Society for Range Management

Macronutrients in Soil and Bromegrass after Long-Term N Fertilization Author(s): J. T. Harapiak, S. S. Malhi, K. S. Gill and N. Flore Source: Journal of Range Management, Vol. 57, No. 2 (Mar., 2004), pp. 219-225 Published by: Allen Press and Society for Range Management Stable URL: http://www.jstor.org/stable/4003922 . Accessed: 12/11/2013 06:34
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J. Range Manage. 57:219-225 March2004

Macronutrients in soil and bromegrass after long-term N fertilization

J. T. HARAPIAK, S. S. MALHI, K. S. GILL, AND N. FLORE
Authors are Chief Agronomist with WesternCo-operative Fertilizers Limited,P.O. Box 2500, Calgary, Alberta, Canada T2P 2N] (Present address: J. T. Harapiak, AgriPlace, Suite 1020, 909-.lth Avenue, Calgary, Alberta, Canada T2R IL7); Research Scientist and Biologist with Agricultureand Agri-Food Canada, P.O. Box 1240, Melfort,Saskatchewan,Canada SOElAO (Presentaddress:K. S. Gill, Soil Plant WaterConsultingInc., 13755-131B Avenue,Edmonton, Alberta,Canada T5L5Al); and AgronomyManagerwith WesternCo-operativeFertilizersLimited,P.O. Box 2500, Calgary,Alberta,Canada T2P 2N1.

Abstract
Information on the long-term impact of repeated annual fertilizer applications of different nitrogen (N) sources on soil and plants is needed to develop sustainable grassland production systems. The concentration of macronutrients in the 0-5, 5-10, 10-15, 15-30, 30-60, 60-90 and 90-120 cm layers in a thin Black Chernozemic (Typic Boroll) soil and in bromegrass (Bromus inermis Leyss.) hay were compared after 15 annual applications of 168 and 336 kg N ha-' as ammonium nitrate, urea, calcium nitrate, and ammonium sulphate, and a zero-N check. The concentration of N03-N was increased by ammonium nitrate and ammonium sulphate at both N rates in most soil layers, by calcium nitrate at both N rates and by urea at 336 kg N ha-' in the 1560 cm soil. The accumulation of N03-N increased with soil depth down to 60 cm, except for urea and ammonium sulphate at 168 kg N ha-', and then it declined in deeper soil layers. The concentration of NH4-N was increased with fertilizer applications in some of the surface soil layers. The concentration of P was increased in the top 15 cm soil by ammonium nitrate and ammonium sulphate. The concentrations of Ca, Mg and K in the surface soil declined with most of the N fertilizer treatments while some treatments increased the Ca and Mg concentrations in the deeper soil layers. Increasing the N rate from 168 to 336 kg N ha-' usually accentuated the above stated N effects on the concentration of macronutrients in the soil. The nitrate-based fertilizers caused more accumulation of N03-N in some soil layers than the ammonium-based fertilizers. The relative increase in the concentration of NH4-N and P and the decline in the concentration of Ca, Mg and K in the soil by N addition was usually associated with the concomitant lowering of soil pH by N fertilization. In bromegrass hay, the total N concentration was increased by N fertilization but the concentration of other elements, except K, usually declined because of the dilution effect of the extra hay yield associated with N addition. Increasing the N rate from 168 to 336 kg N ha-' further elevated the total N concentration but had no effect on the concentration of the other elements. Total N concentration in the hay tended to be greater with ammonium sulphate and ammonium nitrate than with the other 2 fertilizers. The concentration of total S was greater with ammonium sulphate than the other N fertilizers, and the concentration of P, Ca, Mg and K was not affected by the N fertilizer type. Fertilizer-induced high levels of N03-N, NH4-N and P in soil may present potential for environmental pollution at these high N rates. Key Words: concentration, forage, N source, rate of N

