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Commission of the European Communities


Community Bureau of Reference

bcr information
REFERENCE MATERIALS

The certification of
a tomato paste colour
reference tile
CRM 400
Commission of the European Communities
Community Bureau of Reference

bcr information
REFERENCE MATERIALS

The certification of
a tomato paste colour
reference tile
CRM 400

M. Kent
Torry Research Station
Aberdeen, UK

F. Malkin
Ceram Research Ltd
Stoke-on-Trent, UK

J.F. Verrill
National Physical Laboratory
Teddington, UK

D.J. Henshall
Campden Food Research Association
Chipping Campden, UK

PARI L'JilCP Lbliolh.


Directorate-General
Science, Research and Development c.CoH IS.SSS
1991 EUR 13392 EN
OfKjO'f-C T j 0
Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General
Telecommunications, Information Industries and Innovation
L-2920 Luxembourg

LEGAL NOTICE
Neither the Commission of the European Communities nor any person acting on
behalf of the Commission is responsible for the use which might be made of the
following information

DISCLAIMER
Whenever, in this report, a commercial product is identified by the
manufacturer's name or label, such identification should in no instance
be taken as an endorsement by the Commission or as an indication that
the particular product or equipment is necessarily the best available
for the particular purpose

Cataloguing data can be found at the end of this publication

Luxembourg: Office for Official Publications of the European Communities, 1991

ISBN 92-826-2403-X Catalogue number: CD-NA-13392-EN-C

© ECSC-EEC-EAEC, Brussels • Luxembourg, 1991

Printed in Belgium
Page
CONTENTS

1 Introduction

1.1 Background 1
1.2 Determination of tomato paste colour 2
1.3 Specification of the tiles 3

2 Participants

2.1 Preparation of tiles and homogeneity studies 4


2.2 Stability studies 4
2.3 Certification measurements 4
2.4 Primary reference measurements 4
2.5 A method for the colour measurement of unsalted tomato paste 4

3 Preparation of Tiles

3.1 Prototype tiles 5


3.2 Production of the tiles 5
3.3 Visual selection 6
3.4 Study of the need for preliminary irradiation 6
3.5 Study of influence of temperature on L,a,b values 7
3.6 Presentation of reference tiles g

4 Homogeneity of the Batch

4.1 Methods 9

4.2 Results 10

5 Stability

5.1 Long term stability 14

6 Certification of the Individual Tiles

6.1 Strategy 16
6.2 Preliminary calibration of the master tomato tiles 16
6.3 Results for master tomato reference tile (GM89) 17
6.4 Uncertainties in the calibration of the master tomato reference tile 25
6.5 Certified individual reference values and their uncertainties 26
6.6 Colorimeters calibrated in other scales 27
7 Instructions for Use

7.1 Precautions to be taken in handling and storing the tile 28


7.2 Use for calibration 28
7.3 Frequency of calibration 28

Annex A A Method for the Colour Measurement of Unsalted Tomato Paste/


Concentrate

A.l Introduction 31
A.2 Scope and field of application 31
A.3 Materials 31
A.4 Apparatus 31
A. 5 Sampling and samples 32
A.6 Procedure 32

— III —
Annex B Intercomparison of Laboratories and Instruments

B.l Participants 35
B.2 Design of experiment 36
B.3 Results 37

References 41

— IV —
1 INTRODUCTION

1.1 Background

A recent European Community (EC) sponsored project in the field of Physical

Properties of Foods (COST90bis) looked at the various problems associated with

colour measurement of foodstuffs. In particular the measurement of the colour

of tomato paste was judged to be of prime economic importance within the EC

and justified some research effort. The Community production of tomato paste

was valued at 600 Mecu in 1986. Accordingly several laboratories in Europe

collaborated in a programme of intercomparison of colour measurements. These

laboratories were representative of not only State institutes but also

academic and industrial laboratories. The results of these exercises were

finally published in the proceedings of the conference which terminated the


• .(1)
projectv
.

Two important proposals of interest to the tomato industry arose out of this

work. They concerned (a) the need for standardisation of the method of colour

determination of tomato paste and (b) the production of a reference having a

colour close to that of a good quality tomato paste product. In the first of

these proposals, Brimelowv ' suggested a protocol for colour determination,


(3)
a problem also addressed by Hils .

Part of this protocol requires the existence of a suitable reference colour

tile, proposal (b) above. Such a tile would not be for use as a target colour

for tomato paste but for the essential calibration of instruments. Obviously

the closer it is in colour to the product it represents then the more useful

it will be as a calibrant.
The Commission undertook, to produce and certify such a reference tile which is

now available as CRM 400.

1.2 Determination of Tomato Paste Colour

Although there is still no officially recognised European method for the

measurement of tomato paste colour, tomato paste is traded with colour as a

quality criterion. This criterion is adopted for two major reasons, (1) the

colour of the raw tomato is an important indicator of maturity and hence

flavour, and (2) the colour of tomato paste is of obvious importance for food

products and is modified by the processing and storage conditions.

The need to have a common procedure for measurement of colour has been

recognised at both national and company levels and several schemes have been

devised, particularly in the USA. Such systems involve conversion from

measurements of tristimulus colour values to a recognised United States

Department of Agriculture colour score. The conversion factors very often

depend on the type of instrument used.

However, these widely used scoring systems are based on measurements carried

out on fairly dilute pastes (8.5 X total soluble solids (TSS)) and as was

found in the C0ST90bis work, the problems associated with translucency and

colour measurement are more severe at such dilutions than say at 12 X TSS, ,a

dilution at which the Bostwick consistency testv is carried out as a further

quality vector. Colour tiles developed in the USA for calibration of

instruments therefore have colour values which are somewhat removed from those

expected in a good quality tomato paste at the higher soluble solids

concentration of 12 X TSS. In line with the conclusions of the C0ST90bis

studies improved accuracy will be achieved by use of a reference tile which is

much closer in colour to that of a typical tomato paste.


1.3 Specification of the Reference Colour Tiles

This report describes the preparation of ceramic reference tiles suitable for

calibration of colorimeters used for tomato paste colour measurement. The

target values were chosen taking account of recommendations of the C0ST90bis

work and after consultation with industrial users of tomato paste. These

values are considered to be typical of good quality paste diluted to 12 X

total soluble solids content (TSS) and were, in Hunter L,a,b units^ '

L = 24.5±2.0, a = 32.0±2.0 and b = 14.0±0.5 with a typical a/b ratio 2.3±0.1.

