BERNARDI, A. C. de C.

MONTE, M. B. M.

OLIVEIRA, C. R. de

PEREIRA, E. I.

POLIDORO, J. C.

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,QWHUQDWLRQDO6FLHQWL¿F&HQWUHRI)HUWLOL]HUV&,(&Rio de Janeiro, RJ 2014PROCEEDINGS9LQLFLXVGH0HOR%HQLWHV$GLOVRQGH2OLYHLUD-XQLRU3DXOR6HUJLR3DYLQDWR3DXOR&pVDU7HL[HLUD0LOWRQ)HUUHLUD0RUDHV5HJLQD0DULD9LOODV%{DVGH&DPSRV/HLWH5RQDOGR3HUHLUDGH2OLYHLUDEditorsTECHNOLOGICAL INNOVATION FOR A SUSTAINABLE TROPICAL AGRICULTUREOctober 20-24, 2014Rio de Janeiro, RJ - Brazil16th World Fertilizer Congress of CIEC24Introduction Diferent strategies can be taken to increase WKH HI¿FLHQW XVH RI QXWLUHQWV IURP WRPD[LPL]H LWVEHQH¿WV WR WKH SODQWVRLODWPRVSKHUH V\VWHP 1L-trogen is part of all living cells and is an essen-tial constituent of amino acids and hence the pro-teins, enzymes and metabolic processes involved in the synthesis and transfer of energy, and is part of chlorophyll, the green pigment responsible for photosynthesis. Fertilizers are the most important sources of nitrogen used in large-scale cultivation of various non-legumes crops. In general, some changes in agricultural PDQDJHPHQWFDQLQFUHDVHWKHHI¿FLHQF\LQWKHXVHof N fertilizers such as: removing phisical, chemical DQG ELRORJLFDO OLPLWLQJ IDWRUV WR SODQW JURZWK EDO-DQFHGIHUWLOL]DWLRQDGHTXDWHZDWHUVXSO\LQJDGMXVW-PHQWRIIHUWLOL]HUVXSO\LQJWRSODQWGHPDQGRSWLPL-]DWLRQRIUDWHDQGWLPLQJRIIHUWLOL]HUVXSOO\LQJVSOLWIHUWLOL]DWLRQ IHUWLOL]HU VRLOLQFRUSRUDWHG XVHRI FURSURWDWLRQDQGJUHHQPDQXUHDQG¿QDOO\XVLQJVORZRU FRQWUROOHG UHOHDVH IHUWLOL]HUV DQG QLWUL¿FDWLRQ LQ-hibitors with N-fertilizers. The controlled and slow release fertiliz-ers are prepared to release their nutrient content gradually, and if possible, match their release with the crop nutritional requirements, or to extend their availability much more than high solubility fertiliz-ers. The advantages of these nutrient sources are the eliminate the use of topdressing fertilization, la-bor and fuel saving, soil compaction and root dam-age minimizing, and preventing crop damage, as well as reducing environmental contamination. Urea nitrogen has been the most used N-source in Brazil, due to lower cost per unit of N. But 1XVHHI¿FLHQF\RIXUHDPD\EHUHGXFHGEHFDXVHof losses from agricultural system by volatilization of ammonia to atmosphere. This is one of the main IDFWRUV UHVSRQVLEOH IRU WKH ORZ HI¿FLHQF\ RI XUHDand may reach extreme values, close to 80% of N applied, even so in acid soils, since the liming in-creases soil pH and favors volatilization. Mulch form no-tillage or pasture systems may also increase the amount of N lost by volatilization, especially when urea is applied on soil surface. The N-urea losses can be reduced using zeolites as additives in the fertilizers to control the retention and release of NH4+. The use of minerals for agricultural purposes is becoming widespread, and zeolites concentrates have a special niche in this category. Zeolite minerals are crystalline hy-drated aluminosilicates of alkali or alkaline-earth metals, structured in three-dimensional rigid crys-talline network, formed by the tetrahedral AlO4 and SiO4, which come together to compose a system of canals, cavities and pores at nanoscale. These minerals are characterized by the retaining and re-leasing water and exchange cations without chang-es in structure. Other hydrated layered silicates clay minerals, like bentonite, are able to exchange cations, and intercalate neutral molecular species between the interlayer regions by interaction with structural water. The worldwide number of identi-¿HGQDWXUDO]HROLWLFFRQFHQWUDWHVGHPRQVWUDWHVERWKtheir great variety and the present-day interest on their potential applications in the industry and the agriculture. In Brazil there are three regions with sedimentary zeolite which widely varies in the depth of the ocurrence and the stilbite concentration. The largest zeolite reservoirs are found in the Parnaiba river valley, where the stilbite form of the heulandite group dominates reaching approximately 50% of VHGLPHQW5H]HQGH	$QJHOLFD0RQWHHWDO%HUQDUGLHWDOE The main action of zeolite in