Anal Bioanal Chem (2003) 375 : 496504

DOI 10.1007/s00216-002-1731-y

O R I G I N A L PA P E R

Marie E. Lafargue Max H. Feinberg

Jean-Jacques Daudin Douglas N. Rutledge

Homogeneity check of agricultural and food industries samples

using near infrared spectroscopy

Received: 15 July 2002 / Revised: 8 November 2002 / Accepted: 27 November 2002 / Published online: 12 February 2003
Springer-Verlag 2003

Abstract Samples distributed in proficiency testing schemes (PTS) need to be homogeneous in order to be sure
that if a laboratory has a result different from the other
laboratories, its error can be attributed to its analysis
method and not to its sample. This control must be done
according to the ISO 13528 draft standard before sending
the samples to the laboratories. It can be done by determining homogeneity targets by sub-contracting to accredited laboratories using reference methods, but this engenders logistic and financial problems. That is why a homogeneity check using Near Infrared Spectroscopy (NIR)
has been developed for agricultural and food industries
samples prepared for PTS at Bipea (Bureau Interprofessionnel dEtudes Analytiques). To evaluate the homogeneity among samples, this procedure involves a comparison
of NIR spectra, the determination of global homogeneity
criteria and the use of control charts. The method of control developed and carried out at Bipea allows the rapid
and easy monitoring of the performance of the sample
preparation.
Keywords Homogeneity Near infrared spectroscopy
Spectra comparison Distances Control charts
Samples for PTS

M. E. Lafargue ()
Bipea (Bureau Interprofessionnel dtudes Analytiques),
6/14 avenue Louis Roche, 92230 Gennevilliers, France
e-mail: bipea@wanadoo.fr
M. H. Feinberg D. N. Rutledge
Institut National Agronomique Paris-Grignon,
UMR INAPG-INRA
Ingnirie Analytique pour la Qualit des Aliments,
16 rue Claude Bernard, 75005 Paris, France
J.-J. Daudin
Institut National Agronomique Paris-Grignon,
UMR INAPG-INRA Biomtrie,
16 rue Claude Bernard, 75005 Paris, France

Introduction
Laboratories participate in proficiency testing schemes
(PTS) to control the accuracy of their results. PTS can be
defined as regularly organised interlaboratory comparisons to determine the testing performance of laboratories,
which test the same or similar items. The procedure for a
PTS is as follows: each participant in a given PT scheme
receives a sample prepared by the organiser and has to determine a list of analytes, the results are sent back to the
organiser, data are analysed and conventional true values
and tolerance values are calculated according to a reference procedure. Finally, the participating laboratories can
check their accuracy and detect eventual bias.
The Bureau Interprofessionnel dEtudes Analytiques
(Bipea) is a PTS organiser for agricultural, agro-food and
environmental fields, and counts more than 900 laboratories participating in more than 40 schemes. The requirements for PTS organisers are described in ISO guide 43
[1] and in a new standard under preparation, ISO 13528
draft norm [2].
One of the most important requirements of a PT organiser is to provide homogenous samples. In that way, one
can be sure that if a laboratory has a result different from
that of the other laboratories, its error can be attributed to
its analysis method and not to the particular sample. Complete homogeneity is the state of a batch of a material of
which all the elements are rigorously identical whereas
heterogeneity is the state of a batch of material of which
all the elements are not rigorously identical. Two degrees
of heterogeneity can be distinguished: heterogeneity of
constitution (it is inherent and depends on the nature of
the material) and heterogeneity of distribution (it can be
reduced by homogenisation or increased by segregation)
[3]. From a batch of raw material, various steps of homogenisation and division with the correct equipment allow the preparation of N homogeneous samples.
The aim of the homogeneity control is to check if the
samples are identical before sending them to the laboratories. Therefore, in our context, the homogeneity aimed for

