Determination of manganese with crystal violet in plant material in different fertilization

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1 Agronomy Reserch 7(2), , 2009 Determintion of mngnese with crystl violet in plnt mteril in different fertiliztion D.Kostov, M.Kmurov Agriculturl University Plovdiv 12, Mendeleev Str., 4000 Plovdiv, Bulgri E-mil: Astrct. A study in multiple-fctor sttionry field experiment with 16 vrints NPK on ckground with nd without nnul fertiliztion with mnure ws crried out t the Agriculturl University in Plovdiv, Bulgri. The mngnese content in the roots of rdishes, cultivr Red with white tils, ws determined y new extrction-photometric method with Crystl Violet. The ion-ssocite of mngnese (VII) ws completely extrcted in single extrction of only 30 s. The molr sorptivity of the ssocite ws (1.54 ± 0.05) x 10 4 l mol -1 cm -1. This indictes the high sensitivity of the given rection. Mngnese hs een determined y tomic-sorption method, too, in order to compre the results. It ws estlished tht fertiliztion hs n effect upon the mngnese content in the roots of rdishes. The roots of rdishes ccumulte the highest level of mngnese mg/kg in minerl fertiliztion N:P:K = 3:2:1 with 40 t/h mnure. The reltionship etween yield nd mngnese content in rdish roots under the influence of fertiliztion hs een estlished. Key words: mngnese determintion, Crystl Violet, plnts, fertiliztion INTRODUCTION The extremely importnt role of mngnese in the growth of plnts determined the gol of our study. In the conditions of intensive frming, the prolem of trce elements in the soil-plnt system ttined significnt importnce. Mngnese is one of the microelements which re ctively sored y plnts. The iologicl sorption coefficient for mngnese is greter thn those for the other microelements in this group, nmely Zn, Cu, Mo, Ni, Co, P. The formtion of the plnt mss depends on the mngnese provision for the plnts. Mngnese tkes prt in numer of importnt physiologicl nd iologicl processes in the lower nd higher plnt orgnisms in the nitrogen metolism, photosynthesis, rething nd mintining the necessry oxidtion-reduction conditions in the cell (Sidorovich et l., 1987; Udintsev et l., 1981; Nson, 1952). The mngnese content in the plnts vries in wide rnge from one hundred to one thousnd prts of the percentge. Among the field crops, eetroot (the leves) nd leguminous plnts re chrcterized with higher content of mngnese, ut the content is lower in corn (cerels). Fruit tree species lso ccumulte different mounts of mngnese in their tissues when grown under the sme soil conditions. The level of mngnese in plnts is usully incresed with the progress of the vegettion. Higher levels of mngnese were found in plnt orgns in which the 811

2 metolism is more intensive. Experiments on cotton (Nurliev nd Yrovenko, 1980) hve shown tht mngnese ccelertes the entrnce of phosphorus into the plnts nd hs positive effect on growth nd fruit formtion. Mngnese is n importnt element of nitrogen metolism in plnts. Mngnese insufficiency leds to considerle ccumultion of nitrtes, disturnce in the protein synthesis in plnts nd, in some pnts, illness (Nichols, 1961; Bergmnn et l., 1976; Heintze, 1966), nd cuses decrese in C nd Mg content (Shkolnik, 1974). The optiml content of mngnese, its criticl level nd toxic concentrtion t which the growth is depressed nd the yield decresed, hve een estlished for gret numer of crops (Pottuev, 1990). Vrious methods for determintion of mngnese hve een pulished. Anlyses with some regents hve een used (Kdoyshi, 2004; Trfder, 2004; Shr, 2003; Blogh, 2003; Alkn, 2003; Winkler, 2003; Bisws, 2003). The present study is intended to cler up the effect of prolonged fertiliztion (minerl nd orgnic) on the mngnese content in rdishes using new extrctionphotometric method with Crystl Violet for determintion of mngnese (Kostov, in press). We used the triphenylmethne dye Crystl Violet, for the first time, to show tht it cn e pplied to the nlysis of mngnese in plnt mteril. MATERIAL AND METHODS The study ws crried out in the 23 rd yer of multiple-fctor sttionry field experiment. The experiment ws crried out t 5 levels of fertiliztion with nitrogen, 5 levels with phosphorus nd 4 levels with potssium with 16 vrints of NPK, on ckground with nd without nnul fertiliztion of 40 t/h of mnure. The following scheme ws pplied: 1 N 0 P 0 K 0 9 N 240 P 240 K N 120 P 120 K 0 10 N 240 P 360 K N 120 P 0 K N 360 P 120 K N 0 P 120 K N 360 P 240 K N 120 P 120 K N 360 P 360 K N 120 P 240 K N 240 P 240 K N 120 P 360 K N 360 P 360 K N 240 P 120 K N 480 P 480 K 360 The sttionry experiment ws set on strongly leched medow cinnmon soil (cly frction in the 0 20 cm lyer ws from %, the sum of the interchngele ctions rnged from % nd tht of the interchngele C nd Mg from %) with neutrl rection (ph 6.8 to 7.0) with 2.2 % humus content (y Tyurin). 812

