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Validation of the performance of process stream analyzer systems with

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Accred Qual Assur (2014) 19:185–193
DOI 10.1007/s00769-014-1053-8
PRACTITIONER’S REPORT
Validation of the performance of process stream analyzer systems
with nonparametric behavior
Aerenton Ferreira Bueno • Deborah Aparecida Flores Ozaki • Eduardo Barbosa •
Evandro Evangelista dos Santos • Maura Moreira Gomes • Patrı́cia Hiromi Iida •
Soraia Cristina Almeida dos Santos • Fagner Geovani de Sá • Elcio Cruz de Oliveira
Received: 3 January 2014 / Accepted: 8 April 2014 / Published online: 9 May 2014
 Springer-Verlag Berlin Heidelberg 2014
Abstract Literature describes several procedures based
on statistical principles to validate whether the degree of
agreement between the results produced by a stream ana-
lyzer system—systems for determining chemical and
physical characteristics by continual sampling, automatic
analysis, and recording or otherwise signaling of output
data—and those produced by an independent test mea-
surement procedure, which purports to measure the same
property, meets user-specified requirements. However,
these documents always consider that the data gathered
during validation procedure are normally distributed, and
this supposition it is not always true. The aim of this
manuscript is to develop four different procedures applied
to data with nonparametric behavior. The most represen-
tative validation procedure compares measures of position
and dispersion, using typical process samples, while the
less representative one compares only measures of posi-
tion, using a reference sample. These nonparametric data
are also treated using parametric statistics for comparison.
The results show that different conclusions can be reached
when the nonparametric data are treated as parametric. A
A. F. Bueno  D. A. F. Ozaki  E. Barbosa 
E. E. dos Santos  M. M. Gomes  P. H. Iida 
S. C. A. dos Santos  F. G. de Sá
Petróleo Brasileiro S.A., Rio de Janeiro, Brazil
F. G. de Sá  E. C. de Oliveira
Post-Graduation Metrology Programme, Metrology for Quality
and Innovation, Pontifical Catholic University of Rio de Janeiro,
Rio de Janeiro, RJ 22453-900, Brazil
E. C. de Oliveira (&)
Petrobras Transporte S.A., Av. Presidente Vargas,
328, Rio de Janeiro, RJ 20091-060, Brazil
e-mail: elciooliveira@petrobras.com.br
new Brazilian standard is being carried out based on this
subject, in order to complement the international standards.
Keywords Validation  Performance 
Stream analyzer systems  Nonparametric data
Introduction
With the increasing industrial automation, off-line ana-
lyzers (bench or laboratory analyzers) have been replaced
by online analyzers or stream analyzer systems for the
following advantages: high speed, continuous monitoring
suitable for closed-loop control; better accuracy due to
absence of sample manipulation and human error, and less
exposition to risk and hazardous samples.
In this work, a total analyzer system design addresses the
chemical and physical properties of the process or product
stream to be measured, provides a representative sample, and
handles it without adversely affecting the value of the spe-
cific property of interest. Moreover, it includes a sample
loop, piping, hardware, a sampling port, sample conditioning
devices, analyzer unit instrumentation, any data analysis
computer hardware and software, and a readout display [1].
However, when a new stream analyzer is initially
installed, or after major maintenance has been performed, a
set of tests must be performed to demonstrate that the
analyzer meets the manufacturer’s specifications, the his-
torical performance standards, and the specification limits
set by the process being analyzed. These diagnostic tests
may require that the analyzer be adjusted so as to provide
predetermined output levels for certain certified reference
materials (CRMs) or compared with other reliable ana-
lyzers [1]. This practice is considered in this manuscript as
‘‘validation.’’
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186 Accred Qual Assur (2014) 19:185–193

