Bastos, Maria de Lourdes

Pereira, J.A.

Soares, Maria Elisa

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Copper and lead residues in olives after olive tree treatments with three different copper formulations Soares, M.E.' , Pereira, .LA,I, Bastos, M.L. 1 'REQUIMTE. Toxicology Departmcllt, Faculty ofPhannucy. Rua Aníbal Cunha, 164,4099-030 Porto, Ponugal 2c! MO, School af Agricu llu rc, Polytechnic rnstilutc of Br.lgança. Quinto S la Apolónia, Apl. 1172, 5301-855 Brogança, Portug.1I lNTRODUCTION Ficld (csts \Vere pcrformcd to control (\Vil oUve fungai discascs 1([10\\'11 as olive anthracnosc Collecloll'ic/wl/I sflP, and olive Icar spot, SI'i/ocaeu oleagina (Cast.). and to cvaluate lhe pcsticldc rcsiducs ln lhe oli,,!.' fruits h:lrvested aI dlrrercnt timc!'i. Thc cxperiment was c!lrriell QuI in :l Cv Cubrançosa oUve orch:trd located ne.ar Mirandela, Nonlcasl of Portugal. Thc orchard was subdivided ln f[)ur piaIs, thrl'(' of (Item for application of different copper prepararions (Bordeaux mixturc Vallcs - copper sulphatc and C:t(OH)!, Kocidc DF- copper hydroxide, aml Curcnox 50 - copper ta:ychioridc) aml one as controI. ln lhe middle of October lhe differclI( plOIS ",ert' sp ra yed with lhe aqueous suspensions of the pcsticides prcparcd followlng the s upplier indicaliuns, i.e., CuS04 +Ca(OI-lh (20"/0 Cu), Cu(OHh (40% Cu), Cu(OCI)! (50% Cu), and walcr. respcctivcly. Artcr trcarment, at different times - four hours, 8, 13, 28 :tnd 44 d:-.ys - five Irees \Vere randomly selected ln lhe rniddlc uI' c:lch plot, and 60 olive fruits per trec wcre collcctcd in pl:lstic b:-.g~ aml Slm'cd a' -201lC until copper analysis. Thc oUves wcre w:tshcd with tap waler, lhe slones removed wHIl deconlaminaled pl:-.stic material , rhe samples dried ln a stove, pulverized ~md heal digesred wUh 1-110 1 plus I-INO} mlxture. Olher he:l\'y met:lls, Ilamely lead, nlckel and cadmium, were 3150 l:Onsidercd to c"a lunte rhe putntivc residues present in lhe olive frult s duc lo lhe Impurities of lhe pcsticide formulations. The metal conlents wcre measured by atomic abso rption speclromerry wirh gr:-.phitc furn:-.ce.The aim of this work was [o e\'aluate the peslicldc rcsiduC5 in olins h:lI've5[cd a[ different times aftcr the application of three different corper produets. METl-IODS The experiment ",as carricd out in :I 0 -. Cobranços:! olive orchanl loc:-'Ied near Mirandela, Northeast of Portugal. Thc orchard w:-.s su bdivided in four plots, thrcr of lhem for lIpp lie:llion or Ihrcr dif(crent copper preparations (Dordeaux rnixture Valles - copper suljlhate and calcium hydroxide, Kocide DF- co pper hydroxide, and Curcnox SO - copper oxychloride) and IIlIe :-.s control. ln lhe middle of October the difrerellt plots were sprayed wilh rhe aqueo us suspcnsions of lhe peslicides prepared follfJwing lhe supp lil' r Indications, I.e., CuSO" +Ca(OI-l)! (20% Cu), Cu(OHh (40%, Cu), Cu(OCI}z (50% Cu), rcspcctively. A contrai ~rouJl of oli\'e In~es was only sprayed with w:lter. Arter treatment, at differl'nt limcs - four hour5, 8, 13, 28 and 44 days • five trees were )':mdomly sclccled in lhe middle of cach pIai, 3nd 60 olive fruils per Iree wcre collectcd :lIld stored ln plastic bags at -20°C until copper analysis, The olivcs \Vere washcd with tap "'aleI', the stones removed wlth decont~lInil1ated plastic material, the sam pies dried in a stove, pulverized and he:lt digcstcd witlt H101 plus HNO) mixture. The COllpcr :lI1d Icad conlents were rne:tsured by alomic absorption .~JlCClrnmetry wilh graphite furnace (I). Tahlc l.Cnntellts (mean values) ofCu and lead Cu pg/g dry ollve fruits CUS04 + Cu(OHh I Cu(OHh Cu(OClh H,O , Time (days) 120"1. Cu) 140% Cu) (50"1. Cu) - - O 34.4 30.1 63,9 8,5 8 28.4 21,7 I 33.9 9,8 13 23.3 20.6 I 26,2 8,5 28 20.3 11.5 20,1 7,7 44 14 ,5 16.9 23.9 7,9 i --Pb )Jg/kg dry ollve fruits O i 21 .0 26,5 36.Õ I 21.7 44 <11 ,0 <11.0 <11 .0 <11 ,0 RESULTS ln spÍle of the different copper concentrations of the app liec.l pestlclc.les, olive coprer residues \\'erc similar for thl' CuS04 +Ca(OHh (20% Cu) and Cu(OI-l}z (40°/., Cu) :-.pplications (from 34.4 Ilglg to 14.5 f.lglg and from 30.1 to 16.9 Ilg/g, respeclh'ely). Copper contents were abollt lhe c.Iouble ln lhe oll\'e fruits tre:-.tet.l with Cu(QClh (50% Cu) product (from 63.9 to 23.9 Ilglg), for (he I1l'st thrcc colleclion times, the copper contents of the olives from lhe CU(OCl)l treated lrees were s ignincantly higher than those collected from the control trees sprayed with water (from 7.7 to 9.6 'lglg). At the 4 h hllrvcsling time, the olives trea(et.l wilh Cu(OCl)! presented coppcr contents significantly higher than olives trealed with lhe Iwo other fonnulntions. 75 70 €6 -.-CuS04 + Cu{0H)2 -O-Cu{OH), '" -6- Cu{oct), J!l 55 -.- 11,0 :E ,., ,~ 45 <5 '" ~ l5 8 :JO -e> 25 ~ '" 15 10 5 r 1# * T # -.:::::---'" '-,!; , '--L_=-!