Académique Documents
Professionnel Documents
Culture Documents
Further Reading
AOAC (1990) AOAC Ofcial Methods of Analysis, 15th
edn. Arlington, VA: AOAC.
Codex Alimentarius (1969) Codex Alimentarius Sampling
Plan for Prepackaged Foods. Arlington, Virginia CAC/
RM 42-1969.
Hulme AC (1970) The Biochemistry of Fruits and Their
Products. London: Academic Press.
Packaging Materials
A W Lord, Pira International, Leatherhead, UK
& 2005, Elsevier Ltd. All Rights Reserved.
This article is a revision of the previous-edition article by Philip
Tice, pp. 36983706, & 1995, Elsevier Ltd.
Introduction
Analytical measurements on food packaging materials are generally carried out for three main purposes:
To identify the components of the packaging.
To identify and measure substances present that
could migrate into the packaged foods and cause a
health hazard to the consumer of the food. This work
is often accompanied by measurements of the migration of particular substances into either the actual
packaged foods, or into food simulants.
To identify and measure substances present that
could migrate into the packaged foods and result in
adverse effects on the organoleptic properties, such
as taste or odor.
plastics,
regenerated cellulose lms,
paper and board,
metal, and
glass.
Of these, plastics are the most widely used and within this category there are also the largest numbers of
variants. Many packaging materials are, however,
multilayered with either different layers of plastics or
combinations of plastics with paper/board, metal, or
glass. The individual properties of the different materials are used to produce food packaging with the
required characteristics. For example, in a packaging
material with two layers of different plastics, one
layer might provide the basic strength whilst the
other layer enables the packaging to be easily heatsealed. Coatings are also often added to the basic
plastic packaging material to provide additional barriers to the permeation of oxygen and water vapor.
These coatings can be polymeric or vacuum deposited aluminum.
With some metal cans used for foods and
beverages there is an inner lacquer (plastics) coating
for the purpose of either preventing corrosion of
the metal by the food/beverage, or preventing contamination of the food/beverage by the can metal.
A combination of a polymer layer with a board is
used to package liquids such as milk, where the
plastic layer provides the barrier to contain the milk
within the package and the board the basic strength.
Where it is necessary to store the beverage for long
periods, such as fruit juices, additional barrier properties are required to prevent permeation of oxygen
into the food product. To achieve this additional
protection, an aluminum layer is incorporated within
a plastic/board composite.
With many of the multilayer packaging materials
adhesives are used to bind the layers together. The
printing on the outside is a further important component of food packaging.
Typical uses
Polyethylene
Polypropylene
Poly(vinyl chloride),
unplasticized
Poly(vinyl chloride), plasticized
Polystyrene
Poly(ethylene terephthalate)
Polyamide (nylon)
Figure 1 Infrared transmission spectra of: (A) polyethylene/poly(ethylene terephthalate) laminate; (B) separated poly(ethylene
terephthalate) layer; (C) separated polyethylene layer plus adhesive; and (D) separated polyethylene layer with adhesive removed.
Solvents
Polyethylene
Polypropylene
Poly(vinyl chloride)
Poly(ethylene terephthalate)
Polyamide
recycled process scrap. It is quite common for offcuts to be recycled in an inner layer of a coextrusion.
Infrared spectra are then obtained from the surfaces of the packaging material after solvent removal
of any print or lacquer. Spectra are best obtained by
ATR. A further portion of the packaging material is
then subjected to DSC. This is a technique where a
few milligrams of the sample is subjected to a
programmed temperature ramp in a specied atmosphere inside a sample chamber. The heat ow (power) to the sample is monitored against temperature as
the sample is subjected to the heating ramp. For the
purposes discussed here this provides a trace showing
the melting points of the polymers present. Typical
melting ranges for common packaging polymers are
tabulated in Table 3.