497

is the identity between samples (i.e. the between-sample

similarity). For example, if there is 10% of barley in the
initial batch of wheat, in the end we want to have N samples all with 10% barley and 90% wheat. It is not the
within-sample homogeneity that interests us, but the between-sample homogeneity.
Bipea has been producing samples for more than 30
years and has validated preparation devices which are periodically checked to perform acceptable grindings, homogenisations and divisions. At the moment, however,
the homogeneity of the samples is controlled a posteriori by examining the results of the laboratories. To improve the quality of its services to the member laboratories and to fulfil quality-control requirements, Bipea has
set up a procedure using various methodologies in order
to monitor the homogeneity of the samples before they are
sent to the laboratories.
The procedure is the following for each fabrication: N
samples are prepared and ten samples are taken according
to a sequence depending on the number N. If the ten samples are considered homogeneous after the control then
the complete prepared lot is considered homogeneous and
can be sent to the laboratories. In addition to the homogeneity check before the sending of samples (a priori control), a check of the homogeneity is still done, as before,
by examining the laboratories results (a posteriori control).
The control procedure, based on ten samples taken
over the whole preparation, follows the requirements described in ISO 13528, i.e. analysis in replicate of the ten
control samples taken from the population of samples and
determination of homogeneity targets. According to this
standard, the between-samples standard deviation must be
less than 0.3the standard deviation of the results of a
given proficiency test. In other words, the between-sample variability must represent less than 30% of the total
variability of the proficiency test results. This limit of
30% is of course critical as the nature of the homogeneity
target, its concentration and matrix effects will all influence the variability. However, as it is this value which is
required by the standard, it must be used. Later, thanks to
the results of homogeneity controls, it should become
possible to propose and justify the use of other limits
adapted to specific analytes and products.
Recently, a number of papers dealing with homogeneity checking performed for the certification of reference
materials have been published [4, 5, 6]. They all involve
the determination of the certified analytes. In Bipea PT
schemes, the number of such analytes can be as high as
40. For both practical and financial reasons, it is not feasible to monitor each analyte. Furthermore, to choose a single parameter can be dangerous as samples may be homogeneous with respect to one constituent but heterogeneous
with respect to another.
That is why an alternative approach based on Near Infrared Spectroscopy (NIRS) was investigated. NIRS is a
well established technique for the analysis of cereals and
agro-food products. NIRS permits non-destructive, rapid,
cheap and direct analysis (without sample preparation)

and gives global information about the chemical composition of the product (not limited to just one analyte). NIRS
is widely applied for quantitative analysis of chemical
constituents such as protein content, moisture and fats in
cereals, animal feeds, fats, meat and milk, as well as carbohydrates in fruit juices and alcohol in beverages [7, 8].
The aim of this paper is to present the methodology for
the NIRS control of homogeneity of agricultural and food
products.

Materials and methods

Samples
The samples that can be checked by NIRS are presented in Table 1.
They are divided into two groups: solids analysed by reflection
such as cereals, oilseeds, animal feeds and human foodstuffs on the
one hand, or liquid and pasty products analysed by transmission
such as beverages and molasses on the other hand. In the present
paper, flour and alfalfa will be treated. All the samples monitored
are taken during the preparation of the N samples for PTS as described in the introduction.
Analytical method
Depending on the nature of the products, the preparation of the
samples and the NIR measurements are different and have been
adapted after testing various presentations of the products to the
NIR beam in order to have good quality NIR measurements (i.e.
reproducibility of the measurements, acquisition of spectra without
signal saturation).
The sampling of the control samples is done very carefully in
order to ensure the representativeness of the analysed product. Hall
noted the influence of the sample dividing method on forage quality measured by NIRS [9].
Solid and pulverulents products
If necessary before division, in case of very heterogeneous products such as pellets of alfalfa, grinding is done with a laboratory
mill (Model 3600, Perten Instruments). Each controlled sample
which may be as big as 1.5 kg is sub-divided and two sub-samples
with masses between 100 and 250 g, according to the product, are
conserved. A rifles divisor is used for seeds (wheat, rapeseed ...)
and a rotary separator for ground products and pulverulents (semolina, ground animal feeds...). The two sub-samples are analysed
by NIRS in a quartz cell (3 or 9 cm diameter).
Liquid and pasty products
As water is the main constituent of the liquids and pasty products,
it is necessary to have a very thin optical pathlength as water absorbs a lot in the near infrared zone. To obtain such conditions, the
liquid and pasty products are sub-sampled in vials after agitation
and drops, taken with Pasteur pipettes, are put onto 0.1 m Thoma
cells (used normally for microscope cell countings) and covered by
a slide. In the case of carbonated liquids like ciders, sparkling wine
or cola, decarbonation by agitation is necessary.
A Fourier Transform near infrared spectrometer (Bruker Vector 22N/C) equipped with an integration sphere is used for the NIR
measurements. Solid and pulverulent samples are analysed by diffuse reflection whereas liquid and pasty products by transmission.
Sub-samples are randomly analysed and the spectra are recorded
with the OPUS acquisition software (Bruker). Due to instrumental
limitations, the studied spectral range is 9000 to 3800 cm1 (or