Resumen
Paradesarrollar sistemasde produccion sostenibles en pastizales se necesita informaciondel impacto a largo plazo sobre el suelo y las plantasde las aplicaciones anualesrepetidasde diferentes fuentesde nitr6geno(N). La concentracion de macronutrientes en los estratosde 0-5, 5-10, 10-15, 15-30, 30-60, 60-90 y 90-120 cm de un suelo delgado negro Chernozem (Typic Boroll)y en el heno de "Bromegrass" (Bromus inermisLeyss.)se compararon despuesde 15 aplicaciones anualesde 168 y 336 kg N ha-'como nitratode amonio,urea, nitratode calcio,sulfatode amonioy de un controlde cero-nitr6geno. La concentracion de N03-N se incrementoen la mayoriade los estratosde suelo por la aplicacionde nitratode amonioy sulfatode amonioa ambas tasas de aplicaciony en la profundidad de 15-60cm por la aplicacion de nitratode calcio a ambas tasas de aplicaciony por la de urea a 336 kg N ha-'.La acumulacion de N03-N aumentocon la profundidad del suelo hastalos los 60 cm, exceptoparala urea y el sulfatode amonioa 168 kg N ha-',despuesdisminuyoen las capas mas profundasdel suelo. En algunas capas del suelo la concentracionde NH4-N aumento con la aplicacion de fertilizante.La concentracion de P en los primeros15 cm del suelo se incrementocon la aplicacionde nitrato de amonioy sulfato de amonio.Las concentraciones de Ca, Mg y K en la superficiedel suelo disminuyeron con la mayoriade los tratamientos de fertilizacion nitrogenada,mientrasque algunos tratamientosincrementaronlas concentraciones de Ca y Mg en las capasprofundas del suelo. El aumentarla cantidadde nitrogenode 168 a 336 kg N ha-' usualmenteacentuo los efectos del N descritos previamente sobre la concentracio6n de los macronutrientes del suelo. Los fertilizantesa base de nitrato causaronuna mayor acumulaci6nde N03-N en algunascapas del suelo que la obtenidacon los fertilizantesa base de amonio. El incrementorelativoen la concentraci6n de NH4-N y P y la disminucion de la concentracionde Ca, Mg y K en el suelo por la adicionde N usualmente se asociocon la concomitante baja del pH del suelo por la fertilizacion nitrogenada. En el heno de "Bromegrass"laconcentraciontotal de N se incremento con la fertilizacion nitrogenada, pero la concentraci6on de otros elementos,exceptoK, usualmente disminuyodebidoal efectode dilucionde un mayorrendimiento de heno asociado con la aplicaci6nde N. Aumentarla tasa de aplicacionde 168 a 336 kg N ha-'elevo mas la concentraci6n de N pero no tuvo efectoen la concentracion de los otroselementos. La concentraci6n de N total en el heno tendi6a ser mayorcon el sulfato de amonioy el nitrato de amonio que con los otros dos fertilizantes. La concentracion total de S fue mayorcon el sulfato de amonioque con los otros fertilizantesnitrogenados y la concentracionde P, Ca, Mg y K no fue afectadapor el tipo de fertilizantenitrogenado. Los altos nivelesde N03-N, NH4-Ny P en el suelo inducidospor los fertilizantes puedenpresentarun problema potencialde contaminacion con estasaltas tasasde N.

*Corresponding author is S.S. Malhi (Email address: malhis@agr.gc.ca). The authors thank Western Co-operative Fertilizers Limited (WESTCO) for maintaining the long-term research plots. Manuscript accepted 26 Jun. 03.

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Nitrogen(N) fertilizationis essential to sustain high yields of managed forage grasses in the Canadian prairies. The effect of N on forage grass production (Campbellet al. 1986, Malhi et al. 1986, 1992, Ukrainetzand Campbell1988, and soil acidification(Hyot and Hennig 1982, Mahler and Harder 1984) have been shownto vary with the type of N fertilizer applied.Ammoniumsulphate,ammonium nitrate and urea (in a decreasing order) et reducesoil pH (Adams 1984, Harapiak al. 1992). Earlier studies also suggested that the magnitudeof change in soil pH concentration dependson the and nutrient rate of N fertilizer applied (Malhi et al. 1991) for data collected after 16 years. Limited information is available on the long-termeffects of N sources and rates in of macronutrients on the concentration the Canadian prairie grasslands. The was to deterobjectiveof the investigation mine the long-term effects of different rates and sources of N on the concentraat differentdepths tion of macronutrients in the soil andin the bromegrass hay.

Materials and methods

The study was conducted near Crossfield, Alberta, Canada (5?E30' N 114E?3'W) on a thin Black Chemozemic soil (TypicBoroll)with 9.5%organicmatter and a loam texture.The 30-yearmean of the areais 478 mm annualprecipitation with two-thirds of the precipitationnormallyreceivedin the growingseasonfrom Canada). (Environment May to September Nine treatments were applied with 4 N fertilizers(ammonium nitrate,urea, calcieach um nitrate,and ammonium sulphate), appliedat 2 rates(168 and 336 kg N ha-') of 3 plus a zero-N check. Six replications m x 3 m treatment in a plots were arranged randomizedcomplete block design. The experiment began in 1979. Bromegrass (Bromus inermis Leyss) was grown for during hay and the stand was maintained the study period, cut once in mid to late July of each year and anothertime laterif there was sufficientregrowth.The N fertilizerswere surface-broadcast annuallyin mid to late April. For hay samples, all of aboveground bromegrassplant was harvestedat 5 cm height above soil surface in July 1993, driedat 650 C and groundto pass through a 1-mm sieve. To determinethe total N and P in the hay, the samples were subusing hot jected to the Kjeldahlprocedure H2504 and their concentrations in the digests were measured by a Technicon