It is stressed that these values were chosen exclusively for the purpose of

specifying the target values for the reference tile and do not in anyway

provide a definition of "good quality" tomato paste.

3-
2 PARTICIPANTS

2.1 Preparation of Tiles and Homogeneity Studies

Ceram Research Ltd, UK

2.2 Stability Studies

Torry Research Station, UK

2.3 Certification Measurements

Ceram Research Ltd, UK

2.4 Primary Reference Measurements

National Physical Laboratory, UK

2.5 Analytical Method for Paste/Concentration

Campden Food and Drinks Research Association, UK

4-
3 PREPARATION OF THE TILES

The Tomato Paste Reference Tiles were produced in the laboratories of Ceram

Research using the techniques developed for the production of the Colour

Standards which are certified and sold by the National Physical Laboratory

(NPL) <6><7>.

3.1 Prototype Tiles

Initial laboratory trials were carried out to determine the mixture of

pigments required to match the target colour. Instrumental colour matching

techniques were used to aid these trials. As none of the commercially

produced red pigments were strong enough for the task, it was necessary to

rely on batches of red pigment specially produced in the laboratory for the

purpose. It was possible to meet the target specifications by blending the

red pigment batches with either black, or reddish-brown pigments. However, the

recipe including the brown pigment gave a closer match to the spectral curve

of tomato paste. At this point two prototype tiles were produced from this

brown pigment for evaluation.

3.2 Production of the Tiles

The unglazed tiles used for the reference tiles were 101 x 101 x 8 mm nominal

size. They were rigorously selected for the purpose and checked to ensure

that the finished glaze tiles would have a slight convex curvature, and so

would fit properly to the aperture of an instrument.

The bulk glaze was prepared and adjusted to give a satisfactory colour

consisting of a proprietary mixture of 7.25 X red pigment and 0.48 %

reddish-brown pigment in a high lead glaze.

-5
The glaze was applied to the 'biscuit' tiles using a laboratory waterfall

dipping line. Two coatings of glaze were applied, with the tile turned

through 90° between coatings, to ensure an even thickness of glaze.

Sufficient glaze was applied to give a fired glaze thickness of 0.30 mm.

The tiles were fired to 1060 °C with a 4 hour soak in an electric intermittent

kiln fitted with a microprocessor control system. As the kiln only holds some

600 tiles it was necessary to carry out three dipping and firing cycles to

produce sufficient glazed tiles. To check how well the firings repeated, a

sample of 30-40 tiles was taken from each firing and measured on the Hunterlab

Colorimeter. The mean colour values for each firing agreed very closely,

within ± 0.05 unit for L and b, and ±0.1 unit for a. All the tiles could

therefore be merged into one batch. In all some 1700 tiles were produced.

3.3 Visual Selection

As the tiles were taken from the kiln they were given an initial visual

selection. Those with obvious physical or visual faults (eg cracks,

blemishes, damaged edges) were discarded. A more rigorous inspection of the

tiles was made in the laboratory in better lighting conditions. This resulted

in a final selection of 1399 good tiles.

3.4 Study of Need for Preliminary Irradiation

It is normal to allow glazed tiles to stabilize for a period of 2-3 months

after production before using them as colour standards. To check the Tomato

Reference Tiles, 20 tiles were measured in two batches of 10 tiles each at

weekly intervals from the 4th week after production to the 10th week. The

standard deviations of the overall means of the results for the batch

designated as batch 'A' were for L, +0.02, for a, +0.04 and for b, +0.02.
Laboratory temperature fluctuated between 23.0 °C and 24.7 °C during the

measurements.

Part way through these tests the tiles in batch B were irradiated under

artificial daylight lamps for 18 hours at a level of illumination of 500 lux.

Comparison of the overall means of batch A and batch B after irradiation

showed no significant effect (AL = 0.07, Aa = 0.03 and Ab = 0.01). It was

therefore deemed not necessary to irradiate the tiles before calibration.

(This is in line with experience gained in the production of the red tile in

the Ceramic Colour Standards produced by Ceram Research in conjunction with

NPI/ . However as will be seen in Section 5, long-term intense illumination

produces some slight changes.

3.5 Study of the Influence of Temperature on L,a,b Values

The thermochromism of the tiles was investigated in a simple experiment using

the Hunterlab Colorimeter. The surface temperature of a tile was measured

using a digital thermometer with a ribbon surface probe. The tile was placed

on the colorimeter and a reading was taken immediately. Readings were then

taken over a 15 minute period when the tile was removed and the surface

temperature again determined. During the experiment the temperature of the

tile surface rose by 4.3 °C. The corresponding changes in colorimeter

readings are shown in Table 1.

-7-
Table 1 Thermochromic changes in L,a,b values

Change in Hunter L,a,b values and


equivalent colour difference AE*

Temp change/°C AL Aa Ab AE
Actual change +4.3 -0.18 -0.23 -0.13 0.32

Resultant temp +1 -0.042 -0.053 -0.030 0.074


coefficient

* AE = /AL2 + Aa2 + Ab2

The changes expected for a 1 °C temperature rise quoted above are calculated

on the basis of the well established fact that thermochromic changes are

linear with temperature with no observable hysteris .

These values are confirmed by further studies of the thermochromism of the

tiles made by NPL over a temperature range of 20-35 °C (NPL certificate of

calibration ref 1222190038B).

3.6 Presentation of Reference Tiles

Each tile has been sealed into a protective plastic backing tray to guard

against any risk of contamination of the porous tile body which might affect

its calibration. These backing trays carry the inscription 'BCR Reference

Tile'.

For permanent identification the number of the tile has been inscribed on one

corner of the front of the tile. The label fixed to the back of the tile

carries the number of the tile and its individual Hunter L, a and b values.

The Tomato Paste Reference Tiles are supplied in a fitted storage case.

