氮化沸石纳米材料及其在农业中的应用前景外文文献VIP

氮化沸石纳米材料及其在农业中的应用前景外文文献氮化沸石纳米材料及其在农业中的应用前景外文文献 Nitrogenous zeolitenanomaterial andthe possibilityof itsapplicationin agricultureG Tsintskaladzea L Eprikashvili a N Mumladze b V Gabunia a T Sharashenidze a M Zautashvilia T Kordzakhia a T Shatakishvili aaIvane JavakhishviliTbilisi StateUniversity Petre MelikishviliInstitute ofPhysical andOrganic hemistry 31 Politkovskaya Str Tbilisi 0186 Georgiab CartlisAgrosystems Ltd 75b Kostava Str Tbilisi 0160 Georgiaa rt ic le in foArticle history Received27MarchxxAepted29MayxxAvailable online26JulyxxKeywords Natural zeolitesSoilfertilityNanomaterialsNitrogen fertilizerX ray diffractometricab st ra ctNew nanotechnological method isproposed toreduce thenegative effectsof nitrogenous fertilizers andtheirlosses which involvesintroduction of nitrogen containing substanceinto the structure of naturalzeolite The obtainednanomaterials can be used as anitrogen fertilizer which allowsthe gradualtransferof nitrates into the soil andminimizing fertilizationlosses It alsosignif i cantly reducesgroundwatercontamination Also volatilization as well asdrain lossesof nitrogenare signif i cantly reduced Proposedzeolite nanomaterialrepresents astrong reserveof nitrogenpounds required for feedingthe plants Obtained nanomaterialstructure isstudied usingchemical X ray diffractometricand IRspectroscopicmethods Also nanotechnological processof enrichment and extraction of natural zeolite withammo nium nitrateis established For provingthe effectivenessof proposednitrogenous fertilizertests wereconductedon corn crop 108m2 where theaverage harvest on the recording areaamounted92 6kg Inaddition tothe f i eld test the production test was also conductedon1ha where the increasedcorn cropreached1 4t ha which is equal to18 9 xxProduction andhosting byElsevier B V on behalfof AgriculturalUniversity of Georgia This isanopen aess article under the CC BY NC ND license creativemons licenses by nc nd 4 0 IntroductionProviding thepopulation withenvironmentally friendlyprod ucts isone of the greatestchallenges ofour time Nowadays it isimpossibleto geta highharvest withoutusing mineralfertilizers inagriculture Although using increasedamount of these fertilizerscannegatively affectthe qualityof nutrientsas well as thebiochemicalarea of the environment Soil andvegetation isa united interconnected system One ofthemost importantfeatures of the soil is theability tosatisfyplant s requirementsfor foodand water Soil isa sourceof macro and microelementsrequiredfor the plant which can be absorbedbyits rootssystem andits leaves 1 2 Today out of all mineralnitrogen fertilizers ammonium nitrateismost widelyused in the world The plantneeds bigamount ofammonium nitrate forgrowing itsgreen massand providinghighcrop Nitrogen isthe mainnutrient thatproduces organicsubstancesforthe plant Except foramino acids nitrogen isalsoincluded inpurines alkaloids enzymes plant growthregulators chlorophyll andcellular membranes Nitrogen def i ciencyleads tothe failure of the synthesisof normalamount ofchlorophyll andeventuallythe leavesof theplant arediseased withchlorosis Ni trogen circulationin theplant isespecially intensivelyobserved atthemaximum indexof itsheight Plants aremainly usingammoniaand nitrous nitrogen while legumesand someother plantsareusing molecularnitrogen inSymbiosis withmicroorganisms 3e5 Ammonium nitratecontains nitrogenboth innitrous and ammoniaforms Therefore while usingthis fertilizernitrogen volatilizationas well asnitrogen lossesfrom drainedsoil ours Nitrous nitrogendrainedin the soil isheavily pollutinggroundwater 6 The prob lem of the lossof nitrousandammonianitrogen andthe threatofenvironmental hazardin theworld hasnot beensolved yetdue