technol. 29:2333-2338.
Trapp, S, and M. Matthies. 1998. Chemodynanics and environmental modelling. 285 p. Springer, Heidelberg, Germany.
Trapp, S, K.SB. Miglioranza, and H. Mcsbaek 2001. Sa-ption of lipophilic organic compounds to wood and implications for their
environmental fate. Environ. Sci. Technol. 35:1561-1566.
Trapp,
s.,
D. Rasmussen, and L. Samsoe-l'etersen. 2003, Fruit tree model for uptake ct organic compounds from soil. Oar Qsar Environ.Res. 14:17-26.
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