8-
HOMOGENEITY OF THE BATCH

4.1 Methods

The instrument used to study the homogeneity of the batch was a Hunterlab

Colorimeter, D25-9, which has a measurement aperture of 51 mm diameter. It

was calibrated for the Illuminant C/2° observer combination^ . Illumination

of the sample was by twin opposed beams incident at 45° while the detectors

were mounted normal to the sample. The Colorimeter was linked to a micro-

computer for data handling. All measurements were made in the Hunter L,a,b

system^5* at 25 °C.

The instrument repeatability of measurements on the Tomato Reference Tile was

determined by carrying out 11 measurements on a randomly selected tile at

intervals on the same day during calibration sessions.

The day-to-day repeatability of measurements was determined by measuring 20

tiles on 4 occasions over a period of 8 days. A separate tile was designated

as a reference tile to calibrate the colorimeter in this region of colour

space prior to each set of measurements to minimise the affects of instrument

drift and thermochromism. The standard deviations of the different types of

repeatability measurements are shown in Table 2.

The effects of rotation were studied by 5 sets of measurements made at

30 minute intervals on the tiles placed correctly on the instrument, then

subsequently with them rotated through 90°, 180°, 270° and 360° in the

horizontal plane. The standard deviations of these measurements are shown in

Table 2 also. To obtain the total uncertainty at the 95% confidence level the

standard deviations in Table 2 are combined in quadrature and multiplied by

2.1 (see 6.5).


Table 2 Standard deviations for Hunter L,afb values

L a b a/b
Instrumental Repeatability 0.005 0.012 0.006 0.001
Day-to-Day Repeatability 0.04 0.06 0.03 0.003
Orientation Repeatability 0.04 0.12 0.03 0.012
Overall 0.056 0.135 0.043 0.012

The individual measurements on c. 1400 tiles could not be carried out in one

session. Therefore one tile was measured and used as a reference in all other

measurements to overcome the effects of instrument drift. Prior to

measurement all the tiles were cleaned and numbered. The calibration of the

Colorimeter was checked at intervals during each measurement session by use of

NPL reference tiles.

4.2 Results

On examination of the results (which showed a skewed distribution) it was

decided to remove the tiles with a-values below 32.25 (146 tiles) and those

with a-values above 33.25 (21 tiles) from the batch. This left a final batch

of 1232 tiles accepted for use as Tomato Reference Tiles.

The mean and range of L,a,b values for these 1232 tiles are given in Table 3

together with original target values for comparison. Values are illustrated

in Figures 1 and 2. The mean L value is within the required production

tolerance from the target value, and the mean a,b and a/b-values are very

close to the target values.

10
16

15

14
Hon

13

12

11 J I I I
29 30 31 32 33 34 35
a

Figure 1 Mean colour for the tomato reference tile;


Hunter a, b diagram

11
27

26 P.
/
Production
mean
25 —

T.

/
24 Target colour

23 — ^ T o l e r a nee

22 1 1 1 1 f
29 30 31 32 33 34 35
a

Figure 2 Mean colour for the tomato reference tile;


Hunter a, L diagram

12
Table 3 Tomato Paste Reference Tiles - Mean and range of L,a,b values
accepted for the final batch and compared with target range

L a b a/b
Targe t max 26.5 34.0 16.0 2.34
Target min 22.5 30.0 12.0 2.24
Batch mean 26.05 32.80 14.44 2.27
Production max 26.42 33.25 14.63 2.30
Production min 25.41 32.25 14.22 2.23

-13
5 STABILITY

5.1 Long Term Stability

Fifteen tiles have been taken, divided into 3 groups and stored in the

following conditions:

- 2°C in the dark and sealed against moisture condensation.

- 27°C under artificial daylight illumination of 2300 lux.

- 27°C in the dark.

Measurements are being made on all 15 tiles at monthly intervals over a period

of 2 years using a Hunterlab D25 colorimeter with M type reflectance head. In

this instrument the illumination is at 45° and the reflectance is measured at

0° to the normal. The illuminant is illuminant C and measurements are

referred to the 1931 2° standard observerv '. In order to take account of any

instrument fluctuation due to lamp fading or any other cause, the colour

differences are first determined relative to a standard pink enamel plaque

whose stability has been verified over some years. From Table A it can be

seen that those tiles stored in the dark at 2°C and 27°C suffered no

significant changes in L,a,b values over the period of 394 days; significant

that is both with respect to the quoted uncertainties in the certified Hunter

L,a,b values and with respect to the instrument repeatability (Table 12,

Section 6.5). The large excursions from the means at 231 days were probably

due to accidental contamination of the white standard used for calibration. A

comparison of the standard deviations of the measurements made during the

period of 394 days shows comparable values for both sets of tiles stored in

the dark and for the pink enamel standard. The fluctuations that occurred

were due to instrument variation and emphasize the importance of using a

reference colour. The tiles stored under illumination however show a marked

-14
decrease in L, a and b values reflected in the larger standard deviation of

the mean measurements. Changes of -0.2, -0.4 and -0.1 were observed in L, a

and b respectively over the first 2 weeks of storage for those tiles in bright

illumination. Thereafter there seems to be a steady slower change,

especially in a-value. The study continues.

Table 4 Mean L,a,b values for th« 5 tiles in each batch compared with those for a reference pink enamel
til* (Standard No C2-13669, Hunter Associates Lab Inc., Fairfax, Virginia)

Tomato Reference Tiles

Reference Pink
Enamel Tile Illuminated at 27°C Dark at 27°C Dark at 2°C

Days

0 68.96 23.92 12.16 26.04 32.97 14.51 26.06 32.98 14.51 25.85 12.73 1L 4 . 4 5

6 68.94 23.89 12.19 25.83 32.55 14.29 26.00 32.91 14.43 25.83 12.70 1L4.41

27 68.96 23.85 12.20 25.88 32.50 14.29 26.02 32.88 14.44 25.86 12.65 ]L4.41

50 68.85 23.73 12.26 25.75 32.33 14.32 2S.99 32.75 14.47 25.95 12.65 :L4.52

70 68.92 23.68 12.28 25.82 32.28 14.34 26.08 32.77 14.53 26.02 12.59 ]L4.55

98 68.79 24.02 12.06 25.59 32.44 14.16 25.82 33.01 14.39 25.76 12.88 3L4.40

125 68.90 23.99-- 12.07 25.63 32.40 14.18 25.88 32.99 14.41 25.87 12.91 ]L4.47

147 68.87 23.92 12.13 25.65 32.38 14.22 25.90 32.94 14.43 25.88 12.84 1L4.48

184 68.96 23.85 12.17 25.69 32.29 14.21 25.96 32.89 14 . 4 6 25.95 12.80 ]1 4 . 5 0

