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Proficiency Testing in Chemical Analysis of Iron Ore: Comparison of

Statistical Methods for Outlier Rejection

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DOI: 10.1007/s12647-013-0059-8

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MAPAN-Journal of Metrology Society of India (June 2014) 29(2):87–95
DOI 10.1007/s12647-013-0059-8

Proficiency Testing in Chemical Analysis of Iron Ore: Comparison

of Statistical Methods for Outlier Rejection
S. Chakravarty1*, A. Mohanty1, B. Ghosh1, M. Tarafdar1, S. G. Aggarwal2
and P. K. Gupta2
1
CSIR-National Metallurgical Laboratory, Jamshedpur, Jharkhand, India
2
CSIR-National Physical Laboratory, New Delhi, India

Received: 16 May 2013 / Accepted: 30 July 2013 / Published online: 8 September 2013

Ó Metrology Society of India 2013

Abstract: Participation in proficiency testing (PT) is an important task to meet the requirements of ISO/IEC 17025 in the
area of quality assurance of laboratory results. A PT program in the field of chemical analysis of iron ore was organized by
CSIR-National Metallurgical Laboratory, Jamshedpur (nodal laboratory) and CSIR-National Physical Laboratory, New
Delhi (PT Coordinator) during November 2011–January 2012. Twenty-two (22) laboratories in India participated in the PT
program. The results of participating laboratories were first analyzed to identify the distribution patterns and the presence
of outliers. Several parametric and robust statistical methods were used to identify the outliers. Correct outlier rejection is
of utmost importance because the choice of the outlier test method influence the consensus value and standard deviation
which in turn determine the Z-score of a laboratory result in a PT program. In the present study, five parametric outlier tests
were compared: Dixon’s Q test, Grubbs single test, double test, t test, and Z-scores. In addition three robust tests as
alternative to parametric tests were chosen: box plot, Huber test and MAD-based test. It was observed that multiple outlier
test methods should be used to identify the outliers in a PT program especially when the number of participating
laboratories is less. They complement each other and helps give diverse information and better overview of the data set.
Among the 22 participating laboratories, Z-scores of 4 laboratories for analysis of total iron fall outside the acceptable limit
of ±2. Similarly, for analysis of alumina and silica, five laboratories had unacceptable Z-scores.

Keywords: Proficiency testing; Outliers; Iron ore analysis; Statistical methods; Inter laboratory comparison

1. Introduction participating laboratory in PT is evaluated by quantifying

Proficiency testing (PT) is an important way to meet the
requirements of ISO/IEC 17025 in the area of quality
assurance of laboratory results [1]. It is also mandated by
accreditation bodies that laboratories participate in PT
programs for all types of analysis undertaken in that lab-
oratory. PT provides objective evidence that laboratories
are competent and that they can achieve the level of
uncertainty for which they are accredited. All accredited as
well as non accredited laboratories are expected to partic-
ipate in the PT, which will help them indirectly to improve
uncertainty, reliability and reproducibility of their analyti-
cal results [2–6]. The performance of individual
*Corresponding author, E-mail: sanchita@nmlindia.org
the deviation of its results from the assigned reference
value that, in most cases, is a consensus value obtained
from participant’s results [7–9]. As an external quality
assessment tool, PT program has dual objectives. Firstly it
allows accreditation bodies to monitor laboratory compe-
tence in specific tests. Secondly, PT program provides
participating laboratories an opportunity for improvement
since the PT program reports are usually accompanied by
an analysis of results and recommendation for improved
performance. Hence, the manner in which the performance
of an individual participating laboratory is evaluated in a
given PT program is very important.
The present paper reports results of a PT program, PT-
Iron ore/2011-12, organized by CSIR-National Metallur-
gical Laboratory (CSIR-NML), Jamshedpur and CSIR-
National Physical Laboratory (CSIR-NPL), New Delhi in
the area of chemical analysis of iron ore for measurements
of major constituents, i.e., total Fe (%), Al2O3 (%) and