AutoAnalyzer II (Technicon Industrial Systems 1977). Determination of total K, Ca, Mg and S in the hay was done by digestingthe samplesin a mixtureof nitric acid and perchloricacid and the concentrationsin the digests were determined by inductively coupled plasma (ICP) emission spectrometry. Soil samples, composite of 10 cores, fromthe 0-5, 5-10, 10-15, 15-30, 30-60, 60-90 and 90-120 cm depthsin each plot were obtained in the autumn of 1993, using a 2.4 cm diameter coringtubewith a hydraulicsampler.The soil horizons Ap, Ah, Bm and C constitute approximately 0-10, 10-15, 15-40 and > 40 cm of the soil depths, respectively. The samples were air dried at room temperatureand groundto pass througha 2-mm sieve. A 1:5 soil:2MKCl solutionratiowas used to extract NH4-N and N03-N. Phosphorus was extractedusing a modifiedprocedure of Millerand Axley (1956) by shaking10 g soil in 50 ml of 0.03M NH4F+ 0.015M solutionH2SO4for 10 minutes.The conof NH4-N,N03-N andP in the centrations extractswere determined by a Technicon AutoAnalyzer II (Technicon Industrial Systems 1973a, 1973b, 1977).The Ca, Mg and K were extracted using a 1:20soil:IM ammonium acetatesolution(pH 7.0) ratio in the extractswere andthe concentrations measured by ICP. The data for each soil layer and to analysis bromegrass hay were subjected of variance (ANOVA) in GLM (SAS InstituteInc. 1989) and the least significant difference (LSDO05) was used to determinesignificantdifferencesbetween the treatments. Data for differentsoil layers were analysedseparately.

Results and discussion in Soil Macronutrients

Nitrogenadditionand rate effects. The additionof ammoniumsulphatesubstantially increasedthe N03-N concentration in the top 15 cm of the soil at 168kg N ha-', anddownto the 120cm soil depthat 336 kg N ha-'(Table1). Application of ammonium nitrateandcalciumnitrateat 336 kg N ha-' significantlyincreasedN03-N concentration in all soil layers.The N03-N concentrationwas tremendouslyincreasedby a changein the N ratefrom 168 to 336 kg N ha-' in all soil layers with ammonium nitrateand ammonium sulphate,in the 30120 cm soil with urea, and in the 10-120 cm soil with calciumnitrate. The NH4-Nconcentration in the 0-5 cm soil was markedlyincreasedby ammoni-

um nitrate,calciumnitrateandammonium at both N rates.The sulphateapplications was also significantNH4-Nconcentration ly increased in the 5-10 cm layer by at bothN ratesandby ammonium sulphate nitrateat 336 kg N ha-',and in ammonium the 10-15 and 15-30 cm layers by ammonium sulphateat 336 kg N ha. Urea did not change the NH4-N concentration significantly.Changingthe N rate from 168 the NH4-N conto 336 kg N ha-'increased centrationin the top 10 cm of soil with AN and in the top 30 cm of the soil with ammonium The depthof NH4-N sulphate. in the presentinvestigation accumulation was greaterthan that observedin another on the same site with 112 kg N experiment ha-'(Harapiak et al. 1992). The accumulation of NH4-N in the soil was most likely associatedwith the depressionin pH from N sources(Malhiet al. 2000). No different significant effect of the fertilizer treatments was observed on the NH4-N concentration in soil below the 30 cm soil layer. Thoughno statisticalanalysiswas done to comparethe concentration of macronutrients in different layers, the large changes in the N03-N and NH4-N concentrationswith the change in soil depth are pointed out in the following discussion. At both N rates of calcium nitrate and ammoniumnitrate,and at 336 kg N ha-'rate of urea and ammonium sulphate, the N03-N concentration showed a trend of increasewith soil depthdownto the 3060 cm layer and then to decline with increasein soil depth.Also, the difference in N03-N concentration betweenthe 168 and 336 kg N ha-'ratesincreased fromthe 0-5 cm layer(rangeof-3.3 to 15.1mg kg-') down to the 30-60 cm layer(rangeof 28.5 to 333.3 mg kg-')and then declinedin the deepersoil layers.The zone of maximum N03-N concentration(30-60 cm) at the 168 and 336 kg N ha-'in the presentstudy was deeper than the earlier observations (15-30 cm) at the same site in another experimentwith 112 kg N ha-' (Harapiak et al. 1992). This appearsto be due to a combination of higherrates of N application for a longerperiod. At 168 kg N ha-' rate,extractable P concentrationwas significantlyincreasedby ammonium nitratein the top 5 cm of the soil andby ammonium sulphatein the top 10 cm of soil. The concentration of P in the top 15 cm of soil was extractable tremendously increased by ammonium nitrateand ammonium sulphateat 336 kg N ha-' over the check as well as over the 168 kg N ha'l. Urea and calcium nitrate did not influence the P concentrationin

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Table 1. Influence of 15 annual applications of 4 N sources at 2 rates to bromegrass on the concentration of macronutrients in different layers of a thin Black Chernozemic soil at Crossrield, Alberta, Canada.