Validation can be defined as a statistically quantified

judgment, so that the analyzer system or subsystem being
assessed can produce predicted primary test method results
with acceptable precision and bias performance when
compared with actual results from a primary test method
measurement system for common materials [2].
The literature quotes several international standards to
validate the performance stream analyzer systems [1, 3–5].
ASTM D6708 [6] and ASTM D7235 [7] are also cited for
data treating. However, all of them deal specifically with
Gaussian data.
In 2004, a nonparametric statistics study, focused to
sampling in atmospheric chemistry, has been carried out
[8].
The aim of this manuscript is to develop procedures to
validate the performance of the stream analyzer systems
with nonparametric behavior, because this is a common
situation in real-life data, for example, more than 60 % in
oil and gas online analyzers in Brazil.
Fig. 1 Selection of the validation procedure
Procedures
The validation procedure should be selected according
Some definitions are required:
to Fig. 1.
• Reference Test (RT): Measurement procedure used in
the laboratory or portable analyzer to produce reliable Revision of the nonparametric statistical analysis
results under control, which can be compared with
those obtained by the process analyzer (PA); Median absolute deviation (MAD)
• Process Typical Sample (PTS): Sample obtained from
the process stream so as to represent the typical This test applies to data set with behavior that departs from
characteristics of the product; normality and is an important robust univariate spread
• Reference Sample (RS): primary standard, mixing/ measure [9]. In these situations, Grubbs’ test is not
dilution of standards, CRMs or sample from interlab- recommended.
oratory comparisons; The median absolute deviation is considered as a mea-
• Validation Sample (VS): Sample used in the validation sure of statistical dispersion. Moreover, the MAD is a
procedure. It may be a PTS or RS whose parameter of robust statistic, being more resilient to outliers in a data set
interest does not change significantly during the
validation procedure.
Fig. 2 Flow diagram for each procedure: Procedure A (a), Procedure c
Validation is divided into two steps: initial validation B (b), Procedure C (c), and Procedure D (d). a This procedure can be
and continual validation. Continual validation is necessary considered as the best situation, because the validation is most
in order to guarantee that, after initial validation, the stream representative. The results from the analyzer for a set of typical
analyzer systems continue in conformance to CRMs or process samples are obtained, and these same samples are mandato-
rily tested by a reference test. Results are evaluated by specific
other reliable analyzers. Statistical process control (SPC) statistical tests, in order to compare measures of position (paired data)
chart monitoring is carried out with new production sam- and dispersion. b This procedure uses synthesized samples in the
ples. However, continual validation is not treated in this laboratory or reference samples, when it is not possible to obtain
manuscript. typical process samples. The validation process uses comparison of
position (unpaired data) and dispersion measures necessarily using a
reference test. c In this procedure, it is not possible to introduce a
Initial validation validation sample into the analyzer, so dispersion measures cannot be
taken. Comparison of position measures (paired data) necessarily
Initial validation is defined as a relationship between the using a reference test or typical process samples is carried out.
d When there is no reference test available, this procedure is
analyzer results and RT, RS, or PTS. Depending on the recommended. The confidence interval from a reference sample is
approach, the initial validation can be carried out by the compared to the confidence interval derived from the process analyzer
combination of the RT, RS, and PTS. only for position measures

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Accred Qual Assur (2014) 19:185–193 187

(a) (b)

(c) (d)

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188 Accred Qual Assur (2014) 19:185–193