123
88
SiO2 (%) in homogenized iron ore. CSIR-NML acted as the
nodal laboratory for conducting PT and CSIR-NPL was the
PT coordinator. Twenty-two National Accreditation Board
for Testing and Calibration Laboratories (NABL) accred-
ited as well as non accredited laboratories in India partic-
ipated in the PT program during the period of November
2011–January 2012. The data was analyzed to find out best
statistical approach to reject outliers. Performance of the
participating laboratories was assessed on the basis of Z-
scores. Among the 22 participating laboratories, Z-scores
of 4 laboratories for analysis of total iron fall outside the
acceptable limit of ±2. Similarly, for analysis of alumina
and silica, five laboratories had unacceptable Z-scores. An
effort was made to identify the plausible causes for
reporting of incorrect analytical results by these laborato-
ries and the laboratories were informed to initiate necessary
corrective actions.
2. Materials and Methods
2.1. Preparation of Samples
Preparation of samples is a fundamental and critical step in
PT program to ensure that identical samples are analyzed
by all participating laboratories. In this study, iron ore of
Indian origin (50 kg) was collected from Bolani mines,
Keonjhar, Odisha. The ores were first air dried and then
crushed sequentially to -200 mesh using jaw crusher, roll
crusher and pulverizer. Finally, the powdered ore was
homogenized by coning and quartering technique and
stored in 100 g glass bottles before the commencement of
the PT program. Ten bottles were randomly selected from
the pool of 300 bottles as 10 samples and each sample was
analyzed 5 times for determination of total Fe (%), Al2O3
(%) and SiO2 (%) as per IS 1493 (Part I): 1981 [10]. For
homogeneity testing, the chemical analysis data was sta-
tistically evaluated using one way variance analysis
(ANOVA) [11]. The significance level chosen for the
critical value of F was a = 0.05. The values of estimators
of the variance between the bottles and the variance within
the bottles of iron ore samples were calculated for getting
Fcalculated value which was always found to be less than
Fcritical value. Hence the results of the variance analysis
showed that the materials were sufficiently homogeneous
and suitable for distribution to the participants of PT
program.
2.2. Organizing the PT
Testing laboratories in India were asked to participate in
this PT program and the names of interested laboratories
were registered before 15th November, 2011. A total of 22
123
S. Chakravarty et al.
laboratories participated in the PT program. One bottle of
iron ore (100 g) was sent to each participating laboratory in
second week of December, 2011. Participants were
required to determine Fe (total), Al2O3, and SiO2 quanti-
tatively. A standard proforma was provided for data and
information input. Analytical results for iron ore were
requested in % (w/w) to two significant figures with the
expanded measurement uncertainty and coverage factor
stated. Technical details were also requested to be reported.
Participating laboratories were allowed to use any vali-
dated test method normally used by them for the mea-
surement of iron ore. The names of the participating
laboratories are tabulated in Table 1. To maintain confi-
dentiality, each laboratory was assigned a random code
number (1–22) and these numbers are used in this paper.
2.3. Statistical Analysis of Results
Different statistical methods were used to analyze the data
received from participating laboratories. Histograms and
normal Q–Q plots were used to test the distribution patterns
of the experimental data. The number of participants in this
PT program was relatively small (22) and a closer look at
the data suggests presence of some outliers. Outlier is a
data which appear to differ unreasonably from others in the
set. Different outlier test methods, both parametric and
Table 1 Name of the participating laboratories in the PT program
Laboratory name
Aglow Quality Control Lab., Kolkata
Bhagavati Ana Labs Ltd., Hyderabad
Tata Steel, Jamshedpur
Delhi Test House, Delhi
Dr. More RCA Laboratories, Mumbai
Inspection Survey and Surveillance (India) Pvt. Ltd., Kolkata
Inspectorate Griffith India, Bhubaneswar
Inspectorate Griffith India, Chennai
Inspectorate Griffith India, Gandhidham
Inspectorate Griffith India, Goa
Inspectorate Griffith India, Haldia
Inspectorate Griffith India, Hospet
Inspectorate Griffith India, Jaipur
Inspectorate Griffith India, JODA
Inspectorate Griffith India, Mangalore
Inspectorate Griffith India, Raipur
Inspectorate Griffith India, Visakhapatnam
National Metallurgical Laboratory, Jamshedpur
Quality Services & Solutions (Goa), Goa
Quality Services & Solutions (QSS), Gandhidham
Spectro Analytical Lab, Delhi
Usha Martin Limited, Jamshedpur
Proficiency Testing in Chemical Analysis of Iron Ore 89