Rate of N (kg N ha-') 0 168

Source of Na

0-5

Concentrationof macronutrients in different soil layers (cm) 5-10 10-15 15-30 30-60 60-90 N03-N (mg kg-') 0.5 5.3 1.0 1.9 13.2 32.9 1.9 12.0 51.4 9.4

90-120

Check AN Urea CN AS AN Urea CN AS

1.5 2.0 3.7 4.7 20.7 17.1 1.4 9.9 29.4 7.3

0.6 4.3 0.8 2.4 13.0 23.8 0.8 8.2 33.1 7.6

0.8 26.8 2.0 32.0 12.2 154.3 15.2 218.2 92.5 42.3

1.1 27.5 2.0 50.7 5.8 268.8 30.5 384.0 112.8 56.7

0.8 5.9 0.8 16.2 6.1 112.4 18.1 132.1 86.2 37.3

1.2 1.5 0.3 1.5 1.5 18.8 4.5 16.1 35.4 12.5

336

LSDoos

0 168

Check AN Urea CN AS AN Urea CN AS

13.4 42.1 26.4 35.5 58.0 94.0 29.5 34.2 183.7 18.1

11.0 20.1 13.6 14.6 45.9 50.9 15.8 14.5 252.0 18.3

8.8 10.2 8.4 9.5 14.4 14.7 10.3 10.0 162.8 18.2

NH4-N (mg kg-') 8.2 7.5 6.1 9.4 8.4 9.8 7.0 9.8 47.1 8.6 P (mg kg') 0.6 0.1 0.3 0.2 0.3 0.2 0.2 0.0 0.8 0.4 Ca (mg kg"') 2668 2714 2676 2763 2753 2775 2728 2894 3027 108

6.2 6.0 5.9 5.6 5.6 8.5 6.4 6.7 6.5 ns

4.3 4.6 5.0 4.5 4.3 6.1 5.1 4.4 5.2 ns

4.4 5.8 5.6 5.6 4.8 6.0 5.7 4.2 5.5 ns

336

LSDo.os 0 168

Check AN Urea CN AS AN Urea CN AS

9.6 13.8 7.7 7.1 29.9 28.6 8.8 5.8 36.8 3.9

4.3 3.7 2.4 2.8 9.2 11.8 2.9 2.3 34.1 2.9

3.0 2.4 1.5 1.3 1.6 24.4 1.5 1.1 14.8 1.8

0.0 0.2 0.0 0.0 0.3 0.2 0.2 0.3 0.0 ns

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ns

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 ns

336

LSDo.os

0 168

Check AN Urea CN AS AN Urea CN AS

2763 1347 1924 2989 568 509 1809 2939 287 370

2971 2903 2870 3507 2091 1610 2727 3582 588 348

2625 2679 2672 2856 2738 2658 2750 2938 2017 222

2646 2671 2784 2788 2706 2996 2725 2727 3128 222

2406 2645 2634 2170 2406 2600 2541 2217 2304 ns

1948 2398 2139 1933 2168 2136 2168 1938 1970 Ns

336

LSDoos

(Continuedon page 222)

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Rate of N (kg N ha-') 0 168

Source of No Check AN Urea CN AS AN Urea CN AS

0-5 445 183 280 124 82 84 214 72 58 27

Concentration of macronutrients in different soil layers (cm) 5-10 10-15 15-30 30-60 60-90 498 406 443 228 208 171 344 84 61 34 571 540 569 388 367 384 480 142 120 35 Mg (mg kg") 594 543 550 593 552 520 549 465 426 44 K (mg kg-') 258 211 188 188 183 194 205 181 213 660 640 656 767 708 703 662 860 924 138 759 694 792 901 808 838 769 974 977 ns

90-120 925 734 889 1041 975 917 922 1040 1076 ns

336

LSDo.os

0 168

Check AN Urea CN AS AN Urea CN AS

476 272 244 406 344 372 265 484 323

323 198 182 243 224 271 184 320 269

279 199 198 202 177 229 189 222 231

234 245 217 201 211 231 257 198 216

184 175 176 174 171 191 170 161 173 ns

172 165 176 187 172 187 169 171 178 ns

336

50 34 39 34 ns LSDo.o.b 'AN, CN and AS refer to anumonium nitrate,calcium nitrateand ammoniumsulphate,respectively. value is given when the F-test was significantand ns is given when the F-test was not significant. u'Te LSDoos,

