THE STUDY OF LIGAND EFFECTS OF COPPER COMPLEXES ON THE YIELD AND QUALITY OF WINTER WHEAT THESIS OF DOCTORAL (PhD) DISSERTATION BARKÓCZI MARGIT MOSONMAGYARÓVÁR 2004 UNIVERSITY OF WEST HUNGARY FACULTY OF AGRICULTURAL AND FOOD SCIENCES MOSONMAGYARÓVÁR DEPARTMENT OF CHEMISTRY
Plant Production Using Precision Agricultural Methods DOCTORAL SCHOOL Program leader Dr. Kuroli Géza DSc in Agriculture Precision production oriented integration of plant protection methods and plant treatments subprogram Subprogram leader Dr. Kuroli Géza MTA doktora Supervisor: Dr. habil. Szakál Pál university professor, CSc in agriculture THE STUDY OF LIGAND EFFECTS OF COPPER COMPLEXES ON THE YIELD AND QUALITY OF WINTER WHEAT THESIS OF DOCTORAL (PhD) DISSERTATION BARKÓCZI MARGIT Mosonmagyaróvár 2004.
1. Preliminaries of work, objectives Besides maize, winter wheat is the most widely grown crop. It is still true after Hungary joined the European Union. To maintain export, economical product and quality we must provide good nutrition. Nowadays nutrition of cultivated plants is a major problem of the producers, therefore we must utilise our possibilities in an economic way. The production of good quality agricultural produce is only possible through modern and conscious nutrition. Beside the three most important macronutrients N, P, K we must turn our attention to proper microelement nutrition, because in biochemistry their role as enzyme-builders are essential. Copper is one of the most important microelements, which have been studied. Soil examination shows that in productive soils copper is often a limiting factor. Copper has a major role in the life cycle of plants copper deficiency can be trace strongly in cereals. Plant production striving for both high yields and good quality demands adequate copper nutrition of cereals. We can supply copper in the soil or apply as foliar sprays. Soil fertilizer are mainly copper-salts, foliage fertilizers are mainly various copper-compounds, or complexes. During our experiments, we searched for the following answers: What effect does foliage fertilizer have on quantity and quality of winter wheat? Do the complexes of copper have any effect on nutrition uptake and how do they affect winter wheat? Can the copper content of ion exchanged synthetic zeolite be used as copper nutrient to relieve copper deficiency, and how they change wheat properties? Do copper compounds given in the phenological phase of shooting and flowering cause differences in productivity? In what dose do the copper-compounds used in our experiment, have the best effect during shooting and flowering 2. Materials and methods 2.1 The applicability of copper compounds of different ligand and copper-ion-exchanged synthesized zeolite as a foliar fertiliser In the experiments the following copper compounds were used for the copper nutrition of winter wheat: copper-tetramine-hidroxide, copper-saccharose-complex and copper-ionexchanged synthesized zeolite. The compounds were produced at the Department of Inorganic Chemistry of Szeged University and the Department of Chemistry of the West-Hungarian University. The experiments were carried out in Komárom at Solum Agricultural Co. in a copperdeficient, calcareous, Danube alluvial soil for three years between 2000 and 2002 on 10 m 2 plots. The arrangement of the experiment was a randomised block design with four repetitions. The treatments were done at two phenological phases at shooting and at flowering with copper-tetramine-hydroxide and copper-saccharose. The complexes were sprayed with a
pneumatic sprayer in the amount of 0.6 lha -1. The control plots were sprayed with the same amount of water. The copper-ion-exchanged zeolite were applied in the same way. The copper doses applied during the three years were always the same: 0.1; 0.3; 0.5; 1.0; 2.0 kgha -1 respectively. Taking into account the nitrogen content of the copper tetraminehydroxide, control plots were introduced that were treated with the amount of nitrogen contained by the copper-tetramine-hydroxide in the form of ammonium-nitrate solution. There was no significant difference between the nitrogen controls and the water controls. Knowing the chemical composition of the compounds it is quite obvious since a copper dose of 0.5 kgha-1 contains only0.4 kg N. That was the reason why we made no difference between the control plots and treated them uniformly. 2.2 Cultivars used in the experiment and plant protection The experiments were carried out in an alkaline, calcareous soil with medium nitrogen, low copper and zinc status between 2000 and 2002. The wheat cultivar sown was GK Csörnöc. The crop production technology used were identical that of applied at SOLUM Agricultural Co. Weed control were done with 2.0 lha-1 Mecomorn, Granstar and Mecaphar in 2000, 2001 and 2002 respectively as a post emergence treatment at springtime. Against fungi caused diseases Tilt Premium, Alert-S and Eminent 125 SL was used. There was no need to protect wheat against insect pests during the three years. 2.3 Analytical methods The harvest of the experimental plots was done by a plot combine-harvester. After harvest the yield of the plots were measured and the determination of quality parameters were done. The determination of macro- and micro element content was carried out by ICP technique at the Research Institute of Soil Sciences and Agricultural Chemistry of the Hungarian Academy of Sciences, Budapest and at the Department of Chemistry of the West-Hungarian Univerity, Mosonmagyaróvár. The total N content was measured by Kjeldahl-method in Parnass-Wagner equipment. The gluten content was determined by washing out with NaCl solution, the baking quality was measured by pharinograph equipment at the laboratory of Pannon Gabona Co., Győr. 2.4 Statistical evaluation The results were evaluated by analysis of variance and regression analysis using the softwares Statistica for Windows 4.5 and Excel 7.0.
