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AP42 Section: Background Ch Reference:

Title: K. F. Bronson and A. R. Mosier, "Effect of Encapsulated Carbide on Dinitrogen, Nitrous Oxide, , and Carbon Dioxide Emissions from Flooded Rice," Biology and Fertility of Soils, 1 1: 1 16-1 20, 1991 . Bio! Fed Soils (1991) 11:116-120

0 Springer-Verlag 1991

Effect of encapsulated calcium carbide on dinitrogen, nitrous-oxide; methane, and carbon dioxide emissions from flooded rice K.F. Bronson and A.R. Mosier US Department of Agriculturr Agriculture Research Service, P.O. Box E. Fort Collins, CO 80522. USA

Rcccived August 16. 1990

Summary. The efficiency of N use in flooded rice is usu- important "greenhouse ", with 5 times more infrared ally low. chiefly due to gaseous losses. Emission of CH,, sorbing capability than CO, (on a mole basis, consider- a gas implicated in global warming, can also be substan- ing the decay time of in the atmosphere; Rodhe tial in flooded rice. In a greenhouse study, the nitrifica- 1990). tion inhibitor encapsulated calcium carbide (a slow-re- Bouwman (1990) has estimated that 20-45% of the lease source of ) was added with 75, 150, and total global emissions of CH, originate from flooded 225 mg of 75 atom To "N urea-N to flooded pots con- rice fields. Fertilizer N can increase CH, fluxes in rice

taining ' 18-day-old rice (Oryza sativa L.) plants. Urea (Cicerone and Shetter 1981). . , treatments without calcium carbide were included as con- Several workers .have. reported that .'the addition of . trols. After !he application of. encapsulated calcium car- nitrification.inhibitors. such as';nitrapyrin 'or C2H2.with tjda-3.6 g ?,,: 12:4 pi .N;O-N, .and 3i5 mg. CH, were urea indirect1y:reduces. N20 production.in upland soils: emitted per pot. in, 30. days. Without csilcium caibide, (Bre,mner -and: Blackmer..1979; CribbsrandzMills '197% 3.0-2. N,,. 22.8 ig NZO:N; and 39.0 mg CH, per pot Aulakh et al. 1984). Banerjee and Mosier (1989) were the were emitted during the same period. The rate of N added first to demonstrate that encapsulated calcium carbide is had a positive effect on N, and NzO emissions, but the a slow-release source of CzHi that inhibits nitrification !l effect on CH, emissions varied with time. Carbon diox- and reduces NzO fluxes in flooded soils. Acetylene also ide emissions were lower with encapsulated calcium car- inhibits CH, production (Raimbault 1975; Knowles bide than without. The use of encapsulated calcium car- 1979) at 0.0101 x IO6 Pa, a concept that has not been ap- bide appears effective in eliminating NZ losses, and in plied to flooded rice systems. In the present study. there- minimizing emissions of the "greenhouse gases" NzO fore, the use of encapsulated calcium carbide as an inhib- and CH4 in flooded rice. itor of denitrification and CH, pmducth-wasrtcsted in a greenhouse study in flooded rice. Key words: Denitrification - Flooded soil - "N - Urea - Wetland rice - Oryza sativa L. Materials and methods

Two g ground corn (Zen mays L.) straw (0.34% N and 22.9% C) was Gaseous losses of N, and N,O from denitrification, and added IO pots (16 cm high. 189 cm' in area) containing 2 kg Xunn clay NH3 volatilization (De Datta 1981; Fillery et al. 1986; loam soil. (fine, montrnorillonitiz mesic. Aridic.Argiustoll). The soil Mosier et al. 1989; Buresh and De Datta 1990). lead to had.a pH.of 7.9. 2.1% organic matter. 21 mg:kgT! NO;-N electrical low fertilizer-use efficiency in flooded rice. Stategies used conductivity 1.3 mrnhos .cm-'.and medium to high ..levels of . to reduce these losses include slow-release urea (Caner et NH,HCO,-diethylenct"amincpcnlaacetic acidutrpctablc Ca. Mg, P. K. Zn. and Fc The soil in the pou was flooded, and puddled by hand. al..1986), deep placement .of urea supergranules (Cao et Every.3-5 days for:I9 days; and we* 8-IO days thereafter. pH and al. 1984), split.applications of N '(Cao et.al. '1984), and redox potential '@h) were:me&urcd at a.depth:of 5 ?,,with pH and amending urea fertilizer with urease and or nitrification platinum el&troder.in 6'01 rhe~l8pou.~Thr~-l5day-oId.ricc.(O~ inhibitors (Simpson et al. 1985: Buresh.et al. 1988)... rorivo L.).scedlings. cultivar :IR,W, we.w transplanted to;each pot 15 CH4 emissions from rice; while not contributing to days after the start of permanent flooding. Three days latcr;75, 150. or the N fertilizei loss, are of concern because CH4 is an 225 mg (equivalcnt.to 40..80. and 120 kg N ha-') 75 atom % "N-la- bcled urea-N was added to-the pots with or without encapsulated calci- um carbide (0.25 g CaC2 and 0.25 g coating). The 1-2 mm CaC, parti- - cles were coated first with a layer of carnuba wan (45% weight and Offprim requerrr lo: A. R. Mosier CaQ. secondly with a layer of beeswax (45% weight CaCd. and final- ... . 117