498
Table 1 Products controlled by the near infrared technique
Analysis by:

Family of products

Products

Reflection

Cereals

Common and durum wheat

Barley
Maize
Semolina, flour
Rapeseed
Sunflower
Linseed
Soybean
Corn gluten feed
Sunflower, soybean, peanut and rapeseed cakes
Pig, chicken, rabbit and turkey feed
Premix
Pets foods
Milk substitute
Fish flour
Desiccated green forages
Hay
Dehydrated alfalfa
Peas, horse and broad beans
Baby food
Meal substitute
Chocolate powder
Milk powder
Tomato paste

Oilseeds

Animal feeds

Food pulses
Human Food

Transmission

Alcoholic beverages

Non alcoholic beverages

Molasses

Wines (red, white, ros, dry white, sparkling, sweet, aromatized)

Spirits (cognac, whiskey, rum, calvados, aniseed spirit, tequila, crude alcohol)
Liqueur wines (Porto)
Ciders
Fruit juices and nectars (orange, tomato, grape)
Syrups (mint, grenadine)
Colas, sodas
Sugar cane, sugar beet

1111 to 2631 nm) for the reflection mode and 10,500 to 5200 cm1
(or 952 to 1923 nm) for the transmission mode. The resolution is
fixed at 8 cm1 and each spectrum is the average of 32 scans of the
sub-sample. The sample holder is continuously rotated in the reflection mode, whereas in transmission mode the sample is static.
To take into account possible differences between the superficial layer which interacts with the infrared beam, and the rest of
the product, three spectra are acquired for each sub-sample after
remixing. These three repetitions are not done successively, neither are the two sub-samples.

is necessary to perform mathematical pretreatment such as Standard Normal Deviate (SNV) already presented by many authors
[11, 12]. In our application, the aim is to verify that the samples are
homogenous both with respect to their chemical composition and
to their granulometry. That is why both pretreated and raw spectra
are analysed in the study. To illustrate this, Figs. 1 and 2 present
spectra of wheat flour and of alfalfa. For spectra acquired by transmission, scattering is not a problem because of the nature of the
products (liquids and pasty). Spectral processing is done using the
Opus (Bruker) and JMP (SAS Institute) software.

Spectral data processing and pretreatment

Methods applied for homogeneity checking

The spectra obtained in NIRS can be considered as multivariate

fingerprints of the chemical and the physical properties of the
analysed product. In diffuse reflection spectroscopy, the spectrum
is affected by the principal factors:
1. non-specific light scattering from the surface of the sample,
2. the variable spectral pathlength through the products, and
3. the chemical composition of the products.
The first two sources are related to the physical properties of the
products (particles size and distribution) and account for the majority of the variance between spectra, while variance due to chemical composition is usually small [10]. In order to reduce the effect
of scatter and enhance the contribution of chemical composition, it