3 Soil smples from 0 20 cm deep lyer were tken for grochemicl nlysis nd nlysed for moile P 2 O 5 nd K 2 O - y the Egner-Rhiem method; minerl nitrogen (NH 4 -N + NO 3 -N) y distilltion; ph potentiometriclly in queous extrct. The plnts were grown y the technology dopted for the region. Yield of roots per hectre ws tken into ccount; dry mtter per cent ws determined y weight. For the first 16 yers in the sttionry field experiment, erly tomtoes (1 st crop) nd lte-heded cge (2 nd crop) were grown; from the 17 th 20 th yers, medium erly tomtoes with intermedite crop repko were plnted in utumn nd hrvested in spring. Mize for grin ws grown in the 21 st yer, followed in the 22 nd yer y vegetle mrrows, with second crop of spinch; in the 23 rd yer, erly-heded cge nd rdishes cultivr Red with white tils were grown; the ltter crop ws used for the present study. Up to the 16 th yer, fertiliztion with the ove-mentioned mounts of nutrient elements ws pplied to ech of the cultivted crops, ut from the 17 th yer onwrds it ws only pplied to the first crop. An nlysis for mngnese content y vrints of verged root smples ws crried out using new extrction-photometric method with Crystl Violet. Mngnese(VII) forms n ion-ssocition complex with triphenylmethne dye Crystl Violet (CV). To remove the possiility of extrcting the ion ssocite, the following different types of orgnic solvents were tested: hydrocrons (enzene nd toluene), ethers, ketones, lcohols, chloroform, dichlorethne nd tetrchlorethne. The studies showed tht the ssocite is est dissolved in 1,2-dichloroethne. Mximum light sorption of the ssocite is oserved t 250 nm. The molr sorility determined y the Komr-Tolmtchov method (Bultov nd Klinkin, 1972) is 250 = (1.54 ± 0.05) x 10 4 l mol -1 cm -1. The sensitivity of the Sndell method (Sndell, 1959) is W S = 3.57 x 10-3 g cm -2. The otined study results in connection with the method we developed for determintion of mngnese with Crystl Violet re worked with computer progrmme for two-fctor dispersive nlysis nd multispecified comprtive nlysis in Duncn s method (Mokrev nd Murgov, 1988). Apprtus Spectrophotometer VSU with 1-cm light pth qurtz cells. Procedure A wet urning of the plnt smple ws crried out in which mixture of sulphuric nd nitric cids ws used for the oxidtion of the orgnic sustnce. A portion of 2 g of ir-dry plnt mteril ws plced into Kjeldhl flsk nd moistened with 4 ml distilled wter; 5 ml conc. sulphuric cid nd 10 ml conc. nitric cid were dded. The flsk ws slightly heted to void splshing of the solution decomposition nd fuming wy of HNO 3. If the oxidtion of the orgnic sustnce ws not completed, HNO 3 ws dded nd heted gin. When ll the orgnic mteril ws oxidized, the solution ws heted t higher temperture for 10 min (Vzhenin, 1974). After cooling, the solution ws diluted with wter nd filtered. Portions of 3 ml conc. H 2 SO 4, 2 ml conc. H 3 PO 4 813