-75mw ECC 75 i

0 0.00 0 6 12 18 24 30

Days after Forfilizalion nays after Fwtllizatim Fig. 1. C,H, and C2H, emissions from flooded rice after the applica- Fig.2. N, emissions from flooded rice (CV 81%) as affected by N rate tion of encapsulated calcium carbide (CV 178%) and the presence of encapsulated calcium carbide (ECO

ly by a law of shellac (10% weight of CaCL). All treatments were rep- normality (P= 0.05) using the Shapiro-Wilk statistic (Shapiro and Wilk licated 3 limes (is 18 pots). 1965). If the normality assumption was not met. then treatment means At 0. 2. 4, 6. 8, IO. and 12 days after fertilization. 3-liter vented were separated using the Kruskal-WallisTest with P = 0.05 (Krurhl and chambcn (Hutchinson and Mosicr I98 I) were placed over the pots from Wallis 1952). 9 to I0a.m. At 14. 16. 18.20,23,26,and 29 days after fcrtilization. 64- ter chambers were used for the same I-h period. Fifty milliliter samples were taken from four of the pots ai time zero and from all of the pots Results and discussion after I h. NzO was determined by gas chromatography as described by The redox potential in the soil declined rapidly after Mosier and Mack (1980). For N2 analysis. thc chambers were replaced flooding, probably due in part to addition of the readily on the pots and left overnight for 14- 16 h. N, was determined by iso- , i- .. tope rad0 mass spcctromcrry (Mosier et al. 1986) on a VG-,Micromass decomposable corn straw. By 19 days after flooding, Eh 903. (adjusted to pH 7) was -230 mV* 11 (mean+SD) and re- . .. CH,. CtH,. and C2H, were measured by gas chromatography using mained at this level throughout the study, low enough for a flame ionization detector (250'C) and a 3-m stainless steel column CH, production (Ponnamperuma 1972). (3.175 mm outside diameter) containing Porapak (SOT). Samples .. I' -- N Acetylene (C,Hz) emitted from the treatments with were analyzed for CO, on a Tracor MT-ISOG gas chromatograph encapsulated calcium carbide reached 71 mg pot-' (Tmcer Instruments. Austin. Tcxas. U.S.A.) fitted with a ulirasonic dc- rector (IUW after passing through a 3-m stainless steel column day-' on the day of fertilization, then generally declined (3.175 nun outride diameter) containing Porapak Q (75'C). Eightcen (Fig. 1). Between 14 and 26 days after fertilization, the days aftcrfertilization. IO mg 99.9 atom 70 "CH, was injected into the C2H, flux continued to decline from 5 to <0.1 mg pot-' soil of rtx pots fertilized with 225 mg urea-N pot-'. "CH, was inject- day-'. (C,H,) was produced in small amounts ed throd septa in fittings on the sides of the pots after the covers were in the calcium carbide-treated pots only, probably from put in pkfor the night. CO, was analyzed from the hcadspace of the C2H, reduction (Fig. 1). The flux of C2H4was highest coven aRu 16 h by gas chromalography as described abovc For atom on Qo "COlmalysis. enough sample to contain I40pg CO, was injected the day of fenilization (6.3 pg pot-' day-'. For the first through8 septum into an evacuated SWml glass jar that had a cap- 14 days after fertilization, CZH4 emissions correlated sule cormining lOmg Ca(OH),. lOmg V,O,. and 15111 H,O. After well with the C2H2emissions (r = 0.90. P

..