Table 1 Measurement results of zinc mass concentration in eight A more logical approach to a robust analysis, focused
samples of health food (x2,i using EDTA titration, x1,i using atomic set of data with non-normal behavior, can be based on the
spectroscopy) and their difference di
concept of a distance function. A robust estimate of the
i x2,i (mg L-1) x1,i (mg L-1) sgndi |di| (mg L-1) variance [10] of xi values can be obtained from MAD,
Eq. (1):
1 7.2 7.6 –1 0.4
2 6.1 6.8 –1 0.7 MAD ¼ medianjxi  median ðxi Þj ð1Þ
3 5.2 4.6 1 0.6 For the suspect result (lowest or higher value of a set of
4 5.9 5.7 1 0.2 data), x0, if jx0  median ðxi Þj=MAD provides results
5 9.0 9.7 –1 0.7 greater than 5, is rejected being considered as an outlier.
6 8.5 8.7 –1 0.2 For instance, considering the data set (0.380, 0.400,
7 6.6 7.0 –1 0.4 0.401, 0.403, 0.410, 0.411, 0.413), the median of these
8 4.4 4.7 –1 0.3 numbers is 0.403, given in bold font. The absolute ordered
Sgn is the sign function deviations calculated from the median are 0.000, 0.002,
0.003, 0.007, 0.008, 0.010, and 0.023. The MAD is the
median of these seven numbers, that is, 0.007, Eq. (1). For
Table 2 Example of Wilcoxon signed-rank test applied to the data the lowest value of the set one finds, |0.380–0.403|/
presented in Table 1: ordering by absolute difference |di|
0.007 = 3.3, what is lower than the limit 5, and therefore,
i x2,i (mg L-1) x1,i(mg L-1) sgndi |di| (mg L-1) Ri Ri sgndi this value is not considered an outlier [10].
4 8.5 8.9 –1 0.2 1.5 –1.5
6 5.9 5.7 1 0.2 1.5 1.5 Wilcoxon signed-rank test
8 4.4 4.7 –1 0.3 3 –3
1 7.2 7.6 –1 0.4 4.5 –4.5 The Wilcoxon signed-rank test is a nonparametric statisti-
7 6.6 7.0 –1 0.4 4.5 –4.5 cal hypothesis test used as an alternative to the paired
3 5.2 4.6 1 0.6 6 6 Student’s t test, t test for matched pairs, or the t test for
2 6.1 6.8 –1 0.7 7.5 –7.5
dependent sets of data when the population cannot be
5 9.0 9.7 –1 0.7 7.5 –7.5
assumed to be normally distributed [11].
For each pair set, the value of the first set of data is
Bold fonts indicate positive differences di clearly associated with the respective value of the second
set of data. These differences are sorted in ascending
order, and orders are given to them if they are different
Table 3 Example of Wilcoxon rank-sum test
from zero. If two or more differences are identical, the
average order used is that which would have been used if
Measurement Silver Rank Measurement Silver Rank
procedure concentration procedure concentration the observations had differed. Considering a set of sam-
(lg mL-1) (lg mL-1) ples of which the same property is measured using two
different procedures, the difference between the mea-
2 7.7 1 1 9.8 6
surement results for each sample is evaluated and sorted
2 8.0 2 2 9.9 7
with increasing absolute value thus attributing order
2 9.0 3 1 10.2 8
numbers (excluding zero differences). These numbers
1 9.5 4 1 10.5 9
denote the rank Ri unless the absolute differences for two
2 9.7 5 1 10.7 10
or more samples are equal, when the average rank is
attributed to each of them. This is exemplified in Tables
1 and 2 with mass concentration values of zinc, deter-
than the standard deviation, mostly used in parametric mined by two different measurement procedures, for each
statistic. In the standard deviation calculations, the dis- of eight samples of health food [10].
tances from the mean are squared, so large deviations are The ranking of these results presents an additional
weighted more heavily, and thus, outliers can strictly worry, that of tied ranks, as 0.2, 0.4, and 0.7. In such cases,
influence it. In the MAD, the deviations of a small number it is worth verifying that the ranking has been done cor-
of outliers are irrelevant (Fig. 2). rectly by calculating the sum of all the ranks without regard
The median value separates an equal number of higher to sign, so each gets the average of those ranks, 1.5.
values from lower values of a set of data, a population, or a The sum of ranks of positive differences (in bold) is 7.5,
probability distribution, from the lower half. It is recom- whereas the sum related to negative ranks amounts to 28.5.
mended when the data are not parametric. A systematic difference between the data sets x2,i and