3. Results and conclusions In the experiments we applied copper-tetramine-hydroxide and copper-saccharose complexes and synthesized copper-ion exchanged zeolite for the copper nutrition of winter wheat at two phenological phases, at shooting and at tillering. The major results of the three-years experiment are as follows: 3.1 The results of the treatments at tillering As a result of the foliar application of both copper-tetramine hydroxide complex and coppersaccharose the yield increased significantly approximately to the same extent. The raw protein content also increased for the application of both complexes. The higher increase was measured in the case of copper-tetramine hydroxide treatments. The 2.0 kgha -1 copper doses were already toxic. Due to the application of copper-tetramine hydroxide and copper-saccharose the wet gluten content significantly increased and even the 2.0 kgha -1 dose had not toxic effect, the gluten content increases continuously in the dose range applied. Regarding the baking value the copper-saccharose treatments proved to be more effective and improved the baking quality significantly. The 2.0 kgha -1 copper dose slightly diminished the baking quality. 3.2 The results of the treatments at flowering Comparing the results of the treatments at tillering and at flowering we can establish that the flowering treatments increased the yields more effectively. At this phenological phase the smaller doses are more effective and the maximum yield increase can be measured at the 0.3 kgha -1 copper dose, while the higher doses are already toxic. The highest yield increase was achieved by the application of copper-saccharose complex. Studying the raw protein content we can establish that at this phenological phase the copersaccharose complex is more effective. Doses higher than 0.3 kgha -1 are already toxic and decrease the raw protein content. Regarding the raw protein content the tillering treatments were better than flowering treatments. Due to the flowering treatments the wet gluten content increased higher than in the case of the tillering treatments. The maximum wet gluten content was detected at the copper doses of 0.3-0.5 kgha -1 respectively. Higher copper doses proved to be depressive already. The coppersaccharose increased the wet gluten content more effectively than copper-tetraminehydroxide. The baking quality also improved strongly and significantly. The maximum increase was measured at the doses of 0.3-0.5 kgha -1, the higher doses were already toxic. The coppersaccharose had better effect. Altogether, we can establish that the application of copper complexes was more favourable at the phenological phase of flowering than at tillering. Flowering treatments are also more favourable from the economic point of view since at this phenological phase we can achieve the same result by the application of a smaller amount of copper (0.3 kgha -1 ).
4. New scientific results 1. Due to the copper treatments at tillering the yields increased. The best results were given by the copper-tetramine-hydroxide treatments. The maximum yield was measured at the copper dose of 1.0 kgha -1 (control 4,19 tha -1, treatment 4,86 tha -1 ). Regarding the yield the copper treatments at flowering were more effective than if they were applied at the phonological phase of tillering. The best results were given by the 0.3 kgha -1 dose of copper-saccharose complex (control 4,03 tha -1, treatment 5,24 tha -1 ). 2. The effectiveness of the copper complexes, regarding the raw protein content, is approximately the same at both phenological phases (tillering and flowering). The most significant increase was detected at the 1.0 kgha-1 copper dose applied at tillering (control 13,01%, treatment 14,46%). 3. Due to the treatments at tillering the wet gluten content increases largely. The wet gluten content increases parallel to copper doses. If the major goal is the increasing of the gluten content the application of copper-saccharose is more effective. Due to the copper-treatments at flowering the wet gluten content increases up to the copper dose of 0.5 kgha -1 (control 33,28%, treatment 38,19%). Copper-saccharose complex is more effective in increasing the wet gluten content than copper-tetramine-hydroxide treatment (control 58,18, treatment 72,41). 4. Copper complexes applied at the phenological phase of tillering improved the baking quality to a great extent. The copper-saccharose complex was the most effective. Regarding the dose, the 1.0 kgha -1 copper gave the best results. The copper complex treatments applied at flowering improve the baking quality largely. The coppersaccharose complexes were more efficient than the copper-tetramine-hydroxide. Regarding the copper-saccharose complex the best results were achieved by the application of the copper dose of 0.3 kgha -1. 5. Due to the application of higher doses of copper-ion-exchanged zeolite the yield of winter wheat increased and so did the raw protein content. The changing of the raw protein content was proportional to the increasing copper doses (yield 4,42 t/ha by control and 5,83 t/ha by treatment; raw protein 13,48% by control and 14,75% by treatment). 6. Regarding the application time, the administration of copper-tetramine-hydroxide and copper saccharose both at tillering and at flowering improved the yield and quality parameters of winter wheat.
