ORE RESEARCH & EXPLORATION P/L · ABN 28 006 859 856

37A Hosie St · Bayswater North · VIC · 3153 · AUSTRALIA

61 3 9729 0333 61 3 9729 8338
[email protected] www.ore.com.au

CERTIFICATE OF ANALYSIS FOR

MANGANESE ORE
CERTIFIED REFERENCE MATERIAL

OREAS 172

COA-1127-OREAS172-R1 Printed: 03-Sep-2018

 Table 1. Certified Values, SDs, 95% Confidence and Tolerance Limits for OREAS 172.
Certified 95% Confidence Limits 95% Tolerance Limits
Constituent 1SD
Value Low High Low High
Borate Fusion XRF
Al2O3, Aluminium(III) oxide (wt.%) 5.80 0.058 5.76 5.83 5.74 5.86
BaO, Barium oxide (wt.%) 0.285 0.012 0.279 0.292 0.277 0.293
CaO, Calcium oxide (wt.%) 0.095 0.007 0.092 0.099 IND IND
Fe, Iron (wt.%) 3.83 0.040 3.80 3.85 3.80 3.85
K2O, Potassium oxide (wt.%) 1.89 0.032 1.87 1.91 1.88 1.90
MgO, Magnesium oxide (wt.%) 0.141 0.014 0.133 0.149 IND IND
Mn, Manganese (wt.%) 42.75 0.214 42.64 42.87 42.55 42.95
Na2O, Sodium oxide (wt.%) 0.273 0.016 0.264 0.281 0.259 0.286
P, Phosphorus (ppm) 752 17 743 761 738 766
SiO2, Silicon dioxide (wt.%) 14.09 0.085 14.05 14.14 14.03 14.16
TiO2, Titanium dioxide (wt.%) 0.236 0.009 0.233 0.240 0.224 0.249
V2O5, Vanadium(V) oxide (ppm) 501 45 467 536 474 528
Thermogravimetry
LOI1000 (wt.%) 12.04 0.156 11.95 12.13 12.00 12.08
SI unit equivalents: ppm, parts per million ≡ mg/kg ≡ µg/g ≡ 0.0001 wt.% ≡ 1000 ppb, parts per billion.
Note: intervals may appear asymmetric due to rounding.

Table 2. Indicative Values for OREAS 172.

Constituent Unit Value Constituent Unit Value Constituent Unit Value

Borate Fusion XRF

Cr2O3 ppm 98 Pb ppm < 50
Cu ppm 57 S ppm 46.5
Laser Ablation ICP-MS
Ag ppm 0.200 Hf ppb 1705 Sn ppm 1.20
As ppm 31.6 Ho ppb 2330 Sr ppm 295
Ba ppm 2310 In ppm 0.050 Ta ppb 285
Be ppm 3.70 La ppm 83 Tb ppb 2260
Bi ppm 0.24 Lu ppb 735 Te ppb 200
Cd ppm 0.50 Mo ppm 14.9 Th ppm 5.12
Ce ppm 165 Nb ppm 5.87 Tl ppm 1.20
Co ppm 149 Nd ppm 86 Tm ppb 900
Cr ppm 28.0 Ni ppm 72 U ppm 2.48
Cs ppm 1.37 Pb wt.% 0.003 V ppm 260
Cu ppm 151 Pr ppm 23.2 W ppm 3.63
Dy ppm 12.7 Rb ppm 38.8 Y ppm 45.1
Er ppm 6.20 Re ppb < 10 Yb ppb 5380
Eu ppb 4405 Sb ppm 1.65 Zn ppm 148
Ga ppm < 10 Sc ppm 12.8 Zr ppm 60
Gd ppm 14.9 Se ppm 5.00
Ge ppb 800 Sm ppm 18.7
SI unit equivalents: ppm, parts per million ≡ mg/kg ≡ µg/g ≡ 0.0001 wt.% ≡ 1000 ppb, parts per billion.
Note: the number of significant figures reported is not a reflection of the level of certainty of stated values. They are
instead an artefact of ORE’s in-house CRM-specific LIMS.