The technique cannot be used to obtain melting
points for amorphous polymers. The sample polymer
is heated and cooled and then reheated at a controlled rate to record the meting points. This procedure
removes hysterisis effects that may be present in the
polymer as a result of the manufacturing process and
which may alter the perceived melting point. DSC is
capable of identifying polymers and polymer blends
Foil
Polyurethane
adhesive
PET
Surlyn
Nitrocellulose
lacquer/print
(LD-MD) PE
Polyurethane
adhesive
Ethylene-co-acrylic
acid (ionomer)
115130
100115
100110
210260
240260
220
160170
149
For the determination of free vinyl chloride monomer in plastics, the test sample is dissolved or dispersed in N,N-dimethylacetamide in a sealed vial and
then equilibrated at 601C before sampling the headspace. When determining vinyl chloride monomer in
foods or food simulants, N,N-dimethylacetamide is
again used with the sample in a sealed vial, with
equilibration at 601C.
Other volatile plastics monomers with similar
migration limits, such as acrylonitrile and butadiene,
are also determined by the headspace GC technique.
For the measurement of nonvolatile monomers in
plastic food packaging and in foods or food simulants due to migration, high-performance liquid chromatography (HPLC) and ion-exchange chromatography techniques can be employed. Food and
food simulants may give rise to interference problems
with the analysis. Sample clean-up procedures are
widely used such as solid-phase extraction of interference from extracts or size exclusion chromatography to remove fats and oils. Selective detectors
such as mass spectrometers are now widely used for
both liquid and gas chromatography.
Figure 4 is an ion-exchange chromatogram of
phthalic acids. Terephthalic acid and isophthalic acid
are monomers of polyester plastics. Orthophthalic
acid is the internal standard. There are migration
limits for both terephthalic acid and isophthalic acid
in EC regulations of 7.5 and 5.0 mg per kg of food.
The other main classes of substances in the safety
category, which can be present in food packaging
plastics and for which analytical measurements are
required, are the plastics additives. These substances
perform the functions of plasticizers, antioxidants,
antistatics, slip agents, and stabilizers. Of these additives, the plasticizers have been most extensively
studied and analytical methods developed for their
determination in the plastics and in packaged foods.
The techniques are usually based on GC either with
an FID or with a mass spectrometer as the detector.
Key advantages offered by a mass spectrometer are
selectivity of response and the ability to add a deuterated internal standard to the sample to compensate for the incomplete and variable recovery of the
analyte in the analysis.
Migration testing of plastics packaging prior to use
for compliance with any legislation limits is usually
carried out with food simulants rather than actual
foods. First, the analytical task is more often simple
and, second, testing with a food simulant or simulants for a class of foods covers use with all foods in
that class. The food simulants are simple liquids that
represent different classes of foods. For foods where
the liquid phase is largely water, distilled water is
used as the simulant. For acidic foods (typically pH
Table 4 EC food simulants for migration tests and the corresponding classes of foods
Food simulant
Distilled water
3% (w/v) aqueous solution of
acetic acid
10% (v/v) aqueous solution of
ethanola
Olive oil or sunower oil or
HB307
a
For a food or beverage with an alcohol content greater than 10%
(v/v), a simulant with a similar ethanol concentration is used.
possible contaminants include: the toxic heavy elements arsenic, mercury, lead, cadmium, and chromium, plus chlorophenols and polychlorinated
biphenyls (PCBs). With extraction liquids such as
water or dilute aqueous acid solutions, the toxic
heavy elements can be analytically determined using
atomic absorption spectroscopy. Arsenic can be
measured with the hydride generation technique,
mercury with the cold vapor technique, and the other
metals by the standard ame technique. Inductively
coupled plasma atomic emission spectroscopy is now
also widely used. Pentachlorophenol and other
chlorophenols can be determined by either GC or
HPLC. When using GC the chlorophenols are best
derivatized to form the methyl or acetyl derivatives
in order to improve the chromatographic performance and the analytical precision. These analytical
techniques have also been used in the detection and
analysis of chlorophenols suspected of being responsible for odors and food tainting, as described later.
The PCBs are determined in extracts from paper and
board materials by GC with an electron capture detector or mass spectrometer.