231 68.83 24.07 12.02 25.50 32.32 14.08 25.69 32.92 14.31 25.81 12.94 11 4 . 4 3

288 68.96 23.78 12.22 25.64 31.97 14.08 25.84 32.64 14.33 25.88 12.64 IL4.42

336 68.83 23.88 12.10 25.63 31.92 14.07 25.84 32.71 14.40 25.79 12.59 JL4.42

363 68.93 23.87 12.12 25.67 31.87 14.07 25.88 32.69 14.40 25.85 12.58 1L4.44

394 68.90 23.77 12.13 25.77 31.71 14.06 25.94 32.66 14.45 25.87 12.53 IL4.<«

Mean 68.90 23.87 12.15 25.72 32.28 14.21 25.92 32.84 14.43 25.87 12.72 1 4.4:
s.d. +0.06 +0.11 +0.08 ±0.14 ±0.3 2 + 0.13 +0.11 ±0.13 +0.06 ±0.07 >t 0 . 1 4 ito.o;

15
6 CERTIFICATION OF THE INDIVIDUAL TILES

6.1 Strategy

The certification of L,a,b values of each tile depends upon the use of a

single colorimeter at Ceram Research, the calibration of which is directly

traceable to NPL (see 6.5)

6.2 Primary Calibration of a Master Tomato Tile

One of the tiles close to the mean colour has been designated Tomato Master

Tile (Ceram Research number 126: NPL number GM89) and has been calibrated by

NPL for various geometries (NPL Certificate of Calibration Ref 1222190038A,

8th October 1990).

A Cary 14 spectrophotometer fitted with a Cary 1411 reflection attachment and

coupled to an on-line data system, was used to measure the tile at 5 nm

intervals over the spectral range 380 nm to 780 nm. The half height bandwidth

varies continuously during the scan falling from a value of 0.5 nm at 780 nm

to 0.2 nm at 500 nm and then rising to 0.8 nm at 320 nm. An area 17 mm x 5 mm

in the centre of the tile was used. Measurements were made in the normal/

diffuse (0/d: specular excluded), 8°/total (8/t: specular included) and 0°/45°

geometries. The reference was an MS 20 opal glass which had been calibrated

relative to the perfect reflecting diffuser. Measurements were made in the

sequence reference scan, sample scan, reference scan. The dark reading was

subtracted from each reading. The reflectance relative to the reference was

calculated as the sample reading divided by the mean of the reference

readings. Values were then multiplied by the known absolute reflectance of

the opal to give absolute spectral reflectance values.

16-
The spectral curve for this Master Tile and for the 0°/45° geometry is shown

plotted in Figure 4 where it is compared with the curves for a tomato paste

sample and an enamel standard which is currently used for tomato paste colour

measurement.

NPL measurements are traceable to the Physikalische Technische Bundesanstalt

(PTB) scale of diffuse reflectance.

Note: for security, one other tomato tile has also been likewise calibrated

by NPL and is stored at a separate location.

6.3 Results for Master Tomato Reference Tile (GM89)

Spectral reflectance values with respect to the perfect reflecting diffuser

are given in Tables 5, 7 and 9. Colorimetric data are given in Tables 6, 8

and 10 in the CIE x, y, Y system together with u' v' and CIELAB values.

Results are quoted for a temperature of 25 °C.

- 17
60
BCR M a s t e r T i l e

Tomato paste sample


/
50 - Enamel r e f e r e n c e tile /
/

* 40

u
O
*♦■ 30
<D
U
c
D

D 20

10

0
400 500 600 700

Wavelength (nm)

Figure 3 Spec
t ral curves measured using the 0°/45° geometry, for BCR
Master tile, a tomato paste sample and an enamel red tile
currently used as a tomato reference colour.

18
Table 5
Spectral Reflectance Factors (%) for 0/d geometry for
Tomato Reference Tile GM89 (Ceram Research No 126)

Wavelength Reflectance Wavelength Reflectance


(nm) (Z) (nm) (2)
600 13.13
380 0.68 605 16.98
385 0.70 610 20.54
390 0.73 615 23.45
395 0.76 620 25.72

400 0.81 625 27.52


405 0.85 630 28.97
410 0.90 635 30.20
415 0.96 640 31.36
420 1.00 645 32.47

425 1.04 650 33.54


430 1.08 655 34.55
435 1.12 660 35.47
440 1.16 665 36.43
445 1.21 670 36.40

450 1.25 675 38.46


455 1.30 680 39.62
460 1.34 685 40.69
465 1.39 690 41.42
470 1.43 695 42.01

475 1.47 700 42.73


480 1.51 705 43.69
485 1.56 710 44.79
490 1.61 715 45.87
495 1.65 720 46.98

500 1.69 725 47.97


505 1.72 730 48.95
510 1.77 735 49.88
515 1.84 740 50.77
520 1.94 745 51.64

525 2.07 750 52.38


530 2.21 755 53.14
535 2.34 760 53.75
540 2.46 765 54.28
545 2.57 770 54.72

550 2.67 775 55.08


555 2.76 780 55.42
560 2.84
565 2.96
570 3.16

575 3.51
580 4.15
585 5.26
590 7.03
595 9.64

19
Table 6
Colorimetric Data
Geometry 0/d
Tomato Paste Reference Tile GM89 (Ceram Research No 126)

2 Degree Observer

x y Y(%) u' V' L* a* b*


Illuminant A 0.6432 0.3387 9.13 0.4453 0.5275 36.2 45.1 42.1

Illuminant C 0.5787 0.3409 6.52 0.3901 0.5171 30.7 40.4 33.5

Illuminant D65 0.5790 0.3447 6.44 0.3874 0.5189 30.5 41.9 33.0

10 Degree Observer

X y Y(%) u' V L* a* b*
Illuminant A 0.6365 0.3454 8.96 0.4336 0.5294 35.9 41.1 42.1