COA-1127-OREAS172-R1 Page: 2 of 8
 INTRODUCTION

OREAS reference materials are intended to provide a low cost method of evaluating and
improving the quality of analysis of geological samples. To the geologist they provide a
means of implementing quality control in analytical data sets generated in exploration from
the grass roots level through to prospect evaluation, and in grade control at mining
operations. To the analyst they provide an effective means of calibrating analytical
equipment, assessing new techniques and routinely monitoring in-house procedures.

OREAS reference materials enable users to successfully achieve process control of these
tasks because the observed variance from repeated analysis has its origin almost
exclusively in the analytical process rather than the reference material itself.

SOURCE MATERIALS

OREAS 172 is a supergene manganese ore matrix-matched certified reference material

(MMCRM) prepared and certified by Ore Research & Exploration Pty Ltd. The material
was sourced from the Groote Eylandt Mining Company Pty Ltd (GEMCO) Mn deposit
which is hosted within a shallow dipping Lower Cretaceous sedimentary rock unit. Groote
Eylandt is in the Gulf of Carpentaria off the coast of Australia’s Northern Territory. A small
portion (4.6%) of barren siltstone sourced from a quarry north of Melbourne, Australia was
added to lower the grade. OREAS 172 is one of a suite of four Mn ore MMCRMs certified
by borate fusion XRF covering a Mn grade range of 35-46%.

COMMINUTION AND HOMOGENISATION PROCEDURES

The material constituting OREAS 172 was prepared in the following manner:

 Drying to constant mass at 105°C (Mn ore and barren siltstone);

 Crushing and milling to 98% minus 75 microns (Mn ore and barren siltstone);
 Sieving at 150 microns (Mn ore and barren siltstone);
 Blending the ore component with barren siltstone in appropriate proportions to
achieve the desired grades;
 Packaging in 10g units sealed in laminated foil pouches and 1kg units in plastic jars.

ANALYTICAL PROGRAM

Fourteen commercial analytical laboratories participated in the program to characterise the

elements reported in Table 1 using lithium borate fusion with x-ray fluorescence. LOI was
determined at 1000°C using thermogravimetry. Table 2 shows indicative values for a
number of additional elements where data was provided but insufficient for certification
(further explained in the ‘Statistical Analysis’ section). The approximate trace element
composition of OREAS 172 in this table are the means of duplicate assays from one
laboratory.

All analytes were requested to be reported on a dry basis and manganese content to be
determined by direct measurement XRF, not by closure to 100%, or any other assumed
total.

COA-1127-OREAS172-R1 Page: 3 of 8
 For the round robin program eight 200g test units were taken at predetermined intervals
during the bagging stage, immediately following final blending, and are considered
representative of the entire 197kg batch. To maximise representation, the six samples
received by each laboratory were obtained by taking one 10g subsample from each of six of
the eight available test units. Results, together with uncorrected means, medians, standard
deviations, relative standard deviations and percent deviation of lab means from the
corrected mean of means (PDM3) are presented in the certification data file for this CRM
(OREAS 172 DataPack-2.0.181213_172559.xlsx).

STATISTICAL ANALYSIS

Certified Values, Standard Deviations, Confidence and Tolerance Limits have been
determined for each analytical method following removal of individual and laboratory outliers
(see Tables 1). Certified Values are the mean of means after outlier filtering. The 95%
Confidence Limit is a measure of the reliability of the certified value, i.e. the narrower the
Confidence Interval the greater the certainty in the Certified Value. It should not be used as
a control limit for laboratory performance.

