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Eur Food Res Technol (2008) 227:11911198

DOI 10.1007/s00217-008-0836-8

ORIGINAL PAPER

Polycyclic aromatic hydrocarbons (PAHs) in traditional


and industrial smoked beef and pork ham from Serbia
Jasna Djinovic Aleksandar Popovic Wolfgang Jira

Received: 9 November 2007 / Revised: 22 January 2008 / Accepted: 31 January 2008 / Published online: 15 February 2008
Springer-Verlag 2008

Abstract Smoked beef and pork ham samples were analysed during process of smoking (after packing and storing)
for the presence of the 16 EU priority PAHs via Fast GC/
HRMS method. This study showed that there are diVerences in PAH contents between Wnal smoked beef ham
samples from traditional smokehouse (TS) (3.9 g kg1)
and industrial smokehouse (IS), (1.9 g kg1). Also there is
a diVerence in PAH contents in Wnal smoked pork ham
samples (4.9 g kg1, TS; 4.2 g kg1, IS). In beef and
pork ham samples from the same smokehouse diVerent
PAH contents were observed during smoking. The highest
content of examined PAHs in all beef and pork ham samples during smoking showed benzo[c]Xuorene (BcL) (beef
ham: from 0.3 g kg1 to 1.5 g kg1; pork ham: from
0.2 g kg1 to 2.1 g kg1).The maximum level for
benzo[a]pyrene (BaP) of 5 g kg1 in smoked meat products was not exceeded in any samples. Correlation statistic
analysis (P < 0.05) of obtained contents from samples both
from TS and IS showed that BaP is a good marker both for
16 EU priority PAHs and 12 IARC probably and possibly
carcinogenic PAHs (IS: RBaP/16PAHs = 0.95, RBaP/12PAHs =
0.96; TS: RBaP/16PAHs = 0.71, RBaP/12PAHs = 0.88).
J. Djinovic (&) W. Jira
Institute for Chemistry and Physics,
Federal Research Centre for Nutrition and Food,
Location Kulmbach, E.-C.-Baumann-Str. 20,
95326 Kulmbach, Germany
e-mail: djjasna@yahoo.com
A. Popovic
Department of Chemistry, University of Belgrade,
PO Box 158, 11001 Belgrade, Serbia
J. Djinovic
Institute of Meat Hygiene and Technology, Kacanskog 13,
11000 Belgrade, Serbia

Keywords Smoked beef and pork ham


Polycyclic aromatic hydrocarbons
Traditional and industrial smoking

Introduction
Polycyclic aromatic hydrocarbons (PAHs) consist of two or
more condensed aromatic rings and they are formed during
the incomplete combustion of organic material [1]. PAHs
generally become more lipophilic, less soluble and less volatile with increasing molecular weight. There are a lot of
diVerent types of anthropogenic sources that emit PAHs into
the atmosphere such as coal and wood burning, oil and gas
burning, agricultural Wres, etc. [2]. On the way they dissipate
through the atmosphere and become potential pollutants of
foods, vegetables and other plants like tea, etc. [35]. Simonichs and Hitess study [6] showed that 44 18% of the
PAHs emitted into the atmosphere from sources in the
northeast of the United States were removed by vegetation.
Meat and meat products are mainly contaminated with
PAHs during thermal processing, e.g., roasting, charcoal
grilling, and smoking [7, 8]. Smoking is one of the oldest
food preservation methods, exposing meat and meat products to thermal-generated wood smoke. Smoking is deWned
as the process of penetration of volatiles resulting from thermal destruction of wood into the surface of meat products
[9]. Smoke not only gives special taste, colour and aroma to
food, but also enhances preservation due to the dehydrating,
bactericidal and antioxidant properties of smoke [10, 11].
Today the preservative eVect of smoking is achieved by drying the surface and the creation of a microstatic condensate.
This process has been perfected continually by civilisation
in the course of time and smoking established to be a kind of
culinary art. Incomplete wood combustion during process of

