P and S fertilizer reaction products in the seed-row as revealed by XANES

spectroscopyGourango Kar*, Jeff Schoenau, AdamGillespie, and Derek Peak

Department of Soil Science, University of Saskatchewan Canada.

Introduction

2

Sulfur (S) and phosphorus (P) are an essential nutrients for crop production

S and P fertilizers are commonly applied together in bands for crop production in Western Canada

Forms and AvailabilityAvailability depends on Species formed after application Soluble (solution) sulfate and phosphate

immediately available for root uptake Some fertilizers require transformation to

these forms

Understand the fate of applied S andP!

Will help to most beneficially use S and Pcontaining fertilizers

3

Traditional Approaches to Study of S and P Fertilizer Fate

Examining plant availability of the S and P

Through plant nutrient uptake and yieldresponse

Measuring content of total or available formsin soil before and after plant growth

4Photo courtesy T. King

Research Justification

There has been little recent work tofollow the fate and transformation(speciation) of applied S and Pfertilizers in prairie soils in the weeksfollowing application

XANES spectroscopy is under-utilizedas a tool to reveal chemical speciationin agricultural soils

5

Traditional wet chemical analyses methods- May not be able to identify particular S and P species in soil, artifacts created

6

XANES spectroscopy can distinguish different oxidation states of an element

Offers unique ability to followtransformation of fertilizers todifferent forms of varying plantavailability over time.

2.14 2.15 2.16 2.17 2.18

(b)

variscite

Fe(III)PO4

HCO3-NaOH

Energy (keV)

Why XANES

Objective

7

To develop and employ a synchrotrontechnique to assess the fate of differentfertilizer S forms and P added in theseed-row

www.maptown.com/.../canada-topo-maps.html

Black Chernozem MelfortBrown ChernozemCentral Butte

Saskatchewan, Canada

Field Study Sites

8

http://www.maptown.com/.../canada-topo-maps.html

Experiment Details Research design: RCBD Treatment: Urea, ammonium sulfate, calcium

sulfate, elemental S, and monoammoniumphosphate

Application rate: 20 kg S and P2O5 ha-1 in seed-row

Soil sample collection: from the seed-row 1, 4and 8 weeks after seeding canola.

9Photo courtesy T.KingU of S

Analytical Techniques

Wet chemical analysis: CaCl2 extractable available sulfate Available P by modified Kelowna method

XAS spectroscopic techniques: S and P K-edge XANES

Data analysis: Gaussian curve fitting Linear combination fitting

10

11

ResultsAvailable soil sulfate concentration in theseed-row after 1, 4 and 8 weeks of crop growth

Black Chernozem

0

100

200

300

400

Control AS Gypsum ES

Central Butte site

Week 1Week 4Week 8

SO4-

2 -S

(mg

kg-1

soil)

Brown Chernozem

Chart1

ControlControlControlControlControlControlControl13.47512.90718496689.464356.60541949216.60541949219.7606908789.7606908785.6833742625.683374262

ASASASASASASAS119.93513.23305084755.71761446.729629073446.72962907344.43170644614.43170644610.96725949640.9672594964

GypsumGypsumGypsumGypsumGypsumGypsumGypsum429.30539.092778187212.5280299.558731889399.558731889312.435318303212.43531830323.24600399863.2460039986

ESESESESESESES18.27513.01764922627.86956158.28018317038.28018317039.66077529.66077523.38286637753.3828663775

Week 1

Week 4

Week 8

Melfort site

2013 Field PLANT Data HASAN

Total NTotal PTotal S

SitePlotSiteCropTreatmentBlockSerial #Total BiomassBagTotal BiomassTotal BiomassTotal BiomassGrain BiomassGrain BiomassGrain BiomassStraw BiomassStraw BiomassStraw BiomassStrawStrawStrawStrawGrainGrainGrainGrainTN UptakeStrawStrawStrawStrawGrainGrainGrainGrainTP UptakeP RecoveryStrawStrawStrawStrawGrainGrainGrainGrainTS UptakeS RecoverySas Template

and Bag (g)(g)(g)(g/m2)(kg/ha)(g)(g/m2)(kg/ha)(g)(g/m2)(kg/ha)Total NN UptakeTotal NN UptakeGrain+StrawTotal PP UptakeTotal PP UptakeGrain+StrawS UptakeS UptakeGrain+StrawSITEP RecoveryS Recovery

1.0 metre row length harvest. 25.4 cm seed row spacing.1M row lengthug/mlug/gkg/kgkg/haug/mlug/gkg/kgkg/hakg/haug/mlug/gkg/kgkg/haug/mlug/gkg/kgkg/hakg/ha%% Sug/gkg/kgkg/ha% Sug/gkg/kgkg/hakg/ha%Central Butte (CB) = 1SiteSiteCropBlockTreatmentGrain BioTotal BioP UptakeS UptakeSiteCropBlockTreatmentP RecSiteCropBlockTreatmentS Rec

=75ml/0.2500g=300Melfort Herzberg (MH) = 2t/hat/hakg/hakg/ha%%

CB10111110350168182716.57165.483.03326.893268.9098.97389.653896.4610.33683101.040.0031010412.0888.19426458.200.026586.4998.570.7536043015226.08129044120.00022608130.8811.3423402.600.003411.1212.000.151631516.30.00151635.910.208820880.0020886.8312.73Melfort Armstrong (MA) = 3CB11113.277.1712.0012.73111843.97111379.75