4 nd 0,1 g potssium periodte were dded for oxidtion of Mn(II) to Mn(VII). It ws heted to oiling point nd the temperture ws mintined for 10 min (Sndell, 1959). After cooling the solution ws diluted with wter nd filtered, trnsferred into volumetric flsk of 50 ml nd diluted to the mrk with distilled wter. Aliquot prts of this solution were tken for nlysis. In seprtory funnel of 100 ml re introduced the following solutions: 0.3 ml hydrochloric cid 1.2 M, 0.4 ml Crystl Violet 1x10 3 M, liquote of the prepred solution of the plnt smple. It is diluted up to volume of the queous phse of 10 ml with distilled wter nd extrcted with 3 ml of 1,2-dichloroethne for 30 s. The orgnic phse is filtered through dry pper into 1 cm cuvette nd the sornce mesured t 250 nm. A lnk is run in prllel in the sence of plnt smple. A clirtion grph is constructed with stndrds similrly treted. RESULTS AND DISCUSSION The minerl fertiliztion led to considerle chnges in mngnese content in the rdishes. The scheme of fertiliztion vrints is shown in Tles 1 nd 2. Mngnese content in the plnt mteril ws determined y using new extrction-photometric method, triphenylmethne dye Crystl Violet, for the first time,. Tking into ccount the different fertiliztion with N, P nd K (Vrints 2,3, 4) it cn e seen tht rdish ccumulte the lest mngnese 10 mg kg -1 in fertiliztion only with P nd K (N 0 P 120 K 120 ) (Vrint 4). The content of mngnese rises to more thn 5 times if nitric fertilizer N 120 P 120 K 0 (Vrint 2) nd N 120 P 0 K 120 (Vrint 3) cn e used in fertiliztion. Tle 1. Mngnese content in rdish (mg kg -1 dry mss) NPK NVrints Method with CV Reli RSD* AAS Yield Mn mg kg -1 P= 99 % % Mn mg kg -1 kg h -1 1 N 0 P 0 K N 120 P 120 K d N 120 P 0 K N 0 P 120 K N 120 P 120 K N 120 P 240 K d N 120 P 360 K c N 240 P 120 K c N 240 P 240 K f N 240 P 360 K N 360 P 120 K e N 360 P 240 K d N 360 P 360 K N 240 P 240 K f N 360 P 360 K c N 480 P 480 K

5 *Reltive Stndrd Devition for CV method (n = 6),, c, A degree of reliility In constnt level of potssium K 120, mngnese content incresed with the increse of the fertiliztion norm of phosphorus. It is well expressed in the three levels of nitrogen fertiliztion with N 120, N 240 nd N 360. Vrints 5,6, 7 with fertiliztion norm N 120 comprise 15 mg kg -1, mg kg -1 nd mg kg -1 Mn dry mss. In fertiliztion norm N 240 (vrints 8,9,10) the content of mngnese increses to mg kg -1,63.25 mg kg -1 nd mg kg -1 with the incresing content of phosphorus. The ove-mentioned suordintion cn e seen in Vrints 11,12, 13 with N 360, in which the content of mngnese content reches mg kg -1, 26 mg kg -1 nd mg kg -1 with the incresing phosphorus content. The suordintion of yield from the content of mngnese in fertiliztion with P 120 in different levels N is smll negtive with correltion coefficient. r = (Fig. 1). A negtive correltion (r = -0.46) is otined etween the concentrtion of mngnese nd yield in fertiliztion with N 120 in different levels of P nd. With the incresing of the concentrtion of mngnese, the yield decreses (Fig. 2) y = -7,7343x ,6 Yield kg/h Mn mg/kg Fig. 1. The suordintion etween the yield kg h -1 nd Mn content fertiliztion with P 120 in different levels N ; Correltion coefficient r =

6 Yield kg/h y = -58,919x Mn mg/kg 60 Fig. 2. The suordintion etween the yield kg h -1 nd Mn content fertiliztion with N 120 in different levels P ; Correltion coefficient r = A smll negtive correltion (r = -0.18) determines the reltion etween the yield nd mngnese content in rdishes in the vrints from 1 to 16 (Fig.3). Yield kg/h y = -19,028x Mn mg/kg Fig. 3. A generl suordintion etween yield kg h -1 nd Mn content in rdishes with minerl fertiliztion; Correltion coefficient. r =

