Evaluarea reziduurilor de pesticide din fructe i legume de la Xiamen

In the present study an effort has been made to evaluate the residues of selected
insecticides (organophosphorous and pyrethroid) and fungicides (triazoles and
chloronitriles) in fruits and vegetables collected from Xiamen, China, during the
October 2006 to March 2009 monitoring campaign. Gas chromatography with
electron capture detector (GC-ECD) was used to determine the concentrations of
22 pesticide residues among those recommended for pest treatment.
n acest studiul se evalueaza reziduurile de insecticide organofosforice selectate
(i piretroide) i fungicide (triazoli i chloronitriles) din fructe i legume colectate
din Xiamen, China, n perioada octombrie 2006 -martie 2009. Cromatografia
gazoasa cu detector cu captur de electroni (GC-ECD) a fost utilizata pentru a
determina concentraiile de 22 de reziduuri de pesticide.
Pesticides are widely used to ensure high crop yields. They are used during
production and post-harvest treatment of agricultural commodities (FAO/WHO,
2004). However, increased use of chemical pesticides has resulted in
contamination of the environment and also caused many associated long-term
effects on human health
Pesticidele sunt utilizate pe scar larg pentru a asigura un randament ridicat.
Acestea sunt utilizate n timpul produciei i dup recoltare ca si tratament de
produse agricole (FAO / OMS, 2004). Cu toate acestea, utilizarea sporit a
pesticidelor chimice a dus la contaminarea mediului i, de asemenea, cauzeaza
multe efecte pe termen lung asupra sntii umane
A total of 3009 samples of fruits and vegetables were collected from October
2006 to March 2009. The samples were collected during the appropriate season
at randomly selected wholesalers or large supermarkets from each of the 5
districts of Xiamen city.
Un total de 3009 probe de fructe i legume au fost colectate din octombrie 2006
pana in martie 2009. Probele au fost colectate n timpul sezonului adecvat la de
la angrositii selectati aleatoriu sau supermarket-uri dintre cele 5 cartiere ale
oraului Xiamen.
Samples were immediately wrapped in aluminum foil, placed in an ice-chest kept
at 4 and sent to the laboratory until the extraction was done.
Pesticide-grade acetonitrile, methanol, ethyl acetate, and hydrous sodium sulfate
were obtained from Merck (Darmstadt,Germany). Pesticide standards of purity
99.0e99.9% were purchased from the Institute of Food Safety, the Ministry of
Health of China in sealed vials. Glassware used was free from residue
contamination.
The individual stock standard solutions of each pesticide were prepared by
dissolving 100 mg of each compound in 100 ml methanol. A mixed standard
working solutions at various concentrations were daily prepared by appropriate

dilution of aliquots of the stock solution in methanol and stored at 4 in a

refrigerator.
Probele au fost imediat nvelite n folie de aluminiu, plasate ntr-o baie de ghea
pstrate la 4grade i apoi trimise la laborator pn la extracie.
Pesticide precum metanololul, acetat de etil, i sulfat de sodiu hidratat s-au
obinut de la Merck (Darmstadt, Germania). Standardele de pesticide de puritate
99.0-99.9% au fost achiziionate de la Institutul de Sigurana Alimentelor,
Ministerul Sntii din China, n flacoane sigilate. Sticlarie utilizata a fost liber de
contaminare reziduuri.
Soluiile standard stoc de fiecare pesticid au fost preparate prin dizolvarea 100
mg din fiecare compus n 100 ml de metanol.
Gas chromatography is the technique most widely used in pesticide analysis
because of its high resolution capacity and the availability of selective detectors
(Fernndez, Pico, & Manes, 2001).
In laboratory practice it serves as a screening method for over 300 pesticides.
Gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring
(SIM) was chosen because of its capability for sensitive and specific detection
(Sannino, Mambriani, Bandini, & Bolzoni, 1996). GCeMS has been used in
confirmation studies of pesticide residues in fruits and vegetables (Colume,
Cardenas, Gallego, & Valcarcel, 2001; Fernndez-Alba, Valverde, Aguera &
Contreras, 1994; Gelsomino, Petrovicova, Tiburtini, Magnani, & Felici, 1997).
Confirmatory analysis was needed due to the large probability of false positive
results obtained by GC-ECD (Gelsomino et al., 1997)
Cromatografia de gaze e cea mai des utilizata metoda n analiza de pesticide din
cauza capacitii sale de nalt rezoluie i de disponibilitatea de detectoare
selective (Fernndez, Pico, si Manes, 2001).
Cromatografie gazoasa / spectrometrie de mas (GC / MS), cu ion selectiv (SIM)
a fost alesa datorit capacitii sale pentru detectarea sensibil i specific
(Sannino, Mambriani, Bandini, si Bolzoni, 1996).