Two compounds are currently of particular interest in paper and board. Diisopropyl naphthalene
(DIPN) is a mixture of isomers that until recently
were widely used in carbonless copy papers as ink
solvents. Although it is currently being replaced it
occurs as a persistent contaminant in recycled paper
and board. Various studies have shown that it is able
to migrate from paperboard into food. There is a
draft CEN analytical method available. This method
involves acetone extraction and quantication by
GCMS using diethyl naphthalene as an internal
standard. There is currently no limit for DIPN but
levels are being monitored to reduce concentrations
in recycled paperboard.
Two related compounds are 3-monochloropropane-1,2-diol (3-MCPD) and dichloropropanol.
These arise in paper board due to the hydrolysis of
epichlorohydrin-based wet strength agents. 3-MCPD
can occur in food from hydrolyzed vegetable protein.
The limit in food is 120 ppb. In packaging the specific migration limit is 12 ppb in the food. The dichloropropanol does not at present have a limit.
However, the German BGVV recommendations
(widely accepted as useful guidelines) list a limit of
2 ppb in a hot water extract. A convenient method of
analysis is to extract the two compounds with water.
The water extract is then totally absorbed onto a
diatomaceous earth cartridge. The cartridge is then
washed with a large volume of diethyl ether. The
water is retained on the cartridge and the 3-MCPD
and dichloropropanol extracted and eluted by
the diethyl ether. The ether is then concentrated by
epoxyphenolic and
organosol
BFDGE
BADGE
Bisphenol A
Bisphenol F
BADGE and BFDGE undergo hydrolysis and addition of hydrogen chloride released from the PVC
organosol in aqueous foods and a series of reaction
products result. Concern has been raised over these
reaction products. These are listed below:
*
*
*
*
BADGE HCl
BADGE 2HCl
BADGE H2O HCl
BADGE H2O
Figure 5 Chromatogram of volatile substances from a carton-board food packaging printed with a UV-cured ink. Benzophenone, the
printing ink component responsible for tainting of packaged food, is represented by the peak at 15.7 min.
Further Reading
Ashby R, Cooper I, Harvey S, and Tice P (1997) Food
Packaging Migration and Legislation. Leatherhead, UK:
Pira International.
Kolb B (1984) Analysis of food contamination by headspace gas chromatography. In: Gilbert J (ed.) Analysis of
Food Contaminants, pp. 117156. Barking, UK: Elsevier.
Krause, Lange, and Ezrin (1983) Schultheis KR (trans.)
Plastics Analysis Guide Chemical and Instrumental
Methods. Munich: Carl Hanser Verlag.
Lord AWT (2003) Packaging materials as a source of
taints. In: Baigrie B (ed.) Taints and Off-Flavours in
Food, pp. 64111. London: Woodhead Publishing.
MAFF (January 1999) Diisopropylnaphthalenes in Food
Packaging Made from Recycled Paper and Board. Food
Surveillance Information Sheet Number 169, MAFF
Joint Food Safety Standards Group.
Synoptic Document (updated 15 January 2002) European
Commission, Health and Consumer Protection Directorate-General, http://cpf.jrc.it/webpack/.
Tice PA (1993) Packaging as a source of taints. In: Saxby
MJ (ed.) Food Taints and Off-Flavours, pp. 202233.
Glasgow: Blackie Academic Professional.
FORENSIC SCIENCES
Contents
Overview
Alcohol in Body Fluids
Arson Residues
Blood Analysis
Carbon Monoxide and Cyanide from Fire and Accident
DNA Proling
Drug Screening in Sport
Explosives
Fibers
Fingerprint Techniques
Glass
Gunshot Residues
Hair
Illicit Drugs
Paints, Varnishes, and Lacquers
Questioned Documents
Systematic Drug Identication
Thin-Layer Chromatography
Volatile Substances
Overview
P Margot, Universite de Lausanne, Lausanne, Switzerland
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Forensic sciences group the scientific principles and
technical methods applied to the investigation of
crimes, litigations in civil matters, or regulatory and
state administrative matters. Results are presented as