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smoking can produce considerable amounts of PAH compounds [12], which can be adsorbed by the surface of meat.
Investigations on the penetration of PAH compounds into
the inside of smoked meat products showed that nearly 99%
of all PAHs were found in the outer 22% of the total weight
of a cooked sausage [13].
Since 1 April 2005 the Commission Regulation (EC) No
208/2005 of 4 February 2005, which provides maximum
levels for benzo[a]pyrene in diVerent food groups came into
force. Now these maximum levels are part of Commission
Regulation (EC) No 1881/2006 of 19 December 2006. Also
the ScientiWc Committee on Food (SCF) recommended to
the member states of European Union to analyse the contents of 15 PAH compounds, which are classiWed as priority
(15 SCF-PAH) and to check the suitability of
benzo[a]pyrene as a marker for the occurrence and impact
of carcinogenic PAHs in food. Additionally, the European
Food Safety Authority (EFSA) recommends to analyse
benzo[c]Xuorene assessed to be relevant by the Joint FAO/
WHO Experts Committee on Food Additives (JECFA)
[1416]. The 16 EU priority PAHs that are recommended
for analysis represent both 15 SCF-PAHs and JECFA PAH.
Those are: benzo[c]Xuorene (BcL), benzo[a]anthracene
(BaA), cyclopenta[c,d]pyrene (CPP), chrysene (CHR),
5-methylchrysene (5MC), benzo[b]Xuoranthene (BbF),
benzo[j]Xuoranthene (BjF), benzo[k]Xuoranthene (BkF),
benzo[a]pyrene (BaP), benzo[g,h,i]perylene (BgP),
dibenzo[a,h]anthracene (DhA), indeno[1,2,3-cd]pyrene
(IcP), dibenzo[a,e]pyrene (DeP), dibenzo[a,h]pyrene (DhP),
dibenzo[a,i]pyrene (DiP) and dibenzo[a,l]pyrene (DlP).
The International Agency for Research on Cancer
(IARC) classiWed three PAHs of 16 examined PAHs in this
study (BaA, BaP and DhA) as probably carcinogenic to
humans (Group 2A) and nine (5MC, BbF, BjF, BkF, IcP,
DeP, DhP, DiP and DlP) as possibly carcinogenic to
humans (Group 2B) [1719].
Toxicological
investigations
indicated
that
dibenzo[a,l]pyrene probably has a much stronger carcinogenic potential than benzo[a]pyrene [20]. Extensive tumorigenicity studies in rodents revealed that dibenzo[a,l]pyrene
is the most potent carcinogen among all polycyclic aromatic hydrocarbons [21]. DlP was detected in environmental samples and has been characterized as the most potent
carcinogenic species among all PAHs as yet tested in
rodent bioassays [22].
There are a lot of meat industries with a long tradition of
producing smoked meat products in Serbia. Meat industries
from Serbia are interested in following the newest EU regulations about food in order to check and improve food
safety of their products. Zlatibor region, which is about
230 km southwest, far from Belgrade, the Serbian capital,
is famous for both traditional and industrial smoked meat
products.

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Eur Food Res Technol (2008) 227:11911198

The aim of this study was to analyse the contents of the


16 EU priority PAHs in pork and beef ham from meat
industry Zlatibor, Cajetina, Serbia, during process of smoking. These products were smoked both on traditional and
industrial way. The contents of analysed PAHs were compared between traditional and industrial smoked ham samples. The suitability of BaP as a marker for other PAHs was
checked by applying correlation statistic analysis.

Materials and methods


Food samples and sampling
A total of 22 samples of pork and beef ham both from traditional and industrial smokehouses were analysed. All samples were collected from meat industry Zlatibor, Cajetina,
Serbia, in February 2007. Samples were collected every
3 days during 15 days of smoking. As a control, all products were taken before the process of smoking and they
were marked as samples after 0 days of smoking. After
each sampling the meat products were placed in sterile vacuum bags (LDPE Polyethylene vacuum bags; Cryovac
BB4, Cambridge, UK), vacuumed and placed in dark at
T = 18 C. Samples were transported on dry ice from
Serbia to Germany. Packaging and transmission of samples
followed Commission Directive 2005/10/EC [23].
Beef and pork ham from traditional smokehouse
(Samples A) were continuously exposed by smoke during
15 days. The distance between smoke generator and meat
samples was 3 m. In this case smoking was not under
controlled conditions. Temperature and humidity were
under outdoor conditions; the temperature of the smoke
was between T = 18 and 20 C. This, traditional way of
meat smoking is applied in practice only during the winter
in meat industry Zlatibor, Cajetina. Smoke was produced
by beech wood combustion.
Beef and pork ham from industrial smokehouse
(Samples B) were smoked under controlled conditions.
Samples B were under controlled smoking program
during 15 days. During those 15 days Samples B were
smoked t = 64 h. Smoking was performed in four cycles.
In each cycle samples were smoked four times per 4 h.
The temperature and humidity were between T = 1624 C
and 7888%, respectively. Smoke was produced by
Vemag glowing smoke generator H 504/C using beech
wood. Industrial way of smoking is applied in practice
during the whole year.
Reagents
All solvents were obtained in picograde quality from
Promochem (Wesel, Germany). The drying material