robust, were used to find out the best statistical approach to
reject outliers. The parametric outlier tests used were
Dixon’s Q test, Grubb’s single and double tests, t test and
Z-score. The robust outlier tests used were Box plot, Huber
test and MAD-based test. None of the used tests take
measurement uncertainty into account. Uncertainty were
left out deliberately, as not all laboratories have uniform
approach to evaluate uncertainty and some of the labora-
tories did not report any uncertainty estimate together with
the results. The detail of the outlier test methods used is
discussed below.
2.3.1. Parametric Tests
Most well known elementary statistical tools are paramet-
ric. Parametric tests make assumptions about the distribu-
tion of the data. If those assumptions are correct parametric
test can produce an accurate and precise estimation. If
those assumptions are incorrect, parametric test can be very
misleading. For that reason they are often considered as
non-robust. Four parametric tests were employed to iden-
tify outliers in the present study.
for-purpose criterion. The result obtained by a laboratory is
rejected as an outlier if numeric value of Z C 2.
2.3.1.3. Grubbs Test The most commonly used and rec-
ommended test by ISO for outliers is the Grubbs test [13].
This test compares the deviation of the suspect value from
the sample mean with the standard deviation of the sample.
Grubbs test is also known as the maximum normed residual
test.
The Grubbs test statistic (GS) can be represented as:
100jS  SH j
GS ¼ ð3Þ
S
100jS  SL j
GS ¼ ð4Þ
S
where S is the standard deviation of whole data set, SL is
standard deviation of data set where the lowest result is left
out. SH is the standard deviation of the data set where the
highest result is left out. Bigger GS is compared with a
tabulated critical value from the distribution found in the
table [13]. In order to achieve more confidence, Grubbs
double test is also used in PT schemes. It determines

2.3.1.1. t Test t test is a statistical test to compare two

mean values to see if their difference is too large to be
explained by indeterminate error. The value of t is calcu-
lated using Eq. 1:
pffiffiffi
ðx  XÞ n
t¼ ð1Þ
s
where t is t test statistic, x is individual laboratory result,
X is the mean of participants, s is sample standard devia-
tion, and n is sample size. Please note that Eq. (1) has been
modified in order to adopt it with the condition of PT. The
value of t is compared with a critical p value from Stu-
dent’s t distribution, t(a, t) which is determined by the
chosen significance level, a, the degree of freedom for
sample, t. Values for t(a, t) are found in Student’s t dis-
tribution table in literature [12]. If t is greater than t(a, t),
the result is considered as an outlier.

2.3.1.2. Z-Scores The Z-scores in the present study are

used not only as a parameter to evaluate laboratories per-
formance, but also as one way to reject outliers. The Z-
scores, Zi are calculated from the laboratory results, the
assigned value and the standard deviation using Eq. 2:
x  Xa
Zi ¼ ð2Þ
s
where x is the laboratory result, Xa is the assigned value
calculated based on the best estimate of the true value
obtained from different laboratories and s is the ‘target Fig. 1 Histogram (a) and Q–Q plot (b) for Fe (total) content in iron
value for standard deviation’ and is derived from a fitness- ore