tothefact thatways ofretention ofnitrousnitrogenin the soilisnotfound sofar Because ofthat the farmerhas tointroduce ammo niumnitrate into the soil minimumof2e3times duringthe lifecycleoftheplant which isassociated withadditional problems Therefore it s beingmore andmore monto usenon traditional mineral raw resourceslike diatomite marlstone lime stone zeolites tuffs andother materialsin farming 7 8 Corresponding author E mail address leprikashvili hotmail L Eprikashvili Peer reviewunder responsibilityof JournalAnnals ofAgrarian Science Contents listsavailable atScienceDirectAnnals ofAgrarian Sciencejournalhomepage journals elsevier annals of agrarian sciencedx doi 10 1016 j aasci xx 07 0061512 1887 xxProduction andhosting byElsevier B V on behalfof AgriculturalUniversity of Georgia This isan openaessarticleundertheCCBY NC ND license creativemons licenses by nc nd 4 0 Annals ofAgrarian Science15 xx 365e369Natural zeolitesrepresent crystalline hydrating aluminosili cates the structure ofwhich containsgaps thatare oupiedby ionsableto movefreely andwater molecules Zeolites arenanoporousmaterials whosethermal orchemical processingcan resultinbreaking of zeolite structurechains thatmay befollowed bysomechanges inits structure By leavingthe zeolite structure byions andwatermolecules andchanging theinternal volumeit ispossible tochangethe sizesof nanoporesaswell as creatingnew nanopores 9 Georgia isrich indifferent typesof zeolite contained tuffs Thereare15varieties of zeolite mineralsresearched inGeorgia thesupply ofwhich isapproximately300million tons 10 The useof natural zeolites turnedouttobe especiallyeffectiveinagriculture 11 12 The introduction of mineralfertilizers alongwithnatural zeolitescontaining environmentally safe microele ments into the soilallows us to ensurethe durationoftheeffect oftheintroduced fertilizerand toreduce thedrain ofnutrient ponents In addition zeolites regulatethe processof water nitro gen potassium andother macroand microelementsabsorption bytheplant intothesoil 13 Nowadays zeolite fertilizersare widelyused in thepractice ofplants aspart ofsubstrates usedingreenhouse farmsaswell as fertilizerbasis usedin opengrounds 14 Objectives andmethodsAs itwas pointedout naturalzeoliteshave adeveloped andorganizedmicro and nanoporouscrystalline structure Unlikesynthetic zeolitesadditionally theyhave secondary so calledmesoporous structure aswell If weadd main adsorption andmolecular sieve featuresofnaturalzeolites toit in orderto limitnitrogenousfertilizer s negativemovements aordingto allabovementioned and also to signif icantlyincrease thenitrogen absorp tion coeff i cientoftheplant we haveproposed anew nano technologicalmethod 15 16 which allows ustointroducenitrogenous fertilizer namely ammonium nitrateina waythatzeolite structurewon t beviolated Obtained nanomateriale inorganic capsulemolecular sieve canbeused asnitrogenousfertilizer whichallowsusto regulatethe gradualtransition ofni tratesinto soil minimize thewaste offertilizer andalsosignifi cantlyreducethe pollutionof groundwaters bynitrates Natural zeolitefound inGeorgia Kaspi region upper Khandaki Fig 1 X Ray diffractogramsof zeoliteclinoptilolite 1 Natural zeolite clinoptilolite 2 The zeolitematerial afterplete leaching of nitrate ions 3 The zeolitematerial afterplete leachingof nitrate ions 1 1 4 The zeolitematerial afterplete leachingof nitrate ions 1 3 G Tsintskaladze etal Annals ofAgrarian Science15 xx 365e369366 0 5mm clinoptiloliteand ammonium nitrate wasused fortheexperiment The materialshave beenmixed indifferent pro portions andthen saturatedwith moltensalt foran amountof time Produced nanomaterial which ischaracterized byoptical homo geneity andmechanical stiffness was cooleddown