Eur Food Res Technol (2008) 227:11911198

poly(acrylic acid), partial sodium salt-graft-poly(ethylene oxide) was purchased from Sigma Aldrich (Munich,
Germany). Bio Beads S-X3 (200400 mesh) was purchased from Bio-Rad Laboratories (Munich, Germany)
and silica gel 60 (70230 mesh) from Merck (Darmstadt,
Germany). Glass microWbre Wlters (18 mm i.d.) were
obtained from Dionex (Idstein, Germany). The PTFE-Filters
(1 m pore size, 25 mm i.d.) and the SPE-Cartridges
(12 mm i.d.) were purchased from Alltech (Unterhaching,
Germany).
A PAH standard mixture containing isotope-labelled
13
( C and 2H) PAH compounds (benzo[a]anthracene-13C6,
chrysene-13C6, 5-methylchrysene-d3, benzo[b]Xuoranthene13
C6, benzo[k]Xuoranthene-13C6, benzo[a]pyrene-13C4,
dibenzo[a,h]anthracene-d14,
indeno[1,2,3-cd]pyrene-d12,
benzo[g,h,i]perylene-13C12, dibenzo[a,e]pyrene-13C6 and
dibenzo[a,i]pyrene-13C12 in isooctane) and the recovery
PAH
standard
mixture
(benzo[a]anthracene-d12,
benzo[a]pyrene-d12 and benzo[g,h,i]perylene-d12 in isooctane) were obtained as single compounds from Promochem
(Wesel, Germany). Fluorinated PAH standards (13-Xuorodibenzo[a,l]pyrene and 5-Xuorobenzo[c]Xuorine in isooctane)
were obtained from Biochemical Institute for Environmental
Carcinogens (Grosshansdorf, Germany).
Sample preparation for the analysis of meat products
Accelerated solvent extraction (ASE)
About m = 5 g homogenised ham, and m = 3 g homogenised other meat products were levigated with the same
amount of the drying material poly(acrylic acid), partial
sodium salt-graft-poly(ethylene oxide). The resulting material was poured into V = 33 mL cells, which were locked
with glass microWber Wlters at the outlet end of the extraction cells. Afterwards, V = 50 L of the PAH standard mixture containing isotope-labelled (13C and 2H) and
Xuorinated PAH compounds were added as internal standard. The extraction was performed with an ASE 200 from
Dionex (Sunnyvale, USA) and carried out with n-hexane at
T = 100 C and p = 10 MPa at a static time of t = 10 min.
The Xush volume was 60% and the purge time t = 120 s.
Two static cycles were accomplished. The solvent of the
extract was evaporated in a water bath (T = 40 C) using a
nitrogen stream.
Gel permeation chromatography (GPC)
The evaporated ASE-extract was dissolved in
V = 4.5 mL cyclohexane/ethylacetate (50:50 v/v) and
Wltered through a PTFE Wlter with a pore size of 1 m.
The GPC column (25 mm i.d.) was Wlled with Bio-Beads
S-X3 (weight of Wlling m = 60 g). Samples were eluted