Illuminant C 0.5712 0.3463 6.20 0.3800 0.5183 29.9 38.1 . 32.5

Illuminant D65 0.5719 0.3499 6.13 0.3778 0.5201 29.7 39.3 32.1

20-
Table 7
Spectral Reflectance Factors (%) for 8/t geometry
for Tomato Reference Tile GM89

Wavelength Reflectance Wavelength Reflectance


(nm) (Z) (nm) (Z)
600 19.31
380 7.11 605 23.19
385 7.12 610 26.70
390 7.12 615 29.54
395 7.13 620 31.79

400 7.16 625 33.54


405 7.18 630 34.94
410 7.21 635 36.18
415 7.25 640 37.30
420 7.28 645 38.42

425 7.31 650 39.47


430 7.35 655 40.43
435 7.37 660 41.36
440 7.40 665 42.27
445 7.44 670 43.25

450 7.46 675 44.30


455 7.49 680 45.46
460 7.53 685 46.52
465 7.57 690 47.26
470 7.60 695 47.80

475 7.63 700 48.55


480 7.67 705 49.49
485 7.70 710 50.59
490 7.75 715 51.67
495 7.78 720 52.73

500 7.81 725 53.74


505 7.84 730 54.70
510 7.88 735 55.63
515 7.95 740 56.54
520 8.04 745 57.38

525 8.15 750 58.12


530 8.29 755 58.85
535 8.42 760 59.46
540 8.54 765 59.98
545 8.63 770 60.42

550 8.72 775 60.81


555 8.81 780 61.09
560 8.89
565 9.00
570 9.19

575 9.54
580 10.20
585 11.32
590 13.13
595 15.78

21 -
Table 8
Colorimetric Data
Geometry 8/t
Tomato Paste Reference Tile GM89 (Ceram Research No 126)

2 Degree Observer

X y Y(%) u' V L* a* b*

Illuminant A 0.5729 0.3628 15.20 0.3691 0.5260 45.9 34.3 22.1

Illuminant C 0.4426 0.3271 12.60 0.2931 0.4874 42.2 28.4 15.9

Illuminant D65 0.4452 0.3355 12.52 0.2902 0.4921 42.0 29.4 15.7

10 Degree Observer

X y Y(%) u' V' L* a* b*


Illuminant A 0.5681 0.3672 15.03 0.3624 0.5271 45.7 31.0 21.9

Illuminant C 0.4351 0.3308 12.28 0.2853 0.4881 41.7 26.3 15.1

Illuminant D65 0.4383 0.3388 12.22 0.2833 0.4927 41.6 27.1 14.9

22
Table 9
Spectral Reflectance Factors* (%) for 0°/45° geometry for
Tomato Reference Tile GM89

Wavelength Reflectance Wavelength Reflectance


(nm) (%) (nm) (*)

575 3.47
380 0.51 580 4.13
385 0.53 585 5.26
390 0.56 590 7.05
395 0.60 595 9.72

400 0.64 600 13.30


405 0.68 605 17.29
410 0.74 610 20.99
415 0.79 615 24.00
420 0.85 620 26.38

425 0.89 625 28.24


430 0.93 630 29.74
435 0.99 635 31.03
440 1.03 640 32.21
445 1.07 645 33.35

450 1.11 650 34.45


455 1.16 655 35.46
460 1.21 660 36.41
465 1.26 665 37.37
470 1.31 670 38.38

475 1.35 675 39.46


480 1.39 680 40.63
485 1.45 685 41.75
490 1.49 690 42.47
495 1.53 695 43.09

500 1.58 700 43.81


505 1.63 705 44.81
510 1.67 710 45.89
515 1.74 715 47.01
520 1.84 720 48.11

525 1.96 725 49.16


530 2.12 730 50.15
535 2.26 735 51.10
540 2.40 740 52.01
545 2.51 745 52.89

550 2.60 750 53.67


555 2.69 755 54.40
560 2.79 760 55.03
565 2.91 765 55.54
570 3.11 770 55.98

775 56.33
780 56.66

*NB Also known as spectral radiance factors for this geometry for mainlj
historical reasons

23
Table 10
Colorimetric Data
Geometry 0°/45°
Tomato Paste Reference Tile GM89 (Ceram Research No 126)

2 Degree Observer
X y Y(X) u' v' L* a* b*
Illuminant A 0.6460 0.3378 9.25 0.4485 0.5277 36.5 45.9 44.1
Illuminant C 0.5861 0.3419 6.57 0.3953 0.5189 30.8 41.3 35.3
Illuminant D65 0.5862 0.3455 6.48 0.3925 0.5205 30.6 42.8 34.8

10 Degree Observer
X y Y(%) u' v' L* a* b*
Illuminant A 0.6394 0.3446 9.08 0.4367 0.5296 36.1 41.8 44.1
Illuminant C 0.5788 0.3474 6.23 0.3851 0.5201 30.0 38.9 34.3
Illuminant D65 0.5794 0.3508 6.16 0.3830 0.5218 29.8 40.1 34.0

-24
6.4 Uncertainties in the Calibration of the Master Tomato Reference Tile

The uncertainties in the spectral values for the 0/d and 8/t geometries are

given by the formula

dR
AR = ±(0.05 + 0.004R + 0.2 —)%
dX

where R is the spectral reflectance and X the wavelength.

For the 0°/45° geometry the uncertainties in spectral values are

dR
AR = ±(0.05 + 0.008R + 0.2 — ) %
dX

Uncertainties in CIELAB units are

AL* 0.21

Aa* 0.20

Ab* 0.46

AE* 0.54

These do not vary significantly between the geometries.

All uncertainties are at the 95% confidence level. All percentages are with

respect to the 100% level and not the reflectance value. Approximately half

the uncertainty in the spectral values and L* occurs in referring the

calibration to the perfect reflecting diffuser and the remainder is in the

measurement of the tiles.

-25
6.5 Certified Individual Reference Values and their Uncertainties

The NPL calibration data for tile No 126 was provided in terms of the CIE
(9)
L*,a*,b* Systenr . It was therefore, necessary to convert the data for

Illuminant C/2° Observer to Hunter L,a,b values using the microprocessor in

the Hunter Colorimeter. No significant error arises during this conversion.