any soil layer and no fertilizerinfluenced in the soil below the the P concentration in P concentration 15 cm depth.Increased the soil was relatedto greatersoil acidifisulphateand ammocationby ammonium niumnitraterelativeto the otherfertilizers et al. (1992) (Malhiet al. 2000). Harapiak reported strong negative correlation betweenthe soil pH and soil P concentration, at the same site in a differentexperiment. Unlike NO3-N, NH4-N and P, the concentrationof extractableCa was reduced nitrate, in the 0-5 cm layerby ammonium urea and ammoniumsulphate at both N rates,in the 5-10 cm layer by ammonium sulphate at both N rates and ammonium nitrateat 336 kg N ha-',and in the 10-15 sulphateat 336 kg cm layerby ammonium N ha-'. Another noticeable effect of ammonium nitrate and ammonium sulphate applicationswas a higher Ca concentration thanthe check treatment at 336 sulphatein the kg N ha-' with ammonium 15-30 and 30-60 cm layers and with ammonium nitratein the 30-60 cm layer. Withan increasein the N ratefrom 168 to 336 kg N ha-', the concentration of extractable Ca declined in the 0-5 and 5-10 cm layers with ammoniumnitrate and the 5-10 and 10-15 cm layers with

ammonium sulphate. However, it was increased in the 30-60 cm layer with ammonium nitrate,in the 15-30 cm layer with calciumnitrateand in the 15-30 and 30-60 cm layers with ammonium sulphate. It appearsthat ammoniumnitrate and ammonium sulphate displaced Ca from the shallower soil layers, which accumulated in the deeper soil layers. of calciumnitrate(whichconApplication tains Ca) on the other hand significantly in the 5-10 increasedthe Ca concentration and 10-15 cm layers at both N rates,and in the 15-30 cm layerat 336 kg N ha-'. The concentration of extractable Mg was markedlydecreased by all of the N in the 0-5 and 5-10 cm layers, treatments by all N fertilizersat 336 kg N ha-'andby calciumnitrateand ammonium sulphateat 168 kg N ha-' in the 10-15 cm layer, and by all N treatments except calciumnitrate at 168 kg N ha-'in the 15-30 cm layer.On the otherhand,calciumnitrateand ammoniumsulphate at 336 kg N ha-'significantly increasedthe Mg concentration in the 30-60 cm layer. When the N rate was increasedfrom 168 to 336 kg N ha-', the concentration of extractableMg declined in the top 15 cm of the soil with AN and urea,and in the top 30 cm of the soil with calcium nitrateand ammoniumsulphate,

while a significantincreasein the Mg concentrationwas observedin the 30-60 cm layer with ammoniumsulphate.The Mg in the soil below the 60 cm concentration depthdid not show any responseto the N treatments. The concentrationof extractableK in the top 30 cm of the soil, except for the top 10 cm of the soil with calciumnitrate at 336 kg N ha-',was significantly reduced But with a change in by all N treatments. the N ratefrom 168 to 336 kg N ha-',the K was significoncentration of extractable cantly increasedin the top 10 cm of the soil by ammonium nitrate and calcium nitrateas well as in the 5-10 and 10-15 cm layer by ammonium sulphate. The K concentration in the deepersoil layersdid not respondto any of the N treatments. At both 168 and 336 kg N ha-' rates, increasedNO3-N, NH4-N and P concentrations in the surface soil suggested greaterpotentialfor theirloss throughsurface water runoff, denitrification and ammoniavolatilization,while accumulation of N03-N in the deeper soil layers increasedthe potentialfor its leachingto The trendtowardsdecreased groundwater. in the shalCa, Mg and K concentrations lower soil associated with most N treatments was considered to be the direct resultof a greater uptakeof these elements

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in higher yielding bromegrass hay as a resultof fertilization with N. The increased concentrationof Ca in these soil layers of calcium associatedwith the application nitrate occurred due to the fact that Ca addition was takingplace But, an increased concentration of Ca and/orMg in the deeper soil with some ammonium sulphateand calcium nitratetreatmentsindicatedtheir displacement by these treatments from shallower to deepersoil layers.
Fertilizer type effects. There was a

greaterN03-N concentrationin the 0-5, 5-10, 10-15 and 90-120 cm layersresulting from ammonium sulphateapplication, and in the 15-30, 30-60 and 60-90 cm layers from calcium nitrate application comparedto the otherN fertilizers(Table 1). Urea treatmentsat both N rates had lesser N03-N concentrations in all soil layersas compared to the otherN fertilizer treatments.Also, there was a maximum accumulationof N03-N concentration in the 15-30, 30-60, and 60-90 cm layers with nitrate(calciumnitrate),followed by nitrate-ammonium mixed (ammonium nitrate)and ammonium(urea and ammonium sulphate) fertilizers in decreasing order.With 336 kg N ha-'for example,the N03-N concentration in the 30-60 cm layerwas 384.0, 268.0, 112.8 and 30.5 mg kg-' for calcium nitrate, ammonium nitrate, ammonium sulphate and urea, respectively. Similarly, the maximum increasein N03-N concentration due to a changein the N ratefrom 168 to 336 kg N ha-' was 28.3, 107.0, 241.3 and 333.3 mg kg-' for urea,ammonium sulphate,ammonium nitrateand calcium nitrate,respectively. These data show greater N03-N

