products. The same limit was also set in Germany for
smoked cheese and cheese products. In the European
Union, the maximum BaP concentration permitted in
foodstuffs as a result of using flavorings, including
smoke flavorings, is 0.03 mgkg
1
(Council directive
88/388/CEE of 22-06-1988). In addition, another
Council directive (91/493/CEE of 22-07-1991) con-
cerning fishery products lays down some health con-
ditions under which these products must be smoked,
and lists wood materials which cannot be burned in
smoking foods. (See Vegetale Oils: Types and Proper-
ties; Composition and Analysis.)
0014 Waters The following limits were set in the Euro-
pean Union to PAH presence in water intended for
human consumption (Council directive 98/83/EC of
3-11-1998): 0.010 mgl
1
for BaP, and 0.10 mgl
1
for
the sum of benz[e]acephenanthrylene, benzo[k]fluor-
anthene, benzo[ghi]perylene, and indeno[1,2,3-
cd]pyrene. BbFA, BkFA, BghiP, and IP.
0015 Refined oils and fats Some European oil industries
set their own guideline values for refined oils and fats:
5 mgkg
1
for the sum of seven higher-molecular PAHs
(BaP, benzo[e]pyrene (BeP), BghiP, dibenz[a,h]anthra-
cene (DBahA), perylene, anthanthrene, coronene),
and 25 mgkg
1
for the sum of 13 PAHs, including
the previous seven, plus another six lower-molecular
PAHs. (See Chromatography: High-performance
Liquid Chromatography; Gas Chromatography;
Supercritical Fluid Chromatography; Spectroscopy:
Visible Spectroscopy and Colorimetry.)
Analysis
0016 The determination of PAHs in food is complex, time-
consuming, and requires experienced personnel.
Nowadays, it is accepted that it has to be performed
under a program of quality control/quality assurance,
with the aim of providing fully reliable results.
PAH Selection
0017 There is no standard list of PAHs to be determined
and the selection performed by each investigator
is commonly arbitrary, based on the available
instrumentation and reference standards. Almost
invariably, BaP has been determined in every investi-
gation, due to its well-known carcinogenicity. Now-
adays, special attention is generally given to the
determination of other carcinogenic PAHs, especially
in health-related studies. Also when other PAH con-
centrations are available, BaP is usually taken as a
reference compound to compare the contamination
and the toxicological potency of different food items.
This is supported by the fact that BaP is by far the
species of higher toxicological concern, due to the
combination of its carcinogenic potency – relatively
to the other PAHs – with its concentration levels.
Sample Preparation
0018Most foods are not homogeneous and must be care-
fully homogenized prior to analysis. Extraction and
clean-up are crucial steps in the determination
because of the very low amounts of PAHs and the
need to separate them from substances which may
interfere during analysis, especially the lipids. The
general scheme shown in Figure 1 has been widely
used, as such or with some modifications which were
later introduced in its application to a wide range
of foods and to total diet samples. Modifications to
the scheme of Figure 1 most commonly involve the
extraction and partitioning solvents (e.g., dimethyl
sulfoxide replacing N,N-dimethylformamide), the
chromatographic sorbent (e.g., XAD-2 resin com-
bined with other sorbents or florisil or alumina com-
bined with silica gel), and thin-layer chromatography
as the clean-up step. The sonication extraction (e.g.,
of plants and smoked foods) has also been used
efficiently; its advantages are the reduced time of
extraction and possibly superior recovery efficiencies
and reproducibilities, but the results depend on
matrix, solvent, and experimental conditions. Con-
ventional chromatographic columns are often substi-
tuted by prepacked commercial cartridges (solid-
phase extraction), which give advantages in terms of
time and solvents consumed, and of reproducibility
performance.
0019Recently, supercritical fluid extraction (SFE: e.g.,
of smoked and broiled fish, and toast) and accelerated
solvent extraction (ASE: e.g., of smoked meat) have
gained attention as rapid alternatives to conventional
liquid extraction.
Sample Analysis
0020Identification and quantification are performed
by capillary gas chromatography (GC) or by high-
performance liquid chromatography (HPLC). In GC
analysis, the most widely used stationary phases
are the methylpolysiloxanes, especially SE-54 (5%
phenyl, 1% vinyl-substituted) and SE-52 (5% phenyl-
substituted) or equivalent phases. A flame ionization
detector is almost universally employed: it has an
excellent response linearity and, coupled with cold
on-column injections, gives an accurate and precise
quantification; because of its nonselectivity, however,
samples need to be highly purified. Mass-spectromet-
ric detectors are powerful tools in identifying and
confirming compounds, and have gained wide accept-
ance. In HPLC analysis, the most used packed mater-
ial consists of silica particles chemically bonded to
4618 POLYCYCLIC AROMATIC HYDROCARBONS