1193

at a Xow rate of 5 mL min1 applying cyclohexane/ethylacetate (50:50 v/v) (dump time t = 036 min, collect
time t = 3665 min). The solvent was removed with a
rotary evaporator, and the eluate was dried in a nitrogen
stream. The dried GPC-eluate was dissolved in V = 1 mL
cyclohexane.
Solid phase extraction (SPE)
This clean-up step to remove more polar substances was
performed automatically with a modiWed ASPEC Xli [24].
This system was modiWed with a Wtting rack, teXon funnels
and teXon tubes. Silica, dried for t = 12 h at T = 550 C,
was deactivated with 15% water. m = 1 g dried deactivated
silica was Wlled into commercial V = 8 mL SPE columns
(12 mm i.d.). After conditioning of the columns with
V = 3 mL cyclohexane the samples were applied and eluted
with V = 10 mL cyclohexane.
Preparation for GC/MS analysis
The dried eluate of SPE was dissolved in V = 1 mL isooctane and V = 50 L of the PAH-recovery standard mixture
and transferred to a V = 1 mL tapered vial. The remaining
sample was carefully concentrated in a nitrogen stream to a
volume of about V = 50 L.
Reagent and procedural blanks were simultaneously analysed for to detect present PAH in parallel to each series of
samples passing the extraction and cleanup procedures
using drying material instead of real samples.
Fast GC/HRMS method
Gas chromatography
Fast GC/HRMS was performed using a TraceGC Ultra gas
chromatograph (Thermo Fisher ScientiWc, Milan, Italy)
equipped with a split/splitless injection port. Seperation
was performed on a TR-50MS column (10 m 0.1 mm
0.1 m) (Thermo Fisher ScientiWc, Bremen, Germany).
Injection temperature was T = 280 C; injection volume
was V = 1.5 L (splitless). Helium with a constant Xow of
0.6 mL min1 was applied as carrier gas. The following
temperature program was used: isothermal at T = 140 C
for t = 1 min, at 10 C min1 to T = 240 C, at 5 C min1
to T = 270 C, at 30 C min1 to T = 280 C, at 4 C min1
to T = 290 C, at 30 C min1 to T = 315 C and at
3 C min1 to T = 330 C.
Mass spectrometry
IdentiWcation of PAH by GC/HRMS was performed using a
DFS High-Resolution GC/MS (Thermo Fisher ScientiWc,

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Eur Food Res Technol (2008) 227:11911198

Bremen, Germany) working in the electron impact (EI)


positive ion mode and applying an electron energy of
E = 45 eV. The temperatures of the source and the transfer
line were heated up to T = 280 C and T = 300 C. The
resolution of the MS was tuned to 8.000 (10% valley
deWnition).

Results and discussion


The contents of the 16 analysed PAHs in the beef ham
samples both from traditional smokehouse (TS) and
industrial smokehouse (IS) are shown in Table 1.
Table 2 shows the contents of analysed PAH compounds
in the pork ham samples both from TS and IS. The relative standard deviations (RSD) of all PAH compounds
were below 20%. A total of 22 ham samples were analysed. The recoveries ranged from 58 to 64% for samples from TS, and from 61 to 75% for samples from IS.
Results present in this study describe PAH occurrence in
smoked beef and pork ham samples after storage in
LDPE vacuum bags in dark at T = 18 C. All samples
were stored about 2 months before they were analysed.
Figure 1 shows the comparison of PAH contents in beef
(Fig. 1a) and pork (Fig. 1b) ham samples after process of
smoking in TS and IS. The changes of sum 16 PAHs
content in analysed samples are shown in Fig. 2. Some
aspects of statistical analysis of the obtained contents
are shown in Fig. 3.

Traditional smokehouse (TS) and industrial smokehouse


(IS): the content of PAHs
During process of smoking both in TS and IS contents of
analysed PAHs were mostly increasing (Tables 1, 2). The
important factor of PAH contamination is the surface/mass
ratio. That ratio was very similar in analysed ham samples
and considering that fact we could compare PAH contents
between beef and pork ham samples. If we compare PAH
contents in the samples from TS it could be seen that only
the content of DhP in beef ham was higher than in pork
ham during process of smoking. The contents of other
examined PAHs were not constantly higher in one type of
ham.
In the samples from IS the contents of BaA, CHR, BbF,
BjF, BaP, DhA and IcP in pork ham samples were higher
than in the beef ham samples during the process of smoking. The contents of other examined PAHs in the samples
from IS were not constantly higher in one type of ham.
BcL showed the highest contents of all PAH compounds
in beef and pork samples (both in TS and IS). DhA and DlP
showed the lowest content both in beef and pork ham samples from TS and IS, respectively. If we consider only 12
IARC PAHs maximum content belongs to BaA. Contents
of diVerent PAHs in the investigated samples after process
of smoking are shown in Fig. 1.
The progress of the sum content of the 16 PAHs during
the smoking process in beef ham samples was similar to the
progress of the sum content of the 16 PAHs during smoking