Comparison of spectra
For classical near infrared applications, chemical parameters such
as the protein or moisture content of wheat or flour are determined.
In our application, instead of determining these parameters, which
involves lengthy calibration and validation steps, the idea is to
compare the entire spectrum of each samplea spectrum being
considered as the physical and chemical fingerprint of the product,
and for this reason, much richer in information than a single calculated parameter. The assessment of the homogeneity among samples is therefore done by comparing their spectra. However, this
comparison of entire spectra requires the definition of a similarity
criterion. Two metrics were selected for testing:

499

Fig. 1 Wheat flour NIR spectra. (A) Raw spectra. (B) SNV pretreated spectra
Dmax calculated from the Euclidian distance between each spectrum and the average spectrum (d2 (i,m)=[SijSmj]2), computed
for each series of ten control samples. Dmax is the maximal distance (Dmax=maxd2 [i,m]) and is considered as a measure of the
dispersion of the samples;
the Standard deviation spectrum (S spectrum) calculated from
the ten spectra obtained for each series of ten control samples.
The S spectrum shows the variability between the control samples at each absorbency and is also considered as a measurement
of the homogeneity between samples.
In order to decide if the difference between samples is or is not significant, it is necessary to have threshold limits: if the Dmax and the
S spectrum are within the defined limits then it can be concluded
that the differences among samples is not significant. Using set of
homogeneous samples from Bipeas PTS, these thresholds were
estimated. To detect outlier samples, control charts like those used
for quality control were applied as described below.
Application of the control chart method to homogeneity checking
The theory of control charts has been extensively presented by several authors [13, 14, 15, 16, 17] and will not be addressed here.
Two types of control charts were used in this study, usually called
the mean chart (X bar chart) and the standard deviation chart
(S chart). Basically a control chart consists of a Central Line (CL)
for the target value, close to which the measurements are expected
to remain, and the upper and intermediate limits for control and
warning, respectively.
For the homogeneity control, the target value is set to zero as
the parameter measured is a degree of homogeneity but the Central
Line is plotted nevertheless because it represents the average degree of homogeneity. Only the upper control limit is plotted because the lower limit is the zero (which cannot be reached because
perfect homogeneity does not exist in nature...).

Fig. 2 Alfalfa NIR spectra. (A) Raw spectra. (B) SNV pretreated
spectra
The standard formulae used to calculate the limits are:
For the X bar chart:
Upper Control Limit UCL = CL + 3s/n
Upper Warning Limit UWL = CL + 2s/n
where s is equal to the standard deviation of the process under control and n the number of replicates.
For the S chart:
Upper control limit: Fs (F depending on the number of replicates, values of F found in Ref. [17]) with s as the standard deviation of the process under control.
For these calculations, data distribution is assumed to be Normal,
which needs to be checked. If the data are not Normally distributed, the risk of wrongly rejecting a point outside of the limits will
change. Normality was tested with KolmogorovSmirnov test and
Normal probability plot [17].
Two parameters are required to set up a mean chart and define
the limitsa centre line defined by the average level of homogeneity and a standard deviation that measures the accepted variability between homogeneous samples. These parameters must be
determined when the process, here the preparation of the samples,
is under control, that is, the process is producing homogeneous
samples. The parameters are estimated for each kind of product using sets of control samples from preparations judged homogeneous
based on the results of PT Schemes.
To illustrate the setting up of control charts, the example of the
Flour/Alveograph PTS is taken:
eighteen sets of ten wheat flour control samples from eighteen
different preparations were available,
analysis of each set under conditions of repeatability (each set
was analysed three times),
calculation of the three values of Dmax for each set, corresponding to the three repetitions,
calculation of the average Dmax (or central line of the chart) with
the 54 (318) values of Dmax,

500
Table 2 Flour. Results of the setting up of the Dmax chart (on raw
spectra)
Number of sets of control samples
Number of replicates
Average Dmax (central line)
Standard deviation of Dmax
Upper warning limit (UWL)
Upper control limit (UCL)