toroom tem perature andthen grindedand granulatedto grainssized0 5e2mm The structureand featuresof nanomaterial enriched withnewzeolite nitrateswas examinedwith chemical X ray diffractometricandspectroscopic methods It wasconcluded thatafter theintro ductionof ammonium nitrateinto zeolitepores the structureofzeolite didnot change also thenanotechnological gradualextrac tion mechanismof ammonium nitrate fromzeolite structurewasestablished Fig 1shows X ray diffractogramsof zeoliteclynoptilolite initialzeolite 1 samples fusedwith ammonium nitrate withratios1 1 2 and1 3 3 zeolite afterbeing fullyf lushed with ammoniumnitrate water 4 Fig 1 As itis shown on X ray diffractograms after enrichmentwithammonium nitrate the structureof zeoliteremains practicallythesame except forsome minordeformations ofthestructure whichare identifi edby X ray diffractogramdifferences betweenpeaksintensities which istypical forclinoptilolite 2nd and3rd dif fractograms clearlyillustrate unchangedstructures ofsalt as wellaszeolite thatwas ourgoal Nanotechnological processof enrich mentandextractionofnaturalzeolitewithammoniumnitratestudied withIR spectroscopymethod isshownonFig 2 Fig 2 As wecan seefrom thediagram zeolite aswellasammoniumnitrate IR spectrums dramaticallydiffer fromeach otherand theybothcorrespond tothe etalonspectrums whichare characteristicsofeach ofthese substances 17 Zeolite IRspectrum hassignifi cantly changedafter itwas nanotechnologicallytreated withammoniumnitrate andthe resultas itwas expectedis signifi cantlydifferentfrom the initial IRspectrums ofboth clinoptiloliteandammonium nitrate As wecan seefrom thediagram there arenoticeablechanges in thestructureofzeolitewhichisexpressed inIRspectrum informing newlines andalso inchanges ofthe fre quency andintensity ofthe existinglines In particular in thedeformationand valencyvibration regionsof aluminosilicatewehave newlines 594 1596 1712 also lever 879cm 1 which arecharacteristicsto nitrateions 18 Frequencies ofthe deformationandvalency vibrationsofthelines of aluminosilicate havechangedfrom1033cm 1to1056cm 1 from1139cm 1to1149cm 1 fr om3401cm 1to3347cm 1 from3540cm 1to3425cm 1and fromFig 2 IR spectraofthesamples 1 Natural zeolite clinoptilolite 2 Salt ammoniumnitrate 3 The zeolitematerial isenriched withammoniumnitrate 4 The zeolitematerial partialleachingof nitrateions 5 The zeolitematerial afterplete leachingofnitrateions G Tsintskaladze etal Annals ofAgrarian Science15 xx 365e3693673603cm 1to3463cm 1 After treatingsome amountof resultednanomaterial withwa ter the intensityof linestypical tonitrateionsin IRspectrum isreduced Also the frequenciesand intensitiesbetween thelines which wehad ininitial andnanomodif ied examplesofzeolitearereduced After fullwater f l ushingofammoniumnitrateionsfromthe zeolitestructure theIRspectrumis almostequaltotheinitialIRspectrum ofzeolite The differenceis onlychanging thefrequencyand intensityof somelines whichis resultedby partialdeformationof zeolitestructure This factonce againproves thatammoniumnitrate hasentered the zeolitestructure Thus the resultsobtainedby X ray diffractometeranalysis aswellasthe resultsof IRspec troscopic methodare equal As pointedout after theintroduction of nitrogenousfertilizer inparticular ammoniumnitrateintotheso il due tothe bigcon sumption ofnitrate andammonium fertilizers introducing themintothesoilmust berepeated severaltimes insome cases The ionsofammoniumnitratefrom proposednanomaterial areslowlyallocating intothesoilfrom itsporousstructureand isslowlytransmitting totheplantdue tomolecular sieve characteristicsofzeolite so thatthe lossofnitrogenis minimizedand nitrogentransferredtosoilis usedpletely duringwhole lifecycle ofplant Results andanalysisProposed