Methods to determine moisture content of fertilizers applied in various countries of the world

Reference Method description Descriptive statistics Evaluation of the correctness of Use and general
Methods/evaluation criteria Scope/Applicability Health/Environmental Time Complexity Cost&availability Dynamic range
results obtained acceptance
1. 1 2 3 4 5 6 7 8 9 10
Gravimetric assisted (weighing) USA AFPC IX No.2 5 gms, 105 C, two need to be collected correctness of the results obtained is <5% -40 mesh rock, NIST SRM 120C Thermal protection Yes 3 hours Low Low 0-5%
9th Ed -Ground hours not checked method referenced
samples
USA AFPC IX No.2 1000-3000 gms, 105 range 8-12%, r.s.d.= 0.90% see correctness of the results obtained is <25% unground rock Thermal protection Yes 10 hours Low Low 0-25%
9th Ed -unground C, five hours minimum worksheet for raw data not checked
samples 950.01,
AOAC 2 gms, 5 hours in oven need to be collected correctness of the results obtained is generic Thermal protection Yes 5 hours Low Low 0-5%
JAOAC 33, 260(1950) @ 100 C not checked
AOAC 950.01, 2 gms, oven @ 130 C need to be collected correctness of the results obtained is for sodium nitrate, ammonium sulfate, Thermal protection Yes Unknown Low Low 0-5%
JAOAC 33, 260(1950) to constant weight not checked and potassium salts
SPPA Ver 1.1 July 30 gms, oven @ 70 C need to be collected correctness of the results obtained is Treated or untreated potassium chloride Thermal protection Yes 18 hours Low Low 0-5%
1997 for 16 hours not checked fertilizers
CEN 12048 Heating105 C, 5 hours r should not exced r=0.15*sqrt of M - correctness of the results obtained is applicable to phosphatic fertilizers not Thermal protection Yes 5 hours Low Low 0-5%
mean of two values 5% of the time
applicable ammonia compounds or
and R should not exced R=0.6*sqrt
magnesium sulphates - no reference to
of M - mean of two values 5% of the
time not checked potassium based fertilizers

Gravimetric vacuum assisted

CEN 12049 vacuum dessication, 25 r should not exced r=0.1*sqrt of correctness of the results obtained is not applicable to calcium nitrate, Vacuum protection Yes 24 hours Low Low 0-5%
mean M - of two values 5% of the calcium hydroxide, calcium sulphate,
C, 24 hours, 66KPa time and R should not exced magnesium sulphate and salts which
R=0.4*sqrt of M - mean of two effloresce (efflorescence is the loss of
(9PSI) vac. values 5% of the time not checked water from a hydrated or solvated salt)
AOAC 965.08A; ref vacuum dessication, 25- need to be collected correctness of the results obtained is generic for hydroscopic and materials Vacuum protection Yes 20 hours Low Low 0-5%
30 C, 16-18 hours, 22 with volatile substances other than
see below inches vac. not checked water
AOAC 965.08B: vacuum dessication, 50 need to be collected correctness of the results obtained is MAP, DAP Vacuum protection Yes 2 hours - this Low Low 0-30%
JAOAC 46, 582(1963); method is hybrid
C, 2 hours, 22 inches
47,32, 1040(1964); of thermal and
48,98, (1965) vac. not checked vacuum methods

(weighing)
2. Extraction and coulometric AOAC 972.01, JAOC solvent extraction - need to be collected calibration/reference samples All solid mineral fertilizer materials dioxane is relatively non Yes 30 minutes Medium Medium 0-30%
toxic but is a known
52,1127(1969);55,699( dioxane and animal carcinogen, Karl
fisher reagent (pyridine)
1972) coulometric titration commonly used is hazardous
CEN 13466-1 solvent extraction - r = 0.029 + 0.036 * WKFM and calibration/reference samples All solid mineral fertilizer materials Karl fisher reagent Yes 30 minutes Medium Medium 0-30%
methanol and
SPPA coulometric titration R = 0.156 + 0.248 * WKFM commonly used (pyridine) is hazardous
CEN 13466-2 solvent extraction - r = 0.033 + 0.049 * WKFM and calibration/reference samples All solid mineral fertilizer materials Karl fisher reagent Yes 30 minutes Medium Medium 0-30%
propanol and
titration coulometric titration R = 0.177 + 0.293 * WKFM commonly used (pyridine) is hazardous
3.
KF only method with r, R stats - need to collect other method data
What phosphatic fertilizer has 8-12 % moisture - typically <0.5
Gravimetric high temp > 100 C are not suitable to treated or nitrogen based fertilizer products
Comments for discussion Gravimetric vacuum assistedf are not suitable to treated or nitrogen based fertilizer products
Safety issue for pyridine although pyridine is typical of hazardous chemical used in most labs (small quantity and used in fume hood.
Time to complete gravimetric very long - up to 24 hours
I'm not sure where dynamic ranges came from but they are not stated in most methods - suggestion - KF extremely accurate and repeatable for < 1% moisture,
Moisture methods for Fertilizers