The NPL data could then be compared directly with the Ceram Research

measurement on this tile (Table 11).

Table 11 NPL and Ceram Research data for Master Tile GM89

L a b

NPL Calibration 25.61 33.54 14.73


Ceram Research 26.03 32.78 14.44
Difference (NPL-Ceram R) -0.42 +0.76 +0.29

The differences were used to correct the Ceram Research measurements (4.2) on

all the tiles, bringing their L,a,b values into line with the NPL calibration

on the Master Tile. Labels were printed by the computer giving the individual

calibration values for each tile - values which are directly traceable to the

NPL calibration.

The uncertainties in the colour values expressed relative to the master tile

can be derived from the repeatability of the colorimeter used to determine the

individual values after allowance for the small effect arising from different

orientation of a reference tile on the colorimeter.

The overall uncertainties (uC) on the certified L,a,b values are estimated by

quadratic addition of the uncertainties (uB) associated with the calibration

of the master tile and the uncertainties on L,a,b when expressed relative to

the master tile (yA) (Table 2 and section 4.1).

26
These uncertainties are compared in Table 12. In each case they are expressed

at the 95% confidence level.

Table 12 Components of uncertainty in the Tomato Paste Reference Tile


Hunter L,a,b Values

Uncertainty in Overall uncertainty


Uncertainty relative calibration of on certified L,a,b
to the master tile the master tile va].ues
(uA) (ViB) (uC)

L +0.15 +0.20 +0.25


a +0.30 +0.20 +0.36
b +0.20 +0.20 +0.22

In practice, the uncertainties expressed with respect to the master tile will

determine the agreement between colorimeters calibrated with tiles from the

batch CRM 400.

It is therefore these uncertainties which are used in practice but, it is

stressed that they are marginally smaller than the overall uncertainties given

above.

6.6 Colorimeters Calibrated in Other Scales

These calibration data are suitable for most users of the Tomato Reference

Tiles, since the vast majority of measurements are made on colorimeters

reading in Hunter L,a,b values. If other data are needed these may be

calculated readily for the same illuminant/standard observer or geometry.

However, it will be necessary to compare a Tomato Reference Tile with a

specially calibrated Master Tile for any other geometry or Observer/Illuminant

required.

-27-
7 INSTRUCTIONS FOR USE

7.1 Precautions to be taken in Handling and Storing the Tile

7.1.1 Store the reference tile at room temperature in the box provided. Do

not expose it to direct sunlight.

7.1.2 Avoid scratching the glaze surface when handling or cleaning the tile.

7.1.3 Clean the tile by breathing on the glaze surface and drying off with a

soft clean cloth.

7.1.4 Should the tile become badly soiled, gently wipe the glaze surface

with a pad or paper tissue moistened with a mild detergent solution

(or with propan-2-ol) followed by a pad moistened with water. DO NOT

immerse the tile in any solution or use abrasive cleaners. Optically

brightened tissue paper should not be used.

7.2 Use for Calibration

To calibrate the colorimeter use the certified values issued with the tile.

For optimum repeatability always use the tile with the same orientation.

7.3 Frequency of Calibration

Calibration should be checked several times a day if many measurements are

being made. Reference should be made to the instrument manufacturer's

instructions.

28-
NB Avoid excessive exposure to heat during calibration to minimise thermo-

chromic effects (see 3.5). Do not expose the tile within the instrument for

longer than is necessary, in principle a few seconds.

-29
ANNEX A A METHOD FOR THE COLOUR MEASUREMENT OF UNSALTED TOMATO PASTE/

CONCENTRATE (MODIFIED COST90bis PROCEDURE^)

A.l Introduction

The method uses a technique where the tristimulus colorimeter is calibrated by

means of a tomato paste colour reference tile which has a colour typical of

that required by the tomato processing industry and their customers. This

technique has two advantages; the reduction of the effects caused by

long-term drifting of a particular instrument and the improvement of

instrumental reproducibility. A further advantage of this method is the

non-use of a glass plate which, in other methodologies, is inserted between

the calibration tiles and the aperture.

A.2 Scope and Field of Application

The measurement of the colour of unsalted tomato paste (concentrate) using a

tomato paste colour reference tile.

A.3 Materials

A.3.1 Distilled water.

A.4 Apparatus

A.4.1 A suitable tristimulus colorimeter, one having an aperture of 50 mm

diameter is recommended.

A.4.2 Standard black, and white tiles maintained at constant temperature

(25 °C preferably).

31 -
A.4.3 BCR Tomato Paste Colour Reference tile maintained at constant

temperature (25 °C preferably).

A.4.A Optically clear glass specimen cell, diameter 62.5 mm, height 62.5 mm

with a base thickness of 2 mm capable of containing a test sample of

minimum depth 20 mm.

A.4.5 Empty container approximately 100 mm internal diameter and 140 mm high

painted matt black, internally - used as a light shield.

A.4.6 Suitable refractometer with sugar scale in X soluble solids.

A.4.7 Balance - capacity 500 g ± 0.1 g.

A.4.8 Nylon muslin.

A.4.9 Beakers, 400 ml capacity.

A.5 Sampling and Samples

A.5.1 Preparation of test sample: Determine the total soluble solids (£TSS)

of the laboratory sample of the paste as follows:

Cold Break Paste (concentrate) - allow approximately 50 g of paste

to reach 20 °C, stir with a spatula and place approximately 10 g of

this paste in the centre of a square of nylon muslin, gather up the

corners so as to enclose the sample and squeeze progressively so as to

force the serum through the cloth. Reject the first ten drops and

allow two or three drops to fall onto the prism of the refractometer.

Take a reading within 5 seconds and repeat the process starting at

"place approximately 10 g of this paste — " . Repeat until a constant

reading is obtained.

Hot Break Paste (concentrate) - place approximately 0.2 g of paste

directly onto the prism of the refractometer and take a reading.

-32-
A.5.3 Test Sample: for measurement of the colour, a net weight of 300 g of

test sample is required. To determine approximately the weight of

laboratory sample (undiluted paste) (Wp) required use the equation:

12.3
Vp = x 300
%TSS

(12.3 rather than 12.0 to allow for the fact that the percentage of

total solids is greater than the percentage of soluble solids by

this proportion.)