in the soil with nitrate-based accumulation N fertilizers,espethan ammonium-based cially at higherN rates.The lower N03-N concentration with urea than with the other ammonium-based fertilizer(ammoniumsulphate) was probably due to higher ammonia volatilization losses to which ureais more susceptiblewhen it is surface applied(FenandHossener1985). in the top Greater NH4-N concentration 30 cm of the soil was observed with ammoniumsulphaterelative to the other fertilizers,except for the 15-30 cm layer at 168 kg N ha-' (Table 1). On the other hand, mostly urea and sometimecalcium nitrate showed a minimum NH4-N concentration in the top 30 cm of the soil. The greater accumulation of NH4-N with ammoniumsulphate than with the other fertilizerswas associatedwith its reduced nitrification due to lower soil pH (Malhiet al. 1991, 2000). Significantly more extractable P was observed with ammoniumsulphate than thatwith otherN fertilizersin the 0-5 and 5-10 cm layersat bothN application rates, and in the 10-15 and 15-30 cm layers at 336 kg N ha-'. The concentration of P in the top 15 cm of the soil extractable was usually lower with urea and calcium nitrate than with ammonium nitrate or ammonium sulphate. The differences inducedby the fertilizertype in the soil P concentration were attributed to the decreasein soil pH, i.e., higherP concentrations associatedwith a lowerpH. Unlike the concentration of NO3-N, NH4-N and P, the ammonium sulphate treatments had the lowest concentration of extractable Ca in the top 10 cm of the soil at both N rates,and in the 10-15 cm layer

at 336 kg N ha-'.At bothN ratesin the 0-5 cm and at 336 kg N ha-' in the 5-10 cm nitratealso reducedthe layer, ammonium Ca concentrationcomparedto urea and calciumnitrate.The calciumnitrate resulted in significantly higherCa concentration in the top 10 cm of the soil thanthe other fertilizersat both rates, in the 10-15 cm layer comparedto ammonium nitrateand ammonium sulphateat 336 kg N ha-',and in the 15-30 cm layerrelativeto ammonium nitrateand ureaat 336 kg N ha-'.The of ammonium application sulphateat 336 kg N ha-',however,had a higherCa conin the 15-30 cm layercompared centration to all otherfertilizersand in the 30-60 cm layer compared to calcium nitrate and urea. A higherconcentration of Ca in the shallow soil layers with calcium nitrate than with the otherfertilizerswas considered to be due to Ca additionsassociated with the calcium nitrate applications, while more accumulationof Ca in some deeper soil layers with ammonium sulphate was probably associated with soil acidityinduceddisplacement and the subsequentdownwardmovementof Ca from shallower to deepersoil layers. The concentration of extractable Mg was the lowest with ammoniumsulphate in the top 15 cm soil at bothN ratesandin the 15-30 cm layer at 336 kg N ha-'.The concentration of Mg with ureawas significantly higher and much greaterthan that detectedin the calciumnitrateand ammonium sulphatetreatments in the top 15 cm of the soil at both N rates, and in the 15-30 cm layer at 336 kg N ha-'. Similarly, application of ammonium nitratealso tendedto result in higher Mg

Table 2. Influence of 15 annual applications of 4 N sources at 2 rates on the concentration of macronutrients in bromegrass hay on a thin Black Chernozemic soil Crossfield, Alberta, Canada. Concentrationof macronutrients in hay RateofN (kg N ha-') 0 168 SourceofN' Check AN Urea CN AS AN Urea CN AS N 10.6 13.0 12.2 14.7 14.2 15.4 13.6 14.9 15.7 P 1.0 0.8 0.8 0.9 0.9 0.9 0.8 0.8 0.8 S (g kg') 1.40 1.34 1.35 1.56 2.59 1.36 1.30 1.44 2.29 Ca 3.5 2.6 3.0 3.2 3.1 2.7 2.9 2.9 2.9 M 1.24 1.02 1.10 1.16 0.95 1.02 1.10 1.03 0.89 K 12.7 11.8 12.1 12.7 13.1 12.4 12.5 13.3 11.8 0.9 CalMgratio 2.82 2.55 2.73 2.76 3.26 2.65 2.64 2.82 3.26

336

LSDoosb 1.4 0.1 2.14 0.3 0.10 "AN,CN and AS refer to anunoniumnitrate,calcium nitrateand ammoniumsulphate,respectively. bTheLSDo.os value is given when the F-test was significantand ns is given when the F-test was not significant.