5. PUBLICATIONS FROM THE TOPIC OF THE THESIS Publications in Hungarian Schmidt R., - Szakál P., - Barkóczi M., (l987): Zn-tartalmú ipari hulladék mezőgazdasági hasznosítása. VII. Gépipari Környezetvédelmi Napok. Győr p, 386-404.. Szakál P., - Barkóczi M. (l988): A réz-tetramin-hidroxid komplex felhasználása az őszi búza hozamának és sikértartalmának növelésére. HUNGAROCHEM, 88, NEVIKI p., 23-3l. Barkóczi M., - Szakál P., - Tölgyesi E. (l989): Kísérletek hulladékból kinyert hexaminkomplexek mezőgazdasági újrahasznosítására. Agrokémia és Talajtan, 38. p.323-327. Szakál P., - Barkóczi M. (l989): Réztartalmú hulladékból előállított réz-komplex hatása az őszi búza beltartalmára. Agrokémia és Talajtan, 38. 330-334.. Schmidt R., - Barkóczi M., - Szakál P., - Othmar Horak., - Juraj Lesny (1999): Hulladékból előállított fém-komplexek mezőgazdasági újrahasznosítása.xiii. Országos Környezetvédelmi Konferencia. Kiadvány.p. 206-214. Bakóczi M, Szakál P., Schmidt R. (2002): Mikroelem-tartalmú hulladékok mikroelemtartalmának zeolittal történő kinyerése és annak felhasználása növénytáplálási célra. XVI. Országos Környezetvédelmi Konferencia. Proceeding. P. 240-247. Szakál P., Barkóczi M., Schmidt R. (2003): Különböző ligandumu réz-komplexek, rézioncserélt zeolit hatása a növények hozamára és beltartalmára.. NYME Erdőmérnöki Kar. A Magyar Tudomány Napja. 2002. Sopron 2003. p.74-78. Publications in foreign languages Szakál P., - Barkóczi M., - Schmidt R. (l988): The Agricultural Utilization of Zn- Containing Industrial Waste. World Conference on Hasardous Waste. Elsevier Science Publishers. Amsterdam, p.l355-l359. Szakál P., - Schmidt R., - Barkóczi M. (l988): Experiments for the Agricultural Utilization of Copper containing Wasters, World conference on Hasardous Waste, Elsevier Science Publishers. Amsterdam, p.1361-1365. R.Schmidt, - M.Barkóczi, - P.Szakál, - R.Kalocsai (2002): The Ampact of Copper Tetramine Hydroxide Treatments on Wheat Yield. Agrokémia és Talajtan 51. Vol. 51. Nos 1-2. p. 193-200
Papers and posters at Hungarian conferences Szakál P. Barkóczi M.: A Zn szerepe a növénytermesztésben. Növénytáplálkozási tanácskozás. Békéscsaba, 1986. december 6. Szakál P. Barkóczi M: Szuszpenziós műtrágyák. Növénytáplálkozási tanácskozás. Békéscsaba. 1986. december 6. Szakál P. Barkóczi M.: A levéltrágyázás jelentősége. Mikroelemek visszapótlásának lehetőségei. Mezőfalva. 1987. május 27. Szakál P. Barkóczi M: Réztartalmú hulladékból előállított réz-komplex hatása az őszi búza beltartalmára. Talajtani Társaság Vándorgyűlése (poszter). Szarvas, 1988. szeptember 1-2. Barkóczi M. Szakál P. Tölgyesi E.: Kísérletek hulladékból kinyert cink-hexamin-komplex mezőgadzasági újrahasznosítására. Talajtani Társaság Vándogyűlése (poszter) Szarvas, 1988. szeptember 1-2. Szakál P. Barkóczi M.: Réz hatása az őszi búza hozamának és sikértartalmának növelésére. Agrártud. Egyetem. Mosonmagyaróvár. Növénytermesztési Tanácskozás. 1989. márc. 29. Szakál P. Barkóczi M: Mikroelemek szerepe a cukorrépa- és a kukoricatermesztésben. Agrártud. Egyetem. Mosonmagyaróvár. Növénytermesztési Tanácskozás. 