A.5.3.1 Weigh Wp.g of laboratory sample paste into a 400 ml beaker. The

paste should be at 20°C to ensure rapid thermal equilibration in

subsequent steps.

A.5.3.2 Add sufficient distilled water according to the following procedure

at 20°C to give a final %TSS of 12.0+0.1. Add the water in small

amounts and stir after each addition to break, up any lumps. DO NOT

ENTRAP AIR IN THE MIX. As the weight of the test sample approaches

300 g, check the X TSS by placing approximately 0.2 g of the

mixture onto the prism of the refractometer. Adjust carefully to

(12.0 ± 0.1)%, DO NOT adjust to 300 g. Finally, stir thoroughly

and check the X TSS. Should the test sample be too dilute, DO NOT

ADD MORE PASTE - DISCARD THE SAMPLE AND REPEAT.

A.6 Procedure

A.6.1 Colour values are determined in terms of 45°/0° or 0°/45° viewing

geometry, illuminant C/2° observer viewing protocol, specular

reflectance excluded, referenced to a national standard Perfect

White Diffuser and expressed in Hunter L, a and b values.

-33-
A.6.2 An instrument should be used which has an aperture of 50 mm nominal

diameter. A smaller diameter is likely to lead to errors.

A.6.3 Set the colorimeter to a zero scale reading by placing a black tile

supplied for zero adjustment over the aperture and make the zero

adjustment as described in the instrument manual. Ensure that the

black tile is free from dust and blemishes prior to use.

A.6.A To calibrate the instrument on the BCR Tomato. Paste Colour Reference

Tile, use the certified values or equivalent in whatever colour

system is required. Place the tile over the aperture, without using

a glass plate and adjust the instrument to the L,a,b values of the

tile. Ensure that the tile is not permitted to warm up whilst it is

presented to the specimen port. Certified L,a,b values are

established for 25°C. Adjustments should be made as quickly as

possible.

A.6.5 Introduce sufficient of the prepared sample into the sample cell, the

base of which should be in the same plane as the reference tile, to

give a minimum depth of 20 mm. Place the light shield over the sample

and obtain the colour value readings L, a and b as quickly as

possible.

A.6.6 The instrument should be zeroed and calibrated using the BCR tile at

least every 2 hours.

A.6.7 Results should be expressed to 0.1 units.

-34
ANNEX B INTERCOMPARISON OF LABORATORIES AND INSTRUMENTS

B.l Participants

The laboratories participating in these trials were as follows:

The National Food Centre, Dublin, Ireland

Bioteknisk Institut, Denmark

PLM R&D, Odense, Denmark

Star SpA, Parma, Italy

Compagnia Prodotti Conservati SpA, Santa-Rosa, Italy

Compagnia Prodotti Conservati SpA, Castel San Giorgio, Italy

Parma Sole Scrl, Bologna, Italy

Industria Alimentare Greci srl, Ravadese-Parma, Italy

Boschi SpA, Italy

Consorzio Cooperativo Conserve Italia, SRL, San Lazzaro di Savena, Italy

Cirio, Bertolli, De Rica SpA, San Polo di Podenzano, Italy

Stazione Sperimentale per L'Industria delle Conserve Alimentari, Angri, Italy

Stazione Sperimentale per L'Industria delle Conserve Alimentari, Parma, Italy

Co PAD OR Scrl, Collecchio, Italy

Greci, Geremia & Figli srl, Parma, Italy

Gandolfi srl, Parma, Italy

Nuovo Crai SpA, Piana di Monte Verna, Italy

Rodolfi Mansueto srl, Ozzano, Italy

Nomikos, Aliastos, Greece

Frangistas, Aliastos, Greece

Institute of Technology of Agricultural Products, Athens, Greece

Kyknos, Nafplion, Greece

Agricultural University of Athens, Greece

Marabou AB, Stockholm, Sweden

-35
AB Slotts, Uppsala, Sweden

Alsat, Badajoz, Spain

Rich Hengstenberg GmbH, Esslingen am Neckar, Germany

Instituto del Frio, Madrid, Spain

Instituto de Optica, Madrid, Spain

Instituto Valenciano de Investigaciones Agrarias, Valencia, Spain

Instituto de Agroquimica y Tecnologia de Alimentos, Valencia, Spain

Buitoni, Camaret sur Aygues, France

ENSBANA, Dijon, France

Centre Technique de la Conservation des Produits Agricoles, Avignon, France

INRA, Avignon, France

Panzani SA, Marseille, France

ENSIA, Massy, France

William Saurin, Lagny sur Marne, France

Nestle Co Ltd, Croydon, UK

Londreco Ltd, Hayes, UK

Heinz Ltd, Hayes, UK

Campden Food and Drink Research Association, Chipping Campden, UK

Torry Research Station, Aberdeen, UK

Institute of Food Research, Reading, UK

B.l Design of Experiment

During manufacture of the tile a small auxiliary firing was made to produce

50 tiles with high a values. These were to serve as Tile B in the experiment

described below.

Some 400 tiles were rejected at production (3.4) as being outside the limits

of the specification (1.3) or for carrying blemishes. Pairs A & B of the

tiles were chosen from the further discards mentioned in 4.2 (Tile A) and from

36
the special production batch mentioned above (Tile B). These pairs of tiles

were distributed to 52 European laboratories, mostly specialists in the

quality control of tomato products. The participants were asked to measure

Tile B using their normal measurement procedure but without any intervening

glass plate if that was normally used. Measurements were then made on the

same tile using Tile A as a reference tile with the given values. Single

measurements were made on three separate occasions to provide some measure of

the within laboratory variance. No other controls were exercised, ie no

specification of aperture size or any other instrument parameter. In this way

information was obtained on the variance to be expected in practice between

laboratories without standardisation of the method.

B.3 Results

Fifty-three usable sets of results were obtained from 44 separate laboratories

(see B.l above for full list).