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Accred Qual Assur (2014) 19:185–193 189

Table 4 Numerical example of Test of Moses, 2 groups with 3 subsamples each

2 P 2 P
Subsample X ðX  XÞ ðX  XÞ ðX  XÞ ¼ D21i Rank

Group 1
1, 10 5.5 -4.5, 4.5 20.25, 20.25 40.5 4.5
10, 0 5.0 5.0, -5.0 25.00, 25.00 50.0 6
9, 0 4.5 4.5, -4.5 20.25, 20.25 40.5 4.5
2 P 2 P
Subsample X ðX  XÞ ðX  XÞ ðX  XÞ ¼ D22i Rank

Group 2
4, 4 4.0 0.0, 0.0 0.0, 0.0 0.0 1
5, 6 5.5 -0.5, 0.5 0.25, 0.25 0.5 2.5
5, 6 5.5 -0.5, 0.5 0.25, 0.25 0.5 2.5

x1,i must be assumed if the smaller sum is below a critical
value, which for 8 pairs and a probability of 0.05 is 3 [10].
Obviously, the data of the example do not provide evidence
for a systematic difference between the two measurement
procedures.
Wilcoxon rank-sum test
The Wilcoxon rank-sum test is a nonparametric alternative
to the two set of data t test which is based solely on the
order in which the observations from the two sets of data
fall [12].
This statistical test proposes to compare mean values for
two groups (sizes n1 and n2) that are not correlated. The
variances of the groups should be evaluated if they are
statistically identical or different.
Let X11, X12,…, and X21, X22,…, be two independent
random sets of data of sizes n1 B n2 from the contin-
uous populations X1 and X2, that is, populations in
which a random variable is measuring a continuous
characteristic.
The test procedure is as follows. Arrange all n1 ? n2
observations in ascending order of magnitude and assign
ranks to them. If two or more observations are tied (iden-
tical), use the mean of the ranks that would have been
assigned if the observations differed.
Considering W1 as the sum of the ranks in the smaller set
of data, and W2 as the sum of the ranks in the other set of
data [13], then
W2 ¼ ððn1 þ n2 Þ  ðn1 þ n2 þ 1Þ=2Þ  W1 ð2Þ
As an example [11], a sample photographic waste was
analyzed for silver by atomic absorption spectrometry, five
successive measurements giving values of 9.8, 10.2, 10.7,
9.5, and 10.5 lg mL-1, measurement Procedure 1, without
chemical treatment. After chemical treatment, the waste
was analyzed again by the same analytical technique, five
successive measurements giving values of 7.7, 9.7, 8.0, 9.9,
and 9.0 lg mL-1, measurement Procedure 2.
These data are analyzed in ascending order and ranked
as shown in Table 3.
The sum of the ranks for measurement Procedure 1 is
W1 = 4 ? 6 ? 8 ? 9 ? 10 = 37, and for the measure-
ment Procedure 2 is W2 = ((5 ? 5)  (5 ? 5 ? 1)/2) -
37 = 18.
Since neither W1 nor W2 is less than or equal to
W0.05 = 17 [13], there is not a statistically significant dif-
ference between both measurement procedures for a
confidence level of 95 %.
Test of Moses
This statistical test attempts to compare the variability
(dispersion) from two independent populations, when at
least one of them presents non-normal distribution [14].
The observations of each group are randomly distributed
to their respective subgroups m1 and m2.
The sum of the squares of the differences is calculated
P 2 P 2
Dji ¼ Xi  X and sorted increasingly (progres-
sively, gradually), and orders are given. If two or more
observations are identical, the average of the orders due to
different observations is used, where X is the average of all
P
Xi values. Note that the notation D2ji represents the sum
of the squared difference scores of the ith subsample in
each Group j. Here, a subsample is a set of scores derived
from a sample.
The ranks of each group, R1 and R2, are separated into
their respective groups with their respective sums equal to
P P
R1 and R2, subsamples m1 and m2, scores k and
n = mk.
Here, we use an example, Table 4, based on a result of
the small set of data, with each subsample comprised of
k = 2 scores, m1 = 3 subsamples for Group 1, and m2 = 3
subsamples for Group 2. Since n1 = n2 = 32 = 6, 12