7 In the three levels of nitrogen fertiliztion with N 120, N 240 nd N 360, the highest content ws mg kg -1 Mn dry mss fter fertiliztion with N 240 :P 360 :K 120 = 2:3:1. Mngnese content in rdishes increses with the incresing of the fertiliztion norm of N, P nd K. Thus, for instnce, in fertiliztion with N 120 P 120 K 120 the mngnese content in rdishes is mg kg -1 (Vrint 5). With the incresing of the fertiliztion norm of N 240 P 240 K 240, mngnese lso increses to mg kg -1 (Vrint 14); in fertiliztion norm N 360 P 360 K 360, the content of mngnese is highest mg kg -1 (Vrint 15). In the experiment with minerl fertiliztion nd 40 t h -1 mnure, the lowest content of mngnese ws in the roots of rdishes fertilized only with phosphorus nd potssium (N 0 P 120 K 120 ) 16 mg kg -1 Mn dry mss (Vrint 4) (Tle 2). Tle 2. Mngnese content in rdish (mg kg -1 dry mss) NPK + 40 t h -1 mnure N Vrints Method with CV Reli. RSD* AAS Yield Mn mg kg -1 P= 99 % % Mn mg kg -1 kg h -1 1 N 0 P 0 K N 120 P 120 K N 120 P 0 K N 0 P 120 K f N 120 P 120 K c N 120 P 240 K d N 120 P 360 K N 240 P 120 K c N 240 P 240 K f N 240 P 360 K N 360 P 120 K e N 360 P 240 K e N 360 P 360 K N 240 P 240 K N 360 P 360 K c N 480 P 480 K *Reltive Stndrd Devition for CV method (n = 6),, c, A degree of reliility In the three levels of nitrogen fertiliztion with mnure: N 120 (vrints 5, 6, 7), N 240 (vrints 8, 9, 10) nd N 360 (vrints 11, 12, 13) the highest content of mngnese is t P 240. Negtive correltion (r = -0.71) determines the reltion etween yield nd the mngnese content in vrints of fertiliztion with N 120 nd 40 t h -1 mnure in different levels nd (Fig.4). It cn e seen from the figure 4 tht with the incresing of the concentrtion of mngnese, the yield decreses. 817

8 In vrints of fertiliztion with mnure nd P 120 in different levels N nd K mngnese hs positive influence upon yield nd the correltion coefficient is r = 0.25 (Fig.5). The suordintion of yield from the content of mngnese in rdishes with minerl fertiliztion NPK nd 40 t h -1 mnure is negtive with smll correltion coefficient r = (Fig.6). It cn e seen from figure 6 tht with the incresing of the concentrtion of mngnese, the yield decreses. The highest level in minerl fertiliztion with 40 t/h mnure ws mg kg -1 Mn dry mss fter fertiliztion with N:P:K = 3:2:1. The experimentl dt show tht this rtio is different if the fertiliztion hs een crried out only with N, P nd K. Yield kg/h y = -168,84x Mn mg/kg Fig. 4. The suordintion etween the yield kg h -1 nd Mn content fertiliztion with N 120 nd 40 t h -1 mnure in different levels nd ; Correltion coefficient r =

9 y = 57,976x ,4 Yield kh/h Mn mg/kg Fig. 5. The suordintion etween the yield kg h -1 nd Mn content fertiliztion with P 120 nd 40 t/h mnure in different levels N nd K; Correltion coefficient. r = 0.25 It cn e ssumed tht chnges in mngnese content in the plnt roots in this experiment (minerl fertiliztion with 40 t h -1 mnure) were due to the effect of the colloid frctions of the mnure upon the minerl nutrition Yield kg/h y = -43,753x , Mn mg/kg Fig. 6. A generl suordintion etween yield kg h -1 nd Mn content in rdishes with minerl fertiliztion NPK nd 40 t h -1 mnure; Correltion coefficient r =

10 The experimentl dt (Tle 2) show tht in the three levels of nitric fertiliztion the mngnese content increses with the increse of the fertiliztion norm of nitrogen: N 120 P 240 K mg kg -1 Mn (Vrint 6); N 240 P 240 K 120 k mg kg - 1 Mn (Vrint 9); N 360 P 240 K mg kg -1 Mn (Vrint 12). The highest level in minerl fertiliztion with 40 t h -1 mnure ws mg kg -1 Mn dry mss fter fertiliztion with N:P:K = 3:2:1. The experimentl dt show tht this rtio is different if the fertiliztion hs een crried out only with N, P nd K. It cn e ssumed tht chnges in the mngnese content in the plnt roots in this experiment (minerl fertiliztion with 40 t h -1 mnure) were due to the effect of the colloid frctions of the mnure on the minerl nutrition. To check the method tht we propose, prllel determintion of mngnese content ws crried out y the tomic-sorption method ( S). The results otined (Tles 1 nd 2) show stisfctory ccurcy of the method for determintion of mngnese in plnt mteril with triphenylmethne dye Crystl Violet. The reltive stndrd devition of the method using Crystl Violet is 1.5 % t sttisticl reliility of 95%. The experimentl dt y oth methods show tht the proposed extrctionphotometric method with Crystl Violet cn e successfully used for determintion of micro quntities of mngnese in plnt mteril. Some chnges in the yield of the roots occur under the influence of the fertiliztion (Tle 1). When NPK ws individully pplied, the highest yield ws otined in the vrint 14 where it ws fertilized with N 240 P 240 K kg h -1. High yields were lso otined in the vrints 7, 11, 15 nd 16 where the yield vried from to12404 kg h -1. It seems tht in these vrints (with the exception of vrint 11) the yield of the roots decreses with the increse of the mngnese content. In the remining vrints of minerl fertiliztion, definite connection etween the yield otined nd mngnese content in the roots ws not estlished. In the experiment with mnure ckground the yield ws lower (Tle 2). The lowest yield ws in the vrint 12 with N 360 P 240 K kg h -1, nd the highest kg h -1 which ws fertilized with N 240 P 120 K 120 vrint 8. In these two vrints (12 nd 8), s mngnese content increses, the yield of the roots decreses. It could e concluded therefore tht the presence of the highest level of mngnese in the roots leds to the lowest yield. After this fertiliztion with NPK, on the ckground of mnure, gin no connection etween mngnese content nd yield otined ws estlished. The estlished chnges of the mngnese content in the roots nd those of the yield otined y vrints could e explined y chnges of the grochemicl properties of the soil under the influence of prolonged fertiliztion. 820