123
90
whether the two largest or two smallest values at a time
might be outliers.
2.3.1.4. Dixon’s Q Test The Dixon Q test is based on
calculation of the experimental Q value defined as the ratio
given by the distance of the suspected value from its
nearest neighbor divided by the range of the values. If n is
the number of participating laboratories, then the corre-
sponding n values are arranged in ascending order
x1 \ x2 \  \ xn,. For testing the smallest value (x1) or
the largest value (xn) the following equations are used,
respectively:
x2  x1
Q¼ ð5Þ
xn  x1
xn  xn1
Q¼ ð6Þ
xn  x1
If the obtained (experimental) Q value exceeds the
tabulated critical Qcrit value from normal distribution for a
given confidence level found in table, then the suspect
value can be rejected.
2.3.2. Robust Tests
Robust statistics include parameters that are largely unaf-
fected by the presences of extreme values. Median (Me)
Fig. 2 Histogram (a) and Q–Q plot (b) for Al2O3 content in iron ore
123
S. Chakravarty et al.
and median absolute deviation (MAD) are two such
parameters. Three different types of robust tests were used
to determine outliers in the present study.
2.3.2.1. Huber Test In Huber test, deviation between the
laboratory result (x) and median (Me) is calculated first
(|x - Me|). Then |x - Me| is compared with cr, where c is
usually taken to be 1.5 and r = MAD/0.6745. MAD is
calculated using the formula MAD = Me [|xi - Me(xi)|].
The laboratory result will be an outlier if |x - Me| [ 1.5r.
2.3.2.2. MAD Based Test MAD based test is a very
useful robust method for evaluating outliers. Result of a
participating lab is rejected as outliers if [|x - Me|]/
MAD [ 5.
2.3.2.3. Box Plot Tukey has introduced the Box plot
(also known as Box and Whisker plot) as a graphical dis-
play on which outliers can be indicated [12]. It is a diagram
consisting of a rectangle (the box) with two lines (the
whiskers) extending from opposite edges of the box, and a
further line in the box, crossing it parallel to the same
edges. The end of the whiskers indicate the range of non-
outlier data, the edges of the box from which the data
represent the upper (Q3) and lower quartiles (Q1) and line
crossing the box represents the median (Q2) of the data.
The first quartile is the value under which 25 % of the data
lie, and the third quartile is the value over which 25 % of
Fig. 3 Histogram (a) and Q–Q plot (b) for SiO2 content in iron ore
Proficiency Testing in Chemical Analysis of Iron Ore 91

the data are found. Outliers are defined as data points
which are lower than the lower quartile (Q1), or higher
than the upper quartile (Q3) by more than 1.5 times the
interquartile range.
3. Results
It is very important to have information about the distribution
patterns of data (such as normality) before applying any sta-
tistical analysis tools because typical statistical tests incor-
porate assumptions about the underlying distribution of data.
Therefore, the distribution patterns of data obtained in the iron
ore PT program was first investigated. The distribution of
dataset was assessed by drawing histograms and normal Q–Q
plots. The histograms and normal Q–Q plots were also used to
detect visually any unusual observations (outliers) or any gaps
in the data sets. Figures 1, 2 and 3 show histograms and Q–Q
plots for Fe (total), Al2O3 and SiO2 results obtained from all
the participating laboratories. The histogram of Fe (total)
content (Fig. 1a) looked very close to Normal distribution
with slight tailing in higher value region. The histogram also
clearly shows the presence of some results that is much higher
than others, and these results can be considered as outliers.
The histogram gave useful information about dataset, but
since the number of participating laboratories in PT program
was low, it is difficult to make definite conclusions about the
distributions. In order to do that, normal Q–Q plot was drawn
and visually evaluated as these plots are more robust with
respect to number of participating laboratories compared to
histogram. The normal Q–Q plot for Fe (total) content is
presented in Fig. 1b. Presence of outlier data is clearly seen in
Fig. 1b and if the highest value is left out, the distribution
would become Normal. The histograms and normal Q–Q
plots of Al2O3 content and SiO2 content are presented in
Figs. 2 and 3, respectively. For Al2O3 content, tailing of data
is observed in lower value region in histogram and rejection
of the low value data in Fig. 2b as outlier will result in Normal
distribution. Similarly, the histogram of SiO2 content is tailed
towards high value region (Fig. 3a) and rejection of the high
value data as outlier in Q–Q plot (Fig. 3b) will result in
Normal distribution.