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Table 5 Comparing parametric and nonparametric tests Table 6 Comparing mean and median of ammoniacal nitrogen results
from ten different samples by parametric and nonparametric tests
Aim/statistical test Normal Non-normal
distribution distribution Process analyzer (PA) [mg L-1] Reference test (RT) [mg L-1]

Outliers Grubbs’ test Median absolute 8.6 10.4

deviation (MAD) 3.7 4.2
Comparing means/medians Paired t test Wilcoxon signed- 2.1 2.5
rank test 2.3 2.1
Comparing means/medians Unpaired Wilcoxon rank-sum 0.9 1.1
(unpaired samples) t test test 1.3 1.4
Comparing dispersion F-Fischer– Moses 0.8 1.2
measures Snedecor 0.8 1.0
Confidence interval t test Bonett-Price 0.9 1.2
0.8 0.9
Parametric statistics Nonparametric statistics
subjects are employed in the analysis. In this instance, it is
used a table of random numbers to select the scores for Paired t test Wilcoxon signed-rank test
each of the subsamples. tcalculated = 2.237 Wcalculated = 4.00
X \ tcritical = 2.262 \ Wcritical = 8.00
R ¼ 4:5 þ 6 þ 4:5 ¼ 15 and There is not a statistically There is a statistically significant
X1
significant difference difference between the medians
R2 ¼ 1 þ 2:5 þ 2:5 ¼ 6:
between the means

U1, U2, and U are calculated as:

m1  ðm1 þ 1Þ X
U1 ¼ m1  m2 þ  R1 Table 7 Precision evaluation of results from ten replicate measurements
2
3  ð3 þ 1Þ of ammoniacal nitrogen concentration in the same sample by parametric
¼33þ  15 ¼ 0 ð3Þ and nonparametric tests
2
m2  ðn2 þ 1Þ X Process analyzer (PA) [mg L-1] Reference test (RT) [mg L-1]
U2 ¼ m1  m2 þ  R2
2 8.6 8.2
3  ð3 þ 1Þ
¼33þ 6¼9 ð4Þ 8.6 8.6
2
8.5 8.5
Ucalculated is the minimum value between U1 and U2: 8.6 8.6
Ucalculated ¼ min ðU1 ; U2 Þ ¼ 0 8.5 8.5
As Ucalculated ¼ 0  Ucritical ¼ 0, there is not a statisti- 8.6 8.6
cally significant difference between the variances of 8.5 8.5
Groups 1 and 2. 8.5 8.5
8.6 8.6
Test of Bonett-Price [15] 8.7 8.4
SWcalculated = 0.8021 SWcalculated = 0.7733
This test is applied to data sets with nonparametric distri- \ SWcritical = 0.8420 \ SWcritical = 0.8420
butions. In this situation, the confidence interval is based Non-normal distribution Non-normal distribution
on a linear function of medians of the population.
Parametric statistics Nonparametric statistics
The median (Md) of the data set and estimation the
variance, varMd , are calculated by F-Fischer–Snedecor Moses
  2 Fcalculated = 3.417 Ucalculated = 11.00
varMd ¼ Yðnaþ1Þ  YðaÞ 2z \ Fcritical = 3.179 [ Ucritical = 2.00

Y(i) represents the quantitative score of the response vari- There is a statistically There is not a statistically
significant difference significant difference
able in the position i (ordered). between the variances between the variances
a and z are tabulated, in function of the data number and
level of significance [15].
The confidence interval, CI, can be calculated by: 48.64, 51.40, 59.91, 67.98, 79.13, and 103.5. The median,
CI ¼ Md  za=2 ðvarMd ޑ Md, is 51.4. Referring to values of parameters for the Price–
A simple example is related to the salt concentration in Bonett variance estimate [15]: n ¼ 9; a ¼ 2 and z ¼ 2:064:
waste water, expressed in lg mL-1: 13.53, 28.42, 48.11, Y(9-2?1) = Y(8) = 79.13; Y(2) = 28.42.