A portion of sample (200 g) was chopped and homogenized for 3 min at high
speed. Twenty grams of the homogenized sample was mixed with 100 ml ethyl
acetate and 75 g anhydrous sodium sulfate, and the mixture was blended using a
stainless steel-armed blender for 5 min. The resulting mixture wasfiltered through
20 g anhydrous sodium sulfate. The solid residue was washed with 50 ml ethyl
acetate and the organic extract was concentrated to less than 10 ml on a vacuum
rotary evaporator using a water bath at 45 C and 250 mbar. Then it was passed
to a conical tube (15 ml) and evaporated to dryness under a stream of nitrogen
gas. Finally, the extract was reconstituted to 10 ml with ethyl acetate and 2 ml
were analyzed by GC.

O poriune din prob (200 g) a fost tiat i omogenizata timp de 3 min la viteza
mare. Douzeci de grame de proba omogenizat s-a amestecat cu 100 ml acetat
de etil i 75 g de sulfat de sodiu anhidru, iar amestecul a fost pus ntr-un mixer
din oel inoxidabil armat pentru 5 min. Amestecul rezultat a fost filtrat prin 20 g
sulfat de sodiu anhidru. Reziduul solid s-a splat cu 50 ml acetat de etil i
extractul organic a fost concentrat la mai puin de 10 ml pe un evaporator rotativ
sub vid folosind o baie de ap la 45 C i 250 mbar. Apoi a fost pus intr-un tub
conic (15 ml) i se evapor la sec sub un curent de azot gazos. n cele din urm,
extractul a fost reconstituit pn la 10 ml cu acetat de etil i 2 ml au fost
analizate cu GC.
Samples, thus obtained, were injected (1ml) and analyzed for the presence of
pesticides by gas chromatography (Agilent HP 6890 N) with selective electron
capture detector (ECD) that allowed the detection of contaminants even at trace
level concentrations. Compounds were separated on a DB-1701 capillary column
of 30 m, 0.25 mm I.D. and 0.25mmfilm thickness. Super-purified nitrogen was
used as the carrier gas. Injector temperature was set at 250 C. Oven temperature
was initially set at 90 C and held for 2 min, then programmed to 250 C at 8 C min
and then held for 12 min. Detector temperature was set at 240 C. The peak area
was compared to that of the calibration standards to determine the residue
quantitatively. Any detected residues were confirmed using mass spectrometry to
prevent any misinterpretation of results. Detection limits (DL) of the method for
each of the pesticides were 0.01 mg kg , which were found by determining the
lowest concentrations of the residues in each of the matrices that could be
reproducibly measured at the operating conditions of the GC using a signal-tonoise ratio of 3. The spectra were obtained at an ionizing energy of 70 eV in the
selected ion-monitoring (SIM) mode. To test the quality of the method during
each batch, 10 g samples in which no pesticides had been detected previously
were spiked by the addition of 0.1 ml acetonitrile solution of pesticides at 10.0
mg kg of each compound. The samples were prepared for analysis according to
the procedure described above. Each batch consisted of 30 unit extracts. Mean
recoveries of the extraction procedure for all samples ranged from 80 to 120%.
Probele, astfel obinut, s-au injectat (1 ml) i analizate pentru prezena
pesticidelor prin cromatografie n faz gazoas (Agilent HP 6890 N) cu detector
cu captur de electroni (ECD) care a permis detectarea contaminanilor chiar si la
concentraii foarte mici. Compuii au fost separai pe o coloan capilar DB-1701
30 m, 0,25 mm ID i grosimea 0.25mm film. Azotul purificat a fost utilizat drept
gaz purttor. Temperatura injectorului a fost stabilit la 250 C ,temperatura
cuptorului a fost stabilit iniial la 90 C i meninut timp de 2 min, apoi programat
la 250 C timp de 12 min. Temperatura Detector a fost fixat la 240 C .Aria
picului fost comparat cu cea a standardelor de calibrare pentru a determina
reziduul cantitativ. Orice reziduuri detectate au fost confirmate prin spectrometrie
de masa pentru a preveni orice interpretare greit a rezultatelor. Limite de