18
3
0.16
0.03
0.19
0.21

calculation of the variance within each set (with the three Dmax
values calculated) and then the average of the eighteen variances
to obtain the final variance. Its square root gives an estimate of
the final standard deviation,
calculation of the warning and control limits.
The results are presented in Table 2 for raw data and can be used to
build Dmax charts for raw data. These steps are repeated for the data
pretreated by normalization and SNV. Such charts are established
for each kind of product.
It was determined from the Normality tests that the Dmax plotted on the control charts are not distributed Normally but follow a
Gamma probability distribution function. As the limits are based
on the assumption of Normality, it is necessary to evaluate the risk
of wrongly rejecting a data (Type I error).
With Normally distributed data and a classical control chart:
The risk of having a data point wrongly between the warning
limit and the control limit is equal to 2.3% and not 4.6% (probability=95.4 when k=2) because only the upper limit is used
(one-sided risk),
The risk of having a data point wrongly below the control limit
is equal to 0.135% and not 0.27% (probability=99.73 when k=3)
because only the upper limit is used (one- sided risk).
With data distributed according to a Gamma law, the computations
gave:

results. In order to validate this homogeneity check by NIRS, determination of the homogeneity targets by the reference methods
have been done for each PTS. These analyses were subcontracted
to accredited laboratories, except of course when an accreditation
program for a given analysis did not exist. Analyses of variance
were performed on the results to estimate whether the differences
among samples were statistically significant and to calculate the
between-samples standard deviation (Se). The Se value must represent less than 30% of the total variability of the given PTS results.

Results
Examples of control charts for wheat flour and alfalfa
The setting up of the control charts with definition of the
limits was done with the control samples of the 1999/2000
and 2000/2001 campaigns. A campaign begins in July and
ends in June and generally there is a proficiency test each
month for each scheme, except in July and August. During the 2001/2002 campaign, the control charts were used.
Each month, the control samples were analysed by NIRS,
and Dmax and S spectra were calculated from the spectra.
Figures 3 and 4 show D max charts for 2 different schemes
and 2 products in particular: Flour from the Flour/Alveograph PTS and alfalfa from the Forages PTS. Each month
between September 2001 and May 2002, a D max is plotted. For both products, the Dmax are within the control lim-

The risk of having a data point wrongly between the warning

limit and the control limit is between 3 and 5% depending on the
values of the Gamma law parameters,
The risk of having a data point wrongly below the control limit
is between 0.3 and 2% depending on the values of the Gamma
law parameters.
Therefore, the risk to say wrongly that samples are not homogeneous, because Dmax is wrongly below the control limit, is higher
than if the Dmax were Normally distributed (2% instead of
0.135%). The value of 2% is a risk for Bipea to reject a preparation
(Type I error) and it is acceptable and has then non-incidence for
the customers (laboratories).
For the setting up of the S charts, the same principle is followed. For each set of control samples, an S spectrum is calculated
and the average S spectrum is determined and the upper control
limit calculated. The data plotted on the charts are the standard deviation spectra. As for the case of the Dmax chart, an S chart is created for the wheat flour. S charts were also created for the other
products and for each pretreatment.
Samples acceptance rules and validation
The control limits determined for the Dmax charts and the S charts
can be used to judge whether control samples are homogeneous. If
the Dmax and the S spectrum found by near infrared analysis for a
given control of homogeneity are within the fixed limits, then the
set of samples will be considered homogeneous and the total
preparation will be also. If they are outside the limits, there is a
risk of heterogeneity. In this case, there are several possibilities:
destruction of the samples and start of a new preparation, analysis
by reference methods, integration of the heterogeneity into the PT
results (i.e. extension of the tolerance values).
The sets of control samples taken from preparations are considered to be identical following the processing of the laboratories

Fig. 3 D max charts for the Flour/Alveograph PTS on wheat flour,

campaign 2001/2002. (A) Raw spectra. (B) SNV pretreated spectra

501

Fig. 5 Standard deviation charts for the Flour/Alveograph PTS on

wheat flour, December 2001 and April 2002. (A) Raw spectra.
(B) SNV pretreated spectra