partial reduc-tion on NH3 loss by volatilization occurs by the con-trol of retention of ammonium ion, formed by urea hydrolysis in the soil, due to zeolite high cation ex-change capacity and ammonium retention from soil solution. N inputs from fertilizers increase NH4+ and THE USE OF CLAY MINERALS TO IMPROVE NITROGEN FERTILIZER EFFICIENCYALBERTO C. DE CAMPOS BERNARDI1, JOSÉ CARLOS POLIDORO2, MARISA B. M. MONTE3, ELAINE I. PEREIRA4, CAUÊ RIBEIRO DE OLIVEIRA51(PEUDSD3HFXDULD6XGHVWH&[36mR&DUORV63%UD]LO&(3DOEHUWREHUQDUGL#HPEUDSDEU2Embrapa Solos, 5LRGH-DQHLUR5-%UD]LO3&HQWURGH7HFQRORJLDV0LQHUDLV±&(7(05LRGH-DQHLUR5-%UD]LO4Universidade Federal de São &DUORV8)6&DU&KHPLVWU\'HSDUWPHQW6mR&DUORV63%UD]LO5Embrapa Instrumentação, São Carlos-SP, BrazilLectures 25NO3– soil concentrations and may increases the soil emissions of the greenhouse gas (GHG) as NH3 and N22 +RZHYHU LQIRUPDWLRQ RQ KRZ XUHDíDOX-minosilicate slow-release nanocomposites might af-IHFWYRODWLOL]DWLRQQLWUL¿FDWLRQDQGGHQLWUL¿FDWLRQSUR-cesses in the soil still need more studies. Besides retaining large quantities of ammonium ion, these PLQHUDOVDOVRLQWHUIHUHLQWKHSURFHVVRIQLWUL¿FDWLRQ There are many reports in literature dem-RQVWUDWLQJ WKH LQFUHDVHG HI¿FLHQF\ RI 1 XWLOL]DWLRQwhen urea is used together with aluminossilicates. In a laboratory tests, Baptista-Filho et al. (2008) demonstrated the ammonia retention by zeolite us-ing a photoacoustic set-up, which simulated tropical weather temperatures. The positive effect of zeolite ZDVFRQ¿UPHGLQD¿HOGH[SHULPHQWZLWKURVHEXGV ,QD¿HOGH[SHULPHQW%HUQDUGLHWDOevaluated dry matter yield and nutritional levels of nitrogen of silage corn fertilized with urea + zeolite. Treatments comprised two types of stilbite zeolite (natural and concentrated), four levels of nitrogen (0, 50, 100 and 200 kg ha-1) and four ratios of zeo-lite (25%, 50% and 100% of N level). Treatments were applied 60 days after planting in the topdress-ing fertilization. The use of concentrated (650 g kg-1 of stilbite) or natural (470 g kg-1 of stilbite) zeolite with urea increased, respectively 5.5% and 3.6% the silage corn dry matter production and N leaf concentrations.  In a pot experiment with Italian ryegrass Bernardi et al. (2013a) observed differences in the rate of N-NH3 volatilization with addition of 20% of zeolite to urea with an 8% decreasing of accumulat-ed volatilized N-NH3. Results indicated that approxi-mately 21% of applied N was lost as N-NH3+ when there was no addition of zeolite to urea. Addition of 20% zeolite reduced losses to 19.6%. As expected based on previous results, the lowest percentage of loss was obtained from ammonium nitrate N-source which was similar to the control (without N). Clinoptilolite is the most known and used zeolite specie for retaining ammonium cation. Wer-neck et al. (2012) achieved reductions of losses by ammonia volatilization when urea was applied with clinoptilolite. Baptista et al. (2011) showed that the Brazilian zeolite stilbite has the ability to retain half of the quantity of ammonium held by the clinoptilo-lite type.Rech (2014) tested urea-based formulations of ni-trogen fertilizer with the addition of urease inhibitors (NBPT, Cu, B), elemental sulfur and clay minerals of the zeolite group. The results showed that formu-lations produced with urease inhibitor alone (NBPT, B, Cu) embedded in beads and those inhibitors FRPELQHGZLWKWKHFOD\PLQHUDOVKRZHGJUHDWHUHI¿-ciency in reducing losses by volatilization compared to commercial coated fertilizer with the same inhibi-tors. Ammonium and nitrate leaching and soil accu-PXODWLRQVKRZHGQRVLJQL¿FDQWGLIIHUHQFHVEHWZHHQproduced formulations and commercial fertilizers. The N accumulation in corn plants grown with the new formulations was similar to commercial ferti-lizer, being higher to commercial urea. However, it is clear that the incorporation of a urease inhibitor LQXUHDIHUWLOL]HULVPRUHHI¿FLHQWLQWKHUHGXFWLRQRIlosses by volatilization compared to coated fertiliz-ers produced with the same additives. However, the property of cation exchange is shown by the aluminosilicate, represented