Indicative (uncertified) values (Table 2) are provided for trace elements determined by
laser ablation with ICP-MS (Ag to Zr) and are the means of duplicate assays from Bureau
Veritas, Perth. Additional indicative values by fusion XRF are provided where i) the number
of laboratories reporting a particular analyte is insufficient (< 5) to support certification; ii)
inter-laboratory consensus is poor; or iii) a significant proportion of results are outlying or
reported as less than detection limits.

Standard Deviation values (1SDs) are reported in Table 1 and provide an indication of a
level of performance that might reasonably be expected from a laboratory being monitored
by this CRM in a QA/QC program. They take into account errors attributable to
measurement uncertainty and CRM variability. For an effective CRM the contribution of the
latter should be negligible in comparison to measurement errors. The Standard Deviation
values include all sources of measurement uncertainty: between-lab variance, within-run
variance (precision errors) and CRM variability. The SD for each analyte’s certified value is
calculated from the same filtered data set used to determine the certified value, i.e. after
removal of all individual, lab dataset (batch) and 3SD outliers (single iteration). These
outliers can only be removed after the absolute homogeneity of the CRM has been
independently established, i.e. the outliers must be confidently deemed to be analytical
rather than arising from inhomogeneity of the CRM. The standard deviation is then
calculated for each analyte from the pooled accepted analyses generated from the
certification program.

In the application of SD’s in monitoring performance it is important to note that not all
laboratories function at the same level of proficiency and that different methods in use at a
particular laboratory have differing levels of precision. Each laboratory has its own
inherent SD (for a specific concentration level and analyte-method pair) based on the
analytical process and this SD is not directly related to the round robin program.

The majority of data generated in the round robin program was produced by a selection of
world class laboratories. The SD’s thus generated are more constrained than those that
would be produced across a randomly selected group of laboratories. To produce more
generally achievable SD’s the ‘pooled’ SD’s provided in this report include inter-lab bias.
This ‘one size fits all’ approach may require revision at the discretion of the QC manager
concerned following careful scrutiny of QC control charts.

COA-1127-OREAS172-R1 Page: 4 of 8
 Performance Gates in Table 3 are calculated for two and three standard deviations. As a
guide these intervals may be regarded as warning or rejection for multiple 2SD outliers, or
rejection for individual 3SD outliers in QC monitoring, although their precise application
should be at the discretion of the QC manager concerned. A second method utilises a 5%
window calculated directly from the certified value. Standard deviation is also shown in
relative percent for one, two and three relative standard deviations (1RSD, 2RSD and
3RSD) to facilitate an appreciation of the magnitude of these numbers and a comparison
with the 5% window. Caution should be exercised when concentration levels approach
lower limits of detection of the analytical methods employed as performance gates
calculated from standard deviations tend to be excessively wide whereas those
determined by the 5% method are too narrow.

Table 3. Performance Gates for OREAS 172.

Absolute Standard Deviations Relative Standard Deviations 5% window
Certified
Constituent
Value
1SD 2SD Low 2SD High 3SD Low 3SD High 1RSD 2RSD 3RSD Low High

Borate Fusion XRF

Al2O3, wt.% 5.80 0.058 5.68 5.92 5.62 5.97 1.01% 2.02% 3.02% 5.51 6.09
BaO, wt.% 0.285 0.012 0.262 0.309 0.250 0.320 4.10% 8.21% 12.31% 0.271 0.300
CaO, wt.% 0.095 0.007 0.082 0.109 0.076 0.115 6.94% 13.89% 20.83% 0.091 0.100
Fe, wt.% 3.83 0.040 3.75 3.91 3.71 3.95 1.05% 2.11% 3.16% 3.64 4.02
K2O, wt.% 1.89 0.032 1.83 1.95 1.80 1.99 1.67% 3.34% 5.02% 1.80 1.99
MgO, wt.% 0.141 0.014 0.113 0.169 0.100 0.182 9.80% 19.60% 29.40% 0.134 0.148
Mn, wt.% 42.75 0.214 42.32 43.18 42.11 43.40 0.50% 1.00% 1.50% 40.62 44.89
Na2O, wt.% 0.273 0.016 0.240 0.305 0.224 0.322 5.99% 11.98% 17.97% 0.259 0.286
P, ppm 752 17 718 786 701 803 2.27% 4.55% 6.82% 714 790
SiO2, wt.% 14.09 0.085 13.92 14.26 13.84 14.35 0.60% 1.21% 1.81% 13.39 14.80
TiO2, wt.% 0.236 0.009 0.218 0.255 0.209 0.264 3.88% 7.75% 11.63% 0.225 0.248
V2O5, ppm 501 45 412 591 367 635 8.92% 17.85% 26.77% 476 526