As might be expected, the results using the reference technique showed an

improvement over the participants' normal method of measurement, whatever

that had been. In Figures Bla and Bib the results for a/b ratios are plotted

in the form of a histogram. In this diagram the differences of the measured

values from the 'true' values are quantised and the distribution of these

differences around zero is plotted. Note how for. the data using normal

procedures (Fig Bla), the data for Tile B are distributed much more widely

than when the Tile A is used as a reference (Fig Bib). This kind of result is

seen for all the variables and is summarised in Table Bl. Because the

distributions seem not to be symmetrical it is more useful and meaningful to

deal in terms of the interquartile range of the data rather than their

variance. Table Al therefore presents mean, median and interquartile range

for all the colour variables. As is seen the interquartile range is

-37
(a) 100 T

90 4
CO
CD
- 80 4
L
O
4->
70 -•
CO
(_
O
JQ 60 •■
CO

50 -•

<D 40 -•
(0
30 4
C
CD
O
l_ 20 -■
CD
Q.
to -■

3-3-1
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

D i f f e r e n c e from ' t r u e ' value a/b

(b) 100 T

90 -•
<0
- 80 4
L
O
+■>
70 ■•
CO
(_
o
60 -•
(0

50 -•

CD 40
CD
(0
30
C
CD
() 20
(_
CD
Q.
10 -■

■1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

D i f f e r e n c e from ' t r u e ' value a/b

Figure Bl Histogram showing effect of using a reference for colour measurement.


The height of each column is the percentage number of laboratories or instruments
lying within the incremental values on the horizontal axis, the incremental
values being differences from the 'true' result.

(a) Using arbitrary calibration procedure


(b) Using BCR reference tile

38-
considerably reduced when the reference tile A is used. Mean and median also

approach closer to zero ie the measurements are closer to the 'true' values.

Since however the normal method for some participants was apparently to use a

reference red tile of some other provenance, it is interesting to separate

those laboratories (of which there were 23) and to perform the same kind of

analysis of the data. Once again, there is an improvement in the precision of

the measurements demonstrated by the reduction in interquartile range as

Table B2 shows. It is clear therefore that the provision of a reference tile

is more useful if it is close in colour to the colour being measured. The

interquartile range for the complete set of data and for the subset of methods

using some other reference tile are very similar.

Table Bl

Statistical data for differences of L, a, b and a/b from 'true' values.


Subscript 1 refers to normal procedure, subscript 2 to use of reference
tile A.

Number of Interquartile
Vari able measurements Mean Median range

AL1 53 1.494 0.180 0.945

AL2 53 0.104 -0.020 0.160

53 -0.551 0.230 1.525


**!
Aa2 53 -0.385 -0.050 0.400

Abx 53 -0.098 0.070 0.815

Ab2 53 -0.0821 0.0100 0.135

A(ax / \ ) 53 -0.0188 0.0081 0.147

A(a2 /b2) 53 -0.0135 -0.0076 0.030

39-
Table B2

Statistical data for differences of L, a, b and a/b from 'true' values.


Subscript 1 refers to normal procedure using some other red reference tile
and subscript 2 refers to use of reference tile A.

Number of Interquartile
Variable measurements Mean Median range

AL1 23 0.853 0.180 1.05

AL2 23 0.0304 -0.010 0.180

23 1.412 1.030 2.99


*1
Aa2 23 0.065 0.060 0.320

Ab1 23 0.189 -0.080 0.84

Ab2 23 0.083 0.060 0.190

A(a2 / \ ) 23 0.0761 0.092 0.206

A(a2 /b 2 ) 23 -0.0084 -0.0026 0.023

40-
REFERENCES

1 Jowitt, R., Escher, F., Kent, M., McKenna, B. and Roques, M. (1987)

(eds) 'Physical Properties of Foods - 2'. Elsevier Applied Science,

London.

2 Brimelow, C.J.B. (1987). 'Measurement of tomato paste colour:

investigation of some method variables' in Jowitt et al., (eds) 'Physical

Properties of Foods - 2', Elsevier Applied Science, London.

3 Hils, A.K.A. (1987). 'Farbmessung von Tomatenmark-eine Massnahme zur

Qualitatssicherung'. Ind. Obst-Gemuseverwert, 72, 267-276.

4 Lamb, F.C. (1977) 'Tomato Products', Bulletin 27-L, 5th Edition,

National Canners' Research Labs, Washington DC, USA.

5 Hunter, R.S. (1948) 'Accuracy, Precision and Stability of New Photo-

electric Colour-difference Meter'. J. Opt. Soc. Am., 38, 1094A.

6 Malkin, F. and Verrill, J.F. (1983) in J. Schanda (Ed) Proc. CIE 20th

Session, Amsterdam 31 Aug - 8 Sept, 1983, OMIKK Budapest, E37/1-2.

7 Malkin, F. (1987) In C. Burgess and K.D. Mielenz (Eds) "Advances in

Standards and Methodology in Spectrophotometry" Elsevier Science

Publishers BV Amsterdam, pp209-233.

8 CIE International Commission on Illumination, Proceedings 8th Session,

Cambridge, UK, Bureau Central de la CIE, Paris 1931.

-41
CIE International Commission on Illumination. Recommendations on Uniform

Colour Spaces, Colour-Difference Equations, Psychometric Colour Terms,

Supplement No 2 to CIE Publication No 15 (E.1.3.1) 1971/(TC-1.3) 1978,

Bureau Central de la CIE, Paris, 1978.

42-
European Communities — Commission

EUR 13392 — The certification of a tomato paste colour reference


tile (CRM 400)
M. Kent, F. Ma/kin, J.F. Verrill, D.J. Henshall

Luxembourg: Office for Official Publications of the European Communities


1991 — IV, 41 pp. — fig., tab. — 21.0 x 29.7 cm
BCR Information series

ISBN 92-826-2403-X

Catalogue number: CD-NA-13392-EN-C

Price (excluding VAT) in Luxembourg: ECU 5

This report describes the preparation of a reference colour tile designed


specifically for the calibration of colorimeters used to measure the colour of
tomato paste.

The homogeneity of the batch of tiles is discussed and the results of a study
which confirms the stability of the tiles are presented. Details are given of
the procedure used to establish the certified values for individual tiles.

The report describes a method for measurement of the colour of unsalted


tomato paste which includes the use of the reference tile.

The results of a cooperative study in which 44 European laboratories com-


pared colorimeter measurements with and without a reference tile are dis-
cussed and the advantage of the use of the tile is demonstrated.

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