Source fertilizer test method

Authority of Ethiopia ammonium sulfate ES276: 1990
DAP ES ISO 8189/9190:2000 & AOAC 15th edition 965.08B 1990
Urea ES ISO 8189/9190:2000 & AOAC 15th edition 965.08B 1990

Survey by Vinatrol-Viet Nam DAP AOAC: 965.08

Intertek AOAC: 965.08A-05
SGS Vietnam Ltd. AOAC 1995-01
15th edition 965.08B 1990
15th edition 965.08B 1990
 date S1 S2 S3 avg sd rsd
16-Jul 8,61 9,04 8,86 8,84 0,22 2,44%
16-Jul 9,44 9,35 9,55 9,45 0,10 1,06%
16-Jul 9,38 9,7 9,56 9,55 0,16 1,68%
15-Jul 9,67 9,72 9,72 9,70 0,03 0,30% Data is from CFI
14-Jul 8,63 8,75 8,83 8,74 0,10 1,15% receiving for July 11
14-Jul 10,22 10,05 10,04 10,10 0,10 1,00% Three samples are weighed fro
14-Jul 10,46 10,24 10,4 10,37 0,11 1,10%
pounds. Individual sample we
14-Jul 11,05 10,58 10,45 10,69 0,32 2,95%
weighed to 0.1 grams on a cal
14-Jul 12,39 12,23 12,01 12,21 0,19 1,56%
14-Jul 10,94 10,78 10,84 10,85 0,08 0,74%
13-Jul 10,63 10,68 10,6 10,64 0,04 0,38%
13-Jul 8,66 8,62 8,71 8,66 0,05 0,52%
13-Jul 8,37 8,33 8,3 8,33 0,04 0,42%
13-Jul 9,57 9,6 9,56 9,58 0,02 0,22%
13-Jul 8,7 8,66 8,69 8,68 0,02 0,24%
12-Jul 9,73 9,75 9,67 9,72 0,04 0,43% Descriptive statisitics fo
12-Jul 10,14 10,07 10,07 10,09 0,04 0,40%
12-Jul 9,78 9,85 9,61 9,75 0,12 1,27%
12-Jul 9,98 9,88 9,95 9,94 0,05 0,52%
12-Jul 8,6 8,67 8,64 8,64 0,04 0,41%
12-Jul 8,41 8,61 8,8 8,61 0,20 2,27%
12-Jul 9,81 9,85 9,87 9,84 0,03 0,31%
11-Jul 9,29 9,37 9,39 9,35 0,05 0,57%
11-Jul 8,39 8,44 8,47 8,43 0,04 0,48%
11-Jul 11,47 11,51 11,34 11,44 0,09 0,78%
11-Jul 9,4 9,42 9,41 9,41 0,01 0,11%

min 8,37 8,33 8,30 8,33

max 12,39 12,23 12,01 12,21

range 8-12%
Data is from CFI Plant City Complex QC lab on wet rock
receiving for July 11-July 16, 2009.
Three samples are weighed from a bag which weighs about 25
pounds. Individual sample weights are 1200 to 1400 grams,
weighed to 0.1 grams on a calibrated top loading balance.

Descriptive statisitics for rsd

Mean 0,90%
Standard Error 0,15%
Median 0,54%
Mode
Standard Deviation 0,74%
Sample Variance 0,01%
Kurtosis 142,81%
Skewness 142,02%
Range 2,85%
Minimum 0,11%
Maximum 2,95%
Sum 23,29%
Count 26
Appendix 2

Methods to determine moisture content of fertilizers applied in various countries of the world
Metrological evaluation - Evaluation of the correctness Use and general
Methods/evaluation criteria Status of the method Scope/Applicability Health/Environmental Time Complexity Cost&availability Dynamic range

r, R, ∆ of results obtained acceptance

1. Tetraphenylboron method 1 2 3 4 5 6 7 8 9 10
gravimetric (weighing) EU Regional standard pr r and R are given only for correctness of the results 0-99% KCl safety requirements for a regular chemical
2 concentrations -16% and
CEN/TS 15477 Draft 24% K2O obtained is checked
EU Regional standard - Regulation no metrological evaluation correctness of the results 0-99% KCl
(EC) 2003/2003 dd. 13 Oct. 2003
relating to fertlisers Method
4.1 is given obtained is not checked
Russia/Belarus GOST 20851.3-93 r, R, ∆ are given for all the correctness is checked on the 92-99% KCl chemical lab using no extra- yes no data method of standard lab appropriate