Thermogravimetry

LOI1000, wt.% 12.04 0.156 11.73 12.35 11.57 12.51 1.29% 2.59% 3.88% 11.44 12.64
SI unit equivalents: ppm, parts per million ≡ mg/kg ≡ µg/g ≡ 0.0001 wt.% ≡ 1000 ppb, parts per billion.
Note: intervals may appear asymmetric due to rounding

Tolerance Limits (ISO Guide 3207) were determined using an analysis of precision errors
method and are considered a conservative estimate of true homogeneity. The meaning of
tolerance limits may be illustrated for manganese (Mn), where 99% of the time (1-α=0.99) at
least 95% of subsamples (ρ=0.95) will have concentrations lying between 42.55 and 42.95
wt.%. Put more precisely, this means that if the same number of subsamples were taken
and analysed in the same manner repeatedly, 99% of the tolerance intervals so constructed
would cover at least 95% of the total population, and 1% of the tolerance intervals would
cover less than 95% of the total population (ISO Guide 35).

Based on the statistical analysis of the results of the inter-laboratory certification program
it can be concluded that OREAS 172 is fit-for-purpose as a certified reference material
(see ‘Intended Use’ below).

COA-1127-OREAS172-R1 Page: 5 of 8
 PARTICIPATING LABORATORIES

1. ALS, Brisbane, QLD, Australia

2. ALS, Johannesburg, South Africa
3. ALS, Vancouver, BC, Canada
4. Bureau Veritas Geoanalytical, Adelaide, SA, Australia
5. Bureau Veritas Geoanalytical, Cardiff, NSW, Australia
6. Bureau Veritas (Ultra Trace) Geoanalytical, Perth, WA, Australia
7. Intertek Genalysis, Perth, WA, Australia
8. Intertek Minerals (IMI), Jakarta, Indonesia
9. Intertek Testing Services, Darwin, NT, Australia
10. LCT, Sao Paulo, Sao Paulo, Brazil
11. SGS Geosol Laboratorios Ltda, Vespasiano, Minas Gerais, Brazil
12. SGS Lakefield Research Ltd, Lakefield, Ontario, Canada
13. SGS South Africa Pty Ltd, Booysens, Gauteng, South Africa

PREPARER AND SUPPLIER OF THE REFERENCE MATERIAL

Reference material OREAS 172 has been prepared, certified and is supplied by:

ORE Research & Exploration Pty Ltd Tel: +613-9729 0333

37A Hosie Street Fax: +613-9729 8338
Bayswater North VIC 3153 Web: www.ore.com.au
AUSTRALIA Email: [email protected]

It is available in 10g units in single-use laminated foil pouches and in 1kg units in plastic jars.

INTENDED USE

OREAS 172 is intended for the following uses:

 For the monitoring of laboratory performance in the analysis of analytes reported

in Table 1 in geological samples;
 For the verification of analytical methods for analytes reported in Table 1;
 For the calibration of instruments used in the determination of the concentration
of analytes reported in Table 1.

STABILITY AND STORAGE INSTRUCTIONS

OREAS 172 is an oxidised reference material and is stable in the laminated foil pouches.
Under normal conditions of storage it has a shelf life beyond ten years.