1000 - b -6- + ECC 'I -*- ECC - 2400 - -t - ECC 2! : 1800 * .a -9 1200 - r 0 so0 - / ,A --*- . b--d- 0 . . 0' _I 0 6 12 18 24 10 .. 0 6. 12 18 24 30 ...... Ow. alter FertIllza1Ion Day. mttw FenIli~aUen ._.. Fig.3a.b..N20.emissionr from.noode$ ricejC\I 10%) (a) ai affected Fig.4a.b. CH, emissions from-flooded rice (CV 81%) (a) as affected by N rat% average with and without. encapsulated calcium carbide by N ratg average with and without encapsulated calcium carbide .. ' (ECO, and (b) as affected by ECC. averaged over N ,-ate I : ' . (ECO.~and(b) as af@ted,by ECC..averaged OVWN rate ......

measured with and without encapsulated calcium car- pared to unfertilized controls. By 21 days after fertiliza- bide, respectively (Fig. 3 b). The proportion of N20-N to tion in that study, the CH4 emissions were higher from (N,O-N+Nd over the 30-day period was <0.01%. pots with urea than from those without. Many workers Mosier et al. (1989. 1990) reported NzO-N/,(N,O-N+ Nd have studied the effects of N fertilizer on CH4 emissions emissions in flooded rice ranging from I to 6% in green- in flooded rice, with varying results. Holzapfel-Pschorn .... house and field studies. Freney et al. (1981) measured and Seiler (1986)-used 'arious N sources.(including urea) N20 losses from flooded rice at only 0.1% of the N fer- but found no effect on CH, flux. Schiltz et al. (1989a) tilizer applied. The small N20/(N20+NJ ratio mea- observed either a positive or negative urea-N effect, de- sured in the present study was probably due to the low pending on the method of fertilizer application. redox potential. There was no interaction between the N CH4 fluxes reached a maximum of 2816pg pot-' rate and the presence of encapsulated calcium carbide day-' 16 days after fertilization without calcium carbide, (P>O.O5). while only 13.8 pg CH, pot-' day-' was emitted in the Seventeen days after flooding, small CH, emissions presence oi encapsulated calcium carbide (Fig. 4b). hfiei .. :* ' .-- (35 pg pot-' day-') began to appear in all pots; at the 18 days, CH4 evolution in the calcium carbide treated -.._ . -.1 same time Eh neared -230mV. The effect of the N rate pots began to increase,-corresponding to a.disappearance on CH, emissions was not constant over the 30-day peri- of C2H2. A total of 39.0mg CHI (avecagec-overlts-N od (Fig. 4a)., The N rate had a negative effect on CH, rate) was emitted with-urea alone, and only 3.6 mg CH, 't.8 ,. 0, 2. and 4 days.after feqilizauon the was evolved with urea plus calcium carbide. No interac- . flux (Pc0.05).In .. 'I-. period between 6 and 26 days after'fenilizatio,n, the N tion between the N.rate and.the plpsence of encapsulated ....' '- rate.had no effect on.CHi emissions, but by 29 days af-: .. calcium was found (P>OQ5): . . , . . ter- fertilization: CH, evolution had .begun 'to. increase N2, N20, and CH,.gases entrapped in the soil were i-with the N kte (PC0:OI):'TIiiS trehd'agrees in part with assumed to be negligible in this rice-planted system. Rice that observed by Lindau et al. (1990). who reported in a plants serve as a conduit from flooded soil to the atmo- field study that for up to 17 days after fertilization CH, sphere for N2 and N,O (Mosier et al. 1990) and for CHI fluxes were lower in plots given 120 kg urea-N ha-' com- (Schiitz et al. 1989b). I19

300 r rate in flooded systems. In conclusion, encapsulated cal- cium carbide appears to be an effective tool in improving e ECC -A- N-use efficiency in rice and in reducing emissions of the + - ECC radiatively active gases, N20 and CH4. i -). D 200 - 2 .. .. ca References .. .I .. -E" Aulakh MS. Rennie DA. Paul EA (1984) Acetylene and N-Serve effccu 100 - ' *---A upon N,O emissions from NH; and NO; mated soils under acro- bic and anaerobic conditions. Soil Biol Biochem 16351-356 _':' . b-. A- Banerjce NK. Mosier AR (1989) Coated calcium carbide as nitrification inhibitor in upland and flooded soils. J Indian SOC Soil Sci / 37:306-313 Bouwman AF (19%) The role of soils and land use in the greenhouse effect. In: Bouwman AF (ed) Soils and the greenhouse effect. Chich- ester: John Wilcy, pp 575 Oaw atlw Ferliliz.lio0 Bremncr JM,Blackmer AM (1979) Effects of acetylene and soil water Fig.5. CO, emissions from flooded rice (CV 62%) as affected by en- content on mission of niirous oxide from soils. Nature (London) capsulated calcium carbide (ECC).avcraged over N rate 2aO3ao-3ai Burcsh RJ. De Data SK (1990) Denitrification losses from pudd!ed :ice soils in rhc tropics. Biol Fcnil Soils 91- 13 Burcsh RI, De Dam SK. Padilla JL. Samson MI (1988) Field walua- The N rate had no consistent effect on C02 fluxes, tion of two urease inhibilors with transplanted lowland ricc Agron and therefore the data presented are averaged over the N J 80763-768 rate (Fig. 5). C02emissions were lower in the presence of Cao ZH. De Datta SK. Fillery IRP (1984) Effect of placemeni methods on flood-aier properties and recovery of applied N 1"N-labeled C2H2 versus the controls for all dates except one urea) in wetland ricr Soil Sci Soc Am I 48:196-203 (P<0.05). This may have been due to an actual suppres- Caner MF. Vlck PLG. Touchion IT (1986) Agronomic evaluation of sion of soil and root respiration by C,H2. Within the en- ncw urca forms for flooded rice. Soil Sci Soc Am J SO105S- 1060 capsulated calcium carbide treatments, there was a nega- Cicerone RJ. Shelter JD (1981) Sources of atmospheric methane: Mea- tive correlation (r = 0.32, P

