Using the Correct Control Limits
For submission to the Association of Exploration Geochemists Newsletter, Explore
Lynda Bloom1, Maureen Leaver 2
1
Analytical Solutions Ltd. , 1214-3266 Yonge Street, Toronto, ON Canada M4N 2L6
([Link])
2
CCRMP, Canadian Certified Reference Materials Project, Natural Resources Canada, 555 Booth Street
Ottawa, ON K1A 0G1
It is essential that regular submissions of standards and blanks be submitted to a
laboratory to ensure that suitable data quality is being provided. Certified reference
materials (CRMs) are generally sold with information stating an expected range of
values for contained elements as determined by the manufacturer of the CRM.
The statistics usually supplied by the manufacturer are a measure of the homogenization
of the CRM and agreement between the laboratories that participated in the round robin
that was undertaken to determine the accepted values. These statistics cannot be applied
to measure a laboratorys data quality. An understanding of the statistics underlying the
expected range of values for the CRM is crucial.
Gold standard MA-1b, produced by the Canadian Certified Reference Materials Project, a
division of Natural Resources Canada, is used to demonstrate this point. The Certificate
of Analysis for MA-1b reads as follows:
REFERENCE GOLD ORE MA-1b
Recommended Value 95% Confidence Interval
Au 17.0 g/g 0.3 g/g
This is the label on the purchased bottles and many purchasers assume that 95 out of 100
times a laboratorys results for MA-1b should therefore fall within
16.7 to 17.3 g/g Au.
However, it is stipulated in the literature that accompanies the bottle, the uncertainty
estimates the expected range of reproducibility of this mean within 95% probability were
the measurement program to be repeated many times. In fact, the 95% confidence limit
quoted denotes that if the certification program were to be conducted 100 times, the
overall mean in 95 cases would be expected to fall within the prescribed limits. The
certification program for MA-1b, which is similar to that used by most CRM
Analytical Solutions Ltd. 1214-3266 Yonge Street, Toronto M4N 2L6
(416)462-9124 [Link]
manufacturers, included 175 acceptable analytical determinations produced by 28
laboratories.
When the typical user inserts standards into sample batches, there is only one
determination by the laboratory and the 95% confidence limit quoted is not applicable for
measuring the acceptability of this single reported value. Realistically, the range of
values produced by having a single determination will be far greater than the 95%
confidence limit quoted.
Along with the MA-1b documentation is an additional table of statistics that is
reproduced below.
Distribution of results by method
Method No. of No. of (g/g)
Sets Results Mean CI SLc Src CV,%
FA/G 20 113 16.96 0.30 0.61 0.37 1.93
FA/AAS 8 44 17.26 0.85 0.99 0.42 2.30
INAA 3 20 17.21 1.85 0.66 0.65 3.88
FA/INAA 1 4 16.23 0.36 2.25
FA/ICP 1 5 17.36 0.29 1.66
Overall 33 186 17.05 0.26 0.70 0.42 2.22
SLc is the between-set standard deviation and Src is the within-set standard deviation. The
bottles of MA-1b are labelled with the overall mean, 17.0 and the 95% Confidence Limit,
0.30 g/g.
The more meaningful statistics for explorationists, when a single determination by a
single laboratory is being evaluated, are the overall between- and within-set standard
deviations. The within-set standard deviation is a reflection of the homogeneity of the
material in the bottle received by the participating laboratory in combination with that
laboratorys ability to reproduce the analytical method routinely. The between-set
standard deviation is likely the most useful statistic, in addition to the factors described
for the within-set standard deviation; it also takes into account slight biases between
laboratories, the differences between the sub-samples received by the laboratories.
The mean two standard deviations approximates the expected range of values for 95%
of the cases. Using SLc , the between-set standard deviation, of 0.70 g/g and the
calculated mean value of 17.0 g/g , the results for MA-1b are expected to fall within
15.6 to 18.4 g/g Au. Based on the 95% Confidence Limit as indicated on the label of
the bottle, the range of results for MA-1b are 16.7 to 17.3 g/g Au which is a
considerably narrower range of acceptable values.
Analytical Solutions Ltd. 1214-3266 Yonge Street, Toronto M4N 2L6
(416)462-9124 [Link]
This is a complicated subject and using SLc , the between-set standard deviation, to
estimate the allowable range of values is only a first approximation.
The International Standards Organization has several committees that have been working
on these questions for 25 years. The titles of ISO Guides 30 to 35 are listed in the
references for readers who are interested in researching the issue further (or visit
[Link]). There are several statistical approaches documented that evaluate the
acceptance of single and replicate assays, which seem to involve rather sophisticated
equations (as shown below) and each requiring different sets of conditions to be met.
_____________
| XC - XL | 2 Lm2 + Rm2
Further details on the evaluation of results for certified reference materials are described
in a condensed version of ISO Guide 33 available from the Canadian Certified Reference
Materials Project at CANMET, Ottawa, Canada, ccrmp@[Link] or (613) 943-0573.
This discussion points out that a wider range of values, than those generally provided by
suppliers of certified reference materials, are acceptable values. Although suppliers
provide suitable data to verify that their materials are well homogenized and that the
acceptable value is an accurate representation of the content, these values should not be
used to determine which assays should be rejected for a quality control program.
References
ISO Guide 30, Terms and definitions used in connection with reference materials
ISO Guide 31, Contents of certificates of reference materials
ISO Guide 32, Calibration in analytical chemistry and use of certified reference materials
ISO Guide 33, Uses of certified reference materials
ISO Guide 34, Quality system guidelines for the production of reference materials
ISO Guide 35, Certification of reference materials---General and statistical principles
Steger, H.F., 1998. Uses of matrix reference materials. For presentation at the
IUPAC/ISO/REMCO workshop on Reference Materials, Berlin, April 22-23, 1999
and the workshop of the conference of the Canadian Mineral Analysts, Kirkland
Lake, ON, September 17, 2001, and for publication in the respective workshop
proceedings. Project: MMSL No. 600637CCRMP DIVISION REPORT MMSL
98-024 (OP&J)
Verma, S.P., 1997. Sixteen statistical tests for outlier detection and rejection in evaluation
of international geochemical reference materials: example of Microgabbro PM-S.
Geostandards Newsletter, Vol.21, No.1, pp. 59-75.
Analytical Solutions Ltd. 1214-3266 Yonge Street, Toronto M4N 2L6
(416)462-9124 [Link]