HANDLING INSTRUCTIONS
Fine powders pose a risk to eyes and lungs and therefore standard precautions such as
the use of safety glasses and dust masks are advised.

COA-1127-OREAS172-R1 Page: 6 of 8
 INSTRUCTIONS FOR CORRECT USE

The certified values for lithium borate fusion XRF and for LOI are on a dry basis. This
requires the removal of hygroscopic moisture by drying in air to constant mass at 105°C. If
the reference material is not dried prior to analysis, the certified values should be corrected
to the moisture-bearing basis.

METROLOGICAL TRACEABILITY

The analytical samples were selected in a manner to represent the entire batch of
prepared CRM. This ‘representivity’ was maintained in each submitted laboratory sample
batch and ensures the user that the data is traceable from sample selection through to the
analytical results that underlie the consensus values. Each analytical data set has been
validated by its assayer through the inclusion of internal reference materials and QC
checks during analysis.

The laboratories were chosen on the basis of their competence (from past performance in
inter-laboratory programs undertaken by ORE Pty Ltd) for a particular analytical method,
analyte or analyte suite, and sample matrix. Most of these laboratories have and maintain
ISO 17025 accreditation. The certified values presented in this report are calculated from
the means of accepted data following robust statistical treatment as detailed in this report.

Guide ISO/TR 16476:2016, section 5.3.1 describes metrological traceability in reference

materials as it pertains to the transformation of the measurand. In this section it states,
“Although the determination of the property value itself can be made traceable to
appropriate units through, for example, calibration of the measurement equipment used,
steps like the transformation of the sample from one physical (chemical) state to another
cannot. Such transformations may only be compared with a reference (when available), or
among themselves. For some transformations, reference methods have been defined and
may be used in certification projects to evaluate the uncertainty associated with such a
transformation. In other cases, only a comparison among different laboratories using
the same method is possible. In this case, certification takes place on the basis of
agreement among independent measurement results (see ISO Guide 35:2006, Clause 10).”

COMMUTABILITY

The measurements of the results that underlie the certified values contained in this report
were undertaken by methods involving pre-treatment (digestion/fusion) of the sample. This
served to reduce the sample to a simple and well understood form permitting calibration
using simple solutions of the CRM. Due to these methods being well understood and
highly effective, commutability is not an issue for this CRM. All OREAS CRMs are sourced
from natural ore minerals meaning they will display similar behaviour as routine ‘field’
samples in the relevant measurement process. Care should be taken to ensure ‘matrix
matching’ as close as practically achievable. The matrix and mineralisation style of the
CRM is described in the ‘Source Material’ section and users should select appropriate
CRMs matching these attributes to their field samples.

COA-1127-OREAS172-R1 Page: 7 of 8
 LEGAL NOTICE

Ore Research & Exploration Pty Ltd has prepared and statistically evaluated the property
values of this reference material to the best of its ability. The Purchaser by receipt hereof
releases and indemnifies Ore Research & Exploration Pty Ltd from and against all liability
and costs arising from the use of this material and information.

DOCUMENT HISTORY
Revision
Date Changes applied
No
1 3rd Sep, 2018 Added major and trace element characterisation.
0 7th Aug, 2012 First publication.

QMS ACCREDITED

ORE Pty Ltd is accredited to ISO 9001:2008 by Lloyd’s Register Quality Assurance Ltd for
its quality management system including development, manufacturing, certification and
supply of CRMs.

CERTIFYING OFFICER

Craig Hamlyn (B.Sc. Hons - Geology), Technical Manager - ORE P/L

REFERENCES

ISO Guide 30 (2015), Terms and definitions used in connection with reference materials.
ISO Guide 31 (2015), Reference materials – Contents of certificates and labels.
ISO Guide 3207 (1975), Statistical interpretation of data - Determination of a statistical
tolerance interval.
ISO Guide 35 (2017), Certification of reference materials - General and statistical
principals.

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