11 CONCLUSIONS A new extrction spectrophotometric method for the determintion of the concentrtion of mngnese with Crystl Violet in plnt mteril ws used. The method is simple, sensitive nd rpid with stisfctory results nd good reproduciility. Mngnese is determined in roots of rdishes in different fertiliztion. When rdish is fertilized only with NPK, the mngnese content in the roots is incresed with the increse of the fertiliztion norm of phosphorus. In the three levels of nitrogen fertiliztion with N 120, N 240 nd N 360, the highest content ws mg kg -1 Mn dry mss fter fertiliztion with N 240 :P 360 :K 120 = 2:3:1. A smll negtive correltion determines the reltion etween the yield nd the content of mngnese in rdishes fertilized only with NPK. The roots of rdishes ccumulte the highest level of mngnese mg kg -1 in minerl fertiliztion N:P:K = 3:2:1 with 40 t h -1 mnure. The experimentl dt show tht this rtio is different if the fertiliztion hs een crried out only with N, P nd K. The suordintion of yield from the content of mngnese in rdishes with minerl fertiliztion NPK nd 40 t h -1 mnure is negtive. It cn e seen tht with the incresing concentrtion of mngnese, the yield decreses. REFERENCES Alkn M. J. Trce nd Microproe Tech. 21, 3, 479 (2003). Blogh I. :Anl. Bionl. Chem. 377, 4, 709 (2003). Bisws P. J. Indin Chem. Soc. 80, 3, 195 (2003). Bultov M.,Klinkin I., A Prcticl Mnul of Photocolourimetric nd Spectrophotometric Methods of Anlysis, L., Chemistry (1972). Bergmnn W., Neuert P.: Pflnzendignose und Pflnzennlyse, Jen (1976). Heintze S.: Jour. Agr. Sci., 36 (1966). Kdoyshi H, Nkmori T, Ymguchi T, Fujit Y.: Chemistry Letters 33, 5, 610 (2004). Kostov D., Kmurov M.:Solvent extrction of mngnese(vii) with new nlyticl regent, Chemij, in press. Mokrev T., Murgov G., Scientific Works, Higher School of Agriculture, Plovdiv, 1988, XXIII, N 1, 135. Nurliev I., Yrovenko G.: The effect of molydenum nd mngnese on phosphor metolism nd the yield of cotton depending on the minerl nutrition, Agrochemistry, 11, 111 (1980). Nson A., Olderwurte H., Propst M. :Arch. Biochem. Biophys., 38 (1952). Nichols D.: Ann. Rev. Plnt Phisiol., 12 (1961). Pottuev J., et l.: Agrochemicl sustntition of the inclusion of phosphorus nd phosphorus contining fertilizers with ddition of mngnese in the micronutrients, Agrochemistry, 4, 95 (1990). Shkolnik M.: Trce elements in life of the plnts, Leningrd (1974). 821

12 Sndell E.: Colorimetric determintion of Trces of Metls, 3 rd Ed., Interscience, New York (1959). Shr G.:J. Chem. Soc. Pkistn, 25, 1, 28 (2003). Sidorovich E., Rupsov G., Zukov J., Igntenko V., Kuhrenik T.: Agrochemistry, 6, 72 (1987). Trfder P. Chem. Anl. 49, 2, 251 (2004). Udintsev E., Hodorovski J., Zulikov A.: Agrochemistry, 9, 119 (1981). Vzhenin I.: Methods for Determintion of Trce Elements in Soils, Plnts nd Wters, Kolos, Moscow (1974). Winkler W.:Anl. Bionl. Chem. 376, 6, 934 (2003). 822

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