New method for determination of total sulfur using high...
Transcript of New method for determination of total sulfur using high...
New method for determination of total sulfur using high temperature combustion
Tyson RowlandElementar Americas Product Manager
Fertilizer Methods Forum February 2016
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Current method
AOAC Method 980.02
• Gravimetric technique using barium to precipitate sulfate and carbon disulfide to solubilize the elemental S
• Drawbacks: this can be labor intensive and require the handling of hazardous materials
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Proposal – Make a method for HTC
High temperature combustion
• Fast – single element analysis under 5 minutes
• Less chemicals and in most cases not hazardous materials
• Improve safety
• Multi-element analysis!
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Basic operating principle
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CH3(CH2)xCH3+ O2
+ contaminants
CO2 + H2O + NOx +SO2
Schematic 1: Infrared Detection
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Advantage: Sensitive (as low as a under 10 mg/kg)
Disadvantage: Matrix dependent
Schematic 2: Thermal Conductivity Detection
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Advantage: Multi-element analysis for simultaneous N analysis (run in conjunction with AOAC 993.13)
Disadvantage: Sensitivity (as low at 100 mg/kg, 0.01%), time (CNS)
Sample data
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H2O
N2
CO2
SO2
• Powerful, clear peak focusing and separation
• Area underneath peak corresponds to element content
Single-lab validation study
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Point of Study“Combustion analyzers without absorption/desorption chromatography were investigated by
the Office of the Indiana State Chemist (OISC) as an alternative to the gravimetric method. Matrix and concentration sensitivities posed several analytical challenges, especially when S determination for a wide range of fertilizer products or an unknown source was required. Burn rates, scrubber types, and the need for accelerants was a function of the fertilizer type. As a result, different scan shapes and areas were generated for different products, and the most accurate data were obtained when sample and calibration sources matched. For example, a pure ammonium sulfate [(NH4)2SO4] fertilizer source has a quick burn that requires no accelerant, whereas a blended fertilizer product containing potassium-magnesium sulfate (K2MgO8S2) and potassium chloride (KCl) is a slow burn that may require an accelerant and a halogen scrubber. Another requirement was the separation of samples into low and high S concentrations because low concentration required a longer cell length that could be overwhelmed by high concentration samples resulting in carryover for the subsequent samples. As a result, samples were presorted into categories based upon S source, S concentration, and matrix to best match the calibration material and concentration range. If the S source was unknown, the sample was pretested and the scan compared to scans from various fertilizer sources to determine the best calibration material and concentration. For a company or laboratory that knows the source and history of the product, presorting of samples presents no problem but can be a challenge for a laboratory testing largely unknown samples.
The objective of this work was to investigate an automated, matrix-independent method using less hazardous reagents than the current regulatory procedure that allows equally simple. determination in single species and complex blended fertilizer products.”
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SLV Overview
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Instrument: vario MACRO cube
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Sample preparation (solids)
sample formertin boats and tin foil cups
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Sample preparation (liquids)
capsule press
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Sample preparation (liquids)
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Sample preparation (liquids)
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Sample preparation (crucibles)
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Sample preparation (auto-loader)
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Recent Data – Liquid Fertilizers
Name Area [N] Area [S] % N % S Name Area [N] Area [S] % N % S
Sample 1 35289 25063 11.882 26.811 Sample 3 99 10504 0.044 11.158
Sample 1 36909 26239 11.897 26.853 Sample 3 108 10533 0.046 11.172
Sample 1 34296 24640 11.836 27.023 Sample 3 121 10541 0.051 11.127
Sample 1 40842 29128 11.915 26.95 Sample 3 111 10546 0.047 11.086
Sample 1 36939 26530 11.784 26.869 Sample 3 111 10585 0.047 11.194
Sample 1 37605 26904 11.889 26.999 Sample 3 102 10561 0.044 11.111
Avg. 11.867 26.918 Avg. 0.047 11.141
Dev. 0.049 0.086 Dev. 0.003 0.040
Sample 2 117 18286 0.046 18.001 Sample 4 69 9047 0.035 10.048
Sample 2 119 17423 0.049 18.044 Sample 4 75 9570 0.035 9.938
Sample 2 127 18340 0.049 17.918 Sample 4 77 9909 0.034 9.829
Sample 2 132 19171 0.048 18.023 Sample 4 88 10921 0.035 10.156
Sample 2 121 17215 0.05 17.925 Sample 4 90 12868 0.03 9.939
Sample 2 157 18498 0.057 17.971 Sample 4 74 9482 0.035 9.96
Avg. 0.050 17.980 Avg. 0.034 9.978
Dev. 0.004 0.052 Dev. 0.002 0.112
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Recent Data – Liquid Fertilizers
Sample C% N% S% Comb. S% TKI
Sample 1 0.10 11.87 26.92 26.36
Sample 2 0.07 0.05 17.98 17.00
Sample 3 0.07 0.034 11.14 10.65
Sample 4 0.07 0.034 9.98 9.33
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Recent Data – Liquid Fertilizers
C
N
S
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Recent Data – Liquid Fertilizers
C
N
S
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Method Status
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Method OrganizationMaterial Expected S (%) No. of Labsa(b) Mean (%) Recoveryc (%) RSDr (%) RSDR (%)
HorRat
2011‐05 1.56 x (y) 0.01 95.0 1.0 1.5 0.52011‐08 6.392011‐06 11.952011‐01 13.222011‐07 7.76(NH4)SO4 24S 12‐508 90Cysteine 26.72Sulpomag 12‐1773 22(NH4)2SO3 12‐591 26K2SO4 KY12289 18a(b) a = number of labs retained after eliminating outliers, (b) = number of labs removed as outliersc c = when applicable
1. Principle2. Apparatus and Materials
a) Apparatus A: By TCDb) Apparatus B: By IR
3. Reagents4. Calibration Curve and Daily Factor5. Preparation of Test Samples (Analytical Samples)6. Determination7. Calculation8. Appendix
Next: Multi-lab validation study
• Currently we have enough labs who have offered to participate in upcoming ILS.
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Teresa GrantNorth Carolina Dept. of Agriculture & CoFood and Drug Protection Division
Paulo PagliariAsst ProfessorSoil Water ClimateUniversity of Minnesota/SWROC
Keith WegnerColorado Dept of Agriculture***collaborator and stakeholderContact about Leco analyzer
Larry CihacekSoil ScienceNorth Dakota State University
Jason KongOhio Dept. of Agriculture***stakeholder only
Job FugiceIFDC
Jian ZhangNevada Dept of Agriculture
Frank SikoraUniversity of Kentucky
Calum McCuskerElementar Americas
Bill HallMosaic Fertilizer LLC
Brenda KeaveyWest Virginia Department of AgricultureRegulatory and Environmental Affairs Division***needs to borrow analyzer***collaborator and stakeholder
Jack SchmanskyScotts Company****possible sponsor***collaborator and stakeholder
Sabine KrauseElementar Analysensysteme
Craig SpearsInspectorate3904 Corporex Park Dr.Tampa, FL 33619
Thank you!
Dr. Nancy ThiexAOAC International
Bill HallMosiac
Dr. Michael Hojjatie
Tessenderlo Kerely
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