1989. márc. 29. Schmidt R. Barkóczi M. Szakál P. Othmar Horak Juraj Lesny: Hulladékból előállított fém-komplexek mezőgazdasági újrahasznosítása. XIII. Országos Környezetvédelmi Konferencia, Siófok, 1999. szeptember l4-l6. Barkóczi M. Szakál P.: Mikroelem-tartalmú ioncserélt szintetizált zeolit, lombtrágyakénti alkalmazása a búzatermesztésben. Analitikai- és Környezetvédelmi Konferencia. Keszthely. 2002. 04.11.p.12. Barkóczi M. Szakál P. Schmidt R.: Mikroelem-tartalmú hulladékok mikroelemtartalmának zeolittal történő kinyerése és annak felhasználása növénytáplálási célra. XVI. Országos Környezetvédelmi Konferencia és Szakkiállítás. 2002. szeptember 10-12. Barkóczi M. Schmidt R. Szakál P.: Réz-komplexek előállítása és alkalmazásuk a növénytermesztésben. Magyar Tudomány Napja. Kémiai Intézet Tudományos Ülése. 2002. november 7. Szakál P. Schmidt R. Barkóczi M.: Réz- és cink-tartalmú ioncserélt szintetizált zeolit hatása az őszi búza hozamára és fehérjetartalmára. Mikroelemek a táplálékláncban. 2003. április 22-24. Nyíregyháza. p. 43.
Papers and posters at international conferences Schmidt R., - Szakál P., - Barkóczi M.: Cinktartalmú hulladékok mezőgazdasági hasznosítása. VII. Gépipari Környezetvédelmi Napok. Győr, l987. ápr. 7-9. Szakál P.,- Barkóczi M.,- Bóna F.: Experiments for the Agricultural Utilization of Coppercontaining Wastes. World Conference on Hazardous Waste. Budapest. l987. okt. 25-3l. Szakál P.,- Schmidt R., - Barkóczi M.: The Agricultural Utilization of Zn-containing Industrial Waste. World Conference on Hazardous Waste. Budapest. l987. okt. 25-3l. Szakál P., - Barkóczi M.: A réz-tetramin-hidroxid komplex felhasználása az őszi búza hozamának és sikértartalmának növelésére. A mezőgazdaság kemizálása. XVIII. nemzetközi Konferencia. Keszthely. l988. július 6-8. P.Szakál, - M. Barkóczi: The effects of Vinasse and mikroelements and winter what quality. Zum 5. Vinasse- und Feldtag in Bernbrug Anlasslich des 20. Hanrigen Bestehens. Brenburg. 1998. júlus 2-4. Schmidt R., - Barkózi M., - Szakál P., - Othmar Horak., - Juraj Lesny: Hulladékból előállított fém-komplexek mezőgazdasági újrahasznosítása.xiii. Országos Környezetvédelmi Konferencia. Siófok, 1999. szeptember 14-16 Szakál P., - Schmidt R., - Barkóczi M. : Réz- és cink-tartalmú ioncserélt szintetizált zeolit hatása az őszi búza hozamára és fehérje-tartalmára. Mikroelemek a táplálékláncban 2003. április 22-24. Nyíregyháza. p.43. Books Simon L. Szilágyi M. (szerkesztette): Schmidt R. Szakál P. Kalocsai R. Barkóczi M. Giczi Zs. (Szerzők): (2003): N-oldat, valamint Cu- és Zn kezelés hatása az őszi búza hozamára és nyersfehérje tartalmára.183-191. Bessenyei György Könyvkiadó Nyíregyháza, ISBN: 963 9385 81 6 Simon L. Szilágyi M. (szerkesztette): Schmidt R. Szakál P. Kalocsai R. Barkóczi M. Giczi Zs. (Szerzők): (2003): Réztartalmú ioncserélt szintetizált zeolit hatása az őszi búza hozamára és fehérje tartalmára. p 229-236. Bessenyei György Könyvkiadó Nyíregyháza, ISBN: 963 9385 81 6