Table 1 Contents (g kg1) of the analysed PAHs in the beef ham samples
Days of smoking BcL

BaA

CPP

CHR

5MC

BbF

BjF

BkF

BaP

BgP

DhA

IcP

DeP

DhP

DiP

DlP

Sample before process of smoking


0

0.101 0.014 0.026 0.061 ND

0.016 0.011 0.006 ND

0.028 0.006 0.014 0.005 0.004 0.011

0.006

0.300 0.068 0.030 0.128 0.011 0.035 0.019 0.014 0.033 0.030 0.005 0.019 0.008 0.006 0.006

0.002

06

0.570 0.219 0.182 0.328 0.032 0.073 0.053 0.035 0.240 0.062 0.005 0.045 0.013 0.121 0.016

0.008

0.594 0.146 0.046 0.230 0.017 0.059 0.037 0.025 0.050 0.048 0.010 0.040 0.016 0.014 0.018

0.018

12

0.793 0.214 0.082 0.301 0.025 0.076 0.049 0.032 0.081 0.066 0.009 0.049 0.011 0.016 0.017

0.008

15

1.521 0.510 0.124 0.707 0.023 0.174 0.104 0.068 0.268 0.126 0.013 0.092 0.029 0.027 0.080

0.062

Samples from traditional smokehouse

Samples from industrial smokehouse


3

0.447 0.093 0.019 0.164 0.025 0.041 0.013 0.038 0.024 0.030 0.002 0.006 ND

0.002

ND

0.431 0.107 0.024 0.185 0.027 0.047 0.023 0.019 0.027 0.032 0.013 0.005 0.005 0.004 0.005

ND

ND

0.529 0.120 0.036 0.167 0.019 0.043 0.013 0.039 0.049 0.034 0.004 0.018 ND

ND

0.002

ND

12

0.796 0.230 0.161 0.281 0.026 0.078 0.038 0.026 0.081 0.046 0.004 0.016 ND

0.019 0.018

ND

15

0.691 0.163 0.159 0.209 0.019 0.047 0.025 0.016 0.103 0.045 0.005 0.025 0.015 0.032 0.291

ND

Limit of detection, LOD (g kg1)


PAHs

BcL

LOD

0.032 0.010 0.006 0.049 0.013 0.013 0.007 0.003 0.021 0.026 0.001 0.007 0.003 0.004 0.001

ND not detectable

123

BaA

CPP

CHR

5MC

BbF

BjF

BkF

BaP

BgP

DhA

IcP

DeP

DhP

DiP

DlP
0.001

Eur Food Res Technol (2008) 227:11911198

1195

Table 2 Contents (g kg1) of the analysed PAHs in the pork ham samples
Days of smoking BcL

BaA

CPP

CHR

5MC

BbF

BjF

BkF

BaP

BgP

DhA

IcP

DeP

DhP

DiP

DlP

Sample before process of smoking


0

0.075 0.035 0.019 0.127 0.013 0.054 0.014 0.009 0.022 0.049 0.013 0.017 0.006 0.005 0.009

0.003

Samples from traditional smokehouse


3

0.203 0.056 0.021 0.139 ND

0.056 0.019 0.014 0.025 0.037 0.004 0.021 0.009 0.004 0.009

0.005

0.361 0.098 0.054 0.178 0.013 0.069 0.027 0.017 0.045 0.053 0.004 0.027 0.008 0.002 0.019

0.002

0.807 0.225 0.086 0.406 0.028 0.142 0.045 0.020 0.110 0.319 0.010 0.073 0.012 0.010 0.014

0.007

12

0.834 0.168 0.074 0.276 0.018 0.070 0.044 0.026 0.062 0.084 0.008 0.038 0.007 0.012 0.011

0.005

15

2.134 0.625 0.390 0.958 0.035 0.169 0.107 0.067 0.153 0.146 0.011 0.079 0.011 0.007 0.018