nitrogenousfertilizer wastested forits effectivenessoncorncrop in particularon PR32F73 Four optionsofafi eld testwereconducted withthe followingscheme 1 Ammonium nitratewith physical weight 300kg ha 102kg hapure nitrogen 2 Zeolite with physical weight 300kg ha ammonium nitratewithphysical weight 300kg ha 102kg ha purenitrogen 3 Zeolite withphysical weight 200kg ha ammonium nitratewithphysical weight 200kg ha 68kg ha purenitrogen 4 Zeolite withphysical weight 75kg ha ammonium nitratewithphysicalweight 225kg ha 76 5kg ha purenitrogen The fi eldtest wasset on108m2 The recording area 94 5m2 the distancebetween therows 75cm the distancebetween theplantsinarow 18cm The bestcrop ofcorn grainwas observedinthe4th versionwheretheharveston therecordingarea reachedanaverage of92 6kg In thecase ofintroducing nitrogenfertilizeralone theaverage harvestontherecordingareawas75kg Therewas nocredible growthnoticed in the cropbetween2nd and3rdversions Table1 Production testwas conductedalong withthefieldtest ontheabove mentionedversion Division space 1ha Test schemeis thefollowing 1 300kg ha ammoniumnitrate withphysicalweight 2 75kg ha zeolite 225kg ha ammoniumnitrate with physicalweight In thefirst versionthe corngrain cropamounted7 4t ha andinthe secondversion itamounted8 8t ha ofcorn grains The increaseamounted1 4t ha whichis equalto18 9 Table2 ConclusionThus thezeolitenanomaterial obtainedby theproposedmethod cansuessfully beusedasa prolonged action nitrogenousfertilizerto providea plantwith nitrogenthroughout thewholevegetative period The introductionof thisfertilizer intothesoilisdone onlyonce whichreduces logistiosts environmentallysafe reduces theflow ofnitrates intogroundwaters has aprolongedaction Also it regulatesthe absorptionof thewaterandnitrogen bytheplant The abovementioned fertilizercanbeusedinopen fi eldaswellasin greenhousefarms nursery gardensand fordecorativehome plants References 1 G Ya Rinkins V F Hollendorf A BalancedDiet ofPlant Macro and Micro nutrients Zinatne Riga 1982 in Russian 2 V Egorov agro archive ru pochvovedenie The PhysiologicalRole oftheMost ImportantElements Foundin theSoil in the Lifeof Plants xx 3 A A Zavalin G G Blagoveshchenskaya L S Chernov a N Ya Shmyreva Man agement ofplant nitrogennutrition insoil Agrochemical4 xx 35e42 inRussian 4 V I Volyinkin O V Volyinkina The effectoftheposition offertilizer andnitrogendoses duringsystematic usein croprotation andon monocultureofwheat Fertility2 xx 48e54 in Russian 5 M I Kudashkin The infl uenceofnitrogenousand microfertilizers onthe yieldofwinter wheatof varioussowing timesin croprotations ofagrolandscapes inthesouth ofthe non black earthregion Agrochemistry5 xx 26e34 inRussian 6 I Marshania Agrochemistry Ganatleba Tbilisi 1991 in Georgian 7 O Y Zardalishvili T T Urushadze M O Zardalishv ili Local oresofGeorgiaandprospects oftheir usefor fertilizationof agriculturalcrops J Ann Agrar Sci 10 4 xx 57e61 8 G P Tsintskaladze L G Eprikashvili T F Urushad ze T N Kordzakhia T V Sharashenidze M G Zautashvili M N Bur janadze Nanomodif ied naturalzeoliteasa fertilizer ofprolonged activity J Ann Agrar Sci 14 3 xx 15e20 9 G V Tsitsishvili T G Andronikashvili G N Kirov L P Filizova Natural Zeolites Ellis Horwourd London London 1992 10 N I Skhirtladze Sedimentary ZeolitesofGeorgia University Press Tbilisi 1991 in Russian 11 G V Tsitsishvili T G Andronikashvili M B Neste rov V G Labutin Use NaturalZeolitesin PlantGrowing Metsniereba Tbilisi 1997 in Russian 12 J Ramsden Jeremy Nanotechnology inagriculture J Ann Agrar Sci 10 2 xx 104e108 13 Alberto C de CamposBernardi Patricia PerontiAnchro Oliviera Marisa B deMelo Monte Fernando Souza Barros Brazilian sedimentaryzeolite useinagriculture J Microporous MesoporousMater