Table 2 Identification of outliers using different methods for Fe (total) content in iron ore
Lab ID Lab data Grubbs single Grubbs double t test Z-score MAD based test Dixon Q test Huber test

1 63.97 0.56 0.77 0.74 0.15 0.65 0.085

2 63.38 -0.79 -0.65 23.00 -0.63 -3.88 0.505
3 63.38 -0.78 -0.64 23.00 -0.63 -3.88 0.505
4 64 0.63 0.84 0.93 0.19 0.88 0.115
5 66.57 6.43 6.94 17.11 3.64 20.65 0.512 2.685
6 63.69 -0.08 0.1 -1.04 -0.22 -1.50 0.195
7 63.87 0.32 0.52 0.07 0.018 -0.12 0.015
8 63.92 0.43 0.64 0.39 0.08 0.27 0.035
9 64.5 1.76 2.03 4.06 0.86 4.73 0.615
10 63.9 0.39 0.6 0.28 0.05 0.12 0.015
11 63.9 0.39 0.6 0.28 0.05 0.12 0.015
12 63.94 0.49 0.7 0.55 0.11 0.42 0.055
13 63.85 0.27 0.47 -0.06 -0.00 -0.27 0.035
14 63.86 0.3 0.5 0.03 0.00 -0.19 0.025
15 63.87 0.32 0.52 0.07 0.01 -0.12 0.015
16 63.59 -0.32 -0.15 -1.7 -0.35 -2.27 0.295
17 63.93 0.46 0.67 0.47 0.09 0.35 0.045
18 64.03 0.68 0.9 1.08 0.23 1.12 0.145
19 63.31 -0.94 -0.81 23.44 -0.73 -4.42 0.575
20 64.04 0.71 0.93 1.16 0.24 1.19 0.155
21 62.53 22.7 22.65 28.34 -1.78 210.42 0.066 1.355
22 62.8 22.09 22.02 26.66 -1.41 28.35 1.085
No of outliers 0 3 4 7 1 3 1 7
Final mean 63.85 63.84 63.80 63.89 63.73 63.84 63.73 63.89
Final SD 0.74 0.28 0.23 0.12 0.44 0.28 0.44 0.12
Final median 63.88 63.9 63.88 63.9 63.87 63.9 63.87 63.9
Bold values indicate that the data which are omitted from final calculation

123
92 S. Chakravarty et al.

The histograms and normal Q–Q plots indicated pres-
ence of outliers in the dataset. Different outlier rejection
methods (parametric and robust) were then employed to
identify the outliers. The results are summarized in
Tables 2, 3 and 4. In the first two columns the laboratory
number and the actual obtained results are presented. The
subsequent columns present the results obtained with dif-
ferent outlier rejection tests. The results rejected before
calculation of the consensus values and standard deviations
are highlighted. The box plots for Fe (total), Al2O3, and
SiO2 showing outliers (as red marks) are shown in Figs. 4
and 5.
Among the total Fe content data of all participating
laboratories (Table 2; Fig. 4), Dixon Q test and Z-score
identified one outlier, the Grubb’s single, MAD based test
and Box plot identified three outliers, and Grubbs double
test identified four outliers. t test and Huber test were more
severe and both tests identified 7 outliers. It can be noted
that despite detection of different number of outliers using
different test methods, the maximum difference between
outlier-corrected average values was only 0.2 % (range
from 63.89 to 63.73 %) and the outlier-corrected median
value remained practically unchanged. However, the out-
lier-corrected standard deviation differed by up to 72.7 %
(range from 0.44 to 0.12). In case of Al2O3 content com-
parison (Table 3; Fig. 5), Dixon Q test and Z-score iden-
tified one outlier, MAD based test detects two outliers,
Grubbs single and Box plot detected three outliers, and
Grubbs double detected four outliers. Huber test detected 5
outliers whereas t test detected maximum 9 outliers. The
outlier-corrected averages differed maximum up to 1 %
and the outlier-corrected median values remain unchanged.
The outlier-corrected standard deviation differed up to
55.5 % (range from 0.08 to 0.18). Similarly, in the case of
SiO2 content (Table 4; Fig. 5), Dixon Q test and Z-score
identified one outlier, the Grubb’s single and MAD based
test identified three outliers, Grubbs double and Box plot
identified four outliers, Huber test identified five outliers
and the t test identified maximum 8 outliers. The maximum
difference between outlier-corrected average values was
1.8 % (range from 3.64 to 3.71 %) and the outlier-cor-
rected median value differed by up to only 0.8 %.