~ f~\* ------- ~ j ______ I • . . ·~----Y·----------__ ~ ______________ T O o 10 3D 40 Figure I. Olive Cu contents (J..lglg r.hy olive frui IS) aner O, S. 13.28 and 44 tiays of each {realmenl. Results are givcn as mcan ± SD. Cu contcnlS \Vcre compared by {wo way ana lysis of variancc (ANOVA; belwccn groups) rollowed by the ScheITé Tesl. Tlte leveI ofsignificance was sct al P < 0.05. ~cotn purcd wilh l - I~O : .s:comparcd with ('uSO" + CU(OH)2; scompared with CII(OH )~ ; 'ctlmparcd \~ i th time zero days wilhin each IrcalmCnl. CONCLUSIONS I. Tlle trealmcn( of oUve trees \Vilh copper pesticides c:-.n signilicantly increasc fhe metal leveis of the oUve fruiu :1nd the re5ulting olive oils. 2. The copper peslicide formulations sltould not he app lied 10 lhe oUve trces Ilear the harvestlng period ln order to avoid atldiliun:lI copper conlamlnation. 3. Ir is not indifferent lo (real lhe olive trecs diseascs with :lIIy uf the applied copper formulations as it is demonstratec.l by lhe metal residues leveis of lhe sllmples trealed \Vith lhe most concentratec.l copper formularion. ln this case, arter 13 d:-.ys ofl!te application, lhe oUves had still copper contents significantly hlgher t!tan the control one. REFERENCES (I) Soares ME, Areias J, Pedrolo I, Pinho C, Bastos ML. Dose:-.mcn(o de Cobre e Ferro em Fr:Jgmenlos de Biúpsl:-. Hepátic:l hUIlHlnos Jlor espectro fotometria de absorção atómica com :ttumizaçàu electrotérmlca. Jomal POrfllJIlIés de Gtlsfrellferologia 1998; 5:28-33. Copper and lead residues in olives after olive tree treatments with three different copper formulations Soares ME· , Pereira JA", Bastos ML· ·REQUIMTE, Toxicology Department, Faculty of Pharmacy Rua Anibal Cunha, 164, 4099-030 PORTO PORTUGAL Tel:351 222078922 e-mail:mlbastos@ff.up.pt # CIMO, School of Agriculture, Polytechnic Institute of Bragança Quinta Sta Apolónia, Apt. 1172,5301-855 BRAGANÇA PORTUGAL Field tests were performed to control two olive fungai diseases known as olive anlhracnose, Col/etotrichum spp., and olive leaf spol, Spilocae oleagina (Cast.) and to evaluale the pesticide residues in the olive fruits harvested aI different times. The experimenl was carried out in a Cv, Cobrançosa olive orchard located near Mirandela, Northeast of Portugal. The orchard was subdivided in four plols, Ihree of them for application of Ihree different copper preparations (Bordeaux mixture Valles - copper sulphate and calcium hydroxide, Kocide DF-copper hydroxide, and Curenox 50 - copper oxychloride) and one as control. ln the middle of Oclober the different plots were sprayed with the aqueous suspensions of the pesticides prepared following the supplier indications, i.e ., CUS04 +Ca(OH)z (20% Cu), CU(OH)2 (40% Cu), Cu(OCI)2 (50% Cu), and water, respectively. Afier treatment, at different times - four hours, 8, 13, 28 and 44 days - tive trees were randomly selected in the middle of each plot, and 60 olive fruits per tree were collected in plastic bags and stored at -20°C until copper analysis. The olives were washed with tap water, the stones removed with decontaminated plastic material, the samples dried in a stove, pulverized and heat digesled with H202 plus HN03 mixture. Olher heavy metais were also considered to evaluate lhe putative residues present in the olive fruils due to the impurities of these pesticide formulations. Lead, nickel and cadmium were selected for monitoring afier four hours and 44 days of the Ireatment. The metal contents were measured by atomic absorption spectrometry with graphite fumace. Although the different copper concentrations of the applied pesticides, olive copper residues were similar for the CUS04 +Ca(OH)z (20% Cu) and CU(OH)2 (40% Cu) applications (from 34.4 J,lg/g to 14.5 J,lg/g and from 30.1 to 16.9 J,lg/g, respectively, for the tive time collections). Copper contents were about lhe double in lhe olive fruits trealed with CU(OCI)2 (50% Cu) product (from 63.9 to 23.9 J.lg/g). Olives from ali the treated trees had at ali the COllection times copper contents significantly higher than those of Iree controls sprayed with water, ranging the values from 7.7 to 9.6 J.lg/g. Referring to lhe olher metais, lead leveis were signiticantly higher in the first harvesting than afier 44 days. For cadmium and nickel there was no differences in their conlents. ln conclusion, lhe treatmenl of olive trees wilh copper pesticides can signiticantly increase the copper leveis of lhe olive fruits and the resulting olive oils as well as the contamination with lead, 

Copper and lead residues in olives after olive tree treatments with three different copper formulations.

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Copper and lead residues in olives after olive tree treatments with three different copper formulations.

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