St.

Petersburg July 2, 2010

As discussed at our last meeting, we distributed a
comparison matrix for phosphate methods
There no additional comments were received since
the last meeting
We will continue to use this matrix as background
for our investigations moving forward
We agreed to first assess mineral acid soluble P
2
O
5
We eliminated some regional methods that do not
have international implications as being best
practice methods
There is general agreement that a variety of
mineral acids adequately digest phosphate in
commercial products
Because several combinations and sample/solvent
ratios are used, there should be a laboratory
assessment to gain knowledge, address review
criteria and compare methods in wide use
An assessment of specific digestion and detection
techniques linked with these methods is needed
A proposal to do assess these methods is described
Ambiguity and lack of consistency seems apparent in
the use and application of methods
We hope to invite many laboratories to participate and
allow them to use the method they normally use
We will also encourage use of one or both potential
best practice methods selected if they use it routinely
We will assess all methods used by participating labs
We believe much could be learned by a series of tests
evaluating extraction and detection methods in use
Draft Proposal Highlights -
Study Title: Evaluation of Commonly Used
Methods of analysis of Mineral Acid Soluble P2O5
in Internationally Traded Fertilizer Materials.
Study Coordinator: William L. Hall Jr.
Study Monitors: Mokhtar Ben Embrak
(Cerphs/OCP), Harold Falls (CF Industries), Fabian
Janssens, (BASF), Vladimir Onischenko (UralChem
Ltd.), Gang Liu (Shanghai Research Institute)
# Grade Source Material P
2
O
5
Content
1 0-46-0 DAP High CI from Central Florida 46%
2 0-52-0 High CI MAP from Louisiana 52%
3 0-46-0 Moroccan TSP 46%
4 0-61-0 Analytical Grade Mono-ammonium Phosphate 61%
5 0-32-0 Moroccan Rock 32%
6 0-32-0 Florida Rock (AFPC Rock Check #22) 32%
7 0-39-0 Russian Apatite Rock 39%
8 15-15-15 BASF compound N-P-K 15%
9 14-16-14 NIST 695 Blended N-P-K 16%
10 TBD Possible Chinese Phosphate Rock or DAP ??%
Samples were collected from the respective participating
laboratories based on geography, matrix and P
2
O
5
content
Samples received as ground powders were screened with
an ASTM 40 screen.
Granules and crystals were ground using a micropulverizer
fitted with a screen size of .027 inch slots. The ground
samples were then screened through an ASTM 40 screen
A minimum of 40 aliquots for each sample were prepared
using 50 ml plastic digestion bottles with a minimum of 25
grams per bottle.
Ten bottles were chosen randomly and tested for
homogeneity. The ten samples were then returned to the
inventory.
Homogeneity testing was completed according to
ISO & AOACI guidelines using two accepted methods
of analysis. Results are contained in appendix I of the
proposal and satisfy requirements for homogeneity.
I want to thank CF Industries & Sanford for preparing,
analyzing & being willing to distribute these samples
Three materials would be considered
reference materials #4, 6 and 9. Results from
these samples will be compared to the
certified results from the supplying
organizations. This information will be used
to assess accuracy and specificity of the
methods being employed in the study.
If enough laboratories use the reference methods, we will
use this information to assess the two methods as would be
done in a ring test or collaborative study.
Potential methods to be used by participating laboratories:
CEN/ISO
CEN - 3.1.1/ISO - 7497 (see attached)
AOACI/AFPC
AOACI - 2.3.03/AFPC - XI 3.B (see attached)
Other Methods
Determined by the participating laboratory ( by completing
questionnaire)
Great care will be taken to accurately assess
certain specific key steps in the procedures and
equipment used by participating laboratories
Each participating Laboratory will be required to
completely fill out a questionnaire or specifically
state that they use the ISO or AOAC methods
noted above with no modifications
If modifications are made then laboratories are
still encouraged to participate and note the
changes or modifications they employ.
Sensitivity & specificity will be determined through analysis of
the data on the unknown samples
However if additional internal or reference standards are used in
developing calibrations or calculations, they should be noted and
reported.
Calibrations should be noted with specific documentation on
wavelengths, ranges and linearity as well as blanks, reference
material/internal standard performance and detection limits
This data will be used to establish calibration curve precision.
Test Material Precision - Unknown test materials will be
distributed as blind duplicates.
Additionally each lab will be asked to run each sample in duplicate to
establish inter and intra laboratory precision.
Repeatability design will include 2 replicates of 10
test samples on 2 separate days to maximize
variability
Since the test samples represent a variety of
common phosphate containing fertilizer
materials, any matrix affect due to the sample
type can be monitored.
Repeatability or relative standard deviation (i.e.
RSD
r
) will be calculated for each test sample and
compared to the predicted RSD
r
(i.e. PRSD)
Test materials will include 3 reference standards
Test concentrations range from 15 to 61% P
2
O
5
Most of the test samples (i.e. AFPC and NIST
samples) have reported statistics
Means, standard deviations and percent
recoveries for all samples will be reported
Because different laboratories use different
equipment colorimeters (i.e. manufacturers
and models), and different oven and balance
types, some minor method deviations will be
allowed, but mist be noted.
Within the report, performance based
statements will be provided.
A draft report will be submitted to the Steering
Committee for review and comment
Data generated from the study will be used to
generate potential best practice methods or make
recommendations for further study
This report will include, but not be limited to-
Analytical methods used in generation of the data
Electronic records of the emission scans for the standards, controls and
samples
Instruments and equipment used and their operating conditions
Protocol, amendments and any deviations
Names of all scientists, professionals, and supervisory personnel
involved in the study
Analytical data and summary spreadsheets for all acceptable runs
A final report will be provided to the Steering
Committee addressing any comments or
concerns of the reviewers
Upon the approval of the Harmonization
Steering Committee the report can be
forwarded to the IFA technical Committee
The final report can also be offered in the
form of a manuscript for publication in The
JOAC International