Table 3 Identification of outliers using different methods for Al2O3 content in iron ore
Lab ID Lab data Grubbs single Grubbs double t test Z-score MAD based test Dixon Q test Huber test

1 2.84 -0.35 -0.26 -0.06 -0.01 -0.63 0.06

2 3.15 1.31 1.78 4.25 0.91 2.63 0.25
3 3.02 0.61 0.92 2.44 0.52 1.26 0.12
4 3.4 2.65 3.42 7.71 1.64 5.26 0.14 0.5
5 2.79 -0.61 -0.59 -0.75 -0.16 -1.16 0.11
6 2.7 -1.10 -1.18 -2.00 -0.43 -2.11 0.2
7 3 0.51 0.79 2.16 0.46 1.05 0.1
8 2.9 -0.03 0.13 0.78 0.17 0.00 0
9 2.48 22.27 22.63 25.05 -1.08 -4.42 0.42
10 2.9 -0.03 0.13 0.78 0.17 0.00 0
11 2.98 0.40 0.66 1.89 0.40 0.84 0.08
12 2.91 0.03 0.20 0.92 0.20 0.11 0.01
13 2.99 0.45 0.72 2.03 0.43 0.95 0.09
14 2.93 0.13 0.33 1.19 0.25 0.32 0.03
15 2.87 -0.19 -0.07 0.36 0.08 -0.32 0.03
16 2.83 -0.40 -0.33 -0.19 -0.04 -0.74 0.07
17 2.85 -0.29 -0.20 0.08 0.02 -0.53 0.05
18 3 0.51 0.79 2.16 0.46 1.05 0.1
19 3.02 0.61 0.92 2.44 0.52 1.26 0.12
20 2.62 -1.52 -1.71 23.11 -0.66 -2.95 0.28
21 2.83 -0.40 -0.33 -0.19 -0.04 -0.74 0.07
22 1.57 27.14 28.62 217.68 23.77 214.00 0.50 1.33
No of outliers 0 3 4 9 1 2 1 5
Final mean 2.84 2.90 2.88 2.87 2.9 2.88 2.9 2.9
Final STD 0.34 0.12 0.11 0.08 0.18 0.15 0.18 0.09
Final median 2.9 2.9 2.9 2.84 2.9 2.9 2.9 2.9
Bold values indicate that the data which are omitted from final calculation

123
Proficiency Testing in Chemical Analysis of Iron Ore 93

Table 4 Identification of outliers using different methods for SiO2 content in iron ore
Lab ID Lab data Grubbs single Grubbs double t test Z-score MAD based test Dixon Q test Huber test

1 3.67 -0.03 -0.16 -0.89 -0.19 0.09 0.01

2 3.87 0.71 0.66 1.18 0.26 1.91 0.21
3 3.68 0.02 -0.12 -0.78 -0.17 0.18 0.02
4 3.09 -2.14 22.53 26.87 -1.50 25.18 0.13 0.57
5 4.49 2.93 3.19 7.57 1.65 7.55 0.83
6 3.77 0.32 0.25 0.14 0.03 1.00 0.11
7 3.52 -0.56 -0.77 22.43 -0.53 -1.27 0.14
8 – – – – – –
9 3.59 -0.31 -0.49 -1.71 -0.37 -0.64 0.07
10 3.55 -0.46 -0.65 22.12 -0.46 -1.00 0.11
11 3.63 -0.19 -0.32 -1.30 -0.28 -0.27 0.03
12 3.64 -0.14 -0.28 -1.20 -0.26 -0.18 0.02
13 3.53 -0.55 -0.73 22.33 -0.51 -1.18 0.13
14 3.73 0.19 0.09 -0.27 -0.06 0.64 0.07
15 3.56 -0.43 -0.61 -2.02 -0.44 -0.91 0.1
16 3.71 0.12 0.00 -0.47 -0.10 0.45 0.05
17 3.58 -0.34 -0.53 -1.82 -0.40 -0.73 0.08
18 3.66 -0.08 -0.20 -0.99 -0.22 0.00 0
19 3.83 0.54 0.49 0.76 0.17 1.55 0.17
20 3.37 -1.13 21.38 23.98 -0.87 -2.64 0.29
21 5.3 5.89 6.49 15.93 3.48 14.91 0.37 1.64
22 4.1 1.53 1.60 3.55 0.77 4.00 0.44
No of outliers 0 3 4 8 1 3 1 5
Final mean 3.75 3.64 3.68 3.68 3.68 3.71 3.67 3.65
Final STD 0.44 0.12 0.15 0.09 0.27 0.24 0.27 0.10
Final median 3.66 3.64 3.66 3.67 3.65 3.65 3.65 3.65
Bold values indicate that the data which are omitted from final calculation