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Accred Qual Assur (2014) 19:185–193 191

Table 8 Precision and comparing mean and median evaluations of results from the same sample for ethane determination by parametric and
nonparametric tests

Process analyzer (PA) [mmol/mol] Reference test (RT) [mmol/mol]

0.102 0.102 0.103 0.102

0.102 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102 0.102
0.103 0.102 0.102
0.103 0.102 0.102
0.102 0.102 0.102
SWcalculated = 0.591 \ SWcritical = 0.887 SWcalculated = 0.311 \ SWcritical = 0.866
Non-normal distribution Non-normal distribution
Parametric statistics Nonparametric statistics

F-Fischer–Snedecor Moses
Fcalculated = 2.98 [ Fcritical = 2.62 Ucalculated = 4.00 [ Ucritical = 1.00
There is a statistically significant difference between the There is not a statistically significant difference between the
variances variances
Unpaired t test Wilcoxon rank-sum test
tcalculated = 1.656 \ tcritical = 2.056 Wcalculated = 3.05 [ Wcritical = 1.96
There is not a statistically significant difference between the There is a statistically significant difference between the
means medians

The variance estimator, varMd ,
  2
varMd ¼ Yðnaþ1Þ  YðaÞ 2z
¼ ½ð79:13  28:42Þ=ð2  2:064Þ2 ¼ 150:91:
A 95 % confidence interval, CI ¼ Md  za=2 ðvarMd ޑ ¼
51:4  1:96ð150:91ޑ ¼ ð27:33; 75:47Þ.
Experimental
Four case studies, one for each procedure, are discussed in
this work.
Data were collected from Alberto Pasqualini Refinery,
Canoas, Brazil.
In the first study, ammoniacal nitrogen concentration in
effluent samples is determined by RT and PA. Validation is
performed using Procedure A. The process analyzer is GLI
International (IL, USA), model 750-500 ion selective
electrode whose work range is 0–20 mg L-1. The mea-
surement procedure is based on Standard Methods 4500.
In the second study, ethane amount of substance fraction
in the same sample hydrogen recycle is determined by RT
and PA. Validation follows Procedure B. The process
analyzer is a Yokogawa (Tokyo, Japan) chromatograph,
model GC 1000 Mark II, work range 0–1 mmol/mol. The
measurement procedure is correlated to UOP 539.
The next study involves flash point in diesel oil. The
process analyzer is an integrated flash point, Precision
Scientific Petroleum Instruments (IL, USA), model 45624,
work range 10–121 C. The measurement procedure is
correlated with ASTM D93.
For the last study, propane amount of substance fraction
in a reference sample of hydrogen recycle is determined by
PA, validated by Procedure D and compared with the
certified result. The process analyzer is a Yokogawa
chromatograph model GC 1000 Mark II, work range
0–1 mmol/mol. The measurement procedure is correlated
with UOP 539.
Results and discussion
Nonparametric data from case studies are calculated by
both parametric and nonparametric tests, Table 5. Before
choosing one of these tests, it is necessary to assess whe-
ther or not the data follow a normal distribution. In this
work, the Shapiro–Wilk test, named as SW, is used to check
deviation from normality/normal distribution [16].
All calculations are conducted by Microsoft Excel, and
critical values are based on a confidence level of 95 %. No
value is considered as an outlier by Grubbs and MAD tests.
Case study: Procedure A
Comparison of mean and median is evaluated by ten dif-
ferent samples that are analyzed by PA and RT. The mass