0.005

Samples from industrial smokehouse


3

0.396 0.102 0.039 0.211 0.018 0.073 0.026 0.019 0.034 0.042 0.003 0.030 0.005 ND

0.007

ND

0.232 0.141 0.055 0.309 0.021 0.080 0.032 0.026 0.054 0.034 0.005 0.023 ND

ND

ND

0.511 0.122 0.047 0.208 0.020 0.067 0.020 0.045 0.069 0.040 0.005 0.022 0.006 ND

0.012

0.003

12

1.381 0.311 0.051 0.385 0.033 0.097 0.048 0.037 0.089 0.064 0.007 0.043 0.007 ND

0.009

0.003

15

1.539 0.429 0.327 0.584 0.050 0.174 0.088 0.060 0.314 0.458 0.011 0.141 0.009 ND

0.010

0.004

ND

Limit of detection, LOD (g kg1)


PAHs

BcL

LOD

0.032 0.010 0.006 0.049 0.013 0.013 0.007 0.003 0.021 0.026 0.001 0.007 0.003 0.004 0.001

BaA

CPP

CHR

5MC

BbF

BjF

BkF

BaP

BgP

DhA

IcP

DeP

DhP

DiP

DlP
0.001

ND Not detectable

process in pork ham samples in TS (Fig. 2). In the case of


IS the PAH contents both in beef and pork ham were
increasing during the whole time of examined period.

carcinogenic PAHs. DlP in IS beef ham samples was not


detectable.
Pork ham TSpork ham IS

Comparison of the PAH contents in the same type of meat


product
Beef ham TSbeef ham IS
The contents of analysed PAHs in the Wnal beef ham samples were higher in the samples from TS than in the samples from IS, except for CPP and DiP; the contents of 5MC
and DhP were similar in beef ham samples from TS and IS
(Table 1). The sum of the PAHs content during smoking
was not always higher in beef ham samples from TS
(Fig. 2a).
The contribution of BaP in beef ham samples from TS
was 6.3% (median) (in relation to 16 EU PAHs) and varied
from 3.7 to 12.0%. In the case of beef ham samples from IS
the median BaP contribution was 4.0% and varied from 2.7
to 5.6%. If only probably or possibly carcinogenic 12 IARC
PAHs are considered the BaP content in beef ham samples
from TS and IS was on average 17.2% (with variation from
11.2 to 28.0%) and 12.9% (with variation from 9.4 to
16.0%), respectively.
A recent investigation [25] indicates the importance of
analysing DlP because of its carcinogenic properties. In
the present study it was found that DlP in TS beef ham
samples contributed in general 1% to the total content of
the 16 EU PAHs, and 2.8% of 12 IARC possibly or probably

Although the total content of analysed PAHs in pork sample at the end of smoking from TS was higher than in sample from IS, during process of smoking this content was
three times higher in IS than in TS samples (of six altogether measurements) (Fig. 2b).
If we compare our results for BaP in Wnal smoked pork
ham with results reported by Kazerouni et al. [26] it could
be seen that our BaP result for pork sample from TS
(0.15 g kg1) is similar to their BaP content (0.13 g
kg1). BaP content in pork ham sample from IS
(0.31 g kg1) is more than twofold. The median contribution of BaP in the pork ham samples during process of
smoking was 4.0 and 5.1% to the total content of all analysed PAHs in TS and IS, respectively. Relating to the 12
IARC PAHs BaP comprises in general 13.1 and 16.0% in
samples from TS and IS, respectively.
In the case of pork ham samples from TS, our results
showed that DlP comprises in general 0.3 and 1.0% of the
content of the 16 EU and 12 IARC PAHs, respectively. The
content of DlP in pork samples from IS was 0.1% of the
total content of 16 EU PAHs and 0.5% of the total content
of 12 IARC PAHs.
The results reported by Jira et al. [13] showed that BaP
was the dominant compound within the group of other
PAHs with higher carcinogenic potential (DhA, DeP, DhP,

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Fig. 1 The comparison of PAH contents in the beef (a) and pork (b)
ham samples after process of smoking in traditional smokehouse (TS)
and industrial smokehouse (IS). (Djinovic, Popovic & Jira, Polycyclic
aromatic hydrocarbons (PAHs) in traditional and industrial smoked
beef and pork ham from Serbia)