However, the outlier-corrected standard deviation differed
by up to 66.6 % (range from 0.09 to 0.27).
4. Discussions
In this study, the number of participating laboratories was
low (22). The histograms and Q–Q plots showed tailed
distributions and presence of outliers. The data set there-
fore do not fulfill the criteria of parametric tests in strict
sense as the parametric tests require normal distribution of
the dataset. The problem can be overcome by increasing
the number of participating laboratories in the PT program.
However, in the present study, both parametric and robust
test methods for outlier determination were utilized to get a
more detail information, i.e. which outlier method to be
used and which method should be avoided in a PT pro-
gram, where the number of participating laboratories is
less.
It was found that different outlier tests give different
results. Also, it was observed that several parametric and
robust tests give similar number of outliers. In fact, it was
found that every parametric test has an alternative robust
test. For example, Grubbs single test (parametric) and Box
plot (robust) identified equal number of outliers. So the
number of outliers itself does not give a direct answer
which methods (parametric or robust) should be preferred
in case of PTs with small number of participating labora-
tories. Both parametric and robust methods have stricter
and less strict outlier tests. The number of outliers gives the
idea which outlier test should not be used in case of PTs
with small number of laboratories. It has been proposed
that the maximum number of outliers should not be more
than 2/9 of the whole data set [14]. Based on this, in present
study, all the outlier tests except t test and Huber test were
considered suitable for outlier rejection. The next question
is which outlier test method should be adopted in a PT
program. The choice of the outlier test influences the
consensus value and standard deviation. These two char-
acteristics determine the Z-score of a laboratory result. It
can be seen from Tables 2, 3 and 4 that that the outlier-
corrected averages for Fe (total), Al2O3 and SiO2 do not

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94 S. Chakravarty et al.

Table 5 Final assigned values and targeted standard deviations used

to calculate Z-scores of participating laboratories
Parameter Fe (total) Al2O3 SiO2

Assigned value (Xa) (%) 63.84 2.90 3.64

Targeted standard deviation (s) 0.28 0.12 0.12

Table 6 Z-score of the participating laboratories in the PT Program

Lab ID Z-scores
Total iron Alumina Silica

1 0.46 -0.5 0.25

2 -1.64 2.083333 1.916667
3 -1.64 1 0.333333
4 0.57 4.166667 24.58333
Fig. 4 Box plot for Fe (total) content in iron ore
5 9.75 -0.91667 7.083333
6 -0.54 -1.66667 1.083333
7 0.11 0.833333 -1
8 0.29 0 -0.41667
9 2.36 23.5 -0.41667
10 0.21 0 -0.75
11 0.21 0.666667 -0.08333
12 0.36 0.083333 0
13 0.04 0.75 -0.91667
14 0.07 0.25 0.75
15 0.11 -0.25 -0.66667
16 -0.89 -0.58333 0.583333
17 0.32 -0.41667 -0.5
18 0.68 0.833333 0.166667
19 -1.89 1 1.583333
20 0.71 22.33333 22.25
21 24.68 -0.58333 13.83333
Fig. 5 Box plot for 1 Al2O3 and 2 SiO2 content in iron ore 22 23.71 211.0833 3.833333
Bold values indicate that the data which are omitted from final
vary much although different number of outliers was calculation
rejected following different test methods. Similarly the
median values for Fe (total), Al2O3 and SiO2 remained overview of the data set both for the PT organizers and
practically unchanged after rejection of different number of participating laboratories. In the present study, it was
outliers following different test methods. Therefore, med- observed that t test and Huber test are very strict and
ian values are more stable compared to the mean values if eliminate a large number of outliers from the data set.
outliers are present in a data set and hence is a better choice Therefore, these tests should be avoided for outlier deter-
for the determination of consensus value in a PT program. mination. On the other hand, Dixons Q test and Z-score
In the present case, however, both median and mean values were mild and only rejected one outlier. The Grubbs single
can be considered as the consensus value. On the other test, Grubbs double test, MAD based test and Box plot
hand, the outlier-corrected standard deviation for Fe (total), were the most appropriate tests to determine the outliers in
Al2O3 and SiO2 vary significantly with the choice of the the present study. Accordingly, Grubbs single test was
outlier rejection method (Tables 2, 3 and 4). Therefore, chosen as the method to identify the outliers in the present
multiple outlier test methods should be used to identify the study. Thus, the accepted consensus value for Fe (total) is
outliers in a PT program especially when the number of 63.84 % with standard deviation of 0.28. Similarly for
participating laboratories is less. They complement each alumina and silica, the accepted consensus values are 2.90
other and helps give diverse information and better and 3.64 %, respectively with standard deviation of 0.12