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concentrations are shown in Table 6. Shapiro–Wilk test
for the differences of each pair, between PA and RT:
SWcalculated = 0.7253 \ SWcritical = 0.8420. The distribu-
tion is non-normal.
Precision is evaluated by comparing ten results of the
same sample that is analyzed either by PA or RT. The mass
concentrations and the results treated by parametric and
nonparametric tests are shown in Table 7.
Case study: Procedure B
Precision and mean/median are evaluated by the same
sample. PA and RT use sixteen and thirteen replicates,
respectively. The amount of substance, comparing preci-
sion (variance) and mean/median evaluations by
parametric and nonparametric tests, is shown in Table 8.
Case study: Procedure C
Only, comparison of mean and median is evaluated in this
procedure. Ten different samples analyzed by PA and RT are
compared. The flash points and comparison of mean and
median by parametric and nonparametric tests are shown in
Table 9. Shapiro–Wilk test for the differences of each pair,
between PA and RT: SWcalculated = 0.8294 \ SWcritical =
0.8420. The distribution is non-normal.

Table 9 Comparison of mean and median of flash point results from ten different Case study: Procedure D
samples by parametric and nonparametric tests

Process analyzer (PA) [C] Reference test (RT) [C] Only, comparison of mean and median by parametric and
nonparametric tests is evaluated in this procedure. A con-
40.0 39.0
fidence interval derived from twenty-three replicates of a
40.0 41.0
41.0 41.0
reference sample analyzed by PA is compared with the
41.0 41.0 certified value. The amount-of-substance fraction is shown
40.5 40.0 in Table 10.
39.5 39.5
43.0 43.0
Conclusions
43.0 43.0
41.5 41.5
42.0 41.0 New procedures for performance validation of process
stream analyzer systems have been developed to deal with
Parametric statistics Nonparametric statistics
nonparametric data. The procedures can be applied to all
Paired t test Wilcoxon signed-rank test common situations faced in that activity, such as non-
tcalculated = 0.818 \ tcritical = 2.262 Wcalculated = 4.00 \ Wcritical = 8.00
availability of a reference test, impossibility of introduction
There is not a statistically There is a statistically significant
significant difference between the means difference between the medians of the validation sample in the analyzer, and non-avail-
ability of a typical process sample. From the studied

Table 10 Comparison of mean and median of replicates of a reference sample for propane determination by parametric and nonparametric tests

Process analyzer (PA) [mmol/mol]

0.3011 0.3030 0.3041

0.3020 0.3030 0.3040
0.3020 0.3030 0.3052
0.3030 0.3030 0.3050
0.3029 0.3030 0.3050
0.3030 0.3030 0.3060
0.3030 0.3030 0.3061
0.3030 0.3030
SWcalculated = 0.8531 \ SWcritical = 0.9140
Non-normal distribution
Parametric statistics Nonparametric statistics
t test Bonett-Price

Process Analyzer (PA) 0.3029–0.3040 0.3025–0.3035

Reference Sample (RS) 0.3037–0.3043 0.3037–0.3043
There is not a statistically significant There is a statistically significant
difference between the means difference between the medians

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Accred Qual Assur (2014) 19:185–193
examples, it is possible to observe that when parametric
statistics are applied to nonparametric data, different
results can be obtained, leading to wrong conclusions,
which highlight the importance of the use of the right
statistics in each case. This manuscript can be very useful
for readers to understand better this subject given that
international standards do not foresee and deal with it. In
2014, this study will be part of a new Brazilian standard in
order to cover this deficiency.
Acknowledgments This work was supported by Petrobras, and the
original idea and the meetings to elaborate it were sponsored by
Márcia Beatriz Ruiz Del Frari, manager from Products Engineering
and Oil Stockpiling of the Downstream-Refinery.
References
1. ASTM D 3764 (2009). Standard practice for validation of the
performance of process stream analyzer systems. American
Society for Testing and Materials, West Conshohocken
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