not only by zeolites, but especially by clay minerals. Clay minerals are crystalline hydrated aluminum silicates, structurally oriented as silicate lamel-lae bonded to aluminate lamellae. These lamellae are spatially arranged by stacks separated by ex-change able ions and structural water. The crystal-OLQHVWUXFWXUHVDUHFODVVL¿HGLQWRW\SHVVWUXFWXUHV1:1 (kaolinite, serpentine) and structures 2:1 (talc-pyrophyllite, mica, smectite, vermiculite, chlorite, attapulgite, sepiolite). Only a small number of clay minerals are components of industrial clays: kaolin-LWH NDROLQPRQWPRULOORQLWH EHQWRQLWH WDOF WDOFvermiculite (vermiculite) andchrysotile (asbestos). Just as zeolites, the cation exchange capacity in clay minerals is quite pronounced, however, values may range from 10-3 meq·g-1 (phyllites) to 1 meq·g-1 (montmorillonites and vermiculite).  Pereira et al. (2012) demonstrated that a nanocomposite formed from a montmorillonite ex-foliation in a urea matrix controlled the solubiliza-tion process, delaying the N release. The results showed that it was possible to obtain by cold ex-trusion, a high N content and adequate strength compatible to comercial fertilizer. Microstructural analysis of composites indicated that the extru-sion process generated two regions, one compris-ing the nanocomposite itself (montmorillonite and 16th World Fertilizer Congress of CIEC26urea), and other regions with urea granules. Thus, the authors attributed the release process not only to the clay mineral-urea interaction, but also to the creation of barriers to free urea diffusion out of the granule.Conclusions The reduction in ammonia losses by vola-WLOL]DWLRQDQGWKHLQFUHDVHGHI¿FLHQF\RI1XWLOL]DWLRQwhen urea is used together with aluminosilicates ZDV GHPRQVWUDWHG LQ ERWK JUHHQKRXVH DQG ¿HOGexperiments. These results indicate that alumino-VLOLFDWHVPLQHUDOVDUHDEOHWRLPSURYHWKHHI¿FLHQF\of nitrogen use, contribute to increasing N uptake through the control of retention of ammonium ion. .H\ZRUGV Zeolite, stilbite, clinoptilolite, slow-release fertilizer, N losses, ammonia volatization.References%$37,67$),/+206,/9$0*32/,'252-&/81$)-0217(0%0628=$%$5-526 ) 0,./26 $ 9$5*$6 + 'HWHFWLRQ RIammonia released from zeolite by the quantum cascade laser based photoacoustic set-up. Euro-pean Physical Journal A, v.153, p.547-555, 2008.%$37,67$),/+2 0 5,7(5 +* 6,/9$ 0* /81$ )-:(51(&. &* 5(&+ , 32-/,'252 -& 0217( 0%0 628=$%$5-526)0,./26$9$5*$6+$PPRQLDWUDFHVdetection based on photoacoustic spectroscopy for evaluating ammonia volatization from natural zeo-OLWHVDWW\SLFDOFURS¿HOGWHPSHUDWXUH6HQVRUVDQGActuators. B, Chemical, v. 158, p. 241-245, 2011.%(51$5',$&&027$(&$5'2625'0217(0%02/,9(,5$33$$PPRQLDYROD-tilization from soil, dry matter yield, and nitrogen lev-els of Italian Ryegrass. Communications in Soil Sci-ence and Plant Analysis, v. 45, p. 153-162, 2013a.%(51$5', $&& 2/,9(,5$ 33$ 0217(0%0628=$%$5526)%UD]LOLDQVHGLPHQWDU\zeolite use in agriculture. Microporous and Mes-oporous Materials, v.167, p.16-21, 2013b.%(51$5', $&& 628=$ *% 32/,'252-& 0217( 0%0 3$,9$ 353 <LHOG TXDO-ity components, and nitrogen levels of silage corn fertilized with urea and zeolite. Communications in Soil Science and Plant Analysis, v.42, p.1266-1275, 2011.0217(0%0 0,''($$ %(51$5',$&&5(=(1'(1*$0%$37,67$),/+206,/-9$ 0* 9$5*$6 + $025,0 +6 628=$BARROS, F. Nutrient release by a Brazilian sedi-mentary zeolite. Anais da Academia Brasileira de Ciências, v.81, p.641-653, 2009.3(5(,5$(,0,1866,)%&58=&&7%(5-1$5',$&&5,%(,52&8UHD0RQWPRULOORQLWHExtruded Nanocomposites: A novel slow-release material. Journal of agricultural and food chemistry, v.60, p.5267-5272, 2012.:(51(&.&* %5('$ )$ =217$ ( 32-/,'252-&%$/,(,52)&%(51$5',$&&Volatilização de amônia proveniente de ureia com ]HyOLWD QDWXUDO 3HVTXLVD $JURSHFXiULD %UDVLOHLUDv.47, p.466-470, 2012.

The use of clay minerals to improve nitrogen fertilizer efficiency .

http://www.alice.cnptia.embrapa.br/alice/bitstream/doc/999460/1/PROCI2014.00086.pdf

The use of clay minerals to improve nitrogen fertilizer efficiency .

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