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in the top 15 cm of the soil concentrations than calcium nitrateand ammoniumsulphate. In the 30-60 cm layer, however, ammoniumsulphate and calcium nitrate showed a significantlyhigherMg concenat 336 trationthan the otherN treatments kg N ha-'. This trendof lower concentration of Ca and Mg in the upperlayers of soil and higher values in deeper layers indicated their greaterdownwardmovement by ammoniumsulphate relative to the other fertilizers.MinimumK concentrationswere usually observed with urea in the top 15 cm of the soil, while maxiin the top mum levels of K concentration 10 cm of the soil were observedwith calcium nitrateat bothratesof N application. of the The changes in the concentration were often related variousmacronutrients to soil pH that were associated with the chemical form of N fertilizer being applied,as well as the additionof Ca containedin the calciumnitratefertilizer. in Bromegrass Hay Macronutrients All the fertilizertreatments significantly increased the total N concentration in bromegrass hay (Table2). A portionof the increasein N concentration due to N fertilization may have been from inorganicN, as N03-N has been observedto accumulate as a result of N fertilization by other researchers (Malhi et al. 1986, Penney et of totalP, Ca al. 1990). The concentration and Mg (except for the case of Mg with calciumnitrateat 168 kg N ha-')were significantlyreducedby all the N treatments. of total S As expected, the concentration in hay was significantlyincreasedby the applicationof ammoniumsulphatecomNone of the paredto the check treatment. other fertilizers caused any noticeable of the hay. change in the S concentration The K concentration did not show any consistent effects of N addition. The decline of P, Ca and Mg concentrations due to N applicationwas apparentlythe result of the dilutionof these nutrientsin underfergreateramountof hay produced tilized conditions(Malhi et al. 1992). No change in the concentration of K was observedas a resultof fertilizerN application. This suggests that there were sufficient K reservespresentin soil for uptake by bromegrasshay at the elevated yields achievedin responseto bothof the N rates used in the study. Increasingthe ammoniumnitrate,urea and ammoniumsulfaterates from 168 kg N ha-' to 336 kg N ha-' significantly but the increased the totalN concentration, increasefor the calciumnitratetreatments of was not significant.The concentration

the other elements was not consistently in the deepersoil layersthanthe ammonium-basedfertilizers. In bromegrasshay, affectedby the N rate. Amongst the four N sources,the maxi- the total N concentrationwas increased mum total N concentration occurredwith due to the addition of N, butthe concentracalciumnitrateat 168 kg N ha-' and with tion of otherelements,except K, declined ammonium sulphate at 336 kg N ha-' due to the dilutioneffect of the extrahay of withthe application whereasminimumvalues for total N con- yield whichresulted the N ratefrom 168 Increasing centration were observedwith ureaat both N fertilizer. elevatedthe total of total S in the to 336 kg N ha-'further N rates.The concentration in hay buthadno effect on sul- N concentration hay was increasedby the ammonium phateapplication, whichresultedin signif- the concentrationof other elements. The in hay tendedto be valuesthanthe otherN fer- total N concentration icantlygreater with ammonium ammonisulphate, tilizer types. There was no consistent greater andcalciumnitrate thanurea. effect of fertilizer type on the P, Ca, Mg or um nitrate In summary,the source and rate of N K concentrations. The lack of differences theconcentrations of N03-N, NH4in concentration of variousmacronutrients affected with source of N fertilizer was probably N, P, Ca, Mg andK in the soil butonly the in bromegrass due to the fact that the level of N supply totalN and S concentrations compared to the N requirements of hay. Very high levels of N03-N in deeper bromegrass hay was more than enough at soil layers, plus N03-N, NH4-N and P in the shallower soil layersas a resultof fertilbothratesof N application. The Ca/Mg ratio was observed to izer N application clearlyindicatea potento problems increase with application of ammonium tial for environmental pollution of arisein similar situations. sulphateandto declinewith application ammonium nitrate, urea and calcium nitrate.Hypomagnesemia (grass tetany or References staggersdisease)may occurin animalsfed on forage with Mg levels lower than0.18 to 0.20% (Kempet al. 1961, Gruneset al. Adams, S.N. 1984. Some effects of lime, nitrogen and soluble and insolublephosphateon 1970, Molloy 1971). Feeding high levels the yield and mineralcompositionof estabof Ca to animals increases Mg requirelished grassland. J. Agr. Sci. Camb. 102: ment or impairs Mg utilization (Nugara 219-226. and Edwards 1961), which in turn can Campbell, C.A., A.J. Leyshon, H. Ukrainetz, cause grass tetany in animals. In this and R.P. Zentner. 1986. Time of applicaexperiment, Mg concentrations of all tion andsourceof nitrogen fertilizer on yield, bromgrasshay samples were below norfor quality,nitrogenrecoveryandnet returns of N fertilizerfurther dryland forage grasses. Can. J. Plant Sci. mal, and application of Mg in forage. reducedthe concentration 66:915-931. The results of below normalMg concen- Fen, L.B. and L.R. Hossener.1985. Ammonia volatilization from ammonium and ammonitrationandincreasein Ca/Mgratiosin forum-formingnitrogen fertilizers. Adv. Soil in the age in some N fertilizertreatments Sci. 1:123-169. present study suggest insufficient Mg in D.L., P.R. Stout, and J.R. Brownell. forage and the potentialfor tetanydisease Grunes, 1970. Grasstetanyin ruminants. Adv. Agron. in animals. 22:331-374.