(CIS) Regional standard STO basis of a KCl national standard

SPEKS 004—2006 range sample

China National standard GB
6549-1996
Germany VDLUFA 5.2.1
titrimetric (volumetric) Canada/USA SPPA
Standard Analytical Procedures.
Version 1.1; July 1996.
Potassium in KCl.
Official Methods of Analysis,
АОАС 1990. Fifteenth Edition,
958.02
USA Potassium in KCl.
Official Methods of Analysis,
АОАС 1990. Fifteenth Edition,
969.04
Brazil ANDA Normative Rules
Jordan APC Standard Operating no metrological evaluation
r is given for one value - correctness of the results 95% KCl
95% KCl obtained is not checked
r= 0.11%, R= 0.40%, ∆ correctness of the results ~60% K2O
not given obtained is not checked toxic reagents analysis
r= 0.16%, R= 0.51%, ∆ correctness of the results 58-63% K2O safety requirements for a regular chemical
obtained is to be within 1.5
standard deviations of the given
not given grand mean value
no metrological evaluation correctness of the results 2-63% K2O
is given - not enough lab
chemical lab using no extra- yes no data method of standard lab appropriate
participation obtained is not checked
no metrological evaluation correctness of the results no data
is given obtained is not checked
correctness of the results 0-99% KCl

Procedure. Based on AOAC 1970. is given obtained is not checked

India Fertilizer Control Order no metrological evaluation correctness of the results 0-99% KCl
1985 is given obtained is not checked
Chile АОАС 958.02 no metrological evaluation correctness of the results 2-63% KCl
is given obtained is not checked toxic reagents analysis
2. Russia/Belarus Regional standard metrological evaluation is correctness is checked on the 92-99% KCl safety requirements for a regular chemical
given for all the ranges and
components to be
basis of a KCl national standard
measured (NaCl, MgCl2
*6H20, CaSO4, insoluble
Calculation method (method by difference) chemical lab using no extra- yes no data method of standard lab appropriate
STO SPEKS 004—2006 residue, H2O etc.) sample
Canada SPPA metrological evaluation: r inter-and intralab control is > 62% K2O
Standard Analytical Procedures.
Version 1.1; January 2000.
Potassium in white products. ≤ 0.10 K2O provided for
Israel not available toxic reagents analysis
3. X-ray Spectrometry Canada SPPA Metrological evaluation: r correctness of the results 58-62% K2O Safety requirements for a Instrumental special equipment is
Standard Analytical Testing
Procedures. Version 1.0; method of
November 2006. Potassium by obtained is to be within 1.5 chemical lab. Special safety
analysis.
XRF.
no no data appropriate
―Practical X-ray Spectrometry,
Complicated
Second Edition‖, R.Jenkins & standard deviations of the given requirements are needed due to
J.L.De Vries. (KCl pressing is
―An introduction to X-ray
Spectrometry‖, R.Jenkins. ≤ 0.10 K2O grand mean value application of x-ray equipment. applied). required
4. Flame photometric method Brazil ANDA Normative Rules no metrological evaluation correctness of the results ≤63 K2O safety requirements for a instrumental special equipment is
is given
USA AOAC Official Method r= 0.41%, R= 0.85%, ∆ ≤63 K2O
983.02 Potassium in Fertilizers
Flame Photometric Method
(Manual or Automated) First
Action 1983 Final Action 1985 not given
USA AOAC Official Method no metrological evaluation ≤63 K2O
955.06 Potassium in Fertilizers
Flame Photometric Method First
Action 1955 Final Action is given
chemical lab using compressed yes no data method of appropriate
Malaysia Malaysian Standard no metrological evaluation ≤63 K2O
MS Standard 417, Part 5:1994
(The Analysis of Fertilizer Part 5:
Method of Determination of
Potassium – First Revision)
Flame photometry method to
determine К2О in finished products
and control the technological
process is given
Kenya National standard KS no metrological evaluation ≤63 K2O
350:2007 ICS 65.080 is given obtained is not checked
Israel not available flamable gases analysis required
5. Atomic Absorbtion Spectrometry Chile not available Safety requirements for a Instrumental Special equipment is
USA AA Oxalate r= 0.70%, R= 1.45%, ∆ Unknown 2-63% K2O chemical lab. Special safety method of required - an AA
no no data appropriate
requirements are needed due to analysis. spectrophotometer.
not given application of AAS. Complicated. Relatively expensive.
6. Perchlorate method Russia/Belarus Regional standard metrological evaluation is correctness is checked on the 92-99% KCl Safety requirements for a regular chemical
basis of a KCl national standard chemical lab. Special safety
STO SPEKS 004—2006 made sample requirements are needed due to
India Fertilizer Control Order no metrological evaluation correctness of the results not given but 95-99%
application of HClO4 ( a strong yes no data method of standard lab appropriate
1985 is given obtained is not checked KCl is assumed
acid). India: application of
Israel Dead Sea Works no metrological evaluation correctness of the results 96-99% KCl
CH3OH (poison) is provided
Ltd.Procedure № 16.13.47 is given obtained is not checked for. analysis
7. Inductively coupled plasma optical emission USA ICP Citrate r= 0.37%, R= 1.04%, ∆ Unknown 2-63% K2O safety requirements for a Instrumental Special equipment is
required - an optical
not given method of emission spectrometer
Germany VDLUFA 5.2.3 no metrological evaluation correctness of the results 0.5-63% ni no data appropriate
analysis. with inductively coupled
plasma. Relatively
spectroscopy (ICP-OES) is given obtained is not checked chemical lab applying ICP-OES Complicated. expensive.