Fig. 4 Dmax charts for the Forages PTS on alfalfa, campaign 2001/
2002. (A) Raw spectra. (B) SNV pretreated spectra

its, which allows us to conclude that the samples are not

significantly different. It is noticeable that the information
given by parts A and B of each figure are different: part A
(on raw data) underlines homogeneity due to granulometry whereas part B concerns homogeneity due to chemical
composition. Therefore, for the wheat, Fig. 3, it appears
that differences between samples are caused more by their
granulometry characteristic than by their chemical composition.
Those conclusions are confirmed by the S charts in
Figs. 5 and 6. With the new data acquired during the campaign 2001/2002, the limits of the charts will be calculated again to improve them and this will be repeated at
the end of each campaign. The results without pretreatment (part A of the figure) and the results with SNV pretreatment (part B of the figure) can be compared, the former reflecting more the particle sizes and distributions
while the latter reflects the chemical composition. The S
spectra in Figs. 6 and 7, part A, show that the spectral
variations follow the raw spectra presented in Figs 1 and
2, part A: the intensity variation is constant along the
spectral range. On the contrary, the S spectra in Figs 6 and
7, part B, are not constant along the spectral range and
there are some zones more variable than others. This
means that the differences between spectra due to granu-

Fig. 6 Standard deviation charts for the Forages PTS on alfalfa,

December 2001 and April 2002. (A) Raw spectra. (B) SNV pretreated spectra

502

Fig. 8 Standard deviation charts for the Baking test PTS on

wheat, January 2002. (A) Raw spectra. (B) SNV pretreated spectra
Fig. 7 Dmax charts for the Baking test PTS on wheat, January
2002. (A) Raw spectra. (B) SNV pretreated spectra

larity are almost constant along the spectral range,

whereas the differences due to the chemical composition
change along the spectral range.
Furthermore, it is noticeable that the Dmax values and
the S spectra are higher for alfalfa than for flour: the Dmax
chart centre lines are equal to 0.16 (raw data) and 0.14
(SNV data) for flour and 0.55 (raw data) and 0.48 (SNV
data) for alfalfa. This can be explained by the greater degree of inherent heterogeneity of alfalfa compared to
flour, for both chemical composition and granularity.
Performance of the control of the checking procedure
For the Baking ability test PTS, samples of common
barley are prepared and sent to the participating laboratories for analysis of the wheat and of the flour obtained.
During the campaign 2001/2002, a control was able to detect the presence of a few percentage of barley in the samples of common wheat. Dmax and S spectrum are plotted in
the charts in Figs 7 and 8 for the control performed in January 2002. They are all outside of the control limits and it
could be concluded that there was a problem of heterogeneity among the samples. Actually, it turned out that the
wheat contains a small percentage of barley and that the
quantity of barley present was not sufficient for it to be

Fig. 9 Schematic representation of sampling for infrared analysis

of two samples of wheat containing the same small amount of barley. The analysed surface of the two samples obtained after division is not the same

uniformly distributed among the samples to give representative samples of the product. This is summarised in
Fig. 9 where two wheat samples containing six barley
seeds are sampled to be analysed. The surface of the prod-

503
Table 3 Flour and alfalfa. Results of the control by reference method with protein content (expressed in g/100 g) as
homogeneity target

Sample

January 2001
Wheat Flour

1
2
3
4
5
6
7
8
9
10
Mean
Repeatability standard deviation, Sr
Between samples standard deviation, Ss
Assigned value of the PTS
Robust standard deviation of the PTS,
(Ss/)100
F value
Critical value of F