DlP) [27] in smoked meat products. The contribution of


BaP in analysed, smoked raw ham samples was about 8%
(median) and varied from approximately 612%. Results
for BaP from this study (in relation to 16 EU PAHs) are in
the range from approximately 46%.
Statistical calculations
To verify that BaP is a good marker for other PAHs in analysed smoked meat products, the Pearsons correlation
coeYcients (R) (P < 0.05) between BaP values and the
obtained contents of analysed PAHs were calculated.
Figure 3 shows correlations between the content of BaP and
the total content of the 16 EU priority PAHs, as well as
between the content of BaP and the total content of the 12
IARC PAHs in analysed samples of beef and pork ham
from TS (Fig. 3a, b) and IS (Fig. 3c, d).
All correlations that are shown in Fig. 3 are signiWcant
(P < 0.05). Correlation coeYcients between BaP and the
sum of the 16 EU PAHs as well as between BaP and sum of

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Eur Food Res Technol (2008) 227:11911198

Fig. 2 The changes of the sum of the 16 PAH contents in analysed


samples during process of smoking in traditional smokehouse (TS) and
industrial smokehouse (IS) (a Beef ham; b Pork ham). (Djinovic,
Popovic & Jira, Polycyclic aromatic hydrocarbons (PAHs) in traditional and industrial smoked beef and pork ham from Serbia)

12 IARC PAHs in samples from IS (RBaP/16PAHs = 0.95,


RBaP/12PAHs = 0.96) are bigger than the same coeYcients in
the samples from TS (RBaP/16PAHs = 0.71, RBaP/12PAHs =
0.88). Regardless of those diVerences, results indicate that
BaP could be used as a marker both for 16 EU PAHs as
well as for 12 probably and possibly carcinogenic PAHs in
smoked meat products.

Conclusions
This study presents Wrst results concerning the contents of
16 EU priority PAH compounds in smoked hams from
meat industry Zlatibor, Cajetina, Serbia. A comparison of
PAH contents in the same types of ham in diVerent smokehouses (TS and IS) and diVerent types of ham (beef ham
pork ham) in the same smokehouse shows that PAH
contents are diVerent and depend on smoking technology as
well as on type of ham (pork or beef ham).

Eur Food Res Technol (2008) 227:11911198


Traditional smokehouse (beef and pork ham)
BaP = 0.016 + 0.044 16 PAHs
Correlation: R = 0.708

Traditional smokehouse (beef and pork ham)


BaP = -0.012 + 0.180 12 PAHs
Correlation: R = 0.882

95% confidence

0.28

0.28

0.24

0.24

0.20

0.20

0.16

0.16

BaP

BaP

1197

0.12

0.12

0.08

0.08

0.04

0.04

0.00

0.0

0 .5

1.0

1.5

2.0

2 .5

3.0

3.5

4.0

4 .5

5.0

0.00

5 .5

0.0

0.2

0.4

16 PAHs

Industrial smokehouse (beef and pork ham)


BaP = -0.044 + 0.077 16 PAHs
Correlation: R = 0.948

BaP = -0.048 + 0.255 12 PAHs


Correlation: R = 0.962

0.3 5

0.30

0.30

0.25

0.25

0.20

0.15

0.10

0.10

0.05

0.05

0 .5

1.0

1 .5

2.0

2 .5

1.4

1.6

3.0

3.5

4.0

4 .5

16 PAHs

95% confidence

0.20

0.15

1.2

Industrial smokehouse (beef and pork ham)

95% confidence

0.35

0.00

1 .0

12 PAHs

BaP

BaP

0.8

0 .6

95% confidence

0.00

0 .2

0.4

0 .6

0.8

1.0

1.2

1.4

12 PAHs

Fig. 3 Correlations between the content of BaP and the total content
of the 16 EU priority PAHs, as well as between the content of BaP and
the total content of the 12 IARC PAHs in analysed beef and pork ham

samples from traditional and industrial smokehouse. (Djinovic, Popovic & Jira, Polycyclic aromatic hydrocarbons (PAHs) in traditional and
industrial smoked beef and pork ham from Serbia)

Further work is necessary in order to get a more


complete overview about PAH contents in other kind of
smoked meat products from traditional and industrial
smokehouses.