Conclusions
The four N fertilizers (ammonium nitrate,urea,calciumnitrateand ammonium sulphate) appliedannually for 15 years increased the concentrations of N03-N and NH4-N but decreasedthe concentrations of extractable Ca, Mg and K in the surface soil. Increasing the N rate from 168 to 336 kg N ha-'intensifiedthe impact of the N effects on the concentrationof macronutrients in soil for some of the treatments. In general, ammonium sulphate resulted in maximumchanges and ureacausedminimum changesin chemical soil properties.The nitrate-based fertilizers caused more accumulation of N03-N

Hoyt, P.B. and A.M. Hennig. 1982. Soil acidification by fertilizersand longevity of lime in the Peace River region. Can. applications J. Soil Sci. 62:155-163. Harapiak, J.T., S.S. Malhi, M. Nyborg, and N.A. Flore. 1992. Soil chemical properties after long-term nitrogen fertilization of bromegrass: Sourceand time of application. Commun. Soil. Sci. PlantAnal.23:85-100. Kemp, A., W.B. Deijs, O.J. Hemkes, and A.J.H. VanEs. 1961. Hypomagnesemiain milkingcows: Intakeand utilizationof magnesium from herbage by lactating cows. Neth.J. Agric.Sci. 9:134-149. Mahler, R.L. and R.W. Harder. 1984. The influence of tillage methods, cropping sequence,and N rateson the acidification of a northern Idahosoil. Soil Sci. 37:52-60. Malhi, S.S., D.K. McBeath, and V.S. Baron. 1986. Effect of N applicationon yield and qualityof bromegrass hay in centralAlberta. Can.J. PlantSci. 66:609-616.

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Malhi, S.S., J.T. Harapiak, M. Nyborg, and N.A. Flore. 1991. Soil chemical properties of bromegrass: afterlong-term N fertilization nitrogenrate.Commun.Soil Sci. PlantAnal. 22:1447-1458. Malhi, S.S., J.T. Harapiak, M. Nyborg, and N.A. Flore. 1992. Dry matteryield and N recovery from bromegrassin south-central of Albertaas affectedby time of application urea and ammonium nitrate..Commun.Soil Sci. PlantAnal. 23:953-964. Malhi, S.S., J.T. Harapiak, M. Nyborg, and K.S. Gill. 2000. Effectsof long-term applications of variousnitrogensourceson chemical soil properties and composition of bromegrass hay. J. Plant Nutrition. 23:903-912. Miller, J.R. and J.H. Axley. 1956. Correlation of chemicalsoil tests for availablephosphorus with cropresponse,includinga proposed method.Soil Sci. 82:117-127.

Molloy, L.F. 1971. Hypomagnesemictetany and the chemistry of dietary calcium and magnesium. N.Z. Soil Bur.Rep.5. Nugara, D. and H.M. Edwards, Jr. 1961. Effect of calcium and phosphrus on magnesium metabolismin chicks. Fed. Proc., Fed. Am. Soc. Exp. Biol. 20: 294. Penney, D.C., Malhi, S.S., and Kryzanowski, L. 1990. Effect of rateand sourceofN fertilizer on yield, quality and N recovery of bromegrass grown for hay. Fert. Res. 25: 159-166. SAS Institute Inc. 1989. SAS/STAT Users Guide,Version6, Fourth Edition,Volume2, SAS Institute Inc., Cary,NC, U.S.A. 846 pp. Technicon Industrial Systems. 1973a. Ammonium in water and waste water. Industrial Method No. 90-70W. Revised January1978. TechniconIndustrial Systems, Tarrytown, NY, U.S.A.

Technicon Industrial Systems. 1973b. Nitrate and nitrite in water waste water. Industrial Method No. 100-70W-B. Revised January 1978 Technicon Industrial Systems, Tarrytown, NY, U.S.A. Technicon Industrial Systems. 1977. Industrial/simultaneous determination of nitrogen and/or phosphorus in BD acid digests. IndustrialMethodNo. 3334-74/Bt. Technical Industrial Systems, Tarrytown, NY, U.S.A. Ukrainetz, H. and C.A. Campbell. 1988. N andP fertilization on bromegrass in the Dark Brown Soil zone of Saskatchewan.Can. J. PlantSci. 68:457-470.

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