Mulder 1974; Knowles 1979). Krurkal~ ~~~~~~~ WH.. Wallis~~~ WA 11952).. Use of ranks in onc-criterion variance analysis. I Am Star ASSOC47583-621 Linda" CW. Dclaune RD. Pavick Jr WH. Bollich PK (1990) FeRilizer effects on dinitrogcn. NtrousmidLa ' ' &ons from Low. Conclusion. . ... land ricr Soil Sci Soc.Am J 541789-1794 Xlohanty SK. .Mosicr AR (1990) Nitrificationdenitrificaiion in flooded The.5itrification inhibitor, encapsulated calcium carbide. rice soils. Trans 14th Int Congr Soil Sci (Kyoto. Japan) lY326-331 showed a strong mitigating effect. on emissions of N2 Mosier AR. black L (1980) Gas chromatographic system for prccisg and CH4. N20 fluxes were also reduced with calcium rapid analysis of N,O. Soil Sci SOCAm J &I121 - I123 , carbids but the magnitude of losses with urea alone were Mosicr AR. Gucnri WD, Schweizcr EE (1986) Soil losses of dinitrogcn very small in flooded rice. Losses of N2 and in- and nitrous oxide from irrigated crops in Northeastern Colorado, N,O Soil Sci Soc Am J 50344-348 creased with the N rate. The effect of the N rate on CH4 Mosier AR. Chapman SL. Frency JR (1989) Deicrmination of emissions was variable over the 30 days. More research is dinitrogcn emission and retention in floodwater and pomaicr of a needed to determine the response of CH4 fluxes to the N lowland rice field fcnilied with "N-urea. Fen Res 19127-136 :. .. .., . .- I20 I Mosicr AR. Mohanty SK. Bhadmchalam A, Chakravoni SP (1990) SAS Institute (1985) SAS users' guide: Statistics. VeAion 5. Statistical Evolution of dinitrogen and nitrous oxide from soil to the airno- Analpis System Institute Ins Cary. North Carolina sphere through rice plants. Biol Fed Soils 961-67 SchUtz H. Holzapfcl-Pschorn. Conrad .R. Rennenbcrg H. Scilcr W Ponnamncruma FN (1972).. The chemistrf of submeracd- soils. Adv (1989a) A three ycar continuous record on the influence of daytime Agron 2429-96 season and fertilizer treatment on methane emission rates from an Raimbault M (1975) ftude de I'influcnce inhibitrice de I'acerylene sur Italian rice paddy field. J Geophyr Res 9416405-16416 la formation biologiquc du methane dans un sol de rizierc Ann Schiltz H. Seilcr W. Conrad R (1989b) Proccsser involved in formation Xlicrobiol (Inst Pdrteur) 126A247-258 and emission of methane in rice paddies. Biogeochemistry 7:33-J3 Rodhe H (1990) A comparison of the conrribution of various gases to Shapiro SS, Wilk MB (1965) An analysis of variance test for normality the greenhouse effect. Science 248:1217-1219 (complete samples). Biometrika 52591 - 61 1 Rolston DE (1986) Gas flux. In: Klutc A (ed) .Methods of soil analysis: Simpson JR, Frcncy JR, Muirhead WA. Leuning R (1985) Effects of pan I, Physical and mineralogical methods. Am SOCAgron. Madi- phenylphosphorodiamidateand dicyandiamidc on nitrogen loss from son, Wisconsin. pp 1103- I1 19 flooded rice. Soil Sci Soc Am J491426-1431