4. Lin DH, Zhu LZ, He W, Tu YT (2006) J Agric Food Chem


54:36583662
5. Tao S, Jiao XC, Chen SH, Liu WX, Coveney RM Jr, Zhu LZ,
Luo YM (2006) Environ Pollut 140:406415
6. Simonich SL, Hites RA (1994) Nature 370:4951
7. Kimko P (2005) Mol Nutr Food Res 49:637647
8. Kimko P (2002) J Chromatogr B 770:318
9. Tth L (1983) Chemie der Riiucherung, Berlin Verlag Chemie
10. Sunen E, Aristimuno C, Fernandez-Galian B (2003) Food Res Int
36:111116
11. Bratzler LJ, Spooner ME, Weathers JB, Maxey JA (1969) J Food
Sci 34:146148
12. Conde FJ, Ayala JH, Afonso AM, Gonzalez V (2005) J Agric Food
Chem 53:176182
13. Jira W, Ziegenhals K, Speer K (2006) Fleischwirtschaft Int 4:1117
14. European Commission (2005a) Commission Regulation No 208/
2005 of 4 February 2005 amending Regulation (EC) No 466/2001
as regards polycyclic aromatic hydrocarbons. OV J Eur Union
L34:35
15. Joint FAO/WHO Expert Committee on Food Additives (2005) SixtyFourth meeting, Rome, 817 February 2005, JECFA/64/SC, summary
and conclusion. http://www.who.int/ipcs/food/jecfa/summaries/en
16. European Commission (2006) Commission Regulation No 1881/
2006 of 19 December 2006 setting maximum levels for certain
contaminants in foodstuVs. OV J Eur Union L364:524

Acknowledgments J. Djinovics Ph. D. work was sponsored by a


scholarship from the Government of the Republic of Serbia. Also, this
work was supported by the Ministry of Science, Republic of Serbia
(Grant No. 146008). The authors are grateful to Spomenka Zagorac,
the director of meat industry Zlatibor, Cajetina, Serbia, for all the help
she has given us. We also thank Gorica Carapic and Miljko Nesanovic
for their help in collecting samples.

References
1. Smith IM (1984) PAH from coal utilization. Emissions and eVects,
Report No ICTIS/TR29, IEA Coal Research London
2. Baek SO, Field RA, Goldstone ME, Kirk PW, Lester JN, Perry R
(1991) Water Air Soil Pollut 60:279300
3. Fontcuberta M, Arques JF, Martinez M, Suarez A, Villalbi JR,
Centrich F, Serrahima E, Duran J, Casas C (2006) J Food Protect
69:20242028

123

1198
17. IARC (1987) IARC monographs on the evaluation of carcinogenic
risks to humans, overall evaluations of carcinogenicity: an updating of IARC monographs, vol 142, supplement 7, Lyon, p 389
18. IARC (1989) IARC monographs on the evaluation of carcinogenic
risks to humans, vol 46, Lyon, p 41
19. IARC (1996) IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, vol 65, p 33, Lyon, France
20. Higginbotham S, Ramakrishna NVS, Johansson SL, Rogan EG,
Cavalieri EL (1993) Carrinogenesis 14:875878
21. Luch A, Glatt H, Platt KL, Oesch F, Seidel A (1994) Carcinogenesis 15:25072516
22. Schober W, Luch A, Soballa VJ, Raab G, Stegeman JJ, Doehmer
J, Jacob J, Seidel A (2006) Chem Biol Interact 161:3748

123

Eur Food Res Technol (2008) 227:11911198


23. European Commission (2005b) Commission Directive 2005/10/
EC of 4 February 2005 laying down the sampling methods and the
methods of analysis for the oYcial control of the levels of benzo(a)pyrene in foodstuVs OYcial Journal of the European Union,
L34, pp 1520
24. Kleinhenz S, Jira W, Schwind KH (2006) Mol Nutr Food Res
50:362367
25. Pratt MM, Reddy AP, Hendricks JD, Pereira C, Kensler TW, Bailey GS (2007) Carcinogenesis 28:611624
26. Kazerouni N, Sinha R, Hsu CH, Greenberg A, Rothman N (2001)
Food Chem Toxicol 39:423436
27. Muller P, Leece B, Raha D (1995) 15th Int Sym PAH Com Belgirate, Italy, pp 159160

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