Wheat19111219298149149585.75857.563.89251.542515.3584.89334.213342.1312.92043876.120.0038761212.95100.1130033.000.030075.5488.500.7887638603236.62915808820.00023662920.7912.3753712.500.00379.3410.130.174691746.90.00174695.840.264962649.60.00264966.6612.50Wheat11212.525.8610.1312.50112849.62112341.67

(1-48)25111325404162242951.59515.089.27351.463514.57152.41600.046000.399.39122817.360.0028173616.9182.37824713.400.024786.86103.761.1337181985340.11545955880.00034011552.0415.7534725.900.004716.6118.650.151421514.20.00151429.090.246532465.30.00246538.6617.75(1-48)11313.519.5118.6517.75113857.571133-5.09

45111445325145180707.67076.483.80329.923299.2195.94377.723777.1713.76524129.560.0041295615.6092.66627799.800.027891.72107.321.0948295956328.44887867650.00032844891.2412.7393821.700.003812.6113.850.191519150.0019157.230.229862298.60.00229867.5814.82CROP11413.307.0813.8514.821148-38.21114310.14

12112112376168208818.98189.083.39328.313283.07124.61490.594905.9112.17163651.480.0036514817.9190.59627178.800.027289.23107.140.7844399449235.33198345590.0002353321.1511.823546.000.003511.6412.800.137031370.30.00137036.720.223612236.10.00223617.3414.06Wheat = 111123.288.1912.8014.06111932.7711142.73

13112213354145209821.98218.584.39332.243322.44124.36489.614896.0611.76723530.160.0035301617.2893.57328071.900.028193.27110.550.80962875242.8886250.00024288861.1912.2733681.900.003712.2313.420.181218120.0018128.870.266912669.10.00266918.8717.74Canola = 211223.328.2213.4217.741129167.71112485.58

33112333327133194762.57624.886.51340.593405.91107.16421.894218.9012.91083873.240.0038732416.3484.28725286.100.025386.12102.461.3129786765393.89360294120.00039389361.6616.0134803.900.004816.3618.020.169911699.10.00169917.170.230442304.40.00230447.8515.02Peas = 311323.417.6218.0215.021139-39.15113464.66

42112442288115173681.86817.768.05267.912679.13105.12413.864138.5811.93643580.920.0035809214.8288.60926582.700.026671.2286.041.7895860294536.87580882350.00053687582.2211.373411.000.00349.1411.360.155915590.0015596.450.223182231.80.00223185.9812.4311422.686.8211.3612.43114919.1811446.20

711317341168173681.16811.073.41289.022890.1699.59392.093920.8714.37964313.880.0043138816.91102.2730681.000.030788.67105.590.8654667463259.64002389710.000259641.0212.4633738.900.003710.8111.820.346163461.60.003461613.570.246924690.0024697.1420.7179.7511132.896.8111.8220.7111110-6.44111519.32

14113214317114203797.47974.479.47312.873128.74123.08484.574845.6710.44963134.880.0031348815.1985.83625750.800.025880.5795.760.7528940074225.86820220590.00022586821.0910.8353250.500.003310.1711.260.184151841.50.00184158.920.247624760.0024767.7516.6741.67Wheat: Samples 1-4811233.137.9711.2616.6711210-19.75112527.00

29113329354141213838.68386.289.71353.193531.89123.30485.434854.3312.1143634.20.003634217.6479.29823789.400.023884.02101.660.9839349265295.18047794120.00029518051.4310.693207.000.003211.3312.760.203322033.20.00203329.870.208720870.0020877.3717.24-5.09Caniola: Samples 49-9611333.538.3912.7617.241131021.501135-0.43

46113446280107173680.46803.966.79262.952629.53106.03417.444174.4115.30724592.160.0045921619.1795.00528501.500.028574.9594.121.6889018382506.67055147060.00050667062.1213.4854045.500.004010.6412.750.221852218.50.00221859.260.249862498.60.00249866.5715.8310.14Peas: Samples 97-14411432.636.8012.7515.8311410-25.8211451.14

811418303168135531.55315.053.43210.352103.5481.57321.143211.4218.09845429.520.0054295217.4496.22728868.100.028960.7378.161.438434375431.53031250.00043153031.3913.4574037.100.00408.499.880.244182441.80.00244187.840.245542455.40.00245545.1713.012.7311142.105.319.8813.0111111-3.4511160.25

15114215352146206809.98099.273.89290.912909.06131.83519.025190.1620.74326222.960.0062229632.3093.92428177.200.028281.97114.271.6141433824484.24301470590.0004842432.5111.1463343.800.00339.7312.240.252412524.10.002524113.100.273652736.50.00273657.9621.0685.5811242.918.1012.2421.061121150.751126-43.33

351143354271402871131.511315.0100.59396.023960.24186.81735.477354.7221.19926359.760.0063597646.7792.31527694.500.0277109.68156.452.3530268382705.90805147060.00070590815.1916.3814914.300.004919.4624.650.190251902.50.001902513.990.258162581.60.002581610.2224.2264.66RCBD Design11343.9611.3124.6524.2211311-14.191136-57.87

41114441298120178699.66995.768.54269.842698.43109.15429.724297.2415.63724691.160.0046911620.1687.87726363.100.026471.1491.301.8262549632547.87648897060.00054787652.3513.0483914.400.003910.5612.920.217942179.40.00217949.370.224992249.90.00224996.0715.446.20Blocks; 1, 2, 3, 411442.707.0012.9215.441141142.09114635.32

511515336168168661.46614.270.80278.742787.4097.20382.683826.7712.48123744.360.0037443614.3395.04228512.600.028579