mgkg 1
detecie (DL) ale metodei pentru fiecare dintre pesticidele erau 0.01

Spectrele au fost obinute la o energie de ionizare de 70 eV. Pentru a testa

calitatea metodei in timpul fiecarui lot, 10 g proba n care nu au fost detectate
anterior pesticide au fost injectate prin adugarea de 0.1 ml soluie de acetonitril
a pesticidelor la 10,0 mg kg din fiecare compus. Probele au fost preparate pentru
analiz conform procedeului descris mai sus. Fiecare lot a constat din 30 de
extracte unitare. Valorile medii fiind procedura de extracie pentru toate
eantioanele au variat de la 80 la 120%.
Calculul coninutului mediu de pesticide
Ecuaia utilizat pentru a calcula coninutul mediu al unui pesticid ntr-un anumit
produs a fost:

C p, f

Cavg , pos , p , f N pos , p , f

C p, f

N p, f

Cavg , pos , p , f N pos , p , f

N p, f

C p, f
=continutul mediu de pesticide p in produsul f;

Cavg , pos , p , f
= este coninutul mediu de pesticide p n mrfuri f cu reziduuri detectate

N pos , p , f
= este numrul de eantioane cu reziduuri detectate

N p, f
= este numrul de mrfuri analizate pentru pesticidul p.
Produsul

Numarul de
probe
analizate

Mere
Varza
Rosii
Portocale
Brocoli
Salata
Rodie

41
261
231
13
46
147
105

Numarul de
probe fara
reziduuri
detectabile
30(73.2%)
197(75.5%)
138(59.8%)
13(100%)
29(63%)
95(64.6%)
80(76.2%)

Nr de probe
<MRL(%)

Nr de probe
>MRL(%)

11(26.8%)
33(12.6%)
69(29.9%)
0
10(21.7%)
41(27.9%)
15(14.3%)

0
31(11.9%)
24(10.4%)
0
7(15.2%)
11(7.5%)
10(9.5%)

Pesticide detectate in legume si fructe

Pesticidul

Valoarea

mgkg

Limite

Nr de probe
detectate

Nr de probe
>MRL

n acest program de monitorizare, au fost gsite reziduuri de pesticide care

depesc MRL pentru 12 tipuri diferite de pesticide. Reziduuri de metamidofos au
fost gsite in cantitati mai mari decat cele omologate de MRLi (5,5% din probe);
majoritatea acestor probe au fost leguminoase.

Studiul de fa arat c, n ciuda rata apariie mare de reziduuri de pesticide n

fructe i legume din oraul Xiamen 2006-2009, nivelul de contaminare nu a putut
fi considerat o problem serioas de sntate public. Pentru a preveni
expunerea la pesticide, este necesar s se reduc i s controleze utilizarea
pesticidelor n aceste produse de activitile de punere n aplicare. De asemenea,
solicit un control mbuntit reziduurilor la producie, reglementari mai stricte
de pulverizare a pesticidelor i a Regulamentului de asemenea mai stricte, n
vnzarea de pesticide, precum i pentru educaia fermierilor i implementarea
metodelor de management integrat al duntorilor. Cu toate acestea, programe
de monitorizare sunt n ce mai importante i eseniale pentru a asigura un nivel
minim de reziduuri de pesticide din produsele alimentare.