uct scanned by the infrared light is different for the two

samples because there is not enough barley to have representative sub-samples.
To solve the problem, the barley was removed from
each sample manually and the sub-samples were analysed
again. The new Dmax and S spectra are reported in the
charts in Figs. 8 and 9 (control 2). The result is clear: the
samples are not significantly different after removing the
small quantity of barley. Another solution would be to
grind the samples in order to have homogeneous and representative sampled product. It is noticeable that the difference between the wheat samples containing barley is
due not only to the chemical composition but also to the
granularity, as shown in Figs. 8 and 9.
Validation with reference methods
A series of control samples were sent to accredited laboratories for the determination of homogeneity targets. The
results of the analyses are shown in Table 3 for the flour of
the PT of January 2001 and for the alfalfa of February
2001. The homogeneity target for both flour and alfalfa is
the protein content (expressed as %).
According to the ISO 13528 standard, the ratio (expressed as %) of the between-samples standard deviation
to the total standard deviation of the PTS must be below
30%. The calculated ratios are 9.4% for the flour and
16.9% for the alfalfa which are below the threshold value.
Furthermore, the observed F values obtained by analysis of variance are less than the critical F value (3.02) for
both products. Thus, the results of the control show that
the samples are not significantly different for that homogeneity target, i.e. protein content. It can be concluded

February 2001
Alfalfa Pellets

Rep. 1

Rep. 2

Rep. 1

Rep. 2

9.52
9.51
9.48
9.52
9.51
9.51
9.48
9.48
9.47
9.51

9.49
9.52
9.57
9.5
9.53
9.54
9.48
9.48
9.46
9.51
9.50
0.02
0.01
9.52
0.14
9.4
0.23
3.02

24.4
24.0
24.7
24.4
24.5
24.1
24.8
24.4
24.8
24.0

24.9
24.5
24.7
24.3
24.4
24.4
24.2
24.2
24.6
24.0
24.4
0.2
0.1
23.6
0.6
16.9
1.99
3.02

that the samples may be considered homogeneous; this

means that all the manufactured samples may be considered homogeneous for a given proficiency test. It can be
noted that the degree of heterogeneity is higher for the alfalfa than for the flour, as was found in the previous control charts. Since homogeneity among the samples depends largely on the nature of the product, it may be advisable to adapt the value of 30% prescribed in the norm
as a function of the product: for some products the requirement should be lower, for others it may need to be
higher.

Discussion and conclusion

The method of control by NIRS presented in the paper is
suitable to check the homogeneity of the samples manufactured for Bipeas PTS. Actually, it is characterised by:
polyvalent technique adapted to numerous products,
rapid analysis,
non-expensive analyses, and
simple decision rules (use of control charts).
With this control by NIRS, it is possible to have a quick
response in case of heterogeneity problems without being
dependent on external conditions such as the response delay of subcontractors.
The application of pretreatments permits to distinguish
heterogeneity due to the granularity from that due to the
chemical composition. The limit of the technique is the
impossibility to detect compounds present in very small
quantities, such as vitamins or mycotoxins. It is generally
admitted that the limit of detection of the NIR technique is
usually about 0.5 to 1% of a compound in the product;

504

this means that only heterogeneity due to chemical constituents such as moisture or protein content can be easily
detected. The heterogeneity due to compounds present as
traces (vitamins, minerals...) and contaminants cannot be
detected by the technique. If the steps of preparation of
the samples give homogeneous samples for all the major
chemical constituents, then it is reasonable to think the
other constituents should be homogeneous too. This hypothesis could be verified for some trace compounds for a
limited number of products, but it is difficult to do so for
all the products and all traces. The choice of homogeneity
targets is sometimes difficult and the comparison of the
complete spectra could be a solution to avoid this, even if
it is not perfect (i.e. small quantity of barley in wheat).
To demonstrate the performance of NIRS to detect
small differences between samples, studies of heterogeneous samples, artificially manufactured, are currently being carried out at Bipea.
In the future, the method of homogeneity checking by
NIRS will be extended to other products such as oils and
fats. It will be interesting to apply the procedure to samples prepared for besatz (impurities) determination PTS,
in order to see the capacity of the technique to detect impurities, such as damaged grains, foreign seeds...

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Geneva, Switzerland

2. ISO 13528 (2000) (working document) Statistical methods for

use in proficiency testing by interlaboratory comparisons. International Standardisation Organisation, Geneva, Switzerland
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