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Proficiency Testing in Chemical Analysis of Iron Ore
for both. The final assigned/recommended values of Fe
(total), Al2O3, and SiO2 and the target values for standard
deviations are tabulated in Table 5. These values were used
to calculate Z-score of the participating laboratories
(Table 6). Among the 22 participating laboratories, Z-
scores of 4 laboratories (Lab 5, 9, 21, and 22) for analysis
of total iron fall outside the acceptable limit of ±2. Simi-
larly, for analysis of alumina, Lab 2, 4, 9, 20 and 22 has
unacceptable Z-scores whereas for silica, Lab 4, 5, 20, 21,
and 22 has unacceptable Z-scores. It is interesting to note
that laboratory 22 has reported unacceptable results for all
the three parameters whereas laboratory 4, 5, 9, 20, and 21
has reported unacceptable results for two parameters.
Laboratory 2 has reported unacceptable result for alumina
only.
Effort was then made to identify the plausible causes for
adverse performance of the above laboratories in the PT
program. It was observed that Laboratory 22, which has
reported unacceptable results for all three parameters, is
not a NABL accredited laboratory. It was advised to them
to go for NABL accreditation so that they will follow
standard procedures for chemical analysis and will use
appropriate certified reference materials to validate their
results. Similarly, laboratory 5, 9, and 20 has not used any
certified reference materials to validate their results.
5. Conclusion
A number of statistical test methods are available for out-
lier detection in a data set depending on the application,
assumptions and number of participating laboratories.
Correct outlier rejection is of utmost importance because
the choice of the outlier tests influences the consensus
value and standard deviation. These two characteristics
determine the Z-score of a laboratory result in a PT pro-
gram. In the present study, five parametric outlier tests
were compared: Dixon’s Q test, Grubbs single test, double
test, t test, and Z-scores. In addition three robust tests as
alternative to parametric tests were chosen: box plot, Huber
test and MAD-based test. The strictness of these outlier
tests varied in a large range. Huber’s test and t test were the
strictest tests which eliminated large number of data as
outliers. Grubbs single test, Grubbs double test, MAD
based test and Box plot were less strict and was found to be
most appropriate in the present case. Dixons Q test and Z-
score were very mild and only rejected one outlier. Mul-
tiple outlier test methods should be used to identify the
outliers in a PT program, especially when the number of
participating laboratories is less. They complement each
other and helps give diverse information and better over-
view of the data set both for the PT organizers and par-
ticipating laboratories. If outliers are present in a data set,
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95
median values is a better choice for the determination of
consensus value in a PT program as medians are more
stable compared to the mean values. The overall perfor-
mance of the 22 laboratories for quantitative analysis of Fe
(total), Al2O3 and SiO2 content in iron ore was satisfactory.
The present PT program provided an external quality
control mechanism to improve the testing capability of the
testing laboratories in elemental analysis of iron ore.
Acknowledgments The authors thank participating laboratories,
Director, CSIR-National Metallurgical Laboratory, Jamshedpur and
Director, CSIR-National Physical Laboratory, New Delhi for their
support for the program.
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